Title of Invention

"AN ETHYLENE POLYMER AND BLOW MOLDED PRODUCT MADE FROM THE SAID POLYMER"

Abstract An ethylene polymer containing 0.02 to 0.50 mol% of a constitutional unit derived from an a-olefin having 6 to 10 carbon atoms, the polymer having a density of 945 to 975 kg/m3 and satisfying the following requirements [1], [2] and [2b]-[4b] simultaneously [1] in CFC, all the components having a molecular weight of 100,000 or more are eluted at a temperature of 85°C or higher; [2] the components eluted at a temperature of 80°C or lower account for up to 5% of all the components elated in CFC; [2b] the intrinsic viscosity (n) as measured in decalin at 135°C is in the range of 1.6 to 2.8 (dl/g); [3b] the flexural modulus, MPa, as measured at 23°C according to ASTM-D-790 satisfies 600 &#8804; M <1500, and the environmental stress cracking resistance (ESCR), T hr, as measured at 50°C according to ASTM-D-1693 and M satisfy the following equation (Eq-1): T &#8805;-0.8XM+1210 (Eq-1); and [4b] tan 8 (loss modulus G''Vstorage modulus G') as measured at 190°C and at an angular frequency of 100 rad/sec using a dynamic viscoelasticity measuring apparatus, is in the range of 0.6 to 0.9 and a blow molded product made from the said polymer..
Full Text TECHNICAL FIELD
The present invention relates to an ethylene polymer which has excellent fluidity and moldability, and also gives a molded product having excellent properties such as mechanical strength, and to a molded product obtained therefrom.
BACKGROUND ART
High-density polyethylene which is used in wide applications such as films, pipes, and bottle containers, 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 of 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 moldability 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/a-olefin copolymer of a relatively large molecular weight, according to
a continuous polymerization technique using a single-site
catalyst which facilitates the control of the composition
distribution.
JP-A No. 11-106432 discloses a composition prepared by
melt-blending a low molecular weight polyethylene with a high
molecular weight ethylene/a-olefin copolymer which is obtained
by polymerization using a supported geometric constraint type
single-site catalyst (CGC/Borate-based catalyst). However it
is expected that sufficient mechanical strength would not be
exhibited in the case of the carbon number being less than 6
according to the method disclosed in the above-mentioned patent
application. Further because the molecular weight
distribution (Mw/Mn) of the single-stage polymerization product
is broad it is also expected that the mechanical properties of
the product such as impact strength would be insufficient as
compared with the single-stage product having a narrower
molecular weight distribution.
WO 01/25328 discloses an ethylene polymer which is obtained
by solution polymerization in the presence of a catalyst system
comprising CpTiNP(tBu) 3C12 and borate or alumoxane. This
ethylene polymer has a weak crystalline structure due to the
presence of branches in the low molecular weight component and
thus it is expected that the polymer has poor mechanical strength.
EP 1201711 Al discloses an ethylene polymer which is
obtained by slurry polymerization in the presence of a catalyst
system comprising ethylene
bis(4567-tetrahydro-l-indenyl)zirconium dichloride and
methylalumoxane supported on silica. Among these ethylene
polymers a single-stage polymerization product has a wide
molecular weight distribution (Mw/Mn) and thus it is expected
that it would have insufficient impact strength and the like
as compared with a single-stage product of a 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
long lifetime properties such as environmental stress cracking
resistance (ESCR).
JP-A No. 2002-53615 discloses 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 patent application does 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
envisaged to be too small to exhibit a sufficient mechanical
strength.
The ethylene (co)polymer prepared using a Ziegler catalyst
as described in Japanese Patent No. 821037 or the like has methyl
branches in the molecular chain as a result of side production
of methyl branches during the polymerization. It was found that
these methyl branches were embedded in the crystal thus
weakening the crystal and this caused deterioration of
mechanical strength of the ethylene (co)polymer. Further in
regard to the copolymer of ethylene and an a-olefin when the
copolymer contained almost no a-olefin a hard but brittle
component was produced while when an excessive amount of
a-olefin was subject to copolymerization a soft component with
weak crystalline structure was produced and thus it may cause
tackiness due to broad composition distribution. Moreover
since the molecular weight distribution was broad there were
problems such as the phenomenon that a low molecular weight
polymer adheres onto the surface of a molded product as a powdery
substance and so on.
The ethylene polymer that is obtained by polymerization
using a metallocene catalyst as described in JP-A No. 9-183816
or the like causes side production of methyl branches during the
polymerization thereby lowering the mechanical strength.
An ethylene polymer which is obtained by polymerization
using a chromium catalyst exhibits small extension of molecular
chain because of the presence of a long chain branch and thus
has poor mechanical strength and long lifetime properties such
as environmental stress cracking resistance (ESCR). Further
as a result of side production of a methyl branch during the
polymerization there exist methyl branch groups in the molecular
chain. This has been a cause for lowering the mechanical
strength.
The ethylene polymer which is obtained by polymerization
using a constrained geometry catalyst (CGC) as described in WO
93/08221 or the like has methyl branches in the molecular chain
as a result of side production of a methyl branch during the
polymerization. These methyl branches are embedded in the
crystals and thus weaken the crystalline structure. This has
been a cause for lowering the mechanical strength. Further the
molecular extension of molecular chain was small because of the
presence of long chain branches and thus the mechanical strength
and long lifetime properties such as environmental stress
cracking resistance (ESCR) were insufficient.
An ethylene polymer which is obtained by high pressure
radical polymerization has methyl branches or long chain branches
in the molecular chain as a result of side production of methyl
branches or long chain branches during polymerization. These
methyl branches are embedded in the crystals thereby weakening
the crystalline strength. This has been a cause for lowering
the mechanical strength. Further the presence of long chain
branches resulted in small extension of molecular chain as well
as a broad molecular weight distribution and thus the long
lifetime properties such as environmental stress cracking
resistance (ESCR) were poor.
DISCLOSURE OF THE INVENTION
The present inventors have conducted an extensive research
in view of the above conventional technology on an ethylene
polymer which has excellent moldability and also gives a molded
product having excellent mechanical strength and found that an
ethylene polymer (E) containing 0.02 to 1.50 mol% of a
constitutional unit derived from ct-olefin having 6 to 10 carbon
atoms and having the density of 945 to 975 kg/m3 which satisfies
both of the following reguirements [1] and [2] has excellent
moldability and also gives a molded product especially a blow
molded product an extrusion molded product and an injection
molded product having excellent mechanical strength and
excellent appearance thus completing the present invention.
[1] In CFC all the components having a molecular weight
of 100000 or more are eluted at a temperature of 85°C or higher.
[2] The components eluted at temperatures of 80°C or lower
account for up to 5% of all the components eluted in CFC.
The ethylene polymer (E) according to the present invention which is suitably used for blow molding, preferably satisfies, in addition to the above-mentioned requirements, the following requirements [lb] to [4b] simultaneously:
[lb] the polymer contains 0.02 to 0.50 mol% of a constitutional unit derived from α-olefin having 6 to 10 carbon atoms;
[2b] the intrinsic viscosity ( [n]) as measured in decalin at 135°C is in the range of 1.6 to 2.8 (dl/g);
[3b] the fiexural modulus, MPa, as measured at 23 °C according to ASTM-D-790 satisfies 600 ≤ M T≥-0.8XM+1,210 (Eq-1); and"
[4b] tan5 (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 in the range of 0.6 to 0.9.
Incidentally, hereinafter, the ethylene polymers as described above, that is, the ethylene polymers, which are very suitably used for blow molding, and satisfying the requirements [1], [2], [lb], [2b], [3b] and [4b] simultaneously, may be referred to as ethylene polymers (Eb).
In the case of employing the ethylene polymer (E) according to the present invention in the extrusion or injection molding
applications it is preferable that the polymer satisfies in
addition to the foregoing requirements the following
requirements [le] to [5e] simultaneously:
[le] the polymer contains 0.02 to 1.20 mol% of a
constitutional unit derived from a-olefin having 6 to 10 carbon
atoms;
[2e] the intrinsic viscosity ( [t|] ) as measured in decalin
at 135°C is in the range of 2.0 to 3.0 (dl/g);
[3e] the apparent shear stress as measured by a Capillary
Rheometer at 210°C and a shear rate of 194.57 sec'1 is 7.0 MPa
or less;
[4e] the actual stress obtained when it takes 10000 cycles
to fracture due to the tensile fatigue property as measured at
80°C according to JIS K-6744 is from 11 to 17 MPa and the actual
stress obtained when it takes 100000 cycles to fracture is from
9 to 16 MPa; and
[5e] the actual stress obtained when it takes 10000 cycles
to fracture due to the tensile fatigue property as measured at
23°C with an unnotched specimen is from 18 to 22 MPa and the
actual stress obtained when it takes 100000 cycles to fracture
is from 17 to 21 MPa.
Incidentally the ethylene polymers as described above
that is the ethylene polymers which are suitably used for
extrusion or injection molding and satisfying the requirements
[I]/ [2] [le] [2e] [3e] [4e] and [5e] simultaneously may
be referred to as ethylene polymers (Ee) hereinafter.
The present invention relates to a blow molded product an
extrusion molded product a compression molded product or a
vacuum molded product made from the ethylene polymer (E) the
ethylene polymer (Eb) or the ethylene polymer (Ee). Preferred
examples of the blow molded product include gasoline tanks
industrial chemical canisters and bottle containers.
Preferred examples of the extrusion molded product include pipes
electric wire coverings and steel tube/steel wire coverings.
Preferred examples of the injection molded product include pipe
joints or automotive parts.
BRIEF DESCRIPTION OF THE DRAWINGS
Fig. 1 is a CFC contour diagram for the ethylene polymer
as described in Example 2b-
Fig. 2 is a CFC contour diagram for the ethylene polymer
as described in Comparative Example lb.
Fig. 3 is a chart obtained by plotting the flexural modulus
M (MPa) as measured at 23°C against the environmental stress
cracking resistance ESCR (T hr) at 50°C for the representative
ethylene polymers as described in Examples and Comparative
Examples of the present invention.
10
Fig. 4 is a diagram showing a specimen for the tensile
fatigue test at 23°C.
Fig. 5 is a chart indicating the comparison of results of
the tensile fatigue test at 80°C for Examples and Comparative
Examples.
Fig. 6 is a chart indicating the results of the tensile test
at 23°C for Examples and Comparative Examples.
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter the present invention will be described one
after another regarding the ethylene polymer (E) the ethylene
polymer (Eb) which is suitably used for blow molding and the
ethylene polymer (Ee) which is suitably used for extrusion or
injection molding and then the blow molded product the
extrusion molded product the compression molded product or the
vacuum molded product made from the ethylene polymer (E) the
ethylene polymer (Eb) or the ethylene polymer (Ee) will be
described.
Ethylene Polymer (E)
The ethylene polymer (E) according to the present invention
is an ethylene polymer which contains 0.02 to 1.50 mol% 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 6 to 10 carbon atoms.
11
Herein examples of a-olefin having 6 to 10 carbon atoms
(hereinafter may be simply referred to as "a-olefin") include
1-hexene 4-methyl-l-pentene 3-methyl-l-pentene 1-octene
and 1-decene. 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. 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 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.
The constitutional unit derived from a-olefin is contained
in an amount of usually 0.02 to 1.50 mol% and preferably 0.02
to 1.30 mol%. More preferable concentration varies according
to the applications in which the ethylene polymer is used (the
details of which will be described later).
The ethylene polymer (E) according to the present invention
satisfies the following requirements [1] and [2] simultaneously
12
for the cross fractionation chromatography (CFG).
Requirement [1]
The ethylene polymer (E) according to the invention is
characterized in that all the components having a molecular
weight of 100000 or more are eluted at 85°C or higher in cross
fractionation chromatography (CFG). Now the requirement [1]
will be specifically described with reference to the results
described in Examples. As determined by the CFG analysis of the
ethylene polymer employed in Example 2b described later the
temperature at which the component having a molecular weight (M)
of 100000 or more (that is LogM 5.0) starts eluting is 94°C
which satisfies the requirement [1]. The blow molded product
made from the ethylene polymer exhibits good environmental stress
cracking resistance (ESCR) as show in Table 3b. On the other hand
as determined by the CFC analysis of the ethylene polymer employed
in Comparative Example It the temperature at which the component
having a molecular weight (M) of 100000 or more (that is LogM
5.0) starts eluting is 83°C which does not satisfy the
requirement [1] . The blow molded product made from the ethylene
polymer exhibits poorer balance between the stiffness (flexural
modulus) and the environmental stress cracking resistance (ESCR)
as compared with the ethylene polymer of Example 2b as shown in
Table 3b. That is it was found that it is essential that the
ethylene polymer of the present invention should satisfy the
13
requirement [1] in order to provide a molded product with
excellent performances such as stiffness and fluidity and good
balance of the long lifetime property therewith. In order to
provide a molded product with performances such as stiffness and
fluidity and good balance of the long lifetime property
therewith it is preferable that the ethylene polymer of the
present invention should satisfy the following requirement [2]
in addition to the requirement [1].
Requirement [2]
The ethylene polymer (E) according to the present invention
is characterized in that 5% or less of all the components are
eluted at 80°C or lower in cross fractionation chromatography
(CFC). (Here "%" refers to the percentage of the total area
of the peak attributable to the components eluted at 80°C or lower
relative to the total area of the peak attributable to all the
components). Now the requirement [2] will be specifically
described with reference to the results described in Examples.
As determined by the CFC analysis of the ethylene polymer employed
in Example 2b described later the proportion of the components
eluted at 80°C or lower in the all the components is 1.9% which
satisfies the requirement [2] . The blow molded product made from
the ethylene polymer exhibits good balance between the stiffness
(flexural modulus bucking strength) and the environmental
stress cracking resistance (ESCR) as show in Table 3b and 4b. On
14
the other hand as determined by the CFC analysis of the ethylene
polymer employed in Comparative Example lb the proportion of
the components eluted at 80°C or lower in the all the components
is 7.1% which does not satisfy the requirement [2]. The blow
molded product made from the ethylene polymer exhibits poorer
balance between the stiffness (flexural modulus bucking
strength) and the environmental stress cracking resistance
(ESCR) as compared with the ethylene polymer of Example 2b as
show in Table 3b and 4b. (Moreover with reference to the
requirements [1] and [2] the difference of the ethylene polymers
as described in Example 2b and Comparative Example lb can be
understood qualitatively from the CFC contour diagram of Figs.
1 and 2.)
It is meant by the ethylene polymer satisfying the
requirements [1] and [2] that the a-olefin content of the high
molecular weight components having a copolymerized a-olefin is
small and the composition of a-olefin is uniform or that the
polymer does not contain any of such components which have
relatively small molecular weights and also a short chain branch.
In this case a product molded therefrom is improved in long-term
properties and the mechanical strength. The ethylene/a-olefin
copolymer as described in 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 WO
15
01/25328 does not satisfy the above-mentioned scope because even
a component with relatively small molecular weight also has a
short chain branch resulting from copolymerization 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 satisfying the requirements
[1] and [2] can be prepared. Preferred examples of the ethylene
polymers (E) can be mainly categorized to two types of the ethylene
polymers i.e. the ethylene polymer (Eb) which is suitably used
for blow molding and the ethylene polymer (Ee) which is suitably
used for extrusion or injection molding. "Suitably used for a
specific application" means that the substances fully exhibit
their performances according to the present invention in the
specific application without limitation by other fields than
the application field.
Ethylene polymer (Eb)
The ethylene polymer (Eb) is an ethylene polymer which
satisfies in addition to the above-mentioned requirements [1]
and [2] the following requirements [Ib] to [4b] and is
preferably used for blow molding.
16
Requirement [Ib]
The ethylene polymer (Eb) usually contains 0 . 02 to 0. 50 mol%
of a constitutional unit derived from a-olefin having 6 to 10
carbon atoms. When the ethylene polymer (Eb) does not contain
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 in a proportion of usually 99.50 to 99.98
mol% preferably 99.80 to 99.98 mol% and the repeating unit
derived from the a-olefin is present in a proportion of usually
0.02 to 0.50 mol% preferably 0.02 to 0.20 mol%. And the
ethylene polymer (Eb) may occasionally contain 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 in a proportion of
usually 97.50 to 99.96 mol% preferably 99 to 99.96 mol% and
the repeating unit derived from the a-olefin is present in a
proportion of usually 0.04 to 2.50 mol% preferably 0.04 to 1.00
mol%. Here even in the case of containing ethylene homopolymers
the repeating unit derived from the a-olefin is present in a
proportion of usually 0.02 to 0.50 mol% preferably 0.02 to 0.40
mol% based on the total polymer.
Requirement [2b]
The intrinsic viscosity ( [r|] ) of the ethylene polymer (Eb)
17
of the present invention as measured in decalin at 135°C is in
the range of 1.6 to 2.8 dl/g and preferably from 1.8 to 2.8 dl/g.
The ethylene polymer having its intrinsic viscosity within these
ranges is excellent in mechanical strength moldability and the
environmental stress cracking resistance (ESCR). For example
by changing the ratio of the amounts of hydrogen ethylene and
a-olefin fed to the polymerization reactor the ratio of the
polymerization amounts of ethylene homopolymer to
ethylene/a-olefin copolymer or the like the values of intrinsic
viscosity can be increased or decreased within the
above-mentioned numerical ranges. Specifically in the slurry
polymerization of Example 2b using hexane as a solvent when
polymerization is carried out under stirring to render the system
homogeneous the density and [TI] become 962 kg/m3 and 2.15 dl/g
respectively; when ethylene hydrogen and 1-hexene are fed to
the second polymerization reactor at the rates of 4.3 kg/hr 3.0
N-liter/hr and 26 g/hr respectively the density and [T]] become
967 kg/m3 and 2.10 dl/g respectively; and when ethylene and
hydrogen are fed to the first polymerization reactor at the rates
of 7.0 kg/hr and 40 N-liters/hr respectively and ethylene
hydrogen and 1-hexene are fed to the second polymerization
reactor at the rates of 3.8 kg/hr 4.5 N-liter/hr and 180 g/hr
respectively the density and [r|] become 954 kg/m3 and 2.43 dl/g
respectively.Requirement [3b] The ethylene polymer (Eb) according to the present invention has a flexural modulus, MPa, as measured at 23°C according to ASTM-D-790 which satisfies 600 ≤ M T≥-0.8XM+1,210 (Eq-1).
Such the ethylene polymer is stiff and tough, and thus the molded article 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 falling in the above range can be prepared by changing the proportions of hydrogen, ethylene and α-olefin fed to the polymerization reactor 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 4b, the flexural modulus obtained is 1, 490 MPa, and the ESCR is 177 hours up to 50% failure, or when the amount of hydrogen fed to the first polymerization reactor is changed from 75 N-liter/hr to 70 N-liter/hr, the amount of hydrogen fed to the second polymerization reactor is changed from 3. 0 N-liter/hr to 4 .0 N-liter/hr, and the amount of 1-hexene fed to the second polymerization reactor is changed from 52 g/hr
to 65 g/hr under the conditions as described in Example 4t the
f lexural modulus becomes 1410 MPa and the ESCR becomes 188 hours
up to 50% failure.
Requirements [4b]
The ethylene polymer (Eb) according to the present
invention preferably has a tan8 (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 in the range
of 0.6 to 0.9. When tan8 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 or total
molecular weight is decreased tan8 tends to increase. Here
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 . Larger tan8 means stronger viscosity and in this case
the resin is thought to be susceptible to bulging.
Ethylene polymer (Ee)
The ethylene polymer (Ee) is an ethylene polymer which
satisfies in addition to the above-mentioned requirements [1]
and [2] the following requirements [le] to [5e] and is
20
preferably used for extrusion or injection molding.
Requirement [le]
The ethylene polymer (Ee) usually contains 0 . 02 to 1. 20 mol%
of a repeating unit derived from a-olefin. When the ethylene
polymer (Ee) does not contain 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 in a
proportion of usually 98.80 to 99.98 mol% preferably 99.0 to
99.80 mol% and the repeating unit derived from the a-olefin is
present in a proportion of usually 0.02 to 1.2 mol% preferably
0.02 to 1.00 mol%. And the ethylene polymer (Ee) may
occasionally contain 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 in
a proportion of usually 95 to 99.96 mol% preferably 97 . 5 to 99. 96
mol% and the repeating unit derived from the a-olefin is present
in a proportion of usually 0.04 to 5.00 mol% preferably 0.04
to 2.50 mol%. Here even in the case of containing ethylene
homopolymers the repeating unit derived from the a-olefin is
present in a proportion of usually 0.02 to 1.20 mol% preferably
0.02 to 1.00 mol% based on the total polymer.
Requirement [2e]
The intrinsic viscosity ( [r|] ) of the ethylene polymer (Ee)
21
of the present invention as measured in decalin at 135°C is in
the range of 2.0 to 3.0 dl/g and preferably from 2.0 to 2.8 dl/g.
The ethylene polymer having its density and intrinsic viscosity
within these ranges is excellent in fluidity and mechanical
strength and the balance of stiffness and moldability. For
example by changing the ratio of the amounts of hydrogen
ethylene and a-olefin fed to the polymerization reactor the
ratio of the polymerization amounts of ethylene homopolymer to
ethylene/a-olefin copolymer or the like the values can be
increased or decreased within the above-mentioned numerical
ranges. Specifically in the slurry polymerization of Example
3e using hexane as a solvent when polymerization is carried out
under stirring to render the system homogeneous the density and
[T]] become 954 kg/m3 and 2.49 dl/g respectively; when ethylene
hydrogen and 1-hexene are fed to the second polymerization
reactor at the rates of 3.8 kg/hr 4.0 N-liter/hr and 180 g/hr
respectively the density and [r\] become 954 kg/m3 and 2.85 dl/g
respectively; and when ethylene and hydrogen are fed to the first
polymerization reactor at the rates of 5.0 kg/hr and 65
N-liters/hr respectively and ethylene hydrogen and 1-hexene
are fed to the second polymerization reactor at the rates of 3.9
kg/hr 1.2 N-liter/hr and 110 g/hr respectively the density
and [r|] become 958 kg/m3 and 3.21 dl/g respectively.
Requirement [3e]
22
The apparent shear stress of the ethylene polymer (Ee) of
the present invention as measured by a Capillary Rheometer at
210°C and a shear rate of 194.57 sec"1 is 7 MPa or less. By
using a capillary die having an inner diameter of 0.5 mm and
a capillary length of 3.0 mm and a barrel of 9.55 mm the ethylene
polymer having an apparent shear stress as measured at a shear
rate of 194.57 sec"1 in accordance with JIS K7199 falling within
the above-described range has a low resin pressure at a constant
extrusion rate i.e. a constant extrusion amount and excellent
extrusion characteristics. When multistage polymerization as
described later is carried out using a catalyst system as
described later an ethylene polymer falling within the
above-described range can be prepared by controlling the
molecular weights of the respective components the amount of
the a-olefin to be copolymerized with ethylene the composition
distribution and the ratio of polymerized amounts.
Requirements [4e]
The ethylene polymer (Ee) according to the present
invention has an actual stress obtained when it takes 10000
cycles to fracture due to the tensile fatigue property as measured
at 80°C with a notched specimen in the range of 11 MPa to 17
Mpa and an actual stress obtained when it takes 100000 cycles
to fracture in the range of 9 MPa to 16 MPa. An ethylene polymer
with the tensile fatigue strength as measured at 80°C with a
23
notched specimen falling in the above-mentioned range exhibits
a brittle failure mode and has excellent long lifetime properties
When multistage polymerization as described later is carried out
using a catalyst system as described later an ethylene polymer
falling within the above-described range can be prepared by
controlling the molecular weights of the respective components
the amount of the a-olefin copolymerized with ethylene the
composition distribution and the ratio of polymerized amounts.
Requirements [5e]
The ethylene polymer (Ee) according to the present
invention has an actual stress obtained when it takes 10000
cycles to fracture due to the tensile fatigue property as measured
at 23°C with an unnotched specimen in the range of 18 MPa to
22 Mpa and an actual stress obtained when it takes 100 000 cycles
to fracture in the range of 17 MPa to 21 MPa. An ethylene polymer
with the tensile fatigue strength as measured at 23°C with an
unnotched specimen falling in the above-mentioned range
exhibits a ductile failure mode and has excellent long lifetime
properties. When multistage polymerization as described later
is carried out using a catalyst system as described later an
ethylene polymer falling within the above-described range can
be prepared by controlling the molecular weights of the
respective components the amount of the a-olefin copolymerized
with ethylene the composition distribution and the ratio of
24
polymerized amounts.
Process for Preparation of Ethylene Polymer
Hereinbelow preferred method for preparation of the
ethylene polymer of the present invention will be described but
the present invention is not limited thereto and encompasses
other methods as long as the above-described requirements are
satisfied.
The ethylene polymer of the present invention can be
preferably obtained by homopolymerizing ethylene or
copolymerizing ethylene with a-olefin having 6 to 10 carbon atoms
using a catalyst for olefin polymerization that comprises:
(A) a transition metal compound in which a cyclopentadienyl
group and a f luorenyl 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 organometallic compound
(B-2) an organoaluminum oxy-compound and
(B-3) a compound which forms an ion pair by reacting
with a transition metal compound; and
(C) a carrier. Preferred embodiment of each components (A)
(B) and (C) used in the present invention will be described.
(A) Transition Metal Compound
The transition metal compound (A) is a compound represented
by the following formulas (1) or (2):
25
in which formulas (1) and (2) R7 R8 R9 R10 Ru R12 R13
R14 R15 R16 R17 R18 R19 and R20 are selected from hydrogen atom
a hydrocarbon group a halogen-containing hydrocarbon group and
a silicon-containing hydrocarbon group and may be the same or
different from each other and the adjacent substituents R7 to
R18 may be bonded to form a ring; A is a divalent hydrocarbon group
having 2 to 20 carbon atoms which may contain a partially
unsaturated bond and/or an aromatic ring and forms a ring
structure together with Y and may contain two or more ring
structures including the ring formed by A together with Y; Y is
26
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 via
an electron lone pair; and j is an integer between 1 and 4.
Among the transition metal compounds (A) represented by the
aforementioned formula (1) or (2) those in which R7 to R10 are
hydrogen Y is carbon M is Zr and j is 2 are preferably used.
Among the transition metal compounds (A) represented by the
aforementioned formula (1) those in which R12 R13 R16 and R17
are all hydrocarbon groups are preferably used.
Among the transition metal compounds (A) represented by the
aforementioned formula (1) preferably used are the compounds
wherein a bridging atom Y of the covalent bond bridging part has
aryl groups which may be the same as or different from each other
(that is the compounds wherein R19 and R20 are aryl groups which
may be the same as or different from each other). Examples of
the aryl group include a phenyl group a naphthyl group and an
anthracenyl group or these groups having at least one aromatic
hydrogen atom (sp2 hydrogen) substituted with a substituent.
Here examples of the substituent include a hydrocarbon group
(fl) having a total of 1 to 20 carbon atoms a silicon-containing
group (f2) having a total of 1 to 20 carbon atoms and a halogen
atom. Examples of the hydrocarbon group (fl) having a total of
27
1 to 20 carbon atoms includes in addition to alkyl alkenyl
alkynyl and aryl groups which consist of carbon and hydrogen
only a heteroatom-containing hydrocarbon group in which parts
of the hydrogen atoms directly bonded to such carbon atoms are
substituted with a halogen atom an oxygen-containing group a
nitrogen-containing group or a silicon-containing group and
the hydrocarbon group in which any two neighboring hydrogen atoms
form an alicyclic group. Examples of the hydrocarbon group (fl)
include a straight-chain hydrocarbon group such as a methyl group
an ethyl group an n-propyl group an allyl group an n-butyl
group an n-pentyl group an n-hexyl group an n-heptyl group
an n-octyl group an n-nonyl group and an n-decanyl group; a
branched hydrocarbon group such as an isopropyl group a t-butyl
group an amyl group a 3-methylpentyl group a 11-diethylpropyl
group a 11-dimethylbutyl group a 1-methyl-l-propylbutyl group
a 11-propylbutyl group a 1l-dimethyl-2-methylpropyl group
and a l-methyl-l-isopropyl-2-methylpropyl group; a cyclic
saturated hydrocarbon group such as a cyclopentyl group a
cyclohexyl group a cycloheptyl group a cyclooctyl group a
norbornyl group and an adamantyl group; a cyclic unsaturated
hydrocarbon group such as a phenyl group a naphthyl group a
biphenyl group a phenanthryl group and an anthracenyl group
and a nuclear-alkylsubstituted form thereof; a saturated
hydrocarbon group substituted with an aryl group such as a benzyl
28
group and a cumyl group; and a heteroatom-containing hydrocarbon
group such as a methoxy group an ethoxy group a phenoxy group
an N-methylamino group a trifluoromethyl group a
tribromomethyl group a pentafluoroethyl group and
pentafluophenyl group.
The term "silicon-containing group (f2)" means a
groupe.g. in which ring carbons of the cyclopentadienyl group
are directly covalently bonded to a silicon atom and specific
examples thereof include an alkyl silyl group and an aryl silyl
group. Examples of the silicon-containing group (f2) having a
total of 1 to 20 carbon atoms include a trimethylsilyl group
and a triphenylsilyl group.
Specific examples of the aryl group which may be the same
as or different from each other with which the bridging atom
Y of the covalent bond bridging part is bonded include a phenyl
group a tolyl group a t-butylphenyl group a dimethylphenyl
group a biphenyl group a cyclohexylphenyl group a
(trifluoromethyl) phenyl group a bis(trifluoromethyl) phenyl
group a chlorophenyl group and a dichlorophenyl group.
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 present
invention is not limited to these transition metal compounds.
Here the structures of the transition metal compounds
represented by the above formulas (3) and (4) were determined
by 270 MHz:H-NMR (JEOL GSH-270) and FD-mass analysis (JEOL
SX-102 A).
(B-l) Organometallic Compound
Examples of the organometallic compound (B-l) optionally
used in the present invention specifically include the following
organometallic compounds having the metals from Groups 1 2 12
and 13 of the Periodic Table of Elements. It is an organoaluminum
compound represented by the following 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
30
4 carbon atoms; X represents a halogen atom; m is a number such
that 0m3 n is a number such that 0n3 p is a number such
that 0p3 and q is a number such that 0q3 while m+n+p+q=3.
The aluminum compound used in the below-described Examples
of the present invention is triisobutylaluminum or
triethylaluminum.
(B-2) Organoaluminum Oxy-compound
The organoaluminum oxy-compound (B-2) optionally used in
the present invention may be a conventionally known aluminoxane
or a benzene-insoluble organoaluminum oxy-compound as
illustrated in the publication of JP-A No. 2-78687.
The organoaluminum oxy-compound used in the
below-described Examples of the present 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 present invention
(hereinafter referred to as an "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 U.S. Pat.
31
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
kinds. Incidentally as for compound (B) the above-described
two compounds (B-l) and (B-2) are used in the below-described
Examples of the present invention.
(C) Microparticulate Carrier
The microparticulate carrier (C) optionally used in the
present invention 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 ^m 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 cmVg. Such carrier is used after being calcined
at a temperature of from 80 to 1000°C and preferably from 100
to800°C if necessary. Incidentally if not specif led 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 urn a specific surface area of 800
m2/g and a pore volume of 1.0 cm3/g.
The catalyst for olefin polymerization according to the
present 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 organometallic compound (B-2) an
organoaluminum oxy-compound and (B-3) an ionizing ionic compound
and optionally the microparticulate carrier (C) of the present
invention.
(D) Organic Compound Component
According to the present invention the organic compound
component (D) is optionally used for the purpose of improving
the polymerization performance and the properties of produced
polymer. Such organic compound may be exemplified by alcohols
phenolic compounds carboxylic acids phosphorous compounds and
sulfonic acid salts etc.
The ethylene polymer according to the present 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.
Upon polymerization the usage and order of addition for
the respective components are arbitrarily selected but the
following methods (PI) to (P10) may be illustrated.
(PI) A method of adding component (A) and at least one
33
component (B) selected from (B-l) an organometallic compound
(B-2) an organoaluminum oxy-compound and (B-3) an ionizing ionic
compound (hereinafter simply referred to as "component (B)")
to the polymerization reactor 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 reactor.
(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 reactor
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 reactor in an arbitrary order.
(P5) A method of adding a catalyst having component (A) and
component (B) both supported on microparticulate carrier (C) to
the polymerization reactor.
(P6) A method of adding component (B) and a catalyst
component having component (A) and component (B) both supported
on microparticulate carrier (C) to the polymerization reactor
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
34
component having Component (B) supported on microparticulate
carrier (C) to the polymerization reactor 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 reactor 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) both supported on
microparticulate carrier (C) to the polymerization reactor. In
this case the respective components (B) may be the same or
different.
(P10) A method of adding component (B) and a catalyst
component that has been formed by preliminarily contacting
component (B) with a catalyst having Component (A) and Component
(B) both supported on microparticulate carrier (C) to the
polymerization reactor 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) both supported on
35
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.
Further 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 liquid-phase
polymerization such as solution polymerization slurry
polymerization or the like or by gas-phase polymerization and
particularly slurry polymerization and gas-phase polymerization
are preferably employed from the viewpoint of productivity.
Examples of the inactive hydrocarbon medium used in
liquid-phase polymerization specifically include 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 1CT12 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 optionally employed is used in an
amount such that the molar ratio [(B-1)/M] of component (B-l)
to the transition metal atom (M) in Component (A) would be
typically from 0.01 to 100000 and preferably from 0.05 to
50000.
Component (B-2) which is optionally employed is used in an
amount such that the molar ratio [ (B-2)/M] of the aluminum atom
in component (B-2) to the transition metal atom (M) in Component
(A) would be typically from 10 to 500000 and preferably from
20 to 100000.
Component (B-3) which is optionally employed is used in an
amount such that the molar ratio [(B-3)/M] of component (B-3)
to 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 optionally employed 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
37
(B-3) the molar ratio [(D)/(B-3)] would be typically from 0.01
to 10 and preferably from 0.1 to 5.
The temperature 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 atmospheric
pressure to 100 kg/cm2 and preferably from atmospheric 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. By carrying out the
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 ^im|). In the case of
polymerization in the continuous mode in two or more
polymerization reactors 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 is required.
38
When the ethylene polymer according to the present
invention is prepared for example in two stages an ethylene
homopolymer having an intrinsic viscosity of 0.3 to 1.8 dl/g is
prepared in the former stage and a (co)polymer having an
intrinsic viscosity of 3.0 to 10.0 dl/g is prepared in the later
stage. This order may be reversed.
Since the catalyst for olefin polymerization has extremely
high polymerization performance even for the a-olefin (e.g.
1-hexene) to be copolymerized with ethylene there would be
needed a device 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 contents of the polymerization reactor is withdrawn
from the polymerization reactor simultaneously or as
immediately as possible (i) separating the polymer solvent and
unreacted a-olefin with a solvent separator (ii) adding an inert
gas such as nitrogen and the like to the contents compulsorily
to discharge the solvent and unreacted a-olefin out of the system
(iii) controlling the pressure applied to the contents
compulsorily to discharge the solvent and unreacted a-olefin out
of the system (iv) adding a large quantity of solvent to the
contents to dilute the unreacted a-olefin to a concentration at
which substantially no polymerization takes place (v) adding
a substance which deactivates the catalyst for polymerization
39
such as methanol and the like (vi) cooling the contents 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) used.
The polymer particles obtained by polymerization reaction
may be pelletized by the following methods:
(1) a method of mechanically blending the ethylene polymer
particles with other components that are optionally added 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 optionally added 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 a kneader or the like and
cutting into predetermined sizes.
The ethylene polymer according to the present invention may
be blended as desired with additives such as a
weather-resistant stabilizer a heat-resistant stabilizer
40
antistatic agent an anti-slipping agent an anti-blocking agent
an anti-fogging 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 pigments such as carbon
black titanium oxide titanium yellow phthalocyanine
isoindolinone a quinacridone compound a condensed azo compound
ultramarine blue cobalt blue and the like without adversely
affecting the purpose of the present invention.
Molded Product Made from Ethylene Polymer
The ethylene polymer according to the present 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 irregular shapes an
expansion molded product an injection molded product a vacuum
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 present invention gives excellent properties
when used in a blow molded product an extrusion molded product
and an injection molded product among the above-mentioned molded
41
products thus it being desirable.
Preferred examples of the blow molded products according
to the present invention include bottle containers industrial
chemical canisters and bottle containers.
The hollow molded products as prepared by the above method
are suitable as bleaching agent containers detergent containers
softening containers or the like and used as for example
containers for cosmetics laundry detergents domestic
detergents softening finishes shampoos rinses or
conditioners. Also they can be used as kerosene cans gasoline
tanks for electricity generators lawn mowers motorcycles
automotives or the like cans for agrochemicals or medicines
drum cans or the like.
Further the hollow molded products can be used for storage
of foods such as mayonnaise and edible oils or medicines.
In these applications multilayered molded products are
preferably used for suppressing the oxidation of the foods or
the permeation of the contents such as gasoline.
Preferred examples of the extrusion molded product include
pipes electric wire coverings and steel tube/steel wire
coverings. The extrusion molded products as prepared by the
above method can be used as gas pipes water-supply and sewerage
pipes pipes for transporting agricultural water or industrial
water pipes for protecting various contents such as information
42
communication facilities such as optical fibers. Further they
may be used as steel pipe coverings which is preventing corrosion
on the inside of the cast iron pipes or steel wire coverings
for protecting the wires for supporting the buildings. It is
required that these extrusion molded products be not susceptible
to fracture in a short or long term thus it is effective to
use the resin of the present invention in order to make the product
life even longer.
Preferred examples of the injection molded product include
pipe joints or automotive parts. The pipe joints or automotive
parts are preferably used as fused into the hollow molded product
or the extrusion molded product. Examples of the pipe joint
include methods of fusion such as electrofusion joint and
heatfusion joint and various forms of joints by connecting or
branching the pipes according to the purposes any of which can
be preferably used due to its moldability and physical properties
in particular long-term non-breakage. Particularly the
products of the present invention are effectively used from the
viewpoint of enhancing the long-term reliability of the parts
to be fused with the main body of the pipes prepared by the
extrusion molding and against the breakage of the welded part.
A large number of the parts of the automotives are used to
improve the functionality of the gasoline tanks as a hollow molded
product which are thus commonly used as fused parts. By using
43
the products of the present invention the long-term reliability
of the weld parts and the fused parts can be improved.
EXAMPLES
The present invention is described in more detail with
reference to the following examples but the present invention
is not limited by the examples. Here measurement of various
properties and preparation of samples for measurement as
described herein were made by the following methods.
Preparation of Sample for Measurement
To 100 parts by weight of an ethylene polymer in the
particulate form 0.20 part by weight of
tri(24-di-t-butylphenyl)phosphate as a secondary
anti-oxidizing agent 0.20 part by weight of
n-octadecyl-3-(4'-hydroxy-3'5'-di-t-butylphenyl)propionate
as a heat-resistant stabilizer and 0.15 part by weight of calcium
stearate as a hydrochloric acid absorbent were blended.
Thereafter a sample for measurement was prepared by
pelletization 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/#300x4/#60/#40)
manufactured by Placo Co. Ltd.
Measurement of Ethylene Content and a-olefin Content
The ethylene content and the a-olefin content in the
44
molecular chain of the ethylene polymer were measured by 13C-NMR.
Measurement was made using a Lambda 500-type nuclear magnetic
resonance unit (1H: 500 MHz) manufactured by JEOL Ltd with an
integral number of 10000 to 30000. 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 ultra
pure grade hexachlorobutadiene (Wako Pure Chemical Industries
Ltd.) and the mixture 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 - General Remarks and Guidelines to Experimentation [I]"
Kagaku no Ryoiki extra edition No. 141 pp. 132-133.
Measurement of the sample was made under the measurement
conditions such as a measurement temperature of 120°C a
measurement frequency of 125.7 MHz a spectrum width of 250000
Hz a 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 Petrochemical 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 injected 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 be coated with 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 (CaF2 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 pm (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 injected of the internal standard was 0.5 ml the
position of injection was at 3.0 ml and the data sampling time
interval was 0.50 second. Here when pressure abnormality
occurred 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)." Although cross fractionation
chromatography (CFC) per se is said to be an analytic method of
reproducing the results with high analytic precision as far as
the conditions for measurement are strictly maintained constant
the measurements were performed in several times to take the
average in Examples of the present invention.
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 injected was 500 jil
and the detector used was a differential refractometer. For the
standard polystyrene a product by Tosoh Corporation was used
for the molecular weight of Mwl000 and Mw4xl06 and a product
by Pressure Chemical Co. for the molecular weight of
1000Mw4xl06. The molecular weight was a value determined in
terms of polyethylene by means of universal calibration.
Intrinsic Viscosity ( [r|] )
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 45x45x0.5
mm obtained from a sheet of 240x240x0.5 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 an 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.
Measurement of Melt flow rate (MFR)
The MFR was measured according to the method of ASTM D1238-89 at 190°C under a load of 5 kg and 21.6 kg.
* Environmental Stress Cracking 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 80x80x2 mm from a sheet of 240x240x2 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 an SUS plate with a thickness of 5 mm. From the above pressed sheet of 80x80x2 mm, a dumbbell-shaped specimen with a size of 13 mmx38 mm was punched out to provide a sample for evaluation. The test for the property of environmental stress cracking 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: 38x13 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
Holding of sample: The sample is set using a clinching
(Table Removed) 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.
Test on Flexural Modulus of Pressed Sheet
This was measured by the method in accordance with the
section "Flexural Modulus" of "General Properties and Test
conditions therefor" in JIS K6922-2 (Table 3) and the test method
of Flexural Modulus as described in JIS K7171. Specifically
from a pressed sheet having a thickness 4 mm obtained at a
temperature of 40°C under the conditions of a molding temperature
of 180°C and an average cooling rate of 15°C/min a specimen
with a length 80 mm a width 10 mm and a thickness 4 mm was punched
out and the flexural modulus was measured under the conditions
of a testing temperature of 23°C a bending span distance of 64
mm and a test rate of 2.0 mm/min.
tan8 (=loss modulus G'/storage modulus G')
Detailed information on tan8 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 (co (rad/sec) ) dispersion of the
50
storage modulus G' (Pa) and the loss modulus G'1 (Pa) using a
rheometer RDS-II manufactured by Rheometrics Inc. The sample
holder used was a pair of parallel plates with 25 mmf 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. 04to400.
The measurement was obtained at five points per one digit of oo.
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 Cracking 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| core diameter: 21 mm| amount
extruded: 12 kg/hr mold temperature: 25°C rate of clamping:
1.4 sec clamping pressure: 5.5t and blow air pressure: 5 kg/cm2.
Thus a cylindrical bottle having a capacity of 1000 cc and a
net weight of 50 g was obtained.
Environmental Stress Cracking Resistance (ESCR) Property
of Bottle
The bottle prepared as above was charged with 100 cc of
Kitchen Hiter manufactured by Kao Corp. and then was sealed at
51
the opening with resin. The bottle and the contents 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
described 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. 5).
Buckling Strength of Bottle
The bottle obtained by blow molding as described above was
allowed to stand vertically and a load was applied vertically
from the top to the bottom of the bottle at 23°C and a test speed
of 20 mm/min. Upon compression the generated maximum load was
reported as a buckling strength of the bottle.
Apparent Shear Stress
The apparent shear stress was measured using a Capillary
Rheometer manufactured by Toyo Seiki Co. Ltd. with a capillary
die having an inner diameter of 0.5 mm and a length of 3.0 mm
at 190°C and a shear rate of 194.57 sec"1 in accordance with
52
JIS K7199. The barrel diameter of the Capillary Rheometer was
9.55 mm.
Tensile Fatigue Strength at 80°C
A specimen for the measurement of tensile fatigue strength
at 80°C was prepared by molding a 6 mm-thick sheet (spacer-shaped:
4 specimens of a size of 30x60x6 mm obtained from a sheet of a
size of 200x200x6 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 30x60x6 mm a rectangular
column with a size of length 5 to 6 mmxwidth 6 mmxheight 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=l mm) . Summary of the evaluation
conditions are as follows: several points were measured under
the conditions of specimen form: 5 to 6x6x60 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
53
frequency upon fracture of the specimen was taken as the fatigue
strength. Here 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 10000 cycles and 100000 cycles were
determined.
Tensile Fatigue Strength at 23°C
A 3 mm-thick dumbbell (ASTM-D-1822 Type S) as shown in Fig.
4 was prepared by molding (spacer-shaped: the form of ASTM-D-1822
Type S was provided from the sheet having a size of 240x240x3
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 another hydraulic thermal press machine manufactured by
Shinto Metal Industries Ltd. set at 20°C a sample for evaluation
of the tensile fatigue strength at 23°C was taken therefrom. An
SUS plate with a thickness of 5 mm was used as a heating plate.
The tensile fatigue strength at 23°C was measured according to
JIS K-7118 using a Servo-Pulser of the EHF-FG10KN-4 LA type
manufactured by Shimazu Seisakusho Ltd. Summary of the
evaluation conditions are presented below.
54
Specimen shape: ASTM-D-1822 Type S (Dumbbell as described
in Fig. 3 unnotched)
Waveform and frequency for 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) 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
14 to 27 MPa. A 50% elongation of the specimen was defined as
fracture and the oscillation frequency at this time was taken
as the fatigue strength for the actual stress loaded. The actual
stress corresponding to 10000 cycles and 100000 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.
[Synthesis 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
55
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).
[Synthesis 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) suspended in toluene synthesized in Synthesis
Example 1 was added and under stirring 2 liters (61.12 mmol)
of a 31.06 mmol/liter solution of
di(p-tolyl)methylene(cyclopentadienyl)
(octamethyloctahydrodibenzof luorenyl) zirconium dichloride was
added to the suspension at room temperature (20 to 25°C) and
the resulting mixture being stirred for 60 minutes. After
stirring being stopped the supernatant liquid was removed by
decantation and the mixture was washed with 40 liters of n-hexane
for two times. Thus obtained supported catalyst was reslurried
in n-hexane to yield a solid catalyst component (y) as 25 liters
of a catalyst suspension.
56
[Preparation of Solid Catalyst Component (8) 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 and the solids were washed with 35 liters of n-hexane
for 4 times. Thus obtained supported catalyst was suspended in
20 liters of n-hexane to give a solid catalyst component (6) as
a catalyst suspension.
[Example lb]
[Polymerization]
To a first polymerization reactor 45 liters/hr of hexane
0 . 07 mmol/hr (in terms of Zr atoms) of the solid catalyst component
(5) obtained in Synthesis Example 2 20 mmol/hr of
triethylaluminum 7.0 kg/hr of ethylene and 40 N-liters/hr of
hydrogen were continuously supplied. Further a polyethylene
glycol/polypropylene glycol block copolymer having a viscosity
of 500 mPa.s as measured by a B type viscometer at 25°C (Product
57
name: EPAN720 manufactured by Dai-Ichi Kogyo Seiyaku co. Ltd.)
was continuously supplied at 0.5 g/hr. Meanwhile
polymerization was carried out under the conditions such as a
polymerization temperature of 80°C a reaction pressure of 7.6
kg/cm2G and an average residence time of 2.6 hr while
continuously withdrawing the contents in the polymerization
reactor so that the liquid level in the polymerization reactor
would be maintained constant. The contents continuously
withdrawn from the first polymerization reactor were subjected
to substantial removal of unreacted ethylene and hydrogen in a
flash drum maintained at an internal pressure of 0.30 kg/cm2G
and at 60°C.
Then the contents were continuously supplied to a second
polymerization reactor together with 43 liters/hr of hexane
3.0 kg/hr of ethylene 5.5 N-liter/hr of hydrogen and 110 g/hr
of 1-hexene and polymerization was continued under the
conditions such as a polymerization temperature of 75°C a
reaction pressure of 3.3 kg/cm2G and an average residence time
of 1.4 hr.
Also for the second polymerization reactor the contents
of the polymerization reactor were continuously withdrawn so that
the liquid level in the polymerization reactor would be
maintained constant. In order to prevent undesirable
polymerization such as generation of a polymer containing a large
58
proportion of 1-hexene methanol was supplied to the contents
withdrawn from the second polymerization reactor at a rate of
2 liters/hr to deactivate the catalyst for polymerization. Then
the contents were 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 0.20 part by weight of
tri(24-di-t-butylphenyl)phosphate as a secondary
anti-oxidizing agent 0.20 part by weight of
n-octadecyl-3-(4'-hydroxy-3'5'-di-t-butylphenyl)propionate
as a heat-resistant stabilizer and 0.15 part by weight of calcium
stearate as a hydrochloric acid absorbent were blended.
Thereafter a sample for measurement was prepared by
pelletization at a set temperature of 200°C and a resin extrusion
amount of 25 kg/hr using a single screw extruder (screw diameter
65 mm L/D=28 screen mesh 40/60/300x4/60/40) manufactured by
Placo Co. Ltd. Further a pressed sheet was prepared using this
sample to measure the properties. The results are presented in
Tables lb to 3b. As compared with Comparative Examples this
sample is excellent in the balance between stiffness and the ESCR
property. Further a bottle was prepared using this sample to
measure the properties of the bottle. The results are presented
in Tables 4b. As compared with Comparative Examples the bottle
molded product is excellent in the balance between stiffness and
59
the ESCR property.
[Example 2b]
[Polymerization]
To a first polymerization reactor 45 liters/hr of hexane
0.2 mmol/hr (in terms of Zr atoms) of the solid catalyst component
(8) obtained in Synthesis Example 2 20 mmol/hr of
triethylaluminum 11.0 kg/hr of ethylene and 75 N-liters/hr of
hydrogen were continuously supplied. Further a polyethylene
glycol/polypropylene glycol block copolymer having a viscosity
of 370 mPa.s as measured by a B type viscometer at 25°C (Product
name: Adeka Pluronic L-71 manufactured by Adeka Corporation)
was continuously supplied at 0.8 g/hr. Meanwhile
polymerization was carried out under the conditions such as a
polymerization temperature of 85°C a reaction pressure of 7. 5
kg/cm2G and an average residence time of 2.4 hr while
continuously withdrawing the contents of the polymerization
reactor so that the liquid level in the polymerization reactor
would be maintained constant. The contents continuously
withdrawn from the first polymerization reactor were subjected
to substantial removal of unreacted ethylene and hydrogen in a
flash drum maintained at an internal pressure of 0.30 kg/cm2G
and at 60°C.
Then the contents were continuously supplied to a second
polymerization reactor together with 43 liters/hr of hexane
60
5.5 kg/hr of ethylene 4.0 N-liter/hr of hydrogen and 98 g/hr
of 1-hexene and polymerization was continued under the
conditions such as a polymerization temperature of 75°C a
reaction pressure of 2.9 kg/cm2G and an average residence time
of 1.3 hr.
Also for the second polymerization reactor the contents
of the polymerization reactor were continuously withdrawn so that
the liquid level in the polymerization reactor would be
maintained constant. In order to prevent undesirable
polymerization such as generation of a polymer containing a large
proportion of 1-hexene methanol was supplied to the contents
withdrawn from the second polymerization reactor at a rate of
2 liters/hr to deactivate the catalyst for polymerization. Then
the contents were 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 lb were mixed in the same parts by weight.
Thereafter a sample for measurement was prepared by
pelletization at the same set temperature and the same resin
extrusion amount as in Example 1 using a single screw extruder
manufactured by Placo Co. Ltd. Further a pressed sheet was
prepared using this sample to measure the properties. The
61
results are presented in Tables lb to 3b. As compared with
Comparative Examples this sample is excellent in the balance
between stiffness and the ESCR property. Further a bottle was
prepared using this sample to measure the properties of the bottle
The results are presented in Tables 4b. As compared with
Comparative Examples the bottle molded product is excellent in
the balance between stiffness and the ESCR property.
[Example 3b]
[Polymerization]
To a first polymerization reactor 45 liters/hr of hexane
0.2 mmol/hr (in terms of Zr atoms) of the solid catalyst component
(8) obtained in Synthesis Example 2 20 mmol/hr of
triethylaluminum 11.0 kg/hr of ethylene and 80 N-liters/hr of
hydrogen were continuously supplied. Further a polyethylene
glycol/polypropylene glycol block copolymer having a viscosity
of 370 mPa.s as measured by a B type viscometer at 25°C (Product
name: Adeka Pluronic L-71 manufactured by Adeka Corporation)
was continuously supplied at 0.8 g/hr. Meanwhile
polymerization was carried out under the conditions such as a
polymerization temperature of 85°C a reaction pressure of 7.6
kg/cm2G and an average residence time of 2.4 hr while
continuously withdrawing the contents of the polymerization
reactor so that the liquid level in the polymerization reactor
would be maintained constant. The contents continuously
62
withdrawn from the first polymerization reactor were subjected
to substantial removal of unreacted ethylene and hydrogen in a
flash drum maintained at an internal pressure of 0.30 kg/cm2G
and at 60°C.
Then the contents were continuously supplied to a second
polymerization reactor together with 43 liters/hr of hexane
5.5 kg/hr of ethylene 3.4 N-liter/hr of hydrogen and 66 g/hr
of 1-hexene and polymerization was continued under the
conditions such as a polymerization temperature of 75°C a
reaction pressure of 3.0 kg/cm2G and an average residence time
of 1.3 hr.
Also for the second polymerization reactor the contents
of the polymerization reactor were continuously withdrawn so that
the liquid level in the polymerization reactor would be
maintained constant. In order to prevent undesirable
polymerization such as generation of a polymer containing a large
proportion of 1-hexene methanol was supplied to the contents
withdrawn from the second polymerization reactor at a rate of
2 liters/hr to deactivate the catalyst for polymerization. Then
the contents were 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
63
used in Example lb were mixed in the same parts by weight.
Thereafter a sample for measurement was prepared by
pelletization at the same set temperature and the same resin
extrusion amount as in Example lb 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 lb to 3b. As compared with
Comparative Examples this sample is excellent in the balance
between stiffness and the ESCR property. Further a bottle was
prepared using this sample to measure the properties of the bottle.
The results are presented in Tables 4b- As compared with
Comparative Examples the bottle molded product is excellent in
the balance between stiffness and the ESCR property.
[Example 4b]
[Polymerization]
To a first polymerization reactor 45 liters/hr of hexane
0.1 mmol/hr (in terms of Zr atoms) of the solid catalyst component
(8) obtained in Synthesis Example 2 20 mmol/hr of
triethylaluminum 7.0 kg/hr of ethylene and 75 N-liters/hr of
hydrogen were continuously supplied. Further a polyethylene
glycol/polypropylene glycol block copolymer having a viscosity
of 370 mPa.s as measured by a B type viscometer at 25°C (Product
name: Adeka Pluronic L-71 manufactured by Adeka Corporation)
was continuously supplied at 0.8 g/hr. Meanwhile
64
polymerization was carried out under the conditions such as a
polymerization temperature of 85°C a reaction pressure of 7.5
kg/cm2G and an average residence time of 2.6 hr while
continuously withdrawing the contents of the polymerization
reactor so that the liquid level in the polymerization reactor
would be maintained constant. The contents continuously
withdrawn from the first polymerization reactor were subjected
to substantial removal of unreacted ethylene and hydrogen in a
flash drum maintained at an internal pressure of 0.30 kg/cm2G
and at 60°C.
Then the contents were continuously supplied to a second
polymerization reactor together with 43 liters/hr of hexane
3.5 kg/hr of ethylene 3.0 N-liter/hr of hydrogen and 52 g/hr
of 1-hexene and polymerization was continued under the
conditions such as a polymerization temperature of 75°C a
reaction pressure of 3.2 kg/cm2G and an average residence time
of 1.3 hr.
Also for the second polymerization reactor the contents
of the polymerization reactor were continuously withdrawn so that
the liquid level in the polymerization reactor would be
maintained constant. In order to prevent undesirable
polymerization such as generation of a polymer containing a large
proportion of 1-hexene methanol was supplied to the contents
withdrawn from the second polymerization reactor at a rate of
65
2 liters/hr to deactivate the catalyst for polymerization. Then
the contents were 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 lb were mixed in the same parts by weight.
Thereafter a sample for measurement was prepared by
palletization at the same set temperature and the same resin
extrusion amount as in Example lb 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 lb to 3b. As compared with
Comparative Examples this sample is excellent in the balance
between stiffness and the ESCR property. Further a bottle was
prepared using this sample to measure the properties of the bottle.
The results are presented in Tables 4b- As compared with
Comparative Examples the bottle molded product is excellent in
the balance between stiffness and the ESCR property.
[Example 5bl
[Polymerization]
To a first polymerization reactor 45 liters/hr of hexane
0.13 mmol/hr (in terms of Zr atoms) of the solid catalyst component
(8) obtained in Synthesis Example 2 20 mmol/hr of
66
triethylaluminum 11.0 kg/hr of ethylene and 50 N-liters/hr of
hydrogen were continuously supplied. Further a polyethylene
glycol/polypropylene glycol block copolymer having a viscosity
of 370 mPa.s as measured by a B type viscometer at 25°C (Product
name: Adeka Pluronic L-71 manufactured by Adeka Corporation)
was continuously supplied at 0.8 g/hr. Meanwhile
polymerization was carried out under the conditions such as a
polymerization temperature of 75°C a reaction pressure of 7.5
kg/cm2G and an average residence time of 2.6 hr while
continuously withdrawing the contents of the polymerization
reactor so that the liquid level in the polymerization reactor
would be maintained constant. The contents continuously
withdrawn from the first polymerization reactor were subjected
to substantial removal of unreacted ethylene and hydrogen in a
flash drum maintained at an internal pressure of 0.30 kg/cm2G
and at 60°C.
Then the contents were continuously supplied to a second
polymerization reactor together with 43 liters/hr of hexane
4.7 kg/hr of ethylene 3.0 N-liter/hr of hydrogen and 97 g/hr
of 1-hexene and polymerization was continued under the
conditions such as a polymerization temperature of 75°C a
reaction pressure of 3.2 kg/cm2G and an average residence time
of 1.3 hr.
Also for the second polymerization reactor the contents
67
of the polymerization reactor were continuously withdrawn so that
the liquid level in the polymerization reactor would be
maintained constant. In order to prevent undesirable
polymerization such as generation of a polymer containing a large
proportion of 1-hexene methanol was supplied to the contents
withdrawn from the second polymerization reactor at a rate of
2 liters/hr to deactivate the catalyst for polymerization. Then
the contents were 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 lb were mixed in the same parts by weight.
Thereafter a sample for measurement was prepared by
pelletization at the same set temperature and the same resin
extrusion amount as in Example lb 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 lb to 3b- As compared with
Comparative Examples this sample is excellent in the balance
between stiffness and the ESCR property. Further a bottle was
prepared using this sample to measure the properties of the bottle.
The results are presented in Tables 4b. As compared with
Comparative Examples the bottle molded product is excellent in
68
the balance between stiffness and the ESCR property.
[Example 6b]
[Polymerization]
To a first polymerization reactor 45 liters/hr of hexane
0.1 mmol/hr (in terms of Zr atoms) of the solid catalyst component
(8) obtained in Synthesis Example 2 20 mmol/hr of
triethylaluminum 9.1 kg/hr of ethylene and 50 N-liters/hr of
hydrogen were continuously supplied. Further a polyethylene
glycol/polypropylene glycol block copolymer having a viscosity
of 370 mPa.s as measured by a B type viscometer at 25°C (Product
name: Adeka Pluronic L-71 manufactured by Adeka Corporation)
was continuously supplied at 0.8 g/hr. Meanwhile
polymerization was carried out under the conditions such as a
polymerization temperature of 75°C a reaction pressure of 7.5
kg/cm2G and an average residence time of 2.6 hr while
continuously withdrawing the contents of the polymerization
reactor so that the liquid level in the polymerization reactor
would be maintained constant. The contents continuously
withdrawn from the first polymerization reactor were subjected
to substantial removal of unreacted ethylene and hydrogen in a
flash drum maintained at an internal pressure of 0.30 kg/cm2G
and at 60°C.
Then the contents were continuously supplied to a second
polymerization reactor together with 43 liters/hr of hexane
69
3.9 kg/hr of ethylene 1.0 N-liter/hr of hydrogen and 100 g/hr
of 1-hexene and polymerization was continued under the
conditions such as a polymerization temperature of 75°C a
reaction pressure of 3.2 kg/cm2G and an average residence time
of 1.3 hr.
Also for the second polymerization reactor the contents
of the polymerization reactor were continuously withdrawn so that
the liquid level in the polymerization reactor would be
maintained constant. In order to prevent undesirable
polymerization such as generation of a polymer containing a large
proportion of 1-hexene methanol was supplied to the contents
withdrawn from the second polymerization reactor at a rate of
2 liters/hr to deactivate the catalyst for polymerization. Then
the contents were 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 lb were mixed in the same parts by weight.
Thereafter a sample for measurement was prepared by
pelletization at the same set temperature and the same resin
extrusion amount as in Example lb using a single screw extruder
manufactured by Placo Co. Ltd. Further a pressed sheet was
prepared using this sample to measure the properties. The
70
results are presented in Tables lb to 3b. As compared with
Comparative Examples this sample is excellent in the balance
between stiffness and the ESCR property. Further a bottle was
prepared using this sample to measure the properties of the bottle.
The results are presented in Tables 4b. As compared with
Comparative Examples the bottle molded product is excellent in
the balance between stiffness and the ESCR property.
[Example 7b]
[Polymerization]
To a first polymerization reactor 45 liters/hr of hexane
0.1 mmol/hr (in terms of Zr atoms) of the solid catalyst component
(8) obtained in Synthesis Example 2 20 mmol/hr of
triethylaluminum 7.0 kg/hr of ethylene and 75 N-liters/hr of
hydrogen were continuously supplied. Further a polyethylene
glycol/polypropylene glycol block copolymer having a viscosity
of 370 mPa.s as measured by a B type viscometer at 25°C (Product
name: Adeka Pluronic L-71 manufactured by Adeka Corporation)
was continuously supplied at 0.8 g/hr. Meanwhile
polymerization was carried out under the conditions such as a
polymerization temperature of 85°C a reaction pressure of 7.5
kg/cm2G and an average residence time of 2.6 hr while
continuously withdrawing the contents of the polymerization
reactor so that the liquid level in the polymerization reactor
would be maintained constant. The contents continuously
71
withdrawn from the first polymerization reactor were subjected
to substantial removal of unreacted ethylene and hydrogen in a
flash drum maintained at an internal pressure of 0.30 kg/cm2G
and at 60°C.
Then the contents were continuously supplied to a second
polymerization reactor together with 43 liters/hr of hexane
3.5 kg/hr of ethylene 3.0 N-liter/hr of hydrogen and 150 g/hr
of 1-hexene and polymerization was continued under the
conditions such as a polymerization temperature of 75°C a
reaction pressure of 3.2 kg/cm2G and an average residence time
of 1.3 hr.
Also for the second polymerization reactor the contents
of the polymerization reactor were continuously withdrawn so that
the liquid level in the polymerization reactor would be
maintained constant. In order to prevent undesirable
polymerization such as generation of a polymer containing a large
proportion of 1-hexene methanol was supplied to the contents
withdrawn from the second polymerization reactor at a rate of
2 liters/hr to deactivate the catalyst for polymerization. Then
the contents were 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
72
used in Example lb were mixed in the same parts by weight.
Thereafter a sample for measurement was prepared by
pelletization at the same set temperature and the same resin
extrusion amount as in Example lb 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 lb to 3b- As compared with
Comparative Examples this sample is excellent in the balance
between stiffness and the ESCR property. Further a bottle was
prepared using this sample to measure the properties of the bottle.
The results are presented in Tables 4b. As compared with
Comparative Examples the bottle molded product is excellent in
the balance between stiffness and the ESCR property.
[Comparative Example lb]
The pellets of product HI-ZEX 6008 B manufactured by Mitsui
Chemicals Inc. were used as the sample for measurement. The
co-monomer was 1-butene. A pressed sheet was prepared using this
sample to measure the properties. The results are presented in
Tables lb to 3b. As compared with Examples this sample is
inferior in the balance between stiffness and the ESCR property.
Further a bottle was prepared using this sample to measure the
properties of the bottle. The results are presented in Tables
4b. As compared with Examples the bottle molded product is
inferior in properties.
73
[Comparative Example 2b]
The pellets of product HI-ZEX 6700 B manufactured by Mitsui
Chemicals Inc. were used to prepare a pressed sheet and their
properties were measured. The results are presented in Tables
lb to 3b. As compared with Examples this sample is inferior in
stiffness and the ESCR property is not so good. Further a bottle
was prepared using this sample to measure the properties of the
bottle. The results are presented in Tables 4b. As compared with
Examples the bottle molded product is inferior in properties.
[Comparative Example 3b]
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 lb to 3b- As compared with Examples this sample is
inferior both in stiffness and the ESCR property. Further a
bottle was prepared using this sample to measure the properties
of the bottle. The results are presented in Tables 4b. As
compared with Examples the bottle molded product is inferior
in properties.
[Example le]
[Polymerization]
To a first polymerization reactor 45 liters/hr of hexane
0.08mmol/hr (in terms of Zr atoms) of the solid catalyst component
(8) obtained in Synthesis Example 2 20 mmol/hr of
triethylaluminum 7.0 kg/hr of ethylene and 45 N-liters/hr of
hydrogen were continuously supplied. Further a polyethylene
glycol/polypropylene glycol block copolymer having a viscosity
of 500 mPa.s as measured by a B type viscometer at 25°C (Product
name: EPAN720 manufactured by Dai-Ichi Kogyo Seiyaku co. Ltd.)
was continuously supplied at 0.5 g/hr. Meanwhile
polymerization was carried out under the conditions such as a
polymerization temperature of 85°C a reaction pressure of 7.5
kg/cm2G and an average residence time of 2.6 hr while
continuously withdrawing the contents of the polymerization
reactor so that the liquid level in the polymerization reactor
would be maintained constant. The contents continuously
withdrawn from the first polymerization reactor were subjected
to substantial removal of unreacted ethylene and hydrogen in a
flash drum maintained at an internal pressure of 0.30 kg/cm2G
and at 60°C.
Then the s were continuously supplied to a second
polymerization reactor together with 43 liters/hr of hexane
5.5 kg/hr of ethylene 5.0 N-liter/hr of hydrogen and 270 g/hr
of 1-hexene and polymerization was continued under the
conditions such as a polymerization temperature of 75°C a
reaction pressure of 2.3 kg/cm2G and an average residence time
of 1.4 hr.
Also for the second polymerization reactor the contents
75
of the polymerization reactor were continuously withdrawn so that
the liquid level in the polymerization reactor would be
maintained constant. In order to prevent undesirable
polymerization such as generation of a polymer containing a large
proportion of 1-hexene methanol was supplied to the contents
withdrawn from the second polymerization reactor at a rate of
2 liters/hr to deactivate the catalyst for polymerization. Then
the contents were 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 0.1 part by weight of
tri(24-di-t-butylphenyl)phosphate as a secondary
anti-oxidizing agent 0.10 part by weight of
n-octadecyl-3-(4'-hydroxy-3' 5'-di-t-butylphenyl)propionate
as a heat-resistant stabilizer and 0.10 part by weight of calcium
stearate as a hydrochloric acid absorbent were blended.
Thereafter a sample for measurement was prepared by
pelletization at a set temperature of 200°C and a resin extrusion
amount of 25 kg/hr and using a single screw extruder (screw
diameter 65 mm L/D=28 screen mesh 40/60/300x4/60/40)
manufactured by Placo Co. Ltd. Further a pressed sheet was
prepared using this sample to measure the properties. The
results are presented in Tables le to 5e. As compared with
Comparative Examples 2e and 3e this sample has extremely higher
76
tensile fatigue strength at 80°C than that of the samples used
in Comparative Examples 2e and 3e. Further as it can be seen
from the results that the apparent shear stress is almost the
same as that of the samples used in Comparative Examples 2e and
3e this sample has comparative moldability. Further this
sample has tensile fatigue strength at 80°C of no less than that
of the sample used in Comparative Example le and apparent shear
stress is extremely lower than the sample used in Comparative
Example le showing good moldability. That is it can be seen that
as compared with Comparative Examples this sample is excellent
in the balance between tensile fatigue strength and moldability.
[Example 2e]
[Polymerization]
To a first polymerization reactor 45 liters/hr of hexane
0.07mmol/hr (in terms of Zr atoms) of the solid catalyst component
(5) obtained in Synthesis Example 2 20 mmol/hr of
triethylaluminum 7.0 kg/hr of ethylene and 40 N-liters/hr of
hydrogen were continuously supplied. Further a polyethylene
glycol/polypropylene glycol block copolymer having a viscosity
of 500 mPa.s as measured by a B type viscometer at 25°C (Product
name: EPAN720 manufactured by Dai-Ichi Kogyo Seiyaku co. Ltd.)
was continuously supplied at 0.5 g/hr. Meanwhile
polymerization was carried out under the conditions such as a
polymerization temperature of 80°C a reaction pressure of 7.4
77
kg/cm2G and an average residence time of 2.6 hr while
continuously withdrawing the contents of the reactor so that the
liquid level in the polymerization reactor would be maintained
constant. The contents continuously withdrawn from the first
polymerization reactor were subjected to substantial removal of
unreacted ethylene and hydrogen in a flash drum maintained at
an internal pressure of 0.30 kg/cm2G and at 60°C.
Then the contents were continuously supplied to a second
polymerization reactor together with 43 liters/hr of hexane
3.8 kg/hr of ethylene 4.5 N-liter/hr of hydrogen and 180 g/hr
of 1-hexene and polymerization was continued under the
conditions such as a polymerization temperature of 75°C a
reaction pressure of 3.5 kg/cm2G and an average residence time
of 1.4 hr.
Also for the second polymerization reactor the contents
of the polymerization reactor were continuously withdrawn so that
the liquid level in the polymerization reactor would be
maintained constant. In order to prevent undesirable
polymerization such as generation of a polymer containing a large
proportion of 1-hexene methanol was supplied to the contents
withdrawn from the second polymerization reactor at a rate of
2 liters/hr to deactivate the catalyst for polymerization. Then
the contents were subjected to removal of hexane and unreacted
monomer in a solvent separation unit and dried to give the polymer.
78
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 le were mixed in the same parts by weight.
Thereafter a sample for measurement was prepared by
pelletization at the same set temperature and the same resin
extrusion amount as in Example le 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 le to 5e. As in Example le it
can be seen that as compared with Comparative Examples this
sample is extremely excellent in the balance between tensile
fatigue strength and moldability.
[Example 3e]
[Polymerization]
To a first polymerization reactor 45 liters/hr of hexane
0. 07 mmol/hr (in terms of Zr atoms) of the solid catalyst component
(8) obtained in Synthesis Example 2 20 mmol/hr of
triethylaluminum 7.0 kg/hr of ethylene and 40 N-liters/hr of
hydrogen were continuously supplied. Further a polyethylene
glycol/polypropylene glycol block copolymer having a viscosity
of 370 mPa.s as measured by a B type viscometer at 25°C (Product
name: Adeka Pluronic L-71 manufactured by Adeka Corporation)
was continuously supplied at 0.8 g/hr. Meanwhile
79
polymerization was carried out under the conditions such as a
polymerization temperature of 80°C a reaction pressure of 7.4
kg/cm2G and an average residence time of 2.6 hr while
continuously withdrawing the contents of the polymerization
reactor so that the liquid level in the polymerization reactor
would be maintained constant. The contents continuously
withdrawn from the first polymerization reactor were subjected
to substantial removal of unreacted ethylene and hydrogen in a
flash drum maintained at an internal pressure of 0.30 kg/cm2G
and at 60°C.
Then the contents were continuously supplied to a second
polymerization reactor together with 43 liters/hr of hexane
3.8 kg/hr of ethylene 4.5 N-liter/hr of hydrogen and 220 g/hr
of 1-hexene and polymerization was continued under the
conditions such as a polymerization temperature of 75°C a
reaction pressure of 3.5 kg/cm2G and an average residence time
of 1.4 hr.
Also for the second polymerization reactor the contents
of the polymerization reactor were continuously withdrawn so that
the liquid level in the polymerization reactor would be
maintained constant. In order to prevent undesirable
polymerization such as generation of a polymer containing a large
proportion of 1-hexene methanol was supplied to the contents
withdrawn from the second polymerization reactor at a rate of
80
2 liters/hr to deactivate the catalyst for polymerization. Then
the contents were 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 le were mixed in the same parts by weight.
Thereafter a sample for measurement was prepared by
pelletization at the same set temperature and the same resin
extrusion amount as in Example le 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 le to 5e. As in Example le it
can be seen that as compared with Comparative Examples this
sample is extremely excellent in the balance between tensile
fatigue strength and moldability.
[Example 4e]
[Polymerization]
To a first polymerization reactor 45 liters/hr of hexane
0.19mmol/hr (in terms of Zr atoms) of the solid catalyst component
(6) obtained in Synthesis Example 2 20 mmol/hr of
triethylaluminum 11.0 kg/hr of ethylene and 50 N-liters/hr of
hydrogen were continuously supplied. Further a polyethylene
glycol/polypropylene glycol block copolymer having a viscosity
81
of 370 mPa. s as measured by a B type viscometer at 25°C (Product
name: Adeka Pluronic L-71 manufactured by Adeka Corporation)
was continuously supplied at 0.8 g/hr. Meanwhile
polymerization was carried out under the conditions such as a
polymerization temperature of 75°C a reaction pressure of 7. 6
kg/cm2G and an average residence time of 2.4 hr while
continuously withdrawing the contents of the polymerization
reactor so that the liquid level in the polymerization reactor
would be maintained constant. The contents continuously
withdrawn from the first polymerization reactor were subjected
to substantial removal of unreacted ethylene and hydrogen in a
flash drum maintained at an internal pressure of 0.30 kg/cm2G
and at 60°C.
Then the contents were continuously supplied to a second
polymerization reactor together with 43 liters/hr of hexane
7.3 kg/hr of ethylene 5.0 N-liter/hr of hydrogen and 270 g/hr
of 1-hexene and polymerization was continued under the
conditions such as a polymerization temperature of 75°C a
reaction pressure of 3.2 kg/cm2G and an average residence time
of 1.2 hr.
Also for the second polymerization reactor the contents
of the polymerization reactor were continuously withdrawn so that
the liquid level in the polymerization reactor would be
maintained constant. In order to prevent undesirable
82
polymerization such as generation of a polymer containing a large
proportion of 1-hexene methanol was supplied to the contents
withdrawn from the second polymerization reactor at a rate of
2 liters/hr to deactivate the catalyst for polymerization. Then
the contents were 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 le were mixed in the same parts by weight.
Thereafter a sample for measurement was prepared by
pelletization at the same set temperature and the same resin
extrusion amount as in Example le 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 le to 5e. As in Example le it
can be seen that as compared with Comparative Examples this
sample is extremely excellent in the balance between tensile
fatigue strength and moldability.
[Example 5e]
[Polymerization]
To a first polymerization reactor 45 liters/hr of hexane
0.13mmol/hr (in terms of Zr atoms) of the solid catalyst component
(8) obtained in Synthesis Example 2 20 mmol/hr of
83
triethylaluminum 8.1 kg/hr of ethylene and 60 N-liters/hr of
hydrogen were continuously supplied. Further a polyethylene
glycol/polypropylene glycol block copolymer having a viscosity
of 370 mPa.s as measured by a B type viscometer at 25°C (Product
name: Adeka Pluronic L-71 manufactured by Adeka Corporation)
was continuously supplied at 0.8 g/hr. Meanwhile
polymerization was carried out under the conditions such as a
polymerization temperature of 75°C a reaction pressure of 7.5
kg/cm2G and an average residence time of 2.4 hr while
continuously withdrawing the contents of the polymerization
reactor so that the liquid level in the polymerization reactor
would be maintained constant. The contents continuously
withdrawn from the first polymerization reactor were subjected
to substantial removal of unreacted ethylene and hydrogen in a
flash drum maintained at an internal pressure of 0.30 kg/cm2G
and at 60°C.
Then the contens were continuously supplied to a second
polymerization reactor together with 43 liters/hr of hexane
6.6 kg/hr of ethylene 5.0 N-liter/hr of hydrogen and 163 g/hr
of 1-hexene and polymerization was continued under the
conditions such as a polymerization temperature of 75°C a
reaction pressure of 3.2 kg/cm2G and an average residence time
of 1.2 hr.
Also for the second polymerization reactor the contents
84
of the polymerization reactor were continuously withdrawn so that
the liquid level in the polymerization reactor would be
maintained constant. In order to prevent undesirable
polymerization such as generation of a polymer containing a large
proportion of 1-hexene methanol was supplied to the contens
withdrawn from the second polymerization reactor at a rate of
2 liters/hr to deactivate the catalyst for polymerization. Then
the contents were 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 le were mixed in the same parts by weight.
Thereafter a sample for measurement was prepared by
pelletization at the same set temperature and the same resin
extrusion amount as in Example le 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 le to 5e. As in Example le it
can be seen that as compared with Comparative Examples this
sample is extremely excellent in the balance between tensile
fatigue strength and moldability.
[Comparative Example le]
The pellets of product HI-ZEX 7700 M manufactured by Mitsui
85
Chemicals Inc. were used as the sample for measurement. The
co-monomer was 1-butene. A pressed sheet was prepared using this
sample to measure the properties. The results are presented in
Tables le to 5e. It can be seen that as compared with Examples
this sample has the same level of tensile fatigue strength at
80°C but has higher apparent shear stress showing extremely
inferior moldability.
[Comparative Example 2e]
The pellets of product HI-ZEX 6300 M manufactured by Mitsui
Chemicals Inc. were used as the sample for measurement. The
co-monomer was 1-butene. A pressed sheet was prepared using this
sample to measure the properties. The results are presented in
Tables le to 5e. It can be seen that as compared with Examples
this sample has the same level of apparent shear stress but has
extremely inferior tensile fatigue strength at 80°C.
[Comparative Example 3e]
The pellets of product NEO-ZEX 4005 M manufactured by Mitsui
Chemicals Inc. were used as the sample for measurement. The
co-monomer was 1-butene. A pressed sheet was prepared using this
sample to measure the properties. The results are presented in
Tables le to 5e. It can be seen that as compared with Examples
this sample has the same level of apparent shear stress but has
extremely inferior tensile fatigue strength at 80°C.
INDUSTRIAL AVAILABILITY
The ethylene polymer of the present invention is excellent
in moldability and the molded product made therefrom exhibits
excellent mechanical strength and is useful in various industrial
applications.







We Claim:
1. An ethylene polymer containing 0.02 to 0.50 mol% of a constitutional unit derived from
an a-olefin having 6 to 10 carbon atoms, the polymer having a density of 945 to 975
kg/m and satisfying the following requirements [1], [2] and [2b]-[4b] simultaneously:
[1] in CFC, all the components having a molecular weight of 100,000 or more are eluted
at a temperature of 85°C or higher;
[2] the components eluted at a temperature of 80°C or lower account for up to 5% of all
the components elated in CFC;
[2b] the intrinsic viscosity (n) as measured in decalin at 135°C is in the range of 1.6 to 2.8
(d1/g);
[3b] the flexural modulus, MPa, as measured at 23 °C according to ASTM-D-790 satisfies
600 ≤ M measured at 50°C according to ASTM-D-1693 and M satisfy the following equation (Eq-
1):
T ≥-0.8XM+1210 (Eq-1); and
[4b] tan 8 (loss modulus G'Vstorage modulus G') as measured at 190°C and at an angular
frequency of 100 rad/sec using a dynamic viscoelasticity measuring apparatus, is in the
range of 0.6 to 0.9.
2. A blow molded product, an extrusion molded product, a compression molded product or a vacuum molded product, made from the ethylene polymer as claimed in claim 1.

Documents:

2008-DELNP-2007-Abstract-(01-03-2011).pdf

2008-DELNP-2007-Abstract-(09-03-2012).pdf

2008-DELNP-2007-Abstract-(27-06-2011).pdf

2008-delnp-2007-abstract.pdf

2008-DELNP-2007-Claims-(01-03-2011).pdf

2008-DELNP-2007-Claims-(09-03-2012).pdf

2008-DELNP-2007-Claims-(27-06-2011).pdf

2008-delnp-2007-claims.pdf

2008-delnp-2007-Correspodence Others-(12-07-2011).pdf

2008-DELNP-2007-Correspodence Others-(27-06-2011).pdf

2008-DELNP-2007-Correspondence Others-(09-03-2012).pdf

2008-DELNP-2007-Correspondence-Others-(01-03-2011).pdf

2008-DELNP-2007-Correspondence-Others-(24-12-2010).pdf

2008-delnp-2007-correspondence-others-1.pdf

2008-delnp-2007-correspondence-others.pdf

2008-DELNP-2007-Description (Complete)-(01-03-2011).pdf

2008-delnp-2007-description (complete).pdf

2008-delnp-2007-drawings.pdf

2008-DELNP-2007-Form-1-(01-03-2011).pdf

2008-delnp-2007-Form-1-(12-07-2011).pdf

2008-delnp-2007-form-1.pdf

2008-DELNP-2007-Form-13-(01-03-2011).pdf

2008-delnp-2007-Form-18 (21-03-2007).pdf

2008-delnp-2007-form-18.pdf

2008-DELNP-2007-Form-2-(01-03-2011).pdf

2008-delnp-2007-form-2.pdf

2008-DELNP-2007-Form-3-(01-03-2011).pdf

2008-DELNP-2007-Form-3-(24-12-2010).pdf

2008-delnp-2007-form-3.pdf

2008-delnp-2007-form-5.pdf

2008-DELNP-2007-GPA-(01-03-2011).pdf

2008-delnp-2007-gpa.pdf

2008-delnp-2007-pct-210.pdf

2008-delnp-2007-pct-301.pdf

2008-delnp-2007-pct-304.pdf

2008-delnp-2007-pct-306.pdf

2008-delnp-2007-pct-308.pdf

2008-DELNP-2007-Petition 137-(01-03-2011).pdf


Patent Number 254206
Indian Patent Application Number 2008/DELNP/2007
PG Journal Number 40/2012
Publication Date 05-Oct-2012
Grant Date 01-Oct-2012
Date of Filing 15-Mar-2007
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 MASAHIKO OKAMOTO, TETSUJI KASAI,YASUSHI TOHI,KOJI ENDO C/O MITSUI CHEMICALS,INC., 580-32, NAGAURA, SODEGAURA-SHI, CHIBA 299-0265,JAPAN
2 SHIRO OTSUZUKI C/O MITSUI CHEMICALS,INC.,1-2,WAKI 6-CHOME, WAKICHO, KUGA-GUN, YAMAGUCHI 740-0061,JAPAN
3 TAKAHIRO AKASHI, KENJI IWAMASA, YOSHIYUKI HIRASE, KEIKO FUKUSHI C/O MITSUI CHEMICALS, INC., 3, CHIGUSA-KAIGAN, ICHIHARA-SHI, CHIBA 299-0108,JAPAN
PCT International Classification Number C08F 210/16
PCT International Application Number PCT/JP05/015106
PCT International Filing date 2005-08-12
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 2004-236806 2004-08-16 Japan
2 236807 2004-08-16 Japan