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WO2018130194A1 - Composite de caoutchouc, procédé de traitement, produits en caoutchouc mettant en application le composite, et procédé de fabrication - Google Patents

Composite de caoutchouc, procédé de traitement, produits en caoutchouc mettant en application le composite, et procédé de fabrication Download PDF

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Publication number
WO2018130194A1
WO2018130194A1 PCT/CN2018/072365 CN2018072365W WO2018130194A1 WO 2018130194 A1 WO2018130194 A1 WO 2018130194A1 CN 2018072365 W CN2018072365 W CN 2018072365W WO 2018130194 A1 WO2018130194 A1 WO 2018130194A1
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WIPO (PCT)
Prior art keywords
rubber
parts
vulcanization
rubber composition
carbon black
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PCT/CN2018/072365
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English (en)
Chinese (zh)
Inventor
徐涛
傅智盛
吴安洋
Original Assignee
杭州星庐科技有限公司
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Priority claimed from CN201810020838.5A external-priority patent/CN108314850B/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 JP2019559144A priority Critical patent/JP7316484B2/ja
Priority to US16/477,777 priority patent/US11634566B2/en
Publication of WO2018130194A1 publication Critical patent/WO2018130194A1/fr

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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
    • 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—Ethene-propene or ethene-propene-diene copolymers

Definitions

  • the invention belongs to the field of rubber, in particular to a rubber composition and a processing method thereof, and relates to the application of the rubber composition in a rubber product requiring better tear strength and adhesion properties, and production.
  • the method of the rubber article includes, but is not limited to, a rubber product such as an insulating material for a high-strength wire and cable, a high-temperature resistant conveyor belt, and a waterproof coil.
  • the two most commonly used fillers with higher reinforced properties are carbon black and white carbon black, in which a reinforcing filling system using silica and carbon black is used in combination with reinforcing without silica.
  • Filling systems can often give rubber products better tear resistance, adhesion properties, wear resistance and low heat build-up.
  • This kind of reinforcing system with white carbon black and carbon black is used in tire tread rubber and tire tires.
  • the application of side glue, waterproof coil material, conveyor belt cover rubber and the like is more common.
  • Ethylene-propylene rubber is widely used in waterproofing coils and heat-resistant conveyor belts due to its good aging resistance.
  • Sulfur vulcanization and peroxide vulcanization are the two most commonly used vulcanization systems for ethylene propylene rubber, in order to obtain better aging resistance.
  • peroxide vulcanization is used, but the tensile strength and tear strength of peroxide vulcanized ethylene propylene rubber are weaker than that of sulfur vulcanized ethylene propylene rubber, which will offset part of the use of silica.
  • the performance advantage brought by it is relatively easy to be destroyed during use.
  • China Patent Licensing Bulletin No. CN104312018B is a heat-resistant conveyor belt covering rubber, which includes binary ethylene propylene rubber, low Mooney EPDM rubber, high wear-resistant carbon black, zinc methacrylate, white carbon black, paraffin wax, and sticky A combination of a reinforcing agent, a resorcinol, an antioxidant, and the like, which do not emphasize good mechanical properties.
  • Cipheral Patent Publication No. CN105504548A discloses a high tear-resistant peroxide EPDM rubber raw material, which is made of the following raw materials by weight: ethylene propylene diene monomer, zinc oxide, stearic acid, antioxidant RD, Polyethylene glycol PEG4000, white carbon black, carbon black, light calcium carbonate, paraffin oil 2280, sulfur, crosslinker BIPB, TAIC, the main component of the rubber matrix is EPDM rubber, its mechanical properties and natural rubber Or there is still a gap in styrene butadiene rubber. How to further improve the aging resistance and mechanical properties of ethylene propylene rubber is a problem.
  • 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.
  • the chain length is large, the steric hindrance is large, and the free radical reaction is difficult to occur, which leads to difficulty in crosslinking, affecting processing efficiency and product performance.
  • the present invention provides a rubber composition and a processing method thereof, and a production method for manufacturing a rubber product using the rubber composition, which has a branching degree of not less than 50 branches/ A 1000 carbon branched polyethylene replaces some or all of the ethylene propylene rubber, thereby changing the yield of existing rubber products and improving the performance of rubber products.
  • a rubber composition comprising: a rubber matrix and a necessary component, the rubber matrix comprising: a branched polyethylene having a content of a: 0 ⁇ a ⁇ 100 parts, the content of the binary ethylene propylene rubber and the ethylene propylene diene rubber b: 0 ⁇ b ⁇ 100 parts, the necessary components include: 1.5 to 10 parts of the crosslinking agent, and the reinforcing filler 40 ⁇ 200 parts, the reinforcing filler comprises carbon black, white carbon black, calcium carbonate, talc, calcined clay, magnesium silicate, magnesium carbonate, two or more, including carbon black 5 to 100 parts, including white 5 to 60 parts of carbon black, wherein the branching degree of branched polyethylene is not less than 50 branches/1000 carbons, the weight average molecular weight is not less than 50,000, and the Mooney viscosity ML (1+4) is not low 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 present invention and the prior art ethylene propylene diene 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.
  • the content of the branched polyethylene in the rubber matrix is: 10 ⁇ a ⁇ 100 parts, and the content of the binary ethylene propylene rubber and the EPDM rubber is 0 ⁇ b. ⁇ 90 parts;
  • the branched polyethylene is characterized by: it is an ethylene homopolymer, the degree of branching is 60-130 branches/1000 carbons, the weight average molecular weight is 66,000 to 518,000, and the Mooney viscosity is ML ( 1+4) 125 ° C is 6 to 102.
  • the content of the branched polyethylene in the rubber matrix is: 10 ⁇ a ⁇ 100 parts, and the content of the binary ethylene propylene rubber and the EPDM rubber is 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;
  • the content of the branched polyethylene in the rubber matrix is a: 10 ⁇ a ⁇ 100 parts, and the total content of the binary ethylene propylene rubber and the EPDM rubber is b: 0. ⁇ b ⁇ 90 parts;
  • the branched polyethylene is an ethylene homopolymer having a degree of branching of 80 to 105 branches/1000 carbons, a weight average molecular weight of 250,000 to 400,000, and a Mooney viscosity ML (1) +4) 125 ° C is 40 to 95.
  • the content of the branched polyethylene in the rubber matrix is a: 10 ⁇ a ⁇ 100 parts, and the total content of the binary ethylene propylene rubber and the EPDM rubber is b: 0. ⁇ b ⁇ 90 parts;
  • the branched polyethylene is an ethylene homopolymer having a degree of branching of 80 to 105 branches/1000 carbons, a weight average molecular weight of 268,000 to 356,000, and a Mooney viscosity ML (1) +4) 125 ° C is 42 to 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 silica comprises at least one of precipitated silica and fumed silica.
  • the carbon black comprises at least one of N220, N330, N550, N660, N774, N990.
  • the crosslinking agent comprises at least one of a peroxide crosslinking agent and a sulfur
  • the peroxide crosslinking agent is 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.
  • the rubber composition further comprises an auxiliary component, the auxiliary component comprising: 0.2 to 20 parts of a co-crosslinking agent, 5 to 100 parts of a plasticizer, and a stabilizer 1 based on 100 parts by weight of the rubber matrix. ⁇ 3 parts, 2 to 10 parts of metal oxide, 1 to 10 parts of surface modifier, 0 to 3 parts of vulcanization accelerator, and 0 to 20 parts of binder.
  • the stabilizer comprises 2,2,4-trimethyl-1,2-dihydroquinoline (RD), 6-ethoxy-2,2,4-trimethyl-1 At least one of 2-dihydroquinoline (AW), 2-mercaptobenzimidazole (MB), and N-4 (anilinophenyl)maleimide (MC).
  • RD 2,2,4-trimethyl-1,2-dihydroquinoline
  • AW 2-dihydroquinoline
  • MB 2-mercaptobenzimidazole
  • MC N-4 (anilinophenyl)maleimide
  • the co-crosslinking agent comprises triallyl cyanurate, triallyl isocyanurate, ethylene glycol dimethacrylate, ethyl dimethacrylate, and dimethyl Triethyl acrylate, triallyl trimellitate, trimethylolpropane trimethacrylate, ethylene glycol dimethacrylate, N, N'-m-phenylene bismaleimide At least one of N, N'-bis-indenyl acetonone, 1,2-polybutadiene, sulfur, and a metal salt of an unsaturated carboxylic acid.
  • the plasticizer is at least one of pine tar, motor oil, naphthenic oil, paraffin oil, coumarone, RX-80, stearic acid, paraffin wax, and liquid polyisobutylene.
  • stearic acid can also act as an active agent in sulfur-sulfur-based systems, and can form soluble salts with some metal oxides, thereby increasing the activation of metal oxides on promoters.
  • the rational use of plasticizers can increase the flexibility of the compound and the plasticity suitable for process operation.
  • an adhesion promoter such as pine tar, coumarone, RX-80, liquid polyisobutylene or the like.
  • the metal oxide is at least one of zinc oxide, magnesium oxide, and calcium oxide.
  • the surface modifier is polyethylene glycol, diphenyl silicon glycol, triethanolamine, vinyl tris(2-methoxyethoxy)silane having a molecular weight of 2000 or 3400 or 4000. (A-172), at least one of ⁇ -glycidoxypropyltrimethoxysilane (A-187) and ⁇ -mercaptopropyltrimethoxysilane (A-189).
  • the vulcanization accelerator comprises 2-thiol benzothiazole, dibenzothiazyl disulfide, tetramethylthiuram monosulfide, tetramethylthiuram disulfide, tetrazyl disulfide Kethiram, N-cyclohexyl-2-benzothiazolyl sulfenamide, N,N-dicyclohexyl-2-benzothiazolyl sulfenamide, bismaleimide, ethylene thiourea At least one of them.
  • the resorcinol donor may be selected from the group consisting of resorcinol (adhesive R), binder RS, binder RS-11, binder R-80, binder At least one of RL, binder binder PF, binder PE, binder RK, binder RH; the methylene donor may be selected from hexamethylenetetramine (HMTA), bonding At least one of the agent H-80, the binder A, the binder RA, the binder AB-30, the binder Rq, the binder RC, the binder CS963, and the binder CS964.
  • HMTA hexamethylenetetramine
  • the adhesive may also be selected from a triazine adhesive, and the specific commercial grade may be selected from at least one of the adhesive TAR, the adhesive TZ, the adhesive AIR-1, and the adhesive AIR-101.
  • One type, preferably at least one of the binder AIR-1 and the binder AIR-101, can partially replace the above-mentioned resorcinol donor binder, and has the advantages of good adhesion and relatively environmental protection.
  • 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.
  • the tackifier may also be selected from the group consisting of C5 petroleum resin, C9 petroleum resin, hydrogenated rosin, terpene resin, alkyl group.
  • 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 for processing the above rubber composition, the processing method comprising the following steps: Step 1: setting the temperature of the internal mixer and the rotation speed of the rotor, first adding the rubber composition other than the crosslinking system in order of weight Mixing into an internal mixer;
  • Step 2 Then adding a crosslinking system, after being uniformly kneaded, discharging, to obtain a rubber mixture;
  • Step 3 The mixture is thinned on the open mill and then placed on the sheet to be vulcanized;
  • Step 4 then vulcanizing according to a vulcanization process
  • the crosslinking system comprises a crosslinking agent, and further comprises at least one of a crosslinking agent and a vulcanization accelerator.
  • the vulcanization process may be further carried out by a two-stage vulcanization process. . .
  • the present invention provides an insulating material for high-strength wire and cable, and the rubber compound used comprises the above rubber composition.
  • the invention also provides a method for producing an insulating material for high-strength wire and cable, the production method comprising the following steps:
  • Rubber mixing set the temperature of the internal mixer and the rotor speed, add the rubber matrix pre-compression mixing; then add zinc oxide, stearic acid, surface modifier to mix; then add reinforcing filler and the remaining increase
  • the plastic agent is mixed; then the cross-linking agent and the cross-linking agent are added to mix and disperse the glue, and the rubber compound is thinly passed on the open mill, and the lower piece is parked;
  • the present invention also provides a waterproofing membrane comprising the above rubber composition.
  • the present invention also provides a method of waterproofing a coiled material, the method comprising the method of producing the waterproofing membrane comprising the following steps:
  • vulcanization the coiled material is placed in a nitrogen-filled vulcanization kettle for vulcanization;
  • Rewinding re-opening the vulcanized coil, taking out the release liner layer, and then rewinding and packaging into a product.
  • the present invention also provides a high temperature resistant conveyor belt, wherein at least one of the working surface covering rubber and the non-working surface covering rubber comprises the above rubber composition.
  • the invention also provides a method for producing a high temperature resistant conveyor belt, wherein the working surface covering rubber comprises a high temperature resistant conveyor belt of the above rubber composition, the composition and proportion of the working surface covering rubber are in parts, and the production method comprises the steps as follows:
  • Rubber mixing process firstly, the rubber composition except the crosslinking system is sequentially added to the internal mixer for mixing by weight, and then added to the crosslinking system, uniformly kneaded, and discharged to obtain a rubber compound. After the mixture is thinned on the open mill, the tablet is left, parked, and wait 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;
  • the film is closely attached to the preformed adhesive tape strip blank on the forming machine 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 blank is placed in a flat vulcanizing machine for stage vulcanization, the vulcanization time of each plate is 25 to 30 minutes, the vulcanization pressure is 2.5 to 4 MPa, and the vulcanization temperature is 155 to 170 ° C. .
  • the present invention also provides a tire comprising at least one of the above-mentioned rubber composition for the rubber for the sidewall of the tire and the rubber for the tread.
  • the tire provided by the present invention is preferably used as a force tire or an agricultural machine tire.
  • the force tire can be a bicycle tire, a trolley tire, an animal tire, an electric tire, and the like.
  • Agricultural machinery tires can be used on tractors, combine harvesters, and other agricultural vehicles.
  • the rubber composition of the present invention can be used as a side wall rubber, and a tire can be produced by a usual method. That is, the rubber compound is subjected to extrusion processing in accordance with the sidewall shape of the tire design, and is molded together with other tire members by a usual method on a tire molding machine to form an unvulcanized tire, which is subjected to the unvulcanized tire in a vulcanizer. Heating and pressurizing to obtain a tire.
  • the rubber composition of the present invention can be used as a tread rubber, and the tire can be produced by a usual method, that is, the rubber compound is subjected to extrusion processing according to the tread shape of the tire design, and the tire is molded by a usual method and other tires.
  • the components are molded together to form an unvulcanized tire.
  • the unvulcanized tire is heated and pressurized in a vulcanizer to obtain a tire.
  • the steel wire or fiber skeleton used in the above tires is preferably a surface treated with a type which can be well bonded to a non-polar rubber.
  • the surface treatment can be carried out by soaking the RFL impregnation system.
  • the invention has the beneficial effects of providing a new rubber composition, which partially or completely replaces ethylene propylene rubber with branched polyethylene, and applies it to a rubber product which is reinforced by silica and carbon black. Under the peroxide vulcanization system, good heat resistance, compression set resistance and mechanical strength are simultaneously obtained.
  • the crosslinking system contains a crosslinking agent, and may further contain at least one of a co-crosslinking agent and a vulcanization accelerator.
  • the Mooney viscosity ML (1+4) of the ethylene-propylene rubber used is preferably 20 to 50, more preferably 40 to 50, and preferably 4 to 60%.
  • the Mooney viscosity ML (1+4) of the ethylene propylene diene rubber used is preferably 20 to 100, more preferably 40 to 80, the ethylene content is preferably 55% to 75%, and the third monomer is 5-ethylene-2. - norbornene, 5-vinyl-2-norbornene or dicyclopentadiene, the third monomer content being from 1% to 7%.
  • the branched polyethylene used can be obtained by catalyzing the homopolymerization of ethylene by a ( ⁇ -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 branched polyethylenes involved in the examples are 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 ⁇ 102.
  • the rubber composition provided by the invention comprises: a rubber base and a necessary component, and the rubber base further comprises: a content of branched polyethylene a: 0 ⁇ a ⁇ 100 parts, a binary ethylene propylene rubber and an ethylene propylene diene rubber Content b: 0 ⁇ b ⁇ 100 parts, the necessary components include: 1.5 to 10 parts of a crosslinking agent, 40 to 200 parts of a reinforcing filler, and the reinforcing filler contains carbon black, white carbon, calcium carbonate, talc Two or more of powder, calcined clay, magnesium silicate, magnesium carbonate, wherein when the reinforcing filler contains carbon black or white carbon, it contains 5 to 100 parts of carbon black, and contains white carbon black 5 to 60 parts, and the white carbon black in the reinforcing filler comprises at least one of precipitated silica and fumed silica, and the carbon black comprises at least one of N220, N330, N550, N660, N774, N990 .
  • the crosslinking agent comprises at least one of a peroxide crosslinking agent and sulfur, wherein the peroxide crosslinking agent is di-tert-butyl peroxide, dicumyl peroxide, t-butyl cumyl peroxide 1,1-di-tert-butyl peroxide-3,3,5-trimethylcyclohexane, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, 2 ,5-Dimethyl-2,5-di(tert-butylperoxy)hexyne-3, bis(tert-butylperoxyisopropyl)benzene, 2,5-dimethyl-2,5-di At least one of (benzoyl peroxide) hexane, tert-butyl peroxybenzoate, and t-butylperoxy-2-ethylhexyl carbonate.
  • the peroxide crosslinking agent is di-tert-
  • the white carbon black used in the examples of the present invention is a fumed silica or a precipitated silica, and for applications where transparency and electrical insulation are not critical, precipitated silica is preferred, and further preferably highly dispersed.
  • Sex precipitated silica unless otherwise specified, the ordinary precipitation method used in the examples is Solverodi zeosil142, and the highly dispersible silica is Solvay zeosil 165N. .
  • the rubber composition provided by the present invention may further comprise an auxiliary component comprising: 0.2 to 20 parts of a co-crosslinking agent, 5 to 100 parts of a plasticizer, 1 to 3 parts of a stabilizer, and 2 to 10 parts of a metal oxide. 1 to 10 parts of the surface modifier, 0 to 3 parts of the vulcanization accelerator, and 0 to 20 parts of the binder.
  • the stabilizer comprises 2,2,4-trimethyl-1,2-dihydroquinoline polymer (RD), 6-ethoxy-2,2,4-trimethyl-1,2-di At least one of hydrogenated quinoline (AW) and 2-mercaptobenzimidazole (MB).
  • the co-crosslinking agent comprises triallyl cyanurate, triallyl isocyanurate, ethylene glycol dimethacrylate, ethyl dimethacrylate, triethylene glycol dimethacrylate, partial Triallyl trimellitate, trimethylolpropane trimethacrylate, ethylene glycol dimethacrylate, N,N'-m-phenylene bismaleimide, N,N'-double At least one of mercaptoacetone, 1,2-polybutadiene, sulfur, and a metal salt of an unsaturated carboxylic acid.
  • the unsaturated carboxylic acid metal salt contains at least one of zinc acrylate, zinc methacrylate, magnesium methacrylate, calcium methacrylate, and aluminum methacrylate.
  • the plasticizer is at least one of pine tar, motor oil, naphthenic oil, paraffin oil, coumarone, RX-80, stearic acid, and paraffin wax.
  • the metal oxide is at least one of zinc oxide, magnesium oxide, and calcium oxide.
  • the surface modifier is polyethylene glycol, diphenyl silicon glycol, triethanolamine, vinyl tris(2-methoxyethoxy)silane (A-172), ⁇ - having a molecular weight of 2000 or 3400 or 4000. At least one of glycidyloxypropyltrimethoxysilane (A-187) and ⁇ -mercaptopropyltrimethoxysilane (A-189).
  • the vulcanization accelerator comprises 2-thiol benzothiazole, dibenzothiazole disulfide, tetramethylthiuram monosulfide, tetramethylthiuram disulfide, tetraethylthiuram disulfide, N-ring At least one of hexyl-2-benzothiazolylsulfenamide, N,N-dicyclohexyl-2-phenylthiazolylsulfenamide, bismaleimide, and ethylenethiourea.
  • the binder comprises at least one of a resorcinol donor, a methylene donor, and a triazine binder
  • the degree of branching of the branched polyethylene in the above rubber composition is measured by nuclear magnetic resonance spectroscopy, and the molar percentages of various branches are measured by nuclear magnetic carbon spectroscopy, as shown in the following table:
  • Hardness test According to the national standard GB/T 531.1-2008, the test is carried out with a hardness tester, and the test temperature is room temperature;
  • tear strength test in accordance with the national standard GB/T529-2008, using an electronic tensile test machine for testing, the tensile speed is 500mm / min, the test temperature is 23 ⁇ 2 ° C, the sample is a rectangular sample;
  • volume resistivity test in accordance with the national standard GB/T1692-2008, using a high resistance meter for testing;
  • Mooney viscosity test in accordance with the national standard GB/T1232.1-2000, with Mooney viscosity meter for testing, the test temperature is 125 ° C, preheat 1 minute, test 4 minutes;
  • test conditions are 150 ° C ⁇ 72h;
  • the vulcanization conditions of the following Examples 1 to 10 and Comparative Examples 1 and 2 were uniform: temperature: 160 ° C; pressure: 16 MPa; time was Tc90 + 2 min.
  • the branched polyethylene used was numbered PER-5.
  • the processing steps of the rubber composition are as follows:
  • Rubber mixing set the temperature of the internal mixer to 90 ° C, the rotor speed is 50 rpm, add 50 parts of ethylene propylene diene rubber and 50 parts of branched polyethylene for 90 seconds; add 40 parts of carbon Black N550 and 10 parts of white carbon black were mixed for 3 minutes; then 3 parts of cross-linking agent dicumyl peroxide (DCP) was added, and the mixture was kneaded for 2 minutes and then discharged. The mixture was thinly spread on the open mill, and the roll was adjusted to obtain a sheet thickness of about 2.5 mm and parked for 20 hours.
  • DCP cross-linking agent dicumyl peroxide
  • the branched polyethylene used was numbered PER-5.
  • the processing steps of the rubber composition are 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 pre-pressed and kneaded for 90 seconds; add 40 parts of carbon black N550 and 10 parts of white carbon black , mixing for 3 minutes; then adding 3 parts of cross-linking agent dicumyl peroxide (DCP), mixing for 2 minutes and then discharging the glue.
  • DCP cross-linking agent dicumyl peroxide
  • 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 40 parts of carbon black N550 and 10 parts of white carbon. Black, kneaded for 3 minutes; then add 3 parts of cross-linking agent dicumyl peroxide (DCP), mix for 2 minutes and then drain. The mixture was thinly spread on the open mill, and the roll was adjusted to obtain a sheet thickness of about 2.5 mm and parked for 20 hours.
  • DCP dicumyl peroxide
  • the branched polyethylene used was numbered PER-9.
  • the processing steps of the rubber composition are as follows:
  • Rubber mixing set the temperature of the internal mixer to 90 ° C, the rotor speed to 50 rpm, add 90 parts of ethylene propylene diene rubber and 10 parts of branched polyethylene for 90 seconds; then add 5 parts Zinc oxide, 1 part stearic acid, 5 parts polyethylene glycol PEG4000 and 1 part antioxidant 2,2,4-trimethyl-1,2-dihydroquinoline polymer (RD), kneaded for 2 minutes; Then add 80 parts of carbon black N550, 20 parts of white carbon black, 20 parts of calcined clay, 20 parts of petrolatum and 30 parts of paraffin oil SUNPAR 2280, and knead for 3 minutes; then add 6 parts of cross-linking agent dicumyl peroxide (DCP) 2 parts of the co-crosslinking agent triallyl isocyanurate (TAIC) and 0.3 parts of the cross-linking agent sulfur, which were mixed for 2 minutes and then discharged. The mixture was thinly spread on the open mill, and the roll was adjusted to
  • the branched polyethylene used was numbered PER-8.
  • the processing steps of the rubber composition are as follows:
  • Rubber mixing set the temperature of the internal mixer to 90 ° C, the rotor speed is 50 rpm, add 20 parts of ethylene propylene diene rubber, 50 parts of ethylene propylene diene monomer and 30 parts of branched polyethylene pre-pressure mixing.
  • the branched polyethylene used was numbered PER-6.
  • the processing steps of the rubber composition are as follows:
  • the branched polyethylene used was numbered PER-5.
  • the processing steps of the rubber composition are 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 pre-pressed for 90 seconds; then add 5 parts of zinc oxide, 1 part of stearic acid 5 parts of polyethylene glycol PEG4000 and 1 part of antioxidant 2,2,4-trimethyl-1,2-dihydroquinoline polymer (RD), kneaded for 2 minutes; then add 80 parts of carbon black N550, 20 parts of white carbon black, 20 parts of calcined clay, 15 parts of petrolatum and 30 parts of paraffin oil SUNPAR 2280, mixed for 3 minutes; then added 6 parts of cross-linking agent dicumyl peroxide (DCP), 2 parts of cross-linking agent Allyl isocyanurate (TAIC) and 0.2 parts of the cross-linking agent sulfur were mixed and dispersed for 2 minutes. The mixture was thinly spread on the open mill, and the roll was adjusted to obtain a sheet thickness of about 2.5 mm and parked for 20 hours.
  • 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 then add 5 parts of zinc oxide and 1 part of stearin.
  • Acid 5 parts of polyethylene glycol PEG4000 and 1 part of antioxidant 2,2,4-trimethyl-1,2-dihydroquinoline polymer (RD), kneaded for 2 minutes; then add 80 parts of carbon black N550 20 parts of white carbon black, 20 parts of calcined clay, 15 parts of petrolatum and 30 parts of paraffin oil SUNPAR 2280, mixed for 3 minutes; then added 6 parts of cross-linking agent dicumyl peroxide (DCP), 2 parts of cross-linking agent The triallyl isocyanurate (TAIC) and 0.2 parts of the cross-linking agent sulfur were mixed for 2 minutes and then discharged. The mixture was thinly spread on the open mill, and the roll was adjusted to obtain a sheet thickness of about 2.5 mm and parked for 20 hours.
  • DCP
  • Example 2 By comparison of Example 1, Example 2 and Comparative Example 1 and comparison of Examples 3 to 6 and Comparative Example 2, it can be found that the tensile strength of the obtained vulcanized rubber increases as the specific gravity of the branched polyethylene replaces the ethylene-propylene rubber increases. Both strength and tear strength are significantly improved, indicating that better mechanical properties can be obtained with a rubber composition containing branched polyethylene.
  • the branched polyethylene used was numbered PER-5.
  • the processing steps of the rubber composition are as follows:
  • 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 for pre-pressing and kneading for 90 seconds; then add 10 parts of zinc oxide and 2 parts of stearic acid.
  • the branched polyethylene used was numbered PER-4.
  • the processing steps of the rubber composition are 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 pre-pressed for 90 seconds; then add 5 parts of zinc oxide, 1 part of stearic acid 5 parts of polyethylene glycol PEG4000, 1 part of antioxidant 2,2,4-trimethyl-1,2-dihydroquinoline polymer (RD) and 2 parts of vinyltris(2-methoxyethoxy) Silane (A-172), kneaded for 2 minutes; then add 20 parts of carbon black N550, 60 parts of silica, 40 parts of calcined clay, 15 parts of petrolatum and 30 parts of paraffin oil SUNPAR 2280, mix for 3 minutes; then join 8 parts of cross-linking agent dicumyl peroxide (DCP), 1 part of cross-linking agent triallyl isocyanurate (TAIC) and 6 parts of cross-linking agent 1,2-polybutadiene, mixed After 2 minutes of smelting, the glue is discharged.
  • the branched polyethylenes used were numbered PER-2 and PER-6.
  • the processing steps of the rubber composition are as follows:
  • Rubber mixing set the temperature of the internal mixer to 90 ° C, the rotor rotation speed is 50 rpm, add 70 parts of PER-6 and 30 parts of PER-2 pre-pressure mixing for 90 seconds; then add 5 parts of zinc oxide, 1 part stearic acid, 2 parts polyethylene glycol PEG4000 and 1 part antioxidant 2,2,4-trimethyl-1,2-dihydroquinoline polymer (RD), kneaded for 2 minutes; then added 35 Parts carbon black N550, 5 parts white carbon black and 10 parts paraffin oil SUNPAR2280, mixed for 3 minutes; then add 1 part of cross-linking agent dicumyl peroxide (DCP), 0.3 parts of co-crosslinker triallyl Cyanurate (TAIC), 0.5 parts of cross-linking agent sulfur, 1 part of N-cyclohexyl-2-benzothiazole sulfenamide (CZ) and 0.8 parts of tetramethylthiuram disulfide (TMTD), mixed After 2 minutes of smelting, the
  • the branched polyethylenes used were numbered PER-1 and PER-7.
  • the processing steps of the rubber composition are as follows:
  • 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, 2 parts stearic acid, 2 parts polyethylene glycol PEG4000 and 1 part antioxidant 2,2,4-trimethyl-1,2-dihydroquinoline polymer (RD), kneaded for 2 minutes; then added 60 Parts carbon black N330, 20 parts white carbon black and 20 parts paraffin oil SUNPAR2280, mixed for 3 minutes; then add 4 parts of cross-linking agent di-tert-butyl diisopropylbenzene (BIPB), 1.5 parts of cross-linking agent Triallyl isocyanurate (TAIC) and 15 parts of zinc methacrylate were mixed for 2 minutes and then discharged. The mixture was thinly spread on the open mill, and the roll was adjusted to obtain a sheet thickness of about 2.5 mm and parked for 20 hours.
  • BIPB cross-linking
  • the performance test data is as follows:
  • Example 7 Example 8
  • Example 9 Example 10 hardness 67 66 58 71
  • After aging (150 ° C ⁇ 72h) hardness 74 75 62 79
  • Tensile strength retention rate /% 75 83 81 89 Elongation at break elongation /% 72 79 78 87
  • a rubber composition for producing a rubber product comprising an insulating material for producing high-strength wire and cable, a waterproofing membrane, and a high-temperature resistant conveyor belt.
  • An insulating material for high-strength wire and cable, the branched polyethylene is PER-3, and the processing steps are as follows:
  • 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 for pre-pressing and kneading for 90 seconds; then add 10 parts of zinc oxide and 1 part of stearic acid.
  • vulcanization and performance test vulcanization process: steam vulcanization, 155 ° C ⁇ 40 minutes, immersed in water;
  • Performance test hardness: 68; tensile strength: 19.1 MPa; elongation at break: 622%; volume resistivity: 3.8 ⁇ 10 15 ⁇ ⁇ cm; 150 ° C ⁇ 72 h after hot air aging: hardness: 74; tensile strength Retention rate: 75%; elongation at break retention rate: 72%.
  • a waterproof membrane material whose production process is as follows:
  • the block rubber is fed into the open mill for mixing, the temperature of the control roller is between 85 and 95 ° C, and the roll distance is controlled to be less than 1 mm, and the thin pass is not less than four times until the surface of the rubber compound is smooth and shiny. Then turn the head and further mix it, make the thin pass no less than four times, adjust the roll distance to not more than 8mm, mix it three times, and obtain the evenly mixed rubber piece with the thickness below 8mm, and cool it to below 50 °C.
  • vulcanization the rolled material is placed in a nitrogen-containing vulcanization kettle for vulcanization treatment, the temperature of the vulcanization kettle is controlled between 155 and 165 ° C, the pressure is between 20 and 25 MPa, and the vulcanization is for 25 to 30 minutes;
  • Rewinding re-opening the vulcanized coil, taking out the release liner layer, and then rewinding and packaging into a product.
  • the utility model relates to a high-temperature resistant conveyor belt, which comprises a working surface covering glue, a non-working surface covering glue, and a cored tensile canvas provided between the two, and the composition and proportion of the working surface covering glue are divided into parts. Number:
  • One-stage mixing set the internal temperature of the mixer to 90 ° C, the rotor speed to 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, 2 parts of hard Fatty acid, 2 parts of polyethylene glycol PEG4000 and 1 part of antioxidant 2,2,4-trimethyl-1,2-dihydroquinoline polymer (RD), kneaded for 2 minutes; then add 60 parts of carbon black N330, 20 parts of white carbon black, 2.5 parts of resorcinol (RS) and 20 parts of paraffin oil SUNPAR2280, mixing for 3 minutes, debinding; two-stage mixing: setting the internal temperature of the mixer to 90 ° C, the rotor speed is 50 Rpm, then add 2 parts of methylene donor RH, mix for two minutes; then add 4 parts of crosslinker di-tert-butylperoxydiisopropylbenzene (BIPB), 1.5 parts of cross-linker Propyl isocyanur
  • the above rubber mixture is placed in a screw extruder for hot refining, and then supplied to a calender for calendering to be used.
  • the thickness of the film is controlled to be 4.5 to 12 mm when the film is rolled. After being good, keep warm for use.
  • the film is closely attached to the pre-formed adhesive canvas strip on the molding machine to form a strip of the high temperature resistant conveyor belt, and then vulcanized after being rolled up for 4 hours.
  • the formed conveyor belt blank was placed in a flat vulcanizing machine for stage vulcanization, and the vulcanization time per plate was 25 minutes, the vulcanization pressure was 3 MPa, and the vulcanization temperature was 160 °C.
  • a bicycle tire, the processing steps of the sidewall rubber are as follows:
  • Rubber mixing set the temperature of the internal mixer to 90 ° C, the rotor speed to 50 rpm, add 100 parts of branched polyethylene PER-5 pre-pressure mixing for 90 seconds; then add 5 parts of zinc oxide, 1 part Stearic acid, 2 parts of polyethylene glycol PEG4000 and 2 parts of vinyltris(2-methoxyethoxy)silane (A-172), kneaded for 2 minutes; then added 40 parts of carbon black N330, 20 parts high Disperse silica and 10 parts of paraffin oil SUNPAR2280, mix for 3 minutes; then add 4 parts of cross-linking agent dicumyl peroxide (DCP), 1.5 parts of cross-linking agent N, N'-m-phenylene double horse The imide (HVA-2) and 0.3 parts of the co-crosslinking agent sulfur were kneaded for 2 minutes and then discharged. The rubber compound is opened on the open mill and then placed, parked and tested.
  • DCP cross-linking agent dicumyl peroxide
  • Extrusion molding The qualified rubber compound is extruded through an extruder to obtain a rubber member having a side wall shape to be used.
  • a bicycle tire, the processing steps of the sidewall rubber are as follows:
  • Rubber mixing set the temperature of the internal mixer to 90 ° C, the rotor speed to 50 rpm, add 100 parts of branched polyethylene PER-12 pre-pressure mixing for 90 seconds; then add 5 parts of zinc oxide, 1 part Stearic acid, 2 parts of polyethylene glycol PEG4000 and 2 parts of vinyltris(2-methoxyethoxy)silane (A-172), kneaded for 2 minutes; then added 40 parts of carbon black N330, 20 parts high Disperse silica and 10 parts of paraffin oil SUNPAR2280, mix for 3 minutes; then add 4 parts of cross-linking agent dicumyl peroxide (DCP), 1.5 parts of cross-linking agent N, N'-m-phenylene double horse The imide (HVA-2) and 0.3 parts of the co-crosslinking agent sulfur were kneaded for 2 minutes and then discharged. The rubber compound is opened on the open mill and then placed, parked and tested.
  • DCP cross-linking agent dicumyl peroxide
  • Extrusion molding The qualified rubber compound is extruded through an extruder to obtain a rubber member having a side wall shape to be used.
  • a bicycle tire, the processing steps of the tread rubber are as follows:
  • 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, 2 parts stearic acid, 2 parts polyethylene glycol PEG4000 and 1 part antioxidant 2,2,4-trimethyl-1,2-dihydroquinoline polymer (RD), kneaded for 2 minutes; then added 60 Part of carbon black N330, 20 parts of white carbon black and 15 parts of paraffin oil SUNPAR2280, mixing for 3 minutes; then add 4 parts of cross-linking agent di-tert-butylperoxydiisopropylbenzene (BIPB), 1.5 parts of cross-linking agent Triallyl isocyanurate (TAIC) and 15 parts of zinc methacrylate were mixed for 2 minutes and then discharged.
  • the rubber compound is opened on the open mill and then placed, parked, and tested;
  • Tread extrusion using a cold feed extrusion process, extruding into a tread semi-finished product through an extruder.
  • a bicycle tire, the processing steps of the tread rubber are as follows:
  • Rubber mixing set the temperature of the internal mixer to 90 ° C, the rotor speed to 50 rpm, add 70 parts of PER-11 and 30 parts of PER-3 pre-pressure mixing for 90 seconds; then add 10 parts of zinc oxide, 2 parts stearic acid, 2 parts of coumarone resin, 2 parts of modified alkyl phenolic resin TKM-K, 2 parts of polyethylene glycol PEG4000 and 1 part of antioxidant RD, kneaded for 2 minutes; then added 60 parts of carbon black N330, 20 parts of white carbon black and 20 parts of paraffin oil SUNPAR2280, mixed for 3 minutes; then add 4 parts of cross-linking agent di-tert-butylperoxydiisopropylbenzene (BIPB), 1.5 parts of cross-linking agent triene
  • BIPB paraffin oil
  • Tread extrusion using a cold feed extrusion process, extruding into a tread semi-finished product through an extruder.
  • the utility model relates to a high-temperature resistant conveyor belt, which comprises a working surface covering glue, a non-working surface covering glue, and a cored tensile body canvas provided between the two, the working surface covering glue composition and the mixing process as follows:
  • One-stage mixing set the internal temperature of the mixer to 90 ° C, the rotor speed is 50 rpm, add 100 parts of PER-12 pre-pressure mixing for 90 seconds; then add 10 parts of zinc oxide, 2 parts of stearic acid, 2 parts of poly Ethylene glycol PEG4000 and 1 part antioxidant RD, kneaded for 2 minutes; then add 60 parts carbon black N330, 20 parts white carbon black, 5 parts triazine adhesive AIR-1, 1 part resorcinol (RS) And 20 parts of paraffin oil SUNPAR2280, mixing for 3 minutes, debinding; two-stage mixing: setting the temperature of the internal mixer to 90 ° C, the rotor speed is 50 rev / min, then adding 2 parts of methylene donor RH, mixing Two minutes; then add 4 parts of crosslinker di-tert-butylperoxydiisopropylbenzene (BIPB), 1.5 parts of co-crosslinker triallyl isocyanurate (TAIC) and 15 parts of zinc me
  • a rubber for rubber metal shock absorbing parts the composition and mixing process are as follows:

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Abstract

L'invention concerne également un composite de caoutchouc, un procédé de traitement, des applications du composite dans des produits en caoutchouc, et un procédé de fabrication pour les produits en caoutchouc. Le composite de caoutchouc comprend : un substrat en caoutchouc et des composants essentiels. Le substrat en caoutchouc comprend : du polyéthylène ramifié, dont la teneur est a : 0 < a ≤ 100 parties, un caoutchouc monomère d'éthylène propylène et un caoutchouc monomère d'éthylène propylène diène, dont le contenu est b : 0 ≤ b < 100 parties. Les composants essentiels comprennent : 1,5 à 10 parties d'un agent de réticulation et 40 à 200 parties d'une charge de renforcement. La charge de renforcement comprend du noir de carbone, du noir de carbone blanc, peut également comprendre un ou plusieurs du carbonate de calcium, de la poudre de talc, de l'argile calcinée, du silicate de magnésium et du carbonate de magnésium, et contient 5 à 100 parties de noir de carbone et 5 à 60 parties de noir de carbone blanc. Le composite de caoutchouc trouve des applications dans la fabrication des produits en caoutchouc. Les produits en caoutchouc comprennent un matériau isolant utilisé pour fabriquer un fil électrique à haute résistance et un câble, un matériau enroulé étanche à l'eau et une bande transporteuse résistante à une température élevée.
PCT/CN2018/072365 2017-01-13 2018-01-12 Composite de caoutchouc, procédé de traitement, produits en caoutchouc mettant en application le composite, et procédé de fabrication WO2018130194A1 (fr)

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WO2024255147A1 (fr) * 2023-06-12 2024-12-19 芜湖禾田汽车工业有限公司 Composition de caoutchouc pour support d'amortisseur de chocs ainsi que son procédé de préparation et son utilisation
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