JPH02209907A - Ester group-containing (meth)acrylic acid ester (co) polymer and its composition - Google Patents

Abstract

PURPOSE:To obtain the title polymer which is used in automobile parts. because it has a specific composition, viscosity-average molecular weight as well as excellent heat resistance, cold resistance and oil resistance. CONSTITUTION:The copolymerization of a mixture containing (A) 5 to 100wt.% of (meth)acrylic acid ester containing an ester group of the formula (R<1> is H, methyl; R<2> is 3-20C alkylene; R<3> is 1-20C hydrocarbon or its derivative; 1 is integer of 1 to 20) and (B) 0 to 95wt.% of another monomer copolymerizable with component (A), when needed, (C) 0.1 to 10wt.% of a crosslinkable monomer is conducted to give the subject (co)polymer of (meth)acrylic acid ester bearing an ester group of 10,000 to 5,000,000 viscosity-average molecular weight.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention provides heat resistance,
The present invention relates to a (co)polymer containing a specific (meth)acrylic acid ester having cold resistance and oil resistance, and a composition thereof.

[Conventional technology]

Traditionally, natural rubber, styrene-butadiene copolymer rubber (SBR),
Polybutadiene rubber (BR), polyisoprene rubber (I
R), butyl rubber (I IR), acrylonitrile-butadiene copolymer rubber (NBR), chloroprene rubber (C
R), ethylene-propylene-diene ternary copolymer rubber (
EPDM) and acrylic rubber (ACM) are known.

However, in recent years, rubber, which is an industrial material, is required to have advanced functions that cannot be satisfied at the conventional levels of heat resistance, cold resistance, and oil resistance.

In order to improve the physical properties of these rubbers, changes are mainly made to the polymer composition and the types and amounts of compounding agents.

However, even if these changes are made, it is difficult to improve all of the heat resistance, cold resistance, and oil resistance.

For example, in acrylonitrile-butadiene copolymer rubber, increasing the acrylonitrile content improves oil resistance and
Although it is possible to improve heat resistance, cold resistance deteriorates. Therefore, attempts have been made to introduce unsaturated carboxylic acid esters as a means of improving the heat resistance, cold resistance and oil resistance of acrylonitrile-butadiene copolymer rubber. However, although this method improves heat resistance, cold resistance and oil resistance deteriorate.

In addition, for acrylic rubber, a method is known to improve the cold resistance by introducing 2-methoxyethyl acrylate as the main monomer [Journal of the Japan Rubber Association', ■<6> P
2S5 (1980)).

However, although this method improves oil resistance, heat resistance deteriorates.

[Problem to be solved by the invention]

The present invention has been made against the background of the problems of the prior art, and is a (co)polymer composed of an ester group-containing (meth)acrylic ester that can simultaneously satisfy heat resistance, cold resistance, and oil resistance. The object of the present invention is to provide a composition using the (meth)acrylic acid ester or the (co)polymer.

[Means to solve the problem]

The present invention provides (A) an ester group-containing (meth)acrylic ester represented by the following general formula (1) (hereinafter referred to as "component (A)" or "(meth)acrylic ester (■)") 5 to 100% by weight, and (B) 0 to 9 other monomers copolymerizable with the component (A).
The present invention provides an ester group-containing (meth)acrylic ester (co)polymer (hereinafter referred to as "polymer (■)") having a polymerization composition of 5% by weight and a viscosity average molecular weight of 1 to 5 million. .

,,,,, (1) (In the formula, R1 is a hydrogen atom or a methyl group, R1 is an alkylene group having 3 to 20 carbon atoms, R3 is a hydrocarbon group having 1 to 20 carbon atoms or a derivative thereof, and l is 1 to Indicates an integer of 20,
) The present invention also provides (A) 5 to 50% by weight of an ester group-containing (meth)acrylic ester (I), (B-1) an alkyl acrylate whose alkyl group has 3 to 20 carbon atoms, and/or
or alkoxy-substituted alkyl acrylate 10-40
% by weight, (C) crosslinkable monomer 0.1 to 10% by weight, and (B-2) other copolymerizable monomer 0 to 40% by weight, viscosity average molecular weight 1 to 1. Contains 5 million ester groups (meth)
Acrylic ester (co)polymer (hereinafter referred to as “polymer (■
)”.

Furthermore, the present invention provides ester group-containing (meth)acrylic ester (I) 5 to 50% by weight, (B-3> n-butyl acrylate and/or 2-methoxyethyl acrylate 10 to 40% by weight, ( C) Crosslinkable monomer 0.1-10
% by weight, and (B-4) other copolymerizable monomers 0-
Ester group-containing (meth) having a polymerization composition of 40% by weight and a viscosity average molecular weight of 1 to 5 million.
Acrylic ester (co)polymer (hereinafter referred to as “polymer (■
)”.

Furthermore, the present invention includes ester group-containing (meth)acrylic acid ester (■) 5 to 50% by weight, CD) conjugated diene compound 25 to 60% by weight, (E) α,β-unsaturated nitrile compound 20 to 45% by weight. %, and (B-5) other copolymerizable monomers having a polymer composition of 0 to 20% by weight, ester group-containing (meth) having a viscosity average molecular weight of 1 to 5 million.
Acrylic ester (co)polymer (hereinafter referred to as “polymer (■
)”.

Further, in the present invention, 5 to 50 parts by weight of an ester group-containing (meth)acrylic ester (I) and 0.1 to 10 parts by weight of a crosslinking agent are blended with 100 parts by weight of a polymer having rubber elasticity. A rubber composition is provided.

Furthermore, the present invention provides a (meth)acrylic ester prepared by blending a crosslinking agent into at least one ester group-containing (meth)acrylic acid ester (co)polymer selected from the polymers (I) to (IV). An ester (co)polymer composition is provided.

First, to explain the (meth)acrylic acid ester (1) which is the component (A) used in the present invention, the general formula (
In I), R1 is a hydrogen atom or a methyl group, preferably a hydrogen atom.

Further, Rt is an alkylene group having 3 to 20 carbon atoms, preferably 3 to 10 carbon atoms, and examples include a propylene group and a butylene group.

Further, R3 is a hydrocarbon group having 1 to 20 carbon atoms, or a derivative of a hydrocarbon group containing an oxygen atom, a nitrogen atom, a halogen atom, etc., and preferably has 1 to 1 carbon atoms.
0 hydrocarbon group.

This hydrocarbon group having 1 to 10 carbon atoms includes a methyl group,
Alkyl groups such as ethyl group and butyl group; aromatic hydrocarbon groups such as phenyl group, tolyl group and xylyl group; alicyclic hydrocarbon groups such as cyclopentyl group and cyclohexyl group, preferably alkyl groups; Preferred are methyl group and ethyl group.

Furthermore, in -a formula (1), l is an integer of 1 to 20, preferably 1 to 10.

(Meth)acrylic acid ester represented by general formula (1) (
Specific examples of 1) include the following compounds.

CHt ” CHCOOCs Hh COO-CH3,
CHt ”CHCOOCm Hs Coo CH2,
CHg = CHCOOCs HssCOO' CH3,
CHz -CHCOOCI H1@COOCI Hs
-CHz -CHCOOCs Ht. Coo-C,H,
, CHt ” CHC00-Cs HIe COOCs
HIt, CH, -CHCOO(CsHiCOO)t
CzCH! -CHCOO(C4Hs C00) Heavy CICHI -CHCOO-(cs H1@Coo)
! -cmCHt -CI(Coo (Cs Ht.

Coo), -ctCHl =CHCOO-(cs
Ht. Coo) a Cz Hs , CHt =
CHCOO(Cs Hr.C00), -c, R5,
CH,=CHCOO-(cs HteCOO)! -C
, HI7, the (meth)acrylic acid ester (1) is
For example, an unsaturated carboxylic acid represented by the following general formula (II) (hereinafter referred to as "unsaturated carboxylic acid (■)") and an alcohol represented by the following general formula (III) (hereinafter referred to as "alcohol (■)") It can be obtained by an esterification reaction with.

,,,,, (II) [In the formula, R1 to R: and 2 are the same as in the above general formula (1). ] R3-OH, , , (III) [wherein, R3 is the same as in the general formula (1) above. ] The alcohol (II) used in this esterification reaction is
Aliphatic alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, n-7' methyl alcohol, hexyl alcohol, 2-ethylhexyl alcohol; alicyclic alcohols such as cyclopentanol and cyclohexanol; aromatic alcohols such as benzyl alcohol Examples include alcohol. Among these, aliphatic alcohols are preferred from the viewpoint of the balance between oil resistance and cold resistance of the resulting (co)polymer or composition, and methyl alcohol and ethyl alcohol are even better.

This esterification reaction is preferably carried out in the presence of a catalyst. Esterification catalysts include inorganic acids such as sulfuric acid and hydrochloric acid, aromatic compounds sulfonic acid derivatives such as formic acid, acetic acid, propionic acid, p-)luenesulfonic acid, phosphorus oxychloride, polyphosphoric acid, boron trifluoride, and pentoxide. Examples include phosphorus.

These catalysts are characterized by the fact that all reactants [unsaturated carboxylic acid (II)
+alcohol (■)], usually 0.01 to 10
It can be used in a range of 0.1 to 5% by weight, and is preferably used in a range of 0.1 to 5% by weight.

This esterification reaction is an equilibrium reaction, and in order to transfer the equilibrium reaction to the production system, for example, (1) using a large excess of alcohol, (2) using benzene or toluene as a solvent, and using Dean Stark (Dean-5t, 1rk) water as a solvent. The water produced using a separator is separated by azeotropic distillation,
(2) A method of dehydrating the solvent by placing a desiccant such as anhydrous sulfur 7gnesium or molecular sieve SA in a Soxhlet extractor and refluxing the solvent is carried out.

The reaction temperature for esterification is usually 0 to 200°C.
! The temperature is preferably 0 to 100'C.

This esterification reaction can also be carried out using a solvent. As the solvent, in addition to aromatic solvents such as benzene, toluene, and solute, ethers, aliphatic hydrocarbons, esters, and the like can be used. Among these solvents, benzene, toluene, xylene, n-hexane, and the like are preferable because they can be easily and smoothly distilled out of the system by azeotroping with the water produced by the esterification reaction.

In addition, in order to prevent gelation due to radical polymerization during the esterification reaction, 50 to 1,000 ppm of a polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether, methyl hydroquinone, p-benzoquinone, or phenothiazine should be added to the reaction solution. is preferred.

The completion of the esterification reaction can be confirmed by measuring the amount of water produced and distilled off.

Another method for obtaining the (meth)acrylic ester (1) is a (meth)acrylic ester represented by the following general formula (IV) and a hydroxy ester represented by the following general formula (V). A method of synthesizing this by heating in the presence of a catalyst and distilling the released alcohol out of the reaction system is a so-called transesterification reaction.

[In the formula, R1 is the same as in the general formula (1) above, and R4 represents a hydrocarbon group having 1 to 20 carbon atoms or a derivative thereof. ] HO-(R"-C-0)f-R3... (V) [wherein R", R't-' and X c, the above general formula (1)
Same as . ) Note that the catalyst, solvent, and polymerization inhibitor used in this transesterification reaction can be the compounds used in the esterification reaction described above.

A useful (co)polymer of the present invention can be obtained by forming the (meth)acrylic acid ester (1) of the present invention into a homopolymer or a copolymer with other monomers.

At this time, (meth)acrylic acid ester (1
) content is 5-100%, weight is 5-50%
The amount is preferably 5 to 30% by weight, and if it is less than 5% by weight, the effect of improving the heat resistance, cold resistance, and oil resistance of the resulting (co)polymer is small. However, if the amount of (meth)acrylic acid ester (1) is too large, the tensile strength of the (co)polymer will decrease and the compression set at low temperatures will deteriorate.

Other monomers (B) copolymerizable with the (meth)acrylic ester (I) of the present invention include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-methoxyethyl (meth)acrylate,
2-ethoxyethyl (meth)acrylate, 2-butoxyethyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, dimethyl itaconate, diethyl fumarate, di-n-butyl maleate, etc. unsaturated carboxylic acid esters of styrene, vinyltoluene, alpha-methylstyrene, vinylnaphthalene, acrylonitrile, methacyclonitrile, vinyl acetate, vinylidene chloride, vinyl chloride, isobutylene, ethylene and propylene.

Furthermore, the following monomers that can be used as crosslinking points in copolymers (hereinafter referred to as "crosslinkable monomers") can also be mentioned as the copolymerizable monomers.

■Diene monomer, ■Unsaturated carboxylic acid ester containing unsaturated group, ■Vinyl monomer containing epoxy group, ■Vinyl monomer containing carboxyl group, ■Vinyl monomer containing reactive halogen atom, ■Containing hydroxyl group Vinyl monomer, ■ Vinyl monomer containing amide group.

Here, ■ diene monomers include butadiene, ethylidene norbornene, isoprene, piperylene,
Divinylbenzene, vinylcyclohexene, chlorobrene, methylbutadiene, cyclopentadiene, methylpentadiene, dimethylvinylstyrylsilane, etc.
Examples of unsaturated carboxylic acid esters containing unsaturated groups include ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dihydrodicyclopentadienyl(meth)acrylate, dihydrodicyclopentadienyloxyethyl(meth)acrylate, ) acrylate, vinyl (meth)acrylate, dimethylvinylmethacryloxymethylsilane, etc.; ■Epoxy group-containing vinyl monomers include, for example, glycidyl (meth)acrylate, allyl glycidyl ether, etc.; ■carboxyl group-containing vinyl monomers. For example, (meth)acrylic acid, itaconic acid, mono-n-butyl fumarate, monoethyl maleate, mono-n-butyl maleate, 2-methacryloyloxyethylsuccinic acid, 2-methacryloyloxyethyl phthalate, Examples of the reactive halogen atom-containing vinyl monomer include 2-methacryloyloxyethyl hexahydrophthalic acid and 2-methacryloyloxyethylmaleic acid, such as 2-chloroethyl vinyl ether, vinyl chloroacetate, and allyl chloroacetate. , ■
Examples of hydroxyl group-containing vinyl monomers include 2-hydroxyethyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxyethyl methacrylate, N-
Examples of vinyl monomers containing amide groups include methylol (meth)acrylamide and the like.

The above copolymerizable monomers may be used alone or in combination.
More than one species can be used together.

The alkyl acrylate having an alkyl group having 3 to 20 carbon atoms, which is the component (B-1), means an alkyl acrylate in which the alkyl group of the acrylic acid ester has 3 to 20 carbon atoms, and 3g (B-1) component Specific examples include propyl acrylate, n-butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, and 2-ethyl acrylate.
-methoxyethyl, etc., and specific examples of alkoxy-substituted alkyl acrylates include 2-ethoxyethyl acrylate, 2-butoxyethyl acrylate, and the like.

Component (B-2) is the component (B) excluding the component (B-1) and the component (C) described below.

The crosslinkable monomer as component (C) is the same as the crosslinkable monomer in component (B).

Specific examples of the conjugated diene compound as component (D) include butadiene, isoprene, methylbutadiene, chloroprene, etc. in component (B).

Examples of the α,β-unsaturated nitrile compound as component (E) include acrylonitrile and methacrylaterile in component (B).

The component (B-4) is the component obtained by removing the component (B-3) and the component (C) from the component (B).

The component (B-5) is the component (B) minus the components (D) and (E).

The (B-1) component in the polymer ■ is 10 to 40% by weight, and if it is less than 10% by weight, the amount of the (A) component will increase and the low temperature compression set will be poor if you try to obtain sufficient low temperature properties. On the other hand, if it exceeds 40% by weight, the amount of component (A) decreases, resulting in an insufficient balance of cold resistance, heat resistance, and oil resistance.

The content of component (C) in polymers (1) and (2) is from 0.1 to 10% by weight, preferably from 0.1 to 5% by weight; if it is less than 0.1% by weight, the tensile strength of the resulting (co)polymer will decrease. On the other hand, if it exceeds IO weight %, elongation tends to decrease.

The content of component (D) in polymer ■ is 25 to 60% by weight.
If it is less than 25% by weight, the tensile strength is poor;
If it exceeds %, heat resistance will be insufficient.

The content of component (E) in polymer ■ is 20 to 15% by weight.
If it is less than 20% by weight, the oil resistance will be poor, while if it exceeds 45% by weight, the cold resistance will be insufficient. The (co)polymerization method for the combination is not particularly limited, but it can be easily produced by conventional emulsion polymerization, suspension polymerization, bulk polymerization, or solution polymerization, preferably in the presence of a radical polymerization initiator. .

Examples of emulsifiers used in producing a (co)polymer by emulsion polymerization include alkyl sulfates, alkylaryl sulfonates, salts of higher fatty acids, and the like.

The (co)polymerization reaction can be carried out at a temperature of -100 to +200°C, preferably 0 to +60°C.

Examples of radical initiators for initiating polymerization include organic peroxides such as benzoyl peroxide, cumene hydroperoxide, and paramenthane hydroperoxide, azo compounds represented by azobisisobutyronitrile, and potassium persulfate. , inorganic persulfates such as ammonium persulfate, and redox catalysts typified by a combination of organic peroxide and iron sulfate.

These radical initiators are generally used in an amount of 0.01 to 2% by weight based on the monomer mixture.

The molecular weight regulator is used as necessary, and specific examples thereof include t-dodecylmercaptan, dimethylxanthogen disulfide, and the like.

After the polymerization reaction reaches a predetermined polymerization conversion rate, N, N-
A reaction terminator such as diethyl hydroxylamine is added to stop the polymerization reaction, then unreacted monomers in the resulting latex are removed by steam distillation, and anti-aging agents such as phenols and amines are added. A (co)polymer can be obtained by coagulating the latex by further mixing with an aqueous solution of a metal salt such as an aqueous solution of aluminum sulfate or an aqueous solution of calcium chloride, and then drying the latex.

In addition, when producing a (co)polymer by suspension radical polymerization, saponified polyvinyl alcohol is added as a dispersant, and an oil-soluble radical initiator such as azobisisobutyronitrile or benzoyl peroxide is used. After polymerization, a (co)polymer can be obtained by removing water.

Furthermore, even when producing a (co)polymer by solution radical polymerization, methods known for boat fishing can be employed.

The polymerization method can be either continuous or batchwise.

The molecular weight of the (co)polymer of the present invention thus obtained is determined by factors such as the type and amount of the molecular weight regulator, the type and amount of the radical initiator, the polymerization temperature, the type and amount of the solvent, and even the monomer concentration. By changing the reaction conditions, the viscosity average molecular weight is adjusted to 1 to 5 million, preferably 10 to 2 million. If the viscosity average molecular weight of the (co)polymer is less than 10,000, the mechanical strength of the resulting (co)polymer will be poor, and if it exceeds -5,000,000, the processability will deteriorate, which is not preferred.

Next, the (meth)acrylic acid ester (I) is blended with a polymer having rubber elasticity and a crosslinking agent.
It can be used as a rubber composition.

Polymers with rubber elasticity used in the rubber composition of the present invention include natural rubber, styrene-butadiene copolymer rubber, polybutadiene rubber, polyisoprene rubber, butyl rubber, acrylonitrile-butadiene copolymer rubber, chloroprene rubber, and ethylene. -propylene-(diene) copolymer rubber, acrylic rubber, epichlorohydrin rubber, fluororubber, chlorinated polyethylene rubber, urethane rubber, etc., but acrylic rubber, acrylonitrile-butadiene copolymer rubber, and more preferably acrylic rubber are used. be.

The amount of the (meth)acrylic ester (1) of the present invention added to the polymer having rubber elasticity is usually 5 to 50 parts by weight, preferably 5 to 20 parts by weight, based on 100 parts by weight of the polymer.
If it is less than 5 parts by weight, the effect of improving the cold resistance of the obtained rubber composition will not be sufficient, while if it exceeds 50 parts by weight, the mechanical strength of the obtained rubber composition will deteriorate.

In addition, the crosslinking agent to be blended in the rubber composition includes the type of polymer in the rubber composition containing the (meth)acrylic acid ester (1) of the present invention, and the type of crosslinking agent in the (co)polymer composition described later. It varies depending on the type of crosslinking monomer in the (co)polymer to be blended.

For example, the polymer having rubber elasticity in the rubber composition of the present invention may include natural rubber, isoprene rubber, styrene-butadiene copolymer rubber, butadiene rubber, acrylonitrile-
In the case of butadiene copolymer rubber, sulfur, organic sulfur-containing compounds, organic peroxides, etc. are mainly used as the crosslinking agent. Further, in the case of chloroprene rubber and chlorosulfonated polyethylene, a metal oxide or the like is used as the crosslinking agent. Furthermore, in the case of butyl rubber, sulfur, quinone dioxime, modified alkylphenol resin, etc. are used as the crosslinking agent. Furthermore, in the case of ethylene-propylene-(diene) copolymer rubber, sulfur, organic peroxide, etc. are used as the crosslinking agent. Furthermore, in the case of urethane rubber, polyisocyanates, polyamines, organic peroxides, etc. are used as crosslinking agents. Furthermore, in the case of acrylic rubber, metal soaps, polyamines, organic carboxylic acid ammonium salts, sulfur, sulfur-containing compounds, organic peroxides, etc. are used as crosslinking agents depending on the type of crosslinking functional group introduced. used.

Furthermore, as a crosslinking agent, in the case of a copolymer composition whose main components are a (co)polymer composed of the (meth)acrylic acid ester (1) of the present invention described later and a crosslinking agent,
When the (co)polymer is copolymerized with a crosslinkable monomer, the following can be selected as the crosslinking agent.

That is, the crosslinking monomer is a diene monomer and/or
Alternatively, in the case of an unsaturated carboxylic acid ester containing an unsaturated group, sulfur, an organic sulfur-containing compound, or an organic peroxide is used as a crosslinking agent.

In addition, when an epoxy group-containing vinyl monomer is used as a crosslinkable monomer, polyamine, polycarboxylic acid,
Acid anhydrides, polyamides, sulfonamides, dithiocarbamates, organic ammonium carboxylates, and the like are used as crosslinking agents.

Furthermore, when a carboxyl group-containing vinyl monomer is used as the crosslinking monomer, polyamines, polyepoxides, polyols, etc. are used as the crosslinking agent.

Furthermore, when (1) a reactive halogen atom-containing vinyl monomer is used as the crosslinking monomer, metal soaps, organic carboxylic acid ammonium salts, polyamines, polycarbamates, etc. are used as the crosslinking agent.

Furthermore, when a hydroxyl group-containing vinyl monomer is used as a crosslinking monomer, polyisocyanate, polycarboxylic acid, alkoxymethyl melamine, etc. are used as a crosslinking agent.

Furthermore, when an amide group-containing vinyl monomer is used as a crosslinkable monomer, aminoformaldehyde or the like is used as a crosslinking agent.

Among these crosslinking agents, powdered sulfur,
Any of precipitated sulfur, colloidal sulfur, insoluble sulfur, and highly dispersed sulfur can be used.

The organic sulfur-containing compound is a compound that releases active sulfur by thermal dissociation, and includes, for example, thiuram promoters such as tetramethylthiuram disulfide and 4,4'-dithiomorpholine.

Examples of organic peroxides include 2,5-dimethyl-2゜5-di(t-butylperoxy)hexane, 2゜5-dimethyl-2,5-di(t-butylperoxy)hexane,
3-bis(t-butylperoxyisopropyl)benzene, dicumyl peroxide, dibutyl peroxide 1,1, 1-dibutylperoxy-3,3,
5-trimethylcyclohexane, t-butylcumyl peroxide, t-butylperoxy-isopropyl carbonate, etc. are used.

Examples of metal oxides include zinc oxide, magnesium oxide, and lead oxide.

Examples of the quinone dioxime include p-quinone dioxime and P,P'-dibenzoylquinone oxime.

Examples of modified alkylphenol resins include alkylphenol formaldehyde resins and brominated alkylphenol formaldehyde resins.

Examples of the polyisocyanate include hexamethylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, and the like.

Examples of polyamines include triethylenetetramine,
Examples include methylene dianiline and diethylene triamine.

Examples of metal soaps include sodium stearate and potassium stearate.

Examples of organic carboxylic acid ammonium salts include ammonium benzoate and ammonium adipate.

Examples of polycarboxylic acids include adipic acid and octadecyldicarboxylic acid.

Examples of the acid anhydride include pyromellitic anhydride, maleic anhydride, and dodecenylsuccinic anhydride.

Examples of dithiocarbamic acids include hexamethylene diamine carbamate, zinc dimethyldithiocarbamate, and the like.

Examples of the polyepoxide include ethylene glycol diglycidyl ether and 1,6-hexaneshiol diglycidyl ether.

Examples of polyols include 1,4-butanediol,
Examples include 1,1.1-trimethylolpropane.

A crosslinking aid can be added to these crosslinking agents in order to shorten the crosslinking time, lower the crosslinking temperature, and improve the performance of the crosslinked product.

For example, when sulfur is used as a crosslinking agent, thiazoles such as mercaptobenzothiazole, thiurams such as tetramethylthiuram disulfide, guanidines such as diphenylguanidine, and dithiocarbamates such as zinc dimethyldithiocarbamate are used as crosslinking agents. It can be effectively used as an agent.

When using an organic peroxide as a crosslinking agent, ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate , polyethylene glycol dimethacrylate, 1.4-butanediol diacrylate, 1.6-
Hexanediol diacrylate, 2,2'-bis(4
-methacryloyljethoxyphenyl)propane, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, divinylbenzene, N,N'-methylenebisacrylamide, p-quinonedioxime, p
, p'-dibenzoylquinone dioxime, triazinedithiol, triallylcyanurate, triallylisocyanurate, bismaleimide, silicone oil with a high vinyl content, and the like can be effectively used as crosslinking aids.

When using a metal oxide as a crosslinking agent, for example, dipentamethylenethiuram tetrasulfide can be effectively used as a crosslinking aid, if necessary.

When using quinone dioxime as a crosslinking agent, an oxidizing agent such as red lead can be effectively used as a crosslinking aid.

When using modified phenolic resin as a crosslinking agent,
For example, halides such as chlorinated polyethylene and tin chloride can be effectively used as crosslinking aids.

When a metal soap is used as a crosslinking agent, for example, sulfur or dipentamethylenethiuram tetrasulfide can be effectively used as a crosslinking aid.

When using an amine as a crosslinking agent, for example, diphenylguanidine and diorthotolylguanidine can be effectively used as a crosslinking aid.

The blending amount of these crosslinking agents in the rubber composition of the present invention is based on 100 parts by weight of the polymer having rubber elasticity.
It is usually used in a proportion of 0.1 to 10 parts by weight; if it is less than 0.1 part by weight, crosslinking will hardly proceed, while if it exceeds 10 parts by weight, the physical properties of the resulting (co)polymer composition will be impaired. Undesirable.

Next, the novel (meth)acrylic acid ester (1
) is also useful as a (co)polymer composition by blending the above-mentioned crosslinking agent. In this case, the above blending amount in the (co)polymer composition of the present invention is usually , used in a proportion of 0.1 to 10 parts by weight, 0.1
If the amount is less than 10 parts by weight, the crosslinking will hardly proceed, whereas if it exceeds 10 parts by weight, the crosslinking reaction rate will become too high and the physical properties of the resulting (co)polymer composition will be impaired, which is not preferable.

The rubber composition or (co)polymer composition of the present invention is prepared by adding each of the above-mentioned components and, if necessary, various compounding agents, and then using a conventional mixer such as a two-roll mixer or a Banbury mixer. It is prepared by mixing using

Among the compounding agents, fillers include carbon black and white fillers such as silica, calcium carbonate, talc, and magnesium carbonate.

In addition, among the compounding agents, examples of dispersants include higher fatty acids and their metal salts or amide salts; plasticizers include:
For example, phthalic acid derivatives, adipic acid derivatives, polyether esters; softening agents, such as lubricating oils, process oils, castor oil; anti-aging agents, such as 4.4
Amines such as '-(α,α'-dimethylbenzyl)diphenylamine, phenols such as 2,2'-methylenebis(4-methyl6-t-butylphenol), imidazoles; other pigments, crosslinking accelerators, flame retardants , a foaming agent, a scorch inhibitor, a tackifier, a lubricant, etc. can be optionally added.

The rubber composition or (co)polymer composition of the present invention obtained in this manner can be molded and crosslinked under normal crosslinked rubber manufacturing conditions to form a crosslinked product. That is, after molding, the temperature is usually 150 to 180°C and 10 to 60°C.
1-2 minutes at 150-180°C, if necessary
After 0 hours of secondary crosslinking, a crosslinked product with excellent heat resistance, cold resistance, and oil resistance can be obtained.

〔Example〕

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples unless the gist thereof is exceeded.

In the examples, parts and percentages are based on weight unless otherwise specified.

In addition, in the examples, the methods for measuring the properties of the obtained (meth)acrylic acid (co)polymer and crosslinked product are as follows.

infrared analysis Equipment; manufactured by JASCO ■, type A-III The (co)polymer was measured by the KBr tablet method.

1" C-NMR (Model FX100 manufactured by NEC Corporation) A 13C-nuclear magnetic resonance spectrum was obtained after dissolving the polymer in chloroform. The peak of the spectrum was attributed to the rchewical 5hift range
Carbon-13NMR5pectroscopy
(Wolfgang Bremser Burgha
rd Franke Hans Wagner) J.

The chlorine content in the polymer of ROL VINYL was measured and determined by fluorescent X-ray method.

The epoxy equivalent was determined by dissolving a polymer of Alg 1 cidyl ether in chloroform and then measuring the epoxy equivalent using the acetic acid method.

After dissolving the akmyl vinyl polymer in chloroform, the iodine value was determined by the iodine titration method.

U-Gonbai Apparatus: Constant Temperature Water Bath The polymer was dissolved in chloroform and then measured using an Ubbelohde viscometer.

Yusei Tsuku! A rubber sheet or block was prepared from a rubber composition containing acrylic ester (I) or a composition containing this acrylic ester copolymer, and crosslinked for a predetermined period of time using a crosslinking press apparatus. Further, crosslinking was further carried out for a predetermined period of time using gear opening as necessary.

The obtained crosslinked sheet or block was molded using a dumbbell cutter, and its heat resistance, cold resistance, and oil resistance were measured according to JIS K6301.

Reference Example 1 [Production of acrylic acid ester (1)] Unsaturated carboxylic acid having the structural formula shown below (Toagosei Chemical Co., Ltd.
M-5300) CH,=CHCOO(C,H,0C
OO), 300 g of lH (where n is 1 to 5),
138 g of ethyl alcohol 1 ICC of concentrated sulfuric acid and 300 cc of toluene were added to a stirrer and a Dean-Stark (
Dean-Stark) into a flask with a water separator.

Heating was then carried out under reflux, and the water produced was separated from a water separator. Heating was continued until no water formation was observed. After cooling to room temperature, the reaction mixture in the flask was mixed with water (500 cc) and 1% sodium bicarbonate (500 cc).
c) and water (500 cc). moreover,
It was dried with anhydrous sodium sulfate. Unreacted ethyl alcohol and toluene were distilled off under reduced pressure to obtain a colorless viscous liquid product with a yield of 80%. This product is designated as acrylic ester (2).

Reference Example 2 [Production of acrylic acid ester (1)] 2-ethylhexyl alcohol 3 instead of ethyl alcohol
The same procedure as in Example 1 was carried out except that 87 g was used, and a colorless viscous liquid was obtained with a yield of 78%. This product is designated as acrylic ester (2).

Example 1 (Production of acrylic ester copolymer and composition using the copolymer) 100 parts of monomer mixture, 4 parts of sodium lauryl sulfate,
0.25 part of P-menthane hydroperoxide, 0.01 part of ferrous sulfate, 0.025 part of sodium ethylenediaminetetraacetate, and 0.04 part of sodium formaldehyde sulfoxylate were charged into an autoclave purged with nitrogen, and reacted. The reaction was carried out at a temperature of 30°C until the monomer conversion reached 90%, and 0.5 part of N,N-diethylhydroxylamine was added to stop the reaction.

Next, the reaction product was taken out and water vapor was blown into it to remove unreacted monomers. The rubber latex thus obtained was coagulated by adding it to a 0.25% calcium chloride aqueous solution, and the coagulated product was thoroughly washed with water and dried at about 90° C. for 3 hours to obtain copolymer A.

The infrared absorption spectrum of the obtained copolymer A is shown in FIG. The stretching vibration of \C=O of the ester group was observed at 1.730 CIl-', and the stretching vibration of the methylene group was observed at 2,950-2,850/cm-'.

Moreover, the '3C-NMR spectrum of the obtained copolymer A is shown in FIG.

The composition of copolymer A was calculated from the chemical shift of the I3C-NMR spectrum. However, the vinyl chloroacetate content was determined by fluorescent X-ray method, and the results are shown in Table 1.

In addition, the viscosity average molecular weight (M) of the obtained copolymer A is:
It was determined as follows and the results are shown in Table 1.

Cv) = 31.4xlO-” (M) “” (m
l/g) [Polymer Handbook IV-10, 1
975 (Polymer handbook IV-1
0, J., Brandrup, E. H.

Immergut, A i+1ley-1nters
(science publication)) Copolymer A obtained as described above and the crosslinking agent shown in Table 2 were kneaded with a roll to obtain a novel acrylic ester copolymer composition.

The properties of the crosslinked product obtained from this composition were determined according to JIS K
Table 3 shows the results measured according to 6301.

Examples 2 to 5 (Production of acrylic acid ester copolymer and composition using the copolymer), Comparative Examples 1 to 3 Monomers were produced using the same reaction apparatus as in Example 1 and under the same reaction conditions. The mixture was reacted to obtain a copolymer.

The composition and molecular weight of this copolymer were analyzed in the same manner. Allyl glycidyl ether was determined by quantifying epoxy groups, and vinyl acrylate was determined by iodine titration.

The composition of the obtained copolymer is shown in Table 1, the copolymer composition and crosslinking conditions are shown in Table 2, and the properties of the crosslinked product are shown in Table 2 and FIG.

These results show that the acrylic ester copolymer composition of the present invention has superior heat resistance, cold resistance, and oil resistance compared to conventional copolymer compositions.

Examples 6 to 8 (Production of acrylic acid ester copolymer and composition using the copolymer), Comparative Examples 4 to 5 In the same manner as in Example 1 until the monomer mixture reached a conversion rate of 80%. A copolymer was obtained by reaction.

The composition of the copolymer was determined from the IIC-NMR spectrum in the same manner as in Example 1, and the results are shown in Table 3.

In addition, the viscosity average molecular weight (M) of the obtained copolymer A is:
It was determined as follows and the results are shown in Table 3.

[η)=54X10 bow (M)”” (ml!/g) [Polymer Handbook IV-10, 1975
+er handbook IV-10+ J, Br
andrup+ E, H.

1+u+ergut, A wiley-1nters
cfence publication)) To 100 parts of the obtained copolymer were added 5 parts of zinc oxide, 1 part of stearic acid, 60 parts of SRF carbon black, 5 parts of dioctyl phthalate, 0.5 part of sulfur, 1.5 parts of tetramethylenethiuram disulfide, and After adding 2.0 parts of N-cyclohexyl-2-benzothiazylsulfenamide and mixing with a roll, press crosslinking was performed at 160°C for 20 minutes to produce a crosslinked sheet. The properties of the crosslinked product were measured in the same manner as in Example 1, and the results are shown in Table 3.

From the results in Table 3, the copolymer composition using acrylic acid ↓ ster of the present invention has a better balance of heat resistance, cold resistance, and oil resistance than the copolymer composition using conventional acrylic ester. It turns out that it is excellent.

Examples 9 to 11 [Production of rubber compositions containing acrylic ester (1)], Comparative Examples 6 to 8 Using polymer types H and ■ shown in Table 1, various compounding agents shown in Table 4 were prepared. The mixture was kneaded with a roll to obtain a rubber composition. Using this rubber composition, a crosslinked sheet was prepared, and the properties of the crosslinked product were evaluated in Example 1.
The test was carried out in the same manner as above, and the results are shown in Table 4 and FIG. The results show that the rubber composition containing the novel acrylic ester of the present invention as an essential component has a better balance of heat resistance, cold resistance, and oil resistance than conventional rubber compositions.

Examples 12-13 (Production of rubber composition containing acrylic ester (1)), Comparative Examples 9-10
Rubber compositions were prepared using the various compounding agents shown in Table 5 in the same manner as in Example 9, except that BR was used, and the properties of the crosslinked products were measured.

From the results in Table 5, it can be seen that the rubber composition containing the acrylic ester of the present invention as an essential component has a better balance of heat resistance, cold resistance, and oil resistance than conventional rubber compositions.

〔Effect of the invention〕

The (meth)acrylic acid ester (co)polymer of the present invention, a composition containing the (co)polymer, and (meth)
Rubber compositions containing acrylic esters have excellent heat resistance, cold resistance, and oil resistance.

Taking advantage of these properties, the (co)polymer, rubber composition, and (co)polymer composition of the present invention can be used for various industrial materials, such as belts, hoses, rolls, packing, rubberized cloth, and rubber gloves. , additives for synthetic resins, adhesives, etc.

[Brief explanation of the drawing]

Figure 1 shows the infrared absorption spectrum of the acrylic acid ester copolymer obtained in Example 1, and Figure 2 shows the '3C-nuclear magnetic resonance spectrum of the copolymer obtained in Example 1. The figure shows the balance between cold resistance, heat resistance, and cold resistance and oil resistance of a composition using an acrylic ester copolymer, and Figure 4 shows the cold resistance and oil resistance of a rubber composition containing an acrylic ester copolymer. This is a diagram showing the balance between cold resistance and oil resistance.Patent applicant: Japan Synthetic Rubber Co., Ltd. Representative Patent attorney: Shige Takashi Shirai
lφC】Atonement Chart

Claims (6)

[Claims] (1) (A) 5 to 100% by weight of an ester group-containing (meth)acrylic ester represented by the following general formula (I), and (B) other monomers copolymerizable with the component (A) above. 0-9
An ester group-containing (meth)acrylic ester (co)polymer having a polymerization composition of 5% by weight and a viscosity average molecular weight of 1 to 5 million. ▲There are mathematical formulas, chemical formulas, tables, etc.▼． ．． ．． ．． ．． (I) (In the formula, R^1 is a hydrogen atom or a methyl group, R^2 is an alkylene group having 3 to 20 carbon atoms, and R^3 is an alkylene group having 1 to 20 carbon atoms.
is a hydrocarbon group or a derivative thereof, l represents an integer of 1 to 20. ) (2) (A) 5 to 50% by weight of the ester group-containing (meth)acrylic acid ester according to claim 1; (B-1) alkyl acrylate and/or alkoxy-substituted alkyl acrylate in which the alkyl group has 3 to 20 carbon atoms; 10 to 40% by weight, (C) 0.1 to 10% by weight of crosslinkable monomer, and (B-
2) Ester group-containing (meth) with a viscosity average molecular weight of 1 to 5 million, having a polymer composition of 0 to 40% by weight of other copolymerizable monomers
Acrylic acid ester (co)polymer. (3) (A) 5 to 50% by weight of the ester group-containing (meth)acrylic ester according to claim 1, (B-3) 10 to 40% by weight of n-butyl acrylate and/or 2-methoxyethyl acrylate , having a polymer composition of (C) 0.1 to 10% by weight of a crosslinkable monomer, and (B-4) 0 to 40% by weight of another copolymerizable monomer, and a viscosity average molecular weight of 1 to 5 million. Contains an ester group (meth)
Acrylic acid ester (co)polymer. (4) (A) 5 to 50% by weight of the ester group-containing (meth)acrylic ester according to claim 1, (D) 25 to 60% by weight of the conjugated diene compound, (E) α,
Ester group-containing (with a viscosity average molecular weight of 1 to 5 million) having a polymer composition of 20 to 45% by weight of a β-unsaturated nitrile compound and 0 to 20% by weight of (B-5) another copolymerizable monomer. Meta)
Acrylic acid ester (co)polymer. (5) For 100 parts by weight of a polymer having rubber elasticity,
A rubber composition comprising 5 to 50 parts by weight of the ester group-containing (meth)acrylic ester according to claim 1 and 0.1 to 10 parts by weight of a crosslinking agent. (6) A (meth)acrylic ester (co)polymer composition obtained by blending the ester group-containing (meth)acrylic ester (co)polymer according to any one of claims 1 to 4 with a crosslinking agent.