Title of Invention

"AN ETHYLENE POLYMER"

Abstract An ethylene polymer containing 0.01 to 1.20 mol% of a constitutional unit derived from a-olefin having 6 to 10 carbon atoms, which satisfies at least either of the following requirements (1) and (2) with respect to cross fractionation chromatography (CFC): (1) the weight average molecular weight (Mw) of the components eluted at 73 to 76°C does not exceed 4,000; and (2) the following relationship (Eq-l)is satisfied: Sx/Stotal < 0.1 (Eq-1) wherein Sx is the sum of the total peak areas related to the components which are eluted at 70 to 85°C, and is the sum of the total peak areas related to the components which are eluted at 0 to 145°C.
Full Text The present invention relates to an ethylene polymer.
Technical Field The present invention relates to an ethylene polymer which has excellent moldabillty and gives a molded product having excellent mechanical strength and external appearance, and a molded product obtained therefrom.
Background Art
High-density polyethylene which is in use in wide applications such as films, pipes, bottles and the like, has been conventionally prepared by using a Ziegler-Natta catalyst or a chromium catalyst. However, because of the nature of such catalysts, there has been limitation on the control over the molecular weight distribution or composition distribution of the polymer.
In recent years, several methods have been disclosed for preparation of an ethylene polymer having excellent moldabillty and mechanical strength, including an ethylene homopolymer or an ethylene•α-olefin copolymer of relatively small molecular weights and an ethylene homopolymer or an ethylene•α-olefin copolymer of relatively large molecular weights, according to a continuous polymerization technique, using a single-site catalyst which facilitates the control of the composition distribution, or a catalyst having such the single-site

catalyst supported on a carrier.
In the publication of JP-A No. 11-106432, disclosed
is a composition prepared by melt-blending a low molecular
weight polyethylene with a high molecular weight
ethylene-a-olefin copolymer, which are obtained by
polymerization in the presence of a supported, geometric
constraint type single-site catalyst (CGC/Borate-based
catalyst). However, since the molecular weight
distribution of the composition is not broad, fluidity of
the composition may become poor. In addition, although the
claims of the above-mentioned patent application do jhot
disclose a preferred range of the carbon number of aolefin
that is to be copolymerized with ethylene, in the
case of the carbon number being less than 6, it is expected
that sufficient mechanical strength would not be exhibited.
Further, because the molecular weight distribution (fHw/Mn)
h o f t h e single-stage also expected that the product's mechanical properties such
as impact strength and the like would be insufficient, as
compared with the single-stage product of narrower
molecular weight distribution. Moreover, the anticipation
that a broad composition distribution of the single-stage
polymerization product would result in deterioration of the
above-mentioned strength is obvious from the cross
fractionation chromatography (CFC) data described in
"Functional Materials," published by CMC, Inc., Marqh 2001,
p.50, and the cross fractionation chromatography (CFC) data
described in Fig. 2 in the publication of JP-A No. 11-
106432.
In the publication of WO 01/25328, disclosed is an
ethylene polymer which is obtained by solution
polymerization in the presence of a catalyst system
comprising CpTiNP (tBu) aCl2 and borate or alumoxane. This
ethylene polymer has a weak crystalline structure due to
the presence of a branch group in the low molecular weight
component, and thus the polymer is expected to have poor
mechanical strength. Also, since the molecular weight of
the low molecular weight component is relatively large, it
is expected that the polymer has low fluidity. Moreover,
although the claims of the above-mentioned patent
application do not disclose the preferred range of the
carbon number of a-olefin that is to be copolymerized with
ethylene, it is believed that when the carbon number; is
less than 6, sufficient mechanical strength would not be
exhibited.
In the publication of EP 1201711 Al, disclosed is an
ethylene polymer which is obtained by slurry polymerization
in the presence of a catalyst system comprising
ethylene-bis(4,5,6,7-tetrahydro-l-indenyl)zirconium
dichloride with methylalumoxane supported on silica. Among
such ethylene polymers, a single-stage polymerization
product has a wide molecular weight distribution (Mw/Mn),
and thus it is expected that the impact strength and the
like would be insufficient as compared with a single-stage
product of narrower molecular weight distribution, further,
it is inferred that a broad molecular weight distribution
means heterogeneity of the active species, and consequently
there is a concern that the composition distribution
broadens, thereby resulting in deterioration of fatigue
strength. Moreover, in some Examples of the abovementioned
patent application, a single-stage polymerization
product of small molecular weight and a single-stage
polymerization product of large molecular weight arey meltkneaded.
In this kneading method, crystalline structures
that are continuous over more than 10 pun are often produced,
and thus it is expected that sufficient strength would not
be exhibited.
In the publication of JP-A No. 2002-53615, disclosed
is an ethylene polymer which is obtained by slurry
polymerization using a catalyst system comprising
methylalumoxane and a zirconium compound having a specific
salicylaldimine ligand supported on silica. Although the
claims of the patent application do not disclose the:
preferred range of the carbon number of a-olefin that is
to be copolymerized with ethylene, in regard to the
ethylene polymer obtained from 1-butene (number of carbon
atoms = 4) which is used as the a-olefin in Examples of
the patent application, the carbon number is small, and it
is envisaged that sufficient mechanical strength would not
exhibited.
In general, an ethylene polymer shows a multimodal
molecular weight distribution. When the intermodal
molecular weight differences are large, mixing with meltkneading
is difficult, and thus multistage polymerization
is typically employed. Multistage polymerization is in
general often carried out in a continuous manner. In the
case of such multistage polymerization, a distribution is
usually created in the ratio between the residence time in
a polymerization vessel which is under a polymerizing
environment that would produce a low molecular weight
product, and the residence time in a polymerization vessel
which is under a polymerizing environment that would
produce a high molecular weight product. In particular, in
the case of a polymerization method in which the polymer is
produced in a particulate form, such as the gas-phase
method or slurry method, there may exist differences in the
molecular weight among different particles. Such
difference in molecular weight has been recognized even in
the cases of using the Ziegler catalysts as described in
the publication of Japanese Patent No. 821037 or the like.
However, the catalyst is multi-sited, whereas the molecular
weight distribution is broad. Accordingly, polymer
particles are well mixed with each other even upon
conventional pelletization by melt-kneading. On the other
hand, in the case of using a singe-site catalyst, since the
molecular weight distribution is narrow, the polymer
particles are often not mixed sufficiently with each other
during conventional pelletization by melt-kneading. Thus,
in some cases, the history of polymer as having been in a
particulate form was reflected in the mixture, and this
caused disorder in the fluidity to adversely affect the
appearance or sufficient exhibition of mechanical strength.
Also, such ethylene polymer showed a tendency that the
coefficient of smoothness which is determined from the
surface roughness of extruded strands increased.
The ethylene (co)polymer prepared using a Ziegler
catalyst as described in Japanese Patent No. 821037 or the
like has methyl branch groups in the molecular chain; as a
result of side production of a methyl branch group during
the polymerization reaction. It was found that this:methyl
branch group was embedded in the crystal, thus weakening
the crystal (see, for example, Polymer Vol.31, p.1999
(1990)), and this caused deterioration in mechanical
strength of the ethylene (co)polymer. Further, in regard
to the copolymer of ethylene and a-olefin, when the
copolymer contained almost no a-olefin, a tough and
brittle component was produced; on the other hand, when an
excessive proportion of a-olefin was used in
copolymerization, a soft component with weak crystalline
structure was produced, and thus it may cause tackiness.
Moreover, since the molecular weight distribution was broad,
there were problems such as the phenomenon of a low
molecular weight product adhering to the surfaces of molded
products as a powdery substance, and so on.
The ethylene polymer that is obtained by
polymerization using a metallocene catalyst as described in
the publication of JP-A No. 9-183816 or the like has methyl
branch groups in the molecular chain, as a result of side
production of a methyl branch group during the
polymerization reaction. This methyl branch group is
embedded in the crystals, thereby weakening the crystalline
structure. This has been a cause for the lowering of
mechanical strength. Also, an ethylene polymer with
extremely large molecular weight has not been disclosed
heretofore.
An ethylene polymer that is obtained by
polymerization in the presence of a chromium-based catalyst
exhibits low molecular extension because of the presence of
a long-chained branch group, and thus has poor mechanical
strength. Further, as a result of side production of a
methyl branch group during the polymerization reaction,
there exist methyl branch groups in the molecular chain.
These methyl branch groups are embedded in the crystals and
weaken the crystalline structure. This has been a cause
for the lowering of mechanical strength. Further, in
regard to the copolymer of ethylene and an a-olefin, when
the copolymer contained almost no a-olefin, a tough and
brittle product was produced; on the other hand, when aolefin
was copolymerized in an excessive proportion,
tackiness was caused or a soft component with weak
crystalline structure was produced.
The ethylene polymer that is obtained by
polymerization in the presence of a constrained geometry
catalyst (CGC) as described in the publication of WO
93/08221 or the like has methyl branch groups in the
molecular chain, as a result of side production of a: methyl
branch group during the polymerization reaction. These
methyl branch groups are embedded in the crystals and
weaken the crystalline structure. This has been a cause
for the lowering of mechanical strength. Further, the
molecular extension was low because of the presence of
long-chained branch groups, and thus the mechanical
strength was insufficient.
An ethylene polymer that is obtained by high pressure
radical polymerization has methyl branch groups or longchained
branch groups in the molecular chain, as a result
of the side production of methyl branch groups or longchained
branch groups during polymerization. These methyl
branch groups are embedded in the crystals, thereby
weakening the crystalline strength. This has been a cause
for the lowering of mechanical strength. Further, the
presence of long-chained branch groups resulted in l|ow
molecular extension as well as a broad molecular weight
distribution, and thus the mechanical strength was poor.
In regard to the ethylene polymer that is obtained by
cold polymerization using a catalyst containing Ta- or Nbcomplexes
as described in the publication of JP-A No;. 6-
233723, since the ratio (Mw/Mn) of the weight average
molecular weight (Mw) and the number average molecular
weight (Mn) as measured by GPC was small, the moldabitlity
might be insufficient.
Disclosure of the Invention
Based on the prior art as reviewed above, the
inventors conducted an extensive research on an ethylene
polymer which has excellent moldability and which would
give a molded product having excellent mechanical strength,
and found that
an ethylene polymer (E) containing 0.01 to 1.20, mol%
of a constitutional unit derived from a-olefin having 6 to
10 carbon atoms, which satisfies at least either of the
following requirements (1) and (2) with respect to cross
fractionation chromatography (CFC), has excellent
moldability and also gives a molded product, especially a
blow molded product, a pipe and a fitting, having excellent
mechanical strength and excellent external appearance, thus
completing the invention:
(1) the weight average molecular weight (Mw) of the
components which are eluted at 73°C to 76°C is not more
than 4,000; and
(2) the following relationship (Eq-1) is satisfied:
Sx/Stotai S 0.1 (Eq-1)
(wherein Sx is the sum of the total peak areas
related to the components which are eluted at 70 to J35°C,
and Stotai is the sum of the total peak areas related to the
components which are eluted at 0 to 145°C).
The ethylene polymer (E) according to the present
invention preferably satisfies, in addition to the abovementioned
requirements, the following requirements (;1') to
(7'):
(!') the polymer contains 0.02 to 1.00 mol% of a
constitutional unit derived from a-olefin having 6 to 10
carbon atoms;
(21) the density (d) is in the range of 945 to 970
kg/m3;
(3') the intrinsic viscosity ( [r\]) as measured in
decalin at 135°C is in the range of 1.6 to 4.0 (dl/g!j ;
(4f) the ratio (Mw/Mn) of the weight average
molecular weight (Mw) and the number average molecular
weight (Mn) as measured by GPC is in the range of 5 :o 70;
(5') in the cross fractionation chromatography (CFC),
when the elution temperature for the apex of the strpngest
peak in the region corresponding to molecular weights of
less than 100,000 is taken as TI (°C), and the elution
temperature for the apex of the strongest peak in the
region corresponding to molecular weights of 100,000 or
more is taken as T2 (°C), (Ti - T2) (°C) is in the range of
0 to 11°C;
(6') on the GPC curve for the fraction eluted at
[(T2-l) to T2] (°C), the molecular weight for the apfx of
the strongest peak in the region corresponding to mojlecular
weights of 100,000 or more is in the range of 200,0010 to
800,000; and
(V) in the GPC curve for the components eluted at 95
to 96°C, the molecular weight for the apex of the strongest
peak in the region corresponding to molecular weights of
100,000 or less does not exceed 28,000.
Such ethylene polymer may be referred to as an
ethylene polymer (E1) in the following description.
A more preferred ethylene polymer according to the
invention satisfies, in addition to the above-described
requirements, the requirement that the polymer has less
than 0.1 methyl branch group per 1000 carbon atoms when
measured by 13C-NMR (hereinafter, optionally referred to as
Requirement (!"))• Such ethylene polymer may be referred
to as an ethylene polymer (E") in the following description,
A particularly preferred ethylene polymer according
to the invention satisfies, in addition to all of the
above-described requirements, the following requirements
(!'") and (2"') simultaneously:
(I1 1 1) when the GPC curve is divided into two
logarithmic normal distribution curves, the ratio (Mw/Mn)
of the weight average molecular weight (Mw) and the number
average molecular weight (Mn) for each divided curve is
from 1.5 to 3.5, and the weight average molecular weight
(Mw2) for the divided curve representing the higher
molecular weight portion is from 200,000 to 800,000; and
(2'1') the smoothness coefficient R as determined
from the surface roughness of an extruded strand does not
exceed 20 μm.
In the following description, such ethylene polymer
may be referred to as an ethylene polymer (E111).
In the case of applying the ethylene polymer (E) of
the invention to blow molded products, the ethylene polymer
(E) preferably satisfies, in addition to the abovedescribed
requirements to be fulfilled, the following
requirements UB) to (3B) simultaneously:
(1B) the polymer contains 0.02 to 0.20 mol% of a
constitutional unit derived from a-olefin having 6 tp 10
carbon atoms;
(2B) the ratio (Mw/Mn) of the weight average
molecular weight (Mw) and the number average molecular
weight (Mn) as measured by GPC is in the range of 5 to 30;
and
(3B) with respect to cross fractionation
chromatography (CFC) , when the elution temperature for the
apex of the strongest peak in the region corresponding to
molecular weights of less than 100,000 is taken as Tj. (°C),
and the elution temperature for the apex of the strohgest
peak in the region corresponding to molecular weights of
100,000 or more is taken as T2 (°C), (Ti - T2) (°C) i$ in
the range of 0 to 5°C.
In the following description, such ethylene polymer
may be referred to as an ethylene polymer (EB) .
Furthermore, a more preferred ethylene polymer for
blow molded products preferably satisfies, in additibn to
the above-described requirements (1B) to (3B) , the
following requirements UB') and (2B
?) simultaneously [such
ethylene polymer may be referred to as an ethylene pplymer
(EB
?) in the following description], and particularly
preferably the following requirement de") [such ethylene
polymer may be referred to as an ethylene polymer (EB") in
the following description]:
(IB") the flexural modulus as measured at 23°C
according to ASTM-D-790 is in the range of 1,500 to L,800
MPa;
(2B') the environmental stress crack resistance ESCR
(hr) at 50°C as measured according to ASTM-D-1693 is 10
hours or longer before failure; and
(1B") tan 6 (= loss modulus G"/storage modulus G') as
measured at 190°C and at an angular frequency of 100
rad/sec using a dynamic viscoelasticity measuring apparatus,
is from 0.7 to 0.9.
Furthermore, as for the ethylene polymers (EB), (EB')
and (EB") for blow molded products, the ethylene polymer
(E) is preferably an ethylene polymer (Ef) which alsp
satisfies the above-mentioned requirements (1) to (7|) / more
preferably, the ethylene polymer (Ef) is an ethylene!
polymer (E") which also satisfies the above-mentioned
requirement (!"); and particularly preferably, the ethylene
polymer (E") is an ethylene polymer (E'lf) which alsp
satisfies the above-mentioned requirements (I'*') and
(2"') .
In the case of applying the ethylene polymer (E)
according to the invention to a use in pipes, it is
preferable that the polymer satisfy, in addition to the
foregoing requirements that should be satisfied by qthylene
polymer (E), the following requirements (1P) and (2P)
simultaneously:
(If) it contains 0.10 to 1.00 mol% of a
constitutional unit derived from a-olefin having 6 tjo 10
carbon atoms; and
(2P) the ratio (Mw/Mn) of the weight average
molecular weight (Mw) and the number average molecul|ar
weight (Mn) as measured by GPC is in the range of 11 to 70.
In the following description, such ethylene polymer
may be referred to as an ethylene polymer (EP
f).
In addition, a more preferred ethylene polymer for
pipes preferably satisfies, in addition to the aboveh
mentioned requirements (1?) and (2P), the following
i
requirements (!?') and (2P
!) simultaneously [such ethylene
polymer may be referred to as an ethylene polymer (Ep") in
the following description]:
(lp
f) the actual stress obtained when it takes 10,000
cycles to fracture due to the tensile fatigue property as
measured at 80°C according to JIS K-6744, is from 13| MPa to
17 MPa, and the actual stress obtained when it takes!
100,000 cycles to fracture is from 12 to 16 MPa; and|
(2P') the actual stress (S) (MPa) and the density (d)
obtained when it takes 10,000 cycles to fracture due: to the
tensile fatigue property as measured at 23°C according to
JIS K-7118, satisfy the following relationship (Eq-2|) :
(0.12d - 94.84) Furthermore, as for the ethylene polymers (EP') and
(EP") for pipes, the ethylene polymer (E) is preferably an
ethylene polymer (E1) which also satisfies the abovementioned
requirements (1) to (7); more preferably, tne
ethylene polymer (E1) is an ethylene polymer (E") whjich
also satisfies the above-mentioned requirement (!"); and
particularly preferably, the ethylene polymer (E") i|s an
ethylene polymer (E11') which also satisfies the abovementioned
requirements (I1 1 1 ) and (2'1')-
The ethylene polymer according to the invention may
be molded to blow molded products, inflation molded
products, cast molded products, laminated extrusion folded
products, extrusion molded products such as pipes or
various forms, expansion molded products, injection μmolded
products, or the like. Further, the polymer can be used in
the form of fiber, monofilament, non-woven fabric or the
like. These products include those molded products
comprising a portion made of ethylene polymer and anjother
portion made of other resin (laminated products, etc.).
Moreover, this ethylene polymer may be used in the state of
being crosslinked during the molding process. The ethylene
polymer according to the invention shows excellent
properties when used in blow molded products and extrusion
molded products such as pipes or various forms, amonjg the
above-mentioned molded products.
- 16 -
Brief Description of the Drawings
Fig. 1 is a CFC contour diagram for the ethylene
polymer obtained in Example 1.
Fig. 2 is a three-dimensional GPC chart (bird's eye
view) with T2/ as viewed from the lower temperature $ide,
for the ethylene polymer obtained in Example 1.
Fig. 3 is a three-dimensional GPC chart (bird's eye
view) with TI, as viewed from the higher temperature side,
for the ethylene polymer obtained in Example 1.
Fig. 4 is a GPC curve for the eluted components of
the ethylene polymer obtained in Example 1, at peak
temperatures t(T2-l) to T2] (°C).
Fig. 5 is a GPC curve for the components of the
ethylene polymer obtained in Example 1, which are eluted at
73 to 76 (°C).
Fig. 6 is a GPC curve for the components of the;
ethylene polymer obtained in Example 1, which are elated at
95 to 96 (°C).
Fig. 7 is a CFC contour diagram for the ethylene
polymer obtained in Comparative Example 1.
Fig. 8 is a three-dimensional GPC chart (bird's eye
view) with T2, as viewed from the lower temperature side,
for the ethylene polymer obtained in Comparative Example 1.
Fig. 9 is a three-dimensional GPC chart (bird's eye
view) with TI, as viewed from the higher temperature side,
for the ethylene polymer obtained in Comparative Example 1.
Fig. 10 is a GPC curve for the eluted components of
the ethylene polymer obtained in Comparative Example 1, at
peak temperatures [(T2-l) to T2] (°C).
Fig. 11 is a GPC curve for the components of the
ethylene polymer obtained in Comparative Example 1, which
are eluted at 73 to 76 (°C) .
Fig. 12 is a GPC curve for the components of the
ethylene polymer obtained in Comparative Example 1, Which
are eluted at 95 to 96 (°C).
Fig. 13 is a graph indicating the elution curv and
the integral value for the amounts of the components of the
ethylene polymer obtained in Comparative Example 1, which
are eluted at 0 to 145(°C).
Fig. 14 is a CFC contour diagram for the ethylene
polymer obtained in Comparative Example 5.
Fig. 15 is a three-dimensional GPC chart (birds eye
view) with T2, as viewed from the lower temperature $ide,
I
for the ethylene polymer obtained in Comparative Example 5.
Fig. 16 is three-dimensional GPC chart (bird's eye
view) with TI, as viewed from the higher temperature side,
for the ethylene polymer obtained in Comparative Example 5.
Fig. 17 is a GPC curve for the eluted components of
the ethylene polymer obtained in Comparative Example 5 at
peak temperatures [(T2-l) to T2] (°C).
Fig. 18 is a GPC curve for the components of the
ethylene polymer obtained in Comparative Example 5, Which
are eluted at 73 to 76 (°C).
Fig. 19 is a GPC curve for the components of
ethylene polymer obtained in Comparative Example 5, which
are eluted at 95 to 96 (°C).
Fig. 20 is a CFC contour diagram for the ethylene
polymer obtained in Example 3.
Fig. 21 is a three-dimensional GPC chart (birdfs eye
view) with T2, as viewed from the lower temperature side,
for the ethylene polymer obtained in Example 3.
Fig. 22 is three-dimensional GPC chart (bird's eye
view) with TI, as viewed from the higher temperature side
for the ethylene polymer obtained in Example 3.
Fig. 23 is a GPC curve for the eluted components of
the ethylene polymer obtained in Example 3 at peak
temperatures [(T2-l) to T2] (°C).
Fig. 24 is a GPC curve for the components of the
ethylene polymer obtained in Example 3, which are elbted at
73 to 76 (°C).
Fig. 25 is a GPC curve for the components of tljie
ethylene polymer obtained in Example 3, which are elated at
95 to 96 (°C).
Fig. 26 is a graph indicating the elution curve and
the integral value for the amounts of the components of the
ethylene polymer obtained in Example 3, which are elated at
0 to 145(°C).
Fig. 27 is a diagram indicating the accumulated
concentrations (total = 100%) of the amounts of eluted
components as obtained in CFC measurement of several
Examples and Comparative Examples.
Fig. 28 is a GPC chart illustrating an example of the
analysis of GPC separation.
Fig. 29 shows exemplary results (75 times) for the
measurement of the crystalline structure of an ethylene
polymer.
Fig. 30 shows exemplary results (150 times) for the
measurement of the crystalline structure of an ethylene
polymer.
Fig. 31 is a schematic diagram of the pinch-off part.
Fig. 32 shows a specimen for the tensile fatigue test
at 23°C.
Fig. 33 is a chart indicating the comparison of
results of the tensile fatigue test at 80°C for Examples
and Comparative Examples.
Fig. 34 is a chart indicating the comparison of
results of the tensile fatigue test at 23°C for Examples
and Comparative Examples.
Fig. 35 is a chart indicating the results of the
tensile fatigue test at 23°C for Examples and Comparative
Examples, as plotted against the density of the sample.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Hereinafter, the best modes to carry out the present
invention will be described one after another, regarding
the ethylene polymer (E), the ethylene polymer (EB) which
is suitably used for blow molded products and the blow
molded products prepared therefrom, and the ethylene
polymer (Ep) which is suitably used in pipes and the pipes
or fittings prepared therefrom. Next, a representative
process for preparation of the ethylene polymer according
to the invention and various methods for measurement
according to the invention will be described, and finally
Examples will be illustrated.
Ethylene polymer (E)
The ethylene polymer (E) according to the invention
is an ethylene polymer which contains 0.01 to 1.20 mpl% of
a constitutional unit derived from a-olefin having 6 to 10
carbon atoms, and usually comprises homopolymers of
ethylene and copolymers of ethylene/a-olefin having £ to
10 carbon atoms.
Herein, examples of a-olefin having 6 to 10 catbon
atoms (hereinafter, may be simply abbreviated to "aolefin")
include 1-hexene, 4-methyl-l-pentene, 3-metjiyl-lpentene,
1-octene, 1-decene and the like. According to the
invention, it is preferred to use at least one selected
from 1-hexene, 4-methyl-l-pentene and 1-octene among such
a-olefins.
The ethylene polymer (E) according to the invention
is characterized in that it satisfies either of the
following requirements (1) and (2) with respect to cjross
fractionation chromatography (CFC):
(1) the weight average molecular weight (Mw) oil the
components eluted at 73 to 76°C does not exceed 4,0010; and
(2) the polymer satisfies the following relationship
(Eq-1):
Sx/Stotai wherein Sx is the sum of the total peak areas related
to the components eluted at 70 to 85°C in CFC, and Stotai is
the sum of the total peak areas related to the components
eluted at 0 to 145°C.
Such ethylene polymer (E) is excellent in Iong4term
properties such as fatigue properties when applied tp
molded products. Next/ the requirements (1) and (2) will
be explained in detail.
[Requirement (1)]
As for the ethylene polymer (E) according to the
invention, the weight average molecular weight (Mw) 0f the
components that are eluted at 73 to 76°C in cross
fractionation chromatography (CFC), as measured by GiPC,
does not exceed 4,000. More specifically, the weight
average molecular weight (Mw) in association with the GPC
peaks detected in the region for molecular weight of 108 or
less does not exceed 4,000. The weight average molecular
weight (Mw) is preferably in the range of 2,000 to 4,000,
and more preferably in the range of 2,500 to 3,500. It is
meant by such ethylene polymer that the content of the high
molecular weight components having a copolymerized af
olefin is small, or that the polymer does not contain any
of such components which have relatively small molecular
weights and also have a short-chained branch group. In
this case, a product molded therefrom is excellent in longterm
properties such as fatigue strength. The ethylene-ocolefin
copolymer as described in the publication of JP-A No,
11-106432 has a wide composition distribution and thus does
not satisfy the above-mentioned scope. The ethylene
polymer as described in the publication of WO 01/25328 does
not satisfy the above-mentioned scope because even a
component with relatively small molecular weight also has a
short-chained branch group resulting from copolymerijzation
with an a-olefin. The ethylene polymers of prior art
prepared in the presence of a Ziegler catalyst or a
chromium catalyst also have wide composition distributions
and thus do not satisfy the above-mentioned scope.
By setting the polymerization conditions as described
later and using a catalyst system as described later, an
ethylene polymer falling within this scope can be prepared.
Specifically, when polymerization is carried out undbr the
conditions as described in Example 3 of the inventiop, the
weight average molecular weight (Mw) of the components
which are eluted at 73 to 76°C in temperature rising
elution fractionation using a cross fractionation
chromatography (CFC) apparatus is 2,900. Further, ai long
as the catalyst or the polymerization temperature is not
changed, also as long as a-olefin is not supplied to the
first polymerization vessel, and also as long as the aolefin
supplied to the second polymerization vessel in
this case, 1-hexene) is supplied at a rate no more than 900
g/hr, the above-mentioned weight average molecular weight
(Mw) becomes less than 4,000.
[Requirement (2) ]
The ethylene polymer (E) according to the invention
satisfies the relationship as represented by the following
equation (Eq-1):
Sx/Stotai wherein Sx represents the sum of the total peak areas
related to the components which are eluted at 70 to 5°C,
and Stotai represents the sum of the total peak areas
related to the components which are eluted at 0 to 145°C,
in cross fractionation chromatography (CFC).
As it has been explained for the terms in Requirement
(1), it is meant by such ethylene polymer which satisfies
Requirement (2), that the content of the high molecular
weight components having a copolymerized a-olefin is small,
or that the polymer does not contain any of such components
which have relatively small molecular weights and also have
a short-chained branch group. In this case, a product
molded therefrom is excellent in long-term propertied such
as fatigue strength and the like. The ethylene-a-olfin
copolymer as described in the publication of JP-A Noj. 11-
i
106432 does not satisfy the relationship of the abovementioned
equation (Eq-1) because of its wide composition
distribution. The ethylene polymer as described in the
publication of WO 01/25328 does not satisfy the
relationship of the above equation (Eq-1) because ev£n a
component with relatively small molecular weight alsp has a
short-chained branch group resulting from copolymerifcation
with an a-olefin. The ethylene polymers of prior art
prepared in the presence of a Ziegler catalyst or a
chromium catalyst also have wide composition distributions
and thus do not satisfy the relationship of the above
equation (Eq-1) . In addition, since Sx and Stotai in the
above equation (Eq-1) represent the values based on the
infrared analysis of elastic oscillation of the C-H bond,
the value of Sx/Stotai is in principle identical with the
percentage by weight occupied by the components eluted at
70 to 85°C in the components eluted at 0 to 145°C.
Typically, as for the ethylene polymer of the invention,
since all of the components are eluted off by scanning in
the region of 0 to 145°C, the value of Sx/Stotai can b£
otherwise said to be the percentage by weight occupied by
the amount of the components eluted at 70 to 85°C in the
unit weight of the ethylene polymer.
An ethylene polymer falling within this scope dan be
prepared by setting the polymerization conditions as
described later and using a catalyst system as described
later. Specifically, when polymerization is carried out
under the conditions as described in Example 3 of the
invention, the value of the left-hand side of equation (Eq-
1) with respect to cross fractionation chromatographt (CFC)
of the ethylene polymer obtained therefrom, namely,
/ is 0.042. Further, as long as the cataly$t or
the polymerization temperature is not changed, also as long
as a-olefin is not supplied to the first polymerization
vessel, and also as long as the a-olefin supplied to the
second polymerization vessel (in this case, 1-hexene) is
supplied at a rate no more than 900 g/hr, the value for
(Sx/Stotai) satisfies the above relationship (Eq-1) .
A more preferred form of the above-mentioned etthylene
polymer (E) is ethylene polymer (E?) which satisfies the
following requirements (I1) to (V):
(I1) it contains 0.02 to 1.00 mol% of a
constitutional unit derived from a-olefin having 6 to 10
carbon atoms;
(2!) the density (d) is in the range of 945 to 970
kg/m3;
(3') the intrinsic viscosity ([r\]) as measured in
decalin at 135°C is in the range of 1.6 to 4.0 (dl/g);
(4!) the ratio (Mw/Mn) of the weight average
molecular weight (Mw) and the number average molecular
weight (Mn) as measured by GPC is in the range of 5 to 70;
(51) with respect to cross fractionation
chromatography (CFC), when the elution temperature f
apex of the strongest peak in the region corresponding to
molecular weights of less than 100,000 is taken as T1 (°C),
and the elution temperature for the apex of the strongest
peak in the region corresponding to molecular weights of
100,000 or more is taken as T2 (°C), (Tx - T2) (°C) i$ in
the range of 0 to 11°C;
(6f) with respect to cross fractionation
chromatography (CFC), the molecular weight for the aex of
the strongest peak in the region corresponding to molecular
weights of 100,000 or more is in the range of 200,000 to
800,000 on the GPC curve for the fraction eluted at ((T2-l)
to T2]) (°C); and
(71) on the GPC curve for the fraction eluted $t
[(T2-l) to T2]) (°C), the molecular weight at the apex of
the strongest peak in the region corresponding to molecular
weights of 100,000 or less does not exceed 28.000 in the
GPC curve for the components eluted at 95 to 96°C.
Hereinafter, requirements (I1) to (71) will be
explained specifically in succession.
[Requirement (1')]
The ethylene polymer (E1) according to the invention
typically contains 0.02 to 1.00 mol% of a constitutional
unit derived from a-olefin having 6 to 10 carbon atoins.
When ethylene polymer (E1) does not include homopolytners of
ethylene, that is, when the polymer includes only
copolymers of ethylene and a-olefin having 6 to 10 carbon
atoms, the constitutional unit derived from ethylene is
preferably present in a proportion of usually from 90 to
99.98 mol%, preferably from 99.5 to 99.98 mol%, and more
preferably from 99.6 to 99.98 mol%, and the repeating unit
derived from the a-olefin is preferably present in a
proportion of usually from 0.02 to 1 mol%, preferably from
0.02 to 0.5 mol%, and more preferably from 0.02 to Oit4 mol%.
Further, the ethylene polymer (E1) may also include
ethylene homopolymers, and in this case, the constitutional
unit derived from ethylene in the ethylene•a-olefin
copolymer part is preferably present in a proportion of
usually from 95 to 99.96 mol%, preferably from 97.5 to
99.96 mol%, and more preferably from 98 to 99.96 molfc, and
the repeating unit derived from the a-olefin is preferably
present in a proportion of usually from 0.04 to 5 moL%,
preferably from 0.04 to 2.5 mol%, and more preferably from
0.04 to 2.0 mol%. In addition, even in the case of
ethylene homopolymers being included, the repeating unit
derived from the a-olefin occupies a proportion of usually
from 0.02 to 1 mol%, preferably from 0.02 to 0.5 mol%, and
more preferably from 0.02 to 0.4 mol% of the whole polymer.
When the a-olefin has 5 or less carbon atoms, the
probability of the a-olefin being incorporated into the
crystals increases (see Polymer, Vol.31, p.1999 (1990)),
and consequently the strength is weakened, which is not
desirable. When the a-olefin has more than 10 carbon atoms,
the activation energy for fluidity becomes larger, and
there occurs a large change in viscosity during molding,
which is not desirable. Also, when the a-olefin has more
than 10 carbon atoms, the side chain (the branch group
originating from the a-olefin copolymerized with ethylene)
may sometimes undergo crystallization, thereby resulting in
weakening of the non-crystalline part, which is not
desirable.
[Requirement (2') and Requirement (3')]
The density (d) of ethylene polymer (E1) according to
the invention is in the range of 945 to 970 kg/m3,
preferably from 947 to 969 kg/m3, and more preferably from
950 to 969 kg/m3, and the intrinsic viscosity ( [r|]) thereof
as measured in decalin at 135°C is in the range of lj.6 to
4.0 dl/g, preferably from 1.7 to 3.8 dl/g, and more
preferably from 1.8 to 3.7 dl/g. The ethylene polymer
having its density and intrinsic viscosity within these
ranges is well balanced between hardness and moldabi|lity.
For example, by changing the ratio of the amounts of
hydrogen, ethylene and a-olefin fed to the polymerization
vessel, the ratio between the polymerization amounts of
ethylene homopolymer and of ethylene-a-olefin copolypier,
or the like, the values of density and intrinsic visbosity
can be increased or decreased within the above-mentioned
numerical ranges. Specifically, in the slurry
polymerization of Example 3 using hexane as the solvent,
when polymerization is carried out under stirring to render
the system homogeneous, the density and [T^] become 953
kg/m3 and 3.10 dl/g, respectively; when ethylene, hydrogen
and 1-hexene are fed to the second polymerization vessel at
the rates of 6.0 kg/hr, 0.45 N-liter/hr and 300 g/hrr
respectively, the density and [TI] become 944 kg/m3 and 3.6
dl/g, respectively; and when ethylene and hydrogen are fed
to the first polymerization vessel at the rates of 7.0
kg/hr and 125 N-liters/hr, respectively, and when ethylene,
hydrogen and 1-hexene are fed to the second polymerisation
vessel at the rates of 3.0 kg/hr, 0.07 N-liter/hr, and 30
g/hr, respectively, the density and [t|] become 968 kg/m3
and 2.10 dl/g, respectively.
[Requirement (4')]
The ethylene polymer (E1) according to the invention
has the ratio Mw/Mn (Mw: weight average molecular wefLght,
Mn: number average molecular weight) as measured by gel
permeation chromatography (GPC), in the range of usually
from 5 to 70, and preferably from 5 to 50. When multistage
polymerization as described later is carried out usihg a
catalyst system as described later, an ethylene polymer
falling within this scope can be prepared by controlling
the molecular weights of the respective components and the
ratio of polymerization amounts.
For example, Mw/Mn can be increased by increasing the
differences between the molecular weights of the respective
components. The polymer having Mw/Mn within the aboV'ementioned
ranges is well balanced between the mechanical
strength and moldability. Specifically, when
polymerization is carried out under the conditions a£
described in Example 3 of the invention, Mw/Mn is 14,8.
Here, when the amount of ethylene fed to the first
polymerization vessel is changed from 5.0 kg/hr to 710
kg/hr, and that of hydrogen is changed from 57 N-litrs/hr
to 125 N-liters/hr, the molecular weight of the ethylene
polymer produced in the first polymerization vessel
decreases, and thus Mw/Mn becomes about 18. On the other
hand, when the amount of ethylene fed to the second
polymerization vessel is changed from 4.0 kg/hr to 3.3
kg/hr, and that of hydrogen is changed from 0.2 N-liter/hr
to 0.07 N-liter/hr, the molecular weight of the ethylene
polymer produced in the second polymerization-vessel
increases, and thus Mw/Mn becomes about 22. Or else, when
hydrogen is fed to the first polymerization vessel at 52 Nliters/
hr, and ethylene, hydrogen and 1-hexene are fed to
the second polymerization vessel at 6.0 kg/hr, 0.45 Nliter/
hr and 200 g/hr, respectively, Mw/Mn becomes about 12
[Requirement (5')]
In temperature rising elution fractionation of the
ethylene polymer according to the invention using a cross
fractionation chromatography (CFC) apparatus, when the
elution temperature for the apex of the strongest peak in
the region corresponding to molecular weights of less than
100,000 is taken as TI (°C), and the elution temperature
for the apex of the strongest peak in the region
corresponding to molecular weights of 100,000 or more is
taken as T2 (°C), (Ti - T2) (°C) is in the range of 0 to
11°C, preferably in the range of 0 to 10°C, and more
preferably in the range of 0 to 9°C. In addition, in the
CFC analysis according to the invention, the term "peak" as
explained with reference to, for example, Fig.2, indicates
the distribution (chromatogram) of the solute, that is, the
entire peak form; the term "the strongest (or the peak
intensity is the strongest)" means that the height of the
peak is the highest; and the term "apex of the peak" means
the point where the differential value becomes zero (i.e.,
the top of the peak). Furthermore, if the peak does not
have an apex/ it indicates the portion where the
differential value is closest to zero (i.e., shoulder).
; j Such ethylene polymer can be prepared to fall Within
the above-mentioned scope by setting the polymerization
conditions as described later and using a catalyst system
as described later.
The value of (Ti - T2) can be increased or decreased
within these ranges, by increasing or decreasing the amount
of the copolymerized a-olefin within a specific range.
Specifically, when polymerization is carried out under the
conditions as described in Example 3, there exist two peaks
with different molecular weights in temperature rising
elution fractionation using a cross fractionation
chromatography (CFC) apparatus, and the temperature
difference (Ti - T2) (°C) between the temperature (Ti) for
the peak with the strongest peak intensity in the region
corresponding to the eluted components having molecular
weights of less than 100,000, and the temperature (T2) for
the peak with the strongest peak intensity in the region
corresponding to the eluted components having molecular
weights of 100,000 or more, becomes 6°C. When the aminunt
of 1-hexene fed to the second polymerization vessel is
- 32 -
changed from 130'g/hr to 50 g/hr, (Ti - T2) (°C) becomes
1°C, and when the same is changed to 200 g/hr, (T1 - T2)
(°C) becomes 11°c.
[Requirement (61)]
In cross fractionation chromatography (CFC) of
ethylene polymer (E1) according to the invention, on the
GPC curve for the fraction eluted at the above-mentioned
T2(°C), the molecular weight for the apex of the strongest
peak in the region corresponding to molecular weights of
100,000 or more is in the range of from 200,000 to 800,000.
In addition, the fraction eluted at T2(°C) indicates the
fraction of the components eluted at [ (T2 - 1) to T2] (°C) .
Such ethylene polymer is well balanced between the longterm
properties such as fatigue property and the like and
moldability. An ethylene polymer falling within this scope
can be prepared by setting the polymerization conditions as
described later and using a catalyst system as described
later. By means of increases or decreases in the amounts
of the ct-olefin, hydrogen, ethylene and the like supplied
to a polymerization environment which would result in the
preparation of a copolymer, the molecular weight for;the
apex of the peak corresponding to the highest molecular
weight on the GPC curve for the fraction eluted at T2 (°C),
can be increased or decreased within a specific range.
Specifically speaking, when polymerization is carried out
under the conditions as described in Example 3, in the GPC
curve for the above-mentioned fraction eluted at [ (T2. - 1)
to Ta] (°C) in temperature rising elution fractionation
using a cross fractionation chromatography (CFC) apparatus,
the molecular weight for the apex of the strongest peak in
the region corresponding to molecular weights of 100/000 or
more is 493,000. When the amount of 1-hexene fed to the
second polymerization vessel is changed from 130 g/hr to
200 g/hr, that of ethylene is changed from 4.0 kg/hr to 6.0
kg/hr, and that of hydrogen is changed from 0.2 N-lit;er/hr
to 0.45 N-liter/hr, the molecular weight for the apeX of
the strongest peak in the region corresponding to molecular
weights of 100,000 or more in the GPC curve for the abovementioned
fraction eluted at [(T2 - 1) to T2] (°C) in
temperature rising elution fractionation using a cross
fractionation chromatography (CFC) apparatus, becomes
361,000. When the amount of hydrogen fed to the second
polymerization vessel is changed from 0.2 N-liter/hr to 0.1
N-liter/hr, the molecular weight for the apex of the peak
corresponding to the highest molecular weight in the iGPC
|
curve for the above-mentioned fraction eluted at [ (T2 - 1)
to TZ] (°C) in temperature rising elution fractionation
using a cross fractionation chromatography (CFC) apparatus,
becomes 680,000. With those metallocene catalysts
conventionally known, it has been impossible to obtain an
ethylene copolymer having a narrow molecular weight
distribution and such high molecular weight.
[Requirement (7')]
In the GPC curve for the components of the ethylene
polymer according to the invention, which are eluted at 95
to 96°C in cross fractionation chromatography (CFC), the
molecular weight for the apex of the strongest peak does
not exceed 28,000. It is usually in the range of 15,000 to
27,000. It is meant by such ethylene polymer that it does .
not contain any of such components which have low molecular
weights and also have a short-chained branch group, and in
this case, the polymer is excellent in long-term properties
such as fatigue strength.
Such ethylene polymer falling within this scope can
be prepared by setting the polymerization conditions as
described later and using a catalyst system as described
later. Specifically speaking, when polymerization is
carried out under the conditions as described in Example 3,
the molecular weight for the apex of the strongest peak in
the GPC curve for the components eluted at 95 to 96 °C in
temperature rising elution fractionation using a cross
fractionation chromatography (CFC) apparatus, is 22,000.
Further, as long as the catalyst or the polymerization
temperature is not changed, also as long as a-olefin is
not supplied to the first polymerization vessel, and also
as long as the amount of hydrogen supplied to the second
polymerization is not set to 10 N-liters/hr or more, Mw
lies within this range. When a branch group is present
even in a low molecular weight component as described in WO
01/25328, since the crystallinity of the low molecular
weight component is deteriorated, components having larger
molecular weights are eluted off even at the same elution
temperature, thus the requirement being not satisfied.
A more preferred form of the above-mentioned ethylene
polymer (E1) is ethylene polymer (E") in which less than
0.1, preferably less than 0.08, methyl branch group as
measured by 13C-NMR is present per 1000 carbon atoms. Since
such polymer has a strong crystalline structure, the
mechanical strength is excellent. As for the ethylene
polymer prepared by using a catalyst system as illustrated
below, the methyl branch group is not detected because the
quantity of the group is beyond the detection limit (0.08
per 1000 carbon atoms).
A particularly preferred form of ethylene polymer
(E") as described above is the ethylene copolymer (E1 1 1 )
which satisfies the following requirements (I'11) and
(21 1 1 ) simultaneously:
(I1 1 1 ) when the GPC curve is divided into two
logarithmic normal distribution curves, the ratio (Mw/Mn)
of the weight average molecular weight (Mw) and the number
average molecular weight (Mn) for each divided curve is in
the range of 1.5 to 3.5, and the weight average molecular
weight for the divided representing the high molecular
weight side (Mw2) is from 200,000 to 800,000; and
(2f'r) the smoothness coefficient R as determined
from the surface roughness of an extruded strand does not
exceed 20 (Jin.
Hereinafter, the requirements (I1 1 1 ) and (2II!) will
be specifically explained.
[Requirement (I111)]
As for the ethylene polymer (E111) according to the
invention, when the molecular weight curve (GPC curve)
measured by gel permeation chromatography (GPC) is divided
into two logarithmic normal distribution curves, the weight
average molecular weight (Mw)/number average molecular
weight (Mn) for each divided curve is in the range of
usually from 1.5 to 3.5, and preferably from 1.5 to 3.2.
An ethylene polymer falling within this scope can be
prepared by performing multistage polymerization as
described later using a catalyst system as described plater,
and by controlling the type of the catalyst compound, the
number of stages required for the multistage polymerization
process, and the molecular weights of the respective
components, which are selected for the process. It is
possible to obtain a large value for Mw/Mn when
polymerization is carried out in a gas phase, whereas it is
possible to obtain a small value for Mw/Mn when
polymerization is carried out in'a slurry phase, because
heat removal or monomer diffusion occurs more uniformly.
Moreover, when a catalyst component is used without being
supported on a carrier, the system approaches closely to a
homogeneous system, and therefore the Mw/Mn becomes smaller.
When slurry polymerization is carried out using a supported,
geometric constraint type single-site catalyst (CGC/Borate)
as described in the publication of JP-A No. 11-106432, or
when slurry polymerization is carried out using a catalyst
system comprising methylalumoxane and ethylene-bis(4,5,6,7-
tetrahydro-1-indenyl) zirconium chloride supported on
silica as described in the publication of EP 1201711 Al,
the Mw/Mn for single-stage polymerization becomes 4 or more,
thus the products not satisfying the claimed scope of the
invention. Moreover, the Mw/Mn of the ethylene polymer
that can be obtained by single stage slurry polymerization
at 80°C using the catalyst described in Example 1 of the
invention, is approximately 2.3.
Furthermore, when the GPC curve for ethylene polymer
(E111) according to the invention is divided into two
logarithmic normal distribution curves, the weight average
molecular weight (Mwa) for the divided curve representing
the high molecular weight side is in the range of 200,000
to 800,000. An ethylene polymer with its Mwa falling
within the above-mentioned range can be prepared by
appropriately selecting the proportions of hydrogen,
ethylene and a-olefin used in the preparation of ethylene
polymer. Specifically speaking, when polymerization is
carried out under the conditions as described in Example 3,
the weight average molecular weight (Mw2) for the divided
curve representing the high molecular weight side upon
division of the GPC curve into two logarithmic normal
distribution curves, becomes 416,000. When ethylene,
hydrogen and 1-hexene are fed to the second polymerization
vessel at the rates of 6.0 kg/hr, 0.35 N-liter/hr, and 200
g/hr, respectively, MW2 becomes 312,000; and when ethylene
and hydrogen are fed to the second polymerization vessel at
the rates of 3.0 kg/hr and 0.07 N-liter/hr, respectively,
and 1-hexene is fed to the second polymerization vessel at
the rate of 30 g/hr, Mw2 becomes 539,000. The ethylene
polymer having its Mwa within this range is well balanced
between the strength and moldability.
[Requirement (2' ' ')]
As for the ethylene polymer (E'lf) according to the
invention, the smoothness coefficient R as determined from
the surface roughness of an extruded strand does not exceed
20 |im, and preferably 15 urn. When the ethylene polymer
obtained by polymerization such as gas phase polymerization
or slurry polymerization is in a particulate form, the
polymer particles may not be intermixed and dispersed
completely even after being subjected to post-treatment
such as melt-kneading and the like, and there may remain
portions with different viscosities looking like mottles.
In this case, when the molten resin is extruded to a shape
of tube or strand, the surface would have rough skin. In
such case, a product molded therefrom would also have
similar rough skin. The extent can be determined from the
smoothness coefficient R as determined by the measurement
of surface roughness. In general, the size of an ethylene
polymer particle prepared by gas phase polymerization or
slurry polymerization is about a few tens of micrometers to
2 millimeters. When the morphological history of the
polymer particle lingers on, the surface of an extruded
product would have rough skin, resulting in the R value to
increase to over 20 pm, and for example, when a
polymerization method as described later is selected, an
ethylene polymer having an R value not exceeding 20 nm, and
usually not exceeding 15 |^m, can be prepared. If R does
not exceed 20 urn, a fluctuation in the range of 0 to 20 urn
may occur due to incorporation of foreign substances or
scratches in the die upon film formation, measurement error
or the like, regardless of the essential nature. Therefore,
it is meaningful only when R does not exceed 20 μm. In
regard to an ethylene polymer having an R value which would
exceed 20 μm, for example, when the ethylene polymer powder
obtained in Example 3 is melt-kneaded at 190°C and 25 rpm
for a very long time such as 15 minutes or the like using a
Labo-Plastmil (a batch-type counter rotating twin screw
kneader) manufactured by Toyo Seiki Seisakusho, Ltd., an
ethylene polymer having an R less than 20 μm can be
obtained. It is possible to make R smaller by lengthening
the time for kneading, but this may cause structural
changes that are associated with decomposition or
crosslinking. Further, when an ethylene polymer having an
R which would exceed 20 μm is dissolved in a good solvent
such as para-xylene to a proportion of about 5 g to 500 ml
of the solvent, subsequently precipitated in a poor solvent,
such as ice-cooled acetone, of a volume five times the
solution volume at a rate of about 10 ml/min, and then
dried and melt-kneaded, an ethylene polymer having an R
value 10 μm or less can be obtained. Since a polymer
having an R that does not exceed the above-mentioned value
is homogeneous without reflectance of the polymer history
as particle, the mechanical strength is particularly
excellent, and fluidity becomes uniform. Thus, the surface
of a molded product becomes smooth with excellent
appearance. As shown in Example 1 of the invention, when
batch-type two-stage polymerization is carried out, R does
not exceed 20 μm, even without performing melt-kneading for
a long time. Furthermore, when an ethylene polymer which
is obtained by withdrawing an ethylene homopolymer from a
first polymerization vessel and subjecting it to singlestage
slurry polymerization under the conditions of a
separate second polymerization vessel, among the ethylene
polymers obtainable by Example 3, is melt-kneaded, an
ethylene polymer with its R not exceeding 20 |im may be
obtained.
Ethylene polymers (E), (E1), (E") and (E'1)
according to the invention are characterized in that when a
Microtome slice of a 0.5 mm-thick pressed sheet of one of
the polymers obtained after melting at 190°C and cooling at
20°C is observed under a polarized microscope, a
crystalline structure continuous over more than 10 μrn is
not observed.
Specifically speaking, when a Microtome slice of a
0.5 mm-thick pressed sheet obtained by melting at 190°C and
cooling at 20°C is observed by polarized microscopy, a
crystalline structure continuous over more than 10 μm. is
not observed. Such ethylene polymer has excellent
mechanical strength. For example, when the ethylene
polymer powder obtained in Example 3 is melt-kneaded using
a Labo-Plastmil (a batch-type counter rotating twin screw
kneader) manufactured by Toyo Seiki Seisakusho, Ltd., at
190°C and 25 rpm for a long time to some extent such as 10
minutes or more, or the like, an ethylene polymer in which
a crystalline structure continuous over more than 10 μm is
not observed can be obtained. Also, as described in
Example 1, when batch-type two-stage polymerization is
carried out, an ethylene polymer in which a crystalline
structure continuous over more than 10 μm is not observed
can be obtained only with melt-kneading for a very short
time. On the other hand, when an ethylene polymer which is
obtained by withdrawing an ethylene homopolymer from a
first polymerization vessel and subjecting it to singlestage
slurry polymerization under the conditions of a
separate second polymerization vessel, among the ethylene
polymers obtainable by Example 3, is melt-kneaded, even
though the kneading time is extended, a crystalline
structure continuous over more than 10 μm is observed.
In addition, the polymerization process to obtain
ethylene polymers (E) to (E'If) of the invention is
preferably carried out in the slurry phase or in the gas
phase. When polymerization, preferably multistage
polymerization, is carried out in the slurry phase or gas
phase, two ethylene polymers with significantly different
molecular weights are intermixed in the order of primary
particles (nanometer order), which correspond to a single
active site of catalyst, during polymerization, and thus it
is desirable.
Ethylene polymer (EB) suitably used in blow molded
products
Among the ethylene polymers (E), preferably (E1),
more preferably (E"), and particularly preferably (E1'1),
according to the invention, the ethylene polymer (EB) which
is suitably used in blow molded products is preferably
defined as in the following (1B) , (2B) and (3B), in terms of
the concentration of the constitutional unit derived from
a-olefin having 6 to 10 carbon atoms, of the value of
Mw/Mn, and of the value of (Ti - T2) with respect to cross
fractionation chromatography (CFC), respectively:
(1B) the polymer contains 0.02 to 0.20 mol% of a
constitutional unit derived from a-olefin having 6 to 10
carbon atoms;
(2B) the ratio (Mw/Mn) of the weight average
molecular weight (Mw) and the number average molecular
weight (Mn) as measured by GPC is in the range of 5 to 30;
and
(3B) with respect to cross fractionation
chromatography (CFC), when the elution temperature for the
apex of the strongest peak in the region corresponding to
molecular weights of less than 100,000 is taken as TI (°C),
and the elution temperature for the apex of the strongest
peak in the region corresponding to molecular weights of
100,000 or more is taken as T2 (°C), (Ti - T2) (°C) is in
the range of 0 to 5°C.
Hereinafter, supplementary explanation on requirement
(1B) and requirement (3B) will be given.
[Requirement (1B) ]
The ethylene polymer (EB) according to the invention
which is suitably used in blow molded products usually
contains 0.02 to 0.2 mol% of a constitutional unit derived
from a-olefin having 6 to 10 carbon atoms. When ethylene
polymer (EB) of the invention does not include ethylene
homopolymers, that is, when the polymer consists only of
copolymers of ethylene and a-olefin having 6 to 10 carbon
atoms, it is desirable that the constitutional unit derived
from ethylene is present typically in a proportion of 99.80
to 99.98 mol%, and the repeating unit derived from the is present typically in a proportion of 0.02 to 0.20
mol%. Further, the ethylene polymer (EB) may occasionally
include ethylene homopolymers, and in this case, it is
desirable that the constitutional unit derived from
ethylene in the ethylene-a-olefin copolymer part is
present typically in a proportion of 99.00 to 99.96 mol%,
and the repeating unit derived from the a-olefin is
present in a proportion of 0.04 to 1.00 mol%. In addition,
even in the case of including ethylene homopolymers, the
repeating unit derived from the a-olefin normally occupies
0.02 to 0.20 mol% of the whole polymer.
[Requirement (3B) ]
The ethylene polymer (EB) according to the invention
which is suitably used in blow molded products is such that
in temperature rising elution fractionation using a cross
fractionation chromatography (CFC) apparatus, when the
elution temperature for the apex of the strongest peak in
the region corresponding to molecular weights of less than
100,000 is taken as TI (°C), and the elution temperature
for the apex of the strongest peak in the region
corresponding to molecular weights of 100,000 or more is
taken as T2 (°C), (Ti - T2) (°C) is in the range of 0 to 5°C,
preferably from 0 to 4°C, and more preferably from 0 to 3°C.
Here, the term apex of the strongest peak refers to the
part where the differential value is zero (i.e., the top of
the peak), and when there is no apex in the peak, the term
refers to the part where the differential value is closest
to zero (i.e., shoulder part). Such ethylene polymer has
high toughness as well as excellent environmental stress
crack resistance and the like. An ethylene polymer falling
in this scope can be prepared by setting the polymerization
conditions as described later and using a catalyst system
as described later. (Ti - T2) can be increased or decreased
within the above-mentioned ranges by increasing or
decreasing the amount of the copolymerized a-olefin in a
specific range. Specifically, when polymerization is
carried out under the conditions as described in Example 14
using hexane as the solvent, there exist two peaks with
different molecular weights in temperature rising elution
fractionation using a cross fractionation chromatography
(CFC) apparatus, and the temperature difference (Ti - T2)
(°C) between the temperature (Ti) for the peak with the
strongest peak intensity in the region representing the
eluted components with molecular weights of less than
100,000, and the temperature (T2) for the peak with the
strongest peak intensity in the region representing the
eluted components with molecular weights of 100,000 or more,
becomes 1°C. When the amount of 1-hexene fed to the second
polymerization vessel is changed from 50 g/hr to 130 g/hr,
(Ti - T2) (°C) can be adjusted to 5°C.
The ethylene polymer (EB) according to the invention
preferably satisfies, in addition to the above-mentioned
requirements (1B) to (3B), the following requirements (1B')
and (2B') [this ethylene polymer may be referred to as an
ethylene polymer {EB')J/ and more preferably satisfies the
following requirement Us") [this ethylene polymer may be
referred to as an ethylene polymer (EB")]:
(1B') the flexural modulus as measured at 23°C
according to ASTM-D-790 is in the range of 1,500 to 1,800
MPa;
(2B') the environmental stress crack resistance ESCR
(hr) at 50°C as measured according to ASTM-D-1693 is 10
hours or longer before failure; and
(1B") tan 8 (= loss modulus G"/storage modulus G') as
measured at 190°C and at an angular frequency of 100
rad/sec using a dynamic viscoelecticity measuring apparatus,
is from 0.7 to 0.9.
Hereinafter, requirements (1B'), (2B') and (1B") will
be described in detail.
[Requirements (1B') and (2B')1
The ethylene polymer (EB
!) according to the invention
is such that the flexural modulus as measured at 23°C is in
the range of 1,500 to 1,800 MPa, and the environmental
stress crack resistance ESCR (hr) as measured at 50°C is 10
hours or longer before failure, preferably 50 hours or
longer before failure. An ethylene polymer having the
flexural modulus and ESCR values within these ranges is
hard and tough, and thus the molded product obtained
therefrom can be made thinner than conventional ones upon
use. When multistage polymerization as described later is
carried out using a catalyst system as described later, an
ethylene polymer with its [TI] falling in the above range
can be prepared by changing the proportions of hydrogen,
ethylene and a-olefin fed to the polymerization vessel and
thereby controlling the molecular weights and the
proportions of polymerized amounts of the respective
components. Specifically, when an ethylene polymer which
has been polymerized under the conditions as described in
Example 14 using hexane as the solvent, is kneaded at 190°C
and 50 rpm for 10 minutes using a Labo-Plastmil (batch
volume of the unit = 60 cm3) manufactured by Toyo Seiki
Seisakusho, Ltd., the flexural modulus obtained is 1,650
MPa, and the ESCR is 600 hours before failure. When the
amount of 1-hexene fed to the second polymerization vessel
is changed from 50 g/hr to 30 g/hr, and the amount of
ethylene fed to the second polymerization vessel is reduced
from 4.0 kg/hr to 3.0 kg/hr, the flexural modulus becomes
1,780 MPa, and the ESCR becomes 233 hours before near 50%
failure. When the amount of 1-hexene fed to the second
polymerization vessel is changed from 50 g/hr to 65 g/hr,
the flexural modulus becomes 1,520 MPa, and the ESCR
becomes 600 hours before failure.
[Requirement (1B")]
The above-mentioned ethylene polymer (EB') according
to the invention is preferably such that tan 8 (loss
modulus G"/storage modulus G') as measured at 190°C and at
an angular frequency of 100 rad/sec using a dynamic
viscoelasticity measuring apparatus is 0.7 to 0.9. When
tan 6 falls within this range, the pinch-weldability of the
blow molded product is excellent. As the molecular weight
of the low molecular weight ethylene polymer is increased,
and as the molecular weight of the high molecular weight
ethylene-a-olefin copolymer is decreased, tan 6 tends to
increase. In addition, pinch-weldability refers to the
ability of a resin being well attached to the welded parts
with a bulge when molten resin extruded in the shape of
tube from an extruder is welded between the molds. Large
tan 5 means stronger viscosity, and in this case, the resin
is thought to be susceptible to bulging.
Moreover, ethylene polymers (EB) / tEB') and (EB")
according to the invention for use in blow molded products
are preferably soluble in decane at 140°C. This means that
the polymers are not crosslinked, and when the polymers are
not crosslinked, it is possible to recycle them after redissolving
them. Therefore, the preparation process for
molded products is more convenient and desirable.
Further, with regard to ethylene polymers (EB), (EB
and (EB") for use in blow molded products, the ethylene
polymer (E) is preferably the ethylene polymer (E1) which
satisfies the above-mentioned requirements (I1) to (7');
more preferably, the ethylene polymer (E1) is the ethylene
polymer (E") which satisfies the above-mentioned
requirement (!"); and particularly preferably, the ethylene
polymer (E") is the ethylene polymer (E111) which satisfies
the above-mentioned requirements (!'') and (2l l f). In
other words, as for the ethylene polymer of the invention
for use in blow molded products, the ethylene polymer
(E'l!) which satisfies all of the above-mentioned
requirements (1B'), (2B') and (1B") is most suitably used.
Ethylene polymer (EP) suitably used in pipes
Among the ethylene polymers (E), preferably (E1),
more preferably (E") and particularly preferably (E1 1 1),
according to the invention, the ethylene polymer that is
suitably used in pipes is preferably defined as in the
following (1P) and (2P) in terms of the concentration of
the constitutional unit derived from a-olefin having 6 to
10 carbon atoms and of the value of Mw/Mn, respectively.
An ethylene polymer defined as such may be referred to as
an ethylene polymer (EP) in the following description.
dp) The polymer contains 0.10 to 1.00 mol% of a
constitutional unit derived from a-olefin having 6 to 10
carbon atoms; and
(2P) the ratio (Mw/Mn) of the weight average
molecular weight (Mw) and the number average molecular
weight (Mn) as measured by GPC is in the range of 11 to 70.
Hereinafter, requirement (1P) and requirement (2P)
will be explained.
[Requirement (1) ]
The ethylene polymer (EP) according to the invention
that is suitably used in pipes contains usually 0.10 to
1.00 mol% of a constitutional unit derived from a-olefin
having 6 to 10 carbon atoms. When ethylene polymer (EP) of
the invention does not include ethylene homopolymers, that
is, when the polymer includes only copolymers of ethylene
and a-olefin having 6 to 10 carbon atoms, it is preferred
that the constitutional unit derived from ethylene is
usually present in a proportion of 99.00 to 99.90 mol%, and
the repeating unit derived from the a-olefin is usually
present in a proportion of 0.10 to 1.00 mol%. Further, the
ethylene polymer (EP) may occasionally include ethylene
homopolymers, and in this case, it is desirable that the
constitutional unit derived from ethylene is usually
present in a proportion of 95.00 to 99.80 mol%, and the
repeating unit derived from the a-olefin is present in a
proportion of 0.20 to 5.00 mol% in the ethylene-a-olefin
copolymer part. In addition, even when the polymer
includes ethylene homopolymers, the repeating unit derived
from the a-olefin usually occupies 0.10 to 1.00 mol% of
the whole polymer.
[Requirement (2p) ]
The ethylene polymer (Ep) according to the invention
is such that the ratio Mw/Mn (Mw: weight average molecular
weight, Mn: number average molecular weight) as measured by
gel permeation chromatography (GPC) is usually in the range
of 11 to 70, and preferably in the range of 11 to 50. When
multistage polymerization as described later is carried out
using a catalyst system as described later, an ethylene
polymer falling in this scope can be prepared by
controlling the molecular weights and the ratio of
polymerized amounts of the respective components. For
example, when the difference in the molecular weights of
the respective components is increased, the ratio Mw/Mn is
increased. A polymer having Mw/Mn within the mentioned
ranges is well balanced between mechanical strength and
moldability. Specifically, when polymerization is carried
out under the conditions as described in Example 1 using
hexane as the solvent, the ratio Mw/Mn obtained is 14.8.
Here, when the amount of ethylene fed to the first
polymerization vessel is changed from 5.0 kg/hr to 7.0
kg/hr, and that of hydrogen is changed from 57 N-liters/hr
to 125 N-liters/hr, the molecular weight of the ethylene
polymer produced in the first polymerization vessel
decreases, and thus Mw/Mn becomes about 18. On the other
hand, when the amount of ethylene fed to the second
polymerization vessel is changed from 4.0 kg/hr to 3.3
kg/hr, and that of hydrogen is changed from 0.2 N-liter/hr
to 0.07 N-liter/hr, the molecular weight of the ethylene
polymer produced in the second polymerization vessel
increases, and thus Mw/Mn becomes about 22. Further, when
hydrogen is fed to the first polymerization vessel at the
rate of 52 N-liters/hr, and ethylene, hydrogen and 1-hexene
are fed to the second polymerization vessel at the rates of
6.0 kg/hr, 0.45 N-liter/hr and 200 g/hr, respectively,
Mw/Mn becomes about 12.
The ethylene polymer (EP) of the invention preferably
satisfies, in addition to the above-described requirements
(1P) and (2?) , the following requirements (lp?) and (2p')
[this ethylene polymer may be referred to ethylene polymer
(Ep1)]:
(I?1) the actual stress obtained when it takes 10,000
cycles to fracture due to the tensile fatigue property as
measured at 80°C according to JIS K-6744, is from 13 MPa to
17 MPa, and the actual stress obtained when it takes
100,000 cycles to fracture is from 12 to 16 MPa; and
(2P
f) the actual stress (S) (MPa) and density (d)
obtained when it takes 10,000 cycles to fracture due to the
tensile fatigue property as measured at 23°C according to
JIS K-7188, satisfy the following relationship (Eq-2):
(0.12d - 94.84) Hereinafter, requirement (!?') and requirement (2P
will be discussed in detail.
[Requirement (I?1)]
The ethylene polymer (Ep1) according to the invention
is such that the actual stress obtained when it takes
10,000 cycles to fracture due to the tensile fatigue
property as measured at 80°C with a notched specimen, is
from 13 MPa to 17 Mpa, and preferably from 14 MPa to 16 MPa,
and the actual stress obtained when it takes 100,000 cycles
to fracture is in the range of 12 MPa to 17 MPa, and
preferably in the range of 13 MPa to 16 MPa. An ethylene
polymer with the tensile fatigue strength as measured at
80°C with a notched specimen falling in the above-mentioned
ranges, exhibits a brittle failure mode and has excellent
long-term life properties. When multistage polymerization
as described later is carried out using a catalyst system
as described later, an ethylene^polymer falling within this
scope can be prepared by controlling the molecular weights
of the respective components, the amount of the a-olefin
copolymerized with ethylene, the composition distribution,
the ratio of polymerized amounts, and compatibility. For
example, fatigue strength can be enhanced within the scope
of the claims, by increasing the value of [r\] within ;the
claimed scope using a specific single-site catalyst, by
selecting oc-olefin having 6 to 10 carbon atoms as the aolefin
to be copolymerized, by selecting the amount of aolefin
in the copolymer from a range of 0.1 to 5.0 mol%,
and by selecting the polymerization conditions that would
narrow the composition distribution. Specifically, when
polymerization is carried out under the conditions as
described in Example 3 using hexane as the solvent, and
granulation is carried out under the conditions as
described in Example 3, the actual stress obtained when it
takes 10,000 cycles to fracture due to the tensile fatigue
property as measured at 80°C, is 13.7 MPa, and the actual
stress obtained when it takes 100,000 cycles to fracture is
13.1 MPa. When granulation is carried out using a 20 mm single-screw extruder (L/D = 28, compression ratio = 3)
manufactured by Thermoplastics Inc. which is set at 230°C,
100 rpm and at an output rate of 50 g/min with a full
flight screw, the actual stress obtained when it takes
10,000 cycles to fracture due to the tensile fatigue as
measured at 80°C is 12.3 MPa, and the actual stress
obtained when it takes 100,000 cycles to fracture is 11.3
MPa, thus the polymer not satisfying the claimed scope. It
is inferred that this is because compatibility of the
polymerized particles is poor. Further, during
polymerization, when ethylene and hydrogen are fed to the
second polymerization vessel at the rates of 3.3 kg/hr and
0.07 N-liter/hr, respectively, and granulation is carried
out under the conditions as described in Example 3, the
actual stress obtained when it takes 10,000 cycles to
fracture due to the tensile fatigue property as measured at
80°C is 13.9 MPa, and the actual stress obtained when it
takes 100,000 cycles to fracture is 13.4 MPa. Also, when
the polymerization conditions as described in Comparative
Example 1 are employed, the actual stress obtained when it
takes 10,000 cycles to fracture due to the tensile fatigue
property as measured at 80°C is 12.1 MPa, and the actual
stress obtained when it takes 100,000 cycles to fracture is
11.2 MPa, thus the polymer not satisfying the claimed scope,
In contrast, when [r|] of the resin is brought close to the
upper limit defined in the claims, 3.7 dl/g, by having the
same amount of the comonomer as used in Example 1 and
reducing the amount of hydrogen during copolymerization
with the comonomer, there occur increases in the actual
stress values obtained when it takes 10,000 cycles and
100,000 cycles to fracture. Also, even with the same
molecular structure, when a low molecular weight ethylene
homopolymer prepared by single-stage polymerization and a
high molecular weight ethylene-a-olefin copolymer prepared
by single-stage polymerization are melt-blended, there
exists a crystalline structure continuous over more than 10
μm, that is, there also exists a structure continuous over
more than 10 μm which is formed from the low molecular
weight ethylene homopolymer and which is susceptible to
destruction. Thus, the polymer does not show the tensile
fatigue strength as measured at 80°C with notch. Moreover,
if the polymer contains a component whose molecular
structure is likely to weaken the crystalline part, in
other words, if the polymer contains a low molecular weight
component having a short-chained branch group, or a high
molecular weight component having too many short-chained
branch groups, generation of strong tie molecules which
bind crystals to crystals becomes difficult, thereby the
non-crystalline part being weakened. Thus, the tensile
fatigue strength which is measured with a notched specimen
at 80°C is not exhibited. In addition, the phrase "a
crystalline structure continuous over more than 10 μm is
not observed" as used herein is understood from the fact
that when a Microtome slice of a 0.5 mm-thick pressed sheet
obtained by melting at 190°C and cooling at 20°C is
observed under a polarized microscope, a crystalline
structure continuous over more than 10 μm is not observed.
That is to say, it is understood from the fact that when a
0.5 mm-thick pressed sheet is prepared by melting an
ethylene polymer at 190°C, then molding it into a sheet
form under a pressure of 10 MPa and compressing into a
sheet by a cold press set at 20°C, using a hydraulic press
molding machine manufactured by Shinto Metal Industries,
Ltd.; then the pressed sheet is cut into a size of
approximately 0.5 mm (thickness of the pressed sheet) x 10
to 20 μm using a Microtome or the like; subsequently, a
small amount of glycerin is applied on this cut specimen,
which is then adhered to a preparation glass with a cover
glass placed thereon to provide a sample for observation;
and this sample is loaded on the polarized plate of a cross
Nicol prism and observed with an optical microscope at
about 75 magnifications and about 150 magnifications. Figs,
29 and 30 illustrate examples of the case where crystalline
structure is observed only in parts of the visual field,
indicating that a crystalline structure continuous over
more than 10 \m. is absent, and examples of the case where
the crystalline structure is observed over the entire
visual field, indicating that a crystalline structure
continuous over more than 10 um is present. Here, the
scale bar indicates that the whole length corresponds to
0.5 mm. Fig. 29 shows photographs of about 75
magnifications, and Fig. 30 shows those of about 150
magnifications.
[Requirement (2P
f)]
The ethylene polymer (EP') according to the invention
is characterized in that the actual stress (S) (MPa)
obtained when it takes 10,000 cycles to fracture due to the
tensile fatigue property as measured at 23°C with an
unnotched specimen, is in the range of 19.4 to 27.2 MPa,
and preferably in the range of 19.6 to 27.2 MPa, or
ethylene polymer (EP'} according to the invention is
characterized in that the actual stress (S) (MPa) obtained
when it takes 10,000 cycles to fracture due to the tensile
fatigue property as measured at 23°C with an unnotched
specimen, and the density (d) (kg/m3) of a specimen which
has been annealed at 120°C for l.hour and then cooled
linearly to room temperature over 1 hour, as measured by
means of a density gradient column, satisfy the following
relationship (Eq-2):
(0.12d - 94.84) and preferably the following relationship (Eq-3):
(0.20d - 170.84) The tensile fatigue property as measured at 23e|C with
an unnotched specimen may be improved by increasing the
density, that is, by hardening the polymer; however, since
there may be changes in the mechanical properties in
addition to the change of density, this is implied in the
relationship with the density. Therefore, this
relationship indicates that even though the density
(hardness) is the same, the tensile fatigue property as
measured at 23°C with an unnotched specimen is superior to
those obtained in the prior art. Further, the expression
defining the lower limit of S (MPa) is based on the
expression obtained in order to distinguish between the two
relationships as follows, when the relationship between the
tensile fatigue property as measured at 23°C with an
unnotched specimen and the density of an ethylene polymer
obtained by a conventional technique, and the relationship
between the tensile fatigue property as measured at 23°C
with an unnotched specimen and the density as obtained in
the invention are plotted. The plot is shown in Fig. 35.
The expression defining the upper limit of S (MPa) is based
on the expression obtained in order to distinguish between
the region indicating actual measurement values and the
region with no actual measurement values higher than the
above-mentioned values, when the relationship between the
tensile fatigue property as measured at 23°C with an
unnotched specimen and the density as obtained in the
invention is plotted. The plot is shown in Fig. 35. When
multistage polymerization as described later is carried out
using a catalyst system as described later, an ethylene
polymer falling within this scope can be prepared by
controlling the molecular weights of the respective
components, the amount of a-olefin to be copolymerized
with ethylene, the composition distribution, the ratio of
polymerized amounts, and compatibility. For example, the
fatigue strength can be enhanced within the claimed scope,
by increasing the value of [TJ] within the claimed scope
using a specific single-site catalyst, by selecting aolefin
having 6 to 10 carbon atoms as the a-olefin to be
copolymerized, by decreasing the proportion of the aolefin
in the copolymer to the range of 0.1 to 2.0 mol%,
and by selecting the polymerization conditions that would
narrow the composition distribution. Specifically, when
polymerization is carried out under the conditions as
described in Example 3 using hexane as the solvent, and .
granulation is carried out under the conditions as
described in Example 3, the density (d) is 953 kg/m3, and
the actual stress (S) obtained when it takes 10,000 cycles
to fracture due to the tensile fatigue property as measured
at 23°C is 20.2 MPa. When the density (d) is 953 kg/in3,
(S) is in the range of 19.5 to 21.8 MPa.
Moreover, the ethylene polymers (EP) , (EP') and (EP")
according to the invention for use in pipes are preferably
soluble in decane at 140°C. This means that the
crosslinking process is not performed, and when
crosslinking process is not performed, it is possible to
recycle the polymers after re-dissolving them. Thus, the
process for preparation of molded products is more
convenient and desirable.
Further, with regard to ethylene polymers (EP), (EP')
and (EP") for use in pipes, the ethylene polymer (E) is
preferably an ethylene polymer (E1) which satisfies the
above-mentioned requirements (I1) to (71); more preferably,
the ethylene polymer (E1) is an ethylene polymer (E") which
satisfies the above-mentioned requirement- (!"); and
particularly preferably, the ethylene polymer (E") is an
ethylene polymer (E1 1 1) which satisfies the above-mentioned
requirements (I1 1 1 ) and (2'lf). In other words, as for the
ethylene polymer of the invention for use in pipes, the
ethylene polymer (E1 1 1) which satisfies both the abovementioned
requirements (1P') and (2P
!) is most suitably
used.
Process for preparation of ethylene polymer
The ethylene polymer according to the invention can
- 60 -
be obtained by, for example, homopolymerizing ethylene or
copolymerizing ethylene with a-olefin having 6 to 10!;
carbon atoms, using a catalyst for olefin polymerization
that is formed from:
(A) a transition metal compound in which a
cyclopentadienyl group and a fluorenyl group are bonded to
each other via a covalent bond bridge containing an atom of
Group 14;
(B) at least one compound selected from:
(B-l) an organic metal compound,
(B-2) an organic aluminum oxy compound, and
(B-3) a compound which forms an ion pair by
reacting with a transition metal compound; and
(C) a carrier. More specifically speaking,
components (A), (B) and (C) used in Examples of the
invention are as follows.
* (A) Transition metal compound
The transition metal compound (A) is a compound
represented by the following formulas (1) and (2):
[Formula 1]
[Formula 2]
- (2)
in which formulas, R7, R8, R9, R10, R11, R12, R13, R14,
R15, R16, R17, R18, R19 and R20 are selected from hydrogen, a
hydrocarbon group, and a silicon-containing hydrocarbon
group and may be the same or different from each other,
while the adjacent substituents R7 to R18 may be joined
together to form a ring; A is a divalent hydrocarbon group
having 2 to 20 carbon atoms which may partly contain an
unsaturated bond and/or an aromatic ring, and A may form a
ring structure together with Y, thus containing two or more
ring structures including the ring formed by A together
with Y; Y is carbon or silicon; M is a metal selected from
the atoms of Group 4 in the Periodic Table of Elements; Q
may be selected from the same or different combinations of
halogen, a hydrocarbon group, an anionic ligand, or a
neutral ligand which can coordinate to an electron lone
pair; and j is an integer between 1 and 4.
Specifically, R7 to R10 are hydrogen, Y is carbon, M
is Zr, and j is 2.
The transition metal compound (A) used in the
Examples of the present application as described later is
specifically represented by the following formulas (3) and
(4), but the invention is not limited to these transition
metal compounds.
[Figure 3]
In addition, the structures of the transition metal
compounds represented by the above formulas (3) and (4)
were determined by 270 MHz 1H-NMR (JEOL, GSH-270) and FDmass
analysis (JEOL, SX-102 A).
* (B-l) Organic metal compound
As for the organic metal compound (B-l) used in the
invention as needed, mention may be made specifically of
the following organic metal compounds having the metals
from Groups 1, 2, 12 and 13 of the Periodic Table of
Elements. It is an organic aluminum compound represented
by the following formula:
[General Formula]
Ra
mAl(ORb)nHpXq
wherein Ra and Rb may be the same or different and
each represent a hydrocarbon group having 1 to 15,
preferably 1 to 4, carbon atoms; X represents a halogen
atom; m is a number such that 0 that 0 a number such that 0 ^ q The aluminum compound used in the below-described
Examples of the invention is triisobutylaluminum or
triethylaluminum.
. * (B-2) Organic aluminum oxy compound
The organic aluminum oxy compound (B-2) used in the
invention as needed may be a conventionally known
aluminoxane, or a benzene-insoluble organic aluminum oxy
compound as illustrated in the publication of JP-A No. 2-
78687.
The organic aluminum oxy compound used in the belowdescribed
Examples of the invention is a commercially
available MAO (= methylalumoxane)/toluene solution
manufactured by Nippon Aluminum Alkyls, Ltd.
* (B-3) Compound forming an ion pair by reacting with
a transition metal compound
The compound (B-3) which forms an ion pair by
reacting with the bridged metallocene compound (A) of the
invention (hereinafter, referred to as "ionizing ionic
compound") may include the Lewis acids, ionic compounds,
borane compounds, carborane compounds and the like
described in the publications of JP-A No. 1-501950, JP-A NO.
1-502036, JP-A NO. 3-179005, JP-A NO. 3-179006, JP-A NO. 3-
207703, JP-A NO. 3-207704, US Patent No. 5321106 and the
like. It may further include heteropoly compounds and
isopoly compounds. Such ionizing ionic compounds (B-3) are
used independently or in combination of two or more species.
In addition, as for compound (B), the above-described two
compounds (B-l) and (B-2) are used in the below-described
Examples of the invention.
* (C) Microparticulate carrier
The microparticulate carrier (C) used in the
invention as needed is a solid product in the form of
granules or microparticles consisting of an inorganic or
organic compound. Among such compounds/ preferred as the
inorganic compound are porous oxides, inorganic halides,
clay, clay minerals or ion-exchangeable lamellar compounds.
The porous oxides vary in the nature and state depending on
the kind and method of preparation, but the carrier which
is preferably used in the invention has a particle size of
from 1 to 300 Jim, preferably from 3 to 200 urn, a specific
surface area ranging from 50 to 1000 m2/g, preferably from
100 to 800 m2/g, and a pore volume ranging from 0.3 to 3.0
crnVg. Such carrier is used after being calcined at a high
temperature of from 80 to 1000°C, and preferably from 100
to 800°C, if necessary. Further, if not specified
otherwise, the carrier used in the below-described Examples
of the invention was Si02 manufactured by Asahi Glass Co.,
Ltd., which has an average particle size of 12 μm, a
specific surface area of 800 m2/g and a pore volume of 1.0
crnVg.
The catalyst for olefin polymerization according to
the invention may contain a specific organic compound
component (D) as described later, if necessary, together
with the bridged metallocene compound (A), at least one
compound (B) selected from (B-l) an organic metal compound,
(B-2) an organic aluminum oxy compound and (B-3) an
ionizing ionic compound, and optionally the
microparticulate carrier (C) of the invention, and if
desired, a specific organic compound component (D) as
described below.
* (D) Organic compound component
According to the invention, the organic compound
component (D) is used for the purpose of improving the
polymerization performance and the properties of produced
polymer, if necessary. Such organic compound may be
exemplified by alcohols, phenolic compounds, carboxylic
acids, phosphorous compounds and sulfonic acid salts,
without being limited to these.
* Polymerization
The ethylene polymer according to the invention can
be obtained by homopolymerizing ethylene or copolymerizing
ethylene with a-olefin having 6 to 10 carbon atoms as
described above, using a catalyst for olefin polymerization
as described above.
Upon polymerization, the usage and order of addition
for the respective components are arbitrarily selected, but
methods (PI) to (P10) such as the following may be
illustrated.
(PI) A method of adding Component (A) and at least
one Component (B) selected from (B-l) an organic metal
compound, (B-2) an organic aluminum oxy compound and (B-3)
an ionizing ionic compound (hereinafter, simply referred to
as "Component (B)") to the polymerization vessel in an
arbitrary order.
(P2) A method of adding a catalyst in which Component
(A) has been preliminarily brought into contact with
Component (B), to the polymerization vessel.
(P3) A method of adding Component (B) and a catalyst
component in which Component (A) has been preliminarily
brought into contact with Component (B), to the
polymerization vessel in an arbitrary order. In this case,
the respective Components (B) may be the same or different.
(P4) A method of adding Component (B) and a catalyst
component having Component (A) supported on the
microparticulate carrier (C) to the polymerization vessel
in an arbitrary order.
(P5) A method of adding a catalyst having Component
(A) and Component (B) supported on microparticulate carrier
(C) to the polymerization vessel.
(P6) A method of adding Component (B) and a catalyst
component having Component (A) and Component (B) supported
on microparticulate carrier (C) to the polymerization
vessel in an arbitrary order. In this case, the respective
Components (B) may be the same or different.
(P7) A method of adding Component (A) and a catalyst
component having Component (B) supported on
microparticulate carrier (C) to the polymerization vessel
in an arbitrary order.
(P8) A method of adding Component (A), Component (B)
and a catalyst component having Component (B) supported on
microparticulate carrier (C) to the polymerization vessel
in an arbitrary order. In this case, the respective
Components (B) may be the same or different.
(P9) A method of adding a catalyst component that has
been formed by preliminarily contacting Component (B) with
a catalyst having Component (A) and Component (B) supported
on microparticulate carrier (C) , to the polymerization
vessel. In this case, the respective Components (B) may be
the same or different.
(P10) A method of adding Component (B) and a caitalyst
component that has been formed by preliminarily contacting
Component (B) with a catalyst having Component (A) and
Component (B) supported on microparticulate carrier (C), to
the polymerization vessel in an arbitrary order. In ;this
case, the respective Components (B) may be the same or
different.
With respect to each of the above-described methods
(PI) to (P10), the catalyst component may have at least two
or more of the respective components preliminarily brought
into contact.
The above-mentioned solid catalyst component having
Component (A) and Component (B) supported on
microparticulate carrier (C) may be prepolymerized with an
olefin. This prepolymerized solid catalyst component has a
constitution in which polyolefin is usually prepolymerized
in a proportion of from 0.1 to 1000 g, preferably from 0.3
to 500 g, and particularly preferably from 1 to 200 g,
relative to 1 g of the solid catalyst component.
Also, for the purpose of facilitating polymerization,
an antistatic agent or an anti-fouling agent may be used in
combination or supported on the carrier.
Polymerization can be carried out either by liquidphase
polymerization such as solution polymerization,
suspension polymerization or the like, or by gas-phase
polymerization, and particularly suspension polymerization
and gas-phase polymerization are preferably employed.
As for an inactive hydrocarbon medium used in liquidphase
polymerization, mention may be specifically made of
aliphatic hydrocarbons such as propane, butane, pentane,
hexane, heptane, octane, decane, dodecane and kerosene;
alicyclic hydrocarbons such as cyclopentane, cyclohexane
and methylcyclopentane; aromatic hydrocarbons such as
benzene, toluene and xylene; halogenated hydrocarbons such
as ethylene chloride, chlorobenzene and dichloromethane;
and mixtures thereof, and the olefin itself can be also
used as the solvent.
When (co)polymerization is carried out using a
catalyst for olefin polymerization as described above,
Component (A) is typically used in an amount of from 10~12
to 10~2 mole, and preferably from 10~10 to 10"3 mole,
relative to 1 liter of the reaction volume.
Component (B-l) which is used if necessary, is used
in an amount such that the molar ratio [(B-1)/M] of
component (B-l) and the transition metal atom (M) in
Component (A) would be typically from 0.01 to 100,000, and
preferably from 0.05 to 50,000.
Component (B-2) which is used if necessary, is used
in an amount such that the molar ratio [(B-2)/M] of the
aluminum atom in component (B-2) and the transition metal
atom (M) in Component (A) would be typically from 10 to
500,000, and preferably from 20 to 100,000.
Component (B-3) which is used if necessary, is used
in an amount such that the molar ratio [(B-3)/Mj of
component (B-3) and the transition metal atom (M) in
Component (A) would be typically from 1 to 100, and
preferably from 2 to 80.
Component (D) which is used if necessary, is used in
an amount such that when Component (B) is component (B-l),
the molar ratio [(D)/(B-1)] would be typically from 0.01 to
10, preferably from 0.1 to 5, and when Component (B) is
component (B-2), the molar ratio [(D)/(B-2)] would be
typically from 0.001 to 2, and preferably from 0.005 to 1,
and when Component (B) is component (B-3), the molar ratio
[(D)/(B-3)] would be typically from 0.01 to 10, and
preferably from 0.1 to 5.
Further, the temperature for the polymerization
process using such catalyst for olefin polymerization is
typically in the range of -50 to 250°C, preferably 0 to
200°C, and particularly preferably 60 to 170°C. The
polymerization pressure is typically from ambient pressure
to 100 kg/cm2, and preferably from ambient pressure to 50
kg/cm2, and the polymerization reaction can be carried out
in either of the batch mode, semi-continuous mode and
continuous mode. Polymerization is usually carried out in
a gas phase or in a slurry phase in which polymer particles
are precipitated out in a solvent. Furthermore,
polymerization is carried out in two or more stages with
different reaction conditions. In this case, it is
preferably carried out in the batch mode. Also, in the
case of slurry polymerization or gas phase polymerization,
the polymerization temperature is preferably from 60 to
90°C, and more preferably from 65 to 85°C. Via
polymerization within this temperature range, an ethylene
polymer with narrower composition distribution can be
obtained. A polymer obtained as such is in the form of a
particle with a diameter of tens to thousands of |m, In
the case of polymerization in the continuous mode in two or
more polymerization vessels, there is needed an operation
such as precipitation in a poor solvent after dissolution
in a good solvent, sufficient melt-kneading in a specific
kneader, or the like.
When the ethylene polymer according to the invention
is prepared in, for example, two stages, an ethylene
homopolymer having an intrinsic viscosity of 0.3 to 1.8
dl/g is prepared in the first stage, and a (co)polymer
having an intrinsic viscosity of 3.0 to 10.0 dl/g is
prepared in the second stage. This order may be reversed.
Since the catalyst for olefin polymerization has
extremely high polymerization performance even for the aolefin
(e.g., 1-hexene) to be copolymerized with ethylene,
there would be needed a devisal not to produce a copolymer
with excessively high a-olefin content, "after completion
of predetermined polymerization. For example, mention may
be made of methods such as, when the content of the
polymerization vessel is withdrawn from the polymerization
vessel, simultaneously or as immediately as possible, (1)
separating the polymer, solvent and unreacted a-olefin
with a solvent separator, (2) adding an inert gas such as
nitrogen and the like to the content to discharge the
solvent and unreacted a-olefin out of the system, (3)
controlling the pressure applied to the content to
discharge the solvent and unreacted a-olefin out of the
system, (4) adding a large quantity of solvent to the
content to dilute the unreacted a-olefin to a
concentration at which substantially no polymerization
takes place, (5) adding a substance which deactivates the
catalyst for polymerization, such as methanol and the like,
(6) cooling the content to a temperature at which
substantially no polymerization takes place, or the like.
These.methods may be carried out independently or in
combination of several methods.
The molecular weight of the obtained ethylene polymer
can be controlled by adding hydrogen to the polymerization
system or by changing the polymerization temperature. It
can be also controlled by means of the difference in
Components (B) u sed.
The polymer particles obtained by polymerization
reaction may be also pelletized by the following methods:
(1) a method of mechanically blending the ethylene
polymer particles with other components that are added as
needed in an extruder, a kneader or the like, and cutting
into predetermined sizes; and
(2) a.method of dissolving the ethylene polymer and
other components that are added as needed in a suitable
good solvent (e.g., hydrocarbon solvents such as hexane,
heptane, decane, cyclohexane, benzene, toluene, xylene and
the like), subsequently removing the solvent, then
mechanically blending the components using an extruder,
kneader or the like, and cutting into predetermined sizes.
The ethylene polymer according to the invention may
be blended, as desired, with additives such as a weatherresistant
stabilizer, a heat-resistant stabilizer,
antistatic agent, an anti-slipping agent, an anti-blocking
agent, an anti-clouding agent, a lubricant, a dye, a
nucleating agent, a plasticizer, an anti-aging agent, a
hydrochloric acid absorbent, -an anti-oxidizing agent and
the like, carbon black, titanium oxide, Titanium Yellow,
phthalocyanine, isoindolinone, a quinacridone compound, a
condensed azo compound, a pigment such as ultramarine blue,
cobalt blue and the like without adversely affecting the
purpose of the invention.
The ethylene polymer according to the invention can
be molded into a blow molded product, an inflation molded
product, a cast molded product, a laminated extrusion
molded product, an extrusion molded product such as a pipe
or other forms, an expansion molded product, an injection
molded product or the like. Further, the polymer can be
used in the form of a fiber, a monofilament, a non-woven
fabric or the like. These products include those molded
products comprising a portion consisting of an ethylene
polymer and another portion consisting of another resin
(laminated products, etc.). Moreover, this ethylene
polymer may be used in the state of being crosslinked
during molding. The ethylene polymer according to the
invention gives excellent properties when used in a blow
molded product and an extrusion molded product such as a
pipe and various forms, among the above-mentioned molded
products, thus it being desirable.
The ethylene polymer (EB) for use in blow molded
products according to the invention can be molded into
bottles, industrial chemical canisters, gasoline tanks or
the like by blow molding. Such molded products include
those molded products comprising a portion consisting of
ethylene polymer (EB) and a portion consisting of another
resin (laminated products, etc.). Further, when ethylene
polymer (EB) contains pigments, the concentration is
typically from 0.01 to 3.00% by weight.
The ethylene polymer (EP) for use in pipes according
to the invention can be molded into pipes, or fittings that
are molded by injection molding. Such molded products
include those molded products (laminated products, etc.)
comprising a portion consisting of ethylene (co)polymer and
a portion consisting of another resin. Further, when
ethylene polymer (EB) contains pigments, the concentration
is typically from 0.01 to 3.00% by weight.
Measuring methods for various properties
* Preparation of sample for measurement
To 100 parts by weight of an ethylene polymer in the
microparticulate form, 0.1 part by weight of tri(2,4-di-tbutylphenyl)
phosphate as a secondary anti-oxidizing agent,
0.1 part by weight of n-octadecyl-3-(4'-hydroxy-3',5'-di-tbutylphenyl)
propionate as a heat-resistant stabilizer, and
0.05 part by weight of calcium stearate as a hydrochloric
acid absorbent are blended. Then, using a Labo-Plastmil (a
twin screw batch-type melt-kneading apparatus) manufactured
by Toyo Seiki Seisakusho, Ltd., a feed amount 40 g (unit
batch volume = 60 cm3) of the ethylene polymer was meltkneaded
at a set temperature of 190°C and at 50 rpm for 5
minutes or at 50 rpm for 10 minutes, then taken out to be
molded into a sheet form by a cold press at 20°C, and cut
into a suitable size to yield a sample for measurement. It
is also possible to granulate using a conventional extruder.
Yet, in the case of granulating the microparticulate
ethylene polymer obtained by continuous two-stage
polymerization, there would be needed a devisal such as
using a twin screw extruder with long L/D in order to
homogenize the polymer particles sufficiently, or the like.
* Measurement of ethylene content and a-olefin
content
The number of methyl branch groups per 1,000 carbons
in the molecular chain of the ethylene polymer was measured
by 13C-NMR. Measurement was made using a Lambda 500-type
nuclear magnetic resonance unit (:E: 500 MHz) manufactured
by JEOL, Ltd, with an integral number of 10,000 to 30,000.
Further, the peak for the main chain methylene (29.97 ppm)
was used as the reference for chemical shift. A
commercially available quartz glass tube for NMR
measurement with a diameter of 10 mm was charged with 250
to 400 mg of the sample and 2 ml of a mixed solution of
ultra pure grade o-dichlorobenzene (Wako Pure Chemicals
Industry, Ltd.): benzene-d6 (ISOTEC) = 5:1 (volume ratio),
and the content was heated at 120°C and uniformly dispersed
to a solution, which was subjected to NMR measurement. The
assignment of each absorption in the NMR spectrum was based
on "NMR - Introduction and Guidelines to Experimentation,"
Region of Chemistry, extra edition No. 141, pp.132-133.
The composition of the ethylene-a-olefin copolymer is
determined typically by preparing a sample having 250 to
400 mg of the copolymer uniformly dissolved in 2 ml of
hexachlorobutadiene in a test tube of 10 mm, and measuring
the 13C-NMR spectrum of the sample under the measurement
conditions such as measurement temperature of 120°C,
measurement frequency of 125.7 MHz, spectrum width of
250,000 Hz, pulse repetition time of 4.5 seconds and 45°
pulse.
* Cross fractionation chromatography (CFC)
The following measurement was made using a CFC T-150A
type manufactured by Mitsubishi Chemical Co., Ltd. The
separation column consisted of three Shodex AT-806 MS, the
eluent was o-dichlorobenzene, the sample concentration was
0.1 to 0.3 wt/vol%, the feed amount was 0.5 ml, and the
flow rate was 1.0 ml/min. The sample was heated at 145°C
for 2 hours, subsequently cooled to 0°C at a rate of
10°C/hr and further maintained at 0°C for 60 min to coat
the sample. The capacity of the temperature rising elution
column was 0.86 ml, and the line capacity was 0.06 ml. As
for the detector, an infrared spectrometer MIRAN 1A CVF
type (CaFa cell) manufactured by FOXBORO, Inc. set in the
absorbance mode with a response time of 10 seconds, was
used to detect an infrared ray of 3.42 urn (2924 cm"1) . The
elution temperature was such that the range of 0°C to 145°C
was divided into 35 to 55 fractions, and particularly in
the vicinity of an elution peak, the temperature was
divided into fractions corresponding to 1°C each. The
indication of the temperature is all in integers, and for
example, an elution fraction at 90°C indicates a component
eluted at 89°C to 90°C. The molecular weights of the
components not coated even at 0°C and the fraction eluted
at each temperature were measured, which were converted to
the molecular weights in terms of PE using a standard
calibration curve. The SEC temperature was 145°C, the
amount of introduction to the inner mark was 0.5 ml, the
position of introduction was at 3.0 ml, and the data
sampling time interval was 0.50 second. Furthermore, when
there occurred pressure abnormality due to the presence of
too many eluted components within a narrow temperature
range, the sample concentration would be set to less than
0.1 wt/vol%. Data processing was carried out by means of
an analysis program attached to the apparatus, "CFC Data
Processing (version 1.50)." In addition, although cross
fractionation chromatography (CFC) per se is said to be an
analytic method of reproducing the results with high
analytic precision as the conditions for measurement are
strictly maintained constant, it is preferable to perform
several measurements and to take the average.
* Weight average molecular weight (Mw), number
average molecular weight (Mn) and molecular weight curve
Measurement was carried out as follows using a GPC-
150C manufactured by Waters Corp. The separating columns
used were TSKgel GMH6-HT and TSKgel GMH6-HTL, the column
size was each an inner diameter of 7.5 mm and a length of
600 mm, the column temperature was 140°C, the mobile phase
was o-dichlorobenzene (Wako Pure Chemicals Industry, Ltd.)
containing 0.025% by weight of BHT (Takeda Pharmaceutical
Co., Ltd.) as the anti-oxidizing agent, at a flow rate of
1.0 ml/min, the sample concentration was 0.1% by weight,
the amount of sample introduced was 500 μI, and the
detector used was a differential refractometer. For the
standard polystyrene, a product by Tosoh Corporation was
used for the molecular weight of Mw 4xl06,
and a product by Pressure Chemical Co. for the molecular
weight of 1,000 value determined in terms of polyethylene by means of
universal calibration.
* Division of the molecular weight curve
A computational program was created using the Visual
Basic macros of Excel® 97 manufactured by Microsoft Corp.
The two curves to be divided indicated logarithmic normal
distribution, and the molecular weight distribution curve
was divided into two curves with different molecular
weights by convergent calculation. While comparing the
curve resynthesized from the divided two curves with the
molecular weight curve obtained by actual GPC measurement,
calculation was performed by changing the initial values in
order for the two curves to closely match with each other.
Calculation was performed by partitioning the value of
Log(molecular weight) into an interval of 0.02. The
intensities were normalized so that the area under the
molecular weight curve actually measured and the area under
the curve resynthesized from the two divided curves become
unity, respectively, and the calculation for curve division
was repeated until the value obtained by dividing the
absolute value of the difference between the intensity
(height) of the actual measurement and the intensity
(height) of the resynthesized curve for each molecular
weight by the absolute value of the intensity (height),
became 0.4 or less, preferably 0.2 or less, and more
preferably 0.1 or less, for the molecular weight ranging
from 10,000 to 1,000,000, and also 0.2 or less, and
preferably 0.1 or less, at the maximum site of the peak
divided into two. Here, the difference between the ratio
Mw/Mn of the peak assigned to the lower molecular weight
and the ratio Mw/Mn of the peak assigned to the higher
molecular weight should be 1.5 or less. An exemplary
calculation is shown in Fig. 28.
* Smoothness coefficient R
The resin is extruded using a Capillograph IB, a
capillary flow characteristics testing machine manufactured
by Toyo Seiki Co., Ltd., at a resin temperature of 200°C
and a flow rate of 50 mm/min (3.6 cmVmin) . The machine is
equipped with a nozzle having a length L = 60 mm and a
diameter D = 1 mm, or with a cylindrical die (outer
diameter = 4 mm, slit = 1 mm, length =10 mm) which can
extrude a tube-shaped product, instead of a capillary die.
The polymer product may be pelletized, and if the polymer
particles polymerized in the gas phase or in the slurry
phase are not sufficiently intermixed, there would be skin
roughness on the surface of the melt extruded product. The
exterior,of thus obtained strand or tube is taken as the
surface for measurement in measuring the surface roughness.
A Surfcom 1400D manufactured by Tokyo Seimitsu Co., Ltd.
was used for the measurement. The roughness as the average
of 10 points calculated according to the calculation
standard JIS B0601-1982 under the following conditions:
measured length = 10 mm, measurement rate 0.06 mm/sec,
sampling time = 0.01 sec, sampling pitch = 0.6 (im, material
of the measuring needle = diamond, and tip of the measuring
needle = 5 \m$f is referred to as Rz. Rz is the value of
the difference between the average value of the peak
heights of the highest to the fifth highest peaks and the
average value of the valley heights of the deepest to the
fifth deepest valleys, with respect to the average line of
a measured length of 10 mm. Measurement is performed three
times at different sites, and the average value is taken as
the dispersion coefficient R. Here, a standard deviation
of the Rz values obtained from three measurements was
determined. When the standard deviation value is larger
than one half of the R value which is the average of Rz
values measured three times, measurement is carried out
again. When R exceeds 20 urn, the polymer particles do not
intermix sufficiently. As a result, even when a thick
molded product such as pipe or blow bottle is formed, the
flow becomes poor, resulting in not smooth surface skin, or
stress concentration between polymer particles may lead to
insufficient expression of the mechanical strength.
Meanwhile, when R is 20 um or less, it can be viewed that
the history of polymer particles does not remain behind.
* Measurement of a crystalline structure continuous
over more than 10 μm
A pressed sheet with a thickness of 0.5 mm was
prepared by melting an ethylene polymer at 190°C, molding
it into a sheet form at a pressure of 10 MPa, and
compressing into a sheet by a cold press set at 20°C using
a hydraulic press molding machine manufactured by Shinto
Metal Industries, Ltd. Then, the sheet was cut into a size
of approximately 0.5 mm (thickness of pressed sheet) x 10
to 20 μm using a Microtome or the like. After then, a
small amount of glycerin was applied onto the cut specimen,
and the specimen was then adhered to a preparation glass
with a cover glass placed thereon to provide a sample for
observation. This sample was loaded on the polarized plate
of a cross Nicol prism and observed with an optical
microscope at about 75 magnifications and about 150
magnifications. Figs. 29 and 30 illustrate examples of the
case where crystalline structure is observed only in parts
of the visual field, indicating that a crystalline
structure continuous over more than 10 μm is absent, and
examples of the case where the crystalline structure is
observed over the entire visual field, indicating that a
crystalline structure continuous over more than 10 μm is
present. Here, the scale bar indicates that the whole
length corresponds to 0.5 mm.
* Measurement of methyl branch group
The number of methyl branch groups per 1,000 carbon
atoms in the polyethylene molecular chain was measured by
13C-NMR. Measurement was carried out using an EPC500 type
nuclear magnetic resonance unit (1E: 500 MHz) manufactured
by JEOL, Ltd. with an integral number of 10,000 to 30,000.
Further, the peak for the main chain methylene (29.97 ppm)
was used as the reference for chemical shift. A
commercially available quartz glass tube for NMR
measurement with a diameter of 10 mm was charged with 250
to 400 mg of the sample and 3 ml of a mixed solution of
ultra pure grade o-dichlorobenzene (Wako Pure Chemicals
Industry, Ltd.): benzene-d6 (ISOTEC) = 5:1 (volume ratio),
and the content was heated at 120°C and uniformly dispersed
to a solution which was then subjected to measurement. The
assignment of each absorption in the NMR spectrum was based
on "NMR - Introduction and Guidelines to Experimentation
[I]," Region of Chemistry, extra edition No. 141, pp.132-
133. The number of methyl branch groups per 1,000 carbon
atoms was calculated from the ratio of the integrated
strength of the absorption of the methyl group derived from
a methyl branch group (19.9 ppm) to the integral sum of the
absorption appearing in the region of 5 to 45 ppm. When
the number of methyl branch groups per 1,000 carbon atoms
is less than 0.08, the number is below the detection limit
and is not detectable.
* Intrinsic viscosity ([t|])
This is a value measured at 135°C using decalin as
the solvent. That is, about 20 mg of granulated pellets is
dissolved in 15 ml of decalin, and the specific viscosity
r|sp is measured in an oil bath at 135°C. This decalin
solution is diluted by further adding 5 ml of the decalin
solvent, and then the specific viscosity r|Sp is measured in
the same manner. This dilution procedure is further
repeated two times to determine the value of T|sp/C as the
intrinsic viscosity (see the following formula), with the
concentration (C) being extrapolated to zero.
[TI] = lim(Tisp/C) (C -» 0)
* Density (d)
A specimen for measurement was prepared by molding a
sheet having a thickness of 0.5 mm (spacer-shaped; 9 sheets
of 45 x 45 x 0.5 mm obtained from a sheet of 240 x 240 x
0.5 mm) under a pressure of 100 kg/cm2 using a hydraulic
thermal press machine manufactured by Shinto Metal
Industries, Ltd. set at 190°C, and cooling the obtained
sheet via compressing it under a pressure of 100 kg/cm2
using another hydraulic thermal press machine manufactured
by Shinto Metal Industries, Ltd. set at 20°C. The heating
plate used was a SUS plate with a thickness of 5 mm. This
pressed sheet was subjected to heat treatment at 120°C for
one hour and gradual cooling to room temperature linearly
over 1 hour, and then the density was measured using a
density gradient column.
* Solubility in decane
Measurement of the gel content is performed according
to JIS K 6796, except that the solvent used is decane
maintained at 140°C, the sample is either specimens cut
from the 0.5 mm-thick pressed sheet or granulated pellets,
and the concentration set to 1 mg/ml. The sample is
referred to be soluble in decane at 140°C when the
proportion of gel is 1% by weight or less.
* Environmental stress crack resistance test for
pressed sheet: ESCR (hr)
A specimen for measurement was prepared by molding a
sheet having a thickness of 2 mm (spacer-shaped; 4 sheets
of 80 x 80 x 2 mm from a sheet of 240 x 240 x 2 mm) under a
pressure of 100 kg/cm2 using a hydraulic thermal press
machine manufactured by Shinto Metal Industries, Ltd. set
at 190°C, and cooling the obtained sheet via compressing it
under a pressure of 100 kg/cm2 using another hydraulic
thermal press machine manufactured by Shinto Metal
Industries, Ltd. set at 20°C. The heating plate used was a
SUS plate with a thickness of 5 mm. From the above pressed
sheet of 80 x 80 x 2 mm, a dumbbell-shaped specimen with a
size of 13 mm x 38 mm was punched out to provide a sample
for evaluation.
The test for the property of environmental stress
crack resistance ESCR was performed according to ASTM D1693,
The conditions for evaluation (bent strip method) are
summarized in the following:
Shape of sample: Press molding method C
Specimen: 38 x 13 mm, Thickness: 2 mm (HDPE)
Notch length: 19 mm, Depth: 0.35 mm
Testing temperature: 50°C, constant temperature water
bath: capable of controlling at 50.0 ± 0.5°C.
Storage of sample: The sample is set using a
clinching device exclusively used for a specimen holder
with an inner dimension of 11.75 mm and a length of 165 mm.
Surfactant: Nonylphenyl polyoxyethylene ethanol
(commercially available under the product name of Antarox
CO-630) is diluted with water to a concentration of 10% for
use.
Method of evaluation: time to fracture F50 (time to
50% fracture) is determined using logarithmic probability
paper.
* Flexural modulus of pressed sheet
From a pressed sheet having a size of 80 x 80 x 2 mm,
a specimen for measurement of the ESCR property with a
width of 12.7 mm and a length of 63.5 mm was punched out,
and the flexural modulus was measured according to ASTM D-
790 under the conditions of testing temperature of 23°C,
bending rate of 5.0 mm/min and bending span distance of
32.0 mm.
* tan 8 (= loss modulus G"/storage modulus G')
Detailed information on tan 8 is described in, for
example, "Lecture on Rheology", by Japan Society of
Rheology, Kobunshi Kankokai, pp. 20-23. The measurement
was carried out by measuring the angular frequency (CD
(rad/sec)) dispersion of the storage modulus G'(Pa) and the
loss modulus G"(Pa) using a rheometer RDS-II manufactured
by Rheometrics, Inc. The sample holder used was a pair of
parallel plates with 25 mm, and the sample thickness was
about 2 mm. Under the measuring temperature of 190°C, G'
and G" were measured within the range of 0.04 The measurement was obtained at five points per one digit
of co. The amount of strain was suitably selected within
the range of 2 to 25%, under the conditions that the torque
is detectable within the range for measurement, and no
torque-over occurs.
* Preparation of bottle for the measurement of
buckling strength and environmental stress crack resistance
ESCR property and the observation of pinch-off property of
bottle
Using an extrusion blow molding machine (model: 3B
50-40-40) manufactured by Placo Co., Ltd., blow molding was
carried out under the following conditions: set
temperature: 180°C, die diameter: 23 mm mm rate of forming: 1.4 sec, forming pressure: 5.5 t, and blow
air pressure: 5 kg/cm2. Thus, a cylindrical bottle having
a capacity of 1,000 cc and a net weight of 50 g was
obtained.
* Buckling strength of bottle
Thus prepared bottle was subjected to measurement of
the buckling strength of bottle under the condition of a
crosshead speed of 20 mm/min in a universal testing machine
_ O0 0Q _
manufactured by Instron, Inc.
* Environmental stress crack resistance (ESCR)
property of bottle
The bottle prepared as in the above was charged with
100 cc of Kitchen Hiter manufactured by Kao Corp., and then
was sealed at the opening resin. The bottle and the
content were maintained in an oven at 65°C to observe the
time to fracture. Thus, the time to fracture F50 was
determined using logarithmic probability paper.
* Pinch-off property of bottle (measurement of the
thickness ratio of pinched part)
When the bottom of the bottle obtained by blow
molding as in the above was cut in the direction
perpendicular to the matching surface of the mold, the
thickness ratio of the pinched part is represented by (a/b),
wherein a represents the thickness at the central part of
the bottle, and b represents the thickness at the thickest
part. As this value is larger, the state of pinching is
good (see Fig. 31) '.
* Tensile fatigue strength at 80°C
A specimen for the measurement of tensile fatigue
strength at 80°C was prepared by molding a 2 mm-thick sheet
and a 6 mm-thick sheet (spacer-shaped: 4 specimens of a
size of 80 x 80 x 2 mm obtained from a sheet of a size of
240 x 240 x 2 mm, and 4 specimens of a size of 30 x 60 x 6
mm obtained from a sheet of a size of 200 x 200 x 6 mm) at
a pressure of 100 kg/cm2 using a hydraulic thermal press
machine manufactured by Shinto Metal Industries, Ltd. set
at 190°C, and by cooling the sheets via compressing under a
pressure of 100 kg/cm2 using another hydraulic thermal
press machine manufactured by Shinto Metal Industries, Ltd.
set at 20°C. From the pressed sheet having a size of 30 x
60 x 6 mm, a rectangular column with a size of length 5 to
6 mm x width 6 mm x height 60 mm was cut out for use as a
specimen for the evaluation of actual measurement.
The tensile fatigue strength (specimen form) was
measured according to JIS K-6774 using a Servo-Pulser of
the EHF-ERlKNx4-40L type manufactured by Shimazu Seisakusho,
Ltd. (Full-notch type, notch depth = 1 mm). Summary of the
evaluation conditions are as follows: several points were
measured under the conditions of specimen form: 5-6 x 6 x
60 mm, notched rectangular column; waveform and frequency
for testing: rectangular wave, 0.5 Hz; temperature for
testing: 80°C; and actual stress in the range of 10 to 18
MPa. The oscillation frequency upon fracture of the
specimen was taken as the fatigue strength. Further, at
least three points of different actual stress values were
measured, for a three or more digit number of cycles to
fracture, or under an actual stress in the range of 3 MPa
or greater, in order to provide an approximation formula by
means of the least square method with logarithmic
approximation. Thus, the actual stress values with the
numbers of cycles to fracture corresponding to 10,000
cycles and 100,000 cycles were determined.
* Tensile fatigue strength at 23°C
A 3 mm-thick dumbbell (ASTM-D-1822 Type S) as shown
in Fig. 32 was prepared by molding (spacer-shaped: the form
of ASTM-D-1822 Type S was provided from the sheet having a
size of 240 x 240 x 3 mm) under a pressure of 100 kg/cm2
using a hydraulic thermal press machine manufactured Shinto
Metal Industries, Ltd.,set at 190°C, and cooling it via
compressing under a pressure of 100 kg/cm2 using a
hydraulic thermal press machine manufactured by Shinto
Metal Industries, Ltd. set at 20°C. The specimen taken out
from the spacer was used as the evaluation sample for
actual measurement.
The tensile fatigue strength at 23°C was measured
according to JIS K-7118 using a Servo-Pulser of the EHFFG10KN-
4 LA type manufactured by Shimazu Seisakusho, Ltd.
Summary of the evaluation conditions are presented
below.
Specimen shape: ASTM-D-1822 Type S (Dumbbell as
described in Fig. 32, no notches)
Waveform and frequency or testing: sinusoidal wave 4
Hz
Temperature for testing: 23°C
The tensile fatigue strength test was carried out by
measuring at several points under the above-mentioned
conditions (testing temperature, waveform and frequency for
testing), further with a constant minimum load of the load
cell of 4.9 N (0.5 kgf) and an actual stress with the
maximum corrected at the central cross-section of the
specimen prior to testing, in the range of 17 to 25 MPa. A
50% elongation of the specimen was defined as fracture, and
the oscillation frequency at this occasion was taken as the
fatigue strength for the actual stress loaded. The actual
stress corresponding to 10,000 cycles to fracture was
determined by performing measurement for at least one digit
number of cycles to fracture or to obtain an actual stress
in the range of 1 MPa or greater, and providing an
approximation formula by means of the least square method
with logarithmic approximation.
Best Mode for Carrying Out the Invention
Hereinafter, the invention will be explained more
specifically with reference to Examples, which are not
intended to limit the invention.
[Synthetic Example 1]
[Preparation of solid catalyst component (a)]
A suspension was prepared from 8.5 kg of silica dried
at 200°C for 3 hours and 33 liters of toluene, and then
82.7 liters of a methylaluminoxane solution (Al =1.42
mol/liter) was added dropwise over 30 minutes. Then, the
temperature of the mixture was elevated to 115°C over 1.5
hours, and the mixture was allowed to react at that
temperature for 4 hours. Subsequently, the reaction
mixture was cooled to 60°C, and the supernatant liquid was
removed by decantation. Thus obtained solid catalyst
component was washed with toluene three times and
resuspended in toluene to yield a solid catalyst component
(a) (total volume 150 liters).
[Preparation of supported catalyst]
In a two-necked 100 mi-flask which had been
sufficiently purged with nitrogen, 20.39 mmol (in terms of
aluminum) of the solid catalyst component (a) suspended in
20 ml of toluene was added, and under stirring, 45.2 ml
(0.09 mmol) of a toluene solution of
diphenylmethylene(cyclopentadienyl)(2,7-di-tbutylfluorenyl)
zirconium dichloride at a concentration of 2
mmol/liter was added to the suspension at room temperature
(23°C), the resulting mixture being stirred for another 60
minutes. After stirring being stopped, the supernatant
liquid was removed by decantation, the mixture was washed
with 50 ml of n-decane for four times, and thus obtained
supported catalyst was reslurried in 100 ml of n-decane to
yield a solid catalyst component (P) as a catalyst
suspension.
[Example I]
[Polymerization]
A 1000 mi-autoclave which had been sufficiently
purged with nitrogen was charged with 500 ml of n-heptane,
and 0.25 ml (0.25 mmol) of triisobutylaluminum at a
concentration of 1 mol/liter and 3.85 ml of the solid
catalyst component (P) obtained in Synthetic Example 1
(corresponding to 0.003 mmol in terms of Zr atoms)
introduced. The autoclave was pressurized with an
ethylene-hydrogen mix gas having a hydrogen content of 2.53
vol% to a pressure of 8.0 kg/cm2 G, and polymerization was
initiated at 80°C. The ethylene-hydrogen mix gas was added
during polymerization to maintain at 8.0 kg/cm2 G, and
polymerization was carried out for 70 minutes. After
polymerization, pressure was removed, and the autoclave was
purged with nitrogen to remove the ethylene-hydrogen mix
gas.
To this autoclave, 0.25 ml (0.25 mmol) of
triisobutylaluminum at a concentration of 1 mol/liter and
2.7 ml of 1-hexene were introduced, the autoclave was
pressurized with an ethylene-hydrogen mix gas with a
hydrogen content of 0.10 vol% to a pressure of 8.0 kg/cm2 G,
and polymerization was re-initiated at 80°C. The
ethylene-hydrogen mix gas was added during polymerization
to maintain at 8.0 kg/cm2 G, and polymerization was carried
out for 20.5 minutes. After completion of polymerization,
pressure was removed, and the catalyst was deactivated by
addition of methanol. The resulting polymer was filtered,
washed and dried under vacuum at 80°C for 12 hours to give
84.50 g of the polymer.
With respect to 100 parts by weight of this polymer
particle, 0.1 part by weight of tri(2,4-di-t-butylphenyl)
phosphate as a secondary anti-oxidizing agent, 0.1 part by
weight of n-octadecyl-3-(4'-hydroxy-3',5'-di-t-butylphenyl)
propionate as a heat-resistant stabilizer, and 0.05 part by
weight of calcium stearate as a hydrochloric acid absorbent
were mixed. Thereafter, using a Labo-Plastmil (batch-type
twin screw melt-kneading apparatus) manufactured by Toyo
Seiki Co., Ltd. set at 190°C, the resin in a feed amount of
40 g (apparatus batch volume = 60 cm3) was melt-kneaded at
50 rpm for 5 minutes, taken out of the apparatus,
compressed into a sheet by a cold press set at 20°C, and
cut into a suitable size to provide a sample for
measurement. The results are presented in Tables 1 to 3
and Table 6. A contour diagram from cross fractionation
chromatography (CFC) is given in Fig. 1; a threedimensional
chart (bird's eye view) viewed from the lower
temperature side is given in Fig. 2; a three-dimensional
chart (bird's eye view) viewed from the higher temperature
side is given in Fig. 3; a GPC curve for the component
eluted at peak temperature (Ta) (°C) is given in Figure 4;
a GPC curve for the components eluted at 73 to 76 (°C) is
given in Fig. 5; and a GPC curve for the components eluted
at 95 to 96 (°C) is given in Fig. 6. In the polarized
microscopic observation, no crystalline structure
continuous over more than 10 |im is present. Further, it is
found that this sample has extremely high tensile fatigue
strength at 80°C as compared with the samples used in the
Comparative Examples (see Fig. 33) .
[Example 2]
[Polymerization]
A 1000 mi-autoclave which had been sufficiently
purged with nitrogen was charged with 500 ml of n-heptane,
and 0.25 ml (0.25 mmol) of trilsobutylaluminum at a
concentration of 1 mol/liter and 3.90 ml of the solid
catalyst component (0) obtained in Synthetic Example 1
(corresponding to 0.00304 mmol in terms of Zr atoms) were
introduced. The autoclave was pressurized with an
ethylene-hydrogen mix gas having a hydrogen content of 2.53
vol% to a pressure of 8.0 kg/cm2 G, and polymerization was
initiated at 80°C. The ethylene-hydrogen mix gas was added
during polymerization to maintain at 8.0 kg/cm2 G, and
polymerization was carried out for 63 minutes. After
polymerization, pressure was removed, and the autoclave was
purged with nitrogen to remove the ethylene-hydrogen mix
gas.
To this autoclave, 0.25 ml (0.25 mmol) of
triisobutylaluminum at a concentration of 1 mol/liter and
2.7 ml of 1-hexene were introduced, the autoclave was
pressurized with an ethylene-hydrogen mix gas with a
hydrogen content of 0.15 vol% to a pressure of 8.0 kg/cm2 G,
and polymerization was re-initiated at 80°C. The
ethylene-hydrogen mix gas was added during polymerization
to maintain at 8.0 kg/cm2 G, and polymerization was carried
out for 20.5 minutes. After completion of polymerization,
pressure was removed, and the catalyst was deactivated by
addition of methanol. The resulting polymer was filtered,
washed and dried under vacuum at 80°C for 12 hours to give
84.50 g of the polymer.
With respect to 100 parts by weight of this polymer
particle, the same secondary anti-oxidizing agent, heatresistant
stabilizer, and hydrochloric acid absorbent as
those used in Example 1 were mixed in the same parts by
weight. Thereafter, using a Labo-Plastmil manufactured by
Toyo Seiki Co., Ltd., the resin was melt-kneaded under the
same conditions of the set temperature, the resin feed
amount, the rotation speed and the melting time as used in
Example 1, taken out of the apparatus, compressed into a
sheet by a cold press set at 20°C, and cut into a suitable
size to provide a sample for measurement. Also, this
sample was used to prepare a pressed sheet, and properties
thereof were measured. The results are presented in Tables
1 to 3 and Table 6. In the polarized microscopic
observation, no crystalline structure continuous over more
than 10 μm is present. Further, it is found that this
sample has extremely high tensile fatigue strength at 80°C
as compared with the samples used in the Comparative
Examples (see Fig. 33).
[Synthetic Example 2]
[Preparation of supported catalyst]
In a reactor which had been sufficiently purged with
nitrogen, 19.60 mmol (in terms of aluminum) of the solid
catalyst component (a) synthesized in Synthetic Example 1
and suspended in toluene was added, and under stirring, 2
liters (74.76 mmol) of a solution of
diphenylmethylene(cyclopentadienyl)(2,7-di-t-
butylfluorenyl)zirconium dichloride at a concentration of
37.38 mmol/liter was added to the suspension at room
temperature (20 to 25°C), the resulting mixture being
stirred for another 60 minutes. After stirring being
stopped, the supernatant liquid was removed by decantation,
the mixture was washed with 40 liters of n-hexane for two
times, and thus obtained supported catalyst was reslurried
in 25 liters of n-hexane to yield a solid catalyst
component (y) as a catalyst suspension.
[Preparation of solid catalyst component (5) by
prepolymerization of solid catalyst component (y) ]
To a reactor equipped with a stirrer, 15.8 liters of
purified n-hexane and the above-mentioned solid catalyst
component (y) were introduced under a nitrogen atmosphere,
then 5 mol of triisobutylaluminum was added under stirring,
and prepolymerization was carried out with ethylene in an
amount such that 3 g of polyethylene is produced per gram
of the solid component in 4 hours. The polymerization
temperature was maintained at 20 to 25°C. After completion
of polymerization, stirring was stopped, the supernatant
liquid was removed by decantation, the solids were washed
with 35 liters of n-hexane for 4 times, and thus obtained
supported catalyst was suspended in 20 liters of n-hexane
to give a solid catalyst component (8) as a catalyst
suspension.
[Comparative Example 1]
[Polymerization]
To a first polymerization bath, the following
components were continuously supplied: 50 liters/hr of
hexane, 0.15 mmol/hr (in terms of Zr atoms) of the solid
catalyst component (5) obtained in Synthetic Example 2, 20
mmol/hr of triethylaluminum, 5.0 kg/hr of ethylene, and 65
N-liters/hr of hydrogen. Meanwhile, polymerization was
carried out under the conditions such as polymerization
temperature of 85°C, reaction pressure of 8.5 kg/cm2 G and
average residence time of 2.5 hr, while continuously
withdrawing the content of the polymerization bath so that
the liquid level in the polymerization bath would be
maintained constant. The content continuously withdrawn
from the first polymerization bath was subjected to
substantial removal of unreacted ethylene and hydrogen in a
flash drum maintained at an internal pressure of 0.2 kg/cm2
G and at 65°C.
Then, the content was continuously supplied to a
second polymerization bath, together with 20 liters/hr of
hexane, 4.0 kg/hr of ethylene, 0.2 N-liter/hr of hydrogen
and 450 g/hr of 1-hexene, and polymerization was continued
under the conditions such as polymerization temperature of
70°C, reaction pressure of 7 kg/cm2 G and average residence
time of 1.5 hr.
Also for the second polymerization bath, the content
of the polymerization bath was continuously withdrawn so
that the liquid level in the polymerization bath would be
maintained constant. The content was subjected to removal
of hexane and unreacted monomer by a solvent separation
unit, and dried to give the polymer. Further, in this
Comparative Example 1, supply of methanol to the content as
described in Example 3 as described later was not done.
Next, with respect to 100 parts by weight of the
polymer particle, the same secondary anti-oxidizing agent,
heat-resistant stabilizer and hydrochloric acid absorbent
as used in Example 1 were mixed in the same parts by weight.
Thereafter, a sample for measurement was prepared by
granulation at a resin extrusion amount of 60 g/min and at
100 rpm using a 20 mnusingle screw extruder (L/D = 28,
full flight screw, compression ratio = 3, mesh 60/100/60)
manufactured by Thermoplastics Inc., set at 230°C. Further,
a pressed sheet was prepared using this sample to measure
the properties. The results are presented in Tables 1 to 3
and Table 6. In the polarized microscopic observation, no
crystalline structure continuous over more than 10 μm is
present.
The contour diagram for CFC fractionation is given in
Fig. 7; a three-dimensional chart (bird's eye view) viewed
from the lower temperature side is given in Fig. 8; a
three-dimensional chart (bird's eye view) viewed from the
higher temperature side is given in Fig. 9; a GPC curve for
the component eluted at peak temperature (T2) (°C) is given
in Fig. 10; a GPC curve for the components eluted at 73 to
76 (°C) is given in Fig. 11; and a GPC curve for the
components eluted at 95 to 96 (°C) is given in Fig. 12.
Further, Fig. 13 represents a projection (elution curves)
in the y-z plane for the eluted components and the integral
value of the amounts of the eluted components (100 area% in
total), where Log(M) is taken as the x-axis, Temp(°C) is
taken as the y-axis and the vertical axis is taken as the z
axis in the bird's eye view (Fig. 8 or Fig. 9).
As shown in Fig. 33, the tensile fatigue strength at
80°C of this sample is not very high.
[Comparative Example 2]
With respect to 100 parts by weight of the polymer
particle obtained in Comparative Example 1, the same
secondary anti-oxidizing agent, heat-resistant stabilizer
and hydrochloric acid absorbent as those used in Example 1
were mixed in the same amounts. Thereafter, a sample for
measurement was prepared by granulation at a resin
extrusion amount of 22 g/min and at 100 μm using a twin
screw extruder BT-30 (30 mno, L/D = 46, co-rotation, four
kneading zones) manufactured by Placo Co., Ltd., set at a
temperature of 240°C. Also, a pressed sheet was prepared
using the sample to measure the properties. The results
are presented in Tables 1 to 3 and Table 6. In the
polarized microscopic observation, no crystalline structure
continuous over more than 10 μm is present. When compared
with Comparative Example 1, this sample has higher
smoothness and slightly higher tensile fatigue strength at
80°C, but when compared with Example 1, its tensile fatigue
strength at 80°C is lower (see Fig. 33).
[Comparative Example 3]
The pellets of product HI-ZEX 7700 M manufactured by
Mitsui'Chemical Co., Ltd. were used as the sample for
measurement. The co-monomer was 1-butene. A pressed sheet
was prepared using the sample to measure the properties.
The results are presented in Tables 1 to 3 and Tables 6 to
8. In the polarized microscopic observation at 100
magnifications, no crystalline structure continuous over
more than 10 μmis present. As shown in Fig. 33, it is
found that this sample has lower fatigue strength than the
samples of Examples in the measurement of tensile fatigue
at 80°C. Further, as shown in Fig. 34, the sample has
lower strength than the samples of other Examples in the
measurement of tensile fatigue at 23°C.
[Comparative Example 4]
Using the catalyst used in Example 1 described in the
publication of JP-A NO. 2002-53615, an ethylene homopolymer
having [r|] = 0.72 dl/g and an ethylene• 1-butene copolymer
having [T\] = 5.2 dl/g and the content of 1-butene = 1.7
mol% were obtained by slurry polymerization at 80°C. These
were mixed in a ratio of 49/51 (weight ratio), dissolved in
para-xylene at 130°C to a concentration of 10 g/1,000 ml,
stirred for 3 hours and stood for 1 hour. The mixture was
precipitated in 3,000 ml of acetone at 20°C, filtered
through a glass filter, dried under vacuum all day and
night at 60°C, and then melt-kneaded using a Labo-Plastimil
to yield a sample for measurement. Further, a pressed
sheet was prepared using the sample to measure the
properties. The results are presented in Table 1 anq Table
6.
[Comparative Example 5]
The pellets of the HDPE product (product name:
Hostalen, reference name CRP100) manufactured by Basfll
Corp. were used as the sample for measurement. The comonomer
was 1-butene. A pressed sheet was prepared using
the sample to measure the properties. The results are
presented in Tables 1 to 3 and Tables 6 to 8. The contour
diagram obtained from CFC fractionation is presented in Fig.
14; a three-dimensional chart (bird's eye view) viewed from
the lower temperature side is presented in Fig. 15; a
three-dimensional chart (bird's eye view) viewed from the
higher temperature side is presented in Fig. 16; a GPC
curve for the component eluted at peak temperature (Tz)
(°C) is presented in Fig. 17; a GPC curve for the
components eluted at 73 to 76 (°C) is presented in Fig. 18,
and a GPC curve for the components eluted at 95 to 96 (°C)
is presented in Fig. 19. In addition, it is defined herein
as TI = T2. In the polarized microscopic observation, no
crystalline structure continuous over more than 10 μm is
present. As shown in Fig. 33, it is found in the test to
measure the tensile fatigue at 80°C of this sample that the
sample has lower fatigue strength than the samples of
Examples. Further, as shown in Fig. 34, the sample has
lower strength than the samples of other Examples in the
measurement of tensile fatigue at 23°C.
[Example 3]
[Polymerization]
To a first polymerization bath, the following
components were continuously supplied: 45 liters/hr of
hexane, 0.11 mmol/hr (in terms of Zr atoms) of the solid
catalyst component (8) obtained in Synthetic Example 2, 20
mmol/hr of triethylaluminum, 5.0 kg/hr of ethylene and 57
N-liters/hr of hydrogen. Meanwhile, polymerization was
carried out under the conditions such as polymerization
temperature of 85°C, reaction pressure 8.5 kg/cm2 G and
average residence time of 2.5 hr, while continuously
withdrawing the content of the polymerization bath so that
the liquid level in the polymerization bath would be
maintained constant.
The content continuously withdrawn from the first
polymerization bath was subjected to substantial removal of
unreacted ethylene and hydrogen in a flash drum maintained
at an internal pressure of 0.2 kg/cm2 G and 65°C.
Thereafter, the content was continuously supplied to
the second polymerization, together with 35 liters/hr of
hexane, 4.0 kg/hr of ethylene, 0.2 N-liter/hr of hydrogen
and 130 g/hr of 1-hexene, and polymerization was continued
under the conditions such as polymerization temperature
80°C, reaction pressure of 4.5 kg/cm2 G and average
residence time of 1.2 hr.
Also for the second polymerization bath, the content
- 104 -
of the polymerization bath was continuously withdrawn so
that the liquid level in the polymerization bath would be
maintained constant. In order to prevent unwanted
polymerization such as generation of a polymer containing a
large proportion of 1-hexene, methanol was supplied to the
content withdrawn from the second polymerization bath at a
rate of 2 liters/hr to deactivate the catalyst for
polymerization. Then, the content was subjected to removal
of hexane and unreacted monomer in a solvent separation
unit and dried to give the polymer.
Next, with respect to 100 parts by weight of the
polymer particle, the same secondary anti-oxidizing agent,
heat-resistant stabilizer and hydrochloric acid absorbent
as used in Example 1 were mixed in the same parts by weight,
Thereafter, a sample for measurement was prepared using a
twin screw extruder BT-30 manufactured by Placo Co., Ltd.
under the same conditions of the set temperature, the
amount of extruded resin and the rotation speed as in
Comparative Example 2. Further, a pressed sheet was
prepared using this sample to measure the properties, The
results are presented in Tables 1 to 3 and Tables 6 to 8.
A contour diagram for CFC fractionation is presented
in Fig. 20; a three-dimensional chart (bird's eye view)
viewed from the lower temperature side is presented in Fig.
21; a three-dimensional chart (bird's eye view) viewed from
the higher temperature side is presented in Fig. 22; a GPC
curve for the component eluted at peak temperature (T2)
(°C) is presented in Fig. 23; a GPC curve for the
components eluted at 73 to 76 (°C) is presented in Fig. 24;
and a GPC curve for the components eluted at 95 to 96 (°C)
is presented in Fig. 25. Further, Fig. 26 represents a
projection (elution curves) in the y-z plane for the eluted
components and the integral value of the amounts of the
eluted components (100 area% in total), where Log(M) is
taken as the x-axis, Temp(°C) as the y-axis and the
vertical axis as the z axis in the bird's eye view (Fig. 21
or Fig. 22) . Fig. 27 represents only the integral value of
the amount of the eluted components (100 area% in total).
Fig. 27 also illustrates on the ethylene polymers obtained
(or used) in Comparative Examples 1, 3 and 5 described
above and Examples 12 and 13 to be described later.
In the polarized microscopic observation of the
ethylene polymer obtained in the present Example 3, no
crystalline structure continuous over more than 10 μmis
present. As shown in Fig. 33, it is found that this sample
had higher fatigue strength in the test for tensile fatigue
measurement at 80°C, as compared with the polymers in
Comparative Examples. Also, as shown in Fig. 34, the
polymer has higher strength in the tensile fatigue
measurement at 23°C, as compared with the polymers other
Comparative Examples.
[Example 4]
[Polymerization]
To a first polymerization bath, the following
components were continuously supplied: 45 liters/hr of
hexane, 0.11 mmol/hr (in terms of Zr atoms) of the solid
catalyst component (8) obtained in Synthetic Example 2, 20
mmol/hr of triethylaluminum, 7.0 kg/hr of ethylene, and
hydrogen at 125 N-liters/hr. Meanwhile, polymerization was
carried out under the conditions such as polymerization
temperature of 85°C, reaction pressure of 8.5 kg/cm2 G and
average residence time of 2.5 hr, while continuously
withdrawing the content of the polymerization bath so that
the liquid level in the polymerization bath would be
maintained constant.
The content continuously withdrawn from the first
polymerization bath was subjected to substantial removal of
unreacted ethylene and hydrogen in a flash drum maintained
at an internal pressure of 0.2 kg/cm2 G and at 65°C.
Then, the content was continuously supplied to a
second polymerization bath, together with 35 liters/hr of
hexane, 3.0 kg/hr of ethylene, 0.07 N-liter/hr of hydrogen
and 30 g/hr of 1-hexene, and polymerization was continued
under the conditions of polymerization temperature of 80°C,
reaction pressure of 4.5 kg/cm2 G and average residence
time of 0.8 hr.
Also for the second polymerization bath, the content
of the polymerization bath was continuously withdrawn so
that the liquid level in the polymerization bath would be
maintained constant. In order to prevent unwanted
polymerization such as generation of a polymer containing a
large proportion of 1-hexene, methanol was supplied to the
content withdrawn from the second polymerization bath at a
rate of 2 liters/hr to deactivate the catalyst for
polymerization. Then, the content was subjected to removal
of hexane and unreacted monomer in a solvent separation
unit and dried to give the polymer.
Next, with respect to 100 parts by weight of the
polymer particle, the same secondary anti-oxidizing agent,
heat-resistant stabilizer and hydrochloric acid absorbent
as used in Example 1 were mixed in the same parts by weight,
Thereafter, using a Labo-Plastmil manufactured by Toyo
Seiki Co., Ltd., the resin was melt-kneaded under the same
conditions of the set temperature, the resin feed amount,
the rotation speed and the melting time as used in Example
1, taken out of the apparatus, compressed into a sheet by a
cold press set at 20°C, and cut into a suitable size .to
provide a sample for measurement. Also, this sample was
used to prepare a pressed sheet, and properties thereof
were measured. The results are presented in Tables 1 to 41
In the polarized microscopic observation, no crystalline
structure over more than 10 μm is present.
[Comparative Example 6]
The pellets of product HI-ZEX 6200 B manufactured by
Mitsui Chemical Co., Ltd. were used as the sample for
measurement. The co-monomer was 1-butene. A pressed! sheet
was prepared using the sample to measure the properties.
The results are presented in Tables 1 to 5. In the
polarized microscopic observation, no crystalline structure
continuous over more than 10 μm is present. It can be seen
that when compared with Example 4, this sample is inferior
in the balance between toughness and the ESCR property.
[Synthetic Example 3]
[Preparation of supported catalyst]
In a reactor which had been sufficiently purged with
nitrogen, 9.50 mmol (in terms of aluminum) of the solid
catalyst component (a) synthesized in Synthetic Example 1
and suspended in toluene was added, and under stirring,
12.6 milliliters (0.038 mmol) of a 3 mmol/liter solution of
di(p-tolyl)methylene(cyclopentadienyl)
(octamethyloctahydrodibenzofluorenyl) zirconium dichloride
was added to the suspension at room temperature (20 to
25°C), the resulting mixture being stirred for 60 minutes.
After stirring being stopped, the supernatant liquid was
removed by decantation, the mixture was washed with 50 ml
of n-pentane for 4 times, and thus obtained supported
catalyst was reslurried in 50 ml of n-pentane to yield a
solid catalyst component (6) as a catalyst suspension.
[Preparation of solid catalyst component a by
prepolymerization of solid catalyst component (0)]
To a reactor equipped with a stirrer, the abovementioned
solid catalyst component (9) was introduced under
a nitrogen atmosphere, then 1.92 mmol of
triisobutylaluminum was added under stirring, and
prepolymerization was carried out with ethylene in an
amount such that 3 g of polyethylene is produced per,gram
of the solid component in 1 hour. The polymerization
temperature was maintained at 25°C. After completion of
polymerization, stirring was stopped, the supernatant
liquid was removed by decantation, the solids were washed
with 50 milliliters of n-pentane for 4 times, and thus
obtained supported catalyst was suspended in 100
milliliters of n-pentane to give a solid catalyst component
() as a catalyst suspension.
[Example 5]
[Polymerization]
A 1000 mi-autoclave which had been sufficiently
purged with nitrogen was charged with 500 ml of n-heptane,
and 0.25 ml (0.25 mmol) of triisobutylaluminum at a
concentration of 1 mol/liter and 6.50 ml of the solid
catalyst component ((o) obtained in Synthetic Example 3
(corresponding to 0.0018 mmol in terms of Zr atoms) were
introduced. The autoclave was pressurized with an
ethylene-hydrogen mix gas having a hydrogen content of 2.50
vol% to a pressure of 8.0 kg/cm2 G, and polymerization was
initiated at 80°C. The ethylene-hydrogen mix gas was added
during polymerization to maintain at 8.0 kg/cm2 G, and
polymerization was carried out for 70.5 minutes. After
polymerization, pressure was removed, and the autoclave was
purged with nitrogen to remove the ethylene-hydrogen mix
gas.
To this autoclave, 0.25 ml (0.25 mmol) of
triisobutylaluminum at a concentration of 1 mol/liter and
20.0 ml of 1-octene were introduced, the autoclave was
pressurized with an ethylene-hydrogen mix gas with a
hydrogen content of 0.021 vol% to a pressure of 8.0 kg/cm2
G, and polymerization was re-initiated at 65°C. The
ethylene-hydrogen mix gas was added during polymerization
to maintain at 8.0 kg/cm2 G, and polymerization was carried
out for 19.5 minutes. After completion of polymerization,
pressure was removed, and the catalyst was deactivated by
addition of methanol. The resulting polymer was filtered,
washed and dried under vacuum at 80°C for 12 hours to give
104.9 g of the polymer. With respect to 100 parts by weight of this polymer
particle, the same secondary anti-oxidizing agent, heatresistant
stabilizer, and hydrochloric acid absorbent; as
those used in Example 1 were mixed in the same parts ;by
weight. Thereafter, using a Labo-Plastmil manufactured by
Toyo Seiki Co., Ltd., the resin was melt-kneaded under the
same conditions of the set temperature, the resin feed
amount, the rotation speed and the melting time as used in
Example 1, taken out of the apparatus, compressed into a
sheet by a cold press set at 20°C, and cut into a suitable
size to provide a sample for measurement. Also, this
sample was used to prepare a pressed sheet, and properties
thereof were measured. The results are presented in Tables
1 to 3 and Table 6. In the polarized microscopic
observation, no crystalline structure continuous over more
than 10 nm is present.
[Example 6]
[Polymerization]
To a first polymerization bath, the following
components were continuously supplied: 45 liters/hr of
hexane, 0.13 mmol/hr (in terms of Zr atoms) of the solid
catalyst component (8) obtained in Synthetic Example 2, 20
mmol/hr of triethylaluminum, 5.0 kg/hr of ethylene, and 57
N-liters/hr of hydrogen. Meanwhile, polymerization was
carried out under the conditions such as polymerization
temperature of 85°C, reaction pressure of 8.3 kg/cm2 G and
average residence time of 2.6 hr, while continuously
withdrawing the content of the polymerization bath so that
the liquid level in the polymerization bath would be
maintained constant. The content continuously withdrawn
from the first polymerization bath was subjected to
substantial removal of unreacted ethylene and hydrogen in a
flash drum maintained at an internal pressure of 0.35
kg/cm2 G and at 60°C.
Then, the content was continuously supplied to a
second polymerization bath, together with 35 liters/hr of
i
hexane, 3.5 kg/hr of ethylene, 0.5 N-liter/hr of hydrogen
and 220 g/hr of 1-hexene, and polymerization was continued
under the conditions of polymerization temperature of 80°C,
reaction pressure of 3.8 kg/cm2 G and average residence
time of 1.2 hr.
Also for the second polymerization bath, the content
- 112
of the polymerization bath was continuously withdrawn so
that the liquid level in the polymerization bath would be
maintained constant. In order to prevent unwanted
polymerization such as generation of a polymer containing a
large proportion of 1-hexene, methanol was supplied to the
content withdrawn from the second polymerization bath at a
rate of 2 liters/hr to deactivate the catalyst for
polymerization. Then, the content was subjected to removal
of hexane and unreacted monomer in a solvent separation
unit and dried to give the polymer. • -
With respect to 100 parts by weight of the polymer
particle, the same secondary anti-oxidizing agent, heatresistant
stabilizer and hydrochloric acid absorbent as
used in Example 1 were mixed in the same parts by weight.
Thereafter, a sample for measurement was prepared by
granulation at a resin extrusion amount of 25 kg/hr and at
a set temperature of 200°C using a single screw extruder
(screw diameter 65 mm, L/D = 28, screen mesh 40/60/300 x
4/60/40) manufactured by Placo Co., Ltd. Further, a
pressed sheet was prepared using this sample to measure the
properties. The results are presented in Tables 1 to 3 and
Table 6. In the polarized microscopic observation, no
crystalline structure continuous over more than 10 jjift is
present. As shown in Fig. 33, this sample has higher
fatigue strength than the sample used in the Comparative
Examples in the tensile fatigue measurement at 80°C.
[Polymerization]
To a first polymerization bath, the following
components were continuously supplied: 45 liters/hr of
hexane, 0.13 mmol/hr (in terms of Zr atoms) of the solid
catalyst component (8) obtained in Synthetic Example 2, 20
mmol/hr of triethylaluminum, 5.0 kg/hr of ethylene, and 55
N-liters/hr of hydrogen. Meanwhile, polymerization was
carried out under the conditions such as polymerization
temperature of 85°C, reaction pressure of 8.1 kg/cm2 G and
average residence time of 2.6 hr, while continuously
withdrawing the content of the polymerization bath so that
the liquid level in the polymerization bath would be
maintained constant.
The content continuously withdrawn from the first
polymerization bath was subjected to substantial removal of
unreacted ethylene and hydrogen in a flash drum maintained
at an internal pressure of 0.35 kg/cm2 G and at 60°C.;
Then, the content was continuously supplied to a
second polymerization bath, together with 35 liters/hr of
hexane, 3.0 kg/hr of ethylene, 0.5 N-liter/hr of hydrogen
and 130 g/hr of 1-hexene, and polymerization was continued
under the conditions of polymerization temperature of 80°C,
reaction pressure of 3.9 kg/cm2 G and average residence
time of 1.2 hr.
Also for the second polymerization bath, the content
of the polymerization bath was continuously withdrawn so
that the liquid level in the polymerization bath would be
maintained constant. In order to prevent unwanted
polymerization such as generation of a polymer containing a
large proportion of 1-hexene, methanol was supplied to the
content withdrawn from the second polymerization bath at a
rate of 2 liters/hr to deactivate the catalyst for
polymerization. Then, the content was subjected to removal
of hexane and unreacted monomer in a solvent separation
unit and dried to give the polymer. ;
With respect to 100 parts by weight of the polymer
particle, the same secondary anti-oxidizing agent, heatresistant
stabilizer and hydrochloric acid absorbent as
used in Example 1 were mixed in the same parts by weight.
Thereafter, a sample for measurement was prepared by
granulation at the same set temperature and extruded1resin
amount as in Example 6 using a single screw extruder
manufactured by Place Co., Ltd. Further, a pressed sheet
was prepared using this sample to measure the properties.
The results are presented in Tables 1 to 3 and Tables 6 to
8. In the polarized microscopic observation, no
crystalline structure continuous over more than 10 |im is
present. As it can be seen from the results of tensile
fatigue measurement at 80°C shown in Fig. 33, this sample
has higher fatigue strength than the samples used in the
Comparative Examples.
[Synthetic Example 4]
[Preparation of solid catalyst component]
Only for Synthetic Example 4, Si02 manufactured by
- 115 -
Asahi Glass Co., Ltd. having an average particle size of 3
HCTI, a specific surface area of 800 m2/g and a pore volume
of 1.0 cmVg was used as silica.
A suspension was prepared from 9.0 kg of silica which
had been dried at 200°C for 3 hours and 60.7 liters of
toluene, and 61.8 liters of a methylaluminoxane solution
(3.03 mol/liter as Al) was added dropwise over 30 minutes.
Then, the temperature of the mixture was elevated to 115°C
over 1.5 hours, and the mixture was allowed to react at
that temperature for 4 hours. Subsequently, the reaction
mixture was cooled to 60°C, and the supernatant liquid was
removed by decantation. Thus obtained solid catalyst
component was washed with toluene for three times and
resuspended in toluene to yield a solid catalyst component
(e) (total volume 150 liters) .
[Preparation of supported catalyst]
In a reactor which had been sufficiently purged with
nitrogen, 9.58 mol (in terms of aluminum) of the solid
catalyst component (e) was added, and under stirring, 2
liters (24.84 mmol) of a 12.42 mmol/liter solution of di (ptolyl)
methylene(cyclopentadienyl)
(octamethyloctahydrodibenzofluorenyl) zirconium dichloride
was added to the suspension at room temperature (20 to
25°C), the resulting mixture being stirred for another 60
minutes. After stirring being stopped, the supernatant
liquid was removed by decantation, the mixture was washed
with 40 liters of n-hexane for two times, and thus obtained
supported catalyst was reslurried in 25 liters of n-hexane
to yield a solid catalyst component (K) as a catalyst
suspension.
[Preparation of solid catalyst component (X) by
prepolymerization of solid catalyst component (K)]
To a reactor equipped with a stirrer, 21.9 liters of
purified n-hexane and the above-mentioned solid catalyst
component (K) were introduced under a nitrogen atmosphere,
then 1.7 mol of triisobutylaluminum was added under
stirring, and prepolymerization was carried out with
ethylene in an amount such that 3 g of polyethylene jls
produced per gram of the solid component in 2 hours.; The
polymerization temperature was maintained at 20 to 2J5°C.
After completion of polymerization, stirring was stopped,
the supernatant liquid was removed by decantation, tjjie
solids were washed with 40 liters of n-hexane for 3 times,
and thus obtained supported catalyst was suspended iji 20
liters of n-hexane to give a solid catalyst component (X)
as a catalyst suspension.
[Example 8]
[Polymerization]
To a first polymerization bath, the following
components were continuously supplied: 45 liters/hr pf
hexane, 0.11 mmol/hr (in terms of Zr atoms) of the solid
catalyst component (X) obtained in Synthetic Example!4, 15
mmol/hr of triethylaluminum, 7.0 kg/hr of ethylene, and 105
N-liters/hr of hydrogen. Meanwhile, polymerization was
carried out under the conditions such as polymerization
temperature of 85°C, reaction pressure of 7.9 kg/cm2 ^G and
average residence time of 2.5 hr, while continuously
withdrawing the content of the polymerization bath sp that
the liquid level in the polymerization bath would be
maintained constant.
The content continuously withdrawn from the first
polymerization bath was subjected to substantial removal of
unreacted ethylene and hydrogen in a flash drum maintained
at an internal pressure of 0.30 kg/cm2 G and at 60°Cfi
Then, the content was continuously supplied to ia
second polymerization bath, together with 35 liters/hr of
hexane, 4.0 kg/hr of ethylene, 2.0 N-liters/hr of hydrogen
and 80 g/hr of 1-hexene, and polymerization was continued
under the conditions of polymerization temperature of 80°C,
reaction pressure of 2.5 kg/cm2 G and average residence
time of 1.1 hr.
Also for the second polymerization bath, the content
of the polymerization bath was continuously withdraw^ so
that the liquid level in the polymerization bath woujld be
maintained constant. In order to prevent unwanted
polymerization such as generation of a polymer containing a
large proportion of 1-hexene, methanol was supplied [to the
content withdrawn from the second polymerization batjrt at a
rate of 2 liters/hr to deactivate the catalyst for
polymerization. Then, the content was subjected to Removal
of hexane and unreacted monomer in a solvent separation
- 118 -
unit and dried to give the polymer.
Next, with respect to 100 parts by weight of the
polymer particle, the same secondary anti-oxidizing agent,
heat-resistant stabilizer and hydrochloric acid absorbent
as used in Example 1 were mixed in the same parts by weight,
Thereafter, a sample for measurement was prepared by
granulation at the same set temperature and extruded resin
amount as in Example 6 using a single screw extruder
manufactured by Placo Co., Ltd. Further, a pressed sheet
was prepared using this sample to measure the properties.
The results are presented in Tables 1 to 3 and Table 6. In
the polarized microscopic observation, no crystalline
structure continuous over more than 10 jim is present. As
it can be seen from the results of tensile fatigue
measurement at 80°C shown in Fig. 33, this sample has
higher fatigue strength than the samples of the Comparative
Examples.
[Synthetic Example 5]
[Preparation of supported catalyst]
In a reactor which had been sufficiently purged with
nitrogen, 19.60 mol (in terms of aluminum) of the solid
catalyst component (a) synthesized in Synthetic Example 1
and suspended in toluene was added, and under stirring, 2
liters (62.12 mmol) of a 31.06 mmol/liter solution of di(ptolyl)
methylene(cyclopentadienyl)
(octamethyloctahydrodibenzofluorenyl) zirconium dichloride
was added to the suspension at room temperature (20 to
25°C), the resulting mixture being stirred for another 60
minutes. After stirring being stopped, the supernatant
liquid was removed by decantation, the mixture was washed
with 40 liters of n-hexane for 2 times, and thus obtained
supported catalyst was reslurried in 25 liters of n-hexane
to yield a solid catalyst component (T) as a catalyst
suspension.
[Preparation of solid catalyst component (a) by
prepolymerization of solid catalyst component (T) ]
To a reactor equipped with a stirrer, 15.8 liters of
purified n-hexane and the above-mentioned solid catalyst
component (T) were introduced under a nitrogen atmosphere,
then 5 mol of triisobutylaluminum was added under stirring,
and prepolymerization was carried out with ethylene in an
amount such that 3 g of polyethylene is produced per gram
of the solid component in 4 hours. The polymerization
temperature was maintained at 20 to 25°C. After completion
of polymerization, stirring was stopped, the supernatant
liquid was removed by decantation, the solids were washed
with 35 liters of n-hexane for 4 times, and thus obtained
supported catalyst was suspended in 20 liters of n-hexane
to give a solid catalyst component (o>) as a catalyst
suspension.
[Example 9]
[Polymerization]
To a first polymerization bath, the following
components were continuously supplied: 45 liters/hr of
hexane, 0.14 mmol/hr (in terms of Zr atoms) of the siplid
catalyst component (co) obtained in Synthetic Example 5, 20
mmol/hr of triethylaluminum, 7.0 kg/hr of ethylene, and 120
N-liters/hr of hydrogen. Meanwhile, polymerization was
carried out under the conditions such as polymerization
temperature of 85°C, reaction pressure of 7.9 kg/cm2 G and
average residence time of 2.6 hr, while continuously
withdrawing the content of the polymerization bath so that
the liquid level in the polymerization bath would be
maintained constant.
The content continuously withdrawn from the first
polymerization bath was subjected to substantial removal of
unreacted ethylene and hydrogen in a flash drum maintained
at an internal pressure of 0.30 kg/cm2 G and at 60°C;:
Then, the content was continuously supplied to la
second polymerization bath/ together with 35 liters/frr of
hexane, 7.0 kg/hr of ethylene, 3.0 N-liters/hr of hydrogen
and 100 g/hr of 1-hexene, and polymerization was continued
under the conditions of polymerization temperature of 80°C,
reaction pressure of 3.8 kg/cm2 G and average residence
time of 1.1 hr.
Also for the second polymerization bath, the content
of the polymerization bath was continuously withdrawn so
that the liquid level in the polymerization bath woujid be
:
maintained constant. In order to prevent unwanted r
polymerization such as generation of a polymer containing a
large proportion of 1-hexene, methanol was supplied to the
content withdrawn from the second polymerization bath at a
rate of 2 liters/hr to deactivate the catalyst for
polymerization. Then, the content was subjected to removal
of hexane and unreacted monomer in a solvent separation
unit and dried to give the polymer.
Next, with respect to 100 parts by weight of the
polymer particle, the same secondary anti-oxidizing agent,
heat-resistant stabilizer and hydrochloric acid absorbent
as used in Example 1 were mixed in the same parts by!! weight
Thereafter, a sample for measurement was prepared by!
granulation at the same set temperature and extruded!: resin
amount as in Example 6 using a single screw extruder
manufactured by Placo Co., Ltd. Further, a pressed Sheet
was prepared using this sample to measure the properties.
The results are presented in Tables 1 to 3 and Tablej 6. In
the polarized microscopic observation, no crystalline
structure continuous over more than 10 (am is present!. As
it can be seen from the results of tensile fatigue
measurement at 80°C shown in Fig. 33, this sample has
higher fatigue strength than the samples of the Comparative
Examples. Also, as shown in Fig. 34, this sample has
higher strength than the samples of Comparative Examples in
the tensile fatigue measurement at 23°C.
[Example 10]
[Polymerization]
A 1000 mi-autoclave which had been sufficiently
purged with nitrogen was charged with 500 ml of n-heptane,
and 0.25 ml (0.25 mmol) of triisobutylaluminum at a
concentration of I mol/liter and 4.87 ml of the solijj
catalyst component ((3) obtained in Synthetic Example 1
(corresponding to 0.0038 mmol in terms of Zr atoms) were
introduced. The autoclave was pressurized with an
ethylene-hydrogen mix gas having a hydrogen content of 2.50
vol% to a pressure of 8.0 kg/cm2 G, and polymerization was
initiated at 80°C. The ethylene-hydrogen mix gas was added
during polymerization to maintain at 8.0 kg/cm2 G, and
polymerization was carried out for 54.5 minutes. Aftjer
i
polymerization, pressure was removed, and the autoclave was
purged with nitrogen to remove the ethylene-hydrogen mix
gas.
To this autoclave, 0.25 ml (0.25 mmol) of
triisobutylaluminum at a concentration of 1 mol/liter and
1.0 ml of 1-hexene were introduced, the autoclave wajs
pressurized with an ethylene-hydrogen mix gas with a1
hydrogen content of 0.10 vol% to a pressure of 8.0 kg/cm2 G,
and polymerization was re-initiated at 80°C. The
ethylene-hydrogen mix gas was added during polymerization
to maintain at 8.0 kg/cm2 G, and polymerization was carried
out for 15.75 minutes. After completion of polymerization,
pressure was removed, and the catalyst was deactivated by
addition of methanol. The resulting polymer was filtered,
washed and dried under vacuum at 80°C for 12 hours tlo give
102.50 g of the polymer.
With respect to 100 parts by weight of this polymer
particle, the same secondary anti-oxidizing agent, heatresistant
stabilizer and hydrochloric acid absorbent as
used in Example 1 were mixed in the same parts by weight.
Thereafter, using a Labo-Plastmil manufactured by Toyo
Seiki Co., Ltd., the resin was melt-kneaded under the same
conditions of the set temperature, the resin feed amount,
the rotation speed and the melting time as used in Example
1, taken out of the apparatus, compressed into a sheet by a
cold press set at 20°C, and cut into a suitable size! to
provide a sample for measurement. Further, a pressed sheet
was prepared using this sample to measure the properties.
The results are presented in Tables 1 to 4. In the
polarized microscopic observation, no crystalline structure
continuous over more than 10 (Jin is present. This sample
has excellent toughness and ESCR property as compared with
the samples of Comparative Examples.
[Example 11]
[Polymerization]
To a first polymerization bath, the following
components were continuously supplied: 45 liters/hr of
hexane, 0.11 mmol/hr (in terms of Zr atoms) of the solid
catalyst component (8) obtained in Synthetic Example! 2, 20
mmol/hr of triethylaluminum, 6.0 kg/hr of ethylene, and 100
N-liters/hr of hydrogen. Meanwhile, polymerization was
carried out under the conditions such as polymerization
temperature of 85°C, reaction pressure of 8.5 kg/cm2: G and
average residence time of 2.5 hr, while continuously

withdrawing the content of the polymerization bath so that
the liquid level in the polymerization bath would be
maintained constant.
The content continuously withdrawn from the first
polymerization bath was subjected to substantial removal of
unreacted ethylene and hydrogen in a flash drum maintained
at an internal pressure of 0.20 kg/cm2 G and at 65°C^
Then, the content was continuously supplied to a
second polymerization bath, together with 35 liters/hr of
hexane, 5.0 kg/hr of ethylene, 1.5 N-liters/hr of hydrogen
and 55 g/hr of 1-hexene, and polymerization was continued
under the conditions of polymerization temperature of 70°C,
reaction pressure of 6.5 kg/cm2 G and average residence
time of 1.2 hr.
Also for the second polymerization bath, the content
of the polymerization bath was continuously withdrawn so
that the liquid level in the polymerization bath would be
maintained constant. In order to prevent unwanted
polymerization such as generation of a polymer containing a
large proportion of 1-hexene, methanol was supplied to the
content withdrawn from the second polymerization bath at a
rate of 2 liters/hr to deactivate the catalyst for
polymerization. Then, the content was subjected to removal
of hexane and unreacted monomer in a solvent separation
unit and dried to give the polymer.
Next, with respect to 100 parts by weight of the
polymer particle, the same secondary anti-oxidizing
heat-resistant stabilizer and hydrochloric acid absorbent
as used in Example 1 were mixed in the same parts by^ weight,
Thereafter, a sample for measurement was prepared by
granulation at a resin extrusion amount of 20 g/min and at
100 rpm using a twin screw extruder manufactured by placo
Co., Ltd., set at a temperature of 190°C. Further, a
pressed sheet was prepared using this sample to measure the
properties. The results are presented in Tables 1 t4 5.
In the polarized microscopic observation, no crystalline
structure continuous over more than 10 |im is present j. This
sample has excellent toughness and ESCR property as
compared with the samples of Comparative Examples. Also,
it is found that the properties of the bottle molded
product are superior to those of the samples of Comparative
Examples.
[Example 12]
[Polymerization]
To a first polymerization bath, the following
components were continuously supplied: 45 liters/hr Of
hexane, 0.08 mmol/hr (in terms of Zr atoms) of the solid
catalyst component (co) obtained in Synthetic Example: 5, 20
mmol/hr of triethylaluminum, 7.0 kg/hr of ethylene, and 52
N-liters/hr of hydrogen. Meanwhile, polymerization was
carried out under the conditions such as polymerization
temperature of 85°C, reaction pressure of 7.3 kg/cm2 !'G and
average residence time of 2.6 hr, while continuously
withdrawing the content of the polymerization bath so that
the liquid level in the polymerization bath would be
maintained constant.
The content continuously withdrawn from the first
polymerization bath was subjected to substantial removal of
unreacted ethylene and hydrogen in a flash drum maintained
at an internal pressure of 0.30 kg/cm2 G and at 60°C.
Then, the content was continuously supplied to a
second polymerization bath, together with 43 liters/hr of
hexane, 3.8 kg/hr of ethylene, 14.0 N-liters/hr of hydrogen
and 20 g/hr of 1-hexene, and polymerization was continued
under the conditions of polymerization temperature of 75°C,
reaction pressure of 4.2 kg/cm2 G and average residence
time of 1.0 hr.
Also for the second polymerization bath, the content
of the polymerization bath was continuously withdrawn so
that the liquid level in the polymerization bath woujld be
maintained constant. In order to prevent unwanted
polymerization such as generation of a polymer containing a
large proportion of 1-hexene, methanol was supplied to the
content withdrawn from the second polymerization bath at a
rate of 2 liters/hr to deactivate the catalyst for
polymerization. Then, the content was subjected to removal
of hexane and unreacted monomer in a solvent separation
unit and dried to give the polymer.
With respect to 100 parts by weight of the poly^mer
particle, 0.20 part by weight of tri(2,4-di-tbutylphenyl)
phosphate as a secondary anti-oxidizing agent,
0.20 part by weight of n-octadecyl-3- (4 '-hydroxy-3', jj'-dit-
butylphenyl)propionate as a heat-resistant stabiliser,
and 0.15 part by weight of calcium stearate as a
hydrochloric acid absorbent are mixed. Thereafter, a
sample for measurement was prepared by granulation at the
same set temperature and extruded resin amount as in
Example 6 using a single screw extruder manufactured by
Placo Co., Ltd. Further, a pressed sheet was prepared
using this sample to measure the properties. The results
are presented in Tables 1 to 4. Further, the sample;was
molded into a bottle, and its properties were measured, and
the results are presented in Table 5. In the polarised
microscopic observation, no crystalline structure :
continuous over more than 10 (jm is present. The bottle
molded product has excellent toughness as compared with the
samples of Comparative Examples and excellent moldabllity
as compared with the samples of other Examples.
[Example 13] |
[Polymerization]
To the first polymerization bath, the following
components were continuously supplied: 45 liters/hr of
hexane, 0.13 mmol/hr (in terms of Zr atoms) of the solid
catalyst component (eo) obtained in Synthetic Example; 5, 20
mmol/hr of triethylaluminum, 5.0 kg/hr of ethylene, £nd 67
N-liters/hr of hydrogen. Meanwhile, polymerization Was
carried out under the conditions such as polymerization
temperature of 85°C, reaction pressure of 7.4 kg/cm2
;.G and
- 128 -
average residence time of 2.7 hr, while continuously:
withdrawing the content of the polymerization bath so that
the liquid level in the polymerization bath would be
maintained constant.
The content continuously withdrawn from the first
polymerization bath was subjected to substantial removal of
unreacted ethylene and hydrogen in a flash drum maintained
at an internal pressure of 0.30 kg/cm2 G and at 60°C.
Then, the content was continuously supplied to a
second polymerization bath, together with 43 liters/jir of
hexane, 3.9 kg/hr of ethylene, 10.0 N-liters/hr of hydrogen
and 110 g/hr of 1-hexene, and polymerization was continued
under the conditions of polymerization temperature of 75°C,
reaction pressure of 4.5 kg/cm2 G and average residence
time of 1.1 hr.
Also for the second polymerization bath, the content
of the polymerization bath was continuously withdrawh so
that the liquid level in the polymerization bath wou3.d be
maintained constant. In order to prevent unwanted
polymerization such as generation of a polymer containing a
large proportion of 1-hexene, methanol was supplied to the
content withdrawn from the second polymerization bath at a
rate of 2 liters/hr to deactivate the catalyst for
polymerization. Then, the content was subjected to removal
of hexane and unreacted monomer in a solvent separation
unit and dried to give the polymer.
Next, with respect to 100 parts by weight of the
polymer particle, the same secondary anti-oxidizing lagent,
heat-resistant stabilizer and hydrochloric acid absorbent
as used in Example 1 were mixed in the same parts by weight
Thereafter, a' sample for measurement was prepared by
granulation at the same set temperature and extruded resin
amount as in Example 6 using a single screw extruder
manufactured by Placo Co., Ltd. Further, a pressed sheet
was prepared using this sample to measure the properties.
The results are presented in Tables 1 to 3 and Tables 6 to
8. In the polarized microscopic observation, no
crystalline structure continuous over more than 10 u|n is
present. As it can be seen from the results of tensile
fatigue measurement at 80°C shown in Fig. 33, this sample
has higher fatigue strength than the samples used in the
Comparative Examples. Also, as shown in Fig. 34, the
sample has higher strength than the samples of other!
Comparative Examples in the tensile fatigue measurement at
23°C.
[Example 14]
To the first polymerization bath, the following
components were continuously supplied: 45 liters/hr ipf
hexane, 0.24 mmol/hr (in terms of Zr atoms) of the sjolid
catalyst component (8) obtained in Synthetic Example! 2, 20
mmol/hr of triethylaluminum, 7.0 kg/hr of ethylene, land 125
N-liters/hr of hydrogen. Meanwhile, polymerization yas
carried out under the conditions such as polymerization
temperature of 85°C, reaction pressure of 8.5 kg/cm2; G and
average residence time of 2.5 hr, while continuously
withdrawing the content of the polymerization bath so that
the liquid level in the polymerization bath would be
maintained constant.
The content continuously withdrawn from the first
polymerization bath was subjected to substantial rembval of
unreacted ethylene and hydrogen in a flash drum maintained
at an internal pressure of 0.2 kg/cm2 G and at 65°C.
Then, the content was continuously supplied to ;a
second polymerization bath, together with 35 liters/hr of
hexane, 4.0 kg/hr of ethylene, 1.0 N-liter/hr of hydrogen
and 50 g/hr of 1-hexene, and polymerization was continued
under the conditions of polymerization temperature ojf 80°C,
reaction pressure of 2.8 kg/cm2 G and average residence
time of 1.2 hr.
Also for the second polymerization bath, the content
of the polymerization bath was continuously withdrawn so
|
that the liquid level in the polymerization bath would be
maintained constant. In order to prevent unwanted
polymerization such as generation of a polymer containing a
large proportion of 1-hexene, methanol was supplied to the
content withdrawn from the second polymerization bath at a
rate of 2 liters/hr to deactivate the catalyst for
polymerization. Then, the content was subjected to removal
of hexane and unreacted monomer in a solvent separation
unit and dried to give the polymer.
Next, with respect to 100 parts by weight of the
particulate ethylene polymer, the same secondary antjioxidizing
agent, heat-resistant stabilizer and hydrophloric
acid absorbent as used in Example 1 were mixed in thb same
parts by weight. Thereafter, a sample for measurement was
prepared by granulation using a twin screw extruder BT-30
manufactured by Placo Co., Ltd. under the same conditions
of the set temperature, the amount of extruded resin]; and
the rotation speed as in Example 11. In the polarized
microscopic observation of 100 magnifications, no !
crystalline structure continuous over more than 10 ujn is
present. A pressed sheet was prepared using this saijvple to
measure the properties. The results are presented irk
Tables 1 to 4. Also, the sample was molded into a bottle,
and its properties were measured, and the results are
presented in Table 5.
[Example 15]
With respect to 100 parts by weight of the polymer
| •
particle obtained in Example 4, the same secondary ajatioxidizing
agent, heat-resistant stabilizer and hydrophloric
acid absorbent as used in Example 1 were mixed in the same
parts by weight. Thereafter, a sample for measurement was
prepared by granulation using a twin screw extruder ^T-30
manufactured by Placo Co., Ltd. under the same conditions
of the set temperature, the amount of extruded resin!and
the rotation speed as in Example 11. A pressed sheet was
prepared using this sample to measure the properties^ The
results are presented in Tables 1 to 4. In the polarized
microscopic observation, no crystalline structure
continuous over more than 10 pirn is present. In the
polarized microscopic observation of 100 magnifications, no
crystalline structure continuous over more than 10 \m is
present. A pressed sheet was prepared using this saiftple to
measure the properties. The results are presented ih
Tables 1 to 5. Also, the sample was molded into a bottle,
and its properties were measured, and the results arte
presented in Table 5.
[Example 16]
A 1000 mi-autoclave which had been sufficiently
purged with nitrogen was charged with 500 ml of n-heptane,
and 0.25 ml (0.25 mmol) of triisobutylaluminum at a
concentration of 1 mol/liter and 6.70 ml of the solid
catalyst component (p) obtained in Synthetic Example! 1
(corresponding to 0.0038 mmol in terms of Zr atoms) Were
introduced. The autoclave was pressurized with an
ethylene-hydrogen mix gas having a hydrogen content or 2.50
vol% to a pressure of 8.0 kg/cm2 G, and polymerization was
initiated at 80°C. The ethylene-hydrogen mix gas wai added
during polymerization to maintain at 8.0 kg/cm2 G, and
polymerization was carried out for 65 minutes. After
polymerization, pressure was removed, and the autoclave was
purged with nitrogen to remove the ethylene-hydrogen mix
gas.
To this autoclave, 0.25 ml (0.25 mmol) of
triisobutylaluminum at a concentration of 1 mol/liter and
1.5 ml of 1-hexene were introduced, the autoclave was
pressurized with an ethylene-hydrogen mix gas with aj
hydrogen content of 0.10 vol% to a pressure of 8.0 kg/cm2 G,
and polymerization was re-initiated at 80°C. The
ethylene-hydrogen mix gas was added during polymerisation
to maintain at 8.0 kg/cm2 G, and polymerization was carried
out for 10.5 minutes. After completion of polymerization,
pressure was removed, and the catalyst was deactivated by
addition of methanol. The resulting polymer was filtered,
washed and dried under vacuum at 80°C for 12 hours tjo give
97.80 g of the polymer.
With respect to 100 parts by weight of this polymer
particle, the same secondary anti-oxidizing agent, heatresistant
stabilizer and hydrochloric acid absorbent! as
those used in Example 1 were mixed in the same parts! by
weight. Thereafter, using a Labo-Plastmil manufactured by
Toyo Seiki Co., Ltd., the resin was melt-kneaded under the
same conditions of the set temperature, the resin fefed
amount, the rotation speed and the melting time as those
used in Example 1, taken out of the apparatus, compressed
into a sheet by a cold press set at 20°C, and cut into a
suitable size to provide a sample for measurement. |n the
polarized microscopic observation, no crystalline structure
continuous over more than 10 jam is present. The sample is
soluble in decane at 140°C. , Also, a pressed sheet was
prepared using this sample to measure the properties. The
results are presented in Tables 1 to 4. The sample has
excellent toughness and ESCR property as compared with the
samples of Comparative Examples.
[Example 17]
With respect to 100 parts by weight of the polymer
particle obtained in Example 14, the same secondary antioxidizing
agent, heat-resistant stabilizer and hydrochloric
acid absorbent as those used in Example 1 were mixed in the
j
same parts by weight. Thereafter, using a Labo-Plastmil
manufactured by Toyo Seiki Co., Ltd., the resin was meltkneaded
under the same conditions of the set temperature,
the resin feed amount, the rotation speed and the meeting
time as those used in Example 1, taken out of the apparatus,
compressed into a sheet by a cold press set at 20°C, and
cut into a suitable size to provide a sample for
measurement. In the polarized microscopic observation, no
crystalline structure continuous over more than 10 uijn is
present. The sample is soluble in decane at 140°C. Also,
a pressed sheet was prepared using this sample to measure
the properties. The results are presented in Tables1 to 4.
The sample has excellent toughness and ESCR property!as
compared with the samples of Comparative Examples.
[Comparative Example 7]
The pellets of product HI-ZEX 3000 B manufactured by
Mitsui Chemical Co., Ltd. were used to prepare a pressed
sheet, and its properties were measured. The results are
presented in Tables 1 to 4. The sample is inferior in
toughness to the samples of Examples and has not very good
ESCR property.
[Example 18]
A 1000 mi-autoclave which had been sufficiently
purged with nitrogen was charged with 500 ml of n-he^tane,
and 0.25 ml (0.25 mmol) of triisobutylaluminum at a
concentration of 1 mol/liter and 8.00 ml of the solid
catalyst component ((3) obtained in Synthetic Example! 1
(corresponding to 0.0045 mmol in terms of Zr atoms) were
introduced. The autoclave was pressurized with an
ethylene-hydrogen mix gas having a hydrogen content jj>f. 2.53
vol% to a pressure of 8.0 kg/cm2 G, and polymerization was
initiated at 80°C. The ethylene-hydrogen mix gas was added
during polymerization to maintain at 8.0 kg/cm2 G, and
polymerization was carried out for 80 minutes. Aftejr
polymerization, pressure was removed, and the autoclave was
purged with nitrogen to remove the ethylene-hydrogen mix
gas.
To this autoclave, 0.25 ml (0.25 mmol) of
triisobutylaluminum at a concentration of 1 mol/litep and
0.4 ml of 1-hexene were introduced, the autoclave was
pressurized with an ethylene-hydrogen mix gas with a
hydrogen content of 0.10 vol% to a pressure of 8.0 kg/cm2 G,
and polymerization was re-initiated at 80°C. The
ethylene-hydrogen mix gas was added during polymerization
to maintain at 8.0 kg/cm2 G, and polymerization was carried
out for 12.75 minutes. After completion of polymerization,
pressure was removed, and the catalyst was deactivated by
addition of methanol. The resulting polymer was filtered,
washed and dried under vacuum at 80°C for 12 hours to give
110.70 g of the polymer.
Next, with respect to 100 parts by weight of the
polymer particle, the same secondary anti-oxidizing agent,
heat-resistant stabilizer and hydrochloric acid absorbent
as those used in Example 1 were mixed in the same pairts by
weight. Thereafter, using a Labo-Plastmil manufactured by
Toyo Seiki Co., Ltd., the resin was melt-kneaded und^r the
same conditions of the set temperature, the resin feed
amount, the rotation speed and the melting time as those
used in Example 1, taken out of the apparatus, compressed
into a sheet by a cold press set at 20°C, and cut into a
suitable size to provide a sample for measurement. Jn the
polarized microscopic observation, no crystalline structure
continuous over more than 10 nm is present. The sample is
soluble in decane at 140°C. Also, a pressed sheet was
prepared using this sample to measure the properties!. The
results are presented in Tables 1 to 4. The sample has
excellent toughness as compared with the samples of
Comparative Examples.
[Example 19]
With respect to 100 parts by weight of the polymer
particle obtained in Example 4, the same secondary antioxidizing
agent, heat-resistant stabilizer and hydrochloric
acid absorbent as those used in Example 1 were mixed I in the
same parts by weight. Thereafter, a sample for measurement
was prepared by granulation at a resin extrusion amoiunt of
60 g/min and at 100 rpm using a 20 mm extruder manufactured by Thermoplastics Inc., set at 190°C.
In the polarized microscopic observation, no crystalline
structure continuous over more than 10 ^im is present* The
sample is soluble in decane at 140°C. Also, a pressed
sheet was prepared using this sample to measure the
properties. The results are presented in Tables 1 to 4.
The sample has lower smoothness than the sample of Example
4, and thus has lower ESCR property.
[Comparative Example 8]
The pellets of product Novatec HD HB332R manufactured
by Japan Polyethylene Corp. were used to prepare a pressed
sheet, and its properties were measured. The results are
presented in Tables 1 to 4. The sample is inferior in
toughness and ESCR property to the samples of Examples.
[Comparative Example. 9] :
With respect to 100 parts by weight of the polymer
particle obtained in Example 3, the same secondary antioxidizing
agent, heat-resistant stabilizer and hydrochloric
acid absorbent as those used in Example 1 were mixediin the
same parts by weight. Thereafter, a sample for measurement
was prepared by granulation using a 20 mm(|) single screw
extruder manufactured by Thermoplastics Inc. under the same
conditions of the set temperature, the amount of extruded
resin and the rotation speed as those used in Comparative
Example 1, . In the polarized microscopic observation, no
crystalline structure continuous over more than 10 pin is
present. The sample is soluble in decane at 140°C. Also,
a pressed sheet was prepared using this sample to melasure
the properties. The results are presented in Tables 1 to 3
and Table 6. The sample has lower smoothness than the
sample of Example 3, and it is found from the results of
the tensile fatigue measurement at 80°C as shown in Fig. 33
that the sample has lower fatigue strength than the samples
of Comparative Examples. Furthermore, the fractured
surface of the sample after the tensile fatigue measurement
underwent fracture without substantial elongation.
[Synthetic Example 6]
[Preparation of solid catalyst component (n) by
prepolymerization of solid catalyst component (f5)
Into a three-necked glass reactor of 200 ml equipped
with a stirrer, 28 ml of purified hexane, 2 ml (2 mmol) of
triisobutylaluminum and the solid catalyst component;; (p)
synthesized in the above Synthetic Example 1 (corresponding
to 0.03 mmol of Zr atoms) were introduced under a nitrogen
atmosphere, and prepolymerization was carried out with
ethylene in an amount such that 3 g polyethylene can be
produced per gram of the solid component in one hour. The
polymerization temperature was maintained at 20°C. After
completion of polymerization, the reactor was purged with
nitrogen, and the prepolymerization catalyst was filtered
under a nitrogen atmosphere through a glass filter
sufficiently purged with nitrogen, washed with purified
hexane for 3 times, subsequently suspended in about JOO ml
of purified decane, and transferred as the entirety to a
catalyst bottle, thus the solid catalyst component (ft)
being obtained.
{Comparative Example 10]
[Polymerization]
A 1000 mi-autoclave which had been sufficiently
1: purged with nitrogen was charged with 100 ml of n-heptane,
and 0.5 ml (0.5 mmol) of triisobutylaluminum at a !:
concentration of 1 mol/liter and 10.0 ml of the solid
catalyst component (TC) obtained in Synthetic Example i; 6
(corresponding to 0.003 mmol in terms of Zr atoms) w^re
introduced. The autoclave was pressurized with hydroigen to
1.6 kg/cm2 G and then with ethylene to 8.0 kg/cm2 G, and
polymerization was initiated at 80°C. The ethylene was
added during polymerization to maintain at 8.0 kg/cm2; G,
and polymerization was carried out for 40 minutes. Tjjfter
polymerization, pressure was removed, and the autoclave was
purged with nitrogen to remove ethylene and hydrogen.
To this autoclave, 0.25 ml (0.25 mmol) of
triisobutylaluminum at a concentration of I mol/liter and
1.5 ml of 1-hexene were introduced, the autoclave was
pressurized with an ethylene-hydrogen mix gas with a
hydrogen content of 0.0990 vol% to a pressure of 8.0: kg/cm2
G, and polymerization was re-initiated at 80°C. The ii
ethylene-hydrogen mix gas was added during polymerization
to maintain at 8.0 kg/cm2 G, and polymerization was Carried
out for 50 minutes. After completion of polymerization,
pressure was removed, and the catalyst was deactivated by
addition of methanol. The resulting polymer was filtered,
washed and dried under vacuum at 80°C for 12 hours to give
150.2 g of the polymer.
With respect to 100 parts by weight of the polymer
particle, the same secondary anti-oxidizing agent, heatresistant
stabilizer and hydrochloric acid absorbent as
those used in Example 1 were mixed in the same parts ijby
weight. Thereafter, using a Labo-Plastmil manufactured by
Toyo Seiki Co., Ltd., the resin was melt-kneaded under the
same conditions of the set temperature, the resin feed
amount, the rotation speed and the melting time as those
used in Example 1, taken out of the apparatus, compressed
into a sheet by a cold press set at 20°C, and cut into a
suitable size to provide a sample for measurement. In the
polarized microscopic observation, no crystalline structure
continuous over more than 10 urn is present. The sample is
soluble in decane at 140°C. Also, a pressed sheet was
prepared using this sample to measure the properties. The
results are presented in Tables 1 to 3 and Table 6. :As it
can be seen from the results of the tensile fatigue
measurement at 80°C as shown in Fig. 33, this polymer has
lower fatigue strength compared with the polymers described
in Examples. Further, the fractured surface of the
specimen after the tensile fatigue measurement was
fractured without substantial elongation.
[Example 20]
[Polymerization]
A 1000 mi-autoclave which had been sufficiently
purged with nitrogen was charged with 500 ml of n-heptane,
and 0.5 ml (0.5 mmol) of triisobutylaluminum at a
concentration of 1 mol/liter and 7.0 ml of the solid
catalyst component (7t) obtained in Synthetic Example 6
(corresponding to 0.00214 mmol in terms of Zr atoms) were
introduced. The autoclave was pressurized with hydrogen to
1.6 kg/cm2 G and then with ethylene to 8.0-kg/cm2 G, and
polymerization was initiated at 80°C. The ethylene was
added during polymerization to maintain at 8.0 kg/cm2 G,
and polymerization was carried out for 50 minutes. After
polymerization, pressure was removed, and the autoclave was
purged with nitrogen to remove ethylene and hydrogen.
To this autoclave, 0.25 ml (0.25 mmol) of
triisobutylaluminum at a concentration of 1 mol/liter and
2.7 ml of 1-hexene were introduced, the autoclave was
pressurized with an ethylene-hydrogen mix gas with a
hydrogen content of 0.0994 vol% to a pressure of 8.0 kg/cm2
G, and polymerization was re-initiated at 80°C. The
ethylene-hydrogen mix gas was added during polymerization
to maintain at 8.0 kg/cm2 G, and polymerization was carried
out for 70 minutes. After completion of polymerization,
pressure was removed, and the catalyst was deactivated by
addition of methanol. The resulting polymer was filtered,
washed and dried under vacuum at 80°C for 12 hours to give
90.2 g of the polymer.
With respect to 100 parts by weight of the polymer
particle, the same secondary anti-oxidizing agent, heatresistant
stabilizer and hydrochloric acid absorbent as
those used in Example 1 were mixed in the same parts! by
weight. Thereafter, using a Labo-Plastmil manufactured by
Toyo Seiki Co., Ltd., the resin was melt-kneaded under the
same conditions of the set temperature, the resin feed
amount, the rotation speed and the melting time as those
used in Example 1, taken out of the apparatus, compressed
into a sheet by a cold press set at 20°C, and cut into a
suitable size to provide a sample for measurement. In the
polarized microscopic observation, no crystalline structure
continuous over more than 10 ^un is present. The sample is
soluble in decane at 140°C. Also, a pressed sheet was
prepared using this sample to measure the properties. The
results are presented in Tables 1 to 3 and Table 6. ; As it
is clear from the results of the tensile fatigue ;•'
measurement at 80°C as shown in Fig. 33, this sample has
higher fatigue strength compared with the samples described
in Comparative Examples. Further, the fractured surface of
the specimen after the tensile fatigue measurement was
fractured without substantial elongation.
[Example 21]
A polymerization vessel which has been sufficiently
dried and purged with nitrogen was charged with 120Q liters
of hexane, and 650 mmol of triisobutylaluminum was
introduced. Then, the polymerization vessel was
pressurized with ethylene and depressurized three times
repeatedly in order to remove nitrogen in the vessel. The
vessel was heated to elevate the temperature inside to 70°C,
while it was pressurized to 0.50 MPa with ethylene and
further pressurized with hydrogen until the hydrogen
concentration at the gas phase part reached 29 mol%. The
solid catalyst component (CD) obtained in Synthetic Example
5 was introduced in an amount of 1.6 mmol in terms of Zr
atoms, and at the same time, ethylene and hydrogen were fed
at the rates of 30 Nm3/hr and 0.2 NmVhr, respectively, to
initiate polymerization at 80°C. After the beginning of
continuous supply of ethylene, when the accumulated feed
amount of ethylene reached 5.2 Nm3, pressure was removed,
while the supply of ethylene and hydrogen was stopped.
Ethylene and hydrogen were removed by purging with nitrogen,
and the temperature inside the system was lowered to!; 55°C.
After the removal of ethylene and hydrogen inside the
system, the system was heated to 70°C again, 1.95 liters of
1-hexene was added, and then the system was pressurized
with ethylene to 0.35 MPa. Ethylene and hydrogen weire fed
at the rates of 24 Nm3/hr and 1.0 N-liter/hr, respectively,
and polymerization was re-initiated to 80°C. After
beginning of continuous supply of ethylene, when the
accumulated feed amount of ethylene reached 28 Nm3, the
supply of ethylene and hydrogen was stopped, and at the
same time the polymerization slurry was transferred Ijrapidly
to another vessel. .Pressure was removed, ethylene and
hydrogen were removed by purging with nitrogen, and the
catalyst was deactivated by feeding methanol at 20 Nliters/
hr for 1 hour. At this time, the temperature inside
the system was maintained at 60°C.
The polymer was separated from hexane by filtration,
washed with an excess of hexane, and dried for 3 hours.
The amount of thus obtained polymer was 102.5 kg.
Next, with respect to 100 parts by weight of the
polymer particle, the same secondary anti-oxidizing agent,
heat-resistant stabilizer and hydrochloric acid absorbent
as used in Example 1 were mixed in the same parts by weight,
Thereafter, a sample for measurement was prepared by
granulation at a resin extrusion amount of 25 kg/hr and at
a set temperature of 200°C using a single screw extruder
(screw diameter 65 mm, L/D = 28, screen mesh #300 x 4)
manufactured by Placo Co., Ltd. In the polarized
microscopic observation, no crystalline structure
continuous over more than 10 urn is present. The sample was
soluble at 140°C. Further, a pressed sheet was prepared
using this sample to measure the properties. The results
are presented in Tables 1 to 3 and Tables 7 to 8. As it
can be seen from the results of the tensile fatigue
measurement at 23°C as shown in Fig. 34, this sample has
higher strength than the samples used in Comparative;
Examples.
[Example 22]
A polymerization vessel which has been sufficiently
dried and purged with nitrogen was charged with 1200; liters
of hexane, and 650 mmol of triisobutylaluminum was
introduced. Then, the polymerization vessel was
pressurized with ethylene and depressurized three times
repeatedly in order to remove nitrogen in the vessel. The
vessel was heated to elevate the temperature inside to 70°C,
while it was pressurized to 0.50 MPa with ethylene and
further pressurized with hydrogen until the hydrogen
concentration at the gas phase part reached 28 mol%. The
solid catalyst component (eo) obtained in Synthetic Example
5 was introduced in an amount of 1.6 mmol in terms of Zr
atoms, and at the same time, ethylene and hydrogen were fed
at the rates of 32 Nm3/hr and 0.2 NmVhr, respectively, to
initiate polymerization at 80°C. After the beginning of
continuous supply of ethylene, when the accumulated ;feed
amount of ethylene reached 52 Nm3, pressure was removed,
while the supply of ethylene and hydrogen was stopped.
Ethylene and hydrogen were removed by purging with nitrogen,
and the temperature inside the system was lowered to1 55°C.
After the removal of ethylene and hydrogen inside the
system, the system was heated to 70°C again, 1.95 liters of
1-hexene was added, and then the system was pressurized
with ethylene to 0.35 MPa. Ethylene and hydrogen were fed
at the rates of 26 Nm3/hr and 1.1 N-liters/hr, respectively,
and polymerization was re-initiated to 80°C. After
beginning of continuous supply of ethylene, when the
accumulated feed amount of ethylene reached 23 Nm3, the
supply of ethylene and hydrogen was stopped, and at the
same time the polymerization slurry was transferred rapidly
to another vessel. Pressure was removed, ethylene aftd
hydrogen were removed by purging with nitrogen, and the
catalyst was deactivated by feeding methanol at 20 Nliters/
hr for 1 hour. At this time, the temperature inside
the system was maintained at 60°C.
The polymer was separated from hexane by filtration,
washed with an excess of hexane, and dried for 3 hours.
The amount of thus obtained polymer was 99.5 kg.
Next, with respect to 100 parts by weight of the
polymer particle, the same secondary anti-oxidizing agent,
heat-resistant stabilizer and hydrochloric acid absorbent
as used in Example 1 were mixed in the same parts by weight,
Thereafter, a sample for measurement was prepared by
granulation at a resin extrusion amount of 25 kg/hr and at
a set temperature of 200°C using a single screw extruder
(screw diameter 65 mm, L/D = 28, screen mesh #300 x 4)
manufactured by Placo Co., Ltd. In the polarized
microscopic observation, no crystalline structure
continuous over more than 10 urn is present. The sample was
soluble at 140°C. Further, a pressed sheet was prepared
using this sample to measure the properties. The results
are presented in Tables 1 to 3 and Tables 7 to 8. A$ it
can be seen from the results of the tensile fatigue
measurement at 23°C as shown in Fig. 34, this sample has
higher strength than the samples used in Comparative
Examples.
[Example 23]
A polymerization vessel which has been sufficiently
dried and purged with nitrogen was charged with 1200 liters
of hexane, and 650 mmol of triisobutylaluminum was
introduced. Then, the polymerization vessel was
pressurized with ethylene and depressurized three times
repeatedly in order to remove nitrogen in the vessel. The
vessel was heated to elevate the inside temperature to 70°C,
while it was pressurized to 0.50 MPa with ethylene and
further pressurized with hydrogen until the hydrogen
concentration at the gas phase part reached 29 mol%. The
solid catalyst component (o) obtained in Synthetic Example
5 was introduced in an amount of 1.6 mmol in terms oif Zr
atoms, and at the same time, ethylene and hydrogen were fed
at the rates of 32 NitiVhr and 0.1 Nm3/hr, respectively, to
initiate polymerization at 80°C. After the beginning of
continuous supply of ethylene, when the accumulated feed
amount of ethylene reached 40 Nm3, pressure was removed,
while the supply of ethylene and hydrogen was stopped.
Ethylene and hydrogen were removed by purging with nitrogen,
and the temperature inside the system was lowered to 55°C.
After the removal of ethylene and hydrogen inside the
system, the system was heated to 70°C again, 1.39 liters of
1-hexene was added, and then the system was pressurized
with ethylene to 0.35 MPa. Ethylene and hydrogen were fed
at the rates of 26 NmVhr and 3.2 N-liters/hr, respectively,
and polymerization was re-initiated to 80°C. After
beginning of continuous supply of ethylene, when the
accumulated feed amount of ethylene reached 33 Nm3, the
supply of ethylene and hydrogen was stopped, and at the
same time the polymerization slurry was transferred rapidly
to another vessel. Pressure was removed, ethylene and
hydrogen were removed by purging with nitrogen, and the
catalyst was deactivated by feeding methanol at 20 Nr
liters/hr for 1 hour. At this time, the temperature inside
the system was maintained at 60°C.
The polymer was separated from hexane by filtration,
washed with an excess of hexane, and dried for 3 hours.
The amount of thus obtained polymer was 91.0 kg.
Next, with respect to 100 parts by weight of the
polymer particle, the same secondary anti-oxidizing agent,
heat-resistant stabilizer and hydrochloric acid absorbent
as used in Example 1 were mixed in the same parts by|weight.
Thereafter, a sample for measurement was prepared by;
granulation at a resin extrusion amount of 25 kg/hr and at
a set temperature of 200°C using a single screw extruder
(screw diameter 65 mm, L/D = 28, screen mesh §300 x 4)
manufactured by Placo Co., Ltd. In the polarized
microscopic observation, no crystalline structure
continuous over more than 10 |im is present. The sample was
soluble at 140°C. Further, a pressed sheet was prepared
using this sample to measure the properties. The results
are presented in Tables 1 to 3 and Tables 7 to 8. As it
can be seen from the results of the tensile fatigue
measurement at 23°C as shown in Fig. 34, this sample has
higher strength than the samples used in Comparative
Examples.
[Synthetic Example 7]
[Preparation of supported catalyst]
In a glove box, 0.18 g of di (ptolyl)
methylene(cyclopentadienyl)
(octamethyloctahydrodibenzofluorenyl) zirconium dichloride
was weighed into a four-necked 1-liter flask. The flask
was taken out of the glove box, and 46 ml of toluene and
140 ml of a toluene slurry of MAO/Si02 (solids content 8.82
g) were added therein with stirring for 30 minutes under a
nitrogen atmosphere, thus supporting being carried out.
Thus obtained di(ptolyl)
methylene(cyclopentadienyl)(octamethyloctahydrodibenz
ofluorenyl) zirconium dichloride/MAO/Si02/toluene slurry
was substituted with n-heptane to 99%, to obtain a final
slurry amount of 450 ml, thus the solid catalyst component
(a) being prepared. Furthermore, this procedure was
carried out at room temperature.
[Example 24]
[Ethylene polymerization]
An autoclave equipped with a stirrer having a j.
capacity of 200 liters was charged with 86.5 liters of
heptane, 90 mmol of triisobutylaluminum and 9 g of the
solid catalyst component (a) obtained in the above.
Polymerization was carried out while the internal
temperature and pressure were maintained at 80°C and 0.6
MPa/G, respectively, by introducing ethylene and hydrogen.
The amount of charged ethylene was 13.7 kg.
Subsequently, pressure was removed until the pressure
inside the polymerization vessel became 0 MPa/G, and the
polymerization vessel was purged with nitrogen in order to
remove hydrogen inside the vessel.
Next, 340 ml of 1-hexene was introduced.
Polymerization was carried out while maintaining the
internal temperature at 65°C and maintaining the internal
pressure at 0.5 MPa/G by introducing ethylene and hydrogen.
The amount of charged ethylene was 9.0 kg.
The entire amount of thus obtained polyethylene
slurry was transferred to an autoclave equipped with a
stirrer having a capacity of 500 liters, and the catalyst
was deactivated by introducing 10.7 ml of methanol. i This
slurry was transferred to a filter dryer equipped with a
stirrer, filtered and vacuum-dried at 85°C for 6 hours to
yield polyethylene powders.
Next, with 100 parts by weight of this polymer:
particle, the same secondary anti-oxidizing agent, heatresistant
stabilizer and hydrochloric acid absorbent; as
those used in Example 1 were mixed in the same parts; by
weight. Thereafter, using a Labo-Plastmil manufactured by
Toyo Seiki Co., Ltd., the resin was melt-kneaded under the
same conditions of the set temperature, the resin feed
amount, the rotation speed and the melting time as those
used in Example 1, taken out of the apparatus, compressed
into a sheet by a cold press set at 20°C, and cut into a
suitable size to provide a sample for measurement. In the
polarized microscopic observation, no crystalline structure
continuous over more than 10 jum is present. The sample is
soluble in decane at 140°C. Also, a pressed sheet was
prepared using this sample to measure the properties!:. The
results are presented in Tables 1 to 3 and Tables 7 |to 8.
As it can be seen from the results of the tensile fatigue
measurement at 23°C as shown in Fig. 34, this sample has
higher strength than the samples used in Comparative
Examples.
[Example 25]
[Ethylene Polymerization]
An autoclave equipped with a stirrer having a ;
capacity of 200 liters was charged with 86.5 liters of
heptane, 90 mmol of triisobutylaluminum and 9 g of the
solid catalyst component (a) prepared in Synthetic Example
7. Polymerization was carried out while the internal
temperature and pressure were maintained at 80°C and 0.6
MPa/G, respectively, by introducing ethylene and hydrogen.
The amount of charged ethylene was 13.7 kg. :
Subsequently, pressure was removed until the pressure
inside the polymerization vessel became 0 MPa/G, and the
polymerization vessel was purged with nitrogen in order to
remove hydrogen inside the vessel.
Next, 473 ml of 1-hexene was introduced.
Polymerization was carried out while maintaining the
internal temperature at 65°C and maintaining the internal
pressure at 0.5 MPa/G by introducing ethylene and hydrogen.
The amount of charged ethylene was 9.0 kg.
The entire amount of thus obtained polyethylene
slurry was transferred to an autoclave equipped with; a
stirrer having a capacity of 500 liters, and the catalyst
was deactivated by introducing 10.7 ml of methanol. This
slurry was transferred to a filter dryer equipped with a
stirrer, filtered and vacuum-dried at 85°C for 6 hours to
yield polyethylene powders.
Next, with 100 parts by weight of this polymer
particle, the same secondary anti-oxidizing agent, heatresistant
stabilizer and hydrochloric acid absorbent: as
those used in Example 1 were mixed in the same parts!; by
weight. Thereafter, using a Labo-Plastmil manufactured by
Toyo Seiki Co., Ltd., the resin was melt-kneaded under the
same conditions of the set temperature, the resin feed
amount, the rotation speed and the melting time as those
used in Example 1, taken out of the apparatus, compressed
into a sheet by a cold press set at 20°C, and cut into a
suitable size to provide a sample for measurement. In the
polarized microscopic observation, no crystalline structure
continuous over more than 10 nm is present. The sample is
soluble in decane at 140°C. Also, a pressed sheet was
prepared using this sample to measure the properties. The
results are presented in Tables 1 to 3 and Tables 7 jto 8.
As it can be seen from the results of the tensile fajtigue
measurement at 23°C as shown in Fig. 34, this sample has
higher strength than the samples used in Comparative
Examples.
(Table Removed)
Industrial Applicability
The ethylene polymer of the invention provides a
molded product which has excellent moldability and thus
excellent mechanical strength and external appearance. The
polymer imparts excellent properties when used in the
ethylene polymer blow molded products and extrusion molded
products such as pipes or other different forms according
to the invention.


We claim:
1. An ethylene polymer containing 0.01 to 1.00 mol% of a constitutional unit derived from a-olefm having 6 to 10 carbon atoms, wherein the number of methyl branch groups as measured by 13C-NMR is less than 0.1 per 1000 carbon atoms;
which satisfies at least either of the following requirements (1) and (2) with respect to cross fractionation chromatography (CFC):
(1) the weight average molecular weight (Mw) of the components eluted at 73 to 76°C does not exceed 4,000; and
(2) the following relationship (Eq-l)is satisfied:
(Equation Removed)
wherein Sx is the sum of the total peak areas related to the components which are eluted at 70 to 85°C, and Stotai is the sum of the total peak areas related to the components which are eluted at 0 to 145°C;
which simultaneously satisfies the following requirements (V) to (6)
(V) the density (d) is in the range of 945 to 970 kg/m3;
(2) the intrinsic viscosity ([]) as measured in decalin at 135°C is in the range of 1.6 to 4.1 (dl/g);
(3') the ratio (Mw/Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) as measure by GPC is in the range of 5 to 70;
(4) with respect to cross fractionation chromatography (CFC), when the elution temperature for the apex of the strongest peak in the region corresponding to molecular weights of less than 100,000 is taken as Ti (°C), and the elution temperature for the apex of the strongest peak in the region corresponding to molecular weights of 100,000 or more is taken as T2 (°C), (Ti - T2) (°C) is in the range of 0 to 11°C;
(5') with respect to cross fractionation chromatography (CFC), the molecular weight for the apex, of the strongest peak in the region corresponding to molecular weights of 100,000 or more is in the range of 200,000 to 800,000 on the GPC curve for the fraction eluted at [(T2-1) to T2] (°C); and
(6') with respect to cross fractionation chromatography (CFC), the molecular weight for the apex of the strongest peak in the region corresponding to molecular weights of 100,000 or less does not exceed 28,000 on the CFC curve for the components eluted at 95 to 96°C;
which simultaneously satisfies the following requirements (1"') and (2'")
(1'') when the GPC curve is divided into two logarithmic normal distribution curves, the ratio (Mw/Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) for each divided curve is from 1.5 to 3.5, and the weight average molecular weight (MW2) for the divided curve representing the higher molecular weight portion is from 200,000 to 800,000; and (2"") the smoothness coefficient R as determined from the surface roughness of an extruded strand does not exceed 20 µm;
which simultaneously satisfies the following requirements (lp) and (2P)
(1P) the polymer contains 0.10 to 1.00 mol% of a constitutional unit derived from α-olefin having 6 to 10 carbon atoms; and
(2P) the ratio (Mw/Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) as measured by GPC is in the range of 11 to 70.
and which simultaneously satisfies the following requirements (1'p) and )(2p)
(lp') the actual stress obtained when it takes 10,000 cycles to specimen fracture due to the tensile fatigue property as measured at 80°C according to JIS K-6744, is from 13 MPa to 17 MPa, and the actual stress obtained when it takes 100,000 cycles to fracture is from 12 to 16 MPa; and
(2 P') the actual stress (S) (MPa) and the density (d) obtained when it takes 10,000 cycles to fracture due to the tensile fatigue property as measured at 23°C according to JIS K-7118, satisfy the following relationship (Eq-2): (0.12d - 94.84) 2. The ethylene polymer as claimed in claim 1, wherein the polymer satisfies
the following requirements (1B) to (3B) simultaneously:
(1B) the polymer contains 0.02 to 0.20 mol% of a constitutional unit derived
from α-olefin having 6 to 10 carbon atoms;
(2B) the ratio (Mw/Mn) of the weight average molecular weight (Mw) and the
number average molecular weight (Mn) as measured by GPC is in the range of
5 to 30; and
(3B) with respect to cross fractionation chromatography (CFC), when the elution
temperature for the apex of the strongest peak in the region corresponding to
molecular weights of less than 100,000 is taken as T1 (°C), and the elution
temperature for the apex of the strongest peak in the region corresponding to
molecular weights of 100,000 or more is taken as T2 (°C), (T1 - T2) (°C) is in the
range of 0 to 5°C.
3. A molded article prepared by using the ethylene polymer as claimed in any of the preceding claims.

Documents:

3139-DELNP-2005-Abstract-(21-08-2008).pdf

3139-delnp-2005-abstract.pdf

3139-DELNP-2005-Claims-(21-08-2008).pdf

3139-DELNP-2005-Claims-(27-03-2009).pdf

3139-delnp-2005-claims.pdf

3139-delnp-2005-complete specification (granted).pdf

3139-DELNP-2005-Correspondence-Others-(21-08-2008).pdf

3139-delnp-2005-correspondence-others.pdf

3139-delnp-2005-description (complete)-21-08-2008.pdf

3139-delnp-2005-description (complete).pdf

3139-DELNP-2005-Drawings-(21-08-2008).pdf

3139-delnp-2005-drawings.pdf

3139-DELNP-2005-Form-1-(21-08-2008).pdf

3139-delnp-2005-form-1.pdf

3139-delnp-2005-form-18.pdf

3139-DELNP-2005-Form-2-(21-08-2008).pdf

3139-delnp-2005-form-2.pdf

3139-DELNP-2005-Form-3-(21-08-2008).pdf

3139-delnp-2005-form-3.pdf

3139-delnp-2005-form-5.pdf

3139-DELNP-2005-GPA-(21-08-2008).pdf

3139-delnp-2005-gpa.pdf

3139-delnp-2005-pct-301.pdf

3139-delnp-2005-pct-304.pdf

3139-DELNP-2005-Petition-137-(21-08-2008).pdf


Patent Number 233483
Indian Patent Application Number 3139/DELNP/2005
PG Journal Number 14/2009
Publication Date 27-Mar-2009
Grant Date 30-Mar-2009
Date of Filing 15-Jul-2005
Name of Patentee MITSUI CHEMICALS, INC.
Applicant Address 5-2, HIGASHI-SHIMBASHI, 1-CHOME, MINATO-KU, TOKYO 105-7117, JAPAN
Inventors:
# Inventor's Name Inventor's Address
1 YASUO FUNABARA C/O MITSUI CHEMICALS, INC.,3, CHIGUSA-KAIGAN, ICHIHARA-SHI, CHIBA 299-0108,JAPAN.
2 TAKAHIRO AKASHI C/O MITSUI CHEMICALS, INC.,3, CHIGUSA-KAIGAN, ICHIHARA-SHI, CHIBA 299-0108,JAPAN.
3 MAMORU TAKAHASHI, C/O MITSUI CHEMICALS,INC., 580-32, NAGAURA,SODEGAURA-SHI, CHIBA 299-0265, JAPAN.
4 MASAHIKO OKAMOTO C/O MITSUI CHEMICALS,INC., 580-32, NAGAURA,SODEGAURA-SHI, CHIBA 299-0265, JAPAN.
5 TETSUJI KASAI C/O MITSUI CHEMICALS,INC., 580-32, NAGAURA,SODEGAURA-SHI, CHIBA 299-0265, JAPAN.
6 YASUSHI TOHI C/O MITSUI CHEMICALS,INC., 580-32, NAGAURA,SODEGAURA-SHI, CHIBA 299-0265, JAPAN.
7 SHIRO OTSUZUKI C/O MITSUI CHEMICALS, INC.,6-12,WAGI, WAGI-CHO, KUGA-GUN, YAMAGUCHI 740-0061, JAPAN.
8 SHINICHI NAGANO C/O MITSUI CHEMICALS, INC.,3, CHIGUSA-KAIGAN, ICHIHARA-SHI, CHIBA 299-0108,JAPAN.
PCT International Classification Number C08F 210/02
PCT International Application Number PCT/JP2004/001689
PCT International Filing date 2004-02-17
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 2003-038079 2003-02-17 Japan