WO2020011003A1 - 橡胶组合物及加工方法，及应用其的橡胶制品和生产方法 - Google Patents

橡胶组合物及加工方法，及应用其的橡胶制品和生产方法 Download PDF

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WO2020011003A1
WO2020011003A1 PCT/CN2019/092642 CN2019092642W WO2020011003A1 WO 2020011003 A1 WO2020011003 A1 WO 2020011003A1 CN 2019092642 W CN2019092642 W CN 2019092642W WO 2020011003 A1 WO2020011003 A1 WO 2020011003A1
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rubber
parts
rubber composition
composition according
ethylene
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French (fr)
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徐涛
傅智盛
吴安洋
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Hangzhou Xinglu Technology Co Ltd
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Hangzhou Xinglu Technology Co Ltd
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    • A43B13/04—Plastics, rubber or vulcanised fibre
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    • B60—VEHICLES IN GENERAL
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Definitions

  • the present invention belongs to the field of rubber, and particularly relates to a rubber composition and a processing method thereof.
  • the present invention also relates to the application of the rubber composition and a method for producing the rubber product.
  • Butadiene copolymer elastomers occupy an important position in the field of synthetic rubber, of which styrene-butadiene rubber has the largest production capacity.
  • Styrene butadiene rubber has excellent mechanical properties and abrasion resistance with the addition of reinforcing agents, but the heat aging resistance, weather resistance and ozone aging resistance are weak. This is because the molecular chain structure contains double bonds, which is easy. Destruction occurs under the influence of high temperature or ozone, which causes the performance of rubber to deteriorate.
  • Ethylene-propylene rubber is highly saturated and has a stable chemical structure, so it has excellent aging resistance, but its abrasion resistance is weaker than styrene-butadiene rubber.
  • a method in which ethylene-propylene rubber and styrene-butadiene rubber are used in combination is generally used to improve the heat aging resistance, weather resistance and ozone aging resistance of styrene-butadiene rubber, or to improve the wear resistance of ethylene-propylene rubber.
  • Viscosity so that a small amount of ethylene-propylene rubber can be a continuous phase, so that styrene-butadiene rubber is coated in ethylene-propylene rubber, but because of excessive low-molecular-weight plasticizers, the abrasion resistance of the rubber compound is poor.
  • the plan also has obvious limitations.
  • the object of the present invention is to provide a new rubber composition that is more excellent in comprehensive performance in terms of aging resistance, mechanical properties and abrasion resistance.
  • the technical solution proposed by the present invention is to use a branched polyethylene to partially or completely replace the ethylene-propylene rubber in the prior art in combination with a butadiene copolymer elastomer.
  • the branched polyethylene used in the present invention is a type of ethylene homopolymer with a degree of branching of not less than 50 branches / 1000 carbons.
  • its synthesis method mainly uses ( ⁇ -diimide) nickel / palladium catalyst through compounding In situ polymerization catalyzes homopolymerization of ethylene.
  • the molecular chain of the branched polyethylene is completely saturated, and the aging resistance is similar to or better than that of ethylene-propylene rubber.
  • the branched polyethylene has a rich branching distribution, compared to ethylene-propylene rubber whose branching is mainly methyl, the regularity of the molecular chain can be destroyed to a greater extent.
  • the present invention can provide a rubber composition having both good aging resistance, mechanical properties and abrasion resistance.
  • the present invention provides a rubber composition
  • a rubber composition comprising a rubber base, a reinforcing filler and a cross-linking agent, characterized in that, based on parts by weight, the rubber base contains more than 0 parts per 100 parts without More than 99 parts of branched polyethylene, 0 to 75 parts of ethylene-propylene rubber and 1 to 95 parts of butadiene copolymer elastomer, of which branched polyethylene is an ethylene homopolymer having a branched structure.
  • the branched polyethylene has a branching degree 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) at 125 ° C of not less than 2.
  • a further technical solution is that the said rubber matrix contains 5 to 95 parts of branched polyethylene per 100 parts by weight.
  • a further technical solution is that the degree of branching of the branched polyethylene is 50 to 150 branches / 1000 carbons.
  • a further technical solution is that the degree of branching of the branched polyethylene is 60 to 130 branches / 1000 carbons.
  • a further technical solution is that the weight average molecular weight of the branched polyethylene is 66,000 to 518,000, and the Mooney viscosity ML (1 + 4) is 6 to 102 at 125 ° C.
  • Branched polyethylene with a lower degree of branching has a higher molecular weight and Mooney viscosity, and even has a melting point above room temperature.
  • the addition of such branched polyethylene in a combined system can give the overall good aging resistance and wear resistance. Properties, increase rubber stiffness and improve process performance.
  • Branched polyethylene with a higher degree of branching has a lower molecular weight and Mooney viscosity, which can be used to improve the processing properties of ethylene-propylene rubber or branched polyethylene with a slightly lower degree of branching, and make the latter easier to form continuous Phase, so that in the case of a higher specific gravity of styrene-butadiene rubber, it gives better overall aging resistance.
  • the ethylene-propylene rubber comprises at least one of ethylene-propylene rubber, ethylene-propylene rubber and ethylene-propylene rubber.
  • the comonomers of the EPDM rubber and the EPDM rubber include diene monomers, and the diene monomers include 5-ethylene- At least one of 2-norbornene, 5-vinyl-2-norbornene, dicyclopentadiene, and 1,4-hexadiene.
  • diene monomer examples include 1,5-hexadiene, 1,4-pentadiene, 2-methyl-1,4-pentadiene, 3-methyl-1,4 -Hexadiene, 4-methyl-1,4-hexadiene, 1,9-decadiene, 5methylene-2-norbornene, 5-pentyl-2-norbornene, 1 , 5-cyclooctadiene, 1,4-cyclooctadiene, etc.
  • a further technical solution is that the weight ratio of the diene monomer to the ethylene-propylene rubber is 1% to 14%.
  • the ethylene-propylene rubber used is preferably a tertiary or quaternary ethylene-propylene rubber having a Mooney viscosity ML (1 + 4) of 125 to 125 ° C and a weight ratio of diene monomer of 4% to 10%.
  • the compatibility of the polyethylene is very good.
  • the masterbatch method is generally used.
  • Ethylene-propylene rubber and branched polyethylene are a kind of rubber matrix for the masterbatch.
  • the monomer content is high, the polarity of the masterbatch can be increased, and it can help the uniform dispersion of various fillers in the final rubber.
  • the third monomer can also act as a peroxide crosslinker.
  • the molecular chain of EPDM rubber can either co-crosslink sulfur and peroxide with the molecular chain of styrene-butadiene rubber, or co-crosslink with peroxide between branched polyethylene, thereby increasing the rubber.
  • the distribution of cross-linking bonds at the phase interface can further improve the overall co-vulcanizability and physical and mechanical properties, especially when ethylene-propylene rubber contains both 5-ethylene-2-norbornene (ENB) and 5-ethylene.
  • VNB methyl-2-norbornene
  • the butadiene copolymer elastomer comprises a butadiene-styrene copolymer, a butadiene-isoprene copolymer, and a butadiene-isoprene-styrene copolymer. At least one.
  • butadiene copolymer elastomer is styrene-butadiene rubber.
  • the styrene content in the styrene-butadiene rubber is 20% to 50% by weight
  • the 1,2 structure content in the butadiene portion is 10% to 65%
  • the trans-1,4 structure content is 15% to 75%
  • the Tg is- Between 65 and -20 ° C.
  • a further technical solution is that, based on 100 parts by weight of the rubber matrix, the rubber composition includes 10 to 200 parts of a reinforcing filler.
  • the reinforcing filler comprises carbon black, white carbon black, calcium carbonate, calcined clay, talc, magnesium silicate, aluminum silicate, magnesium carbonate, titanium dioxide, montmorillonite And at least one of short fibers.
  • the white carbon black is preferably white carbon black pretreated with alkylation, which is beneficial for improving the dispersion effect of the white carbon black in the rubber matrix of the present invention and improving the physical properties of the rubber.
  • Montmorillonite is preferably modified montmorillonite or nano-montmorillonite. Adding nano-layered montmorillonite is beneficial to improve the mechanical properties and wear resistance of vulcanizate.
  • a further technical solution is that, based on 100 parts by weight of the rubber matrix, the rubber composition includes 0.1 to 10 parts of a crosslinking agent.
  • the cross-linking agent includes at least one of a peroxide cross-linking agent and sulfur
  • the peroxide cross-linking agent is di-t-butyl peroxide, dicumyl peroxide ( DCP), tert-butylcumyl peroxide, 1,1-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-butylperisopropyl) benzene (BIPB ), At least one of 2,5-dimethyl-2,5-di (benzoic acid peroxide) hexane, tert-butyl peroxybenzoate, tert-butyl peroxy-2-ethylhexyl carbonate .
  • DCP di
  • extended scorch organic peroxide F40P-SP2 can be used, or BHT can be added and the amount of peroxide can be appropriately increased.
  • BHT can be added and the amount of peroxide can be appropriately increased.
  • add a cross-linking agent such as N, N'-m-phenylene bismaleimide, which has the effect of extending the scorch time.
  • styrene-butadiene rubber is preferably not filled with oil or naphthenic oil.
  • the rubber composition described above comprises 5 to 95 parts of branched polyethylene, 0 to 60 parts of ethylene-propylene rubber and 5 to 90 parts of styrene-butadiene rubber per 100 parts of the rubber matrix; Based on 100 parts by weight of the rubber matrix, the rubber composition includes 10 to 150 parts of a reinforcing filler and 1 to 8 parts of a crosslinking agent.
  • the rubber composition further includes an auxiliary component.
  • the auxiliary components include a cross-linking aid, a plasticizer, a metal oxide, stearic acid, a surface modifier, a stabilizer, a vulcanization accelerator, a compatibilizer, a tackifier, an adhesive, and a flame retardant. At least one of foaming agents.
  • a further technical solution is that, based on 100 parts by weight of the rubber matrix, the amount of the various auxiliary components used ranges from 0.2 to 10 parts of a cross-linking aid, 0 to 80 parts of a plasticizer, 3 to 30 parts of a metal oxide, and stearin. 0 to 3 parts of acid, 0 to 15 parts of surface modifier, 1 to 6 parts of stabilizer, 0 to 5 parts of vulcanization accelerator, 0 to 15 parts of compatibilizer, 0 to 5 parts of tackifier, 0 -20 parts, flame retardant 0 to 150 parts, foaming agent 0 to 20 parts.
  • the aforesaid co-crosslinking agent includes triallyl cyanurate, triallyl isocyanurate, ethylene glycol dimethacrylate, triethylene dimethacrylate, Triallyl trimellitate, trimethylolpropane trimethacrylate, N, N'-m-phenylenebismaleimide, N, N'-bisfurfurylacetone, 1,2-poly At least one of butadiene, unsaturated carboxylic acid metal salt, and sulfur.
  • liquid 1,2-polybutadiene or liquid polyisobutylene can not only help the crosslinking agent, but also the role of a plasticizer, and can also make the rubber material have a higher hardness after vulcanization, which is suitable for high Where hardness is required. But they are all viscous liquid substances, which are not conducive to adding during processing, so their application is limited to a certain extent.
  • a liquid auxiliary cross-linking agent can be pre-dispersed in a synthetic inorganic filler (such as calcium silicate) to form a polybutadiene powdery substance. It is very convenient to add during processing and has good properties with rubber compounds. Compatibility.
  • the unsaturated carboxylic acid metal salt includes at least one of zinc acrylate, zinc methacrylate, magnesium methacrylate, calcium methacrylate, and aluminum methacrylate.
  • Ionic crosslinking can occur when unsaturated carboxylic acid metal salts such as zinc acrylate or zinc methacrylate are used as peroxide cross-linking agents, and the ionic bonds show good thermal aging stability and slip characteristics.
  • the properties of oxide and sulfur vulcanization can give rubber a good tensile strength, tear strength and heat resistance.
  • unsaturated carboxylic acid metal salts can also be used as a binder to improve the adhesion of rubber compounds to synthetic fibers, metals or other rubber compounds.
  • the plasticizer includes at least one of stearic acid, rosin oil, motor oil, naphthenic oil, paraffin oil, coumarone, RX-80, paraffin, liquid polyisobutylene, and dioctyl sebacate.
  • the plasticizer includes at least one of stearic acid, rosin oil, motor oil, naphthenic oil, paraffin oil, coumarone, RX-80, paraffin, liquid polyisobutylene, and dioctyl sebacate.
  • the metal oxide includes at least one of zinc oxide, magnesium oxide, and calcium oxide.
  • Nano-zinc oxide, nano-magnesium oxide, or nano-calcium oxide having a particle size range of 10 to 100 nm is preferred, and a mixture of nano-zinc oxide and nano-magnesia is more preferred.
  • the amount of nano-metal oxide added is preferably 5-20 parts by mass.
  • the addition of metal oxides not only plays an activation role, but also nano-zinc oxide and nano-magnesium oxide can play the role of high temperature resistance, and can play a role of heat conduction for the vulcanization and application of thick products.
  • the nano-scale oxide has a large specific surface area and a large activity, which is conducive to absorbing the acidic substances released during the aging of the rubber, and has obvious protective effects.
  • the surface modifier includes at least one of polyethylene glycol, diphenylsilicon glycol, triethanolamine, a silane coupling agent, and a titanate coupling agent.
  • the molecular weight of polyethylene glycol is preferably 2000 or 3400 or 4000;
  • the silane coupling agent may be selected from, for example, vinyltriethoxysilane (A-151), vinyltrimethoxysilane (A-171), vinyltrimethoxysilane (2-methoxyethoxy) silane (A-172), ⁇ -glycidyl ether oxypropyltrimethoxysilane (A-187), ⁇ -mercaptopropyltrimethoxysilane (A-189), Bis ( ⁇ -triethoxysilylpropyl) tetrasulfide (Si69), ⁇ -aminopropyltriethoxysilane (KH-550), etc .
  • the titanate coupling agent may be selected from, for example, titanium di
  • silica When silica is contained in the reinforcing filler, it is preferred to add a surface modifier to reduce its activity to reduce the effect on vulcanization, and to promote the combination of silica and macromolecules, improve the dispersion of the rubber, reduce The formation of a filler network further improves the vulcanization characteristics, comprehensive physical properties, dynamic properties, and processability of silica reinforced compounds.
  • a surface modifier For compounds containing peroxide crosslinking agents, vinyl-containing silanes are preferred.
  • the stabilizer comprises 2,2,4-trimethyl-1,2-dihydroquinoline polymer (RD), 6-ethoxy-2,2,4-trimethyl- At least one of 1,2-dihydroquinoline (AW) and 2-mercaptobenzimidazole (MB).
  • RD 2,2,4-trimethyl-1,2-dihydroquinoline polymer
  • AW 6-ethoxy-2,2,4-trimethyl- At least one of 1,2-dihydroquinoline
  • MB 2-mercaptobenzimidazole
  • the vulcanization accelerator includes 2-thiol benzothiazole, dibenzothiazole disulfide (DM), tetramethylthiuram monosulfide, and tetramethylthiuram disulfide (TMTD). , Tetraethylthiuram disulfide, N-cyclohexyl-2-benzothiazolyl sulfenamide (CZ), N, N-dicyclohexyl-2-benzothiazolyl sulfenamide, N-oxydiethyl At least one of a phenylene-2-benzothiazolyl sulfenamide (NOBS), a bismaleimide, and an ethylenethiourea. According to the solubility difference of various types of accelerators in each rubber type, those with relatively high solubility in the branched polyethylene or ethylene-propylene rubber phase are preferred, and sulfenamide-based accelerators are preferred.
  • DM dibenzothiazole disulfide
  • the compatibilizer can be selected from epoxidized natural rubber, functionally modified ethylene-propylene rubber, or branched polyethylene, and the functionally modified monomer used can 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), Fumar Dibutyl acid (DBF), ⁇ -hydroxyethyl methacrylate (HEMA), dibutyl maleate (DBM), diethyl maleate (DEM), halogen element (such as liquid chlorine, liquid bromine, etc.
  • Halogen-containing compounds such as N-bromosuccinimide, bromodimethylhydantoin, carbon adsorbing chlorine, carbon adsorbing bromine, etc.
  • sulfur-containing compounds such as sulfur dioxide, sulfinyl chloride, etc.
  • vinyl Trimethoxysilane VTMS
  • vinyltriethoxysilane VTES
  • 3-methacryloxypropyltrimethoxysilane VMMS
  • ⁇ -methylstyrene ( ⁇ -MSt) acrylonitrile (AN), and the like, or mixtures thereof, are used to improve the compatibility, blending, and co-vulcanizability between branched polyethylene (and ethylene-propylene rubber) and styrene-butadiene rubber.
  • trans-polyoctene elastomer can be used to make the glue more uniform and improve the compatibility.
  • the glass transition temperature of branched polyethylene and ethylene-propylene rubber with high ethylene content is relatively low, and grafting a certain amount of polar functional groups, such as styrene, ⁇ -methylstyrene, etc., is beneficial to increase their glass transition temperature. Therefore, when the rubber composition of the present invention is applied to a tire tread, it can contribute to improving the wet skid resistance of the composition.
  • the tackifier includes at least one of petroleum resin, terpene resin, rosin and derivatives, and coomarone resin.
  • the adhesive includes at least one of a resorcinol donor, a methylene donor, an organic cobalt salt, a maleic anhydride butadiene resin, and a liquid natural rubber.
  • the resorcinol donor may be selected from, for example, resorcinol (Binder R), Binder RS, Binder RS-11, Binder R-80, Binder RL, Binder PF , Adhesive PE, adhesive RK, adhesive RH, etc .;
  • the methylene donor can be selected from, for example, hexamethylenetetramine (HMTA), adhesive H-80, adhesive A, adhesive RA, Adhesive AB-30, Adhesive Rq, Adhesive RC, Adhesive CS963, Adhesive CS964, etc .
  • the organic cobalt salt may be selected from, for example, cobalt naphthenate, cobalt neodecanoate, cobalt borate And cobalt stearate.
  • a resorcinol donor, a methylene donor, and silica are used in combination to form a m-methylene-white system with excellent adhesive properties.
  • the m-a-white system is used in combination with an organic cobalt salt, and the formed m-a-white-cobalt system can further improve the bonding effect and enhance the durability.
  • the rubber material can be more suitable for the occasion where the adhesive performance is required such as the adhesive layer of the conveyor belt or the core rubber, the rubber layer in the hose, and the radial tire belt layer.
  • the aforementioned flame retardant includes aluminum hydroxide, magnesium hydroxide, zinc borate, antimony trioxide, zinc stearate, titanate, decabromodiphenyl ether, and a silane coupling agent modified At least one of hydroxide, red phosphorus, pentaerythritol, ammonium polyphosphate, and triethyl phosphate.
  • the foaming agent includes sodium bicarbonate, azobiscarboxamide (AC), dinitrosopentamethylenetetramine (H), diphenylsulfonyl hydrazide ether (OBSH), and benzenesulfonyl At least one of hydrazine (BSH), urea, and low-boiling-point hydrocarbon-containing microcapsule-type blowing agent.
  • AC azobiscarboxamide
  • H dinitrosopentamethylenetetramine
  • OBSH diphenylsulfonyl hydrazide ether
  • BSH benzenesulfonyl
  • BSH hydrazine
  • urea low-boiling-point hydrocarbon-containing microcapsule-type blowing agent.
  • a further technical solution is that, in 100 parts of the rubber matrix, 0 to 40 parts of natural rubber and 0 to 40 parts of butadiene rubber are further included. Natural rubber can improve the mechanical strength and elasticity of vulcanizates. Butadiene rubber can improve the cold resistance and abrasion resistance of vulcanizates and reduce dynamic heat generation.
  • the rubber composition of the present invention is usually in a suitable mixing device (such as an internal mixer or an open mixer).
  • a suitable mixing device such as an internal mixer or an open mixer.
  • all components except the crosslinking system components such as a cross-linking agent, a vulcanization accelerator, and an auxiliary cross-linking agent are mixed. It is kneaded, and the temperature of the kneading may be from room temperature or below to 150 ° C or higher. If the debinding temperature is higher than the activation temperature of the crosslinking agent, it needs to be cooled below the activation temperature after debinding.
  • the cross-linking system is then blended into the blend by subsequent mixing.
  • One of the solutions is to add most of the filler to rubber with low unsaturation and low polarity to make a masterbatch, then add the combined rubber, and then add the remaining small part of the filler, and continue to press Traditional method of mixing; the second solution is to mix the two rubbers to be mixed together and then mix according to the proportion.
  • the invention provides a method for processing the above rubber composition, which adopts a masterbatch method for rubber mixing: Let the proportion of branched polyethylene and ethylene-propylene rubber be a%, and the proportion of the remaining components including styrene-butadiene rubber be b%, the branched polyethylene and ethylene-propylene rubber are set as the rubber matrix of the master batch (A), and the remaining components in the rubber matrix, including styrene-butadiene rubber, are set as the rubber of the master batch (B)
  • the matrix is characterized in that in the mixing stage of the masterbatch, the reinforcing filler is distributed to the masterbatch (A) at a proportion higher than a%, and the peroxide cross-linking agent is assigned at a proportion higher than a% Assigned to masterbatch (A).
  • Step 1 Mixing in the internal mixer to obtain two types of masterbatch
  • Step 2 Mix the master batch (A) and the master batch (B) in a mixer in proportion to obtain the final compound (C). Film, parked, waiting for further processing.
  • the present invention provides a shoe sole using a rubber comprising the rubber composition described above.
  • a further technical solution is that a foaming agent is contained in the rubber composition for a shoe sole.
  • the reinforcing filler in the rubber composition for a sole described above includes silica having a particle size of not more than 50 nm, preferably a particle size of 15 to 20 nm, which has transparency and reinforcement.
  • the present invention provides a rubber shoe having a midsole, and the rubber used in the midsole comprises the rubber composition described above.
  • a further technical solution is that a foaming agent is contained in the rubber composition for a shoe sole.
  • the present invention provides a tire comprising at least one of a rubber compound for a sidewall and a tread thereof including the above rubber composition.
  • Ethylene-propylene rubber is not suitable for tire tread alone because of its poor wet skid resistance and poor adhesion.
  • ethylene-propylene rubber is often added to the tread or sidewall rubber to improve its weather resistance and ozone aging resistance.
  • branched polyethylene By introducing branched polyethylene to replace part or all of ethylene-propylene rubber, it is possible to improve the tire tread or While improving the weather resistance, ozone aging resistance and high temperature resistance of the sidewall, the overall physical and mechanical properties are improved.
  • Further use of natural rubber in the tread rubber can improve the mechanical strength and adhesion of the tread rubber, and further use of butadiene rubber in the tread rubber can improve the wear resistance of the tread rubber and reduce dynamic heat generation.
  • the ethylene-propylene rubber used in the present invention is preferably a ethylene-propylene rubber with a high propylene content, and specifically, a propylene content of 60 is preferred.
  • the Tg is generally not lower than -40 ° C, preferably the Tg is not lower than -30 ° C.
  • a further technical solution is that the tire is a power tire.
  • the tire is a radial tire or a bias tire.
  • a further technical solution is to use the rubber composition provided by the present invention on the sidewall and tread of the tire at the same time to improve co-vulcanization and adhesion between the two, thereby improving the overall quality of the tire.
  • a further technical solution is that at least one of a tire rubber, a belt layer, and a carcass ply in the radial tire comprises the rubber composition described above.
  • the invention provides a conveyor belt, which includes a working surface covering rubber and a non-working surface covering rubber.
  • a tensile layer is provided between the working surface covering rubber and the non-working surface covering rubber.
  • the working surface covering rubber and the non-working surface covering rubber are provided.
  • the rubber used in at least one layer of the gum comprises the rubber composition described above.
  • the present invention provides a canvas core conveyor belt.
  • the rubber used in the adhesive layer includes the rubber composition.
  • the rubber composition for the adhesive layer may use a certain amount of low molecular weight polymer plasticizer liquid polyisobutylene, liquid polybutadiene, or liquid ethylene-propylene rubber to reduce the viscosity of the branched polyethylene and / or ethylene-propylene rubber. Improve its self-adhesion, and improve the blending and dispersing effect with styrene-butadiene rubber.
  • the rubber composition used in at least one of the working surface covering rubber and the non-working surface covering rubber of the canvas core conveyor belt contains 5 to 100 parts by weight of branched polyethylene per 100 parts by weight of the rubber matrix.
  • the canvas used is any of cotton canvas, vinylon canvas, nylon canvas, polyester canvas, straight-weft polyester-nylon canvas, and aramid canvas.
  • the invention provides a rope core conveyor belt.
  • the rubber used for the adhesive core rubber of the rope core conveyor belt comprises the rubber composition described above.
  • the rubber composition used in at least one of the working surface covering rubber and the non-working surface covering rubber of the core conveyor belt contains 5 to 100 parts by weight of branched polyethylene per 100 parts by weight of the rubber matrix.
  • the rope core is a steel wire rope core or a polymer rope core, and the polymer rope core used is preferably a high-strength rope core such as an aramid rope core or an ultra-high molecular weight polyethylene fiber. .
  • the adhesive rubber used for the canvas core conveyor belt or the rubber composition used for the adhesive core rubber used for the rope core conveyor belt may further include 2 to 5 parts of short fibers for improving the modulus and improving the overall modulus distribution of the conveyor belt.
  • the staple fiber is preferably a product having a pretreated surface and a good blending property with non-polar rubber.
  • the invention provides a conveyor belt having a buffer rubber between a covering rubber and an adhesive rubber, and the rubber used for the buffer rubber comprises the rubber composition described above.
  • the rubber composition used in at least one layer of the working surface covering rubber and the non-working surface covering rubber comprises 5 to 100 parts by weight of branched polyethylene per 100 parts by weight of the rubber matrix.
  • the invention provides a rubber tube, which includes an inner rubber layer, a reinforcing layer, and an outer rubber layer.
  • the rubber used in at least one of the inner rubber layer and the outer rubber layer includes the rubber composition described above.
  • the invention provides a rubber tube, which comprises an inner rubber layer, a first reinforcement layer, a middle rubber layer, a second reinforcement layer and an outer rubber layer from the inside to the outside, wherein the middle rubber layer of the rubber tube comprises the rubber composition described above.
  • the rubber composition used in at least one of the outer rubber layer and the inner rubber layer comprises 5 to 100 parts by weight of branched polyethylene per 100 parts by weight of the rubber matrix.
  • butadiene rubber in the inner or outer rubber layer of the hose can improve the corrosion resistance and elasticity of the vulcanized rubber, and is particularly suitable for the working layer of abrasion-resistant rubber hoses, such as the inner rubber layer of sandblasted hoses.
  • the present invention provides a power transmission belt having a main body of a certain length including a buffer rubber layer and a compression rubber layer, and the rubber used in at least one of the buffer rubber layer and the compression rubber layer includes the above rubber composition.
  • the compression rubber layer includes short fibers, and the buffer rubber layer does not include short fibers.
  • the present invention provides a rubber roller comprising a rubber composition as described above.
  • the molecular structure of the branched polyethylene is completely saturated, and the heat-resistant aging performance is similar to that of the ethylene-propylene rubber, which is better than the ethylene-propylene rubber, and because the branched polyethylene has a relatively high molecular weight and unique branched chain
  • the structure can have better mechanical strength after cross-linking, so it can improve the overall aging resistance and physical and mechanical properties.
  • branched polyethylene can more easily form a continuous phase than ethylene-propylene rubber, so that it can obtain better aging resistance as a whole.
  • branched polyethylene can obtain better mechanical strength after cross-linking, it can reduce the impact on the original physical and mechanical properties of styrene-butadiene rubber when the combined ratio of branched polyethylene is increased, so that the vulcanizate
  • the material has good aging resistance and physical and mechanical properties.
  • the combined use with styrene-butadiene rubber can improve the adhesion properties of ethylene-propylene rubber and / or branched polyethylene, and can be better used in places where aging resistance and adhesion are required.
  • the molecular weight distribution of the branched polyethylene is narrower than that of ethylene-propylene rubber and styrene-butadiene rubber, so it can give the rubber material good resistance to compression and permanent deformation.
  • the above beneficial effects can make the rubber composition more suitable for applications such as tires, hoses, conveyor belts, transmission belts, and rubber shoes that require aging resistance, wear resistance, physical and mechanical properties, and adhesion.
  • a rubber composition comprising a rubber matrix, a reinforcing filler and a cross-linking agent, characterized in that the 100 parts by weight of the rubber matrix contains more than 0 parts and not more than 99 parts of branched polymer.
  • each 100 parts of the rubber matrix contains 10 to 95 parts of branched polyethylene, 0 to 60 parts of ethylene-propylene rubber and 5 to 90 parts of natural rubber; 100 parts by weight of rubber Based on the matrix, the rubber composition contains 15 to 150 parts of a reinforcing filler and 1 to 8 parts of a crosslinking agent.
  • the branched polyethylene used is a type of ethylene homopolymer with a degree of branching of not less than 50 branches / 1000 carbons.
  • its synthesis method mainly uses ( ⁇ -diimide) nickel / palladium catalyst to prepare In situ polymerization catalyzes homopolymerization of ethylene.
  • Branched polyethylene having a degree of branching of 50 to 150 branches / 1000 carbons is preferred, branched polyethylene having a degree of branching of 60 to 130 branches / 1000 carbons is more preferred, and weight of the branched polyethylene is preferred.
  • the average molecular weight is 66,000 to 518,000, and Mooney viscosity ML (1 + 4) is 6 to 102 at 125 ° C.
  • the ethylene-propylene rubber used is preferably a tertiary or quaternary ethylene-propylene rubber having a Mooney viscosity ML (1 + 4) of 15 to 100 at 125 ° C and a weight ratio of diene monomers of 4% to 10%. Diene monomers are preferred.
  • the diene monomer is more preferably an ethylene-propylene rubber having both ENB and VNB, or an ethylene-propylene rubber having ENB and VNB as the third monomer may be used in combination.
  • a preferred embodiment is that auxiliary ingredients can be added to the rubber composition to improve the performance of rubber compounds and products for various specific applications.
  • Auxiliary components such as cross-linking aids, plasticizers, metal oxides, stearic acid, surface modifiers, stabilizers, vulcanization accelerators, compatibilizers, tackifiers, adhesives, flame retardants, hair Foam and so on.
  • Auxiliary ingredients are used in conventional amounts, depending on the application.
  • the auxiliary component further comprises 0 to 15 parts of a compatibilizer based on 100 parts by weight of the rubber matrix to improve co-vulcanization and physical compatibility between the combined rubbers.
  • 0 to 40 parts of natural rubber and 0 to 40 parts of butadiene rubber are further included.
  • Natural rubber can improve the mechanical strength and elasticity of vulcanizates.
  • Butadiene rubber can improve the cold resistance and abrasion resistance of vulcanizates, reduce dynamic heat generation, and make the rubber composition more suitable for specific applications.
  • a masterbatch mixing process is mainly used. Specifically, the proportion of branched polyethylene and ethylene-propylene rubber is set to a%, and the proportions of other components including styrene-butadiene rubber For b%, set the branched polyethylene and ethylene-propylene rubber as the rubber matrix of the master batch (A), and set the remaining components in the rubber matrix including styrene-butadiene rubber as the master batch (B).
  • the rubber matrix is characterized in that in the mixing stage of the master batch, the reinforcing filler is distributed to the master batch (A) at a compounding ratio higher than a%, and the peroxide crosslinking agent is compounded at a higher than a%. Ratio assigned to the masterbatch (A).
  • a further embodiment is the method for kneading the rubber composition, comprising the following steps:
  • Step 1 Mix in a mixer to obtain two types of masterbatch
  • Step 2 Mix the master batch (A) and the master batch (B) in a mixer in proportion to obtain the final compound (C). Film, parked, waiting for further processing.
  • the Mooney viscosity ML (1 + 4) of the selected ethylene-propylene rubber and ethylene-propylene rubber is preferably 20 to 80 at 125 ° C, the ethylene content is preferably 45% to 70%, and the third monomer content is preferably 4% to 12 %.
  • the styrene-butadiene rubber used in the embodiments of the present invention is selected from the following table:
  • Ethylene-propylene rubber number Ethylene content /% Mooney viscosity Third monomer content /% EPDM-1 70 ML (1 + 4) 125 °C : 55 4.5 EPDM-2 50 ML (1 + 4) 125 °C : 30 8 EPDM-3 50 ML (1 + 4) 125 °C : 65 9 EPDM-4 55 ML (1 + 8) 100 °C : 55 11.5 EPDM-5 70 ML (1 + 4) 125 °C : 20 0.6
  • the selected branched polyethylene is characterized by a degree of branching of 60 to 130 branches / 1000 carbons, a weight average molecular weight of 66,000 to 518,000, and a Mooney viscosity of ML (1 + 4) of 125 to 6 to 102. .
  • the degree of branching was measured by nuclear magnetic hydrogen spectroscopy, and the mole percent content of various branch chains was measured by nuclear magnetic carbon spectroscopy.
  • the natural rubber grade used in the examples of the present invention is Vietnam 3L.
  • the Mooney viscosity ML (1 + 4) of the butadiene rubber used in the examples of the present invention is 45 at 100 ° C., and the cis-1,4 structure content is 96%.
  • Hardness test According to the national standard GB / T 531.1-2008, use a hardness tester to test, the test temperature is room temperature;
  • Mooney viscosity test According to the national standard GB / T1232.1-2000, use Mooney viscometer to test, the test temperature is 125 °C, warm up for 1 minute, test for 4 minutes;
  • Hot air accelerated aging test According to the national standard GB / T3512-2001, conducted in a thermal aging test box;
  • Adhesive strength test According to the national standard GB6759-86, the adhesive strength of rubber and canvas layers is tested. At a speed of 100 mm / min on a tensile machine, a certain length of peeling was caused between the adhesive layers of the sample according to the "one layer at a time” method (A method), and the adhesive strength was calculated using the automatically recorded peel force curve. The adhesive strength at a high temperature was measured on the high-temperature tensile tester by the above-mentioned A method.
  • Compression permanent deformation test According to the national standard GB / T7759-1996, use the compression permanent deformation device for testing. Type B, the compression amount is 25%, and the test temperature is 70 ° C;
  • Ozone resistance aging test According to the national standard GB / T7762-2003, in an ozone aging phase box, under a certain static tensile strain condition, exposed to a certain ozone concentration in the air, at a specified temperature (40 ° C) without Resistance to ozone cracking in environments directly affected by light;
  • Tc90 test of positive vulcanization time conducted in a rotorless vulcanizer in accordance with the national standard GB / T16584-1996;
  • Dynamic mechanical performance test The dynamic mechanical properties of vulcanizates were analyzed using DMA-242 dynamic mechanical analyzer produced by NETZSCH Germany. The test conditions are as follows: double cantilever beam mode, frequency 10Hz, tensile displacement 7%, test temperature range- 100 °C ⁇ 100 °C, heating rate is 3K / min;
  • DIN abrasion test According to the national standard GB / T9867-2008, test on a DIN abrasion tester;
  • Bond strength test of steel wire rope core According to the national standard GB / T5755-2000, the steel wire is embedded at a depth of 50mm and the pull-out speed is 100mm / min;
  • Density of foamed materials Test the density of foamed materials in accordance with GB / T6343-2009;
  • Resilience test According to ASTM-D2632-200 standard, the resilience test of the sample is tested by the vertical resilience tester;
  • Anti-slip test According to ASTM-F1677 standard, the shaft-slip type anti-slip meter is used to test the anti-slip performance of the material.
  • Test for tensile strength and elongation at break of foamed materials Test the tensile strength and elongation at break of foamed materials according to the national standard GB / T6344-2008. The tensile speed is 500mm / min and the test temperature is 23 ⁇ 2 ° C, the sample is a type 2 dumbbell-shaped sample.
  • the vulcanization conditions of the following Examples 1 to 40 and Comparative Examples 1 to 11 are unified as: temperature: 160 ° C; pressure: 16MPa; vulcanization time of samples less than 6mm is Tc90 + 2min; thickness is not low The vulcanization time of the sample at 6mm is Tc90 + 8min.
  • the invention provides a rubber composition with good physical and mechanical properties and aging resistance, which is suitable for preparing a tire car tread rubber. Specific formulations are taken as examples 1 to 5.
  • Examples 1 to 5 and Comparative Example 1 were processed according to the following method: 50% of the reinforcing filler, 50% of zinc oxide and stearic acid, all BIPB and TAIC, 50% of sulfur and the accelerator were first mixed with Ethylene-propylene rubber and branched polyethylene are mixed to obtain a masterbatch, and the remaining rubber matrix components (natural rubber is first plasticized) are mixed with the aforementioned masterbatch for 1 minute, and then the remaining components are added in the usual order and mixed. Mix 2 portions and drain. The mixed rubber was thinned on an open mill with a roller temperature of 60 ° C., and the roll distance was enlarged to 2 mm, and the film was left for 20 hours. After being cured for 16 hours, various tests were performed.
  • Example 1 By comparing Example 1 with Comparative Example 1, it can be found that by replacing a part of ethylene-propylene rubber with a small amount of high molecular weight branched polyethylene, the overall physical and mechanical properties can be improved without affecting the original improvement of aging resistance.
  • Example 2 By comparing Example 1 with Comparative Example 1, it can be found that when all ethylene-propylene rubber is replaced with branched polyethylene, the tear strength can be significantly improved, and it can also be understood as weakening the addition of ethylene-propylene rubber to styrene-butadiene The effect of the original tear strength of rubber. This effect means that more branched polyethylene can be used in the compound to improve the aging resistance of the compound without significantly affecting the physical and mechanical properties of the compound.
  • Example 5 It can also be confirmed from the performance of Example 5.
  • Examples 3 and 4 show that the physical and mechanical properties of rubber compounds can be further improved by using a certain amount of natural rubber in combination.
  • the formulas of Examples 1 to 5 can be used to prepare a tire tread rubber with good aging resistance.
  • Examples 6-9 and the processing methods of Comparative Examples 2 and 3 50% of reinforcing filler, 50% of zinc oxide and stearic acid, all BIPB, 50% of sulfur and accelerator are firstly mixed with ethylene-propylene rubber Mix with branched polyethylene to obtain a masterbatch, and then mix the remaining rubber matrix components (natural rubber is first plasticized) with the aforementioned masterbatch for 1 minute, then add the remaining components in the usual order and mix for 2 minutes Back row of rubber.
  • the mixed rubber was thinned on an open mill with a roller temperature of 60 ° C., and the roll distance was enlarged to 2 mm, and the film was left for 20 hours. After being cured for 16 hours, various tests were performed.
  • Example 6 By comparing Examples 6, 7 and Comparative Example 2 and Example 9 and Comparative Example 3, it can be found that replacing part or all of ethylene-propylene rubber with branched polyethylene can improve the overall mechanics of the rubber compound. The strength can also reduce the permanent compression deformation. In Example 6, a part of ethylene-propylene rubber with a high third monomer content is retained, so that the whole can obtain better co-vulcanization, and the elongation at break is higher than that in Example 7. The comparison between Example 8 and Example 7 can explain that further increasing the amount of branched polyethylene with high molecular weight is expected to further improve the overall aging resistance, physical and mechanical properties, and compression set resistance of the rubber compound. The above formula is suitable for the side wall of a power tire or a car tire.
  • the invention provides a new rubber composition for a tire tread rubber, which simultaneously has ideal physical and mechanical properties, and meets the requirements of wet skid resistance and low rolling resistance.
  • Examples 10 to 15 are taken as examples.
  • Examples 10 to 15 and Comparative Example 4 Processing method: 50% of reinforcing filler, 50% of zinc oxide and stearic acid, all BIPB and TAIC, 50% of sulfur and accelerator, and ethylene-propylene rubber Mix with branched polyethylene to obtain a masterbatch, and then mix the remaining rubber matrix components (natural rubber is first plasticized) with the aforementioned masterbatch for 1 minute, then add the remaining components in the usual order and mix for 2 minutes Back row of rubber.
  • the mixed rubber was thinned on an open mill with a roller temperature of 60 ° C., and the roll distance was enlarged to 2 mm, and the film was left for 20 hours. After being cured for 16 hours, various tests were performed.
  • Examples 10 to 15 effectively improved the overall wet skid resistance of the rubber compound by introducing a high styrene content styrene-butadiene rubber, and the presence of branched polyethylene or ethylene-propylene rubber effectively reduced the overall rubber compound.
  • the rolling resistance can be illustrated by comparison between Example 10 and Comparative Example 4. Replacing ethylene-propylene rubber with branched polyethylene can make the whole have better physical and mechanical properties, significantly improve tear strength, and better meet the tread Use of glue.
  • the invention provides a new type of abrasion-resistant and age-resistant rubber composition, which simultaneously has good physical and mechanical properties, abrasion resistance and aging resistance. It is suitable for covering the inner and outer layers of the rubber belt and hose. Take examples 16 to 24 as examples.
  • Examples 16-20 and the processing method of Comparative Example 5 50% of the reinforcing filler, 50% of zinc oxide and stearic acid, all DCP and TAIC, 50% of sulfur and accelerator and ethylene propylene rubber Mix with branched polyethylene to obtain a masterbatch. Then, styrene-butadiene rubber is mixed with the aforementioned masterbatch for 1 minute, and then the remaining components are added in the usual order. The mixture is discharged after 2 minutes of mixing. The mixed rubber was thinned on an open mill with a roller temperature of 60 ° C., and the roll distance was enlarged to 2 mm, and the film was left for 20 hours. After being cured for 16 hours, various tests were performed.
  • Examples 21 to 24 and Comparative Examples 6 and 7 Formulation processing method: 50% of the reinforcing filler, 50% of zinc oxide and stearic acid, all DCP and TAIC, 50% of sulfur and accelerator and B
  • the propylene rubber and the branched polyethylene are mixed to obtain a master batch, and the styrene-butadiene rubber is mixed with the aforementioned master batch for 1 minute, and then the remaining components are added in a conventional order, and the mixture is discharged after 2 minutes of mixing.
  • the mixed rubber was thinned on an open mill with a roller temperature of 60 ° C, and the roll distance was enlarged to 2 mm, and the film was left for 20 hours. After being cured for 16 hours, various tests were performed.
  • the invention provides a rubber composition for bonding, which can be used as an adhesive layer rubber for bonding non-polar rubbers such as branched polyethylene and ethylene-propylene rubber, and their compositions, and reinforcing materials such as fibers, canvas, and steel wire rope cores.
  • the final product may be a hose, a conveyor belt, or other rubber products containing a reinforcing layer. Take Examples 25 to 31 as examples.
  • Examples 25-29 and the processing method of Comparative Example 8 50% of zinc oxide, stearic acid, binder RS, coomarone resin, carbon black, white carbon black, and softener, all DCP and TAIC, 50% of sulfur and accelerator are firstly mixed with ethylene-propylene rubber and branched polyethylene to obtain a masterbatch, and then the remaining rubber matrix components (natural rubber is first plasticized, and Mooney viscosity ML (1 + 4) after plasticization) 100 ° C (about 40 ° C) is mixed with the aforementioned master batch for 2 minutes, and then the remaining components are added in the usual order.
  • the mixing temperature is controlled to 60 ° C to 80 ° C, and the rubber is discharged after 5 minutes of mixing.
  • the kneaded rubber was thinned on an open mill with a roller temperature of 60 ° C, and the roll distance was enlarged to 2mm, and the film was allowed to stand for 20 hours. After that, it was laminated with an aramid canvas impregnated at room temperature and vulcanized at 180 ° C. Samples were tested for 16 hours after parking.
  • Example 25-28 and Comparative Example 8 can show that partial or full replacement of ethylene-propylene rubber with branched polyethylene can improve the overall aging resistance and obtain better adhesion after aging or at high temperature Combined strength, low Mooney viscosity branched polyethylene can more easily form a continuous phase, thereby better improving the overall aging resistance.
  • Examples 26 to 28 it is shown that compared to a rubber composition containing only styrene-butadiene rubber and branched polyethylene in a rubber matrix, when a small amount of ethylene-propylene rubber having a high third monomer content is further blended, It improves the adhesive strength before aging in absolute value.
  • Examples 30 and 31 and Comparative Example 9 Processing method of zinc oxide, stearic acid, binder RC, cobalt boryl RC-23, carbon black, white carbon black, silane coupling agent, softener 50%, all DCP and co-crosslinking agent, 50% sulfur and accelerator are first mixed with ethylene-propylene rubber and branched polyethylene to obtain a masterbatch, and then styrene-butadiene rubber is mixed with the aforementioned masterbatch for 2 minutes. Then add the remaining components in the usual order, control the kneading temperature to be 60 ° C to 80 ° C, and discharge the glue after 5 minutes of mixing.
  • the kneaded rubber is thinned on an open mill with a roller temperature of 60 ° C, and the roll distance is enlarged to 2 mm, and the film is left for 20 hours; vulcanized at 180 ° C to obtain a tensile sample and a sample bonded to a galvanized steel wire. Tests were performed after 16 hours of parking.
  • the invention also provides a wiper strip with a smooth surface and good wiping performance.
  • the rubber composition used in the wiper strip is described in Examples 32 to 36 as examples.
  • the formula processing method of Examples 32 to 36 and Comparative Example 10 Put all rubber bases together in an internal mixer and knead for 2 minutes; then add zinc oxide, stearic acid and antioxidant, and knead for 1 minute; then add reinforcement The filler is kneaded for 30 seconds; then the softener is added and kneaded for 2 minutes; then the remaining components are added and kneaded for 2 minutes to discharge the rubber; the kneaded rubber is thinned on an opener with a roller temperature of 60 ° C and the roller is enlarged The film is placed at a distance of 2mm and is parked for 20 hours; after curing, it is parked for 16 hours for testing.
  • the invention also provides an anti-aging shock-absorbing and abrasion-resistant foaming material, which is suitable for making rubber products such as shoe soles and shock-absorbing pads.
  • the formula of the rubber composition used is exemplified in Examples 37 to 40.
  • Examples 37-40 and the processing method of Comparative Example 11 50% of reinforcing filler and silane coupling agent, 50% of zinc oxide and stearic acid, all DCP and TAIC, 50% of sulfur and accelerator
  • it is mixed with ethylene-propylene rubber and branched polyethylene to obtain a masterbatch, and then the styrene-butadiene rubber is mixed with the aforementioned masterbatch for 1 minute, and then the remaining components are added in a conventional order, and the mixture is discharged after 2 minutes of mixing.
  • the mixed rubber was thinned on an open mill with a roller temperature of 60 ° C., and the roll distance was enlarged to 2 mm, and the film was left for 20 hours. After being cured for 16 hours, various tests were performed.

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Abstract

本发明公开了一种橡胶组合物及加工方法，以及应用橡胶组合物的制品及生产方法，一种橡胶组合物，其包括：橡胶基体、补强填充剂和交联剂，所述100重量份橡胶基体包含：支化聚乙烯1～99份，乙丙橡胶0～90份，丁二烯共聚物弹性体1～95份。其有益效果是，该橡胶组合物具有良好的耐磨性、耐老化性、物理机械性能和粘结性能，可用于生产轮胎、胶管、输送带、鞋底材料等橡胶制品。

Description

橡胶组合物及加工方法，及应用其的橡胶制品和生产方法 技术领域
本发明属于橡胶领域，具体涉及到一种橡胶组合物及其加工方法，本发明还涉及到该橡胶组合物的应用，以及生产该橡胶制品的方法。
背景技术
丁二烯共聚物弹性体在合成橡胶领域占有重要地位，其中丁苯橡胶的产能最大。丁苯橡胶在补强剂的配合下具有优异的力学性能、耐磨性，但耐热老化性、耐天候老化性和耐臭氧老化性较弱，这是由于分子链结构中含有双键，容易在高温或者臭氧的影响下发生破坏，从而导致橡胶的性能劣化。而乙丙橡胶由于分子主链高度饱和，化学结构稳定，因此具有极佳的耐老化性，但耐磨性弱于丁苯橡胶。现有技术中通常采用乙丙橡胶与丁苯橡胶并用的方法，来改善丁苯橡胶的耐热老化性、耐天候老化性以及耐臭氧老化性，或者来改善乙丙橡胶的耐磨性。但是由于两者的共硫化性能较差、各胶种自身存在性能缺陷等因素的影响，并用较多乙丙橡胶会造成丁苯橡胶的耐磨性变差，并用较多丁苯橡胶也会造成乙丙橡胶的耐老化性变差，另外两者的整体力学性能也会下降。现有技术中对于改善乙丙橡胶与丁苯橡胶共硫化性能已经有比较充分的研究，采用过氧化物硫化体系或者硫磺和过氧化物共用的复合硫化体系已经可以达到比较理想的共硫化程度。但是各胶种固有的性能缺陷一直没有得到明显改善，因而两者并用的橡胶制品的综合性能还存在进一步提升的需求和空间。
尤其是对于力学性能或者耐磨性要求较高的应用场合，为了不影响使用效果，往往只能并用较少的乙丙橡胶，无法进一步改善制品的耐老化性能。例如，为了在改善丁苯橡胶耐老化性的基础上，不明显影响原有的力学性能和耐磨性能，现有技术通过向乙丙橡胶中添加增塑剂，来降低乙丙橡胶的门尼粘度，使少量的乙丙橡胶可以呈连续相，进而使丁苯橡胶包覆在乙丙橡胶中，但由于过多的低分子量增塑剂对导致胶料的耐磨性变差，所以这种方案也存在明显的局限性。
发明内容
针对现有技术中存在的问题，本发明的目的是提供一种在耐老化性能、力学性能和耐磨性能等方面的综合表现更为优异的新型橡胶组合物。
为了实现上述目的，本发明提出的技术方案是：使用支化聚乙烯部分或者全部替代现 有技术中的乙丙橡胶来与丁二烯共聚物弹性体并用。本发明所用支化聚乙烯是一类支化度不低于50个支链/1000个碳的乙烯均聚物，目前它的合成方法主要采用(α-二亚胺)镍/钯催化剂通过配位聚合催化乙烯均聚得到。
支化聚乙烯的分子链完全饱和，耐老化性能类似于甚至优于乙丙橡胶。同时由于支化聚乙烯具有丰富的支链分布，相对于支链主要为甲基的乙丙橡胶而言，可以在更大程度上破坏分子链的规整性，在同等分子量下，拥有更低的门尼粘度和更好的加工性能，与丁苯橡胶等其他胶种并用的时候容易形成连续相，从而使整体具有更好的耐老化性；另一方面，在同等门尼粘度下，支化聚乙烯可以具有更高的分子量，而且支化聚乙烯的不同长度的支链可以在过氧化物硫化时在分子主链之间形成多种不同长度的C-C交联键，有效避免应力集中，从而赋予整体更高的物理机械性能。所以本发明可以提供同时具有良好的耐老化性能、力学性能和耐磨性能的橡胶组合物。
为了实现上述目的，本发明提供一种橡胶组合物，包含橡胶基体、补强填充剂和交联剂，其特征在于，按重量份计，所述每100份橡胶基体中包含大于0份且不超过99份的支化聚乙烯，0～75份乙丙橡胶和1～95份丁二烯共聚物弹性体，其中支化聚乙烯为有支链结构的乙烯均聚物。其中，支化聚乙烯的支化度不低于50个支链/1000个碳，重均分子量不低于5万，门尼粘度ML(1+4)125℃不低于2。
进一步的技术方案是，所述每100重量份橡胶基体中含有5～95份支化聚乙烯。
进一步的技术方案是，所述支化聚乙烯的支化度为50～150个支链/1000个碳。
进一步的技术方案是，所述支化聚乙烯的支化度为60～130个支链/1000个碳。
进一步的技术方案是，所述支化聚乙烯的重均分子量为6.6万～51.8万，门尼粘度ML(1+4)125℃为6～102。
支化度较低的支化聚乙烯具有较高的分子量和门尼粘度，甚至在室温以上具有熔点，在并用体系中加入这类支化聚乙烯，可以赋予整体良好的耐老化性、耐磨性，增加胶料挺性及改善工艺性能。
支化度较高的支化聚乙烯具有较低的分子量和门尼粘度，可以用来改善乙丙橡胶或者支化度略低的支化聚乙烯的加工性能，并且使后者更加容易形成连续相，从而在丁苯橡胶比重较高的情况下，赋予整体更好的耐老化性能。
进一步的实施方案是，所述乙丙橡胶包含二元乙丙橡胶、三元乙丙橡胶和四元乙丙橡胶中的至少一种。
进一步的技术方案是，除乙烯和丙烯外，所述三元乙丙橡胶和四元乙丙橡胶的共聚单体 包含二烯类单体，所述二烯类单体包含5-亚乙基-2-降冰片烯、5-乙烯基-2-降冰片烯、双环戊二烯和1,4-己二烯中的至少一种。所述二烯类单体可选用的例子还有如1,5-己二烯、1,4-戊二烯、2-甲基-1,4-戊二烯、3-甲基-1,4-己二烯、4-甲基-1,4-己二烯、1,9-癸二烯、5亚甲基-2-降冰片烯、5-亚戊基-2-降冰片烯、1,5-环辛二烯、1,4-环辛二烯等。
进一步的技术方案是，二烯类单体占乙丙橡胶的重量比重为1％～14％。
所用的乙丙橡胶优选门尼粘度ML(1+4)125℃在15～100，二烯类单体重量比重为4％～10％的三元或四元乙丙橡胶，乙丙橡胶与支化聚乙烯的相容性极佳，混炼时，一般采用母炼胶法，乙丙橡胶与支化聚乙烯共为一种母炼胶的橡胶基体，当三元乙丙橡胶中的二烯单体含量较高时，既可以提高该母炼胶的极性，有助于终炼胶中各种填料的均匀分散，同时第三单体也可以起到过氧化物的助交联剂作用，提高交联效率。三元乙丙橡胶的分子链既可以与丁苯橡胶分子链之间发生硫磺和过氧化物的共交联，也可以与支化聚乙烯之间发生过氧化物的共交联，从而增加橡胶相界面上的交联键分布，可以进一步改善整体的共硫化性，提高物理机械性能，尤其是乙丙橡胶中当同时含有5-亚乙基-2-降冰片烯(ENB)和5-乙烯基-2-降冰片烯(VNB)这两种二烯单体时或者同时并用分别以ENB和VNB作为第三单体的乙丙橡胶时，由于ENB容易与硫磺反应，而VNB一般只与过氧化物交联剂反应，所以这样的乙丙橡胶(组合)可以更好的发挥共硫化剂的作用。
进一步的技术方案是，所述丁二烯共聚物弹性体包含丁二烯-苯乙烯共聚物、丁二烯-异戊二烯共聚物和丁二烯-异戊二烯-苯乙烯共聚物中的至少一种。
进一步的技术方案是，所述丁二烯共聚物弹性体为丁苯橡胶。
优选丁苯橡胶中苯乙烯含量为20wt％～50wt％，丁二烯部分中1,2结构含量为10％～65％，反-1,4结构含量为15％～75％，并且Tg在-65至-20℃之间。
进一步的技术方案是，以100重量份橡胶基体计，橡胶组合物包含10～200份补强填充剂。
进一步的技术方案是，其特征在于，所述补强填充剂包含炭黑、白炭黑、碳酸钙、煅烧陶土、滑石粉、硅酸镁、硅酸铝、碳酸镁、钛白粉、蒙脱土、短纤维中的至少一种。
白炭黑优选经过烷基化预处理的白炭黑，有利于改善白炭黑在本发明橡胶基体中的分散效果，并提高橡胶的物理性能。蒙脱土优选改性蒙脱土或者纳米蒙脱土，加入纳米层状蒙脱土有利于改善硫化胶的力学性能和耐磨性。
进一步的技术方案是，以100重量份橡胶基体计，所述橡胶组合物包含0.1～10份交联剂。
进一步的技术方案是，所述交联剂包含过氧化物交联剂和硫磺中的至少一种，所述过氧化物交联剂为二叔丁基过氧化物、二枯基过氧化物(DCP)、叔丁基枯基过氧化物、1,1-二叔丁基过氧化物-3,3,5-三甲基环己烷、2,5-二甲基-2,5-二(叔丁基过氧基)己烷、2,5-二甲基-2,5-二叔丁基过氧化基-3-己炔、双(叔丁基过氧化异丙基)苯(BIPB)、2,5-二甲基-2,5-二(过氧化苯甲酸)己烷、过氧化苯甲酸叔丁酯、叔丁基过氧化-2-乙基己基碳酸酯中的至少一种。
由于过氧化物硫化的焦烧时间一般比硫黄硫化短，若制品生产工艺要求延长焦烧时间，可采用延长焦烧型有机过氧化物F40P-SP2，或者加入BHT并适当增加过氧化物的用量，或者添加如N,N’-间苯撑双马来酰亚胺这样具有延长焦烧时间作用的助交联剂。
为了避免芳烃油对于过氧化物硫化的影响，丁苯橡胶优选不充油牌号或者充环烷油牌号。
进一步的技术方案是，上述橡胶组合物，按重量份计，每100份橡胶基体中包含5～95份的支化聚乙烯，0～60份乙丙橡胶和5～90份丁苯橡胶；以100重量份橡胶基体计，橡胶组合物包含10～150份补强填充剂，1～8份交联剂。
进一步的技术方案是，上述的橡胶组合物还包括辅助成分。所述的辅助成分包含助交联剂、增塑剂、金属氧化物、硬脂酸、表面改性剂、稳定剂、硫化促进剂、增容剂、增粘剂、粘合剂、阻燃剂、发泡剂中的至少一种。
进一步的技术方案是，以100重量份橡胶基体计，上述各种辅助成分的用量范围为助交联剂0.2～10份，增塑剂0～80份，金属氧化物3～30份，硬脂酸0～3份，表面改性剂0～15份，稳定剂1～6份，硫化促进剂0～5份、增容剂0～15份、增粘剂0～5份、粘合剂0～20份、阻燃剂0～150份、发泡剂0～20份。
进一步的技术方案是，上述助交联剂包含三烯丙基氰脲酸酯、三烯丙基异氰脲酸酯、乙二醇二甲基丙烯酸酯、二甲基丙烯酸三乙二酯、偏苯三酸三烯丙酯、三甲基丙烯酸三羟甲基丙烷酯、N,N’-间苯撑双马来酰亚胺、N,N’-双亚糠基丙酮、1,2-聚丁二烯、不饱和羧酸金属盐和硫磺中的至少一种。
上述液态1,2-聚丁二烯或者液态聚异丁烯有助交联剂的作用外，还具有增塑剂的作用，并且还可以使胶料在硫化之后具有较高的硬度，适用于对高硬度有需求的场合。但都是粘稠状液体物质，不利于在加工过程中添加，因此在一定程度上限制了其应用。现有技术中可以将液态的助交联剂预分散在合成无机填充剂(如硅酸钙)中，形成聚丁二烯粉末状物质，在加工过程中添加非常方便，且与胶料有良好的相容性。
上述不饱和羧酸金属盐包含丙烯酸锌、甲基丙烯酸锌、甲基丙烯酸镁、甲基丙烯酸钙、甲基丙烯酸铝中的至少一种。使用不饱和羧酸金属盐如丙烯酸锌或甲基丙烯酸锌作为过氧化物的助交联剂时可以发生离子交联，离子键表现出良好的耐热老化稳定性和滑移特性，结合了过氧化物和硫黄硫化的特性，可以赋予胶料很好的拉伸强度、撕裂强度以及耐热性能。此外，不饱和羧酸金属盐还可以作为粘合剂改善胶料与合成纤维、金属或者其他胶料的粘合性。
进一步的技术方案是，上述增塑剂包含硬脂酸、松香油、机油、环烷油、石蜡油、古马隆、RX-80、石蜡、液态聚异丁烯、癸二酸二辛酯中的至少一种。
进一步的技术方案是，所述金属氧化物包含氧化锌、氧化镁、氧化钙中的至少一种。优选粒径范围为10～100nm的纳米氧化锌、纳米氧化镁或纳米氧化钙，进一步优选为纳米氧化锌与纳米氧化镁的混合物，纳米金属氧化物的加入量优选为5～20质量份。添加金属氧化物不仅起到活化作用，而且其中纳米氧化锌和纳米氧化镁可以起到耐高温的作用，对于厚制品的硫化和应用可以起到导热的作用。此外纳米级氧化物比表面积大，活性大，有利于吸收橡胶老化过程中放出的酸性物质，具有明显的防护作用。
进一步的技术方案是，上述表面改性剂包含聚乙二醇、二苯基硅二醇、三乙醇胺、硅烷偶联剂、钛酸酯偶联剂中的至少一种。其中聚乙二醇的分子量优选为2000或3400或4000；硅烷偶联剂可以选自如乙烯基三乙氧基硅烷(A-151)、乙烯基三甲氧基硅烷(A-171)、乙烯基三(2-甲氧基乙氧基)硅烷(A-172)、γ-缩水甘油醚氧丙基三甲氧基硅烷(A-187)、γ-巯基丙基三甲氧基硅烷(A-189)、双(γ-三乙氧基硅烷基丙基)四硫化物(Si69)、γ-氨基丙基三乙氧基硅烷(KH-550)等；钛酸酯偶联剂可以选自如二油酰基钛酸亚乙酯、三异硬脂酰基钛酸异丙酯、三油酰基钛酸异丙酯等。
优选在当补强填充剂中含有白炭黑时，加入表面改性剂来降低其活性以减轻对硫化的影响，并促进白炭黑与橡胶大分子的结合，提高胶料的分散性，减轻填料网络的形成，进而改善白炭黑补强胶料的硫化特性、综合物理性能、动态性能和加工性能。对于含有过氧化物交联剂的胶料，优选含有乙烯基的硅烷。
进一步的技术方案是，上述稳定剂包含2,2,4-三甲基-1,2-二氢化喹啉聚合体(RD)、6-乙氧基-2,2,4-三甲基-1,2-二氢化喹啉(AW)、2-巯基苯并咪唑(MB)中的至少一种。
进一步的技术方案是，上述硫化促进剂包含2-硫醇基苯并噻唑、二硫化二苯并噻唑(DM)、一硫化四甲基秋兰姆、二硫化四甲基秋兰姆(TMTD)、二硫化四乙基秋兰姆、N-环己基-2-苯并噻唑基次磺酰胺(CZ)、N，N-二环己基-2-苯噻唑基次磺酰胺、N-氧二乙撑基-2-苯并噻唑次磺酰胺(NOBS)、双马来酰亚胺、亚乙基硫脲中的至少一种。根据各类促进剂在各胶种中的溶解性差异，优选在支化聚乙烯或者乙丙橡胶相中溶解度相对较高的种类，优选次磺酰胺类促进剂。
进一步的技术方案是，上述增容剂可以选自环氧化天然橡胶、官能化改性的乙丙橡胶或支化聚乙烯，所用的官能化改性单体可选自马来酸酐(MAH)、甲基丙烯酸(MA)、丙烯酸(AA)、衣康酸(IA)、富马酸(FA)、异氰酸酯、甲基丙烯酸缩水甘油酯(GMA)、甲基丙烯 酸甲脂(MMA)、富马酸二丁酯(DBF)、甲基丙烯酸β-羟乙酯(HEMA)、马来酸二丁酯(DBM)、马来酸二乙酯(DEM)、卤素单质(如液氯、液溴等)、含卤化合物(如N-溴代琥珀酰亚胺、溴二甲基乙内酰脲、炭吸附氯、碳吸附溴等)、含硫化合物(如二氧化硫、亚磺酰氯等)、乙烯基三甲氧基硅烷(VTMS)、乙烯基三乙氧基硅烷(VTES)、3-甲基丙烯酰氧基丙基三甲氧基硅烷(VMMS)、苯乙烯(St)、α-甲基苯乙烯(α-MSt)、丙烯腈(AN)等或其混合物，其作用是改善支化聚乙烯(和乙丙橡胶)与丁苯橡胶之间的相容性、共混炼性和共硫化性。也可以选用如反式聚辛烯弹性体，可以使并用胶形成更加均匀的形态，从而改善相容性。支化聚乙烯和高乙烯含量的乙丙橡胶的玻璃化转变温度相对较低，接枝一定量的极性官能团，例如苯乙烯、α-甲基苯乙烯等，有利于提高其玻璃化转变温度，从而当本发明的橡胶组合物应用于轮胎胎面时，可以有助于改善组合物的抗湿滑性。
进一步的技术方案是，上述增粘剂包含石油树脂、萜烯树脂、松香及衍生物、古马隆树脂中的至少一种。
进一步的技术方案是，上述粘合剂包含间苯二酚给予体、亚甲基给予体、有机钴盐、马来酸酐丁二烯树脂、液态天然橡胶中的至少一种。
所述间苯二酚给予体可以选自如间苯二酚(粘合剂R)、粘合剂RS、粘合剂RS-11、粘合剂R-80、粘合剂RL、粘合剂PF、粘合剂PE、粘合剂RK及粘合剂RH等；亚甲基给予体可以选自如六亚甲基四胺(HMTA)、粘合剂H-80、粘合剂A、粘合剂RA、粘合剂AB-30、粘合剂Rq、粘合剂RC、粘合剂CS963及粘合剂CS964等；有机钴盐可以选自如环烷酰钴、新癸酸钴、硼酰化钴及硬脂酸钴等。间苯二酚给予体、亚甲基给予体与白炭黑并用，可以形成粘合性能优异的间-甲-白体系。间-甲-白体系与有机钴盐并用，形成的间-甲-白-钴体系还可以进一步提高黏结效果并增强耐久性。通过配合粘合剂，可以使胶料更加适合于输送带粘合层或者粘合芯胶、胶管中胶层、子午线轮胎带束层等对粘合性能有要求的场合。
进一步的技术方案是，上述的阻燃剂包含氢氧化铝、氢氧化镁、硼酸锌、三氧化二锑、硬脂酸锌、钛酸酯、十溴联苯醚、硅烷偶联剂改性的氢氧化物、红磷、季戊四醇、聚磷酸铵、三乙基磷酸酯中的至少一种。
进一步的技术方案是，上述发泡剂包含碳酸氢钠、偶氮二甲酰胺(AC)、二亚硝基亚戊基四胺(H)、二苯磺酰肼醚(OBSH)、苯磺酰肼(BSH)、尿素、含低沸点烃微胶囊型发泡剂中的至少一种。含有发泡剂的上述橡胶组合物特别适用于生产轻便弹性好的鞋底材料。
进一步的技术方案是，在100份橡胶基体中，进一步包含天然橡胶0～40份，顺丁橡胶0～40份。天然橡胶可以改善硫化胶的力学强度和弹性等。顺丁橡胶可以改善硫化胶的耐寒 性、耐磨性，减小动态生热。
本发明的橡胶组合物通常是在合适的混炼装置中(如密炼机或开炼机)，首先把除了交联剂、硫化促进剂和助交联剂等交联体系成分以外的所有成分加以混炼，混炼的温度可从室温或室温以下直到150℃或更高的温度。如果排胶温度高于交联剂的活化温度，在排胶后需冷却到低于活化温度。然后通过随后的混炼把交联体系混入共混物中。
由于采用上述混炼方法时各种填充剂在并用胶各橡胶相中的不均匀分配，会导致硫化不均或者应力集中等负面影响，导致并用橡胶硫化胶物理机械性能的下降。解决的办法之一，是将大部分填充剂先加到不饱和度低和极性低的橡胶中制成母炼胶，然后加入并用的橡胶，再加入剩余的小部分填充剂，并继续按传统方法混炼；解决的方法之二，是将欲并用的两种橡胶分别先制成混炼胶，然后按比例进行混炼。
本发明提供一种加工上述橡胶组合物的方法，采取母炼胶法进行橡胶混炼：设支化聚乙烯和乙丙橡胶的比重为a％，包括丁苯橡胶在内的其余组分比重为b％，将支化聚乙烯和乙丙橡胶设定为母炼胶(A)的橡胶基体，将橡胶基体中包括丁苯橡胶在内的其余组分设定为母炼胶(B)的橡胶基体，其特征在于，在母炼胶的混炼阶段，补强填充剂按高于a％的配比分配给母炼胶(A)，过氧化物交联剂按高于a％的配比分配给母炼胶(A)。
进一步的技术方案是，上述橡胶组合物的混炼方法，包含以下步骤：
步骤一：在密炼机中分别混炼得到两种母炼胶；
步骤二：将母炼胶(A)和母炼胶(B)按比例在密炼机中混炼，得到终炼胶(C)，将终炼胶(C)在开炼机上薄通后下片，停放，等待进一步加工。
本发明提供一种鞋底，其所用橡胶包含上述橡胶组合物。
进一步的技术方案是上述鞋底用橡胶组合物中包含发泡剂。
进一步的技术方案是上述鞋底用橡胶组合物中补强填充剂包含粒径不超过50nm，优选粒径为15～20nm的白炭黑，其具备透明性和补强性。
本发明提供一种胶鞋，具有中底，该中底所用橡胶包含上述橡胶组合物。
进一步的技术方案是上述鞋底用橡胶组合物中包含发泡剂。
本发明提供一种轮胎，其胎侧和胎面所用的胶料中至少一种包含上述橡胶组合物。
乙丙橡胶因为抗湿滑性不佳，粘合性较差，目前难以单独用于轮胎胎面。现有技术中经常通过向胎面或者胎侧胶中加入乙丙橡胶来改善其耐候性和耐臭氧老化性，通过引入支化聚乙烯替换部分或全部乙丙橡胶，可以在改善轮胎胎面或胎侧的耐候性、耐臭氧老化性和耐高温性的同时，提高整体的物理机械性能。在胎面胶中进一步并用天然橡胶可以改善胎面胶的力学强度和黏着性，在胎面胶中进一步并用顺丁橡胶可以改善胎面胶的耐磨性，减小动态生热。在胎侧胶中加入顺丁橡胶可以减小胎侧的动态生热，改善其耐屈挠特性，延长使用寿命。进一步的技术方案是，为了通过提高整体的玻璃化转变温度来改善橡胶组合物的抗湿滑性， 本发明所用的乙丙橡胶优选高丙烯含量的乙丙橡胶，具体地，优选丙烯含量为60％～95％的乙丙橡胶，其Tg一般不低于-40℃，优选Tg不低于-30℃。
进一步的技术方案是，所述轮胎为力车胎。
进一步的技术方案是，所述轮胎为子午线轮胎或者斜交轮胎。
进一步的技术方案是，上述轮胎的胎侧和胎面同时使用本发明提供的橡胶组合物，改善两者之间的共硫化性和粘合性、从而改善轮胎的整体质量。
进一步的技术方案是，所述子午线轮胎中胎肩胶、带束层和胎体帘布层中的至少一种包含上述橡胶组合物。通过使用上述的橡胶组合物可以改善轮胎整体的共硫化性和各部位之间的粘合性。
本发明提供一种输送带，包含工作面覆盖胶和非工作面覆盖胶，并在工作面覆盖胶与非工作面覆盖胶之间设有抗拉层，其工作面覆盖胶和非工作面覆盖胶中的至少一层所用橡胶包含上述橡胶组合物。
本发明提供一种帆布芯输送带，其粘合层所用橡胶包含上述橡胶组合物。
所述粘合层用橡胶组合物可以选用一定量的低分子量聚合物增塑剂液态聚异丁烯、液态聚丁二烯或液态乙丙橡胶来降低支化聚乙烯和/或乙丙橡胶的粘度，提高其自粘性，并改善与丁苯橡胶的共混分散效果。
进一步的技术方案是，所述帆布芯输送带的工作面覆盖胶与非工作面覆盖胶中至少一层所用橡胶组合物包含的每100重量份橡胶基体中包含支化聚乙烯5～100重量份，所用帆布为棉帆布、维纶帆布、锦纶帆布、聚酯帆布、直径直纬聚酯-锦纶帆布、芳纶帆布中的任意一种。
本发明提供一种绳芯输送带，绳芯输送带的粘合芯胶所用橡胶包含上述橡胶组合物。
进一步的技术方案是，绳芯输送带的工作面覆盖胶与非工作面覆盖胶中至少一层所用橡胶组合物包含的每100重量份橡胶基体中包含支化聚乙烯5～100重量份，所用绳芯为钢丝绳芯或者聚合物绳芯，所用聚合物绳芯优选自芳纶绳芯、超高分子量聚乙烯纤维等高强度绳芯。。
上述帆布芯输送带所用的粘合胶或者绳芯输送带所用的粘合芯胶所用橡胶组合物可以进一步包含2～5份短纤维用于提高模量，改善输送带整体的模量分布。短纤维优选表面经过预处理的，与非极性橡胶共混性能良好的品种。
本发明提供一种输送带，其覆盖胶和粘合胶之间有缓冲胶，所述缓冲胶所用橡胶包含上述橡胶组合物。进一步的技术方案是，其工作面覆盖胶与非工作面覆盖胶至少一层所用橡胶组合物的每100重量份橡胶基体中包含支化聚乙烯5～100重量份。
本发明提供一种胶管，其包含内胶层、增强层和外胶层，其内胶层和外胶层中的至少一层所用橡胶包含上述橡胶组合物。
本发明提供一种胶管，其由内到外包含内胶层、第一增强层、中胶层、第二增强层和外胶层，其中该胶管的中胶层包含上述橡胶组合物。进一步的技术方案是，外胶层和内胶层中至少一层所用橡胶组合物的每100重量份橡胶基体中包含支化聚乙烯5～100重量份。
在胶管的内胶层或外胶层胶料中并用顺丁橡胶可以提高硫化胶的耐腐蚀性和弹性，尤其适用于耐磨胶管的工作层，如喷砂胶管的内胶层。
本发明提供一种动力传送带，其具有一定长度的包括缓冲橡胶层和压缩橡胶层的主体，并且缓冲橡胶层和压缩橡胶层中的至少一层所用橡胶包含上述橡胶组合物。其中压缩橡胶层包含短纤维，缓冲橡胶层不包含短纤维。
本发明提供一种胶辊，其所用橡胶包含上述橡胶组合物。
本发明的有益效果是：
第一、支化聚乙烯的分子结构完全饱和，耐热老化性能与二元乙丙橡胶类似，优于三元乙丙橡胶，并且由于支化聚乙烯具有相对较高的分子量和独特的支链结构，可以在交联后具有更好的力学强度，因此可以提高整体的耐老化性和物理机械性能。
第二、在同等分子量和用量下，支化聚乙烯相对于乙丙橡胶可以更加容易形成连续相，从而整体可以获得更好的耐老化性。
第三、由于支化聚乙烯在交联后可以获得较好的力学强度，所以可以在提高支化聚乙烯的并用比例时减小对于丁苯橡胶原有物理机械性能的影响，从而使硫化胶料同时具有良好的耐老化性和物理机械性能。
第四、与丁苯橡胶并用，可以改善乙丙橡胶和/或支化聚乙烯的粘合性能，可以更好的用于对耐老化性和粘接性有要求的场合。
第五、支化聚乙烯的分子量分布比乙丙橡胶和丁苯橡胶窄，因而可以赋予胶料良好的抗压缩永久变形性能。
以上有益效果可以使橡胶组合物更加适用于轮胎、胶管、输送带、传动带、胶鞋等对耐老化性、耐磨性、物理机械性能以及粘结性有要求的应用场合。
具体实施方式
下面给出实施例以对本发明做进一步说明，但不是用来限制本发明的范围，该领域的技术熟练人员根据发明内容对本发明做出的一些非本质的改进和调整仍属于本发明的保护范围。
本发明提供的橡胶组合物的具体实施方式是：
提供一种橡胶组合物，包含橡胶基体、补强填充剂和交联剂，其特征在于，按重量份计，所述每100份橡胶基体中包含大于0份且不超过99份的支化聚乙烯，0～75份乙丙橡胶和1～95份丁二烯共聚物弹性体，以100重量份橡胶基体计，橡胶组合物包含10～200份补强填充剂，0.1～10份交联剂。
优选的实施方案，是按重量份计，所述每100份橡胶基体中包含10～95份的支化聚乙烯，0～60份乙丙橡胶和5～90份天然橡胶；以100重量份橡胶基体计，橡胶组合物包含15～150份补强填充剂，1～8份交联剂。
其中使用的支化聚乙烯是一类支化度不低于50个支链/1000个碳的乙烯均聚物，目前它的合成方法主要采用(α-二亚胺)镍/钯催化剂通过配位聚合催化乙烯均聚得到。优选支化度为50～150个支链/1000个碳的支化聚乙烯，进一步优选支化度为60～130个支链/1000个碳的支化聚乙烯，优选支化聚乙烯的重均分子量为6.6万～51.8万，门尼粘度ML(1+4)125℃为6～102。
所用的乙丙橡胶优选门尼粘度ML(1+4)125℃在15～100，二烯类单体重量比重为4％～10％的三元或四元乙丙橡胶，二烯单体优选为ENB，二烯单体进一步优选为ENB和VNB均有的乙丙橡胶，或者也可以并用分别以ENB和VNB作为第三单体的乙丙橡胶。
优选的实施方案是，可向橡胶组合物中加入辅助成分，针对各种具体应用来提升胶料和制品的性能。
辅助成分，如助交联剂、增塑剂、金属氧化物、硬脂酸、表面改性剂、稳定剂、硫化促进剂、增容剂、增粘剂、粘合剂、阻燃剂、发泡剂等等。辅助成分以常规用量使用，具体用量取决于用途。
优选的实施方式是，以100重量份单位橡胶基体计，辅助成分进一步包含增容剂0～15份，来改善并用胶之间的共硫化性和物理相容性。
优选的实施方式是，在100份橡胶基体中，进一步包含天然橡胶0～40份，顺丁橡胶0～40份。天然橡胶可以改善硫化胶的力学强度和弹性等。顺丁橡胶可以改善硫化胶的耐寒性、耐磨性，减小动态生热，使橡胶组合物更加适用于具体的应用场合。
对于本发明提供的橡胶组合物的加工方法，主要采用母炼胶混炼工艺，具体的，设支化聚乙烯和乙丙橡胶的比重为a％，包括丁苯橡胶在内的其余组分比重为b％，将支化聚乙烯和乙丙橡胶设定为母炼胶(A)的橡胶基体，将橡胶基体中包括丁苯橡胶在内的其余组分设定为母炼胶(B)的橡胶基体，其特征在于，在母炼胶的混炼阶段，补强填充剂按高于a％的配比分配给母炼胶(A)，过氧化物交联剂按高于a％的配比分配给母炼胶(A)。
进一步的实施方案是，上述橡胶组合物的混炼方法，包含以下步骤：
步骤一：在密炼机中混炼得到两种母炼胶；
步骤二：将母炼胶(A)和母炼胶(B)按比例在密炼机中混炼，得到终炼胶(C)，将终炼胶(C)在开炼机上薄通后下片，停放，等待进一步加工。
为了更清楚的叙述本发明的实施方式，下面对本发明所涉及到的材料做个定义。
所选用的二元乙丙橡胶和三元乙丙橡胶的门尼粘度ML(1+4)125℃优选20～80，乙烯含 量优选45％～70％，第三单体含量优选4％～12％。
具体的，本发明实施例中使用的丁苯橡胶选自下表：
Figure PCTCN2019092642-appb-000001
本发明实施例中使用的乙丙橡胶选自下表：
乙丙橡胶编号 乙烯含量/％ 门尼粘度 第三单体含量/％
EPDM-1 70 ML(1+4)125℃：55 4.5
EPDM-2 50 ML(1+4)125℃：30 8
EPDM-3 50 ML(1+4)125℃：65 9
EPDM-4 55 ML(1+8)100℃：55 11.5
EPDM-5 70 ML(1+4)125℃：20 0.6
所选用的支化聚乙烯特征为：支化度为60～130个支链/1000个碳、重均分子量为6.6万～51.8万，门尼粘度ML(1+4)125℃为6～102。其中，支化度通过核磁氢谱测得，各种支链摩尔百分含量通过核磁碳谱测得。
具体如下表：
Figure PCTCN2019092642-appb-000002
Figure PCTCN2019092642-appb-000003
本发明实施例中使用的天然橡胶牌号为越南3L。
本发明实施例中使用的顺丁橡胶门尼粘度ML(1+4)100℃为45，顺-1,4结构含量为96％。橡胶性能测试方法：
1、硬度测试：按照国标GB/T 531.1-2008，用硬度测试仪进行测试，测试温度为室温；
2、拉伸强度、断裂伸长率性能测试：按照国标GB/T528-2009，用电子拉力试验机进行测试，拉伸速度为500mm/min，测试温度为23±2℃，试样为2型哑铃状试样；
3、门尼粘度测试：按照国标GB/T1232.1-2000，用门尼粘度仪进行测试，测试温度为125℃，预热1分钟，测试4分钟；
4、热空气加速老化试验：按照国标GB/T3512-2001，在热老化试验箱中进行；
5、粘合强度测试：按照国标GB6759-86对橡胶和帆布层粘合强度进行测试。在拉力机上以100mm/min的速度按“一次一层法”(A法)在试样粘合层间引起一定长度的剥离，利用自动记录的剥离力曲线计算粘合强度。在高温拉力试验机上以上述A法测得高温下的粘合强度。
6、压缩永久变形测试：按照国标GB/T7759-1996，用压缩永久变形装置进行测试，B型式样，压缩量为25％，测试温度为70℃；
7、耐臭氧老化测试：按照国标GB/T7762-2003，在臭氧老化相箱内，在一定的静态拉伸应变条件下，暴露于一定臭氧浓度的空气中，在规定温度(40℃)且无光线直接影响的环境中耐臭氧龟裂测试；
8、正硫化时间Tc90测试：按照国标GB/T16584-1996，在无转子硫化仪中进行；
9、动态力学性能测试：采用德国耐驰生产的DMA-242动态力学分析仪分析硫化胶的动态力学性能，测试条件如下：双悬臂梁模式，频率10Hz，拉伸位移7％，测试温度范围-100℃～100℃，升温速率为3K/min；
10、DIN磨耗测试：按照国标GB/T9867-2008，在DIN磨耗试验机上进行测试；
11、钢丝绳芯粘合强度测试：按照国标GB/T5755-2000，钢丝埋置深度50mm，拔脱速度100mm/min；
12、发泡材料密度：按照国标GB/T 6343-2009对发泡材料的密度进行测试；
13、回弹性测试：依据ASTM-D2632-200标准，试样的回弹性测试采用垂直回弹性测试仪进行测试；
14、发泡材料压缩永久变形测试：按照标准HG/T 2876-2009，将泡沫材料试样制成标 准样品，在压缩器上经过50℃压缩5h后，然后经室温冷却30min，最后测定其形变量；
15、止滑性测试：依据ASTM-F1677标准，采用轴节式止滑仪测试材料的止滑性能
16、发泡材料拉伸强度、断裂伸长率性能测试：按照国标GB/T 6344-2008测试泡沫材料的拉伸强度和断裂伸长率，拉伸速度为500mm/min，测试温度为23±2℃，试样为2型哑铃状试样。
如无特别注明，以下实施例1～40和对照例1～11的硫化条件统一为：温度：160℃；压力：16MPa；厚度小于6mm的试样的硫化时间为Tc90+2min；厚度不低于6mm的试样的硫化时间为Tc90+8min。
本发明提供一种物理机械性能和耐老化性良好的橡胶组合物，适用于制备力车胎胎面胶。具体配方以实施例1～5为例。
实施例1～5和对照例1的基本配方如表1所示：(其中列出了相对于每100重量份橡胶基体，所用各组分的重量份数，下同)
表1
组分 实施例1 实施例2 实施例3 实施例4 实施例5 对照例1
丁苯橡胶1502 70 70 40 30 30 70
乙丙橡胶EPDM-2 25         30
支化聚乙烯 5 30 30 50 70  
支化聚乙烯编号 PER-8 PER-7 PER-7 PER-6 PER-6  
天然橡胶     30 20    
氧化锌 5 5 5 5 5 5
硬脂酸 2 2 2 2 2 2
乙烯基三(2-甲氧基乙氧基)硅烷       2    
碳酸钙       40 35  
钛酸酯偶联剂         1  
煅烧陶土 50 50 50     50
白炭黑       20    
炭黑N330 60 60 60   35 60
石蜡油 20 20 20 10 10 20
Escorez 1102树脂 3 3 3 3 3 3
BIPB 1 1 1 1 3 1
硫磺 2 2 2 2 1 2
TAIC 0.3 0.3 0.3 0.3 0.6 0.3
促进剂CZ/TMTD 1/0.5 1/0.5 1/0.5 1/0.5 1/0.5 1/0.5
ZDMA     2 2 2  
实施例1～5以及对照例1的配方按照以下的方法加工：将50％的补强填充剂，50％的氧化锌和硬脂酸，全部BIPB和TAIC，50％的硫磺与促进剂先与乙丙橡胶和支化聚乙烯混炼得到母炼胶，再将其余橡胶基体成分(天然橡胶先经过塑炼)与前述母炼胶混炼1分钟，然后依常规顺序加入剩余的组份，混炼2两份后排胶。将混炼胶在辊温为60℃的开炼机上薄通后放大辊距至2mm下片，停放20小时；硫化后停放16小时后进行各项测试。
实施例1～5和对照例1的测试结果如表2所示：
表2
Figure PCTCN2019092642-appb-000004
测试结果分析：通过实施例1与对照例1对比，可以发现：通过使用少量的高分子量支化聚乙烯替换部分乙丙橡胶，可以提高整体的物理机械性能，而且不影响原有改善耐老化性的效果；通过实施例2和对照例1的对比可以发现：在用支化聚乙烯替换全部乙丙橡胶的情况下，可以明显改善撕裂强度，也可以理解为减弱加入乙丙橡胶对丁苯橡胶原有撕裂强度造成的影响，这一效果意味着可以让胶料中并用更多的支化聚乙烯，来提升胶料的耐老化性能，同时不明显影响胶料的物理机械性能，这也可以从实施例5的性能表现加以证实。实施例3和4说明可以通过并用一定量的天然橡胶进一步改善胶料的物理机械性能。实施例1～5的配方可用于制备耐老化性能良好的力车胎胎面胶。
实施例6～9以及对照例2和3的基本配方如表3所示：
表3
组分 实施例6 实施例7 实施例8 实施例9 对照例2 对照例3
丁苯橡胶1502 25 25 25 30 25 30
乙丙橡胶EPDM-2 10       30 35
支化聚乙烯 20 30 30/15 35    
支化聚乙烯编号 PER-3 PER-5 PER-5/PER-8 PER-6    
天然橡胶 45 45 30 35 45 35
氧化锌 5 5 5 5 5  
硬脂酸 1 1 1 1 1  
防老剂RD 2 2 2 2 2 2
二氧化钛       30   30
炭黑N330 50 50 50   50  
环烷油 20 20 20 10 20 10
BIPB 0.8 0.8 0.8 0.8 0.8 0.8
硫磺 0.5 0.5 0.5 0.5 0.5 0.5
促进剂CZ 0.75 0.75 0.75 0.75 0.75 0.75
实施例6～9以及对照例2和3的配方加工方法：将50％的补强填充剂、50％的氧化锌和硬脂酸、全部BIPB、50％的硫磺与促进剂先与乙丙橡胶和支化聚乙烯混炼得到母炼胶，再将其余橡胶基体成分(天然橡胶先经过塑炼)与前述母炼胶混炼1分钟，然后依常规顺序加入剩余的组份，混炼2分钟后排胶。将混炼胶在辊温为60℃的开炼机上薄通后放大辊距至2mm下片，停放20小时；硫化后停放16小时后进行各项测试。
实施例6～9以及对照例2和3的性能测试结果如表4所示
表4
Figure PCTCN2019092642-appb-000005
测试结果分析：通过实施例6、7与对照例2的对比以及实施例9与对照例3的对比，都可以发现用支化聚乙烯替换部分或者全部乙丙橡胶，可以提高胶料整体的力学强度，同时还可以降低压缩永久变形，实施例6中保留了一部分高第三单体含量的乙丙橡胶，可以使整体获得更好的共硫化性，断裂伸长率高于实施例7。实施例8与实施例7对比可以说明进一步增加高分子量的支化聚乙烯的用量，有望进一步改善胶料整体的耐老化性、物理机械性能和抗压缩永久变形性能。上述配方适用于力车胎或者汽车轮胎的胎侧。
本发明提供一种新型汽车轮胎胎面胶用橡胶组合物，它同时具有理想的物理机械性能，以及满足要求的抗湿滑性和较低的滚动阻力，以实施例10～15为例。
实施例10～15以及对照例4的基本配方如表5所示：
表5
Figure PCTCN2019092642-appb-000006
实施例10～15以及对照例4的配方加工方法：将50％的补强填充剂、50％的氧化锌和硬脂酸、全部BIPB和TAIC、50％的硫磺与促进剂先与乙丙橡胶和支化聚乙烯混炼得到母炼胶，再将其余橡胶基体成分(天然橡胶先经过塑炼)与前述母炼胶混炼1分钟，然后依常规 顺序加入剩余的组份，混炼2分钟后排胶。将混炼胶在辊温为60℃的开炼机上薄通后放大辊距至2mm下片，停放20小时；硫化后停放16小时后进行各项测试。
实施例10～15以及对照例4的测试结果如表6所示：
表6
Figure PCTCN2019092642-appb-000007
测试数据分析：实施例10～15通过引入高苯乙烯含量的丁苯橡胶有效改善了胶料整体的抗湿滑性，同时支化聚乙烯或者乙丙橡胶的存在，有效降低了胶料整体的滚动阻力，通过实施例10和对照例4的对比可以说明，用支化聚乙烯替换乙丙橡胶，可以使整体具有更好的物理机械性能，撕裂强度明显提高，可以更好地满足胎面胶的使用需求。
本发明提供一类新型的耐磨耐老化橡胶组合物，同时具备良好的物理机械性能、耐磨性能和耐老化性。适用于输送带覆盖胶、胶管内外层。以实施例16～24为例。
实施例16～20以及对照例5的基本配方如表7所示：
表7
Figure PCTCN2019092642-appb-000008
实施例16～20以及对照例5的配方加工方法：将50％的补强填充剂、50％的氧化锌和硬脂酸、全部DCP和TAIC、50％的硫磺与促进剂先与乙丙橡胶和支化聚乙烯混炼得到母炼胶，再将丁苯橡胶与前述母炼胶混炼1分钟，然后依常规顺序加入剩余的组份，混炼2分钟后排 胶。将混炼胶在辊温为60℃的开炼机上薄通后放大辊距至2mm下片，停放20小时；硫化后停放16小时后进行各项测试。
实施例16～20以及对照例5的性能测试结果如表8所示
表8
Figure PCTCN2019092642-appb-000009
测试结果分析：向乙丙橡胶或者支化聚乙烯中引入丁苯橡胶，是一种可以改善整体耐磨性的有效技术方案，通过实施例16～20与对照例5的对比，可以发现用支化聚乙烯部分或者全部替代乙丙橡胶有利于提升整体的物理机械性能和耐老化性，当引入高分子量支化聚乙烯时，还可以进一步改善耐磨性，但同时通过实施例16和17的对比可以发现，少量乙丙橡胶的存在有利于改善整体的共硫化性，从而提升胶料的综合性能。
实施例21～24以及对照例6和7的基本配方如表9所示：
表9
组分 实施例21 实施例22 实施例23 实施例24 对照例6 对照例7
丁苯橡胶1502 70 70 80 90 70 100
乙丙橡胶EPDM-2 15       30  
支化聚乙烯 15 30 20 10    
支化聚乙烯编号 PER-2 PER-2 PER-2 PER-2    
氧化锌 10 10 10 10 10 10
硬脂酸 2 2 2 2 2 2
防老剂RD 2 2 2 2 2 2
炭黑N330 50 50 50 50 50 50
石蜡油 10 10 10 10 10 10
DCP 3 3 3 3 3 3
硫磺 0.3 0.3 0.3 0.3 0.3 0.3
TAIC 1 1 1 1 1 1
实施例21～24以及对照例6和7的配方加工方法：将50％的补强填充剂、50％的氧化锌和硬脂酸、全部DCP和TAIC、50％的硫磺与促进剂先与乙丙橡胶和支化聚乙烯混炼得到母炼胶，再将丁苯橡胶与前述母炼胶混炼1分钟，然后依常规顺序加入剩余的组份，混炼2分钟后排胶。将混炼胶在辊温为60℃的开炼机上薄通后放大辊距至2mm下片，停放20小 时；硫化后停放16小时后进行各项测试。
实施例21～24以及对照例6和7的性能测试结果如表10所示
表10
Figure PCTCN2019092642-appb-000010
测试结果分析：向丁苯橡胶中引入乙丙橡胶或者支化聚乙烯，是一种可以改善丁苯橡胶耐老化性的有效技术方案，通过实施例21、22与对照例6的对比可以说明当使用分子量更高、门尼粘度更低的支化聚乙烯部分或者全部替代乙丙橡胶时，可以使整体获得更好的耐老化性和物理机械性能。通过实施例23与对照例6的对比说明由于支化聚乙烯的门尼粘度低，更容易形成连续相，因此在进一步减少支化聚乙烯的用量的情况下，还可以起到良好的改善丁苯橡胶耐老化性的作用，同时进一步减小对丁苯橡胶物理机械性能和耐磨性的负面影响。
本发明提供一种粘合用橡胶组合物，可作为粘合层橡胶用于粘结支化聚乙烯和乙丙橡胶等非极性橡胶及其组合物与纤维、帆布和钢丝绳芯等增强材料。最终制品可以为胶管、输送带或其他含有增强层的橡胶制品。以实施例25～31为例。
实施例25～29以及对照例8的基本配方如表11所示：
表11
Figure PCTCN2019092642-appb-000011
Figure PCTCN2019092642-appb-000012
实施例25～29以及对照例8的配方加工方法：将氧化锌、硬脂酸、粘合剂RS、古马隆树脂、炭黑、白炭黑、软化剂的50％，全部DCP和TAIC，50％的硫磺和促进剂依次先与乙丙橡胶和支化聚乙烯混炼得到母炼胶，再将其余橡胶基体成分(天然橡胶先经过塑炼，塑炼后门尼粘度ML(1+4)100℃约为40)与前述母炼胶混炼2分钟，然后依常规顺序加入剩余的组份，控制混炼温度为60℃～80℃，混炼5分钟后排胶。将混炼胶在辊温为60℃的开炼机上薄通后放大辊距至2mm下片，停放20小时；之后与浸胶的芳纶帆布常温贴合，180℃下硫化，得到粘合试样，停放16小时后进行各项测试。
实施例25～29以及对照例8的性能测试结果如表12所示
表12
Figure PCTCN2019092642-appb-000013
测试结果分析：通过实施例25～28与对照例8的对比可以说明用支化聚乙烯部分或者全部替代乙丙橡胶，可以提高整体的耐老化性，在老化后或者高温下获得更好的粘合强度，低门尼粘度的支化聚乙烯可以更容易形成连续相，从而更好地改善整体的耐老化性。通过实施例26～28之间的对比，说明相对于橡胶基体中只含丁苯橡胶和支化聚乙烯的橡胶组合物，当进一步配合少量第三单体含量较高的乙丙橡胶时，可以在绝对值上提高老化前的粘合强度。
实施例30和31以及对照例9的基本配方如表13所示：
表13
Figure PCTCN2019092642-appb-000014
Figure PCTCN2019092642-appb-000015
实施例30和31以及对照例9的配方加工方法：将氧化锌、硬脂酸、粘合剂RC、硼酰化钴RC-23、炭黑、白炭黑、硅烷偶联剂、软化剂的50％，全部DCP和助交联剂，50％的硫磺和促进剂先与乙丙橡胶和支化聚乙烯混炼得到母炼胶，再将丁苯橡胶与前述母炼胶混炼2分钟，然后依常规顺序加入剩余的组份，控制混炼温度为60℃～80℃，混炼5分钟后排胶。将混炼胶在辊温为60℃的开炼机上薄通后放大辊距至2mm下片，停放20小时；180℃下硫化，得到拉伸试样以及与镀锌钢丝粘合的试样，停放16小时后进行各项测试。
实施例30和31以及对照例9的性能测试结果如表14所示
表14
Figure PCTCN2019092642-appb-000016
测试结果分析：通过实施例30、31和对照例9的对比可以说明，在对于耐老化性有较高要求的钢丝粘合用橡胶组合物中用支化聚乙烯替代部分乙丙橡胶可以改善胶料的力学强度和耐老化性，与钢丝间的粘合强度虽然有所降低，但还是令人满意的。当与其他含有支化聚乙烯的胶层(比如输送带覆盖胶或者胶管内外层)粘合时，根据相似相容原理，可以使整体具有更好的粘合强度。
本发明还提供一种表面爽滑，擦拭性能良好的雨刷条，其所用橡胶组合物配方以实施例32～36为例。
实施例32～36以及对照例10的基本配方如表15所示：
表15
Figure PCTCN2019092642-appb-000017
Figure PCTCN2019092642-appb-000018
实施例32～36以及对照例10的配方加工方法：将所有橡胶基体一起投入密炼机中混炼2分钟；然后加入氧化锌、硬脂酸和防老剂，混炼1分钟；然后加入补强填充剂混炼30秒；然后加入软化剂，混炼2分钟；然后加入余下组分，混炼2分钟后排胶；将混炼胶在辊温为60℃的开炼机上薄通后放大辊距至2mm下片，停放20小时；硫化后停放16小时进行测试。
实施例32～36以及对照例10的性能测试结果如表16所示
表16
Figure PCTCN2019092642-appb-000019
测试结果分析：通过实施例32～36与对照例10进行对比，可以说明用支化聚乙烯部分或者全部替代乙丙橡胶，可以改善整体的物理机械性能、抗压缩永久变形性性能和耐老化性能。
本发明还提供一种耐老化的减震耐磨发泡材料，适用于制作鞋底、减震垫等橡胶制品。所用橡胶组合物配方以实施例37～40为例。
实施例37～40以及对照例11的基本配方如表17所示：
表17
Figure PCTCN2019092642-appb-000020
Figure PCTCN2019092642-appb-000021
实施例37～40以及对照例11的配方加工方法：将50％的补强填充剂和硅烷偶联剂，50％的氧化锌和硬脂酸，全部DCP和TAIC，50％的硫磺与促进剂先与乙丙橡胶和支化聚乙烯混炼得到母炼胶，再将丁苯橡胶与前述母炼胶混炼1分钟，然后依常规顺序加入剩余的组份，混炼2分钟后排胶。将混炼胶在辊温为60℃的开炼机上薄通后放大辊距至2mm下片，停放20小时；硫化后停放16小时后进行各项测试。
实施例37～40以及对照例11的性能测试结果如表18所示
表18
Figure PCTCN2019092642-appb-000022
测试结果分析：通过实施例37～40与对照例11的对比，可以说明用同等门尼粘度的支化聚乙烯部分或者全部替代乙丙橡胶，由于其分子量更高，分子量分布窄，因此可以改善胶料整体的物理机械性能、抗压缩永久变形性能和耐磨性能。又因为支化聚乙烯不含极性第三单体，其与丁苯橡胶之间的相容性不如乙丙橡胶，使表面的不均匀性提高，从而止滑系数也有所提升。所以上述配方适用于制备鞋底。

Claims (46)

  1. 一种橡胶组合物，包含橡胶基体、补强填充剂和交联剂，其特征在于，按重量份计，所述每100份橡胶基体中包含大于0份且不超过99份的支化聚乙烯，0～75份乙丙橡胶和1～95份丁二烯共聚物弹性体，其中支化聚乙烯为有支链结构的乙烯均聚物。
  2. 根据权利要求1所述的橡胶组合物，其特征在于，所述支化聚乙烯的支化度为50～150个支链/1000个碳。
  3. 根据权利要求2所述的橡胶组合物，其特征在于，所述支化聚乙烯的支化度为60～130个支链/1000个碳。
  4. 根据权利要求3所述的橡胶组合物，其特征在于，所述支化聚乙烯的重均分子量为6.6万～51.8万，门尼粘度ML(1+4)125℃为6～102。
  5. 根据权利要求1所述的橡胶组合物，其特征在于，所述乙丙橡胶包含二元乙丙橡胶、三元乙丙橡胶和四元乙丙橡胶中的至少一种。
  6. 根据权利要求5所述的橡胶组合物，其特征在于，所述三元乙丙橡胶和四元乙丙橡胶的共聚单体包含二烯类单体，所述二烯类单体包含5-亚乙基-2-降冰片烯、5-乙烯基-2-降冰片烯、双环戊二烯和1,4-己二烯中的至少一种。
  7. 根据权利要求6所述的橡胶组合物，其特征在于，所述二烯类单体占乙丙橡胶的重量比重为1％～14％。
  8. 根据权利要求1所述的橡胶组合物，其特征在于，所述丁二烯共聚物弹性体包含丁二烯-苯乙烯共聚物、丁二烯-异戊二烯共聚物和丁二烯-异戊二烯-苯乙烯共聚物中的至少一种。
  9. 根据权利要求8所述的橡胶组合物，其特征在于，所述丁二烯共聚物弹性体为丁苯橡胶。
  10. 根据权利要求1所述的橡胶组合物，其特征在于，以100重量份橡胶基体计，所述橡胶组合物包含10～200份补强填充剂。
  11. 根据权利要求1所述的橡胶组合物，其特征在于，所述补强填充剂包含炭黑、白炭黑、碳酸钙、煅烧陶土、滑石粉、硅酸镁、硅酸铝、碳酸镁、钛白粉、蒙脱土、短纤维中的至少一种。
  12. 根据权利要求1所述的橡胶组合物，其特征在于，以100重量份橡胶基体计，所述橡胶组合物包含0.1～10份交联剂。
  13. 根据权利要求1所述的橡胶组合物，其特征在于，所述交联剂包含过氧化物交联剂和硫磺中的至少一种，所述过氧化物交联剂为二叔丁基过氧化物、二枯基过氧化物、叔丁基枯基过氧化物、1,1-二叔丁基过氧化物-3,3,5-三甲基环己烷、2,5-二甲基-2,5-二(叔丁基过氧基)己烷、2,5-二甲基-2,5-二叔丁基过氧化基-3-己炔、双(叔丁基过氧化异丙基)苯、2,5-二甲基-2,5-二(过氧化苯甲酸)己烷、过氧化苯甲酸叔丁酯、叔丁基过氧化-2-乙基己基碳酸酯中的至少一种。
  14. 根据权利要求1所述的橡胶组合物，其特征在于，按重量份计，所述每100份橡胶基体中包含5～95份支化聚乙烯，0～60份乙丙橡胶和5～90份丁苯橡胶；以100重量份橡胶基体计，橡胶组合物还包含10～150份补强填充剂，1～8份交联剂。
  15. 根据权利要求1～14任一所述的橡胶组合物，其特征在于，所述橡胶组合物中还包含辅助成分。
  16. 根据权利要求15所述的橡胶组合物，其特征在于，所述辅助成分包含助交联剂、增塑剂、金属氧化物、硬脂酸、表面改性剂、稳定剂、硫化促进剂、增容剂、增粘剂、粘合剂、阻燃剂、发泡剂中的至少一种。
  17. 根据权利要求16所述的橡胶组合物，其特征在于，以100重量份橡胶基体计，所述辅助成分的用量范围为助交联剂0.2～10份，增塑剂0～80份，金属氧化物3～30份，硬脂酸0～3份，表面改性剂0～15份，稳定剂1～6份，硫化促进剂0～5份、增容剂0～15份、增粘剂0～5份、粘合剂0～20份、阻燃剂0～150份、发泡剂0～20份。
  18. 根据权利要求16所述的橡胶组合物，其特征在于，所述助交联剂包含三烯丙基氰脲酸酯、三烯丙基异氰脲酸酯、乙二醇二甲基丙烯酸酯、二甲基丙烯酸三乙二酯、偏苯三酸三烯丙酯、三甲基丙烯酸三羟甲基丙烷酯、N,N’-间苯撑双马来酰亚胺、N,N’-双亚糠基丙酮、1,2-聚丁二烯、不饱和羧酸金属盐和硫磺中的至少一种。
  19. 根据权利要求16所述的橡胶组合物，其特征在于，所述增塑剂包含硬脂酸、松香油、机油、环烷油、石蜡油、古马隆、RX-80、石蜡、液态聚异丁烯、癸二酸二辛酯中的至少一种。
  20. 根据权利要求16所述的橡胶组合物，其特征在于，所述表面改性剂包含聚乙二醇、二苯基硅二醇、三乙醇胺、硅烷偶联剂、钛酸酯偶联剂中的至少一种。
  21. 根据权利要求16所述的橡胶组合物，其特征在于，所述稳定剂包含2,2,4-三甲基-1,2-二氢化喹啉聚合体(RD)、6-乙氧基-2,2,4-三甲 基-1,2-二氢化喹啉(AW)、2-巯基苯并咪唑(MB)中的至少一种。
  22. 根据权利要求16所述的橡胶组合物，其特征在于，所述硫化促进剂包含2-硫醇基苯并噻唑、二硫化二苯并噻唑、一硫化四甲基秋兰姆、二硫化四甲基秋兰姆、二硫化四乙基秋兰姆、N-环己基-2-苯并噻唑基次磺酰胺、N，N-二环己基-2-苯噻唑基次磺酰胺、N-氧二乙撑基-2-苯并噻唑次磺酰胺、双马来酰亚胺、亚乙基硫脲中的至少一种。
  23. 根据权利要求16所述的橡胶组合物，其特征在于，所述增粘剂包含石油树脂、萜烯树脂、松香及衍生物、古马隆树脂中的至少一种。
  24. 根据权利要求16所述的橡胶组合物，其特征在于，所述粘合剂包含间苯二酚给予体、亚甲基给予体、有机钴盐、马来酸酐丁二烯树脂、液态天然橡胶中的至少一种。
  25. 根据权利要求1～14所述的橡胶组合物，其特征在于，按重量份计，所述每100份橡胶基体中还包含0～40份异戊二烯类弹性体和0～40份顺丁橡胶。
  26. 根据权利要求25所述的橡胶组合物，其特征在于，所述异戊二烯类弹性体为天然橡胶。
  27. 一种权利要求1～26任一所述橡胶组合物的加工方法，其混炼工艺采取母炼胶法，假设橡胶基体中，支化聚乙烯和乙丙橡胶的比重为a％，将支化聚乙烯和乙丙橡胶设定为母炼胶(A)的橡胶基体，将橡胶基体中其余组分设定为母炼胶(B)的橡胶基体，其特征在于，补强填充剂按高于a％的配比分配给母炼胶(A)，过氧化物交联剂按高 于a％的配比分配给母炼胶(A)。
  28. 一种鞋底，其特征在于，所用橡胶包含权利要求1～26中任一所述橡胶组合物。
  29. 一种胶鞋，其具有中底，其特征在于，所述中底所用橡胶包含权利要求1～26中任一所述橡胶组合物。
  30. 一种轮胎，其特征在于，所述轮胎的胎侧和胎面所用的胶料中至少一种包含权利要求1～26中任一所述橡胶组合物。
  31. 根据权利要求30所述的轮胎，其特征在于，所述轮胎为力车胎
  32. 根据权利要求30所述的轮胎，其特征在于，所述轮胎为子午线轮胎或斜交轮胎。
  33. 根据权利要求32所述的子午线轮胎，包含胎肩胶、带束层和胎体帘布层，其特征在于，所述胎肩胶、带束层和胎体帘布层中的至少一层所用橡胶包含权利要求1～26所述的橡胶组合物。
  34. 一种输送带，包含工作面覆盖胶与非工作面覆盖胶，所述工作面覆盖胶与非工作面覆盖胶之间设有抗拉层，其特征在于，所述工作面覆盖胶和非工作面覆盖胶中至少一层所用橡胶包含权利要求1～26任一所述橡胶组合物。
  35. 一种帆布芯输送带，其特征在于，所述帆布芯输送带的覆盖胶与浸胶帆布之间具有粘合层，其中粘合层所用橡胶包含权利要求1～26任一所述橡胶组合物。
  36. 根据权利要求35所述的帆布芯输送带，其特征在于，工作面覆盖胶与非工作面覆盖胶中至少一层所用橡胶包含橡胶组合物，所述橡 胶组合物的每100重量份橡胶基体中包含支化聚乙烯5～100重量份，所述帆布芯输送带所用的帆布为棉帆布、维纶帆布、锦纶帆布、聚酯帆布、直径直纬聚酯-锦纶帆布、芳纶帆布中的任意一种。
  37. 一种绳芯输送带，其特征在于，所述绳芯输送带的粘合芯胶所用橡胶包含权利要求1～26任一所述橡胶组合物。
  38. 根据权利要求37所述的绳芯输送带，其特征在于，所述绳芯输送带的工作面覆盖胶与非工作面覆盖胶至少一层所用橡胶包含橡胶组合物，所述橡胶组合物的每100重量份橡胶基体中包含支化聚乙烯5～100重量份，所述绳芯输送带所用的绳芯为钢丝绳芯或芳纶绳芯。
  39. 一种输送带，其覆盖胶和粘合胶之间有缓冲胶，其特征在于，所述缓冲胶所用橡胶包含权利要求1～26任一所述橡胶组合物。
  40. 根据权利要求35所述的输送带，其特征在于，工作面覆盖胶与非工作面覆盖胶至少一层所用橡胶包含橡胶组合物，所述橡胶组合物的每100重量份橡胶基体中包含支化聚乙烯5～100重量份。
  41. 一种胶管，包含内胶层、增强层和外胶层，其特征在于，所述内胶层和外胶层中的至少一层包含权利要求1～26任一所述橡胶组合物。
  42. 一种胶管，由内到外包含内胶层、第一增强层、中胶层、第二增强层和外胶层，其特征在于，所述中胶层所用橡胶包含权利要求1～26任一所述橡胶组合物。
  43. 根据权利要求42所述的胶管，其特征在于，外胶层和内胶层中至少一层所用橡胶包含橡胶组合物，所述橡胶组合物的每100重量份 橡胶基体中包含支化聚乙烯5～100重量份。
  44. 一种动力传送带，其包括：具有一定长度的包括缓冲橡胶层和压缩橡胶层的主体，其特征在于，缓冲橡胶层和压缩橡胶层中的至少一层所用橡胶包含权利要求1～26任一所述橡胶组合物。
  45. 一种胶辊，其特征在于，所用橡胶包含权利要求1～26中任一所述橡胶组合物。
  46. 一种密封条，其特征在于，所用橡胶包含权利要求1～26中任一所述橡胶组合物。
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