WO2018130199A1 - Composite de caoutchouc, procédé de traitement, tube de caoutchouc mettant en application un composite et procédé de fabrication - Google Patents

Composite de caoutchouc, procédé de traitement, tube de caoutchouc mettant en application un composite et procédé de fabrication Download PDF

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WO2018130199A1
WO2018130199A1 PCT/CN2018/072374 CN2018072374W WO2018130199A1 WO 2018130199 A1 WO2018130199 A1 WO 2018130199A1 CN 2018072374 W CN2018072374 W CN 2018072374W WO 2018130199 A1 WO2018130199 A1 WO 2018130199A1
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Prior art keywords
rubber
parts
hose
layer
vulcanization
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PCT/CN2018/072374
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English (en)
Chinese (zh)
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 CN201810020852.5A external-priority patent/CN108299745B/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 JP2019559147A priority Critical patent/JP7157464B2/ja
Priority to US16/477,518 priority patent/US12060476B2/en
Publication of WO2018130199A1 publication Critical patent/WO2018130199A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
    • B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/06—Sulfur
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/14—Peroxides
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/45—Heterocyclic compounds having sulfur in the ring
    • C08K5/46—Heterocyclic compounds having sulfur in the ring with oxygen or nitrogen in the ring
    • C08K5/47—Thiazoles
    • 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
    • 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
    • C08L23/08—Copolymers of ethene
    • 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
    • C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
    • F16L11/00—Hoses, i.e. flexible pipes
    • F16L11/04—Hoses, i.e. flexible pipes made of rubber or flexible plastics

Definitions

  • the present invention relates to the field of rubber technology, and in particular to a rubber composition and a processing method for obtaining the rubber composition, and to a hose for applying the rubber composition, and a method for producing the product.
  • Ethylene-propylene rubber has a wide range of applications in the field of hoses.
  • hose applications such as automotive radiator hoses and brake hoses
  • the hose vulcanization process has been adopted from the original.
  • Sulfur vulcanization gradually tended to use peroxide vulcanization, in order to obtain better heat resistance and compression set resistance.
  • the tear strength of the rubber after peroxide vulcanization is lower than sulfur vulcanization, which causes the hose to cause more waste in the production process, reduce production efficiency and increase production cost.
  • 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 rubber composition, and its application and production method in a hose, using a branched polyethylene having a branching degree of not less than 50 branches/1000 carbons.
  • the new rubber composition can be used as a rubber inner layer and/or outer rubber layer compound, or as a pure rubber compound.
  • the rubber matrix of the rubber composition of the present invention may be composed entirely of branched polyethylene, or may be composed of branched polyethylene and ethylene propylene rubber, composed of branched polyethylene and ethylene propylene diene rubber, and branched polycondensation.
  • Ethylene is composed of ethylene propylene diene rubber and ethylene propylene diene monomer.
  • the combination of branched polyethylene and ethylene propylene diene rubber can improve the mechanical properties and processing properties of ethylene propylene diene rubber.
  • the combination of branched polyethylene and EPDM rubber can improve the heat aging resistance of EPDM rubber.
  • mechanical properties, a small amount of diene in EPDM plays the same role as an intrinsic co-crosslinker in peroxide vulcanization.
  • the technical solution adopted by the present invention relates to a rubber composition
  • a rubber matrix comprising, by weight, a rubber matrix and an essential component
  • the rubber matrix comprises: the content of the branched polyethylene is a: 0 ⁇ a ⁇ 100 parts; the sum of the contents of the binary ethylene propylene rubber and the ethylene propylene diene rubber b: 0 ⁇ b ⁇ 100 parts; and the necessary components include: 1.5 to 8 parts of the crosslinking agent, based on 100 parts by weight of the rubber substrate, 50 to 200 parts of the reinforcing filler and 10 to 100 parts of the 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.
  • 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. Therefore, the technical solution of the present invention can provide a rubber compound and a hose which have both good heat resistance and 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 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 60 to 130 branches/1000 carbons, a weight average molecular weight of 66,000 to 518,000, and a Mooney viscosity of ML (1+4). ) 125 ° C is 6 ⁇ 102.
  • a further preferred technical solution for the branched polyethylene is that the degree of branching is 70 to 116 branches/1000 carbons, the weight average molecular weight is 201,000 to 436,000, and the Mooney viscosity ML (1+4) is 125 ° C. ⁇ 101.
  • a further preferred technical solution for the branched polyethylene is that the degree of branching is from 80 to 105 branches/1000 carbons, the weight average molecular weight is from 250,000 to 400,000, and the Mooney viscosity ML (1+4) is 40 °C. ⁇ 95.
  • a further preferred technical solution for the branched polyethylene is that the degree of branching is 80 to 105 branches/1000 carbons, the weight average molecular weight is 268,000 to 356,000, and the Mooney viscosity ML (1+4) is 125 ° C. ⁇ 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-norbornate Alkene, 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-hexad
  • 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 comprising di-tert-butyl peroxide, dicumyl peroxide, and tert-butyl Kecumyl peroxide, 1,1-di-tert-butyl peroxide-3,3,5-trimethylcyclohexane, 2,5-dimethyl-2,5-di(tert-butyl Oxidation) hexane, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne-3, bis(tert-butylperoxyisopropyl)benzene, 2,5-dimethyl At least one of -2,5-bis(benzoyl peroxy)hexane, tert-butyl peroxybenzoate, t-butylperoxy-2-ethylhexyl carbonate, more preferably, a crosslink
  • the reinforcing filler comprises at least one of carbon black, calcium carbonate, calcined clay, magnesium silicate, aluminum silicate, magnesium carbonate, talc, diatomaceous earth, preferably, in 100 parts by weight.
  • the rubber base meter further contains 40 to 150 parts by weight of carbon black, and the carbon black is used as a rubber reinforcing agent to greatly improve the mechanical strength of the rubber compound.
  • the talc powder herein may be more preferably a talc powder treated with a vinyl silane coupling agent.
  • the plasticizer comprises at least one of stearic acid, pine tar, motor oil, naphthenic oil, paraffin oil, coumarone, RX-80, paraffin, liquid polyisobutylene, and dioctyl sebacate.
  • stearic acid can also act as an active agent in a system mainly based on sulfur vulcanization, and can form a soluble salt with some metal oxides, thereby increasing the activation effect of the metal oxide on the promoter.
  • 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
  • the auxiliary component comprises: 0.2 to 8 parts of a co-crosslinking agent, 2 to 15 parts of a metal oxide, and 1 to 3 parts of a stabilizer, based on 100 parts by weight of the rubber matrix. 1 to 5 parts of polyethylene glycol and 0 to 3 parts of vulcanization accelerator.
  • the co-crosslinking agent comprises triallyl cyanurate, triallyl isocyanurate, ethylene glycol dimethacrylate, ethyl dimethacrylate, dimethacrylate Triethylene diester, triallyl trimellitate, trimethylolpropane trimethacrylate, ethylene glycol dimethacrylate, N, N'-m-phenylene bismaleimide, N At least one of N'-bis-indenyl acetonone, 1,2-polybutadiene, a metal salt of an unsaturated carboxylic acid, and sulfur.
  • the unsaturated carboxylic acid metal salt contains at least one of zinc acrylate, zinc methacrylate, magnesium methacrylate, calcium methacrylate, and aluminum methacrylate.
  • the metal oxide comprises at least one of zinc oxide, magnesium oxide, and calcium oxide.
  • the stabilizer comprises 2,2,4-trimethyl-1,2-dihydroquinoline polymer (RD), 6-ethoxy-2,2,4-trimethyl-1 At least one of 2-dihydroquinoline (AW) and 2-mercaptobenzimidazole (MB).
  • the polyethylene glycol comprises at least one of polyethylene glycol having a molecular weight of 2000, 3400, and 4000.
  • the vulcanization accelerator comprises 2-thiol benzothiazole, dibenzothiazyl disulfide, tetramethyl thiuram monosulfide, tetramethyl thiuram disulfide, tetrazyl disulfide Kethiram, zinc di-n-butyldithiocarbamate, N-cyclohexyl-2-benzothiazolyl sulfenamide, N,N-dicyclohexyl-2-benzothiazolyl sulfenamide, double horse At least one of imide and ethylene thiourea.
  • 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, and the vulcanized rubber may also be simply referred to as a vulcanizate.
  • the present invention also provides a method of processing the above rubber composition, the processing method comprising the steps of:
  • 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 rubber compound is filled into the cavity of the mold, heated and pressurized by vulcanization on the flat vulcanizer, and then the mold is released to obtain the vulcanized rubber.
  • further Vulcanization is carried out using a two-stage vulcanization process
  • the present invention also provides a pure rubber hose, the rubber compound comprising the above rubber composition.
  • a method for producing the above pure rubber hose comprising the following steps:
  • 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. After the rubber compound is thinned on the open mill, the film is to be vulcanized, the crosslinking system comprises a crosslinking agent, and at least one of a crosslinking agent and a vulcanization accelerator may be further included;
  • 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 invention also provides an automobile radiator hose, wherein at least one of the inner rubber layer and the outer rubber layer comprises the above rubber composition.
  • the invention also provides a method for producing a car radiator hose, comprising the following steps:
  • Rubber kneading setting the appropriate temperature of the internal mixer and the rotor rotation speed, and adding the rubber composition other than the crosslinking system to the internal mixer in order of mixing, and then kneading, and then adding the crosslinking system to be kneaded. After uniformly discharging, the mixture is obtained, the mixture is thinned on the open mill, and then the sheet is to be vulcanized, the crosslinking system contains a crosslinking agent, and at least one of a crosslinking agent and a vulcanization accelerator may be further included. Species
  • Vulcanization The mandrel is inserted into the tube blank, cooled by steam vulcanization, de-core, trimmed, inspected, and stored in the warehouse to obtain a car radiator hose.
  • the present invention also provides an air conditioning hose, wherein at least one of an inner rubber layer and an outer rubber layer comprises the above rubber composition.
  • the invention also provides a method for producing an air conditioning hose, comprising the following steps:
  • Rubber kneading setting the appropriate temperature of the internal mixer and the rotor rotation speed, and adding the rubber composition other than the crosslinking system to the internal mixer in order of mixing, and then kneading, and then adding the crosslinking system to be kneaded. After uniform discharge, the mixture is obtained, and the rubber mixture is thinned on the open mill and then placed under 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;
  • Vulcanization vulcanization, disintegration, core removal and truncation. Get the air conditioning hose.
  • the rubber compound used in the outer rubber layer of the radiator hose or the air-conditioning hose may further comprise a binder to enhance the bonding property with the fiber reinforced layer.
  • the component of the binder may be a polyisocyanate salt, and the amount thereof is preferably from 1 to 3 parts by weight.
  • the present invention also provides a rubber hose assembly in which at least one of an inner rubber layer and an outer rubber layer comprises the above rubber composition.
  • the present invention also provides a method of producing a rubber hose assembly comprising the steps of:
  • Tube blank forming the inner rubber layer is extruded by a cold feed extruder, and the aramid fiber layer is knitted on the outer surface of the inner rubber layer, and finally the outer rubber compound is extruded through an outer rubber layer extruder. And coating on the outer surface of the aramid fiber layer to form a tube blank;
  • the present invention has the beneficial effects that the rubber composition containing the branched polyethylene has higher tensile strength and tearing properties under the same or similar conditions of other formulation ingredients.
  • the production of a hose from such a rubber composition can significantly reduce the probability of tearing of the hose during production and use.
  • its resistance to 150 ° C hot air aging performance is maintained at the same level as the rubber composition of ethylene propylene rubber alone, or a slight advantage, can meet the high temperature use requirements of the current similar radiator hoses and air conditioning hoses.
  • the crosslinking system contains a crosslinking agent, and may further contain at least one of a co-crosslinking agent and a vulcanization accelerator.
  • the ethylene-propylene rubber selected from the rubber base has a Mooney viscosity ML (1+4) of preferably 20 to 50 at 125 ° C and an ethylene content of preferably 45% to 60%.
  • the ethylene propylene rubber used has a Mooney viscosity ML (1+4) of preferably 20 to 100 at 125 ° C, an ethylene content of preferably 55% to 75%, and a third monomer of 5-ethylidene-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;
  • tear performance 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;
  • 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;
  • the positive curing time Tc90 test in accordance with the national standard GB/T16584-1996, in the rotorless vulcanizer, the test temperature is 170 ° 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-7.
  • Rubber mixing set the temperature of the internal mixer to 100 ° C, the rotor speed is 50 rpm, add 90 parts of ethylene propylene diene rubber and 10 parts of branched polyethylene for 90 seconds; add 2 parts of PEG 4000 1 part of antioxidant RD, mixing for 30 seconds; then adding 80 parts of carbon black N550, 20 parts of paraffin oil SUNPAR2280 to the compound, mixing for 3 minutes; finally adding 3 parts of cross-linking agent dicumyl peroxide (DCP) 1 part of the co-crosslinking agent, triallyl isocyanurate (TAIC), was mixed for 2 minutes and then discharged.
  • DCP dicumyl peroxide
  • 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 to 50 rpm, add 85 parts of EPDM rubber and 15 parts of branched polyethylene pre-pressed for 90 seconds; add 2 parts of PEG4000 1 part of antioxidant RD, mixing for 30 seconds; then adding 80 parts of carbon black N550, 30 parts of paraffin oil SUNPAR2280 to the compound, mixing for 3 minutes; finally adding 3 parts of cross-linking agent dicumyl peroxide (DCP) 1 part of the co-crosslinking agent, triallyl isocyanurate (TAIC), after 2 minutes of mixing, the rubber is discharged, and the mixture is thinned on an open mill with a roll temperature of 60 ° C to obtain about 2.5 mm. Thick sheet, parked for 20 hours;
  • DCP dicumyl peroxide
  • TAIC triallyl isocyanurate
  • the branched polyethylene used was numbered PER-4.
  • Rubber mixing set the temperature of the internal mixer to 70 ° C, the rotor speed to 50 rpm, add 70 parts of EPDM rubber and 30 parts of branched polyethylene pre-pressed for 90 seconds; add 2 parts of PEG4000 1 part of antioxidant RD, mixing for 30 seconds; then adding 80 parts of carbon black N550, 30 parts of paraffin oil SUNPAR2280 to the compound, mixing for 3 minutes; finally adding 3 parts of cross-linking agent dicumyl peroxide (DCP) 1 part of the co-crosslinking agent, triallyl isocyanurate (TAIC), was mixed for 2 minutes and then discharged.
  • DCP dicumyl peroxide
  • TAIC triallyl isocyanurate
  • 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 monomer and 50 parts of branched polyethylene for 90 seconds; add 2 parts of PEG 4000 1 part of antioxidant RD, mixing for 30 seconds; then adding 80 parts of carbon black N550, 30 parts of paraffin oil SUNPAR2280 to the compound, mixing for 3 minutes; finally adding 3 parts of cross-linking agent dicumyl peroxide (DCP) 1 part of the co-crosslinking agent, triallyl isocyanurate (TAIC), after 2 minutes of mixing, the rubber is discharged, and the mixture is thinned on an open mill with a roll temperature of 60 ° C to obtain about 2.5 mm. Thick sheet, parked for 20 hours;
  • DCP dicumyl peroxide
  • TAIC triallyl isocyanurate
  • 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 20 parts of ethylene propylene diene rubber, 30 parts of ethylene propylene diene monomer and 50 parts of prepolymerized polyethylene. 90 seconds; add 2 parts of PEG4000, 1 part of antioxidant RD, mix for 30 seconds; then add 100 parts of carbon black N550, 30 parts of paraffin oil SUNPAR2280 in the compound, mix for 3 minutes; finally add 3 parts of crosslinker Dicumyl peroxide (DCP), 1 part of the cross-linking agent, triallyl isocyanurate (TAIC), after 2 minutes of mixing, the rubber is discharged, and the mixture is melted at a roll temperature of 60 ° C. Thin on the machine, get a sheet thickness of about 2.5mm, park for 20 hours;
  • DCP crosslinker Dicumyl peroxide
  • TAIC triallyl isocyanurate
  • the branched polyethylene used was numbered PER-5.
  • Rubber mixing set the temperature of the internal mixer to 90 ° C, the rotor speed to 50 rpm, add 30 parts of EPDM rubber and 70 parts of branched polyethylene pre-pressed for 90 seconds; add 2 parts of PEG4000 2 parts of anti-aging agent RD, mixing for 30 seconds; then adding 170 parts of carbon black N550, 100 parts of paraffin oil SUNPAR2280 to the compound, mixing for 3 minutes; finally adding 8 parts of cross-linking agent dicumyl peroxide (DCP) 3 parts of the co-crosslinking agent, triallyl isocyanurate (TAIC), was mixed for 2 minutes and then discharged.
  • DCP dicumyl peroxide
  • TAIC triallyl isocyanurate
  • 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 branched polyethylene pre-pressed and kneaded for 90 seconds; add 2 parts of PEG4000, 1 part of antioxidant RD, mix Refining for 30 seconds; then adding 80 parts of carbon black N550, 20 parts of paraffin oil SUNPAR 2280 to the compound, mixing for 3 minutes; finally adding 3 parts of cross-linking agent dicumyl peroxide (DCP), 1 part of cross-linking agent
  • DCP dicumyl peroxide
  • TAIC triallyl isocyanurate
  • Rubber mixing rubber mixing: set the temperature of the internal mixer to 90 ° C, the rotor speed is 50 rpm, add 100 parts of EPDM rubber for 90 seconds, and add 2 parts of PEG 4000, 1 part.
  • Anti-aging agent RD mixing for 30 seconds; then adding 80 parts of carbon black N550 and 20 parts of paraffin oil SUNPAR2280 to the compound, mixing for 3 minutes; finally adding 3 parts of cross-linking agent dicumyl peroxide (DCP), 1
  • DCP dicumyl peroxide
  • the cross-linking agent, triallyl isocyanurate (TAIC) was mixed for 2 minutes and then discharged.
  • 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 for 20 hours.
  • the branched polyethylenes used were numbered PER-3 and PER-5.
  • Rubber mixing set the temperature of the internal mixer to 90 ° C, the rotor speed is 50 rpm, add 30 parts of PER-3 and 70 parts of PER-5 pre-pressure mixing for 90 seconds; add 5 parts of zinc oxide, 1 Part of stearic acid, 2 parts of PEG4000, 1 part of antioxidant RD, kneaded for 30 seconds; then add 100 parts of carbon black N550, 100 parts of calcium carbonate and 80 parts of paraffin oil SUNPAR2280 to the compound, knead for 3 minutes; 4 parts of cross-linking agent dicumyl peroxide (DCP), 2 parts of the cross-linking agent triallyl isocyanurate (TAIC), and the mixture was mixed for 2 minutes and then discharged.
  • the kneaded rubber was thinly passed on an open mill with a roll temperature of 60 ° C to obtain a sheet having a thickness of about 2.5 mm, and was left for 20 hours;
  • the branched polyethylene used was numbered PER-4.
  • Rubber mixing set the temperature of the internal mixer to 60 ° C, the rotor speed to 50 rpm, add 30 parts of ethylene propylene diene rubber and 70 parts of branched polyethylene pre-pressure mixing for 90 seconds; add 5 parts of oxidation Zinc, 1 part stearic acid, 2 parts PEG4000, 1 part antioxidant RD, kneaded for 30 seconds; then add 30 parts carbon black N550, 50 parts carbon black N774, 15 parts paraffin oil SUNPAR2280 in the rubber compound, mix 3 Minutes; finally, 3 parts of cross-linking agent dicumyl peroxide (DCP) and 1 part of cross-linking agent triallyl isocyanurate (TAIC) were added, and after 2 minutes of mixing, the gum was discharged.
  • 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 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 to 50 rpm, add 70 parts of EPDM rubber and 30 parts of branched polyethylene pre-pressed for 90 seconds; add 3 parts of oxidation Zinc, 2 parts PEG4000, 1 part antioxidant RD, kneaded for 30 seconds; then add 50 parts carbon black N550, 10 parts paraffin oil SUNPAR2280 in the rubber compound, mix for 3 minutes; finally add 1 part cross-linking agent peroxide Cumene (DCP), 0.3 parts of co-crosslinker triallyl isocyanurate (TAIC), 0.5 part of crosslinker sulfur, 1 part of N-cyclohexyl-2-benzothiazole sulfenamide ( CZ) and 0.8 parts of tetramethylthiuram disulfide (TMTD), which were mixed for 2 minutes and then discharged.
  • the kneaded rubber was thinly passed on an open mill with a roll temperature of 60 ° C to obtain a sheet having
  • the branched polyethylenes used were numbered PER-2 and PER-5.
  • Rubber mixing set the temperature of the internal mixer to 90 ° C, the rotor speed is 50 rpm, add 20 parts of PER-2 and 80 parts of PER-5 pre-pressure mixing for 90 seconds; add 10 parts of zinc oxide, 1 a portion of stearic acid, 2 parts of PEG4000, 1 part of antioxidant RD, kneaded for 30 seconds; then add 40 parts of carbon black N550, 60 parts of carbon black 774, 20 parts of paraffin oil SUNPAR 2280 to the compound, and knead for 3 minutes; 3 parts of cross-linking agent dicumyl peroxide (DCP), 8 parts of co-crosslinking agent 1,2-polybutadiene were added, and the mixture was kneaded for 2 minutes and then discharged.
  • the kneaded rubber was thinly passed on an open mill with a roll temperature of 60 ° C to obtain a sheet having a thickness of about 2.5 mm, and was left for 20 hours;
  • the branched polyethylenes used were numbered PER-1 and PER-5.
  • Rubber mixing set the temperature of the internal mixer to 90 ° C, the rotor speed to 50 rpm, add 10 parts of PER-1 and 90 parts of PER-5 pre-pressing for 90 seconds; add 5 parts of magnesium oxide, 1 Stearic acid, 2 parts PEG4000, 1 part antioxidant RD, kneaded for 30 seconds; then add 100 parts carbon black N550, 30 parts paraffin oil SUNPAR2280 in the rubber compound, mix for 3 minutes; finally add 5 parts crosslinker Dicumyl peroxide (DCP), 2 parts of the cross-linking agent, triallyl isocyanurate (TAIC), was mixed for 2 minutes and then discharged.
  • DCP Dicumyl peroxide
  • TAIC triallyl isocyanurate
  • Rubber mixing set the temperature of the internal mixer to 60 ° C, the rotor speed to 50 rpm, add 100 parts of EPDM rubber for 90 seconds, and add 5 parts of zinc oxide and 1 part of stearic acid. 2 parts of PEG4000, 1 part of antioxidant RD, kneaded for 30 seconds; then add 30 parts of carbon black N550, 50 parts of carbon black N774, 30 parts of paraffin oil SUNPAR2280 in the compound, mix for 3 minutes; finally add 3 parts The mixture of dicumyl peroxide (DCP), 1 part of the cross-linking agent, triallyl isocyanurate (TAIC), was mixed for 2 minutes and then discharged. The kneaded rubber was thinly passed on an open mill with 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 dicumyl peroxide
  • TAIC triallyl isocyanurate
  • Rubber mixing set the temperature of the internal mixer to 90 ° C, the rotor speed is 50 rpm, add 100 parts of branched polyethylene pre-pressed and kneaded for 90 seconds; add 2 parts of PEG4000, 1 part of antioxidant RD, mix Refining for 30 seconds; then adding 80 parts of carbon black N550, 20 parts of paraffin oil SUNPAR 2280 to the compound, mixing for 3 minutes; finally adding 3 parts of cross-linking agent dicumyl peroxide (DCP), 1 part of cross-linking agent Triallyl isocyanurate (TAIC), after 2 minutes of mixing, the gum was discharged. The mixture is thinned on the open mill and then placed on the sheet to be vulcanized.
  • DCP dicumyl peroxide
  • TAIC cross-linking agent Triallyl isocyanurate
  • Vulcanization The mandrel is inserted into the tube blank, vulcanized by high temperature steam, the temperature is 165 ° C, the steam pressure is 1 MPa, and after vulcanization for 25 minutes, it is cooled, cored, trimmed, inspected, and stored in the warehouse to obtain a car radiator hose.
  • the rubber composition used for the inner rubber layer was the rubber composition used in Example 7.
  • An air-conditioning hose wherein the rubber composition used for the inner rubber layer is the rubber composition used in the embodiment 9.
  • the production process is as follows:
  • Rubber mixing set the temperature of the internal mixer to 60 ° C, the rotor speed to 50 rpm, add 30 parts of ethylene propylene diene rubber and 70 parts of branched polyethylene pre-pressure mixing for 90 seconds; add 5 parts of oxidation Zinc, 1 part stearic acid, 2 parts PEG4000, 1 part antioxidant RD, kneaded for 30 seconds; then add 30 parts carbon black N550, 50 parts carbon black N774, 15 parts paraffin oil SUNPAR2280 in the rubber compound, mix 3 Minute; finally added 3 parts of cross-linking agent dicumyl peroxide (DCP), 1 part of cross-linking agent N, N'-m-phenylene bismaleimide (HVA-2), 0.3 parts of cross-linking Sulphur, glued for 2 minutes and then discharged. The mixture is thinned on the open mill and then placed on the sheet to be vulcanized.
  • DCP dicumyl peroxide
  • HVA-2 N'-m-phenylene bismaleimide
  • Vulcanization The vulcanization process is applied, the temperature is 165 ° C, the steam pressure is 1 MPa, the vulcanization time is 25 minutes, and then the cloth is uncoated, cored off, and cut off. Get the air conditioning hose.
  • An air-conditioning hose whose rubber composition for the outer rubber layer is the rubber composition used in the ninth embodiment.
  • the production process is the same as in Example 16.
  • An air-conditioning hose wherein the rubber composition used for the inner rubber layer and the outer rubber layer is the rubber composition used in the embodiment 9.
  • the production process is the same as in Example 16.
  • a rubber hose assembly whose production process is as follows:
  • (1) rubber compound inner rubber layer rubber composition composition and content: 100 parts of branched polyethylene PER-4, 1 part of antioxidant RD, 80 parts of carbon black N550, 20 parts of calcium carbonate, 40 parts of paraffin oil SUNPAR2280, 3 parts of dicumyl peroxide (DCP) and 1 part of N,N'-m-phenylene bismaleimide.
  • the composition and content of the rubber composition of the outer rubber layer are: 100 parts of branched polyethylene PER-4, 1 part of antioxidant RD, 80 parts of carbon black N550, 20 parts of calcium carbonate, 50 parts of paraffin oil SUNPAR 2280, 3 parts of dioxygen peroxide Propylene (DCP) and 1 part of N,N'-m-phenylene bismaleimide.
  • the raw materials of the inner rubber layer and the outer rubber layer are respectively processed into an inner layer rubber mixture and an outer layer rubber mixture by an open mill or an internal mixer, and the impurities are filtered out after passing the test;
  • Tube blank forming the inner rubber layer is extruded by a cold feed extruder, and the aramid fiber layer is knitted on the outer surface of the inner rubber layer, and finally the outer rubber compound is extruded through an outer rubber layer extruder. And coating on the outer surface of the aramid fiber layer to form a tube blank;
  • An air conditioning hose wherein the rubber composition used for the inner rubber layer and the outer rubber layer is the same rubber composition.
  • the production process is as follows:
  • Rubber mixing set the temperature of the internal mixer to 60 ° C, the rotor speed to 50 rpm, add 100 parts of branched polyethylene PER-10 pre-pressure mixing for 90 seconds; add 5 parts of zinc oxide, 1 part of hard Fatty acid, 2 parts PEG4000, 1 part antioxidant MB, mixed for 30 seconds; then add 30 parts carbon black N550, 50 parts carbon black N774, 15 parts paraffin oil SUNPAR2280 in the rubber compound, mix for 3 minutes; finally add 3 Cross-linking agent dicumyl peroxide (DCP), 1 part of cross-linking agent N, N'-m-phenylene bismaleimide (HVA-2), 0.3 parts of cross-linking agent sulfur, mixing Discharge the glue after 2 minutes. The mixture is thinned on the open mill and then placed on the sheet to be vulcanized.
  • DCP dicumyl peroxide
  • HVA-2 N'-m-phenylene bismaleimide
  • Vulcanization using a cloth vulcanization process, the temperature is 165 ° C, the steam pressure is 1 MPa, the vulcanization time is 25 minutes, and then the cloth is uncoated, cored off, and cut off. Get the air conditioning hose.
  • the rubber composition of the present embodiment was molded into a test sample by molding, and the test performance was as follows:
  • the utility model relates to an automobile radiator hose, wherein the rubber composition used for the inner rubber layer and the outer rubber layer is the same rubber composition.
  • the production process is as follows:
  • Rubber mixing set the temperature of the internal mixer to 90 ° C, the rotor speed is 50 rpm, add 100 parts of branched polyethylene PER-11 pre-pressing and kneading for 90 seconds; add 2 parts of PEG4000, 1 part of anti-aging agent MB, 1 part of antioxidant RD, 3 parts of solid coumarone, mixing for 30 seconds; then add 70 parts of carbon black N550, 15 parts of paraffin oil SUNPAR2280 in the compound, mixing for 3 minutes; finally adding 3 parts of crosslinking agent Dicumyl peroxide (DCP), 1 part of the co-crosslinking agent, triallyl isocyanurate (TAIC), was kneaded for 2 minutes and then discharged. The mixture is thinned on the open mill and then placed on the sheet to be vulcanized.
  • DCP Dicumyl peroxide
  • TAIC triallyl isocyanurate
  • Vulcanization The mandrel is inserted into the tube blank, vulcanized by high temperature steam, the temperature is 165 ° C, the steam pressure is 1 MPa, and after vulcanization for 25 minutes, it is cooled, cored, trimmed, inspected and stored, and the automobile radiator hose is obtained.
  • 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: 27.8 MPa; elongation at break: 532%; tear strength: 62 N/mm.
  • the utility model relates to an automobile radiator hose, wherein the rubber composition used for the inner rubber layer and the outer rubber layer is the same rubber composition.
  • the production process is as follows:
  • Rubber mixing set the temperature of the internal mixer to 90 ° C, the rotor speed is 50 rpm, add 100 parts of branched polyethylene PER-12 pre-pressure mixing for 90 seconds; add 2 parts of PEG4000, 1 part of antioxidant MB, 2 parts solid coumarone, 3 parts modified alkyl phenolic resin TKM-M, compounded for 30 seconds; then add 80 parts of carbon black N550, 20 parts of paraffin oil SUNPAR2280 to the compound, and mix for 3 minutes; 3 parts of cross-linking agent dicumyl peroxide (DCP), 1 part of the cross-linking agent triallyl isocyanurate (TAIC) were added, and the mixture was kneaded for 2 minutes and then discharged. The mixture is thinned on the open mill and then placed on the sheet to be vulcanized.
  • DCP cross-linking agent dicumyl peroxide
  • TAIC cross-linking agent triallyl isocyanurate
  • Vulcanization The mandrel is inserted into the tube blank, vulcanized by high temperature steam, the temperature is 165 ° C, the steam pressure is 1 MPa, and after vulcanization for 25 minutes, it is cooled, cored, trimmed, inspected and stored, and the automobile radiator hose is obtained.
  • the rubber composition of the present embodiment was molded into a test sample by molding, and the test performance was as follows:
  • the rubber composition containing the branched polyethylene has higher tensile strength and tearing properties under the same or similar conditions of the other formulation components.
  • the use of such a rubber composition as a raw material for the production of a hose can significantly reduce the probability of tearing of the hose during production and use.
  • its resistance to 150 °C hot air aging is maintained at the same level as the rubber composition of ethylene propylene rubber alone, which can meet the high temperature resistance requirements of the current similar radiator hoses and air conditioning hoses.
  • the rubber substrate used in Example 23 was 100 parts of PER-9, and the rubber substrate used in Example 24 was 50 parts of PER-9 and 50 parts of ethylene propylene diene monomer (ML (1+4) 125 ° C was 80, and the ethylene content was 55. %, ENB content 5.5%), the rubber substrate used in Comparative Example 3 was 100 parts of the ethylene propylene diene rubber used in Example 24. The rest of the formula is consistent.
  • the rubber compound was thinly passed on an open mill with a roll temperature of 60 ° C to obtain a sheet having a thickness of about 2.5 mm, and the vulcanization property was tested after standing for 20 hours;
  • test conditions were 175 ° C, 30 min, and the test results were as follows:
  • Example 23 Example 24 Comparative Example 3 ML, dN.m 2.02 1.20 0.6 MH, dN.m 12.74 11.94 11.23 MH-ML, dN.m 10.72 10.74 10.63 Tc90,min 6.8 7.5 8.2
  • the rubber composition of Example 19 has the shortest Tc90 and the MH-ML value is higher than that of Comparative Example 3, indicating that the branched polyethylene used in the present embodiment can be slightly superior in cross-linking ability to the conventional EPDM rubber.
  • the Tc90 of Example 20 was between Example 19 and Comparative Example 3, and the MH-ML of Example 20 was larger than that of Example 19 and Comparative Example 3, indicating that the combination of both was expected to increase the overall crosslinking density.

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Abstract

L'invention concerne un composite de caoutchouc, un procédé de traitement du composite de caoutchouc, un tube en caoutchouc comprenant le composite de caoutchouc, et un procédé de fabrication. Le composite de caoutchouc comprend en termes de parties unitaires en poids : 100 parties d'un substrat en caoutchouc, 1,5 à 8 parties d'un agent de réticulation, 50 à 200 parties d'une charge de renfort , et 10 à 100 parties d'un plastifiant, et comprend également 0,2 à 8 parties d'un agent d'aide à la réticulation, 2 à 15 parties d'un oxyde métallique, 1 à 3 parties d'un stabilisant, et 1 à 5 parties de polyéthylène glycol, le substrat de caoutchouc, calculé à 100 parties en poids, comprenant : du polyéthylène ramifié, dont la teneur est a : 0 < a ≤ 100 parties, un caoutchouc de monomère d'éthylène propylène et un caoutchouc de monomère d'éthylène propylène diène, dont la teneur est b :0 ≤ b < 100 parties.
PCT/CN2018/072374 2017-01-13 2018-01-12 Composite de caoutchouc, procédé de traitement, tube de caoutchouc mettant en application un composite et procédé de fabrication WO2018130199A1 (fr)

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CN112159565A (zh) * 2020-09-25 2021-01-01 河北友联橡胶制品有限公司 一种耐高温热水的橡胶配置方法
CN113789013A (zh) * 2021-09-16 2021-12-14 漯河市久隆液压科技有限公司 一种输R134a制冷剂的汽车空调胶管
CN114213772A (zh) * 2021-12-29 2022-03-22 苏州技佳橡塑有限公司 一种能耐涡轮系统高温的三元乙丙橡胶配方
CN114589900A (zh) * 2022-03-01 2022-06-07 君海管业(山东)有限公司 一种高粘合的pe修复内衬软管及其制作方法
CN114734567A (zh) * 2022-03-03 2022-07-12 江阴市昌雄金属科技有限公司 一种轮胎气门嘴用高强度橡胶密封垫片的加工工艺
CN114957858A (zh) * 2022-06-22 2022-08-30 广州市奈森化工有限公司 一种液压胶管生产行业专用塑料软芯及其生产方法
CN116082721A (zh) * 2022-11-18 2023-05-09 江苏冠联新材料科技股份有限公司 一种汽车马达电机用o型圈混炼胶及其制备方法
CN118325245A (zh) * 2024-06-14 2024-07-12 山东玲珑轮胎股份有限公司 一种自密封性橡胶组合物及其制备方法

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