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WO2018130187A1 - Composite de caoutchouc, procédé de traitement, applications et procédé de fabrication de produits en caoutchouc à haute résistance - Google Patents

Composite de caoutchouc, procédé de traitement, applications et procédé de fabrication de produits en caoutchouc à haute résistance Download PDF

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

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene

Definitions

  • the invention belongs to the technical field of rubber, and particularly relates to a rubber composition with high mechanical strength and a processing method thereof, and a high-strength rubber product using the rubber composition and a production method thereof.
  • Sulfur vulcanization and peroxide vulcanization are the two most commonly used vulcanization processes for ethylene propylene rubber.
  • a peroxide-based vulcanization system is often used.
  • the mechanical strength of peroxide-cured ethylene-propylene rubber is lower than that of sulfur-vulcanized ethylene-propylene rubber.
  • Unsaturated carboxylic acid metal salts such as zinc acrylate and zinc methacrylate can be used as a co-crosslinking agent for peroxide vulcanization to improve the vulcanization rate and crosslinking efficiency, and can also be used as a reinforcing filler for rubber when the amount is high. Improve the mechanical strength of rubber.
  • an unsaturated carboxylic acid metal salt is often added to an ethylene-propylene rubber product having high mechanical strength requirements.
  • this due to the weak strength of the ethylene-propylene rubber under the peroxide vulcanization system, this also limits the application range of the ethylene-propylene rubber product reinforced with the unsaturated carboxylic acid metal salt to some extent. In the case where the content of the unsaturated carboxylic acid metal salt is large, the compression set resistance is also deteriorated to some extent.
  • Ethylene-propylene rubber is a synthetic rubber with saturated molecular chain. It can be divided into two major categories: ethylene-propylene rubber and EPDM rubber. Both of them have good aging resistance. They are commonly used in ethylene-propylene rubber products. It is EPDM rubber, but because EPDM rubber contains a third monomer, the molecular chain contains double bonds, and the ethylene-propylene rubber molecular chain is completely saturated, so the ethylene-propylene rubber has more excellent resistance to aging. Sex, therefore, in the case of high requirements for aging resistance, it is a common technical solution to improve the aging resistance of EPDM by using ethylene propylene diene rubber together. However, the mechanical strength of the binary ethylene propylene rubber is low, which will affect the overall physical and mechanical properties.
  • Diethylene propylene rubber is a copolymer of ethylene and propylene and belongs to the copolymer of ethylene and ⁇ -olefin.
  • Ethylene and ⁇ -olefin copolymers are polymers containing only hydrocarbon elements and saturated molecular chains.
  • the common types of carbon atoms in such polymers are generally classified into primary, secondary and tertiary carbons, while tertiary carbons are the most It is easy to be trapped by hydrogen to form free radicals, so the ratio of tertiary carbon atoms to all carbon atoms is generally considered to be a major factor affecting the aging resistance of ethylene and ⁇ -olefin copolymers. The lower the ratio, the better the aging resistance.
  • the ratio can be expressed by the degree of branching.
  • a diethylene propylene rubber having a propylene content of 60% by weight can be calculated to contain 200 propylene units per 1000 carbon atoms, that is, 200 tertiary carbon atoms or 200.
  • One methyl branch so its degree of branching is 200 branches / 1000 carbons.
  • Ethylene ethylene propylene rubber generally has a weight percentage of 40% to 65% or 40% to 60%, so its branching degree is generally 117 to 200 branches/1000 carbons or 133 to 200 branches/ This degree of branching can be considered to be higher than other common ethylene and alpha-olefin copolymers in the 1000 carbon range.
  • the ⁇ -olefin in the common ethylene and ⁇ -olefin copolymer may be an ⁇ -olefin having a carbon number of not less than 4 in addition to propylene, and may be selected from a C 4 - C 20 ⁇ -olefin. It is usually selected from the group consisting of 1-butene, 1-hexene and 1-octene. If the degree of branching of the copolymer of ethylene and ⁇ -olefin is too low, the melting point and crystallinity are too high, and it is not suitable for use as a rubber component.
  • a polyolefin obtained by copolymerizing ethylene with 1-butene or ethylene and 1-octene may be referred to as a polyolefin plastomer or a polyolefin elastomer according to the degree of crystallinity and melting point, and a part of the polyolefin is elastic. Due to its proper crystallinity and melting point, it can be used well with ethylene propylene rubber and has a low degree of branching. It is considered to be an ideal material for improving the aging resistance of ethylene propylene rubber.
  • the polyolefin elastomer commonly used in rubber products is generally ethylene.
  • the octene weight percentage is generally not higher than 45%, more commonly not higher than 40%, the corresponding degree of branching is generally not higher than 56 branches / 1000 carbon, The more commonly used degree of branching is not higher than 50 branches/1000 carbons, which is much lower than the degree of branching of ethylene dipropylene rubber, so it has excellent aging resistance and good physical and mechanical properties.
  • the copolymer of ethylene and ⁇ -olefin may be peroxide cross-linking or irradiation cross-linking, both of which are mainly obtained by capturing tertiary carbon.
  • a hydrogen atom forms a tertiary carbon radical, and then forms a carbon-carbon crosslink by radical bonding, but a copolymer of ethylene and 1-octene (hereinafter referred to as POE) has fewer tertiary carbon atoms and is attached to a tertiary carbon atom.
  • Chain length, large steric hindrance, difficulty in radical reaction, resulting in difficulty in crosslinking, affecting processing efficiency and product performance, such as compression set resistance is unsatisfactory.
  • the object of the present invention is to solve the above problems and provide a novel rubber composition, which is partially or completely replaced with ethylene-propylene rubber with a branching degree of not less than 50 branches/1000 carbons, and continues to use peroxidation.
  • a rubber composition comprising: a rubber matrix and an essential component, the rubber matrix comprising: a content of branched polyethylene a: 0 ⁇ a ⁇ 100 parts;
  • the content of the ethylene propylene rubber and the ethylene propylene diene rubber is b: 0 ⁇ b ⁇ 100 parts;
  • the essential component comprises: 1 to 10 parts of the crosslinking agent, and the unsaturated carboxylic acid metal salt, based on 100 parts by weight of the rubber matrix.
  • branching degree of the branched polyethylene is not less than 50 branches/1000 carbons, the weight average molecular weight is not less than 50,000, and the Mooney viscosity ML (1+4) is not lower than 125 °C. 2.
  • Branched polyethylene in the prior art means, in addition to a branched ethylene homopolymer, a branched saturated vinyl copolymer, such as an ethylene- ⁇ -olefin copolymer, which may be POE, although POE performs well in physical and mechanical properties and aging resistance, but cross-linking performance is not good, although the branched polyethylene of the present invention can contain both branched ethylene homopolymer and POE, but a better choice It is a branched polyethylene having a high proportion of branched polyethylene or a branched ethylene homopolymer. In a preferred embodiment of the invention, the branched polyethylene contains only branched ethylene homopolymer.
  • the branched polyethylene used is a branched ethylene homopolymer unless otherwise specified.
  • the branched polyethylene used in the present invention is a kind of ethylene homopolymer having a branching degree of not less than 50 branches/1000 carbons, and can be called Branched Polyethylene or Branched PE.
  • the synthesis method is mainly composed of a late transition metal catalyst.
  • the homopolymerization of ethylene is catalyzed by a "chain walking mechanism", and the preferred late transition metal catalyst may be one of ( ⁇ -diimine) nickel/palladium catalysts.
  • the nature of the chain walking mechanism refers to the late transition metal catalyst.
  • the ( ⁇ -diimine) nickel/palladium catalyst is more likely to undergo ⁇ -hydrogen elimination reaction and re-insertion reaction in the process of catalyzing olefin polymerization, thereby causing branching.
  • Branched chains of such branched polyethylenes may have different numbers of carbon atoms, specifically 1 to 6, or more carbon atoms.
  • the production cost of the ( ⁇ -diimine) nickel catalyst is significantly lower than that of the ( ⁇ -diimine) palladium catalyst, and the ( ⁇ -diimine) nickel catalyst catalyzes the high rate of ethylene polymerization and high activity, and is more suitable for industrial applications. Therefore, the branched polyethylene prepared by the ethylene polymerization of the ( ⁇ -diimine) nickel catalyst is preferred in the present invention.
  • the degree of branching of the branched polyethylene used in the present invention is preferably 50 to 130 branches/1000 carbons, further preferably 60 to 130 branches/1000 carbons, further preferably 60 to 116 branches/1000.
  • a carbon, the degree of branching between POE and ethylene-propylene rubber, is a new technical solution that is different from the prior art, and can have excellent aging resistance and good cross-linking performance.
  • Cross-linking performance includes factors such as crosslink density and cross-linking rate, which is the specific performance of the cross-linking ability of the rubber matrix during processing.
  • the branched polyethylene used in the present invention preferably has a methyl branch content of 40% or more or 50% or more, and has a certain similarity with the structure of the ethylene propylene diene rubber.
  • the degree of branching (tertiary carbon atom content) and the steric hindrance around the tertiary carbon atom are the two main factors affecting the cross-linking ability of the saturated polyolefin.
  • the branched polyethylene used in the present invention is low in degree of branching relative to the ethylene propylene rubber, and since the branched polyethylene has a branch having a carbon number of not less than 2, the branched polycondensation used in the present invention
  • the steric hindrance around the tertiary carbon atom of ethylene is theoretically larger than that of ethylene propylene rubber. It can be judged by combining two factors that the crosslinking ability of the branched polyethylene used in the present invention should be weaker than that of the ethylene propylene rubber.
  • EPDM rubber In EPDM rubber. However, the actual cross-linking ability of the partially branched polyethylene used in the present invention is close to that of EPDM rubber, and may even be equal to or better than EPDM rubber. This means that the rubber composition of the present invention can obtain a good aging resistance, can also not weaken the crosslinking ability, and can even have excellent crosslinking performance to achieve an unexpected beneficial effect.
  • secondary branched structure refers to a structure in which branches are further branched. This is also known as "branch-on-branch" during chain walking. Because of the low steric hindrance around the tertiary carbon atoms of the secondary branches, cross-linking reactions are more likely to occur. Having a secondary branched structure is a distinct distinction between the branched polyethylene used in the preferred embodiment of the invention and the prior art ethylene dipropylene rubber or the conventional ethylene- ⁇ -olefin copolymer.
  • the vinyl copolymer refers to a copolymer of ethylene and a branched ⁇ -olefin, and has a secondary branched structure, wherein the branched ⁇ -olefin may be selected from the group consisting of isobutylene and 3-methyl-1- Butylene, 4-methyl-1-pentene, 3-methyl-1-pentene, 2-methyl-1-heptene, 3-methyl-1-heptene, 4-methyl-1- The heptene, 5-methyl-1-heptene, 6-methyl-1-heptene, and the like, the comonomer may also contain a common linear alpha-olefin.
  • branched polyethylene prepared by the ( ⁇ -diimine) nickel catalyst is difficult to exist in the secondary branched structure, and at least it is difficult to sufficiently distinguish it.
  • the technical solution of the present invention is also to analyze the branched polycondensation.
  • the structure of ethylene provides a new idea.
  • the cross-linking point of the branched polyethylene can be generated on the tertiary chain of the main chain during the peroxide crosslinking process. It can also be produced on the branched tertiary carbon of the secondary structure, so the rubber network formed by the cross-linking of the branched polyethylene has a richer CC connecting segment between the main chains than the ethylene-propylene rubber. The length can effectively avoid stress concentration and help to obtain better mechanical properties, including tear strength.
  • a further technical solution is that, in 100 parts by weight, the content of branched polyethylene in the rubber matrix is a: 10 ⁇ a ⁇ 100 parts; the content of binary ethylene propylene rubber and ethylene propylene diene rubber is b: 0 ⁇ b ⁇ 90 parts; the branched polyethylene is an ethylene homopolymer having a degree of branching of 60 to 130 branches/1000 carbons, a weight average molecular weight of 66,000 to 518,000, and a Mooney viscosity ML (1+4) ) 125 ° C is 6 ⁇ 102;
  • a further technical solution is that, in 100 parts by weight, the content of branched polyethylene in the rubber matrix is a: 10 ⁇ a ⁇ 100 parts; the content of binary ethylene propylene rubber and ethylene propylene diene rubber is b: 0 ⁇ b ⁇ 90 parts; the branched polyethylene is an ethylene homopolymer having a branching degree of 70-116 branches/1000 carbons, a weight average molecular weight of 201,000 to 436,000, and a Mooney viscosity ML (1+4) ) 125 ° C is 23 ⁇ 101.
  • a further technical solution is that, in 100 parts by weight of the rubber matrix, the content of the branched polyethylene is: 10 ⁇ a ⁇ 100 parts; the content of the binary ethylene propylene rubber and the ethylene propylene diene rubber is b: 0 ⁇ b ⁇ 90
  • the branched polyethylene is an ethylene homopolymer having a degree of branching of 80 to 105 branches/1000 carbons, a weight average molecular weight of 250,000 to 400,000, and a Mooney viscosity of ML (1+4) 125. °C is 40 to 95.
  • a further technical solution is that, in 100 parts by weight of the rubber matrix, the content of the branched polyethylene is: 10 ⁇ a ⁇ 100 parts; the content of the binary ethylene propylene rubber and the ethylene propylene diene rubber is b: 0 ⁇ b ⁇ 90
  • the branched polyethylene is an ethylene homopolymer having a degree of branching of 80 to 105 branches/1000 carbons, a weight average molecular weight of 268,000 to 356,000, and a Mooney viscosity of ML (1+4) 125. °C is 42-80.
  • the third monomer of the ethylene propylene diene monomer is preferably a diene monomer, specifically selected from the group consisting of 5-ethylidene-2-norbornene and 5-vinyl-2-nor Borneene, dicyclopentadiene, 1,4-hexadiene, 1,5-hexadiene, 1,4-pentadiene, 2-methyl-1,4-pentadiene, 3-methyl- 1,4-Hexadiene, 4-methyl-1,4-hexadiene, 1,9-decadiene, 5-methylene-2-norbornene, 5-pentylene-2-nor Borbornene, 1,5-cyclooctadiene, 1,4-cyclooctadiene, and the like.
  • a diene monomer specifically selected from the group consisting of 5-ethylidene-2-norbornene and 5-vinyl-2-nor Borneene, dicyclopentadiene, 1,4-hexadiene
  • the ethylene propylene rubber may contain two or more kinds of diene monomers at the same time, such as 5-ethylidene-2-norbornene and 5-vinyl-2-norbornene.
  • the functional group of the diene monomer can play the same role as the intrinsic co-crosslinking agent in the peroxide vulcanization, thereby improving the crosslinking efficiency. This helps to reduce the amount and residual amount of crosslinker and co-crosslinker required and the cost of adding them.
  • the weight specific gravity of the diene monomer to the ethylene propylene rubber is preferably from 1% to 14%, more preferably from 3% to 10%, still more preferably from 4% to 7%.
  • the crosslinking agent comprises at least one of a peroxide crosslinking agent and a sulfur
  • the peroxide crosslinking agent comprises di-tert-butyl peroxide, dicumyl peroxide, Tert-butyl cumyl peroxide, 1,1-di-tert-butyl peroxide-3,3,5-trimethylcyclohexane, 2,5-dimethyl-2,5-di(tert-butyl) Base oxidized) hexane, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne-3, bis(tert-butylperoxyisopropyl)benzene, 2,5-di At least one of methyl-2,5-bis(benzoyl peroxy)hexane, tert-butyl peroxybenzoate, and t-butylperoxy-2-ethylhexyl carbonate.
  • a further technical solution is that the content of the crosslinking agent is from 1.5 to 6 parts based on 100 parts by weight of the rubber matrix.
  • the unsaturated carboxylic acid metal salt comprises at least one of zinc acrylate, zinc methacrylate, magnesium methacrylate, calcium methacrylate, and aluminum methacrylate.
  • a further technical solution is that the content of the unsaturated carboxylic acid metal salt is 5 to 30 parts based on 100 parts by weight of the rubber matrix.
  • the rubber composition further comprises an auxiliary component, wherein the auxiliary component is in parts by weight, based on 100 parts by weight of the rubber matrix, and comprises: a co-crosslinking agent other than the unsaturated carboxylic acid metal salt 0.2 to 10
  • the reinforcing filler is 10 to 150 parts
  • the plasticizer is 5 to 80 parts
  • the stabilizer is 1 to 3 parts
  • the metal oxide is 2 to 20 parts
  • the vulcanization accelerator is 0 to 3 parts.
  • the co-crosslinking agent comprises triallyl cyanurate, triallyl isocyanurate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, Triallyl trimellitate, trimethylolpropane trimethacrylate, N,N'-m-phenylene bismaleimide, N,N'-bis-indenylacetone, 1,2- At least one of polybutadiene and sulfur.
  • the reinforcing filler comprises at least one of carbon black, white carbon, calcium carbonate, talc, calcined clay, and magnesium carbonate.
  • the plasticizer comprises at least one of pine tar, engine oil, naphthenic oil, paraffin oil, coumarone, RX-80, stearic acid, paraffin, liquid ethylene propylene rubber, and liquid polyisobutylene.
  • the rational use of plasticizers can increase the flexibility of the compound and the plasticity suitable for process operation.
  • an adhesion promoter such as pine tar, coumarone, RX-80, liquid polyisobutylene or the like.
  • the stabilizer comprises 2,2,4-trimethyl-1,2-dihydroquinoline polymer (RD), 6-ethoxy-2,2,4-trimethyl At least one of -1,2-dihydroquinoline (AW), 2-mercaptobenzimidazole (MB), and N-4 (anilinophenyl)maleimide (MC).
  • the metal oxide comprises at least one of zinc oxide, magnesium oxide, and calcium oxide.
  • the vulcanization accelerator comprises 2-thiol benzothiazole, dibenzothiazyl disulfide, tetramethyl thiuram monosulfide, tetramethyl thiuram disulfide, tetrazyl disulfide Kethiram, N-cyclohexyl-2-benzothiazolyl sulfenamide, N,N-dicyclohexyl-2-benzothiazolyl sulfenamide, bismaleimide, ethylene thiourea At least one of them.
  • the rubber composition in order to improve the viscosity of the rubber compound, may further comprise a tackifier, wherein the plasticizer is pine tar, coumarone resin, RX-80, and liquid polyisobutylene.
  • a tackifier wherein the plasticizer is pine tar, coumarone resin, RX-80, and liquid polyisobutylene.
  • a commonly used tackifier such as a phenol resin, a modified alkyl phenol resin, or an alkyl phenol-acetylene resin, and the tackifier is generally not more than 30 parts by weight, further preferably not more than 10 parts by weight, based on 100 parts by weight of the rubber base. It is further preferably not more than 5 parts by weight.
  • crosslinking agent the co-crosslinking agent and the vulcanization accelerator involved in the rubber composition provided by the present invention all belong to a crosslinking system.
  • the rubber composition of the present invention may be present in the form of an uncrosslinked rubber compound, and may be present in the form of a vulcanized rubber after further crosslinking reaction.
  • Vulcanized rubber can also be referred to simply as vulcanizate.
  • the present invention also provides a method of processing the above rubber composition, the processing method comprising the steps of:
  • Rubber kneading First, the rubber composition other than the cross-linking system is sequentially added to the internal mixer according to the parts by weight for kneading, and then added to the cross-linking system, uniformly kneaded, and discharged to obtain a rubber compound. The rubber compound is thinned on the open mill, and then the film is left to be vulcanized, wherein the crosslinking system comprises a crosslinking agent, and may further comprise at least one of a crosslinking agent and a vulcanization accelerator;
  • Vulcanization The rubber compound is filled into the cavity of the mold, and after being vulcanized by vulcanization on a flat vulcanizer, the vulcanized rubber is obtained by demolding.
  • the present invention also provides an application for the production of insulating gloves using the above rubber composition, the production steps of which include the following:
  • Rubber kneading First, the rubber composition other than the cross-linking system is sequentially added to an internal mixer for kneading, and then added to a cross-linking system, which is uniformly kneaded and discharged to obtain a kneaded rubber. The mixture is thinned on the open mill and then discharged, and is parked for vulcanization, wherein the crosslinking system comprises a crosslinking agent, and may further comprise at least one of a co-crosslinking agent and a vulcanization accelerator;
  • Vulcanization The formed film is filled into the cavity of the mold, and the mold is placed on a flat vulcanizing machine for pressure vulcanization, then cooled and demolded, and trimmed to obtain a rubber insulated glove.
  • the present invention also provides an application for producing a hose using the above rubber composition, and the production method thereof comprises the following steps:
  • Rubber kneading First, the rubber composition other than the cross-linking system is sequentially added to the internal mixer for mixing by weight, and then added to the cross-linking system, uniformly kneaded, and discharged to obtain a rubber compound. The rubber compound is thinned on the open mill, and then the film is left to be vulcanized, wherein the crosslinking system comprises a crosslinking agent, and may further comprise at least one of a crosslinking agent and a vulcanization accelerator;
  • Extrusion and molding a cold feed extruder is used to extrude the rubber layer on the mandrel to obtain a tube blank, which is cooled by steam vulcanization, de-core, trimmed, inspected, and stored in a warehouse to obtain a hose.
  • the present invention also provides an application of the above rubber composition, which can be used for producing a conveyor belt, wherein at least one of the working surface covering rubber and the non-working surface covering rubber comprises the above rubber composition, and the production method comprises the following steps:
  • Rubber kneading process First, the rubber composition other than the cross-linking system is sequentially added to an internal mixer in terms of parts by weight for kneading, and then added to a cross-linking system, which is uniformly kneaded and discharged to obtain a kneaded rubber. The mixture is thinned on the open mill and then placed on the sheet to be vulcanized.
  • the crosslinking system comprises a crosslinking agent, and may further comprise at least one of a co-crosslinking agent and a vulcanization accelerator;
  • the film is closely attached to the pre-formed adhesive canvas strip blank on the forming machine to form a strip of high temperature resistant conveyor belt, and then rolled up for waiting for vulcanization;
  • the present invention also provides an application of the above rubber composition, which can be used for producing a conveyor belt, wherein the rubber used for the adhesive layer comprises the above rubber composition, and the rubber composition preferably comprises a tackifier, and the production method thereof comprises the following steps:
  • Rubber kneading process First, the rubber composition other than the cross-linking system is sequentially added to an internal mixer in terms of parts by weight for kneading, and then added to a cross-linking system, which is uniformly kneaded and discharged to obtain a kneaded rubber. The mixture is thinned on the open mill and then discharged, and is parked for vulcanization, wherein the crosslinking system comprises a crosslinking agent, and may further comprise at least one of a co-crosslinking agent and a vulcanization accelerator;
  • Adhesive glue the rubber compound and the cloth layer are finished at a normal temperature by a double roll or a four roll calender to complete the bonding of the adhesive glue and the canvas layer to obtain a rubberized canvas strip;
  • the present invention also provides an application of the above rubber composition, which can be used for producing a shock absorbing member, which can be a rubber shock absorbing member, and can also be rubber because the rubber composition has good bonding property with metal.
  • Metal composite shock absorber which can be used for producing a shock absorbing member, which can be a rubber shock absorbing member, and can also be rubber because the rubber composition has good bonding property with metal.
  • the beneficial effects of the invention are: since the branch of the ethylene-propylene rubber is substantially methyl, the branched polyethylene has more branches in the molecular structure, and the branch length has a certain distribution, and the branched polyethylene has An appropriate number of secondary branched structures.
  • the crosslinking point of the branched polyethylene can be generated on the tertiary chain of the main chain or on the branched tertiary carbon of the secondary structure, so
  • the rubber network formed by cross-linking of branched polyethylene has a richer CC connecting segment length between the main chains, which can effectively avoid stress concentration and facilitate better mechanics. Performance, including tear strength.
  • the compression set property is related to the molecular weight distribution of the rubber material, and the rubber having a narrow molecular weight distribution has a relatively low compression set.
  • the molecular weight distribution of ethylene propylene rubber is mostly between 3 and 5, and the highest is 8 to 9.
  • the molecular weight distribution of a small amount of ethylene propylene rubber is close to 2 and convenient for processing, but the cost is high.
  • the molecular weight distribution of the branched polyethylene is generally lower than 2.5, which is significantly smaller than the molecular weight distribution of the ordinary ethylene propylene rubber
  • the rubber composition of the present invention has a lower compression set after vulcanization, and can be compensated to some extent.
  • the rubber composition provided by the present invention can obtain a rubber product having high mechanical strength and good compression set resistance.
  • the Mooney viscosity ML (1+4) of the ethylene propylene rubber used is preferably 20 to 50 at 125 ° C, and the ethylene content is preferably 45% to 60%.
  • the Mooney viscosity ML (1+4) of the ethylene propylene diene rubber used is preferably 20 to 100, more preferably 30 to 80, the ethylene content is preferably 50 to 75%, and the third monomer is 5-ethylene-2. -norbornene, 5-vinyl-2-norbornene or dicyclopentadiene, the third monomer content being from 1% to 7%.
  • the branched polyethylene used can be obtained by catalyzing the homopolymerization of ethylene by a ( ⁇ -diimine) nickel catalyst under the action of a cocatalyst.
  • the structure, synthesis method and method for preparing branched polyethylene by using the ( ⁇ -diimine) nickel catalyst are disclosed in the prior art, and can be used but are not limited to the following documents: CN102827312A, CN101812145A, CN101531725A, CN104926962A, US6103658, US6660677.
  • the selected branched polyethylene is characterized by a branching degree of 60 to 130 branches/1000 carbons, a weight average molecular weight of 66,000 to 518,000, and a Mooney viscosity of ML (1+4) of 125 ° C of 6 to 102. .
  • the degree of branching is measured by nuclear magnetic resonance spectroscopy, and the molar percentages of various branches are measured by nuclear magnetic carbon spectroscopy.
  • Hardness test According to the national standard GB/T 531.1-2008, the test is carried out with a hardness tester, and the test temperature is room temperature;
  • Mooney viscosity test According to the national standard GB/T1232.1-2000, the test is carried out with a Mooney viscometer. The test temperature is 125 ° C, preheating for 1 minute, testing for 4 minutes;
  • test conditions 150 ° C ⁇ 72h;
  • tear performance test in accordance with the national standard GB/T529-2008, using an electronic tensile testing machine for testing, the stretching speed is 500mm / min, the test temperature is 23 ⁇ 2 ° C, the sample is a rectangular sample;
  • compression permanent deformation test in accordance with the national standard GB/T7759-1996, using a compression permanent deformation device for testing, type B, the compression is 25%, the test temperature is 70 ° C;
  • the vulcanization conditions of the following Examples 1 to 12 and Comparative Examples 1 and 2 were as follows: temperature: 170 ° C; pressure: 16 MPa; time was Tc90 + 1 min.
  • the branched polyethylene used was numbered PER-6.
  • Rubber mixing set the temperature of the internal mixer to 90 ° C, the rotor speed is 50 rpm, add 70 parts of EPDM rubber and 30 parts of branched polyethylene for 90 seconds; then in the rubber compound 35 parts of zinc methacrylate was added and kneaded for 4 minutes; finally, 6 parts of cross-linking agent dicumyl peroxide (DCP) was added, and after 2 minutes of mixing, the rubber was discharged, and the mixture was placed at a roll temperature of 60 ° C. The thin open on the open mill, the sheet with a thickness of about 2.5mm, and parked for 20 hours.
  • DCP cross-linking agent dicumyl peroxide
  • the branched polyethylene used was numbered PER-5.
  • Rubber mixing set the temperature of the internal mixer to 90 ° C, the rotor speed is 50 rpm, add 50 parts of ethylene propylene diene rubber and 50 parts of branched polyethylene for 90 seconds; then in the rubber compound Add 50 parts of zinc methacrylate, mix for 4 minutes; finally add 10 parts of cross-linking agent dicumyl peroxide (DCP), mix for 2 minutes, then drain the glue, the mixture is at a roll temperature of 60 ° C.
  • DCP dicumyl peroxide
  • the branched polyethylene used was numbered PER-5.
  • Rubber mixing set the temperature of the internal mixer to 90 ° C, the rotor rotation speed is 50 rpm, and add 100 parts of branched polyethylene to pre-press and knead for 90 seconds; then add 35 parts of zinc methacrylate to the rubber compound. , mixing for 4 minutes; finally adding 5 parts of cross-linking agent dicumyl peroxide (DCP), mixing for 2 minutes, then discharging the glue, and the mixture is thinned on an open mill with a roll temperature of 60 ° C to obtain 2.5. A sheet of about mm thickness is parked for 20 hours.
  • DCP cross-linking agent dicumyl peroxide
  • Rubber mixing set the temperature of the internal mixer to 90 ° C, the rotor speed to 50 rpm, add 100 parts of EPDM rubber for 90 seconds, and then add 35 parts of methacrylic acid to the compound. Zinc, kneading for 4 minutes; finally adding 5 parts of cross-linking agent dicumyl peroxide (DCP), mixing for 2 minutes, then discharging the glue, and the mixture is thinned on an open mill with a roll temperature of 60 ° C. A sheet of thickness of about 2.5 mm is parked for 20 hours.
  • DCP dicumyl peroxide
  • test data of Examples 1-3 and Comparative Example 1 are as follows:
  • Example 1 Example 2
  • Example 3 Comparative Example 1 hardness 71 75 69
  • Elongation at break % 312 279 349 307 Tear strength N/mm 57 59 62
  • the branched polyethylene used was numbered PER-9.
  • Rubber mixing set the temperature of the mixer to 90 ° C, the rotor speed is 50 rpm, add 90 parts of EPDM rubber and 10 parts of branched polyethylene for 90 seconds; then add 6 parts. Zinc oxide, 1 part stearic acid and 8 parts zinc methacrylate, kneaded for 2 minutes; then add 50 parts of carbon black N550 to the compound, knead for 3 minutes; finally add 4 parts of cross-linking agent diisopropyl peroxide Benzene (DCP), 1 part of triallyl isocyanurate (TAIC) and 0.3 parts of sulfur, after 2 minutes of mixing, the rubber was discharged, and the mixture was thinned on an open mill with a roll temperature of 60 ° C to obtain A sheet of thickness of about 2.5 mm is parked for 20 hours.
  • DCP diisopropyl peroxide Benzene
  • TAIC triallyl isocyanurate
  • the branched polyethylene used was numbered PER-6.
  • Rubber mixing set the temperature of the internal mixer to 90 ° C, the rotor speed is 50 rpm, add 30 parts of EPDM rubber and 70 parts of branched polyethylene for 90 seconds; then add 6 parts. Zinc oxide, 1 part stearic acid and 5 parts zinc methacrylate, kneaded for 2 minutes; then add 50 parts of carbon black N550 to the compound, knead for 3 minutes; finally add 1 part of cross-linking agent diisopropyl peroxide Benzene (DCP), 0.5 parts of sulfur, 1.5 parts of 2-mercaptobenzimidazole and 1.5 parts of N-cyclohexyl-2-benzothiazolyl sulfenamide, after 3 minutes of mixing, the rubber is discharged, and the rubber is mixed at the roll temperature. It was thin on the 60 ° C open mill, and a sheet having a thickness of about 2.5 mm was obtained and parked for 20 hours.
  • DCP diisopropyl peroxide Benzene
  • the branched polyethylene used was numbered PER-4.
  • Rubber mixing set the temperature of the internal mixer to 90 ° C, the rotor speed to 50 rpm, and add 100 parts of branched polyethylene pre-pressed for 90 seconds; then add 6 parts of zinc oxide and 1 part of stearic acid. And 8 parts of zinc methacrylate, mixing for 2 minutes; then adding 50 parts of carbon black N550 to the compound, mixing for 3 minutes; finally adding 4 parts of cross-linking agent dicumyl peroxide (DCP), 1 part three Allyl isocyanurate (TAIC) and 0.3 parts of sulfur were mixed for 2 minutes, and the rubber was drained. The mixture was thinned on an open mill with a roll temperature of 60 ° C to obtain a sheet having a thickness of about 2.5 mm. 20 hours.
  • DCP dicumyl peroxide
  • TAIC Allyl isocyanurate
  • Rubber mixing set the temperature of the internal mixer to 90 ° C, the rotor speed to 50 rpm, add 100 parts of EPDM rubber for 90 seconds, and then add 6 parts of zinc oxide and 1 part of stearin. Acid and 8 parts of zinc methacrylate, kneaded for 2 minutes; then add 50 parts of carbon black N550 to the compound, mix for 3 minutes; finally add 4 parts of cross-linking agent dicumyl peroxide (DCP), 1 part Triallyl isocyanurate (TAIC) and 0.3 parts of sulfur, after 2 minutes of mixing, the rubber was discharged, and the rubber mixture was thinly passed through an open mill having a roll temperature of 60 ° C to obtain a sheet having a thickness of about 2.5 mm. Park for 20 hours.
  • DCP dicumyl peroxide
  • TAIC Triallyl isocyanurate
  • test data of Examples 4 to 6 and Comparative Example 2 are as follows:
  • the branched polyethylenes used were numbered PER-1 and PER-7.
  • Rubber mixing set the temperature of the internal mixer to 90 ° C, the rotor rotation speed is 50 rpm, add 80 parts of PER-7 and 20 parts of PER-1 pre-pressure mixing for 90 seconds; then add 10 parts of zinc oxide, 1 part stearic acid and 1 part antioxidant 2,2,4-trimethyl-1,2-dihydroquinoline polymer (RD), kneaded for 2 minutes; then add 30 parts of methacrylic acid to the compound Zinc, 50 parts of carbon black N330 and 15 parts of paraffin oil SUNPAR 2280, mixed for 3 minutes; finally added 4 parts of cross-linking agent dicumyl peroxide (DCP), 1.5 parts of triallyl isocyanurate (TAIC) And 0.3 parts of sulfur, after 2 minutes of kneading, the rubber was discharged, and the rubber mixture was thinly passed through an open mill having a roll temperature of 60 ° C to obtain a sheet having a thickness of about 2.5 mm, and was left for 20 hours.
  • DCP cross-linking agent di
  • the branched polyethylene used was numbered PER-8.
  • Rubber mixing set the temperature of the internal mixer to 90 ° C, the rotor speed to 50 rpm, add 80 parts of EPDM rubber and 20 parts of PER-8 pre-pressure mixing for 90 seconds; then add 10 parts of oxidation.
  • Zinc 1 part stearic acid, 1 part antioxidant RD and 1 part 2-mercaptobenzimidazole (MB), kneaded for 2 minutes; then 30 parts of zinc methacrylate, 60 parts of carbon black N330 and then added to the compound 20 paraffin oil SUNPAR 2280, mixed for 3 minutes; finally added 3 parts of cross-linking agent dicumyl peroxide (DCP), 1 part triallyl isocyanurate (TAIC) and 9 parts of cross-linking agent 1,2-polybutadiene, after 2 minutes of kneading, the rubber was discharged, and the kneaded rubber was thinly passed through an open mill having a roll temperature of 60 ° C to obtain a sheet having a thickness of about 2.5 mm, and was left to stand
  • the branched polyethylene used was numbered PER-7.
  • Rubber mixing set the temperature of the internal mixer to 90 ° C, the rotor speed is 50 rpm, add 20 parts of ethylene propylene diene rubber, 50 parts of ethylene propylene diene monomer and 30 parts of PER-7 pre-pressure mixing.
  • the branched polyethylene used was numbered PER-3.
  • Rubber mixing set the temperature of the internal mixer to 90 ° C, the rotor speed to 50 rpm, add 20 parts of ethylene propylene diene rubber, 30 parts of EPDM rubber and 50 parts of PER-3 pre-pressure mixing 90 seconds; then add 20 parts of zinc oxide, 2 parts of stearic acid, 1 part of antioxidant RD and 1 part of 2-mercaptobenzimidazole (MB), knead for 2 minutes; then add 30 parts of methacrylic acid to the compound Zinc, 80 parts of carbon black N330 and 20 parts of paraffin oil SUNPAR 2280, mixing for 3 minutes; finally adding 1 part of cross-linking agent dicumyl peroxide (DCP), mixing for 2 minutes, then discharging the glue, the glue is
  • the sheet was rolled on a mill with a roll temperature of 60 ° C to obtain a sheet having a thickness of about 2.5 mm and parked for 20 hours.
  • the branched polyethylene used was numbered PER-5.
  • Rubber mixing set the temperature of the internal mixer to 90 ° C, the rotor speed is 50 rpm, add 100 parts of PER-5 pre-pressure mixing for 90 seconds; then add 15 parts of zinc oxide, 2 parts of stearic acid, 1 part of antioxidant RD, kneaded for 2 minutes; then add 25 parts of zinc methacrylate, 60 parts of carbon black N330 and 15 parts of paraffin oil SUNPAR 2280 to the compound, mix for 3 minutes; finally add 4 parts of cross-linking agent Dicumyl oxide (DCP) and 1.5 parts of N, N'-m-phenylene bismaleimide (HVA-2), after 2 minutes of mixing, the rubber is discharged, and the mixture is at a roll temperature of 60 ° C.
  • DCP Dicumyl oxide
  • HVA-2 N, N'-m-phenylene bismaleimide
  • the branched polyethylenes used were numbered PER-2 and PER-6.
  • Rubber mixing set the temperature of the internal mixer to 90 ° C, the rotor speed to 50 rpm, add 30 parts of PER-2 and 70 parts of PER-6 pre-pressure mixing for 90 seconds; then add 10 parts of zinc oxide, 2 parts of stearic acid, 1 part of antioxidant RD, mixing for 2 minutes; then adding 15 parts of zinc methacrylate, 50 parts of carbon black N330 and 15 parts of paraffin oil SUNPAR 2280 to the compound, mixing for 3 minutes; 3 parts of cross-linking agent dicumyl peroxide (DCP) and 1 part of triallyl isocyanurate (TAIC), after 2 minutes of mixing, the rubber was discharged, and the mixture was opened at a roll temperature of 60 ° C. Thin on the refiner, a sheet with a thickness of about 2.5 mm, and parked for 20 hours.
  • DCP dicumyl peroxide
  • TAIC triallyl isocyanurate
  • test data of Examples 7 to 12 are as follows:
  • a light-colored pure rubber pipe produced by using the rubber composition provided by the present invention comprising the following steps:
  • the 60mm cold feed extruder is equipped with a T-type head.
  • the rubber layer is extruded on the mandrel to obtain the tube blank, which is cooled, de-core, trimmed, inspected and stored after being vulcanized.
  • the vulcanization process is steam vulcanization at 160 ° C, steam pressure 0.6 MPa, time 30 minutes.
  • An insulating glove produced by using the rubber composition provided by the present invention comprising the following steps:
  • a high temperature resistant conveyor belt using the rubber composition provided by the present invention as a working surface covering glue comprising the following steps:
  • the high temperature resistant conveyor belt of the embodiment is provided with a cored tensile canvas between the working surface covering glue and the non-working surface covering glue, and they are made into a solid whole by molding and vulcanization process.
  • Rubber mixing process set the temperature of the internal mixer to 90 ° C, the rotor speed is 50 rpm, add 100 parts of PER-5 pre-pressure mixing for 90 seconds; then add 15 parts of zinc oxide, 2 parts of stearic acid, 1 part Anti-aging agent RD, mixing for 2 minutes; then adding 25 parts of zinc methacrylate, 60 parts of carbon black N330 and 15 parts of paraffin oil SUNPAR 2280 to the compound, mixing for 3 minutes; finally adding 4 parts of cross-linking agent peroxide Cumene (DCP) and 1.5 parts of N,N'-m-phenylene bismaleimide (HVA-2) were mixed for 2 minutes and then discharged.
  • DCP cross-linking agent peroxide Cumene
  • HVA-2 N,N'-m-phenylene bismaleimide
  • Calendering process The above mixing rubber is placed in a screw extruder for hot refining, and then supplied to a calender for calendering to be used, and the film thickness is controlled to be 4.5 to 12 mm when calendering. After being good, keep warm for use.
  • the film is closely attached to the preformed adhesive canvas strip to form a strip of the high temperature resistant conveyor belt, and then rolled up for 4 hours and then vulcanized.
  • Vulcanization process The above-mentioned formed conveyor belt blanks are placed in a flat vulcanizing machine for stage vulcanization, each of which has a vulcanization time of 25 minutes, a vulcanization pressure of 3 kg/cm 2 and a vulcanization temperature of 160 ° C.
  • Trimming and inspection After the vulcanization is finished, it is trimmed, inspected, and then packaged into the warehouse.
  • a high-temperature resistant conveyor belt using the rubber composition provided by the present invention as an adhesive layer comprising the following steps:
  • the high temperature resistant conveyor belt of the embodiment is provided with a rubberized canvas as a tensile layer between the working surface covering rubber and the non-working surface covering rubber, and they are made into a solid whole through molding and vulcanization processes.
  • composition and ratio of the adhesive layer rubber for the appliqué canvas according to the embodiment are in parts:
  • the rubber compound and the cloth layer are pasted at a normal temperature by a double roll or a four roll calender to complete the bonding of the adhesive glue and the canvas layer to obtain a rubberized canvas strip;
  • the formed adhesive canvas strip and the cover film are closely attached together on a molding machine to form a strip of a high temperature resistant conveyor belt, and then rolled up for 4 hours and then vulcanized.
  • the formed conveyor belt blanks were placed in a flat vulcanizing machine for stage vulcanization, each of which had a vulcanization time of 25 minutes, a vulcanization pressure of 3 kg/cm2, and a vulcanization temperature of 160 °C.
  • the vulcanization After the vulcanization is finished, it is trimmed, inspected, and then packaged into the warehouse.
  • An insulating glove produced by using the rubber composition provided by the present invention comprising the following steps:
  • Example 14 The rest of the production process is in accordance with Example 14.
  • the rubber composition of the present embodiment was molded into a test sample by molding, and the test performance was as follows:
  • Hardness 66; tensile strength: 25.9 MPa; elongation at break: 512%; tear strength 61 N/mm; 50 kV power frequency withstand voltage for 1 minute without breakdown without flashover.
  • a high temperature resistant conveyor belt using the rubber composition provided by the invention as a working surface covering glue, the composition and mixing process of the working surface covering glue is as follows:
  • a high temperature resistant conveyor belt using the rubber composition provided by the present invention as an adhesive layer rubber, and the composition and mixing process of the adhesive layer rubber for the adhesive canvas are as follows:
  • Rubber mixing set the temperature of the internal mixer to 100 ° C, the rotor speed to 50 rpm, add 100 parts of PER-10 and 15 parts of paraffin oil SUNPAR 2280 pre-pressed and kneaded for 90 seconds; then add 5 parts of zinc oxide, 1 part stearic acid, 2 parts of binder RS, 2 parts of polyethylene glycol PEG4000 and 1 part of antioxidant RD, kneaded for 2 minutes; then add 60 parts of carbon black N330, 20 parts of white carbon black, 10 parts of methyl Zinc acrylate and 15 parts paraffin oil SUNPAR2280, mixed for 3 minutes; then add 3 parts of binder RA-65, knead for 1 minute; then add 4 parts of cross-linking agent di-tert-butylperoxydiisopropylbenzene (BIPB 1 part of a co-crosslinking agent, triallyl isocyanurate (TAIC), and 0.3 parts of sulfur, which were mixed for 2 minutes and then discharged.
  • Vulcanization process the rubber material and the surface-treated and coated metal parts are laminated according to the process requirements, and then loaded into the preheated mold, and then vulcanized into a flat vulcanizing machine, and the vulcanization temperature is 160. °C, steam pressure 0.6MPa, time is 25 minutes.
  • the damper member of the embodiment can be used for a high temperature portion such as an engine and an exhaust pipe.

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  • 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, des produits mettant en application le composite de caoutchouc et un procédé de fabrication. Le composite de caoutchouc comprend : un substrat en caoutchouc et des composants essentiels. Le substrat en caoutchouc comprend : du polyéthylène ramifié, dont la teneur est a : 0 < a ≤ 100 parties, un caoutchouc monomère d'éthylène propylène et un caoutchouc monomère d'éthylène propylène diène, dont la teneur est b : 0 ≤ b < 100 parties. Les composants essentiels comprennent : 1 à 10 parties d'un agent de réticulation et 5 à 50 parties d'un carboxylate métallique insaturé. Les effets bénéfiques sont tels que le composite de caoutchouc est applicable dans des produits en caoutchouc tels que des gants isolants, une courroie transporteuse résistante à la chaleur, et un tube en caoutchouc, et les produits en caoutchouc présentent une grande performance mécanique.
PCT/CN2018/072351 2017-01-13 2018-01-12 Composite de caoutchouc, procédé de traitement, applications et procédé de fabrication de produits en caoutchouc à haute résistance WO2018130187A1 (fr)

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CN201810020849.3A CN108314852B (zh) 2017-01-13 2018-01-10 橡胶组合物及加工方法与应用，及生产高强度橡胶制品的方法

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CN109206820A (zh) * 2018-08-13 2019-01-15 中铁二院工程集团有限责任公司 一种耐老化三元乙丙橡胶密封材料及其制备方法
WO2020039536A1 (fr) * 2018-08-23 2020-02-27 Compagnie Generale Des Etablissements Michelin Composition de caoutchouc
CN114149648A (zh) * 2021-12-18 2022-03-08 陕西特种橡胶制品有限公司 一种核电厂密封用耐辐照氟橡胶材料及制备方法
CN114539680A (zh) * 2022-02-19 2022-05-27 陈溪水 一种耐高温橡胶制品的生产工艺
CN115322455A (zh) * 2022-09-02 2022-11-11 湖北工业大学 一种改性涤纶短纤维复合天然橡胶减振材料及其制备方法
CN118290925A (zh) * 2024-04-02 2024-07-05 成都海程防腐涂料有限公司 一种弹性地砖及其制备工艺
CN119978636A (zh) * 2025-01-21 2025-05-13 珠海科茂威新材料有限公司 一种bipb硫化三元乙丙橡胶及其制备方法

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CN101250305A (zh) * 2008-04-07 2008-08-27 北京化工大学 一种高耐热输送带覆盖层用橡胶复合材料
CN102337092A (zh) * 2011-07-22 2012-02-01 北京化工大学 一种耐高温帆布输送带用粘合层橡胶材料及其使用方法
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Publication number Priority date Publication date Assignee Title
CN109206820A (zh) * 2018-08-13 2019-01-15 中铁二院工程集团有限责任公司 一种耐老化三元乙丙橡胶密封材料及其制备方法
CN109206820B (zh) * 2018-08-13 2020-08-04 中铁二院工程集团有限责任公司 一种耐老化三元乙丙橡胶密封材料及其制备方法
WO2020039536A1 (fr) * 2018-08-23 2020-02-27 Compagnie Generale Des Etablissements Michelin Composition de caoutchouc
CN114149648A (zh) * 2021-12-18 2022-03-08 陕西特种橡胶制品有限公司 一种核电厂密封用耐辐照氟橡胶材料及制备方法
CN114149648B (zh) * 2021-12-18 2023-08-29 陕西特种橡胶制品有限公司 一种核电厂密封用耐辐照氟橡胶材料及制备方法
CN114539680A (zh) * 2022-02-19 2022-05-27 陈溪水 一种耐高温橡胶制品的生产工艺
CN115322455A (zh) * 2022-09-02 2022-11-11 湖北工业大学 一种改性涤纶短纤维复合天然橡胶减振材料及其制备方法
CN115322455B (zh) * 2022-09-02 2023-09-15 湖北工业大学 一种改性涤纶短纤维复合天然橡胶减振材料及其制备方法
CN118290925A (zh) * 2024-04-02 2024-07-05 成都海程防腐涂料有限公司 一种弹性地砖及其制备工艺
CN119978636A (zh) * 2025-01-21 2025-05-13 珠海科茂威新材料有限公司 一种bipb硫化三元乙丙橡胶及其制备方法

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