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WO2018130195A1 - Composite de caoutchouc, procédé de traitement, applications, procédé de fabrication des applications - Google Patents

Composite de caoutchouc, procédé de traitement, applications, procédé de fabrication des applications Download PDF

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Publication number
WO2018130195A1
WO2018130195A1 PCT/CN2018/072367 CN2018072367W WO2018130195A1 WO 2018130195 A1 WO2018130195 A1 WO 2018130195A1 CN 2018072367 W CN2018072367 W CN 2018072367W WO 2018130195 A1 WO2018130195 A1 WO 2018130195A1
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WIPO (PCT)
Prior art keywords
rubber
parts
vulcanization
rubber composition
crosslinking agent
Prior art date
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PCT/CN2018/072367
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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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Filing date
Publication date
Priority claimed from CN201810020839.XA external-priority patent/CN108314851B/zh
Application filed by 杭州星庐科技有限公司 filed Critical 杭州星庐科技有限公司
Priority to US16/477,654 priority Critical patent/US20190359805A1/en
Publication of WO2018130195A1 publication Critical patent/WO2018130195A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/74—Mixing; Kneading using other mixers or combinations of mixers, e.g. of dissimilar mixers ; Plant
    • B29B7/7476—Systems, i.e. flow charts or diagrams; Plants
    • B29B7/7495—Systems, i.e. flow charts or diagrams; Plants for mixing rubber
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/002—Methods
    • B29B7/005—Methods for mixing in batches
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/74—Mixing; Kneading using other mixers or combinations of mixers, e.g. of dissimilar mixers ; Plant
    • B29B7/7461—Combinations of dissimilar mixers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/80—Component parts, details or accessories; Auxiliary operations
    • B29B7/88—Adding charges, i.e. additives
    • B29B7/90—Fillers or reinforcements, e.g. fibres
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/02—Mixing; Kneading non-continuous, with mechanical mixing or kneading devices, i.e. batch type
    • B29B7/06—Mixing; Kneading non-continuous, with mechanical mixing or kneading devices, i.e. batch type with movable mixing or kneading devices
    • B29B7/10—Mixing; Kneading non-continuous, with mechanical mixing or kneading devices, i.e. batch type with movable mixing or kneading devices rotary
    • B29B7/18—Mixing; Kneading non-continuous, with mechanical mixing or kneading devices, i.e. batch type with movable mixing or kneading devices rotary with more than one shaft
    • B29B7/183—Mixing; Kneading non-continuous, with mechanical mixing or kneading devices, i.e. batch type with movable mixing or kneading devices rotary with more than one shaft having a casing closely surrounding the rotors, e.g. of Banbury type
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
    • B29B7/34—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices
    • B29B7/38—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/02—Making granules by dividing preformed material
    • B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion

Definitions

  • the invention belongs to the technical field of rubber, and particularly relates to a rubber composition reinforced by white carbon black and a processing method thereof, and a rubber product and a production method using the rubber composition.
  • White carbon black is the most commonly used light color filler with good reinforcing properties. Ethylene-propylene rubber reinforced with white carbon black tends to have good tear resistance, high adhesion strength, resistance to slippery, abrasion and health. The characteristics of small heat can be used to produce waterproof rubber coils, conveyor belts, plastic runways, washing machine door seals, rubber rollers, rubber stoppers, rubber stoppers, inner tubes, tire treads, tire sidewalls, air-conditioning hoses and other rubber products. However, it is weaker than ethylene-propylene rubber products reinforced by carbon black in terms of resilience and compression set resistance. Sulfur vulcanization and peroxide vulcanization are the two most commonly used vulcanization systems for ethylene-propylene rubber.
  • peroxide vulcanization can make vulcanizates have better heat resistance, aging resistance, resilience and compression set resistance.
  • the mechanical strength will be weaker than the sulfur vulcanized rubber compound. Therefore, how to obtain better aging resistance, resilience, mechanical properties and compression set resistance of rubber products reinforced by silica in a peroxide-based vulcanization system is a problem to be solved.
  • 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 a processing method thereof, which partially or completely replace ethylene-propylene rubber with a branched polyethylene having a branching degree of not less than 50 branches/1000 carbons. It can be applied to rubber products mainly reinforced by silica, and can obtain good heat resistance, compression set resistance and mechanical strength under the peroxide vulcanization system, and the defects of the prior art can be improved.
  • a rubber composition comprising: a rubber matrix and an essential component, the rubber matrix comprising: a content of branched polyethylene a: 0 ⁇ a ⁇ 100 parts; the content of the binary ethylene propylene rubber and the ethylene propylene diene rubber b: 0 ⁇ b ⁇ 100 parts; the essential component comprises: 1 to 10 parts of the crosslinking agent, based on 100 parts by weight of the rubber matrix, white
  • the carbon black is 15 to 80 parts, wherein 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 is ML (1+4) 125 ° C. Not less than 2.
  • Branched polyethylene in the prior art means, in addition to a branched ethylene homopolymer, a branched saturated vinyl copolymer, such as an ethylene- ⁇ -olefin copolymer, which may be POE, although POE performs well in physical and mechanical properties and aging resistance, but cross-linking performance is not good, although the branched polyethylene of the present invention can contain both branched ethylene homopolymer and POE, but a better choice It is a branched polyethylene having a high proportion of branched polyethylene or a branched ethylene homopolymer. In a preferred embodiment of the invention, the branched polyethylene contains only branched ethylene homopolymer.
  • the branched polyethylene used is a branched ethylene homopolymer unless otherwise specified.
  • the branched polyethylene used in the present invention is a kind of ethylene homopolymer having a branching degree of not less than 50 branches/1000 carbons, and can be called Branched Polyethylene or Branched PE.
  • the synthesis method is mainly composed of a late transition metal catalyst.
  • the homopolymerization of ethylene is catalyzed by a "chain walking mechanism", and the preferred late transition metal catalyst may be one of ( ⁇ -diimine) nickel/palladium catalysts.
  • the nature of the chain walking mechanism refers to the late transition metal catalyst.
  • the ( ⁇ -diimine) nickel/palladium catalyst is more likely to undergo ⁇ -hydrogen elimination reaction and re-insertion reaction in the process of catalyzing olefin polymerization, thereby causing branching.
  • Branched chains of such branched polyethylenes may have different numbers of carbon atoms, specifically 1 to 6, or more carbon atoms.
  • the production cost of the ( ⁇ -diimine) nickel catalyst is significantly lower than that of the ( ⁇ -diimine) palladium catalyst, and the ( ⁇ -diimine) nickel catalyst catalyzes the high rate of ethylene polymerization and high activity, and is more suitable for industrial applications. Therefore, the branched polyethylene prepared by the ethylene polymerization of the ( ⁇ -diimine) nickel catalyst is preferred in the present invention.
  • the degree of branching of the branched polyethylene used in the present invention is preferably 50 to 130 branches/1000 carbons, further preferably 60 to 130 branches/1000 carbons, further preferably 60 to 116 branches/1000.
  • a carbon, the degree of branching between POE and ethylene-propylene rubber, is a new technical solution that is different from the prior art, and can have excellent aging resistance and good cross-linking performance.
  • Cross-linking performance includes factors such as crosslink density and cross-linking rate, which is the specific performance of the cross-linking ability of the rubber matrix during processing.
  • the branched polyethylene used in the present invention preferably has a methyl branch content of 40% or more or 50% or more, and has a certain similarity with the structure of the ethylene propylene diene rubber.
  • the degree of branching (tertiary carbon atom content) and the steric hindrance around the tertiary carbon atom are the two main factors affecting the cross-linking ability of the saturated polyolefin.
  • the branched polyethylene used in the present invention is low in degree of branching relative to the ethylene propylene rubber, and since the branched polyethylene has a branch having a carbon number of not less than 2, the branched polycondensation used in the present invention
  • the steric hindrance around the tertiary carbon atom of ethylene is theoretically larger than that of ethylene propylene rubber. It can be judged by combining two factors that the crosslinking ability of the branched polyethylene used in the present invention should be weaker than that of the ethylene propylene rubber.
  • EPDM rubber In EPDM rubber. However, the actual cross-linking ability of the partially branched polyethylene used in the present invention is close to that of EPDM rubber, and may even be equal to or better than EPDM rubber. This means that the rubber composition of the present invention can obtain a good aging resistance, can also not weaken the crosslinking ability, and can even have excellent crosslinking performance to achieve an unexpected beneficial effect.
  • secondary branched structure refers to a structure in which branches are further branched. This is also known as "branch-on-branch" during chain walking. Because of the low steric hindrance around the tertiary carbon atoms of the secondary branches, cross-linking reactions are more likely to occur. Having a secondary branched structure is a distinct distinction between the branched polyethylene used in the preferred embodiment of the invention and the prior art ethylene dipropylene rubber or the conventional ethylene- ⁇ -olefin copolymer.
  • the vinyl copolymer refers to a copolymer of ethylene and a branched ⁇ -olefin, and has a secondary branched structure, wherein the branched ⁇ -olefin may be selected from the group consisting of isobutylene and 3-methyl-1- Butylene, 4-methyl-1-pentene, 3-methyl-1-pentene, 2-methyl-1-heptene, 3-methyl-1-heptene, 4-methyl-1- The heptene, 5-methyl-1-heptene, 6-methyl-1-heptene, and the like, the comonomer may also contain a common linear alpha-olefin.
  • branched polyethylene prepared by the ( ⁇ -diimine) nickel catalyst is difficult to exist in the secondary branched structure, and at least it is difficult to sufficiently distinguish it.
  • the technical solution of the present invention is also to analyze the branched polycondensation.
  • the structure of ethylene provides a new idea.
  • the cross-linking point of the branched polyethylene can be generated on the tertiary chain of the main chain during the peroxide crosslinking process. It can also be produced on the branched tertiary carbon of the secondary structure, so the rubber network formed by the cross-linking of the branched polyethylene has a richer CC connecting segment between the main chains than the ethylene-propylene rubber. The length can effectively avoid stress concentration and help to obtain better mechanical properties.
  • a further technical solution is that, in 100 parts by weight, the content of branched polyethylene in the rubber matrix is a: 10 ⁇ a ⁇ 100 parts; the content of binary ethylene propylene rubber and ethylene propylene diene rubber is b: 0 ⁇ b ⁇ 90 parts; the branched polyethylene is an ethylene homopolymer having a degree of branching of 60 to 130 branches/1000 carbons, a weight average molecular weight of 66,000 to 518,000, and a Mooney viscosity ML (1+4) ) 125 ° C is 6 ⁇ 102.
  • the content of the branched polyethylene in the 100 parts by weight of the rubber matrix is a: 10 ⁇ a ⁇ 100 parts; the content of the binary ethylene propylene rubber and the EPDM rubber is b: 0 ⁇ b ⁇ 90 parts
  • the branched polyethylene is an ethylene homopolymer having a degree of branching of 70 to 116 branches/1000 carbons, a weight average molecular weight of 201,000 to 436,000, and a Mooney viscosity of ML (1+4) 125 ° C. It is 23 to 101.
  • the content of the branched polyethylene in the 100 parts by weight of the rubber matrix is a: 10 ⁇ a ⁇ 100 parts; the content of the binary ethylene propylene rubber and the 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 40,600, and a Mooney viscosity of ML (1+4) of 125 ° C. It is 40 to 95.
  • a further technical solution is that, in 100 parts by weight, the content of the branched polyethylene in the rubber matrix is a: 10 ⁇ a ⁇ 100 parts; the 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 ⁇ 80.
  • the third monomer of the ethylene propylene diene monomer is preferably a diene monomer, specifically selected from the group consisting of 5-ethylidene-2-norbornene and 5-vinyl-2-nor Borneene, dicyclopentadiene, 1,4-hexadiene, 1,5-hexadiene, 1,4-pentadiene, 2-methyl-1,4-pentadiene, 3-methyl- 1,4-Hexadiene, 4-methyl-1,4-hexadiene, 1,9-decadiene, 5-methylene-2-norbornene, 5-pentylene-2-nor Borbornene, 1,5-cyclooctadiene, 1,4-cyclooctadiene, and the like.
  • a diene monomer specifically selected from the group consisting of 5-ethylidene-2-norbornene and 5-vinyl-2-nor Borneene, dicyclopentadiene, 1,4-hexadiene
  • the ethylene propylene rubber may contain two or more kinds of diene monomers at the same time, such as 5-ethylidene-2-norbornene and 5-vinyl-2-norbornene.
  • the functional group of the diene monomer can play the same role as the intrinsic co-crosslinking agent in the peroxide vulcanization, thereby improving the crosslinking efficiency. This helps to reduce the amount and residual amount of crosslinker and co-crosslinker required and the cost of adding them.
  • the weight specific gravity of the diene monomer to the ethylene propylene rubber is preferably from 1% to 14%, more preferably from 3% to 10%, still more preferably from 4% to 7%.
  • the crosslinking agent comprises at least one of a peroxide crosslinking agent and a sulfur
  • the peroxide crosslinking agent comprises di-tert-butyl peroxide, dicumyl peroxide, Tert-butyl cumyl peroxide, 1,1-di-tert-butyl peroxide-3,3,5-trimethylcyclohexane, 2,5-dimethyl-2,5-di(tert-butyl) Base oxidized) hexane, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne-3, bis(tert-butylperoxyisopropyl)benzene, 2,5-di At least one of methyl-2,5-bis(benzoyl peroxy)hexane, tert-butyl peroxybenzoate, and t-butylperoxy-2-ethylhexyl carbonate.
  • the essential component contains 2 to 7 parts of a crosslinking agent and 30 to 60 parts of white carbon black based on 100 parts by weight of the rubber base.
  • the white carbon black is at least one of a precipitation method white carbon black and a fumed silica
  • the precipitation method white carbon black is a highly dispersible precipitation method white carbon black.
  • transparent white carbon black may be used, and the particle diameter is preferably 10 to 50 nm, and more preferably 15 to 30 nm.
  • the rubber composition further comprises an auxiliary component, which comprises: 0.2 to 10 parts of a co-crosslinking agent, 20 to 120 parts of an inorganic filler, and a plasticizer, based on 100 parts by weight of the rubber matrix. 2 to 130 parts, stabilizer 1 to 3 parts, metal oxide 2 to 20 parts, surface modifier 1 to 20 parts, coloring agent 1 to 10 parts, vulcanization accelerator 0 to 3 parts, binder 0 to 20 Share.
  • an auxiliary component which comprises: 0.2 to 10 parts of a co-crosslinking agent, 20 to 120 parts of an inorganic filler, and a plasticizer, based on 100 parts by weight of the rubber matrix. 2 to 130 parts, stabilizer 1 to 3 parts, metal oxide 2 to 20 parts, surface modifier 1 to 20 parts, coloring agent 1 to 10 parts, vulcanization accelerator 0 to 3 parts, binder 0 to 20 Share.
  • the stabilizer comprises 2,2,4-trimethyl-1,2-dihydroquinoline polymer (RD), 6-ethoxy-2,2,4-trimethyl At least one of -1,2-dihydroquinoline (AW) and 2-mercaptobenzimidazole (MB).
  • RD 2,2,4-trimethyl-1,2-dihydroquinoline polymer
  • AW 6-ethoxy-2,2,4-trimethyl
  • MB 2-mercaptobenzimidazole
  • 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, a metal salt of an unsaturated carboxylic acid, and sulfur.
  • the unsaturated carboxylic acid metal salt contains at least one of zinc acrylate, zinc methacrylate, and magnesium methacrylate.
  • the plasticizer comprises at least one of pine tar, engine oil, naphthenic oil, paraffin oil, coumarone, RX-80, stearic acid, and paraffin wax.
  • 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 comprises at least one of zinc oxide, magnesium oxide, and calcium oxide.
  • the inorganic filler comprises at least one of calcium carbonate, talc, calcined clay, magnesium silicate, magnesium carbonate, and barium sulfate.
  • the surface modifier comprises 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 colorant comprises at least one of titanium dioxide, indigo blue, indocyanine green, and carbon black.
  • the vulcanization accelerator comprises 2-thiol benzothiazole, dibenzothiazyl disulfide, tetramethyl thiuram monosulfide, tetramethyl thiuram disulfide, tetrazyl disulfide Kethiram, N-cyclohexyl-2-benzothiazolyl sulfenamide, N,N-dicyclohexyl-2-benzothiazolyl sulfenamide, bismaleimide, ethylene thiourea At least one of them.
  • the binder comprises at least one of a resorcinol donor and a methylene donor.
  • the resorcinol donor may be selected from the group consisting of resorcinol (adhesive R), binder RS, binder RS-11, binder R-80, binder RL, binder binder At least one of PF, binder PE, binder RK, binder RH; the methylene donor may be selected from hexamethylenetetramine (HMTA), binder H-80, binder A, at least one of 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.
  • a tackifier wherein the plasticizer is pine tar, coumarone resin, RX-80, and liquid polyisobutylene.
  • a commonly used tackifier such as a phenol resin, a modified alkyl phenol resin, or an alkyl phenol-acetylene resin, and the tackifier is generally not more than 30 parts by weight, further preferably not more than 10 parts by weight, based on 100 parts by weight of the rubber base. It is further preferably not more than 5 parts by weight.
  • crosslinking agent the co-crosslinking agent and the vulcanization accelerator involved in the rubber composition provided by the present invention all belong to a crosslinking system.
  • the rubber composition of the present invention may be present in the form of an uncrosslinked rubber compound, and may be present in the form of a vulcanized rubber after further crosslinking reaction.
  • Vulcanized rubber can also be referred to simply as vulcanizate.
  • the present invention also provides a method of processing the above rubber composition, the processing method comprising the steps of:
  • Rubber kneading First, the rubber composition other than the cross-linking system is sequentially added to the internal mixer for mixing by weight, and then added to the cross-linking system, uniformly kneaded, and discharged to obtain a rubber compound. The rubber compound is thinned on the open mill and then 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 The rubber compound is filled into the cavity of the mold, and after being vulcanized by vulcanization on a flat vulcanizer, the vulcanized rubber is obtained by demolding.
  • the present invention also provides a rubber pellet for a plastic track surface layer, the rubber compound used comprising the above rubber composition.
  • the invention also provides a method for producing rubber particles for a plastic track surface layer, the production method comprising the following steps:
  • Rubber kneading First, the rubber composition components other than the cross-linking system are sequentially added to an internal mixer in terms of parts by weight, and then kneaded, and then added to the cross-linking system, uniformly kneaded, and discharged to obtain a rubber compound to be mixed. Use, the rubber compound is thinned on the open mill, the next piece, parked for 20 hours, refining, triangle bag on the open mill, adjust the roll distance, the next piece.
  • the crosslinking system comprises a crosslinking agent, and may further comprise at least one of a co-crosslinking agent and a vulcanization accelerator;
  • Extrusion and vulcanization The extrusion vulcanization process should adopt an evacuation extruder, and after the extrusion, a salt bath vulcanization process is adopted;
  • the present invention also provides an insulating layer or sheathing layer for a cable, the compound used comprising the above rubber composition.
  • the invention also provides a method for producing an insulating layer or a sheath layer rubber for a cable, and the production process steps are as follows:
  • Rubber kneading First, the rubber composition components other than the cross-linking system are sequentially added to an internal mixer in terms of parts by weight, and then kneaded, and then added to the cross-linking system, uniformly kneaded, and discharged to obtain a rubber compound to be mixed. The mixture is thinly passed on the open mill, the lower piece is left for 20 hours, and the refining is carried out. The triangle package is set on the open mill to adjust the roll distance and the lower piece.
  • the cross-linking system contains a crosslinking agent. At least one of a co-crosslinking agent and a vulcanization accelerator may also be included;
  • the present invention also provides a high temperature resistant conveyor belt having at least one layer of the working surface covering rubber and the non-working surface covering rubber comprising the rubber composition provided by the present invention.
  • the invention also provides a method for producing a high temperature resistant conveyor belt, wherein the working surface covering glue comprises the above rubber composition, and the production method comprises the following steps:
  • (1) kneading the components of the rubber composition other than the cross-linking system are sequentially added to an internal mixer according to parts by weight, and then kneaded, and then added to the cross-linking system, uniformly kneaded, and discharged, to obtain a kneaded rubber to be used.
  • 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 and then vulcanized;
  • the present invention also provides a waterproofing membrane comprising the above rubber composition.
  • the present invention also provides a method of producing a waterproof membrane, the production method comprising the following steps:
  • (1) kneading the components of the rubber composition other than the cross-linking system are sequentially added to an internal mixer according to parts by weight, and then kneaded, and then added to the cross-linking system, uniformly kneaded, and discharged, to obtain a kneaded rubber to be used.
  • the block rubber is fed into an open mill and kneaded to obtain a film with a smooth and uniform surface, which is cooled to below 50 ° C to be discharged and stacked.
  • the crosslinking system comprises a crosslinking agent, and may further comprise at least one of a co-crosslinking agent and a vulcanization accelerator;
  • Hot-smelting the film is uniformly heated on the open mill, smoothed and evenly rolled into a roll;
  • vulcanization the coiled material is placed in a 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 rubber stopper comprising the above rubber composition.
  • the invention also provides a method of producing a rubber stopper comprising the following steps:
  • the rubber composition components other than the cross-linking system are sequentially added to an internal mixer in terms of parts by weight, and kneaded, and then added to the cross-linking system to be uniformly kneaded and discharged.
  • the rubber compound is opened and compressed on an open mill, and then parked for use, the crosslinking system comprises a crosslinking agent, and may further comprise at least one of a crosslinking agent and a vulcanization accelerator;
  • vulcanization vulcanizing the extruded rubber by an injection molding vulcanizer
  • Post-treatment punching, cleaning and silicidation, obtaining finished products, packaging and storage.
  • the present invention also provides a rubber roller comprising the above rubber composition.
  • the invention also provides a method of producing a rubber roller comprising the following production steps:
  • Rubber mixing setting the temperature of the internal mixer and the rotation speed of the rotor, and adding the components other than the crosslinking system in the rubber composition to the internal mixer for mixing; then adding the crosslinking system, mixing and arranging gum.
  • the crosslinking system comprises a crosslinking agent, and may further comprise at least one of a co-crosslinking agent and a vulcanization accelerator. The rubber compound is thinned in the open mill, parked and tested;
  • Post-treatment The vulcanized rubber roller is rough-processed on a lathe, and then finished on a grinding machine for inspection and inspection to obtain a finished product.
  • the present invention also provides an inner tube having a rubber composition comprising the above rubber composition.
  • the invention also provides a method for producing a inner tube, comprising the steps of: first kneading rubber, filtering and parking; then extruding through an extruder, cutting according to the length required by the process, sticking the valve, splicing After parking; then inflated and shaped, steam vulcanized, cooled, inspected, trimmed to get the finished product.
  • the present invention also provides a tire comprising at least one of a rubber for a sidewall and a rubber for a tread comprising the above rubber composition.
  • a further technical solution is a rubber composition for a tread or a side wall in which the content of the branched polyethylene is not less than 70 parts by weight in 100 parts by weight of the rubber base.
  • the tire provided by the present invention is preferably used as a force tire.
  • the tires can be non-motorized tires such as bicycle tires, trolley tires, animal tires, and electric tires.
  • it can be preferably used as a white or colored bicycle tire.
  • 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 kneaded rubber 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. The unvulcanized tire is heated and pressurized in a vulcanizer to obtain a tire.
  • the rubber composition of the present invention can be used as a tread rubber, and a tire can be produced by a usual method. That is, the kneaded rubber is subjected to extrusion processing in accordance with the tread 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. 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 present invention also provides an air-conditioning hose comprising, in order from the inside to the outside, a barrier layer, an inner rubber layer, a braid layer and an outer rubber layer; wherein the rubber compound used in the inner rubber layer comprises the rubber composition.
  • the invention also provides a method for producing an air-conditioning hose, comprising the steps of: extruding a nylon layer on a hose mold core rod, and coating a nylon layer on the core rod to form a barrier layer, and then in a core with a barrier layer
  • the inner rubber layer is extruded on the rod, and the outer surface of the inner rubber layer is woven, which is a braid layer, and then the outer rubber layer is extruded on the braid layer, which is a semi-finished air-conditioning hose, and the semi-finished rubber tube is vulcanized, and the core rod is Take out and get the finished hose.
  • the present invention also provides a catheter characterized in that the compound used comprises the above rubber composition.
  • the catheter provided by the present invention is suitable for use as a medical catheter or a food catheter.
  • the present invention also provides a method of producing the above-mentioned catheter, characterized in that the molding method is extrusion molding or compression molding, and the vulcanization method is selected from the group consisting of compression vulcanization or high temperature steam vulcanization.
  • the molding method is preferably an extrusion molding method, and the high-temperature steam vulcanization process is suitable for a peroxide crosslinking system, and the peroxide is preferably bis(2,4-dichlorobenzoyl peroxide) or 2,5-dimethyl-2 peroxide. Further, 5-di(tert-butylperoxy)hexane, the peroxide addition form is more preferably a paste.
  • the vulcanization system in the rubber composition of the hose can be selected from a radiation crosslinking system, and the vulcanization method selects a radiation crosslinking process, when a small amount of peroxidation is contained.
  • the object such as DCP
  • the speed of radiation crosslinking can be significantly accelerated.
  • the invention has the beneficial effects that since the molecular structure of the branched polyethylene is completely saturated, the heat aging resistance is similar to that of the ethylene propylene rubber, which is superior to the EPDM rubber, and can be used.
  • the oxide system is vulcanized.
  • the branched polyethylene has more branches in its molecular structure, and the length of the branch has a certain length and length distribution, and a proper number of secondary branched structures exist, in the process of peroxide crosslinking, branching
  • the cross-linking point of polyethylene can be produced on the tertiary chain of the main chain or on the branched tertiary carbon of the secondary structure, so the rubber network formed by crosslinking of the branched polyethylene by peroxide cross-links with ethylene-propylene rubber.
  • the main chain there is a richer CC link segment length, which can effectively avoid stress concentration and help to obtain better mechanical properties.
  • 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 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 45, more preferably 40 to 45, and preferably 50 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, preferably ethylene, 50% to 75%, and the third monomer is 5-ethylene. 2-norbornene, 5-vinyl-2-norbornene or dicyclopentadiene, the third monomer content being from 1% to 7%.
  • the ethylene-propylene rubber and the ethylene-propylene diene rubber selected from the rubber base have a Mooney viscosity ML (1+4) of 125 ° C, preferably 40 to 80, and an ethylene content of preferably 45% to 75%.
  • 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 strength test in accordance with the national standard GB/T529-2008, using an electronic tensile test machine for testing, the tensile speed is 500mm / min, the test temperature is 23 ⁇ 2 ° C, the sample is a rectangular sample;
  • compression permanent deformation test in accordance with the national standard GB/T7759-1996, using a compression permanent deformation device for testing, type B, the compression is 25%, the test temperature is 70 ° C;
  • Mooney viscosity test in accordance with the national standard GB/T1232.1-2000, with Mooney viscosity meter for testing, the test temperature is 125 ° C, preheat 1 minute, test 4 minutes;
  • test conditions are 150 ° C ⁇ 72h;
  • the vulcanization conditions of the following Examples 1 to 18 and Comparative Examples 1 to 3 were as follows: temperature: 160 ° C; pressure: 16 MPa; time was Tc90 + 2 min.
  • the branched polyethylene used was numbered PER-4.
  • Rubber mixing set the temperature of the mixer to 90 ° C, the rotor speed is 50 rpm, add 70 parts of EPDM rubber and 30 parts of branched polyethylene pre-pressed for 90 seconds; add 40 parts of white Carbon black, kneading for 3 minutes; then adding 2 parts of cross-linking agent dicumyl peroxide (DCP), mixing for 2 minutes and then discharging the glue.
  • DCP cross-linking agent dicumyl peroxide
  • the branched polyethylene used was numbered PER-4.
  • Rubber mixing set the temperature of the internal mixer to 90 ° C, the rotor speed to 50 rpm, add 50 parts of EPDM rubber and 50 parts of branched polyethylene pre-pressed for 90 seconds; add 40 parts of white Carbon black, kneading for 3 minutes; then adding 2 parts of cross-linking agent dicumyl peroxide (DCP), mixing for 2 minutes and then discharging the glue.
  • DCP cross-linking agent dicumyl peroxide
  • the branched polyethylene used was numbered PER-4.
  • Rubber mixing set the temperature of the internal mixer to 90 ° C, the rotor rotation speed is 50 rev / min, add 100 parts of branched polyethylene pre-pressure mixing for 90 seconds; add 40 parts of white carbon black, mix for 3 minutes; Then, 2 parts of cross-linking agent dicumyl peroxide (DCP) was added, and after 2 minutes of mixing, the gum was discharged.
  • DCP cross-linking agent dicumyl peroxide
  • the branched polyethylene used was numbered PER-4.
  • Rubber mixing set the temperature of the internal mixer to 90 ° C, the rotor rotation speed is 50 rev / min, add 100 parts of branched polyethylene pre-pressure mixing for 90 seconds; add 40 parts of white carbon black, mix for 3 minutes; Then, 2 parts of a cross-linking agent, dicumyl peroxide (DCP) and 0.2 parts of a cross-linking agent, sulfur were 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. Refining, three times on the open mill triangle, adjust the roller distance to 2.5mm, the next piece.
  • DCP dicumyl peroxide
  • Rubber mixing set the temperature of the mixer to 90 ° C, the rotor speed is 50 rpm, add 100 parts of EPDM rubber for 90 seconds, add 40 parts of silica, and mix for 3 minutes. Then, 2 parts of cross-linking agent dicumyl peroxide (DCP) was added, and after 2 minutes of mixing, the gum was 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. Refining, three times on the open mill triangle, adjust the roller distance to 2.5mm, the next piece.
  • DCP dicumyl peroxide
  • the branched polyethylene used was numbered PER-5.
  • Rubber mixing set the temperature of the internal mixer to 90 ° C, the rotor speed is 50 rpm, add 90 parts of EPDM rubber and 10 parts of branched polyethylene for 90 seconds; 40 parts of white Carbon black, mixing for 3 minutes; then adding 3 parts of cross-linking agent dicumyl peroxide (DCP) and 1 part of the cross-linking agent triallyl isocyanurate (TAIC), mixing for 2 minutes gum.
  • DCP dicumyl peroxide
  • TAIC cross-linking agent 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, 50 parts of ethylene propylene diene monomer and 30 parts of branched polyethylene pre-pressure mixing. 90 seconds; add 40 parts of silica, mix for 3 minutes; then add 3 parts of cross-linking dicumyl peroxide (DCP) and 1 part of cross-linking agent triallyl isocyanurate (TAIC) ), after 2 minutes of mixing, the glue is 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. Refining, three times on the open mill triangle, adjust the roller distance to 2.5mm, the next piece.
  • DCP cross-linking dicumyl peroxide
  • TAIC cross-linking agent 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 EPDM rubber and 80 parts of branched polyethylene pre-pressed for 90 seconds; add 40 parts of white Carbon black, mixing for 3 minutes; then adding 3 parts of cross-linking agent dicumyl peroxide (DCP) and 1 part of the cross-linking agent triallyl isocyanurate (TAIC), mixing for 2 minutes gum.
  • DCP dicumyl peroxide
  • TAIC cross-linking agent triallyl isocyanurate
  • the branched polyethylene used was numbered PER-5.
  • Rubber mixing set the temperature of the internal mixer to 90 ° C, the rotor rotation speed is 50 rev / min, add 100 parts of branched polyethylene pre-pressure mixing for 90 seconds; add 40 parts of white carbon black, mix for 3 minutes; Then, 3 parts of a cross-linking agent, dicumyl peroxide (DCP) and 1 part of a cross-linking agent, triallyl isocyanurate (TAIC), were 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. Refining, three times on the open mill triangle, adjust the roller distance to 2.5mm, the next piece.
  • DCP dicumyl peroxide
  • TAIC triallyl isocyanurate
  • Rubber mixing set the temperature of the mixer to 90 ° C, the rotor speed is 50 rpm, add 100 parts of EPDM rubber for 90 seconds, add 40 parts of silica, and mix for 3 minutes. Then, 3 parts of cross-linking agent dicumyl peroxide (DCP) and 1 part of cross-linking agent triallyl isocyanurate (TAIC) were 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. Refining, three times on the open mill triangle, adjust the roller distance to 2.5mm, the next piece.
  • DCP dicumyl peroxide
  • TAIC cross-linking agent triallyl isocyanurate
  • the branched polyethylene used was numbered PER-9.
  • Rubber mixing set the temperature of the internal mixer to 100 ° C, the rotor speed to 50 rpm, add 90 parts of EPDM rubber and 10 parts of branched polyethylene for 90 seconds premixing; add 5 parts of oxidation Zinc, 1 part stearic acid, 3 parts polyethylene glycol PEG4000, 2 parts vinyl tris(2-methoxyethoxy) silane (A-172) and 1 part antioxidant 2,2,4-trimethyl Base-1,2-dihydroquinoline polymer (RD), kneaded for 2 minutes; then add 60 parts of white carbon black, 20 parts of calcined clay and 20 parts of paraffin oil SUNPAR 2280 to the compound, and knead for 3 minutes; 4 parts of cross-linking agent dicumyl peroxide (DCP) and 1 part of the cross-linking agent triallyl isocyanurate (TAIC) were added, and the mixture was kneaded for 2 minutes and then discharged.
  • the rubber compound was thinly spread on an open mill to obtain
  • the branched polyethylene used was numbered PER-8.
  • Rubber mixing set the temperature of the internal mixer to 100 ° C, the rotor speed to 50 rpm, add 80 parts of ethylene propylene diene monomer and 20 parts of branched polyethylene for 90 seconds; add 5 parts of oxidation Zinc, 1 part stearic acid, 3 parts polyethylene glycol PEG4000, 2 parts vinyl tris(2-methoxyethoxy) silane (A-172) and 1 part antioxidant 2,2,4-trimethyl Base-1,2-dihydroquinoline polymer (RD), kneaded for 2 minutes; then add 60 parts of silica, 20 parts of calcined clay and 20 parts of paraffin oil SUNPAR 2280 to the compound, and knead for 3 minutes; 4 parts of cross-linking agent dicumyl peroxide (DCP) and 1 part of the cross-linking agent triallyl isocyanurate (TAIC) were added, and the mixture was kneaded for 2 minutes and then discharged.
  • the rubber compound was thinly spread on an open
  • 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 20 parts of ethylene propylene diene rubber, 30 parts of ethylene propylene diene rubber and 50 parts of polyethylene pre-pressure mixing 90 seconds; add 5 parts of zinc oxide, 1 part of stearic acid, 3 parts of polyethylene glycol PEG4000, 2 parts of vinyltris(2-methoxyethoxy)silane (A-172) and 1 part of antioxidant 2 , 2,4-trimethyl-1,2-dihydroquinoline polymer (RD), kneaded for 2 minutes; then add 60 parts of silica, 20 parts of calcined clay and 20 parts of paraffin oil SUNPAR2280 to the compound.
  • the branched polyethylene used was numbered PER-7.
  • Rubber mixing set the temperature of the internal mixer to 100 ° C, the rotor speed to 50 rpm, add 100 parts of branched polyethylene pre-pressed and kneaded for 90 seconds; add 5 parts of zinc oxide, 1 part of stearic acid, 3 parts of polyethylene glycol PEG4000, 2 parts of vinyltris(2-methoxyethoxy)silane (A-172) and 1 part of antioxidant 2,2,4-trimethyl-1,2-dihydrogenation Quinoline polymer (RD), kneaded for 2 minutes; then add 60 parts of silica, 20 parts of calcined clay, 10 parts of titanium dioxide and 20 parts of paraffin oil SUNPAR 2280 to the compound, knead for 3 minutes; finally add 4 parts
  • the cross-linking agent dicumyl peroxide (DCP), 1 part of the cross-linking agent triallyl isocyanurate (TAIC) and 0.3 parts of the cross-linking agent sulfur were mixed for 2 minutes and then discharged.
  • the branched polyethylenes used were numbered PER-1 and PER-7.
  • Rubber mixing set the temperature of the internal mixer to 100 ° C, the rotor speed to 50 rpm, add 70 parts of PER-7 and 30 parts of PER-1 pre-pressing for 90 seconds; add 10 parts of zinc oxide, 2 Parts stearic acid, 2 parts polyethylene glycol PEG4000, 1 part vinyl tris(2-methoxyethoxy) silane (A-172) and 1 part antioxidant 2,2,4-trimethyl-1 , 2-dihydroquinoline polymer (RD), kneaded for 2 minutes; then add 10 parts of titanium dioxide, 15 parts of white carbon, 60 parts of calcined clay, 40 parts of aluminum silicate and 120 parts of paraffin oil to the compound.
  • the branched polyethylene used was numbered PER-4.
  • Rubber mixing set the temperature of the internal mixer to 100 ° C, the rotor speed is 50 rpm, add 100 parts of branched polyethylene pre-pressed and kneaded for 90 seconds; add 20 parts of zinc oxide, 2 parts of stearic acid, 5 parts polyethylene glycol PEG4000, 2 parts vinyl tris(2-methoxyethoxy)silane (A-172) and 1 part antioxidant 2,2,4-trimethyl-1,2-dihydrogenation Quinoline polymer (RD), kneaded for 2 minutes; then add 40 parts of silica, 80 parts of talc and 20 parts of paraffin oil SUNPAR2280 to the compound, knead for 3 minutes; finally add 5 parts of cross-linking agent peroxidation Dicumyl (DCP) and 2 parts of the cross-linking agent, triallyl isocyanurate (TAIC), were mixed for 2 minutes and then discharged.
  • the rubber compound was thinly spread on an open mill to obtain a sheet having a thickness of about 2.5 mm
  • the branched polyethylenes used were numbered PER-3 and PER-6.
  • Rubber mixing set the temperature of the internal mixer to 100 ° C, the rotor speed to 50 rpm, add 80 parts of PER-6 and 20 parts of PER-3 pre-pressure mixing for 90 seconds; add 10 parts of zinc oxide, 2 Stearic acid, 10 parts polyethylene glycol PEG4000, 3 parts vinyl tris(2-methoxyethoxy)silane (A-172) and 1 part antioxidant 2,2,4-trimethyl-1 , 2-dihydroquinoline polymer (RD), kneaded for 2 minutes; then add 80 parts of silica, 50 parts of calcined clay and 50 parts of paraffin oil SUNPAR 2280 to the compound, knead for 3 minutes; finally add 10 parts Cross-linking agent dicumyl peroxide (DCP), 2 parts of cross-linking agent triallyl isocyanurate (TAIC) and 8 parts of 1,2-polybutadiene, after 2 minutes of mixing .
  • DCP cross-linking agent dicumyl peroxide
  • TAIC cross-
  • the branched polyethylene used was numbered PER-6.
  • Rubber mixing set the temperature of the internal mixer to 100 ° C, the rotor rotation speed is 50 rpm, add 100 parts of branched polyethylene pre-pressure mixing for 90 seconds; add 10 parts of zinc oxide, 2 parts of stearic acid, 5 parts polyethylene glycol PEG4000, 2 parts vinyl tris(2-methoxyethoxy)silane (A-172) and 1 part antioxidant 2,2,4-trimethyl-1,2-dihydrogenation Quinoline polymer (RD), kneaded for 2 minutes; then add 5 parts of iron oxide red, 60 parts of silica, 70 parts of calcined clay, 50 parts of calcium carbonate and 55 parts of paraffin oil SUNPAR 2280 in the compound, mixing 3 Minute; finally add 6 parts of cross-linking agent dicumyl peroxide (DCP), 2 parts of cross-linking agent N, N'-m-phenylene bismaleimide (HVA-2) and 0.3 parts of sulfur, mixed After 2 minutes of smelting, the glue is discharged.
  • DCP
  • the branched polyethylene used was numbered PER-5.
  • Rubber mixing set the temperature of the internal mixer to 100 ° C, the rotor speed to 50 rpm, add 100 parts of PER-5 pre-pressure mixing for 90 seconds; add 5 parts of zinc oxide, 1 part of stearic acid, 2 Polyethylene glycol PEG4000, 1 part vinyltris(2-methoxyethoxy)silane (A-172) and 1 part antioxidant 2,2,4-trimethyl-1,2-dihydroquine
  • the porphyrin polymer (RD) was kneaded for 2 minutes; then 10 parts of titanium dioxide, 40 parts of silica, 40 parts of calcined clay and 70 parts of paraffin oil SUNPAR 2280 were added to the compound, and kneaded for 3 minutes;
  • the rubber compound was thinly spread on an open mill to obtain a sheet having a thickness of about 2.5
  • the branched polyethylene used was numbered PER-4.
  • Rubber mixing set the temperature of the internal mixer to 100 ° C, the rotor speed to 50 rpm, add 100 parts of PER-4 pre-pressure mixing for 90 seconds; add 5 parts of zinc oxide, 0.5 parts of stearic acid and 2 Part of vinyl tris(2-methoxyethoxy)silane (A-172), kneaded for 2 minutes; then add 4 parts of iron oxide red, 60 parts of silica, 50 parts of calcium carbonate and 30 to the compound. Part 300# paraffin oil, kneaded for 3 minutes; finally added 4 parts of cross-linking agent dicumyl peroxide (DCP), and kneaded for 2 minutes and then discharged.
  • the rubber compound was thinly spread on an open mill to obtain a sheet having a thickness of about 2.5 mm and parked for 20 hours. Refining, three times on the open mill triangle, adjust the roller distance to 2.5mm, the next piece.
  • a high-voltage insulating sheathing compound, the branched polyethylene used is numbered PER-4.
  • Vulcanization process steam vulcanization, 155 ° C ⁇ 40 minutes, immersed in water.
  • Performance test hardness: 71; tensile strength: 14.7 MPa; elongation at break: 566%; volume resistivity: 2.5 ⁇ 10 ⁇ 15; 150 ° C ⁇ 72 h after hot air aging: hardness: 78; tensile strength retention : 76%; elongation at break retention: 78%.
  • the high temperature resistant conveyor belt is provided with a cored tensile canvas between the working surface covering rubber and the non-working surface covering rubber, which makes them a solid whole through molding and vulcanization process.
  • 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 2.5 MPa, and the vulcanization temperature was 160 °C.
  • 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 vulcanization kettle for vulcanization treatment, the temperature of the vulcanization kettle is controlled between 155 and 165 ° C, the pressure is between 20 and 50 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.
  • a plastic rubber track surface layer is made of red rubber particles, and the production process steps are as follows:
  • Rubber mixing set the temperature of the internal mixer to 100 ° C, the rotor speed is 50 rpm, add 100 parts of branched polyethylene PER-8 pre-pressure mixing for 90 seconds; add 10 parts of zinc oxide, 2 parts of hard Fatty acid, 5 parts polyethylene glycol PEG4000, 2 parts vinyltris(2-methoxyethoxy)silane (A-172) and 1 part antioxidant 2,2,4-trimethyl-1,2 - a dihydroquinoline polymer (RD), kneaded for 2 minutes; then 5 parts of iron oxide red, 60 parts of silica, 70 parts of calcined clay, 50 parts of calcium carbonate and 55 parts of paraffin oil SUNPAR 2280 were added to the compound.
  • RD dihydroquinoline polymer
  • the extrusion vulcanization process should adopt vacuum pumping extruder.
  • the temperature of the extruder is set to 100 °C
  • the screw temperature is 75 °C
  • the head pressure should be controlled at 23 MPa
  • the extruder speed is 25 rpm.
  • Min using salt bath vulcanization process, the temperature of the spray section is 240 ° C
  • the temperature of the dipping section is 220 ° C
  • the temperature of the dipping section is 220 ° C
  • the transmission speed is 40 m / min
  • the cooling section temperature is 25 ° C.
  • a rubber plug, the molding vulcanization production process comprises the following steps:
  • Rubber mixing set the temperature of the internal mixer to 80 ° C, the rotor speed to 50 rpm, add 100 parts of branched polyethylene PER-4 and 3 parts of zinc oxide pre-pressure mixing for 90 seconds; Add 50 parts of barium sulfate, 10 parts of titanium dioxide, 35 parts of highly dispersible white carbon and 2 parts of petrolatum, mix for 3 minutes; finally add 3 parts of crosslinker bis(tert-butylperoxyisopropyl)benzene, 1 part of the cross-linking agent TAIC, after 2 minutes of mixing, the glue was discharged.
  • the rubber compound was opened and rolled on an open mill with a roll temperature of 60 ° C, and the mixture was allowed to stand for 20 hours. The rubber compound was opened and compressed on an open mill, and then parked for use;
  • vulcanization the calendered rubber is placed in a mold, and is subjected to mold vulcanization at a temperature of 160 ° C, a pressure of 15 MPa, a time of 25 minutes, and after a predetermined curing time, demolding is cooled;
  • Post-treatment punching, cleaning and silicidation, obtaining finished products, packaging and storage.
  • a rubber roller whose production processing steps are as follows:
  • vulcanization tank vulcanization the rubberized rubber roller is sent to the vulcanization tank, after closing the tank door, steam is vulcanized into the vulcanization tank, and the compressed air valve is opened while steam is introduced, and the compressed air is passed to vulcanize.
  • the pressure in the tank reaches 4.5 to 5 atmospheres in 0.5 hours; the vulcanization procedure is: firstly heat up to 70-80 ° C, keep warm for 2 hours; then heat up to 100-110 ° C, keep warm for 0.5 hours; then heat up to 120-130 ° C, keep warm 0.5 hours; further increase to 135 ⁇ 140 ° C, heat 8 ⁇ 10 hours.
  • the exhaust valve is opened, the pressure drops, and when the pressure gauge pointer points to zero, the safety pin is opened, and the steam is discharged from the pin hole, and the vulcanization tank is half-opened to lower the temperature until the temperature in the tank is lower than 60 ° C or Pull out the rubber roller when it is equivalent to room temperature;
  • the vulcanized rubber roller is rough-processed on a lathe, and then finished on a grinding machine for inspection and inspection to obtain a finished product.
  • Rubber mixing set the temperature of the internal mixer to 100 ° C, the rotor speed to 50 rpm, add 100 parts of branched polyethylene PER-5 pre-pressure mixing for 90 seconds; add 5 parts of zinc oxide, 1 part of hard Fatty acid, 5 parts of polyethylene glycol PEG4000 and 2 parts of vinyltris(2-methoxyethoxy)silane (A-172), kneaded for 2 minutes; then add 40 parts of white carbon black to the compound.
  • 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 add 30 parts of highly dispersible white carbon, 30 parts of calcium carbonate, 5 parts of coumarone resin and 10 parts of paraffin oil SUNPAR 2280, mixed for 3 minutes; then added 4 parts of cross-linking agent dicumyl peroxide (DCP), 1.5 parts of cross-linking agent N, N' - M-phenylene bismaleimide (HVA-2) and 0.3 parts of a cross-linking agent sulfur, which were kneaded for 2 minutes and then discharged.
  • DCP cross-linking agent dicumyl peroxide
  • HVA-2 cross-link
  • 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 20 Part of high dispersibility silica, 40 parts of light calcium carbonate, 5 parts of coumarone resin and 10 parts of paraffin oil SUNPAR2280, mixing for 3 minutes; then adding 4 parts of crosslinker di-tert-butylperoxy cumene (BIPB), 1.5 parts of the cross-linking agent triallyl isocyanurate (TAIC) and 3 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 color tire 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 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 polyethylene glycol PEG4000, 2 parts of coumarone resin, 2 parts of Escorez-1102 tackifying resin and 1 part of antioxidant RD, kneaded for 2 minutes; then add 2 parts of yellow masterbatch, 20 parts of highly disperse white Carbon black, 40 parts of light calcium carbonate and 10 parts of paraffin oil SUNPAR2280, mixed for 3 minutes; then added 4 parts of cross-linking agent bis-tert-butylperoxy isopropylbenzene (BIPB), 1.5 parts of cross-linking agent triene Propyl isocyanurate (TAIC) and 3 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 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 add 30 parts of highly dispersible white carbon, 30 parts of calcium carbonate, 5 parts of coumarone resin and 10 parts of paraffin oil SUNPAR 2280, mixed for 3 minutes; then added 4 parts of cross-linking agent dicumyl peroxide (DCP), 1.5 parts of cross-linking agent N, N' - M-phenylene bismaleimide (HVA-2) and 0.3 parts of a cross-linking agent sulfur, which were kneaded for 2 minutes and then discharged.
  • DCP cross-linking agent dicumyl peroxide
  • HVA-2 cross-link
  • Extrusion molding The qualified rubber compound is extruded through an extruder to obtain a rubber member having a side wall shape to be used.
  • Inner rubber layer rubber mixing one-stage mixing: set the temperature of the internal mixer to 80 ° C, the rotor rotation speed is 50 rpm, and add 100 parts of branched polyethylene PER-3 pre-pressing and kneading for 90 seconds; Parts of zinc oxide, 1 part stearic acid, 2 parts of polyethylene glycol PEG4000 and 2 parts of vinyl tris(2-methoxyethoxy)silane (A-172), kneaded for 2 minutes; then in the compound Add 30 parts of white carbon black, 3 parts of RS and 15 parts of liquid polyisobutylene, mix for 3 minutes, and disperse the glue; two-stage mixing: set the temperature of the internal mixer to 80 ° C, the rotor speed is 50 rev / min, the master will be Add the glue to the internal mixer, add 10 parts of AB-30, mix for 2 minutes; finally add 4 parts of cross-linking agent dicumyl peroxide (DCP) and 2 parts of cross-linking agent N, N'-
  • the hose mold core rod is passed through a PPA (polyphthalamide) extruder, and the PPA raw material is extruded on the core rod, and the PPA is coated on the core rod to form a barrier layer;
  • the inner rubber layer is woven, the fiber reinforced layer is woven, and the outer rubber layer is extruded;
  • 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.
  • a medical catheter adopting an extrusion molding and high-temperature steam vulcanization production process, which comprises the following steps:
  • Rubber mixing set the temperature of the internal mixer to 80 ° C, the rotor speed to 50 rpm, add 100 parts of branched polyethylene PER-12 pre-pressure mixing for 90 seconds; then add 30 parts of transparent in the rubber White carbon black (Suzhou Dongwu Chemical TS3), 10 parts of colorless paraffin oil, mixed for 3 minutes; finally added 4 parts of cross-linking agent 2,5-dimethyl-2,5-di(tert-butylperoxide) Hexane (paste, 50% active ingredient), 1 part of the cross-linking agent TAIC, and the mixture was kneaded for 2 minutes and then discharged.
  • the rubber compound was opened on a mill with a roll temperature of 60 ° C and left for 20 hours for use;
  • Post-treatment cleaning, obtaining finished products, packaging and storage.
  • a white door and window sealing strip whose production process is as follows:
  • the internal temperature of the mixer should be set to 80 ° C, the rotor speed should be 50 rpm, 100 parts of branched polyethylene PER-11 pre-pressed and kneaded for 90 seconds; 5 parts of zinc oxide and 1 part of hard Fatty acid, 5 parts calcium oxide, 2 parts polyethylene glycol PEG4000 and 2 parts vinyltris(2-methoxyethoxy)silane (A-172), kneaded for 1 minute; then add 50 to the compound Parts of silica, 50 parts of calcium carbonate, 60 parts of paraffin oil SUNPAR2280, mixing for 3 minutes; finally adding 4 parts of cross-linking agent bis-tert-butylperoxy isopropylbenzene (BIPB), 1.5 parts of cross-linking agent triene Propyl isocyanurate (TAIC) and 0.3 parts of sulfur, after 2 minutes of mixing, the rubber is discharged, the rubber is automatically cut into a twin-screw extruder and extruded into pieces, and then
  • Extrusion and vulcanization uses a vacuum extruder.
  • the temperature of the extruder is set at 90-100 °C, the screw temperature is 70-80 °C, and the head pressure should be controlled at 15-20 MPa.
  • Machine speed 25 ⁇ 30 rev / min using salt bath vulcanization process, spray section temperature 250 ° C, dip wheel section temperature 220 ° C, dipping section temperature 220 ° C, transmission speed 35-45 m / min, cooling section temperature 25 to 30 ° C.
  • a plastic rubber track surface layer is made of red rubber particles, and the branched polyethylene used is PER-10, and the remaining composition formula and processing technology are the same as those in the embodiment 22.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne un composite de caoutchouc, un procédé de traitement associé, et des applications du composite utilisé dans le traitement de produits en caoutchouc renforcés de noir de carbone blanc. 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; du caoutchouc de monomère d'éthylène propylène et du caoutchouc de monomère d'éthylène propylène diène, dont le contenu est b : 0 < b < 100 parties. Les composants essentiels comprennent : un agent de réticulation à hauteur de 1 à 10 parties et du noir de carbone blanc à hauteur de 15 à 80 parties. Le composite de caoutchouc est applicable dans la fabrication d'un matériau de caoutchouc de manchon de protection isolant haute tension, d'une bande transporteuse à haute résistance thermique, d'un matériau laminé étanche à l'eau, d'un granulé de caoutchouc destiné à être utilisé sur une surface de piste en plastique, d'un bouchon en caoutchouc, d'un rouleau en caoutchouc, d'un tube interne, d'une surface de pneu, d'une paroi latérale de pneu et d'une couche de caoutchouc interne d'un tube en caoutchouc de climatiseur.
PCT/CN2018/072367 2017-01-13 2018-01-12 Composite de caoutchouc, procédé de traitement, applications, procédé de fabrication des applications WO2018130195A1 (fr)

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Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110744740A (zh) * 2019-10-28 2020-02-04 万力轮胎股份有限公司 一种橡胶地板自动化制备系统和制备方法
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
CN112852028A (zh) * 2021-01-15 2021-05-28 河北皋端建材科技有限公司 一种运动地板用热塑性弹性体组合物及其制备方法
CN112895504A (zh) * 2021-01-15 2021-06-04 江苏彩阳环保科技有限公司 一种基于网格芳纶氟橡胶布的高温黏合定型制备工艺
CN112920515A (zh) * 2021-01-29 2021-06-08 厦门麦丰密封件有限公司 一种epdm密封件的制备工艺及其制品
CN113603945A (zh) * 2021-08-12 2021-11-05 中铁工程装备集团有限公司 耐油耐热耐磨损的橡胶材料及制法和在盾构机密封中应用
CN113789139A (zh) * 2021-10-12 2021-12-14 际华三五三七有限责任公司 防白变型鞋面布与围条橡胶的高效粘合物及其制作方法与应用
CN114539682A (zh) * 2022-03-30 2022-05-27 盘锦大奔金蚁橡胶制品有限公司 一种氯锌阻燃耐高温输送带及制备方法
CN114770999A (zh) * 2022-04-29 2022-07-22 陕西特种橡胶制品有限公司 钠冷堆主设备通道门用c型密封圈的制备方法
CN115304868A (zh) * 2021-05-07 2022-11-08 宣城新润发高分子科技有限公司 一种环保无害化处理的阻燃橡胶地板及其制备方法
CN115709618A (zh) * 2022-11-23 2023-02-24 广饶吉星轮胎有限公司 一种轮胎及轮胎制造方法
CN116120749A (zh) * 2023-02-27 2023-05-16 昆山力普电子橡胶有限公司 一种用于表带氟硅胶材料及其制备方法
CN117384431A (zh) * 2023-12-08 2024-01-12 衡水唯禹防水工程技术有限公司 一种缓膨型遇水膨胀橡胶材料及其制备方法
CN117757163A (zh) * 2023-12-22 2024-03-26 济南天齐特种平带有限公司 一种高速织机用橡胶卷取材料的制备方法
CN117887152A (zh) * 2024-03-14 2024-04-16 潍坊顺福昌橡塑有限公司 一种轮胎带束层橡胶组合物及其制备方法
CN118791804A (zh) * 2024-06-13 2024-10-18 长春中势旭阳橡胶有限公司 一种抗冲击的三元乙丙橡胶及在密封产品中的应用
CN119388783A (zh) * 2025-01-02 2025-02-07 洛阳双瑞橡塑科技有限公司 一种无胶黏剂复配成型方法

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Cited By (25)

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Publication number Priority date Publication date Assignee Title
CN110744740A (zh) * 2019-10-28 2020-02-04 万力轮胎股份有限公司 一种橡胶地板自动化制备系统和制备方法
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
CN112852028A (zh) * 2021-01-15 2021-05-28 河北皋端建材科技有限公司 一种运动地板用热塑性弹性体组合物及其制备方法
CN112895504A (zh) * 2021-01-15 2021-06-04 江苏彩阳环保科技有限公司 一种基于网格芳纶氟橡胶布的高温黏合定型制备工艺
CN112852028B (zh) * 2021-01-15 2023-07-04 河北皋端建材科技有限公司 一种运动地板用热塑性弹性体组合物及其制备方法
CN112920515B (zh) * 2021-01-29 2023-06-23 厦门麦丰密封件有限公司 一种epdm密封件的制备工艺及其制品
CN112920515A (zh) * 2021-01-29 2021-06-08 厦门麦丰密封件有限公司 一种epdm密封件的制备工艺及其制品
CN115304868A (zh) * 2021-05-07 2022-11-08 宣城新润发高分子科技有限公司 一种环保无害化处理的阻燃橡胶地板及其制备方法
CN113603945A (zh) * 2021-08-12 2021-11-05 中铁工程装备集团有限公司 耐油耐热耐磨损的橡胶材料及制法和在盾构机密封中应用
CN113603945B (zh) * 2021-08-12 2023-08-04 中铁工程装备集团有限公司 耐油耐热耐磨损的橡胶材料及制法和在盾构机密封中应用
CN113789139A (zh) * 2021-10-12 2021-12-14 际华三五三七有限责任公司 防白变型鞋面布与围条橡胶的高效粘合物及其制作方法与应用
CN113789139B (zh) * 2021-10-12 2023-09-19 际华制鞋工业有限公司 防白变型鞋面布与围条橡胶的高效粘合物及其制作方法与应用
CN114539682A (zh) * 2022-03-30 2022-05-27 盘锦大奔金蚁橡胶制品有限公司 一种氯锌阻燃耐高温输送带及制备方法
CN114770999B (zh) * 2022-04-29 2024-04-26 陕西特种橡胶制品有限公司 钠冷堆主设备通道门用c型密封圈的制备方法
CN114770999A (zh) * 2022-04-29 2022-07-22 陕西特种橡胶制品有限公司 钠冷堆主设备通道门用c型密封圈的制备方法
CN115709618A (zh) * 2022-11-23 2023-02-24 广饶吉星轮胎有限公司 一种轮胎及轮胎制造方法
CN116120749B (zh) * 2023-02-27 2023-12-05 昆山力普电子橡胶有限公司 一种用于表带氟硅胶材料及其制备方法
CN116120749A (zh) * 2023-02-27 2023-05-16 昆山力普电子橡胶有限公司 一种用于表带氟硅胶材料及其制备方法
CN117384431A (zh) * 2023-12-08 2024-01-12 衡水唯禹防水工程技术有限公司 一种缓膨型遇水膨胀橡胶材料及其制备方法
CN117384431B (zh) * 2023-12-08 2024-02-13 衡水唯禹防水工程技术有限公司 一种缓膨型遇水膨胀橡胶材料及其制备方法
CN117757163A (zh) * 2023-12-22 2024-03-26 济南天齐特种平带有限公司 一种高速织机用橡胶卷取材料的制备方法
CN117757163B (zh) * 2023-12-22 2024-07-02 济南天齐特种平带有限公司 一种高速织机用橡胶卷取材料的制备方法
CN117887152A (zh) * 2024-03-14 2024-04-16 潍坊顺福昌橡塑有限公司 一种轮胎带束层橡胶组合物及其制备方法
CN118791804A (zh) * 2024-06-13 2024-10-18 长春中势旭阳橡胶有限公司 一种抗冲击的三元乙丙橡胶及在密封产品中的应用
CN119388783A (zh) * 2025-01-02 2025-02-07 洛阳双瑞橡塑科技有限公司 一种无胶黏剂复配成型方法

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