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WO2018130192A1 - 橡胶组合物，及应用其的耐老化橡胶制品和生产方法 - Google Patents

橡胶组合物，及应用其的耐老化橡胶制品和生产方法 Download PDF

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Publication number
WO2018130192A1
WO2018130192A1 PCT/CN2018/072361 CN2018072361W WO2018130192A1 WO 2018130192 A1 WO2018130192 A1 WO 2018130192A1 CN 2018072361 W CN2018072361 W CN 2018072361W WO 2018130192 A1 WO2018130192 A1 WO 2018130192A1
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WIPO (PCT)
Prior art keywords
rubber
vulcanization
parts
mixing
temperature
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Application number
PCT/CN2018/072361
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English (en)
French (fr)
Inventor
徐涛
傅智盛
吴安洋
Original Assignee
杭州星庐科技有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from CN201810020850.6A external-priority patent/CN108329559B/zh
Application filed by 杭州星庐科技有限公司 filed Critical 杭州星庐科技有限公司
Priority to US16/477,747 priority Critical patent/US11479661B2/en
Priority to JP2019559143A priority patent/JP7250341B2/ja
Publication of WO2018130192A1 publication Critical patent/WO2018130192A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/02—Ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/02—Organic and inorganic ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene

Definitions

  • the invention belongs to the technical field of rubber, and particularly relates to a rubber composition and a processing method thereof, and an anti-aging product and a production method using the rubber composition.
  • Ethylene-propylene rubber is widely used in various applications where high resistance to aging and/or compression set is required due to its excellent aging resistance and good compression set resistance.
  • Sulfur vulcanization and peroxide vulcanization are two conventional vulcanization methods for ethylene-propylene rubber.
  • a peroxide crosslinking system is now gradually being used.
  • the mechanical strength of peroxide-vulcanized ethylene-propylene rubber will be lower than that of sulfur-vulcanized ethylene-propylene rubber, which will lead to an increase in the risk of damage to the product during actual use, so at the same time improve the aging resistance and mechanics of ethylene-propylene rubber.
  • Strength is a technical problem that needs to be solved urgently.
  • 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 ⁇ -olefin.
  • Ethylene and ⁇ -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 ⁇ -olefin copolymers. The lower the ratio, the better the aging resistance.
  • the ratio can be expressed by the degree of branching.
  • 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.
  • the ⁇ -olefin in the common ethylene and ⁇ -olefin copolymer may be an ⁇ -olefin having a carbon number of not less than 4 in addition to propylene, and may be selected from a C 4 - C 20 ⁇ -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 ⁇ -olefin is too low, the melting point and crystallinity are too high, and it is not suitable for use as a rubber component.
  • 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.
  • the polyolefin elastomer commonly used in rubber products is generally ethylene.
  • 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 copolymer of ethylene and ⁇ -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.
  • the present invention provides a novel rubber composition and the ethylene-propylene rubber which is present in the prior art is easily aged by sulfur vulcanization, and the peroxide is vulcanized to make the ethylene-propylene rubber have a tear strength lower than that of the sulfur vulcanized ethylene-propylene rubber.
  • the processing method also provides an application and processing method for processing an anti-aging rubber product by the rubber composition.
  • a rubber composition comprising, in parts by weight, a rubber matrix and a necessary component, the rubber matrix comprising: a branched polymer
  • the necessary components include: 1.5 to 10 parts of a crosslinking agent, 30-200 parts of strong filler, 5 ⁇ 250 parts of plasticizer, wherein the branching degree of branched polyethylene is not less than 50 branches/1000 carbons, the weight average molecular weight is not less than 50,000, Mooney viscosity ML (1+4) 125 ° C is not less than 2.
  • Branched polyethylene in the prior art means, in addition to a branched ethylene homopolymer, a branched saturated vinyl copolymer, such as an ethylene- ⁇ -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.
  • 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.
  • 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 ( ⁇ -diimine) nickel/palladium catalysts.
  • the nature of the chain walking mechanism refers to the late transition metal catalyst.
  • the ( ⁇ -diimine) nickel/palladium catalyst is more likely to undergo ⁇ -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 ( ⁇ -diimine) nickel catalyst is significantly lower than that of the ( ⁇ -diimine) palladium catalyst, and the ( ⁇ -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 ( ⁇ -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.
  • 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.
  • EPDM 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.
  • 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- ⁇ -olefin copolymer.
  • the vinyl copolymer refers to a copolymer of ethylene and a branched ⁇ -olefin, and has a secondary branched structure, wherein the branched ⁇ -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.
  • branched polyethylene prepared by the ( ⁇ -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.
  • the cross-linking point of the branched polyethylene can be generated on the tertiary chain of the main chain during the peroxide crosslinking process. It can also be produced on the branched tertiary carbon of the secondary structure, so the rubber network formed by the cross-linking of the branched polyethylene has a richer CC connecting segment between the main chains than the ethylene-propylene rubber. The length can effectively avoid stress concentration and help to obtain better mechanical properties, including tear strength.
  • the rubber composition comprises, in parts by weight, a rubber matrix comprising 100 parts of branched polyethylene, and the necessary components, wherein the necessary components are included in 100 parts by weight of the rubber matrix. 2 to 7 parts of the crosslinking agent, 30 to 200 parts of the reinforcing filler, and 8 to 150 parts of the plasticizer.
  • the crosslinking agent includes at least one of a peroxide crosslinking agent and sulfur, and the peroxide crosslinking agent includes di-tert-butyl peroxide, dicumyl peroxide, and tert-butyl group.
  • the reinforcing filler comprises at least one of carbon black, white carbon black, calcium carbonate, talc, calcined clay, magnesium silicate, and magnesium carbonate.
  • the plasticizer comprises at least at least of pine tar, motor oil, naphthenic oil, paraffin oil, coumarone, RX-80, stearic acid, paraffin, liquid polyisobutylene, fatty acid derivatives, and mixtures thereof.
  • the plasticizer is further preferably used in an amount of 15 to 120 parts by weight.
  • stearic acid can also act as an active agent in sulfur-sulfur-based systems, and can form soluble salts with some metal oxides, thereby increasing the activation of metal oxides on promoters.
  • the rational use of plasticizers can increase the flexibility of the compound and the plasticity suitable for process operation.
  • an adhesion promoter such as pine tar, coumarone, RX-80, liquid polyisobutylene or the like.
  • the rubber composition further comprises an auxiliary component, wherein the auxiliary component comprises: 0.2 to 10 parts of a co-crosslinking agent, 0.5 to 3 parts of a stabilizer, and a metal oxide 2 to 1 part by weight of the rubber matrix. 15 parts, vulcanization accelerator 0 to 3 parts.
  • the co-crosslinking agent comprises triallyl cyanurate, triallyl isocyanurate, ethylene glycol dimethacrylate, ethyl dimethacrylate, dimethyl Triethylene glycol acrylate, triallyl trimellitate, trimethylolpropane trimethacrylate, ethylene glycol dimethacrylate, N, N'-m-phenylene bismaleimide, At least one of N,N'-bis-indenyl acetonide, 1,2-polybutadiene, p-nonane, sulphur, and a metal salt of an unsaturated carboxylic acid.
  • the unsaturated carboxylic acid metal salt contains at least one of zinc acrylate, zinc methacrylate, magnesium methacrylate, calcium methacrylate, and aluminum methacrylate.
  • the metal oxide is at least one of zinc oxide, magnesium oxide, calcium oxide, lead monoxide, and lead tetraoxide.
  • 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).
  • RD 2,2,4-trimethyl-1,2-dihydroquinoline polymer
  • AW 6-ethoxy-2,2,4-trimethyl- At least one of 1,2-dihydroquinoline
  • MB 2-mercaptobenzimidazole
  • the vulcanization accelerator comprises 2-thiol benzothiazole, dibenzothiazole disulfide, tetramethylthiuram monosulfide, tetramethylthiuram disulfide, tetraethyl disulfide Of thiuram, N-cyclohexyl-2-benzothiazolyl sulfenamide, N,N-dicyclohexyl-2-phenylthiazolyl sulfenamide, bismaleimide, ethylene thiourea At least one.
  • a further solution is that the selected ethylene-propylene rubber and ethylene propylene diene rubber have a Mooney viscosity ML (1+4) of 20 to 80 at 125 ° C and an ethylene content of 45% to 70%.
  • the content of the branched polyethylene in the 100 parts by weight of the rubber matrix is a: 10 ⁇ a ⁇ 100 parts; the total content of the binary ethylene propylene rubber and the EPDM rubber is b: 0 ⁇ b ⁇ 90
  • the branched polyethylene is characterized by being 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 ML (1+). 4) 125 ° C is 6 to 102.
  • the content of the branched polyethylene in the 100 parts by weight of the rubber matrix is a: 10 ⁇ a ⁇ 100 parts; 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 23-101;
  • the content of the branched polyethylene in the 100 parts by weight of the rubber matrix is a: 10 ⁇ a ⁇ 100 parts; 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 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) 125. °C is 40 to 95.
  • the content of the branched polyethylene in the 100 parts by weight of the rubber matrix is a: 10 ⁇ a ⁇ 100 parts; 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 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) 125. °C is 42-80.
  • 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-norbornene.
  • 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%.
  • the rubber composition in order to improve the viscosity of the rubber compound, may further comprise a tackifier, wherein the plasticizer is pine tar, coumarone resin, RX-80, and liquid polyisobutylene.
  • a tackifier wherein the plasticizer is pine tar, coumarone resin, RX-80, and liquid polyisobutylene.
  • a commonly used tackifier such as a phenol resin, a modified alkyl phenol resin, or an alkyl phenol-acetylene resin, and the tackifier is generally not more than 30 parts by weight, further preferably not more than 10 parts by weight, based on 100 parts by weight of the rubber base. It is further preferably not more than 5 parts by weight.
  • 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 processing the above rubber composition, comprising the steps of:
  • Rubber mixing setting the temperature of the internal mixer and the rotation speed of the rotor, and sequentially adding the components other than the crosslinking system in the rubber composition to the internal mixer for mixing; then adding the crosslinking system, and discharging the rubber after mixing. , the rubber compound is thinly passed through the open mill and parked, wherein the crosslinking system comprises a crosslinking agent, and may further comprise at least one of a crosslinking agent and a vulcanization accelerator;
  • Vulcanization The bottled rubber after filling is filled into the cavity of the preheating mold, and subjected to high temperature pressure vulcanization. After the vulcanization is completed, the vulcanized rubber is obtained by demoulding. 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 bridge plate type rubber support comprising a steel sheet and a rubber sheet layer, wherein the rubber sheet layer comprises the above rubber composition.
  • the present invention also provides a bridge plate type rubber support comprising a steel sheet, a polytetrafluoroethylene sheet and a rubber sheet layer, wherein the rubber sheet layer comprises the above rubber composition.
  • the invention also provides a method for producing a bridge plate rubber bearing, which is formed by pressing and vulcanizing a rubber sheet between each layer and a steel plate and a polytetrafluoroethylene plate by a coating adhesive, and then bonding the whole into a whole.
  • the steps involved in its production method are as follows:
  • the crosslinking system comprises a crosslinking agent, and may further comprise at least one of a co-crosslinking agent and a vulcanization accelerator;
  • the present invention also provides a basin type rubber support, the rubber pressure receiving plate comprising the above rubber composition.
  • the invention also provides a method for producing a basin rubber bearing, wherein the basin rubber bearing comprises an upper support plate, a stainless steel plate, a polytetrafluoroethylene plate, an intermediate steel plate, a sealing ring, a rubber bearing plate and a lower branch.
  • the seat plate and the anchor bolt are assembled, and the production method includes the following steps:
  • the crosslinking system comprises a crosslinking agent, and may further comprise at least one of a crosslinking agent and a vulcanization accelerator. .
  • Vulcanization molding process the film is loaded into a preheated mold, and then vulcanized into a flat vulcanizer;
  • the present invention also provides a bridge rubber expansion device, the rubber expansion body comprising the above rubber composition.
  • the invention also provides a method for producing a bridge rubber expansion device, wherein the rubber expansion body adopts an extrusion method and the steps included in the production method are as follows:
  • Rubber mixing process setting the temperature of the internal mixer and the rotation speed of the rotor, and adding the components other than the crosslinking system in the rubber composition to the internal mixer for mixing; then adding the crosslinking system, after mixing Discharging, laminating the rubber in the open mill, parking and testing, wherein the crosslinking system comprises a crosslinking agent, and may further comprise at least one of a crosslinking agent and a vulcanization accelerator;
  • Extrusion and vulcanization The extrusion vulcanization process should adopt a vacuum extruder, and after the extrusion, a salt bath vulcanization process is adopted, and the vulcanizate is obtained by spraying, dipping, dipping, and cooling;
  • the invention also provides a method for producing a bridge rubber expansion device, wherein the rubber expansion body adopts the molding method and comprises the following steps, as follows:
  • the cross-linking system contains a crosslinking agent, and may also contain a crosslinking agent and vulcanization promotion. At least one of the agents;
  • Molding vulcanization the formed rubber compound is placed in a mold and vulcanized by a high temperature steam vulcanization process;
  • the present invention also provides a rubber steel plate combined type expansion and contraction device, wherein the rubber expandable body comprises the above rubber composition.
  • the invention also provides a method for producing a bridge rubber expansion device, the production method comprising the following steps:
  • the cross-linking system contains a crosslinking agent, and may also contain a crosslinking agent and vulcanization promotion. At least one of the agents;
  • the present invention also provides a rubber sleeper pad comprising the rubber composition of the above claims.
  • the invention also provides a method for producing a rubber sleeper pad, the production method comprising the following steps:
  • Rubber mixing and molding setting the temperature of the internal mixer and the rotation speed of the rotor, and adding the components other than the crosslinking system in the rubber composition to the internal mixer for mixing; then adding the crosslinking system and kneading Rear glue. After being parked and tested, it is subjected to hot-smelting, and then discharged according to the required thickness, and cut into a desired shape for use in a vulcanization process, wherein the cross-linking system contains a crosslinking agent, and may also include a co-crosslinking agent and a vulcanization accelerator. At least one of them.
  • the present invention also provides a rubber fender comprising the above rubber composition.
  • the present invention also provides a method of producing a rubber fender, the production method comprising the steps of:
  • Rubber mixing setting the temperature of the internal mixer and the rotation speed of the rotor, adding the components other than the crosslinking system in the rubber composition to the internal mixer, and then adding the crosslinking system, mixing and arranging a glue, wherein the crosslinking system comprises a crosslinking agent, and may further comprise at least one of a crosslinking agent and a vulcanization accelerator;
  • the present invention also provides a rubber waterstop tape comprising the above rubber composition.
  • the invention also provides a method for producing a rubber waterstop, the production method comprising the following steps:
  • the cross-linking system contains a crosslinking agent, and may also contain a crosslinking agent and vulcanization promotion. At least one of the agents;
  • the present invention also provides a steel belt rubber waterstop tape, the rubber compound used comprising the above rubber composition.
  • the invention also provides a method for producing a steel belt rubber waterstop, the production method comprising the following steps:
  • the cross-linking system contains a crosslinking agent, and may also contain a crosslinking agent and vulcanization promotion. At least one of the agents;
  • the present invention also provides a shock absorbing mount for a vehicle, the rubber compound used comprising the above rubber composition.
  • the invention also provides a method for producing a shock absorber support for a vehicle, the production method comprising the following steps:
  • the cross-linking system contains a crosslinking agent, and may also contain a crosslinking agent and vulcanization promotion. At least one of the agents;
  • the present invention also provides a rubber roller comprising the above rubber composition.
  • the invention also provides a method for producing a rubber roller, the production method comprising the following steps:
  • Rubber mixing setting the temperature of the internal mixer and the rotation speed of the rotor, and adding the components other than the crosslinking system in the rubber composition to the internal mixer for mixing; then adding the crosslinking system, mixing and arranging a glue, the rubber compound is thinly passed through the open mill, parked and tested, wherein the crosslinking system comprises a crosslinking agent, and may further comprise at least one of a crosslinking agent and a vulcanization accelerator;
  • the rubberized rubber roller is sent to the vulcanization tank, after closing the tank door, steam is vulcanized into the vulcanization tank, and the compressed air valve is opened while steam is introduced, and the compressed air is passed to vulcanize.
  • the pressure in the tank reaches 4.5 to 5 atmospheres in 0.5 hours; the vulcanization procedure is: firstly heat up to 70-80 ° C, keep warm for 2 hours; then heat up to 100-110 ° C, keep warm for 0.5 hours; then heat up to 120-130 ° C, keep warm 0.5 hours; further heating to 135 ⁇ 140 ° C, holding 8 ⁇ 10 hours, the end of vulcanization, open the exhaust valve, the pressure drops, when the pressure gauge pointer points to zero, open the insurance pin, and the steam hole in the pin hole, half Open the vulcanization tank and let the temperature drop.
  • the rubber roller is pulled out;
  • the vulcanized rubber roller is rough-processed on a lathe, and then finished on a grinding machine for inspection and inspection to obtain a finished product;
  • the present invention also provides a high temperature resistant V-ribbed belt comprising a compression layer and a buffer layer, the buffer layer compound comprising the above rubber composition.
  • the invention also provides a method for producing a high temperature resistant V-ribbed belt, the production method comprising the following steps:
  • Rubber kneading wherein the mixing of the buffer layer rubber is: setting the temperature of the internal mixer and the rotation speed of the rotor, and sequentially adding the components other than the crosslinking system in the rubber composition to the internal mixer for mixing; Then, the crosslinking system is added, the rubber is mixed after the mixing, and the rubber mixture is thinly passed through the open mill, and is parked and tested.
  • the crosslinking system contains a crosslinking agent, and may also include a crosslinking agent and a vulcanization accelerator. At least one of them;
  • Molding The reverse molding method is adopted. First, hang the optical mold on the molding machine, clean the mold, apply a small amount of release agent, and after it is volatilized, wrap the V-ribbed top cloth on the optical mold, and then wrap the buffer layer rubber to correct the tension of the rope. After winding the strength layer, the buffer rubber is applied, and finally the wedge rubber is wrapped to the outer circumference required by the molding process to obtain a strip;
  • Vulcanization The vulcanized vulcanization process is used to feed the strip into the vulcanization tank for vulcanization.
  • the vulcanization temperature is 155-175 ° C
  • the internal pressure is 0.45-0.55 MPa
  • the external pressure is 1.0-1.2 MPa
  • the vulcanization time is 25-30. minute;
  • Post-treatment After the end of vulcanization, the mold is cooled and cooled, and the belt is fed into the cutting process, and cut according to the required width. Grinding the back, grinding the wedge, and trimming the product to obtain the finished product.
  • the present invention also provides a wiper strip comprising the above rubber composition.
  • the invention also provides a method for producing a wiper strip, the production method comprising the following steps:
  • Rubber mixing setting the temperature of the internal mixer and the rotation speed of the rotor, and adding the components other than the crosslinking system in the rubber composition to the internal mixer for mixing; then adding the crosslinking system, mixing and arranging a glue, the rubber compound is thinly passed through the open mill, parked and tested, wherein the crosslinking system comprises a crosslinking agent, and may further comprise at least one of a crosslinking agent and a vulcanization accelerator;
  • the present invention also provides a seal ring comprising a rubber composition as described above.
  • the invention also provides a method for producing a sealing ring, the production method comprising the following steps:
  • the cross-linking system contains a crosslinking agent, and may also contain a crosslinking agent. And at least one of a vulcanization accelerator;
  • Vulcanization one-stage compression vulcanization: temperature is 155-170 ° C, vulcanization time is 20-25 minutes; second-stage oven vulcanization: temperature 145-155 ° C, time 40-80 minutes.
  • the present invention also provides a waterproofing membrane comprising the above rubber composition.
  • the invention also provides a method for producing a waterproof coil, the production method comprising the following steps:
  • Rubber mixing setting the temperature of the internal mixer and the rotation speed of the rotor, and adding the components other than the crosslinking system in the rubber composition to the internal mixer for mixing; then adding the crosslinking system, mixing and arranging Glue, the kneaded rubber is fully thinned and kneaded in the open mill to obtain a uniformly mixed rubber flakes, cooled to below 50 ° C to be discharged and stacked, wherein the cross-linking system contains a crosslinking agent, and may also contain a cross-linking agent. At least one of a agent and a vulcanization accelerator;
  • vulcanization the rolled material is placed in a nitrogen-containing vulcanization kettle for vulcanization treatment, the temperature of the vulcanization kettle is controlled between 155 and 165 ° C, the pressure is between 20 and 25 MPa, and the vulcanization is for 25 to 30 minutes;
  • Rewinding re-opening the vulcanized coil, taking out the release liner layer, and then rewinding and packaging into a product.
  • the present invention also provides a weather strip comprising the above rubber composition.
  • the rubber sealing strip provided by the invention can be used as a radiator plate rubber seal of an engine cooling system.
  • the present invention also provides a method of producing a weather strip using a process of compression vulcanization and stage vulcanization, comprising the steps of:
  • Rubber mixing setting the temperature of the internal mixer and the rotation speed of the rotor, and adding the components other than the crosslinking system in the rubber composition to the internal mixer for mixing; then adding the crosslinking system, mixing and arranging a glue, the rubber compound is thinly passed through the open mill, parked and tested, wherein the crosslinking system comprises a crosslinking agent, and may further comprise at least one of a crosslinking agent and a vulcanization accelerator;
  • the rubber compound after passing the test is extruded through an extruder, cut off, placed in a mold of a vulcanization apparatus, and subjected to a vulcanization under high temperature and high pressure.
  • the pressure is preferably 14 to 16 MPa
  • the temperature is preferably 170 to 185 ° C
  • the curing time is preferably 2 to 3 minutes;
  • the trimmed product is subjected to two-stage vulcanization at a high temperature.
  • the temperature is preferably 165 to 175 ° C, and the time is preferably 25 to 35 minutes;
  • the present invention also provides an inner tube characterized in that the rubber used for the carcass comprises the above rubber composition.
  • the invention also provides a method for producing a inner tube, comprising the steps of: first kneading rubber, filtering and parking; then extruding through an extruder, cutting according to the length required by the process, sticking the valve, splicing After parking; then inflated and shaped, steam vulcanized, cooled, inspected, trimmed to get the finished product.
  • the invention has the beneficial effects of providing a new rubber composition, partially or completely replacing ethylene propylene rubber with branched polyethylene, and applying it to high requirements for aging resistance and/or compression set resistance. On the rubber product, it can obtain good heat resistance, compression set resistance and mechanical strength under the peroxide vulcanization system.
  • the principle is that the molecular structure of the branched polyethylene is completely saturated, the heat aging resistance is similar to that of the ethylene propylene rubber, and it is superior to the EPDM rubber, and both can be vulcanized using a peroxide system.
  • the molecular structure of the branched polyethylene has more branches, and the length of the branch has a certain length and length distribution
  • the crosslinking point of the branched polyethylene may be generated on the tertiary carbon of the main chain, or may be generated on the branched tertiary carbon of the secondary structure, so the rubber network formed by crosslinking the branched polyethylene through peroxide is Compared with ethylene-propylene rubber, the main chain has a richer CC chain segment length, similar to the polysulfide bond distribution in the sulfur vulcanization system, which can effectively avoid stress concentration and facilitate better mechanical properties.
  • the compression set property is related to the molecular weight distribution of the rubber material.
  • the rubber with narrow molecular weight distribution has relatively low compression set.
  • the molecular weight distribution of ethylene propylene rubber is mostly between 3 and 5, and the highest is 8-9.
  • the partial ethylene propylene rubber has a molecular weight distribution close to 2 and is convenient to process, but the cost is high. Since the molecular weight distribution of the branched polyethylene is narrow, generally less than 2.5, which is significantly smaller than the molecular weight distribution of the ordinary ethylene propylene rubber, the rubber composition of the present invention It has a lower compression set after vulcanization.
  • a rubber composition comprising, in parts by weight, a rubber matrix and a necessary component, wherein the rubber matrix comprises: a content of branched polyethylene a: 0 ⁇ a ⁇ 100 parts, content of ethylene propylene rubber b : 0 ⁇ b ⁇ 100 parts, the necessary components include: 1.5 to 10 parts of a crosslinking agent, 30 to 200 parts of a reinforcing filler, and 5 to 250 parts of a plasticizer.
  • 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.
  • the rubber composition comprises, in parts by weight, a rubber matrix comprising 100 parts of branched polyethylene, and 100 parts by weight of the rubber matrix, the necessary components including 2 to 7 parts of the crosslinking agent, 30 to 200 parts of the reinforcing filler, and 8 to 150 parts of the plasticizer.
  • the crosslinking agent includes at least one of a peroxide crosslinking agent and sulfur
  • the peroxide crosslinking agent includes di-tert-butyl peroxide, dicumyl peroxide, and t-butyl Base peroxide, 1,1-di-tert-butyl peroxide-3,3,5-trimethylcyclohexane, 2,5-dimethyl-2,5-di(tert-butylperoxide) Hexane, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne-3, bis(tert-butylperoxyisopropyl)benzene, 2,5-dimethyl-2 At least one of 5-di(benzoyl peroxide)hexane, tert-butyl peroxybenzoate, and t-butylperoxy-2-ethylhexyl carbonate.
  • the reinforcing filler includes at least one of carbon black, white carbon black, calcium carbonate, talc, calcined clay, magnesium silicate, and magnesium carbonate.
  • the plasticizer includes at least one of pine tar, motor oil, naphthenic oil, paraffin oil, coumarone, RX-80, stearic acid, paraffin, liquid polyisobutylene, fatty acid derivatives, and mixtures thereof.
  • the rubber composition further includes an auxiliary component comprising 0.2 to 10 parts of a co-crosslinking agent, 0.5 to 3 parts of a stabilizer, 2 to 15 parts of a metal oxide, and 0 to 3 parts of a vulcanization accelerator.
  • the co-crosslinking agent comprises triallyl cyanurate, triallyl isocyanurate, ethylene glycol dimethacrylate, ethyl dimethacrylate, triethylene glycol dimethacrylate , triallyl trimellitate, trimethylolpropane trimethacrylate, ethylene glycol dimethacrylate, N, N'-m-phenylene bismaleimide, N, N'- At least one of bis-indenyl acetonide, 1,2-polybutadiene, p-quinone quinone, sulfur, zinc acrylate, zinc methacrylate, magnesium methacrylate, calcium methacrylate, and aluminum methacrylate.
  • the metal oxide is at least one of zinc oxide, magnesium oxide, calcium oxide, lead monoxide, and lead tetraoxide.
  • Stabilizers include 2,2,4-trimethyl-1,2-dihydroquinoline (RD), 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline At least one of porphyrin (AW) and 2-mercaptobenzimidazole (MB).
  • RD 2,2,4-trimethyl-1,2-dihydroquinoline
  • AW porphyrin
  • MB 2-mercaptobenzimidazole
  • 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 system comprises a crosslinking agent, which may further comprise at least one of a co-crosslinking agent and a vulcanization accelerator.
  • the Mooney viscosity ML (1+4) of the ethylene propylene rubber used is preferably 20 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 20 to 80, the ethylene content is preferably 50% 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 ( ⁇ -diimine) nickel catalyst under the action of a cocatalyst.
  • the structure, synthesis method and method for preparing branched polyethylene by using the ( ⁇ -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.
  • branching degree is 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 degree of branching is measured by nuclear magnetic resonance spectroscopy, and the molar percentages of various branches are measured by nuclear magnetic carbon spectroscopy.
  • Hardness test According to the national standard GB/T 531.1-2008, the test is carried out with a hardness tester, and the test temperature is room temperature;
  • tear strength test in accordance with the national standard GB/T529-2008, using an electronic tensile test machine for testing, the tensile speed is 500mm / min, the test temperature is 23 ⁇ 2 ° C, the sample is a rectangular sample;
  • compression permanent deformation test in accordance with the national standard GB/T7759-1996, using a compression permanent deformation device for testing, type B, the compression is 25%, the test temperature is 70 ° C;
  • 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;
  • test conditions are 150 ° C ⁇ 72h;
  • the vulcanization conditions of the following Examples 1 to 29 and Comparative Examples 1 to 6 were uniform: temperature: 160 ° C; pressure: 16 MPa; time was Tc90 + 2 min.
  • the branched polyethylene used was numbered PER-6.
  • the processing steps of the rubber composition are as follows:
  • the rubber composition of this embodiment can be used for the rubber sheet of the plate bridge support.
  • the number of branched polyethylene is PER-6.
  • the rubber composition processing steps are as follows:
  • the branched polyethylene was numbered PER-5.
  • the rubber composition processing steps are as follows:
  • the branched polyethylene was numbered PER-5.
  • the processing steps of the rubber composition are as follows:
  • the branched polyethylene was numbered PER-5.
  • the processing steps of the rubber composition are as follows:
  • EPDM rubber is used as the rubber matrix.
  • the bridge rubber expansion device produced by the extrusion method uses ethylene propylene diene monomer and branched polyethylene as the rubber base, and the branched polyethylene is PER-10.
  • the processing steps of the rubber expansion compound are as follows:
  • the branched polyethylene was numbered PER-9.
  • the processing steps of the rubber composition are as follows:
  • the branched polyethylene was numbered PER-5.
  • the processing steps of the rubber composition are as follows:
  • the branched polyethylene was numbered PER-4.
  • the processing steps of the rubber composition are as follows:
  • the branched polyethylene was numbered PER-4.
  • the processing steps of the rubber composition are as follows:
  • the branched polyethylene was numbered PER-4.
  • the processing steps of the rubber composition are as follows:
  • the branched polyethylenes were numbered PER-1 and PER-7.
  • the processing steps of the rubber composition are as follows:
  • the branched polyethylene was numbered PER-8.
  • the processing steps of the rubber composition are as follows:
  • the rubber composition can be used to produce a rubber sleeper pad.
  • the branched polyethylenes used were numbered PER-2 and PER-8.
  • the processing steps of the rubber composition are as follows:
  • the branched polyethylene used was numbered PER-7.
  • the processing steps of the rubber composition are as follows:
  • the branched polyethylene used was numbered PER-4.
  • the processing steps of the rubber composition are as follows:
  • the branched polyethylene used was numbered PER-6.
  • the processing steps of the rubber composition are as follows:
  • the branched polyethylene used was numbered PER-6.
  • the processing steps of the rubber composition are as follows:
  • the branched polyethylene used was numbered PER-3.
  • the processing steps of the rubber composition are as follows:
  • the branched polyethylene used was numbered PER-5.
  • the processing steps of the rubber composition are as follows:
  • the branched polyethylene used was numbered PER-4.
  • the processing steps of the rubber composition are as follows:
  • the branched polyethylene used was numbered PER-4.
  • the processing steps of the rubber composition are as follows:
  • the branched polyethylene used was numbered PER-7.
  • the processing steps of the rubber composition are as follows:
  • the branched polyethylene used was numbered PER-6.
  • the branched polyethylene used was numbered PER-5.
  • the branched polyethylene used was numbered PER-4.
  • the branched polyethylene used was numbered PER-5.
  • the branched polyethylene used was numbered PER-5.
  • the branched polyethylene used was numbered PER-4.
  • the invention also provides various applications of the above rubber composition, such as the production and processing of bridge rubber expansion device, rubber sleeper pad, bridge plate rubber bearing, basin rubber bearing, rubber steel plate combined telescopic device, rubber fender , rubber water stop belt, vehicle shock absorption bearing, rubber roller, kind of high temperature resistant V-ribbed belt, wiper strip, sealing ring, waterproof coil, etc., the specific implementation is as follows:
  • the bridge plate rubber bearing comprises a steel plate and a rubber sheet layer, and each layer of the rubber sheet and the steel plate are pressed and vulcanized by a coating adhesive to be bonded together, and the rubber composition used in the rubber sheet layer in the embodiment is pressed.
  • the composition and ratio described in Example 2 were weighed and kneaded:
  • Rubber mixing process set the temperature of the mixer to 90 ° C, the rotor speed is 50 rpm, add 100 parts of branched polyethylene pre-pressed for 90 seconds; then add 5 parts of zinc oxide and 1 part of stearin Acid, knead for 1 minute; add 50 parts of carbon black N330 and 5 parts of paraffin oil SUNPAR2280, mix for 3 minutes; finally add 3 parts of cross-linking agent dicumyl peroxide (DCP), 5 parts of cross-linking agent methyl Zinc acrylate and 0.2 parts of the cross-linking agent sulphur were mixed for 2 minutes and then discharged. The open mill is thinned, parked and tested. After numbering, refining, and calendering, the semi-finished film is punched into the required specifications for use in the vulcanization process;
  • DCP dicumyl peroxide
  • Vulcanization process the film and the surface-treated and coated adhesive steel plate are laminated and synthesized according to the process requirements, and then loaded into the preheated mold, and then vulcanized into a flat vulcanizing machine, and the vulcanization temperature is 160 ° C. , steam pressure 0.6MPa, time is 25 minutes;
  • the bridge plate rubber bearing comprises a steel plate, a polytetrafluoroethylene plate and a rubber sheet layer, and each layer of the rubber sheet is pressed and vulcanized by a coating adhesive between the steel plate and the polytetrafluoroethylene plate to be bonded into one whole.
  • the rubber composition for the rubber sheet layer in this example was weighed and kneaded according to the composition and ratio described in Example 2:
  • Rubber mixing process set the temperature of the internal mixer to 90 ° C, the rotor speed is 50 rpm, add 100 parts of branched polyethylene PER-6 pre-pressure mixing for 90 seconds; then add 5 parts of zinc oxide and 1 Stearic acid, mixing for 1 minute; adding 50 parts of carbon black N330 and 5 parts of paraffin oil SUNPAR2280, mixing for 3 minutes; finally adding 3 parts of cross-linking agent dicumyl peroxide (DCP), 5 parts of cross-linking The zinc methacrylate and 0.2 parts of the crosslinking agent sulfur were mixed and the rubber was discharged after 2 minutes. The open mill is thinned, parked and tested. After numbering, refining, and calendering, the semi-finished film is punched into the required specifications for use in the vulcanization process;
  • Vulcanization process the film and the surface-treated and coated adhesive steel plate and the polytetrafluoroethylene plate are sequentially laminated according to the process requirements, and then loaded into the preheated mold, and then vulcanized into the flat vulcanizing machine.
  • the vulcanization temperature is 160 ° C
  • the steam pressure is 0.6 MPa
  • the time is 25 minutes;
  • the basin type rubber support in this embodiment comprises an upper support plate, a stainless steel plate, a polytetrafluoroethylene plate, an intermediate steel plate, a seal ring, a rubber bearing plate, a lower support plate and a support anchor.
  • the rubber bearing plate in this embodiment is the same rubber composition as in Example 5, and the processing steps are as follows:
  • Rubber mixing process set the temperature of the internal mixer to 90 ° C, the rotor speed is 50 rpm, add 30 parts of EPDM rubber and 70 parts of branched polyethylene PER-5 pre-pressure mixing for 90 seconds; Then add 5 parts of zinc oxide and 1 part of stearic acid, mix for 1 minute; add 65 parts of carbon black N330 and 5 parts of paraffin oil SUNPAR 2280, mix for 3 minutes; finally add 3 parts of cross-linking agent dicumyl peroxide ( DCP) and 1 part of the cross-linking agent, triallyl isocyanurate (TAIC), after 2 minutes of mixing, the rubber is discharged, and the open mill is thinned, placed, and tested;
  • DCP dicumyl peroxide
  • TAIC triallyl isocyanurate
  • the rubber bearing plate is assembled with other components to obtain a basin rubber bearing.
  • a rubber expansion body for a bridge rubber expansion device is obtained by an extrusion production process, and the specific steps are as follows:
  • the rubber elastic body described in the present embodiment was the rubber composition described in Example 8, and the temperature of the internal mixer was set to 90 ° C, the rotor rotation speed was 50 rpm, and 100 parts of branched polyethylene PER was added.
  • the extrusion vulcanization process should adopt vacuum pumping extruder.
  • the temperature of the extruder is set to 90 ⁇ 100 °C
  • the screw temperature is 70-80 °C
  • the head pressure should be controlled at 15-20 MPa.
  • the output speed is 25 ⁇ 30 rev/min
  • the salt bath vulcanization process is adopted.
  • the temperature of the spray section is 250 °C
  • the temperature of the dipping section is 220 °C
  • the temperature of the immersion section is 220 °C
  • the transmission speed is 35 ⁇ 45 m/min
  • the cooling section Temperature 25 ⁇ 30 ° C;
  • a rubber expansion body for a bridge rubber expansion device is obtained by a molding process, and the specific steps are as follows:
  • the rubber elastic body described in the present embodiment was the rubber composition described in Example 11, and the temperature of the internal mixer was set to 90 ° C, the rotor rotation speed was 40 rpm, and 100 parts of branched polyg were added.
  • Ethylene PER-4 pre-compression mixing for 90 seconds; then adding 5 parts of zinc oxide, 1 part of stearic acid and 2 parts of antioxidant RD, mixing for 1 minute; adding 50 parts of carbon black N330, 10 parts of calcium carbonate, 5 parts of paraffin
  • the oil SUNPAR 2280 and 4 parts of coumarone resin were mixed for 3 minutes; finally, 3 parts of cross-linking agent dicumyl peroxide (DCP) and 0.3 parts of cross-linking agent sulfur were added, and the mixture was mixed for 2 minutes and then discharged.
  • the open mill is thinned, parked and tested. Refining the film and weighing it.
  • the rubber part was the rubber composition described in Example 11, the temperature of the internal mixer was set to 90 ° C, the rotor speed was 40 rpm, and 100 parts of branched polyethylene PER-4 was pre-compressed. 90 seconds; then add 5 parts of zinc oxide, 1 part of stearic acid and 2 parts of antioxidant RD, mixing for 1 minute; add 50 parts of carbon black N330, 10 parts of calcium carbonate, 5 parts of paraffin oil SUNPAR 2280 and 4 parts of Gu Ma Long resin, kneaded for 3 minutes; finally, 3 parts of cross-linking agent dicumyl peroxide (DCP) and 0.3 parts of cross-linking agent sulfur were added, and the mixture was mixed for 2 minutes and then discharged. The open mill is thinned, parked and tested. Refining the film, weighing and forming;
  • Vulcanization process the film and the surface-treated and coated adhesive steel sheet are laminated according to the process requirements, and then loaded into the preheated mold, and then vulcanized into a flat vulcanizing machine, and the vulcanization temperature is 160 ° C.
  • the steam pressure is 0.6 MPa and the time is 25 minutes;
  • Kneading The rubber composition described in Example 14 was used, and the temperature of the internal mixer was set to 90 ° C, the rotor rotation speed was 40 rpm, and 80 parts of PER-8 and 20 parts of PER-1 pre-compression kneading were added.
  • a rubber fender processing step is as follows:
  • DCP Dicumyl oxide
  • TAIC triallyl isocyanurate
  • Rubber part kneading and molding The rubber composition described in Example 16 was used, and the temperature of the internal mixer was set to 90 ° C, the rotor rotation speed was 40 rpm, and 100 parts of branched polyethylene PER-4 preload was added.
  • Vulcanization process the film and the surface-treated and coated adhesive steel sheet are laminated according to the process requirements, and then loaded into the preheated mold, and then vulcanized into a flat vulcanizer, and the vulcanization temperature is 160 ° C.
  • the steam pressure is 0.6 MPa and the time is 25 minutes.
  • Rubber part kneading and molding The rubber composition described in Example 17 was used, and the temperature of the internal mixer was set to 90 ° C, the rotor rotation speed was 40 rpm, and 100 parts of branched polyethylene pre-pressure kneading was added.
  • Vulcanization process the rubber material and the surface-treated and coated metal parts are laminated according to the process requirements, and then loaded into the preheated mold, and then vulcanized into a flat vulcanizing machine, and the vulcanization temperature is 160. °C, steam pressure 0.6MPa, time is 25 minutes.
  • the damper mount of the present embodiment can be used for high temperature parts such as an engine and an exhaust pipe.
  • vulcanization tank vulcanization the rubberized rubber roller is sent to the vulcanization tank, after closing the tank door, steam is vulcanized into the vulcanization tank, and the compressed air valve is opened while steam is introduced, and the compressed air is passed to vulcanize.
  • the pressure in the tank reaches 4.5 to 5 atmospheres in 0.5 hours; the vulcanization procedure is: firstly heat up to 70-80 ° C, keep warm for 2 hours; then heat up to 100-110 ° C, keep warm for 0.5 hours; then heat up to 120-130 ° C, keep warm 0.5 hours; further increase to 135 ⁇ 140 ° C, heat 8 ⁇ 10 hours.
  • the exhaust valve is opened, the pressure drops, and when the pressure gauge pointer points to zero, the safety pin is opened, and the steam is discharged from the pin hole, and the vulcanization tank is half-opened to lower the temperature until the temperature in the tank is lower than 60 ° C or Pull out the rubber roller when it is equivalent to room temperature;
  • the vulcanized rubber roller is rough-processed on a lathe, and then finished on a grinding machine for inspection and inspection to obtain a finished product.
  • a high temperature resistant V-ribbed belt, the buffer layer of which uses the rubber composition provided by the invention, and the production processing steps are as follows:
  • Compressed layer compound 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 6 parts of zinc oxide, 1 part stearic acid, 2 parts of antioxidant RD, kneaded for 1 minute; then add 45 parts of carbon black N330, 5 parts of paraffin oil SUNPAR 2280 and 5 parts of coumarone resin to the compound, mix for 3 minutes; then add 60 parts of nylon short fibers of 1 mm length, mixed for 2 minutes; finally added 4 parts of cross-linking agent dicumyl peroxide (DCP), 1.5 parts of cross-linking agent triallyl isocyanurate (TAIC) After 2 minutes of mixing, the glue is discharged.
  • DCP dicumyl peroxide
  • TAIC cross-linking agent triallyl isocyanurate
  • the kneaded rubber was thinly passed on an open mill with a roll temperature of 80 ° C, and was thinned 7 times at a roll gap of 0.5 mm to fully orient the short fibers, and the roll gap was obtained to obtain a sheet thickness of about 2.5 mm and parked for 20 hours. .
  • (2) buffer layer compound mixing set the temperature of the mixer to 90 ° C, the rotor speed is 40 rev / min, add 100 parts of branched polyethylene PER-5 pre-pressure mixing for 90 seconds; then add 6 parts of zinc oxide 2 parts of antioxidant RD and 1 part of stearic acid, mixing for 1 minute; adding 55 parts of carbon black N330, 5 parts of paraffin oil SUNPAR 2280 and 5 parts of coumarone resin, mixing for 3 minutes; finally adding 4 parts of crosslinking agent Dicumyl peroxide (DCP), 1.5 parts of cross-linking agent triallyl isocyanurate (TAIC), 10 parts of cross-linking agent zinc methacrylate and 0.3 parts of cross-linking agent sulfur, mixing Discharge the glue after 2 minutes.
  • DCP Dicumyl peroxide
  • TAIC cross-linking agent triallyl isocyanurate
  • molding the use of reverse molding. Firstly, the optical mold is hung on the molding machine, the mold is cleaned, and a small amount of release agent is applied. After it is volatilized, the V-ribbed top cloth is wrapped on the optical mold, and then the buffer rubber is wrapped to correct the tension of the rope, and the winding is smooth. After the strong layer, the buffer rubber is applied, and finally the wedge rubber is wrapped to the outer circumference required by the molding process to obtain a strip.
  • Vulcanization The strip is sent to the vulcanization section for vulcanization.
  • the vulcanization temperature is 160 ° C
  • the internal pressure is 0.45-0.55 MPa
  • the external pressure is 1.0-1.2 MPa
  • the vulcanization time is 30 minutes.
  • Post-treatment After the vulcanization is finished, the mold is cooled and released, and the belt is sent to the cutting process to cut according to the required width. Grinding the back, grinding the wedge, and trimming the product to obtain the finished product.
  • Vulcanization one-stage compression vulcanization: temperature is 160 ° C, vulcanization time is 20 minutes; second-stage oven vulcanization: temperature 150 ° C, time 1 hour.
  • the block rubber is fed into the open mill for mixing, the temperature of the control roller is between 85 and 95 ° C, and the roll distance is controlled to be less than 1 mm, and the thin pass is not less than four times until the surface of the rubber compound is smooth and shiny. Then turn the head and further mix it, make the thin pass no less than four times, adjust the roll distance to not more than 8mm, mix it three times, and obtain the evenly mixed rubber piece with the thickness below 8mm, and cool it to below 50 °C.
  • vulcanization the rolled material is placed in a nitrogen-containing vulcanization kettle for vulcanization treatment, the temperature of the vulcanization kettle is controlled between 155 and 165 ° C, the pressure is between 20 and 25 MPa, and the vulcanization is for 25 to 30 minutes;
  • Rewinding re-opening the vulcanized coil, taking out the release liner layer, and then rewinding and packaging into a product.
  • An engine cooling system radiator plate rubber sealing strip adopts a process of compression vulcanization and stage vulcanization, and comprises the following steps:
  • Rubber mixing set the internal temperature of the mixer to 80 ° C and the rotor speed to 40 rpm, add 100 parts of branched polyethylene PER-5 pre-pressure mixing for 90 seconds; then add 5 parts of zinc oxide, 1 part Stearic acid, 1 part of antioxidant RD and 2 parts of fatty acid derivative mixture WB42, kneaded for 1 minute; 60 parts of carbon black N550, 25 parts of paraffin oil SUNPAR 2280, mixed for 3 minutes; finally added 4 parts of crosslinker Butylperoxydiisopropylbenzene (BIPB), 1 part of the co-crosslinking agent, triallyl isocyanurate (TAIC), and 0.3 parts of the cross-linking agent sulfur were mixed and dispersed for 2 minutes. Parking and testing;
  • BIPB crosslinker Butylperoxydiisopropylbenzene
  • TAIC triallyl isocyanurate
  • the rubber compound after passing the test is extruded through an extruder, cut into pieces and placed in a mold of a vulcanization apparatus, the vulcanization pressure is 15 MPa, the vulcanization temperature is 180 ° C, and the vulcanization time is preferably 2.5 minutes;
  • the trimmed product is subjected to two-stage vulcanization at a high temperature.
  • the temperature is 170 ° C, the time is 30 minutes;
  • Rubber mixing set the temperature of the internal mixer to 100 ° C, the rotor speed to 50 rpm, add 100 parts of branched polyethylene PER-5 pre-pressure mixing for 90 seconds; add 5 parts of zinc oxide, 1 part of hard Fatty acid and 3 parts of coumarone resin, mixing for 2 minutes; then adding 60 parts of carbon black N660 and 20 parts of paraffin oil SUNPAR2280 to the compound, mixing for 3 minutes; finally adding 4 parts of cross-linking agent diisopropyl peroxide Benzene (DCP) and 2 parts of co-crosslinking agent N, N'-m-phenylene bismaleimide (HVA-2) were mixed for 2 minutes and then discharged. After the filter is glued, the rubber compound is opened on the open mill and parked for 20 hours.
  • DCP diisopropyl peroxide Benzene
  • HVA-2 co-crosslinking agent
  • a bridge plate type rubber support wherein the rubber base in the rubber composition is 100 parts of branched polyethylene PER-12, and the remaining components in the rubber composition and the processing technique are the same as those in the embodiment 30.
  • the rubber compound used in the rubber composition was subjected to compression molding to prepare a test sample, and the test performance was as follows:
  • Hardness 65; tensile strength: 27.3 MPa; elongation at break: 446%; compression set (70 ° C ⁇ 22 h): 8%.
  • a vehicle shock absorbing support wherein the rubber matrix in the rubber composition is 70 parts of branched polyethylene PER-10 and 30 parts of branched polyethylene PER-12, the remaining components in the rubber composition and the processing technology and Example 40 is identical.
  • the rubber compound used in the rubber composition was subjected to compression molding to prepare a test sample, and the test performance was as follows:
  • Hardness 63; tensile strength: 27.5 MPa; elongation at break: 382%; compression set (70 ° C ⁇ 22 h): 9%.
  • a rubber sleeper pad having a rubber base of 100 parts of branched polyethylene PER-11, the remaining components of the rubber composition and the processing technique are the same as those of the embodiment 36.
  • the rubber compound used in the rubber composition was subjected to compression molding to prepare a test sample, and the test performance was as follows:
  • the rubber composition of the present invention is superior to the prior art ethylene-propylene rubber-based rubber composition in comprehensive physical properties, and can significantly optimize the anti-aging rubber at low cost.
  • the use effect of the product broaden the application range of anti-aging rubber products.

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Abstract

一种橡胶组合物及加工方法，以及应用橡胶组合物的耐老化制品及生产方法，所述橡胶组合物包括：橡胶基体和必要组份，所述橡胶基体包含：支化聚乙烯的含量a：0＜a≤100份，二元乙丙橡胶和三元乙丙橡胶的含量b：0≤b＜100份，所述必要组份包含：交联剂1.5～10份，补强填充剂30～200份，增塑剂5～250份。有益效果是，该橡胶组合物具有良好的加工性能，可用来制作对耐老化性能、抗压缩永久变形性能有较高要求的橡胶制品。

Description

橡胶组合物，及应用其的耐老化橡胶制品和生产方法 技术领域
本发明属于橡胶技术领域，具体涉及一种橡胶组合物及加工方法，以及应用该橡胶组合物的耐老化制品及生产方法。
背景技术
乙丙橡胶由于具有极佳的耐老化性和良好的抗压缩永久变形性，被广泛应用于各种对于耐老化性和(或)抗压缩永久变形性能有较高要求的场合。硫黄硫化和过氧化物硫化是乙丙橡胶的两种传统硫化方法，为了获得更好的耐老化性和抗压缩永久变形性，现在逐步趋向于采用过氧化物交联体系。但是采用过氧化物硫化的乙丙橡胶的力学强度会低于硫黄硫化的乙丙橡胶，这会导致制品在实际使用中过程发生破坏的风险上升，所以同时改善乙丙橡胶的耐老化性和力学强度是一个亟待解决的技术问题。
乙丙橡胶是一种分子主链饱和的合成橡胶，可分为二元乙丙橡胶和三元乙丙橡胶两大类，两者都具有很好的耐老化性，乙丙橡胶类制品中常用的是三元乙丙橡胶，但是由于三元乙丙橡胶含有第三单体，分子链含有双键，而二元乙丙橡胶分子链完全饱和，所以二元乙丙橡胶具有更加优异的耐老化性，因此在对耐老化性能有较高要求的场合，通过并用二元乙丙橡胶来改善三元乙丙橡胶的耐老化性是一种常见的技术方案。但二元乙丙橡胶的力学强度偏低，会影响整体的物理机械性能。
二元乙丙橡胶是一种乙烯与丙烯的共聚物，属于乙烯与α-烯烃共聚物。乙烯与α-烯烃共聚物是只含碳氢元素且分子链饱和的聚合物，此类聚合物中常见的碳原子类型一般可分为伯碳、仲碳、叔碳，而叔碳原子是最容易被夺氢而形成自由基的，所以叔碳原子占所有碳原子的比例一般被认为是影响乙烯与α-烯烃共聚物耐老化性的主要因素，该比例越低则耐老化性越好，该比例可用支化度来表述，例如丙烯重量百分含量为60％的二元乙丙橡胶，可计算得到其每1000个碳原子中包含200个丙烯单元，即有200个叔碳原子或者200个甲基支链，因此其支化度是200个支链/1000个碳。二元乙丙橡胶的乙烯重量百分含量一般在40％～65％或者40％～60％，故其支化度一般在117～200个支链/1000个碳或者133～200个支链/1000个碳的区间内，该支化度可以认为高于其它常见的乙烯与α-烯烃共聚物。
现有技术中，常见的乙烯与α-烯烃共聚物中的α-烯烃除了选用丙烯外，还可以选用碳原子数不小于4的α-烯烃，可以选自C 4-C 20的α-烯烃，通常选自1-丁烯、1-己烯和1-辛烯。若乙烯与α-烯烃共聚物的支化度偏低，则熔点和结晶度过高，不适合作为橡胶组份使用，若支化度偏高，则α-烯烃的含量较高，这会导致工艺难度和原料成本偏高，可操作性和经济性较低。现有技术中，乙烯与1-丁烯或者乙烯与1-辛烯共聚得到的聚烯烃根据结晶度和熔点的高低，可以被称为聚烯烃塑性体或者聚烯烃弹性体，其中部分聚烯烃弹性体牌号由于结晶度与熔点适当，可以与乙丙橡胶良好并用，且支化度较低，被视为是一种改善乙丙橡胶耐老化性的理想材料，在一定程度上可以替代乙丙橡胶使用。由于相对于乙烯与1-丁烯共聚物，乙烯与1-辛烯共聚物分子链更柔软、更具橡胶弹性和良好的物理机械性能，所以目前橡胶制品中常用的聚烯烃弹性体一般为乙烯和1-辛烯的共聚物，其辛烯重量百分含量一般不高于45％，更常用的不高于40％，对应的支化度一般不高于56个支链/1000个碳，更常用的支化度不高于50个支链/1000个碳，远低于二元乙丙橡胶的支化度，因此其具有非常优异的耐老化性，而且物理机械性能良好。
橡胶一般需要交联后使用，在乙丙橡胶常用的交联方式中，适合乙烯与α-烯烃共聚物的可以是 过氧化物交联或辐照交联，两者主要都是通过夺取叔碳氢原子，形成叔碳自由基，再通过自由基结合形成碳碳交联，但是乙烯和1-辛烯的共聚物(以下简称POE)的叔碳原子较少，且和叔碳原子相连的支链长，空间位阻大，较难发生自由基反应，导致交联困难，影响加工效率和制品性能，比如抗压缩永久变形性难以令人满意。
所以目前需要一种更好的技术方案，可以改善乙丙橡胶的耐老化性能，同时可以具备较好的物理机械性能和交联表现，并且有望针对橡胶制品所需的特定功能性指标(如抗压缩永久变形性等)有良好表现。
发明内容
针对现有技术中存在的乙丙橡胶采用硫黄硫化容易老化，而采用过氧化物硫化使乙丙橡胶的撕裂强度低于硫黄硫化的乙丙橡胶，本发明提供一种新型的橡胶组合物及加工方法，还提供一种通过该橡胶组合物加工耐老化橡胶制品的应用和加工方法。
为了实现上述目的，本发明采用以下技术方案：提供一种橡胶组合物，其中，所述橡胶组合物以重量份计，其包括：橡胶基体和必要组份，所述橡胶基体包含：支化聚乙烯的含量a：0＜a≤100份，乙丙橡胶的含量b：0≤b＜100份，以100重量份橡胶基体计，所述必要组份包含：交联剂1.5～10份，补强填充剂30～200份，增塑剂5～250份，其中支化聚乙烯的支化度不低于50个支链/1000个碳，重均分子量不低于5万，门尼粘度ML(1+4)125℃不低于2。
“支化聚乙烯”在现有技术中除了指有支链的乙烯均聚物外，也可以指有支链的饱和乙烯基共聚物，常用的如乙烯-α-烯烃共聚物，其可以是POE，尽管POE在物理机械性能和耐老化性上表现良好，但是交联表现不佳，所以虽然本发明所述支化聚乙烯可以同时包含支化乙烯均聚物和POE，但较好的选择是支化聚乙烯高比例包含或者仅包含支化乙烯均聚物，本发明优选的技术方案是支化聚乙烯中仅包含支化乙烯均聚物。
在对本发明技术方案的进一步阐述中，如无特殊说明，则所采用的支化聚乙烯均为支化乙烯均聚物。
本发明所用支化聚乙烯是一类支化度不低于50个支链/1000个碳的乙烯均聚物，可称为Branched Polyethylene或者Branched PE，目前它的合成方法主要由后过渡金属催化剂基于“链行走机理”催化乙烯均聚得到，优选的后过渡金属催化剂可以为(α-二亚胺)镍/钯催化剂的其中一种。其链行走机理的本质是指后过渡金属催化剂，如(α-二亚胺)镍/钯催化剂在催化烯烃聚合过程中较为容易发生β-氢消除反应和再插入反应，从而导致支链产生。这类支化聚乙烯基于主链的支链可以具有不同碳原子数，具体可以是1～6个，或者更多的碳原子。
(α-二亚胺)镍催化剂的生产成本明显低于(α-二亚胺)钯催化剂，而且(α-二亚胺)镍催化剂催化乙烯聚合的速率高且活性高，更加适合工业化应用，所以本发明优选通过(α-二亚胺)镍催化剂催化乙烯聚合制备的支化聚乙烯。
本发明所用的支化聚乙烯的支化度优选为50～130个支链/1000个碳，进一步优选为60～130个支 链/1000个碳，进一步优选为60～116个支链/1000个碳，支化度介于POE与二元乙丙橡胶之间，是一种区别于现有技术的全新技术方案，可以兼具优异的耐老化性和良好的交联表现。
交联表现包括交联密度和交联速率等因素，是橡胶基体的交联能力在加工过程中的具体表现。
本发明所用的支化聚乙烯优选具有40％以上或者50％以上的甲基支链含量，与二元乙丙橡胶的结构具有一定的相似性。就交联能力而言，支化度(叔碳原子含量)以及叔碳原子周围的空间位阻是影响饱和聚烯烃的交联能力的两个主要因素。相对于二元乙丙橡胶，本发明所用的支化聚乙烯在支化度上偏低，而且由于支化聚乙烯存在碳原子数不低于2的支链，所以本发明所用的支化聚乙烯的叔碳原子周围的空间位阻理论上要大于二元乙丙橡胶，综合两个因素可以判断，本发明所用的支化聚乙烯的交联能力应该弱于二元乙丙橡胶，更加弱于三元乙丙橡胶。但是本发明采用的部分支化聚乙烯的实际交联能力接近三元乙丙橡胶，甚至可以等同或优于三元乙丙橡胶。这意味着本发明的橡胶组合物在可以获得良好的耐老化性的同时，还可以不弱化交联能力，甚至可以具有优异的交联表现，达到意想不到的有益效果。
这或许可以被解释为本发明优选的技术方案中采用的支化聚乙烯上可能存在数量适当的二级支链结构，所谓二级支链结构是指支链上进一步存在支链的结构，在链行走过程中产生，这种结构也被称为“branch-on-branch”，因为二级支链的叔碳原子周围空间位阻低，更容易发生交联反应。具有二级支链结构是本发明优选的技术方案中所用的支化聚乙烯与现有技术中的二元乙丙橡胶或常见的乙烯-α-烯烃共聚物的明显区别。
利用空间位阻较低的二级支链结构来改善饱和聚烯烃弹性体交联能力是一种的新的技术方案。在本发明的技术方案下，当橡胶基体中包含带有二级支链结构的乙烯基共聚物或者其他饱和碳氢聚合物，也被认为在本发明的技术保护范围内。所述乙烯基共聚物是指乙烯与带有支链的α-烯烃的共聚物，具备二级支链结构，其中带有支链的α-烯烃可以选自异丁烯、3-甲基-1-丁烯、4-甲基-1-戊烯、3-甲基-1-戊烯、2-甲基-1-庚烯、3-甲基-1-庚烯、4-甲基-1-庚烯、5-甲基-1-庚烯、6-甲基-1-庚烯等，共聚单体还可以同时包含常见的直链α-烯烃。
现有技术中普遍认为通过(α-二亚胺)镍催化剂制备的支化聚乙烯是难以存在二级支链结构的，至少是难以充分辨别的，本发明的技术方案也为分析支化聚乙烯的结构提供了一种新的思路。
相对于乙丙橡胶而言，当支化聚乙烯有数量适当的二级支链结构时，在过氧化物交联过程中，支化聚乙烯的交联点可以在主链叔碳上产生，也可以在二级结构的支链叔碳上产生，所以支化聚乙烯通过过氧化物交联所形成的橡胶网络与乙丙橡胶相比，主链之间具有更为丰富的C-C连接链段长度，可以有效避免应力集中，有利于获得更好的力学性能，包括撕裂强度。另一方面，更好的交联能力可以有效提高交联密度，并且支化聚乙烯的分子量分布接近2，窄于一般的乙丙橡胶，所以也有望获得更好的抗压缩永久变形性能。
进一步的方案是，所述橡胶组合物以重量份计，其包括橡胶基体和必要组份，所述橡胶基体包含支化聚乙烯100份，以100重量份橡胶基体计，所述必要组份包括交联剂2～7份，补强填充剂30～200 份，增塑剂8～150份。
进一步的方案是，所述交联剂包括过氧化物交联剂和硫磺中的至少一种，过氧化物交联剂包括二叔丁基过氧化物、二枯基过氧化物、叔丁基枯基过氧化物、1,1-二叔丁基过氧化物-3,3,5-三甲基环己烷、2,5-二甲基-2,5-二(叔丁基过氧化)己烷、2,5-二甲基-2,5-二(叔丁基过氧化)己炔-3、双(叔丁基过氧化异丙基)苯、2,5-二甲基-2,5-二(苯甲酰过氧化)己烷、过氧化苯甲酸叔丁酯、叔丁基过氧化-2-乙基己基碳酸酯中的至少一种。
进一步的方案是，所述补强填充剂包括炭黑、白炭黑、碳酸钙、滑石粉、煅烧陶土、硅酸镁、碳酸镁中的至少一种。
进一步的方案是，所述增塑剂包括松焦油、机油、环烷油、石蜡油、古马隆、RX-80、硬脂酸、石蜡、液态聚异丁烯、脂肪酸衍生物及其混合物中的至少一种。增塑剂进一步优选的用量是15～120重量份。其中，硬脂酸也可以在硫黄硫化为主的体系中作为活性剂的作用，能与一些金属氧化物形成可溶性盐，从而增加金属氧化物对促进剂的活化作用。合理使用增塑剂可以提高胶料的弹性和适合工艺操作的可塑性。为了提高粘性，还可优选采用有增粘作用的助剂，如松焦油、古马隆、RX-80、液态聚异丁烯等。
进一步的方案是，所述橡胶组合物还包括辅助成分，以100重量份橡胶基体计，所述辅助成分包含：助交联剂0.2～10份，稳定剂0.5～3份，金属氧化物2～15份，硫化促进剂0～3份。
进一步的方案是，所述助交联剂包含三烯丙基氰脲酸酯、三烯丙基异氰脲酸酯、乙二醇二甲基丙烯酸酯、二甲基丙烯酸乙酯、二甲基丙烯酸三乙二酯、偏苯三酸三烯丙酯、三甲基丙烯酸三羟甲基丙烷酯、双甲基丙烯酸乙二醇酯、N,N’-间苯撑双马来酰亚胺、N,N’-双亚糠基丙酮、1,2-聚丁二烯、对醌二肟、硫磺和不饱和羧酸金属盐中的至少一种。所述不饱和羧酸金属盐包含丙烯酸锌、甲基丙烯酸锌、甲基丙烯酸镁、甲基丙烯酸钙、甲基丙烯酸铝中的至少一种。
进一步的方案是，所述金属氧化物为氧化锌、氧化镁、氧化钙、一氧化铅、四氧化三铅的至少一种。
进一步的方案是，所述稳定剂包括2,2,4-三甲基-1,2-二氢化喹啉聚合体(RD)、6-乙氧基-2,2,4-三甲基-1,2-二氢化喹啉(AW)、2-巯基苯并咪唑(MB)中的至少一种。
进一步的方案是，所述硫化促进剂包含2-硫醇基苯并噻唑、二硫化二苯并噻唑、一硫化四甲基秋兰姆、二硫化四甲基秋兰姆、二硫化四乙基秋兰姆、N-环己基-2-苯并噻唑基次磺酰胺、N，N-二环己基-2-苯噻唑基次磺酰胺、双马来酰亚胺、亚乙基硫脲中的至少一种。
进一步的方案是，所选用的二元乙丙橡胶和三元乙丙橡胶的门尼粘度ML(1+4)125℃为20～80，乙烯含量为45％～70％。
进一步的方案是，所述100重量份橡胶基体中支化聚乙烯的含量为a：10≤a≤100份；二元乙丙橡胶与三元乙丙橡胶的含量总和b：0≤b≤90份；所述支化聚乙烯特征为：是乙烯均聚物，其支化度为60～130个支链/1000个碳、重均分子量为6.6万～51.8万，门尼粘度ML(1+4)125℃为6～102。
进一步的技术方案是，所述100重量份橡胶基体中支化聚乙烯的含量为a：10≤a≤100份；二元乙丙橡胶与三元乙丙橡胶的含量b：0≤b≤90份；所述支化聚乙烯是乙烯均聚物，其支化度为70～116个支链/1000个碳，重均分子量为20.1万～43.6万，门尼粘度ML(1+4)125℃为23～101；
进一步的技术方案是，所述100重量份橡胶基体中支化聚乙烯的含量为a：10≤a≤100份；二元乙丙橡胶与三元乙丙橡胶的含量b：0≤b≤90份；所述支化聚乙烯是乙烯均聚物，其支化度为80～105个支链/1000个碳，重均分子量为25.0万～40.0万，门尼粘度ML(1+4)125℃为40～95。
进一步的技术方案是，所述100重量份橡胶基体中支化聚乙烯的含量为a：10≤a≤100份；二元乙丙橡胶与三元乙丙橡胶的含量b：0≤b≤90份；所述支化聚乙烯是乙烯均聚物，其支化度为80～105个支链/1000个碳，重均分子量为26.8万～35.6万，门尼粘度ML(1+4)125℃为42～80。
进一步的方案是，所述三元乙丙橡胶的第三单体优选为二烯类单体，具体可选自5-亚乙基-2-降冰片烯、5-乙烯基-2-降冰片烯、双环戊二烯、1,4-己二烯、1,5-己二烯、1,4-戊二烯、2-甲基-1,4-戊二烯、3-甲基-1,4-己二烯、4-甲基-1,4-己二烯、1,9-癸二烯、5-亚甲基-2-降冰片烯、5-亚戊基-2-降冰片烯、1,5-环辛二烯、1,4-环辛二烯等。特殊的，乙丙橡胶可以同时包含两种及以上的二烯类单体，如同时包含5-亚乙基-2-降冰片烯、5-乙烯基-2-降冰片烯。二烯单体的官能团在过氧化物硫化中可以起到固有助交联剂一样的作用，提高交联效率。这有助于降低所需交联剂和助交联剂的用量和残留量以及添加它们所需的成本。二烯类单体占乙丙橡胶的重量比重优选为1％～14％，进一步优选为3％～10％，进一步优选为4％～7％。
在本发明的实施方式中，为了改善胶料的粘性，橡胶组合物可以进一步包含增粘剂，前述增塑剂中的是松焦油、古马隆树脂、RX-80、液态聚异丁烯同时具有增粘剂的作用，其中液态古马隆树脂相比固态古马隆树脂具有更好的增粘效果，增粘剂还可以选自C5石油树脂、C9石油树脂、氢化松香、萜烯树脂、烷基酚醛树脂、改性烷基酚醛树脂、烷基苯酚-乙炔树脂等常用增粘剂，以100重量份橡胶基体计，增粘剂的用量一般不超过30重量份，进一步优选不超过10重量份，进一步优选不超过5重量份。
本发明提供的橡胶组合物中涉及的交联剂、助交联剂和硫化促进剂均属于交联体系。
本发明的橡胶组合物可以以未交联的混炼胶的形式存在，在进一步发生交联反应之后可以以硫化橡胶的形式存在。硫化橡胶也可以简称为硫化胶。
本发明还提供一种加工上述橡胶组合物的方法，其包含以下步骤：
(1)橡胶混炼：设置密炼机温度和转子转速，将橡胶组合物中除交联体系以外的组分依次加入到密炼机中混炼；然后加入交联体系，混炼后排胶，将混炼胶在开炼机上薄通下片，停放，其中，交联体系包含交联剂，还可以包含助交联剂和硫化促进剂中的至少一种；
(2)硫化：将停放后的混炼胶填入预热模具的模腔，进行高温加压硫化，硫化完成后，脱模得到硫化胶。为了改善硫化胶的抗压缩永久变形性，还可以进一步采用二段硫化工艺进行硫化。
本发明还提供一种桥梁板式橡胶支座，其包含钢板和橡胶片层，其中橡胶片层包含上述橡胶组合物。
本发明还提供一种桥梁板式橡胶支座，其包含钢板、聚四氟乙烯板和橡胶片层，其中橡胶片层包含上述的橡胶组合物。
本发明还提供一种生产桥梁板式橡胶支座的方法，其是通过将各层橡胶片与钢板及聚四氟乙烯板之间经涂布胶黏剂加压硫化后粘接成的一个整体，其生产方法包含的步骤如下：
(1)橡胶混炼工艺：设置密炼机温度和转子转速，将橡胶片层所用橡胶组合物中除交联体系以 外的组分依次加入到密炼机中混炼；然后加入交联体系，混炼后排胶，将混炼胶在开炼机薄通下片，停放和检测，经编号、回炼、压延出片后冲裁成所需规格的半成品胶片，供硫化工序使用，其中，交联体系包含交联剂，还可以包含助交联剂和硫化促进剂中的至少一种；
(2)硫化工艺：将胶片与经表面处理并涂布胶黏剂的钢板和聚四氟乙烯板按工艺要求依次叠合成型，然后装入已预热的模具中，再进入平板硫化机硫化成型；
(3)后处理：硫化完成后拉出并拆卸模具，取出橡胶支座成品，冷却停放并修整，得到成品。
本发明还提供一种盆式橡胶支座，其橡胶承压板包含上述橡胶组合物。
本发明还提供一种生产盆式橡胶支座的方法，所述盆式橡胶支座由上支座板、不锈钢板、聚四氟乙烯板、中间钢板、密封圈、橡胶承压板、下支座板和支座锚栓组装而成，其生产方法包含的步骤如下：
(1)橡胶混炼工艺：设置密炼机温度和转子转速，将橡胶承压板所用橡胶组合物中除交联体系以外的组分依次加入到密炼机中混炼；然后加入交联体系，混炼后排胶，将混炼胶在开炼机薄通下片，停放和检测，其中，交联体系包含交联剂，还可以包含助交联剂和硫化促进剂中的至少一种。
(2)硫化成型工艺：将胶片装入已预热的模具中，再进入平板硫化机硫化；
(3)后处理：硫化完成后拉出并拆卸模具，取出橡胶支座成品，冷却停放并修整，得到橡胶承压板；
(4)组装：将橡胶承压板与其他部件组装得到盆式橡胶支座。
本发明还提供一种桥梁橡胶伸缩装置，其橡胶伸缩体包含上述橡胶组合物。
本发明还提供一种生产桥梁橡胶伸缩装置的方法，其橡胶伸缩体采用挤出法生产方法包含的步骤具体如下：
(1)橡胶混炼工艺：设置密炼机温度和转子转速，将所用橡胶组合物中除交联体系以外的组分依次加入到密炼机中混炼；然后加入交联体系，混炼后排胶，将混炼胶在开炼机薄通下片，停放和检测，其中，交联体系包含交联剂，还可以包含助交联剂和硫化促进剂中的至少一种；
(2)挤出和硫化：挤出硫化工艺宜采用抽真空挤出机，挤出后采用盐浴硫化工艺，经过喷淋、浸轮、浸压、冷却得到硫化胶；
(3)再经修边、检验、得到成品。
本发明还提供一种生产桥梁橡胶伸缩装置的方法，其橡胶伸缩体采用模压法生产方法包含如下步骤，具体如下：
(1)橡胶混炼和成型：设置密炼机温度和转子转速，将所用橡胶组合物中除交联体系以外的组分依次加入到密炼机中混炼，然后加入交联体系，混炼后排胶，将混炼胶在开炼机薄通下片，停放和检测，回炼出片、称量成型，其中，交联体系包含交联剂，还可以包含助交联剂和硫化促进剂中的至少一种；
(2)模压硫化：将成型的混炼胶放入模具中，采用高温蒸汽硫化工艺进行硫化；
(3)冷却、修边、检验、得到成品。
本发明还提供一种橡胶钢板组合型伸缩装置，其橡胶伸缩体包含上述橡胶组合物。
本发明还提供一种生产桥梁橡胶伸缩装置的方法，生产方法包含如下步骤：
(1)橡胶混炼和成型：设置密炼机温度和转子转速，将所用橡胶组合物中除交联体系以外的组分依次加入到密炼机中混炼，然后加入交联体系，混炼后排胶，将混炼胶在开炼机薄通下片，停放和检测，回炼出片、称量成型，其中，交联体系包含交联剂，还可以包含助交联剂和硫化促进剂中的至少一种；
(2)硫化工艺：将胶片与经表面处理并涂布胶黏剂的钢板按工艺要求贴合成型，然后装入已预热的模具中，再进入平板硫化机加热加压硫化；
(3)后处理：硫化完成后拉出并拆卸模具，取出制品，冷却停放并修整，得到成品。
本发明还提供一种橡胶轨枕垫，其所用胶料包含权利要求上述橡胶组合物。
本发明还提供一种生产橡胶轨枕垫的方法，生产方法包含如下步骤：
(1)橡胶混炼和成型：设置密炼机温度和转子转速，将所用橡胶组合物中除交联体系以外的组分依次加入到密炼机中混炼；然后加入交联体系，混炼后排胶。经停放和检测后进行热炼，然后按所需厚度出片，裁切成所需规格形状供硫化工序使用，其中，交联体系包含交联剂，还可以包含助交联剂和硫化促进剂中的至少一种。
(2)硫化：将裁切好的胶料放入模具中，将模具放入平板硫化机，加热加压硫化；
(3)后处理：硫化完成后拉出并拆卸模具，取出制品，冷却停放并修整，得到成品。
本发明还提供一种橡胶护舷，其所用胶料包含上述橡胶组合物。
本发明还提供一种生产橡胶护舷的方法，生产方法包含如下步骤：
(1)橡胶混炼：设置密炼机温度和转子转速，将所用橡胶组合物中除交联体系以外的组分依次加入到密炼机中混炼，然后加入交联体系，混炼后排胶，其中，交联体系包含交联剂，还可以包含助交联剂和硫化促进剂中的至少一种；
(2)模压及硫化：将混炼胶投入模腔，然后合模，胶料充分流动，排气，合模，硫化。
(3)开模，取出制品，修边、检验、得到成品。
本发明还提供一种橡胶止水带，其所用胶料包含上述橡胶组合物。
本发明还提供一种生产橡胶止水带的方法，生产方法包含如下步骤：
(1)橡胶混炼和成型：设置密炼机温度和转子转速，将所用橡胶组合物中除交联体系以外的组分依次加入到密炼机中混炼；然后加入交联体系，混炼后排胶，将混炼胶在开炼机薄通下片，停放和检测，回炼出片、称量成型，其中，交联体系包含交联剂，还可以包含助交联剂和硫化促进剂中的至少一种；
(2)硫化：将裁切好的胶料放入模具中，将模具放入平板硫化机，加热加压硫化；
(3)后处理：硫化完成后拉出并拆卸模具，取出制品，冷却停放并修整，得到成品。
本发明还提供一种钢带橡胶止水带，其所用胶料包含上述橡胶组合物。
本发明还提供一种生产钢带橡胶止水带的方法，生产方法包含如下步骤：
(1)橡胶混炼和成型：设置密炼机温度和转子转速，将所用橡胶组合物中除交联体系以外的组分依次加入到密炼机中混炼，然后加入交联体系，混炼后排胶，将混炼胶在开炼机薄通下片，停放和检测，回炼出片、称量成型，其中，交联体系包含交联剂，还可以包含助交联剂和硫化促进剂中的至少一种；
(2)硫化：将胶片与经表面处理并涂布胶黏剂的薄钢板按工艺要求贴合成型，然后装入已预热的模具中，再进入平板硫化机高温高压硫化；
(3)后处理：硫化完成后拉出并拆卸模具，取出制品，冷却停放并修整，得到成品。
本发明还提供一种车用减震支座，其所用胶料包含上述橡胶组合物。
本发明还提供一种生产车用减震支座的方法，生产方法包含如下步骤：
(1)橡胶混炼和成型：设置密炼机温度和转子转速，将所用橡胶组合物中除交联体系以外的组分依次加入到密炼机中混炼，然后加入交联体系，混炼后排胶，将混炼胶在开炼机薄通下片，停放和检测，回炼出片、称量成型，其中，交联体系包含交联剂，还可以包含助交联剂和硫化促进剂中的至少一种；
(2)硫化：将胶片与经表面处理并涂布胶黏剂的金属件按工艺要求贴合成型，然后装入已预热的模具中，再进入平板硫化机高温高压硫化；
(3)后处理：硫化完成后拉出并拆卸模具，取出制品，冷却停放并修整，得到成品。
本发明还提供一种胶辊，其所用胶料包含上述橡胶组合物。
本发明还提供一种生产胶辊的方法，生产方法包含如下步骤：
(1)橡胶混炼：设置密炼机温度和转子转速，将所用橡胶组合物中除交联体系以外的组分依次加入到密炼机中混炼；然后加入交联体系，混炼后排胶，将混炼胶在开炼机薄通下片，停放和检测，其中，交联体系包含交联剂，还可以包含助交联剂和硫化促进剂中的至少一种；
(2)缠绕包胶：将混炼胶投入螺杆挤出机，挤出工艺要求的厚度和宽度的胶片，待胶片均匀一致后启动旋转包布机，将胶片缠绕在准备好的金属辊芯上，逐层缠绕包胶，直到包胶单边厚度达到规定厚度，然后在胶面上缠绕尼龙水布2～3层，得到包胶完毕的胶辊；
(3)硫化罐硫化，将包胶完毕的胶辊送入硫化罐，关闭罐门后，往硫化罐中通入蒸汽进行硫化，通入蒸汽的同时打开压缩空气阀门，通入压缩空气使硫化罐内压力在0.5小时内达到4.5～5大气压；硫化程序为：首先升温到70～80℃，保温2小时；再升温到100～110℃，保温0.5小时；再升温到120～130℃，保温0.5小时；再升温到135～140℃，保温8～10小时，硫化结束，开排气阀，压力下降，等压力表指针指到零时，打开保险销，等销孔内排出蒸汽飘动，半开硫化罐，让温度下降，待罐内温度低于60℃或与室温相当时，将胶辊拉出；
(4)后处理：将硫化好的胶辊在车床上粗加工，再在磨床上精加工，检验，得到成品；
本发明还提供一种耐高温多楔带，包含压缩层和缓冲层，其缓冲层胶料包含上述橡胶组合物。
本发明还提供一种生产耐高温多楔带的方法，生产方法包含如下步骤：
(1)橡胶混炼：其中缓冲层胶料的混炼为：设置密炼机温度和转子转速，将所用橡胶组合物中除交联体系以外的组分依次加入到密炼机中混炼；然后加入交联体系，混炼后排胶，将混炼胶在开炼机薄通下片，停放和检测，其中，交联体系包含交联剂，还可以包含助交联剂和硫化促进剂中的至少一种；
(2)成型：采用反成型法。先将光模吊上成型机，清洁模具，涂上少量隔离剂，待其挥发后在光模上包贴多楔带顶布，然后包贴缓冲层胶料，校正线绳的张紧力，平整缠绕强力层后再包贴缓冲胶，最后包贴楔胶至成型工艺要求的外周长，得到带坯；
(3)硫化：采用胶套硫化工艺，将带坯送入硫化罐进行硫化，硫化温度为155～175℃，内压为0.45～0.55MPa，外压为1.0～1.2MPa，硫化时间25～30分钟；
(4)后处理：硫化结束后冷却脱模，将带筒送入切割工序，按要求宽度切割。磨背，磨楔，修边后通过检验，得到成品。
本发明还提供一种雨刷条，其所用胶料包含上述橡胶组合物。
本发明还提供一种生产雨刷条的方法，生产方法包含如下步骤：
(1)橡胶混炼：设置密炼机温度和转子转速，将所用橡胶组合物中除交联体系以外的组分依次加入到密炼机中混炼；然后加入交联体系，混炼后排胶，将混炼胶在开炼机薄通下片，停放和检测，其中，交联体系包含交联剂，还可以包含助交联剂和硫化促进剂中的至少一种；
(2)硫化：将混炼胶注射入模腔，在高温高压下硫化成型；
(3)后处理：将硫化后的制品进行表面处理，检验，得到成品。
本发明还提供一种密封圈，其所用胶料包含上述橡胶组合物。
本发明还提供一种生产密封圈的方法，生产方法包含的步骤如下：
(1)橡胶混炼及成型：设置密炼机温度和转子转速，将所用橡胶组合物中除交联体系以外的组分依次加入到密炼机中混炼；然后加入交联体系，混炼后排胶，将混炼胶在开炼机上薄通下片，物性检测，胶料返炼，然后采用挤出法得到半成品，其中，交联体系包含交联剂，还可以包含助交联剂和硫化促进剂中的至少一种；
(2)硫化：一段模压硫化：温度为155～170℃、硫化时间为20～25分钟；二段烘箱硫化：温度145～155℃，时间40～80分钟。
本发明还提供一种防水卷材，其所用胶料包含上述橡胶组合物。
本发明还提供一种生产防水卷材的方法，生产方法包含的步骤如下：
(1)橡胶混炼：设置密炼机温度和转子转速，将所用橡胶组合物中除交联体系以外的组分依次加入到密炼机中混炼；然后加入交联体系，混炼后排胶，将混炼胶在开炼机充分薄通混炼、获得混合均匀的胶料毛片，冷却至50℃以下出片、堆放，其中，交联体系包含交联剂，还可以包含助交联剂和硫化促进剂中的至少一种；
(2)热炼：将混合均匀的胶料毛片在开炼机上进行热炼，直至胶料片光滑均匀后初步成卷；
(3)压延：将经热炼初步成卷的胶料片放入压延机上，按成品厚度要求调节辊距进行压延，获得符合成品厚度规格要求的半成品卷材；
(4)收卷：按成品卷材的规格长度要求，夹设隔离衬垫层、将半成品卷材整理成卷；
(5)硫化：将整理成卷的卷材放入充氮硫化釜中进行硫化处理，控制硫化釜温度在155～165℃之间、压力在20～25MPa之间、硫化25至30分钟；
(6)复卷：将经硫化后的卷材重新打开、取出隔离衬垫层后再复卷、包装成产品。
本发明还提供一种密封条，其所用胶料包含上述橡胶组合物。本发明提供的橡胶密封条可以作为发动机冷却系统散热器板式橡胶密封条。
本发明还提供一种生产密封条的方法，其采用模压硫化和分段硫化的工艺，包含以下步骤：
(1)橡胶混炼：设置密炼机温度和转子转速，将所用橡胶组合物中除交联体系以外的组分依次 加入到密炼机中混炼；然后加入交联体系，混炼后排胶，将混炼胶在开炼机薄通下片，停放和检测，其中，交联体系包含交联剂，还可以包含助交联剂和硫化促进剂中的至少一种；
(2)将检测合格后的混炼胶通过挤出机挤出成型，截断后放入硫化设备的模具内，在高温高压下进行一段硫化。压力优选14～16MPa，温度优选170～185℃，硫化时间优选2～3分钟；
(3)将硫化处理过的产品进行修边；
(4)将修边后的产品在高温下进行二段硫化。温度优选165～175℃，时间优选25～35分钟；
(5)对产品进行检验，合格后入库。
本发明还提供一种内胎，其特征在于，其胎体所用胶料包含上述橡胶组合物。
本发明还提供一种生产内胎的方法，其特征在于，包含以下步骤：首先混炼橡胶，滤胶并停放；然后通过挤出机挤出，并按工艺要求的长度裁断，贴气门嘴，拼接后停放；然后充气定型，蒸汽硫化，冷却后，检查，修边得到成品。
本发明的有益效果是：提供一种新的橡胶组合物，用支化聚乙烯部分或者全部替代乙丙橡胶，将其应用在对于耐老化性和(或)耐压缩永久变形性能有较高要求的橡胶制品上，可以在过氧化物硫化体系下，同时获得良好的耐热性、抗压缩永久变形性和力学强度。原理是由于支化聚乙烯的分子结构完全饱和，耐热老化性能与二元乙丙橡胶类似，优于三元乙丙橡胶，并且都可以使用过氧化物体系硫化。而且由于支化聚乙烯的分子结构上具有较多的支链，且支链长度存在一定的长短分布，当支化聚乙烯有数量适当的二级支链结构时，在过氧化物交联过程中，支化聚乙烯的交联点可以在主链叔碳上产生，也可以在二级结构的支链叔碳上产生，所以支化聚乙烯通过过氧化物交联所形成的橡胶网络与乙丙橡胶相比，主链之间具有更为丰富的C-C连接链段长度，类似于硫黄硫化体系中的多硫键分布，可以有效避免应力集中，有利于获得更好的力学性能。
压缩永久变形性能与橡胶材料的分子量分布有关，分子量分布窄的橡胶具有相对较低的压缩永久变形，乙丙橡胶的分子量分布大部分在3～5之间，最高可达8～9，有少部分乙丙橡胶的分子量分布接近2并且方便加工，但成本较高，由于支化聚乙烯的分子量分布窄，普遍低于2.5，明显小于普通乙丙橡胶的分子量分布，所以本发明的橡胶组合物在硫化之后具有更低的压缩永久变形。
具体实施方式
下面给出实施例以对本发明做进一步说明，但不是用来限制本发明的范围，该领域的技术熟练人员根据发明内容对本发明做出的一些非本质的改进和调整仍属于本发明的保护范围。
本发明提供的橡胶组合物的具体实施方式是，
提供一种橡胶组合物，橡胶组合物以重量份计包括：橡胶基体和必要组份，其中，橡胶基体包含：支化聚乙烯的含量a：0＜a≤100份，乙丙橡胶的含量b：0≤b＜100份，必要组份包含：交联剂1.5～10份，补强填充剂30～200份，增塑剂5～250份。其中支化聚乙烯的支化度不低于50个支链/1000个碳，重均分子量不低于5万，门尼粘度ML(1+4)125℃不低于2。
优选的实施方式是，所述橡胶组合物以重量份计包括橡胶基体和必要组份，所述橡胶基体包含支化聚乙烯100份，以100重量份橡胶基体计，所述必要组份包括交联剂2～7份，补强填充剂30～200份，增塑剂8～150份。
在本实施方式中，交联剂包括过氧化物交联剂和硫磺中的至少一种，过氧化物交联剂包括二叔丁 基过氧化物、二枯基过氧化物、叔丁基枯基过氧化物、1,1-二叔丁基过氧化物-3,3,5-三甲基环己烷、2,5-二甲基-2,5-二(叔丁基过氧化)己烷、2,5-二甲基-2,5-二(叔丁基过氧化)己炔-3、双(叔丁基过氧化异丙基)苯、2,5-二甲基-2,5-二(苯甲酰过氧化)己烷、过氧化苯甲酸叔丁酯、叔丁基过氧化-2-乙基己基碳酸酯中的至少一种。补强填充剂包括炭黑、白炭黑、碳酸钙、滑石粉、煅烧陶土、硅酸镁、碳酸镁中的至少一种。增塑剂包括松焦油、机油、环烷油、石蜡油、古马隆、RX-80、硬脂酸、石蜡、液态聚异丁烯、脂肪酸衍生物及其混合物中的至少一种。
橡胶组合物中还包括辅助成分，所述辅助成分包含：助交联剂0.2～10份，稳定剂0.5～3份，金属氧化物2～15份，硫化促进剂0～3份。其中，助交联剂包含三烯丙基氰脲酸酯、三烯丙基异氰脲酸酯、乙二醇二甲基丙烯酸酯、二甲基丙烯酸乙酯、二甲基丙烯酸三乙二酯、偏苯三酸三烯丙酯、三甲基丙烯酸三羟甲基丙烷酯、双甲基丙烯酸乙二醇酯、N,N’-间苯撑双马来酰亚胺、N,N’-双亚糠基丙酮、1,2-聚丁二烯、对醌二肟、硫磺、丙烯酸锌、甲基丙烯酸锌、甲基丙烯酸镁、甲基丙烯酸钙和甲基丙烯酸铝中的至少一种。
松焦油
金属氧化物为氧化锌、氧化镁、氧化钙、一氧化铅、四氧化三铅的至少一种。
稳定剂包括2,2,4-三甲基-1,2-二氢化喹啉聚合体(RD)、6-乙氧基-2,2,4-三甲基-1,2-二氢化喹啉(AW)、2-巯基苯并咪唑(MB)中的至少一种。硫化促进剂包含2-硫醇基苯并噻唑、二硫化二苯并噻唑、一硫化四甲基秋兰姆、二硫化四甲基秋兰姆、二硫化四乙基秋兰姆、N-环己基-2-苯并噻唑基次磺酰胺、N，N-二环己基-2-苯噻唑基次磺酰胺、双马来酰亚胺、亚乙基硫脲中的至少一种。
交联体系包含交联剂，其还可以包含助交联剂和硫化促进剂中的至少一种。
所用二元乙丙橡胶的门尼粘度ML(1+4)125℃优选20～50，乙烯含量优选45％～60％。
所用三元乙丙橡胶的门尼粘度ML(1+4)125℃优选20～100，进一步优选20～80，乙烯含量优选50％～75％，第三单体为5-亚乙基-2-降冰片烯、5-乙烯基-2-降冰片烯或双环戊二烯，第三单体含量为1％～7％。
所用支化聚乙烯可通过(α-二亚胺)镍催化剂在助催化剂的作用下催化乙烯均聚得到。所用(α-二亚胺)镍催化剂的结构、合成方法及通过其制备支化聚乙烯的方法是公开的现有技术，可以采用但不限于以下文献：CN102827312A、CN101812145A、CN101531725A、CN104926962A、US6103658、US6660677。
支化聚乙烯特征为：支化度为60～130个支链/1000个碳、重均分子量为6.6万～51.8万，门尼粘度ML(1+4)125℃为6～102，其中，支化度通过核磁氢谱测得，各种支链摩尔百分含量通过核磁碳谱测得。
具体如下表：
Figure PCTCN2018072361-appb-000001
Figure PCTCN2018072361-appb-000002
橡胶性能测试方法：
1、硬度测试：按照国标GB/T 531.1-2008，用硬度测试仪进行测试，测试温度为室温；
2、拉伸强度、断裂伸长率性能测试：按照国标GB/T528-2009，用电子拉力试验机进行测试，拉伸速度为500mm/min，测试温度为23±2℃，试样为2型哑铃状试样；
3、撕裂强度测试：按照国标GB/T529-2008，用电子拉力试验机进行测试，拉伸速度为500mm/min，测试温度为23±2℃，试样为直角形试样；
4、压缩永久变形测试：按照国标GB/T7759-1996，用压缩永久变形装置进行测试，B型式样，压缩量为25％，测试温度为70℃；
5、门尼粘度测试：按照国标GB/T1232.1-2000，用门尼粘度仪进行测试，测试温度为125℃，预热1分钟，测试4分钟；
6、热空气加速老化试验：按照国标GB/T3512-2001，在热老化试验箱中进行，试验条件为150℃×72h；
7、正硫化时间Tc90测试：按照国标GB/T16584-1996，在无转子硫化仪中进行，试验温度为160℃。
以下实施例1～29和对照例1～6的硫化条件统一为：温度：160℃；压力：16MPa；时间为Tc90+2min。
以下实施例中将公开可以使用本发明所提供橡胶组合物的部分应用领域，并对橡胶组合物的硫化胶性能进行测试和分析。
实施例1：
采用的支化聚乙烯的编号为PER-6。
橡胶组合物的加工步骤如下:
(1)混炼：设置密炼机温度为90℃，转子转速为50转/分钟，加入50份三元乙丙橡胶和50份支化聚乙烯预压混炼90秒；然后加入5份氧化锌和1份硬脂酸，混炼1分钟；加入50份炭黑N330和5份石蜡油SUNPAR2280，混炼3分钟；最后加入3份交联剂过氧化二异丙苯(DCP)、5份助交联剂甲基丙烯酸锌和0.2份助交联剂硫磺，混炼2分钟后排胶，将混炼胶在辊温为60℃的开炼机上薄通， 得到2.5mm左右厚度的薄片，停放20小时。
(2)硫化后停放16小时后进行各项测试。
本实施例中的橡胶组合物可用于板式桥梁支座的橡胶片层的胶料。
实施例2：
采用支化聚乙烯的编号为PER-6。
橡胶组合物加工步骤如下:
(1)混炼：设置密炼机温度为90℃，转子转速为50转/分钟，加入100份支化聚乙烯预压混炼90秒；然后加入5份氧化锌和1份硬脂酸，混炼1分钟；加入50份炭黑N330和5份石蜡油SUNPAR2280，混炼3分钟；最后加入3份交联剂过氧化二异丙苯(DCP)、5份助交联剂甲基丙烯酸锌和0.2份助交联剂硫磺，混炼2分钟后排胶。将混炼胶在辊温为60℃的开炼机上薄通，得到2.5mm左右厚度的薄片，停放20小时。
(2)硫化后停放16小时后进行各项测试。
对照例1：
加工步骤如下:
(1)混炼：设置密炼机温度为90℃，转子转速为50转/分钟，加入100份三元乙丙橡胶预压混炼90秒；然后加入5份氧化锌和1份硬脂酸，混炼1分钟；加入50份炭黑N330和5份石蜡油SUNPAR2280，混炼3分钟；最后加入3份交联剂过氧化二异丙苯(DCP)、5份助交联剂甲基丙烯酸锌和0.2份助交联剂硫磺，混炼2分钟后排胶，将混炼胶在辊温度为60℃的开炼机上薄通，得到2.5mm左右厚度的薄片，停放20小时。
(2)硫化后停放16小时后进行各项测试。
实施例3：
采用支化聚乙烯编号为PER-5。
橡胶组合物加工步骤如下:
(1)混炼：设置密炼机温度为90℃，转子转速为50转/分钟，加入70份三元乙丙橡胶和30份支化聚乙烯预压混炼90秒；然后加入5份氧化锌和1份硬脂酸，混炼1分钟；加入65份炭黑N330和5份石蜡油SUNPAR2280，混炼3分钟；最后加入3份交联剂过氧化二异丙苯(DCP)和1份助交联剂三烯丙基异氰脲酸酯(TAIC)，混炼2分钟后排胶，将混炼胶在辊温为60℃的开炼机上薄通，得到2.5mm左右厚度的薄片，停放20小时。
(2)硫化后停放16小时后进行各项测试。
实施例4：
采用支化聚乙烯编号为PER-5。
橡胶组合物的加工步骤如下:
(1)混炼：设置密炼机温度为90℃，转子转速为50转/分钟，加入20份二元乙丙橡胶、30份三元乙丙橡胶和50份支化聚乙烯预压混炼90秒；然后加入5份氧化锌和1份硬脂酸，混炼1分钟；加入65份炭黑N330和5份石蜡油SUNPAR2280，混炼3分钟；最后加入3份交联剂过氧化二异丙苯(DCP)和1份助交联剂三烯丙基异氰脲酸酯(TAIC)，混炼2分钟后排胶，将混炼胶在辊温为60℃ 的开炼机上薄通，得到2.5mm左右厚度的薄片，停放20小时。
(2)硫化后停放16小时后进行各项测试。
实施例5：
采用支化聚乙烯编号为PER-5。
橡胶组合物的加工步骤如下:
(1)混炼：设置密炼机温度为90℃，转子转速为50转/分钟，加入30份三元乙丙橡胶和70份支化聚乙烯预压混炼90秒；然后加入5份氧化锌和1份硬脂酸，混炼1分钟；加入65份炭黑N330和5份石蜡油SUNPAR2280，混炼3分钟；最后加入3份交联剂过氧化二异丙苯(DCP)和1份助交联剂三烯丙基异氰脲酸酯(TAIC)，混炼2分钟后排胶，将混炼胶在辊温为60℃的开炼机上薄通，得到2.5mm左右厚度的薄片，停放20小时。
(2)硫化后停放16小时后进行各项测试。
对照例2：
采用三元乙丙橡胶作为橡胶基体。
加工步骤如下:
(1)混炼：设置密炼机温度为90℃，转子转速为50转/分钟，加入100份三元乙丙橡胶预压混炼90秒；然后加入5份氧化锌和1份硬脂酸，混炼1分钟；加入65份炭黑N330和5份石蜡油SUNPAR2280，混炼3分钟；最后加入3份交联剂过氧化二异丙苯(DCP)和1份助交联剂三烯丙基异氰脲酸酯(TAIC)，混炼2分钟后排胶，将混炼胶在辊温为60℃的开炼机上薄通，得到2.5mm左右厚度的薄片，停放20小时。
(2)硫化后停放16小时后进行各项测试。
实施例1～5及对照例1、2的性能测试数据如下表：
Figure PCTCN2018072361-appb-000003
实施例6：
采用挤出法生产的桥梁橡胶伸缩装置，其橡胶伸缩体采用三元乙丙橡胶和支化聚乙烯作为橡胶基体，所用支化聚乙烯编号为PER-10。
橡胶伸缩体用胶料的加工步骤如下:
(1)混炼：设置密炼机温度为90℃，转子转速为50转/分钟，加入90份三元乙丙橡胶和10份支化聚乙烯预压混炼90秒；然后加入5份氧化锌、7份氧化钙和1份硬脂酸，混炼1分钟；加入90份炭黑N550、15份碳酸钙和60份石蜡油SUNPAR2280，混炼3分钟；最后加入3份交联剂过氧化二异丙苯(DCP)和0.3份助交联剂硫磺，混炼2分钟后排胶，将混炼胶在辊温为60℃的开炼机上薄通，得到2.5mm左右厚度的薄片，停放20小时。
(2)硫化后停放16小时后进行各项测试。
实施例7：
采用支化聚乙烯编号为PER-9。
橡胶组合物的加工步骤如下:
(1)混炼：设置密炼机温度为90℃，转子转速为50转/分钟，加入70份三元乙丙橡胶和30份支化聚乙烯预压混炼90秒；然后加入5份氧化锌、7份氧化钙和1份硬脂酸，混炼1分钟；加入90份炭黑N550、15份碳酸钙和60份石蜡油SUNPAR2280，混炼3分钟；最后加入3份交联剂过氧化二异丙苯(DCP)和0.3份助交联剂硫磺，混炼2分钟后排胶，将混炼胶在辊温为60℃的开炼机上薄通，得到2.5mm左右厚度的薄片，停放20小时。
(2)硫化后停放16小时后进行各项测试。
实施例8：
采用支化聚乙烯编号为PER-5。
橡胶组合物的加工步骤如下:
(1)混炼：设置密炼机温度为90℃，转子转速为50转/分钟，加入100份支化聚乙烯预压混炼90秒；然后加入5份氧化锌、7份氧化钙和1份硬脂酸，混炼1分钟；加入90份炭黑N550、15份碳酸钙和60份石蜡油SUNPAR2280，混炼3分钟；最后加入3份交联剂过氧化二异丙苯(DCP)和0.3份助交联剂硫磺，混炼2分钟后排胶，将混炼胶在辊温为60℃的开炼机上薄通，得到2.5mm左右厚度的薄片，停放20小时。
(2)硫化后停放16小时后进行各项测试。
对照例3：
加工步骤如下:
(1)混炼：设置密炼机温度为90℃，转子转速为50转/分钟，加入100份三元乙丙橡胶预压混炼90秒；然后加入5份氧化锌、7份氧化钙和1份硬脂酸，混炼1分钟；加入90份炭黑N550、15份碳酸钙和60份石蜡油SUNPAR2280，混炼3分钟；最后加入3份交联剂过氧化二异丙苯(DCP)和0.3份助交联剂硫磺，混炼2分钟后排胶，将混炼胶在辊温为60℃的开炼机上薄通，得到2.5mm左右厚度的薄片，停放20小时。
(2)硫化后停放16小时后进行各项测试。
实施例9：
采用支化聚乙烯编号为PER-4。
橡胶组合物的加工步骤如下:
(1)混炼：设置密炼机温度为90℃，转子转速为40转/分钟，加入80份三元乙丙橡胶和20份 支化聚乙烯预压混炼90秒；然后加入5份氧化锌、1份硬脂酸和2份防老剂2,2,4-三甲基-1,2-二氢化喹啉聚合体(RD)，混炼1分钟；加入50份炭黑N330、10份碳酸钙、5份石蜡油SUNPAR2280和4份古马隆树脂，混炼3分钟；最后加入3份交联剂过氧化二异丙苯(DCP)和0.3份助交联剂硫磺，混炼2分钟后排胶，将混炼胶在辊温为60℃的开炼机上薄通，得到2.5mm左右厚度的薄片，停放20小时。
(2)硫化后停放16小时后进行各项测试。
实施例10：
采用支化聚乙烯编号为PER-4。
橡胶组合物的加工步骤如下:
(1)混炼：设置密炼机温度为90℃，转子转速为40转/分钟，加入50份三元乙丙橡胶和50份支化聚乙烯预压混炼90秒；然后加入5份氧化锌、1份硬脂酸和2份防老剂RD，混炼1分钟；加入50份炭黑N330、10份碳酸钙、5份石蜡油SUNPAR2280和4份古马隆树脂，混炼3分钟；最后加入3份交联剂过氧化二异丙苯(DCP)和0.3份助交联剂硫磺，混炼2分钟后排胶，将混炼胶在辊温为60℃的开炼机上薄通，得到2.5mm左右厚度的薄片，停放20小时。
(2)硫化后停放16小时后进行各项测试。
实施例11：
采用支化聚乙烯编号为PER-4。
橡胶组合物的加工步骤如下:
(1)混炼：设置密炼机温度为90℃，转子转速为40转/分钟，加入100份支化聚乙烯预压混炼90秒；然后加入5份氧化锌、1份硬脂酸和2份防老剂RD，混炼1分钟；加入50份炭黑N330、10份碳酸钙、5份石蜡油SUNPAR2280和4份古马隆树脂，混炼3分钟；最后加入3份交联剂过氧化二异丙苯(DCP)和0.3份助交联剂硫磺，混炼2分钟后排胶，将混炼胶在辊温为60℃的开炼机上薄通，得到2.5mm左右厚度的薄片，停放20小时。
(2)硫化后停放16小时后进行各项测试。
实施例12：
采用支化聚乙烯编号为PER-1和PER-7。
橡胶组合物的加工步骤如下:
(1)混炼：设置密炼机温度为90℃，转子转速为40转/分钟，加入30份PER-1和70份PER-7预压混炼90秒；然后加入5份氧化锌、1份硬脂酸和2份防老剂RD，混炼1分钟；加入50份炭黑N330、10份碳酸钙、5份石蜡油SUNPAR2280和4份古马隆树脂，混炼3分钟；最后加入3份交联剂过氧化二异丙苯(DCP)和0.3份助交联剂硫磺，混炼2分钟后排胶，将混炼胶在辊温为60℃的开炼机上薄通，得到2.5mm左右厚度的薄片，停放20小时。
(2)硫化后停放16小时后进行各项测试。
对照例4：
加工步骤如下:
(1)混炼：设置密炼机温度为90℃，转子转速为40转/分钟，加入100份三元乙丙橡胶预压混 炼90秒；然后加入5份氧化锌、1份硬脂酸和2份防老剂RD，混炼1分钟；加入50份炭黑N330、10份碳酸钙、5份石蜡油SUNPAR2280和4份古马隆树脂，混炼3分钟；最后加入3份交联剂过氧化二异丙苯(DCP)和0.3份助交联剂硫磺，混炼2分钟后排胶，将混炼胶在辊温为60℃的开炼机上薄通，得到2.5mm左右厚度的薄片，停放20小时。
(2)硫化后停放16小时后进行各项测试。
实施例6～12及对照例3、4的性能测试数据如下表：
Figure PCTCN2018072361-appb-000004
实施例13：
采用支化聚乙烯编号为PER-8。
橡胶组合物的加工步骤如下:
(1)混炼：设置密炼机温度为90℃，转子转速为40转/分钟，加入50份三元乙丙橡胶和50份支化聚乙烯预压混炼90秒；然后加入5份氧化锌和1份硬脂酸，混炼1分钟；加入75份炭黑N330和20份氢化松香，混炼3分钟；最后加入3.5份交联剂过氧化二异丙苯(DCP)、3份N,N’-间苯撑双马来酰亚胺和1份助交联剂对醌二肟，混炼2分钟后排胶，将混炼胶在辊温为60℃的开炼机上薄通，得到2.5mm左右厚度的薄片，停放20小时。
(2)硫化后停放16小时后进行各项测试。
该橡胶组合物可用于生产一种橡胶轨枕垫。
实施例14：
采用的支化聚乙烯编号为PER-2和PER-8。
橡胶组合物的加工步骤如下:
(1)混炼：设置密炼机温度为90℃，转子转速为40转/分钟，加入80份PER-8和20份PER-2预压混炼90秒；然后加入5份氧化锌和1份硬脂酸，混炼1分钟；加入75份炭黑N330和20份氢化松香，混炼3分钟；最后加入3.5份交联剂过氧化二异丙苯(DCP)、3份N,N’-间苯撑双马来酰亚胺和1份助交联剂对醌二肟，混炼2分钟后排胶，将混炼胶在辊温度为60℃的开炼机上薄通，得到2.5mm左右厚度的薄片，停放20小时。
(2)硫化后停放16小时后进行各项测试。
对照例5：
加工步骤如下:
(1)混炼：设置密炼机温度为90℃，转子转速为40转/分钟，加入100份三元乙丙橡胶预压混炼90秒；然后加入5份氧化锌和1份硬脂酸，混炼1分钟；加入75份炭黑N330和20份氢化松香，混炼3分钟；最后加入3.5份交联剂过氧化二异丙苯(DCP)、3份N,N’-间苯撑双马来酰亚胺和1份助交联剂对醌二肟，混炼2分钟后排胶，将混炼胶在辊温为60℃的开炼机上薄通，得到2.5mm左右厚度的薄片，停放20小时。
(2)硫化后停放16小时后进行各项测试。
实施例15：
采用的支化聚乙烯编号为PER-7。
橡胶组合物的加工步骤如下:
(1)混炼：设置密炼机温度为90℃，转子转速为40转/分钟，加入100份支化聚乙烯预压混炼90秒；然后加入5份氧化锌和1份硬脂酸，混炼1分钟；加入125份炭黑N330、80份石蜡油SUNPAR2280和5份聚乙烯蜡，混炼3分钟；最后加入4份交联剂过氧化二异丙苯(DCP)和1份助交联剂三烯丙基异氰脲酸酯(TAIC)，混炼2分钟后排胶，将混炼胶在辊温为60℃的开炼机上薄通，得到2.5mm左右厚度的薄片，停放20小时。
(2)硫化后停放16小时后进行各项测试。
实施例16：
采用的支化聚乙烯编号为PER-4。
橡胶组合物的加工步骤如下:
(1)混炼：设置密炼机温度为90℃，转子转速为40转/分钟，加入100份支化聚乙烯预压混炼90秒；然后加入5份氧化锌和1份硬脂酸，混炼1分钟；加入45份炭黑N330、5份石蜡油SUNPAR2280和3份古马隆树脂，混炼3分钟；最后加入3份交联剂过氧化二异丙苯(DCP)、1份助交联剂三烯丙基异氰脲酸酯(TAIC)和0.3份助交联剂硫磺，混炼2分钟后排胶。将混炼胶在辊温为60℃的开炼机上薄通，得到2.5mm左右厚度的薄片，停放20小时。
(2)硫化后停放16小时后进行各项测试。
实施例17：
采用的支化聚乙烯编号为PER-6。
橡胶组合物的加工步骤如下:
(1)混炼：设置密炼机温度为90℃，转子转速为40转/分钟，加入100份支化聚乙烯预压混炼90秒；然后加入10份氧化锌，1份防老剂RD和1份硬脂酸，混炼1分钟；加入80份炭黑N550和100份石蜡油SUNPAR2280，混炼3分钟；最后加入3份交联剂过氧化二异丙苯(DCP)、0.5份N-环已基-2-苯并噻唑次磺酰胺(CZ)、1.25份二硫化四甲基秋兰姆(TT)和0.3份助交联剂硫磺，混炼2分钟后排胶。将混炼胶在辊温为60℃的开炼机上薄通，得到2.5mm左右厚度的薄片，停放20小时。
(2)硫化后停放16小时后进行各项测试。
实施例18：
采用的支化聚乙烯编号为PER-6。
橡胶组合物的加工步骤如下:
(1)混炼：设置密炼机温度为90℃，转子转速为40转/分钟，加入100份支化聚乙烯预压混炼90秒；然后加入5份氧化锌和1份硬脂酸，混炼1分钟；加入65份炭黑N330和45份石蜡油SUNPAR2280，混炼3分钟；最后加入3份交联剂过氧化二异丙苯(DCP)和2份助交联剂二甲基丙烯酸乙二醇酯，混炼2分钟后排胶。将混炼胶在辊温为60℃的开炼机上薄通，得到2.5mm左右厚度的薄片，停放20小时。
(2)硫化后停放16小时后进行各项测试。
实施例19：
采用的支化聚乙烯编号为PER-3。
橡胶组合物的加工步骤如下:
(1)混炼：设置密炼机温度为90℃，转子转速为40转/分钟，加入100份支化聚乙烯预压混炼90秒；然后加入5份氧化锌和1份硬脂酸，混炼1分钟；加入60份炭黑N550、80份碳酸钙和120份石蜡油SUNPAR2280，混炼3分钟；最后加入1份交联剂过氧化二异丙苯(DCP)、0.3份助交联剂三烯丙基异氰脲酸酯(TAIC)、0.5份交联剂硫磺、1份N-环已基-2-苯并噻唑次磺酰胺(CZ)和0.8份二硫化四甲基秋兰姆(TMTD)，混炼2分钟后排胶，将混炼胶在辊温为60℃的开炼机上薄通，得到2.5mm左右厚度的薄片，停放20小时。
(2)硫化后停放16小时后进行各项测试。
实施例20：
采用的支化聚乙烯编号为PER-5。
橡胶组合物的加工步骤如下:
(1)混炼：设置密炼机温度为90℃，转子转速为40转/分钟，加入100份支化聚乙烯预压混炼90秒；然后加入5份氧化锌和1份硬脂酸，混炼1分钟；加入50份炭黑N330、60份炭黑N550和240份石蜡油SUNPAR2280，混炼3分钟；最后加入8份交联剂过氧化二异丙苯(DCP)、2份助交联剂三烯丙基异氰脲酸酯(TAIC)和8份助交联剂1,2-聚丁二烯，混炼2分钟后排胶。将混炼胶在辊温为60℃的开炼机上薄通，得到2.5mm左右厚度的薄片，停放20小时。
(2)硫化后停放16小时后进行各项测试。
实施例13～20及对照例5的性能测试数据如下表：
Figure PCTCN2018072361-appb-000005
Figure PCTCN2018072361-appb-000006
实施例21：
采用的支化聚乙烯编号为PER-4。
橡胶组合物的加工步骤如下:
(1)混炼：设置密炼机温度为90℃，转子转速为40转/分钟，加入100份支化聚乙烯和1份硬脂酸预压混炼90秒；然后加入30份炭黑N550和5份石蜡油SUNPAR2280，混炼3分钟；最后加入4份交联剂过氧化二异丙苯(DCP)，混炼2分钟后排胶。将混炼胶在辊温为60℃的开炼机上薄通，得到2.5mm左右厚度的薄片，停放20小时。
(2)硫化后停放16小时后进行各项测试。
实施例22：
采用的支化聚乙烯编号为PER-4。
橡胶组合物的加工步骤如下:
(1)混炼：设置密炼机温度为90℃，转子转速为40转/分钟，加入100份支化聚乙烯预压混炼90秒；然后加入5份氧化锌和1份硬脂酸，混炼1分钟；加入120份炭黑N550、80份碳酸钙和180份石蜡油SUNPAR2280，混炼3分钟；最后加入10份交联剂过氧化二异丙苯(DCP)、3份助交联剂三烯丙基异氰脲酸酯(TAIC)和7份助交联剂1,2-聚丁二烯，混炼2分钟后排胶。将混炼胶在辊温为60℃的开炼机上薄通，得到2.5mm左右厚度的薄片，停放20小时。
(2)硫化后停放16小时后进行各项测试。
实施例23：
采用的支化聚乙烯编号为PER-7。
橡胶组合物的加工步骤如下:
(1)混炼：设置密炼机温度为90℃，转子转速为40转/分钟，加入100份支化聚乙烯预压混炼90秒；然后加入5份氧化锌和1份硬脂酸，混炼1分钟；加入30份炭黑N330、50份炭黑N550和5份石蜡油SUNPAR2280，混炼3分钟；最后加入3.5份交联剂过氧化二异丙苯(DCP)，混炼2分钟后排胶。将混炼胶在辊温为60℃的开炼机上薄通，得到2.5mm左右厚度的薄片，停放20小时。
(2)硫化后停放16小时后进行各项测试。
实施例24：
采用的支化聚乙烯编号为PER-6。
加工步骤如下:
(1)混炼：设置密炼机温度为90℃，转子转速为40转/分钟，加入100份支化聚乙烯预压混炼90秒；然后加入6份氧化锌，2份防老剂RD和1份硬脂酸，混炼1分钟；加入55份炭黑N330、5份石蜡油SUNPAR2280和5份古马隆树脂，混炼3分钟；最后加入4份交联剂过氧化二异丙苯(DCP)、 1.5份助交联剂三烯丙基异氰脲酸酯(TAIC)、8份助交联剂甲基丙烯酸锌和0.3份助交联剂硫磺，混炼2分钟后排胶。将混炼胶在辊温为60℃的开炼机上薄通，得到2.5mm左右厚度的薄片，停放20小时。
(2)硫化后停放16小时后进行各项测试。
实施例25：
采用的支化聚乙烯编号为PER-5。
加工步骤如下:
(1)混炼：设置密炼机温度为90℃，转子转速为40转/分钟，加入100份支化聚乙烯预压混炼90秒；然后加入5份氧化锌和1份硬脂酸，混炼1分钟；加入100份炭黑N550和75份石蜡油SUNPAR2280，混炼3分钟；最后加入2份交联剂过氧化二异丙苯(DCP)、1份助交联剂三烯丙基异氰脲酸酯(TAIC)和0.2份助交联剂硫磺，混炼2分钟后排胶。将混炼胶在辊温为60℃的开炼机上薄通，得到2.5mm左右厚度的薄片，停放20小时。
(2)硫化后停放16小时后进行各项测试。
实施例26：
采用的支化聚乙烯编号为PER-4。
加工步骤如下:
(1)混炼：设置密炼机温度为90℃，转子转速为40转/分钟，加入100份支化聚乙烯预压混炼90秒；然后加入5份氧化锌和1份硬脂酸，混炼1分钟；加入50份炭黑N550和5份聚乙烯蜡，混炼3分钟；最后加入3.5份交联剂过氧化二异丙苯(DCP)、1份助交联剂三烯丙基异氰脲酸酯(TAIC)，混炼2分钟后排胶。将混炼胶在辊温为60℃的开炼机上薄通，得到2.5mm左右厚度的薄片，停放20小时。
(2)硫化后停放16小时后进行各项测试。
实施例21～26的性能测试数据如下表：
Figure PCTCN2018072361-appb-000007
实施例27：
采用的支化聚乙烯编号为PER-5。
加工步骤如下:
(1)混炼：设置密炼机温度为90℃，转子转速为40转/分钟，加入100份支化聚乙烯预压混炼90秒；然后加入5份氧化锌和1份硬脂酸，混炼1分钟；加入70份炭黑N330、30份炭黑N550、40份石蜡油SUNPAR2280和5份古马隆树脂，混炼3分钟；最后加入4份交联剂过氧化二异丙苯(DCP)、1份助交联剂三烯丙基异氰脲酸酯(TAIC)和0.3份助交联剂硫磺，混炼2分钟后排胶。将混炼胶在辊温为60℃的开炼机上薄通，得到2.5mm左右厚度的薄片，停放20小时。
(2)硫化后停放16小时后进行各项测试。
实施例28：
采用的支化聚乙烯编号为PER-5。
加工步骤如下:
(1)混炼：设置密炼机温度为90℃，转子转速为40转/分钟，加入100份支化聚乙烯预压混炼90秒；然后加入120份炭黑N330、30份滑石粉和105份石蜡油SUNPAR2280，混炼3分钟；最后加入5份交联剂过氧化二异丙苯(DCP)和2份助交联剂三烯丙基异氰脲酸酯(TAIC)，混炼2分钟后排胶。将混炼胶在辊温为60℃的开炼机上薄通，得到2.5mm左右厚度的薄片，停放20小时。
(2)硫化后停放16小时后进行各项测试。
对照例6：
加工步骤如下:
(1)混炼：设置密炼机温度为90℃，转子转速为40转/分钟，加入100份三元乙丙橡胶预压混炼90秒；然后加入5份氧化锌和1份硬脂酸，混炼1分钟；加入70份炭黑N330、30份炭黑N550、40份石蜡油SUNPAR2280和5份古马隆树脂，混炼3分钟；最后加入4份交联剂过氧化二异丙苯(DCP)、1份助交联剂三烯丙基异氰脲酸酯(TAIC)和0.3份助交联剂硫磺，混炼2分钟后排胶。将混炼胶在辊温为60℃的开炼机上薄通，得到2.5mm左右厚度的薄片，停放20小时。
(2)硫化后停放16小时后进行各项测试。
实施例27、28和对照例6的性能测试数据如下：
Figure PCTCN2018072361-appb-000008
实施例29：
采用的支化聚乙烯编号为PER-4。
加工步骤如下:
(1)混炼：设置密炼机温度为90℃，转子转速为40转/分钟，加入100份支化聚乙烯预压混炼90秒；然后加入5份氧化锌和1份硬脂酸，混炼1分钟；加入40份炭黑N330、60份硫酸钡、10份石蜡油SUNPAR2280和8份聚乙烯蜡，混炼3分钟；最后加入7份交联剂过氧化二异丙苯(DCP)，混炼2分钟后排胶。将混炼胶在辊温为60℃的开炼机上薄通，得到2.5mm左右厚度的薄片，停放20小时。
(2)硫化后停放16小时后进行各项测试。
本发明还提供上述橡胶组合物的多种应用，这类应用为生产加工桥梁橡胶伸缩装置，橡胶轨枕垫，桥梁板式橡胶支座，盆式橡胶支座，橡胶钢板组合型伸缩装置，橡胶护舷，橡胶止水带，车用减震支座，胶辊，种耐高温多楔带，雨刷条，密封圈，防水卷材等，具体的实施例如下：
实施例30：
一种桥梁板式橡胶支座加工步骤如下：
该桥梁板式橡胶支座包含钢板和橡胶片层，各层橡胶片与钢板之间经涂布胶黏剂加压硫化后粘接成一个整体，本实施例中的橡胶片层所用橡胶组合物按实施例2所述的组成和配比称量并混炼：
(1)橡胶混炼工艺：设置密炼机温度为90℃，转子转速为50转/分钟，加入100份支化聚乙烯预压混炼90秒；然后加入5份氧化锌和1份硬脂酸，混炼1分钟；加入50份炭黑N330和5份石蜡油SUNPAR2280，混炼3分钟；最后加入3份交联剂过氧化二异丙苯(DCP)、5份助交联剂甲基丙烯酸锌和0.2份助交联剂硫磺，混炼2分钟后排胶。开炼机薄通下片，停放和检测。经编号、回炼、压延出片后冲裁成所需规格的半成品胶片，供硫化工序使用；
(2)硫化工艺：将胶片与经表面处理并涂布胶黏剂的钢板按工艺要求依次叠合成型，然后装入已预热的模具中，再进入平板硫化机硫化，硫化温度为160℃，蒸汽压力0.6MPa，时间为25分钟；
(3)后处理：硫化完成后拉出并拆卸模具，取出橡胶支座成品，冷却停放并修整，得到成品。
实施例31：
一种桥梁板式橡胶支座加工步骤如下：
该桥梁板式橡胶支座包含钢板、聚四氟乙烯板和橡胶片层，各层橡胶片与钢板及聚四氟乙烯板之间经涂布胶黏剂加压硫化后粘接成一个整体。本实施例中的橡胶片层所用橡胶组合物按实施例2所述的组成和配比称量并混炼：
(1)橡胶混炼工艺：设置密炼机温度为90℃，转子转速为50转/分钟，加入100份支化聚乙烯PER-6预压混炼90秒；然后加入5份氧化锌和1份硬脂酸，混炼1分钟；加入50份炭黑N330和5份石蜡油SUNPAR2280，混炼3分钟；最后加入3份交联剂过氧化二异丙苯(DCP)、5份助交联剂甲基丙烯酸锌和0.2份助交联剂硫磺，混炼2分钟后排胶。开炼机薄通下片，停放和检测。经编号、回炼、压延出片后冲裁成所需规格的半成品胶片，供硫化工序使用；
(2)硫化工艺：将胶片与经表面处理并涂布胶黏剂的钢板及聚四氟乙烯板按工艺要求依次叠合成型，然后装入已预热的模具中，再进入平板硫化机硫化，硫化温度为160℃，蒸汽压力0.6MPa，时间为25分钟；
(3)后处理：硫化完成后拉出并拆卸模具，取出橡胶支座成品，冷却停放并修整，得到一种适用于较大跨径结构的简直桥梁用橡胶支座。
实施例32：
本实施例中的盆式橡胶支座包含上支座板、不锈钢板、聚四氟乙烯板、中间钢板、密封圈、橡胶承压板、下支座板和支座锚栓。本实施例中的橡胶承压板采用与实施例5相同的橡胶组合物，其加工步骤如下：
(1)橡胶混炼工艺：设置密炼机温度为90℃，转子转速为50转/分钟，加入30份三元乙丙橡胶和70份支化聚乙烯PER-5预压混炼90秒；然后加入5份氧化锌和1份硬脂酸，混炼1分钟；加入65份炭黑N330和5份石蜡油SUNPAR2280，混炼3分钟；最后加入3份交联剂过氧化二异丙苯(DCP)和1份助交联剂三烯丙基异氰脲酸酯(TAIC)，混炼2分钟后排胶，开炼机薄通下片，停放和检测；
(2)硫化工艺：采用模压硫化，硫化温度160℃，蒸汽压力0.6MPa，硫化时间25分钟；
(3)冷却停放、修边整理得到橡胶承压板。
将橡胶承压板与其他部件组装得到盆式橡胶支座。
实施例33：
一种桥梁橡胶伸缩装置用橡胶伸缩体采用挤出法生产工艺得到，具体步骤如下：
(1)混炼：本实施例所述的橡胶伸缩体采用实施例8所述橡胶组合物，设置密炼机温度为90℃，转子转速为50转/分钟，加入100份支化聚乙烯PER-5预压混炼90秒；然后加入5份氧化锌、7份氧化钙和1份硬脂酸，混炼1分钟；加入90份炭黑N550、15份碳酸钙和60份石蜡油SUNPAR2280，混炼3分钟；最后加入3份交联剂过氧化二异丙苯(DCP)和0.3份助交联剂硫磺，混炼2分钟后排胶。开炼机薄通下片，停放和检测；
(2)挤出和硫化：挤出硫化工艺宜采用抽真空挤出机，挤出机温度设置机头90～100℃,螺杆温度70～80℃，机头压力应控制在15～20MPa，挤出机转速25～30转/min，采用盐浴硫化工艺，喷淋段温度250℃，浸轮段温度220℃，浸压段温度在220℃，传动速度在35～45米/min,冷却段温度25～30℃；
(3)冷却、修边、检验、得到成品。
实施例34：
一种桥梁橡胶伸缩装置用橡胶伸缩体采用模压法生产工艺得到，具体步骤如下：
(1)混炼及成型：本实施例所述的橡胶伸缩体采用实施例11所述橡胶组合物，设置密炼机温度为90℃，转子转速为40转/分钟，加入100份支化聚乙烯PER-4预压混炼90秒；然后加入5份氧化锌、1份硬脂酸和2份防老剂RD，混炼1分钟；加入50份炭黑N330、10份碳酸钙、5份石蜡油SUNPAR2280和4份古马隆树脂，混炼3分钟；最后加入3份交联剂过氧化二异丙苯(DCP)和0.3份助交联剂硫磺，混炼2分钟后排胶。开炼机薄通下片，停放和检测。回炼出片、称量成型。
(2)模压硫化：硫化温度160℃，蒸汽压力0.6MPa，硫化时间25分钟。
(3)冷却、修边、检验、得到成品。
实施例35：
一种橡胶钢板组合型伸缩装置的加工步骤如下：
(1)混炼及成型：橡胶部分采用实施例11所述橡胶组合物，设置密炼机温度为90℃，转子转速 为40转/分钟，加入100份支化聚乙烯PER-4预压混炼90秒；然后加入5份氧化锌、1份硬脂酸和2份防老剂RD，混炼1分钟；加入50份炭黑N330、10份碳酸钙、5份石蜡油SUNPAR2280和4份古马隆树脂，混炼3分钟；最后加入3份交联剂过氧化二异丙苯(DCP)和0.3份助交联剂硫磺，混炼2分钟后排胶。开炼机薄通下片，停放和检测。回炼出片、称量成型；
(2)硫化工艺：将胶片与经表面处理并涂布胶黏剂的钢板按工艺要求贴合成型，然后装入已预热的模具中，再进入平板硫化机硫化，硫化温度为160℃，蒸汽压力0.6MPa，时间为25分钟；
(3)后处理：硫化完成后拉出并拆卸模具，取出橡胶支座成品，冷却停放并修整，得到成品。
实施例36：
一种橡胶轨枕垫的加工步骤如下：
(1)混炼：采用实施例14所述橡胶组合物，设置密炼机温度为90℃，转子转速为40转/分钟，加入80份PER-8和20份PER-1预压混炼90秒；然后加入5份氧化锌和1份硬脂酸，混炼1分钟；加入75份炭黑N330和20份氢化松香，混炼3分钟；最后加入3.5份交联剂过氧化二异丙苯(DCP)、3份N,N’-间苯撑双马来酰亚胺和1份助交联剂对醌二肟，混炼2分钟后排胶。经停放和检测后进行热炼，然后按所需厚度出片，裁切成所需规格形状供硫化工序使用。
(2)模压硫化：硫化温度为160℃，蒸汽压力0.6MPa，时间为25分钟。
(3)修边、检验、得到成品。
实施例37：
一种橡胶护舷的加工步骤如下：
(1)混炼：采用实施例15所述橡胶组合物，设置密炼机温度为90℃，转子转速为40转/分钟，加入100份支化聚乙烯PER-7预压混炼90秒；然后加入5份氧化锌和1份硬脂酸，混炼1分钟；加入125份炭黑N330、80份石蜡油SUNPAR2280和5份聚乙烯蜡，混炼3分钟；最后加入4份交联剂过氧化二异丙苯(DCP)和1份助交联剂三烯丙基异氰脲酸酯(TAIC)，混炼2分钟后排胶。
(2)模压及硫化：将混炼胶投入模腔，然后合模，胶料充分流动，排气，合模，硫化。硫化温度为160℃，时间为25分钟。
(3)开模，取出制品，修边、检验、得到成品。
实施例38：
一种橡胶止水带的加工步骤如下：
(1)混炼及成型：采用实施例16所述的橡胶组合物，设置密炼机温度为90℃，转子转速为40转/分钟，加入100份支化聚乙烯PER-4预压混炼90秒；然后加入5份氧化锌和1份硬脂酸，混炼1分钟；加入45份炭黑N330、5份石蜡油SUNPAR2280和3份古马隆树脂，混炼3分钟；最后加入3份交联剂过氧化二异丙苯(DCP)、1份助交联剂三烯丙基异氰脲酸酯(TAIC)和0.3份助交联剂硫磺，混炼2分钟后排胶。停放检验、回炼出片、称量成型。
(2)模压硫化：硫化温度为160℃，蒸汽压力0.6MPa，时间为25分钟。
(3)修边整理、检验、得到成品。
实施例39：
一种钢带橡胶止水带的加工步骤如下：
(1)橡胶部分混炼及成型：采用实施例16所述的橡胶组合物，设置密炼机温度为90℃，转子转速为40转/分钟，加入100份支化聚乙烯PER-4预压混炼90秒；然后加入5份氧化锌和1份硬脂酸，混炼1分钟；加入45份炭黑N330、5份石蜡油SUNPAR2280和3份古马隆树脂，混炼3分钟；最后加入3份交联剂过氧化二异丙苯(DCP)、1份助交联剂三烯丙基异氰脲酸酯(TAIC)和0.3份助交联剂硫磺，混炼2分钟后排胶。停放检验、回炼出片、称量成型。
(2)硫化工艺：将胶片与经表面处理并涂布胶黏剂的薄钢板按工艺要求贴合成型，然后装入已预热的模具中，再进入平板硫化机硫化，硫化温度为160℃，蒸汽压力0.6MPa，时间为25分钟。
(3)修边整理、检验、得到成品。
实施例40：
一种车用减震支座的加工步骤如下：
(1)橡胶部分混炼及成型：采用实施例17所述的橡胶组合物，设置密炼机温度为90℃，转子转速为40转/分钟，加入100份支化聚乙烯预压混炼90秒；然后加入10份氧化锌，1份防老剂RD和1份硬脂酸，混炼1分钟；加入80份炭黑N550和100份石蜡油SUNPAR2280，混炼3分钟；最后加入3份交联剂过氧化二异丙苯(DCP)、0.5份N-环已基-2-苯并噻唑次磺酰胺(CZ)、1.25份二硫化四甲基秋兰姆(TT)和0.3份助交联剂硫磺，混炼2分钟后排胶。停放检验、回炼出片、称量成型。
(2)硫化工艺：将胶料与经表面处理并涂布胶黏剂的金属件按工艺要求贴合成型，然后装入已预热的模具中，再进入平板硫化机硫化，硫化温度为160℃，蒸汽压力0.6MPa，时间为25分钟。
(3)修边整理、检验、得到成品。
本实施例的减震支座可用于发动机和排气管等高温部位。
实施例41：
一种胶辊的生产加工步骤如下：
(1)混炼：采用实施例18所述的橡胶组合物，设置密炼机温度为90℃，转子转速为40转/分钟，加入100份支化聚乙烯PER-6预压混炼90秒；然后加入5份氧化锌和1份硬脂酸，混炼1分钟；加入65份炭黑N330和45份石蜡油SUNPAR2280，混炼3分钟；最后加入3份交联剂过氧化二异丙苯(DCP)和2份助交联剂二甲基丙烯酸乙二醇酯，混炼2分钟后排胶。将混炼胶在开炼机上薄通出片后停放24小时。
(2)缠绕包胶：将混炼胶投入螺杆挤出机，挤出工艺要求的厚度和宽度的胶片，待胶片均匀一致后启动旋转包布机，将胶片缠绕在准备好的金属辊芯上，逐层缠绕包胶，直到包胶单边厚度达到规定厚度，然后在胶面上缠绕尼龙水布2～3层，得到包胶完毕的胶辊。
(3)硫化罐硫化，将包胶完毕的胶辊送入硫化罐，关闭罐门后，往硫化罐中通入蒸汽进行硫化，通入蒸汽的同时打开压缩空气阀门，通入压缩空气使硫化罐内压力在0.5小时内达到4.5～5大气压；硫化程序为：首先升温到70～80℃，保温2小时；再升温到100～110℃，保温0.5小时；再升温到120～130℃，保温0.5小时；再升温到135～140℃，保温8～10小时。硫化结束，开排气阀，压力下降，等压力表指针指到零时，打开保险销，等销孔内排出蒸汽飘动，半开硫化罐，让温度下降，待罐内温度低于60℃或与室温相当时，将胶辊拉出；
(4)将硫化好的胶辊在车床上粗加工，再在磨床上精加工，检验，得到成品。
实施例42：
一种耐高温多楔带，其缓冲层使用本发明提供的橡胶组合物，生产加工步骤如下：
1、混炼：
(1)压缩层胶料混炼：设置密炼机温度为90℃，转子转速为50转/分钟，加入100份支化聚乙烯PER-5预压混炼90秒；加入6份氧化锌、1份硬脂酸、2份防老剂RD，混炼1分钟；然后在胶料中加入45份炭黑N330、5份石蜡油SUNPAR2280和5份古马隆树脂，混炼3分钟；然后再加入60份长度为1mm的尼龙短纤维，混炼2分钟；最后加入4份交联剂过氧化二异丙苯(DCP)、1.5份助交联剂三烯丙基异氰脲酸酯(TAIC)，混炼2分钟后排胶。将混炼胶在辊温为80℃的开炼机上薄通，在0.5mm辊距下薄通7次，使短纤维充分取向，放大辊距得到2.5mm左右厚度的薄片下片，停放20小时。
(2)缓冲层胶料混炼：设置密炼机温度为90℃，转子转速为40转/分钟，加入100份支化聚乙烯PER-5预压混炼90秒；然后加入6份氧化锌，2份防老剂RD和1份硬脂酸，混炼1分钟；加入55份炭黑N330、5份石蜡油SUNPAR2280和5份古马隆树脂，混炼3分钟；最后加入4份交联剂过氧化二异丙苯(DCP)、1.5份助交联剂三烯丙基异氰脲酸酯(TAIC)、10份助交联剂甲基丙烯酸锌和0.3份助交联剂硫磺，混炼2分钟后排胶。
2、成型：采用反成型法。先将光模吊上成型机，清洁模具，涂上少量隔离剂，待其挥发后在光模上包贴多楔带顶布，然后包贴缓冲胶，校正线绳的张紧力，平整缠绕强力层后再包贴缓冲胶，最后包贴楔胶至成型工艺要求的外周长，得到带坯。
3、硫化：将带坯送入硫化工段进行硫化，硫化温度为160℃，内压为0.45～0.55MPa，外压为1.0～1.2MPa，硫化时间30分钟。
4、后处理：硫化结束后冷却脱模，将带筒送入切割工序，按要求宽度切割。磨背，磨楔，修边后通过检验，得到成品。
实施例43：
一种雨刷条的生产加工步骤如下：
(1)混炼：采用实施例25所述的橡胶组合物，设置密炼机温度为90℃，转子转速为40转/分钟，加入100份支化聚乙烯PER-5预压混炼90秒；然后加入5份氧化锌和1份硬脂酸，混炼1分钟；加入65份炭黑N330和45份石蜡油SUNPAR2280，混炼3分钟；最后加入3份交联剂过氧化二异丙苯(DCP)和2份助交联剂二甲基丙烯酸乙二醇酯，混炼2分钟后排胶。将混炼胶在开炼机上薄通出片后停放24小时。
(2)将混炼胶注射入模腔，在160℃下硫化25分钟，成型。
(3)将硫化后的制品进行表面处理，检验，得到成品。
实施例44：
一种密封圈的加工步骤如下：
(1)混炼：采用实施例26所述的橡胶组合物，设置密炼机温度为90℃，转子转速为40转/分钟，加入100份支化聚乙烯PER-4预压混炼90秒；然后加入5份氧化锌和1份硬脂酸，混炼1分钟；加入50份炭黑N550和5份聚乙烯蜡，混炼3分钟；最后加入3.5份交联剂过氧化二异丙苯(DCP)、1 份助交联剂三烯丙基异氰脲酸酯(TAIC)，混炼2分钟后排胶。在开炼机上薄通下片，物性检测，胶料返炼，采用挤出法得到半成品。
(2)硫化：一段模压硫化：温度为160℃、硫化时间为20分钟；二段烘箱硫化：温度150℃，时间1小时。
(3)修边、检验、得到成品。
实施例45：
一种防水卷材的加工步骤如下：
(1)混炼：采用实施例27所述的橡胶组合物，设置密炼机温度为90℃，转子转速为40转/分钟，加入100份支化聚乙烯PER-5预压混炼90秒；然后加入5份氧化锌和1份硬脂酸，混炼1分钟；加入70份炭黑N330、30份炭黑N550、40份石蜡油SUNPAR2280和5份古马隆树脂，混炼3分钟；最后加入4份交联剂过氧化二异丙苯(DCP)、1份助交联剂三烯丙基异氰脲酸酯(TAIC)和0.3份助交联剂硫磺，混炼2分钟后排胶。将块状胶料送入开炼机中混炼，控制辊温在85至95℃之间，并控制辊距小于1mm、薄通不少于四次，直至胶料表面光滑均一有光泽为止，再掉头进一步混炼，薄通不少于四次，再将辊距调整至不超过8mm，混炼三遍，获得厚度在8mm以下的混合均匀的胶料毛片，冷却至50℃以下出片、堆放；
(2)热炼：将混合均匀的胶料毛片在开炼机上进行热炼，控制辊温在85至95℃之间，辊距在6mm以下，直至胶料片光滑均匀后初步成卷；
(3)压延：将经热炼初步成卷的胶料片放入压延机上，按成品厚度要求调节辊距进行压延，获得符合成品厚度规格要求的半成品卷材；
(4)收卷：按成品卷材的规格长度要求，夹设隔离衬垫层、将半成品卷材整理成卷；
(5)硫化：将整理成卷的卷材放入充氮硫化釜中进行硫化处理，控制硫化釜温度在155～165℃之间、压力在20～25MPa之间、硫化25至30分钟；
(6)复卷：将经硫化后的卷材重新打开、取出隔离衬垫层后再复卷、包装成产品。
实施例46：
一种发动机冷却系统散热器板式橡胶密封条，其采用模压硫化和分段硫化的工艺，包含以下步骤：
(1)橡胶混炼：设置密炼机温度为80℃和转子转速为40转/分钟，加入100份支化聚乙烯PER-5预压混炼90秒；然后加入5份氧化锌、1份硬脂酸、1份防老剂RD和2份脂肪酸衍生物混合物WB42，混炼1分钟；加入60份炭黑N550、25份石蜡油SUNPAR2280，混炼3分钟；最后加入4份交联剂双叔丁基过氧化二异丙基苯(BIPB)、1份助交联剂三烯丙基异氰脲酸酯(TAIC)和0.3份助交联剂硫磺，混炼2分钟后排胶。停放和检测；
(2)将检测合格后的混炼胶通过挤出机挤出成型，截断后放入硫化设备的模具内，硫化压力为15MPa，硫化温度为180℃，硫化时间优选2.5分钟；
(3)将硫化处理过的产品进行修边；
(4)将修边后的产品在高温下进行二段硫化。温度为170℃，时间为30分钟；
(5)对产品进行检验，合格后入库。
实施例47：
一种内胎，其生产工艺如下：
(1)橡胶混炼：设置密炼机温度为100℃，转子转速为50转/分钟，加入100份支化聚乙烯PER-5预压混炼90秒；加入5份氧化锌、1份硬脂酸和3份古马隆树脂，混炼2分钟；然后在胶料中加入60份炭黑N660和20份石蜡油SUNPAR2280，混炼3分钟；最后加入4份交联剂过氧化二异丙苯(DCP)和2份助交联剂N,N’-间苯撑双马来酰亚胺(HVA-2)，混炼2分钟后排胶。滤胶后将混炼胶在开炼机上开炼薄通，停放20小时。
(2)挤出：挤出机温度设为85℃，口型温度设为115℃，输送带的速度与挤出速度匹配。装气门嘴。
(3)接头：采用接头机接头，之后停放。
(4)充气定型及硫化：第一次充气至70％，停15秒；第二次充气至定型尺寸。硫化温度为180℃，蒸汽压力为0.9MPa，硫化时间为8分钟。硫化结束后，取出，冷却。
(5)检查、修边、得到内胎成品。
实施例48：
一种桥梁板式橡胶支座，其橡胶组合物中的橡胶基体为100份支化聚乙烯PER-12，橡胶组合物中的其余组份以及加工工艺与实施例30一致。
所用橡胶组合物的混炼胶经模压硫化制备测试样，测试性能如下：
硬度：65；拉伸强度：27.3MPa；断裂伸长率：442％；压缩永久变形(70℃×22h)：8％。
实施例49：
一种车用减震支座，其橡胶组合物中的橡胶基体为70份支化聚乙烯PER-10和30份支化聚乙烯PER-12，橡胶组合物中的其余组份以及加工工艺与实施例40一致。
所用橡胶组合物的混炼胶经模压硫化制备测试样，测试性能如下：
硬度：63；拉伸强度：27.5MPa；断裂伸长率：382％；压缩永久变形(70℃×22h)：9％。
实施例50：
一种橡胶轨枕垫，其橡胶组合物中的橡胶基体为100份支化聚乙烯PER-11，橡胶组合物中的其余组份以及加工工艺与实施例36一致。
所用橡胶组合物的混炼胶经模压硫化制备测试样，测试性能如下：
硬度：75；拉伸强度：26.8MPa；断裂伸长率：347％；压缩永久变形(70℃×22h)：9％。
综上，通过对比可以发现本发明的橡胶组合物相对于现有技术中以乙丙橡胶为基体的橡胶组合物，在综合物理性能上表现更加优异，可以在低成本下，明显优化耐老化橡胶制品的使用效果，拓宽耐老化橡胶制品的应用范围。

Claims (46)

  1. 一种橡胶组合物，其特征在于，所述橡胶组合物以重量份计，其包括：橡胶基体和必要成分，所述橡胶基体包含：支化聚乙烯的含量a：0＜a≤100份，乙丙橡胶的含量b：0≤b＜100份，以100重量份橡胶基体计，所述必要成分包含：交联剂1.5～10份，补强填充剂30～200份，增塑剂5～250份，其中支化聚乙烯包含乙烯均聚物，其支化度不低于50个支链/1000个碳，重均分子量不低于5万，门尼粘度ML(1+4)125℃不低于2。
  2. 根据权利要求1所述的一种橡胶组合物，其特征在于，所述100重量份橡胶基体中支化聚乙烯的含量a：10≤a≤100份；二元乙丙橡胶与三元乙丙橡胶的含量b：0≤b≤90份；所述支化聚乙烯特征为：是乙烯均聚物，其支化度为60～130个支链/1000个碳、重均分子量为6.6万～51.8万，门尼粘度ML(1+4)125℃为6～102。
  3. 根据权利要求1所述的橡胶组合物，其特征在于，所述橡胶组合物以重量份计，其包括橡胶基体和必要组份，所述橡胶基体包含支化聚乙烯100份，以100重量份橡胶基体计，所述必要组份包括交联剂1.5～10份，补强填充剂30～200份，增塑剂8～150份。
  4. 根据权利要求1所述的橡胶组合物，其特征在于，所述交联剂包括过氧化物交联剂和硫磺中的至少一种，过氧化物交联剂包括二叔丁基过氧化物、二枯基过氧化物、叔丁基枯基过氧化物、1,1-二叔丁基过氧化物-3,3,5-三甲基环己烷、2,5-二甲基-2,5-二(叔丁基过氧化)己烷、2,5-二甲基-2,5-二(叔丁基过氧化)己炔-3、双(叔丁基过氧化异丙基)苯、2,5-二甲基-2,5-二(苯甲酰过氧化)己烷、过氧化苯甲酸叔丁酯、叔丁基过氧化-2-乙基己基碳酸酯中的至少一种。
  5. 根据权利要求1所述的橡胶组合物，其特征在于，所述补强填充剂包括炭黑、白炭黑、碳酸钙、滑石粉、煅烧陶土、硅酸镁、碳酸镁中的至少一种。
  6. 根据权利要求1所述的一种橡胶组合物，其特征在于，所述增塑剂包括松焦油、机油、环烷油、石蜡油、古马隆、RX-80、硬脂酸、石蜡、液态聚异丁烯中的至少一种。
  7. 根据权利要求1所述的橡胶组合物，其特征在于，所述橡胶组合物还包括辅助成分，以100重量份橡胶基体计，所述辅助成分包含：助交联剂0.2～10份，稳定剂0.5～3份，金属氧化物2～15份，硫化促进剂0～3份。
  8. 根据权利要求7所述的橡胶组合物，其特征在于，所述助交联剂包含三烯丙基氰脲酸酯、三烯丙基异氰脲酸酯、乙二醇二甲基丙烯酸酯、二甲基丙烯酸乙酯、二甲基丙烯酸三乙二酯、偏苯三酸三烯丙酯、三甲基丙烯酸三羟甲基丙烷酯、双甲基丙烯酸乙二醇酯、N,N’-间苯撑双马来酰亚胺、N,N’-双亚糠基丙酮、1,2-聚丁二烯、对醌二肟、硫磺和不饱和羧酸金属盐中的至少一种。
  9. 根据权利要求7所述的橡胶组合物，其特征在于，所述金属氧化物为氧化锌、氧化镁、氧化钙、一氧化铅、四氧化三铅的至少一种。
  10. 根据权利要求7所述的橡胶组合物，其特征在于，所述稳定剂包括2,2,4-三甲基-1,2-二氢化喹啉聚合体、6-乙氧基-2,2,4-三甲基-1,2-二氢化喹啉、2-巯基苯并咪唑中的至少一种。
  11. 根据权利要求7所述的橡胶组合物，其特征在于，所述硫化促进剂包含2-硫醇基苯并噻唑、二硫化二苯并噻唑、一硫化四甲基秋兰姆、二硫化四甲基秋兰姆、二硫化四乙基秋兰姆、N-环己基-2-苯并噻唑基次磺酰胺、N，N-二环己基-2-苯噻唑基次磺酰胺、双马来酰亚胺、亚乙基硫脲中的至少一种。
  12. 一种加工权利要求1～11中任一所述橡胶组合物的方法，其包含以下步骤：
    (1)橡胶混炼：设置密炼机温度和转子转速，将橡胶组合物中除交联体系以外的组分依次加入到密炼机中混炼；然后加入交联体系，混炼后排胶，将混炼胶在开炼机薄通下片，停放，其中，交联体系包含交联剂，还可以包含助交联剂和硫化促进剂中的至少一种；
    (2)硫化：将停放后的混炼胶填入预热模具的模腔，进行高温加压硫化，硫化完成后，脱模得到硫化胶。
  13. 一种桥梁板式橡胶支座，包含钢板和橡胶片层，其特征在于，橡胶片层包含权利要求1～11任一所述的橡胶组合物。
  14. 一种桥梁板式橡胶支座，包含钢板、聚四氟乙烯板和橡胶片层，其特征在于，橡胶片层包含权利要求1～11任一所述的橡胶组合物。
  15. 一种生产权利要求14所述的桥梁板式橡胶支座的方法，其特征在于，该桥梁板式橡胶支座是通过各层橡胶片与钢板及聚四氟乙烯板之间经涂布胶黏剂加压硫化后粘接成的一个整体，其生产方法包含以下步骤：
    (1)橡胶混炼工艺：设置密炼机温度和转子转速，将橡胶片层所用橡胶组合物中除交联体系以外的组分依次加入到密炼机中混炼；然后加入交联体系，混炼后排胶，将混炼胶在开炼机薄通下片，停放和检测，经编号、回炼、压延出片后冲裁成所需规格的半成品胶片，供硫化工序使用，其中，交联体系包含交联剂，还可以包含助交联剂和硫化促进剂中的至少一种；
    (2)硫化工艺：将胶片与经表面处理并涂布胶黏剂的钢板和聚四氟乙烯板按工艺要求依次叠合成型，然后装入已预热的模具中，再进入平板硫化机硫化成型；
    (3)后处理：硫化完成后拉出并拆卸模具，取出橡胶支座成品，冷却停放并修整，得到成品。
  16. 一种盆式橡胶支座，其特征在于，所述盆式橡胶支座中的橡胶承压板包含权利要求1～11任一所述的橡胶组合物。
  17. 一种生产权利要求16所述盆式橡胶支座的方法，其特征在于，所述盆式橡胶支座由上支座板、不锈钢板、聚四氟乙烯板、中间钢板、密封圈、橡胶承压板、下支座板和支座锚栓组装而成，生产方法包含如下步骤：
    (1)橡胶混炼工艺：设置密炼机温度和转子转速，将橡胶承压板所用橡胶组合物中除交联体系以外的组分依次加入到密炼机中混炼；然后加入交联体系，混炼后排胶，将混炼胶在开炼机薄通下片，停放和检测，其中，交 联体系包含交联剂，还可以包含助交联剂和硫化促进剂中的至少一种；
    (2)硫化成型工艺：将胶片装入已预热的模具中，再进入平板硫化机硫化；
    (3)后处理：硫化完成后拉出并拆卸模具，取出橡胶支座成品，冷却停放并修整，得到橡胶承压板。
    (4)组装：将橡胶承压板与其他部件组装得到盆式橡胶支座。
  18. 一种桥梁橡胶伸缩装置，其特征在于，所用橡胶伸缩体包含权利要求1～11任一所述的橡胶组合物。
  19. 一种生产权利要求18所述桥梁橡胶伸缩装置的方法，其特征在于，橡胶伸缩体采用挤出法生产方法包含如下步骤：
    (1)橡胶混炼工艺：设置密炼机温度和转子转速，将所用橡胶组合物中除交联体系以外的组分依次加入到密炼机中混炼；然后加入交联体系，混炼后排胶，将混炼胶在开炼机薄通下片，停放和检测，其中，交联体系包含交联剂，还可以包含助交联剂和硫化促进剂中的至少一种；
    (2)挤出和硫化：挤出硫化工艺宜采用抽真空挤出机，挤出后采用盐浴硫化工艺，经过喷淋、浸轮、浸压、冷却得到硫化胶。
    (3)再经修边、检验、得到成品。
  20. 一种生产权利要求18所述桥梁橡胶伸缩装置的方法，其特征在于，其橡胶伸缩体采用模压法生产方法包含的步骤具体如下：
    (1)橡胶混炼和成型：设置密炼机温度和转子转速，将所用橡胶组合物中除交联体系以外的组分依次加入到密炼机中混炼；然后加入交联体系，混炼后排胶，将混炼胶在开炼机薄通下片，停放和检测，回炼出片、称量成型，其中，交联体系包含交联剂，还可以包含助交联剂和硫化促进剂中的至少一种；
    (2)模压硫化：将成型的混炼胶放入模具中，采用高温蒸汽硫化工艺进行硫化；
    (3)冷却、修边、检验、得到成品。
  21. 一种橡胶钢板组合型伸缩装置，其特征在于，橡胶伸缩体包含权利要求1～11任一所述的橡胶组合物。
  22. 一种生产权利要求21所述的橡胶钢板组合型伸缩装置的方法，其特征在于，生产方法包含如下步骤：
    (1)橡胶混炼和成型：设置密炼机温度和转子转速，将所用橡胶组合物中除交联体系以外的组分依次加入到密炼机中混炼；然后加入交联体系，混炼后排胶，将混炼胶在开炼机薄通下片，停放和检测，回炼出片、称量成型，其中，交联体系包含交联剂，还可以包含助交联剂和硫化促进剂中的至少一种；
    (2)硫化工艺：将胶片与经表面处理并涂布胶黏剂的钢板按工艺要求贴合成型，然后装入已预热的模具中，再进入平板硫化机加热加压硫化；
    (3)后处理：硫化完成后拉出并拆卸模具，取出制品，冷却停放并修整，得到成品。
  23. 一种橡胶轨枕垫，其特征在于，所用胶料包含权利要求1～11任一所述的橡胶组合物。
  24. 一种生产权利要求23所述橡胶轨枕垫的方法，其特征在于，生产方法包含如下步骤：
    (1)橡胶混炼和成型：设置密炼机温度和转子转速，将所用橡胶组合物中除交联体系以外的组分依次加入到密炼机中混炼；然后加入交联体系，混炼后排胶，经停放和检测后进行热炼，然后按所需厚度出片，裁切成所需规格形状供硫化工序使用，其中，交联体系包含交联剂，还可以包含助交联剂和硫化促进剂中的至少一种；
    (2)硫化：将裁切好的胶料放入模具中，将模具放入平板硫化机，加热加压硫化；
    (3)后处理：硫化完成后拉出并拆卸模具，取出制品，冷却停放并修整，得到成品。
  25. 一种橡胶护舷，其特征在于，所用胶料包含权利要求1～11任一所 述的橡胶组合物。
  26. 一种生产权利要求25所述橡胶护舷的方法，其特征在于，生产方法包含如下步骤：
    (1)橡胶混炼：设置密炼机温度和转子转速，将橡胶片层所用橡胶组合物中除交联体系以外的组分依次加入到密炼机中混炼；然后加入交联体系，混炼后排胶，其中，交联体系包含交联剂，还可以包含助交联剂和硫化促进剂中的至少一种；
    (2)模压及硫化：将混炼胶投入模腔，然后合模，胶料充分流动，排气，合模，硫化。
    (3)开模，取出制品，修边、检验、得到成品。
  27. 一种橡胶止水带，其特征在于，所用胶料包含权利要求1～11任一所述的橡胶组合物。
  28. 一种生产权利要求27所述的橡胶止水带的方法，其特征在于，生产方法包含如下步骤：
    (1)橡胶混炼和成型：设置密炼机温度和转子转速，将所用橡胶组合物中除交联体系以外的组分依次加入到密炼机中混炼；然后加入交联体系，混炼后排胶，将混炼胶在开炼机薄通下片，停放和检测，回炼出片、称量成型，其中，交联体系包含交联剂，还可以包含助交联剂和硫化促进剂中的至少一种；
    (2)硫化：将裁切好的胶料放入模具中，将模具放入平板硫化机，加热加压硫化；
    (3)后处理：硫化完成后拉出并拆卸模具，取出制品，冷却停放并修整，得到成品。
  29. 一种钢带橡胶止水带，其特征在于，所用胶料包含权利要求1～11任一所述的橡胶组合物。
  30. 一种生产权利要求29所述的钢带橡胶止水带的方法，其特征在于，生产方法包含如下步骤：
    (1)橡胶混炼和成型：设置密炼机温度和转子转速，将所用橡胶组合物中除交联体系以外的组分依次加入到密炼机中混炼；然后加入交联体系，混炼后排胶，将混炼胶在开炼机薄通下片，停放和检测，回炼出片、称量成型，其中，交联体系包含交联剂，还可以包含助交联剂和硫化促进剂中的至少一种；
    (2)硫化：将胶片与经表面处理并涂布胶黏剂的薄钢板按工艺要求贴合成型，然后装入已预热的模具中，再进入平板硫化机高温高压硫化；
    (3)后处理：硫化完成后拉出并拆卸模具，取出制品，冷却停放并修整，得到成品。
  31. 一种车用减震支座，其特征在于，所用胶料包含权利要求1～11任一所述的橡胶组合物。
  32. 一种生产权利要求31所述车用减震支座的方法，其特征在于，生产方法包含如下步骤：
    (1)橡胶混炼和成型：设置密炼机温度和转子转速，将所用橡胶组合物中除交联体系以外的组分依次加入到密炼机中混炼；然后加入交联体系，混炼后排胶，将混炼胶在开炼机薄通下片，停放和检测，回炼出片、称量成型，其中，交联体系包含交联剂，还可以包含助交联剂和硫化促进剂中的至少一种；
    (2)硫化：将胶片与经表面处理并涂布胶黏剂的金属件按工艺要求贴合成型，然后装入已预热的模具中，再进入平板硫化机高温高压硫化；
    (3)后处理：硫化完成后拉出并拆卸模具，取出制品，冷却停放并修整，得到成品。
  33. 一种胶辊，其特征在于，所用胶料包含权利要求1～11任一所述的橡胶组合物。
  34. 一种生产权利要求33所述胶辊的方法，其特征在于，生产方法包含的步骤如下：
    (1)橡胶混炼：设置密炼机温度和转子转速，将所用橡胶组合物中除 交联体系以外的组分依次加入到密炼机中混炼；然后加入交联体系，混炼后排胶，将混炼胶在开炼机薄通下片，停放和检测，其中，交联体系包含交联剂，还可以包含助交联剂和硫化促进剂中的至少一种；
    (2)缠绕包胶：将混炼胶投入螺杆挤出机，挤出工艺要求的厚度和宽度的胶片，待胶片均匀一致后启动旋转包布机，将胶片缠绕在准备好的金属辊芯上，逐层缠绕包胶，直到包胶单边厚度达到规定厚度，然后在胶面上缠绕尼龙水布2～3层，得到包胶完毕的胶辊；
    (3)硫化罐硫化，将包胶完毕的胶辊送入硫化罐，关闭罐门后，往硫化罐中通入蒸汽进行硫化，通入蒸汽的同时打开压缩空气阀门，通入压缩空气使硫化罐内压力在0.5小时内达到4.5～5大气压；
    硫化程序为：首先升温到70～80℃，保温2小时；再升温到100～110℃，保温0.5小时；再升温到120～130℃，保温0.5小时；再升温到135～140℃，保温8～10小时，硫化结束，开排气阀，压力下降，等压力表指针指到零时，打开保险销，等销孔内排出蒸汽飘动，半开硫化罐，让温度下降，待罐内温度低于60℃或与室温相当时，将胶辊拉出；
    (4)后处理：将硫化好的胶辊在车床上粗加工，再在磨床上精加工，检验，得到成品。
  35. 一种耐高温多楔带，包含压缩层和缓冲层，其特征在于，缓冲层胶料包含权利要求1～11任一所述的橡胶组合物。
  36. 一种生产权利要求35所述耐高温多楔带的方法，其特征在于，生产方法包含的步骤如下：
    (1)橡胶混炼：其中缓冲层胶料的混炼为：设置密炼机温度和转子转速，将所用橡胶组合物中除交联体系以外的组分依次加入到密炼机中混炼；然后加入交联体系，混炼后排胶，将混炼胶在开炼机薄通下片，停放和检测，其中，交联体系包含交联剂，还可以包含助交联剂和硫化促进剂中的至少一种；
    (2)成型：采用反成型法。先将光模吊上成型机，清洁模具，涂上少 量隔离剂，待其挥发后在光模上包贴多楔带顶布，然后包贴缓冲层胶料，校正线绳的张紧力，平整缠绕强力层后再包贴缓冲胶，最后包贴楔胶至成型工艺要求的外周长，得到带坯；
    (3)硫化：采用胶套硫化工艺，将带坯送入硫化罐进行硫化，硫化温度为155～175℃，内压为0.45～0.55MPa，外压为1.0～1.2MPa，硫化时间25～30分钟；
    (4)后处理：硫化结束后冷却脱模，将带筒送入切割工序，按要求宽度切割，磨背，磨楔，修边后通过检验，得到成品。
  37. 一种雨刷条，其特征在于，所用胶料包含权利要求1～11任一所述的橡胶组合物。
  38. 一种生产权利要求37所述雨刷条的方法，其特征在于，生产方法包含的步骤如下：
    (1)橡胶混炼：设置密炼机温度和转子转速，将所用橡胶组合物中除交联体系以外的组分依次加入到密炼机中混炼；然后加入交联体系，混炼后排胶，将混炼胶在开炼机薄通下片，停放和检测，其中，交联体系包含交联剂，还可以包含助交联剂和硫化促进剂中的至少一种；
    (2)硫化：将混炼胶注射入模腔，在高温高压下硫化成型；
    (3)后处理：将硫化后的制品进行表面处理，检验，得到成品。
  39. 一种密封圈，其特征在于，所用胶料包含权利要求1～11任一所述的橡胶组合物。
  40. 一种生产权利要求39所述密封圈的方法，其特征在于，生产方法包含的步骤如下：
    (1)橡胶混炼及成型：设置密炼机温度和转子转速，将所用橡胶组合物中除交联体系以外的组分依次加入到密炼机中混炼；然后加入交联体系，混炼后排胶，将混炼胶在开炼机上薄通下片，物性检测，胶料返炼，然后采用挤出法得到半成品，其中，交联体系包含交联剂，还可以包含助交联剂和硫化促进剂中的至少一种；
    (2)硫化：一段模压硫化：温度为155～170℃、硫化时间为20～25分钟；二段烘箱硫化：温度145～155℃，时间40～80分钟。
  41. 一种防水卷材，其特征在于，所用胶料包含权利要求1～11任一所述的橡胶组合物。
  42. 一种生产权利要求41所述防水卷材的方法，其特征在于，生产方法包含的步骤如下：
    (1)橡胶混炼：设置密炼机温度和转子转速，将所用橡胶组合物中除交联体系以外的组分依次加入到密炼机中混炼；然后加入交联体系，混炼后排胶，将混炼胶在开炼机充分薄通混炼、获得混合均匀的胶料毛片，冷却至50℃以下出片、堆放，其中，交联体系包含交联剂，还可以包含助交联剂和硫化促进剂中的至少一种；
    (2)热炼：将混合均匀的胶料毛片在开炼机上进行热炼，直至胶料片光滑均匀后初步成卷；
    (3)压延：将经热炼初步成卷的胶料片放入压延机上，按成品厚度要求调节辊距进行压延，获得符合成品厚度规格要求的半成品卷材；
    (4)收卷：按成品卷材的规格长度要求，夹设隔离衬垫层、将半成品卷材整理成卷；
    (5)硫化：将整理成卷的卷材放入充氮硫化釜中进行硫化处理，控制硫化釜温度在155～165℃之间、压力在20～25MPa之间、硫化25至30分钟；
    (6)复卷：将经硫化后的卷材重新打开、取出隔离衬垫层后再复卷、包装成产品。
  43. 一种密封条，其特征在于，所用胶料包含权利要求1～11任一所述橡胶组合物。
  44. 一种生产权利要求43所述密封条的方法，其特征在于，采用模压硫化和分段硫化的生产方法，包含以下步骤：
    (1)橡胶混炼：设置密炼机温度和转子转速，将所用橡胶组合物中除 交联体系以外的组分依次加入到密炼机中混炼；然后加入交联体系，混炼后排胶，将混炼胶在开炼机薄通下片，停放和检测，其中，交联体系包含交联剂，还可以包含助交联剂和硫化促进剂中的至少一种；
    (2)将检测合格后的混炼胶通过挤出机挤出成型，截断后放入硫化设备的模具内，在高温高压下进行一段硫化；
    (3)将硫化处理过的产品进行修边；
    (4)将修边后的产品在高温下进行二段硫化；
    (5)对产品进行检验，合格后入库。
  45. 一种内胎，其特征在于，其胎体所用胶料包含权利要求1～11任一所述橡胶组合物。
  46. 一种生产权利要求45所述内胎的方法，其特征在于，包含以下步骤：首先混炼橡胶，滤胶并停放；然后通过挤出机挤出，并按工艺要求的长度裁断，贴气门嘴，拼接后停放；然后充气定型，蒸汽硫化，冷却后，检查，修边得到成品。
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CN110003576A (zh) * 2019-02-28 2019-07-12 常州苏通海平机电科技有限公司 一种植物纤维增强型橡胶垫片的制备方法
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