JPS61285233A - High-strength and high-rigidity rubber composition - Google Patents

Abstract

PURPOSE:A rubber composition, obtained by incorporating a conjugated diene based rubber containing an acenaphthylene based monomer as constituent com ponents, having a high strength and high rigidity and suitable for tires, safety bumpers, etc. CONSTITUTION:A composition obtained by incorporating >=5wt%, preferably >=20wt% diene based rubber, obtained by polymerizing an acenaphthalene based monomer with another conjugated diene monomer or a monomer copoly merizable therewith, e.g. 1,3-butadiene or isoprene, and containing 2-60wt%, preferably 5-40wt% acenaphthylene based monomer and compounding ingredients, e.g. sulfur or vulcanizing assistant, with raw material rubber.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a rubber composition that contains a conjugated diene rubber containing an acenaphthylene monomer by polymerizing it and provides a high-strength, high-legged vulcanizate in the raw rubber. be.

Widely used methods include blending fine particulate reinforcing agents such as carbon black and silica with rubber, and blending short fibers such as polyester and nylon. However, these methods have a drawback in that as the amount of particulate reinforcing agent or short fiber blended is increased in order to improve the till property, the strength decreases.

(The world problem that the invention aims to solve) As a result of intensive research to solve the above-mentioned drawbacks, the inventors have found that by using a conjugated diene rubber containing an acenaphthylene monomer as a constituent component, high strength and strength can be achieved. It was discovered that a raw rubber composition could be obtained, and based on this finding, the present invention was completed.

A means (support) for solving the zero weight point It is an object of the present invention to contain at least 5% by weight of a conjugated diene rubber containing a compounding agent and 2 to 60% by weight of an acenaphthylene polymer in the raw material rubber. This is achieved by using a rubber composition containing.

The conjugated diene rubber containing the acenaphthylene monomer (hereinafter sometimes referred to as acenaphthylene-conjugated diene rubber) used in the present invention contains (1) an acenaphthylene monomer as a monomer; A rubber-like copolymer copolymerized with a conjugated diene monomer or a conjugated diene monomer and other copolymerizable monomers, (2) an acenaphthylene monomer or the monomer; and (3) a rubbery block copolymer having a polymer block of a monomer copolymerizable with this and a conjugated diene rubber block in the same molecule, and (3) a conjugated diene rubber containing an acenaphthylene monomer or It includes a rubber-like graft copolymer obtained by grafting a polymer of the monomer and a monomer copolymerizable with the monomer.

The acenaphthylene monomer is acenaphthylene and acenaphthylene having at least one substituent on the carbon and naphthalene rings of the vinylene group that does not inhibit polymerization. Any of the above substituents (for example, alkyl, dichlorokyl, alkenyl, aralkyl, alkynylene, aralkylene, halogen, hydroxy, alkoxy, carboxy, alkylcarboxy, mercapto, amino, N-alkylamino, N, N-dialkyl) Amino Tomoki is defeated.

The monomer constituting the conjugated diene rubber other than the acenaphthylene monomer used in the present invention is a conjugated diene monomer or a combination thereof with a monomer copolymerizable with it. For example, conjugated diene i-mers such as 1,3-butadiene, isoprene, 1,3-pentadiene, 1-chlorobutadiene, and 2-chloroprene; styrenic monomers such as styrene, α-methylstyrene, and 2-chlorostyrene; unsaturated nitrile monomers such as acrylonitrile, methacrylaterile, acrylates or methacrylates such as methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, acrylamide, unsaturated amides such as N,N-dimethylacrylamide, etc. .

The content of acenaphthylene monomer is 2 to 2 in the above polymer.
If it is less than 2% by weight, the effect of the present invention cannot be obtained, and if it exceeds 60% by weight, rubber elasticity is lost [fJI
It becomes lt4i. Preferably it is 5 to 40% by weight. The proportion of the remaining conjugated 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 obtained conjugated diene rubber is 0° C. or lower.

In the acenaphthylene-conjugated diene rubber composition of the present invention, it is used as a raw material rubber either alone or blended with other rubbers. The amount of acenaphthylene-conjugated diene rubber used in the raw rubber is at least 5% by weight, and if it is less than 5% by weight, a high elasticity, MW raw rubber composition cannot be obtained. Preferably it is 10% by weight or more, more preferably 20% by weight or more.

Other raw rubbers used in the present invention include polybutadiene rubber, polyisoprene rubber (σ-added and synthetic),
Styrene-butadiene copolymer rubber, acrylonitrile-
Butadiene copolymer rubber, chloroprene rubber, ethylene-
Examples include propylene-diene monomer ternary copolymer rubber, acrylic rubber, 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.

Normally used in the rubber industry, such as reinforcing agents such as bomb black and silica, fillers such as charcoal and talc, inorganic or organic fibrous reinforcing agents, plasticizers, softeners, processing aids, anti-aging agents, etc. Compounding agents can be used, and the types and amounts are determined as appropriate depending on the purpose of the rubber composition.

Thus, according to the present invention, compared to the prior art, high strength and
Rubber with high eM'Jl can be obtained.

The rubber composition of the present invention has high green strength when the acenaphthylene-conjugated diene rubber is a rubbery polymer made from an acenaphthylene monomer and butadiene or isoprene, or a rubbery polymer made from butadiene or isoprene and styrene. High impact resilience, low heat generation, excellent properties in ml production, and rubber-like polymers made from acenaphthylene monomers, butadiene and/or isoprene and acrylonitrile, and rubber-like polymers made from chlorobrene. When an oil-resistant rubber such as a polymer is used, high strength and MITI properties can be imparted to the vulcanizate without impairing solvent resistance.

The rubber composition of the present invention is suitable for automobile parts such as various tires, safety bumpers, brake parts, various hoses, interior decoration products, various boots, belts, etc. Suitable for applications such as hoses, industrial parts of Rono Akebono, fenders, marine hoses and other marine related materials, oil well parts such as oil well parts, footwear, etc.

The present invention will be specifically explained below using Examples.

Polymer production process IJ l According to the polymerization recipe shown in Table 1, polymerization was carried out at 50°C until the monomer conversion rate reached 70% using an autoclave having an internal volume of II. After the polymerization was completed, a phenolic antioxidant was added to the latex and coagulated in a large amount of methanol. The obtained polymer was washed three times with methanol containing phenolic anti-aging agent and dried in a vacuum dryer. The amount of acenaphthylene bonded to each bonded acrylonitrinolyte in the polymer was determined by C-NMR measurement.

(See Table 1 Monomer C1) 100 parts Hensen 20 parts water
250 parts Potassium rosin acid
2.5 parts Sodium dodecylbenzenesulfonate 1.1 Sodium sulfate 0
．． 2 parts potassium persulfate 0.4
0.1 parts sulfuric acid 0.3 parts t-dodecyl mercaptan A rubber compound composition was obtained. This was press cured at 160° C. for IO minutes. The properties of the vulcanizate were evaluated according to JIS K6301. The results are shown in Table 3.

Table 2 R combination recipe) Rubber-like polymer (see Table 13) 100 parts Ms
N03 5 parts stearic acid 1 part sulfur 0.5 parts tetramethylthiuram disulfide 1.5 parts N-cyclohexyl-2-bendothiazylsulfenamide 1. Part 5 Qo (*l) Nippon Zeon Co., Ltd. NIPOL D
N108 (*2) NIPO manufactured by Nippon Seon Co., Ltd.
L DNOO3 (*3) JIS fuel oil B at 40℃
Rubber-like polymer B of Example 1 and acrylonitrile-cyclodiene copolymer rubber (NIPOL DNI0 manufactured by Nippon Zeon Co., Ltd.) containing 91138% by weight of acryloethoethane bonded with the rubbery polymer B of Example 1 for 72 hours.
8) and bound acrylonitrile) L450% by weight acrylonitrile-butadiene copolymer rubber manufactured by Tamoto Zeon Co., Ltd.
NTPOLDNOO3) were mixed in the proportions shown in Table 4, a rubber compound was prepared according to the compounding recipe in Table 2, and this was press-vulcanized at 160° C. for 10 minutes to obtain a vulcanizate.

An engraving of Daifunari 1 and the same specifications (no changes to the contents) Acenaphthylene 1ooaa in an autoclave with an internal volume of 11
100 parts of benzene, 0.0 parts of polydiacyl peroxide.
6 parts were charged, and polymerization was carried out at 50°C until the monomer conversion rate reached 20%. The resulting polymer was coagulated with a large amount of methanol, washed twice with methanol, and dried under reduced pressure to obtain a peroxide group-containing polymer (weight average molecular weight in terms of polystyrene determined by GPC: 10,600).

Then, according to the polymerization recipe shown in Table 5, polymerization was carried out at 50° C. using an autoclave having an internal volume of 1 liter until the monomer conversion rate reached 40%.

A block polymer was obtained in the same manner as in Polymer Production Example 1. The weight average molecular weight of this polymer is converted to polystyrene,
It was 38,100.

Table 5 (polymerized styrene 24 parts butadiene
76 parts benzene
200 parts peroxide group-containing polymer 30 parts block polymer and styrene-butadiene copolymer rubber (N[)OL1500 manufactured by Nippon Zeon Co., Ltd.) were dissolved in Hensen in the proportions shown in Table 7 and mixed. It was coagulated with methanol and dried under reduced pressure. This mixture was mixed on a roll according to the formulation shown in Table 6 to obtain a rubber compound composition.

Rubber mixture (see Table 6) 100 parts Stearic acid 5 parts Stearic acid 1 part Sulfur 1.5 parts Tetramethylthiuram disulfide 0. 5 parts N-cyclohexyl-2-benzothiazylsulfenamide 1.5 parts (*5
) HAF carbon black 4 is added to the formulation in Table 6.
Example 3 of producing a polymer by blending 0 parts: After purging an autoclave with an internal volume of 11 with nitrogen, 300 g of benzene, 300 g of isoprene, and 37.5 mmol of n-butyllithium were added to the autoclave with a volume of 11. 1. ．． Polymerization was carried out at 40°C for 2 hours. 100 mmol of p-vinylbenzyl chloride was added to this autoclave and reacted for 15 minutes. Pour the contents into methanol to separate the liquid polymer,
Dry.

The weight average molecular weight of this liquid polymer was 9,800 in terms of polystyrene. 100 g of this liquid polymer, 50 g of acenaphthylene, and 20 g of benzene were collected in a glass bottle with an internal capacity of 200 ml, and 0.4 g of azobisisobutyltolyl was added. Enter 6
Polymerization was carried out at 0°C until the conversion of acenaphthylene reached 40%. The obtained polymer was taken out in methanol containing a phenolic anti-aging agent, and after coagulating, it was washed twice with n-hexane containing a phenolic anti-aging agent and dried under vacuum to obtain a graft polymer. . The weight average molecular weight of this graft polymer was 68,400 in terms of polystyrene.

Separately, IOg of polyacenaphthylene with a weight average molecular weight of 286.000 obtained by thermally polymerizing acenaphthylene at 110°C for 70 hours and 10g of the above-mentioned graft polymer were mixed in benzene with Nibor 1R2200 (manufactured by Nippon Zeon Co., Ltd.) 80g.
g and freeze-dried to obtain a blended rubber.

45 parts of carbon black, 2.5 parts of sulfur, 0.8 parts of N-oxydiethylene-2-hendithiazylsulfenamide
2.6 to di-t-methyl-4-methylphenol and vulcanized at 0°C for 20 minutes. The physical properties of this vulcanizate include tensile strength of 305 kg/cm, elongation of 560%, and stress of 100 kg/cm of 39 k.
g/cm, hardness (JIS) 63, Id4i property ()+) 7
``Claw 9-'', Av 69%, heat generation (Flexmeter) HBU 14.3°C, pico abrasion 1.91 x 10ml.

Nihoru IR220 with the same composition and vulcanization conditions except that the HAF carbon blank was changed to 50 parts as a ratio.
As a result of evaluating 0, the tensile strength was 301 kg/cm, and the elongation was 5.
90%, 100% stress 49kg/cm, hardness (JIS)
62, rebound resilience 63%, heat generation 20, 4℃, pico wear 2.
03×10ml.

It can be seen that the balance of the rubber commercial product of the present invention is improved.

Patent applicant: Zeon Corporation Procedural amendment (@bud) Showa KO July evening

Claims (1)

[Claims] 1. A high-strength, high-rigidity rubber composition characterized in that the raw rubber contains at least 5% by weight of a diene rubber containing 2 to 60% by weight of a compounding agent and an acenaphthylene monomer polymerized.