JPS6230155A - High strength, high rigidity rubber composition - Google Patents

Abstract

PURPOSE:The titled composition, obtained by adding a compounding ingredient to a nonconjugated diene based rubber containing an acenaphthylene based monomer as a copolymerization component or a mixture thereof with another rubber, having a high strength and high rigidity and suitable for safety bumpers, or the like. CONSTITUTION:A high-strength and high-rigidity rubber composition obtained by incorporating a raw material rubber which is a nonconjugated rubber containing acenaphthylene or a monomer which is acenaphthylene having one or more substituent groups, e.g. alkyl group, without inhibiting the polymerizability on the carbon atoms of vinylene groups and naphthalene ring in an amount of 2-60wt% as a copolymerization component or a mixture of >=5wt% above-mentioned nonconjugated diene based rubber with another rubber, e.g. polybutadiene rubber, with a compounding ingredient.

Description

Detailed Description of the Invention (Industrial Field of Application) The present invention is a high-strength non-diene rubber containing an acenaphthylene monomer as a copolymerization component or a mixture of this and other rubbers as a raw material rubber. The present invention relates to a rubber composition that provides a highly rigid vulcanizate.

(Prior art) Conventionally, in the rubber industry, methods for improving the strength and rigidity of rubber include methods of blending fine particulate reinforcing agents such as carbon blank and silica with rubber, and methods of blending short fibers such as polyester and nylon. However, these methods had the disadvantage that the stiffness could be increased (by increasing the amount of particulate reinforcing agents and short fibers blended), resulting in a decrease in strength. The inventors solved the above-mentioned drawbacks by using a non-diene rubber containing an acenaphthylene monomer as a copolymer component. 90 (Means for Solving Problems) The object of the present invention is to obtain a rubber composition based on this knowledge. This is achieved by using a rubber composition obtained by adding a compounding agent to a non-diene rubber contained as a polymerization component or a mixture of this and other rubbers.

The non-diene rubber containing an acenaphthylene monomer as a copolymerization component (hereinafter sometimes referred to as non-diene rubber) used in the present invention is characterized by (1) a non-diene rubber containing an acenaphthylene monomer as a monomer; A rubber-like copolymer copolymerized with a diene monomer or a non-diene monomer and other copolymerizable monomers, or an acenaphthylene monomer, or the monomer and the same. (3) A rubber-like block copolymer having a blocked non-diene rubber block in the same molecule with a monomer that can be copolymerized with It includes a rubber-like graft copolymer obtained by grafting a copolymer of the monomer and a monomer copolymerizable with the monomer.

The acenaphthylene monomer is an acenaphthylene having a small number of substituents (one substituent that does not inhibit polymerization) on the carbon and naphthalene rings of the acenaphthylene and vinylene groups.There are no particular restrictions on the substituents as long as they are listed above, but examples include alkyl, Substituents include cycloalkyl, alkenyl, aralkyl, alkynylene, aralkylene, halogen, hydroxy, alkoxy, carboxy, alkylcarboxy, mercapto, amino, N-alkylamino, N, N-dialkylamino, and the like.

Monomers other than the acenaphthylene monomer constituting the non-diene rubber of the present invention are olefin monomers such as ethylene, propylene, and 1-butene that can be copolymerized with the non-diene rubber; vinyl chloride, vinylidene chloride, and fluorinated monomers. Halogen-substituted olefin monomers such as vinyl, vinylidene fluoride, tetrafluoroethylene, and hexafluoropropylene; Styrenic monomers such as styrene, 2-chlorostyrene, and p-chloromethylstyrene; Saturated nitrile monomers; acrylates such as methyl acrylate, ethyl acrylate, globyl acrylate, ruby acrylate, ruby octyl acrylate, methoxymethyl acrylate, methoxyethyl acrylate, ethoxyethyl acrylate, and their corresponding methacrylates: vinyl acetate, globionic acid Vinyl esters such as vinyl and vinyl butyrate; Vinyl ketones such as methyl vinyl ketone and ethyl vinyl ketone; Unsaturated amide monomers such as acrylamide, N, N-dimethyl acrylamide; β-hydroxylethyl acrylate, 4-hydroxyl butyl acrylate, etc. vinyl monomer having a hydroxyl group; glycidyl acrylate, glycidyl methacrylate, used as a crosslinking site;
Epoxy group-containing 1 such as vinyl glycidyl ether, allyl glycidyl ether, methallyl glycidyl ether, etc.
1-mer, 2-chloroethyl vinyl ether, vinyl chloroacetate, allyl chloroacetate, halogen-containing monomers such as vinylbenzyl chloride, carboxyl group-containing monomers such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, monomethyl maleate, etc. These monomers can be used in combination of 11!1 or two or more. Among the above-mentioned exemplified monomers, particularly preferred are monomers capable of radical copolymerization with acenaphthylene monomers.

The content of acenaphthylene monomer is 2 in the above copolymer.
It is preferable that the amount is equal to or higher than the weight ratio, and if it is less than 2% by weight, the effect of the present invention will be small. Moreover, if it exceeds 60% by weight, the rubber elasticity is lost and the resin becomes resinous, which is not preferable. More preferably 5-40
Weight%. The ratio of the remaining non-diene monomers and copolymerizable monomers can be arbitrarily determined depending on the compatibility with other rubbers as raw material rubber, the intended use of the rubber composition, etc. There is no particular restriction as long as the glass transition temperature of the non-diene rubber is 10°C or less.

Examples of the non-diene rubber of the present invention include acenaphthylene-butyl acrylate copolymer rubber, acenaphthylene-ethyl acrylate-methoxyethyl acrylate-glycidyl methacrylate copolymer rubber, acenaphthylene-ethylene-vinyl acetate copolymer rubber, and acenaphthylene-ethylene-vinyl acetate copolymer rubber.
Vinyl acetate-chlorovinyl ether copolymer rubber, (polyacenaphthylene)-(vinylidene fluoride-hexafluoropropylene copolymer) block copolymer, ethylene-
Examples include propylene-diene ternary copolymer rubber-graft-acenaphthylene-non-diene rubber.

The non-diene rubber of the present invention is used alone or blended with other rubbers as a raw material rubber in the rubber composition of the present invention. The preferred amount of non-diene rubber in the raw rubber is at least 5% by weight, and if it is less than 5% by weight, a rubber composition with high elasticity and high rigidity cannot be obtained. Preferably 1
It is 0% by weight or more, more preferably 20% by weight or more.

Other raw rubbers used according to the invention include polybutadiene rubber, polyisoprene rubber (natural and threatened).
, styrene-butadiene copolymer rubber, acrylonitrile-butadiene copolymer rubber, chloroglene rubber, ethylene-globylene-diene monomer ternary copolymer rubber, acrylic rubber, fluororubber, and the like.

The rubber composition of the present invention can be obtained by mixing the above-mentioned raw material rubber and compounding agents using a conventional mixer.

The compounding agents used in the present invention include a sulfur vulcanization system containing sulfur or a sulfur-donating compound, a vulcanization aid, a vulcanization accelerator, etc.; an organic peroxide vulcanization system; a polyamine vulcanization system; an organic carboxylic acid ammonium vulcanization system; Vulcanization systems such as sulfur-based and non-sulfur-based vulcanization systems such as polyol vulcanization systems, carbon blanks, reinforcing agents such as silica, fillers such as charcoal and talc, inorganic or organic fibrous reinforcing agents, and plasticizers. , softeners, processing aids, anti-aging agents, and other compounding agents commonly used in the rubber industry can be used, and the types and amounts are appropriately determined depending on the purpose of the rubber composition.

Thus, according to the present invention, compared to the prior art, high strength and
Highly rigid rubber can be obtained.

The rubber composition of the present invention is applicable to various tires, safety bumpers, brake parts, various hoses, interior repair related parts, various boots, automotive parts such as belts, belts, hoses, etc. Suitable for applications such as industrial parts such as rolls, fenders, ships such as marine hoses, marine related materials, oil well parts such as oil well parts, footwear, etc.

The present invention will be specifically explained below with reference to Examples.

The parts used in the polymer production examples and examples are based on weight.

Polymer Production Example 1 In an autoclave with an internal volume of 2-e, the following polymerization recipe (I
) and (II), the monomer mixtures shown in Table 1 were polymerized. Prior to polymerization, each component of the polymerization recipe (I) was charged into an autoclave, the pH was adjusted to 7, the temperature in the system was brought to 5°C while stirring, and the system was replaced with nitrogen.
Each component was added to initiate polymerization. Polymerization was completed in 15 hours. The polymerization conversion rate was within the range of 88 to 98 inches. After completion of the polymerization, the polymerization product was salted out, thoroughly washed with water, dissolved in acetone, coagulated with a large amount of hexane, and dried under reduced pressure to obtain a polymer.

Polymerization recipe CI) Water
i oootanium dodecylbenzene sulfonate 20? Sodium naphthalene sulfonate 102 Sodium sulfate
5y ethylenediaminetetraacetic acid tetrasodium salt
(1,2y ethylenediaminetetraacetic acid sodium ferric salt Q, 005F monomer mixture (1st
Table) Polymerization recipe (II) Na2S204 Q, 2 tanasodium formaldehyde "sulfoxylate"
0.2fp-menthane hydroperoxide
Production example 2 of 0.1y polymer: 200 g of acenaphthylene was placed in an autoclave with an internal volume of 1-e.
parts, 200 parts of benzene, polydiacylno(-oxide(
An amount of active oxygen of 4% and an average degree of polymerization of 1.2 parts were charged, and polymerization was carried out at 50° C. until the monomer conversion rate reached 20 or more. After polymerization, the polymer was coagulated with a large amount of methanol, and the obtained polymer was washed twice with methanol and dried under reduced pressure to obtain a polymer containing oxide groups. The polymer had a weight average molecular weight of 106,000 according to GPO.

Next, according to the polymerization recipe @), polymerization was carried out at 70 °C using an autoclave with an internal volume of 12 until the monomer conversion rate reached 50%. After polymerization, it was coagulated with methanol, and after washing twice with methanol, the pressure was reduced. A polymer was obtained by drying. The fluorine content in this polymer was 593% by weight (polymer number E).

Polymerization recipe-] Vinylidene fluoride 70 parts Hexafluoroglobylene 30 Dimethylformamide 400 Benzene
100 Peroxide-containing polymer 30' Example 1 The rubbery polymer shown in Table 1 obtained in Polymer Production Example 1 was kneaded on a roll according to the formulation shown in Table 2 to obtain a rubber compound. After adjustment, press vulcanization was performed at 170'O for 20 minutes, and then heat treatment was further performed at 150°C for 4 hours. The properties of the vulcanizate were measured according to K<5301 from J. The results are shown in Table 3.

2nd Notation Combination Formulation Example 2 After mixing the polymers obtained in Polymer Production Example 1 on a roll in the proportions listed in Table 5, each formulation was The rubber compound was prepared by adding the agent. These rubber compounds were press-vulcanized at 170°C for 20 minutes, and then further heat treated at 150°C for 4 hours. The properties of the obtained vulcanizate were the same as in Example 1, and j
j! I decided.

The results are shown in Table 5.

Table 4 Compounding recipe Example 3 Block polymer E obtained in polymer production example 2 and fluororubber (Montefluos S, P, Technoflon N manufactured by Company A)
H) is dissolved and mixed in ethyl acetate in the proportions listed in Table 7,
After freezing by dropping into liquid nitrogen, the frozen product is taken out and placed in hexane previously cooled to about -60'C with dry ice to solidify the polymer, washed and dried under reduced pressure to form a blended rubber. A polymer was obtained. The obtained rubbery polymer and the fluororubber Technoflon FOR listed in Table 7
45 (manufactured by Montefluos S, P, A) according to the formulation listed in Table 6, each compounding agent was kneaded on a roll to prepare a rubber compound, and press vulcanization was performed at 170°C for 10 minutes. After that, heat treatment was further performed at 230° C. for 16 hours.

The physical properties of the obtained vulcanizate were measured in the same manner as in Example 1. The results are shown in Table 7.

As described above in Examples 1 to 3, the rubber composition containing the non-diene rubber containing the polymerized acenaphthylene monomer of the present invention in the raw material rubber is more effective than the conventional reinforcement using carbon black or the like. The result was that a vulcanizate with excellent high strength and high rigidity was obtained.

Claims (1)

[Claims] A high-strength, high-rigidity rubber composition characterized by adding a compounding agent to a non-diene rubber containing an acenaphthylene monomer as a copolymerization component or a mixture of this rubber and another rubber.