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WO2018130192A1 - Composite de caoutchouc, produit de caoutchouc résistant au vieillissement utilisant ce composite, et procédé de fabrication - Google Patents

Composite de caoutchouc, produit de caoutchouc résistant au vieillissement utilisant ce composite, et procédé de fabrication Download PDF

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

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

Definitions

  • the invention belongs to the technical field of rubber, and particularly relates to a rubber composition and a processing method thereof, and an anti-aging product and a production method using the rubber composition.
  • Ethylene-propylene rubber is widely used in various applications where high resistance to aging and/or compression set is required due to its excellent aging resistance and good compression set resistance.
  • Sulfur vulcanization and peroxide vulcanization are two conventional vulcanization methods for ethylene-propylene rubber.
  • a peroxide crosslinking system is now gradually being used.
  • the mechanical strength of peroxide-vulcanized ethylene-propylene rubber will be lower than that of sulfur-vulcanized ethylene-propylene rubber, which will lead to an increase in the risk of damage to the product during actual use, so at the same time improve the aging resistance and mechanics of ethylene-propylene rubber.
  • Strength is a technical problem that needs to be solved urgently.
  • Ethylene-propylene rubber is a synthetic rubber with saturated molecular chain. It can be divided into two major categories: ethylene-propylene rubber and EPDM rubber. Both of them have good aging resistance. They are commonly used in ethylene-propylene rubber products. It is EPDM rubber, but because EPDM rubber contains a third monomer, the molecular chain contains double bonds, and the ethylene-propylene rubber molecular chain is completely saturated, so the ethylene-propylene rubber has more excellent resistance to aging. Sex, therefore, in the case of high requirements for aging resistance, it is a common technical solution to improve the aging resistance of EPDM by using ethylene propylene diene rubber together. However, the mechanical strength of the binary ethylene propylene rubber is low, which will affect the overall physical and mechanical properties.
  • Diethylene propylene rubber is a copolymer of ethylene and propylene and belongs to the copolymer of ethylene and ⁇ -olefin.
  • Ethylene and ⁇ -olefin copolymers are polymers containing only hydrocarbon elements and saturated molecular chains.
  • the common types of carbon atoms in such polymers are generally classified into primary, secondary and tertiary carbons, while tertiary carbons are the most It is easy to be trapped by hydrogen to form free radicals, so the ratio of tertiary carbon atoms to all carbon atoms is generally considered to be a major factor affecting the aging resistance of ethylene and ⁇ -olefin copolymers. The lower the ratio, the better the aging resistance.
  • the ratio can be expressed by the degree of branching.
  • a diethylene propylene rubber having a propylene content of 60% by weight can be calculated to contain 200 propylene units per 1000 carbon atoms, that is, 200 tertiary carbon atoms or 200.
  • One methyl branch so its degree of branching is 200 branches / 1000 carbons.
  • Ethylene ethylene propylene rubber generally has a weight percentage of 40% to 65% or 40% to 60%, so its branching degree is generally 117 to 200 branches/1000 carbons or 133 to 200 branches/ This degree of branching can be considered to be higher than other common ethylene and alpha-olefin copolymers in the 1000 carbon range.
  • the ⁇ -olefin in the common ethylene and ⁇ -olefin copolymer may be an ⁇ -olefin having a carbon number of not less than 4 in addition to propylene, and may be selected from a C 4 - C 20 ⁇ -olefin. It is usually selected from the group consisting of 1-butene, 1-hexene and 1-octene. If the degree of branching of the copolymer of ethylene and ⁇ -olefin is too low, the melting point and crystallinity are too high, and it is not suitable for use as a rubber component.
  • a polyolefin obtained by copolymerizing ethylene with 1-butene or ethylene and 1-octene may be referred to as a polyolefin plastomer or a polyolefin elastomer according to the degree of crystallinity and melting point, and a part of the polyolefin is elastic. Due to its proper crystallinity and melting point, it can be used well with ethylene propylene rubber and has a low degree of branching. It is considered to be an ideal material for improving the aging resistance of ethylene propylene rubber.
  • the polyolefin elastomer commonly used in rubber products is generally ethylene.
  • the octene weight percentage is generally not higher than 45%, more commonly not higher than 40%, the corresponding degree of branching is generally not higher than 56 branches / 1000 carbon, The more commonly used degree of branching is not higher than 50 branches/1000 carbons, which is much lower than the degree of branching of ethylene dipropylene rubber, so it has excellent aging resistance and good physical and mechanical properties.
  • the copolymer of ethylene and ⁇ -olefin may be peroxide cross-linking or irradiation cross-linking, both of which are mainly obtained by capturing tertiary carbon.
  • a hydrogen atom forms a tertiary carbon radical, and then forms a carbon-carbon crosslink by radical bonding, but a copolymer of ethylene and 1-octene (hereinafter referred to as POE) has fewer tertiary carbon atoms and is attached to a tertiary carbon atom.
  • Chain length, large steric hindrance, difficulty in radical reaction, resulting in difficulty in crosslinking, affecting processing efficiency and product performance, such as compression set resistance is unsatisfactory.
  • the present invention provides a novel rubber composition and the ethylene-propylene rubber which is present in the prior art is easily aged by sulfur vulcanization, and the peroxide is vulcanized to make the ethylene-propylene rubber have a tear strength lower than that of the sulfur vulcanized ethylene-propylene rubber.
  • the processing method also provides an application and processing method for processing an anti-aging rubber product by the rubber composition.
  • a rubber composition comprising, in parts by weight, a rubber matrix and a necessary component, the rubber matrix comprising: a branched polymer
  • the necessary components include: 1.5 to 10 parts of a crosslinking agent, 30-200 parts of strong filler, 5 ⁇ 250 parts of plasticizer, wherein the branching degree of branched polyethylene is not less than 50 branches/1000 carbons, the weight average molecular weight is not less than 50,000, Mooney viscosity ML (1+4) 125 ° C is not less than 2.
  • Branched polyethylene in the prior art means, in addition to a branched ethylene homopolymer, a branched saturated vinyl copolymer, such as an ethylene- ⁇ -olefin copolymer, which may be POE, although POE performs well in physical and mechanical properties and aging resistance, but cross-linking performance is not good, although the branched polyethylene of the present invention can contain both branched ethylene homopolymer and POE, but a better choice It is a branched polyethylene having a high proportion of branched polyethylene or a branched ethylene homopolymer. In a preferred embodiment of the invention, the branched polyethylene contains only branched ethylene homopolymer.
  • the branched polyethylene used is a branched ethylene homopolymer unless otherwise specified.
  • the branched polyethylene used in the present invention is a kind of ethylene homopolymer having a branching degree of not less than 50 branches/1000 carbons, and can be called Branched Polyethylene or Branched PE.
  • the synthesis method is mainly composed of a late transition metal catalyst.
  • the homopolymerization of ethylene is catalyzed by a "chain walking mechanism", and the preferred late transition metal catalyst may be one of ( ⁇ -diimine) nickel/palladium catalysts.
  • the nature of the chain walking mechanism refers to the late transition metal catalyst.
  • the ( ⁇ -diimine) nickel/palladium catalyst is more likely to undergo ⁇ -hydrogen elimination reaction and re-insertion reaction in the process of catalyzing olefin polymerization, thereby causing branching.
  • Branched chains of such branched polyethylenes may have different numbers of carbon atoms, specifically 1 to 6, or more carbon atoms.
  • the production cost of the ( ⁇ -diimine) nickel catalyst is significantly lower than that of the ( ⁇ -diimine) palladium catalyst, and the ( ⁇ -diimine) nickel catalyst catalyzes the high rate of ethylene polymerization and high activity, and is more suitable for industrial applications. Therefore, the branched polyethylene prepared by the ethylene polymerization of the ( ⁇ -diimine) nickel catalyst is preferred in the present invention.
  • the degree of branching of the branched polyethylene used in the present invention is preferably 50 to 130 branches/1000 carbons, further preferably 60 to 130 branches/1000 carbons, further preferably 60 to 116 branches/1000.
  • a carbon, the degree of branching between POE and ethylene-propylene rubber, is a new technical solution that is different from the prior art, and can have excellent aging resistance and good cross-linking performance.
  • Cross-linking performance includes factors such as crosslink density and cross-linking rate, which is the specific performance of the cross-linking ability of the rubber matrix during processing.
  • the branched polyethylene used in the present invention preferably has a methyl branch content of 40% or more or 50% or more, and has a certain similarity with the structure of the ethylene propylene diene rubber.
  • the degree of branching (tertiary carbon atom content) and the steric hindrance around the tertiary carbon atom are the two main factors affecting the cross-linking ability of the saturated polyolefin.
  • the branched polyethylene used in the present invention is low in degree of branching relative to the ethylene propylene rubber, and since the branched polyethylene has a branch having a carbon number of not less than 2, the branched polycondensation used in the present invention
  • the steric hindrance around the tertiary carbon atom of ethylene is theoretically larger than that of ethylene propylene rubber. It can be judged by combining two factors that the crosslinking ability of the branched polyethylene used in the present invention should be weaker than that of the ethylene propylene rubber.
  • EPDM rubber In EPDM rubber. However, the actual cross-linking ability of the partially branched polyethylene used in the present invention is close to that of EPDM rubber, and may even be equal to or better than EPDM rubber. This means that the rubber composition of the present invention can obtain a good aging resistance, can also not weaken the crosslinking ability, and can even have excellent crosslinking performance to achieve an unexpected beneficial effect.
  • secondary branched structure refers to a structure in which branches are further branched. This is also known as "branch-on-branch" during chain walking. Because of the low steric hindrance around the tertiary carbon atoms of the secondary branches, cross-linking reactions are more likely to occur. Having a secondary branched structure is a distinct distinction between the branched polyethylene used in the preferred embodiment of the invention and the prior art ethylene dipropylene rubber or the conventional ethylene- ⁇ -olefin copolymer.
  • the vinyl copolymer refers to a copolymer of ethylene and a branched ⁇ -olefin, and has a secondary branched structure, wherein the branched ⁇ -olefin may be selected from the group consisting of isobutylene and 3-methyl-1- Butylene, 4-methyl-1-pentene, 3-methyl-1-pentene, 2-methyl-1-heptene, 3-methyl-1-heptene, 4-methyl-1- The heptene, 5-methyl-1-heptene, 6-methyl-1-heptene, and the like, the comonomer may also contain a common linear alpha-olefin.
  • branched polyethylene prepared by the ( ⁇ -diimine) nickel catalyst is difficult to exist in the secondary branched structure, and at least it is difficult to sufficiently distinguish it.
  • the technical solution of the present invention is also to analyze the branched polycondensation.
  • the structure of ethylene provides a new idea.
  • the cross-linking point of the branched polyethylene can be generated on the tertiary chain of the main chain during the peroxide crosslinking process. It can also be produced on the branched tertiary carbon of the secondary structure, so the rubber network formed by the cross-linking of the branched polyethylene has a richer CC connecting segment between the main chains than the ethylene-propylene rubber. The length can effectively avoid stress concentration and help to obtain better mechanical properties, including tear strength.
  • the rubber composition comprises, in parts by weight, a rubber matrix comprising 100 parts of branched polyethylene, and the necessary components, wherein the necessary components are included in 100 parts by weight of the rubber matrix. 2 to 7 parts of the crosslinking agent, 30 to 200 parts of the reinforcing filler, and 8 to 150 parts of the plasticizer.
  • the crosslinking agent includes at least one of a peroxide crosslinking agent and sulfur, and the peroxide crosslinking agent includes di-tert-butyl peroxide, dicumyl peroxide, and tert-butyl group.
  • the reinforcing filler comprises at least one of carbon black, white carbon black, calcium carbonate, talc, calcined clay, magnesium silicate, and magnesium carbonate.
  • the plasticizer comprises at least at least of pine tar, motor oil, naphthenic oil, paraffin oil, coumarone, RX-80, stearic acid, paraffin, liquid polyisobutylene, fatty acid derivatives, and mixtures thereof.
  • the plasticizer is further preferably used in an amount of 15 to 120 parts by weight.
  • stearic acid can also act as an active agent in sulfur-sulfur-based systems, and can form soluble salts with some metal oxides, thereby increasing the activation of metal oxides on promoters.
  • the rational use of plasticizers can increase the flexibility of the compound and the plasticity suitable for process operation.
  • an adhesion promoter such as pine tar, coumarone, RX-80, liquid polyisobutylene or the like.
  • the rubber composition further comprises an auxiliary component, wherein the auxiliary component comprises: 0.2 to 10 parts of a co-crosslinking agent, 0.5 to 3 parts of a stabilizer, and a metal oxide 2 to 1 part by weight of the rubber matrix. 15 parts, vulcanization accelerator 0 to 3 parts.
  • the co-crosslinking agent comprises triallyl cyanurate, triallyl isocyanurate, ethylene glycol dimethacrylate, ethyl dimethacrylate, dimethyl Triethylene glycol acrylate, triallyl trimellitate, trimethylolpropane trimethacrylate, ethylene glycol dimethacrylate, N, N'-m-phenylene bismaleimide, At least one of N,N'-bis-indenyl acetonide, 1,2-polybutadiene, p-nonane, sulphur, and a metal salt of an unsaturated carboxylic acid.
  • the unsaturated carboxylic acid metal salt contains at least one of zinc acrylate, zinc methacrylate, magnesium methacrylate, calcium methacrylate, and aluminum methacrylate.
  • the metal oxide is at least one of zinc oxide, magnesium oxide, calcium oxide, lead monoxide, and lead tetraoxide.
  • the stabilizer comprises 2,2,4-trimethyl-1,2-dihydroquinoline polymer (RD), 6-ethoxy-2,2,4-trimethyl- At least one of 1,2-dihydroquinoline (AW) and 2-mercaptobenzimidazole (MB).
  • RD 2,2,4-trimethyl-1,2-dihydroquinoline polymer
  • AW 6-ethoxy-2,2,4-trimethyl- At least one of 1,2-dihydroquinoline
  • MB 2-mercaptobenzimidazole
  • the vulcanization accelerator comprises 2-thiol benzothiazole, dibenzothiazole disulfide, tetramethylthiuram monosulfide, tetramethylthiuram disulfide, tetraethyl disulfide Of thiuram, N-cyclohexyl-2-benzothiazolyl sulfenamide, N,N-dicyclohexyl-2-phenylthiazolyl sulfenamide, bismaleimide, ethylene thiourea At least one.
  • a further solution is that the selected ethylene-propylene rubber and ethylene propylene diene rubber have a Mooney viscosity ML (1+4) of 20 to 80 at 125 ° C and an ethylene content of 45% to 70%.
  • the content of the branched polyethylene in the 100 parts by weight of the rubber matrix is a: 10 ⁇ a ⁇ 100 parts; the total content of the binary ethylene propylene rubber and the EPDM rubber is b: 0 ⁇ b ⁇ 90
  • the branched polyethylene is characterized by being an ethylene homopolymer having a degree of branching of 60 to 130 branches/1000 carbons, a weight average molecular weight of 66,000 to 518,000, and a Mooney viscosity ML (1+). 4) 125 ° C is 6 to 102.
  • the content of the branched polyethylene in the 100 parts by weight of the rubber matrix is a: 10 ⁇ a ⁇ 100 parts; the content of the binary ethylene propylene rubber and the ethylene propylene diene rubber is b: 0 ⁇ b ⁇ 90
  • the branched polyethylene is an ethylene homopolymer having a degree of branching of 70 to 116 branches/1000 carbons, a weight average molecular weight of 201,000 to 436,000, and a Mooney viscosity of ML(1+4)125. °C is 23-101;
  • the content of the branched polyethylene in the 100 parts by weight of the rubber matrix is a: 10 ⁇ a ⁇ 100 parts; the content of the binary ethylene propylene rubber and the ethylene propylene diene rubber is b: 0 ⁇ b ⁇ 90
  • the branched polyethylene is an ethylene homopolymer having a degree of branching of 80 to 105 branches/1000 carbons, a weight average molecular weight of 250,000 to 400,000, and a Mooney viscosity of ML (1+4) 125. °C is 40 to 95.
  • the content of the branched polyethylene in the 100 parts by weight of the rubber matrix is a: 10 ⁇ a ⁇ 100 parts; the content of the binary ethylene propylene rubber and the ethylene propylene diene rubber is b: 0 ⁇ b ⁇ 90
  • the branched polyethylene is an ethylene homopolymer having a degree of branching of 80 to 105 branches/1000 carbons, a weight average molecular weight of 268,000 to 356,000, and a Mooney viscosity of ML (1+4) 125. °C is 42-80.
  • the third monomer of the ethylene propylene diene monomer is preferably a diene monomer, specifically selected from the group consisting of 5-ethylidene-2-norbornene and 5-vinyl-2-norbornene.
  • the ethylene propylene rubber may contain two or more kinds of diene monomers at the same time, such as 5-ethylidene-2-norbornene and 5-vinyl-2-norbornene.
  • the functional group of the diene monomer can play the same role as the intrinsic co-crosslinking agent in the peroxide vulcanization, thereby improving the crosslinking efficiency. This helps to reduce the amount and residual amount of crosslinker and co-crosslinker required and the cost of adding them.
  • the weight specific gravity of the diene monomer to the ethylene propylene rubber is preferably from 1% to 14%, more preferably from 3% to 10%, still more preferably from 4% to 7%.
  • the rubber composition in order to improve the viscosity of the rubber compound, may further comprise a tackifier, wherein the plasticizer is pine tar, coumarone resin, RX-80, and liquid polyisobutylene.
  • a tackifier wherein the plasticizer is pine tar, coumarone resin, RX-80, and liquid polyisobutylene.
  • a commonly used tackifier such as a phenol resin, a modified alkyl phenol resin, or an alkyl phenol-acetylene resin, and the tackifier is generally not more than 30 parts by weight, further preferably not more than 10 parts by weight, based on 100 parts by weight of the rubber base. It is further preferably not more than 5 parts by weight.
  • crosslinking agent the co-crosslinking agent and the vulcanization accelerator involved in the rubber composition provided by the present invention all belong to a crosslinking system.
  • the rubber composition of the present invention may be present in the form of an uncrosslinked rubber compound, and may be present in the form of a vulcanized rubber after further crosslinking reaction.
  • Vulcanized rubber can also be referred to simply as vulcanizate.
  • the present invention also provides a method of processing the above rubber composition, comprising the steps of:
  • Rubber mixing setting the temperature of the internal mixer and the rotation speed of the rotor, and sequentially adding the components other than the crosslinking system in the rubber composition to the internal mixer for mixing; then adding the crosslinking system, and discharging the rubber after mixing. , the rubber compound is thinly passed through the open mill and parked, wherein the crosslinking system comprises a crosslinking agent, and may further comprise at least one of a crosslinking agent and a vulcanization accelerator;
  • Vulcanization The bottled rubber after filling is filled into the cavity of the preheating mold, and subjected to high temperature pressure vulcanization. After the vulcanization is completed, the vulcanized rubber is obtained by demoulding. In order to improve the compression set resistance of the vulcanizate, it is further possible to carry out vulcanization using a two-stage vulcanization process.
  • the present invention also provides a bridge plate type rubber support comprising a steel sheet and a rubber sheet layer, wherein the rubber sheet layer comprises the above rubber composition.
  • the present invention also provides a bridge plate type rubber support comprising a steel sheet, a polytetrafluoroethylene sheet and a rubber sheet layer, wherein the rubber sheet layer comprises the above rubber composition.
  • the invention also provides a method for producing a bridge plate rubber bearing, which is formed by pressing and vulcanizing a rubber sheet between each layer and a steel plate and a polytetrafluoroethylene plate by a coating adhesive, and then bonding the whole into a whole.
  • the steps involved in its production method are as follows:
  • the crosslinking system comprises a crosslinking agent, and may further comprise at least one of a co-crosslinking agent and a vulcanization accelerator;
  • the present invention also provides a basin type rubber support, the rubber pressure receiving plate comprising the above rubber composition.
  • the invention also provides a method for producing a basin rubber bearing, wherein the basin rubber bearing comprises an upper support plate, a stainless steel plate, a polytetrafluoroethylene plate, an intermediate steel plate, a sealing ring, a rubber bearing plate and a lower branch.
  • the seat plate and the anchor bolt are assembled, and the production method includes the following steps:
  • the crosslinking system comprises a crosslinking agent, and may further comprise at least one of a crosslinking agent and a vulcanization accelerator. .
  • Vulcanization molding process the film is loaded into a preheated mold, and then vulcanized into a flat vulcanizer;
  • the present invention also provides a bridge rubber expansion device, the rubber expansion body comprising the above rubber composition.
  • the invention also provides a method for producing a bridge rubber expansion device, wherein the rubber expansion body adopts an extrusion method and the steps included in the production method are as follows:
  • Rubber mixing process setting the temperature of the internal mixer and the rotation speed of the rotor, and adding the components other than the crosslinking system in the rubber composition to the internal mixer for mixing; then adding the crosslinking system, after mixing Discharging, laminating the rubber in the open mill, parking and testing, wherein the crosslinking system comprises a crosslinking agent, and may further comprise at least one of a crosslinking agent and a vulcanization accelerator;
  • Extrusion and vulcanization The extrusion vulcanization process should adopt a vacuum extruder, and after the extrusion, a salt bath vulcanization process is adopted, and the vulcanizate is obtained by spraying, dipping, dipping, and cooling;
  • the invention also provides a method for producing a bridge rubber expansion device, wherein the rubber expansion body adopts the molding method and comprises the following steps, as follows:
  • the cross-linking system contains a crosslinking agent, and may also contain a crosslinking agent and vulcanization promotion. At least one of the agents;
  • Molding vulcanization the formed rubber compound is placed in a mold and vulcanized by a high temperature steam vulcanization process;
  • the present invention also provides a rubber steel plate combined type expansion and contraction device, wherein the rubber expandable body comprises the above rubber composition.
  • the invention also provides a method for producing a bridge rubber expansion device, the production method comprising the following steps:
  • the cross-linking system contains a crosslinking agent, and may also contain a crosslinking agent and vulcanization promotion. At least one of the agents;
  • the present invention also provides a rubber sleeper pad comprising the rubber composition of the above claims.
  • the invention also provides a method for producing a rubber sleeper pad, the production method comprising the following steps:
  • Rubber mixing and molding setting the temperature of the internal mixer and the rotation speed of the rotor, and adding the components other than the crosslinking system in the rubber composition to the internal mixer for mixing; then adding the crosslinking system and kneading Rear glue. After being parked and tested, it is subjected to hot-smelting, and then discharged according to the required thickness, and cut into a desired shape for use in a vulcanization process, wherein the cross-linking system contains a crosslinking agent, and may also include a co-crosslinking agent and a vulcanization accelerator. At least one of them.
  • the present invention also provides a rubber fender comprising the above rubber composition.
  • the present invention also provides a method of producing a rubber fender, the production method comprising the steps of:
  • Rubber mixing setting the temperature of the internal mixer and the rotation speed of the rotor, adding the components other than the crosslinking system in the rubber composition to the internal mixer, and then adding the crosslinking system, mixing and arranging a glue, wherein the crosslinking system comprises a crosslinking agent, and may further comprise at least one of a crosslinking agent and a vulcanization accelerator;
  • the present invention also provides a rubber waterstop tape comprising the above rubber composition.
  • the invention also provides a method for producing a rubber waterstop, the production method comprising the following steps:
  • the cross-linking system contains a crosslinking agent, and may also contain a crosslinking agent and vulcanization promotion. At least one of the agents;
  • the present invention also provides a steel belt rubber waterstop tape, the rubber compound used comprising the above rubber composition.
  • the invention also provides a method for producing a steel belt rubber waterstop, the production method comprising the following steps:
  • the cross-linking system contains a crosslinking agent, and may also contain a crosslinking agent and vulcanization promotion. At least one of the agents;
  • the present invention also provides a shock absorbing mount for a vehicle, the rubber compound used comprising the above rubber composition.
  • the invention also provides a method for producing a shock absorber support for a vehicle, the production method comprising the following steps:
  • the cross-linking system contains a crosslinking agent, and may also contain a crosslinking agent and vulcanization promotion. At least one of the agents;
  • the present invention also provides a rubber roller comprising the above rubber composition.
  • the invention also provides a method for producing a rubber roller, the production method comprising the following steps:
  • Rubber mixing setting the temperature of the internal mixer and the rotation speed of the rotor, and adding the components other than the crosslinking system in the rubber composition to the internal mixer for mixing; then adding the crosslinking system, mixing and arranging a glue, the rubber compound is thinly passed through the open mill, parked and tested, wherein the crosslinking system comprises a crosslinking agent, and may further comprise at least one of a crosslinking agent and a vulcanization accelerator;
  • the rubberized rubber roller is sent to the vulcanization tank, after closing the tank door, steam is vulcanized into the vulcanization tank, and the compressed air valve is opened while steam is introduced, and the compressed air is passed to vulcanize.
  • the pressure in the tank reaches 4.5 to 5 atmospheres in 0.5 hours; the vulcanization procedure is: firstly heat up to 70-80 ° C, keep warm for 2 hours; then heat up to 100-110 ° C, keep warm for 0.5 hours; then heat up to 120-130 ° C, keep warm 0.5 hours; further heating to 135 ⁇ 140 ° C, holding 8 ⁇ 10 hours, the end of vulcanization, open the exhaust valve, the pressure drops, when the pressure gauge pointer points to zero, open the insurance pin, and the steam hole in the pin hole, half Open the vulcanization tank and let the temperature drop.
  • the rubber roller is pulled out;
  • the vulcanized rubber roller is rough-processed on a lathe, and then finished on a grinding machine for inspection and inspection to obtain a finished product;
  • the present invention also provides a high temperature resistant V-ribbed belt comprising a compression layer and a buffer layer, the buffer layer compound comprising the above rubber composition.
  • the invention also provides a method for producing a high temperature resistant V-ribbed belt, the production method comprising the following steps:
  • Rubber kneading wherein the mixing of the buffer layer rubber is: setting the temperature of the internal mixer and the rotation speed of the rotor, and sequentially adding the components other than the crosslinking system in the rubber composition to the internal mixer for mixing; Then, the crosslinking system is added, the rubber is mixed after the mixing, and the rubber mixture is thinly passed through the open mill, and is parked and tested.
  • the crosslinking system contains a crosslinking agent, and may also include a crosslinking agent and a vulcanization accelerator. At least one of them;
  • Molding The reverse molding method is adopted. First, hang the optical mold on the molding machine, clean the mold, apply a small amount of release agent, and after it is volatilized, wrap the V-ribbed top cloth on the optical mold, and then wrap the buffer layer rubber to correct the tension of the rope. After winding the strength layer, the buffer rubber is applied, and finally the wedge rubber is wrapped to the outer circumference required by the molding process to obtain a strip;
  • Vulcanization The vulcanized vulcanization process is used to feed the strip into the vulcanization tank for vulcanization.
  • the vulcanization temperature is 155-175 ° C
  • the internal pressure is 0.45-0.55 MPa
  • the external pressure is 1.0-1.2 MPa
  • the vulcanization time is 25-30. minute;
  • Post-treatment After the end of vulcanization, the mold is cooled and cooled, and the belt is fed into the cutting process, and cut according to the required width. Grinding the back, grinding the wedge, and trimming the product to obtain the finished product.
  • the present invention also provides a wiper strip comprising the above rubber composition.
  • the invention also provides a method for producing a wiper strip, the production method comprising the following steps:
  • Rubber mixing setting the temperature of the internal mixer and the rotation speed of the rotor, and adding the components other than the crosslinking system in the rubber composition to the internal mixer for mixing; then adding the crosslinking system, mixing and arranging a glue, the rubber compound is thinly passed through the open mill, parked and tested, wherein the crosslinking system comprises a crosslinking agent, and may further comprise at least one of a crosslinking agent and a vulcanization accelerator;
  • the present invention also provides a seal ring comprising a rubber composition as described above.
  • the invention also provides a method for producing a sealing ring, the production method comprising the following steps:
  • the cross-linking system contains a crosslinking agent, and may also contain a crosslinking agent. And at least one of a vulcanization accelerator;
  • Vulcanization one-stage compression vulcanization: temperature is 155-170 ° C, vulcanization time is 20-25 minutes; second-stage oven vulcanization: temperature 145-155 ° C, time 40-80 minutes.
  • the present invention also provides a waterproofing membrane comprising the above rubber composition.
  • the invention also provides a method for producing a waterproof coil, the production method comprising the following steps:
  • Rubber mixing setting the temperature of the internal mixer and the rotation speed of the rotor, and adding the components other than the crosslinking system in the rubber composition to the internal mixer for mixing; then adding the crosslinking system, mixing and arranging Glue, the kneaded rubber is fully thinned and kneaded in the open mill to obtain a uniformly mixed rubber flakes, cooled to below 50 ° C to be discharged and stacked, wherein the cross-linking system contains a crosslinking agent, and may also contain a cross-linking agent. At least one of a agent and a vulcanization accelerator;
  • vulcanization the rolled material is placed in a nitrogen-containing vulcanization kettle for vulcanization treatment, the temperature of the vulcanization kettle is controlled between 155 and 165 ° C, the pressure is between 20 and 25 MPa, and the vulcanization is for 25 to 30 minutes;
  • Rewinding re-opening the vulcanized coil, taking out the release liner layer, and then rewinding and packaging into a product.
  • the present invention also provides a weather strip comprising the above rubber composition.
  • the rubber sealing strip provided by the invention can be used as a radiator plate rubber seal of an engine cooling system.
  • the present invention also provides a method of producing a weather strip using a process of compression vulcanization and stage vulcanization, comprising the steps of:
  • Rubber mixing setting the temperature of the internal mixer and the rotation speed of the rotor, and adding the components other than the crosslinking system in the rubber composition to the internal mixer for mixing; then adding the crosslinking system, mixing and arranging a glue, the rubber compound is thinly passed through the open mill, parked and tested, wherein the crosslinking system comprises a crosslinking agent, and may further comprise at least one of a crosslinking agent and a vulcanization accelerator;
  • the rubber compound after passing the test is extruded through an extruder, cut off, placed in a mold of a vulcanization apparatus, and subjected to a vulcanization under high temperature and high pressure.
  • the pressure is preferably 14 to 16 MPa
  • the temperature is preferably 170 to 185 ° C
  • the curing time is preferably 2 to 3 minutes;
  • the trimmed product is subjected to two-stage vulcanization at a high temperature.
  • the temperature is preferably 165 to 175 ° C, and the time is preferably 25 to 35 minutes;
  • the present invention also provides an inner tube characterized in that the rubber used for the carcass comprises the above rubber composition.
  • the invention also provides a method for producing a inner tube, comprising the steps of: first kneading rubber, filtering and parking; then extruding through an extruder, cutting according to the length required by the process, sticking the valve, splicing After parking; then inflated and shaped, steam vulcanized, cooled, inspected, trimmed to get the finished product.
  • the invention has the beneficial effects of providing a new rubber composition, partially or completely replacing ethylene propylene rubber with branched polyethylene, and applying it to high requirements for aging resistance and/or compression set resistance. On the rubber product, it can obtain good heat resistance, compression set resistance and mechanical strength under the peroxide vulcanization system.
  • the principle is that the molecular structure of the branched polyethylene is completely saturated, the heat aging resistance is similar to that of the ethylene propylene rubber, and it is superior to the EPDM rubber, and both can be vulcanized using a peroxide system.
  • the molecular structure of the branched polyethylene has more branches, and the length of the branch has a certain length and length distribution
  • the crosslinking point of the branched polyethylene may be generated on the tertiary carbon of the main chain, or may be generated on the branched tertiary carbon of the secondary structure, so the rubber network formed by crosslinking the branched polyethylene through peroxide is Compared with ethylene-propylene rubber, the main chain has a richer CC chain segment length, similar to the polysulfide bond distribution in the sulfur vulcanization system, which can effectively avoid stress concentration and facilitate better mechanical properties.
  • the compression set property is related to the molecular weight distribution of the rubber material.
  • the rubber with narrow molecular weight distribution has relatively low compression set.
  • the molecular weight distribution of ethylene propylene rubber is mostly between 3 and 5, and the highest is 8-9.
  • the partial ethylene propylene rubber has a molecular weight distribution close to 2 and is convenient to process, but the cost is high. Since the molecular weight distribution of the branched polyethylene is narrow, generally less than 2.5, which is significantly smaller than the molecular weight distribution of the ordinary ethylene propylene rubber, the rubber composition of the present invention It has a lower compression set after vulcanization.
  • a rubber composition comprising, in parts by weight, a rubber matrix and a necessary component, wherein the rubber matrix comprises: a content of branched polyethylene a: 0 ⁇ a ⁇ 100 parts, content of ethylene propylene rubber b : 0 ⁇ b ⁇ 100 parts, the necessary components include: 1.5 to 10 parts of a crosslinking agent, 30 to 200 parts of a reinforcing filler, and 5 to 250 parts of a plasticizer.
  • the branching degree of the branched polyethylene is not less than 50 branches/1000 carbons, the weight average molecular weight is not less than 50,000, and the Mooney viscosity ML (1+4) is not lower than 2 at 125 °C.
  • the rubber composition comprises, in parts by weight, a rubber matrix comprising 100 parts of branched polyethylene, and 100 parts by weight of the rubber matrix, the necessary components including 2 to 7 parts of the crosslinking agent, 30 to 200 parts of the reinforcing filler, and 8 to 150 parts of the plasticizer.
  • the crosslinking agent includes at least one of a peroxide crosslinking agent and sulfur
  • the peroxide crosslinking agent includes di-tert-butyl peroxide, dicumyl peroxide, and t-butyl Base peroxide, 1,1-di-tert-butyl peroxide-3,3,5-trimethylcyclohexane, 2,5-dimethyl-2,5-di(tert-butylperoxide) Hexane, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne-3, bis(tert-butylperoxyisopropyl)benzene, 2,5-dimethyl-2 At least one of 5-di(benzoyl peroxide)hexane, tert-butyl peroxybenzoate, and t-butylperoxy-2-ethylhexyl carbonate.
  • the reinforcing filler includes at least one of carbon black, white carbon black, calcium carbonate, talc, calcined clay, magnesium silicate, and magnesium carbonate.
  • the plasticizer includes at least one of pine tar, motor oil, naphthenic oil, paraffin oil, coumarone, RX-80, stearic acid, paraffin, liquid polyisobutylene, fatty acid derivatives, and mixtures thereof.
  • the rubber composition further includes an auxiliary component comprising 0.2 to 10 parts of a co-crosslinking agent, 0.5 to 3 parts of a stabilizer, 2 to 15 parts of a metal oxide, and 0 to 3 parts of a vulcanization accelerator.
  • the co-crosslinking agent comprises triallyl cyanurate, triallyl isocyanurate, ethylene glycol dimethacrylate, ethyl dimethacrylate, triethylene glycol dimethacrylate , triallyl trimellitate, trimethylolpropane trimethacrylate, ethylene glycol dimethacrylate, N, N'-m-phenylene bismaleimide, N, N'- At least one of bis-indenyl acetonide, 1,2-polybutadiene, p-quinone quinone, sulfur, zinc acrylate, zinc methacrylate, magnesium methacrylate, calcium methacrylate, and aluminum methacrylate.
  • the metal oxide is at least one of zinc oxide, magnesium oxide, calcium oxide, lead monoxide, and lead tetraoxide.
  • Stabilizers include 2,2,4-trimethyl-1,2-dihydroquinoline (RD), 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline At least one of porphyrin (AW) and 2-mercaptobenzimidazole (MB).
  • RD 2,2,4-trimethyl-1,2-dihydroquinoline
  • AW porphyrin
  • MB 2-mercaptobenzimidazole
  • the vulcanization accelerator comprises 2-thiol benzothiazole, dibenzothiazole disulfide, tetramethylthiuram monosulfide, tetramethylthiuram disulfide, tetraethylthiuram disulfide, N-ring At least one of hexyl-2-benzothiazolylsulfenamide, N,N-dicyclohexyl-2-phenylthiazolylsulfenamide, bismaleimide, and ethylenethiourea.
  • the crosslinking system comprises a crosslinking agent, which may further comprise at least one of a co-crosslinking agent and a vulcanization accelerator.
  • the Mooney viscosity ML (1+4) of the ethylene propylene rubber used is preferably 20 to 50 at 125 ° C, and the ethylene content is preferably 45% to 60%.
  • the Mooney viscosity ML (1+4) of the ethylene propylene diene rubber used is preferably 20 to 100, more preferably 20 to 80, the ethylene content is preferably 50% to 75%, and the third monomer is 5-ethylene-2. - norbornene, 5-vinyl-2-norbornene or dicyclopentadiene, the third monomer content being from 1% to 7%.
  • the branched polyethylene used can be obtained by catalyzing the homopolymerization of ethylene by a ( ⁇ -diimine) nickel catalyst under the action of a cocatalyst.
  • the structure, synthesis method and method for preparing branched polyethylene by using the ( ⁇ -diimine) nickel catalyst are disclosed in the prior art, and can be used but are not limited to the following documents: CN102827312A, CN101812145A, CN101531725A, CN104926962A, US6103658, US6660677.
  • branching degree is 60-130 branches/1000 carbons
  • weight average molecular weight is 66,000-518,000
  • Mooney viscosity ML(1+4) 125°C is 6-102
  • the degree of branching is measured by nuclear magnetic resonance spectroscopy, and the molar percentages of various branches are measured by nuclear magnetic carbon spectroscopy.
  • Hardness test According to the national standard GB/T 531.1-2008, the test is carried out with a hardness tester, and the test temperature is room temperature;
  • tear strength test in accordance with the national standard GB/T529-2008, using an electronic tensile test machine for testing, the tensile speed is 500mm / min, the test temperature is 23 ⁇ 2 ° C, the sample is a rectangular sample;
  • compression permanent deformation test in accordance with the national standard GB/T7759-1996, using a compression permanent deformation device for testing, type B, the compression is 25%, the test temperature is 70 ° C;
  • Mooney viscosity test in accordance with the national standard GB/T1232.1-2000, with Mooney viscosity meter for testing, the test temperature is 125 ° C, preheat 1 minute, test 4 minutes;
  • test conditions are 150 ° C ⁇ 72h;
  • the vulcanization conditions of the following Examples 1 to 29 and Comparative Examples 1 to 6 were uniform: temperature: 160 ° C; pressure: 16 MPa; time was Tc90 + 2 min.
  • the branched polyethylene used was numbered PER-6.
  • the processing steps of the rubber composition are as follows:
  • the rubber composition of this embodiment can be used for the rubber sheet of the plate bridge support.
  • the number of branched polyethylene is PER-6.
  • the rubber composition processing steps are as follows:
  • the branched polyethylene was numbered PER-5.
  • the rubber composition processing steps are as follows:
  • the branched polyethylene was numbered PER-5.
  • the processing steps of the rubber composition are as follows:
  • the branched polyethylene was numbered PER-5.
  • the processing steps of the rubber composition are as follows:
  • EPDM rubber is used as the rubber matrix.
  • the bridge rubber expansion device produced by the extrusion method uses ethylene propylene diene monomer and branched polyethylene as the rubber base, and the branched polyethylene is PER-10.
  • the processing steps of the rubber expansion compound are as follows:
  • the branched polyethylene was numbered PER-9.
  • the processing steps of the rubber composition are as follows:
  • the branched polyethylene was numbered PER-5.
  • the processing steps of the rubber composition are as follows:
  • the branched polyethylene was numbered PER-4.
  • the processing steps of the rubber composition are as follows:
  • the branched polyethylene was numbered PER-4.
  • the processing steps of the rubber composition are as follows:
  • the branched polyethylene was numbered PER-4.
  • the processing steps of the rubber composition are as follows:
  • the branched polyethylenes were numbered PER-1 and PER-7.
  • the processing steps of the rubber composition are as follows:
  • the branched polyethylene was numbered PER-8.
  • the processing steps of the rubber composition are as follows:
  • the rubber composition can be used to produce a rubber sleeper pad.
  • the branched polyethylenes used were numbered PER-2 and PER-8.
  • the processing steps of the rubber composition are as follows:
  • the branched polyethylene used was numbered PER-7.
  • the processing steps of the rubber composition are as follows:
  • the branched polyethylene used was numbered PER-4.
  • the processing steps of the rubber composition are as follows:
  • the branched polyethylene used was numbered PER-6.
  • the processing steps of the rubber composition are as follows:
  • the branched polyethylene used was numbered PER-6.
  • the processing steps of the rubber composition are as follows:
  • the branched polyethylene used was numbered PER-3.
  • the processing steps of the rubber composition are as follows:
  • the branched polyethylene used was numbered PER-5.
  • the processing steps of the rubber composition are as follows:
  • the branched polyethylene used was numbered PER-4.
  • the processing steps of the rubber composition are as follows:
  • the branched polyethylene used was numbered PER-4.
  • the processing steps of the rubber composition are as follows:
  • the branched polyethylene used was numbered PER-7.
  • the processing steps of the rubber composition are as follows:
  • the branched polyethylene used was numbered PER-6.
  • the branched polyethylene used was numbered PER-5.
  • the branched polyethylene used was numbered PER-4.
  • the branched polyethylene used was numbered PER-5.
  • the branched polyethylene used was numbered PER-5.
  • the branched polyethylene used was numbered PER-4.
  • the invention also provides various applications of the above rubber composition, such as the production and processing of bridge rubber expansion device, rubber sleeper pad, bridge plate rubber bearing, basin rubber bearing, rubber steel plate combined telescopic device, rubber fender , rubber water stop belt, vehicle shock absorption bearing, rubber roller, kind of high temperature resistant V-ribbed belt, wiper strip, sealing ring, waterproof coil, etc., the specific implementation is as follows:
  • the bridge plate rubber bearing comprises a steel plate and a rubber sheet layer, and each layer of the rubber sheet and the steel plate are pressed and vulcanized by a coating adhesive to be bonded together, and the rubber composition used in the rubber sheet layer in the embodiment is pressed.
  • the composition and ratio described in Example 2 were weighed and kneaded:
  • Rubber mixing process set the temperature of the mixer to 90 ° C, the rotor speed is 50 rpm, add 100 parts of branched polyethylene pre-pressed for 90 seconds; then add 5 parts of zinc oxide and 1 part of stearin Acid, knead for 1 minute; add 50 parts of carbon black N330 and 5 parts of paraffin oil SUNPAR2280, mix for 3 minutes; finally add 3 parts of cross-linking agent dicumyl peroxide (DCP), 5 parts of cross-linking agent methyl Zinc acrylate and 0.2 parts of the cross-linking agent sulphur were mixed for 2 minutes and then discharged. The open mill is thinned, parked and tested. After numbering, refining, and calendering, the semi-finished film is punched into the required specifications for use in the vulcanization process;
  • DCP dicumyl peroxide
  • Vulcanization process the film and the surface-treated and coated adhesive steel plate are laminated and synthesized according to the process requirements, and then loaded into the preheated mold, and then vulcanized into a flat vulcanizing machine, and the vulcanization temperature is 160 ° C. , steam pressure 0.6MPa, time is 25 minutes;
  • the bridge plate rubber bearing comprises a steel plate, a polytetrafluoroethylene plate and a rubber sheet layer, and each layer of the rubber sheet is pressed and vulcanized by a coating adhesive between the steel plate and the polytetrafluoroethylene plate to be bonded into one whole.
  • the rubber composition for the rubber sheet layer in this example was weighed and kneaded according to the composition and ratio described in Example 2:
  • Rubber mixing process set the temperature of the internal mixer to 90 ° C, the rotor speed is 50 rpm, add 100 parts of branched polyethylene PER-6 pre-pressure mixing for 90 seconds; then add 5 parts of zinc oxide and 1 Stearic acid, mixing for 1 minute; adding 50 parts of carbon black N330 and 5 parts of paraffin oil SUNPAR2280, mixing for 3 minutes; finally adding 3 parts of cross-linking agent dicumyl peroxide (DCP), 5 parts of cross-linking The zinc methacrylate and 0.2 parts of the crosslinking agent sulfur were mixed and the rubber was discharged after 2 minutes. The open mill is thinned, parked and tested. After numbering, refining, and calendering, the semi-finished film is punched into the required specifications for use in the vulcanization process;
  • Vulcanization process the film and the surface-treated and coated adhesive steel plate and the polytetrafluoroethylene plate are sequentially laminated according to the process requirements, and then loaded into the preheated mold, and then vulcanized into the flat vulcanizing machine.
  • the vulcanization temperature is 160 ° C
  • the steam pressure is 0.6 MPa
  • the time is 25 minutes;
  • the basin type rubber support in this embodiment comprises an upper support plate, a stainless steel plate, a polytetrafluoroethylene plate, an intermediate steel plate, a seal ring, a rubber bearing plate, a lower support plate and a support anchor.
  • the rubber bearing plate in this embodiment is the same rubber composition as in Example 5, and the processing steps are as follows:
  • Rubber mixing process set the temperature of the internal mixer to 90 ° C, the rotor speed is 50 rpm, add 30 parts of EPDM rubber and 70 parts of branched polyethylene PER-5 pre-pressure mixing for 90 seconds; Then add 5 parts of zinc oxide and 1 part of stearic acid, mix for 1 minute; add 65 parts of carbon black N330 and 5 parts of paraffin oil SUNPAR 2280, mix for 3 minutes; finally add 3 parts of cross-linking agent dicumyl peroxide ( DCP) and 1 part of the cross-linking agent, triallyl isocyanurate (TAIC), after 2 minutes of mixing, the rubber is discharged, and the open mill is thinned, placed, and tested;
  • DCP dicumyl peroxide
  • TAIC triallyl isocyanurate
  • the rubber bearing plate is assembled with other components to obtain a basin rubber bearing.
  • a rubber expansion body for a bridge rubber expansion device is obtained by an extrusion production process, and the specific steps are as follows:
  • the rubber elastic body described in the present embodiment was the rubber composition described in Example 8, and the temperature of the internal mixer was set to 90 ° C, the rotor rotation speed was 50 rpm, and 100 parts of branched polyethylene PER was added.
  • the extrusion vulcanization process should adopt vacuum pumping extruder.
  • the temperature of the extruder is set to 90 ⁇ 100 °C
  • the screw temperature is 70-80 °C
  • the head pressure should be controlled at 15-20 MPa.
  • the output speed is 25 ⁇ 30 rev/min
  • the salt bath vulcanization process is adopted.
  • the temperature of the spray section is 250 °C
  • the temperature of the dipping section is 220 °C
  • the temperature of the immersion section is 220 °C
  • the transmission speed is 35 ⁇ 45 m/min
  • the cooling section Temperature 25 ⁇ 30 ° C;
  • a rubber expansion body for a bridge rubber expansion device is obtained by a molding process, and the specific steps are as follows:
  • the rubber elastic body described in the present embodiment was the rubber composition described in Example 11, and the temperature of the internal mixer was set to 90 ° C, the rotor rotation speed was 40 rpm, and 100 parts of branched polyg were added.
  • Ethylene PER-4 pre-compression mixing for 90 seconds; then adding 5 parts of zinc oxide, 1 part of stearic acid and 2 parts of antioxidant RD, mixing for 1 minute; adding 50 parts of carbon black N330, 10 parts of calcium carbonate, 5 parts of paraffin
  • the oil SUNPAR 2280 and 4 parts of coumarone resin were mixed for 3 minutes; finally, 3 parts of cross-linking agent dicumyl peroxide (DCP) and 0.3 parts of cross-linking agent sulfur were added, and the mixture was mixed for 2 minutes and then discharged.
  • the open mill is thinned, parked and tested. Refining the film and weighing it.
  • the rubber part was the rubber composition described in Example 11, the temperature of the internal mixer was set to 90 ° C, the rotor speed was 40 rpm, and 100 parts of branched polyethylene PER-4 was pre-compressed. 90 seconds; then add 5 parts of zinc oxide, 1 part of stearic acid and 2 parts of antioxidant RD, mixing for 1 minute; add 50 parts of carbon black N330, 10 parts of calcium carbonate, 5 parts of paraffin oil SUNPAR 2280 and 4 parts of Gu Ma Long resin, kneaded for 3 minutes; finally, 3 parts of cross-linking agent dicumyl peroxide (DCP) and 0.3 parts of cross-linking agent sulfur were added, and the mixture was mixed for 2 minutes and then discharged. The open mill is thinned, parked and tested. Refining the film, weighing and forming;
  • Vulcanization process the film and the surface-treated and coated adhesive steel sheet are laminated according to the process requirements, and then loaded into the preheated mold, and then vulcanized into a flat vulcanizing machine, and the vulcanization temperature is 160 ° C.
  • the steam pressure is 0.6 MPa and the time is 25 minutes;
  • Kneading The rubber composition described in Example 14 was used, and the temperature of the internal mixer was set to 90 ° C, the rotor rotation speed was 40 rpm, and 80 parts of PER-8 and 20 parts of PER-1 pre-compression kneading were added.
  • a rubber fender processing step is as follows:
  • DCP Dicumyl oxide
  • TAIC triallyl isocyanurate
  • Rubber part kneading and molding The rubber composition described in Example 16 was used, and the temperature of the internal mixer was set to 90 ° C, the rotor rotation speed was 40 rpm, and 100 parts of branched polyethylene PER-4 preload was added.
  • Vulcanization process the film and the surface-treated and coated adhesive steel sheet are laminated according to the process requirements, and then loaded into the preheated mold, and then vulcanized into a flat vulcanizer, and the vulcanization temperature is 160 ° C.
  • the steam pressure is 0.6 MPa and the time is 25 minutes.
  • Rubber part kneading and molding The rubber composition described in Example 17 was used, and the temperature of the internal mixer was set to 90 ° C, the rotor rotation speed was 40 rpm, and 100 parts of branched polyethylene pre-pressure kneading was added.
  • Vulcanization process the rubber material and the surface-treated and coated metal parts are laminated according to the process requirements, and then loaded into the preheated mold, and then vulcanized into a flat vulcanizing machine, and the vulcanization temperature is 160. °C, steam pressure 0.6MPa, time is 25 minutes.
  • the damper mount of the present embodiment can be used for high temperature parts such as an engine and an exhaust pipe.
  • vulcanization tank vulcanization the rubberized rubber roller is sent to the vulcanization tank, after closing the tank door, steam is vulcanized into the vulcanization tank, and the compressed air valve is opened while steam is introduced, and the compressed air is passed to vulcanize.
  • the pressure in the tank reaches 4.5 to 5 atmospheres in 0.5 hours; the vulcanization procedure is: firstly heat up to 70-80 ° C, keep warm for 2 hours; then heat up to 100-110 ° C, keep warm for 0.5 hours; then heat up to 120-130 ° C, keep warm 0.5 hours; further increase to 135 ⁇ 140 ° C, heat 8 ⁇ 10 hours.
  • the exhaust valve is opened, the pressure drops, and when the pressure gauge pointer points to zero, the safety pin is opened, and the steam is discharged from the pin hole, and the vulcanization tank is half-opened to lower the temperature until the temperature in the tank is lower than 60 ° C or Pull out the rubber roller when it is equivalent to room temperature;
  • the vulcanized rubber roller is rough-processed on a lathe, and then finished on a grinding machine for inspection and inspection to obtain a finished product.
  • a high temperature resistant V-ribbed belt, the buffer layer of which uses the rubber composition provided by the invention, and the production processing steps are as follows:
  • Compressed layer compound mixing set the temperature of the internal mixer to 90 ° C, the rotor speed is 50 rpm, add 100 parts of branched polyethylene PER-5 pre-pressure mixing for 90 seconds; add 6 parts of zinc oxide, 1 part stearic acid, 2 parts of antioxidant RD, kneaded for 1 minute; then add 45 parts of carbon black N330, 5 parts of paraffin oil SUNPAR 2280 and 5 parts of coumarone resin to the compound, mix for 3 minutes; then add 60 parts of nylon short fibers of 1 mm length, mixed for 2 minutes; finally added 4 parts of cross-linking agent dicumyl peroxide (DCP), 1.5 parts of cross-linking agent triallyl isocyanurate (TAIC) After 2 minutes of mixing, the glue is discharged.
  • DCP dicumyl peroxide
  • TAIC cross-linking agent triallyl isocyanurate
  • the kneaded rubber was thinly passed on an open mill with a roll temperature of 80 ° C, and was thinned 7 times at a roll gap of 0.5 mm to fully orient the short fibers, and the roll gap was obtained to obtain a sheet thickness of about 2.5 mm and parked for 20 hours. .
  • (2) buffer layer compound mixing set the temperature of the mixer to 90 ° C, the rotor speed is 40 rev / min, add 100 parts of branched polyethylene PER-5 pre-pressure mixing for 90 seconds; then add 6 parts of zinc oxide 2 parts of antioxidant RD and 1 part of stearic acid, mixing for 1 minute; adding 55 parts of carbon black N330, 5 parts of paraffin oil SUNPAR 2280 and 5 parts of coumarone resin, mixing for 3 minutes; finally adding 4 parts of crosslinking agent Dicumyl peroxide (DCP), 1.5 parts of cross-linking agent triallyl isocyanurate (TAIC), 10 parts of cross-linking agent zinc methacrylate and 0.3 parts of cross-linking agent sulfur, mixing Discharge the glue after 2 minutes.
  • DCP Dicumyl peroxide
  • TAIC cross-linking agent triallyl isocyanurate
  • molding the use of reverse molding. Firstly, the optical mold is hung on the molding machine, the mold is cleaned, and a small amount of release agent is applied. After it is volatilized, the V-ribbed top cloth is wrapped on the optical mold, and then the buffer rubber is wrapped to correct the tension of the rope, and the winding is smooth. After the strong layer, the buffer rubber is applied, and finally the wedge rubber is wrapped to the outer circumference required by the molding process to obtain a strip.
  • Vulcanization The strip is sent to the vulcanization section for vulcanization.
  • the vulcanization temperature is 160 ° C
  • the internal pressure is 0.45-0.55 MPa
  • the external pressure is 1.0-1.2 MPa
  • the vulcanization time is 30 minutes.
  • Post-treatment After the vulcanization is finished, the mold is cooled and released, and the belt is sent to the cutting process to cut according to the required width. Grinding the back, grinding the wedge, and trimming the product to obtain the finished product.
  • Vulcanization one-stage compression vulcanization: temperature is 160 ° C, vulcanization time is 20 minutes; second-stage oven vulcanization: temperature 150 ° C, time 1 hour.
  • the block rubber is fed into the open mill for mixing, the temperature of the control roller is between 85 and 95 ° C, and the roll distance is controlled to be less than 1 mm, and the thin pass is not less than four times until the surface of the rubber compound is smooth and shiny. Then turn the head and further mix it, make the thin pass no less than four times, adjust the roll distance to not more than 8mm, mix it three times, and obtain the evenly mixed rubber piece with the thickness below 8mm, and cool it to below 50 °C.
  • vulcanization the rolled material is placed in a nitrogen-containing vulcanization kettle for vulcanization treatment, the temperature of the vulcanization kettle is controlled between 155 and 165 ° C, the pressure is between 20 and 25 MPa, and the vulcanization is for 25 to 30 minutes;
  • Rewinding re-opening the vulcanized coil, taking out the release liner layer, and then rewinding and packaging into a product.
  • An engine cooling system radiator plate rubber sealing strip adopts a process of compression vulcanization and stage vulcanization, and comprises the following steps:
  • Rubber mixing set the internal temperature of the mixer to 80 ° C and the rotor speed to 40 rpm, add 100 parts of branched polyethylene PER-5 pre-pressure mixing for 90 seconds; then add 5 parts of zinc oxide, 1 part Stearic acid, 1 part of antioxidant RD and 2 parts of fatty acid derivative mixture WB42, kneaded for 1 minute; 60 parts of carbon black N550, 25 parts of paraffin oil SUNPAR 2280, mixed for 3 minutes; finally added 4 parts of crosslinker Butylperoxydiisopropylbenzene (BIPB), 1 part of the co-crosslinking agent, triallyl isocyanurate (TAIC), and 0.3 parts of the cross-linking agent sulfur were mixed and dispersed for 2 minutes. Parking and testing;
  • BIPB crosslinker Butylperoxydiisopropylbenzene
  • TAIC triallyl isocyanurate
  • the rubber compound after passing the test is extruded through an extruder, cut into pieces and placed in a mold of a vulcanization apparatus, the vulcanization pressure is 15 MPa, the vulcanization temperature is 180 ° C, and the vulcanization time is preferably 2.5 minutes;
  • the trimmed product is subjected to two-stage vulcanization at a high temperature.
  • the temperature is 170 ° C, the time is 30 minutes;
  • Rubber mixing set the temperature of the internal mixer to 100 ° C, the rotor speed to 50 rpm, add 100 parts of branched polyethylene PER-5 pre-pressure mixing for 90 seconds; add 5 parts of zinc oxide, 1 part of hard Fatty acid and 3 parts of coumarone resin, mixing for 2 minutes; then adding 60 parts of carbon black N660 and 20 parts of paraffin oil SUNPAR2280 to the compound, mixing for 3 minutes; finally adding 4 parts of cross-linking agent diisopropyl peroxide Benzene (DCP) and 2 parts of co-crosslinking agent N, N'-m-phenylene bismaleimide (HVA-2) were mixed for 2 minutes and then discharged. After the filter is glued, the rubber compound is opened on the open mill and parked for 20 hours.
  • DCP diisopropyl peroxide Benzene
  • HVA-2 co-crosslinking agent
  • a bridge plate type rubber support wherein the rubber base in the rubber composition is 100 parts of branched polyethylene PER-12, and the remaining components in the rubber composition and the processing technique are the same as those in the embodiment 30.
  • the rubber compound used in the rubber composition was subjected to compression molding to prepare a test sample, and the test performance was as follows:
  • Hardness 65; tensile strength: 27.3 MPa; elongation at break: 446%; compression set (70 ° C ⁇ 22 h): 8%.
  • a vehicle shock absorbing support wherein the rubber matrix in the rubber composition is 70 parts of branched polyethylene PER-10 and 30 parts of branched polyethylene PER-12, the remaining components in the rubber composition and the processing technology and Example 40 is identical.
  • the rubber compound used in the rubber composition was subjected to compression molding to prepare a test sample, and the test performance was as follows:
  • Hardness 63; tensile strength: 27.5 MPa; elongation at break: 382%; compression set (70 ° C ⁇ 22 h): 9%.
  • a rubber sleeper pad having a rubber base of 100 parts of branched polyethylene PER-11, the remaining components of the rubber composition and the processing technique are the same as those of the embodiment 36.
  • the rubber compound used in the rubber composition was subjected to compression molding to prepare a test sample, and the test performance was as follows:
  • the rubber composition of the present invention is superior to the prior art ethylene-propylene rubber-based rubber composition in comprehensive physical properties, and can significantly optimize the anti-aging rubber at low cost.
  • the use effect of the product broaden the application range of anti-aging rubber products.

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  • 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)
  • Processes Of Treating Macromolecular Substances (AREA)

Abstract

L'invention concerne un composite de caoutchouc, un procédé de traitement, un produit de caoutchouc résistant au vieillissement utilisant le composite de caoutchouc, et un procédé de fabrication. Le composite de caoutchouc comprend : un substrat de caoutchouc et des constituants essentiels. Le substrat de caoutchouc comprend : polyéthylène ramifié, dont la teneur est a : 0 < a ≤ 100 parties, caoutchouc éthylène propylène monomère et caoutchouc éthylène propylène diène monomère, dont la teneur est b : 0 ≤ b < 100 parties. Les constituants essentiels comprennent : un agent de réticulation (1,5 à 10 parties), une charge de renforcement (30 à 200 parties), et un plastifiant (5 à 250 parties). Les effets avantageux sont tels que le composite de caoutchouc présente de bonnes performances de traitement, peut être utilisé pour la fabrication de produits de caoutchouc présentant des exigences élevées de performance de résistance au vieillissement et de performance de résistance à une déformation permanente sous compression.
PCT/CN2018/072361 2017-01-13 2018-01-12 Composite de caoutchouc, produit de caoutchouc résistant au vieillissement utilisant ce composite, et procédé de fabrication WO2018130192A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
US16/477,747 US11479661B2 (en) 2017-01-13 2018-01-12 Rubber composition, aging-resistant rubber product using the same
JP2019559143A JP7250341B2 (ja) 2017-01-13 2018-01-12 ゴム組成物、それを用いた老化防止ゴム製品および製造方法

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CN201710025140.8 2017-01-13
CN201710025140 2017-01-13
CN201810020850.6 2018-01-10
CN201810020850.6A CN108329559B (zh) 2017-01-13 2018-01-10 橡胶组合物，及应用其的耐老化橡胶制品和生产方法

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CN110003576A (zh) * 2019-02-28 2019-07-12 常州苏通海平机电科技有限公司 一种植物纤维增强型橡胶垫片的制备方法
CN110041711A (zh) * 2019-05-13 2019-07-23 河北宝瑞橡胶制品有限公司 一种硅橡胶漂浮空心球及其制备方法
CN112920536A (zh) * 2021-02-25 2021-06-08 宁国市瑞普密封件有限公司 一种耐低温密封圈的制备方法
CN114324840A (zh) * 2021-12-13 2022-04-12 天津六0九电缆有限公司 一种快速判定电缆料喷霜的试验方法
WO2022189858A1 (fr) * 2021-03-08 2022-09-15 Airboss Of America Corp. Composition d'epdm thermorésistante et procédé et parties de formulation associés
CN115891330A (zh) * 2022-12-28 2023-04-04 深圳德邦界面材料有限公司 一种高抗穿刺的高导热绝缘片及其制备方法
CN117050437A (zh) * 2023-09-12 2023-11-14 潍坊潍星联合橡塑有限公司 一种耐油耐高温矿用电缆护套材料

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CN103980596A (zh) * 2014-05-13 2014-08-13 浙江大学 一种聚乙烯橡胶及其加工方法
CN104877225A (zh) * 2015-06-20 2015-09-02 浙江大学 一种气密层材料的制备方法及其原料配方
CN104910487A (zh) * 2015-06-01 2015-09-16 浙江大学 一种高耐磨鞋底材料及其制备方法

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EP0050039A2 (fr) * 1980-10-13 1982-04-21 Montedison S.p.A. Compositions élastomères et procédé pour sa fabrication
CN103980596A (zh) * 2014-05-13 2014-08-13 浙江大学 一种聚乙烯橡胶及其加工方法
CN104910487A (zh) * 2015-06-01 2015-09-16 浙江大学 一种高耐磨鞋底材料及其制备方法
CN104877225A (zh) * 2015-06-20 2015-09-02 浙江大学 一种气密层材料的制备方法及其原料配方

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110003576A (zh) * 2019-02-28 2019-07-12 常州苏通海平机电科技有限公司 一种植物纤维增强型橡胶垫片的制备方法
CN110041711A (zh) * 2019-05-13 2019-07-23 河北宝瑞橡胶制品有限公司 一种硅橡胶漂浮空心球及其制备方法
CN112920536A (zh) * 2021-02-25 2021-06-08 宁国市瑞普密封件有限公司 一种耐低温密封圈的制备方法
WO2022189858A1 (fr) * 2021-03-08 2022-09-15 Airboss Of America Corp. Composition d'epdm thermorésistante et procédé et parties de formulation associés
CN114324840A (zh) * 2021-12-13 2022-04-12 天津六0九电缆有限公司 一种快速判定电缆料喷霜的试验方法
CN114324840B (zh) * 2021-12-13 2024-01-23 天津六0九电缆有限公司 一种快速判定电缆料喷霜的试验方法
CN115891330A (zh) * 2022-12-28 2023-04-04 深圳德邦界面材料有限公司 一种高抗穿刺的高导热绝缘片及其制备方法
CN117050437A (zh) * 2023-09-12 2023-11-14 潍坊潍星联合橡塑有限公司 一种耐油耐高温矿用电缆护套材料
CN117050437B (zh) * 2023-09-12 2024-01-26 潍坊潍星联合橡塑有限公司 一种耐油耐高温矿用电缆护套材料

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