JPH0251508A - Water-absorbing crosslinked product and its composition - Google Patents

Abstract

PURPOSE:To prepare a water-absorbing crosslinked product which gives a compsn. having high water-absorbing power in an aq. soln. of a polyvalent metal salt and high water-absorbing power or hydrophilicity when compounded in various elastomers by crosslinking a sulfonated product of a conjugated diene compd. CONSTITUTION:At least one member selected from the group consisting of a sulfonated product of a conjugated diene compd. of formula I [wherein each of R<1>-R<6> is H, 1-8C alkyl, 6-20C aryl, 1-8C alkyl-contg. trialkyltin, 1-8C alkyl- contg. trialkylsilicon or -SO3X (wherein X is H, a metal atom, NH4 or NH2) and at least one of R<1>-R<6> is -SO3X], a polymer of said sulfonated product [wherein repeating units of formula II, III and/or IV (each of R<1>-R<6> is as described above) are contained], a copolymer of said sulfonated product with other monomer and a sulfonated product of the conjugated diene polymer is crosslinked in the presence or absence of a vinyl monomer and/or a crosslinkable monomer, to produce a water-absorbing crosslinked product having high water-absorbing power esp. in an aq. soln. of a polyvalent metal salt. Because said crosslinked product contains double bonds, it gives a compsn. with good cocrosslinkability with various elastomers.

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to a water-absorbing crosslinked body and a composition thereof.

[Conventional technology]

Traditionally, water-absorbing resins have been widely used in sanitary products such as disposable diapers and sanitary products; gardening products such as plant root desiccation inhibitors and fertilizer retention agents; and civil engineering and construction applications such as soil stabilizers, sludge prevention agents, and sealants. It is used in

These water-absorbing resins include carboxymethylcellulose crosslinked products (Japanese Patent Application Laid-open No. 104901/1982), crosslinked polyoxyethylene (Japanese Patent Publications No. 48-27039, JP61-13024), starch-acrylonitrile Hydrolyzate of graft copolymer (Special Publication No. 1983
-46199), acrylic acid (salt) (Unexamined Japanese Patent Publication No. 1983)
131608), crosslinked methacrylic acid (salt) polymers, and crosslinked acrylic acid (salt) or methacrylic acid (salt) copolymers.

Among these, carboxymethylcellulose crosslinked products and polyoxyethylene crosslinked products have not been found to have satisfactory water absorption and water retention abilities.

Furthermore, since the hydrolyzate of the starch-acrylonitrile graft copolymer uses starch, which is a natural polymer, it has poor heat resistance and has the problem of rotting and decomposing.

On the other hand, crosslinked acrylic acid (salt) or methacrylic acid (salt) polymers or crosslinked acrylic acid (salt) or methacrylic acid (salt) copolymers have poor water absorption capacity, water retention capacity, and quality stability. However, the water absorption capacity for aqueous solutions of polyvalent metal salts such as sodium chloride, calcium chloride, and magnesium chloride present in soil is not satisfactory.

Sulfonic acid (salt) has been introduced as a means to improve the water absorption capacity of aqueous solutions of polyvalent metal salts such as sodium chloride, calcium chloride, and magnesium chloride. salt),
And methacrylsulfonic acid (salt) has the drawbacks of low polymerization activity, no increase in molecular weight, and low copolymerizability.

On the other hand, p-vinylsulfonic acid (salt), vinyltoluenesulfonic acid (salt), acrylamide methanesulfonic acid (salt), and 2-acrylamide 2-methylpropanesulfonic acid (salt) have high polymerization activity and copolymerizability. However, these compounds are expensive and cannot be used in large quantities industrially.

The present invention has been made against the background of the above-mentioned problems of the prior art, and provides a crosslinked product with excellent water absorption ability for an aqueous solution of a polyvalent metal salt such as sodium chloride, calcium chloride, or magnesium chloride. The purpose is to provide a composition with excellent water absorption or hydrophilicity by blending it with an elastomer or synthetic resin.

[Means to solve the problem]

The present invention provides a sulfonated product of a conjugated diene represented by the formula (I) (hereinafter referred to as "sulfonated product"), (b)
The sulfonated polymer (hereinafter referred to as "sulfonated polymer")
(c) copolymers of the sulfonated product and other monomers (hereinafter referred to as "sulfonated copolymers"), and (dl sulfonated products of conjugated diene polymers (hereinafter referred to as "conjugated diene polymers") A water-absorbing cross-linked product (hereinafter referred to as a "water-absorbing cross-linked product") obtained by cross-linking at least one type of sulfonated product (hereinafter referred to as a "combined sulfonated product") in the presence or absence of a vinyl monomer and/or a cross-linkable monomer. ”).

RI R6 Fortune-telling, fortune-telling, fortune-telling, song (in the formula, RI, R6 are hydrogen atoms, alkyl groups having 1 to 8 carbon atoms, aryl groups having 6 to 20 carbon atoms, 1 to 8 carbon atoms)
trialkyltin having an alkyl group of 1 to 8 carbon atoms
trialkyl silicon having an alkyl group, or -3
O3X, where X is a hydrogen atom, a metal atom, an ammonium group or an amino group, and at least one of R1-R6 is 5OjX. ) The present invention also provides an elastomer composition containing the water-absorbing crosslinked material and an elastomer.

Furthermore, the present invention provides a resin composition containing the water-absorbing crosslinked material and a synthetic resin.

The sulfonated compound (a) used in the present invention is a compound in which a sulfone group is introduced into a conjugated diene while leaving two double bonds of the diene.

In the present invention, examples of the conjugated diene used in the (al sulfonated product) include 1,3-butadiene, 1,2-
Butadiene, 1,2-pentadiene, l.

3-pentadiene, 2.3-pentadiene, isoprene, 1.2-hexadiene, 1.3-hexadiene, 1.
4-hexadiene, 1,5-hexadiene, 2.3-hexadiene, 2.4-hexadiene, 2.3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene, 1.2 -hebutadiene, 1,3-heptadiene, 1
．． 4-hebutadiene, 1, 5-hebutadiene, 1.6-
Examples include hebutadiene, 2,3-hebutadiene, 2.5-heptadiene, 3.4-hebutadiene, 3.5-heptadiene, 2-phenylbutadiene, and various branched dienes.

These conjugated dienes can be used alone or in combination of two or more.

To produce (a) sulfonated product of this conjugated diene,
For example, it can be produced by sulfonating the double bond of a conjugated diene by the method shown below.

That is, a conjugated diene can be sulfonated using sulfonation agent as a sulfonating agent under known conditions as described in Experimental Chemistry Course edited by the Chemical Society of Japan.

As the sulfonating agent in this case, in addition to sulfur dioxide alone, a complex of sulfur dioxide and an electron-donating compound is usually used.

Here, the electron-donating compounds include ethers such as N,N-dimethylformamide, dioxane, dibutyl ether, tetrahydrofuran, and diethyl ether; amines such as pyridine, piperazine, trimethylamine, triethylamine, and tributylamine; dimethyl sulfide, diethyl Examples include sulfides such as sulfide; nitrile compounds such as acetonitrile, ethylnitrile, and propylnitrile; among these, N.

N-dimethylformamide and dioxane are preferred.

The amount of the sulfonating agent is usually 0.1 to 10 mol, preferably 0 mol in terms of sulfur trioxide, per 1 mol of conjugated diene.
．． If the amount is less than 0.1 mol, the reaction yield will be low, while if it exceeds 10 mol, unreacted sulfur trioxide will increase, and after neutralization with alkali, a large amount of sodium sulfate will be produced, resulting in poor purity. This is not preferable because it lowers the temperature.

During this sulfonation, it is also possible to use a solvent that is inert to the sulfonating agent, sulfur trioxide, such as halogenated hydrocarbons such as chloroform, dichloroethane, tetrachloroethane, tetrachloroethylene, and dichloromethane. ; nitro compounds such as nitromethane and nitrobenzene; liquid sulfur dioxide, and aliphatic hydrocarbons such as propane, butane, pentane, hexane, and cyclohexane.

These solvents can be used in combination of two or more kinds as appropriate.

The reaction temperature for this sulfonation is usually -70 to 200°C.
The temperature is preferably -30 to 50 DEG C. If the temperature is less than 70 DEG C., the sulfonation reaction slows down and is not economical, while if it exceeds 200 DEG C., side reactions may occur and the product may turn black, which is not preferred.

In this way, a cyclic intermediate in which sulfur trioxide is cyclically bonded to a conjugated diene (cyclic sulfonic acid ester of a conjugated diene, general name: sultone, hereinafter referred to as "cyclic intermediate") is produced.

The sulfonated compound represented by formula (1) used in the present invention can be obtained by changing the cyclic bond into a double bond to which a sulfone group is bonded by acting a basic compound on this cyclic intermediate. (hereinafter referred to as "double bonding").

Examples of this basic compound include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, and lithium hydroxide; sodium methoxide, sodium ethoxide, potassium methoxide, sodium-1-butoxide, potassium-t-butoxide, etc. alkali metal alkoxide;
Methyllithium, ethyllithium, n-butyllithium, 5ec-butyllithium, amyllithium, propyl sodium, methylmagnesium chloride, ethylmagnesium bromide, probylmagnesium iodide, diethylmagnesium, diethylzinc, triethylaluminum, triisobutylaluminum, etc. Organometallic compounds; amines such as aqueous ammonia, trimethylamine, triethylamine, tripropylamine, tributylamine, pyridine, piperazine; sodium,
Mention may be made of metal compounds such as lithium, potassium, calcium and zinc.

These basic compounds can be used alone or
Moreover, two or more types can also be used together.

Among these basic compounds, alkali metal hydroxides are preferred, and sodium hydroxide is particularly preferred.

The amount of the basic compound used is, per mole of conjugated diene,
Usually, the amount is 0.1 to 3 mol, preferably 0.5 to 3 mol, and if it is less than 0.1 mol, the formation of a cyclic bond into a double bond will not be promoted and the cyclic compound may remain as a -formula% A hydroxyolefin represented by the formula % (wherein R1-Rh is the same as above) is produced, and a compound having almost no polymerization performance is produced.

On the other hand, if it exceeds 10 moles, a large amount of unreacted alkali remains and the purity of the product decreases, which is not preferable.

When forming this cyclic intermediate into a double bond, the basic compound can be used in the form of an aqueous solution, or dissolved in an organic solvent inert to the basic compound.

Examples of the organic solvent include, in addition to the above-mentioned various aqueous solvents, aromatic hydrocarbon compounds such as benzene, toluene, and xylene; and alcohols such as methanol, ethanol, propatool, isopropanol, and ethylene glycol.

These solvents can be used in combination of two or more kinds as appropriate.

When the basic compound is used as an aqueous solution or an organic solvent solution, the concentration of the basic compound is usually about 1 to 70% by weight, preferably about 10 to 50% by weight.

In addition, the reaction temperature for forming a double bond is usually -30 to 150
°C, preferably -10 to 70 °C, more preferably 0 to 5 °C
It is carried out at 0°C, and can be carried out under normal pressure, reduced pressure or increased pressure.

Furthermore, the reaction time for forming a double bond is usually 0. 1-2
4 hours, preferably 0.5 to 5 hours.

Further, in forming this double bond, the desired sulfonated product represented by the general formula (1) can also be obtained by adding water or alcohol to the cyclic intermediate and then performing a dehydration reaction or a dealcoholization reaction.

The cation type of the sulfonated product thus obtained is not particularly limited, but in order to make it water-soluble, hydrogen, alkali metals, alkaline earth metals, ammonium, amines, etc. are preferable.

The alkali metals include sodium, potassium, etc., and the amines include alkylamines such as methylamine, ethylamine, propylamine, dimethylamine, diethylamine, triethylamine, butylamine, dibutylamine, tributylamine, ethylenediamine, diethylenetriamine, triethylenetetramine, etc. Examples of the alkaline earth metal include polyamine, morpholine, piperidine, etc., and calcium, magnesium, etc.

Additionally, these cationic species can be interchanged with other cationic species by various ion exchange techniques.

Next, (b) the sulfonated polymer has the above general formula (1
) is obtained by polymerizing the (al sulfonated product), but during this polymerization, in addition to (a) the sulfonated product, other monomers copolymerizable with it (hereinafter referred to as "other monomers") are used. 99% by weight or less, preferably 1 to 98%
It is also possible to obtain a sulfonated product copolymer (C) by copolymerizing the amount by weight, more preferably about 10 to 90 weight%.

Other copolymerizable monomers include styrene, α-
Aromatic compounds such as methylstyrene, vinyltoluene, p-methylstyrene; methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, etc. Alkyl esters of acrylic acid or methacrylic acid; mono- or dicarboxylic acids or anhydrides of dicarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid; butadiene, isoprene, 2-
Aliphatic conjugated dienes such as chloro-1,3-butadiene and 1-chloro-1,3-butadiene; acrylonitrile;
Vinyl cyanide compounds such as methacrylonitrile; vinyl chloride, vinylidene chloride, vinyl methyl ethyl ketone,
Vinyl methyl ether, vinyl acetate, vinyl formate, allyl acetate, methalylacetate, acrylamide, methacrylamide, N-methylolacrylamide, glycidyl acrylate, glycidyl methacrylate, acrolein, allyl alcohol, and the like are used.

In order to obtain the sulfonated polymer (011) or the sulfonated copolymer (C), for example, the formula (1)
The sulfonated compound represented by the above and, if necessary, other monomers that can be copolymerized with the sulfonated compound are added to a radical polymerization initiator, a chain transfer agent, etc. in the presence of a polymerization solvent such as water or an organic solvent. Radical polymerization is performed using

Here, the organic solvent for polymerization used in radical polymerization includes, for example, alcohols such as methanol, ethanol, and isopropanol; aromatic hydrocarbons such as xylene, toluene, and benzene; butane, pentane, hexane, cyclohexane, Mention may be made of aliphatic hydrocarbons such as heptane.

Among these polymerization solvents, water or methanol is preferred.

Examples of radical polymerization initiators include persulfate initiators such as potassium persulfate, sodium persulfate, and ammonium persulfate; inorganic initiators such as hydrogen peroxide; cumene hydroperoxide, isopropylbenzene hydroperoxide, and paramenthane hydroperoxide. Organic peroxides such as peroxide and benzoyl peroxide; or azo initiators such as azobisisobutyronitrile; and 2.
Examples include organic initiators typified by water-soluble azo initiators such as 2'-azobis(2-amidinopropane) dihydrochloride.

The amount of this radical polymerization initiator used is the total amount of monomers 1
00 parts by weight, preferably 0.01 to 10 parts by weight, particularly preferably 0.1 to 5 parts by weight.

As the chain transfer agent, t-dodecylmercaptan, octylmercaptan, n-tetradecylmercaptan, octylmercaptan, t-hexylmercaptan, n-
Mercaptans such as hexyl mercaptan; halogen compounds such as carbon tetrachloride and ethylene bromide are usually used in an amount of about 0.001 to 10 parts by weight per 100 parts by weight of the total amount of monomers.

In addition, in order to promote radical polymerization, for example, reduction of sodium pyrobisulfite, sodium sulfite, sodium bisulfite, ferrous sulfate, glucose, sodium formaldehyde sulfoxylate, L-ascorbic acid and its salts, sodium hydrogen sulfite, etc. Chelating agents; chelating agents such as glycine, alanine, and sodium ethylenediaminetetraacetate can also be used in combination.

During radical polymerization, 1. In addition to the above-mentioned radical initiator, chain transfer agent, etc., various electrolytes, pH adjusters, etc. are used in combination as necessary, and 50 to 50 to 100 parts of water is added to 100 parts by weight of the total monomers. 1.000 parts by weight or 50 parts of organic solvent
~1,000 parts by weight, and the radical initiator, chain transfer agent, etc. are used in the amounts within the above range, and the polymerization temperature is -50~1,000 parts by weight.
200°C, preferably 0 to 150°C, particularly preferably 5
Radical polymerization is carried out under polymerization conditions of ~80°C and polymerization time of 0.1 to 40 hours.

The method of adding the monomer containing the sulfonated product as a main component is not particularly limited, and any method such as a stalk addition method, a continuous addition method, or a divided addition method may be employed.

Note that the obtained (b) sulfonated polymer or (
The final polymerization conversion rate of the Cl sulfonate copolymer is 1
It is preferably 0% or more, particularly 30% or more.

Furthermore, the above polymerization method is not limited to the above-mentioned radical polymerization, and conventionally known anionic polymerization may also be used to obtain the desired sulfonated polymer or (C)
A sulfonated copolymer can be obtained.

The bl sulfonated polymer obtained in this way is
It has a repeating structural unit represented by the following formula (■), formula (III) and/or general formula (TV).

R'-C-R"R'-C-R' [-In formulas (II) to (TV), Rl,, R
6 is the same as the formula (1) above. ] Next, the sulfonated dl conjugated diene polymer used in the present invention is obtained by sulfonating the conjugated diene polymer.

Here, examples of the conjugated diene used in the conjugated diene polymer include various conjugated dienes used in the above-mentioned +al sulfonated product. Other monomers used in producing the polymer can also be used in combination. Furthermore, the method for sulfonating this conjugated diene polymer is the same as the sulfonation method used in the production of the sulfonated product (a).

Specific examples of sulfonated dl conjugated diene polymers include sulfonated polybutadiene, sulfonated polyisoprene, sulfonated butadiene-isoprene copolymer, sulfonated polypiperylene, sulfonated butadiene-
Sulfonated products of conjugated diene polymers such as 1-chlorobutadiene copolymer and sulfonated poly-2-chlorobutadiene; sulfonated butadiene-styrene copolymer, sulfonated isoprene-styrene copolymer, sulfonated butadiene- Conjugated dienes and olefinic monomers such as (meth)acrylic acid copolymers, sulfonated isoprene-(meth)acrylic acid copolymers, sulfonated butadiene-acrylonitrile copolymers, and sulfonated isoprene-acrylonitrile copolymers. Examples include sulfonated copolymers of .

Thus obtained (bl sulfonate polymer, (
The weight average molecular weight of the Cl sulfonated copolymer or (d) conjugated diene polymer sulfonate in terms of sodium polystyrene sulfonate cannot be uniquely determined depending on the intended use, but is usually 500 to 5,0.
00,000. Preferably 1.000 to 500,000
It is.

In addition, these (b) sulfonated polymers, (C) sulfonated copolymers, or (dl conjugated diene polymer sulfonated products) can be prepared by ion exchange method, neutralization reaction, etc. as with the above fa) sulfonated products. can be mutually exchanged into acid form or salts of alkali metals, alkaline earth metals, ammonium, amines, etc.

Note that (a) the sulfonated product used in the present invention, (b) the sulfonated product obtained therefrom, or (C)
The structure of sulfonated copolymers and sulfonated dl conjugated diene polymers can be confirmed from the absorption of sulfone groups by infrared absorption spectroscopy, and their composition ratios can be determined by acid/alkali titration, such as potential difference and conductivity. be able to.

Furthermore, the structure can be confirmed by the presence of alkyl groups, olefinic hydrogen, etc. by nuclear magnetic resonance spectroscopy.

The above components (al to (d)) may be used alone or in combination of two or more.

The water-absorbing crosslinked product of the present invention is obtained by crosslinking at least one of the components (a) to +d), and at this time, a vinyl monomer and/or a crosslinkable monomer may be used in combination. .

Examples of the vinyl monomer include (meth)acrylic acid or an alkali metal salt or ammonium salt thereof, (
meth)acrylamide, N,N-dimethyl(meth)acrylamide, 2-hydroxyethyl(meth)acrylamide, 2-hydroxyethyl(meth)acrylate, 2
- In addition to (meth)acrylic acids such as hydroxypropyl (meth)acrylate and polyethylene glycol mono (meth)acrylate, 2-vinylpyridine, 4-vinylpyridine, vinyl acetate, vinyl formate, and N.

N-dimethylaminopropylacrylamide, N-methylolacrylamide, (meth)allyl acetate, (
Glycidyl meth)acrylate, acrolein, allyl alcohol, vinyl methyl ethyl ketone, vinyl methyl ether, 2-acrylamido-2-methylpropanesulfonic acid, 2-acryloylethanesulfonic acid, p-vinylstyrenesulfonic acid (salt), vinyltoluenesulfonic acid (salts), etc., and the above-mentioned acrylic acids are preferred, and these are used alone or in combination.

These vinyl monomers can be used within a range that does not reduce the performance of the water-absorbing crosslinked product of the present invention during crosslinking. The amount of vinyl monomer used is usually 98% by weight or less, preferably 95% by weight or less, more preferably 90% by weight or less, based on the total amount of components (a) to (d) and vinyl monomer. % by weight or less.

In addition, the crosslinkable monomers used in the present invention include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, and polyethylene glycol di(meth)acrylate. (meth)acrylate, glycerin tri(meth)acrylate, N.

Examples include N'-methylenebis(meth)acrylamide, diallyl phthalate, diallyl maleate, diallyl terephthalate, triallyl cyanurate, triallyl isocyanurate, triallyl phosphate, and the like, which may be used alone or in combination.

The amount of the crosslinking monomer to be used is determined by taking into consideration the water absorption capacity, gel strength, etc. of the water absorbent crosslinked product obtained, but (al~(
d) Based on the total amount of component and vinyl monomer, usually 1
0% by weight or less, preferably 0.001 from the viewpoint of gel strength
~5% by weight, more preferably 0.002~2% by weight,
Particularly preferably o, oos to 0.5% by weight, 10
If it exceeds % by weight, the water absorption capacity decreases.

In addition, (al~(d) contained in the water-absorbing crosslinked body of the present invention
The total amount of the components is 2% by weight or more, preferably 3 to 70% by weight, more preferably 5 to 50% by weight, and if it is less than 2% by weight, it is difficult to obtain the effects of the present invention.

Thus, in order to obtain the water-absorbing crosslinked product of the present invention, +a) to
(d+ acid component, the vinyl monomer and/or crosslinking monomer used as necessary are used together, and the following ■ to ■
Cross-link using the method described below.

(2) A method of polymerizing and crosslinking at least one of the components (al to (d)), a vinyl monomer, and a crosslinkable monomer using a crosslinking agent.

(2) A method of polymerizing and crosslinking at least one of the components (a) to (d) and a crosslinkable monomer using a crosslinking agent.

(2) A method of polymerizing and crosslinking at least one of the components (al to (d)) and a vinyl monomer using a crosslinking agent.

(2) A method of crosslinking at least one of (a) to (d+acid components) using a crosslinking agent.

(2) A method of crosslinking at least one of the components (b) to (d) by heat or the like in the absence of a crosslinking agent.

(2) A method in which component (d) is crosslinked simultaneously with the sulfonation reaction of the conjugated diene polymer.

Among these crosslinking methods, methods 1 to 2 are preferred, methods 1 to 2 are more preferred, and methods 1 to 2 are particularly preferred.

In addition, among the components (al to (d)), (bl to (d)
Component d) is preferred.

Furthermore, the crosslinking agent is not particularly limited, but sulfur, inorganic sulfur compounds, organic sulfur compounds, radical generators, and the like can be used.

In particular, when a vinyl monomer or a crosslinkable monomer is present as in the methods (1) to (2) above, it is preferable to use a radical generator, particularly a water-soluble radical generator.

Examples of this radical generator include the radical generators used in the (co)polymerization of the (bl component or (C1 component) described above. The amount is usually about 0.01 to 10% by weight, preferably about 0.1 to 2% by weight, based on the total amount of vinyl monomers and/or crosslinkable monomers used as necessary.

In the present invention, when components (al to (d)) are crosslinked in the presence of a vinyl monomer and/or a crosslinking monomer used as necessary, a solvent is not particularly necessary; The crosslinking is preferably carried out in the presence of. Examples of this solvent include organic solvents used in the (co)polymerization of the component (b) or the FC+ component.

In addition, in the crosslinking method of the present invention, in addition to the solvent crosslinking method using water as a solvent, for example, sorbitan fatty acid esters are used as a dispersant to form a stable water-in-oil type suspension (reverse phase suspension crosslinking). Polymerization) method is also preferably used.

The crosslinking temperature is usually 0 to 150°C, preferably 5 to 100°C, and the crosslinking time is usually 0.5 to 4°C.
It takes about 8 hours.

During this crosslinking, the method of adding components (a) to (d), vinyl monomers and/or crosslinkable monomers used as necessary, is not particularly limited; addition,
Any method such as a continuous addition method or a divided addition method may be employed.

The water-absorbing crosslinked product of the present invention obtained in this way can be produced in the acid form, alkali metals, alkaline earth metals, ammonium, amines, etc. by ion exchange method or neutralization reaction, as in the above-mentioned (a) to (dl components). can be interchanged with salts such as.

By blending the water-absorbing crosslinked material of the present invention with various elastomers in appropriate proportions, an elastomer composition having excellent performance as a water-absorbing or hydrophilic elastomer can be obtained.

Further, by appropriately blending the water-absorbing crosslinked body of the present invention with a synthetic resin such as a thermoplastic resin or a thermosetting resin, a resin composition having excellent water absorption or hydrophilicity can be obtained.

Among these, the elastomer is natural rubber (NR
) i Diene-based synthetic rubbers such as polyisoprene rubber (IR), styrene-butadiene rubber (SBR), polybutadiene rubber (BR), acrylonitrile-butadiene rubber (NBR), and chloroprene rubber (CR); ethylene-propylene rubber (EPR) , ethylene-propylene-diene rubber (EPDM), acrylic rubber (ACM, , AN
M), non-diene synthetic rubber such as fluororubber, and preferably NR, IR, SBR, and BR.

In addition to the various natural rubbers and synthetic rubbers mentioned above, examples of elastomers include syndiotactic 1,2-polybutadiene, trans-1,4-polyisoprene, ethylene-vinyl acetate copolymer, and aromatic vinyl-conjugated diene blocks. Copolymers: Examples include styrene grafted ethylene-propylene elastomer, thermoplastic polyester elastomer, thermoplastic polyamide elastomer, vinyl chloride elastomer, ethylene ionomer resin, and preferably syndiotactic l, 2 polybutadiene, styrene-butadiene prosol. It is a copolymer.

On the other hand, thermoplastic resins used as synthetic resins include polyethylene, polypropylene, polyvinyl chloride, polycarbonate, and polyethylene terephthalate (PET).
), polybutylene terephthalate (PBT), polyacetal, polyamide, epoxy resin, polyphenylene sulfide resin (PPS), polyetheretherketone, polyphenylene oxide resin (PPO), rubber-modified PPO, styrene-maleimide copolymer, rubber Modified styrene-maleimide copolymer, polystyrene, polychlorostyrene, polyα-methylstyrene, styrene-acrylonitrile copolymer, styrene-methyl methacrylate copolymer, styrene-maleic anhydride copolymer, styrene-α- Methylstyrene copolymer, styrene-α-methylstyrene-methyl methacrylate copolymer,
Examples include styrene resins such as styrene-α-methylstyrene-acrylonitrile-methyl methacrylate copolymer and rubber modified products thereof.

Furthermore, examples of thermosetting resins used as synthetic resins include phenol resins, epoxy resins, urea resins, melamine resins, and prepolymers of these resins.

The mixing ratio of the water-absorbing crosslinked material of the present invention and the elastomer and/or synthetic resin is not particularly limited and can be blended in an appropriate ratio depending on the purpose, but the former/latter (weight ratio) is usually , 1/99 to 99/1, preferably 2/98 to 90/10, more preferably 5/95 to 9
5/20°, particularly preferably 7/93 to 50150°.

In particular, the water-absorbing crosslinked material used in the present invention has a double bond in its molecule, so it can contain natural rubber, styrene-butadiene rubber, polybutadiene rubber, acrylonitrile-butadiene rubber, chloroprene rubber, butylene rubber, ethylene-propylene rubber, etc. - Co-crosslinking with various elastomers having unsaturated bonds such as diene rubber and unsaturated acrylic rubber is possible.

In the present invention, a water-absorbing crosslinked body, an elastomer and/or
Alternatively, as a blending method with the synthetic resin, both can be added and kneaded simultaneously, or the additive can be mixed in advance with one component and the remaining component can be added.

Mixing is done using various extruders, Banbury mixers and kneaders.
temperature: 80 to 250°C, preferably 10
0-200°C, time: 0.1-2 hours, preferably 0.
This can be done by kneading for about 2 to 1 hour, and preferred kneading methods include a Banbury mixer,
This is a method using an internal mixer such as a kneader.

The composition of the present invention has a water-absorbing crosslinked material, an elastomer, and/or a synthetic resin as its main components, but in addition to these, various commonly used compounding agents can be added.

These additives may be added during the process of producing the composition of the present invention, or may be added after producing the composition, if necessary.

That is, examples of reinforcing fillers and extenders include carbon black, fumed silica, wet silica, fine quartz powder, diatomaceous earth, zinc white, basic magnesium carbonate, activated calcium carbonate, magnesium silicate, aluminum silicate, titanium dioxide, Mention may be made of talc, mica powder, aluminum sulfate, calcium sulfate, barium sulfate, asbestos, glass fibers, organic reinforcing agents, organic fillers.

Examples of dispersion aids include higher fatty acids and metal amine salts thereof; examples of plasticizers include dioctyl phthalate, dibutyl phthalate, diethyl phthalate, dimethyl phthalate, tricresyl phthalate, tricresyl phosphate, triethyl phosphate, tributyl phosphate, and tri-2 = Phthalic acid derivatives such as ethylhexyl phosphate and trimellitic acid, adipic acid derivatives such as dioctyl adipate, and other dioctyl azelate, dioctyl sebacate, and epoxy fatty acids; Liquid rubbers include liquid polybutadiene rubber and liquid polyisoprene. Rubber, liquid NBR rubber, liquid butyl rubber, liquid acrylic rubber, liquid EP rubber; Examples of softeners include lubricating oil, process oil, coal tar, castor oil, calcium stearate, and polybutene; Examples of anti-aging agents include phenylene diamines. , phosphates, quinolines, cresols, phenols, dithiocarbamate metal salts; heat-resistant agents such as iron oxide, cerium oxide, potassium hydroxide, iron naphthenate, potassium naphthenate; other colorants, ultraviolet absorbers, Flame retardants, oil resistance improvers, foaming agents, scorch inhibitors, tackifiers, lubricants, etc. can be optionally added.

These compositions are prepared by adding crosslinking agents such as organic peroxides and crosslinking co-agents, polyol vulcanizing agents, vulcanization accelerators, and amine vulcanizing agents using conventional kneading machines such as rolls and Banbury mixers. After kneading, molding and vulcanization can be carried out under normal vulcanized rubber production conditions.

Examples of the organic peroxide include the aforementioned various organic peroxides used in the production of water-absorbing crosslinked bodies.

Examples of crosslinking aids include the following compounds.

That is, ethylene glycol dimethacrylate, 1
, 3-butanediol dimethacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, polyethylene glycol dimethacrylate, 1゜4-butanediol dimethacrylate, 1,6-hexane diol diacrylate, 2
．． 2'-bis(4-methacryloyljethoxyphenyl)propane, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, divinylbenzene, N,N'-methylenebisacrylamide, p-quinonedioxime, These include p,p'-dibenzoylquinone dioxime, triazinedithiol, triallyl cyanurate, triallyl isocyanurate, bismaleimide, and the like.

The amount of the crosslinking aid added is 0.1 to 10 parts by weight, preferably 0.5 to 7 parts by weight, per 100 parts by weight of the composition.

As the polyol vulcanizing agent, polyhydroxy aromatic compounds such as hydroquinone, bisphenol A, bisphenol AF, and salts thereof are preferably used. Further, fluorine-containing aliphatic diols can also be used. The amount of these polyol vulcanizing agents added is 100% of the composition.
The amount per part by weight is usually about 0.1 to 20 parts by weight, preferably about 1 to 10 parts by weight.

As a vulcanization accelerator, methyltrioctylammonium chloride, hensyltriethylammonium chloride,
Quaternary ammonium compounds such as tetrahexylammonium tetrafluoroborate; 8-methyl-1,8-
Quaternary ammonium compounds such as diaza-cyclo(54,O)-7-unzocenyl chloride; 4 such as benzyltriphenylphosphonium chloride, m-trifluoromethylbenzyltrioctylphosphonium chloride, hensyltrioctylphosphonium bromide Class phosphonium compounds are preferred.

The amount of the vulcanization accelerator added is usually about 0.2 to 10 parts by weight per 100 parts by weight of the composition.

Amine vulcanizing agents include various alkyl amines such as hexamethylene diamine, tetraethylene pentamine, and triethylene tetramine, various aromatic amines such as aniline, pyridine, and diaminobenzene, and carbamic acids and cinnamylidenic acids of these amines. Salts of fatty acids such as these can be used.

The amount of the amine vulcanizing agent added is usually 0.1 to 10 parts by weight, preferably 0.5 to 10 parts by weight, per 100 parts by weight of the composition.
It is about 5 parts by weight.

To vulcanize the composition, usually primary vulcanization is performed at 80 to 200°C for several minutes to 3 hours under a pressure of 20 to 200 kg/cut, and if necessary, 1 to 48°C at 80 to 200°C.
The product is subjected to secondary vulcanization for a period of time to form a crosslinked product.

As described above, the water-absorbing crosslinked material of the present invention can be used in sanitary products such as disposable diapers, sanitary napkins, urinary incontinence materials, and pet excrement disposal materials, as well as agricultural and horticultural applications such as soil water retention materials and soil improvement materials. Sealing materials, sludge prevention materials, backing materials,
It can be used in civil engineering applications such as a solidifying agent for muddy water, and in architectural applications such as water-absorbing/hygroscopic sheet materials, wall materials for preventing condensation, and water-absorbing laminates.

In addition, the composition of the present invention, which is a blend of the water-absorbing crosslinked material with an elastomer and/or a synthetic resin, can increase the strength of the water-absorbing crosslinked material and impart hydrophilicity, water absorption, oil resistance, etc. to the elastomer or synthetic resin. It can be used in a wide range of applications that take advantage of these characteristics.

〔Example〕

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples.

In addition, in the examples, % and parts are based on weight unless otherwise specified.

In addition, in the examples, water absorption capacity was measured by the following test method.

Pure water II in a beaker with water absorption capacity Iz! , and immersed a 12×10 cm paperback containing approximately 50 μm of polymer at 20° C. for 24 hours), weighed the weight after immersion, and calculated the water absorption capacity of pure water according to the following formula.

Water absorption capacity (g/g polymer) = [Weight of paperback after soaking 1 (g) - Charged polymer weight 1jt (g) - Weight of paperback soaked without polymer (g)) / Charged weight Combined weight (g) Salt water absorption The salt water absorption capacity was measured in the same manner as above, except that pure water 11 was replaced with salt water 11 with a concentration of 0.9%. did.

Calcium chloride aqueous solution (Ca C12z water) water absorption capacity In the above pure water absorption capacity test, instead of 1 liter of pure water, a concentration of 0
．． The water absorption capacity of the calcium chloride aqueous solution was measured in the same manner except that 9% calcium chloride aqueous solution 11 was used.

Reference Example 1 After purging a four-loaf flask with an internal volume of 111 with nitrogen, methylene chloride 400 was previously subjected to dehydration and deoxidation treatment.
mj+ was added, and then 31 mff of dehydrated and deoxidized dioxane was added, and the mixture was cooled to 5 to 10° C. with stirring.

Next, 15 ml of sulfur trioxide (28.8 g = 0.36
mol) was added dropwise to form a complex of sulfur trioxide and dioxane. Further, the reaction was continued for 15 minutes.

A methylene chloride solution of 24.5 g (0.36 mol) of isoprene (2-methyl-1,3-butadiene) dissolved in this solution was 150 mj! was added dropwise over a period of 1 hour, and after the addition was completed, stirring was continued for an additional 30 minutes.

Next, water solution i in which 14.4 g of sodium hydroxide was dissolved
The product (crude 2-
60.5 g of sodium methyl-1,3-butadiene-1-sulfonate was obtained.

After dissolving this product in 300 cc of water, 200 cc of toluene was added and vigorously shaken to extract the toluene soluble content, and the aqueous solution was dried to give 2-methyl-1,3-butadiene-1- Sodium sulfonate (rMBSN)
50.0 g of the product was obtained.

Reference Example 2 After purging a pressure bottle with an internal volume of 300 mJ+ with nitrogen, 50 g of MBSN obtained in the same manner as in Reference Example 1 and 150 g of water were added to make an aqueous solution, and 0.1 g of potassium persulfate was further added to the bottle at 70°C. Polymerization was carried out for 3 hours.

The weight average molecular weight of the obtained sodium polyisoprene sulfonate was 20×10'.

Moreover, the yield was 85%.

Example 1 400 g of cyclohexane and 5 g of sorbitan monostearate were placed in a 11-capacity four-tube adjustable flask equipped with a stirrer, reflux condenser, dropping funnel, and nitrogen gas introduction tube.
was added and dissolved, nitrogen gas was blown in to drive out the dissolved oxygen, and the internal temperature was brought to 70° C. under a nitrogen gas atmosphere.

Next, in a dropping funnel with a volume of 1509 ml, 20 g of the MBSN and 80 g of acrylic acid completely neutralized with sodium hydroxide in a water bath were added, followed by 0.1 g of N,N'-methylenebisacrylamide and 0.3 g of ammonium persulfate. was added to prepare a 300 ml aqueous solution.

The contents of the dropping funnel were added to the contents of the four-piece collapsible flask, and the mixture was stirred (300 rpm) for 70 minutes.
Polymerization was carried out at ℃ for 1 hour.

After the polymerization reaction is complete, when stirring is stopped, the swollen polymer particles settle to the bottom of the flask, and decantation yields a wet polymer (water-absorbing crosslinked product), which can be easily pulverized by drying under reduced pressure at 80°C. A polymer was obtained. Table 1 shows the results of the water absorption capacity test for this polymer.

Example 2 400 g of n-hexane and 4 g of sorbitan monostearate were added and dissolved in a 11z volume separable flask equipped with a stirrer, a reflux condenser, a dropping funnel, and a nitrogen gas inlet tube, and then nitrogen gas was added. Gas was blown in to drive out dissolved oxygen, and the internal temperature was brought to 70° C. under a nitrogen gas atmosphere.

Next, 100 g of the above MBSN, 0.1 g of N,N'-methylenebisacrylamide, and 0.3 g of potassium persulfate were added to a dropping funnel with a capacity of 50 QmJ, and 30 g of potassium persulfate was added.
It was prepared as an aqueous solution of QmJ.

The contents of the dropping funnel were added to the contents of the four-piece parallel flask, and the mixture was stirred (300 rpm) for 70 minutes.
Polymerization was carried out at ℃ for 1 hour.

After the polymerization reaction is complete, when stirring is stopped, the swollen polymer particles settle to the bottom of the flask, and decantation yields a wet polymer (water-absorbing crosslinked product), which can be easily pulverized by drying under reduced pressure at 80°C. A polymer was obtained. Table 1 shows the results of the water absorption capacity test for this polymer.

Example 3 Instead of 20g of MBSN in Example 1, Reference Example 2
20g of sodium polyisoprene sulfonate obtained in
Polymerization was carried out using the same recipe as in Example 1, except that
Post-processed.

The obtained polymer (water-absorbing crosslinked product) was a powder containing lumps that could be easily crushed. Table 1 shows the results of the water absorption test for this polymer.

Example 4 Polymerization and post-treatment were carried out according to the same recipe as in Example 1, except that 80 g of methacrylic acid, which had been completely neutralized in a water bath, was used instead of acrylic acid in Example 1.

The obtained polymer (water-absorbing crosslinked product) was a powder containing lumps that could be easily crushed. Table 1 shows the results of the water absorption capacity test for this polymer.

Example 5 Polymerization was carried out according to the same recipe as in Example 1, except that 60 g of methacrylic acid neutralized to 70 mol% in a water bath was used in place of acrylic acid and N,N'methylenebisacrylamide in Example 1, and then Processed.

The obtained polymer (water-absorbing crosslinked product) was a powder containing lumps that could be easily crushed. Table 1 shows the results of the water absorption test for this polymer.

Example 6 In place of MBSN, N, N'-methylenebisacrylamide and acrylic acid in Example 1, polyisoprene sulfonated product [sulfonation rate 60 mol%, weight average molecular weight (MW = 20 x 10' Mw/Mn (number average Polymerization was carried out using the same recipe as in Example 1, except that 30 g of methacrylic acid (molecular weight) = 1.7) and 70 g of methacrylic acid, which had been neutralized to 70 mol% in a water bath, were used and post-treated.

The obtained polymer (water-absorbing crosslinked product) was a powder containing lumps that could be easily crushed. Table 1 shows the results of the water absorption test for this polymer.

Example 7 In place of MBSN in Example 1, 20 g of polyisoprene sulfonate [sulfonation rate 70 mol%, weight average molecular weight (Mw) = 5X 10', Mw/Mn (number average molecular weight) = 1.5] was used. Polymerization was carried out using the same recipe as in Example 1, except that 2,2'-azobis(2-amidinopropane) dihydrochloride was used in place of ammonium persulfate, and post-treatment was performed. The obtained polymer (water-absorbing crosslinked product) was a powder containing lumps that could be easily crushed.

Table 1 shows the results of the water absorption capacity test for this polymer.

Example 8 Instead of MBSN in Example 1, polybutadiene sulfonate (sulfonation rate 80 mol%, Mw = 12X
10', Mw/Mn=2.3) 20g, N, N'-
Polymerization was carried out using the same recipe as in Example 1, except that 0.1 g of diethylene glycol diacrylate was used instead of methylene bisacrylamide, and post-treatment was performed.

The obtained polymer (water-absorbing crosslinked product) was a powder containing lumps that could be easily crushed. Table 1 shows the results of the water absorption capacity test for this polymer.

Example 9 Polybutadiene sulfonated product (sulfonation rate 50 mol%
, M W =12 x 10', M W / M
n = 3.1) 100 g, N,N'-methylenebisacrylamide 11 g 1 water 100 and ammonium persulfate 0
, 5g was placed in a pressure bottle, and the atmosphere was replaced with nitrogen.
The reaction was carried out at 0°C for 48 hours.

The obtained polymer was insoluble in water and was a crosslinked product. Table 1 shows the results of the water absorption capacity test of this crosslinked product.

Comparative Example 1 400 g of cyclohexane and 5 g of sorbitan monostearate were placed in a four-way adjustable flask with a capacity of IA equipped with a stirrer, a reflux condenser, a dropping funnel, and a nitrogen gas introduction tube.
was added and dissolved, nitrogen gas was blown in to drive out the dissolved oxygen, and the internal temperature was brought to 70° C. under a nitrogen gas atmosphere.

Next, 10 ml of acrylic acid, which had been completely neutralized with sodium hydroxide in a water bath, was placed in a dropping funnel with a volume of 500 ml.
0g, then add 0.1g of N,N'-methylenebisacrylamide and 0.3g of ammonium persulfate to
00mj! It was prepared as an aqueous solution.

The contents of the dropping funnel were added to the contents of the four-piece separable flask, and the mixture was stirred (300 rpm) for 70 minutes.
Polymerization was carried out at ℃ for 1 hour.

After the polymerization reaction is complete, when stirring is stopped, the swollen polymer particles settle to the bottom of the flask, and decantation yields a wet polymer, which is dried under reduced pressure at 80°C to yield a polymer that can be easily crushed. Ta. Table 1 shows the results of the water absorption capacity test for this polymer.

Comparative Example 2 Comparative Example 1 except that 100 g of methacrylic acid completely neutralized in a water bath was used instead of acrylic acid in Comparative Example 1, and 0.1 g of diethylene glycol diacrylate was used instead of N,N'-methylenebisacrylamide. Polymerization and post-treatment were carried out using the same recipe. The resulting polymer was a powder containing lumps that could be easily ground. Table 1 shows the results of the water absorption capacity test for this polymer.

Table 1 As is clear from Table 1, the water-absorbing crosslinked material obtained according to the present invention has a large water-absorbing ability, especially in the presence of sodium chloride or calcium chloride (multivalent ions) compared to the comparative example. The difference in ability is clear.

Example 10 The water-absorbing crosslinked product synthesized in Example 1 was kneaded with a 6-inch roll according to the following formulation to obtain a rubber compound.

This rubber compound was press-vulcanized at 145°C for 25 minutes to obtain a 2u thick sheet.

Regarding this sheet, tensile test (measurement method, JISK63
01), a pure water water absorption test (measured according to the above-mentioned water absorption test except that the sample was immersed at 20° C. for 5 days) was conducted. The results are shown in Table 2.

Housing prescription (department) Natural rubber
100 zinc white
5 stearic acid
1HAF Carbon Black 30 Calcium Carbonate 30 Sulfur
IN-cyclohexyl-2-benzothiazolesulfenamide
1.5 Water-absorbing crosslinked body 50 Example 11 Instead of the water-absorbing crosslinked body synthesized in Example 1, Example 3
A rubber compound was obtained using the same formulation as in Example 6, except that the water-absorbing crosslinked body synthesized in Example 6 was used, and physical property tests were conducted in the same manner.

The results are shown in Table 2.

Comparative Example 3 Comparative Example 1 was used instead of the water-absorbing crosslinked product synthesized in Example 1.
A rubber compound was obtained using the same formulation as in Example 6, except that the water-absorbing crosslinked body synthesized in Example 6 was used, and physical property tests were conducted in the same manner.

The results are shown in Table 2.

(Margins below) Table 2 Example 12 20 parts of the water-absorbing crosslinked material synthesized in Example 2, 50 parts of ethylene-vinyl acetate copolymer, and 50 parts of polystyrene,
The mixture was kneaded using a roll at 120°C to prepare a film with a thickness of 0.5 fins, and its water absorption capacity was measured. Water absorption capacity is 1.0g
/g composition.

Comparative Example 4 Comparative Example 2 was used instead of the water-absorbing crosslinked product synthesized in Example 2.
A film was prepared using the same formulation as in Example 12, except that 20 parts of the water-absorbing crosslinked material synthesized in Example 12 was used, and the water absorption capacity was measured.

The water absorption capacity was 0.6 g/g composition.

Example 13 The water-absorbing crosslinked material synthesized in Example 3 was kneaded with a 6-inch roll according to the following formulation to obtain a rubber compound.

This rubber compound product was press-cured at 145°C for 35 minutes,
A sheet with a thickness of 2 cranes was obtained.

Regarding this sheet, tensile test, pure water absorption ability test (2
Measurements were carried out in accordance with the water absorption test described above, except that the samples were immersed at 0°C for 5 days.

The results are shown in Table 3.

Combination prescription (part) SL552
(Manufactured by Japan Synthetic Rubber) 100 water absorbent crosslinked body
50HAF carbon black
50 Zinc white 3 Stearic acid l Diphenylguanidine 0. 3 dibenzothiazyl disulfide 0.6 sulfur
1.75 Comparative Example 5 Comparative Example 1 was used instead of the water-absorbing crosslinked product synthesized in Example 3.
A rubber compound product was obtained using the same formulation as in Example 13, except that 50 parts of the water-absorbing crosslinked material synthesized in Example 13 was used, and a tensile test and a pure water water absorption capacity test were conducted in the same manner. The results are shown in Table 3.

Table 3 Example 14 The water-absorbing crosslinked product synthesized in Example 7 was kneaded in a plastomill according to the following formulation to obtain a rubber compound. This rubber compound product was press-vulcanized at 160° C. for 35 minutes to obtain a foamed sheet.

This foam sheet was subjected to a pure water absorption test (measured in the same manner as the water absorption test described above, except that it was immersed at 20° C. for 5 days).

The results are shown in Table 4.

■Prescription now (Part) Natural rubber
100RB830 (manufactured by Nippon Synthetic Rubber) 40 water-absorbing crosslinked body 10
0 Zinc white 5 Stearic acid 4 Calcium carbonate
150 dibenzothiazyl disulfide
0.6 paraffin wax 1
．． 52.6-di-t-butyl-4-methylphenol
1 Diethylene glycol 2 Nichicol 20
5ON 40 dibenzothiazyl disulfide 1. 3-mercaptobenzothiazole
0.2 sulfur
1.3 Tetramethylthiuram disulfide 0. 2
Comparative Example 6 Comparative Example 1 was used instead of the water-absorbing crosslinked product synthesized in Example 7.
A foamed sheet was obtained using the same formulation as in Example 14, except that 100 parts of the water-absorbing crosslinked material synthesized in Example 14 was used, and a pure water absorption test was conducted in the same manner.

The results are shown in Table 4.

Table 4 [Effects of the Invention] The water-absorbing crosslinked material of the present invention has extremely excellent water-absorbing ability, especially water-absorbing ability for aqueous solutions of polyvalent metal salts. Also,
Since the water-absorbing crosslinked product of the present invention contains a double bond,
It is possible to provide a composition that exhibits good co-crosslinking properties with various elastomers such as natural rubber and synthetic rubber elastomers containing unsaturated bonds. Therefore, the water-absorbing crosslinked material of the present invention can be blended with various elastomers and synthetic resins in appropriate proportions to provide a composition with excellent water absorption or hydrophilicity.

Patent applicant: Japan Synthetic Rubber Co., Ltd. Agent: Patent Attorney Takashi Shirai

Claims (3)

[Claims] (1) (a) A sulfonated product of the conjugated diene represented by the general formula (I), (b) a polymer of the sulfonated product, (c) a copolymer of the sulfonated product and another monomer, and (d) A water-absorbing crosslinked product obtained by crosslinking at least one sulfonated product of a conjugated diene polymer in the presence or absence of a vinyl monomer and/or a crosslinkable monomer. ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・( I
) (In the formula, R^1 to R^6 are hydrogen atoms, alkyl groups having 1 to 8 carbon atoms, aryl groups having 6 to 20 carbon atoms, and 1 to 8 carbon atoms.
trialkyltin having an alkyl group of 1 to 8 carbon atoms
trialkyl silicon having an alkyl group of, or -S
O_3X, where X is a hydrogen atom, a metal atom, an ammonium group, or an amino group, and at least one of R^1 to R^6 is -SO_3X. ) (2) An elastomer composition comprising the water-absorbing crosslinked material according to claim 1 and an elastomer. (3) A resin composition comprising the water-absorbing crosslinked material according to claim 1 and a synthetic resin.