WO2018130187A1 - 橡胶组合物及加工方法与应用，及生产高强度橡胶制品的方法 - Google Patents

橡胶组合物及加工方法与应用，及生产高强度橡胶制品的方法 Download PDF

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WO2018130187A1
WO2018130187A1 PCT/CN2018/072351 CN2018072351W WO2018130187A1 WO 2018130187 A1 WO2018130187 A1 WO 2018130187A1 CN 2018072351 W CN2018072351 W CN 2018072351W WO 2018130187 A1 WO2018130187 A1 WO 2018130187A1
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rubber
parts
vulcanization
rubber composition
crosslinking agent
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PCT/CN2018/072351
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English (en)
French (fr)
Inventor
徐涛
傅智盛
吴安洋
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杭州星庐科技有限公司
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Priority claimed from CN201810020849.3A external-priority patent/CN108314852B/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
Publication of WO2018130187A1 publication Critical patent/WO2018130187A1/zh

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    • 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 with high mechanical strength and a processing method thereof, and a high-strength rubber product using the rubber composition and a production method thereof.
  • Sulfur vulcanization and peroxide vulcanization are the two most commonly used vulcanization processes for ethylene propylene rubber.
  • a peroxide-based vulcanization system is often used.
  • the mechanical strength of peroxide-cured ethylene-propylene rubber is lower than that of sulfur-vulcanized ethylene-propylene rubber.
  • Unsaturated carboxylic acid metal salts such as zinc acrylate and zinc methacrylate can be used as a co-crosslinking agent for peroxide vulcanization to improve the vulcanization rate and crosslinking efficiency, and can also be used as a reinforcing filler for rubber when the amount is high. Improve the mechanical strength of rubber.
  • an unsaturated carboxylic acid metal salt is often added to an ethylene-propylene rubber product having high mechanical strength requirements.
  • this due to the weak strength of the ethylene-propylene rubber under the peroxide vulcanization system, this also limits the application range of the ethylene-propylene rubber product reinforced with the unsaturated carboxylic acid metal salt to some extent. In the case where the content of the unsaturated carboxylic acid metal salt is large, the compression set resistance is also deteriorated to some extent.
  • 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 object of the present invention is to solve the above problems and provide a novel rubber composition, which is partially or completely replaced with ethylene-propylene rubber with a branching degree of not less than 50 branches/1000 carbons, and continues to use peroxidation.
  • a rubber composition comprising: a rubber matrix and an essential component, the rubber matrix comprising: a content of branched polyethylene a: 0 ⁇ a ⁇ 100 parts;
  • the content of the ethylene propylene rubber and the ethylene propylene diene rubber is b: 0 ⁇ b ⁇ 100 parts;
  • the essential component comprises: 1 to 10 parts of the crosslinking agent, and the unsaturated carboxylic acid metal salt, based on 100 parts by weight of the rubber matrix.
  • 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 125 °C. 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.
  • a further technical solution is that, in 100 parts by weight, the content of branched polyethylene in the rubber matrix is a: 10 ⁇ a ⁇ 100 parts; the content of binary ethylene propylene rubber and ethylene propylene diene rubber is b: 0 ⁇ b ⁇ 90 parts; the branched polyethylene is an ethylene homopolymer having a degree of branching of 60 to 130 branches/1000 carbons, a weight average molecular weight of 66,000 to 518,000, and a Mooney viscosity ML (1+4) ) 125 ° C is 6 ⁇ 102;
  • a further technical solution is that, in 100 parts by weight, the content of branched polyethylene in the rubber matrix is a: 10 ⁇ a ⁇ 100 parts; the content of binary ethylene propylene rubber and ethylene propylene diene rubber is b: 0 ⁇ b ⁇ 90 parts; the branched polyethylene is an ethylene homopolymer having a branching degree of 70-116 branches/1000 carbons, a weight average molecular weight of 201,000 to 436,000, and a Mooney viscosity ML (1+4) ) 125 ° C is 23 ⁇ 101.
  • a further technical solution is that, in 100 parts by weight of the rubber matrix, the content of the branched polyethylene is: 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.
  • a further technical solution is that, in 100 parts by weight of the rubber matrix, the content of the branched polyethylene is: 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-nor Borneene, dicyclopentadiene, 1,4-hexadiene, 1,5-hexadiene, 1,4-pentadiene, 2-methyl-1,4-pentadiene, 3-methyl- 1,4-Hexadiene, 4-methyl-1,4-hexadiene, 1,9-decadiene, 5-methylene-2-norbornene, 5-pentylene-2-nor Borbornene, 1,5-cyclooctadiene, 1,4-cyclooctadiene, and the like.
  • a diene monomer specifically selected from the group consisting of 5-ethylidene-2-norbornene and 5-vinyl-2-nor Borneene, dicyclopentadiene, 1,4-hexadiene
  • 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 crosslinking agent comprises at least one of a peroxide crosslinking agent and a sulfur
  • the peroxide crosslinking agent comprises di-tert-butyl peroxide, dicumyl peroxide, Tert-butyl cumyl peroxide, 1,1-di-tert-butyl peroxide-3,3,5-trimethylcyclohexane, 2,5-dimethyl-2,5-di(tert-butyl) Base oxidized) hexane, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne-3, bis(tert-butylperoxyisopropyl)benzene, 2,5-di At least one of methyl-2,5-bis(benzoyl peroxy)hexane, tert-butyl peroxybenzoate, and t-butylperoxy-2-ethylhexyl carbonate.
  • a further technical solution is that the content of the crosslinking agent is from 1.5 to 6 parts based on 100 parts by weight of the rubber matrix.
  • the unsaturated carboxylic acid metal salt comprises at least one of zinc acrylate, zinc methacrylate, magnesium methacrylate, calcium methacrylate, and aluminum methacrylate.
  • a further technical solution is that the content of the unsaturated carboxylic acid metal salt is 5 to 30 parts based on 100 parts by weight of the rubber matrix.
  • the rubber composition further comprises an auxiliary component, wherein the auxiliary component is in parts by weight, based on 100 parts by weight of the rubber matrix, and comprises: a co-crosslinking agent other than the unsaturated carboxylic acid metal salt 0.2 to 10
  • the reinforcing filler is 10 to 150 parts
  • the plasticizer is 5 to 80 parts
  • the stabilizer is 1 to 3 parts
  • the metal oxide is 2 to 20 parts
  • the vulcanization accelerator is 0 to 3 parts.
  • the co-crosslinking agent comprises triallyl cyanurate, triallyl isocyanurate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, Triallyl trimellitate, trimethylolpropane trimethacrylate, N,N'-m-phenylene bismaleimide, N,N'-bis-indenylacetone, 1,2- At least one of polybutadiene and sulfur.
  • the reinforcing filler comprises at least one of carbon black, white carbon, calcium carbonate, talc, calcined clay, and magnesium carbonate.
  • the plasticizer comprises at least one of pine tar, engine oil, naphthenic oil, paraffin oil, coumarone, RX-80, stearic acid, paraffin, liquid ethylene propylene rubber, and liquid polyisobutylene.
  • 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 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), 2-mercaptobenzimidazole (MB), and N-4 (anilinophenyl)maleimide (MC).
  • the metal oxide comprises at least one of zinc oxide, magnesium oxide, and calcium oxide.
  • the vulcanization accelerator comprises 2-thiol benzothiazole, dibenzothiazyl disulfide, tetramethyl thiuram monosulfide, tetramethyl thiuram disulfide, tetrazyl disulfide Kethiram, N-cyclohexyl-2-benzothiazolyl sulfenamide, N,N-dicyclohexyl-2-benzothiazolyl sulfenamide, bismaleimide, ethylene thiourea At least one of them.
  • the 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, the processing method comprising the steps of:
  • Rubber kneading First, the rubber composition other than the cross-linking system is sequentially added to the internal mixer according to the parts by weight for kneading, and then added to the cross-linking system, uniformly kneaded, and discharged to obtain a rubber compound. The rubber compound is thinned on the open mill, and then the film is left to be vulcanized, 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 rubber compound is filled into the cavity of the mold, and after being vulcanized by vulcanization on a flat vulcanizer, the vulcanized rubber is obtained by demolding.
  • the present invention also provides an application for the production of insulating gloves using the above rubber composition, the production steps of which include the following:
  • Rubber kneading First, the rubber composition other than the cross-linking system is sequentially added to an internal mixer for kneading, and then added to a cross-linking system, which is uniformly kneaded and discharged to obtain a kneaded rubber. The mixture is thinned on the open mill and then discharged, and is parked for vulcanization, wherein the crosslinking system comprises a crosslinking agent, and may further comprise at least one of a co-crosslinking agent and a vulcanization accelerator;
  • Vulcanization The formed film is filled into the cavity of the mold, and the mold is placed on a flat vulcanizing machine for pressure vulcanization, then cooled and demolded, and trimmed to obtain a rubber insulated glove.
  • the present invention also provides an application for producing a hose using the above rubber composition, and the production method thereof comprises the following steps:
  • Rubber kneading First, the rubber composition other than the cross-linking system is sequentially added to the internal mixer for mixing by weight, and then added to the cross-linking system, uniformly kneaded, and discharged to obtain a rubber compound. The rubber compound is thinned on the open mill, and then the film is left to be vulcanized, 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 molding a cold feed extruder is used to extrude the rubber layer on the mandrel to obtain a tube blank, which is cooled by steam vulcanization, de-core, trimmed, inspected, and stored in a warehouse to obtain a hose.
  • the present invention also provides an application of the above rubber composition, which can be used for producing a conveyor belt, wherein at least one of the working surface covering rubber and the non-working surface covering rubber comprises the above rubber composition, and the production method comprises the following steps:
  • Rubber kneading process First, the rubber composition other than the cross-linking system is sequentially added to an internal mixer in terms of parts by weight for kneading, and then added to a cross-linking system, which is uniformly kneaded and discharged to obtain a kneaded rubber. The mixture is thinned on the open mill and then placed on the sheet to be vulcanized.
  • the crosslinking system comprises a crosslinking agent, and may further comprise at least one of a co-crosslinking agent and a vulcanization accelerator;
  • the film is closely attached to the pre-formed adhesive canvas strip blank on the forming machine to form a strip of high temperature resistant conveyor belt, and then rolled up for waiting for vulcanization;
  • the present invention also provides an application of the above rubber composition, which can be used for producing a conveyor belt, wherein the rubber used for the adhesive layer comprises the above rubber composition, and the rubber composition preferably comprises a tackifier, and the production method thereof comprises the following steps:
  • Rubber kneading process First, the rubber composition other than the cross-linking system is sequentially added to an internal mixer in terms of parts by weight for kneading, and then added to a cross-linking system, which is uniformly kneaded and discharged to obtain a kneaded rubber. The mixture is thinned on the open mill and then discharged, and is parked for vulcanization, wherein the crosslinking system comprises a crosslinking agent, and may further comprise at least one of a co-crosslinking agent and a vulcanization accelerator;
  • Adhesive glue the rubber compound and the cloth layer are finished at a normal temperature by a double roll or a four roll calender to complete the bonding of the adhesive glue and the canvas layer to obtain a rubberized canvas strip;
  • the present invention also provides an application of the above rubber composition, which can be used for producing a shock absorbing member, which can be a rubber shock absorbing member, and can also be rubber because the rubber composition has good bonding property with metal.
  • Metal composite shock absorber which can be used for producing a shock absorbing member, which can be a rubber shock absorbing member, and can also be rubber because the rubber composition has good bonding property with metal.
  • the beneficial effects of the invention are: since the branch of the ethylene-propylene rubber is substantially methyl, the branched polyethylene has more branches in the molecular structure, and the branch length has a certain distribution, and the branched polyethylene has An appropriate number of secondary branched structures.
  • the crosslinking point of the branched polyethylene can be generated on the tertiary chain of the main chain or on the branched tertiary carbon of the secondary structure, so
  • the rubber network formed by cross-linking of branched polyethylene has a richer CC connecting segment length between the main chains, which can effectively avoid stress concentration and facilitate better mechanics. Performance, including tear strength.
  • the compression set property is related to the molecular weight distribution of the rubber material, and the rubber having a narrow molecular weight distribution has a relatively low compression set.
  • the molecular weight distribution of ethylene propylene rubber is mostly between 3 and 5, and the highest is 8 to 9.
  • the molecular weight distribution of a small amount of ethylene propylene rubber is close to 2 and convenient for processing, but the cost is high.
  • the molecular weight distribution of the branched polyethylene is generally lower 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 has a lower compression set after vulcanization, and can be compensated to some extent.
  • the rubber composition provided by the present invention can obtain a rubber product having high mechanical strength and good compression set resistance.
  • 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 30 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.
  • the selected branched polyethylene is characterized by a branching degree of 60 to 130 branches/1000 carbons, a weight average molecular weight of 66,000 to 518,000, and a Mooney viscosity of ML (1+4) of 125 ° C of 6 to 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;
  • Mooney viscosity test According to the national standard GB/T1232.1-2000, the test is carried out with a Mooney viscometer. The test temperature is 125 ° C, preheating for 1 minute, testing for 4 minutes;
  • test conditions 150 ° C ⁇ 72h;
  • tear performance test in accordance with the national standard GB/T529-2008, using an electronic tensile testing machine for testing, the stretching 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;
  • the vulcanization conditions of the following Examples 1 to 12 and Comparative Examples 1 and 2 were as follows: temperature: 170 ° C; pressure: 16 MPa; time was Tc90 + 1 min.
  • the branched polyethylene used was numbered PER-6.
  • Rubber mixing set the temperature of the internal mixer to 90 ° C, the rotor speed is 50 rpm, add 70 parts of EPDM rubber and 30 parts of branched polyethylene for 90 seconds; then in the rubber compound 35 parts of zinc methacrylate was added and kneaded for 4 minutes; finally, 6 parts of cross-linking agent dicumyl peroxide (DCP) was added, and after 2 minutes of mixing, the rubber was discharged, and the mixture was placed at a roll temperature of 60 ° C. The thin open on the open mill, the sheet with a thickness of about 2.5mm, and parked for 20 hours.
  • DCP cross-linking agent dicumyl peroxide
  • the branched polyethylene used was numbered PER-5.
  • Rubber mixing set the temperature of the internal mixer to 90 ° C, the rotor speed is 50 rpm, add 50 parts of ethylene propylene diene rubber and 50 parts of branched polyethylene for 90 seconds; then in the rubber compound Add 50 parts of zinc methacrylate, mix for 4 minutes; finally add 10 parts of cross-linking agent dicumyl peroxide (DCP), mix for 2 minutes, then drain the glue, the mixture is at a roll temperature of 60 ° C.
  • DCP dicumyl peroxide
  • the branched polyethylene used was numbered PER-5.
  • Rubber mixing set the temperature of the internal mixer to 90 ° C, the rotor rotation speed is 50 rpm, and add 100 parts of branched polyethylene to pre-press and knead for 90 seconds; then add 35 parts of zinc methacrylate to the rubber compound. , mixing for 4 minutes; finally adding 5 parts of cross-linking agent dicumyl peroxide (DCP), mixing for 2 minutes, then discharging the glue, and the mixture is thinned on an open mill with a roll temperature of 60 ° C to obtain 2.5. A sheet of about mm thickness is parked for 20 hours.
  • DCP cross-linking agent dicumyl peroxide
  • Rubber mixing set the temperature of the internal mixer to 90 ° C, the rotor speed to 50 rpm, add 100 parts of EPDM rubber for 90 seconds, and then add 35 parts of methacrylic acid to the compound. Zinc, kneading for 4 minutes; finally adding 5 parts of cross-linking agent dicumyl peroxide (DCP), mixing for 2 minutes, then discharging the glue, and the mixture is thinned on an open mill with a roll temperature of 60 ° C. A sheet of thickness of about 2.5 mm is parked for 20 hours.
  • DCP dicumyl peroxide
  • test data of Examples 1-3 and Comparative Example 1 are as follows:
  • Example 1 Example 2
  • Example 3 Comparative Example 1 hardness 71 75 69
  • Elongation at break % 312 279 349 307 Tear strength N/mm 57 59 62
  • the branched polyethylene used was numbered PER-9.
  • Rubber mixing set the temperature of the mixer to 90 ° C, the rotor speed is 50 rpm, add 90 parts of EPDM rubber and 10 parts of branched polyethylene for 90 seconds; then add 6 parts. Zinc oxide, 1 part stearic acid and 8 parts zinc methacrylate, kneaded for 2 minutes; then add 50 parts of carbon black N550 to the compound, knead for 3 minutes; finally add 4 parts of cross-linking agent diisopropyl peroxide Benzene (DCP), 1 part of triallyl isocyanurate (TAIC) and 0.3 parts of sulfur, after 2 minutes of mixing, the rubber was discharged, and the mixture was thinned on an open mill with a roll temperature of 60 ° C to obtain A sheet of thickness of about 2.5 mm is parked for 20 hours.
  • DCP diisopropyl peroxide Benzene
  • TAIC triallyl isocyanurate
  • the branched polyethylene used was numbered PER-6.
  • Rubber mixing 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 for 90 seconds; then add 6 parts. Zinc oxide, 1 part stearic acid and 5 parts zinc methacrylate, kneaded for 2 minutes; then add 50 parts of carbon black N550 to the compound, knead for 3 minutes; finally add 1 part of cross-linking agent diisopropyl peroxide Benzene (DCP), 0.5 parts of sulfur, 1.5 parts of 2-mercaptobenzimidazole and 1.5 parts of N-cyclohexyl-2-benzothiazolyl sulfenamide, after 3 minutes of mixing, the rubber is discharged, and the rubber is mixed at the roll temperature. It was thin on the 60 ° C open mill, and a sheet having a thickness of about 2.5 mm was obtained and parked for 20 hours.
  • DCP diisopropyl peroxide Benzene
  • the branched polyethylene used was numbered PER-4.
  • Rubber mixing set the temperature of the internal mixer to 90 ° C, the rotor speed to 50 rpm, and add 100 parts of branched polyethylene pre-pressed for 90 seconds; then add 6 parts of zinc oxide and 1 part of stearic acid. And 8 parts of zinc methacrylate, mixing for 2 minutes; then adding 50 parts of carbon black N550 to the compound, mixing for 3 minutes; finally adding 4 parts of cross-linking agent dicumyl peroxide (DCP), 1 part three Allyl isocyanurate (TAIC) and 0.3 parts of sulfur were mixed for 2 minutes, and the rubber was drained. The mixture was thinned on an open mill with a roll temperature of 60 ° C to obtain a sheet having a thickness of about 2.5 mm. 20 hours.
  • DCP dicumyl peroxide
  • TAIC Allyl isocyanurate
  • Rubber mixing set the temperature of the internal mixer to 90 ° C, the rotor speed to 50 rpm, add 100 parts of EPDM rubber for 90 seconds, and then add 6 parts of zinc oxide and 1 part of stearin. Acid and 8 parts of zinc methacrylate, kneaded for 2 minutes; then add 50 parts of carbon black N550 to the compound, mix for 3 minutes; finally add 4 parts of cross-linking agent dicumyl peroxide (DCP), 1 part Triallyl isocyanurate (TAIC) and 0.3 parts of sulfur, after 2 minutes of mixing, the rubber was discharged, and the rubber mixture was thinly passed through an open mill having a roll temperature of 60 ° C to obtain a sheet having a thickness of about 2.5 mm. Park for 20 hours.
  • DCP dicumyl peroxide
  • TAIC Triallyl isocyanurate
  • test data of Examples 4 to 6 and Comparative Example 2 are as follows:
  • the branched polyethylenes used were numbered PER-1 and PER-7.
  • Rubber mixing set the temperature of the internal mixer to 90 ° C, the rotor rotation speed is 50 rpm, add 80 parts of PER-7 and 20 parts of PER-1 pre-pressure mixing for 90 seconds; then add 10 parts of zinc oxide, 1 part stearic acid and 1 part antioxidant 2,2,4-trimethyl-1,2-dihydroquinoline polymer (RD), kneaded for 2 minutes; then add 30 parts of methacrylic acid to the compound Zinc, 50 parts of carbon black N330 and 15 parts of paraffin oil SUNPAR 2280, mixed for 3 minutes; finally added 4 parts of cross-linking agent dicumyl peroxide (DCP), 1.5 parts of triallyl isocyanurate (TAIC) And 0.3 parts of sulfur, after 2 minutes of kneading, the rubber was discharged, and the rubber mixture was thinly passed through an open mill having a roll temperature of 60 ° C to obtain a sheet having a thickness of about 2.5 mm, and was left for 20 hours.
  • DCP cross-linking agent di
  • the branched polyethylene used was numbered PER-8.
  • Rubber mixing set the temperature of the internal mixer to 90 ° C, the rotor speed to 50 rpm, add 80 parts of EPDM rubber and 20 parts of PER-8 pre-pressure mixing for 90 seconds; then add 10 parts of oxidation.
  • Zinc 1 part stearic acid, 1 part antioxidant RD and 1 part 2-mercaptobenzimidazole (MB), kneaded for 2 minutes; then 30 parts of zinc methacrylate, 60 parts of carbon black N330 and then added to the compound 20 paraffin oil SUNPAR 2280, mixed for 3 minutes; finally added 3 parts of cross-linking agent dicumyl peroxide (DCP), 1 part triallyl isocyanurate (TAIC) and 9 parts of cross-linking agent 1,2-polybutadiene, after 2 minutes of kneading, the rubber was discharged, and the kneaded rubber was thinly passed through an open mill having a roll temperature of 60 ° C to obtain a sheet having a thickness of about 2.5 mm, and was left to stand
  • the branched polyethylene used was numbered PER-7.
  • Rubber mixing set the temperature of the internal mixer to 90 ° C, the rotor speed is 50 rpm, add 20 parts of ethylene propylene diene rubber, 50 parts of ethylene propylene diene monomer and 30 parts of PER-7 pre-pressure mixing.
  • the branched polyethylene used was numbered PER-3.
  • Rubber mixing set the temperature of the internal mixer to 90 ° C, the rotor speed to 50 rpm, add 20 parts of ethylene propylene diene rubber, 30 parts of EPDM rubber and 50 parts of PER-3 pre-pressure mixing 90 seconds; then add 20 parts of zinc oxide, 2 parts of stearic acid, 1 part of antioxidant RD and 1 part of 2-mercaptobenzimidazole (MB), knead for 2 minutes; then add 30 parts of methacrylic acid to the compound Zinc, 80 parts of carbon black N330 and 20 parts of paraffin oil SUNPAR 2280, mixing for 3 minutes; finally adding 1 part of cross-linking agent dicumyl peroxide (DCP), mixing for 2 minutes, then discharging the glue, the glue is
  • the sheet was rolled on a mill with a roll temperature of 60 ° C to obtain a sheet having a thickness of about 2.5 mm and parked for 20 hours.
  • the branched polyethylene used was numbered PER-5.
  • Rubber mixing set the temperature of the internal mixer to 90 ° C, the rotor speed is 50 rpm, add 100 parts of PER-5 pre-pressure mixing for 90 seconds; then add 15 parts of zinc oxide, 2 parts of stearic acid, 1 part of antioxidant RD, kneaded for 2 minutes; then add 25 parts of zinc methacrylate, 60 parts of carbon black N330 and 15 parts of paraffin oil SUNPAR 2280 to the compound, mix for 3 minutes; finally add 4 parts of cross-linking agent Dicumyl oxide (DCP) and 1.5 parts of N, N'-m-phenylene bismaleimide (HVA-2), after 2 minutes of mixing, the rubber is discharged, and the mixture is at a roll temperature of 60 ° C.
  • DCP Dicumyl oxide
  • HVA-2 N, N'-m-phenylene bismaleimide
  • the branched polyethylenes used were numbered PER-2 and PER-6.
  • Rubber mixing set the temperature of the internal mixer to 90 ° C, the rotor speed to 50 rpm, add 30 parts of PER-2 and 70 parts of PER-6 pre-pressure mixing for 90 seconds; then add 10 parts of zinc oxide, 2 parts of stearic acid, 1 part of antioxidant RD, mixing for 2 minutes; then adding 15 parts of zinc methacrylate, 50 parts of carbon black N330 and 15 parts of paraffin oil SUNPAR 2280 to the compound, mixing for 3 minutes; 3 parts of cross-linking agent dicumyl peroxide (DCP) and 1 part of triallyl isocyanurate (TAIC), after 2 minutes of mixing, the rubber was discharged, and the mixture was opened at a roll temperature of 60 ° C. Thin on the refiner, a sheet with a thickness of about 2.5 mm, and parked for 20 hours.
  • DCP dicumyl peroxide
  • TAIC triallyl isocyanurate
  • test data of Examples 7 to 12 are as follows:
  • a light-colored pure rubber pipe produced by using the rubber composition provided by the present invention comprising the following steps:
  • the 60mm cold feed extruder is equipped with a T-type head.
  • the rubber layer is extruded on the mandrel to obtain the tube blank, which is cooled, de-core, trimmed, inspected and stored after being vulcanized.
  • the vulcanization process is steam vulcanization at 160 ° C, steam pressure 0.6 MPa, time 30 minutes.
  • An insulating glove produced by using the rubber composition provided by the present invention comprising the following steps:
  • a high temperature resistant conveyor belt using the rubber composition provided by the present invention as a working surface covering glue comprising the following steps:
  • the high temperature resistant conveyor belt of the embodiment is provided with a cored tensile canvas between the working surface covering glue and the non-working surface covering glue, and they are made into a solid whole by molding and vulcanization process.
  • Rubber mixing process set the temperature of the internal mixer to 90 ° C, the rotor speed is 50 rpm, add 100 parts of PER-5 pre-pressure mixing for 90 seconds; then add 15 parts of zinc oxide, 2 parts of stearic acid, 1 part Anti-aging agent RD, mixing for 2 minutes; then adding 25 parts of zinc methacrylate, 60 parts of carbon black N330 and 15 parts of paraffin oil SUNPAR 2280 to the compound, mixing for 3 minutes; finally adding 4 parts of cross-linking agent peroxide Cumene (DCP) and 1.5 parts of N,N'-m-phenylene bismaleimide (HVA-2) were mixed for 2 minutes and then discharged.
  • DCP cross-linking agent peroxide Cumene
  • HVA-2 N,N'-m-phenylene bismaleimide
  • Calendering process The above mixing rubber is placed in a screw extruder for hot refining, and then supplied to a calender for calendering to be used, and the film thickness is controlled to be 4.5 to 12 mm when calendering. After being good, keep warm for use.
  • the film is closely attached to the preformed adhesive canvas strip to form a strip of the high temperature resistant conveyor belt, and then rolled up for 4 hours and then vulcanized.
  • Vulcanization process The above-mentioned formed conveyor belt blanks are placed in a flat vulcanizing machine for stage vulcanization, each of which has a vulcanization time of 25 minutes, a vulcanization pressure of 3 kg/cm 2 and a vulcanization temperature of 160 ° C.
  • Trimming and inspection After the vulcanization is finished, it is trimmed, inspected, and then packaged into the warehouse.
  • a high-temperature resistant conveyor belt using the rubber composition provided by the present invention as an adhesive layer comprising the following steps:
  • the high temperature resistant conveyor belt of the embodiment is provided with a rubberized canvas as a tensile layer between the working surface covering rubber and the non-working surface covering rubber, and they are made into a solid whole through molding and vulcanization processes.
  • composition and ratio of the adhesive layer rubber for the appliqué canvas according to the embodiment are in parts:
  • the rubber compound and the cloth layer are pasted at a normal temperature by a double roll or a four roll calender to complete the bonding of the adhesive glue and the canvas layer to obtain a rubberized canvas strip;
  • the formed adhesive canvas strip and the cover film are closely attached together on a molding machine to form a strip of a high temperature resistant conveyor belt, and then rolled up for 4 hours and then vulcanized.
  • the formed conveyor belt blanks were placed in a flat vulcanizing machine for stage vulcanization, each of which had a vulcanization time of 25 minutes, a vulcanization pressure of 3 kg/cm2, and a vulcanization temperature of 160 °C.
  • the vulcanization After the vulcanization is finished, it is trimmed, inspected, and then packaged into the warehouse.
  • An insulating glove produced by using the rubber composition provided by the present invention comprising the following steps:
  • Example 14 The rest of the production process is in accordance with Example 14.
  • the rubber composition of the present embodiment was molded into a test sample by molding, and the test performance was as follows:
  • Hardness 66; tensile strength: 25.9 MPa; elongation at break: 512%; tear strength 61 N/mm; 50 kV power frequency withstand voltage for 1 minute without breakdown without flashover.
  • a high temperature resistant conveyor belt using the rubber composition provided by the invention as a working surface covering glue, the composition and mixing process of the working surface covering glue is as follows:
  • a high temperature resistant conveyor belt using the rubber composition provided by the present invention as an adhesive layer rubber, and the composition and mixing process of the adhesive layer rubber for the adhesive canvas are as follows:
  • Rubber mixing set the temperature of the internal mixer to 100 ° C, the rotor speed to 50 rpm, add 100 parts of PER-10 and 15 parts of paraffin oil SUNPAR 2280 pre-pressed and kneaded for 90 seconds; then add 5 parts of zinc oxide, 1 part stearic acid, 2 parts of binder RS, 2 parts of polyethylene glycol PEG4000 and 1 part of antioxidant RD, kneaded for 2 minutes; then add 60 parts of carbon black N330, 20 parts of white carbon black, 10 parts of methyl Zinc acrylate and 15 parts paraffin oil SUNPAR2280, mixed for 3 minutes; then add 3 parts of binder RA-65, knead for 1 minute; then add 4 parts of cross-linking agent di-tert-butylperoxydiisopropylbenzene (BIPB 1 part of a co-crosslinking agent, triallyl isocyanurate (TAIC), and 0.3 parts of sulfur, which were mixed for 2 minutes and then discharged.
  • 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 member of the embodiment can be used for a high temperature portion such as an engine and an exhaust pipe.

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Abstract

橡胶组合物及加工方法，以及应用该橡胶组合物的制品及生产方法。该橡胶组合物包括：橡胶基体和必要组分，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；必要组分包含：交联剂1～10份，不饱和羧酸金属盐为5～50份，其有益效果是，该橡胶组合物可应用于绝缘手套、耐热输送带、胶管等橡胶制品，该橡胶制品具有良好的力学性能。

Description

橡胶组合物及加工方法与应用，及生产高强度橡胶制品的方法 技术领域
本发明属于橡胶技术领域，具体涉及一种具有高力学强度的橡胶组合物及加工方法，以及应用该橡胶组合物的高强度橡胶制品及其生产方法。
技术背景
硫黄硫化和过氧化物硫化是乙丙橡胶最常用的两种硫化工艺。在乙丙橡胶制品的生产过程中，为了获得良好的回弹性、电绝缘性、耐热老化性，往往采用以过氧化物为主的硫化体系。但是采用过氧化物硫化的乙丙橡胶的力学强度低于硫黄硫化的乙丙橡胶。不饱和羧酸金属盐如丙烯酸锌、甲基丙烯酸锌可以作为过氧化物硫化的助交联剂来提高硫化速度和交联效率，在用量较高的时候还可以作为橡胶的补强填充剂来提高橡胶的力学强度。目前在对力学强度有较高要求的乙丙橡胶制品中经常添加不饱和羧酸金属盐。但是由于过氧化物硫化体系下的乙丙橡胶自身强度较弱，这也在一定程度上限制了采用不饱和羧酸金属盐补强的乙丙橡胶制品的适用范围。在不饱和羧酸金属盐含量较多的情况下，抗压缩永久变形性也会一定程度的劣化。
所以如何在不饱和羧酸金属盐的存在下，进一步综合改善乙丙橡胶的耐老化性、力学强度以及一些功能性指标(如抗压缩永久变形性)是一个有待解决的技术问题。
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
本发明的目的在于解决上述问题，提供一种新型的橡胶组合物，用支化度不低于50个支链/1000个碳的支化聚乙烯部分或者全部替代乙丙橡胶，继续采用过氧化物为主的硫化体系，并加入不饱和羧酸金属盐来辅助交联和补强，让胶料具有更好的力学强度。
为了实现上述目的，本发明采用以下技术方案：一种橡胶组合物，其包括：橡胶基体和必要组分，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；以100重量份橡胶基体计，所述必要组分包含：交联剂1～10份，不饱和羧酸金属盐为5～50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***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。
进一步的技术方案是，以100重量份计，所述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，以100重量份计，所述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，100重量份橡胶基体中，所述支化聚乙烯的含量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，100重量份橡胶基体中，所述支化聚乙烯的含量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。
进一步的技术方案是，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％。
进一步的技术方案是，所述交联剂包含过氧化物交联剂和硫磺中的至少一种，所述过氧化物交联剂包含二叔丁基过氧化物、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。
进一步的技术方案是，以100重量份橡胶基体计，所述交联剂的含量为1.5～6份。
进一步的技术方案是，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。
进一步的技术方案是，以100重量份橡胶基体计，所述不饱和羧酸金属盐的含量为5～30份。
进一步的技术方案是，所述橡胶组合物还包括辅助成分，以100重量份橡胶基体计，辅助成分按重量份计，其包含：除不饱和羧酸金属盐以外的助交联剂0.2～10份，补强填充剂10～150份，增塑剂5～80份，稳定剂1～3份，金属氧化物2～20份，硫化促进剂0～3份。
进一步的技术方案是，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、N,N’-间苯撑双马来酰亚胺、N,N’-双亚糠基丙酮、1,2-聚丁二烯和硫磺中的至少一种。
进一步的技术方案是，所述补强填充剂包含炭黑、白炭黑、碳酸钙、滑石粉、煅烧陶土、碳酸镁中的至少一种。
进一步的技术方案是，所述增塑剂包含松焦油、机油、环烷油、石蜡油、古马隆、RX-80、硬脂酸、石蜡、液态乙丙橡胶、液态聚异丁烯中的至少一种。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。
进一步的技术方案是，所述稳定剂包含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)、N-4(苯胺基苯基)马来酰亚胺(MC)中的至少一种。
进一步的技术方案是，所述金属氧化物包含氧化锌、氧化镁、氧化钙的至少一种。
进一步的技术方案是，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。
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，该加工方法包括以下步骤：
(1)橡胶混炼：首先将除交联体系以外的橡胶组合物按照重量份依次添加到密炼机中进行混炼，然后加入交联体系经混炼均匀后排出，得到混炼胶，将混炼胶在开炼机上薄通后下片，停放等待硫化，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：将混炼胶填入模具的模腔，在平板硫化机上加压硫化后，脱模即可得到硫化橡胶。
本发明还提供一种利用上述橡胶组合物的应用，可用于生产绝缘手套，其生产步骤包括如下：
(1)橡胶混炼：首先将除交联体系以外的橡胶组合物按重量份依次添加到密炼机中进行混炼，然后加入交联体系经混炼均匀后排出，得到混炼胶。将混炼胶在开炼机上薄通后下片，停放等待硫化，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)裁片：将胶片停放一段时间后，按模具型腔尺寸大小进行裁片成型；
(3)硫化：将成型的胶片填入模具的模腔，将模具放在平板硫化机上加压硫化后，冷却脱模，修边即可得到橡胶绝缘手套。
本发明还提供一种利用上述橡胶组合物的应用，可用于生产胶管，其生产方法包括以下步骤：
(1)橡胶混炼：首先将除交联体系以外的橡胶组合物按重量份依次添加到密炼机中进行混炼，然后加入交联体系经混炼均匀后排出，得到混炼胶，将混炼胶在开炼机上薄通后下片，停放等待硫化，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)挤出及成型：采用冷喂料挤出机，在芯棒上挤出胶层，得到管坯，经蒸汽硫化后冷却，脱芯，修整、检验、入库，得到胶管。
本发明还提供一种利用上述橡胶组合物的应用，可用于生产输送带，其工作面覆盖胶和非工作面覆盖胶中的至少一层包含上述橡胶组合物，其生产方法包括以下步骤：
(1)橡胶混炼工艺：首先将除交联体系以外的橡胶组合物按照重量份依次添加到密炼机中进行混炼，然后加入交联体系经混炼均匀后排出，得到混炼胶。将混炼胶在开炼机上薄通后下片，停放待硫化。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)压延工艺：将以上混炼胶放到螺杆挤出机中热炼，然后供到压延机中进行压延出片保温待用；
(3)成型工艺：胶片在成型机上和预先成型好的贴胶帆布带坯紧密地贴合在一起成型为耐高温输送带的带坯，然后卷起停放等待硫化；
(4)将上述成型好的输送带带坯放到平板硫化机中进行分段硫化；
(5)硫化结束后进行修整、检验，然后包装入库。
本发明还提供一种利用上述橡胶组合物的应用，可用于生产输送带，其粘合层所用橡胶包含上述橡胶组合物，所述橡胶组合物优选包含增粘剂，其生产方法包括以下步骤：
(1)橡胶混炼工艺：首先将除交联体系以外的橡胶组合物按照重量份依次添加到密炼机中进行混炼，然后加入交联体系经混炼均匀后排出，得到混炼胶。将混炼胶在开炼机上薄通后下片，停放等待硫化，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)贴胶：混炼胶和布层在常温下经过双辊或四辊压延机完成粘合胶与帆布层的贴合，得到贴胶帆布带坯；
(3)成型工艺：将成型好的贴胶帆布带坯与覆盖胶胶片在成型机上紧密地贴合在一起成型为耐高温输送带的带坯，然后卷起待硫化；
(4)将上述成型好的输送带带坯放到平板硫化机中进行分段硫化，
(5)硫化结束后进行修整、检验，然后包装入库。
本发明还提供一种利用上述橡胶组合物的应用，可用于生产减震件，所述减震件可以是橡胶减震件，并且由于上述橡胶组合物与金属粘结性能良好，也可以是橡胶金属复合减震件。
本发明的有益效果是：由于乙丙橡胶的支链基本上为甲基，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分布，且支化聚乙烯有数量适当的二级支链结构，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，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，可以在一定程度上弥补加入不饱和羧酸金属盐对胶料的抗压缩永久变形性能造成的不利影响。综合而言，使用本发明提供的橡胶组合物可以得到力学强度高、耐压缩永久变形性能好的橡胶制品。
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。
为了更清楚的叙述本发明的实施方式，下面对本发明所涉及到的材料做个定义。
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30～80，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。
所选用的支化聚乙烯特征为：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。
Figure PCTCN2018072351-appb-000001
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、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；
4、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；
5、撕裂性能测试：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；
6、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℃；
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170℃。
以下实施例1～12以及对照例1和2的硫化条件统一为：温度：170℃；压力：16MPa；时间为Tc90+1min。
实施例1：
采用的支化聚乙烯编号为PER-6。
加工步骤如下:
(1)橡胶混炼：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；然后在胶料中加入35份甲基丙烯酸锌，混炼4分钟；最后加入6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2：
采用的支化聚乙烯编号为PER-5。
加工步骤如下:
(1)橡胶混炼：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；然后在胶料中加入50份甲基丙烯酸锌，混炼4分钟；最后加入10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3：
采用的支化聚乙烯编号为PER-5。
加工步骤如下:
(1)橡胶混炼：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；然后在胶料中加入35份甲基丙烯酸锌，混炼4分钟；最后加入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。
对照例1：
加工步骤如下:
(1)橡胶混炼：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；然后在胶料中加入35份甲基丙烯酸锌，混炼4分钟；最后加入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1～3和对照例1的测试数据如下：
测试项目 实施例1 实施例2 实施例3 对照例1
硬度 71 75 69 70
拉伸强度/MPa 16.7 16.9 17.5 13.2
断裂伸长率％ 312 279 349 307
撕裂强度N/mm 57 59 62 52
压缩永久变形(70℃×22h) 16 17 13 19
实施例4：
采用的支化聚乙烯编号为PER-9。
加工步骤如下:
(1)橡胶混炼：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6份氧化锌、1份硬脂酸和8份甲基丙烯酸锌，混炼2分钟；然后在胶料中加入50份炭黑N550，混炼3分钟；最后加入4份交联剂 过氧化二异丙苯(DCP)、1份三烯丙基异氰脲酸酯(TAIC)和0.3份硫磺，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5：
采用的支化聚乙烯编号为PER-6。
加工步骤如下:
(1)橡胶混炼：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6份氧化锌、1份硬脂酸和5份甲基丙烯酸锌，混炼2分钟；然后在胶料中加入50份炭黑N550，混炼3分钟；最后加入1份交联剂过氧化二异丙苯(DCP)、0.5份硫磺、1.5份2-巯基苯并咪唑和1.5份N-环己基-2-苯并噻唑基次磺酰胺，混炼3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：
采用的支化聚乙烯编号为PER-4。
加工步骤如下:
(1)橡胶混炼：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6份氧化锌、1份硬脂酸和8份甲基丙烯酸锌，混炼2分钟；然后在胶料中加入50份炭黑N550，混炼3分钟；最后加入4份交联剂过氧化二异丙苯(DCP)、1份三烯丙基异氰脲酸酯(TAIC)和0.3份硫磺，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2：
加工步骤如下:
(1)橡胶混炼：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6份氧化锌、1份硬脂酸和8份甲基丙烯酸锌，混炼2分 钟；然后在胶料中加入50份炭黑N550，混炼3分钟；最后加入4份交联剂过氧化二异丙苯(DCP)、1份三烯丙基异氰脲酸酯(TAIC)和0.3份硫磺，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4～6和对照例2的测试数据如下：
Figure PCTCN2018072351-appb-000002
实施例7：
采用的支化聚乙烯编号为PER-1和PER-7。
加工步骤如下:
(1)橡胶混炼：设置密炼机温度为90℃，转子转速为50转/分钟，加入80份PER-7和20份PER-1预压混炼90秒；然后加入10份氧化锌、1份硬脂酸和1份防老剂2,2,4-三甲基-1,2-二氢化喹啉聚合体(RD)，混炼2分钟；然后在胶料中加入30份甲基丙烯酸锌、50份炭黑N330和15份石蜡油SUNPAR 2280，混炼3分钟；最后加入4份交联剂过氧化二异丙苯(DCP)、1.5份三烯丙基异氰脲酸酯(TAIC)和0.3份硫磺，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：
采用的支化聚乙烯编号为PER-8。
加工步骤如下:
(1)橡胶混炼：设置密炼机温度为90℃，转子转速为50转/分钟，加入80份三元乙丙橡胶和20份PER-8预压混炼90秒；然后加入10份氧化锌、1份硬脂酸、1份防老剂RD 和1份2-巯基苯并咪唑(MB)，混炼2分钟；然后在胶料中加入30份甲基丙烯酸锌、60份炭黑N330和20份石蜡油SUNPAR 2280，混炼3分钟；最后加入3份交联剂过氧化二异丙苯(DCP)、1份三烯丙基异氰脲酸酯(TAIC)和9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9：
采用的支化聚乙烯编号为PER-7。
加工步骤如下:
(1)橡胶混炼：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、50份三元乙丙橡胶和30份PER-7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1份N-4(苯胺基苯基)马来酰亚胺(MC)，混炼2分钟；然后在胶料中加入20份甲基丙烯酸锌、50份炭黑N330和10份液态聚异丁烯(数均分子量为1200)，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N,N’-间苯撑双马来酰亚胺(HVA-2)，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：
采用的支化聚乙烯编号为PER-3。
加工步骤如下:
(1)橡胶混炼：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PER-3预压混炼90秒；然后加入20份氧化锌、2份硬脂酸、1份防老剂RD和1份2-巯基苯并咪唑(MB)，混炼2分钟；然后在胶料中加入30份甲基丙烯酸锌、80份炭黑N330和20份石蜡油SUNPAR 2280，混炼3分钟；最后加入1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11：
采用的支化聚乙烯编号为PER-5。
加工步骤如下:
(1)橡胶混炼：设置密炼机温度为90℃，转子转速为50转/分钟，加入100份PER-5预压混炼90秒；然后加入15份氧化锌、2份硬脂酸、1份防老剂RD，混炼2分钟；然后在胶料中加入25份甲基丙烯酸锌、60份炭黑N330和15份石蜡油SUNPAR 2280，混炼3分钟；最后加入4份交联剂过氧化二异丙苯(DCP)和1.5份N,N’-间苯撑双马来酰亚胺(HVA-2)，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：
采用的支化聚乙烯编号为PER-2和PER-6。
加工步骤如下:
(1)橡胶混炼：设置密炼机温度为90℃，转子转速为50转/分钟，加入30份PER-2和70份PER-6预压混炼90秒；然后加入10份氧化锌、2份硬脂酸、1份防老剂RD，混炼2分钟；然后在胶料中加入15份甲基丙烯酸锌、50份炭黑N330和15份石蜡油SUNPAR 2280，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7～12的测试数据如下：
Figure PCTCN2018072351-appb-000003
Figure PCTCN2018072351-appb-000004
实施例13：
一种使用本发明提供的橡胶组合物生产的浅色纯胶管，其生产方法包含的步骤如下：
(1)橡胶混炼：
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；然后在胶料中加入35份甲基丙烯酸锌，混炼4分钟；最后加入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)挤出及成型：
采用60mm冷喂料挤出机，配备T型机头，在90℃下，在芯棒上挤出胶层，得到管坯，经硫化工艺处理后冷却、脱芯、修整、检验、入库，其中，硫化工艺为160℃蒸汽硫化，蒸汽压力0.6MPa，时间30分钟。
实施例14：
一种使用本发明提供的橡胶组合物生产的绝缘手套，其生产方法包含的步骤如下：
(1)橡胶混炼：
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-4预压混炼90秒；然后加入6份氧化锌、1份硬脂酸和8份甲基丙烯酸锌，混炼2分钟；然后在胶料中加入50份炭黑N550，混炼3分钟；最后加入4份交联剂过氧化二异丙苯(DCP)、1份三烯丙基异氰脲酸酯(TAIC)和0.3份硫磺，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)裁片：将胶片停放一段时间后，按模具型腔尺寸大小进行裁片成型；
(3)在模具内涂上脱模剂并预热至150℃，然后将三块步骤2裁剪得到的胶片放入模具中，并将模具放入硫化机上，加压至20MPa，保温保压硫化5min，接着取出模具，冷却至环境温度后开模，最后将开模后得到的绝缘手套干燥24h，即得绝缘手套。
实施例15：
一种使用本发明提供的橡胶组合物作为工作面覆盖胶的耐高温输送带，其生产方法包含的步骤如下：
本实施例的耐高温输送带在工作面覆盖胶与非工作面覆盖胶之间设有带芯抗拉体帆布，通过成型和硫化工艺使它们成为一个牢固的整体。
本实施例所述的工作面覆盖胶的组成和配比按份数计：
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PER-5预压混炼90秒；然后加入15份氧化锌、2份硬脂酸、1份防老剂RD，混炼2分钟；然后在胶料中加入25份甲基丙烯酸锌、60份炭黑N330和15份石蜡油SUNPAR 2280，混炼3分钟；最后加入4份交联剂过氧化二异丙苯(DCP)和1.5份N,N’-间苯撑双马来酰亚胺(HVA-2)，混炼2分钟后排胶。
压延工艺：将以上混炼胶放到螺杆挤出机中热炼，然后供到压延机中进行压延出片待用，压延出片时胶片厚度控制在4.5～12mm。出好后保温待用。
成型工艺：胶片在成型机上和预先成型好的贴胶帆布带坯紧密地贴合在一起成型为耐高温输送带的带坯，然后卷起4小时后再硫化。
硫化工艺：将上述成型好的输送带带坯放到平板硫化机中进行分段硫化，每板硫化时间为25分钟，硫化压力为3Kg/cm 2，硫化温度为160℃。
修整、检验：硫化结束后进行修整、检验，然后包装入库。
实施例16：
一种使用本发明提供的橡胶组合物作为粘合层的耐高温输送带，其生产方法包含的步骤如下：
本实施例的耐高温输送带在工作面覆盖胶与非工作面覆盖胶之间设有贴胶帆布作为抗拉层，通过成型和硫化工艺使它们成为一个牢固的整体。
本实施例所述的贴胶帆布用粘合层橡胶的组成和配比按份数计：
(1)橡胶混炼：
设置密炼机温度为90℃，转子转速为50转/分钟，加入100份PER-4预压混炼90秒；然后加入5份纳米氧化锌、1份硬脂酸、1份防老剂RD和1份N-4(苯胺基苯基)马来酰亚胺(MC)，混炼2分钟；然后在胶料中加入15份甲基丙烯酸锌、20份炭黑N330、30份高分散白炭黑和15份液态聚异丁烯(数均分子量为1200)，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N,N’-间苯撑双马来酰亚胺(HVA-2)，混炼2分钟后排胶，将混炼胶在辊温为60℃的开炼机上薄通，下片，停放20小时；
(2)贴胶：
混炼胶和布层在常温下经过双辊或四辊压延机完成粘合胶与帆布层的贴合，得到贴胶帆布带坯；
(3)成型工艺：
将成型好的贴胶帆布带坯与覆盖胶胶片在成型机上紧密地贴合在一起成型为耐高温输送带的带坯，然后卷起4小时后再硫化。
(4)硫化工艺：
将上述成型好的输送带带坯放到平板硫化机中进行分段硫化，每板硫化时间为25分钟，硫化压力为3Kg/cm2，硫化温度为160℃。
(5)修整、检验：
硫化结束后进行修整、检验，然后包装入库。
实施例17：
一种使用本发明提供的橡胶组合物生产的绝缘手套，其生产方法包含的步骤如下：
(1)橡胶混炼：
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-11预压混炼90秒；然后加入6份氧化锌、1份硬脂酸和8份甲基丙烯酸锌，混炼2分钟；然后在胶料中加入50份炭黑N550和10份石蜡油，混炼3分钟；最后加入4份交联剂过氧化二异丙苯(DCP)、1份三烯丙基异氰脲酸酯(TAIC)和0.3份硫磺，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。
其余生产工艺与实施例14一致。将本实施例的橡胶组合物混炼胶在经模压制成测试样品，测试性能如下：
硬度：66；拉伸强度：25.9MPa；断裂伸长率：512％；撕裂强度61N/mm；50KV工频耐压1分钟无击穿无闪络。
实施例18：
一种使用本发明提供的橡胶组合物作为工作面覆盖胶的耐高温输送带，所述的工作面覆盖胶的组成和混炼工艺如下：
设置密炼机温度为90℃，转子转速为50转/分钟，加入100份PER-12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、1份防老剂MB、2份古马隆树脂和2份RX-80树脂，混炼2分钟；然后在胶料中加入25份甲基丙烯酸锌、60份炭黑N330和20份石蜡油SUNPAR 2280，混炼3分钟；最后加入4份交联剂过氧化二异丙苯(DCP)和1.5份N,N’-间苯撑双马来酰亚胺(HVA-2)，混炼2分钟后排胶。其余加工工艺与实施例15一致。
实施例19：
一种使用本发明提供的橡胶组合物作为粘合层橡胶的耐高温输送带，所述的贴胶帆布用粘合层橡胶的组成和混炼工艺如下：
设置密炼机温度为90℃，转子转速为50转/分钟，加入100份PER-12预压混炼90秒；然后加入5份纳米氧化锌、1份硬脂酸、1份防老剂RD和2份改性烷基酚醛树脂TKM-K，混炼2分钟；然后在胶料中加入15份甲基丙烯酸锌、20份炭黑N330、30份高分散白炭黑、2份粘合剂RS和15份石蜡油，混炼3分钟；最后加入2份粘合剂RH、3份交联剂过氧化二异丙苯(DCP)和1份N,N’-间苯撑双马来酰亚胺(HVA-2)，混炼2分钟后排胶，将混炼胶在辊温为60℃的开炼机上薄通，下片，停放20小时；
实施例20：
一种橡胶金属减震件的加工步骤如下：
(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PER-10和15份石蜡油SUNPAR2280预压混炼90秒；然后加入5份氧化锌、1份硬脂酸、2份粘合剂RS、2份聚乙二醇PEG4000和1份防老剂RD，混炼2分钟；然后加入60份炭黑N330、20份白炭黑、10份甲基丙烯酸锌和15份石蜡油SUNPAR2280，混炼3分钟；然后加入3份粘合剂RA-65，混炼1分钟；然后加入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份硫磺，混炼2分钟后排胶。将混炼胶在开炼机上开炼后下片，停放待用。
(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。
本实施例的减震件可用于发动机和排气管等高温部位。

Claims (21)

  1. 一种橡胶组合物，其特征在于，所述橡胶组合物包括：橡胶基体和必要组分，所述橡胶基体包含：支化聚乙烯的含量为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；以100重量份橡胶基体计，所述必要组分包含：交联剂1～10份，不饱和羧酸金属盐5～50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所述的橡胶组合物，其特征在于，以100重量份单位计，所述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；所述支化聚乙烯为乙烯均聚物，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6～10。
  3. 根据权利要求1所述的一种橡胶组合物，其特征在于，所述交联剂包含过氧化物交联剂和硫磺中的至少一种，所述过氧化物交联剂包含二叔丁基过氧化物、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。
  4. 根据权利要求1所述的一种橡胶组合物，其特征在于，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。
  5. 根据权利要求1所述的一种橡胶组合物，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，所述辅助成分按重量份计，其包含：除不饱和羧酸金属盐以外的助交联剂0.2～10份，补强填充剂10～150份，增塑剂5～80份，稳定剂1～3份，金属氧化物2～20份，硫化促进剂0～3份。
  6. 根据权利要求5所述的一种橡胶组合物，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、N,N’-间苯撑双马来酰亚胺、N,N’-双亚糠基丙酮、1,2-聚丁二烯和硫磺中的至少一种。
  7. 根据权利要求5所述的一种橡胶组合物，其特征在于，所述补强填充剂包含炭黑、白炭黑、碳酸钙、滑石粉、煅烧陶土、碳酸镁中的至少一种。
  8. 根据权利要求5所述的一种橡胶组合物，其特征在于，所述增塑剂包含松焦油、机油、环烷油、石蜡油、古马隆、RX-80、硬脂酸、石蜡、液态乙丙橡胶、液态聚异丁烯中的至少一种。
  9. 根据权利要求5所述的一种橡胶组合物，其特征在于，所述稳定剂包含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)、N-4(苯胺基苯基)马来酰亚胺(MC)中的至少一种。
  10. 根据权利要求5所述的一种橡胶组合物，其特征在于，所述 金属氧化物包含氧化锌、氧化镁、氧化钙的至少一种。
  11. 根据权利要求5所述的一种橡胶组合物，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，其特征在于，该加工方法包括以下步骤：
    (1)橡胶混炼：首先将除交联体系以外的橡胶组合物按重量份依次添加到密炼机中进行混炼，然后加入交联体系经混炼均匀后排出，得到混炼胶，将混炼胶在开炼机上薄通后下片，停放等待硫化，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：将混炼胶填入模具的模腔，在平板硫化机上加压硫化后，脱模即可得到硫化橡胶。
  13. 一种绝缘手套，其特征在于，绝缘手套所用胶料包含权利要求1～11任一所述橡胶组合物.
  14. 一种生产权利要求13所述的绝缘手套的方法，其特征在于，生产方法包含的步骤如下：
    (1)橡胶混炼：首先将除交联体系以外的橡胶组合物按重量份依次添加到密炼机中进行混炼，然后加入交联体系经混炼均匀后排出，得到混炼胶。将混炼胶在开炼机上薄通后下片，停放等待硫化， 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)裁片：将胶片停放一段时间后，按模具型腔尺寸大小进行裁片成型；
    (3)硫化：将成型的胶片填入模具的模腔，将模具放在平板硫化机上加压硫化，冷却脱模，修边即可得到橡胶绝缘手套。
  15. 一种胶管，其特征在于，所用胶料包含权利要求1～11中任一所述橡胶组合物。
  16. 一种生产权利要求15所述胶管的方法，其特征在于，该生产方法包括以下步骤：
    (1)橡胶混炼：首先将除交联体系以外的橡胶组合物按重量份依次添加到密炼机中进行混炼，然后加入交联体系经混炼均匀后排出，得到混炼胶，将混炼胶在开炼机上薄通后下片，停放等待硫化，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)挤出及成型：采用冷喂料挤出机，在芯棒上挤出胶层，得到管坯，经蒸汽硫化后冷却，脱芯，修整、检验、入库，得到胶管。
  17. 一种输送带，其特征在于，其工作面覆盖胶和非工作面覆盖胶中的至少一层包含权利要求1～11中任一所述橡胶组合物。
  18. 一种生产权利要求17所述输送带的方法，其特征在于，该生产方法包括以下步骤：
    (1)橡胶混炼工艺：首先将除交联体系以外的橡胶组合物按重 量份依次添加到密炼机中进行混炼，然后加入交联体系经混炼均匀后排出，得到混炼胶，将混炼胶在开炼机上薄通后下片，停放等待硫化，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)压延工艺：将以上混炼胶放到螺杆挤出机中热炼，然后供到压延机中进行压延出片保温待用；
    (3)成型工艺：胶片在成型机上和预先成型好的贴胶帆布带坯紧密地贴合在一起成型为耐高温输送带的带坯，然后卷起停放等待硫化；
    (4)将上述成型好的输送带带坯放到平板硫化机中进行分段硫化；
    (5)硫化结束后进行修整、检验，然后包装入库。
  19. 一种输送带，其特征在于，输送带的粘合层所用橡胶包含权利要求1～11中任一所述橡胶组合物。
  20. 一种生产权利要求19所述输送带的方法，其特征在于，该生产方法包括以下步骤：
    (1)橡胶混炼工艺：首先将除交联体系以外的橡胶组合物按重量份依次添加到密炼机中进行混炼，然后加入交联体系经混炼均匀后排出，得到混炼胶，将混炼胶在开炼机上薄通后下片，停放等待硫化，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)贴胶：混炼胶和布层在常温下经过双辊或四辊压延机完成 粘合胶与帆布层的贴合，得到贴胶帆布带坯；
    (3)成型工艺：将成型好的贴胶帆布带坯与覆盖胶胶片在成型机上紧密地贴合在一起成型为耐高温输送带的带坯，卷起停放后再硫化；
    (4)将上述成型好的输送带带坯放到平板硫化机中进行分段硫化；
    (5)硫化后进行修整、检验，然后包装入库。
  21. 一种减震件，其特征在于，减震件为橡胶减震件或橡胶金属复合减震件，所用橡胶包含权利要求1～11中任一所述橡胶组合物。
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109206820A (zh) * 2018-08-13 2019-01-15 中铁二院工程集团有限责任公司 一种耐老化三元乙丙橡胶密封材料及其制备方法
WO2020039536A1 (en) * 2018-08-23 2020-02-27 Compagnie Generale Des Etablissements Michelin A rubber composition
CN114149648A (zh) * 2021-12-18 2022-03-08 陕西特种橡胶制品有限公司 一种核电厂密封用耐辐照氟橡胶材料及制备方法
CN114539680A (zh) * 2022-02-19 2022-05-27 陈溪水 一种耐高温橡胶制品的生产工艺
CN115322455A (zh) * 2022-09-02 2022-11-11 湖北工业大学 一种改性涤纶短纤维复合天然橡胶减振材料及其制备方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6103658A (en) * 1997-03-10 2000-08-15 Eastman Chemical Company Olefin polymerization catalysts containing group 8-10 transition metals, processes employing such catalysts and polymers obtained therefrom
CN101250305A (zh) * 2008-04-07 2008-08-27 北京化工大学 一种高耐热输送带覆盖层用橡胶复合材料
CN102337092A (zh) * 2011-07-22 2012-02-01 北京化工大学 一种耐高温帆布输送带用粘合层橡胶材料及其使用方法
CN103980596A (zh) * 2014-05-13 2014-08-13 浙江大学 一种聚乙烯橡胶及其加工方法
CN104877225A (zh) * 2015-06-20 2015-09-02 浙江大学 一种气密层材料的制备方法及其原料配方

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6103658A (en) * 1997-03-10 2000-08-15 Eastman Chemical Company Olefin polymerization catalysts containing group 8-10 transition metals, processes employing such catalysts and polymers obtained therefrom
CN101250305A (zh) * 2008-04-07 2008-08-27 北京化工大学 一种高耐热输送带覆盖层用橡胶复合材料
CN102337092A (zh) * 2011-07-22 2012-02-01 北京化工大学 一种耐高温帆布输送带用粘合层橡胶材料及其使用方法
CN103980596A (zh) * 2014-05-13 2014-08-13 浙江大学 一种聚乙烯橡胶及其加工方法
CN104877225A (zh) * 2015-06-20 2015-09-02 浙江大学 一种气密层材料的制备方法及其原料配方

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109206820A (zh) * 2018-08-13 2019-01-15 中铁二院工程集团有限责任公司 一种耐老化三元乙丙橡胶密封材料及其制备方法
CN109206820B (zh) * 2018-08-13 2020-08-04 中铁二院工程集团有限责任公司 一种耐老化三元乙丙橡胶密封材料及其制备方法
WO2020039536A1 (en) * 2018-08-23 2020-02-27 Compagnie Generale Des Etablissements Michelin A rubber composition
CN114149648A (zh) * 2021-12-18 2022-03-08 陕西特种橡胶制品有限公司 一种核电厂密封用耐辐照氟橡胶材料及制备方法
CN114149648B (zh) * 2021-12-18 2023-08-29 陕西特种橡胶制品有限公司 一种核电厂密封用耐辐照氟橡胶材料及制备方法
CN114539680A (zh) * 2022-02-19 2022-05-27 陈溪水 一种耐高温橡胶制品的生产工艺
CN115322455A (zh) * 2022-09-02 2022-11-11 湖北工业大学 一种改性涤纶短纤维复合天然橡胶减振材料及其制备方法
CN115322455B (zh) * 2022-09-02 2023-09-15 湖北工业大学 一种改性涤纶短纤维复合天然橡胶减振材料及其制备方法

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