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WO2018130196A1 - Composite de caoutchouc, applications dans un produit mousseux, et procédé de fabrication - Google Patents

Composite de caoutchouc, applications dans un produit mousseux, et procédé de fabrication Download PDF

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Publication number
WO2018130196A1
WO2018130196A1 PCT/CN2018/072368 CN2018072368W WO2018130196A1 WO 2018130196 A1 WO2018130196 A1 WO 2018130196A1 CN 2018072368 W CN2018072368 W CN 2018072368W WO 2018130196 A1 WO2018130196 A1 WO 2018130196A1
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WIPO (PCT)
Prior art keywords
rubber
parts
vulcanization
foaming
crosslinking
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PCT/CN2018/072368
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English (en)
Chinese (zh)
Inventor
徐涛
傅智盛
吴安洋
Original Assignee
杭州星庐科技有限公司
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Publication date
Priority claimed from CN201810020851.0A external-priority patent/CN108299744B/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 JP2019559145A priority Critical patent/JP7166639B2/ja
Priority to US16/477,524 priority patent/US20200123362A1/en
Publication of WO2018130196A1 publication Critical patent/WO2018130196A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/16—Ethene-propene or ethene-propene-diene copolymers

Definitions

  • the invention belongs to the field of rubber, in particular to a rubber composition and a processing method thereof, and to the application of the rubber composition in a foamed product, and a method for producing a foamed rubber product using the rubber composition
  • Foamed rubber products include, but are not limited to, sponge seals, high expansion ratio foam materials, shock-absorbing foam rubber sheets, light-colored high-strength foam sheets, foamed solid composite seals, and solid tires filled with foamed elastomers. .
  • the vulcanization system of ethylene propylene rubber foaming material is mainly sulfur and peroxide vulcanization system.
  • a sulfur vulcanization system When a sulfur vulcanization system is used, the foamed material forms a crosslinked structure mainly composed of polysulfide bonds, which has high tensile strength and high tear strength, but has poor heat resistance and aging resistance;
  • the foamed material forms a single carbon-carbon crosslink bond, it has excellent heat resistance and aging resistance, small compression set (good stress relaxation stability), and elongation at break is comparable to that of the sulfur vulcanization system foaming material. Therefore, it is preferable to use a peroxide vulcanization system for preparing a high-performance foaming material having low heat resistance, ageing resistance and compression set, but this also has a problem that the tensile strength and the tear strength are lowered.
  • 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 key technology for the preparation of rubber foaming materials is to achieve the problem of rubber vulcanization and foaming agent decomposition rate matching.
  • the rubber compound is required to have a certain degree of pre-crosslinking before the foaming agent is thermally decomposed, and should reach 30% of the degree of complete vulcanization of the rubber. Therefore, the pre-vulcanization stage of the rubber is the most critical step, which determines whether a suitable cell structure and the density of the foamed material produced can be formed.
  • the conventional method is achieved by adding a super-speed accelerator to the rubber to achieve rapid pre-crosslinking of the rubber, but this method is difficult to achieve the matching of vulcanization and foaming;
  • Step molding process that is, the first molding at a lower temperature (l20 ⁇ 140 ° C), the time is 20 ⁇ 50min, so that the rubber has a certain degree of pre-crosslinking and begins to partially foam, and then the specification is larger than the original 20
  • the second heating is carried out in ⁇ 50% of the mold, so that the foaming agent is completely decomposed and vulcanized and shaped.
  • the present invention provides a rubber composition and a processing method thereof, and the present invention also provides a method for producing a foamed material by using the rubber composition, which has a branching degree of not less than 50 branches.
  • /1000 carbon branched polyethylene to replace some or all of the ethylene propylene rubber is expected to improve the technical defects of the existing rubber foaming materials difficult to have good heat resistance, aging resistance and mechanical properties, and due to branching
  • the presence of polyethylene requires the use of a peroxide-based cross-linking system.
  • the present invention also provides a vulcanization process that combines a low-temperature radiation pre-vulcanization process with a high-temperature peroxide vulcanization foaming process to overcome the peroxide.
  • the vulcanization system is difficult to pre-vulcanize at low temperatures.
  • 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: 0.5 to 10 parts of a crosslinking agent, and 1.5 to 25 parts of a foaming agent, based on 100 parts by weight of the rubber base.
  • the branching degree of the branched polyethylene is not less than 50 branches/1000 carbons, the weight average molecular weight is not less than 50,000, and the Mooney viscosity ML (1+4) is not lower than 2 at 125 °C.
  • Branched polyethylene in the prior art means, in addition to a branched ethylene homopolymer, a branched saturated vinyl copolymer, such as an ethylene- ⁇ -olefin copolymer, which may be POE, although POE performs well in physical and mechanical properties and aging resistance, but cross-linking performance is not good, although the branched polyethylene of the present invention can contain both branched ethylene homopolymer and POE, but a better choice It is a branched polyethylene having a high proportion of branched polyethylene or a branched ethylene homopolymer. In a preferred embodiment of the invention, the branched polyethylene contains only branched ethylene homopolymer.
  • the branched polyethylene used is a branched ethylene homopolymer unless otherwise specified.
  • the branched polyethylene used in the present invention is a kind of ethylene homopolymer having a branching degree of not less than 50 branches/1000 carbons, and can be called Branched Polyethylene or Branched PE.
  • the synthesis method is mainly composed of a late transition metal catalyst.
  • the homopolymerization of ethylene is catalyzed by a "chain walking mechanism", and the preferred late transition metal catalyst may be one of ( ⁇ -diimine) nickel/palladium catalysts.
  • the nature of the chain walking mechanism refers to the late transition metal catalyst.
  • the ( ⁇ -diimine) nickel/palladium catalyst is more likely to undergo ⁇ -hydrogen elimination reaction and re-insertion reaction in the process of catalyzing olefin polymerization, thereby causing branching.
  • Branched chains of such branched polyethylenes may have different numbers of carbon atoms, specifically 1 to 6, or more carbon atoms.
  • the production cost of the ( ⁇ -diimine) nickel catalyst is significantly lower than that of the ( ⁇ -diimine) palladium catalyst, and the ( ⁇ -diimine) nickel catalyst catalyzes the high rate of ethylene polymerization and high activity, and is more suitable for industrial applications. Therefore, the branched polyethylene prepared by the ethylene polymerization of the ( ⁇ -diimine) nickel catalyst is preferred in the present invention.
  • the degree of branching of the branched polyethylene used in the present invention is preferably 50 to 130 branches/1000 carbons, further preferably 60 to 130 branches/1000 carbons, further preferably 60 to 116 branches/1000.
  • a carbon, the degree of branching between POE and ethylene-propylene rubber, is a new technical solution that is different from the prior art, and can have excellent aging resistance and good cross-linking performance.
  • 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 in the main chain during peroxide crosslinking or radiation crosslinking.
  • Produced on carbon can also be produced on the branched tertiary carbon of the secondary structure, so the rubber network formed by the cross-linking or radiation cross-linking of the branched polyethylene is compared with the ethylene-propylene rubber, and the main chain has The richer CC cross-linking length can effectively avoid stress concentration and help to obtain better mechanical properties, including tear strength.
  • the technical solution of the present invention can provide a foamed article which has both good heat resistance, mechanical strength and compression set resistance.
  • the content of the branched polyethylene is: 10 ⁇ a ⁇ 100 parts based on 100 parts by weight of the rubber matrix; the content of the binary ethylene propylene rubber and the 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 of ML (1+4) 125 ° C. It is 9 to 102.
  • the content of the branched polyethylene is a: 10 ⁇ a ⁇ 100 parts based on 100 parts by weight of the rubber matrix; 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 9 to 102.
  • the content of the branched polyethylene is: 10 ⁇ a ⁇ 100 parts based on 100 parts by weight of the rubber matrix; the content of the binary ethylene propylene rubber and the ethylene propylene diene rubber is b: 0 ⁇ b ⁇ 90 parts
  • the branched polyethylene is an ethylene homopolymer having a degree of branching of 80 to 105 branches/1000 carbons, a weight average molecular weight of 250,000 to 400,000, and a Mooney viscosity of ML (1+4) of 125 ° C. It is 40 to 95.
  • the content of the branched polyethylene is: 10 ⁇ a ⁇ 100 parts based on 100 parts by weight of the rubber matrix; the content of the binary ethylene propylene rubber and the ethylene propylene diene rubber is b: 0 ⁇ b ⁇ 90 parts
  • the branched polyethylene is an ethylene homopolymer having a degree of branching of 80 to 105 branches/1000 carbons, a weight average molecular weight of 268,000 to 356,000, and a Mooney viscosity of ML (1+4) of 125 ° C. It is 42 to 80.
  • the third monomer of the ethylene propylene diene monomer is preferably a diene monomer, specifically selected from the group consisting of 5-ethylidene-2-norbornene and 5-vinyl-2-nor Borneene, dicyclopentadiene, 1,4-hexadiene, 1,5-hexadiene, 1,4-pentadiene, 2-methyl-1,4-pentadiene, 3-methyl- 1,4-Hexadiene, 4-methyl-1,4-hexadiene, 1,9-decadiene, 5-methylene-2-norbornene, 5-pentylene-2-nor Borbornene, 1,5-cyclooctadiene, 1,4-cyclooctadiene, and the like.
  • a diene monomer specifically selected from the group consisting of 5-ethylidene-2-norbornene and 5-vinyl-2-nor Borneene, dicyclopentadiene, 1,4-hexadiene
  • the ethylene propylene rubber may contain two or more kinds of diene monomers at the same time, such as 5-ethylidene-2-norbornene and 5-vinyl-2-norbornene.
  • the functional group of the diene monomer can play the same role as the intrinsic co-crosslinking agent in the peroxide vulcanization, thereby improving the crosslinking efficiency. This helps to reduce the amount and residual amount of crosslinker and co-crosslinker required and the cost of adding them.
  • the weight specific gravity of the diene monomer to the ethylene propylene rubber is preferably from 1% to 14%, more preferably from 3% to 10%, still more preferably from 4% to 7%.
  • the 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.
  • crosslinking agent is preferably used in an amount of from 0.5 to 6 parts by weight based on 100 parts by weight of the rubber base.
  • the foaming agent comprises sodium hydrogencarbonate, azodicarbonamide (AC), dinitrosopentylenetetramine (H), diphenylsulfonyl oxime ether (OBSH), benzenesulfonate. At least one of hydrazide (BSH), urea, and a low-boiling hydrocarbon microcapsule-type foaming agent.
  • the rubber composition comprises an auxiliary component, which comprises: 0.2 to 10 parts of a co-crosslinking agent, 30 to 200 parts of a reinforcing filler, and a plasticizer, based on 100 parts by weight of the rubber matrix. 10 to 100 parts, stabilizer 1 to 3 parts, metal oxide 2 to 20 parts, silane coupling agent 3 to 7 parts, polyethylene glycol 1 to 5 parts, stearic acid 0.5 to 3 parts, vulcanization accelerator 0 ⁇ 3 servings.
  • an auxiliary component which comprises: 0.2 to 10 parts of a co-crosslinking agent, 30 to 200 parts of a reinforcing filler, and a plasticizer, based on 100 parts by weight of the rubber matrix. 10 to 100 parts, stabilizer 1 to 3 parts, metal oxide 2 to 20 parts, silane coupling agent 3 to 7 parts, polyethylene glycol 1 to 5 parts, stearic acid 0.5 to 3 parts, vulcanization accelerator 0 ⁇ 3 servings.
  • the silane coupling agent comprises vinyl tris(2-methoxyethoxy)silane (A-172), ⁇ -glycidoxypropyltrimethoxysilane (A-187) At least one of ⁇ -mercaptopropyltrimethoxysilane (A-189).
  • the stabilizer comprises 2,2,4-trimethyl-1,2-dihydroquinoline polymer (RD), 6-ethoxy-2,2,4-trimethyl At least one of -1,2-dihydroquinoline (AW) and 2-mercaptobenzimidazole (MB).
  • RD 2,2,4-trimethyl-1,2-dihydroquinoline polymer
  • AW 6-ethoxy-2,2,4-trimethyl
  • MB 2-mercaptobenzimidazole
  • the co-crosslinking agent comprises triallyl cyanurate, triallyl isocyanurate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, Triallyl trimellitate, trimethylolpropane trimethacrylate, N,N'-m-phenylene bismaleimide, N,N'-bis-indenylacetone, 1,2- At least one of polybutadiene, a metal salt of an unsaturated carboxylic acid, and sulfur.
  • the unsaturated carboxylic acid metal salt contains at least one of zinc acrylate, zinc methacrylate, and magnesium methacrylate.
  • the plasticizer comprises at least one of pine tar, engine oil, naphthenic oil, paraffin oil, coumarone, RX-80, petrolatum, and paraffin wax.
  • the rational use of plasticizers can increase the flexibility of the compound and the plasticity suitable for process operation.
  • an adhesion promoter such as pine tar, coumarone, RX-80, liquid polyisobutylene or the like.
  • the metal oxide comprises at least one of zinc oxide, magnesium oxide, and calcium oxide.
  • the reinforcing filler comprises at least one of carbon black, white carbon black, calcium carbonate, talc, calcined clay, magnesium silicate, and magnesium carbonate.
  • 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.
  • 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 the above rubber composition, the processing method comprising the steps of:
  • Vulcanization The rubber compound is filled into the cavity of the mold, vulcanized on the flat vulcanizing machine, and then demolded to obtain a vulcanized rubber. 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 sponge sealing strip comprising the above rubber composition.
  • the invention also provides a method for producing a sponge sealing strip, the production method comprising the following steps:
  • Rubber kneading First, the rubber composition components other than the crosslinking system and the foaming agent are sequentially added to the internal mixer for mixing, and then the crosslinking system and the foaming system are kneaded. After uniform discharge, the mixture is obtained. After the mixture is thinned on the open mill, the sheet is left to be vulcanized, and the crosslinking system comprises a crosslinking agent, and may further comprise at least one of a co-linking agent and a vulcanization accelerator;
  • the present invention also provides a high expansion ratio foam material comprising the above rubber composition.
  • the present invention also provides a shock absorbing foam rubber sheet comprising the above rubber composition.
  • Rubber kneading First, the rubber composition components other than the crosslinking system and the foaming agent are sequentially added to the internal mixer for mixing, and then the crosslinking system and the foaming system are kneaded. After being uniformly discharged, a rubber mixture is obtained, and the rubber mixture is thinned on the open mill, and then left to be left to be vulcanized.
  • the crosslinking system contains a crosslinking agent, and may also include a crosslinking agent and a vulcanization accelerator. At least one
  • Rubber kneading First, the rubber composition components other than the crosslinking system and the foaming agent are sequentially added to the internal mixer according to the parts by weight for kneading, and then the rubber is discharged, and the mixture is placed on the open mill after being parked. Coupling system and foaming agent, complete the mixing; after parking, re-smelting on the open mill or extrusion molding machine, forming and waiting for use, the crosslinking system contains a crosslinking agent and has a radiation sensitizing function. The co-crosslinking agent may also contain a vulcanization accelerator.
  • High-temperature foaming vulcanization The radiation-pre-vulcanized sheet is placed in a mold, vulcanized and foamed under high temperature and high pressure, and then released from mold release to obtain a rubber foamed material.
  • the electron accelerator beam energy used in the radiation pre-vulcanization is 2-10 MeV, and the emitted ray particles can completely penetrate the green film material, and the electron beam scanning width is 0.2-1.6 m, and the raw film material is sputtered.
  • the radiation atmosphere is oxygen-limited environment, using inert gas protection, the time required for radiation pre-vulcanization, the average time per sheet is less than 5 minutes, wherein the conditions of foaming and vulcanization are 160-180 ° C, 6 ⁇ 15MPa, 10 ⁇ 20min.
  • the present invention also provides a light-colored high-strength foamed sheet comprising the above rubber composition.
  • the invention also provides a method for producing a light-colored high-strength foamed sheet, the production method comprising the following steps:
  • Rubber kneading First, the rubber composition components other than the crosslinking system and the foaming agent are sequentially added to the internal mixer for mixing, and then the crosslinking system and the foaming system are kneaded. After uniform discharge, the mixture is obtained. The rubber compound is thinned on the open mill and then discharged to be vulcanized.
  • the cross-linking system contains a crosslinking agent and a co-crosslinking agent having a radiation sensitizing function, and may further contain a vulcanization accelerator.
  • High-temperature foaming vulcanization The radiation-pre-vulcanized sheet is placed in a mold, vulcanized and foamed under high temperature and high pressure, then demolded and cooled, and trimmed to obtain a light-colored high-strength foamed sheet.
  • the present invention also provides a method of producing a foamed solid composite weather strip comprising the following steps:
  • the present invention also provides a solid tire having an inner layer which is a foamed elastomer, and the compound for filling the foamed elastomer therein comprises the above rubber composition, preferably a rubber composition comprising a reinforcing filler.
  • the force tire can be a bicycle tire, a trolley tire, an animal tire, an electric tire, and has the advantage of resisting the tie.
  • the invention also provides a method for producing a solid tire tire whose inner layer is a foamed elastic body, which comprises the following steps: firstly kneading the inner layer rubber in an internal mixer, after discharging the rubber, opening the lower sheet, dip the separating liquid, Cooling and parking; then extruding the rubber through the extruder to obtain a strip of suitable cross-section size, and then cutting the splicing to obtain a squeegee semi-finished product; then installing the squeegee semi-finished product on the mold and putting on the finished tire And the steel tube is evenly pierced at the top of the tire, and then placed in a vulcanization oven for vulcanization, foaming, and vulcanization to obtain a finished product.
  • the energy of the electron beam is preferably 0.1 to 10 MeV, and more preferably 0.3 to 5 MeV, and irradiation is performed so that the absorbed dose is preferably 5 to 350 kGy, and more preferably 5 to 100kGy.
  • the invention has the beneficial effects that the ethylene-propylene rubber in the foamed rubber composition is partially or completely replaced by the branched polyethylene, and the peroxide curing system or the peroxide and the sulfur are used together.
  • the vulcanization system because the branched polyethylene has more branches in the molecular structure, and the length of the branch has a certain length and length distribution and a certain number of secondary branched structures, in the process of peroxide crosslinking or radiation crosslinking In the middle, the crosslinking point of the branched polyethylene may be generated on the tertiary carbon of the main chain or on the branched tertiary carbon of the secondary structure, so the branched polyethylene is formed by peroxide crosslinking or radiation crosslinking.
  • the rubber network Compared with ethylene-propylene rubber, the rubber network has a richer CC cross-linking length between the main chains, similar to the polysulfide bond in the sulfur vulcanization system, but the bond energy is higher, which can effectively avoid stress concentration. With good cross-linking efficiency, overall mechanical properties are expected to be obtained. Moreover, branched polyethylene has more long-chain branches, and has higher melt strength, which is more favorable for foaming, especially pre-expansion. And since the molecular weight distribution of the branched polyethylene is narrow, generally lower than 2.5, the rubber composition of the present invention has a lower compression set after vulcanization.
  • a peroxide-based crosslinking system is more required, and the peroxide crosslinking system cannot achieve pre-crosslinking at a low temperature, and the radiation pretreatment process of the present invention does not need to be performed.
  • the crosslinking of some rubber macromolecules can be quickly achieved by heating, so that the foaming agent does not decompose, and the degree of pre-vulcanization of the rubber can be accurately controlled by controlling the radiation dose.
  • the rubber sheet treated with a certain radiation dose has a certain pre-crosslinking strength before the foaming agent is thermally decomposed, and the modulus of the rubber compound is increased, which can resist the pressure of the gas generated when the foaming agent is decomposed without cracking.
  • the crosslinking system contains a crosslinking agent, and may further contain at least one of a co-crosslinking agent and a vulcanization accelerator.
  • the present invention relates to a rubber composition
  • a rubber composition comprising: a rubber matrix and a necessary component, the rubber matrix comprising: a branched polyethylene having a content of a: 0 ⁇ a ⁇ 100 parts, a degree of branching of 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 sum of binary ethylene propylene rubber and EPDM rubber b : 0 ⁇ b ⁇ 100 parts, Mooney viscosity ML (1 + 4) 125 ° C is preferably 50-90, ethylene content is preferably 40% - 70%; based on 100 parts by weight of the rubber matrix, the necessary components include: cross-linking The agent is 0.5 to 10 parts, and the foaming agent is 1.5 to 25 parts.
  • the silane coupling agent comprises vinyl tris(2-methoxyethoxy)silane (A-172), ⁇ -glycidoxypropyltrimethoxysilane (A-187), ⁇ -mercaptopropyl At least one of the group of trimethoxysilanes (A-189).
  • the co-crosslinking agent comprises triallyl cyanurate, triallyl isocyanurate, ethylene glycol dimethacrylate, ethyl dimethacrylate, triethylene glycol dimethacrylate, partial Triallyl trimellitate, trimethylolpropane trimethacrylate, ethylene glycol dimethacrylate, N,N'-m-phenylene bismaleimide, N,N'-double At least one of mercaptoacetone, 1,2-polybutadiene, zinc acrylate, zinc methacrylate, magnesium methacrylate, calcium methacrylate, aluminum methacrylate, and sulfur.
  • the crosslinking agent includes at least one of a peroxide crosslinking agent and a sulfur crosslinking agent, and the peroxide crosslinking agent is di-tert-butyl peroxide, dicumyl peroxide, and tert-butyl cumyl peroxide.
  • the Mooney viscosity ML (1+4) of the ethylene propylene rubber used is preferably 30 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 55% to 75%, and the third monomer is 5-ethylene-2. - norbornene, 5-vinyl-2-norbornene or dicyclopentadiene, the third monomer content being from 1% to 7%.
  • the branched polyethylene used can be obtained by catalyzing the homopolymerization of ethylene by a ( ⁇ -diimine) nickel catalyst under the action of a cocatalyst.
  • the structure, synthesis method and method for preparing branched polyethylene by using the ( ⁇ -diimine) nickel catalyst are disclosed in the prior art, and can be used but are not limited to the following documents: CN102827312A, CN101812145A, CN101531725A, CN104926962A, US6103658, US6660677.
  • Density measured according to national standard GB/T533-1991;
  • 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;
  • the processing steps of the rubber composition are as follows:
  • Rubber mixing set the temperature of the internal mixer to 90 ° C, the rotor speed to 50 rpm, add 90 parts of EPDM rubber and 10 parts of branched polyethylene pre-pressed for 90 seconds; add 10 parts of oxidation Zinc and 2 parts of stearic acid, kneaded for 1 minute; then add 5 parts of calcium oxide and 2 parts of polyethylene glycol PEG4000, and knead for 1 minute; then add 50 parts of carbon black N550 in two batches of medium size.
  • the branched polyethylene used was numbered PER-2.
  • Rubber mixing set the temperature of the internal mixer to 90 ° C, the rotor speed is 50 rpm, add 20 parts of ethylene propylene diene rubber, 50 parts of ethylene propylene diene monomer and 30 parts of branched polyethylene pre-pressure mixing.
  • TAIC Linked triallyl isocyanurate
  • AC blowing agent azodicarbonamide
  • Urea foaming agent Urea
  • the branched polyethylene used was numbered PER-5.
  • the branched polyethylene used was numbered PER-5.
  • the branched polyethylene used was numbered PER-5.
  • Oil SUNPAR2280 was mixed for 4 minutes; finally, 4 parts of cross-linking agent dicumyl peroxide (DCP), 1 part of cross-linking agent triallyl isocyanurate (TAIC), 0.3 parts of cross-linking agent sulfur were added. 2 parts of foaming agent azodicarbonamide (AC) and 2 parts of foaming agent diphenylsulfonyl oxime ether (OBSH), after 3 minutes of mixing, the rubber is discharged, and the mixing rubber is opened at a roll temperature of 80 ° C. Thin on the refiner, then increase the roll distance to obtain a sheet of thickness of about 2.2 ⁇ 2.5mm, and park for 20 hours.
  • DCP cross-linking agent dicumyl peroxide
  • TAIC cross-linking agent triallyl isocyanurate
  • sulfur 0.3 parts of cross-linking agent sulfur were added.
  • Rubber mixing set the temperature of the internal mixer to 90 ° C, the rotor speed is 50 rpm, add 20 parts of ethylene propylene rubber, 60 parts of ethylene propylene diene rubber and 20 parts of prepolymerized polyethylene. 90 seconds; then add 0.5 part of cross-linking agent dicumyl peroxide (DCP), 6 parts of foaming agent azodicarbonamide (AC), mix for 3 minutes, then drain the glue, the mixture is at the roll temperature It is thin on the 80 °C open mill, and then the roll is adjusted to obtain a sheet thickness of about 2.2 to 2.5 mm and parked for 20 hours.
  • DCP cross-linking agent dicumyl peroxide
  • AC foaming agent azodicarbonamide
  • 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-6.
  • the processing steps of the rubber composition are as follows:
  • the processing steps of the rubber composition are as follows:
  • Rubber mixing set the temperature of the internal mixer to 70 ° C, the rotor speed to 50 rpm, add 100 parts of branched polyethylene pre-pressure mixing for 90 seconds; then add 10 parts of 30# engine oil and 4 parts of vinyl Tris(2-methoxyethoxy)silane (A-172), kneaded for 1 minute; then add 50 parts of precipitated white carbon black N255, 3 parts of polyethylene glycol, 10 parts of zinc oxide for 2 minutes. Finally, 2 parts of cross-linking agent dicumyl peroxide (DCP) and 6 parts of foaming agent azodicarbonamide (AC) were added, and after 3 minutes of mixing, the rubber was discharged, and the mixture was heated at a roll temperature of 60 ° C. On the open mill, the thin pass, the roll distance is set to 0.4mm, thin through 10 times, then increase the roll distance to obtain a sheet of thickness of about 2.2 ⁇ 2.5mm, and park for 20 hours.
  • DCP cross-linking agent dicumyl peroxide
  • AC
  • Rubber mixing set the temperature of the internal mixer to 90 ° C, the rotor speed is 50 rpm, add 100 parts of EPDM rubber and pre-press and knead for 90 seconds; then add 0.5 part of cross-linking agent.
  • Propylene (DCP) 6 parts of foaming agent azodicarbonamide (AC), after 3 minutes of mixing, the rubber is discharged, and the mixture is thinned on an open mill with a roll temperature of 80 ° C, and then the roll is adjusted. A sheet of a thickness of about 2.2 to 2.5 mm was obtained and left for 20 hours.
  • the performance test data is as follows:
  • shock-absorbing foam rubber sheet whose production process is as follows:
  • Rubber mixing set the temperature of the internal mixer to 90 ° C, the rotor speed to 50 rpm, add 100 parts of branched polyethylene pre-pressed and kneaded for 90 seconds; add 5 parts of zinc oxide, 2 parts of stearic acid and 2 parts of antioxidant RD, mixing for 2 minutes; then add 50 parts of carbon black N550, 20 parts of carbon black N330 and 55 parts of paraffin oil SUNPAR2280, mixing for 4 minutes; finally adding 2 parts of cross-linking agent dicumyl peroxide (DCP), 0.3 parts of cross-linking agent sulfur, 0.5 part of N-cyclohexyl-2-benzothiazolyl sulfenamide, 0.3 part of tetramethylthiuram disulfide and 2 parts of blowing agent diphenylsulfonyl hydrazide Ether (OBSH), after 3 minutes of mixing, the glue is discharged;
  • DCP cross-linking agent dicumyl peroxide
  • OBSH blowing agent dipheny
  • High-temperature molding vulcanization foaming The raw film after radiation pretreatment is vulcanized in a vulcanization molding machine at 175 ° C and 10 MPa for 15 min, and the mold is discharged, and after natural cooling, trimming is performed to obtain a light-colored high-strength foam. Plate.
  • a foamed solid composite sealing strip whose production process is as follows:
  • a light-colored high-strength foamed sheet comprising the following steps:

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

Abstract

La présente invention concerne un composite de caoutchouc, son procédé de transformation, des applications et un procédé d'utilisation du composite dans la fabrication d'un matériau mousseux. Le composite de caoutchouc comprend : un substrat de caoutchouc et des constituants essentiels. Le substrat de caoutchouc comprend : du polyéthylène ramifié, sa teneur étant a : 0 < a ≤ 100 parties ; un caoutchouc monomère d'éthylène propylène et un caoutchouc monomère d'éthylène propylène diène, sa teneur étant b : 0 ≤ b < 100 parties. Les constituants essentiels comprennent : de 0,5 à 10 parties d'un agent de réticulation et de 1,5 à 25 parties d'un agent de moussage. Les applications sont une bande d'étanchéité en éponge traitée, un matériau de moussage à rapport élevé de moussage, un matériau de plaque de caoutchouc en mousse absorbant les chocs, un matériau en plaque mousseuse de haute résistance de couleur claire, une bande d'étanchéité composite solide mousseuse, et un pneumatique solide rempli d'un élastomère mousseux. Les effets bénéfiques sont tels que, en plus des courtes chaînes ramifiées telles que le méthyle, éthyle, propyle, butyle, et pentyle, le polyéthylène ramifié est également muni de longues chaînes de ramification de 6 atomes de carbone ou plus, en utilisant le polyéthylène ramifié pour remplacer partiellement ou entièrement le caoutchouc d'éthylène propylène dans un composite de caoutchouc mousseux, la résistance à la fusion du composite de caoutchouc étant accrue, la capacité de moussage du composite, particulièrement le pré-moussage, et les produits de caoutchouc ainsi fabriqués présentant une déformation permanente sous compression réduite.
PCT/CN2018/072368 2017-01-13 2018-01-12 Composite de caoutchouc, applications dans un produit mousseux, et procédé de fabrication WO2018130196A1 (fr)

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CN113308118A (zh) * 2021-04-08 2021-08-27 苏州歌诗夫新材料有限公司 一种环保型发泡阻燃硅橡胶材料及其制备方法
CN113388209A (zh) * 2021-06-21 2021-09-14 海程新材料(芜湖)有限公司 一种可低温发泡的高膨胀率自粘性膨胀胶块及其制备方法
CN113549279A (zh) * 2021-07-29 2021-10-26 三联泵业股份有限公司 一种耐磨防腐内衬材料及具有其的耐磨防腐泵
JP2022504913A (ja) * 2018-10-08 2022-01-13 チョン イ、ソ 高弾性押出発泡体用組成物
CN114106451A (zh) * 2021-12-27 2022-03-01 上海新上化高分子材料有限公司 一种乙烯-乙烯醋酸共聚物eva冰箱门封条颗粒及其制备方法
CN114235607A (zh) * 2021-11-12 2022-03-25 中策橡胶集团股份有限公司 一种胎体帘布混炼胶预交联的评价方法、设备和计算机可读载体介质
CN114685885A (zh) * 2022-05-06 2022-07-01 北京中景橙石科技股份有限公司 一种弹性胀缝板及其制备方法
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JP2022504913A (ja) * 2018-10-08 2022-01-13 チョン イ、ソ 高弾性押出発泡体用組成物
CN110836080A (zh) * 2019-11-07 2020-02-25 江苏恩菡新材料科技有限公司 一种高温三元乙丙特种胶条
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