阅读说明：本技术 一种耐老化的极性橡胶组合物及加工方法与应用 (Anti-aging polar rubber composition, and processing method and application thereof ) 是由 不公告发明人 于 2018-07-13 设计创作，主要内容包括：本发明公开了一种耐老化的极性橡胶组合物及加工方法与应用,其中,该橡胶组合物包括：橡胶基体和配合组份,按重量份计,每100份橡胶基体中包含0～99份高度支化聚乙烯P1、0～100份高度支化聚乙烯P1与极性单体的反应物P2,0～50份乙烯与α-烯烃的共聚物与极性单体的反应物P3,0～50份单烯烃与二烯类单体的二元或三元及以上的共聚物与极性单体的反应物P4,且P1与P2的含量之和为50～100份；其中,P1为有支链结构的乙烯均聚物,其支化度不低于50个支链/1000个碳；配合组份包含硫化体系。本发明提供了一种兼具耐老化性和一定极性的橡胶组合物,拓宽了高度支化聚乙烯作为弹性体的使用范围,使其更加适用于对粘结性、耐油性等与极性相关的性能有要求的场合。(The invention discloses an anti-aging polar rubber composition, a processing method and application thereof, wherein the rubber composition comprises the following components: the rubber comprises a rubber matrix and matching components, wherein each 100 parts of the rubber matrix comprises 0-99 parts by weight of hyperbranched polyethylene P1, 0-100 parts by weight of reactant P2 of hyperbranched polyethylene P1 and a polar monomer, 0-50 parts by weight of reactant P3 of a copolymer of ethylene and alpha-olefin and the polar monomer, 0-50 parts by weight of reactant P4 of a copolymer of mono-olefin and diene monomer and the polar monomer, and the sum of the contents of P1 and P2 is 50-100 parts; wherein, P1 is an ethylene homopolymer with a branched chain structure, and the branching degree of the ethylene homopolymer is not less than 50 branches/1000 carbons; the compounding component comprises a vulcanization system. The invention provides a rubber composition with aging resistance and certain polarity, which widens the application range of highly branched polyethylene as an elastomer and is more suitable for occasions with requirements on performances related to polarity, such as cohesiveness, oil resistance and the like.)

1. A rubber composition comprises a rubber matrix and a compounding component, and is characterized in that, per 100 parts of the rubber matrix, the rubber composition comprises the following components in parts by weight: 0-99 parts of highly branched polyethylene P1, 0-100 parts of highly branched polyethylene P1 and a polar monomer reactant P2, 0-50 parts of an ethylene and alpha-olefin copolymer and polar monomer reactant P3, 0-50 parts of a monoolefin and diene monomer binary or ternary or higher copolymer and polar monomer reactant P4, wherein the sum of the contents of P1 and P2 is 50-100 parts; the compounding component comprises a vulcanization system.

2. The rubber composition according to claim 1, wherein the P1 is an ethylene homopolymer having a branched structure, and the branching degree is not less than 50 branches/1000 carbons.

3. The rubber composition according to claim 2, wherein the branching degree of P1 is 50 to 150 branches/1000 carbons.

4. The rubber composition according to claim 3, wherein the branching degree of P1 is 60 to 130 branches/1000 carbons.

5. The rubber composition according to claim 4, wherein the weight average molecular weight of P1 is 6.6 to 51.8 ten thousand, and the Mooney viscosity ML (1+4) at 125 ℃ is 6 to 102.

6. The rubber composition of claim 1, wherein the alpha-olefin in the copolymer of ethylene and alpha-olefin has 3 to 30 carbon atoms and comprises at least one of propylene, 1-butene, 1-pentene, 3-methyl-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, 1-docosene, 1-tetracosene, 1-hexacosene, 1-dioctadecene, and 1-triacontene; the binary copolymer of monoolefin and diolefin is butyl rubber; the terpolymer of the monoolefine and the diolefin is ethylene propylene diene monomer.

7. The rubber composition according to claim 1, the polar monomer used for preparing the P2, P3 and P4 comprises at least one of Maleic Anhydride (MAH), Methacrylic Acid (MA), Acrylic Acid (AA), Itaconic Acid (IA), Fumaric Acid (FA), isocyanate, Glycidyl Methacrylate (GMA), Methyl Methacrylate (MMA), dibutyl fumarate (DBF), beta-hydroxyethyl methacrylate (HEMA), dibutyl maleate (DBM), diethyl maleate (DEM), elemental halogen, halogen-containing compounds, sulfur-containing compounds, Vinyltrimethoxysilane (VTMS), Vinyltriethoxysilane (VTES), 3-methacryloxypropyltrimethoxysilane (VMMS), styrene (St), alpha-methylstyrene (alpha-MSt), Acrylonitrile (AN).

8. The rubber composition of claim 7, wherein the P2 is a halogen-containing branched polyethylene, wherein the polar group comprises at least one of a chloro group, a bromo group, a chlorosulfonyl group, and a bromosulfonyl group; p4 is at least one of chlorinated butyl rubber, brominated butyl rubber, chlorinated ethylene propylene rubber, brominated ethylene propylene rubber and halogen sulfonated ethylene propylene rubber.

9. The rubber composition of claim 8, wherein the halogen-containing branched polyethylene comprises 0.2 to 51.3% by weight of halogen in the halogen-containing branched polyethylene, and the halogen-containing branched polyethylene comprises at least one of chlorinated branched polyethylene and brominated branched polyethylene.

10. The rubber composition of claim 9, wherein the halogen-containing branched polyethylene is chlorinated branched polyethylene, and wherein chlorine is present in an amount of 0.5 to 45.5% by weight of the chlorinated branched polyethylene.

11. The rubber composition of claim 9, wherein the halogen-containing branched polyethylene is brominated branched polyethylene, and wherein the bromine content is 0.8-4% by weight of the brominated branched polyethylene.

12. The rubber composition of claim 1, wherein the cure system is selected from at least one of a peroxide cure system, a sulfur cure system, a thiourea cure system, a metal oxide cure system, and a radiation cure sensitized system.

13. The rubber composition of claim 12, wherein the curing system is a peroxide curing system, the amount of the peroxide is 1-10 parts by weight based on 100 parts by weight of the rubber matrix, and the peroxide crosslinking agent is at least one of di-tert-butyl peroxide, dicumyl peroxide, tert-butyl cumyl peroxide, 1-di-tert-butyl peroxide-3, 3, 5-trimethylcyclohexane, 2, 5-dimethyl-2, 5-di (tert-butylperoxy) hexane, 2, 5-dimethyl-2, 5-di-tert-butylperoxy-3-hexyne, bis (tert-butylperoxyisopropyl) benzene, 2, 5-dimethyl-2, 5-di (peroxybenzoic acid) hexane, tert-butyl peroxybenzoate and tert-butylperoxy-2-ethylhexyl carbonate.

14. The rubber composition of claim 13, wherein the peroxide curing system further comprises 0.2-20 parts by weight of an auxiliary crosslinking agent, and the auxiliary crosslinking agent comprises at least one of triallyl cyanurate, triallyl isocyanurate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, triallyl trimellitate, trimethylolpropane trimethacrylate, N '-m-phenylene bismaleimide, N' -difurfurylacetone, 1, 2-polybutadiene, metal salts of unsaturated carboxylic acids, and sulfur.

15. The rubber composition according to claim 1, wherein the compounding ingredients further comprise, based on 100 parts by weight of the rubber base, 10 to 200 parts of a reinforcing filler, 0 to 80 parts of a plasticizer, 3 to 30 parts of a metal oxide, 0 to 3 parts of stearic acid, 0 to 15 parts of a surface modifier, 0 to 6 parts of a stabilizer, 0 to 5 parts of a tackifier, 0 to 20 parts of an adhesive, 0 to 150 parts of a flame retardant, 0 to 20 parts of a foaming agent, and 0 to 30 parts of a gas barrier agent.

16. A tire characterized in that at least one of the rubber compounds used for the sidewall and the tread of the tire comprises the rubber composition according to any one of claims 1 to 15.

17. A tyre as claimed in claim 16, wherein said tyre is a cycle tyre.

18. A vibration-damping mount characterized in that the rubber used comprises the rubber composition according to any one of claims 1 to 15.

19. A rubber plug characterized in that the rubber used comprises the rubber composition according to any one of claims 1 to 15.

20. An inner tube, wherein the rubber used comprises the rubber composition according to any one of claims 1 to 15.

21. A tubeless tire comprising an inner liner, wherein a rubber for the inner liner comprises the rubber composition according to any one of claims 1 to 15.

22. A conveyor belt, comprising working surface covering rubber and non-working surface covering rubber, wherein a tensile layer is arranged between the working surface covering rubber and the non-working surface covering rubber, and the conveyor belt is characterized in that at least one layer of rubber used in the working surface covering rubber and the non-working surface covering rubber comprises the rubber composition disclosed in any one of claims 1-15.

23. A canvas core conveyer belt is characterized in that an adhesive layer is arranged between covering rubber and impregnated canvas of the canvas core conveyer belt, wherein the rubber used for the adhesive layer comprises the rubber composition according to any one of claims 1 to 15, and the canvas is any one of cotton canvas, vinylon canvas, nylon canvas, polyester canvas, diameter straight weft polyester-nylon canvas and aramid canvas.

24. A cord conveyor belt, characterized in that the rubber used for the core rubber of the cord conveyor belt comprises the rubber composition of any one of claims 1 to 15, and the cord is a steel cord or a polymer cord.

25. A conveyor belt comprising a cushion rubber between a cover rubber and an adhesive rubber, wherein the rubber for the cushion rubber comprises the rubber composition according to any one of claims 1 to 15.

26. A hose comprising an inner rubber layer and an outer rubber layer, wherein at least one of the inner rubber layer and the outer rubber layer comprises the rubber composition of any one of claims 1 to 15.

27. A rubber tube, from inside to outside, comprises an inner rubber layer, a middle rubber layer and an outer rubber layer, and is characterized in that rubber used for at least one of the inner rubber layer, the middle rubber layer and the outer rubber layer comprises the rubber composition disclosed in any one of claims 1-15.

28. A power transmission belt, comprising: a body having a predetermined length and comprising a cushion rubber layer and a compression rubber layer, wherein at least one of the cushion rubber layer and the compression rubber layer is made of a rubber composition as recited in any one of claims 1 to 15.

29. Rubber roll, characterized in that the rubber used comprises a rubber composition according to any one of claims 1 to 15.

30. A cable, wherein a rubber for at least one of a sheath layer and an insulation layer comprises the rubber composition according to any one of claims 1 to 15.

31. An electric wire characterized in that a rubber for an insulating layer comprises the rubber composition according to any one of claims 1 to 15.

32. A waterproof roll characterized in that a rubber used for an insulating layer contains the rubber composition according to any one of claims 1 to 15.

Technical Field

The invention belongs to the technical field of rubber, and particularly relates to an anti-aging polar rubber composition, a processing method and application thereof.

Background

The highly branched polyethylene is an elastomer obtained by homopolymerization of ethylene, has relatively low raw material cost, has excellent aging resistance as a polyolefin elastomer with saturated molecular chains, can be applied to the fields of sealing elements, wires and cables, waterproof rolls, heat-resistant conveying belts, heat-resistant rubber tubes and the like, is a nonpolar material due to the fact that the molecular structure of the highly branched polyethylene only contains carbon and hydrogen elements and is completely saturated, and has poor performances related to polarity such as cohesiveness, oil resistance, dyeing property, flame retardance, blending compatibility with polar materials and the like, and the application range of the highly branched polyethylene is limited.

Disclosure of Invention

Aiming at the problems in the prior art, the invention provides an anti-aging polar rubber composition based on hyperbranched polyethylene, and the rubber matrix of the composition at least comprises one of polarization-modified hyperbranched polyethylene and other anti-aging elastomers which have polarity and good compatibility with the hyperbranched polyethylene, so that the rubber composition has good anti-aging property and certain polarity as a whole, and the application range of the branched polyethylene can be effectively widened.

In order to achieve the purpose, the invention adopts the technical scheme that: a rubber composition comprises a rubber matrix and compounding ingredients, wherein each 100 parts of the rubber matrix comprises 0-99 parts by weight of hyperbranched polyethylene P1, 0-100 parts by weight of hyperbranched polyethylene P1 and a reactant P2 of a polar monomer, 0-50 parts by weight of a reactant P3 of a copolymer of ethylene and alpha-olefin and a polar monomer, and 0-50 parts by weight of a reactant P4 of a copolymer of mono-olefin and diene monomer, which is binary or ternary or more, and a polar monomer, wherein the sum of the contents of P1 and P2 is 50-100 parts, and the sum of the contents of P2, P3 and P4 is not less than 3 parts; wherein P1 is an ethylene homopolymer with a branched structure, and the branching degree of the ethylene homopolymer is not less than 50 branches/1000 carbons; the compounding component comprises a vulcanization system.

The highly Branched Polyethylene used in the invention is an ethylene homopolymer with the branching degree of not less than 50 branches/1000 carbons, which can be called Branched Polyethylene or Branched PE, and the synthesis method of the highly Branched Polyethylene is mainly obtained by catalyzing ethylene homopolymerization by a late transition metal catalyst based on a chain walking mechanism, and the preferred late transition metal catalyst can be one of (alpha-diimine) nickel/palladium catalysts. The essence of the chain walking mechanism means that a late transition metal catalyst, such as an (alpha-diimine) nickel/palladium catalyst, is easy to generate beta-hydrogen elimination reaction and reinsertion reaction in the process of catalyzing olefin polymerization, so that branched chains are generated. The branched chain of the main chain of the highly branched polyethylene can have different carbon atoms, and specifically, the number of the carbon atoms can be 1-6, or more.

The production cost of the (alpha-diimine) nickel catalyst is obviously lower than that of the (alpha-diimine) palladium catalyst, and the catalyst is more suitable for industrial application, so the invention preferably selects the highly branched polyethylene prepared by ethylene polymerization catalyzed by the (alpha-diimine) nickel catalyst.

The branching degree of the highly branched polyethylene raw material used in the invention is not less than 50 branches/1000 carbons, and the weight average molecular weight is not less than 6.6 ten thousand; the degree of branching is more preferably 60 to 130 branches/1000 carbons, and the weight average molecular weight is more preferably 6.6 to 51.8 ten thousand; the degree of branching is more preferably 70 to 120 branches/1000 carbons, and the weight average molecular weight is more preferably 8.2 to 43.6 ten thousand. The Mooney viscosity is preferably 6 to 102, and more preferably 12 to 93.

The alpha-olefin in the copolymer of ethylene and alpha-olefin used in the invention has 3-30 carbon atoms, and the alpha-olefin comprises at least one of propylene, 1-butene, 1-pentene, 3-methyl-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, 1-docosene, 1-tetracosene, 1-hexacosene, 1-dioctadecene and 1-triacontene. Specifically, the copolymer of ethylene and α -olefin may be selected from at least one of ethylene propylene copolymer, ethylene butene copolymer, ethylene hexene copolymer and ethylene octene copolymer, preferably ethylene butene copolymer or ethylene octene copolymer.

The binary copolymer of a monoolefin and a diene monomer used in the present invention is preferably a copolymer of isobutylene and isoprene, and may be specifically butyl rubber.

The ternary or higher copolymer of the monoolefin and the diene monomer used in the present invention is preferably an ethylene-propylene-diene rubber, and the third monomer may specifically be selected from the group consisting of 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene, dicyclopentadiene, 1, 4-hexadiene, 1, 5-hexadiene, 1, 4-pentadiene, 2-methyl-1, 4-pentadiene, 3-methyl-1, 4-hexadiene, 4-methyl-1, 4-hexadiene, 1, 9-decadiene, 5-methylene-2-norbornene, 5-amylidene-2-norbornene, 1, 5-cyclooctadiene, 1, 4-cyclooctadiene and the like, preferably 5-ethylidene-2-norbornene, ethylene-propylene-diene rubber, 5-vinyl-2-norbornene, dicyclopentadiene, 1, 4-hexadiene.

In the present invention, the polar monomer used for preparing P2, P3 and P4 may be selected from Maleic Anhydride (MAH), Methacrylic Acid (MA), Acrylic Acid (AA), Itaconic Acid (IA), Fumaric Acid (FA), isocyanate, Glycidyl Methacrylate (GMA), Methyl Methacrylate (MMA), dibutyl fumarate (DBF), beta-hydroxyethyl methacrylate (HEMA), dibutyl maleate (DBM), diethyl maleate (DEM), elementary halogen (e.g., liquid chlorine, liquid bromine, etc.), halogen-containing compound (e.g., N-bromosuccinimide, bromodimethylhydantoin, carbon-adsorbed chlorine, carbon-adsorbed bromine, etc.), sulfur-containing compound (e.g., sulfur dioxide, sulfinyl chloride, etc.), Vinyltrimethoxysilane (VTMS), Vinyltriethoxysilane (VTES), 3-methacryloxypropyltrimethoxysilane (VMMS), Styrene (St), α -methylstyrene (α -MSt), Acrylonitrile (AN), etc., and the polar monomer used preferably contains at least one of the above polar monomers.

The preparation method of the P2 used in the invention can be that the highly branched polyethylene and the polar monomer are grafted under the action of one or more of free radical initiator, high temperature, high shearing force, high energy radiation, ultrasonic wave and the like by the solution grafting method, the swelling grafting method, the hot-melt grafting method, the radiation grafting method, the emulsion grafting method, the suspension grafting method and the like, and the conventional preparation method is that the grafting reaction is carried out under the action of the free radical initiator by the solution method or the melt method. The solvent used in the solution grafting method comprises toluene, xylene, benzene, n-hexane, cyclohexane, n-heptane, carbon tetrachloride, chlorobenzene, trichlorobenzene, etc. or a mixed solvent of the above solvents. Wherein the polar monomer used may be one kind or two or more kinds. In order to improve the grafting efficiency or inhibit the side reactions such as degradation or crosslinking in the grafting reaction process, two or more than two multi-monomer grafting modification technologies can be adopted, for example, styrene is used as a monomer, so that the grafting efficiency can be improved or the side reactions such as degradation or crosslinking in the grafting reaction process can be inhibited, and the grafting effect can be improved.

In the present invention, P2 may be selected from highly branched polyethylene-grafted maleic anhydride, highly branched polyethylene-grafted acrylonitrile, highly branched polyethylene-grafted styrene, halogen-containing highly branched polyethylene, and the like, and P2 is preferably halogen-containing branched polyethylene in which the polar group contains at least one of a chlorine group, a bromine group, a chlorosulfonyl group, and a bromosulfonyl group, from the viewpoint of cost. The polar monomer is preferably at least one of elementary halogen, halogen-containing compound or sulfur-containing compound, more preferably elementary chlorine or elementary bromine, and the halogen content is preferably 0.2% to 51.3%. The reaction method is preferably to react with chlorine or liquid bromine under the action of a free radical initiator by a solution method to obtain chlorinated branched polyethylene or brominated branched polyethylene, wherein the chlorine content is preferably 0.5-45.5%, or 0.5-35.6%, or 0.5-25.6%, or 1.2-10.4%, or 1.2-6.3%, or 3.1-25.6%, or 10.4-35.6%; the bromine content is preferably 0.5% to 4%, more preferably 0.8% to 4%, and still more preferably 1% to 3.2%; the branched polyethylene can be further sulfonated in the chlorination process, and the content of the sulfur element is preferably 0.5-2%.

Can further react with polar monomers such as maleic anhydride, acrylonitrile, styrene and the like on the basis of chlorination or bromination to obtain more targeted modified highly branched polyethylene.

The P3 used in the invention can be selected from halogenated ethylene propylene rubber, halogenated ethylene octene copolymer, maleic anhydride modified ethylene propylene rubber or maleic anhydride modified ethylene octene copolymer, etc.

The P4 used in the invention can be selected from chlorinated ethylene propylene diene monomer, brominated ethylene propylene diene monomer, chlorosulfonated ethylene propylene diene monomer, maleic anhydride modified ethylene propylene diene monomer, acrylonitrile modified triethylene propylene rubber, chlorinated butyl rubber, brominated butyl rubber and the like.

Among the above P3 and P4, P4 is preferable, and chlorinated butyl rubber or brominated butyl rubber is more preferable, from the viewpoint of market maturity. The chlorinated butyl rubber can improve the adhesive property of the rubber composition, enrich the selectable vulcanization system of the rubber composition, improve the dynamic properties such as dynamic ozone aging resistance and damping property, and is more suitable for the application fields of tire walls, conveyer belts, shock absorption pieces and the like.

The rubber composition of the present invention has a vulcanizing system selected from a peroxide vulcanizing system, a sulfur vulcanizing system, a thiourea vulcanizing system, a thiadiazole vulcanizing system, a triazole dimercaptoamine salt vulcanizing system, a metal oxide vulcanizing system, a phenolic resin vulcanizing system, an N, N' -m-phenylene bismaleimide vulcanizing system, a radiation vulcanization sensitization system, etc., and is preferably selected from at least one of a peroxide vulcanizing system, a sulfur vulcanizing system, a thiourea vulcanizing system, a metal oxide vulcanizing system, and a radiation vulcanization sensitization system.

The peroxide vulcanization system comprises a peroxide crosslinking agent and an auxiliary crosslinking agent, and the further technical scheme is that the amount of the peroxide crosslinking agent is 2-10 parts and the amount of the auxiliary crosslinking agent is 0.2-10 parts based on 100 parts by weight of the rubber matrix. Wherein the peroxide crosslinking agent comprises at least one of di-tert-butyl peroxide, dicumyl peroxide, tert-butylcumyl peroxide, 1-di-tert-butyl peroxide-3, 3, 5-trimethylcyclohexane, 2, 5-dimethyl-2, 5-di (tert-butylperoxy) hexane, 2, 5-dimethyl-2, 5-di (tert-butylperoxy) hexyne-3, bis (tert-butylperoxyisopropyl) benzene (BIBP), 2, 5-dimethyl-2, 5-di (benzoylperoxy) hexane (DBPMH), tert-butyl peroxybenzoate and tert-butylperoxy-2-ethylhexyl carbonate, and the auxiliary crosslinking agent comprises triallyl cyanurate, triallyl isocyanurate, ethylene glycol dimethacrylate, tert-butylcumyl peroxide, Ethyl dimethacrylate, triethylene dimethacrylate, triallyl trimellitate, trimethylolpropane trimethacrylate, ethylene glycol dimethacrylate, N '-m-phenylene bismaleimide (HVA-2), N' -difurfurylideneacetone, 1, 2-polybutadiene, p-quinonedioxime, sulfur, and at least one of metal salts of unsaturated carboxylic acids including at least one of zinc acrylate, zinc methacrylate (ZDMA), magnesium methacrylate, calcium methacrylate, and aluminum methacrylate. The addition of a suitable amount of metal salt of unsaturated carboxylic acid, such as zinc methacrylate, is effective in improving the physical and mechanical properties, especially tensile strength, of the vulcanizate. The HVA-2 is taken as an auxiliary crosslinking agent to accelerate the vulcanization speed, improve the crosslinking density and improve the crosslinking network, and under the condition that halogenated butyl rubber exists in a rubber matrix, the HVA-2 can also be taken as a vulcanizing agent of the halogenated butyl rubber, so that the improvement of the co-vulcanization property of P1 or P2 and the halogenated butyl rubber is facilitated, and the overall performance of the rubber compound is further improved.

The sulfur vulcanization system comprises sulfur and an accelerator, and the further technical scheme is that the sulfur is used in an amount of 0.3-2 parts and the accelerator is used in an amount of 0.5-3 parts based on 100 parts by weight of the rubber matrix. The accelerator may be at least one selected from the group consisting of 2-mercaptobenzothiazole, dibenzothiazyl disulfide, tetramethylthiuram monosulfide, tetramethylthiuram disulfide, tetraethylthiuram disulfide, N-cyclohexyl-2-benzothiazylsulfenamide, N-dicyclohexyl-2-benzothiazylsulfenamide, bismaleimide, and 1, 2-ethylenethiourea. The sulfur vulcanization system can further comprise 3-6 parts of zinc oxide and 0-1 part of magnesium oxide based on 100 parts of the rubber matrix. When the technical scheme that the peroxide vulcanization system and the sulfur vulcanization system are used together is adopted, a certain amount of ethylene propylene diene monomer can be contained in the rubber matrix to improve the overall co-vulcanization property of the rubber composition, and specifically, 0-30 parts of ethylene propylene diene monomer is contained in each 100 parts by weight of the rubber matrix.

The thiourea curing system is generally composed of thiourea and a small amount of sulfur, wherein the thiourea may be selected from ethylthiourea or ethylenethiourea. The thiourea curing system can cure the halogenated branched polyethylene with higher halogen content, the curing mechanism is similar to that of the conventional Chlorinated Polyethylene (CPE), the thiourea curing system is also suitable for curing the halogenated butyl rubber, and the halogenated butyl rubber vulcanized by the thiourea has good heat resistance and high mechanical strength, so when the rubber composition of the invention simultaneously contains the branched polyethylene with high halogen content and the halogenated butyl rubber, the certain thiourea component contained in the curing system is beneficial to improving the co-curing property and the mechanical strength.

The thiadiazole vulcanization system and the triazole dimercaptoamine salt vulcanization system are suitable for rubber compositions with vulcanized rubber matrixes with higher halogen content. The thiadiazole vulcanization system consists of a cross-linking agent and an accelerant, wherein the cross-linking agent is mainly a thiadiazole derivative cross-linking agent, commonly comprises ECHO.A, TDD, PT75, TDDS and the like, and commonly comprises Vanax 808, EataAccelDH, NC, Accel 903, BF and the like. And mixing with a certain amount of acid acceptor such as high-activity magnesium oxide or superfine magnesium hydroxide. The triazole dimercapto amine salt vulcanizing system is a single substance integrating effective groups of a thiadiazole vulcanizing agent and an accelerant (a condensate of n-butyl aldehyde and aniline), overcomes the defect of irregular distribution of bonds after the thiadiazole and the accelerant crosslink rubber, and enables the rubber crosslinked body to be a stable structure. Compared with a thiadiazole system, the salt changes the pH value of the system due to the introduction of special groups, changes strong acidity into neutrality, changes the adverse effect of acidic fillers on the system, and enables rubber to have more chemical activity during crosslinking. Therefore, the physical property or the chemical property of the cross-linked rubber of the system is improved. The vulcanizing agent is suitable for the low-temperature pressureless low-pressure vulcanizing process conditions, has high vulcanizing speed, small addition amount, no decomposition in the vulcanizing temperature, no odor, environmental protection and no toxicity. Representative products are: vulcanizing agent FSH, cross-linking agent TEHC.

The metal oxide cure system comprises zinc oxide, further comprising magnesium oxide, which has the effect of a scorch retarder, and stearic acid, which has the effect of assisting the dispersion of the metal oxide and regulating the rate of vulcanization, in the presence of a halogenated butyl rubber in the rubber matrix.

The main component of the radiation vulcanization sensitization system is a radiation sensitizer which can be selected from triallyl cyanurate, triallyl isocyanurate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, trimethylolpropane trimethacrylate and the like. The radiation sensitization system is particularly suitable for the application field of wires and cables with requirements on electrical insulation performance or medical rubber products with higher requirements on material cleanliness.

The rubber composition further comprises, by weight, 100 parts of a rubber matrix, 10-200 parts of a reinforcing filler, 0-80 parts of a plasticizer, 3-30 parts of a metal oxide, 0-3 parts of stearic acid, 0-15 parts of a surface modifier, 0-6 parts of a stabilizer, 0-5 parts of a tackifier, 0-20 parts of an adhesive, 0-150 parts of a flame retardant, 0-20 parts of a foaming agent and 0-40 parts of a gas barrier agent.

The further technical scheme is that the reinforcing filler comprises at least one of carbon black, white carbon black, calcium carbonate, calcined argil, talcum powder, magnesium silicate, aluminum silicate, magnesium carbonate, titanium dioxide, montmorillonite, short fiber, kaolin and bentonite.

The further technical scheme is that the plasticizer comprises at least one of pine tar, engine oil, naphthenic oil, paraffin oil, aromatic oil, liquid 1, 2-polybutadiene, liquid polyisobutylene, ethylene glycol dimethacrylate, liquid ethylene propylene rubber, coumarone, RX-80, stearic acid, paraffin, chlorinated paraffin, dioctyl adipate, dioctyl sebacate, epoxidized soybean oil, dibutyl phthalate, dioctyl phthalate, diisodecyl phthalate, ditridecyl phthalate and trioctyl trimellitate. For improving the viscosity, it is also preferable to use a plasticizer having a thickening effect, such as pine tar, coumarone, RX-80, liquid polyisobutylene, ethylene glycol dimethacrylate, etc. In order to improve cold resistance, dioctyl adipate, dioctyl sebacate, dioctyl phthalate, and the like can be preferably used. For halogen-containing rubber matrices, epoxidized soybean oil has the effect of stabilizing the rubber matrix during processing.

The further technical scheme is that the metal oxide comprises at least one of zinc oxide, magnesium oxide, aluminum oxide, lead oxide and calcium oxide. The metal oxide may assist in crosslinking and absorb hydrogen chloride or hydrogen bromide.

The stabilizer is selected from 2,2, 4-trimethyl-1, 2-dihydroquinoline polymer (RD), 6-ethoxy-2, 2, 4-trimethyl-1, 2-dihydroquinoline (AW), 2-Mercaptobenzimidazole (MB), N-phenyl-N ' -cyclohexyl-p-phenylenediamine (4010), N-isopropyl-N ' -phenyl-p-phenylenediamine (4010NA), N- (1, 3-dimethyl) butyl-N ' -phenyl-p-phenylenediamine (4020), etc., and the stabilizer can be further selected from basic lead salt compounds, metal soap compounds, organotin compounds, epoxy compounds, phosphite compounds, etc. for rubber compositions with high halogen content in the rubber matrix, And polyhydric alcohol compounds, wherein the basic lead salt compound is selected from lead stearate, dibasic lead titanate, basic lead silicate, lead phthalate, and the like.

The further technical scheme is that the flame retardant comprises at least one of pentaerythritol, ammonium polyphosphate, triethyl phosphate, aluminum hydroxide, magnesium hydroxide, zinc borate, antimony trioxide, zinc stearate, titanate, decabromodiphenyl ether, hydroxide modified by a silane coupling agent and red phosphorus. The aluminum hydroxide, the magnesium hydroxide and the hydroxide modified by the silane coupling agent are respectively nano aluminum oxide and nano magnesium hydroxide and nano hydroxide modified by the silane coupling agent, and the red phosphorus is microencapsulated red phosphorus.

The further technical proposal is that the surface modifier comprises at least one of polyethylene glycol, diphenyl silanediol, triethanolamine, silane coupling agent and titanate coupling agent.

The adhesive comprises at least one of resorcinol donor, methylene donor, organic cobalt salt, maleic anhydride butadiene resin and liquid natural rubber. The resorcinol donor may be selected from at least one of resorcinol (adhesive R), adhesive RS-11, adhesive R-80, adhesive RL, adhesive PF, adhesive PE, adhesive RK, adhesive RH; the methylene donor may be at least one selected from the group consisting of Hexamethylenetetramine (HMTA), adhesive H-80, adhesive A, adhesive RA, adhesive AB-30, adhesive Rq, adhesive RC, adhesive CS963, and adhesive CS 964. Organic cobalt salts such as cobalt boracylate are effective in improving the adhesive strength between the rubber composition and metal. The further technical scheme is that the adhesive can also be selected from triazine adhesive, and the specific commercial brand can be selected from at least one of adhesive TAR, adhesive TZ, adhesive AIR-1 and adhesive AIR-101, preferably at least one of adhesive AIR-1 and adhesive AIR-101, can partially replace the resorcinol donor adhesive, and has the advantages of good adhesive property and relative environmental protection. The synergistic effect of the bonding system and the white carbon black can have good bonding property.

In the embodiment of the present invention, in order to improve the tackiness of the rubber compound, the rubber composition may further comprise a tackifier, and the plasticizer may be pine tar, coumarone resin, RX-80, or liquid polyisobutylene and may also function as a tackifier, wherein the liquid coumarone resin has better tackifying effect than solid coumarone resin, and the tackifier can be selected from C5 petroleum resin, C9 petroleum resin, Escorez 1102 resin, hydrogenated rosin, terpene resin, alkyl phenolic resin, modified alkyl phenolic resin, alkyl phenol-acetylene resin, metal salt of unsaturated carboxylic acid, etc., the tackifier is generally used in an amount of not more than 30 parts by weight based on 100 parts by weight of the rubber matrix, wherein the metal salt of unsaturated carboxylic acid such as methacrylate has the function of a stabilizer while improving the adhesive property, and improves the high temperature aging resistance of the rubber composition.

The foaming agent comprises at least one of sodium bicarbonate, Azodicarbonamide (AC), dinitrosopentamethylenetetramine (H), diphenyl sulfonyl hydrazide ether (OBSH), benzenesulfonyl hydrazide (BSH), urea and a microcapsule type foaming agent containing low-boiling-point hydrocarbon. The above rubber composition containing a foaming agent is particularly suitable for producing a light and elastic sole material.

According to a further technical scheme, the gas barrier agent can be selected from NM360 or EVOH. The addition of the gas barrier agent can enable the rubber composition of the invention to be better applied to occasions with requirements on air tightness.

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 has occurred. The vulcanized rubber may also be referred to simply as vulcanized rubber.

The invention also provides a processing method A of the rubber composition, and as the rubber matrixes of the invention are all nonpolar polymers or polarization modified substances of the nonpolar polymers and have good compatibility, the following processing methods can be selected, and the mixing process comprises the following steps:

(1) setting the temperature of an internal mixer and the rotating speed of a rotor;

(2) putting the rubber matrix into an internal mixer for mixing;

(3) sequentially adding the components except the vulcanization system in the matching components into an internal mixer according to the sequence of the dry auxiliary agent and the liquid auxiliary agent, and mixing until the power is stable;

(4) when the temperature of the internal mixer is proper, adding the components of the vulcanization system into the internal mixer for mixing, and then discharging rubber; or directly discharging rubber after the operation of the step (3), and adding a vulcanization system on an open mill with proper temperature;

(5) and (3) thinly passing, discharging, cooling, standing for 16-24 hours on an open mill or a multi-roll calender, and then back-milling to obtain the sheet.

When the rubber matrix comprises two or more than two components, the invention also provides another processing method B of the rubber composition, which specifically comprises the steps of dividing various rubber matrices into at least two groups by adopting a master batch method, preparing mixing master batch from each group of rubber matrices according to the steps 1-3 in the method A, then putting all the mixing master batches into an internal mixer or an open mill together for mixing, then adding a vulcanization system, and thinly passing through a lower sheet after uniform mixing.

When the rubber matrix comprises two or more than two components, the invention also provides another processing method C of the rubber composition, which specifically comprises the steps of dividing various rubber matrices into at least two groups by adopting a master batch method, preparing mixing master batch from each group of rubber matrices according to the steps of 1-4 in the method A, then putting all the mixing master batches into an internal mixer or an open mill together, mixing uniformly, and then thinly discharging the mixture.

The present invention provides a tire, wherein at least one of rubber compounds used for a sidewall and a tread thereof comprises the above rubber composition.

The tire provided by the invention can be a radial tire, a bias tire or a hand-drawn tire. The hand-drawn vehicle tyre may be bicycle tyre, hand-drawn vehicle tyre, animal-drawn vehicle tyre, electric vehicle tyre, etc. Cycle tires may be preferred, in particular, as white or colored bicycle tires.

The rubber composition of the present invention can be used as a side rubber to manufacture a tire by a usual method. That is, the rubber compound is extruded in accordance with the shape of the side wall of the tire, and molded together with other tire members by a usual method on a tire molding machine to form an unvulcanized tire. The unvulcanized tire is heated and pressurized in a vulcanizer to obtain a tire.

The rubber composition of the present invention can be used as a tread rubber to manufacture a tire by a usual method. That is, the rubber compound is extruded in accordance with the tread shape of the tire design, and is molded together with other tire members by a usual method on a tire molding machine to form an unvulcanized tire. The unvulcanized tire is heated and pressurized in a vulcanizer to obtain a tire. The glass transition temperature of the branched polyethylene can be increased after grafting a part of the polar monomer (such as styrene), thereby being beneficial to improving the wet skid resistance when the branched polyethylene is used as a tread rubber.

The further technical scheme is that the sidewall and the tread of the tire simultaneously use the rubber composition provided by the invention to improve the co-vulcanization property and the adhesiveness between the sidewall and the tread, thereby improving the overall quality of the tire.

The steel wire or the fiber skeleton used in the tire is preferably one having a surface treated so as to be well adhered to a non-polar rubber. The surface treatment can be realized by soaking an RFL dipping system.

The invention also provides a damping support, wherein the rubber used in the damping support comprises the rubber composition, and the further technical scheme is that in order to reduce the influence of creep and stress relaxation on the performance of the rubber support, the use amount of the plasticizer in the rubber composition is preferably 0-15 parts, and low-molecular-weight polymer plasticizers such as liquid polyisobutylene, liquid ethylene propylene rubber and the like are further preferably selected. The damping support can be specifically a bridge plate type rubber support, a basin type rubber support, an engine damping support, an automobile oil-resistant damping pad, an automobile exhaust pipe damping support, a sleeper pad or a building shock insulation rubber support and the like. The rubber composition has good compression set resistance, flex fatigue resistance, high temperature resistance and ozone aging resistance, and can also have good performance on damping performance in the presence of halogenated butyl rubber.

The invention also provides a rubber plug, and the rubber used by the rubber plug comprises the rubber composition. The rubber plug provided by the invention has good aging resistance, acid and alkali resistance, compression permanent deformation resistance and good air tightness. The rubber plug can be used as a medical bottle plug, and the vulcanizing system of the rubber plug is preferably a zinc oxide vulcanizing system or a radiation crosslinking system. When a zinc oxide vulcanization system is used, the rubber matrix preferably contains halogenated butyl rubber and halogenated branched polyethylene, more preferably brominated butyl rubber and brominated branched polyethylene, and the brominated butyl rubber is preferably used in an amount of 40 to 50 parts by weight based on 100 parts by weight of the rubber matrix.

The invention also provides an inner tube, the rubber used in the inner tube comprises the rubber composition, and the inner tube has good processing effect in the inflating valve attaching process due to good adhesiveness of the rubber.

The invention also provides a tubeless tire which comprises an inner liner, wherein the rubber used for the inner liner comprises the rubber composition.

The invention also provides a conveyor belt, which comprises working surface covering rubber and non-working surface covering rubber, wherein at least one layer of the working surface covering rubber and the non-working surface covering rubber comprises the rubber composition. The rubber composition of the invention is used as the covering rubber of the conveyer belt, so that the adhesion performance between the covering rubber and the adhesive layer of the conveyer belt can be improved. And improves one or more of antistatic property, flame retardance, oil resistance and the like to a certain extent.

The invention also provides a canvas core conveyer belt, wherein the rubber used for the bonding layer of the canvas core conveyer belt comprises the rubber composition, and the canvas is any one of cotton canvas, vinylon canvas, nylon canvas, polyester canvas, diameter straight weft polyester-nylon canvas and aramid canvas. The further technical scheme is that every 100 parts by weight of rubber matrix of at least one layer of rubber used by the working surface covering rubber and the non-working surface covering rubber of the conveyer belt comprises 5-100 parts by weight of branched polyethylene or modified branched polyethylene.

The adhesive rubber for the canvas core conveyer belt or the rubber composition for the adhesive core rubber for the rope core conveyer belt can further comprise 2-5 parts of short fibers for improving the modulus and improving the overall modulus distribution of the conveyer belt. The short fiber is preferably a variety with the surface being pretreated and good blending performance with non-polar rubber.

The invention also provides a rope core conveying belt, wherein the rubber used for bonding the core rubber comprises the rubber composition, the rope core is a steel wire rope core or a polymer rope core, and the polymer rope core can be selected from aramid rope cores, ultra-high molecular weight polyethylene fiber rope cores and the like. The further technical scheme is that every 100 parts by weight of rubber matrix of at least one layer of rubber used by the working surface covering rubber and the non-working surface covering rubber of the conveyer belt comprises 5-100 parts by weight of branched polyethylene or modified branched polyethylene.

The invention also provides a conveyer belt, wherein a buffer rubber is arranged between the covering rubber and the adhesive rubber, and the rubber used by the buffer rubber comprises the rubber composition. The further technical scheme is that every 100 parts by weight of rubber matrix of at least one layer of rubber used by the working surface covering rubber and the non-working surface covering rubber of the conveyer belt comprises 5-100 parts by weight of branched polyethylene or modified branched polyethylene.

The invention also provides a single-layer rubber hose, and the rubber material used by the single-layer rubber hose comprises the rubber composition. The hose can be selected from water hose, oil hose, acid (alkali) hose and the like.

The invention also provides a rubber hose which comprises an inner rubber layer and an outer rubber layer, wherein at least one of the inner rubber layer and the outer rubber layer comprises the rubber composition. The rubber tube is selected from an air conditioner rubber tube, a brake rubber tube, a steam rubber tube, a vacuum rubber tube and the like.

The invention also provides a rubber tube which comprises an inner rubber layer, a middle rubber layer and an outer rubber layer, wherein at least one of the inner rubber layer, the middle rubber layer and the outer rubber layer comprises the rubber composition. The rubber tube can be selected from hydraulic rubber tubes such as automobile brake rubber tubes and mining hydraulic rubber tubes.

The invention further provides a rubber hose assembly matched with the rubber hose, wherein the rubber composition used for the outer rubber layer comprises the rubber composition.

The present invention also provides a power transmission belt comprising: a body having a predetermined length and comprising a cushion rubber layer and a compression rubber layer, wherein at least one of the cushion rubber layer and the compression rubber layer is made of a rubber containing the above rubber composition. The cushion rubber layer may use the same rubber matrix as the compression rubber layer, and may or may not contain the above short fibers, and preferably does not contain short fibers for the purpose of improving the adhesion property.

The load-bearing core wire in the buffer rubber layer is preferably of a variety having high strength and low elongation, and can be specifically selected from polyester fibers, aramid fibers, glass fibers, ultra-high molecular weight polyethylene fibers and the like, and the polyester fibers can be selected from polyarylate fibers, polybutylene terephthalate fibers, polyethylene terephthalate fibers, polypropylene terephthalate fibers, polyethylene naphthalate fibers and the like. The above-mentioned bearing core wire is preferably subjected to an adhesion treatment for improving the adhesion property of the bearing core wire to the rubber, and the adhesion treatment may be carried out by dipping the bearing core wire in a treatment solution such as resorcinol-formaldehyde latex (PFL dip) and heating to dry.

The power transmission belt according to the present invention further includes a reinforcing fabric, which is generally located outside the cushion rubber layer, and which may be a plain, twill, satin weave fabric of cotton fiber, polyester fiber, aramid fiber, polyamide fiber, ultra-high molecular weight polyethylene fiber, or the like, and preferably a rubber canvas coated with a rubber composition and subjected to RFL treatment is used as the reinforcing fabric.

The further technical scheme aiming at the power transmission belt is as follows: the compression rubber layer further comprises 10-80 parts by weight of solid lubricant based on 100 parts by weight of the rubber substrate, wherein the solid lubricant comprises at least one of graphite, mica, molybdenum disulfide and polytetrafluoroethylene, and the solid lubricant is further preferably 10-60 parts by weight.

Transmission belts produced using the rubber compositions provided by the present invention as compression layer compounds also include, but are not limited to, the following types: the belt is a cloth wrapping type common V belt, a cloth wrapping type narrow V belt, a cloth wrapping type combined belt, a cloth wrapping type agricultural machine belt, a hexagonal belt, an edge cutting type V belt, an edge cutting type narrow V belt, an edge cutting type combined V belt, an edge cutting type mechanical variable speed V belt, an edge cutting type industrial variable speed V belt, a motorcycle variable speed V belt, a poly V belt and the like.

The power transmission belt of the invention is not limited to the above configuration. For example, a V-belt without a cushion rubber layer, a V-belt provided with a backing rubber layer instead of a reinforcing fabric and rubber exposed to the back of the belt are also included in the technical scope of the present invention.

The invention also provides a synchronous belt, and the rubber used by the synchronous belt comprises the rubber composition.

The invention also provides a rubber roller, and the rubber used by the rubber roller comprises the rubber composition.

The invention also provides a cable, wherein the rubber used in at least one of the sheath layer and the insulation layer comprises the rubber composition.

The invention also provides an electric wire, and the rubber used for the insulating layer of the electric wire comprises the rubber composition.

The invention also provides a waterproof coiled material, and the rubber material used by the waterproof coiled material comprises the rubber composition. It has better binding workability.

The invention has the beneficial effects that:

(1) the limit of nonpolar of the highly branched polyethylene is effectively overcome, the rubber composition with aging resistance and certain polarity is provided, the use range of the highly branched polyethylene as an elastomer is widened, and the highly branched polyethylene elastomer is more suitable for occasions with requirements on performances related to polarity, such as cohesiveness, oil resistance and the like;

(2) the rubber composition can be improved in one or more aspects of crosslinking speed, crosslinking efficiency, mechanical strength, wear resistance, gas barrier property and the like according to different processing and application requirements.

Detailed Description

The following examples are given to further illustrate the present invention, but not to limit the scope of the present invention, and those skilled in the art should be able to make certain insubstantial modifications and adaptations of the invention based on the teachings of the present invention.