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WO2018130191A1 - Composite de caoutchouc à photoréticulation, applications et procédé de fabrication pour les applications - Google Patents

Composite de caoutchouc à photoréticulation, applications et procédé de fabrication pour les applications Download PDF

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Publication number
WO2018130191A1
WO2018130191A1 PCT/CN2018/072360 CN2018072360W WO2018130191A1 WO 2018130191 A1 WO2018130191 A1 WO 2018130191A1 CN 2018072360 W CN2018072360 W CN 2018072360W WO 2018130191 A1 WO2018130191 A1 WO 2018130191A1
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Prior art keywords
rubber
parts
rubber composition
composition according
add
Prior art date
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PCT/CN2018/072360
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English (en)
Chinese (zh)
Inventor
徐涛
傅智盛
吴安洋
Original Assignee
杭州星庐科技有限公司
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Priority claimed from CN201810020837.0A external-priority patent/CN108299742B/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 JP2019559142A priority Critical patent/JP7156709B2/ja
Priority to US16/477,691 priority patent/US11499041B2/en
Publication of WO2018130191A1 publication Critical patent/WO2018130191A1/fr

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Classifications

    • A—HUMAN NECESSITIES
    • A41—WEARING APPAREL
    • A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
    • A41D19/00—Gloves
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F6/00—Contraceptive devices; Pessaries; Applicators therefor
    • A61F6/02—Contraceptive devices; Pessaries; Applicators therefor for use by males
    • A61F6/04—Condoms, sheaths or the like, e.g. combined with devices protecting against contagion
    • 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
    • C08L23/08—Copolymers of ethene
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/28—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances natural or synthetic rubbers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins

Definitions

  • the invention belongs to the field of rubber, and in particular relates to a rubber composition using photocrosslinking and a processing method thereof, and to the application of the rubber composition and a method for producing the same.
  • Ethylene-propylene rubber has excellent elasticity, electrical insulation properties, aging resistance and ozone resistance.
  • the crosslinking methods used mainly include peroxide vulcanization and high energy radiation.
  • the high-energy radiation method limits its application due to factors such as high equipment investment and harsh protective measures.
  • the peroxide vulcanization method has high energy consumption and low production efficiency due to the need for crosslinking for a long period of time.
  • UV cross-linking is a new cross-linking process developed in recent years. It has the advantages of simple process, low investment, easy operation, less stringent safety protection requirements, convenient maintenance, high energy utilization rate, no pollution to the environment, etc. Both CN101434728 and CN101486819 can see that the ultraviolet light crosslinking is easily affected by the filler to obtain inferior processing properties and mechanical properties, which affects the use properties and application range of the material.
  • 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, and the photocrossing described in the technical background of the present invention
  • Lian is also a kind of irradiation cross-linking, mainly by taking a tertiary hydrocarbon atom to form a tertiary carbon radical, and then forming a carbon-carbon cross-linking by radical bonding, but a copolymer of ethylene and 1-octene (hereinafter referred to as POE) has fewer tertiary carbon atoms and a longer branch with a tertiary carbon atom.
  • POE copolymer of ethylene and 1-octene
  • the present invention provides a photocrosslinked rubber composition, which adopts no branching degree. Partial or complete replacement of ethylene-propylene rubber with less than 50 branched/1000 carbon branched polyethylenes also provides for the application of such rubber compositions, and methods of producing the same.
  • a rubber composition comprising a rubber matrix and an initiator, the rubber matrix comprising: a content of branched polyethylene a: 0 ⁇ a ⁇ 100 parts, ethylene propylene
  • the content of the rubber b 0 ⁇ b ⁇ 100 parts; comprising 0.1 to 10 parts of the initiator based on 100 parts by weight of the rubber base, the initiator comprising at least one of a cationic photoinitiator and a radical photoinitiator
  • 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.
  • 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 may be generated on the tertiary carbon of the main chain during the photocrosslinking process, or It is 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 length between the main chains than the ethylene-propylene rubber, which can be effective. Avoid stress concentration and help to obtain better mechanical properties.
  • a further technical solution is that the content of the initiator is 0.5 to 5 parts.
  • the cationic photoinitiator comprises an aromatic diazonium salt, a diaryliodonium salt, a triarylsulfonium salt, an alkylsulfonium salt, a ferrocenium salt, a sulfonyloxyketone and a triaryl group.
  • At least one of the siloxanes preferably a triaryl sulfonium hexafluorophosphate, an aryl hexafluorophosphate, a triphenyl hexafluoroantimonate sulphate, a dodecyl benzene hexafluoro arsenate At least one of iodonium salts.
  • the radical photoinitiator comprises at least one of an intramolecular cleavage type and an intermolecular hydrogen abstraction type photoinitiator, preferably benzophenone, diphenylacetone, dialkoxy At least one of acetophenone, benzoin dimethyl ether, ⁇ -hydroxyisobutyrylbenzene, acylphosphine oxide, benzoin isopropyl ether, benzoin n-butyl ester, anthracene, anthrone.
  • an intramolecular cleavage type and an intermolecular hydrogen abstraction type photoinitiator preferably benzophenone, diphenylacetone, dialkoxy At least one of acetophenone, benzoin dimethyl ether, ⁇ -hydroxyisobutyrylbenzene, acylphosphine oxide, benzoin isopropyl ether, benzoin n-butyl ester, anthracene, anthrone.
  • the rubber composition further comprises an auxiliary component comprising: 0.1 to 5 parts of a crosslinking agent, 0.01 to 2 parts of an antioxidant, and a plasticizer 3 to 25 parts by weight of 100 parts by weight.
  • the fraction is 0 to 10 parts of the metal oxide, 0 to 200 parts of the inorganic filler, and 0.3 to 5 parts of the coupling agent.
  • the crosslinking agent comprises triallyl cyanurate (TAC), triallyl isocyanurate (TAIC), trimethylolpropane triacrylate (TMPTA), three At least one of trimethylolpropane methacrylate (TMPTMA), pentaerythritol triallyl ether, pentaerythritol ester tetraallyl ether.
  • TAC triallyl cyanurate
  • TAIC triallyl isocyanurate
  • TMPTA trimethylolpropane triacrylate
  • TMPTMA trimethylolpropane methacrylate
  • pentaerythritol triallyl ether pentaerythritol ester tetraallyl ether.
  • a further technical solution is that the content of the crosslinking agent is 0.5 to 3 parts based on 100 parts by weight of the rubber matrix.
  • the plasticizer comprises at least one of polyethylene wax, pine tar, motor oil, aromatic oil, naphthenic oil, paraffin oil, microcrystalline wax, and coumarone resin.
  • the metal oxide is at least one of zinc oxide, magnesium oxide, calcium oxide, lead monoxide, and lead tetraoxide.
  • the inorganic filler includes at least one of white carbon black, calcium carbonate, talc, calcined clay, magnesium silicate, magnesium carbonate, aluminum hydroxide, and magnesium hydroxide.
  • the coupling agent comprises vinyl tris(2-methoxyethoxy)silane (A-172), ⁇ -glycidoxypropyltrimethoxysilane (A-187), At least one of ⁇ -mercaptopropyltrimethoxysilane (A-189) and ⁇ -methacryloxypropyltrimethoxysilane (KH570).
  • the antioxidant comprises 2,6-di-tert-butylphenol, 2,4,6-tri-tert-butylphenol, 4,4'-thiobis(6-tert-butyl-3) -methylphenol), triphenyl phosphite, tris(2,4-di-tert-butylphenyl) phosphite (antioxidant 168), triisooctyl phosphite, triphenylmethyl phosphate, tetra [ 3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propanoic acid] pentaerythritol ester (antioxidant 1010), dilauryl thiodipropionate (DLTP), thiodipropionic acid At least one of lauryl octaester or di(tris) thiodipropionate.
  • the content of the branched polyethylene in the 100 parts by weight of the rubber matrix is a: 10 ⁇ a ⁇ 100 parts; the sum of the contents of the binary ethylene propylene rubber and the EPDM rubber b: 0 ⁇ b ⁇ 90 parts; the branched polyethylene is characterized by: an ethylene homopolymer having a degree of branching of 60 to 130 branches/1000 carbons, a weight average molecular weight of 66,000 to 518,000, and a Mooney viscosity ML (1) +4) 125 ° C is 6 to 102.
  • the content of the branched polyethylene in the 100 parts by weight of the rubber matrix is a: 10 ⁇ a ⁇ 100 parts; the content of the binary ethylene propylene rubber and the EPDM rubber is b: 0 ⁇ b ⁇ 90 parts
  • the branched polyethylene is an ethylene homopolymer having a degree of branching of 70 to 116 branches/1000 carbons, a weight average molecular weight of 201,000 to 436,000, and a Mooney viscosity of ML (1+4) of 125 ° C. 23 to 101;
  • the content of the branched polyethylene in the 100 parts by weight of the rubber matrix is a: 10 ⁇ a ⁇ 100 parts; the content of the binary ethylene propylene rubber and the EPDM rubber is b: 0 ⁇ b ⁇ 90 parts
  • the branched polyethylene is an ethylene homopolymer having a degree of branching of 80 to 105 branches/1000 carbons, a weight average molecular weight of 250,000 to 400,000, and a Mooney viscosity of ML (1+4) of 125 ° C. It is 40 to 95.
  • the content of the branched polyethylene in the 100 parts by weight of the rubber matrix is a: 10 ⁇ a ⁇ 100 parts; the content of the binary ethylene propylene rubber and the EPDM rubber is b: 0 ⁇ b ⁇ 90 parts
  • the branched polyethylene is an ethylene homopolymer having a degree of branching of 80 to 105 branches/1000 carbons, a weight average molecular weight of 268,000 to 356,000, and a Mooney viscosity of ML (1+4) of 125 ° C. It is 42 to 80.
  • the weight ratio of the diene monomer to the ethylene propylene rubber is preferably from 1% to 14%, more preferably from 3% to 10%, still more preferably from 4% to 7%.
  • the rubber composition 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 mixing and forming set the temperature and speed of the mixer, add the rubber matrix pre-compression mixing; then add the remaining components in turn, fully mix and disperse the glue, use the open mill to pass the thinner, and mix the rubber in the flat
  • the vulcanizer is pressed into a sample, and then irradiated and crosslinked under ultraviolet light to be parked.
  • the present invention also provides an electric wire comprising a conductor layer and an insulating layer, the insulating layer comprising the above rubber composition.
  • the present invention also provides a cable comprising a conductor layer, an insulating layer and a sheath layer, at least one of the insulating layer and the sheath layer comprising the above rubber composition.
  • the invention also provides a method of producing a cable, the production method comprising the steps of:
  • Rubber mixing set the temperature of the internal mixer and the rotor speed, add the rubber matrix pre-compression mixing; then add the remaining components in turn, fully mix and disperse the glue;
  • the rubber compound is extruded through a twin-screw extruder to form a cable insulation material or a sheath material; then, it is melt-extruded and coated on the conductive core of the cable to form an insulating layer, and then In the ultraviolet radiation irradiation crosslinking device, the insulating layer is melted and continuously irradiated by ultraviolet radiation, and after being inspected and cabled, it is melt-extruded and coated into a sheath layer, and then irradiated with ultraviolet light. In the cross-linking device, the sheath layer is melted in a continuous continuous ultraviolet radiation cross-linking.
  • the present invention also provides a medical catheter comprising the above rubber composition.
  • the invention also provides a method of producing a medical catheter, the production method comprising the steps of:
  • Rubber mixing set the temperature of the internal mixer and the rotor speed, add the rubber matrix pre-compression mixing; then add the remaining components in turn, fully mix and disperse the glue;
  • the present invention also provides a condom comprising the above rubber composition.
  • the invention also provides a method of producing a condom, the production method comprising the steps of:
  • Rubber mixing set the temperature of the internal mixer and the rotor speed, add the rubber matrix pre-compression mixing; then add the remaining components in turn, fully mix and disperse the glue;
  • the present invention also provides a glove comprising the above rubber composition.
  • the invention also provides a method of producing a glove, the production method comprising the steps of:
  • Rubber mixing set the temperature of the internal mixer and the rotor speed, add the rubber matrix pre-compression mixing; then add the remaining components in turn, fully mix and disperse the glue;
  • the invention has the beneficial effects of providing a new rubber composition, which partially or completely replaces ethylene propylene rubber with branched polyethylene, and applies it to a rubber product crosslinked by ultraviolet light, and can obtain excellent elasticity, It also has good mechanical strength while achieving electrical insulation properties, aging resistance and ozone resistance.
  • Principle Since the molecular structure of branched polyethylene is completely saturated, its electrical insulation and heat aging resistance are similar to those of ethylene propylene diene rubber, which is superior to EPDM rubber, and because of the molecular structure of branched polyethylene. There are many branches, and the length of the branch has a certain length and length distribution.
  • the branched polyethylene has a proper number of secondary branched structures.
  • the cross-linking point of the branched polyethylene can be in the tertiary chain of the main chain. It can also be produced on the branched tertiary carbon of the secondary structure. Therefore, the rubber network formed by the cross-linking of the branched polyethylene has a richer CC chain between the main chains than the ethylene-propylene rubber.
  • the length of the segment similar to the polysulfide bond distribution in the sulfur vulcanization system, can effectively avoid stress concentration and facilitate better mechanical properties. Therefore, in general, when the rubber matrix contains branched polyethylene, the rubber composition can obtain better mechanical strength after cross-linking by ultraviolet radiation, and can be well applied to the insulation of wires and cables.
  • the new rubber composition has high mechanical strength and no protein, so there is no risk of allergies. It can also be used to make films, condoms, gloves and other products.
  • a specific embodiment of the present invention provides a rubber composition
  • a rubber matrix comprising a rubber matrix and an initiator
  • the rubber matrix comprising: a content of branched polyethylene a: 0 ⁇ a ⁇ 100 parts, ethylene propylene rubber
  • the content b 0 ⁇ b ⁇ 100 parts; 0.1 to 10 parts by weight of the initiator, preferably 0.5 to 5 parts, based on 100 parts by weight of the rubber base.
  • the initiator comprises at least one of a cationic photoinitiator and a free radical photoinitiator.
  • the branching degree of the branched polyethylene is not less than 50 branches/1000 carbons, the weight average molecular weight is not less than 50,000, and the Mooney viscosity ML (1+4) is not lower than 2 at 125 °C.
  • the branching degree of the branched polyethylene is 60 to 130 branches/1000 carbons, the weight average molecular weight is 66,000 to 518,000, and the Mooney viscosity ML (1+4) is 6 to 102 at 125 ° C.
  • the initiator includes At least one of a cationic photoinitiator and a free radical photoinitiator.
  • the cationic photoinitiator comprises at least one of an aromatic diazonium salt, a diaryliodonium salt, a triarylsulfonium salt, an alkylsulfonium salt, a ferrocenium salt, a sulfonyloxyketone, and a triarylsiloxysiloxane.
  • it may be at least one of a triarylsulfonium hexafluorophosphate, an aromatic iron hexafluorophosphate, a triphenylhexafluoroantimonate salt, and a dodecylbenzene hexafluoroarsenate iodonium salt.
  • the free radical photoinitiator comprises at least one of an intramolecular cleavage type and an intermolecular hydrogen abstraction photoinitiator, and specifically may be benzophenone, diphenylacetone, dialkoxyacetophenone, benzoin dimethyl ether And at least one of ⁇ -hydroxyisobutyrylbenzene, acylphosphine oxide, benzoin isopropyl ether, benzoin n-butyl ester, hydrazine, and anthrone.
  • the rubber composition further comprises an auxiliary component comprising, in an amount of 100 parts by weight, 0.1 to 5 parts of a crosslinking agent, 0.01 to 2 parts of an antioxidant, 3 to 25 parts of a plasticizer, and 0 to 10 parts of a metal oxide. Parts, inorganic filler 0-200, coupling agent 0.3-5 parts.
  • the crosslinking agent includes triallyl cyanurate (TAC), triallyl isocyanurate (TAIC), trimethylolpropane triacrylate (TMPTA), trimethyl methacrylate At least one of a propane ester (TMPTMA), a pentaerythritol triallyle ether, and a pentaerythritol ester tetraallyl ether.
  • the plasticizer comprises at least one of polyethylene wax, pine tar, motor oil, aromatic oil, naphthenic oil, paraffin oil, microcrystalline wax, and coumarone resin.
  • the metal oxide is at least one of zinc oxide, magnesium oxide, calcium oxide, lead monoxide, and lead tetraoxide.
  • the inorganic filler includes at least one of white carbon black, calcium carbonate, talc, calcined clay, magnesium silicate, magnesium carbonate, aluminum hydroxide, and magnesium hydroxide.
  • the coupling agent comprises vinyl tris(2-methoxyethoxy)silane (A-172), ⁇ -glycidoxypropyltrimethoxysilane (A-187), ⁇ -mercaptopropyltrimethoxy At least one of silane (A-189) and ⁇ -methacryloxypropyltrimethoxysilane (KH570).
  • Antioxidants include 2,6-di-tert-butylphenol, 2,4,6-trit-butylphenol, 4,4'-thiobis(6-tert-butyl-3-methylphenol), phosphorous acid Triphenyl ester, tris(2,4-di-tert-butylphenyl)phosphite (antioxidant 168), triisooctyl phosphite, triphenylmethyl phosphate, tetra [3-(3', 5' -di-tert-butyl-4'-hydroxyphenyl)propionic acid] pentaerythritol ester (antioxidant 1010), dilauryl thiodipropionate (DLTP), leucoyl thiodipropionate or thiodi At least one of di(tris)propionate.
  • DLTP dilauryl thiodipropionate
  • the selected ethylene-propylene rubber and ethylene propylene diene rubber have a Mooney viscosity ML (1+4) of preferably 50 to 80 at 125 ° C, and an ethylene content of preferably 50% to 70%.
  • the body is 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene or dicyclopentadiene, and the third monomer content is from 1% to 7%.
  • the branched polyethylene used can be obtained by catalyzing the homopolymerization of ethylene by a ( ⁇ -diimine) nickel catalyst under the action of a cocatalyst.
  • the structure, synthesis method and method for preparing branched polyethylene by using the ( ⁇ -diimine) nickel catalyst are disclosed in the prior art, and can be used but are not limited to the following documents: CN102827312A, CN101812145A, CN101531725A, CN104926962A, US6103658, US6660677.
  • branching degree is 60-130 branches/1000 carbons
  • weight average molecular weight is 66,000-518,000
  • Mooney viscosity ML(1+4) 125°C is 6-102
  • the degree of branching is measured by nuclear magnetic resonance spectroscopy, and the molar percentages of various branches are measured by nuclear magnetic carbon spectroscopy.
  • Tensile strength and elongation at break performance test According to the national standard GB/T528-2009, the test is carried out with an electronic tensile testing machine. The tensile speed is 250mm/min, the test temperature is 23 ⁇ 2°C, and the sample is type 2 Dumbbell sample
  • 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;
  • volume resistivity test in accordance with the national standard GB/T1692-2008, using a high resistance meter for testing;
  • the oxygen index is tested in accordance with the national standard GB/T2046.2-2009;
  • the invention adopts ultraviolet light with a dominant wavelength of 200-400 nm and a light intensity of 400-4000 mW/cm 2 to carry out irradiation cross-linking at 160 ° C, and the lamp distance is controlled at 4-10 cm.
  • the branched polyethylene used was numbered PER-7.
  • Rubber mixing and forming setting the temperature of the internal mixer to 100 ° C, the rotor speed to 50 rpm, adding 70 parts of EPDM rubber and 30 parts of branched polyethylene for pre-pressing and mixing for 2 minutes; 1 part of benzoin dimethyl ether, after 3 minutes of mixing, the rubber is discharged, and after thinning with an open mill, the mixture is pressed into a 1 mm thick sample on a flat vulcanizing machine;
  • the branched polyethylene used was numbered PER-7.
  • Rubber mixing and forming set the temperature of the internal mixer to 100 ° C, the rotor speed to 50 rpm, add 50 parts of ethylene propylene diene monomer and 50 parts of branched polyethylene for pre-pressing and mixing for 2 minutes; 1 part of benzoin dimethyl ether, after 3 minutes of mixing, the rubber is discharged, and after thinning with an open mill, the mixture is pressed into a 1 mm thick sample on a flat vulcanizing machine;
  • the branched polyethylene used was numbered PER-7.
  • Rubber mixing and forming set the temperature of the internal mixer to 100 ° C, the rotor speed to 50 rpm, add 100 parts of branched polyethylene pre-mixed for 2 minutes; add 1 part of benzoin dimethyl ether, mix After 3 minutes of smelting, the rubber is discharged, and after being thinned by an open mill, the mixture is pressed into a 1 mm thick sample on a flat vulcanizing machine;
  • Rubber mixing and forming set the temperature of the internal mixer to 100 ° C, the rotor speed to 50 rpm, and add 100 parts of EPDM rubber for pre-press mixing for 2 minutes; then add 1 part of benzoin dimethyl ether. After mixing for 3 minutes, the rubber is discharged, and after being thinned by an open mill, the rubber mixture is pressed into a 1 mm thick sample on a flat vulcanizing machine;
  • the branched polyethylene used was numbered PER-6.
  • Rubber mixing and forming set the temperature of the internal mixer to 100 ° C, the rotor speed to 50 rpm, add 50 parts of ethylene propylene diene monomer and 50 parts of branched polyethylene for pre-pressing and mixing for 2 minutes; 3 parts of benzoin dimethyl ether and 1 part of trimethylolpropane triacrylate (TMPTA), after 3 minutes of mixing, the rubber is discharged, and after thinning with an open mill, the mixture is pressed into a 1 mm thick layer on a flat vulcanizing machine.
  • TMPTA trimethylolpropane triacrylate
  • the branched polyethylene used was numbered PER-6.
  • Rubber mixing and forming set the temperature of the internal mixer to 100 ° C, the rotor speed to 50 rpm, and add 100 parts of branched polyethylene for pre-press mixing for 2 minutes; then add 3 parts of benzoin and 1 Trimethylolpropane triacrylate (TMPTA), after 3 minutes of mixing, the rubber is discharged, and after thinning with an open mill, the mixture is pressed into a 1 mm thick sample on a flat vulcanizer;
  • TMPTA Trimethylolpropane triacrylate
  • the branched polyethylene used was numbered PER-9.
  • Rubber mixing and forming setting the internal temperature of the mixer to 100 ° C, the rotor speed to 50 rpm, adding 30 parts of ethylene propylene diene rubber, 60 parts of ethylene propylene diene monomer and 10 parts of branched polyethylene.
  • the branched polyethylene used was numbered PER-8.
  • Rubber mixing and forming set the temperature of the internal mixer to 100 ° C, the rotor speed to 50 rpm, add 10 parts of ethylene propylene rubber, 60 parts of ethylene propylene diene monomer, 30 parts of branched polyethylene and 0.1 part of antioxidant 1010 was pre-pressed and kneaded for 2 minutes; 5 parts of paraffin oil SUNPAR 2280, 2.5 parts of triarylsulfonium hexafluorophosphate and 1 part of benzoin dimethyl ether and 1 part of trimethylolpropane triacrylate ( TMPTA), after 3 minutes of mixing, the rubber is discharged, and after thinning with an open mill, the rubber mixture is pressed into a 1 mm thick sample on a flat vulcanizing machine;
  • the branched polyethylene used was numbered PER-8.
  • Rubber mixing and forming set the temperature of the internal mixer to 100 ° C, the rotor speed to 50 rpm, add 100 parts of EPDM rubber for pre-press mixing for 2 minutes; add 3 parts of benzoin and 1 part of trimethylolpropane triacrylate (TMPTA), after 3 minutes of mixing, the rubber is discharged, and after thinning with an open mill, the mixture is pressed into a 1 mm thick sample on a flat vulcanizer;
  • TMPTA trimethylolpropane triacrylate
  • the branched polyethylene used was numbered PER-5.
  • Rubber mixing set the temperature of the internal mixer to 100 ° C, the rotor speed to 50 rpm, add 50 parts of ethylene propylene diene monomer, 50 parts of branched polyethylene, 0.8 parts of silane coupling agent KH570, 0.2 parts.
  • Antioxidant 1010 and 0.1 part of antioxidant DLTP pre-pressed and kneaded for 2 minutes; then added 60 parts of calcined clay, 40 parts of talc, 5 parts of paraffin oil SUNPAR2280, mixed for 3 minutes; then added 3.5 parts of ferrocene-four - fluoroborate, 1 part of benzoin dimethyl ether, 2 parts of triallyl isocyanurate (TAIC), after 3 minutes of mixing;
  • the rubber compound is extruded through a twin-screw extruder to form a cable material; then it is melt-extruded and coated on the conductive core of the cable to form an insulating layer or a sheath layer, and then in the ultraviolet In the light irradiation cross-linking device, the insulating layer or the sheath layer is melted in a continuous continuous ultraviolet light irradiation cross-linking, and the irradiation time is 10 seconds.
  • the branched polyethylene used was numbered PER-5.
  • Rubber mixing set the temperature of the internal mixer to 100 ° C, the rotor speed to 50 rpm, add 30 parts of ethylene propylene diene monomer, 70 parts of branched polyethylene, 0.8 parts of silane coupling agent KH570 and 0.2 parts.
  • Antioxidant 1010 pre-pressed and kneaded for 2 minutes; then added 60 parts of calcined clay, 40 parts of talc and 5 parts of paraffin oil SUNPAR 2280, and kneaded for 3 minutes; then added 3 parts of benzoin and 2 parts of triallyl Cyanurate (TAIC), after 3 minutes of mixing, draining;
  • the rubber compound is extruded through a twin-screw extruder to form a cable material; then it is melt-extruded and coated on the conductive core of the cable to form an insulating layer or a sheath layer, and then in the ultraviolet In the light irradiation cross-linking device, the insulating layer or the sheath layer is melted in a continuous continuous ultraviolet light irradiation cross-linking, and the irradiation time is 10 seconds.
  • the branched polyethylene used was numbered PER-5.
  • Rubber mixing set the temperature of the internal mixer to 100 ° C, the rotor speed to 50 rpm, add 100 parts of branched polyethylene pre-pressure, 0.8 parts of silane coupling agent KH570, 0.2 parts of antioxidants 1010 and 0.1 Mixing antioxidant DLTP for 2 minutes; adding 60 parts of calcined clay, 40 parts of talc and 5 parts of paraffin oil SUNPAR2280, mixing for 3 minutes; adding 3.5 parts of ferrocene-tetra-fluoroborate, 1 Dibenzophenone and 2 parts of trimethylolpropane triacrylate (TMPTA), after 3 minutes of mixing;
  • TMPTA trimethylolpropane triacrylate
  • the rubber compound is extruded through a twin-screw extruder to form a cable material; then it is melt-extruded and coated on the conductive core of the cable to form an insulating layer or a sheath layer, and then in the ultraviolet In the light irradiation cross-linking device, the insulating layer or the sheath layer is melted in a continuous continuous ultraviolet light irradiation cross-linking, and the irradiation time is 10 seconds.
  • Rubber mixing set the temperature of the internal mixer to 100 ° C, the rotor speed to 50 rpm, add 100 parts of EPDM rubber, 0.8 parts of silane coupling agent KH570 and 0.2 parts of antioxidant 1010 pre-mixed 2 minutes of refining; add 60 parts of calcined clay, 40 parts of talc and 5 parts of paraffin oil SUNPAR2280, mix for 3 minutes; add 3 parts of benzoin dimethyl ether and 2 parts of trimethylolpropane triacrylate (TMPTA) , after 3 minutes of mixing, the glue is discharged;
  • TMPTA trimethylolpropane triacrylate
  • the rubber compound is extruded through a twin-screw extruder to form a cable material; then it is melt-extruded and coated on the conductive core of the cable to form an insulating layer or a sheath layer, and then in the ultraviolet In the light irradiation cross-linking device, the insulating layer or the sheath layer is melted in a continuous continuous ultraviolet light irradiation cross-linking, and the irradiation time is 10 seconds.
  • the branched polyethylenes used were numbered PER-2 and PER-5.
  • Rubber mixing set the internal temperature of the mixer to 100 ° C, the rotor speed to 50 rpm, add 70 parts of PER-5, 30 parts of PER-2, 1 part of silane coupling agent A-172 and 0.2 parts of anti-
  • the oxygen agent 1010 is pre-pressed and kneaded for 2 minutes; then 80 parts of calcined clay and 5 parts of paraffin oil SUNPAR 2280 are added and kneaded for 3 minutes; 0.5 part of benzophenone and 1 part of trimethylolpropane triacrylate (TMPTA) are further added. , after 3 minutes of mixing, the glue is discharged;
  • the rubber compound is extruded through a twin-screw extruder to form a cable material; then it is melt-extruded and coated on the conductive core of the cable to form an insulating layer or a sheath layer, and then in the ultraviolet In the light irradiation cross-linking device, the insulating layer or the sheath layer is melted and continuously cross-linked by ultraviolet light irradiation, and the irradiation time is 15 seconds.
  • the branched polyethylene used was numbered PER-3.
  • Rubber mixing set the temperature of the internal mixer to 100 ° C, the rotor speed is 50 rpm, add 50 parts of ethylene propylene diene monomer, 50 parts of branched polyethylene, 3 parts of zinc oxide, 0.3 parts of silane coupling.
  • Agent A-172 and 0.3 parts of antioxidant 1010 pre-pressed and kneaded for 2 minutes; then add 10 parts of highly dispersible white carbon, 40 parts of calcined clay and 5 parts of paraffin oil SUNPAR 2280, knead for 3 minutes; then add 5 parts of aromatic Ferrocene hexafluorophosphate, 5 parts of benzophenone and 3 parts of trimethylolpropane triacrylate (TMPTA), after 3 minutes of mixing;
  • the rubber compound is extruded through a twin-screw extruder to form a cable material; then it is melt-extruded and coated on the conductive core of the cable to form an insulating layer or a sheath layer, and then in the ultraviolet In the light irradiation cross-linking device, the insulating layer or the sheath layer is melted in a continuous continuous ultraviolet light irradiation cross-linking, and the irradiation time is 10 seconds.
  • the branched polyethylene used was numbered PER-4.
  • Rubber mixing set the internal temperature of the mixer to 100 ° C, the rotor speed to 50 rpm, add 50 parts of ethylene propylene diene monomer, 50 parts of branched polyethylene, 0.3 parts of antioxidant 1010 and 0.2 parts of DLTP. Pre-press mixing for 2 minutes; add 150 parts of silane coupling agent modified aluminum hydroxide and 10 parts of paraffin oil SUNPAR2280, mix for 3 minutes; add 3 parts of ferrocene hexafluorophosphate, 2 parts of diphenyl Ketone and 0.5 parts of trimethylolpropane triacrylate (TMPTA), after 3 minutes of mixing, draining;
  • TMPTA trimethylolpropane triacrylate
  • the rubber compound is extruded through a twin-screw extruder to form a cable material; then it is melt-extruded and coated on the conductive core of the cable to form an insulating layer or a sheath layer, and then in the ultraviolet In the light irradiation cross-linking device, the insulating layer or the sheath layer is melted in a continuous continuous ultraviolet light irradiation cross-linking, and the irradiation time is 10 seconds.
  • the branched polyethylenes used were numbered PER-1 and PER-7.
  • Rubber mixing set the internal temperature of the mixer to 100 ° C, the rotor speed to 50 rpm, add 80 parts of PER-7, 20 parts of PER-1, 0.3 parts of antioxidant 1010 and 0.2 parts of antioxidant DLTP Pre-pressing and kneading for 2 minutes; adding 180 parts of silane coupling agent-modified aluminum hydroxide, 20 parts of calcined clay and 10 parts of paraffin oil SUNPAR 2280, mixing for 3 minutes; adding 4.5 parts of ferrocene hexafluorophosphate, 3.5 parts of benzoin dimethyl ether and 1 part of trimethylolpropane triacrylate (TMPTA), after 3 minutes of mixing;
  • TMPTA trimethylolpropane triacrylate
  • the rubber compound is extruded through a twin-screw extruder to form a cable material; then it is melt-extruded and coated on the conductive core of the cable to form an insulating layer or a sheath layer, and then in the ultraviolet In the light irradiation cross-linking device, the insulating layer or the sheath layer is melted in a continuous continuous ultraviolet light irradiation cross-linking, and the irradiation time is 10 seconds.
  • Embodiments of the present invention also include the use of the above rubber composition for making rubber articles including wire and cable, films, gloves, condoms, medical catheters.
  • a medical catheter the processing steps are as follows:
  • the branched polyethylenes used were numbered PER-8 and PER-2.
  • Rubber mixing set the internal temperature of the mixer to 100 ° C, the rotor speed to 50 rpm, add 80 parts of PER-8, 20 parts of PER-2, 0.3 parts of antioxidant 1010 and 0.2 parts of antioxidant DLTP Pre-press mixing for 2 minutes; add 60 parts of talc and 3 parts of paraffin oil SUNPAR2280, mix for 3 minutes; add 2 parts of iron hexafluorophosphate, 2 parts of benzophenone and 1 part of trimethylol Propane triacrylate (TMPTA), after 3 minutes of mixing, draining;
  • TMPTA trimethylol Propane triacrylate
  • a medical catheter the processing steps are as follows:
  • the branched polyethylene used was numbered PER-7.
  • Rubber mixing set the temperature of the internal mixer to 100 ° C, the rotor speed to 50 rpm, and add 100 parts of PER-7, 0.3 parts of antioxidant 1010 and 0.2 parts of antioxidant DLTP for pre-pressing and mixing for 2 minutes. Add 40 parts of talc and 3 parts of paraffin oil SUNPAR2280, mix for 3 minutes; add 0.1 part of benzophenone and 0.1 part of trimethylolpropane triacrylate (TMPTA), mix for 3 minutes and then drain;
  • TMPTA trimethylolpropane triacrylate
  • a condom the processing steps are as follows:
  • the branched polyethylenes used were numbered PER-7 and PER-2.
  • Rubber mixing set the temperature of the internal mixer to 100 ° C, the rotor speed to 50 rpm, and add 70 parts of PER-7, 30 parts of PER-4 and 0.2 parts of antioxidant DLTP to pre-press and knead for 2 minutes; Add 2 parts of benzophenone and 1 part of trimethylolpropane triacrylate (TMPTA), mix for 3 minutes and then drain the glue;
  • TMPTA trimethylolpropane triacrylate
  • the condom has a thickness of 41 ⁇ m, a burst volume of 29 dm 3 , a burst pressure of 1.3 kPa, a tensile strength of 18.9 MPa, and an elongation at break of 768%, which meets the international condom standard (55EN ISO 4074:2002 Natural latex rubber condoms: Requirements) And test methods) requirements for performance.
  • the branched polyethylene used is numbered PER-7
  • Rubber mixing set the temperature of the internal mixer to 100 ° C, the rotor speed to 50 rpm, add 100 parts of PER-7, 0.8 parts of silane coupling agent A-172, 0.3 parts of antioxidant 1010 and 0.2 parts.
  • Antioxidant DLTP pre-mixed for 2 minutes; add 20 parts of talc powder, mix for 3 minutes; add 2 parts of ferrocene hexafluorophosphate, 2 parts of benzophenone and 1 part of trimethylolpropane Acrylate (TMPTA), after 3 minutes of mixing, draining;
  • the dip molding process is: after the mold is cleaned and dried, the coagulant is dipped, dried, dipped in latex, raised, irradiated by ultraviolet radiation for 30 seconds, parked, coated, rolled, demolded, finished, Gloves were obtained.
  • the tearing force of the gloves was 8.3 N, the elongation was 780%, and the adhesion rate was 0, which met the requirements of the national standard (GB 10213-2006 disposable medical rubber inspection gloves).
  • a medical catheter adopting a rubber matrix as a branched polyethylene PER-12, and the remaining formula components and processing steps are the same as those in the embodiment 16.
  • the catheter material has a tensile strength of 13.4 MPa and an elongation at break of 810%, which satisfies the requirements of various medical catheters for various performances.
  • a condom comprising a rubber matrix as a branched polyethylene PER-12, and the remaining formulation components and processing steps are in accordance with Example 17.
  • the obtained condom has a thickness of 32 ⁇ m, a burst volume of 31 dm 3 , a burst pressure of 1.4 kPa, a tensile strength of 22.9 MPa, and an elongation at break of 733%, which meets the international condom standard (55EN ISO 4074:2002 Natural latex rubber condoms). :Requirements and test methods) requirements for each performance.
  • the obtained glove has a tearing force of 11.8 N, an elongation of 660%, and a blocking ratio of 0, which meets the requirements of various national performances (GB10213-2006 disposable medical rubber inspection gloves).

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Abstract

L'invention concerne un composite de caoutchouc utilisant la photoréticulation et des applications du composite. Le composite de caoutchouc, calculé à 100 parties en poids, comprend : un substrat en caoutchouc et un initiateur. Le substrat en caoutchouc comprend : du polyéthylène ramifié, dont la teneur est a : 0 < a ≤ 100 parties et un caoutchouc d'éthylène propylène, dont la teneur est b : b: 0 ≤ b < 100 parties. L'initiateur comprend de 0,1 à 10 parties. L'initiateur comprend : au moins l'un d'un photoinitiateur cationique et d'un photoinitiateur de radicaux libres. Les applications sont dans la fabrication de produits en caoutchouc. Les produits en caoutchouc comprennent des fils électriques et des câbles, des films minces, des gants, des préservatif et des cathéters médicaux. Les effets bénéfiques sont tels que le caoutchouc d'éthylène propylène est partiellement ou entièrement remplacé par l'utilisation de polyéthylène ramifié, son application sur les produits en caoutchouc réticulé par la lumière ultraviolette permet la fourniture d'une grande élasticité, d'une grande performance d'isolation électrique, d'une grande résistance au vieillissement et d'une grande performance de résistance à l'ozone et, en même temps, la fourniture d'une grande résistance mécanique.
PCT/CN2018/072360 2017-01-13 2018-01-12 Composite de caoutchouc à photoréticulation, applications et procédé de fabrication pour les applications WO2018130191A1 (fr)

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US16/477,691 US11499041B2 (en) 2017-01-13 2018-01-12 Photo-crosslinked rubber composition, and rubber product using the same

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021153234A1 (fr) * 2020-01-31 2021-08-05 Nok株式会社 Composition de caoutchouc ignifuge
CN113980301A (zh) * 2021-11-12 2022-01-28 上海凯波电缆特材股份有限公司 一种电动汽车用紫外光辐照交联高电性能充电桩绝缘电缆料及其制备方法
CN114085482A (zh) * 2021-12-13 2022-02-25 哈尔滨理工大学 一种紫外光交联低压乙丙橡胶绝缘材料及其制备方法
CN115424784A (zh) * 2022-08-24 2022-12-02 东莞市民兴电缆有限公司 一种辐照型橡套电缆的制备工艺
CN115716902A (zh) * 2022-11-23 2023-02-28 山东一诺威聚氨酯股份有限公司 有机硅改性耐磨tpu及其制备方法和应用
CN115975332A (zh) * 2023-03-22 2023-04-18 山东泰瑞丰新材料有限公司 一种丁基橡胶离聚体改性的sebs及其制备方法
WO2024251298A1 (fr) * 2023-06-05 2024-12-12 上海海优威新材料股份有限公司 Garniture intérieure d'automobile douce et respectueuse de l'environnement
CN119132709A (zh) * 2024-07-31 2024-12-13 广东日昭电工有限公司 一种新型双层防护防水母线

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59215342A (ja) * 1983-05-24 1984-12-05 Nippon Petrochem Co Ltd 電力ケ−ブル用樹脂組成物
CN103980596A (zh) * 2014-05-13 2014-08-13 浙江大学 一种聚乙烯橡胶及其加工方法
CN104877225A (zh) * 2015-06-20 2015-09-02 浙江大学 一种气密层材料的制备方法及其原料配方
CN104910487A (zh) * 2015-06-01 2015-09-16 浙江大学 一种高耐磨鞋底材料及其制备方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59215342A (ja) * 1983-05-24 1984-12-05 Nippon Petrochem Co Ltd 電力ケ−ブル用樹脂組成物
CN103980596A (zh) * 2014-05-13 2014-08-13 浙江大学 一种聚乙烯橡胶及其加工方法
CN104910487A (zh) * 2015-06-01 2015-09-16 浙江大学 一种高耐磨鞋底材料及其制备方法
CN104877225A (zh) * 2015-06-20 2015-09-02 浙江大学 一种气密层材料的制备方法及其原料配方

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021153234A1 (fr) * 2020-01-31 2021-08-05 Nok株式会社 Composition de caoutchouc ignifuge
JPWO2021153234A1 (fr) * 2020-01-31 2021-08-05
JP7420839B2 (ja) 2020-01-31 2024-01-23 Nok株式会社 難燃性ゴム組成物
CN113980301A (zh) * 2021-11-12 2022-01-28 上海凯波电缆特材股份有限公司 一种电动汽车用紫外光辐照交联高电性能充电桩绝缘电缆料及其制备方法
CN114085482A (zh) * 2021-12-13 2022-02-25 哈尔滨理工大学 一种紫外光交联低压乙丙橡胶绝缘材料及其制备方法
CN114085482B (zh) * 2021-12-13 2024-03-22 哈尔滨理工大学 一种紫外光交联低压乙丙橡胶绝缘材料及其制备方法
CN115424784A (zh) * 2022-08-24 2022-12-02 东莞市民兴电缆有限公司 一种辐照型橡套电缆的制备工艺
CN115716902A (zh) * 2022-11-23 2023-02-28 山东一诺威聚氨酯股份有限公司 有机硅改性耐磨tpu及其制备方法和应用
CN115975332A (zh) * 2023-03-22 2023-04-18 山东泰瑞丰新材料有限公司 一种丁基橡胶离聚体改性的sebs及其制备方法
CN115975332B (zh) * 2023-03-22 2023-05-12 山东泰瑞丰新材料有限公司 一种丁基橡胶离聚体改性的sebs及其制备方法
WO2024251298A1 (fr) * 2023-06-05 2024-12-12 上海海优威新材料股份有限公司 Garniture intérieure d'automobile douce et respectueuse de l'environnement
CN119132709A (zh) * 2024-07-31 2024-12-13 广东日昭电工有限公司 一种新型双层防护防水母线

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