WO2018130191A1

WO2018130191A1 - Photocrosslinking rubber composite, applications, and manufacturing method for the applications

Info

Publication number: WO2018130191A1
Application number: PCT/CN2018/072360
Authority: WO
Inventors: 徐涛; 傅智盛; 吴安洋
Original assignee: 杭州星庐科技有限公司
Priority date: 2017-01-13
Filing date: 2018-01-12
Publication date: 2018-07-19

Abstract

Disclosed are a rubber composite employing photocrosslinking and applications of the composite. The rubber composite, calculated at 100 parts by weight, comprises: a rubber substrate and an initiator. The rubber substrate comprises: branched polyethylene, the content thereof being a: 0 < a ≤ 100 parts and ethylene propylene rubber, the content thereof being b: 0 ≤ b < 100 parts. The initiator comprises 0.1-10 parts. The initiator comprises: at least one of a cationic photoinitiator and a free radical photoinitiator. The applications are in the manufacturing of rubber products. The rubber products comprise electric wire and cable, a thin film, gloves, a condom, and a medical catheter. The beneficial effects are such that, ethylene propylene rubber is partially or entirely replaced by utilizing branched polyethylene, the application thereof on the rubber products crosslinked by ultraviolet light allows the provision of great elasticity, electric insulation performance, aging resistance, and ozone resistance performance and, at the same time, the provision of great mechanical strength.

Description

Photocrosslinked rubber composition and application, and production method of the same

Technical field

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.

Background technique

Ethylene-propylene rubber has excellent elasticity, electrical insulation properties, aging resistance and ozone resistance. When used in applications where high performance is required, 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.

How to improve the performance of the rubber composition to make it better suited to the requirements of aging resistance and mechanical properties is an ongoing technical problem.

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 α-olefin. Ethylene and α-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 α-olefin copolymers. The lower the ratio, the better the aging resistance. The ratio can be expressed by the degree of branching. For example, 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.

In the prior art, the α-olefin in the common ethylene and α-olefin copolymer may be an α-olefin having a carbon number of not less than 4 in addition to propylene, and may be selected from a C ₄ - C ₂₀ α-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 α-olefin is too low, the melting point and crystallinity are too high, and it is not suitable for use as a rubber component. If the degree of branching is high, the content of α-olefin is high, which may result in Process difficulty and raw material cost are high, and operability and economy are low. In the prior art, 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. It can replace ethylene propylene rubber to a certain extent. use. Since the molecular chain of ethylene and 1-octene copolymer is softer, more rubbery and has good physical and mechanical properties relative to the copolymer of ethylene and 1-butene, the polyolefin elastomer commonly used in rubber products is generally ethylene. And the copolymer of 1-octene, 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 rubber generally needs to be used after cross-linking. In the cross-linking mode commonly used for ethylene-propylene rubber, the copolymer of ethylene and α-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. The steric hindrance is large, and the free radical reaction is difficult to occur, resulting in difficulty in crosslinking, affecting processing efficiency and product performance.

Therefore, there is a need for a better technical solution to improve the aging resistance of ethylene propylene rubber, while having good physical and mechanical properties and cross-linking performance, and it is expected to target specific functional indicators (such as electricity) for rubber products. Insulation performance, etc.) have a good performance.

Summary of the invention

In view of the technical defects of the prior art, such as peroxide vulcanization method and high energy radiation method, and ultraviolet light crosslinking to produce ethylene propylene rubber, 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.

In order to achieve the above object, the present invention adopts the following technical solution: 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-α-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.

In the further elaboration of the technical solution of the present invention, 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. Currently, 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 (α-diimine) nickel/palladium catalysts. The nature of the chain walking mechanism refers to the late transition metal catalyst. For example, the (α-diimine) nickel/palladium catalyst is more likely to undergo β-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 (α-diimine) nickel catalyst is significantly lower than that of the (α-diimine) palladium catalyst, and the (α-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 (α-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. In terms of cross-linking ability, 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. 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.

This may be explained by the fact that there may be an appropriate number of secondary branched structures on the branched polyethylene used in the preferred embodiment of the present invention, and the so-called 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-α-olefin copolymer.

It is a new technical solution to improve the cross-linking ability of saturated polyolefin elastomer by using the secondary steric structure with lower steric hindrance. Under the technical solution of the present invention, it is also considered to be within the technical protection of the present invention to include a vinyl copolymer having a secondary branched structure or other saturated hydrocarbon polymer in the rubber matrix. The vinyl copolymer refers to a copolymer of ethylene and a branched α-olefin, and has a secondary branched structure, wherein the branched α-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.

It is generally believed in the prior art that the branched polyethylene prepared by the (α-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.

Compared with ethylene propylene rubber, when the branched polyethylene has an appropriate number of secondary branched structures, 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.

A further technical solution is that 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.

A further technical solution is that 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, α-hydroxyisobutyrylbenzene, acylphosphine oxide, benzoin isopropyl ether, benzoin n-butyl ester, anthracene, anthrone.

According to a further aspect of the invention, 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.

A further technical solution is that 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.

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.

In a further technical solution, the plasticizer comprises at least one of polyethylene wax, pine tar, motor oil, aromatic oil, naphthenic oil, paraffin oil, microcrystalline wax, and coumarone resin.

In a further technical solution, the metal oxide is at least one of zinc oxide, magnesium oxide, calcium oxide, lead monoxide, and lead tetraoxide.

In a further technical solution, 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.

In a further technical solution, the coupling agent comprises vinyl tris(2-methoxyethoxy)silane (A-172), γ-glycidoxypropyltrimethoxysilane (A-187), At least one of γ-mercaptopropyltrimethoxysilane (A-189) and γ-methacryloxypropyltrimethoxysilane (KH570).

In a further technical solution, 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.

A further technical solution is that 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.

A further technical solution is that 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;

A further technical solution is that 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.

A further technical solution is that 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.

In a further aspect, 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:

(1) 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;

(2) Extrusion and cross-linking: 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.

(3) Inspection, printing, and obtaining the finished cable.

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:

(2) Extrusion and vulcanization: the rubber compound is extruded into a rubber tube through a twin-screw extruder, and then the molten material is melted in a continuous ultraviolet light irradiation cross-linking in an ultraviolet irradiation crosslinking device. The medical catheter is irradiated.

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:

(2) preparing a latex: after dissolving the rubber mixture in a solvent, emulsification and dispersion to obtain a latex;

(3) Dip molding: Then, by using a mold, after being immersed and dried several times in the latex, it is irradiated with ultraviolet light, and then subjected to crimping, demoulding, finishing, electric inspection, packaging, and finally obtaining a condom.

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:

(3) Dip molding: the process is followed by cleaning and drying of the mold, dipping coagulant, drying, dipping latex, proposing, UV irradiation, cross-linking, parking, coating, crimping, demoulding, finishing, obtaining gloves .

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. During the photocrosslinking process, 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. In addition, 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.

detailed description

The following examples are given to further illustrate the present invention, but are not intended to limit the scope of the present invention, and some non-essential improvements and adjustments made by those skilled in the art based on the present invention remain within the scope of the present invention. .

A specific embodiment of the present invention provides a rubber composition comprising 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.

Preferably, 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. Specifically, 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 α-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. Among them, 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), γ-glycidoxypropyltrimethoxysilane (A-187), γ-mercaptopropyltrimethoxy At least one of silane (A-189) and γ-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.

In the present embodiment, 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 (α-diimine) nickel catalyst under the action of a cocatalyst. The structure, synthesis method and method for preparing branched polyethylene by using the (α-diimine) nickel catalyst are disclosed in the prior art, and can be used but are not limited to the following documents: CN102827312A, CN101812145A, CN101531725A, CN104926962A, US6103658, US6660677.

The characteristics of branched polyethylene are: 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, wherein 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.

The details are as follows:

Rubber performance test method:

1. 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

2. 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;

3, hot air accelerated aging test: in accordance with the national standard GB/T3512-2001, in the heat aging test chamber, the test conditions are 135 ° C × 168h;

4, volume resistivity test: in accordance with the national standard GB/T1692-2008, using a high resistance meter for testing;

5. 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.

Example 1:

The branched polyethylene used was numbered PER-7.

The processing and crosslinking steps are as follows:

(1) 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;

(2) After 16 seconds of radiation cross-linking under ultraviolet light, it was parked for 16 hours, and then the samples were subjected to various tests.

Example 2:

The branched polyethylene used was numbered PER-7.

The processing and crosslinking steps are as follows:

(1) 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;

Example 3:

The branched polyethylene used was numbered PER-7.

The processing and crosslinking steps are as follows:

(1) 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;

Comparative Example 1:

The processing and crosslinking steps are as follows:

(1) 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;

Example 4:

The branched polyethylene used was numbered PER-6.

The processing and crosslinking steps are as follows:

(1) 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. Sample

Example 5:

The branched polyethylene used was numbered PER-6.

The processing and crosslinking steps are as follows:

(1) 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;

Example 6

The branched polyethylene used was numbered PER-9.

The processing and crosslinking steps are as follows:

(1) 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. Press and knead for 2 minutes; add 3 parts of paraffin oil SUNPAR 2280, 0.1 part of antioxidant 1010, 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;

Example 7

The branched polyethylene used was numbered PER-8.

The processing and crosslinking steps are as follows:

(1) 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;

Comparative Example 2:

The branched polyethylene used was numbered PER-8.

The processing and crosslinking steps are as follows:

(1) 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;

The performance test data of Examples 1-7 and Comparative Examples 1 and 2 are as follows:

Example 8

The branched polyethylene used was numbered PER-5.

(1) 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;

(2) Extrusion and cross-linking: 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.

Example 9

The branched polyethylene used was numbered PER-5.

(1) 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;

Example 10:

The branched polyethylene used was numbered PER-5.

(1) 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;

Comparative Example 3:

(1) 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;

Example 11

The branched polyethylenes used were numbered PER-2 and PER-5.

(1) 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;

(2) Extrusion and cross-linking: 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.

Example 12

The branched polyethylene used was numbered PER-3.

(1) 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;

Example 13

The branched polyethylene used was numbered PER-4.

(1) 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;

Example 14

The branched polyethylenes used were numbered PER-1 and PER-7.

(1) 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;

The performance test data of the UV-crosslinked cable materials prepared in Examples 8-14 and Comparative Example 3 were as follows:

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.

The specific embodiments thereof are described below.

Example 15

A medical catheter, the processing steps are as follows:

The branched polyethylenes used were numbered PER-8 and PER-2.

(1) 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;

(2) Extrusion and vulcanization: the rubber compound is extruded into a rubber tube through a twin-screw extruder, and then the molten material is melted in a continuous ultraviolet light irradiation cross-linking in an ultraviolet irradiation crosslinking device. . The irradiation time was 15 seconds, and a medical catheter was obtained. The tensile strength of the catheter material was 18.5 MPa, and the elongation at break was 680%, which satisfies the requirements of various medical catheters for various performances.

Example 16:

A medical catheter, the processing steps are as follows:

The branched polyethylene used was numbered PER-7.

(1) 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;

(2) Extrusion and vulcanization: the rubber compound is extruded into a rubber tube through a twin-screw extruder, and then the molten material is melted in a continuous ultraviolet light irradiation cross-linking in an ultraviolet irradiation crosslinking device. . The irradiation time was 15 seconds, and a medical catheter was obtained. The catheter material has a tensile strength of 10.5 MPa and an elongation at break of 880%, which satisfies the requirements of various medical catheters for various performances.

Example 17

A condom, the processing steps are as follows:

The branched polyethylenes used were numbered PER-7 and PER-2.

(1) 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;

(2) preparing a latex: after dissolving the rubber mixture in n-octane, emulsification and dispersion to obtain a latex;

(3) Dip molding: Then, after being immersed and dried several times in the latex by a specific mold, it is irradiated with ultraviolet light for 30 seconds, and then subjected to crimping, demoulding, finishing, electric inspection, packaging, and finally obtaining a condom. The condom has a thickness of 41 μm, 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.

Example 18

A glove whose processing steps are as follows:

The branched polyethylene used is numbered PER-7

(1) 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;

(3) 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).

Example 19

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.

Example 20

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 μm, 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.

Example 21:

A glove using a rubber matrix as a branched polyethylene PER-11, and the remaining formulation components and processing steps are in accordance with Example 18.

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).

Claims

A rubber composition comprising a rubber matrix and an initiator, the rubber matrix comprising: a content of branched polyethylene a: 0 < a ≤ 100 parts, and a content of ethylene propylene rubber b: 0 ≤ b < 100 parts; comprising 0.1 to 10 parts of an initiator, based on 100 parts by weight of the rubber matrix, the initiator comprising: at least one of a cationic photoinitiator and a radical photoinitiator, wherein the branched poly Ethylene is an ethylene homopolymer having a degree of branching of not less than 50 branches/1000 carbons, a weight average molecular weight of not less than 50,000, and a Mooney viscosity of ML (1+4) of not less than 2 at 125 °C.
A rubber composition according to claim 1, wherein the initiator is contained in an amount of from 0.5 to 5 parts.
A rubber composition according to claim 1, wherein said cationic photoinitiator comprises an aromatic diazonium salt, a diaryliodonium salt, a triarylsulfonium salt, an alkylsulfonium salt, and a ferrocene salt. At least one of an iron salt, a sulfonyloxy ketone, and a triaryl siloxane having a triaryl sulfonium hexafluorophosphate.
A rubber composition according to claim 1, wherein said radical photoinitiator comprises at least one of an intramolecular cleavage type or an intermolecular hydrogen abstraction type photoinitiator, said intramolecular cleavage type Or intermolecular hydrogen abstraction photoinitiators are benzophenone, diphenylacetone, dialkoxyacetophenone, benzoin dimethyl ether, α-hydroxyisobutyrylbenzene, acylphosphine oxide, benzoin isopropyl ether And at least one of benzoin n-butyl ester, hydrazine, and fluorenone.
A rubber composition according to claim 1, wherein said rubber composition further comprises an auxiliary component based on 100 parts by weight of the rubber base, said auxiliary component comprising: 0.1 to 5 parts of a crosslinking agent; The oxygen agent is 0.01 to 2 parts, the plasticizer is 3 to 25 parts, the metal oxide is 0 to 10 parts, the inorganic filler is 0 to 200 parts, and the coupling agent is 0.3 to 5 parts.
A rubber composition according to claim 5, wherein said crosslinking agent comprises triallyl cyanurate, triallyl isocyanurate, trimethylolpropane triacrylate At least one of trimethylolpropane trimethacrylate, pentaerythritol triallyl ether, and pentaerythritol tetraethenyl ether.
A rubber composition according to claim 5, wherein said plasticizer comprises polyethylene wax, pine tar, motor oil, aromatic oil, naphthenic oil, paraffin oil, microcrystalline wax, coumarone resin At least one of them.
The rubber composition according to claim 5, wherein the metal oxide is at least one of zinc oxide, magnesium oxide, calcium oxide, lead monoxide, and lead tetraoxide.
A rubber composition according to claim 5, wherein said inorganic filler comprises white carbon black, calcium carbonate, talc, calcined clay, magnesium silicate, magnesium carbonate, aluminum hydroxide, magnesium hydroxide At least one of them.
A rubber composition according to claim 5, wherein said coupling agent comprises vinyl tris(2-methoxyethoxy)silane, γ-glycidoxypropyltrimethoxysilane At least one of γ-mercaptopropyltrimethoxysilane and γ-methacryloxypropyltrimethoxysilane.
A rubber composition according to claim 5, wherein said 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, triisooctyl phosphite, triphenyl phosphate Methyl ester, tetrakis[3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionic acid] pentaerythritol ester, dilauryl thiodipropionate, lauric octadecyl thiodipropionate Or at least one of di(tris) thiodipropionate.
The rubber composition according to claim 1, wherein the content of the branched polyethylene in the rubber matrix is a: 10 ≤ a ≤ 100 parts; the ethylene propylene rubber and the three The content of ethylene-propylene rubber b: 0 ≤ b ≤ 90 parts; the characteristics of the branched polyethylene are: branching degree of 60-130 branches / 1000 carbon, weight average molecular weight of 66,000 ~ 518,000, the door The viscosity ML (1+4) at 125 ° C is 6 to 102.
A method of processing the rubber composition according to any one of claims 1 to 12, characterized in that the processing method comprises the steps of:

Step 1: Rubber mixing and forming: set the temperature and rotation speed of the mixer, and add the rubber matrix pre-compression mixing;

Step 2: Add the remaining components in turn, and mix and disperse the glue.

Step 3: After thinning with an open mill, the rubber compound is pressed into a sample on a flat vulcanizer, and then irradiated under ultraviolet light to be crosslinked.
An electric wire comprising a conductor layer and an insulating layer, wherein the insulating layer comprises the rubber composition according to any one of claims 1 to 12.
A cable comprising a conductor layer, an insulating layer and a sheath layer, wherein at least one layer of the insulating layer and the sheath layer comprises the rubber composition according to any one of claims 1 to 12.
A method of producing the cable of claim 15 wherein the method of producing comprises the steps of:

(1) 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;

(2) Extrusion and cross-linking: 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. According to the cross-linking device, the sheath layer is melted in a continuous continuous ultraviolet light irradiation cross-linking;

(3) Inspection, printing, and obtaining the finished cable.
A medical catheter characterized in that the compound used comprises the rubber composition according to any one of claims 1 to 12.
A method of producing the medical catheter of claim 17 wherein the method of producing comprises the steps of:

(1) 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;

(2) Extrusion and vulcanization: the rubber compound is extruded into a rubber tube through a twin-screw extruder, and then the molten material is melted in a continuous ultraviolet light irradiation cross-linking in an ultraviolet irradiation crosslinking device. The medical catheter is irradiated.
A condom characterized in that the compound used comprises the rubber composition according to any one of claims 1 to 12.
A method of producing a condom according to claim 19, characterized in that the production method comprises the following steps:

(1) 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;

(2) preparing a latex: after dissolving the rubber mixture in a solvent, emulsification and dispersion to obtain a latex;

(3) Dip molding: Then, by using a mold, after being immersed and dried several times in the latex, it is irradiated with ultraviolet light, and then subjected to crimping, demoulding, finishing, electric inspection, packaging, and finally obtaining a condom.
A glove comprising the rubber composition according to any one of claims 1 to 12.
A method of producing the glove of claim 21, wherein the production method comprises the steps of:

(1) 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;

(2) preparing a latex: after dissolving the rubber mixture in a solvent, emulsification and dispersion to obtain a latex;

(3) Dip molding: the process is followed by cleaning and drying of the mold, dipping coagulant, drying, dipping latex, proposing, UV irradiation, cross-linking, parking, coating, crimping, demoulding, finishing, obtaining gloves .