CN110713634B - Rubber composition, processing method and application - Google Patents

Rubber composition, processing method and application Download PDF

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CN110713634B
CN110713634B CN201810771273.4A CN201810771273A CN110713634B CN 110713634 B CN110713634 B CN 110713634B CN 201810771273 A CN201810771273 A CN 201810771273A CN 110713634 B CN110713634 B CN 110713634B
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rubber
parts
rubber composition
polybutadiene
weight
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CN110713634A (en
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不公告发明人
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Zhejiang University ZJU
Hangzhou Xinglu Technology Co Ltd
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Hangzhou Xinglu Technology Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
    • B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65G—TRANSPORT OR STORAGE DEVICES, e.g. CONVEYORS FOR LOADING OR TIPPING, SHOP CONVEYOR SYSTEMS OR PNEUMATIC TUBE CONVEYORS
    • B65G15/00—Conveyors having endless load-conveying surfaces, i.e. belts and like continuous members, to which tractive effort is transmitted by means other than endless driving elements of similar configuration
    • B65G15/30—Belts or like endless load-carriers
    • B65G15/32—Belts or like endless load-carriers made of rubber or plastics
    • B65G15/34—Belts or like endless load-carriers made of rubber or plastics with reinforcing layers, e.g. of fabric
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/02—Organic and inorganic ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/06—Sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/14—Peroxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

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  • Chemical & Material Sciences (AREA)
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Abstract

The invention discloses a rubber composition and a processing method and application thereof, wherein the rubber composition comprises a rubber matrix and matching components, and each 100 parts of the rubber matrix comprises 10-85 parts of polybutadiene rubber, 5-90 parts of branched polyethylene and 0-70 parts of ethylene propylene rubber in parts by weight; wherein the branched polyethylene has a degree of branching of not less than 50 branches/1000 carbons; the compounding component comprises a vulcanization system. The rubber composition provided by the invention has good aging resistance, mechanical property and wear resistance.

Description

Rubber composition, processing method and application
Technical Field
The invention belongs to the field of rubber, and particularly relates to a rubber composition and a processing method thereof, and an application of the rubber composition.
Technical Field
Polybutadiene rubber is a general synthetic rubber synthesized by using butadiene as a monomer and adopting different catalysts and polymerization methods, plays an important role in the field of synthetic rubber, and is the second most common synthetic rubber in the world which is second to styrene butadiene rubber at present. Polybutadiene rubbers can be classified into high cis polybutadiene rubbers (cis-1, 4 structure 90% or more), low cis polybutadiene rubbers (cis-1, 4 structure 35% to 40%, abbreviated as LCBR), medium vinyl polybutadiene rubbers (1,2 structure 35% to 65%), high vinyl polybutadiene rubbers (1,2 structure 65% or more), and high trans polybutadiene rubbers (trans-1, 4 structure 65% or more), according to the microstructure of the polymer. The microstructure differs depending mainly on the catalyst, the polymerization solvent and the polymerization temperature. The cobalt, titanium, nickel and rare earth catalysts are mainly used for producing high cis-1, 4-polybutadiene rubber, and other polybutadiene rubber varieties mainly adopt lithium catalyst systems.
The polybutadiene rubbers with different microstructures generally have the common advantage of good abrasion resistance in terms of the properties of the polybutadiene rubber compared with most common synthetic rubbers or natural rubbers, and therefore the abrasion resistance of other rubbers is often improved by using the polybutadiene rubber in combination in the prior art.
Various polybutadiene rubbers have excellent mechanical properties under the condition of the combination of the reinforcing agent, and have wide application in the production of rubber products such as tires, adhesive tapes, rubber tubes, rubber shoes and the like. However, various polybutadiene rubbers are poor in heat aging resistance, weather aging resistance and ozone aging resistance, and the double bonds contained in the molecular chain structure are liable to be broken at high temperature or under the influence of ozone, thereby deteriorating the properties of the rubbers.
The ethylene propylene rubber has excellent aging resistance due to high molecular main chain saturation and stable chemical structure, but the wear resistance is obviously weaker than that of polybutadiene rubber. In the prior art, a method of combining ethylene propylene rubber and polybutadiene rubber is generally adopted to improve the heat aging resistance, weather aging resistance and ozone aging resistance of the polybutadiene rubber, or to improve the wear resistance of the ethylene propylene rubber. However, due to the influence of factors such as poor co-vulcanization performance of the polybutadiene rubber and various rubbers with performance defects, the wear resistance of the polybutadiene rubber is deteriorated when ethylene propylene rubber is used in combination in a large amount, the heat aging resistance, weather aging resistance and ozone aging resistance of the ethylene propylene rubber are deteriorated when ethylene propylene rubber is used in combination in a large amount, and the overall mechanical properties of the two rubbers are also deteriorated. In the prior art, relatively sufficient research is already carried out on improving the co-vulcanization performance of ethylene propylene rubber and polybutadiene rubber, and a peroxide vulcanization system or a composite vulcanization system shared by sulfur and peroxide can achieve relatively ideal co-vulcanization degree. However, the inherent performance defects of each rubber are not improved obviously all the time, so that the comprehensive performance of the rubber product combined by the two rubber products still has the need and space for further improvement.
Disclosure of Invention
In view of the problems in the prior art, the present invention aims to provide a novel rubber composition having excellent overall performance in terms of aging resistance, wear resistance, mechanical properties, and the like.
In order to achieve the purpose, the invention provides the technical scheme that: the rubber composition comprises a rubber matrix and a matching component, wherein each 100 parts of the rubber matrix comprises 10-85 parts of polybutadiene rubber, 5-90 parts of branched polyethylene and 0-70 parts of ethylene propylene rubber in parts by weight; wherein the highly branched polyethylene is an ethylene homopolymer having a degree of branching of not less than 50 branches/1000 carbons; the compounding component comprises a vulcanization system.
The 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 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 molecular chain of the branched polyethylene is completely saturated, and the aging resistance is similar to or even superior to that of ethylene propylene rubber. Meanwhile, as the branched polyethylene has rich branched chain distribution, compared with ethylene propylene rubber with the branched chain mainly being methyl, the branched polyethylene can destroy the regularity of a molecular chain to a greater extent, thereby having lower glass transition temperature and better low-temperature performance, and under the same molecular weight, having lower Mooney viscosity and better processing performance, and easily forming a continuous phase when being used together with other rubber species such as polybutadiene rubber and the like, thereby leading the whole to have better aging resistance; on the other hand, under the same Mooney viscosity, the branched polyethylene can have higher molecular weight, and branched chains with different lengths of the branched polyethylene can form various C-C crosslinking bonds with different lengths between molecular main chains during peroxide vulcanization, so that stress concentration is effectively avoided, and the branched polyethylene can have higher tensile strength and tear strength, thereby endowing the whole higher physical and mechanical properties. Therefore, the present invention can provide a rubber composition having good aging resistance, mechanical properties and abrasion resistance.
The further technical scheme is that every 100 parts by weight of the rubber matrix contains 10-80 parts of branched polyethylene, 0-30 parts of ethylene propylene rubber and 10-70 parts of polybutadiene rubber.
The branching degree of the 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 degree of branching is more preferably 72 to 112 branches/1000 carbons, and the weight average molecular weight is more preferably 15.8 to 37.8 ten thousand. The Mooney viscosity ML (1+4) at 125 ℃ is preferably 6 to 102, more preferably 12 to 93, and still more preferably 20 to 70.
The branched polyethylene with low branching degree has high molecular weight and Mooney viscosity, even has a melting point above room temperature, and the branched polyethylene can be added into a combined system to endow the whole with good aging resistance and wear resistance, increase the stiffness of the rubber material and improve the process performance.
The branched polyethylene with higher branching degree has lower molecular weight and Mooney viscosity, can be used for improving the processing performance of ethylene propylene rubber or branched polyethylene with slightly lower branching degree, and enables the latter to form a continuous phase more easily, thereby endowing better aging resistance to the whole body under the condition that the specific gravity of polybutadiene rubber is higher.
In a further embodiment, the ethylene-propylene rubber comprises at least one of ethylene-propylene-diene rubber, and ethylene-propylene-diene rubber.
The ethylene-propylene-diene monomer and the ethylene-propylene-diene monomer are prepared by copolymerizing ethylene and propylene, and the ethylene-propylene-diene monomer are prepared by copolymerizing ethylene and propylene, wherein the ethylene-propylene-diene monomer and the ethylene-propylene-diene monomer comprise at least one of 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene, dicyclopentadiene and 1, 4-hexadiene. Examples of the diene monomer 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, 5-methylene-2-norbornene, 5-pentamethylene-2-norbornene, 1, 5-cyclooctadiene, 1, 4-cyclooctadiene, and the like.
The further technical proposal is that the diene monomer accounts for 1 to 14 percent of the weight of the ethylene propylene rubber.
The ethylene propylene rubber used in the invention is preferably ternary or quaternary ethylene propylene rubber with Mooney viscosity ML (1+4) at 125 ℃ of 15-100 and diene monomer weight proportion of 4-10%, the compatibility of the ethylene propylene rubber and branched polyethylene is excellent, a master batch method is generally adopted during mixing, the ethylene propylene rubber and the branched polyethylene are used as a rubber matrix of the master batch, when the content of the diene monomer in the ethylene propylene diene rubber is higher, the polarity of the master batch can be improved, the uniform dispersion of various fillers in final rubber is facilitated, and meanwhile, the third monomer can also play a role of a cross-linking assistant agent of peroxide, so that the cross-linking efficiency is improved. The molecular chain of the ethylene-propylene-diene monomer rubber can be subjected to co-crosslinking of sulfur and peroxide with the molecular chain of the butadiene rubber, and can also be subjected to co-crosslinking of peroxide with branched polyethylene, so that the distribution of crosslinking bonds on a rubber phase interface is increased, the integral co-vulcanization property can be further improved, and the physical and mechanical properties are improved.
The polybutadiene rubber comprises at least one of high cis-polybutadiene rubber, low cis-polybutadiene rubber, medium vinyl polybutadiene rubber, high vinyl polybutadiene rubber and high trans-polybutadiene rubber.
The cis-1, 4 structure content of the high-cis polybutadiene rubber is not less than 90%, preferably not less than 92%, more preferably not less than 96%, and still more preferably 96% to 98%. The cis-1, 4 structure content of the low cis-polybutadiene rubber is 35-40%. The 1,2 structure content of the medium vinyl polybutadiene rubber is 35-65%, preferably 35-55%. The 1,2 structure content of the high-vinyl polybutadiene rubber is not less than 65%, preferably not less than 70%.
Besides excellent wear resistance, various polybutadiene rubbers have other performance advantages depending on the microstructure. For example, high cis-polybutadiene rubber has excellent low temperature resistance, glass transition temperature of below-100 deg.c, good elasticity, low heat generation, less hysteresis loss, high bending resistance, high crack resistance, high dynamic performance and other advantages, but has poor wet skid resistance. Polybutadiene rubber with a higher vinyl content can have better wet skid resistance, but with the increase of the vinyl content, the glass transition temperature can be increased along with the good wet skid resistance, and the low temperature resistance can be obviously weakened. The low cis-polybutadiene rubber has an advantage of having good low temperature compression set resistance. Therefore, by selecting a suitable polybutadiene rubber type, the rubber composition can be provided with good performance in terms of cold resistance, wet skid resistance, low-temperature compression set resistance, and the like.
At present, polybutadiene rubber is most commonly used high-cis polybutadiene rubber which has excellent low temperature resistance, the glass transition temperature of the polybutadiene rubber can be lower than minus 100 ℃, the glass transition temperature of ethylene propylene rubber is about minus 50 ℃, and even higher, but the glass transition temperature of branched polyethylene is generally lower than minus 60 ℃, so when the ethylene propylene rubber is partially or completely replaced by the branched polyethylene to improve the aging resistance of the high-cis polybutadiene rubber, the negative influence on the low temperature resistance of the polybutadiene rubber can be reduced, and the overall low temperature resistance is improved.
For the purpose of improving the aging resistance of the polybutadiene rubber, the rubber composition of the present invention preferably contains 50 to 80 parts by weight of the polybutadiene rubber per 100 parts by weight of the rubber matrix, and more preferably 60 to 75 parts by weight.
For the purpose of improving the abrasion resistance or cold resistance of ethylene propylene rubber or branched polyethylene, the rubber composition of the present invention preferably contains 2 to 50 parts by weight, more preferably 5 to 45 parts by weight, still more preferably 10 to 40 parts by weight, and yet more preferably 20 to 30 parts by weight of polybutadiene rubber per 100 parts by weight of the rubber matrix. The polybutadiene rubber used is preferably a high cis-polybutadiene rubber or a low cis-polybutadiene rubber. Under a peroxide vulcanization system, when the usage amount of a small amount (such as 2-10 parts) of polybutadiene rubber is low, the cross-linking degree of ethylene propylene rubber or branched polyethylene can be improved by playing a role of an auxiliary cross-linking agent, and further, the wear resistance or cold-resistant compressibility is improved.
According to a further technical scheme, the vulcanization system in the rubber composition can be at least one selected from a peroxide vulcanization system, a sulfur vulcanization system and a radiation vulcanization sensitization system. Peroxide curing systems or curing systems using a combination of peroxide and sulfur are preferred.
The further technical proposal is that the peroxide curing system comprises a peroxide crosslinking agent, based on 100 weight portions of the rubber matrix, the peroxide cross-linking agent is used in an amount of 0.1-10 parts, and 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.
The further technical scheme is that the peroxide vulcanization system further comprises an auxiliary cross-linking agent, the using amount of the auxiliary cross-linking agent is 0.1-20 parts by weight based on 100 parts by weight of the rubber matrix, the auxiliary cross-linking agent comprises at least one of triallyl cyanurate, triallyl isocyanurate, ethylene glycol dimethacrylate, ethyl dimethacrylate, triethylene glycol dimethacrylate, triallyl trimellitate, trimethylolpropane trimethacrylate, ethylene glycol dimethacrylate, N '-m-phenylene bismaleimide (HVA-2), N' -difurfurylideneacetone, liquid 1, 2-polybutadiene, p-quinone dioxime, sulfur and metal salt of unsaturated carboxylic acid, the metal salt of unsaturated carboxylic acid contains at least one of zinc acrylate, zinc methacrylate (ZDMA), magnesium methacrylate, calcium methacrylate, and aluminum methacrylate.
Since the scorch time of peroxide vulcanization is generally shorter than that of sulfur vulcanization, if the production process of the article requires an extended scorch time, the extended scorch type organic peroxide F40P-SP2 can be used, or BHT can be added and the amount of peroxide can be increased appropriately, or a crosslinking assistant having the effect of extending the scorch time such as N, N' -m-phenylene bismaleimide can be added.
The liquid 1, 2-polybutadiene or liquid polyisobutylene has the function of an auxiliary crosslinking agent and also has the function of a plasticizer, and the rubber material has higher hardness after being vulcanized, so that the rubber material is suitable for occasions with requirements on high hardness. But the liquid substances are viscous liquid substances and are not beneficial to being added in the processing process, so the application of the liquid substances is limited to a certain extent. In the prior art, a liquid auxiliary crosslinking agent can be pre-dispersed in a synthetic inorganic filler (such as calcium silicate) to form a polybutadiene powdery substance, and the polybutadiene powdery substance is very convenient to add in the processing process and has good compatibility with a rubber material.
The metal salt of unsaturated carboxylic acid contains at least one of zinc acrylate, zinc methacrylate, magnesium methacrylate, calcium methacrylate, and aluminum methacrylate. When the unsaturated carboxylic acid metal salt such as zinc acrylate or zinc methacrylate is used as the auxiliary crosslinking agent of peroxide, ionic crosslinking can occur, the ionic bond shows good heat aging resistance stability and slip characteristic, and the characteristics of peroxide and sulfur vulcanization are combined, so that the rubber material can be endowed with good tensile strength, tear strength and heat resistance. In addition, the metal salt of an unsaturated carboxylic acid may also act as a binder to improve the adhesion of the size to synthetic fibers, metals, or other sizes.
To avoid the effect of aromatic oils on peroxide vulcanization, the polybutadiene rubber is preferably not oil-extended or naphthenic oil-extended.
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.
When the technical scheme that a peroxide vulcanization system and a 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, specifically, 0-15 parts of ethylene propylene diene monomer is contained in each 100 parts by weight of the rubber matrix, and the ethylene propylene diene monomer with high content of the third monomer is preferably used.
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, based on 100 parts by weight of a rubber substrate, 10-200 parts of a reinforcing filler, 0-80 parts of a plasticizer, 0-30 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 vulcanization accelerator, 0-15 parts of a compatibilizer, 0-15 parts of a tackifier, 0-20 parts of an adhesive, 0-150 parts of a flame retardant and 0-20 parts of a foaming 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. Without improving the cold resistance, dioctyl adipate, dioctyl sebacate, dioctyl phthalate, etc. may be preferably used.
The further technical scheme is that the metal oxide comprises at least one of zinc oxide, magnesium oxide and calcium oxide. The nano zinc oxide, the nano magnesium oxide or the nano calcium oxide with the particle size range of 10-100 nm are preferred, the mixture of the nano zinc oxide and the nano magnesium oxide is further preferred, and the addition amount of the nano metal oxide is preferably 5-20 parts by mass. The added metal oxide not only plays an activating role, but also the nano zinc oxide and the nano magnesium oxide can play a high temperature resistant role, and can play a heat conducting role in the vulcanization and application of thick products. In addition, the nano-scale oxide has large specific surface area and high activity, is beneficial to absorbing acidic substances released in the rubber aging process, and has obvious protective effect.
The further technical scheme is that the surface modifier comprises at least one of polyethylene glycol, diphenyl silanediol, triethanolamine, a silane coupling agent and a titanate coupling agent. Wherein the molecular weight of the 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), vinyltris (2-methoxyethoxy) silane (A-172), gamma-glycidoxypropyltrimethoxysilane (A-187), gamma-mercaptopropyltrimethoxysilane (A-189), bis (gamma-triethoxysilylpropyl) tetrasulfide (Si69), gamma-aminopropyltriethoxysilane (KH-550), etc.; the titanate coupling agent can be selected from ethylene dioleoyl titanate, isopropyl triisostearoyl titanate, isopropyl trioleoyl titanate, and the like.
Preferably, when the reinforcing filler contains the white carbon black, the surface modifier is added to reduce the activity of the white carbon black so as to reduce the influence on vulcanization, promote the combination of the white carbon black and rubber macromolecules, improve the dispersity of the rubber material, reduce the formation of a filler network, and further improve the vulcanization characteristic, comprehensive physical property, dynamic property and processing property of the white carbon black reinforcing rubber material. For compounds containing peroxide crosslinking agents, silanes containing vinyl groups are preferred.
Further technical means is that 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.
Further, the vulcanization accelerator may contain at least one of 2-mercaptobenzothiazole, dibenzothiazyl Disulfide (DM), tetramethylthiuram monosulfide, tetramethylthiuram disulfide (TMTD), tetraethylthiuram disulfide, N-cyclohexyl-2-benzothiazylsulfenamide (CZ), N-dicyclohexyl-2-benzothiazylsulfenamide, N-oxydiethylene-2-benzothiazylsulfenamide (NOBS), bismaleimide and ethylenethiourea. The type of accelerator having a relatively high solubility in the branched polyethylene or ethylene-propylene rubber phase is preferred, and the type of accelerator is preferably a sulfenamide type accelerator, depending on the difference in solubility of each type of accelerator in each rubber phase.
The compatibilizer may be selected from polarization-modified ethylene propylene rubber or branched polyethylene, and the polar monomer used for polarization modification 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, bromodimethyl hydantoin, carbon-adsorbed chlorine, carbon-adsorbed bromine, etc.), sulfur-containing compound (e.g., sulfur dioxide, sulfenyl chloride, etc.), Vinyltrimethoxysilane (VTMS), Vinyltriethoxysilane (VTES), and the like, 3-methacryloxypropyltrimethoxysilane (VMMS), styrene (St), alpha-methylstyrene (alpha-MSt), Acrylonitrile (AN), etc., which serve to improve the co-vulcanization properties of a mixture of ethylene-propylene rubber and branched polyethylene and polybutadiene rubber. Trans-polyoctene elastomers, for example, may also be selected to allow the use of the blend to form a more uniform morphology, thereby improving compatibility.
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, the type 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, the resorcinol donor adhesive can be partially replaced, and the adhesive 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 further technical scheme is that the flame retardant comprises at least one of aluminum hydroxide, magnesium hydroxide, zinc borate, antimony trioxide, zinc stearate, titanate, decabromodiphenyl ether, hydroxide modified by a silane coupling agent, red phosphorus, pentaerythritol, ammonium polyphosphate and triethyl phosphate.
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 rubber composition containing the foaming agent is particularly suitable for producing light and elastic sole materials.
The further technical scheme is that the rubber matrix of 100 parts further comprises 0-40 parts of butyl rubber or halogenated butyl rubber, 0-60 parts of natural rubber and 0-60 parts of styrene butadiene rubber. The halogenated butyl rubber can improve the dynamic ozone aging resistance of vulcanized rubber, has excellent compatibility with ethylene propylene rubber and branched polyethylene, and can improve the integral co-vulcanization property of the rubber composition; the natural rubber can improve the mechanical strength, elasticity, cohesiveness and the like of vulcanized rubber; the styrene-butadiene rubber can improve wet skid resistance, adhesion and the like of vulcanized rubber.
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 rubber composition of the present invention is usually prepared by first mixing all the components except the crosslinking system components such as the crosslinking agent, the vulcanization accelerator and the co-crosslinking agent in a suitable mixing apparatus (e.g., an internal mixer or an open mill) at a temperature of from room temperature or below up to 150 ℃ or higher. If the binder removal temperature is higher than the activation temperature of the cross-linking agent, cooling to be lower than the activation temperature is needed after binder removal. The crosslinking system is then mixed into the blend by subsequent mixing.
Due to the uneven distribution of various fillers in the rubber phases of the rubber composition during the mixing process, uneven vulcanization or stress concentration and other negative effects can be caused, and the physical and mechanical properties of the rubber composition are reduced. One solution is to add most of the filler into the rubber with low unsaturation degree and low polarity to prepare master batch, then add the used rubber and the rest of the filler, and continue to mix by the traditional method; the second solution is to mix the two rubbers to be used together into a rubber compound, and then mix the rubber compounds in proportion.
The invention provides a method for processing the rubber composition, which adopts a master batch method to mix the following rubber: assuming that the specific gravity of the branched polyethylene and the ethylene-propylene rubber is a% and the specific gravity of the remaining components including the polybutadiene rubber is B%, the branched polyethylene and the ethylene-propylene rubber are set as a rubber matrix of the masterbatch (A) and the remaining components including the polybutadiene rubber in the rubber matrix are set as a rubber matrix of the masterbatch (B), characterized in that, in the mixing stage of the masterbatch, the reinforcing filler is distributed to the masterbatch (A) at a ratio higher than a%, and the peroxide crosslinking agent is distributed to the masterbatch (A) at a ratio higher than a%.
The further technical scheme is that the mixing method of the rubber composition comprises the following steps:
the method comprises the following steps: respectively mixing in an internal mixer to obtain two master batches;
step two: and (3) mixing the master batch (A) and the master batch (B) in an internal mixer according to a ratio to obtain a final batch (C), thinly passing the final batch (C) on an open mill, then discharging, standing, and waiting for further processing.
The invention provides a conveyor belt, which comprises 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 rubber used in at least one layer of the working surface covering rubber and the non-working surface covering rubber comprises the rubber composition.
The preferable working surface covering rubber of the conveyor belt comprises the rubber composition, the covering rubber comprising the rubber composition is expected to have good wear resistance and heat aging resistance, and the amount of the polybutadiene rubber is preferably 10-85 parts, more preferably 20-80 parts, and even more preferably 30-70 parts per 100 parts by weight of the rubber matrix. If the polybutadiene rubber used contains a high cis-polybutadiene rubber, good low temperature resistance can be imparted to the cover rubber, and the cover rubber can be more suitably used in cold working environments.
The tensile layer of the conveyer belt can be canvas, a polymer rope core or a metal rope core.
The present invention provides a canvas core conveyor belt, wherein the rubber used for the adhesive layer comprises the rubber composition.
The rubber composition for the bonding layer can select a certain amount of low molecular weight polymer plasticizer such as liquid polyisobutylene, liquid 1, 2-polybutadiene or liquid ethylene propylene rubber to reduce the viscosity of branched polyethylene and/or ethylene propylene rubber, improve the self-adhesiveness of the branched polyethylene and/or ethylene propylene rubber and improve the blending and dispersing effect of the branched polyethylene and/or ethylene propylene rubber.
The technical scheme is that the rubber composition used for at least one layer of the working surface covering rubber and the non-working surface covering rubber of the canvas core conveyer belt comprises 5-100 parts by weight of branched polyethylene in every 100 parts by weight of the rubber matrix, and the used canvas is any one of cotton canvas, vinylon canvas, chinlon canvas, polyester canvas, diameter straight weft polyester-chinlon canvas and aramid canvas.
The invention provides a rope core conveying belt, wherein rubber used for bonding core rubber of the rope core conveying belt comprises the rubber composition, the rope core used is a steel wire rope core or a polymer rope core, and the polymer is preferably aramid.
The polybutadiene rubber contained in the adhesive core rubber is preferably high cis-polybutadiene rubber or low cis-polybutadiene rubber, and the high cis-polybutadiene rubber or low cis-polybutadiene rubber has the advantages of small hysteresis loss, low heat generation, good fatigue resistance and the like, so that the fatigue drawing resistance of the steel wire rope core or the aramid rope core in the adhesive core rubber can be improved.
The further technical scheme is that the rubber composition used for at least one layer of the working surface covering rubber and the non-working surface covering rubber of the rope core conveyer belt comprises 5-100 parts by weight of branched polyethylene in every 100 parts by weight of the rubber matrix, so that the aging resistance, the co-vulcanization property and the bonding property of the whole conveyer belt can be improved.
The adhesive rubber for the canvas core conveyer belt or the rubber composition for the adhesive core rubber for the rope core conveyer belt preferably comprises 3 to 20 parts by weight of the adhesive relative to 100 parts by weight of the rubber matrix to improve the adhesion with the covering rubber and the reinforcing material, and can further comprise 2 to 5 parts of short fibers to improve the modulus and improve the modulus distribution of the whole conveyer belt. The short fiber is preferably a variety with the surface being pretreated and good blending performance with non-polar rubber.
The invention provides a conveyor belt, wherein a buffer rubber is arranged between a covering rubber and an adhesive rubber, and the rubber used for the buffer rubber comprises the rubber composition.
The buffer glue is arranged between the covering glue and the adhesive glue, so that the adhesive force between the covering glue and the adhesive glue can be increased, the impact force of conveyed materials can be absorbed and dispersed, the buffer function of the buffer glue needs to have good adhesion, and the buffer glue has good elasticity, small heat generation and good heat dissipation performance.
The rubber composition comprises 5-100 parts by weight of branched polyethylene in each 100 parts by weight of a rubber matrix, wherein the rubber matrix is used for at least one layer of the working surface covering glue, the non-working surface covering glue and the adhesive glue.
The invention provides a hose which is a single-layer hose, and the rubber used comprises the rubber composition.
The further technical proposal is that the single-layer rubber pipe contains a reinforcing material.
The invention provides a rubber hose, which comprises an inner rubber layer, a reinforcing layer and an outer rubber layer, wherein the rubber used in at least one of the inner rubber layer and the outer rubber layer comprises the rubber composition.
The invention provides a rubber hose which comprises an inner rubber layer, a first reinforcing layer, a middle rubber layer, a second reinforcing layer and an outer rubber layer from inside to outside, wherein the middle rubber layer of the rubber hose comprises the rubber composition. The rubber composition for at least one of the outer rubber layer and the inner rubber layer comprises 5-100 parts by weight of branched polyethylene per 100 parts by weight of the rubber matrix.
The styrene butadiene rubber is used in the inner rubber layer or the outer rubber layer of the rubber pipe to improve the stiffness of the rubber material, and is particularly suitable for the inner rubber layer of the rubber pipe formed by a coreless method to improve the setting property.
The rubber tube can be applied to occasions with requirements on aging resistance, wear resistance, cold resistance, flexing resistance and the like.
The present invention provides a power transmission belt having a body including a cushion rubber layer and a compression rubber layer with a certain length, and a rubber used for at least one of the cushion rubber layer and the compression rubber layer contains the above rubber composition. Wherein the compression rubber layer contains short fibers and the cushion rubber layer does not contain short fibers.
When the power transmission belt is likely to be applied to a low-temperature environment, the polybutadiene rubber used in the rubber matrix of the rubber composition of the present invention is preferably a low-cis polybutadiene rubber, and the low-temperature compression resistance of the power transmission belt can be improved.
The invention provides a rubber roller, and the rubber used by the rubber roller comprises the rubber composition.
The invention provides a cable sheath material, and rubber used by the cable sheath material comprises the rubber composition.
The cable sheath material has good wear resistance, aging resistance and electrical insulation. When the polybutadiene rubber used in the rubber composition is high cis-polybutadiene rubber or low cis-polybutadiene rubber, the low temperature resistance and the flexing resistance can be good.
The present invention provides a sealing material, wherein the rubber used for the sealing material comprises the rubber composition. The sealing material can be a sealing ring, a sealing strip or other forms of sealing elements, and the polybutadiene rubber used in the rubber composition is preferably high cis-polybutadiene rubber or low cis-polybutadiene rubber, so that the sealing material has good low temperature resistance, especially low temperature compression resistance.
The invention provides a damping support, and the rubber used by the damping support comprises the rubber composition.
The damping support is suitable for occasions with requirements on cold resistance and low-temperature compression resistance.
The invention provides a sole, wherein the rubber used by the sole comprises the rubber composition.
The sole has excellent wear resistance, flexibility resistance and aging resistance. The rubber used for the sole can also have good wet skid resistance under the condition that the rubber comprises medium vinyl polybutadiene rubber or high ethylene polybutadiene rubber. The blended styrene butadiene rubber is beneficial to improving the wet skid resistance and the caking property of the sole.
The rubber composition for shoe soles further comprises a foaming agent.
The rubber composition for shoe soles further comprises a reinforcing filler which is composed of white carbon black with the particle size not more than 50nm, preferably 15-20 nm, and has transparency and reinforcing property.
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 high cis-polybutadiene rubber and the low cis-polybutadiene rubber have better wear resistance, elasticity, low temperature performance and aging resistance than natural rubber and styrene-butadiene rubber, so the rubber is particularly suitable for being used as a tire, especially a tread material. The tire tread mixed with the high cis-polybutadiene rubber and the low cis-polybutadiene rubber can obviously reduce heat generation and rolling resistance, improve wear resistance and prolong service life under severe driving conditions (high vehicle speed, poor road surface and low air temperature). The high cis-polybutadiene rubber and the low cis-polybutadiene rubber are mixed in the tire sidewall, so that the dynamic heat generation in the driving process can be reduced, the flexing resistance of the tire can be improved, and the service life of the tire can be prolonged. The low cis-polybutadiene rubber is preferably used at the contact part of the tire side and the wheel rim, so that good mechanical properties can be still kept at low temperature. The polybutadiene rubber having a higher vinyl content, although not as excellent as the high cis-polybutadiene rubber or the low cis-polybutadiene rubber in terms of low temperature resistance and low rolling resistance, may have a better wet skid resistance, the vinyl content range is preferably 35% to 75%, more preferably 55% to 75%, and the polybutadiene rubber having a higher vinyl content may have good performances in terms of wet skid resistance, wear resistance and rolling resistance at the same time.
Therefore, when the rubber composition of the present invention is used for producing tires (such as automobile tires) with high requirements on wet skid resistance, a preferred technical solution is to select a polybutadiene rubber with a high vinyl content in the rubber matrix, and the vinyl content is preferably in the range of 35% to 75%, and more preferably in the range of 55% to 75%.
In the prior art, the weather resistance and ozone aging resistance of the tire tread or sidewall rubber are improved by adding ethylene propylene rubber into the tire tread or sidewall rubber, and the weather resistance and ozone aging resistance of the tire tread or sidewall can be improved and the overall physical and mechanical properties can be improved by introducing branched polyethylene to replace part or all of the ethylene propylene rubber.
Because the adhesion of polybutadiene rubber, ethylene propylene rubber and branched polyethylene is poor, when the rubber composition is used for manufacturing tires, the preferable technical scheme is that the rubber composition further comprises 5-20 parts of tackifier relative to 100 parts by weight of rubber matrix.
The rubber composition for the tire can further comprise 5-40 parts of halogenated butyl rubber per 100 parts of rubber matrix to improve the yield resistance and the dynamic ozone aging resistance of the rubber material.
The rubber composition for the tire can further comprise 5-50 parts of natural rubber per 100 parts of rubber matrix, so that the mechanical strength and the adhesive property of rubber materials are improved.
The rubber composition for the tire can further comprise 5-50 parts of styrene-butadiene rubber per 100 parts of rubber matrix to improve the wet skid resistance and the bonding property of rubber materials.
The further technical scheme is that the tire is a hand-drawn tire. The hand-drawn vehicle tire can be a bicycle tire, a hand-drawn vehicle tire or an animal-drawn vehicle tire, and is preferably a bicycle tire.
The further technical scheme is that the tire is a radial tire or a bias tire.
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.
Further, at least one of the shoulder rubber, the belt layer and the carcass ply in the radial tire comprises the rubber composition. The use of the rubber composition can improve the co-vulcanization of the entire tire and the adhesion between the respective portions.
The invention has the beneficial effects that:
first, the branched polyethylene has a completely saturated molecular structure, heat aging resistance similar to that of ethylene propylene diene monomer, and better than that of ethylene propylene diene monomer, and the branched polyethylene has relatively high molecular weight and unique branched structure, so that the whole aging resistance and physical and mechanical properties can be improved.
Secondly, under the same molecular weight and dosage, the branched polyethylene can more easily form a continuous phase relative to ethylene propylene rubber, so that better aging resistance can be obtained integrally.
Thirdly, the wear resistance of the ethylene-propylene rubber and the branched polyethylene is lower than that of the polybutadiene rubber, and based on the second beneficial effect, the equivalent aging resistance can be obtained under the condition of using a smaller amount of the branched polyethylene, so that the negative influence on the wear resistance of the polybutadiene rubber is reduced, and the overall wear resistance is improved.
Fourthly, the molecular weight distribution of the branched polyethylene is narrower than that of the ethylene propylene rubber and the polybutadiene rubber, so that the rubber material can have good compression permanent deformation resistance.
Fifth, the glass transition temperature of branched polyethylene is generally lower than that of ethylene-propylene rubber, so partial or complete replacement of ethylene-propylene rubber with branched polyethylene can improve overall low temperature resistance.
The rubber composition has good aging resistance, wear resistance, physical and mechanical properties and low temperature resistance, and is suitable for application occasions with requirements on the properties of tires, rubber tubes, conveying belts, power transmission belts, rubber shoes, shock absorption, sealing and the like.
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.
Examples the alternative branched polyethylene feedstock is characterized by: the degree of branching is preferably 50 to 130 branches/1000 carbons, and the weight average molecular weight is preferably 6.6X 104～53.4×104g/mol, the Mooney viscosity ML (1+4) is preferably 6-105 ℃ at 125 ℃. Wherein the branching degree is measured by nuclear magnetic hydrogen spectroscopy, and the mole percentage of each branch is measured by nuclear magnetic carbon spectroscopy.
The branched polyethylene feedstock is further preferably from the following table:
Figure BDA0001730321340000161
the ethylene propylene rubber used in the examples of the present invention may be selected from the following table:
Figure BDA0001730321340000162
Figure BDA0001730321340000171
the polybutadiene rubber used in the examples of the present invention may be selected from the following table:
polybutadiene rubber class Numbering The structure is characterized in that: mooney viscosity ML (1+4)100 DEG C
High cis-polybutadiene rubber PBR-1 Cis-1, 4 structure content: 96 percent 45
Low cis-polybutadiene rubber PBR-2 Cis-1, 4 structure content: 38 percent of 42
Medium vinyl polybutadiene rubber PBR-3 Vinyl content: 45 percent of 46
High vinyl polybutadiene rubber PBR-4 Vinyl content: 72 percent 50
The rubber performance test method comprises the following steps:
1. and (3) hardness testing: testing by a hardness tester according to the national standard GB/T531.1-2008, wherein the testing temperature is room temperature;
2. and (3) testing the tensile strength and the elongation at break: according to the national standard GB/T528-2009, an electronic tensile testing machine is used for testing, the tensile speed is 500mm/min, the testing temperature is 23 +/-2 ℃, and the test sample is a 2-type dumbbell-shaped test sample;
3. mooney viscosity test: according to the national standard GB/T1232.1-2000, a Mooney viscometer is used for testing, the testing temperature is set according to actual conditions, preheating is carried out for 1 minute, and testing is carried out for 4 minutes;
4. hot air accelerated aging test: according to the national standard GB/T3512-2001, the method is carried out in a thermal aging test box, and the temperature and the time are set according to actual conditions;
5. ozone aging resistance test: according to the national standard GB/T7762-2003, in an ozone aging phase box, under a certain static tensile strain condition, the ozone aging phase box is exposed to air with a certain ozone concentration, and the ozone cracking resistance test is carried out in an environment without direct influence of light at a specified temperature (40 ℃);
6. testing of compression cold resistance coefficient: measured in a compression cold resistance coefficient measuring instrument according to the standard HG/T3866-2008.
Examples 1 to 4 and comparative examples 1 and 2
The rubber compositions of examples 1 to 4 and comparative examples 1 and 2 had the formulation components shown in Table 1: (wherein the parts by weight of each component used per 100 parts by weight of the rubber base are shown)
TABLE 1
Components Comparative example 1 Comparative example 2 Example 1 Example 2 Example 3 Example 4
Polybutadiene rubber numbering PBR-1 PBR-1 PBR-1 PBR-1 PBR-1 PBR-1
Amount of polybutadiene rubber 70 70 70 70 70 70
Ethylene propylene rubber numbering EPDM-1 EPDM-1 EPDM-1 EPDM-3
Amount of ethylene propylene rubber 30 25 15 5
Branched polyethylene numbering PER-8 PER-8 PER-8 PER-8
The amount of branched polyethylene used 5 15 25 30
Natural rubber 30
Zinc oxide 5 5 5 5 5 5
Stearic acid 2 2 2 2 2 2
Anti-aging agent MB 2 2 2 2 2 2
Antiager RD 2 2 2 2 2 2
Carbon Black N220 50 50 50 50 50 50
Paraffin oil Sunpar2280 6 6 6 6 6 6
Sulfur 2 1.5 1.5 1.5 1.5 1.5
Accelerant CZ 1 1 1 1 1 1
DCP 0.9 0.9 0.9 0.9 0.9
TAIC 0.4 0.4 0.4 0.4 0.4
The formulations of examples 1-4 and comparative example 2 were processed as follows: 50 percent of carbon black, 50 percent of zinc oxide and stearic acid, all DCP and TAIC, 50 percent of sulfur and an accelerator are mixed with a rubber matrix except polybutadiene rubber to obtain a master batch, then the polybutadiene rubber is mixed with the master batch for 1 minute, then the rest components are added according to the conventional sequence, and after 2 parts of mixing, rubber discharging is carried out. Thin-passing the rubber compound on an open mill with the roll temperature of 60 ℃, then discharging the rubber compound, and standing for 20 hours; after 16 hours of standing after vulcanization, the tests were carried out.
The processing method of comparative example 1 was: plasticating natural rubber, mixing the plasticated natural rubber with polybutadiene rubber for 1 minute, then adding zinc oxide, stearic acid and an anti-aging agent, mixing for 1 minute, then adding carbon black and paraffin oil, mixing for 2 minutes, after rubber removal, adding sulfur and an accelerator on an open mill, thinly passing, then discharging, and standing for 20 hours; after vulcanization, the test was carried out for 16 hours.
The test results of examples 1-4 and comparative examples 1 and 2 are shown in Table 2:
TABLE 2
Figure BDA0001730321340000181
Figure BDA0001730321340000191
Through comparison between comparative examples 1 and 2, it can be shown that the ethylene propylene rubber has weak mechanical strength and wear resistance, and although the ozone aging resistance of the rubber composition can be improved by using the ethylene propylene rubber together, the physical and mechanical properties of the rubber composition are affected, and the requirements of the wear-resistant conveyor belt covering rubber cannot be met.
Through comparison between examples 1-4 and comparative example 2, the branched polyethylene is used for replacing ethylene propylene rubber, so that the physical and mechanical properties can be improved on the premise of improving the ozone aging resistance, and the rubber compositions in examples 3 and 4 can meet the requirements of a wear-resistant conveyor belt and have good ozone aging resistance. The physical and mechanical properties of example 3 are better than those of example 4, probably because a small amount of ethylene propylene diene monomer rubber improves the co-vulcanization between the branched polyethylene and the polybutadiene rubber.
The rubber composition of example 3 or 4 can be used in the fields requiring wear resistance and aging resistance, such as wear-resistant conveyor belt covering rubber and shoe soles.
Examples 5 to 11 and comparative examples 3 and 4
The rubber compositions of examples 4 to 11 and comparative examples 3 and 4 had the formulation components shown in Table 3: (wherein the parts by weight of each component used per 100 parts by weight of the rubber base are shown)
TABLE 3
Figure BDA0001730321340000201
The formulations of examples 5-11 and comparative examples 3 and 4 were processed as follows: putting a rubber matrix into an internal mixer for prepressing and mixing for 90 seconds, then adding zinc oxide, stearic acid and an anti-aging agent for mixing for 1 minute, then adding carbon black and paraffin oil for mixing for 2 minutes, then adding DCP and TAIC, mixing for 2 minutes, and discharging rubber; thin-passing the rubber compound on an open mill with the roll temperature of 60 ℃, then discharging the rubber compound, and standing for 20 hours; the test was carried out after 16 hours of parking after vulcanization.
The test results of examples 5 to 11 and comparative examples 3 and 4 are shown in Table 4:
TABLE 4
Figure BDA0001730321340000202
Figure BDA0001730321340000211
By comparing examples 5 and 7 with comparative example 3 or comparing examples 6 and 11 with comparative example 4, it can be seen that the rubber composition can have a higher cold-resistant compression coefficient by replacing part or all of the ethylene-propylene rubber with branched polyethylene, and the cold-resistant compression coefficient of the rubber composition further increases as the specific gravity of the polybutadiene rubber increases.
The rubber compositions of examples 5 to 12 can be used for producing vibration-damping products or sealing products having excellent aging resistance and low-temperature resistance.
While preferred embodiments of the present invention are described herein, these embodiments are provided by way of example only. It is to be understood that variations of the embodiments of the invention described herein may also be used in the practice of the invention. Those skilled in the art will appreciate that various modifications, changes, and substitutions can be made without departing from the scope of the invention. It should be understood that the scope of the various aspects of the invention is defined by the claims and that methods and structures within the scope of these claims and their equivalents are intended to be covered thereby.

Claims (19)

1. A rubber composition comprises a rubber matrix and a matching component, and is characterized in that each 100 parts of the rubber matrix comprises, by weight, 10-85 parts of polybutadiene rubber, 5-90 parts of branched polyethylene and 0-70 parts of ethylene propylene rubber; wherein the branched polyethylene is an ethylene homopolymer with the branching degree of 60-130 branches/1000 carbons; the compounding component comprises a vulcanization system.
2. The rubber composition of claim 1, wherein the branched polyethylene has a degree of branching of 60 to 105 branches per 1000 carbons.
3. The rubber composition of claim 1, wherein the ethylene-propylene rubber comprises at least one of ethylene-propylene-diene rubber, and ethylene-propylene-diene rubber.
4. The rubber composition of claim 3, wherein the comonomer of the ethylene-propylene-diene monomer comprises a diene monomer comprising at least one of 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene, dicyclopentadiene, and 1, 4-hexadiene.
5. The rubber composition according to claim 4, wherein the diene monomer accounts for 1 to 14 weight percent of the ethylene-propylene rubber.
6. The rubber composition of claim 1, wherein the polybutadiene rubber comprises at least one of cis-1, 4-polybutadiene, trans-1, 4-polybutadiene, and 1, 2-polybutadiene.
7. The rubber composition of claim 6, wherein the polybutadiene rubber has a cis-1, 4 structure content of not less than 80%.
8. The rubber composition of claim 1, wherein the curing system is selected from at least one of a peroxide curing system, a sulfur curing system, and a radiation cure sensitized system.
9. The rubber composition of claim 8, wherein the curing system is a peroxide curing system, the rubber composition comprises a rubber substrate and a peroxide crosslinking agent, wherein the rubber substrate comprises 100 parts by weight of the rubber substrate, the peroxide dosage is 0.1-10 parts by weight, 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-butyl peroxy) hexane, 2, 5-dimethyl-2, 5-di (peroxy benzoic acid) hexane, tert-butyl peroxy benzoate and tert-butyl peroxy-2-ethylhexyl carbonate.
10. The rubber composition according to claim 9, wherein the peroxide curing system comprises 0.1-20 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, liquid 1, 2-polybutadiene, metal salt of unsaturated carboxylic acid, and sulfur.
11. 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, 0 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 vulcanization accelerator, 0 to 15 parts of a compatibilizer, 0 to 15 parts of a tackifier, 0 to 20 parts of an adhesive, 0 to 150 parts of a flame retardant, and 0 to 20 parts of a foaming agent.
12. The rubber composition of claim 11, wherein the reinforcing filler comprises at least one of carbon black, white carbon black, calcium carbonate, calcined kaolin, talc, magnesium silicate, aluminum silicate, magnesium carbonate, titanium dioxide, montmorillonite, and short fibers.
13. The rubber composition of claim 11, wherein the plasticizer comprises at least one of pine tar, machine oil, naphthenic oil, paraffin oil, aromatic oil, liquid polyisobutylene, coumarone, RX-80, stearic acid, paraffin wax, chlorinated paraffin wax, dioctyl adipate, dioctyl sebacate, epoxidized soybean oil, dibutyl phthalate, dioctyl phthalate, diisodecyl phthalate, ditridecyl phthalate, trioctyl trimellitate.
14. The rubber composition according to claim 1 to 13, wherein the rubber matrix contains 0 to 40 parts by weight of a butyl rubber or a halogenated butyl rubber, 0 to 50 parts by weight of an isoprene-based elastomer and 0 to 40 parts by weight of a styrene-butadiene rubber per 100 parts by weight of the rubber matrix.
15. The rubber composition according to claim 14, wherein the isoprene-based elastomer comprises at least one of natural rubber and synthetic polyisoprene.
16. A conveyor belt comprising a working face coating rubber and a non-working face coating rubber, wherein at least one layer of the working face coating rubber and the non-working face coating rubber comprises the rubber composition according to any one of claims 1 to 15.
17. A shoe sole, wherein the rubber used comprises the rubber composition according to any one of claims 1 to 15.
18. A vibration damper comprising a rubber composition according to any one of claims 1 to 15.
19. 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.
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