WO2018130196A1

WO2018130196A1 - Rubber composite, applications in foamed product, and manufacturing method

Info

Publication number: WO2018130196A1
Application number: PCT/CN2018/072368
Authority: WO
Inventors: 徐涛; 傅智盛; 吴安洋
Original assignee: 杭州星庐科技有限公司
Priority date: 2017-01-13
Filing date: 2018-01-12
Publication date: 2018-07-19

Abstract

Disclosed are a rubber composite, a processing method therefor, applications and a method for utilizing the composite in manufacturing a foamed material. The rubber composite comprises: a rubber substrate and essential components. The rubber substrate comprises: branched polyethylene, the content thereof being a: 0 < a ≤ 100 parts; ethylene propylene monomer rubber and ethylene propylene diene monomer rubber, the content thereof being b: 0 ≤ b < 100 parts. The essential components comprise: a crosslinking agent 0.5-10 parts and a foaming agent 1.5-25 parts. The applications are a processed sponge sealing strip, a high foaming ratio foaming material, a shock-absorbing foam rubber plate material, a light-colored high-strength foamed plate material, a foamed solid composite sealing strip, and a solid tire filled with a foamed elastomer. The beneficial effects are such that, in addition to short branch chains such as methyl, ethyl, propyl, butyl, and pentyl, the branched polyethylene is also provided with long branch chains of 6 carbons or more, by using the branched polyethylene to replace partially or entirely ethylene propylene rubber in a foamed rubber composite, the melt strength of the rubber composite is increased, the foamability of the composite, particularly pre-foaming, and rubber products so manufactured have reduced permanent deformation under compression.

Description

Rubber composition, and application and production method in foamed product

Technical field

The invention belongs to the field of rubber, in particular to a rubber composition and a processing method thereof, and to the application of the rubber composition in a foamed product, and a method for producing a foamed rubber product using the rubber composition Foamed rubber products include, but are not limited to, sponge seals, high expansion ratio foam materials, shock-absorbing foam rubber sheets, light-colored high-strength foam sheets, foamed solid composite seals, and solid tires filled with foamed elastomers. .

Background technique

The vulcanization system of ethylene propylene rubber foaming material is mainly sulfur and peroxide vulcanization system. When a sulfur vulcanization system is used, the foamed material forms a crosslinked structure mainly composed of polysulfide bonds, which has high tensile strength and high tear strength, but has poor heat resistance and aging resistance; When the foamed material forms a single carbon-carbon crosslink bond, it has excellent heat resistance and aging resistance, small compression set (good stress relaxation stability), and elongation at break is comparable to that of the sulfur vulcanization system foaming material. Therefore, it is preferable to use a peroxide vulcanization system for preparing a high-performance foaming material having low heat resistance, ageing resistance and compression set, but this also has a problem that the tensile strength and the tear strength are lowered.

Ethylene-propylene rubber is a synthetic rubber with saturated molecular chain. It can be divided into two major categories: ethylene-propylene rubber and EPDM rubber. Both of them have good aging resistance. They are commonly used in ethylene-propylene rubber products. It is EPDM rubber, but because EPDM rubber contains a third monomer, the molecular chain contains double bonds, and the ethylene-propylene rubber molecular chain is completely saturated, so the ethylene-propylene rubber has more excellent resistance to aging. Sex, therefore, in the case of high requirements for aging resistance, it is a common technical solution to improve the aging resistance of EPDM by using ethylene propylene diene rubber together. However, the mechanical strength of the binary ethylene propylene rubber is low, which will affect the overall physical and mechanical properties.

Diethylene propylene rubber is a copolymer of ethylene and propylene and belongs to the copolymer of ethylene and α-olefin. Ethylene and α-olefin copolymers are polymers containing only hydrocarbon elements and saturated molecular chains. The common types of carbon atoms in such polymers are generally classified into primary, secondary and tertiary carbons, while tertiary carbons are the most It is easy to be trapped by hydrogen to form free radicals, so the ratio of tertiary carbon atoms to all carbon atoms is generally considered to be a major factor affecting the aging resistance of ethylene and α-olefin copolymers. The lower the ratio, the better the aging resistance. The ratio can be expressed by the degree of branching. For example, a diethylene propylene rubber having a propylene content of 60% by weight can be calculated to contain 200 propylene units per 1000 carbon atoms, that is, 200 tertiary carbon atoms or 200. One methyl branch, so its degree of branching is 200 branches / 1000 carbons. Ethylene ethylene propylene rubber generally has a weight percentage of 40% to 65% or 40% to 60%, so its branching degree is generally 117 to 200 branches/1000 carbons or 133 to 200 branches/ This degree of branching can be considered to be higher than other common ethylene and alpha-olefin copolymers in the 1000 carbon range.

In the prior art, the α-olefin in the common ethylene and α-olefin copolymer may be an α-olefin having a carbon number of not less than 4 in addition to propylene, and may be selected from a C ₄ - C ₂₀ α-olefin. It is usually selected from the group consisting of 1-butene, 1-hexene and 1-octene. If the degree of branching of the copolymer of ethylene and α-olefin is too low, the melting point and crystallinity are too high, and it is not suitable for use as a rubber component. If the degree of branching is high, the content of α-olefin is high, which may result in Process difficulty and raw material cost are high, and operability and economy are low. In the prior art, a polyolefin obtained by copolymerizing ethylene with 1-butene or ethylene and 1-octene may be referred to as a polyolefin plastomer or a polyolefin elastomer according to the degree of crystallinity and melting point, and a part of the polyolefin is elastic. Due to its proper crystallinity and melting point, it can be used well with ethylene propylene rubber and has a low degree of branching. It is considered to be an ideal material for improving the aging resistance of ethylene propylene rubber. It can replace ethylene propylene rubber to a certain extent. use. Since the molecular chain of ethylene and 1-octene copolymer is softer, more rubbery and has good physical and mechanical properties relative to the copolymer of ethylene and 1-butene, the polyolefin elastomer commonly used in rubber products is generally ethylene. And the copolymer of 1-octene, the octene weight percentage is generally not higher than 45%, more commonly not higher than 40%, the corresponding degree of branching is generally not higher than 56 branches / 1000 carbon, The more commonly used degree of branching is not higher than 50 branches/1000 carbons, which is much lower than the degree of branching of ethylene dipropylene rubber, so it has excellent aging resistance and good physical and mechanical properties.

The rubber generally needs to be used after cross-linking. In the cross-linking mode commonly used for ethylene-propylene rubber, the copolymer of ethylene and α-olefin may be peroxide cross-linking or irradiation cross-linking, both of which are mainly obtained by capturing tertiary carbon. a hydrogen atom forms a tertiary carbon radical, and then forms a carbon-carbon crosslink by radical bonding, but a copolymer of ethylene and 1-octene (hereinafter referred to as POE) has fewer tertiary carbon atoms and is attached to a tertiary carbon atom. Chain length, large steric hindrance, difficulty in radical reaction, resulting in difficulty in crosslinking, affecting processing efficiency and product performance, such as compression set resistance is unsatisfactory.

Therefore, there is a need for a better technical solution to improve the aging resistance of ethylene propylene rubber, while having good physical and mechanical properties and cross-linking performance, and it is expected to be specific functional indicators required for foamed rubber products. (such as compression set, etc.) have a good performance.

Secondly, the key technology for the preparation of rubber foaming materials is to achieve the problem of rubber vulcanization and foaming agent decomposition rate matching. In order to achieve a good match, the rubber compound is required to have a certain degree of pre-crosslinking before the foaming agent is thermally decomposed, and should reach 30% of the degree of complete vulcanization of the rubber. Therefore, the pre-vulcanization stage of the rubber is the most critical step, which determines whether a suitable cell structure and the density of the foamed material produced can be formed. In the conventional rubber foaming process, the conventional method is achieved by adding a super-speed accelerator to the rubber to achieve rapid pre-crosslinking of the rubber, but this method is difficult to achieve the matching of vulcanization and foaming; Step molding process, that is, the first molding at a lower temperature (l20 ~ 140 ° C), the time is 20 ~ 50min, so that the rubber has a certain degree of pre-crosslinking and begins to partially foam, and then the specification is larger than the original 20 The second heating is carried out in ~50% of the mold, so that the foaming agent is completely decomposed and vulcanized and shaped.

In order to obtain good heat resistance, aging resistance and compression set resistance, some ethylene propylene rubber foam materials will use a peroxide cure system, and the foam material will form a single carbon-carbon crosslink bond, but compared to In the sulfur vulcanization system, there is also a problem that the tensile strength and the tear strength are lowered, and it is difficult to pre-vulcanize at a relatively low temperature of 120 to 140 °C.

Summary of the invention

In view of the problems existing in the prior art, the present invention provides a rubber composition and a processing method thereof, and the present invention also provides a method for producing a foamed material by using the rubber composition, which has a branching degree of not less than 50 branches. /1000 carbon branched polyethylene to replace some or all of the ethylene propylene rubber, is expected to improve the technical defects of the existing rubber foaming materials difficult to have good heat resistance, aging resistance and mechanical properties, and due to branching The presence of polyethylene requires the use of a peroxide-based cross-linking system. The present invention also provides a vulcanization process that combines a low-temperature radiation pre-vulcanization process with a high-temperature peroxide vulcanization foaming process to overcome the peroxide. The vulcanization system is difficult to pre-vulcanize at low temperatures.

In order to achieve the above object, the present invention adopts the following technical solution: a rubber composition comprising: a rubber matrix and an essential component, the rubber matrix comprising: a content of branched polyethylene a: 0 < a ≤ 100 parts; The content of the ethylene propylene rubber and the ethylene propylene diene rubber is b: 0 ≤ b < 100 parts; the essential component comprises: 0.5 to 10 parts of a crosslinking agent, and 1.5 to 25 parts of a foaming agent, based on 100 parts by weight of the rubber base. Share. The branching degree of the branched polyethylene is not less than 50 branches/1000 carbons, the weight average molecular weight is not less than 50,000, and the Mooney viscosity ML (1+4) is not lower than 2 at 125 °C.

"Branched polyethylene" in the prior art means, in addition to a branched ethylene homopolymer, a branched saturated vinyl copolymer, such as an ethylene-α-olefin copolymer, which may be POE, although POE performs well in physical and mechanical properties and aging resistance, but cross-linking performance is not good, although the branched polyethylene of the present invention can contain both branched ethylene homopolymer and POE, but a better choice It is a branched polyethylene having a high proportion of branched polyethylene or a branched ethylene homopolymer. In a preferred embodiment of the invention, the branched polyethylene contains only branched ethylene homopolymer.

In the further elaboration of the technical solution of the present invention, the branched polyethylene used is a branched ethylene homopolymer unless otherwise specified.

The branched polyethylene used in the present invention is a kind of ethylene homopolymer having a branching degree of not less than 50 branches/1000 carbons, and can be called Branched Polyethylene or Branched PE. Currently, the synthesis method is mainly composed of a late transition metal catalyst. The homopolymerization of ethylene is catalyzed by a "chain walking mechanism", and the preferred late transition metal catalyst may be one of (α-diimine) nickel/palladium catalysts. The nature of the chain walking mechanism refers to the late transition metal catalyst. For example, the (α-diimine) nickel/palladium catalyst is more likely to undergo β-hydrogen elimination reaction and re-insertion reaction in the process of catalyzing olefin polymerization, thereby causing branching. Branched chains of such branched polyethylenes may have different numbers of carbon atoms, specifically 1 to 6, or more carbon atoms. The production cost of the (α-diimine) nickel catalyst is significantly lower than that of the (α-diimine) palladium catalyst, and the (α-diimine) nickel catalyst catalyzes the high rate of ethylene polymerization and high activity, and is more suitable for industrial applications. Therefore, the branched polyethylene prepared by the ethylene polymerization of the (α-diimine) nickel catalyst is preferred in the present invention.

The degree of branching of the branched polyethylene used in the present invention is preferably 50 to 130 branches/1000 carbons, further preferably 60 to 130 branches/1000 carbons, further preferably 60 to 116 branches/1000. A carbon, the degree of branching between POE and ethylene-propylene rubber, is a new technical solution that is different from the prior art, and can have excellent aging resistance and good cross-linking performance.

Cross-linking performance includes factors such as crosslink density and cross-linking rate, which is the specific performance of the cross-linking ability of the rubber matrix during processing.

The branched polyethylene used in the present invention preferably has a methyl branch content of 40% or more or 50% or more, and has a certain similarity with the structure of the ethylene propylene diene rubber. In terms of cross-linking ability, the degree of branching (tertiary carbon atom content) and the steric hindrance around the tertiary carbon atom are the two main factors affecting the cross-linking ability of the saturated polyolefin. The branched polyethylene used in the present invention is low in degree of branching relative to the ethylene propylene rubber, and since the branched polyethylene has a branch having a carbon number of not less than 2, the branched polycondensation used in the present invention The steric hindrance around the tertiary carbon atom of ethylene is theoretically larger than that of ethylene propylene rubber. It can be judged by combining two factors that the crosslinking ability of the branched polyethylene used in the present invention should be weaker than that of the ethylene propylene rubber. In EPDM rubber. However, the actual cross-linking ability of the partially branched polyethylene used in the present invention is close to that of EPDM rubber, and may even be equal to or better than EPDM rubber. This means that the rubber composition of the present invention can obtain a good aging resistance, can also not weaken the crosslinking ability, and can even have excellent crosslinking performance to achieve an unexpected beneficial effect.

This may be explained by the fact that there may be an appropriate number of secondary branched structures on the branched polyethylene used in the preferred embodiment of the present invention, and the so-called secondary branched structure refers to a structure in which branches are further branched. This is also known as "branch-on-branch" during chain walking. Because of the low steric hindrance around the tertiary carbon atoms of the secondary branches, cross-linking reactions are more likely to occur. Having a secondary branched structure is a distinct distinction between the branched polyethylene used in the preferred embodiment of the invention and the prior art ethylene dipropylene rubber or the conventional ethylene-α-olefin copolymer.

It is a new technical solution to improve the cross-linking ability of saturated polyolefin elastomer by using the secondary steric structure with lower steric hindrance. Under the technical solution of the present invention, it is also considered to be within the technical protection of the present invention to include a vinyl copolymer having a secondary branched structure or other saturated hydrocarbon polymer in the rubber matrix. The vinyl copolymer refers to a copolymer of ethylene and a branched α-olefin, and has a secondary branched structure, wherein the branched α-olefin may be selected from the group consisting of isobutylene and 3-methyl-1- Butylene, 4-methyl-1-pentene, 3-methyl-1-pentene, 2-methyl-1-heptene, 3-methyl-1-heptene, 4-methyl-1- The heptene, 5-methyl-1-heptene, 6-methyl-1-heptene, and the like, the comonomer may also contain a common linear alpha-olefin.

It is generally believed in the prior art that the branched polyethylene prepared by the (α-diimine) nickel catalyst is difficult to exist in the secondary branched structure, and at least it is difficult to sufficiently distinguish it. The technical solution of the present invention is also to analyze the branched polycondensation. The structure of ethylene provides a new idea.

Compared with ethylene-propylene rubber, when the branched polyethylene has an appropriate number of secondary branched structures, the cross-linking point of the branched polyethylene can be in the main chain during peroxide crosslinking or radiation crosslinking. Produced on carbon, can also be produced on the branched tertiary carbon of the secondary structure, so the rubber network formed by the cross-linking or radiation cross-linking of the branched polyethylene is compared with the ethylene-propylene rubber, and the main chain has The richer CC cross-linking length can effectively avoid stress concentration and help to obtain better mechanical properties, including tear strength. On the other hand, better cross-linking ability can effectively increase the cross-linking density, and the molecular weight distribution of the branched polyethylene is close to 2, which is narrower than that of the general ethylene-propylene rubber, so that it is also expected to obtain better compression set resistance. Therefore, the technical solution of the present invention can provide a foamed article which has both good heat resistance, mechanical strength and compression set resistance.

A further technical solution is that the content of the branched polyethylene is: 10 ≤ a ≤ 100 parts based on 100 parts by weight of the rubber matrix; the content of the binary ethylene propylene rubber and the ethylene propylene diene rubber is b: 0 ≤ b ≤ 90 parts The branched polyethylene is an ethylene homopolymer having a degree of branching of 60 to 130 branches/1000 carbons, a weight average molecular weight of 66,000 to 518,000, and a Mooney viscosity of ML (1+4) 125 ° C. It is 9 to 102.

A further technical solution is that the content of the branched polyethylene is a: 10 ≤ a ≤ 100 parts based on 100 parts by weight of the rubber matrix; the content of the binary ethylene propylene rubber and the ethylene propylene diene rubber is b: 0 ≤ b ≤ 90 The branched polyethylene is an ethylene homopolymer having a degree of branching of 70 to 116 branches/1000 carbons, a weight average molecular weight of 201,000 to 436,000, and a Mooney viscosity of ML(1+4)125. °C is 9 to 102.

A further technical solution is that the content of the branched polyethylene is: 10 ≤ a ≤ 100 parts based on 100 parts by weight of the rubber matrix; the content of the binary ethylene propylene rubber and the ethylene propylene diene rubber is b: 0 ≤ b ≤ 90 parts The branched polyethylene is an ethylene homopolymer having a degree of branching of 80 to 105 branches/1000 carbons, a weight average molecular weight of 250,000 to 400,000, and a Mooney viscosity of ML (1+4) of 125 ° C. It is 40 to 95.

A further technical solution is that the content of the branched polyethylene is: 10 ≤ a ≤ 100 parts based on 100 parts by weight of the rubber matrix; the content of the binary ethylene propylene rubber and the ethylene propylene diene rubber is b: 0 ≤ b ≤ 90 parts The branched polyethylene is an ethylene homopolymer having a degree of branching of 80 to 105 branches/1000 carbons, a weight average molecular weight of 268,000 to 356,000, and a Mooney viscosity of ML (1+4) of 125 ° C. It is 42 to 80.

A further technical solution is that the third monomer of the ethylene propylene diene monomer is preferably a diene monomer, specifically selected from the group consisting of 5-ethylidene-2-norbornene and 5-vinyl-2-nor Borneene, dicyclopentadiene, 1,4-hexadiene, 1,5-hexadiene, 1,4-pentadiene, 2-methyl-1,4-pentadiene, 3-methyl- 1,4-Hexadiene, 4-methyl-1,4-hexadiene, 1,9-decadiene, 5-methylene-2-norbornene, 5-pentylene-2-nor Borbornene, 1,5-cyclooctadiene, 1,4-cyclooctadiene, and the like. Specifically, the ethylene propylene rubber may contain two or more kinds of diene monomers at the same time, such as 5-ethylidene-2-norbornene and 5-vinyl-2-norbornene. The functional group of the diene monomer can play the same role as the intrinsic co-crosslinking agent in the peroxide vulcanization, thereby improving the crosslinking efficiency. This helps to reduce the amount and residual amount of crosslinker and co-crosslinker required and the cost of adding them. The weight specific gravity of the diene monomer to the ethylene propylene rubber is preferably from 1% to 14%, more preferably from 3% to 10%, still more preferably from 4% to 7%.

In a further technical solution, the crosslinking agent comprises at least one of a peroxide crosslinking agent and a sulfur, and the peroxide crosslinking agent comprises di-tert-butyl peroxide, dicumyl peroxide, Tert-butyl cumyl peroxide, 1,1-di-tert-butyl peroxide-3,3,5-trimethylcyclohexane, 2,5-dimethyl-2,5-di(tert-butyl) Base oxidized) hexane, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne-3, bis(tert-butylperoxyisopropyl)benzene, 2,5-di At least one of methyl-2,5-bis(benzoyl peroxy)hexane, tert-butyl peroxybenzoate, and t-butylperoxy-2-ethylhexyl carbonate.

A further technical solution is that the crosslinking agent is preferably used in an amount of from 0.5 to 6 parts by weight based on 100 parts by weight of the rubber base.

A further technical solution is that the foaming agent comprises sodium hydrogencarbonate, azodicarbonamide (AC), dinitrosopentylenetetramine (H), diphenylsulfonyl oxime ether (OBSH), benzenesulfonate. At least one of hydrazide (BSH), urea, and a low-boiling hydrocarbon microcapsule-type foaming agent.

A further technical solution is that the rubber composition comprises an auxiliary component, which comprises: 0.2 to 10 parts of a co-crosslinking agent, 30 to 200 parts of a reinforcing filler, and a plasticizer, based on 100 parts by weight of the rubber matrix. 10 to 100 parts, stabilizer 1 to 3 parts, metal oxide 2 to 20 parts, silane coupling agent 3 to 7 parts, polyethylene glycol 1 to 5 parts, stearic acid 0.5 to 3 parts, vulcanization accelerator 0 ~3 servings.

In a further technical solution, the silane coupling agent comprises vinyl tris(2-methoxyethoxy)silane (A-172), γ-glycidoxypropyltrimethoxysilane (A-187) At least one of γ-mercaptopropyltrimethoxysilane (A-189).

In a further technical solution, the stabilizer comprises 2,2,4-trimethyl-1,2-dihydroquinoline polymer (RD), 6-ethoxy-2,2,4-trimethyl At least one of -1,2-dihydroquinoline (AW) and 2-mercaptobenzimidazole (MB).

A further technical solution is that the co-crosslinking agent comprises triallyl cyanurate, triallyl isocyanurate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, Triallyl trimellitate, trimethylolpropane trimethacrylate, N,N'-m-phenylene bismaleimide, N,N'-bis-indenylacetone, 1,2- At least one of polybutadiene, a metal salt of an unsaturated carboxylic acid, and sulfur. The unsaturated carboxylic acid metal salt contains at least one of zinc acrylate, zinc methacrylate, and magnesium methacrylate.

In a further technical solution, the plasticizer comprises at least one of pine tar, engine oil, naphthenic oil, paraffin oil, coumarone, RX-80, petrolatum, and paraffin wax. The rational use of plasticizers can increase the flexibility of the compound and the plasticity suitable for process operation. In order to increase the viscosity, it is also preferred to use an adhesion promoter such as pine tar, coumarone, RX-80, liquid polyisobutylene or the like.

In a further technical solution, the metal oxide comprises at least one of zinc oxide, magnesium oxide, and calcium oxide.

According to a further technical solution, the reinforcing filler comprises at least one of carbon black, white carbon black, calcium carbonate, talc, calcined clay, magnesium silicate, and magnesium carbonate.

According to a further technical proposal, the vulcanization accelerator comprises 2-thiol benzothiazole, dibenzothiazyl disulfide, tetramethyl thiuram monosulfide, tetramethyl thiuram disulfide, tetrazyl disulfide Kethiram, N-cyclohexyl-2-benzothiazolyl sulfenamide, N,N-dicyclohexyl-2-benzothiazolyl sulfenamide, bismaleimide, ethylene thiourea At least one of them.

The crosslinking agent, the co-crosslinking agent and the vulcanization accelerator involved in the rubber composition provided by the present invention all belong to a crosslinking system.

The rubber composition of the present invention may be present in the form of an uncrosslinked rubber compound, and may be present in the form of a vulcanized rubber after further crosslinking reaction. Vulcanized rubber can also be referred to simply as vulcanizate.

The present invention also provides a method of the above rubber composition, the processing method comprising the steps of:

(1) Rubber kneading: First, the rubber composition components other than the crosslinking system and the foaming agent are sequentially added to the internal mixer for mixing, and then the crosslinking system and the foaming system are kneaded. After uniform discharge, the mixture is obtained. After the mixture is thinned on the open mill, the sheet is left to be vulcanized, the crosslinking system comprises a crosslinking agent, and may further comprise at least one of a crosslinking agent and a vulcanization accelerator;

(2) Vulcanization: The rubber compound is filled into the cavity of the mold, vulcanized on the flat vulcanizing machine, and then demolded to obtain a vulcanized rubber. In order to improve the compression set resistance of the vulcanizate, it is further possible to carry out vulcanization using a two-stage vulcanization process.

The present invention also provides a sponge sealing strip comprising the above rubber composition.

The invention also provides a method for producing a sponge sealing strip, the production method comprising the following steps:

(1) Rubber kneading: First, the rubber composition components other than the crosslinking system and the foaming agent are sequentially added to the internal mixer for mixing, and then the crosslinking system and the foaming system are kneaded. After uniform discharge, the mixture is obtained. After the mixture is thinned on the open mill, the sheet is left to be vulcanized, and the crosslinking system comprises a crosslinking agent, and may further comprise at least one of a co-linking agent and a vulcanization accelerator;

(2) mixing, filming, cooling, and parking;

(3) Extruder extrusion, salt bath vulcanization, molding, cooling, punching, cutting.

The present invention also provides a high expansion ratio foam material comprising the above rubber composition.

The present invention also provides a method for producing a high expansion ratio foam material, the production method comprising the following steps:

(1) Rubber kneading: First, the rubber composition components other than the crosslinking system and the foaming agent are sequentially added to the internal mixer for mixing, and then the crosslinking system and the foaming system are kneaded. After uniform discharge, the mixture is obtained, and the rubber mixture is thinned on the open mill, and then the film is to be vulcanized, and the rubber compound is thinned and opened on the open mill, and the cross-linking system contains a crosslinking agent. And may further comprise at least one of a co-crosslinking agent and a vulcanization accelerator;

(2) Putting the compounding compound into a mold of 60 to 80 ° C, pressurizing on a flat vulcanizing machine, and preforming;

(3) placing the pre-formed film in a mold and foaming at a high temperature for a period of time;

(4) After the compound is cooled, it is taken out from the mold to obtain a foamed material.

The present invention also provides a shock absorbing foam rubber sheet comprising the above rubber composition.

The invention also provides a method for producing a shock-absorbing foam rubber sheet, the production method comprising the following steps:

(1) Rubber kneading: First, the rubber composition components other than the crosslinking system and the foaming agent are sequentially added to the internal mixer for mixing, and then the crosslinking system and the foaming system are kneaded. After being uniformly discharged, a rubber mixture is obtained, and the rubber mixture is thinned on the open mill, and then left to be left to be vulcanized. The crosslinking system contains a crosslinking agent, and may also include a crosslinking agent and a vulcanization accelerator. At least one

(2) After cooling the discharged rubber, the film is thinned on the open mill with a roll gap of less than 1 mm, and parked;

(3) Put the parked rubber into the open mill to heat the sheet;

(4) Forming the hot rubber after parking according to the size of the mold cavity;

(5) inserting the cut film into the mold cavity to form a mold vulcanization;

(6) Hot demoulding, trimming, and obtaining foamed rubber sheet products.

The shock-absorbing foamed rubber product can be used as a sole by a sewing process or by applying an adhesive. The adhesive used herein may be an adhesive commonly used in ethylene propylene rubber in the prior art, preferably an environmentally friendly adhesive. The shock absorbing foamed rubber product may also be directly used as an insole, wherein the crosslinking agent is preferably vulcanized. Less odorous varieties such as bis(tert-butylperoxyisopropyl)benzene.

The invention also provides a method of processing the above rubber foaming material, the processing method comprising the following steps:

(1) Rubber kneading: First, the rubber composition components other than the crosslinking system and the foaming agent are sequentially added to the internal mixer according to the parts by weight for kneading, and then the rubber is discharged, and the mixture is placed on the open mill after being parked. Coupling system and foaming agent, complete the mixing; after parking, re-smelting on the open mill or extrusion molding machine, forming and waiting for use, the crosslinking system contains a crosslinking agent and has a radiation sensitizing function. The co-crosslinking agent may also contain a vulcanization accelerator.

(2) Radiation pre-vulcanization: The formed rubber compound is irradiated under normal temperature and normal pressure to make the rubber sheet have a certain degree of pre-crosslinking.

(3) High-temperature foaming vulcanization: The radiation-pre-vulcanized sheet is placed in a mold, vulcanized and foamed under high temperature and high pressure, and then released from mold release to obtain a rubber foamed material.

A further technical solution is that the electron accelerator beam energy used in the radiation pre-vulcanization is 2-10 MeV, and the emitted ray particles can completely penetrate the green film material, and the electron beam scanning width is 0.2-1.6 m, and the raw film material is sputtered. According to the absorbed dose of 5 ~ 60KGy, the radiation atmosphere is oxygen-limited environment, using inert gas protection, the time required for radiation pre-vulcanization, the average time per sheet is less than 5 minutes, wherein the conditions of foaming and vulcanization are 160-180 ° C, 6 ~ 15MPa, 10~20min.

The present invention also provides a light-colored high-strength foamed sheet comprising the above rubber composition.

The invention also provides a method for producing a light-colored high-strength foamed sheet, the production method comprising the following steps:

(1) Rubber kneading: First, the rubber composition components other than the crosslinking system and the foaming agent are sequentially added to the internal mixer for mixing, and then the crosslinking system and the foaming system are kneaded. After uniform discharge, the mixture is obtained. The rubber compound is thinned on the open mill and then discharged to be vulcanized. The cross-linking system contains a crosslinking agent and a co-crosslinking agent having a radiation sensitizing function, and may further contain a vulcanization accelerator.

(2) cutting the sliced sheet according to the size of the mold cavity;

(3) Radiation pre-vulcanization: The formed rubber compound is irradiated under normal temperature and normal pressure to make the rubber sheet have a certain degree of pre-crosslinking.

(4) High-temperature foaming vulcanization: The radiation-pre-vulcanized sheet is placed in a mold, vulcanized and foamed under high temperature and high pressure, then demolded and cooled, and trimmed to obtain a light-colored high-strength foamed sheet.

The present invention also provides a foamed solid composite sealing strip, the compound used for the foaming portion comprising the above rubber composition, preferably a rubber composition comprising a reinforcing filler.

The present invention also provides a method of producing a foamed solid composite weather strip comprising the following steps:

(1) kneading: mixing the solid rubber and the foaming part in the internal mixer, and after the open on the open mill, the lower piece is cooled and parked;

(2) Composite extrusion and vulcanization: the solid part of the rubber compound and the foamed part vulcanizate are co-extruded through a composite machine head, and then vulcanized by a salt bath vulcanization process.

(3) After the vulcanization is finished, it is cooled, trimmed, and cut to obtain a finished product.

The present invention also provides a solid tire having an inner layer which is a foamed elastomer, and the compound for filling the foamed elastomer therein comprises the above rubber composition, preferably a rubber composition comprising a reinforcing filler. The force tire can be a bicycle tire, a trolley tire, an animal tire, an electric tire, and has the advantage of resisting the tie.

The invention also provides a method for producing a solid tire tire whose inner layer is a foamed elastic body, which comprises the following steps: firstly kneading the inner layer rubber in an internal mixer, after discharging the rubber, opening the lower sheet, dip the separating liquid, Cooling and parking; then extruding the rubber through the extruder to obtain a strip of suitable cross-section size, and then cutting the splicing to obtain a squeegee semi-finished product; then installing the squeegee semi-finished product on the mold and putting on the finished tire And the steel tube is evenly pierced at the top of the tire, and then placed in a vulcanization oven for vulcanization, foaming, and vulcanization to obtain a finished product.

In the heat vulcanization method for the rubber composition provided by the present invention, a heating tank having a heating method such as hot air, a glass bead fluidized bed, ultra high frequency electromagnetic wave (UHF), steam, and a hot molten salt bath (LCM) may be used. And metal molds. The heating temperature is preferably from 150 to 170 ° C; and the heating time is preferably from 1 to 30 minutes.

In the electron beam radiation vulcanization method for the rubber composition provided by the present invention, the energy of the electron beam is preferably 0.1 to 10 MeV, and more preferably 0.3 to 5 MeV, and irradiation is performed so that the absorbed dose is preferably 5 to 350 kGy, and more preferably 5 to 100kGy.

Compared with the prior art, the invention has the beneficial effects that the ethylene-propylene rubber in the foamed rubber composition is partially or completely replaced by the branched polyethylene, and the peroxide curing system or the peroxide and the sulfur are used together. The vulcanization system, because the branched polyethylene has more branches in the molecular structure, and the length of the branch has a certain length and length distribution and a certain number of secondary branched structures, in the process of peroxide crosslinking or radiation crosslinking In the middle, the crosslinking point of the branched polyethylene may be generated on the tertiary carbon of the main chain or on the branched tertiary carbon of the secondary structure, so the branched polyethylene is formed by peroxide crosslinking or radiation crosslinking. Compared with ethylene-propylene rubber, the rubber network has a richer CC cross-linking length between the main chains, similar to the polysulfide bond in the sulfur vulcanization system, but the bond energy is higher, which can effectively avoid stress concentration. With good cross-linking efficiency, overall mechanical properties are expected to be obtained. Moreover, branched polyethylene has more long-chain branches, and has higher melt strength, which is more favorable for foaming, especially pre-expansion. And since the molecular weight distribution of the branched polyethylene is narrow, generally lower than 2.5, the rubber composition of the present invention has a lower compression set after vulcanization. On the other hand, due to the presence of branched polyethylene, a peroxide-based crosslinking system is more required, and the peroxide crosslinking system cannot achieve pre-crosslinking at a low temperature, and the radiation pretreatment process of the present invention does not need to be performed. The crosslinking of some rubber macromolecules can be quickly achieved by heating, so that the foaming agent does not decompose, and the degree of pre-vulcanization of the rubber can be accurately controlled by controlling the radiation dose. The rubber sheet treated with a certain radiation dose has a certain pre-crosslinking strength before the foaming agent is thermally decomposed, and the modulus of the rubber compound is increased, which can resist the pressure of the gas generated when the foaming agent is decomposed without cracking. The closed cell structure is formed, and it is not easy to run the gas, and the vulcanization speed and the foaming speed can be matched to prepare a rubber foamed product with good performance. By adding a radiation cross-linking sensitizer, while satisfying the increase of the green strength of the rubber compound, the rubber compound has a certain degree of pre-crosslinking degree, the irradiation dose can be greatly reduced, the radiation processing energy of the rubber sheet is saved, the time is saved, and the time is greatly improved. Productivity. The radiation crosslinking sensitizer can also act as a co-crosslinking agent for the peroxide crosslinking agent to improve the crosslinking efficiency and crosslinking depth of the peroxide vulcanization.

detailed description

The following examples are given to further illustrate the present invention, but are not intended to limit the scope of the present invention, and some non-essential improvements and adjustments made by those skilled in the art based on the present invention remain within the scope of the present invention. .

In order to more clearly describe the embodiments of the present invention, the materials to which the present invention relates are defined below.

The crosslinking system contains a crosslinking agent, and may further contain at least one of a co-crosslinking agent and a vulcanization accelerator.

The present invention relates to a rubber composition comprising: a rubber matrix and a necessary component, the rubber matrix comprising: a branched polyethylene having a content of a: 0 < a ≤ 100 parts, a degree of branching of 60 ～ 130 branches/1000 carbons, weight average molecular weight is 66,000 ~ 518,000, Mooney viscosity ML (1 + 4) 125 ° C is 6 ~ 102, the sum of binary ethylene propylene rubber and EPDM rubber b : 0 ≤ b < 100 parts, Mooney viscosity ML (1 + 4) 125 ° C is preferably 50-90, ethylene content is preferably 40% - 70%; based on 100 parts by weight of the rubber matrix, the necessary components include: cross-linking The agent is 0.5 to 10 parts, and the foaming agent is 1.5 to 25 parts.

The rubber composition further comprises an auxiliary component comprising: 0.2 to 10 parts of a co-crosslinking agent, 30 to 200 parts of a reinforcing filler, 10 to 100 parts of a plasticizer, 1 to 3 parts of a stabilizer, a metal oxide. 2 to 20 parts, 3 to 7 parts of a silane coupling agent, 1 to 5 parts of polyethylene glycol, 0.5 to 3 parts of stearic acid, and 0 to 3 parts of a vulcanization accelerator.

Wherein the silane coupling agent comprises vinyl tris(2-methoxyethoxy)silane (A-172), γ-glycidoxypropyltrimethoxysilane (A-187), γ-mercaptopropyl At least one of the group of trimethoxysilanes (A-189).

The stabilizer comprises 2,2,4-trimethyl-1,2-dihydroquinoline polymer (RD), 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline At least one of porphyrin (AW) and 2-mercaptobenzimidazole (MB).

The co-crosslinking agent comprises triallyl cyanurate, triallyl isocyanurate, ethylene glycol dimethacrylate, ethyl dimethacrylate, triethylene glycol dimethacrylate, partial Triallyl trimellitate, trimethylolpropane trimethacrylate, ethylene glycol dimethacrylate, N,N'-m-phenylene bismaleimide, N,N'-double At least one of mercaptoacetone, 1,2-polybutadiene, zinc acrylate, zinc methacrylate, magnesium methacrylate, calcium methacrylate, aluminum methacrylate, and sulfur.

The plasticizer is at least one of pine tar, motor oil, naphthenic oil, paraffin oil, coumarone, RX-80, petrolatum, and paraffin wax.

The metal oxide is at least one of zinc oxide, magnesium oxide, and calcium oxide. The reinforcing filler is at least one of carbon black, white carbon black, calcium carbonate, talc, calcined clay, magnesium silicate, and magnesium carbonate.

The vulcanization accelerator comprises 2-thiol benzothiazole, dibenzothiazole disulfide, tetramethylthiuram monosulfide, tetramethylthiuram disulfide, tetraethylthiuram disulfide, N-ring At least one of hexyl-2-benzothiazolylsulfenamide, N,N-dicyclohexyl-2-phenylthiazolylsulfenamide, bismaleimide, and ethylenethiourea.

The crosslinking agent includes at least one of a peroxide crosslinking agent and a sulfur crosslinking agent, and the peroxide crosslinking agent is di-tert-butyl peroxide, dicumyl peroxide, and tert-butyl cumyl peroxide. 1,1-di-tert-butyl peroxide-3,3,5-trimethylcyclohexane, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, 2 ,5-Dimethyl-2,5-di(tert-butylperoxy)hexyne-3, bis(tert-butylperoxyisopropyl)benzene, 2,5-dimethyl-2,5-di At least one of (benzoyl peroxide) hexane, tert-butyl peroxybenzoate, and t-butylperoxy-2-ethylhexyl carbonate.

The blowing agent comprises sodium hydrogencarbonate, azodicarbonamide (AC), dinitrosopentylenetetramine (H), diphenylsulfonyl oxime ether (OBSH), benzenesulfonyl hydrazide (BSH), urea, At least one of a low-boiling hydrocarbon microcapsule-type foaming agent.

The Mooney viscosity ML (1+4) of the ethylene propylene rubber used is preferably 30 to 50 at 125 ° C, and the ethylene content is preferably 45% to 60%. The Mooney viscosity ML (1+4) of the ethylene propylene diene rubber used is preferably 20 to 100, more preferably 30 to 80, the ethylene content is preferably 55% to 75%, and the third monomer is 5-ethylene-2. - norbornene, 5-vinyl-2-norbornene or dicyclopentadiene, the third monomer content being from 1% to 7%.

The branched polyethylene used can be obtained by catalyzing the homopolymerization of ethylene by a (α-diimine) nickel catalyst under the action of a cocatalyst. The structure, synthesis method and method for preparing branched polyethylene by using the (α-diimine) nickel catalyst are disclosed in the prior art, and can be used but are not limited to the following documents: CN102827312A, CN101812145A, CN101531725A, CN104926962A, US6103658, US6660677.

The branched polyethylene is characterized by a branching degree of 60 to 130 branches/1000 carbons, a weight average molecular weight of 66,000 to 518,000, and a Mooney viscosity of ML (1+4) of 125 ° C of 9 to 102. Among them, the degree of branching is measured by nuclear magnetic resonance spectroscopy, and the molar percentages of various branches are measured by nuclear magnetic carbon spectroscopy.

The details are as follows:

Rubber performance test method:

1. Density: measured according to national standard GB/T533-1991;

2, tensile strength, elongation at break performance test: in accordance with the national standard GB/T10654-2001, using an electronic tensile testing machine for testing, the stretching speed is 500mm / min, the test temperature is 23 ± 2 ° C;

3, Mooney viscosity test: in accordance with the national standard GB/T1232.1-2000, with Mooney viscosity meter for testing, the test temperature is 125 ° C, preheat 1 minute, test 4 minutes;

4. Vulcanization-foaming curve test: tested according to national standard GB/T16584;

5, compression permanent deformation test: in accordance with the national standard GB/T7759-1996, using a compression permanent deformation device for testing, type B, compression is 25%, test temperature is 70 ° C, compression time is 70 hours.

The specific implementation is as follows:

Example 1:

The branched polyethylene used was numbered PER-9.

The processing steps of the rubber composition are as follows:

(1) Rubber mixing: set the temperature of the internal mixer to 90 ° C, the rotor speed to 50 rpm, add 90 parts of EPDM rubber and 10 parts of branched polyethylene pre-pressed for 90 seconds; add 10 parts of oxidation Zinc and 2 parts of stearic acid, kneaded for 1 minute; then add 5 parts of calcium oxide and 2 parts of polyethylene glycol PEG4000, and knead for 1 minute; then add 50 parts of carbon black N550 in two batches of medium size. 20 parts of carbon black N765, 50 parts of calcium carbonate and 70 parts of paraffin oil SUNPAR2280 were mixed for 4 minutes; finally, 3 parts of cross-linking agent dicumyl peroxide (DCP), 1 part of cross-linking agent triallyl isocyanide were added. Urea ester (TAIC), 20 parts of foaming agent azodicarbonamide (AC) and 2 parts of foaming agent urea were mixed for 3 minutes and then discharged. The kneaded rubber was thinly passed on an open mill having a roll temperature of 80 ° C, and then the roll was adjusted to obtain a sheet having a thickness of about 2.2 to 2.5 mm and left for 20 hours.

(2) After the vulcanization, the test was carried out for 16 hours.

Example 2:

The branched polyethylene used was numbered PER-2.

The processing steps of the rubber composition are as follows:

(1) Rubber mixing: set the temperature of the internal mixer to 90 ° C, the rotor speed is 50 rpm, add 20 parts of ethylene propylene diene rubber, 50 parts of ethylene propylene diene monomer and 30 parts of branched polyethylene pre-pressure mixing. 90 seconds; add 10 parts of zinc oxide and 2 parts of stearic acid, mix for 1 minute; then add 5 parts of calcium oxide and 2 parts of polyethylene glycol PEG4000, mix for 1 minute; then divide the two batches in the rubber A total of 75 parts of carbon black N550, 50 parts of carbon black N765, 75 parts of calcium carbonate and 90 parts of paraffin oil SUNPAR2280 were added for 4 minutes; finally, 6 parts of cross-linking agent dicumyl peroxide (DCP), 2 parts of helper were added. Linked triallyl isocyanurate (TAIC), 8 parts of cross-linking agent liquid 1,2-polybutadiene, 20 parts of blowing agent azodicarbonamide (AC) and 2 parts of foaming agent Urea, rubberized after 3 minutes of mixing. The kneaded rubber was thinly passed on an open mill having a roll temperature of 80 ° C, and then the roll was adjusted to obtain a sheet having a thickness of about 2.2 to 2.5 mm and left for 20 hours.

(2) After the vulcanization, the test was carried out for 16 hours.

Example 3:

The branched polyethylene used was numbered PER-5.

The processing steps of the rubber composition are as follows:

(1) Rubber mixing: set the temperature of the internal mixer to 90 ° C, the rotor speed is 50 rpm, add 50 parts of ethylene propylene diene monomer and 50 parts of branched polyethylene for 90 seconds; add 10 parts of oxidation Zinc and 2 parts of stearic acid, mixed for 1 minute; then add 5 parts of calcium oxide and 2 parts of polyethylene glycol PEG4000, and knead for 1 minute; then add 75 parts of carbon black N550 in two batches of medium size. 50 parts of carbon black N765, 75 parts of calcium carbonate and 70 parts of paraffin oil SUNPAR 2280 were mixed for 4 minutes; finally, 3 parts of cross-linking agent dicumyl peroxide (DCP), 1 part of cross-linking agent triallyl isocyanide were added. Urea (TAIC), 22 parts of foaming agent azodicarbonamide (AC) and 3 parts of foaming agent urea, after 3 minutes of mixing, the rubber is discharged, and the rubber mixture is placed on an open mill with a roll temperature of 80 °C. Thin pass, then increase the roll distance to obtain a sheet of thickness of about 2.2 ~ 2.5mm, and park for 20 hours.

(2) After the vulcanization, the test was carried out for 16 hours.

Example 4:

The branched polyethylene used was numbered PER-5.

The processing steps of the rubber composition are as follows:

(1) Rubber mixing: set the temperature of the internal mixer to 90 ° C, the rotor speed to 50 rpm, add 100 parts of branched polyethylene pre-pressed and kneaded for 90 seconds; add 10 parts of zinc oxide and 2 parts of stearic acid. Mixing for 1 minute; then adding 5 parts of calcium oxide and 2 parts of polyethylene glycol PEG4000, mixing for 1 minute; then adding a total of 75 parts of carbon black N550, 50 parts of carbon black N765, 75 parts in two batches of the compound. Calcium carbonate and 70 parts of paraffin oil SUNPAR2280 were mixed for 4 minutes; finally, 3 parts of cross-linking agent dicumyl peroxide (DCP), 1 part of cross-linking agent triallyl isocyanurate (TAIC), 20 Part of the foaming agent azodicarbonamide (AC) and 2 parts of foaming agent urea, after 3 minutes of mixing, the rubber is discharged. The kneaded rubber was thinly passed on an open mill having a roll temperature of 80 ° C, and then the roll was adjusted to obtain a sheet having a thickness of about 2.2 to 2.5 mm and left for 20 hours.

(2) After the vulcanization, the test was carried out for 16 hours.

Example 5:

The branched polyethylene used was numbered PER-5.

The processing steps of the rubber composition are as follows:

(1) Rubber mixing: set the temperature of the internal mixer to 90 ° C, the rotor speed is 50 rpm, add 50 parts of ethylene propylene diene monomer and 50 parts of branched polyethylene for 90 seconds; add 10 parts of oxidation Zinc and 1 part stearic acid, kneaded for 1 minute; then add 5 parts of calcium oxide and 2 parts of polyethylene glycol PEG4000, and knead for 1 minute; then add 60 parts of carbon black N550 in two batches of medium size. 60 parts of carbon black N765 and 70 parts of paraffin oil SUNPAR2280, mixed for 4 minutes; finally added 4 parts of cross-linking agent dicumyl peroxide (DCP), 1 part of cross-linking agent triallyl isocyanurate ( TAIC), 0.3 parts of cross-linking agent sulphur, 2 parts of blowing agent azodicarbonamide (AC) and 2 parts of blowing agent diphenyl sulfonyl oxime ether (OBSH), after 3 minutes of mixing, debinding, mixing The rubber was thinned on an open mill with a roll temperature of 80 ° C, and then the roll was adjusted to obtain a sheet thickness of about 2.2 to 2.5 mm and parked for 20 hours.

(2) After the vulcanization, the test was carried out for 16 hours.

Example 6

The branched polyethylene used was numbered PER-5.

The processing steps of the rubber composition are as follows:

(1) Rubber mixing: set the temperature of the internal mixer to 90 ° C, the rotor speed to 50 rpm, add 100 parts of branched polyethylene pre-pressed and kneaded for 90 seconds; add 10 parts of zinc oxide and 1 part of stearic acid, Mixing for 1 minute; then adding 5 parts of calcium oxide 2 parts of polyethylene glycol PEG4000, mixing for 1 minute; then adding 60 parts of carbon black N550, 60 parts of carbon black N765 and 70 parts of paraffin in the middle of the batch. Oil SUNPAR2280 was mixed for 4 minutes; finally, 4 parts of cross-linking agent dicumyl peroxide (DCP), 1 part of cross-linking agent triallyl isocyanurate (TAIC), 0.3 parts of cross-linking agent sulfur were added. 2 parts of foaming agent azodicarbonamide (AC) and 2 parts of foaming agent diphenylsulfonyl oxime ether (OBSH), after 3 minutes of mixing, the rubber is discharged, and the mixing rubber is opened at a roll temperature of 80 ° C. Thin on the refiner, then increase the roll distance to obtain a sheet of thickness of about 2.2 ~ 2.5mm, and park for 20 hours.

(2) After the vulcanization, the test was carried out for 16 hours.

Comparative Example 1:

The processing steps are as follows:

(1) Rubber mixing: set the temperature of the internal mixer to 90 ° C, the rotor speed is 50 rpm, add 100 parts of EPDM rubber for 90 seconds, and add 10 parts of zinc oxide and 2 parts of stearic acid. , mixing for 1 minute; then adding 5 parts of calcium oxide 2 parts of polyethylene glycol PEG4000, mixing for 1 minute; then adding a total of 75 parts of carbon black N550, 50 parts of carbon black N765, 75 parts in two batches of the compound. Calcium carbonate and 70 parts of paraffin oil SUNPAR2280 were mixed for 4 minutes; finally, 3 parts of cross-linking agent dicumyl peroxide (DCP), 1 part of cross-linking agent triallyl isocyanurate (TAIC), 20 Part of the foaming agent azodicarbonamide (AC) and 2 parts of foaming agent urea, after 3 minutes of mixing, the rubber is discharged, and the rubber compound is thinned on the open mill with a roll temperature of 80 ° C, and then the roll is adjusted. A sheet of a thickness of about 2.2 to 2.5 mm was obtained and left for 20 hours.

(2) After the vulcanization, the test was carried out for 16 hours.

Comparative Example 2:

The processing steps are as follows:

(1) Rubber mixing: set the temperature of the internal mixer to 90 ° C, the rotor speed to 50 rpm, add 100 parts of EPDM rubber for 90 seconds, and add 10 parts of zinc oxide and 1 part of stearic acid. , mixing for 1 minute; then adding 5 parts of calcium oxide 2 parts of polyethylene glycol PEG4000, mixing for 1 minute; then adding 60 parts of carbon black N550, 60 parts of carbon black N765 and 70 parts in two batches of medium size Paraffin oil SUNPAR2280 was mixed for 4 minutes; finally, 4 parts of cross-linking agent dicumyl peroxide (DCP), 1 part of cross-linking agent triallyl isocyanurate (TAIC), 0.3 parts of cross-linking agent were added. Sulfur, 2 parts of foaming agent azodicarbonamide (AC) and 2 parts of foaming agent diphenylsulfonyl oxime ether (OBSH), after 3 minutes of mixing, the rubber is discharged, and the mixing rubber is at a roll temperature of 80 ° C. The thin open on the open mill, and then increase the roll distance to obtain a sheet of thickness of about 2.2 ~ 2.5mm, and park for 20 hours.

(2) After the vulcanization, the test was carried out for 16 hours.

The performance test data is as follows:

Data analysis: By comparing Examples 1 to 4 and Comparative Example 1 or Comparative Examples 5 and 6 and Comparative Example 2, it was found that the styrofoam obtained by vulcanization increased with the increase in the specific gravity of the branched polyethylene instead of the ethylene propylene rubber. The tensile strength is increased, and the compression set is reduced, and the overall performance is improved.

Example 7

The branched polyethylene used was numbered PER-8.

The processing steps of the rubber composition are as follows:

(1) Rubber mixing: set the temperature of the internal mixer to 90 ° C, the rotor speed is 50 rpm, add 20 parts of ethylene propylene rubber, 60 parts of ethylene propylene diene rubber and 20 parts of prepolymerized polyethylene. 90 seconds; then add 0.5 part of cross-linking agent dicumyl peroxide (DCP), 6 parts of foaming agent azodicarbonamide (AC), mix for 3 minutes, then drain the glue, the mixture is at the roll temperature It is thin on the 80 °C open mill, and then the roll is adjusted to obtain a sheet thickness of about 2.2 to 2.5 mm and parked for 20 hours.

(2) After the vulcanization, the test was carried out for 16 hours.

Example 8

The branched polyethylene used was numbered PER-7.

The processing steps of the rubber composition are as follows:

(1) Rubber mixing: set the temperature of the internal mixer to 90 ° C, the rotor speed is 50 rpm, add 50 parts of EPDM rubber, 50 parts of branched polyethylene pre-pressing and kneading for 90 seconds; then add 0.5 parts. Cross-linking agent Dicumyl peroxide (DCP), 6 parts of foaming agent azodicarbonamide (AC), after 3 minutes of mixing, the rubber is discharged, and the rubber compound is thinned on a mill with a roll temperature of 80 °C. Pass, then increase the roll distance to obtain a sheet of thickness of about 2.2 ~ 2.5mm, and park for 20 hours.

(2) After the vulcanization, the test was carried out for 16 hours.

Example 9

The branched polyethylenes used were numbered PER-1 and PER-7.

The processing steps of the rubber composition are as follows:

(1) Rubber mixing: set the temperature of the internal mixer to 90 ° C, the rotor speed to 50 rpm, add 20 parts of PER-1 and 80 parts of PER-7 pre-pressed for 90 seconds; then add 0.5 part of cross-linking agent. Dicumyl peroxide (DCP), 6 parts of foaming agent azodicarbonamide (AC), after 3 minutes of mixing, the rubber is drained, and the rubber compound is thinned on an open mill with a roll temperature of 80 ° C. Increase the roll distance to obtain a sheet with a thickness of about 2.2 to 2.5 mm and leave it for 20 hours.

(2) After the vulcanization, the test was carried out for 16 hours.

Example 10:

The branched polyethylene used was numbered PER-3.

The processing steps of the rubber composition are as follows:

(1) Rubber mixing: set the temperature of the internal mixer to 90 ° C, the rotor speed is 50 rpm, add 100 parts of branched polyethylene pre-pressure mixing for 90 seconds; then add 30 parts of carbon black N550, mix for 2 minutes. Then, 0.5 parts of cross-linking agent dicumyl peroxide (DCP) and 6 parts of foaming agent azodicarbonamide (AC) were added, and after 3 minutes of mixing, the rubber was discharged, and the mixture was heated at a roll temperature of 80 ° C. The thinning on the open mill, and then increase the roll distance to obtain a sheet of thickness of about 2.2 ~ 2.5mm, and park for 20 hours.

(2) After the vulcanization, the test was carried out for 16 hours.

Example 11

The branched polyethylene used was numbered PER-6.

The processing steps of the rubber composition are as follows:

(1) Rubber mixing: set the temperature of the internal mixer to 90 ° C, the rotor speed is 50 rpm, add 50 parts of ethylene propylene diene rubber and 50 parts of branched polyethylene for 90 seconds; add 5 parts of oxidation Zinc, 2 parts of stearic acid and 2 parts of antioxidant RD, kneaded for 2 minutes; then add 50 parts of carbon black N550, 20 parts of carbon black N330 and 55 parts of paraffin oil SUNPAR2280, knead for 4 minutes; finally add 2 parts Bis-butyl diperoxide (DCP), 0.3 parts of cross-linking agent sulfur, 0.5 parts of N-cyclohexyl-2-benzothiazolyl sulfenamide, 0.3 parts of tetramethylthiuram disulfide, 0.5 parts The foaming agent azodicarbonamide (AC) and 1 part of the foaming agent diphenylsulfonyl oxime ether (OBSH) were mixed for 3 minutes, and the rubber was discharged on a mill with a roll temperature of 80 ° C. Pass, then increase the roll distance to obtain a sheet of thickness of about 2.2 ~ 2.5mm, and park for 20 hours.

(2) After the vulcanization, the test was carried out for 16 hours.

Example 12

The branched polyethylene used was numbered PER-6.

The processing steps of the rubber composition are as follows:

(1) Rubber mixing: set the temperature of the internal mixer to 90 ° C, the rotor speed to 50 rpm, add 100 parts of branched polyethylene pre-pressed and kneaded for 90 seconds; add 5 parts of zinc oxide, 2 parts of stearic acid and 2 parts of antioxidant RD, mixing for 2 minutes; then add 50 parts of carbon black N550, 20 parts of carbon black N330 and 55 parts of paraffin oil SUNPAR2280, mixing for 4 minutes; finally adding 2 parts of cross-linking agent dicumyl peroxide (DCP), 0.3 parts of cross-linking agent sulfur, 0.5 part of N-cyclohexyl-2-benzothiazolyl sulfenamide, 0.3 part of tetramethylthiuram disulfide and 2 parts of blowing agent diphenylsulfonyl hydrazide Ether (OBSH), after 3 minutes of mixing, the glue was discharged. The kneaded rubber was thinly passed on an open mill having a roll temperature of 80 ° C, and then the roll was adjusted to obtain a sheet having a thickness of about 2.2 to 2.5 mm and left for 20 hours.

(2) After the vulcanization, the test was carried out for 16 hours.

Example 13

The branched polyethylene used was numbered PER-4.

The processing steps of the rubber composition are as follows:

(1) Rubber mixing: set the temperature of the internal mixer to 70 ° C, the rotor speed to 50 rpm, add 50 parts of ethylene propylene diene rubber and 50 parts of branched polyethylene for 90 seconds; then add 10 parts. 30# engine oil and 4 parts of vinyl tris(2-methoxyethoxy)silane (A-172), kneaded for 1 minute; then add 50 parts of precipitated white carbon black N255, 3 parts of polyethylene glycol, 10 parts of zinc oxide was kneaded for 2 minutes; finally, 2 parts of cross-linking agent dicumyl peroxide (DCP) and 6 parts of blowing agent azodicarbonamide (AC) were added, and the mixture was kneaded for 3 minutes and then discharged. The kneaded rubber was thinly passed on the mill, the roll distance was set to 0.4 mm, and the thin pass was made 10 times. Then, the roll gap was adjusted to obtain a sheet thickness of about 2.2 to 2.5 mm, and the plate was left for 20 hours.

(2) After the vulcanization, the test was carried out for 16 hours.

Example 14

The branched polyethylene used was numbered PER-4.

The processing steps of the rubber composition are as follows:

(1) Rubber mixing: set the temperature of the internal mixer to 70 ° C, the rotor speed to 50 rpm, add 100 parts of branched polyethylene pre-pressure mixing for 90 seconds; then add 10 parts of 30# engine oil and 4 parts of vinyl Tris(2-methoxyethoxy)silane (A-172), kneaded for 1 minute; then add 50 parts of precipitated white carbon black N255, 3 parts of polyethylene glycol, 10 parts of zinc oxide for 2 minutes. Finally, 2 parts of cross-linking agent dicumyl peroxide (DCP) and 6 parts of foaming agent azodicarbonamide (AC) were added, and after 3 minutes of mixing, the rubber was discharged, and the mixture was heated at a roll temperature of 60 ° C. On the open mill, the thin pass, the roll distance is set to 0.4mm, thin through 10 times, then increase the roll distance to obtain a sheet of thickness of about 2.2 ~ 2.5mm, and park for 20 hours.

(2) After the vulcanization, the test was carried out for 16 hours.

Comparative Example 3:

(1) Rubber mixing: set the temperature of the internal mixer to 90 ° C, the rotor speed is 50 rpm, add 100 parts of EPDM rubber and pre-press and knead for 90 seconds; then add 0.5 part of cross-linking agent. Propylene (DCP), 6 parts of foaming agent azodicarbonamide (AC), after 3 minutes of mixing, the rubber is discharged, and the mixture is thinned on an open mill with a roll temperature of 80 ° C, and then the roll is adjusted. A sheet of a thickness of about 2.2 to 2.5 mm was obtained and left for 20 hours.

(2) After the vulcanization, the test was carried out for 16 hours.

Comparative Example 4:

The processing steps are as follows:

(1) Rubber mixing: set the temperature of the internal mixer to 90 ° C, the rotor speed is 50 rpm, add 100 parts of EPDM rubber for 90 seconds, and add 5 parts of zinc oxide and 2 parts of stearic acid. And 2 parts of antioxidant RD, mixing for 2 minutes; then add 50 parts of carbon black N550, 20 parts of carbon black N330 and 55 parts of paraffin oil SUNPAR2280, mixing for 4 minutes; finally adding 2 parts of cross-linking agent diisopropyl peroxide Benzene (DCP), 0.3 parts of cross-linking agent sulfur, 0.5 part of N-cyclohexyl-2-benzothiazolyl sulfenamide, 0.3 part of tetramethylthiuram disulfide and 2 parts of blowing agent diphenylsulfonyl Ethyl ether (OBSH), after 3 minutes of mixing, the rubber is discharged, and the rubber mixture is thinly passed on an open mill with a roll temperature of 80 ° C, and then the roll is adjusted to obtain a sheet thickness of about 2.2 to 2.5 mm, and parked 20 hour.

(2) After the vulcanization, the test was carried out for 16 hours.

Comparative Example 5:

(1) Rubber mixing: set the temperature of the internal mixer to 70 ° C, the rotor speed to 50 rpm, add 100 parts of EPDM rubber for 90 seconds, and then add 10 parts of 30# oil and 4 parts of ethylene. Base tris(2-methoxyethoxy)silane (A-172), kneaded for 1 minute; then add 50 parts of precipitated white carbon black N255, 3 parts of polyethylene glycol, 10 parts of zinc oxide mixture 2 Minutes; finally, add 2 parts of cross-linking agent dicumyl peroxide (DCP) and 6 parts of foaming agent azodicarbonamide (AC), mix for 3 minutes, then drain the glue, and mix the mixture at a roll temperature of 60. The °C open mill has a thin pass, the roll distance is set to 0.4mm, and the thin pass is 10 times. Then, the roll is adjusted to obtain a sheet thickness of about 2.2 to 2.5 mm and parked for 20 hours.

(2) After the vulcanization, the test was carried out for 16 hours.

The performance test data is as follows:

Data analysis: By comparing Examples 7 to 10 and Comparative Example 3 or Comparative Examples 11, 12 and Comparative Example 4 or Comparative Examples 13, 14 and Comparative Example 5, it was found that the branched polyethylene was replaced with ethylene-propylene rubber. The specific gravity is increased, the tensile strength of the styrofoam obtained by vulcanization is increased, and the compression set is reduced, and the overall performance is improved.

The embodiment of the invention also relates to the use of the rubber composition, wherein the application of the rubber composition is to make a foamed material, the foamed material comprises a sponge sealing strip, a high expansion ratio foam material, a shock absorbing foam Rubber sheet, light-colored high-strength foam sheet, as follows:

Example 15

A sponge sealing strip, the production method comprising the following steps:

(1) Rubber mixing: set the temperature of the internal mixer to 90 ° C, the rotor speed is 50 rpm, add 100 parts of branched polyethylene PER-5 pre-pressure mixing for 90 seconds; add 10 parts of zinc oxide and 1 part of hard Fatty acid, kneaded for 1 minute; then add 5 parts of calcium oxide 2 parts of polyethylene glycol PEG4000, knead for 1 minute; then add 60 parts of carbon black N550, 60 parts of carbon black N765 and two batches in the middle of the batch. 70 parts of paraffin oil SUNPAR2280 was mixed for 4 minutes; finally, 4 parts of cross-linking agent dicumyl peroxide (DCP), 1 part of cross-linking agent triallyl isocyanurate (TAIC), 0.3 parts of helper were added. The joint sulphur, 2 parts of the foaming agent azodicarbonamide (AC) and 2 parts of the blowing agent diphenyl sulfonyl oxime ether (OBSH), and the rubber is discharged after 3 minutes of mixing;

(2) mixing, filming, cooling, and parking;

(3) Extruder extrusion, salt bath vulcanization 220 ° C × 1.5 minutes, forming, cooling, punching, cutting.

Example 16:

A high expansion ratio foam material, the production method comprising the following steps:

(1) Rubber mixing: set the temperature of the internal mixer to 90 ° C, the rotor rotation speed is 50 rpm, add 100 parts of branched polyethylene PER-3 pre-pressure mixing for 90 seconds; then add 0.5 part of cross-linking agent for peroxidation. Diisopropylbenzene (DCP), 6 parts of foaming agent azodicarbonamide (AC), after 3 minutes of mixing, the rubber is discharged, and the rubber mixture is thinned on an open mill with a roll temperature of 80 ° C, and then adjusted. The roll distance is obtained as a sheet piece having a thickness of about 3 mm;

(2) pre-forming the compounding compound in a mold at 70 ° C for 15 minutes under a pressure of 5 MPa;

(3) placing the pre-formed film in a mold and foaming at 160 ° C for 10 minutes;

Example 17

A shock-absorbing foam rubber sheet whose production process is as follows:

(1) Rubber mixing: set the temperature of the internal mixer to 90 ° C, the rotor speed to 50 rpm, add 100 parts of branched polyethylene pre-pressed and kneaded for 90 seconds; add 5 parts of zinc oxide, 2 parts of stearic acid and 2 parts of antioxidant RD, mixing for 2 minutes; then add 50 parts of carbon black N550, 20 parts of carbon black N330 and 55 parts of paraffin oil SUNPAR2280, mixing for 4 minutes; finally adding 2 parts of cross-linking agent dicumyl peroxide (DCP), 0.3 parts of cross-linking agent sulfur, 0.5 part of N-cyclohexyl-2-benzothiazolyl sulfenamide, 0.3 part of tetramethylthiuram disulfide and 2 parts of blowing agent diphenylsulfonyl hydrazide Ether (OBSH), after 3 minutes of mixing, the glue is discharged;

(2) After cooling the discharged rubber to 30 ° C, it is thinned 5 times on a mill with a roll gap of less than 1 mm, and is placed at a thickness of 6-8 mm for 24 hours;

(3) Put the parked rubber into the open mill to heat the sheet, the ratio of the thickness of the sheet to the thickness of the product is 0.6:1, and the temperature of the process is controlled below 65 °C;

(4) The hot rubber compound that has been parked for more than 24 hours is cut into pieces according to the size of the mold cavity;

(5) The cut film is placed in a mold cavity and vulcanized, and the vulcanization temperature is 165 ° C for 30 minutes;

(6) Hot demoulding, trimming, and obtaining foamed rubber sheet products.

Example 18

A light-colored high-strength foamed sheet, the production method comprising the following steps:

(1) Rubber mixing: set the temperature of the internal mixer to 70 ° C, the rotor speed to 50 rpm, add 100 parts of branched polyethylene PER-4 pre-pressure mixing for 90 seconds; then add 10 parts of 30# oil, mix 1 minute; add 50 parts of precipitated white carbon black N255, 3 parts of polyethylene glycol, 10 parts of zinc oxide for 2 minutes; finally add 10 parts of crosslinker bis (tert-butylperoxyisopropyl) Benzene, 6 parts of a radiation-sensitizing co-crosslinking agent trimethylolpropane trimethacrylate (TMPTMA) and 6 parts of a blowing agent azodicarbonamide (AC), which are mixed for 3 minutes and then discharged. The rubber compound is thinly passed on an open mill with a roll temperature of 60 ° C, thinned 10 times at a roll gap of 0.4 mm, and then gradually increased the roll pitch to obtain a film under the thickness of about 5 mm;

(2) Park the film for 24 hours, and cut the sheet according to the size of the mold cavity;

(3) Radiation pre-vulcanization: The cut rubber sheet is fixed on the tension-free traction beam conveyor under the electron accelerator for uniform radiation treatment. The electron accelerator beam energy is 10 MeV, and the electron beam scanning width is 1 m. The film radiation absorption dose is selected to be 30KGy, and the irradiation atmosphere is oxygen-limited, that is, nitrogen protection; the average radiation pretreatment time required for each film is 2.5 minutes.

(4) High-temperature molding vulcanization foaming: The raw film after radiation pretreatment is vulcanized in a vulcanization molding machine at 175 ° C and 10 MPa for 15 min, and the mold is discharged, and after natural cooling, trimming is performed to obtain a light-colored high-strength foam. Plate.

Example 19

A foamed solid composite sealing strip whose production process is as follows:

(1) rubber mixing: the mixing process of the rubber used in the foaming part is the same as in the embodiment 15;

(2) Composite extrusion and vulcanization: the solid part of the rubber mixture and the foamed part of the vulcanized rubber are co-extruded through the composite machine head, the temperature of the extruder is set to 90 to 100 ° C, and the screw temperature is 70 to 80 ° C. The head pressure should be controlled at 15~20MPa, the extruder speed is 25~30rev/min, the salt bath vulcanization process is adopted, the spray section temperature is 250°C, the dipping wheel section temperature is 220°C, the dipping section temperature is 220°C, the transmission speed At 35 to 45 m/min, the vulcanization time is 1.5 minutes, and the cooling zone temperature is 25 to 30 °C.

(3) Cooling, trimming, cutting, and getting the finished product.

Example 20

A solid bicycle tire whose inner layer is a foamed elastic body, and the production process thereof is as follows:

(1) Inner layer rubber mixing: adding 100 parts of branched polyethylene PER-4 pre-pressing and kneading for 90 seconds; adding 5 parts of zinc oxide and 1 part of stearic acid, mixing for 1 minute; then adding 5 to the rubber compound Vaseline, 10 paraffin oil SUNPAR2280 and 20 parts calcium carbonate, mixed for 3 minutes; finally added 4 parts of cross-linking agent dicumyl peroxide (DCP), 1 part of cross-linking agent triallyl isocyanuric acid Ester (TAIC), 3 parts of foaming agent soda ash and 2 parts of foaming agent diphenylsulfonyl oxime ether (OBSH) were mixed for 3 minutes and then discharged. After being opened on an open mill at 60 ° C, the lower sheet was cooled, and after immersing the separating liquid, it was cooled and parked.

(2) Molding: Add the rubber compound to the extruder, extrude a round strip of suitable diameter, cut the length according to the process requirements, and connect the two ends to obtain a semi-finished styrofoam strip.

(3) Foaming vulcanization: The semi-finished product of the styrofoam rubber is installed on the mold, and the finished tire casing is put on, and the top of the tire casing is evenly pierced with a 2 mm diameter steel needle at intervals of 2.5 to 4 cm, and then placed in a vulcanization oven. Vulcanization, foaming, time is 30 minutes, temperature is 160 °C. The foamed inner tube and the outer tube are combined to achieve the purpose of preventing inflation and stab.

Example 21:

(1) Inner layer rubber mixing: adding 50 parts of branched polyethylene PER-3 and 50 parts of branched polyethylene PER-11 pre-pressing and kneading for 90 seconds; adding 5 parts of zinc oxide and 1 part of stearic acid, mixing 1 minute; then 5 parts of petrolatum, 10 parts of paraffin oil SUNPAR 2280 and 20 parts of calcium carbonate were added to the compound, and kneaded for 3 minutes; finally, 4 parts of cross-linking agent dicumyl peroxide (DCP), 1 part of auxiliary The combined triallyl isocyanurate (TAIC), 3 parts of foaming agent soda ash and 2 parts of foaming agent diphenylsulfonyl oxime ether (OBSH) were mixed for 3 minutes and then discharged. After being opened on an open mill at 60 ° C, the lower sheet was cooled, and after immersing the separating liquid, it was cooled and parked.

(2) Molding: the rubber compound is added to the extruder, and a round strip of suitable diameter is extruded, the length is cut according to the process requirement, and the two ends are joined to obtain a semi-finished product of the styrofoam strip.

Example 22

(1) Rubber mixing: set the temperature of the internal mixer to 70 ° C, the rotor speed is 50 rpm, add 100 parts of branched polyethylene PER-10 pre-pressure mixing for 90 seconds; then add 20 parts of 30# oil, mix 1 minute; add 50 parts of precipitated white carbon black N255, 3 parts of polyethylene glycol, 10 parts of zinc oxide for 2 minutes; finally add 10 parts of crosslinker bis (tert-butylperoxyisopropyl) Benzene, 6 parts of a radiation-sensitizing co-crosslinking agent trimethylolpropane trimethacrylate (TMPTMA) and 6 parts of a blowing agent azodicarbonamide (AC), which are mixed for 3 minutes and then discharged. The rubber compound is thinly passed on an open mill with a roll temperature of 60 ° C, thinned 10 times at a roll gap of 0.4 mm, and then gradually increased the roll pitch to obtain a film under the thickness of about 5 mm;

Example 23

A sponge sealing strip, the production method comprising the following steps:

(1) Rubber mixing: set the temperature of the internal mixer to 90 ° C, the rotor speed is 50 rpm, add 100 parts of branched polyethylene PER-12 pre-pressure mixing for 90 seconds; add 10 parts of zinc oxide and 1 part of hard Fatty acid, kneaded for 1 minute; then add 5 parts of calcium oxide 2 parts of polyethylene glycol PEG4000, knead for 1 minute; then add 60 parts of carbon black N550, 60 parts of carbon black N765 and two batches in the middle of the batch. 70 parts of paraffin oil SUNPAR2280 was mixed for 4 minutes; finally, 4 parts of cross-linking agent dicumyl peroxide (DCP), 1 part of cross-linking agent triallyl isocyanurate (TAIC), 0.3 parts of helper were added. The joint sulphur, 2 parts of the foaming agent azodicarbonamide (AC) and 2 parts of the blowing agent diphenyl sulfonyl oxime ether (OBSH), and the rubber is discharged after 3 minutes of mixing;

(2) mixing, filming, cooling, and parking;

The foamed sample prepared according to the formulation used in this example had a tensile strength of 3.2 MPa, an elongation at break of 353%, and a compression set of 15% at 70 ° C × 70 h.

Claims

A rubber composition comprising: a rubber matrix and an essential component, the rubber matrix comprising: a content of branched polyethylene a: 0 < a ≤ 100 parts; a binary ethylene propylene rubber And the content of ethylene propylene diene monomer b: 0 ≤ b < 100 parts; based on 100 parts by weight of the rubber matrix, the essential components include: 0.5 to 10 parts of a crosslinking agent, 1.5 to 25 parts of a foaming agent, wherein The polyethylene comprises an ethylene homopolymer having a degree of branching of not less than 50 branches/1000 carbons, a weight average molecular weight of not less than 50,000, and a Mooney viscosity of ML (1+4) of not less than 2 at 125 °C.
The rubber composition according to claim 1, wherein the content of the branched polyethylene in the 100 parts by weight of the rubber matrix is a: 10 ≤ a ≤ 100 parts; the ethylene propylene rubber and the ethylene propylene diene rubber Content b: 0 ≤ b ≤ 90 parts; the branched polyethylene is an ethylene homopolymer having a degree of branching of 60 to 130 branches/1000 carbons, and a weight average molecular weight of 66,000 to 518,000, Mooney Viscosity ML (1 + 4) 125 ° C is 9 ~ 102;
The rubber composition according to claim 1, wherein the crosslinking agent comprises at least one of a peroxide crosslinking agent and sulfur, and the peroxide crosslinking agent comprises di-tert-butyl peroxidation. , dicumyl peroxide, tert-butyl cumyl peroxide, 1,1-di-tert-butyl peroxide-3,3,5-trimethylcyclohexane, 2,5-dimethyl -2,5-di(tert-butylperoxy)hexane, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne-3, bis(tert-butylperoxyperoxide) Of phenyl, 2,5-dimethyl-2,5-bis(benzoyl peroxy)hexane, tert-butyl peroxybenzoate, t-butylperoxy-2-ethylhexyl carbonate At least one.
The rubber composition according to claim 1, wherein said foaming agent comprises sodium hydrogencarbonate, azodicarbonamide (AC), dinitrosopentylenetetramine (H), diphenylsulfonate. At least one of hydrazide ether (OBSH), benzenesulfonyl hydrazide (BSH), urea, and a low-boiling hydrocarbon microcapsule-type foaming agent.
The rubber composition according to claim 1, wherein the rubber composition further comprises an auxiliary component based on 100 parts by weight of the rubber base, the auxiliary component comprising: 0.2 to 10 parts by weight of the crosslinking agent, and a reinforcing filler. 30 to 200 parts, plasticizer 10 to 100 parts, stabilizer 1 to 3 parts, metal oxide 2 to 20 parts, silane coupling agent 3 to 7 parts, polyethylene glycol 1 to 5 parts, stearic acid 0.5 ~3 parts, vulcanization accelerator 0 to 3 parts.
The rubber composition according to claim 5, wherein the silane coupling agent comprises vinyl tris(2-methoxyethoxy)silane (A-172), γ-glycidyloxypropyl group At least one of trimethoxysilane (A-187) and γ-mercaptopropyltrimethoxysilane (A-189).
The rubber composition according to claim 5, wherein the stabilizer comprises 2,2,4-trimethyl-1,2-dihydroquinoline (RD), 6-ethoxy- At least one of 2,2,4-trimethyl-1,2-dihydroquinoline (AW) and 2-mercaptobenzimidazole (MB).
The rubber composition according to claim 5, wherein the co-crosslinking agent comprises triallyl cyanurate, triallyl isocyanurate, ethylene glycol dimethacrylate, Triethylene glycol dimethacrylate, triallyl trimellitate, trimethylolpropane trimethacrylate, N,N'-m-phenylene bismaleimide, N,N'-double At least one of mercaptoacetone, 1,2-polybutadiene, a metal salt of an unsaturated carboxylic acid, and sulfur.
The rubber composition according to claim 5, wherein the plasticizer comprises at least one of pine tar, motor oil, naphthenic oil, paraffin oil, coumarone, RX-80, petrolatum, and paraffin wax.
The rubber composition according to claim 5, wherein the metal oxide contains at least one of zinc oxide, magnesium oxide, and calcium oxide.
The rubber composition according to claim 5, wherein the reinforcing filler comprises at least one of carbon black, white carbon, calcium carbonate, talc, calcined clay, magnesium silicate, and magnesium carbonate.
The rubber composition according to claim 5, wherein the vulcanization accelerator comprises 2-thiol benzothiazole, dibenzothiazole disulfide, tetramethylthiuram monosulfide, and tetrasulfide disulfide. Kethiram, tetraethylthiuram disulfide, N-cyclohexyl-2-benzothiazolyl sulfenamide, N,N-dicyclohexyl-2-phenylthiazolyl sulfenamide, bismaleyl At least one of an imine and an ethylene thiourea.
A method of processing the rubber composition according to any one of claims 1 to 12, characterized in that the processing method comprises the steps of:

(1) Rubber kneading: First, the rubber composition components other than the crosslinking system and the foaming agent are sequentially added to the internal mixer for mixing, and then the crosslinking system and the foaming system are kneaded. After being uniformly discharged, a rubber mixture is obtained, and the rubber mixture is thinned on the open mill, and then left to be left to be vulcanized. The crosslinking system contains a crosslinking agent, and may also include a crosslinking agent and a vulcanization accelerator. At least one

(2) Vulcanization: The rubber compound is filled into the cavity of the mold, vulcanized on the flat vulcanizing machine, and then demolded to obtain a vulcanized rubber.
A sponge sealing strip, characterized in that the rubber compound used for the sponge sealing strip comprises the rubber composition according to any one of claims 1 to 12.
A method of producing a sponge seal according to claim 14, wherein the production method comprises the following steps:

(1) Rubber kneading: First, the rubber composition components other than the crosslinking system and the foaming agent are sequentially added to the internal mixer for mixing, and then the crosslinking system and the foaming system are kneaded. After being uniformly discharged, a rubber mixture is obtained, and the rubber mixture is thinned on the open mill, and then left to be left to be vulcanized. The crosslinking system contains a crosslinking agent, and may also include a crosslinking agent and a vulcanization accelerator. At least one

(2) mixing, filming, cooling, and parking;

(3) Extruder extrusion, salt bath vulcanization, molding, cooling, punching, cutting.
A high expansion ratio foam material characterized in that the rubber composition for a high expansion ratio foam material comprises the rubber composition according to any one of claims 1 to 12.
A method of producing a high expansion ratio foam material according to claim 16, wherein the production method comprises the following steps:

(1) Rubber kneading: First, the rubber composition components other than the crosslinking system and the foaming agent are sequentially added to the internal mixer for mixing, and then the crosslinking system and the foaming system are kneaded. After uniform discharge, the mixture is obtained, the rubber mixture is thinned on the open mill, and then the lower part is placed, and the mixture is to be vulcanized, and the rubber mixture is thinly passed on the open mill, and the lower part, wherein the cross-linking system includes a crosslinking agent, which may further comprise at least one of a co-crosslinking agent and a vulcanization accelerator;

(2) Putting the compounding compound into a mold of 60 to 80 ° C, pressurizing on a flat vulcanizing machine, and preforming;

(3) placing the pre-formed film in a mold and foaming at a high temperature for a period of time;

(4) After the compound is cooled, it is taken out from the mold to obtain a foamed material.
A shock absorbing foam rubber sheet characterized in that the rubber compound used contains the rubber composition according to any one of claims 1 to 12.
A method of producing a shock-absorbing foam rubber sheet according to claim 18, wherein the production method comprises the following steps:

(1) Rubber kneading: First, the rubber composition components other than the crosslinking system and the foaming agent are sequentially added to the internal mixer for mixing, and then the crosslinking system and the foaming system are kneaded. After being uniformly discharged, a rubber mixture is obtained, and the rubber mixture is thinned on the open mill, and then left to be left to be vulcanized. The crosslinking system contains a crosslinking agent, and may also include a crosslinking agent and a vulcanization accelerator. At least one

(2) After cooling the discharged rubber, the film is thinned on the open mill with a roll gap of less than 1 mm, and parked;

(3) Put the parked rubber into the open mill to heat the sheet;

(4) Forming the hot rubber after parking according to the size of the mold cavity;

(5) inserting the cut film into the mold cavity to form a mold vulcanization;

(6) Hot demoulding, trimming, and obtaining foamed rubber sheet products.
A method of processing the rubber foamed material according to any one of claims 1 to 12, wherein the co-crosslinking agent comprises triallyl isocyanurate (TAIC), ethylene glycol dimethyl At least one of acrylate (EGDMA), triethylene glycol dimethacrylate (TEGDMA), trimethylolpropane trimethacrylate (TMPTMA), and a crosslinking agent having a function of a radiation crosslinking sensitizer The processing method of the rubber foaming material comprises the following steps:

(1) Rubber mixing: the components other than the crosslinking system and the foaming agent are sequentially added to the internal mixer for mixing, and then the rubber is discharged, and after the parking, a crosslinking system and a foaming agent are added to the open mill to complete Mixing; after parking, refining on an open mill or an extrusion molding machine, forming and waiting for use, the crosslinking system comprising a crosslinking agent and a crosslinking aid having a radiation sensitizing function, and may also contain Vulcanization accelerator.

(2) Radiation pre-vulcanization: the formed rubber mixture is irradiated under normal temperature and normal pressure to make the rubber sheet have a certain degree of pre-crosslinking degree;

(3) High-temperature foaming vulcanization: The radiation-pre-vulcanized sheet is placed in a mold, vulcanized and foamed under high temperature and high pressure, and then released from mold release to obtain a rubber foamed material.
The method for processing a rubber foamed material according to claim 20, wherein the electron accelerator beam energy used in the radiation pre-vulcanization is 2 to 10 MeV, and the emitted ray particles can completely penetrate the green film material, and the electron beam The scanning width is 0.2-1.6m, the radiation dose of the raw film material is 5~60KGy, the radiation atmosphere is oxygen-limited environment, the inert gas protection is used, and the time required for radiation pre-vulcanization is not more than 5 minutes per piece. The conditions for the foaming and vulcanization are 160 to 180 ° C, 6 to 15 MPa, and 10 to 20 minutes.
A light-colored high-strength foamed sheet material comprising the rubber composition according to any one of claims 1 to 12, wherein the compound for a light-colored high-strength foamed sheet material comprises the rubber composition according to any one of claims 1 to 12.
A method for producing a light-colored high-strength foamed sheet according to claim 22, characterized in that the production process steps are as follows:

(1) Rubber kneading: First, the rubber composition components other than the crosslinking system and the foaming agent are sequentially added to the internal mixer for mixing, and then the crosslinking system and the foaming system are kneaded. After uniform discharge, the mixture is obtained, the rubber mixture is thinned on the open mill, and then the lower part is placed, and the mixture is to be vulcanized, and the rubber mixture is thinly passed on the open mill, and the lower part, wherein the cross-linking system includes a crosslinking agent and a co-crosslinking agent having a radiation sensitizing function, and may further comprise a vulcanization accelerator;

(2) cutting the sliced sheet according to the size of the mold cavity;

(3) Radiation pre-vulcanization: The formed rubber compound is irradiated under normal temperature and normal pressure to make the rubber sheet have a certain degree of pre-crosslinking.

(4) High-temperature foaming vulcanization: The radiation-pre-vulcanized sheet is placed in a mold, vulcanized and foamed under high temperature and high pressure, then demolded and cooled, and trimmed to obtain a light-colored high-strength foamed sheet.
A foamed solid composite sealing strip characterized in that the rubber compound used in the foaming portion comprises the rubber composition according to any one of claims 1 to 12.
A method of producing the weather strip of claim 24, comprising the steps of:

(1) kneading: mixing the solid rubber and the foaming part in the internal mixer, and after the open on the open mill, the lower piece is cooled and parked;

(2) Composite extrusion and vulcanization: the solid part of the rubber compound and the foamed part vulcanizate are co-extruded through a composite machine head, and then vulcanized by a salt bath vulcanization process.

(3) After the vulcanization is finished, it is cooled, trimmed, and cut to obtain a finished product.
A solid tire filled with a foamed elastomer, characterized in that the rubber for internal foaming elastomer comprises the rubber composition according to any one of claims 1 to 12.
A method for producing a solid tire according to claim 26, comprising the steps of: first kneading the inner rubber in an internal mixer, discharging the lower sheet after debinding, dip the separating liquid, and cooling the parking; The rubber compound is extruded through an extruder to obtain a strip with a suitable cross-section size, and then the splicing is performed to obtain a semi-finished styrofoam strip; then the squeegee strip semi-finished product is mounted on the mold, and the finished tire casing is placed on the tire casing. The top is evenly pierced with a steel needle and placed in a vulcanization oven for vulcanization and foaming, and the finished product is obtained after the vulcanization is completed.