Title of Invention

WATER-SOLUBLE POROUS POLYMER AND METHOD FOR PRODUCTION OF THE SAME

Abstract The invention discloses a method for the production of a water-soluble porous polymer such as herein described having a water-insoluble content of not more than 10 wt.%, comprising polymerizing an aqueous monomer solution such as herein described by exposure to radiation selected among gamma ray, X ray, electron ray, ultraviolet light, near ultraviolet light and visible light, while having bubbles contained in said aqueous monomer solution, wherein said aqueous monomer solution contains a photopolymerization initiator, and has a specific viscosity of 0.001 - 1.2 Pa.s and a concentration of not less than 40 wt.%.
Full Text WATER%SOLUBLE POROUS POLYMER AND METHOD FOR PRODUCTION OF THE SAME
DESCRIPTION
Technical Field
This invention relates to a method for the production
of a water-soluble porous polymer. More particularly, it
relates to a method for producing a water-soluble porous
polymer by polymerizing an aqueous polymer solution
containing an ethylenically unsaturated monomer while causing
the aqueous solution to contain bubbles therein and a
water-soluble porous polymer having a void ratio in the range
of 5 - 80% and a water-insoluble content of not more than
10 wt.%.
Background Art
The water-soluble polymers have hitherto come in various
kinds of products such as natural macromolecules like gelatin
and polysaccharides and synthetic polymers like polyacrylic
acid, poly(2-hydroxyethyl methacrylate) , polyacrylamide,
and polyvinyl alcohol. They are extensively utilized as
medical accessories including laceration dressing agents,
contact lenses, artificial muscles, and artificial organs,
breeding materials including planting materials and
artificial planting soils, and tackifiers, waste water
cleaning agents, dispersants, pigments, and organism
immobilizing carriers. In consequence of the growth of the
demand for water-soluble polymers, the desirability of
developing a technique for attaining quantity production of
a water-soluble polymer inexpensively has been finding
popular approval.
It has been known to obtain a polymer by irradiating

an acrylic monomer with a light energy. As a means to produce
an acrylic polymer gel continuously, a method for continuously
producing a polymer gel by adjusting a monomer solution
containing an acrylic type monomer and a photopolymerization
initiator to an oxygen concentration of not more than 1 mg/1,
then delivering the monomer solution in the shape of a thin
layer, and irradiating the thin film with a light energy thereby
polymerizing the monomer solution has been known
(JP-A-1989-138210) . To produce the polymer of fine quality
stably, this method is required to control the layer of the
gel during the stage of polymerization to a fixed thickness.
When the gel has a high acrylic acid concentration, it is
causedby the heat of polymerization during the polymerization
to assume a bumping state consequently suffer loss of the
uniformly concentration of itself and induce dispersion of
the degree of polymerization and the bumping possibly scatters
the monomer. In consideration of this disadvantage, the
practice of preparing the aqueous solution having a monomer
content in the range of 20 - 80 wt.% and, with a further view
to precluding occurrence of an unpolymerized moiety,
imparting to the aqueous solution an oxygen concentration
of not more than 1 mg/1 and delivering the aqueous solution
in a layer thickness in the range of 3 - 20 mm has been prevailing.
The polymer gel at the age of 180 minutes after the start
of the delivery of the solution of the monomer mixture has
a solids content of 40.8%. The ribbon of the polymer gel
consequently obtained is disintegrated into the shape of chips
or grains, pulverized with a pulverizer into particles about
3 mm in diameter, and then dried at 80 oC for about one hour.
As ameans to produce a lowmolecular weight water-soluble
polymer, a method which produces a low molecular weight
water-soluble polymer by photopolymerizing a vinyl type

monomer in an aqueous solution thereof in the presence of
a hydrogen sulfite ion and a photopolymerization initiator
has been known (JP-A-2002-69104). In contrast with the
conventional method which obtains a water-soluble polymer
of a high molecular weight useful as macromolecular
flocculating agents by delivering an aqueous monomer solution
of a high concentration in the shape of a thin layer and
irradiating the thin layer with an ultraviolet light emitted
from above, the present method has been developed for the
purpose of producing a water-soluble polymer having a sharp
molecular weight distribution and it produces a water-soluble
polymer having a weight average molecular weight in the range
of 2,000 - 10,000 by adding 5 - 85 wt.% of an aqueous vinyl
type monomer solution, a hydrogen sulfite ion as a chain
transfer agent, and a photopolymerization initiator together,
and polymerizing the resultant reaction solution while
stirring it. In the working examples, the solids contents
indicated were in the range of 36 - 44 wt.%.
For the purpose of producing a partially neutralized
(meth)acrylic acid type polymer manifesting a specific
intrinsic viscosity at 30°C and a specific insoluble content
in deionized water, a method for the production of a partially
neutralized (meth)acrylic acid type polymer, characterized
by polymerizing a monomer component containing as main
components an acid type monomer and a (meth) acrylate treated
with activated carbon has been disclosed (JP-A-2000-212222) .
This invention, in view of the fact that the conventional
product has no satisfactory degree of polymerization and is
incapable of forming a medium possessing hardness and
viscosity, is aimed at producing a partially neutralized
(meth)acrylic type polymer having a high degree of
polymerization.

Since a water-soluble monomer is used for the production
of a water-soluble polymer, the reaction solution is
automatically an aqueous solution. After the production of
the water-soluble polymer, therefore, it is necessary that
the water used for the reaction solution be separated from
the polymer and that the reaction product be dried. Further,
it occurs at times that the water-soluble polymer thus produced
is disintegrated and pulverized to suit the purpose of use
and the efficiency of disintegrating or pulverization is
varied as well by the water content of the polymer.
Particularly in the continuous production of the
water-soluble polymer, the drying step calls for a long time
when the continuous operation is carried out in concert with
the speed of the polymerization. For the sake of expediting
the drying treatment, the treatment is required to be effected
at an elevated temperature, with the result that the thermal
energy will be unduly increased and the cost of production
will be consequently boosted. Particularly when the
water-soluble polymer forms the target for the drying
treatment, it is not easily dried on account of its quality.
The simplification of such a drying step of the water-soluble
polymer, therefore, constitutes an important element
responsible for enhancing the efficiency of production and
lowering the cost of production.
In the light of the true state of affairs, this invention
is aimed at providing a method for producing a water-soluble
polymer by a simple procedure at a low cost.
Disclosure of the Invention
The present inventor has found that the polymerization
of an aqueous monomer solution containing an ethylenically
unsaturatedmonomer, when effected while positively supplying

bubbles into the reaction solution, is enabled to produce
a water-soluble porous polymer, that the polymer acquires
an enlarged surface area and therefore facilitates
dissipation of the water and the heat of polymerization
entrapped therein, curtails the time required for drying,
enhances the efficiency of pulverization at the subsequent
step of pulverization, and lowers the cost of production,
that the water-soluble porous polymer, even when sliced and
pulverized, is capable of manifesting the same degree of
viscosity as a non-porous polymer, and that the water-soluble
porous polymer has a smaller residual monomer content than
the unfoamed polymer, permits the reaction of polymerization
to proceed more uniformly, and allows further polymerization.
This invention has been perfected as a result.
By this invention, the water-soluble porous polymer can
be produced easily and conveniently.
This invention is particularly characterized by causing
the aqueous monomer solution containing an ethylenically
unsaturated monomer to be polymerized while, containing
bubbles therein. When the porous polymer after completion
of the polymerization acquires a volume 1.1 - 20 times the
volume of the aqueous monomer solution prior to the
polymerization, the produced water-soluble porous polymer
has a small residual monomer content and a large molecular
weight.
The water-soluble porous polymer of this invention
really abounds in water solubility as evinced by such a small
water-insoluble content as not more than 10 wt.% and, owing
to its fabrication in a porous texture, excels in an aqueous
solution-forming property.
Best Mode for Embodying the Invention

The first aspect of this invention is directed toward
a method for the production of a water-soluble porous polymer
comprising a step of polymerization of an aqueous monomer
solution while having bubbles contained in the monomer
solution, thereby obtaining the porous polymer having a
water-insoluble content of not more than 10 wt. %. A technique
for producing a porous polymer with the object of enhancing
an absorbent property already exists. It was obtained by
polymerizing a monomer component containing an inner
cross-linking agent, which polymer was a hydrophilic but not
dissolved in water. Since the water-soluble polymer requires
a long time for polymerization of an aqueous monomer solution,
it is difficult to remain bubbles through the polymerization.
Thus, absolutely no development has been made of a
water-soluble porous polymer. This invention, however, has
succeeded in developing a water-soluble porous polymer by
curtailing the polymerization time of the aqueous monomer
solution by including a photopolymerization initiator in the
solution and the exposure of the solution to an ultraviolet
light or a near ultraviolet light, or by enabling the foaming
to continue for a long time owing to the adjustment of the
viscosity of the aqueous monomer solution. Now, this
invention will be described in detail below.
(1) Preparation of aqueous monomer solution
The water-soluble porous polymer of this invention can
be produced by polymerizing a relevant monomer in a medium.
The monomers include ethylenically unsaturated monomers,
carbonyl compounds, alcohols, and carboxylic acids, for
example.
As concrete examples of the ethylenically unsaturated
monomer, anionic monomers such as (meth) acrylic acid, maleic
acid, maleic anhydride, fumaric acid, crotonic acid, itaconic

acid, 2-(meth)acryloyl ethane sulfonic acid,
2-(meth)acryloyl propane sulfonic acid,
2-(meth)acrylamide-2-methyl propane sulfonic acid, vinyl
sulfonic acid, and styrene sulfonic acid and lithium, sodium,
potassium, and other alkali metal salts thereof and ammonium
salts thereof; nonionic hydrophilic group-containing
monomers such as (meth)acrylamide, N-substituted
(meth)acrylamide, 2-hydroxyethyl (meth)acrylate,
2-hydroxypropyl (meth)acrylate, methoxypolyethylene glycol
(meth)acrylate, polyethylene glycol (meth)acrylate, and
N-vinyl acetamide; and amino group-containing unsaturated
monomers such as N,N-dimethylaminoethyl (meth)acrylate,
N,N-dimethylaminopropyl(meth)acrylate, and
N,N-methylaminopropyl(meth)acrylamide and the products of
quaternization thereof may be cited. Incidentally, N-vinyl
pyrrolidone may be used specifically for copolymerization.
It is permissible to use additionally such acrylic esters
as methyl (meth)acrylate, ethyl (meth)acrylate, and butyl
(meth) acrylate and hydrophobic monomers such as vinyl acetate
and vinyl propionate in an amount incapable of impairing the
water-soluility of the produced polymer.
As concrete examples of the carbonyl compound, aldehydes
and ketones, cyclic ethers and lactones may be cited. As
concrete examples of the alcohols, aliphatic alcohols,
aromatic alcohols, and diols may be cited. As concrete
examples of the carboxylic acids, aliphatic carboxylic acids,
aromatic carboxylic acids, amines, and thiols may be cited.
These monomers may be used either singly or in the form of
a combination of two or more members.
In this invention, it is preferable to use ethylenically
unsaturated monomers among them. It is particularly
preferable to use at least one member selected from the group

consisting of (meth)acrylic acid and salts thereof,
2-(meth)acryloyl ethane sulfonic acid and salts thereof,
2- (meth) acrylamide-2-methyl propane sulfonic acid and salts
thereof, (meth)acrylamide, methoxypolyethylene glycol
(meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate and
the products of quaternization thereof. It is still more
preferable to use a monomer component which contains
(meth) acrylic acid or a salt thereof as an essential component.
When the monomer component forms a "salt" such as an acrylate,
it is permissible to prepare an aqueous solution containing
an acid type acrylic acid as a monomer component and
subsequently transform the monomer component by addition of
an alkali into a neutral salt. Otherwise, it is permissible
to use a neutral salt type acrylic acid as a monomer component.
As concrete examples of the "salt, " the salts of alkali metals
and alkaline earth metals may be cited.
The viscosity of the aqueous monomer solution does not
need to be particularly restricted. The adjustment of this
viscosity in the range of 0.001 to 1.2 Pa.s, preferably 0.001
to 1.0 Pa.S, and still more preferably 0.001 to 0.6 Pa.s,
however, enables the bubbles to be stably dispersed in the
aqueous monomer solution. If the viscosity exceeds 1.2 Pa. s,
the excess will possibly render difficult uniform dispersion
in the aqueous monomer solution of a foaming agent which is
usable in this invention. Further, the aqueous monomer
solution may be not easy to transfer with a pump by the excess
viscosity.
The concentration of the aqueous monomer solution is
not particularly restricted. When it is adjusted to a level
of not less than 40 wt.%, it can be simplify the drying and
pulverization steps of the obtained polymer. It is preferably
not less than 50 wt.%, still more preferably not less than

60 wt.%, and the most preferably not less than 70 wt.%. If
the concentration of the aqueous monomer solution is lower
than 40 wt.%, the shortage will be at a disadvantage in
increasing the water content of the solution, requiring the
drying to be carried out at a higher temperature for a longer
time, necessitating an increase in the size of the device,
and impairing the efficiency of production. The increase of
the concentration of the aqueous monomer solution brings a
proportionate decrease in the water content of the produced
polymer and consequently enhances the efficiency of the
treatments of drying and pulverization proportionately. It
occurs at times that the higher concentration possibly allows
omission of the step of drying. When the aqueous monomer
solution is polymerized at a high concentration, the product
of the polymerization can be immediately pulverized and
obtained the powder aimed at easily. The increase of the
concentration of the aqueous monomer solution results in
heightening the viscosity of itself and consequently adding
to the power of holding bubbles and ensuring production of
a water-soluble porous polymer of high quality.
For the sake of heightening the viscosity of the aqueous
monomer solution, the solution may incorporate a thickening
agent therein. The thickening agent is required to be a
water-soluble polymer. For example, oligoacrylic acid
(salt) , polyacrylicacid (salt) , polyvinyl alcohol, polyvinyl
pyrrolidone, polyacrylamide, polyethylene oxide,
hydroxyethyl cellulose, carboxymethyl cellulose, and hydroxy
propyl cellulose are usable. These water-soluble polymers
usable as a thickening agent have a weight average molecular
weight in the range of 1,000- 10,000,000 and preferably 10, 000
- 5,000,000. If the average molecular weight falls short of
1,000, the shortage will be at a disadvantage in increasing

the amount of the thickening agent to be added and possibly
degrading the water solubility. The amount of the thickening
agent to be added does not need to be particularly restricted
but is only required to allow the viscosity of the aqueous
monomer solution to reach a level of not more than 1.2 Pa.s.
Generally, this amount is in the range of 0.01 - 3 wt.%,
preferably 0.1 - 1 wt.% based on the weight of the monomer.
If the amount of the thickening agent to be added falls short
of 0.01 wt.%, the shortage will possibly prevent the effect
of enhancing the viscosity from being satisfactorily
manifested.
For the sake of adjusting the viscosity in the range
specified above, when the monomer component is an
ethylenically unsaturated monomer, for example, the amount
of the neutral salt type monomer to be incorporated may be
controlled in the range of 5 - 100 mol%, preferably 10 - 100
mol%. The ethylenically unsaturated monomer may possibly
have the viscosity thereof in the aqueous solution vary between
the acid type and the neutralized salt type of itself.
Generally, the neutralized salt type has a higher viscosity.
Thus, the viscosity can be controlled by adjusting the amount
of the neutralized salt type to be incorporated. Since it
is made possible to adjust the viscosity and allow the bubbles
to be retained advantageously during the course of the
polymerization by controlling the amount of the neutralized
salt type monomer, the obtained polymer may be reverted to
the acid type by treatment with an acid or adjusted to the
wholly neutralized salt type by treatment with an alkali.
Furthermore, by adjusting the amount of the alkali to be used
in the treatment, it is made possible to obtain a water-soluble
porous polymer containing a neutralized salt as expected.
This procedure is at an advantage in allowing the viscosity

to be adjusted without requiring incorporation of such
additives as a thickening agent, for example.
The production of a hydrophilic polymer possessing a
cross-linked structure has been attained hitherto by
positively supplying the scene of polymerization with bubbles.
In the case of the water-soluble polymer having a small
water-insoluble content contemplated by this invention, the
production of a water-soluble porous polymer by the procedure
of positively supplying bubbles has not been realized. It
seems that in the case of a hydrophilic polymer possessing
a cross-linked structure, the reaction solution has a very
high viscosity and is enabled to retain bubbles easily therein.
The water-soluble polymer of this invention having a small
water-insoluble content is a hydrophilic polymer possessing
no cross-linked structure. Owing to the absence of the
cross-linked structure, the reaction solution has a low
viscosity and is not enabled to retain bubbles till completion
of the polymerization. Now, this invention has realized the
synthesis of a water-soluble porous polymer by exalting the
power of the reaction solution to retain bubbles therein by
adjusting the viscosity of the reaction solution in accordance
with the method described above and adopting as well a varying
foaming means described herein below.
When the aqueous monomer solution mentioned above is
polymerized, it is preferable to have a radical polymerization
initiator dissolved or dispersed in advance in the aqueous
polymer solution. Such radical polymerization initiators
include azo compounds such as azonitrile compounds,
azoamidine compounds, cyclic azoamidine compounds, azoamide
compounds, alkyl azo compounds,
2,2'-azobis (2-amidinopropane) dihydrochlori.de, and
2,2'-azobis[2-(2-imidazolin-2-yl)propane]

dihydrochloride) ; persulfates such as ammonium persulfate,
potassium persulfate, and sodium persulfate; peroxides such
as hydrogen peroxide, methylethyl ketone peroxide, benzoyl
peroxide, cumene hydroperoxide, and di-t-butyl peroxide; and
redox initiators formed by combining the peroxides mentioned
above with such reducing agents as sulphites, bisulfites,
thiosulfates, formamidine sulfinic acid, and ascorbic acid,
for example. These radical polymerization initiators may be
used either singly or in the form of a combination of two
or more members. The radical polymerization initiator usable
advantageously in this invention is incorporated in an amount
falling preferably in the range of 0.0001 - 10 wt. parts,
more preferably 0.0005 - 5 wt. parts, and particularly
preferably 0.001 - 1 wt. part, based on 100 wt. parts of the
ethylenically unsaturated monomer.
Further, this invention allows use of such
photopolymerization initiators as benzoin derivatives,
benzyl derivatives, acetophenone derivatives, benzophenone
derivatives, and azo compounds for the purpose of initiating
polymerization as a polymerization initiator. Use of a
photopolymerization initiator and ultraviolet light and/or
near ultraviolet light proves a preferable method.
As concrete examples of the photopolymerization
initiator usable herein, azo type photopolymerization
initiators such as 2, 2'-azobis(2-amidinopropane),
2,2'-azobis(N,N'-dimethylene isobutylamidine),
2,2'-azobis[2-(5-methyl-2-imidazolin-2-yl)propane],
1,1'-azobis(1-amidino-l-cyclopropylethane),
2,2'-azobis(2-amidino-4-methylpentane),
2,2'-azobis(2-N-phenyl-aminoamidinopropane),
2,2'-azobis(l-imino-l-ethylamino-2-methylpropane),
2,2'-azobis(l-allylamino-l-imino-2-methylbutane),

2,2'-azobis(2-N-cyclohexylamidinopropane),
2,2'-azobis(2-N-benzylaminopropane), hydrochlorides,
sulfates, and acetates thereof, 4,4'-azobis(4-cyanovaleric
acid) and alkali metal salt, ammonium salt, and amine salt
thereof, 2-(carbamoylazo) isobutylonitrile,
2,2'-azobis(isobutylamiide),
2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propionamide],
2,2'-azobis[2-methyl-N-(1,1'-bis(hydroxymethyl)ethyl)pro
pionamide], and
2,2'-azobis[2-methyl-N-l,1'-bis(hydroxyethyl)
propionamide];
benzoyl type photopolymerization initiators such as
eutectic mixtures of 2, 2-dimethoxy-l, 2-diphenylethan-l-on,
1-hydroxy-cyclohexyl-phenyl-ketone,
2-hydroxy-2-methyl-1-phenyl-propan-1-on, and
1-hydroxy-cyclohexyl-phenyl-ketone (Irgacure 184) with
benzophenone; 3:7 mixtures of
2-hydroxy-2-methyl-l-phenyl-propan-l-on (Darocur 1173),
1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-l-prop
an-l-on,
2-methyl-l-[4-(methylthio)phenyl)]-2-morpholinopropan-l-
on,
2-benzyl-2-dimethylamino-l-(4-morpholinophenyl)-butanon-
1, and
2-benzyl-2-dimethylamino-l-(4-morpholinophenyl)-butanon-
1 (Irgacure 369) with 2,2-dimethoxy-l,2-diphenylethan-l-on
(Irgacure 651); 1:3 mixtures of
bis(2,4,6-trimethylbenzoyl)-phenylphosphinoxide (Irgacure
819) , bis(2,4,6-trimethylbenzoyl)-phenylphosphinoxide, and
bis(2,6-dimethoxybenzoyl)-2,4,4-trimethyl-pentylphosphin
oxide (CG1403) with
2-hydroxy-2-methyl-l-phenyl-propan-l-on, 1:3 mixture of

bis(2,6-dimethoxybenzoyl)-2,4,4-trimethyl-pentylphosphin
oxide (CG1403) with 1-hydroxy-chlorohexyl-phenyl-ketone
(Irgacure 184), al:l mixture of
bis(2,6-dimethoxybenzoyl-2,4,4-trimethyl-pentylphosphino
xide (CG14034) with 1-hydroxy-cyclohexyl-phenyl-ketone
(Irgacure 184), al:l liquid mixture of
2,4-6-trimethylbenzoyl-diphenyl-phosphinoxide with
2-hydroxy-2-methyl-l-phenyl-propan-l-on (Darocur 1173),
and
bis (n5-2, 4-cyclopentadien-l-yl)bis(2, 6-difluoro-3-(lH-pyr
rol-l-yl)-phenyl)titanium,
eutectic mixtures of
oligo[2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]prop
anone and 2,4,6-trimethylbenzophenone with
4-methylbenzophenone, a liquid mixture of
4-methylbenzophenone with banzophenone, a liquid mixture of
2,4,6-trimethylbenzoyldiphenylphosphinoxide with
oligo[2-hydroxy-2-methyl-l-[4-(1-methylvinyl)phenyl]prop
anone] and a methylbenzophenone derivative;
1-[4-(4-benzoylphenylsulfanyl)phenyl]-2-methyl-2-(4-meth
ylphenylsulfanyl)propan-1-on, benzyldimethylketal,
2-hydroxy-2-methyl-l-phenyl-l-propanone,
a-hydroxycyclohexyl-phenylketone,
ethyl-4-dimethylaminobenzoate, acrylamine synergist,
benzoin (iso- and n-)butylester, acryl sulfonium (mono,
di)hexafluorophosphate, 2-isopropyl thioxanthone,
4-benzoyl-4'-methyldiphenylsulfide,
2-butoxyethyl-4-(dimethylamino)benzoate, and
ethyl-4-(dimethylamino)benzoate, and
benzoin, benzoin alkyl ether, benzoin hydroxy alkylether,
diacetyl and derivatives thereof, anthraquinone and
derivatives thereof, diphenyl disulfide and derivatives

thereof, benzophenone and derivatives thereof, and benzyl
and derivatives thereof may be cited. These
photopolymerization initiators may be used either singly or
in the form of a combination of two or more members.
Among other photopolymerization initiators enumerated
above, the benzoin type photopolymerization initiators such
as, for example, 2-hydroxy-2-methyl-l-phenyl-propan-l-on
and bis(2,4,6-trimethylbenzoyl)-phenylphosphinoxide are
used particularly advantageously.
The amount of the photopolymerization initiator to be
used is preferably in the range of 0.0001 - 10 wt. parts,
more preferably 0.0005 - 5 wt. parts, and particularly
preferably 0.001 - 1 wt. part, based on 100 wt. parts of the
monomer. If the amount of the initiator falls short of 0. 0001
wt. part, the shortage will result in greatly lowering the
polymerization velocity. Conversely, if this amount exceeds
10 wt. parts, the overage will possibly result in emitting
an unduly large heat and increasing the water-insoluble
content.
This invention permits addition of a chain transfer agent
to the reaction system. The chain transfer agents which are
usable herein include sulfur-containing compounds,
phosphorous acid type compounds, hypophosphorous acid type
compounds, and alcohols, for example. By adding such a chain
transfer agent, it is made possible to adjust the cross-linking
reaction, keeping the water-insoluble content to less than
10 wt.%, and repressing the occurrence of a short-chain
polymer.
As concrete examples of the sulfur-containing compound,
hypophosphorous acids (salts) such as sodium hydrogen sulfite,
potassium hydrogen sulfite, and ammonium hydrogen sulfite,
thiols such as mercapto ethanol, thioglycerol, thioglycolic

acid, thioaceticacid, mercaptoethanol, 2-mercapto propionic
acid, 3-mercapto propionic acid, thiomalic acid, octyl
thioglycolate, octyl 3-mercapto propionate, and 2-mercapto
ethane sulfonic acid, and thiolic acids may be cited. As
concrete examples of the phosphorous acid type compound,
phosporous acid and sodium phosphite may be cited. As concrete
examples of the hypophosphorous acid type compound,
hypophosphorous acid and sodium hypophosphite may be cited.
As concrete examples of the alcohol, methyl alcohol, ethyl
alcohol, isopropyl alcohol, and n-butyl alcohol may be cited.
These compounds may be used either singly or in the form of
a combination of two or more members. Among other compounds
enumerated above, hydophosphorous acid type compounds prove
advantageous and sodium hypophosphite proves more
advantageous.
The amount of the chain transfer agent to be incorporated
may be properly set so as to suit the polymerization velocity
and the combination of this agent with a photopolymerization
initiator. It is preferably in the range of 0.0001 - 10 wt.
parts and more preferably 0.005 - 5 wt. parts, based on 100
wt. parts of the monomer.
As regards the relation between the polymerization
initiator and the chain transfer agent, the ratio of their
combination (polymerization initiator/chain transfer agent) ,
in terms of the weight per 1 mol of the monomer, is not more
than 10, preferably not more than 5, and the most preferably
not more than 3. If this ratio of combination exceeds 10,
the overage will be at a disadvantage in suffering the
water-insoluble content of the resultant porous product and
the powder to exceed 10 wt.%.
Further, the aqueous monomer solution may incorporate
therein a surfactant with the object of facilitating the

generation and retention of bubbles in the solution. The
surfactants which are usable herein include anionic
surfactants, nonionic surfactants, cationic surfactants,
amphoteric surfactants, fluorine type surfactants, and
organic metal surfactants, for example.
As concrete examples of the anionic surfactant,
aliphatic acid salts such as mixed fatty acid sodium soap,
semi-hard tallow fatty acid sodium soap, sodium stearate soap,
potassium oleate soap, and castor oil potassium soap; alkyl
sulfuric ester salts such as sodium lauryl sulfcite, higher
alcohol sodium sulfate, lauryl sodium sulfate, and lauryl
sulfuric acid triethanol amine; alkylbenzene sulfonates such
as sodium dodecylbenzene sulfonate; alkyl naphthalene
sulfonates such as sodium alkylnaphthalene sulfonate; alkyl
sulfosuccinates such as sodium dialkyl sulfosuccinate; alkyl
diphenyl ether disulfonates such as sodium alkyldiphenyl
ether disulf onate; alkyl phosphorates such as potassium alkyl
phosphate; polyoxyethylene alkyl (or alkylallyl) sulfuric
acid ester salts such as polyoxyethylene lauryl ether sodium
sulfate, polyoxyethylene alkyl ether sodium sulfate,
polyoxyethylene alkyl ether sulfuric acid triethanol amine,
and polyoxyethylene alkylphenyl ether sodiumsulf ate; special
reaction type anionic surfactants; special caraboxylic acid
type surfctants; naphthalene sulfonic acid formalin
condensates such as sodium salts of β-naphthalene sulfonic
acid formalin condensate and sodium salts of special aromatic
sulfonic acid formalin condensate; special polycarbonic acid
type macomolecular surfactants; and polyoxyethylene
alkylphospholic acid esters may be cited.
As concrete examples of the nonionic surfactant, sucrose
fatty acid esters; polyoxyethylene alkyl ethers such as
polyoxyethylene lauryl ether, polyoxyethylene cetyl ether,

polyoxyethylene stearyl ether, polyoxyethylene oleyl ether
and, polyoxyethylene higher alcohol ethers, polyoxyethylene
alkylaryl ethers such as polyoxyethylene nonylphenyl ether;
polyoxyethylene derivatives; sorbitan fatty acid esters
such as sorbitan monolaurate, sorbitan monopaImitate,
sorbitan monostearate, sorbitan tristearate, sorbitan
monooleate, sorbitan trioleate, sorbitan sesquioleate, and
sorbitan distearate; polyoxyethylene sorbitan fatty acid
esters such as polyoxyethylene sorbitan monolaurate,
polyoxyethylene sorbitan monopalminate, polyoxyethylene
sorbitan monostearate, polyoxyethylene sorbitan tristearate,
polyoxyethylene sorbitan monooleate, and polyoxyethylene
sorbitan trioleate; polyoxyethylene sorbitol fatty acid
esters such as tetraoleic acid polyoxyethylene sorbit;
glycerin fatty acid esters such as glycerol monostearate,
glycerol monooleate, and self-emulsifying glycerol
monostearate; polyoxyethylene fatty acid esters such as
polyethylene glycol monolaurate, polyethylene glycol
monostearate, polyethylene glycol distearate, and
polyethylene glycol monooleate; polyoxyethylene alkyl amine;
polyoxyethylene hardened castor oil; and alkyl alkanol amides
may be cited.
As concrete examples of the cationic surfactant and the
amphoteric surfactant, alkyl amine salts such as coconut amine
acetate and stearyl amine acetate; quaternary ammonium salts
such as lauryl trimethyl ammonium chloride, stearyl trimethyl
ammmonium chloride, cetyl trimethyl ammonium chloride,
distearyl dimethyl ammonium chloride, and alkylbenzyl
dimethyl ammonium chloride; alkyl betaines such as lauryl
betaine, stearyl betaine, and lauryl carboxymethyl
hydroxyethyl imidazolinium betaine; and amine oxides such
as lauryl dimethyl amine oxide may be cited. By using a

cationic surfactant, it may be made possible to impart an
antifungal property to the water-soluble polymer to be
produced.
The surfactants usable herein further include fluorine
type surfactants. By using a fluorine type surfactant, it
is made possible to have bubbles of an inert gas retained
as stably dispersed in the aqueous monomer solution for a
long time. The amount and the diameter of such bubbles are
also controlled easily. The water-soluble polymer is
consequently obtained in the form of a porous foamed mass.
It can be endowed with an antibacterial property. The fluorine
type surfactants which are usable in this invention are known
in various kinds. They result from transforming the
lipophilic group of an ordinary surfactant into a
perf luoroalkyl group by the substitution of the hydrogen atom
in the oleophilic group with a fluorine atom. They acquire
a decisively intensified surface activity owing to the
transformation.
The hydrophilic group of the fluorine type surfactant
can be varied into four kinds, i.e. anionic type, nonionic
type, cationic type, and amphoteric type. The hydrophobic
group thereof makes use of the fluorocarbon chain of the same
configuration more often than not. The carbon chain which
is the hydrophobic group may be used alike in the straight
chain form or the branched form. Typical fluorine type
surfactants are those which are enumerated below.
Fluoroalkyl (C2 - C10) carboxylic acids,
N-perfluorooctane sulfonyl glutamic acid disodium,
3-[fluoroalkyl (C6 - C11) oxy]-l-alkyl (C3 - C4) sulfonic acid
sodium, 3- [w-fluoroalkanoyl (C6-
C8)-N-ethylamino]-1-propane sulfonic acid sodium,
N-[3-(perflfuorooctane sulfonamide)

propyl]-N,N-dimethyl-N-carboxymethylene ammonium betaine,
fluoroalkyl (C11- C20) carboxylic acid, perf luoroalkyl
carboxylic acid (C7 - C13) , perfluorooctane sulfonic acid
diethanol amide, perf luoroallkyl (C4 - C12) sulfonic acid salt
(Li, K, Na) , N-propyl-N-(2-hydroxyethyl)perfluorooctane
sulfonamide, perfluoroalkyl (C6 - C10) sulfonamide propyl
trimethyl ammonium salt, perfluoroalkyl (C6-
C10)-N-ethylsulfonyl glycin salt (K) , phosphoric acid
bis(N-perfluorooctyl sulfonyl-N-ethylaminoethyl) ,
monoperfluoroalkyl (C6 - C16) ethylphosphoric acid ester,
perfluoroalkyl quaternary ammonium iodide (a cationic
fluorine type surfactant made by Sumitomo 3M K.K. and sold
under the trademark designation of "Florard FC-135"),
perfluoroalkyl alkoxylate (a nonionic surfactant made by
Sumitomo 3M K.K. and sold under the trademark designation
of "Florard FC-171"), and perflfuoroalkylsulfonic acid
potassium salt (an anionic surfactant made by Sumitomo 3M
K.K. and sold under the trademark designation of "Florard
FC-95 and FC-98").
The organic metal surfactants are also usable herein.
The term "organic metal surfactant" refers to a molecule having
such metals as Si, Ti, Sn, Zr, and Ge in the main chain or
the side chain thereof. Among other conceivable organicmetal
surfactants, those which have Si in the main chain of the
molecule prove particularly advantageous. Siloxane type
surfactants prove more advantageous.
As typical organicmetal surfactants, those represented
by the following formulas (1) - (19) may be cited (Yoshida,
Kondo, Ohgaki, and Yamanaka, "Surfactant Handbook, new
edition,"Kogaku Tosho (1966), p. 34).




As the metals to be contained in the organic metal
surfactants represented by the foregoing formulas (1) - (19),
Sn, Zr, Ge, etc. may be used in the place of Si or Ti.
The surfactants mentioned above are incapable of
emitting bubbles in themselves or enabling the aqueous monomer
solution to contain bubbles. When they are added to the
aqueous monomer solution, they enable the aqueous solution
to retain the bubbles to be generated by a stirring and mixing
operation or by the use of a foaming agent.
Kinds of surfactants to be used may be selected based
on factors of the aqueous monomer solution such as pH, for
example, and their amounts to be incorporated are also decided
in accordance with the due data offered above with respect
to the foregoing surfactants. Incidentally, these
surfactants may be utilized as an agent for regulating the
foaming, depending on the condition of use.

They may be used either singly or in the form of a
combination of two or more members. This invention prefers
use of sucrose fatty acid esters and sorbitan type surfactants,
especially sorbitan monostearate, particularly among other
surfactants enumerated above.
These surfactants are used in an amount in the range
of 0.001 - 100 wt. parts, preferably 0.005 - 80 wt. parts,
and particularly preferably 0.01 - 30 wt. parts, based on
100 wt. parts of the monomer to be used. If this amount falls
short of 0.001 wt. part, the shortage will possibly render
difficult the adjustment of the volume of the porous polymer
after completion of polymerization to 1.1 - 20 times the volume
of the aqueous monomer solution existing at the time of starting
polymerization. Conversely, if the amount exceeds 100 wt.
parts, the overage may possibly fail to bring a proportionate
addition to the effect expected.
The aqueous monomer solution to be used in this invention
allows additional incorporation therein of the aqueous
solution of starch, a derivative of starch, a water-soluble
polymer of cellulose, poly(sodium acrylate), and
poly(ethylene oxide).
As the solvent to be used in the production of a
water-soluble porous polymer, water proves a proper choice.
It is nevertheless permissible to use an aqueous solution
of such lower alcohol as methanol, ethanol, or propanol, an
amide such as dimethyl formamide or dimethyl acetamide, or
an ether such as diethyl ether, dioxane, or tetrahydrofuran.
(2) Preparation of bubbles
This invention is characterized by polymerizing the
aqueous monomer solution mentioned above while keeping the
presence of bubbles in the solution. As a means to induce
bubbles therein during the course of polymerization, (I) a

method which polymerizes a product obtained by stirring and
mixing an inert gas with the aqueous monomer solution in advance,
(II) a method which comprises adding a foaming agent to the
aqueous monomer solution and polymerizing the resultant
mixture while foaming it by the heat of polymerization, and
(III) a method of boiling point polymerization are available.
The method (I) of stirring and mixing the inert gas is
known in such forms as (1-1) a method of extruding the aqueous
monomer solution in the form of mousse and feeding it to the
polymerization device, (1-2) a method of stirring and mixing
the aqueous monomer solution in a mixing device adapted to
allow incorporation of the inert gas into the solution under
treatment therein, (1-3) a method of generating bubbles
resembling soap bubbles by means of bubbling, and (1-4) a
method of causing nitrogen gas or carbon dioxide to be dissolved
in the aqueous monomer solution under pressure. As the inert
gas to be incorporated in the aqueous monomer solution,
nitrogen, carbon dioxide, argon, and helium are available.
(1-1): For the sake of preparing the aqueous monomer
solution in the form of mousse, the aqueous monomer solution
is extruded in the form of mousse through a pump type nozzle,
for example. When the aqueous monomer solution has a
surfactant incorporated therein at this time, the surfactant
is effective in retaining the bubbles during the course of
polymerization. By selecting the kind of surfactant and
properly controlling the amount thereof, it is made possible
to regulate the pore diameter and the water-solubility of
the produced water-soluble porous polymer.
(1-2) : For the sake of stirring and mixing the aqueous
monomer solution in a mixing device thereby inducing bubbles
in the solution, a method which comprises preparing an aqueous
monomer solution incorporating therein the surfactant and

causing the aqueous solution to foam by the use of a static
mixer is available. The static mixer has lateral elements
alternately disposed inside a pipe. On admitting the streams
of the aqueous monomer solution and the inert gas therein,
this static mixer mixes them and gives rise to the aqueous
monomer solution containing the gas.
As a means to induce bubbles by stirring and mixing,
a method which, as disclosed in JP-A-1998-251310, comprises
mixing the aqueous monomer solution and the inert gas by
advancing them in parallel flow and causing either of the
two parallel streams to be projected via a nozzle into the
other stream may be adopted. By mixing the aqueous monomer
solution and the inert gas both in the form of fluid, it is
made possible to have the inert gas to be dispersed uniformly
and stably in the aqueous monomer solution. Then, by
polymerizing the aqueous monomer solution in a state having
the inert gas disposed in advance therein, it is made possible
to facilitate the control of the pore diameter and produce
a porous polymer abounding in water solubility. To be specific,
a method which effects mixture of the streams of the aqueous
monomer solution and the inert gas by causing either of the
two streams to be injected via a nozzle into the other stream
is available. The mixture is accomplished, for example, by
causing the inert gas injected through one nozzle to flow
parallelly to the stream of the aqueous monomer solution
injected through another nozzle or by causing the aqueous
monomer solution injected through one nozzle to flow
parallelly to the stream of the inert gas injected through
another nozzle. It is permissible to have the inert gas
directly blown into the stream of the aqueous monomer solution.
For the sake of stirring and mixing the two streams, they
may be projected in a parallel flow or a counterflow or in

a perpendicular flow. The mode of projecting them in a
parallel flow is preferred over the other modes. The
projection in the parallel flow allows the bubbles to be
uniformly dispersed. The projection in the counter flow
possibly results in causing the two streams to scatter, adhere
to the inner wall of the mixing device, and yield per se to
polymerization.
As the device for stirring and mixing the two streams,
an aspirator and an ejector may be used. Subsequently, by
introducing the mixture of the aqueous monomer solution and
the inert gas into a mixing zone which is furnished with a
corrugation and/or a packing adapted to obstruct the flow
of a fluid, it is made possible to effect uniform mixture
of the two components in the mixture. As concrete examples
of the corrugation or the packing serving to obstruct the
flow of a fluid, mixing zones provided with projections, vanes,
baffle plates, and packing materials maybe cited. Themixing
device of this construction may be operated by following the
procedure which is disclosed in JP-A-1998-251310.
For the sake of enabling the porous polymer resulting
from the polymerization to assume a volume 1.1 - 20 times
the volume of the aqueous monomer solution prior to the
polymerization, the amount of the gas to be mixed is adjusted.
(1-3) : The expression "the method of generating bubbles
resembling soap bubbles by means of bubbling" used herein
refers to a method which comprise adding the aqueous monomer
solution and the aforementioned surfactant together in
advance and causing the foam generated by the introduction
of an inert gas such as nitrogen gas, carbon dioxide, or argon
gas to be introduced as occasion demands into the
polymerization phase.
(1-4) The expression "the method of dissolving nitrogen

gas and carbon dioxide under pressure" refers to a method
which comprises mixing the inert gas into the aqueous monomer
solution in advance and then polymerizing the aqueous monomer
solution while enabling the gas to be radiated by the heat
of polymerization during the polymerization and enabling the
aqueous monomer solution to contain the bubbles.
The method comprises placing the aqueous monomer
solution in a pressure vessel such as an autoclave, introducing
an inert gas such as nitrogen gas or carbon dioxide therein,
retaining the interior of the vessel under pressure of not
more than 5 MPa, and causing the inert gas to be dissolved
in the aqueous monomer solution thereby inducing bubbles
therein. This method exalts the content of bubbles in the
aqueous monomer solution because the amount of the inert gas
to be dissolved into the aqueous monomer solution is larger
under pressure than under normal pressure. This method brings
an effect of enabling the aqueous monomer solution to be
efficiently transferred into the polymerization phase by
relieving the vessel of the pressure. If the pressure in the
vessel exceeds 5MPa at this time, the overage will be at a
disadvantage in endangering the operation.
(II): The expression "the method of incorporating a
foaming agent" refers to a method which comprises having the
foaming agent mixed and dispersed or dissolved in advance
in the aqueous monomer solution and enabling the foaming agent
to generate bubbles by the heat of polymerization. As the
foaming technique, the use of a chemical foaming agent or
a physical forming agent has been known. Generally, the
chemical foaming agent and the physical foaming agent are
each divided broadly under an organic type and an inorganic
type. The chemical foaming agent can be further divided
broadly under a thermal decomposition type and a reaction

type. The chemical foaming agents of the organic thermal
decomposition type include azo compounds such as azodicarbon
amide and AIBN, hydrazidocompounds, semicarbazidocompounds,
hydrazo compounds, tetrazole compounds, triazine compounds,
and ester compounds such as malonate, for example. The
chemical foaming agents of the organic reaction type include
isocyanate compounds, for example.
Then, the chemical foaming agents of the inorganic
thermal decomposition type include carbonates such as
bicarbonates, sodium carbonate, potassium carbonate,
ammonium carbonate, magnesium carbonate, calcium carbonate,
sodium hydrogen carbonate, potassium hydrogen carbonate,
ammonium hydrogen carbonate, magnesium hydrogen carbonate,
calcium hydrogen carbonate, zinc carbonate, and barium
carbonate, nitrites, and hydrides, for example. The chemical
foaming agents of the inorganic reaction type include
combinations of bicarbonates and acids, combinations of
hydrogen peroxide and yeast, and combinations of aluminum
and acids or alkalis, for example. The physical foaming agents
of the organic type include aliphatic hydrocarbons formed
of such volatile liquids as butane and pentane, and halogenated
hydrocarbons such as dichloromethane, trichloroethane, and
trifluforoethane, for example. The physical foaming agents
of the inorganic type include nitrogen gas and carbonic acid
gas, for example.
When the generation of bubbles is implemented by
combining sodium carbonate or ammonium carbonate with an acid,
the generation of bubbles occurs copiously immediately after
mixture and it ceases to continue with the advance of the
neutralization reaction. When the combination mentioned
above is adopted, the polymerization is preferably initiated
as soon as possible after the mixture of the chemical foaming

agent of the inorganic type and the acid, specifically within
two hours, preferably within one hour after the mixture.
It is also permissible to use foaming particulates which
are formed of a core part of a low boiling organic solvent
and a shell part of a nitrile type copolymer such as, for
example, nitrile type thermally expandingmicrocapsules (sold
under the product name of "Matsumoto Microsphere F-36") and
nitrile type thermally expanding microcapsules (sold under
the product name of "Matsumoto Microsphere F-20").
In this invention, these foaming agents maybe used either
singly or in the form of a combination of two or more members.
The foaming agents which are advantageously usable in this
invention are low boiling organic solvents such as pentane,
butane, and fleon, thermally expanding microcapsules
enclosing such volatile liquids therewith, inorganic foaming
agents such as sodium bicarbonate and ammonium carbonate,
and organic foaming agents such as azodicarboxylic acid amide
and AIBN among other foaming agents enumerated above. Besides,
the foaming agents which are disclosed in JP-A-1999-35691,
JP-A-1999-292919, JP-A-1999-302391, and JP-A-2000-63527are
advantageously usable.
When the foaming agent is incorporated in the aqueous
monomer solution, the amount thereof to be used is in the
range of 0.001 - 100 wt. parts, more preferably 0.005 - 80
wt. parts, and particularly preferably 0.01 - 30 wt. parts
based on 100 wt. parts of the monomer. Such characteristic
elements of the voids in the produced foamed article such
as continuity, dependence, size, shape, distribution, and
uniformity of size can be controlled by properly setting the
foaming conditions to suit the purpose of foaming.
More specifically, a method which comprises preparing
an aqueous monomer solution, adding this solution and a

carbonate type foaming agent together thereby forming a
carbonate-containing monomer solution, polymerizing this
solution thereby obtaining a water-soluble porous polymer,
or polymerizing an aqueous monomer solution having a low
boiling organic solvent such as hexane dispersed therein
thereby producing amicroporous water-soluble porous polymer,
or having a water-insoluble foaming agent dispersed in an
aqueous monomer solution through the medium of a surfactant
and subsequently polymerizing the solution while causing the
foaming agent to emit bubbles in the solution is also available.
It is also permissible to adopt a method which effects
polymerization by the use of an azo initiator having a 10-hour
half life at a temperature in the range of 30 - 120 °C (refer
to WO 95/17455) and a method which consists in polymerizing
a water-soluble monomer in the presence of a foaming agent
formed of an acrylic acid salt complex of azo compound (refer
to WO 96/17884).
In the conventional polymerization using a foaming agent,
the reaction solution has been required to possess such
viscosity as to retain bubbles therein. When a cross-linked
structure is contained, the solution possesses sufficient
viscosity and can produce a porous polymer. When no
cross-linked structure is contained, however, the solution
fails to retain bubbles therein and can not produce porous
polymer. The water-soluble polymer produced by this invention
has a high polymerization velocity and has an ability to adjust
the polymerization temperature at a low level. Thus, it excels
in the ability to retain bubbles from start of the
polymerization to completion of it, therefore, allows
production of a water-soluble porous polymer of high quality.
Particularly, the addition of a surfactant results in the
retention of bubbles in original diameters.

(III): The term "the method of boiling point
polymerization" refers to a method of repressing radiation
of heat and heightening the polymerization velocity by causing
the polymerization to start at a temperature approximating
the boiling point of the aqueous monomer solution. The fact
that the polymerization temperature can be retained in the
neighborhood of the boiling point brings the advantage of
nearly fixing the amount of heat during the course of
polymerization and repressing the cross-linking reaction.
At this time, the boiling may be utilized in generating bubbles .
That is, this method consists in enabling the polymer to contain
bubbles therein by completing the polymerization before the
bubbles vanish.
The interval between the preparation of the bubbles
mentioned above and the start of polymerization to be described
below is preferably within two hours, more preferably within
1 hour, furthermore preferably within 30 minutes, and the
most preferably within 10 minutes. When the bubbles are
prepared by stirring and mixing an inert gas and they are
then left standing for a period exceeding two hours, they
will possibly vanish. Also when such a basic foaming agent
as a carbonate is used where the monomer happens to be acrylic
acid, the generation of a gas will possibly decrease with
the elapse of time.
(3) Polymerization
The method for polymerizing the monomer does not need
to be particularly restricted but is only required to enable
an aqueous monomer solution having a polymerization initiator
incorporated in advance therein to be polymerized while
continuing to contain bubbles therein. Generally, the
polymerization is effected thermally with the object of
promoting the polymerization. For this thermal

polymerization, any of the known methods such as aqueous
solution polymerization, reversed-phase suspension
polymerization, bulk polymerization, and precipitation
polymerization may be adopted. The reaction conditions such
as reaction temperature and reaction time do not need to be
particularly restricted but may be properly selected to suit
the composition of the monomer component to be used, the method
of generating bubbles, and the kind and amount of a foaming
agent.
Instead of the thermal polymerization, this invention
may resort to the photopolymerization which is effected by
having an aqueous monomer solution incorporate therein a
photopolymerization initiator in advance and exposing the
aqueous monomer solution to a radiation such as gamma ray,
Xray, or electronrayor an ultraviolet light, near ultraviolet
light, or visible light. It is also permissible to use the
thermal polymerization and the photopolymerization together,
namely to carry out the thermal polymerization while the
photopolymerization is being performed by virtue of the
exposure to the radiation such as gamma ray, X ray, or electron
ray or ultraviolet light, near ultraviolet light, or visible
light. This invention prefers sole use of
photopolymerization or combined use of thermal polymerization
and photopolymerization. The photopolymerization enjoys a
short polymerization time and a low polymerization
temperature and, therefore, brings such advantages as
manifesting an excellent ability to retain bubbles, forming
a small residual monomer, and ensuring production of a
water-soluble porous polymer of a large weight average
molecular weight. The water-soluble porous polymer
consequently obtained, when used as a sanitary material,
inflicts no significant stimulus on the skin because of the

small residual monomer content and, when used to form an aqueous
solution, allows an increase in the intrinsic viscosity of
the produced solution because of the high weight average
molecular weight.
As concrete examples of the light exposure device,
high-pressure mercury lamp, low-pressure mercury lamp, metal
halide lamp, fluorescent chemical lamp, fluorescent blue
color lamp, blacklight mercury lamp, and xenon lamp may be
cited. The wavelength of the light is in the range of 100
- 800 nm, more preferably 100 - 500 nm and particularly
preferably 200 - 500 nm. If the wavelength falls short of
100 nm, the shortage will possibly render difficult the control
of polymerization because of its strong effect of promoting
polymerization, giving rise to bumping at times, and
increasing to the insoluble component. Conversely, if the
wavelength exceeds 800 nm, the overage will result in requiring
the polymerization time to be increased. This problem can
be solved by weakening the intensity first and then enhancing
the intensity subsequently.
The intensity of irradiation is not more than 100 W/m2,
preferably not more than 80 W/m2, and more preferably not more
than 50 W/m2. Thus, it is made possible to promote the
polymerization quickly and produce a water-soluble porous
polymer having a small residual monomer content and a
relatively large weight average molecular weight. The
photopolymerization may be performed with the intensity of
exposure kept constant. Preferably, the intensity is kept
constant below 100 W/m2 and increased in the intermediate stage
rather than at the start of the polymerization.
In the photopolymerization of this kind, the aqueous
monomer solution is supplied in a thickness of not more than
100 mm, preferably not more than 50 mm, more preferably not

more than 30 mm, and the most preferably not more than 10
mm and the thickness of the solution is exposed to the light.
When the polymerization is started, the heat of polymerization
is emitted. The temperature during the polymerization varies
with the method of generating bubbles. Generally, this
temperature is controlled in the range of 20 - 200 °C, preferably
50 - 180 °C, and more preferably 60 - 150 °C.
This invention prefers the volume of the porous polymer
after completion of the polymerization to be 1.1 - 20 times,
preferably 1.3 - 20 times, and particularly preferably 1.5
- 20 times, the volume of the aqueous monomer solution prior
to the polymerization. In the conventional operation of
polymerization reaction performed in a stirred state, the
change of volume due to the addition of bubbles does not reach
1.01 times the original volume. The change of volume exceeding
1.1 times the original volume may well be regarded as resulting
fromintentionallyincorporatingbubbles. Incidentally, the
change in volume of the aqueous monomer solution during the
polymerization can be easily confirmed because it is
manifested as a proportionate change in height of the water
line. If the volume of the water-soluble porous polymer after
completion of the polymerization falls short of 1.1 times
the volume of the aqueous monomer solution at the time of
starting the polymerization, the shortage will possibly
result in degrading the efficiency with which the molecular
weight is increased and the cost of production is lowered
by bubbling. If the volume exceeds 20 times the original
volume, the overage will possibly degrade the efficiency with
which the drying and the disintegrating are effected
proportionately to the bulkiness.
In the case of the thermal polymerization, the time of
starting polymerization is when the heating is started. In

the case of the photopolymerization, the time of starting
polymerization is when the exposure to the light is started.
The time of completing polymerization is when the reaction
of polymerization is completed. In the case of the thermal
polymerization, this is when the heating is discontinued.
In the case of the photopolymerization, this is when the
exposure to light is discontinued.
When the aqueous monomer solution is made to contain
therein bubbles in the form of mousse by the method of (1-1)
mentioned above, generally, the mousse is extruded in a
thickness in the range of 1 - 30 mm and more preferably 1
- 20 mm and the mousse is exposed to a light of an intensity
of 5 - 100 W/m2 and a wavelength of 200 - 600 nm for a period
in the range of 30 seconds - 30 minutes, more pireferably 1
- 20 minutes, and particularly preferably 1 - 15 minutes,
though variable with the content of bubbles. If the thickness
exceeds 30 mm, the overage will result in preventing the light
from reaching the bottom part of the mousse and unduly adding
to the polymerization time. If the intensity of the light
exceeds 100 W/m2 and if the light exposure time exceeds 30
minutes, the overage will possibly result in bringing the
disadvantage of encouraging a cross-linking reaction. When
the aqueous monomer solution supplied in the form of a mousse
is polymerized by the exposure of light, the polymerization
time can be shortened as compared with the thermal
polymerization and the polymerization can be advanced
smoothly in spite of a low polymerization temperature and,
as a result, the retention of bubbles is attained favorably
and the product is obtained in a high concentration.
When the aqueous solution polymerization is applied to
the aqueous monomer solution enabled to contain bubbles by
the method of (1-2) mentioned above, this aqueous solution

is fed in a height in the range of 1 - 20 mm and more preferably
1 - 10 mm and the sheet of the solution is exposed to a light
of an intensity of 5 - 100 W/m2 and a wavelength of 200 -
600 nm for a period in the range of 2 - 30 minutes and more
preferably 2-20 minutes. At this time, the polymerization
temperature is preferably in the range of 20 - 150 °C and more
preferably 30 - 120 °C. If these conditions deviate from the
relevant ranges specified above, the deviation will possibly
result in rendering difficult the adjustment of the volume
of the produced polymer to 1.1 - 20 times the original volume.
When the bubbles are generated in the form of soap bubbles
by the method of (1-3) mentioned above, the mass of bubbles
is extruded in a thickness in the range of 1 - 30 mm and more
preferably 1-20 mm and the extruded sheet of bubbles is
exposed to a light of an intensity of 5 - 100 W/m2 and a wavelength
of 200 - 600 nm for a period in the range of 2 - 30 minutes,
more preferably 2-20 minutes, and particularly preferably
2-15 minutes. If the thickness of the bubbles exceeds 30
mm, the overage will result in preventing the light from
reaching the bottom part and unduly adding to the
polymerization time. If the intensity of the light exceeds
100 W/m2 and if the exposure time exceeds 30 minutes, the overage
will possibly result in inducing vanishment of bubbles.
When the aqueous monomer solution is caused to have air
bubbled dissolved therein by the method of (1-4) mentioned
above, this aqueous monomer solution is extruded in a height
in the range of 1 - 20 mm and more preferably 1 - 10 mm and
the extruded sheet is exposed to a light of an intensity of
5 - 100 W/m2 and a wavelength of 200 - 600 nm for a period
in the range of 2 - 30 minutes and more preferably 2-20
minutes. At this time, the polymerization is performed at
a temperature preferably in the range of 20 - 150 °C and more

preferably 30 - 120 °C. If these conditions deviate from the
relevant ranges specified above, the deviation will possibly
result in rendering difficult the adjustment of the volume
of the resultant polymer to 1.1 - 20 times the original volume.
When the aqueous monomer solution containing a
photopolymerization initiator is caused to have a foaming
agent dissolved or dispersed therein by the method of (II)
mentioned above, this aqueous monomer solution is preferred
to be subjected to photopolymerization under the same
conditions as when the aqueous monomer solution is supplied
in the form of mousse. The aqueous monomer solution prior
to polymerization is supplied in a thickness in the range
of 0.5 - 30 mm, more preferably 1 - 20 mm and particularly
preferably 1-10 mm. As a result, the polymerization by the
exposure to light can be initiated and advanced fully
satisfactorily even when the volume thereof is increased by
bubbling.
In the case of the boiling point polymerization of (III) ,
it is preferred to be performed under the same conditions
as in the case of (II) mentioned above.
For the polymerization reaction, either continuous
polymerization or batch polymerization may be adopted. The
polymerization may be carried out under a reduced pressure,
an increased pressure, or normal pressure. Incidentally, the
polymerization is preferred to be performed in a stream of
such an inert gas as nitrogen, helium, argon, or carbonic
acid gas . When the oxygen concentration in the aqueous monomer
solution is satisfactorily decreased, the polymerization may
be carried out in an atmosphere of air.
(4) Water-soluble porous polymer
The shape of the water-soluble porous polymer obtained
as described above varies with the method of polymerization

used. The polymer may be in any of various shapes such as
particles, a belt, a plate, or a clayish mass. The
water-soluble porous polymer obtained by the method described
above has a weight average molecular weight, determined by
the GPC as reduced to polyacrylic acid, in the range of 1, 000
- 10,000,000, preferably 5,000 - 10,000,000, and more
preferably 5,000 - 8,000,000. Since the polymerization
proceeds in the aqueous monomer solution containing bubbles,
the polymerization is performed uniformly and the polymer
consequently formed has a higher molecular weight then ever.
This polymer has a water-insoluble content of not more than l0
wt.%, more preferably not more than 7 wt.% and the most
preferably not more than 5 wt.%. Thus, the porous polymer
truly excels in water-solubility as compared with the
conventional porous polymer. It is provided that the
"water-insoluble content" is determined by the method which
is described in the working examples cited herein below.
The water-soluble porous polymer mentioned above has
an air bubble content in the range of 2 - 90% and preferably
5 - 80%. Since this polymer has a voids ratio in the range
mentioned above, it enjoys an enhanced water-solubility. The
percentage of voids is determined by photographing the cross
section of the porous polymer by the use of a scanning electron
microscope (made by Hitachi, Ltd. and sold under the product
code of "SEM: S-3500N type") and analyzing the photograph
with an image analyzing device (made by Nippon Shokubai K.K.)
thereby calculating the total area of the bubbles in accordance
with the following formula.
Percentage of voids (%) = 100 x(area of bubbles/total
area analyzed)
The water-soluble porous polymer obtained by the method
described above has viscosity preferably in the range of 0 . 001

- 10 Pa.s, more preferably 0.002 - 5 Pa.s, and particularly
preferably 0.003 - 2 Pa.s. When the viscosity is in the range
specified above, the water-soluble porous polymer can
manifest a truly excellent effect as a flocculant and a
tackifier. The viscosity is the numerical value obtained by
preparing an aqueous 0.2 wt.% solution of the powder and
measuring the solution for viscosity by the use of a B type
viscosimeter at 25 °C. This invention can accomplish the
polymerization in a short time at a low temperature owing
to the photopolymerization and can effect the production of
a water-soluble porous polymer of a high molecular weight
in a short time owing to the incorporation of a chain transfer
agent. While the viscosity of a water-soluble polymer depends
on the molecular weight of the polymer, this invention can
produce a water-soluble porous polymer of high viscosity by
a simple and convenient process.
The water-soluble porous polymer obtained by the
polymerization can be sliced or crushed in its unmodified
state and put to use or can be sliced and crushed and then
dried. Otherwise, it may be dried in advance and then sliced
or crushed.
(5) Drying
The drying temperature to be used for the resultant
hydrated water-soluble porous polymer is not particularly
restricted. When the drying is performed under normal
pressure, the drying temperature is in the range of 50 - 250
°C and more preferably 100 - 200 °C. When the drying is carried
out under a reduced pressure, the drying temperature is
particularly preferably in the range from the boiling point
of water under the reduced pressure to 200 °C. The drying
time is not particularly restricted. Properly it is in the
approximate range of 10 seconds - five hours. The hydrated

water-soluble porous polymer may be treated with an acid or
may be neutralized with a basic substance before it is dried.
Consequently, the water-soluble porous polymer may be
obtained in an acid type or a neutral salt type.
The drying methods usable herein include drying in a
fluidized phase, drying by heating, drying with hot air, drying
under a reduced pressure, drying with an infrared ray, drying
with a microwave, drying in a drum drier, dehydration by the
use of an azeotrope with a hydrophobic organic solvent, and
high-humidity drying by the use of steam of a high temperature,
for example, though not exclusively. Among other drying
methods cited above, the drying in a fluidized phase and drying
with hot air prove particularly advantageous.
The water-soluble porous polymer of this invention is
a porous material as implied by its name. Thus, it abounds
in surface areas for contact with the ambient air and excels
in drying efficiency as compared with a nonporous polymer
and allows a reduction in the drying time.
Further, since this polymer also excels in the cooling
efficiency for the same reason, it can curtail the cooling
time after polymerization or after drying. As a result, the
process which continues till disintegratingand/or crushing
can be performed efficiently.
(6) Disintegrating and/or crushing
The water-soluble porous polymer after drying or
occasionally after polymerization may be disintegrated and/or
crushed by a prescribed method into fragments measuring 10
μm - 1000 mm, preferably lOum - 100 mm, and particularly
preferably lOum - 10 mm. After the water-soluble porous
polymer has been dried by the method described above, it has
a water content of not more than 15 wt.%, more preferably
not more than 10 wt.% and particularly preferably not more

than 5 wt. %. This polymer may be disintegrated and/or crushed
by a disintegrating and/or crushing device which fits the
water content. Particularly, the water-soluble porous
polymer which is obtained by the method of this invention
copiously contains pores formed by the numerous bubbles in
the texture of the polymer and the polymer layer forming these
pores has a small thickness. By the application of the same
power as used when the conventional unfoamed water-soluble
polymer is disintegrated, therefore, this polymer can be
disintegrated or crushed into minuter fragments. The
crushing devices which are usable herein include those of
impact type, compression type, and shear type. As concrete
examples of the crushing device, a cutter mill, a vibration
mill, a roll granulater, a knuckle type crushing device, a
roll mill, a jaw crusher, a planar crusher, a shred crusher,
high-speed rotary crushing devices (pin mill, hammer mill,
screw mill, and roll mill) , and a cylindrical mixer may be
cited.
Incidentally, the water content mentioned above is found
by weighing 1 g of a sample in an aluminum cup, drying the
sample with a hot air drier (made by Tabai K.K.) at 130 °C
for two hours, and calculating the difference in weight of
the sample before and after the drying.
The second aspect of this invention is directed towarda
water-soluble porous polymer obtained by polymerizing an
aqueous monomer solution containing an ethylenically
unsaturated monomer, which polymer has a voids ratio in the
range of 5 - 80% based on the volume of the polymer and a
water-insoluble content of not more than 10 wt.%. The
water-soluble porous polymer of this quality can be produced
by the method according to the first aspect of this invention.
The method for the production of this polymer, however, does

percentage of voids falls short of 5%, the shortage will result
in lessening the effect of enhancing the solubility in water.
If it exceeds 80%, the overage will possibly degrade the
strength of the powder formed by crushing. Incidentally, the
percentage of voids is calculated by the method described
in the preceding section (4) titled "the water-soluble porous
polymer." The term "porous" as used in this invention means
the presence of voids originating in numerous bubbles in the
interior of a resin and the consequent deficiency in apparent
density of the resin. Incidentally, the average diameter
of the pores in the water-soluble porous polymer is variable
with the number of bubbles and the diameters of these bubbles.
It is in the range of 3um - 100 mm, preferably 5um - 50 mm,
and particularly preferably 10pm - 30 mm.
The third aspect of this invention is directed toward
a powdered water-soluble porous polymer obtained by crushing
the water-soluble porous polymer mentioned above. When the
water-soluble polymer is crushed and then dissolved, as
occasional demands, in an aqueous solution, the powder
obtained from the porous material manifests a high solubility
in water. This preference may be explained by a supposition
that since the water-soluble polymer is porous before it is
crushed, the surface area thereof per unit weight is
proportionately exalted by the crushing. Further, the
powdered water-soluble porous polymer allows more addition
to the ease with which the water-soluble porous polymer
mentioned above is prepared in the form of a solution. Thus,
it is handled easily and conveniently when it is used in its
unmodified for an agent for sewage treatment and a thickener
for wallplates, for example. It occurs at times that the
powdered water-soluble porous polymer obtained by crushing
is devoid of a porous texture, depending on the side thereof.

This invention embraces this powdered water-soluble porous
polymer devoid of a porous texture in the range of the powdered
water-soluble porous polymer contemplated by this invention
so long as it has resulted from crushing the aforementioned
water-soluble porous polymer.
The powdered water-soluble porous polymer of this
invention can be prepared by disintegrating or crushing the
aforementioned water-soluble porous polymer into fragments
measuring about 10pm - 10 mm, more preferably about 30um -
5 mm, and particularly preferably about 50um- 3 mm. The extent
of this crushing or disintegrating may be properly selected,
depending on the water content of the water-soluble porous
polymer not yet crushed. When the water content is 10 wt.%,
for example, the aforementioned crushing device may be used.
Particularly, the powdered water-soluble porous polmer which
is obtained by the method of this invention is prepared by
crushing a porous material and, by the application of the
same power as used when the conventional non-porous
water-soluble polymer is disintegrated, can be disintegrated
or crushed into minuter fragments.
The water-soluble porous polymer has a bulk specific
gravity preferably in the range of 0.1 - 1.2 g/ml, more
preferably 0.1 - 1.0 g/ml, and the most preferably 0.1 - 0.7
g/ml. If the bulk specific gravity falls short of 0.1 g/ml,
the shortage will result in unduly increasing impalpable
powder and rendering difficult the handling as a powder.
Conversely, if it exceeds 1.2 g/ml, the overage will result
in degrading the speedof dissolution in water. Incidentally,
the bulk specific gravity is found by accurately weighing
100 ml of a given powdered water-soluble porous polymer and
weighing this sample.
The water-soluble porous polymer and the powdered

water-soluble porous polymer of this invention do not
particularly need to restrict the viscosity which they
manifest when they are dissolved in a solution. The viscosity
is preferably in the range of 0.001 - 10 Pa. s, more preferably
0.002 - 5 Pa.s, and particularly preferably 0.003 - 2 Pa.s.
As stated in the foregoing section (4) titled "water-soluble
porous polymer," the scope is commended because the polymers
having a viscosity falling in this range are capable of
manifesting a truly outstanding effect as a flocculant and
a thickener. Incidentally, the viscosiy is the numerical
value determined by preparing an aqueous 0.2 wt.% solution
of a given powder and measuring the aqueous solution for
viscosity with a B type viscosimeter at 25 °C.
The water-soluble porous polymer and the powdered
water-soluble porous polymer of this invention, when
necessary, may further incorporate therein deodorant, perfume,
dye, hydrophilic short fibers, plasticizer, tackifier,
surfactant, fertilizer, oxidizing agent, reducing agent,
water, and salt so as to endow the water-soluble porous polymer
and the powdered water-soluble porous polymer with various
functions.
The water-soluble porous polymer and the powdered
water-soluble porous polymer which are obtained by this
invention can be advantageously used for such implements for
medical care as laceration dressing agent, contact lens,
artificial muscle, and artificial internal organs, such
breeding articles as plant cultivating materials and
artificial soil cultivating materials, tackifiers, agents
for waste disposal, dispersants, agents for treating
excavated soil, adhesive agents, concrete admixtures,
carriers for immobilizing living organisms, flocculants for
sewage disposal and industrial waste disposal, tackifiers

for wallplates, water-retaining agents for excavation, agents
for stabilizing viscosity of dispersant, water treating
agents, ion sequestering agents, detergent builders, and
ceramic damping agents. They can be made usable as pigments
and coating materials by controlling their granularity and
the shape during the course of crushing.
Now, this invention will be described more specifically
below with reference to working examples and comparative
examples.
Example 1
A vessel made of stainless steel and measuring 10 cm
in inside diameter and 500 ml in inner volume was equipped
with a nitrogen introducing pipe, a gas release pipe, and
a silicone rubber plug fitted with a thermometer. In this
vessel, 2.57 g of purified water, 58.18g of an aqueous 37%
sodium acrylate solution, and 37.7 3 g of acrylic acid were
placed and stirred with a magnetic stirrer and the entrapped
air was thoroughly displaced with nitrogen till the dissolved
oxygen content fell to not more than 0.5 ppm. In this while,
the stainless steel vessel was cooled with ice water to keep
the inner temperature thereof to not higher than 10 °C.
Subsequently, 0.7 6 g of an aqueous 1% sodium hypophosphite
solution, 0.7 6 g of a 1% acrylic acid solution having a
photopolymerization initiator (made by Ciba Specialty
Chemicals K.K. and sold under the trademark designation of
"Irgacure 819") dissolved therein, and 0.50 g of a foaming
agent (made by Matsumoto Yushi Seiyaku K.K. and sold under
the trademark designation of "Matsumoto Microsphere F-36")
were additionally placed and uniformly mixed to obtain a
reaction solution.
This solution was fed within 5 minutes after addition

of the foaming agent into a polymerization vessel made of
polytetrafluoroethylene (sold under the trademark
designation of "Teflon") measuring 200 mm in diameter and
displaced with nitrogen till a thickness of 3 mm and was
irradiated for 3 minutes with an ultraviolet light of an
intensity of 22 W/m2. The peak temperature of the heat
generated by the polymerization was 101 °C. After the
polymerization was completed, a white foam swelled to 1.4
times the volume existing when the polymerization was started
was obtained. The percentage of voids in this foam was 30%.
When this foam was dried with a hot air drier till the water
content fell to not more than 5 wt.%, 140 °C and 10 minutes
were necessary. The foam was further crushed with a bench
mill at 15, 7 00 rpm for 30 seconds to obtain a powder of 8 0-mesh
pass in an amount of 55% of the whole amount. The bulk specific
gravity of this powder was 0.32 g/ml. An aqueous 0.2 wt.%
solution of this powder was prepared and was tested for
viscosity with a B type viscosimeter. The viscosity was found
to be 390 mPa.s. The water-insoluble content of the solution
was 0. 2 wt. % . An aqueous 0.1 wt. % solution of the powder was
prepared and determined concentration of acrylic acid in the
solution by liquid chromatography and calculated a residual
acrylic acid content in the powder. This content was found
to be 700 ppm.

Incidentally, the percentage of voids was found by
photographing the cross section of a given porous material
by using a scanning type electron microscope (made by Hitachi,
Ltd. and sold under the trademark designation of "SEM: S-3500N
type"), calculating the total surface area of bubbles from
the photograph with an image analyzing device (made by Nippon

Shokubai K.K.), and calculating the percentage of voids in
accordance with the following formula.
Percentage of voids (%) = 100 * (area of bubbles/total
area analyzed)

Then, the water-insoluble content was found by
accurately weighing 0.80 g as solids of a sample, dissolving
the sample in deionized water to a total amount of 400.0 g
thereby preparing a 0.20 wt.% sample solution, passing the
sample solution through a 250-um sieve (JIS {Japanese
Industrial Standard} Z 8801-1953) thereby withdrawing an
insoluble substance of a hydrated state, and calculating the
water-insoluble content in accordance with the following
formula.
Insoluble content (wt.%) = 100 * (weight of insoluble
substance (g)/400 (g) )
Example 2
A vessel made of stainless steel and measuring 10 cm
in inside diameter and 500 ml in inner volume was equipped
with a nitrogen introducing pipe, an air release pipe, a
thermometer, and a silicone rubber plug fitted with a pump
typenozzleadaptedtoproducebubbles. In this vessel, 122.68
gof anaqueous 0.1 wt .%poly (sodiumacrylate) solution, 135.75
g of an aqueous 37% sodiumacrylate solution, 88. 01 gof acrylic
acid, and 4.2 g of sorbitan monostearate (made by Kao
Corporation and sold under the trademark designation of
"Rheodol SP-S10") were placed and stirred with a magnetic
stirrer and the entrapped air was thoroughly displaced with
nitrogen till the dissolved oxygen content fell to not more
than 0.5 ppm. At this time, the stainless steel vessel was

cooled with ice water to keep the inner temperature thereof
to not higher than 10 °C. Subsequently, 1.78 g of an aqueous
1% sodium hypophosphite solution and 1.78 g of a 1% acrylic
acid solution having a photopolymerization initiator (made
by Ciba Specialty Chemicals K.K. and sold under the trademark
designation of "Darocur 1173") dissolved therein were
additionally placed and uniformly mixed to obtain a reaction
solution. This solution was fed via the pump type nozzle in
the form of mousse into a polymerization vessel made of Teflon
measuring 200 mm in diameter and displaced with nitrogen till
a thickness of 10 mm and was immediately irradiated for 10
minutes with an ultraviolet light of an intensity of 22 W/m2.
The peak temperature of the heat generated by the
polymerization was 92 °C. After the polymerization was
completed, a white mousse-like foam was obtained. The
percentage of voids in this foam was 21%. When this foam was
coarsely crushed with a meat chopper (made by Masuko K.K.)
and dried with a hot air drier till the water content fell
to not more than 5 wt.%, 140 °C and 15 minutes were necessary.
The dried foam was further crushed with a bench mill at 15, 700
rpm for 30 seconds to obtain a powder of 80-mesh pass in an
amount of 28% of the whole amount. The bulk specific gravity
of this powder was 0.41 g/ml. An aqueous 0.2 wt.% solution
of this powder was prepared and was tested for viscosity with
a B type viscosimeter. The viscosity was found to be 4 90 mPa. s.
The water-insoluble content of the solution was 0.2 wt.%.
An aqueous 0.1 wt.% solution of the powder was prepared and
determined concentration of acrylic acid in the solution by
liquid chromatography and calculated a residual acrylic acid
content in the powder. This content was found to be 1,700
ppm.

Example 3
A vessel made of stainless steel and measuring 10 cm
in inside diameter and 500 ml in inner volume was equipped
with a nitrogen introducing pipe, an air release pipe, and
a silicone rubber plug fitted with a thermometer. In this
vessel, 67.60 g of acrylic acid was placed and stirred with
a magnetic stirrer and the entrapped air was thoroughly
displaced with nitrogen till the dissolved oxygen content
fell to not more than 0.5 ppm. At this time, the stainless
steel vessel was cooled with ice water to keep the inner
temperature thereof to not higher than 10 °C. Subsequently,
0.94 g of an aqueous 1% sodium hypophosphite solution and
0.94 g of a 1% acrylic acid solution having a
photopolymerization initiator (made by Ciba Specialty
Chemicals K.K. and sold under the trademark designation of
"Darocur 1173") dissolved therein were additionally placed
and uniformly mixed to obtain a reaction solution. Separately,
a solution having 14.93 g of sodium carbonate dissolved in
48.25 g of purified water was prepared and displaced similarly
with nitrogen. These solutions were uniformly mixed and
immediately fed into a polymerization vessel made of Teflon
and measuring 200 mm in diameter and displaced with nitrogen
till a thickness of 3.5 mm and was irradiated for 15 minutes
with an ultraviolet light having an intensity of 22 w/m2. The
peak temperature of the heat generated by the polymerization
was 108 °C. After the polymerization was completed, a white
foam swelled to 1.7 times the volume existing when the
polymerization was started was obtained. The percentage of
voids in this foam was 41%.
When this foam was dried with a hot air drier till the
water content fell to not more than 5 wt.%, 140 °C and 10 minutes
were necessary. The foam was further crushed with a bench

mill at 15,700 rpm for 30 seconds to obtain a powder of 80-mesh
pass in an amount of 39% of the whole amount. The bulk specific
gravity of this powder was 0.38 g/ml. An aqueous 0.2 wt.%
solution of this powder was prepared and was tested for
viscosity with a B type viscosimeter. The viscosity was found
to be 390 mPa. s. The water-insoluble content of the solution
was 0. 3 wt. % . An aqueous 0.1 wt. % solution of the powder was
prepared and determined concentration of acrylic acid in the
solution by liquid chromatography and calculated a residual
acrylic acid content in the powdered. This content was found
to be 1,900 ppm.
Comparative Example 1
A vessel made of stainless steel and measuring 10 cm
in inside diameter and 500 ml in inner volume was equipped
with a nitrogen introducing pipe, an air release pipe, and
a silicone rubber plug fitted with a thermometer. In this
vessel, 122.68 g of purified water, 135.75 g of an aqueous
37% sodium acrylate solution, and 88.01 g of acrylic acid
were placed and stirred with a magnetic stirrer and the
entrapped air was thoroughly displaced with nitrogen till
the dissolved oxygen content fell to not more than 0.5 ppm.
At this time, the stainless steel vessel was cooled with ice
water to keep the inner temperature thereof to not higher
than 10 °C. Subsequently, 1.78 g of an aqueous 1% sodium
hypophosphite solution and 1. 78 g of a 1% acrylic acid solution
having a photopolymerization initiator (made by Ciba
Specialty Chemicals K.K. and sold under the trademark
designation of "Darocur 1173") dissolved therein were
additionally placed and uniformly mixed to obtain a reaction
solution. This solution was transferred via a Teflon tube
into a polymerization vessel made of Teflon and measuring

200 mm in diameter and displaced with nitrogen till a thickness
of 10 mm and was irradiated for 30 minutes with an ultraviolet
light of an intensity of 22 W/m2. The peak temperature of
the heat generated by the polymerization was 88 °C. After
the polymerization was completed, about 350 g of a colorless
transparent gel was obtained. The percentage of voids in this
foam was 0.1%. When this gel was coarsely crushed with a meat
chopper (made by Masuko K.K.) and was dried with a hot air
drier till the water content fell to not more than 5 wt.%,
140 °C and 90 minutes were necessary. When it was not coarsely
crushed with the meat chopper, 140 °C and 180 minutes were
necessary for drying it till the water content fell to not
more than 5 wt.%. The dried gel was further crushed with a
bench mill at 15,700 rpm for 30 seconds to obtain a powder
of 80-mesh pass in an amount of 5% of the whole amount. The
bulk specific gravity of this powder was 0.91 g/ml. An aqueous
0.2 wt.% solution of this powder was prepared and was tested
for viscosity with a B type viscosimeter. The viscosity was
found to be 4 90 mPa.s. The water-insoluble content of the
solution was 0.2 wt.%. An aqueous 0.1 wt.% solution of the
powder was prepared and determined concentration of acrylic
acid in the solution by liquid chromatography and calculated
a residual acrylic acid content in the powder. This content
was found to be 4,500 ppm.
Example 4
A vessel made of stainless steel and measuring 10 cm
in inside diameter and 500 ml in inner volume was equipped
with a nitrogen introducing pipe, an air release pipe, and
a silicone rubber plug fitted with a thermometer. In this
vessel, 122.68 g of purified water, 135.75 g of an aqueous
37% sodium acrylate solution, and 88.01 g of acrylic acid

were placed and stirred with a magnetic stirrer and the
entrapped air was thoroughly displaced with nitrogen till
the dissolved oxygen content fell to not more than 0.5 ppm.
At this time, the stainless steel vessel was cooled with ice
water to keep the inner temperature thereof to not higher
than 10 °C. Subsequently, 1.78 g of an aqueous 1% sodium
hypophosphite solution and 1.78 g of a 1% acrylic acid solution
having a photopolymerization initiator (made by Ciba
Specialty Chemicals K.K. and sold under the trademark
designation of "Darocur 1173") dissolved therein were
additionally placed and uniformly mixed to obtain a reaction
solution. This solution was fed into a polymerization vessel
made of Teflon and measuring 200 mm in diameter and displaced
with nitrogen till a thickness of 10 mm and the resultant
mixture was foamed by starting nitrogen bubbling and
irradiated with an ultraviolet light of an intensity of 22
W/m2 for 20 minutes. The peak temperature of the heat generated
by the polymerization was 85 °C.
After the polymerization was completed, a white gel
containing countless minute bubbles was obtained. When this
gel was tested for percentage of voids, the percentage of
voids was found to be 17%. When this gel was coarsely crushed
with a meat chopper (made by Masuko K.K.) and dried with a
hot air drier till the water content fell to not more than
5 wt.%, 140 °C and 40 minutes were necessary. The dried gel
was further crushed with a bench mill at 15,700 rpm for 30
seconds to obtain a powder of 80-mesh pass in an amount of
28% of the whole amount. The bulk specific gravity of this
powder was 0.59 g/ml. An aqueous 0.2 wt.% solution of this
gel was prepared and was tested for viscosity with a B type
viscosimeter. The viscosity was found to be 4 60 mPa.s. The
water-insoluble content of the solution was 0.1 wt.%. An

aqueous 0.1 wt.% solution of the powder was prepared and
determined concentration of acrylic acid in the solution by
liquid chromatography and calculated a residual acrylic acid
content in the powder. This content was found to be 3,800
ppm.
Example 5
A vessel made of stainless steel and measuring 10 cm
in inside diameter and 500 ml in inner volume was equipped
with a nitrogen introducing pipe, an air release pipe, and
a silicone rubber plug fitted with a thermometer. In this
vessel, 2.57 g of purified water, 58.18g of an aqueous 37%
sodium acrylate solution, and 37.73 g of acrylic acid were
placed and stirred with a magnetic stirrer and the entrapped
air was thoroughly displaced with nitroten till the dissolved
oxygen content fell to not more than 0.5 ppm. At this time,
the stainless steel vessel was cooled with ice water to keep
the inner temperature thereof to not higher than 10 °C.
Subsequently, 0.7 6 g of an aqueous 1% sodium hypophosphite
solution and 0.76 g of a 1% acrylic acid solution having a
photopolymerization initiator (made by Ciba Specialty
Chemicals K.K. and sold under the trademark designation of
"Irgacure 819") dissolved therein were additionally placed
and uniformly mixed to obtain a reaction solution. This
solution was fed into a polymerization vessel made of Teflon
and measuring 200 mm in diameter and displaced with nitrogen
till a thickness of 3 mm and was irradiated for 10 minutes
with an ultraviolet light of an intensity of 30 W/m2. The
peak temperature of the heat generated by the polymerization
was 100 °C. After the polymerization was completed, a white
foam swelled to 1.3 times the volume existing when the
polymerization was started was obtained. The percentage of

voids in this foam was 29%. When this foam was dried with
a hot air drier till the water content fell to not more than
5 wt.%, 140 °C and 40 minutes were necessary. The foam was
further crushed with a bench mill at 15, 700 rpm for 30 seconds
to obtain a powder of 80-mesh pass in an amount of 24% of
the whole amount. The bulk specific gravity of this powder
was 0.4 9 g/ml. An aqueous 0.2 wt.% solution of this powder
was prepared and was tested for viscosity with a B type
viscosimeter. The viscosity was found to be 350 mPa.s. The
water-insoluble content of the solution was 1.2 wt.%. An
aqueous 0.1 wt.% solution of the powder was prepared and
determined concentration of acrylic acid in the solution by
liquid chromatography and calculated a residual acrylic acid
content in the powder. This content was found to be 5,600
ppm.
Example 6
An autoclave made of stainless steel and measuring 10
cm in inside diameter and 800 ml in inner volume was equipped
with a nitrogen introducing pipe, an air release pipe, a
thermometer, stirring vanes, and a pressure gauge. In this
autoclave, 122.68 g of purified water, 135.75 of an aqueous
37% sodium acrylate solution, and 88.01 g of acrylic acid
were placed and stirred and the entrapped air was thoroughly
displaced with nitrogen till the dissolved oxygen content
fell to not more than 0.5 ppm. At this time, the stainless
steel autoclave was cooled with ice water to keep the inner
temperature thereof to not higher than 10°C. Subsequently,
1.78 g of an aqueous 1% sodium hypophosphite solution and
1.78 g of a 1% acrylic acid solution having a
photopolymerization initiator (made by Ciba Specialty
Chemicals K.K. and sold under the trademark designation of

"Darocur 1173") dissolved therein were additionally placed
and uniformly mixed to obtain a reaction solution. The system
interior was sealed, made to introduce nitrogen till the inner
pressure rose to 3 MPa, and retained in the ensuant state
for five minutes to allow dissolution of nitrogen into the
liquid phase therein. The autoclave was relieved of the
pressure and, at the same time, the solution was fed into
a polymerization vessel made of Teflon and measuring 200 mm
in diameter and displaced with nitrogen till a thickness of
10 mm and was irradiated for 20 minutes with an ultraviolet
light of an intensity of 22 W/m2. The peak temperature of
the heat generated by the polymerization was 94 °C. After
the polymerization was completed, a gel containing countless
minute bubbles was obtained. The percentage of voids in this
foam was 20%. When this gel was coarsely crushed with a meat
chopper (made by Masuko K.K.) and dried with a hot air drier
till the water content fell to not more than 5 wt.%, 140 °C
and 35 minutes were necessary. The dried gel was further
crushed with a bench mill at 15,700 rpm for 30 seconds to
obtain a powder of 80-mesh pass in an amount of 48% of the
whole amount. The bulk specific gravity of this powder was
0.49 g/ml. An aqueous 0.2 wt.% solution of this powder was
prepared and was tested for viscosity with a B type viscosimeter.
The viscosity was found to be 410 mPa. s . The water-insoluble
content of the solution was 0.7 wt.%. An aqueous 0.1 wt.%
solution of the powder was prepared and determined
concentration of acrylic acid in the solution by liquid
chromatography and calculated a residual acrylic acid content
in the powder. This content was found to be 3,100 ppm.
Example 7
A vessel made of stainless steel and measuring 10 cm

in inside diameter and 500 ml in inner volume was equipped
with a nitrogen introducing pipe, an air release pipe, and
a silicone rubber plug fitted with a thermometer. In this
vessel, 19.77 g of purified water, 12.26 g of an aqueous 37%
sodium acrylate solution, 27.11 g of acrylic acid, and 9.91
g of 2-acrylamide-2-methylpropane sulfonic acid were placed
and stirred with a magnetic stirrer and the entrapped air
was thoroughly displaced with nitrogen till the dissolved
oxygen content fell to not more than 0.5 ppm. Subsequently,
0.48 g of an aqueous 1% sodium hypophosphite solution and
0.48 g of a 1% acrylic acid solution having a
photopolymerization initiator (made by Ciba Specialty
Chemicals K.K. and sold under the trademark designation of
"Irgacure 819") dissolved therein and 0. lg of a foaming agent
(made by Matsumoto Yushi Seiyaku K.K and sold under the
trademark designation of "Matsumoto Microsphere F-36") were
additionally placed and uniformly mixed to obtain a reaction
solution. This solution was fed within 5 minutes after addition
of the foaming agent into a polymerization vessel made of
Teflon, measuring 200 mm in diameter, and displaced with
nitrogen till a thickness of 2 mm and was irradiated for 5
minutes with an ultraviolet light of an intensity of 22 W/m2.
The peak temperature of the heat generated by the
polymerization was 94 °C. After the polymerization was
completed, a white foam swelled to 1. 5 times the volume existing
when the polymerization was started was obtained. The
percentage of voids in this foam was 33%. When this foam was
dried with a hot air drier till the water content fell to
not more than 5 wt.%, 140 °C and 10 minutes were necessary.
The foam was further crushed with a bench mill at 15,700 rpm
for 30 seconds to obtain a powder of 80-mesh pass in an amount
of 48% of the whole amount. The bulk specific gravity of this

powder was 0.37 g/ml. An aqueous 0.2 wt. % solution of this
powder was prepared and was tested for viscosity with a B
type viscosimeter. The viscosity was found to be 110 mPa . s .
The water-insoluble content of the solution was 0.2 wt.%.
An aqueous 0.1 wt. % solution of the powder was prepared and
determined concentrations of acrylic acid and
2-acryliamide-2-methylpropane sulfonic acid by liquid
chromatography and calculated a residual acrylic acid and
2-acrylamice-2-methylpropane sulfonic acid contents in the
powder. This contents were found to be 2,100 ppm and 4,000
ppm respectively.
Example 8
A vessel made of stainless steel and measuring 10 cm
in inside diameter and 500 ml in inner volume was equipped
with a nitrogen introducing pipe, an air release pipe, and
a silicone rubber plug fitted with a thermometer. In this
vessel, 2.37 g of purified water, 153.04 g of an aqueous 37%
sodium acrylate solution, and 42.18 g of acrylic acid were
placed and stirred with a magnetic stirrer and the entrapped
air was thoroughly displaced with nitrogen till the dissolved
oxygen content fell to less than 0.5 ppm. At this time, the
stainless steel vessel was cooled with ice water to keep the
inner temperature thereof to not higher than 10 °C.
Subsequently, 1.20 g of an aqueous 1% sodium hypophosphite
solution, 1.20 g of a 1% acrylic acid solution having a
photopolymerization initiator (made by Ciba Specialty
Chemicals K.K. and sold under the trademark designation of
"Darocur 1173") dissolved therein, and 0.50 g of a foaming
agent (made by Matsumoto Yushi Seiyaku K.K. and sold under
the trademark designation of "Matsumoto Microsphere F-36")
were additionally placed and uniformly mixed to obtain a

reaction solution. This solution was fed within 5 minutes
after addition of the foaming agent into a polymerization
vessel made of Teflon, measuring 200 mm in diameter, and
displaced with nitrogen till a thickness of 5 mm and was
irradiated for 5 minutes with an ultraviolet light of an
intensity of 40 W/m2. The peak temperature of the heat
generated by the polymerization was 108 °C. After the
polymerization was completed, a white foam swelled to 1.6
times the volume existing when the polymerization was started
was obtained. The percentage of voids in this foam was 36%.
When this foam was dried with a hot air drier till the water
content fell to not more than 5 wt.%, 140 °C and 8 minutes
were necessary. The foam was further crushed with a bench
mill at 15, 700 rpm for 30 seconds to obtain a powder of 80-mesh
pass in an amount of 61% of the whole amount. The bulk specific
gravity of this powder was 0.32 g/ml. An aqueous 0.2 wt.%
solution of this powder was prepared and was tested for
viscosity with a B type viscosimeter. The viscosity was found
to be 550 mPa. s. The water-insoluble content of the solution
was 0 . 6 wt. % . An aqueous 0 .1 wt. % solution of the powder was
prepared and determined concentration of acrylic acid in the
solution by liquid chromatography and calculated a residual
acrylic acid content in the powder. This content was found
to be 5,100 ppm.
Example 9
In a mixing device provided with beater type stirring
vanes, 100 wt. parts of soil for evaluation (evaluation value:
1) was placed and stirred at 160 rpm and 0.20 wt.part of the
powdered water-soluble porous polymer obtained in Example
1 was added thereto and stirred together for 150 seconds.
The resultant mixture and 5 wt. parts of Portland cement

(hydraulic substance made by Taiheiyo Cement K.K.) added
thereto were further stirred for 20 seconds to treat the soil
for evaluation. The conditions of the evaluation soil
resulting from the treatment were evaluated in accordance
with the standards shown in the following table. The
evaluation value was 6.

Samples winning evaluation values of 4 or over were passed
This was a hydrated soil formed by thoroughly mixing
5 wt. parts of Toyoura standard sand, 7 5 wt. parts of silt,
270 wt. parts of clay, and 350 wt. parts of tap water. The
flow value of this evaluation soil was 250 mm


and samples winning evaluation values of 3 or less were rejected.
The samples winning evaluation values of 4 and 5 were fully
granulated to permit easy transportation on trucks.
Depending on places of use, they were usable as refilling
materials. The samples winning evaluation value of 6 were
usable satisfactorily for soil refilling materials.

The flow value of a soil for evaluation was found by
placing a hollow cylinder measuring 55 mm in inside diameter
and 55 mm in height on a table, filling the cylinder with
the soil, lifting the cylinder vertically and consequently
allowing the soil to spread on the table, measuring the diameter
of the spread soil in two directions, and averaging these
two diameters.
Example 10
In a mixing device provided with beater type stirring
vanes, 100 wt. parts of a given soil for evaluation (evaluation
value: 1) was placed and stirred at 160 rpm and 0.18 wt. part
of the powdered water-soluble porous polymer obtained in
Example 7 was added thereto and stirred together for 120 seconds.
The resultant mixture and 5 wt. parts of portland cement
(hydraulic substance made by Taiheiyo Cement K.K.) added
thereto were stirred together for 20 seconds to treat the
soil. The conditions of the soild after the treatment were
evaluated in accordance with the standard shown in the
preceding table. The evaluation value was 6.
Example 11
A vessel made of stainless steel and measuring 10 cm
in inside diameter and 500 ml in inner volume was equipped

with a nitrogen introducing pipe, an air release pipe, and
a silicone rubber plug fitted with a thermometer. In this
vessel, 7.12 g of purified water, 38.54 g of an aqueous 37%
sodium acrylate solution, 85.21 g of acrylic acid, 31.16 g
of 2-acrylamide-2-methylpropane sulfonic acid, and 0.66 g
of a dispersant (made by Kao Corporation and sold under the
trademark designation of "Rheodol SP-S10V") were placed and
stirred with a magnetic stirrer and the entrapped air was
thoroughly displaced with nitrogen till the dissolved oxygen
content fell to not more than 0.5 ppm. Subsequently, 1.51
g of an aqueous 1% sodium hypophosphite solution, 1.51 g of
a 1% acrylic acid solution having a photopolymerization
initiator (made by Ciba Specialty Chemicals K.K. and sold
under the trademark designation of "Irgacure 819") dissolved
therein, and 0.50 g of a foaming agent (made by Matsumoto
Yushi Seiyaku K.K. and sold under the trademark designation
of "Matsumoto Microsphere F-36") were additionally placed
and uniformly mixed to obtain a reaction solution.
This solution was fed into a polymerization vessel made
of Teflon measuring 200 mm in diameter and displaced with
nitrogen till a thickness of 5 mm and was irradiated for 4
minutes with an ultraviolet light of an intensity of 22 W/
m2. The peak temperature of the heat generated by the
polymerization was 106 °C. After the polymerization was
completed, a white foam swelled to 1. 3 times the volume existing
when the polymerization was started was obtained. The
percentage of voids in this foam was 23%. The water content
of this foam was 8%. When this foam in its undried state was
crushed with a bench mill at 15,700 rpm for 30 seconds to
obtain a powder of 80-mesh pass in an amount of 47% of the
whole amount. The bulk specific gravity of this powder was
0.38 g/ml. An aqueous 0.2 wt. % solution of this powder was

prepared and was tested for viscosity with a B type viscosimeter.
The viscosity was found to be 7 6 mPa.s. The water-insoluble
content of the solution was 0.1 wt.%. An aqueous 0.1 wt.%
solution of the powder was prepared and determined
concentrations of acrylic acid and
2-acryliamide-2-methylpropane sulfonic acid by liquid
chromatography and calculated a residual acrylic acid content
and a residual 2-acrylamide-6-methylpropane sulfonic acid
content in the powder. The contents were respectively found
to be 4,000 ppm and 2,100 ppm.
Example 12
A vessel made of stainless steel and measuring 10 cm
in inside diameter and 500 ml in inner volume was equipped
with a nitrogen introducing pipe, an air release pipe, and
a silicone rubber plug fitted with a thermometer. In this
vessel, 16.99 g of purified water, 36.13 g of an aqueous 37%
sodium acrylate solution, 79.88 g of acrylic acid, 29.21 g
of 2-acrylamide-2-methylpropane sulfonic acid, and 0.62 g
of a dispersant (made by Kao Corporation and sold under the
trademarak designation of "Rheodol SP-S10V") were placed and
stirred with a magnetic stirrer and the entrapped air was
thoroughly displaced with nitrogen till the dissolved oxygen
content fell to not more than 0.5 ppm. Subsequently, 1.41
g of an aqueous 1% sodium hypophosphite solution, 1.41 g of
a 1% acrylic acid solution having a photopolymerization
initiator (made by Ciba Specialty Chemicals K.K. and sold
under the trademark designation of "Irgacure 819") dissolved
therein, and 0.50 g of a foaming agent (made by Matsumoto
Yushi Seiyaku K.K. and sold under the trademark designation
of "Matsumoto Microsphere F-36") were additionally placed
and uniformly mixed to obtain a reaction solution.

This solution was fed into a polymerization vessel made
of Teflon, measuring 200 mm in diameter, and displaced with
nitrogen till a thickness of 5 mm and was irradiated for 5
minutes with an ultraviolet light of an intensity of 22 W/m2.
The peak temperature of the heat generated by the
polymerization was 104 °C. After the polymerization was
completed, a white foam swelled to 1. 3 times the volume existing
when the polymerization was started was obtained. The
percentage of voids in this foam was 21%. The water content
of the foam was 13%. When this foam in an undried state was
crushed with a bench mill at 15,700 rpm for 30 seconds to
obtain a powder of 80-mesh pass in an amount of 41% of the
whole amount. The bulk specific gravity of this powder was
0.3 9 g/ml. An aqueous 0.2 wt. % solution of this powder was
prepared and was tested for viscosity with a B type viscosimeter.
The viscosity was found to be 106 mPa. s . The water-insoluble
content of the solution was 0.7 wt.%. An aqueous 0.1 wt.%
solution of the powder was prepared and determined
concentrations of acrylic acid and
2-acryliamide-2-methylpropane sulfonic acid in the solution
by liquid chromatography and calculated a residual acrylic
acid content and a residual 2-acrylamide-2-methylproppane
sulfonic acid content in the powder. These contents were
respectively found to be 12,000 ppm and 7,300 ppm.
Example 13
A vessel made of stainless steel and measuring 10 cm
in inside diameter and 500 ml in inner volume was equipped
with a nitrogen introducing pipe, an air release pipe, and
a silicone rubber plug fitted with a thermometer. In this
vessel, 53.71 g of purified water, 67.44 g of an aqueous 37%
sodium acrylate solution, 149.11 g of acrylic acid, 54.52

g of 2-acrylamide-2-methylpropane sulfonic acid, 1.16 g of
a dispersant (made by Kao Corporation and sold under the
trademark designation of "Rheodol SP-S10V"), and 0.99 g of
a foaming agent (made by Matsumoto Yushi Seiyaku K.K. and
sold under the trademark designation of "Matsumoto Micosphere
F-36") were placed and stirred with a magnetic stirrer and
the entrapped air was thoroughly displaced with nitrogen at
room temperature till the dissolved oxygen content fell to
not more than 0.5 ppm. Subsequently, 2. 63 g of an aqueous
1% sodium hypophosphite solution and 2.63 g of a 1% acrylic
acid solution having a photopolymerization initiator (made
by Ciba Specialty Chemicals K.K. and sold under the trademark
designation of "Irgacure 819") dissolved therein were
additionally placed and uniformly mixed to obtain a reaction
solution.
This solution was fed into a polymerization vessel made
of Teflon, measuring 200 mm in diameter, and displaced with
nitrogen till a thickness of 10 mm and was irradiated for
10 minutes with an ultraviolet light of an intensity of 22
W/m2. The peak temperature of the heat generated by the
polymerization was 106 °C. After the polymerization was
completed, a white foam swelled to 1. 4 times the volume existing
when the polymerization was started was obtained. The
percentage of voids in this foam was 30%. When this foam in
an undried state was crushed with a bench mill at 15,700 rpm
for 30 seconds to obtain a powder of 80-mesh pass in an amount
of 55% of the whole amount. The bulk specific gravity of this
powder was 0.39 g/ml. An aqueous 0.2 wt. % solution of this
powder was prepared and was tested for viscosity with a B
type viscosimeter. The viscosity was found to be 121 mPa.s.
The water-insoluble content of the solution was 0.9 wt.%.
An aqueous 0.1 wt.% solution of the powder was prepared and

determined concentrations of acrylic acid and
2-acryliamide-2-methylpropane sulfonic acid in the solution
by liquid chromatography and calculated a residual acrylic
acid content and a residual 2-acrylamide-2-methylpropane
sulfonic acid content in the powder. These contents were
respectively found to be 13,000 ppm and 5,900 ppm
Example 14
A vessel made of stainless steel and measuring 10 cm
in inside diameter and 500 ml in inner volume was equipped
with a nitrogen introducing pipe, an air release pipe, and
a silicone rubber plug fitted with a thermometer. In this
vessel, 16.99 g of purified water, 36.13 g of an aqueous 37%
sodium acrylate solution, 78.88 g of acrylic acid, 29.21 g
of 2-acrylamide-2-methylproppane sulfonic acid, and 0.62 g
of a dispersant (made by Kao Incorporation and sold under
the trademark designation of "Rheodol SP-S10V) were placed
and stirred with a magnetic stirrer and the entrapped air
was thoroughly displaced with nitrogen till the dissolved
oxygen content fell to not more than 0.5 ppm. Subsequently,
1.41 g of an aqueous 1% sodium hypophosphite solution, 1.41
g of a 1% acrylic acid solution having a photopolymerization
initiator (made by Ciba Specialty Chemicals K.K. and sold
under the trademark designation of "Irgacure 819") dissolved
therein, and 0.50 g of a foaming agent (made by Matsumoto
Yushi Seiyaku K.K. Aand sold under the trademark designation
of "Matsumoto Microsphere F-36") were additionally placed
and uniformly mixed to obtain a reaction solution.
This solution was fed into a polymerization vessel made
of Teflon measuring 200 mm in diameter till a thickness of
5 mm and was irradiated for 5 minutes with an ultraviolet
light of an intensity of 22 W/m2. The peak temperature of

the heat generated by the polymerization was 98 °C. After
the polymerization was completed, a white foam swelled to
1.3 times the volume existing when the polymerization was
started was obtained. The percentage of voids in this foam
was 20%. The water content of this foam was 13%. When this
foam in its undried state was crushed with a bench mill at
15,700 rpm for 30 seconds to obtain a powder of 80-mesh pass
in an amount of 39% of the whole amount. The bulk specific
gravity of this powder was 0.39 g/ml. An aqueous 0.2 wt.%
solution of this powder was prepared and was tested for
viscosity with a B type viscosimeter. The viscosity was found
to be 100 mPa. s. The water-insoluble content of the solution
was 0 . 5 wt. % . An aqueous 0.1 wt. % solution of the powder was
prepared and determined concentrations of acrylic acid and
2-acryliamide-2-methylpropane sulfonic acid in the solution
by liquid chromatography and calculated a residual acrylic
acid content and a residual 2-acrylamide-2-methylpropane
sulfonic acid content in the powder. These contents were
respectively found to be 19,000 ppm and 9,000 ppm.
Example 15
A vessel made of stainless steel and measuring 10 cm
in inside diameter and 500 ml in inner volume was equipped
with a nitrogen introducing pipe, an air release pipe, and
a silicone rubber plug fitted with a thermometer. In this
vessel, 8.92 g of purified water, 88.64 g of an aqueous 37%
sodium acrylate solution, 53.14 g of acrylic acid , 12.01
g of 2-acrylamide-2-methylpropane sulfonic acid, and 0.50
g of a dispersant (made by Kao Corporations and sold under
the trademark designation of "Rheodol SP-S10V") were placed
and stirred with a magnetic stirrer and the entrapped air
was thoroughly displaced with nitrogen till the dissolved

oxygen content fell to not more than 0.5 ppm. Subsequently,
1.16 g of an aqueous 1% sodium hypophosphite solution, 1.16
g of a 1% acrylic acid solution having a photopolymerization
initiator (made by Ciba Specialty Chemicals K.K. and sold
under the trademark designation of "Irgacure 819") dissolved
therein, and 0.50 g of a foaming agent (made by Matsumoto
Yushi Seiyaku K.K. and sold under the trademark designation
of "Matsumoto Microsphere F-36") were additionally placed
and uniformly mixed to obtain a reaction solution.
This solution was fed into a polymerization vessel made
of Teflon and measuring 200 mm in diameter in an atmosphere
of air till a thickness of 5 mm and was irradiated for 5 minutes
with an ultraviolet light of an intensity of 22 W/m2. The
peak temperature of the heat generated by the polymerization
was 101 °C. After the polymerization was completed, a white
foam swelled to 1.4 times the volume existing when the
polymerization was started was obtained . The percentage of
voids in this foam was 27%. When this foam was dried with
a hot air drier till the water content fell to not more than
5 wt.%, 140 °C and 8 minutes were necessary. The foam was
further crushed with a bench mill at 15, 700 rpm for 30 seconds
to obtain a powder of 80-mesh pass in an amount of 53% of
the whole amount. The bulk specific gravity of this powder
was 0 . 37 g/ml. An aqueous 0.2 wt. % solution of this foam was
prepared and was tested for viscosity with a B type viscosimeter.
The viscosity was found to be 510 mPa. s . The water-insoluble
content of the solution was 0.2 wt.%. An aqueous 0.1 wt.%
solution of the foam was prepared and determined
concentrations of acrylic acid and
2-acryliamide-2-methylpropane sulfonic acid in the solution
by liquid chromatography and calculated a residual acrylic
acid content and a residual 2-acrylamide-2-methylpropane

sulfonic acid content in the powder. These contents were
respectively found to be 9,300 ppm and 4,700 ppm.
Example 16
A vessel made of stainless steel and measuring 10 cm
in inside diameter and 500 ml in inner volume was equipped
with a nitrogen introducing pipe, an air release pipe, and
a silicone rubber plug fitted with a thermometer. In this
vessel, 5.42 g of purified water, 57.98 g of an aqueous 48%
sodium hydroxide solution, 98.82 g of acrylic acid, and 1.16
g of a dispersant (made by Kao Corporations and sold under
the trademark designation of "Rheodol SP-S10V") were placed
and stirred with a magnetic stirrer and the entrapped air
was thoroughly displaced with nitrogen at room temperature
till the dissolved oxygen content fell to not more than 0.5
ppm. Subsequently, 1.39 g of an aqueous 1% sodium
hypophosphite solution, 1.39 g of a 1% acrylic acid solution
having a photopolymerization initiator (made by Ciba
Specialty Chemicals K.K. and sold under the trademark
designation of "Darocur 1173") dissolved therein, and 0.17
g of a foaming agent (made by Matsumoto Yushi Seiyaku K.K.
and sold under the trademark designation of "Matsumoto
Microsphere F-36") were additionally placed and uniformly
mixed to obtain a reaction solution.
This solution was fed into a polymerization vessel made
of Teflon, measuring 200 mm in diameter, and displaced with
nitrogen till a thickness of 5 mm and was irradiated for 5
minutes with an ultraviolet light of an intensity of 22 W/m2.
The peak temperature of the heat generated by the
polymerization was 108 °C. After the polymerization was
completed, a white foam swelled to 1. 5 times the volume existing
when the polymerization was started was obtained. The

percentage of voids in this foam was 31%. The water content
of this foam was 14%. When this foam in an undried state was
crushed with a bench mill at 15,700 rpm for 30 seconds to
obtain a powder of 80-mesh pass in an amount of 28% of the
whole amount. The bulk specific gravity of this powder was
0.37 g/ml. An aqueous 0.2 wt.% solution of this powder was
prepared and was tested for viscosity with a B type viscosimeter.
The viscosity was found to be 572 mPa. s . The water-insoluble
content of the solution was 0.4 wt.%. An aqueous 0.1 wt.%
solution of the powder was prepared and determined
concentration of acrylic acid in the solution by liquid
chromatography and calculated a residual acrylic acid content
in the powder. This content was found to be 8,800 ppm.
Example 17
A vessel made of stainless steel and measuring 10 cm
in inside diameter and 500 ml in inner volume was equipped
with a nitrogen introducing pipe, an air release pipe, and
a silicone rubber plug fitted with a thermometer. In this
vessel, 39.51 g of purified water, 122.05 g of acrylic acid,
and 1.17 g of a dispersant (made by Kao Corporations and sold
under the trademark designation of Rheodol SP-S10V") were
placed and stirred with a magnetic stirrer and the entrapped
air was thoroughly displaced with nitrogen at room temperature
till the dissolved oxygen content fell to not more than 0.5
ppm. Subsequently, 1.72 g of an aqueous 1% sodium
hypophosphite solution, 1.72 g of a 1% acrylic acid solution
having a photopolymerization initiator (made by Ciba
Specialty Chemicals K.K. and sold under the trademark
designation of "Irgacure 819") dissolved therein, and 0.34
g of a foaming agent (made by Matsumoto Yushi Seiyaku K.K.
and sold under the trademark designation of "Matsumoto

Microsphere F-36") were additionally placed and uniformly
mixed to obtain a reaction solution.
This solution was fed into a polymerization vessel made
of Teflon, measuring 200 mm in diameter, and displaced with
nitrogen till a thickness of 5 mm and was irradiated for 5
minutes with an ultraviolet light of an intensity of 22 W/m2.
The peak temperature of the heat generated by the
polymerization was 109 °C. After the polymerization was
completed, a white foam swelled to 1. 3 times the volume existing
when the polymerization was started was obtained. The
percentage of voids in this foam was 27%. The water content
of this foam was 10%. When this foam in the undried state
was crushed with a bench mill at 15,700 rpm for 30 seconds
to obtain a powder of 80-mesh pass in an amount of 21% of
the whole amount. The bulk specific gravity of this powder
was 0.37 g/ml. An aqueous 0.2 wt.% solution of this powder
was prepared and was tested for viscosity with a B type
viscosimeter. The viscosity was found to be 11 mPa.s. The
water-insoluble content of the solution was 0., 9 wt.%. An
aqueous 0.1 wt.% solution of the powder was prepared and
determined concentration of acrylic acid in the solution by
liquid chromatography and calculated a residual acrylic acid
content in the powder. This content was found to be 9,900
ppm.
Example 18
A vessel made of stainless steel and measuring 10 cm
in inside diameter and 500 ml in inner volume was equipped
with a nitrogen introducing pipe, an air release pipe, and
a silicone rubber plug fitted with a thermometer. In this
vessel, 16.99 g of purified water, 36.13 g of an aqueous 37%
sodium acrylate solution, 79.88 g of acrylic acid, 29.21 g

of 2-acrylamide-2-methylpropane sulfonic acid, and 0.62 g
of a dispersant (made by Kao Corporations and sold under the
trademark designation of "Rheodol SP-S10V") were placed and
stirred with a magnetic stirrer and the entrapped air was
thoroughly displaced with nitrogen at room temperature till
the dissolved oxygen content fell to not more than 0.5 ppm.
Subsequently, 1.41 g of an aqueous 1% sodium hypophosphite
solution, 1.41 g of a 1% aqueous solution having an azo type
polymerization initiator (made by Wako Pure Chemical
Industries, Ltd. and sold under the product code of "V-50") ,
and 0. 50 g of a foaming agent (made by Matsumoto Yushi Seiyaku
K.K. and sold under the trademark designation of "Matsumoto
Microsphere F-36") were additionally placed and uniformly
mixed to obtain a reaction solution.
This solution was fed into a polymerization vessel made
of Teflon, measuring 200 mm in diameter till a thickness of
5 mm and was irradiated for 5 minutes in an atmosphere of
air with an ultraviolet light, of an intensity of 22 W/m2. The
peak temperature of the heat generated by the polymerization
was 103 °C. After the polymerization was completed, a white
foam swelled to 1.4 times the volume existing when the
polymerization was started was obtained. The percentage of
voids in this foam was 27%. The water content of the foam
was 12%. When this foam in the undried state was crushed with
a bench mill at 15,700 rpm for 30 seconds to obtain a powder
of 80-mesh pass in an amount of 31% of the whole amount. The
bulk specific gravity of this powder was 0 . 37 g/ml. An aqueous
0.2 wt.% solution of this powder was prepared and. was tested
for viscosity with a B type viscosimeter. The viscosity was
found to be 94 mPa.s. The water-insoluble content of the
solution was 0.7 wt.%. An aqueous 0.1 wt.% solution of the
powder was prepared and determined concentrations of acrylic

acid and 2-acrylamide-2-methylpropane sulfonic acid in the
solution by liquid chromatography and calculated a residual
acrylic acid content and a residual
2-acrylamide-2-methylpropane sulfonic acid content in the
powder. These contents were respectively found to be 10, 000
ppm and 6,600 ppm.
Example 19
A vessel made of stainless steel and measuring 10 cm
in inside diameter and 500 ml in inner volume was equipped
with a nitrogen introducing pipe, an air release pipe, and
a silicone rubber plug fitted with a thermometer. In this
vessel, 16.99 g of purified water, 36.13 g of an aqueous 37%
sodium acrylate solution, 79.88 g of acrylic acid, 29.21 g
of 2-acrylmide-2-methylpropane sulfonic acid, and 0.62 g of
a dispersant (made by Kao Corporations and sold under the
trademark designation of "Rheodol SP-S10V") were placed and
stirred with a magnetic stirrer and the entrapped air was
thoroughly displaced with nitrogen till the dissolved oxygen
content fell to not more than 0.5 ppm. Subsequently, 1.41
g of an aqueous 1% sodium hypophosphite solution, 0.70 g of
a 1% acrylic acid solution having a photopolymerization
initiator (made by Ciba Specialty Chemicals K.K. and sold
under the trademark designation of "Irgacure 819") dissolved
therein, 0.70 g of an aqueous 1% solution having a thermal
polymerization initiating agent (made by Wako Pure Chemical
Indusries K.K. and sold under the product code of "V-50"),
and 0. 50 g of a foaming agent (made by Matsumoto Yushi Seiyaku
K.K. and sold under the trademark designation of "Matsumoto
Microsphere F-36") were additionally placed and uniformly
mixed to obtain a reaction solution.
This solution was fed into a polymerization vessel made

of Teflon, measuring 200 mm in diameter in a thickness of
5 mm and was irradiated for 4 minutes with an ultraviolet
light of an intensity of 22 W/m2. The peak temperature of
the heat generated by the polymerization was 105 °C. After
the polymerization was completed, a white foam swelled to
1.5 times the volume existing when the polymerization was
started was obtained . The percentage of voids in this foam
was 35%. The water content of this foam was 11%, When this
foam in the undried state was crushed with a bench mill at
15,700 rpm for 30 seconds to obtain a powder of 80-mesh pass
in an amount of 41% of the whole amount. The bulk specific
gravity of this powder was 0.35 g/ml. An aqueous 0.2 wt.%
solution of this foam was prepared and was tested for viscosity
with a B type viscosimeter. The viscosity was found to be
108 mPa.s. The water-insoluble content of the solution was
0.5 wt.%. An aqueous 0.1 wt.% solution of the powder was
prepared and determined concentrations of acrylic acid and
2-acrylamide-2-methyl propane sulfonic acid in the solution
by liquid chromatography and calculated a residual acrylic
acid content and a residual 2-acrylamide-2-methylpropane
sulfonic acid content in the powder. These contents were
respectively found to be 4,100 ppm and 3,800 ppm.
Comparative Example 2
A vessel made of stainless steel and measuring 10 cm
in inside diameter and 500 ml in inner volume was equipped
with a nitrogen introducing pipe, an air release pipe, and
a silicone rubber plug fitted with a thermometer. In this
vessel, 67.60 g of acrylic acid, 48.25 g of purified water,
and 14.93 g of sodium carbonate were placed and stirred with
a magnetic stirrer and the entrapped air was thoroughly
displaced with nitrogen at room temperature till the dissolved

oxygen content fell to not more than 0.5 ppm. Subsequently,
0.94 g of an aqueous 1% sodium hypophosphite solution and
0.94 g of a 1% acrylic acid solution having a
photopolymerization initiator (made by Ciba Specialty
Chemicals K.K. and sold under the trademark designation of
"Darocur 1173") dissolved therein were additionally placed
and uniformly mixed to obtain a reaction solution. In the
vessel, this reaction solution was left standing as shielded
from light for 3 hours while the entrapped air was displaced
with nitrogen. During the first period of about 10 minutes,
the reaction solution violently effervesced because of the
reaction between acrylic acid and sodium carbonate.
Thereafter, no effervescence was observed. The resultant
reaction solution was fed into a polymerization vessel made
of Teflon, measuring 200 mm in diameter, and displaced with
nitrogen till a thickness of 3.5 mm and was irradiated for
20 minutes with an ultraviolet light of an intensity of 22
W/m2. In this while, absolutely no effervescence was observed.
The peak temperature of the heat generated by the
polymerization was 107 °C. After the polymerization was
completed, a colorless transparent gel containing no air
bubble was obtained. The percentage of voids in this foam
was 0% . When this gel was coarsely crushed with a meat chopper
(made by Masuko K.K.) and dried with a hot air drier till
the water content fell to not more than 5 wt.%, 140 °C and
90 minutes were necessary. When the gel was not coarsely
crushed with the meat chopper, the drying performed till the
water content fell to not more than 5 wt.% required 140 °C
and 195 minutes. The gel was further crushed with a bench
mill at 15, 700 rpm for 30 seconds to obtain a powder of 80-mesh
pass in an amount of 5% of the whole amount. The bulk specific
gravity of this gel was 0. 93 g/ml. An aqueous 0. 2 wt. % solution

of this powder was prepared and was tested for viscosity with
a B type viscosimeter. The viscosity was found to be 440 mPa. s.
The water-insoluble content of the solution was 3.1 wt. %.
An aqueous 0.1 wt.% solution of the powder was prepared and
determined concentration of acrylic acid in the solution by
liquid chromatography and calculated a residual acrylic acid
content in the powder. This content was found to be 11,500
ppm.
Example 20
A vessel made of stainless steel and measuring 5 cm in
inside diameter and 250 ml in inner volume was equipped with
a nitrogen introducingpipe, anairreleasepipe, anda silicone
rubber plug fitted with a thermometer. In this vessel, 33.00
g of purified water, 110.08 g of methoxypolyethylene glycol
(average additionmol number of ethylene oxide 25 mols) , 21. 92
g of methacrylic acid, 1.45 g of mercaptopropionic acid, and
1.52 g of a photopolymerizaation initiator (made by Ciba
Specialty Chemicals K.K. and sold under the trademark
designation of "Darocur 1173") were placed, and stirred with
a magnetic stirrer as shielded from light and the entrapped
air was thoroughly displaced with nitrogn till the dissolved
oxygen content fell to not more than 0.5 ppm. Subsequently,
1.65 g of a foaming agent (made by Matsumoto Yushi Seiyaku
K.K. and sold under the trademark designation of "Matsumoto
Microsphere F-36") was additionally placed and uniformly
mixed to obtain a reaction solution.
This solution was fed within 5 minutes after the addition
of the foaming agent into a polymerization vessel made of
Teflon, measuring 200 mm in diameter, and displaced with
nitrogen till a thickness of 5 mm and was irradiated for 3
minutes with an ultraviolet light of an intensity of 22 W/m2.

The peak temperature of the heat generated by the
polymerization was 90 °C. After the polymerization was
completed, a brown foam swelled to 1.2 times the volume existing
when the polymerization was started was obtained. The
percentage of voids in this foam was 19%. This foam in the
undried state was crushed with a bench mill at 15,700 rpm
for 30 seconds to obtain a powder of 80-mesh pass in an amount
of 41% of the whole amount. The bulk specific gravity of this
powder was 0.39 g/ml. An aqueous 0.2 wt.% solution of this
powder was prepared and was tested for viscosity with a B
type viscosimeter. The viscosity was found to be 106 mPa. s .
The water-insoluble content of the solution was 0.7 wt.%.
An aqueous 0.1 wt.% solution of the powder was prepared and
determined concentrations of acrylic acid and
2-acrylamide-2-methylpropane sulfonic acid in the solution
by liquid chromatography and calculated a residual acrylic
acid content and a residual 2-acrylamide-2-methylpropane
sulfonic acid content in the powder. These contents were
respectively found to be 12,000 ppm and 7,300 ppm.
Example 21
A vessel made of stainless steel and measuring 100 ml
in inner volume was equipped with a nitrogen introducing pipe,
an air release pipe, and a silicone rubber plug fitted with
a thermometer. In this vessel, 3. 39 gof purified water, 15.57
g of acrylic acid, 2.43 g of 2-acrylamide-2-methylpropane
sulfonic acid, and 3.91 g of an aqueous 48% sodium hydroxide
solution were placed, and stirred with a magnetic stirrer
till a solution was formed, and then 0.23 g of an aqueous
0.5% sodium hypophosphite solution and 0.47 g of an aqueous
1% acrylic acid solution having a photopolymerization
initiator (made by Ciga Specialty Chemicals K.K. and sold

under the trademark designation of "Irgacure 819") dissolved
therein were additionally placed and uniformly mixed to obtain
a reaction solution. At this time, the stainless steel vessel
was cooled with ice water to keep the inner temperature thereof
to not higher than 30 °C. Subsequently, the vessel was given
nitrogen bubbling and the dissolved oxygen in the reaction
solution was thoroughly displaced with nitrogen till the
dissolved oxygen content fell to not more than 0.1 ppm. At
this time, the nitrogen bubbling was terminated. Within 30
seconds of terminating the nitrogen bubbling, the reaction
solution was transferred into a vat made of Teflon andmeasuring
5.5 cm in width and 8.5 cm in length and exposed for 5 minutes
to an ultraviolet light having an intensity of 22 W/m2. The
peak temperature of the heat generated by the polymerization
was 124 °C. After the polymerization was completed, a white
foam swelled to 1.8 times the volume existing when the
polymerization was started was obtained. The percentage of
voids in this foam was 45%. An aqueous 0.2 wt.% solution of
this foam was prepared and was tested for viscosity with a
B type viscosimeter. The viscosity was found to be 275mPa.s.
The water-insoluble content of the solution was 0.5 wt.%.
An aqueous 0.02 wt.% solution of the powder was prepared and
determined concentrations of acrylic acid and
2-acrylamide-2-methylpropane sulfonic acid in the solution
by liquid chromatography and calculated acrylic acid and
2~acrylamide-2-methylpropane sulfonic acid contents in the
powder. These contents were found to be 8,000 ppm and 12,000
ppm respectively.
Example 22
A vessel made of stainless steel and measuring 10 cm
in inside diameter and 500 ml in inner volume was equipped

with a nitrogen introducing pipe, an air release pipe, and
a silicone rubber plug fitted with a thermometer. In this
vessel, 36. 5 g of 37% sodium acrylate, 63 . 5 g of acrylic acid,
and 0.50 g of a foaming agent (made by Matsumoto Yushi Seiyaku
K.K. and sold under the trademark designation of "Matsumoto
Microsphere F-36") were placed, and stirred with a magnetic
stirrer, and displaced thoroughly with nitrogen till the
dissolved oxygen content fell to not more than 0.5 ppm. At
this time, the stainless steel vessel was cooled with ice
water to keep the inner temperature thereof to not higher
than 10 °C. Subsequently, 0.45 g of an aqueous 45% sodium
hypophosphite solution and 0.76 g of an aqueous 1% acrylic
acid solution having a photopolymerization initiator (made
by Ciba Specialty Chemicals K.K. and sold under the trademark
designation of "Irgacure 819") dissolved therein were
additionally placed and uniformly mixed to obtain a reaction
solution.
This solution was fed into a polymerization vessel made
of Teflon, measuring 200 mm in diameter, and displaced with
nitrogen till and irradiated for 3 minutes with an ultraviolet
light of an intensity of 22 W/m2. The peak temperature of
theheat generatedby the polymerization was 113°C. The volume
of the foam was changed to 4 times the original volume before
the foaming and the solid content was 87%. When this foam
was dried with a hot air drier till the water content fell
to not more than 5%, 140 °C and 13 minutes were necessary.
The voids ratio in the dried foam was 7 0% . The foam was further
crushed with a bench mill at 15,700 rpm for 30 seconds to
obtain a powder of 80-mesh pass in an amount of 55% of the
whole amount. The bulk specific gravity of this powder was
0.33 g/ml. When the resultant reaction product was tested
for residual acrylic acid content in the powder by the same

method as in Example 1, this content was found to be 7,000
ppm. The weight average molecular weight measured by gel
permeation chromatography was 400,000.
Example 23
A vessel made of stainless steel and measuring 10 cm
in inside diameter and 500 ml in inner volume was equipped
with a nitrogen introducing pipe, an air release pipe, and
a silicone rubber plug fitted with a thermometer. In this
vessel, 36. 5 g of 37% sodium acrylate, 63. 5 g of acrylic acid,
and 0.50 g of a foaming agent (made by Matsumoto Yushi Seiyaku
K.K. and sold under the trademark designation of "Matsumoto
Microsphere F-36") were placed and stirred with a magnetic
stirrer and displaced thoroughly with nitrogen till the
dissolved oxygen content fell to not more than 0.5 ppm. In
this case, the stainless steel vessel was cooled with ice
water to retain the inner temperature thereof to not higher
than 10 °C. Subsequently, 2.0 g of an aqueous 45% sodium
phosphite solution and 0.7 6 g of an aqueous 1% acrylic acid
solution having a photopolymerization initiator (made by Ciba
Specialty Chemicals K.K. and sold under the trademark
designation of "Irgacure 819") dissolved therein were
additionally placed and uniformly mixed to obtain a reaction
solution.
This solution was fed into a polymerization vessel made
of Teflon, measuring 200 mm in diameter, and displaced with
nitrogen and was irradiated for 3 minutes with an ultraviolet
light of an intensity of 22 W/m2. The peak temperature of
theheat generated by the polymerization was 113°C. The volume
of the foam was changed to 2 . 2 times the original volume prior
to the foaming and the solids content was 85%. When this
foam was dried with a hot air drier till the water content

fell to not more than 5%, 140 °C and 17 minutes were necessary.
The voids ratio in the dried foam was 52%. The foam was further
crushed with a bench mill at 15,700 rpm for 30 seconds to
obtain a powder of 80-mesh pass in an amount of 59% of the
whole amount. The bulk specific gravity of this powder was
0.34 g/ml. When the foam was tested for residual acrylic acid
content in the powder by the same method as in Example 1,
the result was 2, 000 ppm. By the gel permeation chromatography,
the polymer was found to have a weight average molecular weight
of 180,000.
Example 24
A vessel made of stainless steel and measuring 10 cm
in inside diameter and 500 ml in inner volume was equipped
with a nitrogen introducing pipe, an air release pipe, and
a silicone rubber plug fitted with a thermometer. In this
vessel, 36.5 g of 37% sodium acrylate, 63. 5 g of acrylic acid,
and 0. 50 g of a foaming agent (made by Matsumoto Yushi Seiyaku
K.K. and sold under the trademark designation of "Matsumoto
Microsphere F-36") were placed and stirred with a magnetic
stirrer and displaced thoroughly with nitrogen till the
dissolved oxygen content fell to not more than 0.5 ppm. In
this case, the stainless steel vessel was cooled with ice
water to retain the inner temperature thereof to not higher
than 10 °C. Subsequently, 4.56 g of an aqueous 45% sodium
phosplhite solution and 0.7 6 g of an aqueous 1% acrylic acid
solution having a photopolymerization initiator (made by Ciba
Specialty Chemicals K.K. and sold under the trademark
designation of "Irgacure 819") dissolved therein were
additionally placed and uniformly mixed to obtain a reaction
solution.
This solution was fed into a polymerization vessel made

of Teflon, measuring 200 mm in diameter, and displaced with
nitrogen and was irradiated for 3 minutes with an ultraviolet
light of an intensity of 22 W/m2. The peak temperature of
the heat generatedby the polymerization was 113°C. The volume
of the foam was changed to 1. 6 times the original volume prior
to the foaming and the solids content was 88.8%.. When this
foam was dried with a hot air drier till the water content
fell to not more than 5%, 140 °C and 10 minutes were necessary.
The voids ratio in the dried foam was 30% . The foam was further
crushed with a bench mill at 15,700 rpm for 30 seconds to
obtain a powder of 80-mesh pass in an amount of 56% of the
whole amount. The bulk specific gravity of this powder was
0. 34 g/ml. When the foam was tested for residual acrylic acid
content in the powder by the same method as in Example 1,
the result was 1, 500 ppm. By the gel permeation chromatography,
the polymer was found to have a weight average molecular weight
of 80,000.
Industrial Applicability
By this invention, a water-soluble porous polymer can
be produced easily and conveniently. The product of this
method has a small residual monomer content and assumes a
porous texture and, therefore, proves useful because it excels
in solubility in water.

We Claim :
1. A method for the production of a water-soluble
porous polymer such as herein described having a water-
insoluble content of not more than 10 wt.%, comprising
polymerizing an aqueous monomer solution such as herein
described by exposure to radiation selected among gamma
ray, X ray, electron ray, ultraviolet light, near
ultraviolet light and visible light, while having bubbles
contained in said aqueous monomer solution,
wherein said aqueous monomer solution contains a
photopolymerization initiator, and has a specific viscosity
of 0.001 - 1.2 Pa.s and a concentration of not less than 40
wt.%.
2. A method as claimed in claim 1, wherein said
aqueous monomer solution contains an ethylenically
unsaturated monomer such as herein described.
3. A method as claimed in claim 1 or claim 2,
wherein the volume of the water-soluble porous polymer
after completing polymerization is 1.1 - 20 times the
volume of said aqueous monomer solution prior to the
polymerization.
4. A method according to any of claims 1-3,
wherein said bubbles are generated by the addition of a
foaming agent such as herein described.
5. A method according to any of claims 1-4,
wherein said aqueous monomer solution further contains a
surfactant such as herein described.
6. A method as claimed in any of claims 1 - 5,
wherein said bubbles are contained by the stirring and
mixing of a gas.
7. A method as claimed in claim 6, wherein said
aqueous monomer solution is made to contain said bubbles in
the form of mousse, and the resultant mousse is extruded in

a thickness in the range of 1 - 30 mm, and is fed to the
polymerization device.
8. A method as claimed in any of claims 1 - 7,
wherein said polymerization is effected in the form of
thermal polymerization and photopolymerization.
9. A method as claimed in any of claims 1 - 8,
wherein said aqueous monomer solution further contains a
thermal polymerization initiator.
10. A method as claimed in any of claims 2-9,
wherein said ethylenically unsaturated monomer is acrylic
acid and/or a salt thereof.
11. A water-soluble porous polymer having a void
ratio in the range of 5 - 80% based on the volume of the
polymer and a water-insoluble content of not more than 10
wt.%, formed by polymerizing an aqueous monomer solution by
exposure to radiation selected among gamma ray, X ray,
electron ray, ultraviolet light, near ultraviolet, light and
visible light, while having bubbles contained in said
aqueous monomer solution,
wherein said aqueous monomer solution contains an
ethylenically unsaturated monomer and a photopolymerization
initiator, has a specific viscosity of 0.001 - 1.2 Pa.s,
and a concentration of not less than 40 wt.%.
12. A powdered water-soluble porous polymer
obtained by crushing a water-soluble porous polymer as
claimed in claim 11.
13. A water-soluble porous polymer as claimed in
claim 11 or claim 12, wherein an ethylenically unsaturated
monomer contains a (meth)acrylic acid and/or a salt
thereof, and a residual acrylic, acid content is in the
range of 700 - 19000 ppm.
14. A water-soluble porous polymer as claimed in
any of claims 11 - 13, utilized as at least one member
selected from the group consisting of tackifier, waste

water cleaning agent, dispersant, pigment, coating
material, agent for treating excavated soil, concrete
admixture, adhesive agent, carrier for immobilizing
organism, flocculant for sewage disposal and industrial
waste water disposal, tackifier for wall plates, water-
retaining agent for excavation, stabilizer for viscosity of
dispersed solution, water treating agent, ion sequestering
agent, cleaner builder, and damping agent for ceramics.

The invention discloses a method for the production of a
water-soluble porous polymer such as herein described having a
water-insoluble content of not more than 10 wt.%, comprising
polymerizing an aqueous monomer solution such as herein
described by exposure to radiation selected among gamma ray, X
ray, electron ray, ultraviolet light, near ultraviolet light and
visible light, while having bubbles contained in said aqueous
monomer solution,
wherein said aqueous monomer solution contains a
photopolymerization initiator, and has a specific viscosity of
0.001 - 1.2 Pa.s and a concentration of not less than 40 wt.%.

Documents:

2496-kolnp-2005-granted-abstract.pdf

2496-kolnp-2005-granted-assignment.pdf

2496-kolnp-2005-granted-claims.pdf

2496-kolnp-2005-granted-correspondence.pdf

2496-kolnp-2005-granted-description (complete).pdf

2496-kolnp-2005-granted-examination report.pdf

2496-kolnp-2005-granted-form 1.pdf

2496-kolnp-2005-granted-form 18.pdf

2496-kolnp-2005-granted-form 3.pdf

2496-kolnp-2005-granted-form 5.pdf

2496-kolnp-2005-granted-gpa.pdf

2496-kolnp-2005-granted-reply to examination report.pdf

2496-kolnp-2005-granted-specification.pdf


Patent Number 226755
Indian Patent Application Number 2496/KOLNP/2005
PG Journal Number 52/2008
Publication Date 26-Dec-2008
Grant Date 24-Dec-2008
Date of Filing 06-Dec-2005
Name of Patentee NIPPON SHOKUBAI CO., LTD.
Applicant Address 1-1, KORAIBASHI, 4-CHOME, CHUO-KU, OSAKA-SHI, OSAKA
Inventors:
# Inventor's Name Inventor's Address
1 YAMADA, SATOSHI 7-11-301, MINAMITAKAHAMACHO, SUITA-SHI, OSAKA 5640025
2 TORIYA, SHUICHI 9-10-307, TAKASHIROCHO, SHITA-SHI, OSAKA 5640024
3 KOZUKI, HIDEKAZU 337-1, YAMASHITA, IBOCHO, TATSUNO-SHI, HYOGO 6794151
4 ISHIKAWA, MASARU 1-2-3, TSUJII, HIMEJI-SHI, HYOGO 6700083
5 NOZAKI, SHIGEYUKI A-301, 1-21, SHISHIGAYA, TSURUMI-KU, YOKOHAMA-SHI, KANAGAWA 2300073
6 IMAI, DAISUKE 4-52, NAKANOSHIMACHO, SUITA-SHI, OSAKA 5640035
PCT International Classification Number C08F 20/06, 2/10
PCT International Application Number PCT/JP2004/010544
PCT International Filing date 2004-07-16
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 2003-277023 2003-07-18 Japan