WO2018130194A1 - Rubber composite, processing method, rubber products applying composite, and manufacturing method - Google Patents

Abstract

A rubber composite, a processing method, applications of the composite in rubber products, and a manufacturing method for the rubber products. The rubber composite comprises: a rubber substrate and essential components. The rubber substrate comprises: branched polyethylene, the content thereof being a: 0 < a ≤ 100 parts, ethylene propylene monomer rubber and ethylene propylene diene monomer rubber, the content thereof being b: 0 ≤ b < 100 parts. The essential components comprise: a crosslinking agent 1.5-10 parts and a reinforcing filler 40-200 parts. The reinforcing filler comprises carbon black, white carbon black, may also comprise one or more of calcium carbonate, talcum powder, calcined clay, magnesium silicate, and magnesium carbonate, and containing carbon black 5-100 parts and white carbon black 5-60 parts. The applications of the rubber composite are in the manufacturing of the rubber products. The rubber products comprise an insulating material used for manufacturing high-strength electric wire and cable, a waterproof rolled material, and a high temperature-resistant conveyor belt.

Description

Rubber composition and processing method, and rubber product and production method thereof Technical field

The invention belongs to the field of rubber, in particular to a rubber composition and a processing method thereof, and relates to the application of the rubber composition in a rubber product requiring better tear strength and adhesion properties, and production. The method of the rubber article includes, but is not limited to, a rubber product such as an insulating material for a high-strength wire and cable, a high-temperature resistant conveyor belt, and a waterproof coil.

Background technique

In the field of rubber products, the two most commonly used fillers with higher reinforced properties are carbon black and white carbon black, in which a reinforcing filling system using silica and carbon black is used in combination with reinforcing without silica. Filling systems can often give rubber products better tear resistance, adhesion properties, wear resistance and low heat build-up. This kind of reinforcing system with white carbon black and carbon black is used in tire tread rubber and tire tires. The application of side glue, waterproof coil material, conveyor belt cover rubber and the like is more common. Ethylene-propylene rubber is widely used in waterproofing coils and heat-resistant conveyor belts due to its good aging resistance. Sulfur vulcanization and peroxide vulcanization are the two most commonly used vulcanization systems for ethylene propylene rubber, in order to obtain better aging resistance. For the properties of high temperature and high temperature, peroxide vulcanization is used, but the tensile strength and tear strength of peroxide vulcanized ethylene propylene rubber are weaker than that of sulfur vulcanized ethylene propylene rubber, which will offset part of the use of silica. The performance advantage brought by it is relatively easy to be destroyed during use.

China Patent Licensing Bulletin No. CN104312018B is a heat-resistant conveyor belt covering rubber, which includes binary ethylene propylene rubber, low Mooney EPDM rubber, high wear-resistant carbon black, zinc methacrylate, white carbon black, paraffin wax, and sticky A combination of a reinforcing agent, a resorcinol, an antioxidant, and the like, which do not emphasize good mechanical properties.

Chinese Patent Publication No. CN105504548A discloses a high tear-resistant peroxide EPDM rubber raw material, which is made of the following raw materials by weight: ethylene propylene diene monomer, zinc oxide, stearic acid, antioxidant RD, Polyethylene glycol PEG4000, white carbon black, carbon black, light calcium carbonate, paraffin oil 2280, sulfur, crosslinker BIPB, TAIC, the main component of the rubber matrix is EPDM rubber, its mechanical properties and natural rubber Or there is still a gap in styrene butadiene rubber. How to further improve the aging resistance and mechanical properties of ethylene propylene rubber is a problem.

Ethylene-propylene rubber is a synthetic rubber with saturated molecular chain. It can be divided into two major categories: ethylene-propylene rubber and EPDM rubber. Both of them have good aging resistance. They are commonly used in ethylene-propylene rubber products. It is EPDM rubber, but because EPDM rubber contains a third monomer, the molecular chain contains double bonds, and the ethylene-propylene rubber molecular chain is completely saturated, so the ethylene-propylene rubber has more excellent resistance to aging. Sex, therefore, in the case of high requirements for aging resistance, it is a common technical solution to improve the aging resistance of EPDM by using ethylene propylene diene rubber together. However, the mechanical strength of the binary ethylene propylene rubber is low, which will affect the overall physical and mechanical properties.

Diethylene propylene rubber is a copolymer of ethylene and propylene and belongs to the copolymer of ethylene and α-olefin. Ethylene and α-olefin copolymers are polymers containing only hydrocarbon elements and saturated molecular chains. The common types of carbon atoms in such polymers are generally classified into primary, secondary and tertiary carbons, while tertiary carbons are the most It is easy to be trapped by hydrogen to form free radicals, so the ratio of tertiary carbon atoms to all carbon atoms is generally considered to be a major factor affecting the aging resistance of ethylene and α-olefin copolymers. The lower the ratio, the better the aging resistance. The ratio can be expressed by the degree of branching. For example, a diethylene propylene rubber having a propylene content of 60% by weight can be calculated to contain 200 propylene units per 1000 carbon atoms, that is, 200 tertiary carbon atoms or 200. One methyl branch, so its degree of branching is 200 branches / 1000 carbons. Ethylene ethylene propylene rubber generally has a weight percentage of 40% to 65% or 40% to 60%, so its branching degree is generally 117 to 200 branches/1000 carbons or 133 to 200 branches/ This degree of branching can be considered to be higher than other common ethylene and alpha-olefin copolymers in the 1000 carbon range.

In the prior art, the α-olefin in the common ethylene and α-olefin copolymer may be an α-olefin having a carbon number of not less than 4 in addition to propylene, and may be selected from a C ₄ - C ₂₀ α-olefin. It is usually selected from the group consisting of 1-butene, 1-hexene and 1-octene. If the degree of branching of the copolymer of ethylene and α-olefin is too low, the melting point and crystallinity are too high, and it is not suitable for use as a rubber component. If the degree of branching is high, the content of α-olefin is high, which may result in Process difficulty and raw material cost are high, and operability and economy are low. In the prior art, a polyolefin obtained by copolymerizing ethylene with 1-butene or ethylene and 1-octene may be referred to as a polyolefin plastomer or a polyolefin elastomer according to the degree of crystallinity and melting point, and a part of the polyolefin is elastic. Due to its proper crystallinity and melting point, it can be used well with ethylene propylene rubber and has a low degree of branching. It is considered to be an ideal material for improving the aging resistance of ethylene propylene rubber. It can replace ethylene propylene rubber to a certain extent. use. Since the molecular chain of ethylene and 1-octene copolymer is softer, more rubbery and has good physical and mechanical properties relative to the copolymer of ethylene and 1-butene, the polyolefin elastomer commonly used in rubber products is generally ethylene. And the copolymer of 1-octene, the octene weight percentage is generally not higher than 45%, more commonly not higher than 40%, the corresponding degree of branching is generally not higher than 56 branches / 1000 carbon, The more commonly used degree of branching is not higher than 50 branches/1000 carbons, which is much lower than the degree of branching of ethylene dipropylene rubber, so it has excellent aging resistance and good physical and mechanical properties.

The rubber generally needs to be used after cross-linking. In the cross-linking mode commonly used for ethylene-propylene rubber, the copolymer of ethylene and α-olefin may be peroxide cross-linking or irradiation cross-linking, both of which are mainly obtained by capturing tertiary carbon. a hydrogen atom forms a tertiary carbon radical, and then forms a carbon-carbon crosslink by radical bonding, but a copolymer of ethylene and 1-octene (hereinafter referred to as POE) has fewer tertiary carbon atoms and is attached to a tertiary carbon atom. The chain length is large, the steric hindrance is large, and the free radical reaction is difficult to occur, which leads to difficulty in crosslinking, affecting processing efficiency and product performance.

Therefore, there is a need for a better technical solution that can improve the aging resistance of ethylene propylene rubber, and at the same time, it can have better physical and mechanical properties and cross-linking performance, and is expected to be specific to the functional indexes required for rubber products (such as anti- Compression, permanent deformation, etc.) have a good performance.

Summary of the invention

In view of the problems in the prior art, the present invention provides a rubber composition and a processing method thereof, and a production method for manufacturing a rubber product using the rubber composition, which has a branching degree of not less than 50 branches/ A 1000 carbon branched polyethylene replaces some or all of the ethylene propylene rubber, thereby changing the yield of existing rubber products and improving the performance of rubber products.

In order to achieve the above object, the present invention adopts the following technical solution: a rubber composition is provided, wherein the rubber composition comprises: a rubber matrix and a necessary component, the rubber matrix comprising: a branched polyethylene having a content of a: 0<a≤100 parts, the content of the binary ethylene propylene rubber and the ethylene propylene diene rubber b: 0 ≤ b < 100 parts, the necessary components include: 1.5 to 10 parts of the crosslinking agent, and the reinforcing filler 40 ～ 200 parts, the reinforcing filler comprises carbon black, white carbon black, calcium carbonate, talc, calcined clay, magnesium silicate, magnesium carbonate, two or more, including carbon black 5 to 100 parts, including white 5 to 60 parts of carbon black, wherein the branching degree of branched polyethylene is not less than 50 branches/1000 carbons, the weight average molecular weight is not less than 50,000, and the Mooney viscosity ML (1+4) is not low at 125 °C. At 2.

"Branched polyethylene" in the prior art means, in addition to a branched ethylene homopolymer, a branched saturated vinyl copolymer, such as an ethylene-α-olefin copolymer, which may be POE, although POE performs well in physical and mechanical properties and aging resistance, but cross-linking performance is not good, although the branched polyethylene of the present invention can contain both branched ethylene homopolymer and POE, but a better choice It is a branched polyethylene having a high proportion of branched polyethylene or a branched ethylene homopolymer. In a preferred embodiment of the invention, the branched polyethylene contains only branched ethylene homopolymer.

In the further elaboration of the technical solution of the present invention, the branched polyethylene used is a branched ethylene homopolymer unless otherwise specified.

The branched polyethylene used in the present invention is a kind of ethylene homopolymer having a branching degree of not less than 50 branches/1000 carbons, and can be called Branched Polyethylene or Branched PE. Currently, the synthesis method is mainly composed of a late transition metal catalyst. The homopolymerization of ethylene is catalyzed by a "chain walking mechanism", and the preferred late transition metal catalyst may be one of (α-diimine) nickel/palladium catalysts. The nature of the chain walking mechanism refers to the late transition metal catalyst. For example, the (α-diimine) nickel/palladium catalyst is more likely to undergo β-hydrogen elimination reaction and re-insertion reaction in the process of catalyzing olefin polymerization, thereby causing branching. Branched chains of such branched polyethylenes may have different numbers of carbon atoms, specifically 1 to 6, or more carbon atoms.

The production cost of the (α-diimine) nickel catalyst is significantly lower than that of the (α-diimine) palladium catalyst, and the (α-diimine) nickel catalyst catalyzes the high rate of ethylene polymerization and high activity, and is more suitable for industrial applications. Therefore, the branched polyethylene prepared by the ethylene polymerization of the (α-diimine) nickel catalyst is preferred in the present invention.

The degree of branching of the branched polyethylene used in the present invention is preferably 50 to 130 branches/1000 carbons, further preferably 60 to 130 branches/1000 carbons, further preferably 60 to 116 branches/1000. A carbon, the degree of branching between POE and ethylene-propylene rubber, is a new technical solution that is different from the prior art, and can have excellent aging resistance and good cross-linking performance.

Cross-linking performance includes factors such as crosslink density and cross-linking rate, which is the specific performance of the cross-linking ability of the rubber matrix during processing.

The branched polyethylene used in the present invention preferably has a methyl branch content of 40% or more or 50% or more, and has a certain similarity with the structure of the ethylene propylene diene rubber. In terms of cross-linking ability, the degree of branching (tertiary carbon atom content) and the steric hindrance around the tertiary carbon atom are the two main factors affecting the cross-linking ability of the saturated polyolefin. The branched polyethylene used in the present invention is low in degree of branching relative to the ethylene propylene rubber, and since the branched polyethylene has a branch having a carbon number of not less than 2, the branched polycondensation used in the present invention The steric hindrance around the tertiary carbon atom of ethylene is theoretically larger than that of ethylene propylene rubber. It can be judged by combining two factors that the crosslinking ability of the branched polyethylene used in the present invention should be weaker than that of the ethylene propylene rubber. In EPDM rubber. However, the actual cross-linking ability of the partially branched polyethylene used in the present invention is close to that of EPDM rubber, and may even be equal to or better than EPDM rubber. This means that the rubber composition of the present invention can obtain a good aging resistance, can also not weaken the crosslinking ability, and can even have excellent crosslinking performance to achieve an unexpected beneficial effect.

This may be explained by the fact that there may be an appropriate number of secondary branched structures on the branched polyethylene used in the preferred embodiment of the present invention, and the so-called secondary branched structure refers to a structure in which branches are further branched. This is also known as "branch-on-branch" during chain walking. Because of the low steric hindrance around the tertiary carbon atoms of the secondary branches, cross-linking reactions are more likely to occur. Having a secondary branched structure is a distinct distinction between the branched polyethylene used in the preferred embodiment of the present invention and the prior art ethylene propylene diene rubber or the conventional ethylene-α-olefin copolymer.

It is a new technical solution to improve the cross-linking ability of saturated polyolefin elastomer by using the secondary steric structure with lower steric hindrance. Under the technical solution of the present invention, it is also considered to be within the technical protection of the present invention to include a vinyl copolymer having a secondary branched structure or other saturated hydrocarbon polymer in the rubber matrix. The vinyl copolymer refers to a copolymer of ethylene and a branched α-olefin, and has a secondary branched structure, wherein the branched α-olefin may be selected from the group consisting of isobutylene and 3-methyl-1- Butylene, 4-methyl-1-pentene, 3-methyl-1-pentene, 2-methyl-1-heptene, 3-methyl-1-heptene, 4-methyl-1- The heptene, 5-methyl-1-heptene, 6-methyl-1-heptene, and the like, the comonomer may also contain a common linear alpha-olefin.

It is generally believed in the prior art that the branched polyethylene prepared by the (α-diimine) nickel catalyst is difficult to exist in the secondary branched structure, and at least it is difficult to sufficiently distinguish it. The technical solution of the present invention is also to analyze the branched polycondensation. The structure of ethylene provides a new idea.

Compared with ethylene propylene rubber, when the branched polyethylene has an appropriate number of secondary branched structures, the cross-linking point of the branched polyethylene can be generated on the tertiary chain of the main chain during the peroxide crosslinking process. It can also be produced on the branched tertiary carbon of the secondary structure, so the rubber network formed by the cross-linking of the branched polyethylene has a richer CC connecting segment between the main chains than the ethylene-propylene rubber. The length can effectively avoid stress concentration and help to obtain better mechanical properties.

In a preferred embodiment, the content of the branched polyethylene in the rubber matrix is: 10 ≤ a ≤ 100 parts, and the content of the binary ethylene propylene rubber and the EPDM rubber is 0 ≤ b. ≤90 parts; the branched polyethylene is characterized by: it is an ethylene homopolymer, the degree of branching is 60-130 branches/1000 carbons, the weight average molecular weight is 66,000 to 518,000, and the Mooney viscosity is ML ( 1+4) 125 ° C is 6 to 102.

In a preferred embodiment, the content of the branched polyethylene in the rubber matrix is: 10 ≤ a ≤ 100 parts, and the content of the binary ethylene propylene rubber and the EPDM rubber is 0 ≤ b. ≤90 parts; the branched polyethylene is an ethylene homopolymer having a branching degree of 70-116 branches/1000 carbons, a weight average molecular weight of 201,000 to 436,000, and a Mooney viscosity ML (1+4) ) 125 ° C is 23 ~ 101;

In a preferred embodiment, the content of the branched polyethylene in the rubber matrix is a: 10 ≤ a ≤ 100 parts, and the total content of the binary ethylene propylene rubber and the EPDM rubber is b: 0. ≤ b ≤ 90 parts; the branched polyethylene is an ethylene homopolymer having a degree of branching of 80 to 105 branches/1000 carbons, a weight average molecular weight of 250,000 to 400,000, and a Mooney viscosity ML (1) +4) 125 ° C is 40 to 95.

In a preferred embodiment, the content of the branched polyethylene in the rubber matrix is a: 10 ≤ a ≤ 100 parts, and the total content of the binary ethylene propylene rubber and the EPDM rubber is b: 0. ≤ b ≤ 90 parts; the branched polyethylene is an ethylene homopolymer having a degree of branching of 80 to 105 branches/1000 carbons, a weight average molecular weight of 268,000 to 356,000, and a Mooney viscosity ML (1) +4) 125 ° C is 42 to 80.

In a preferred embodiment, the third monomer of the ethylene propylene diene monomer is preferably a diene monomer, specifically selected from the group consisting of 5-ethylidene-2-norbornene and 5-vinyl-2-nor Borneene, dicyclopentadiene, 1,4-hexadiene, 1,5-hexadiene, 1,4-pentadiene, 2-methyl-1,4-pentadiene, 3-methyl- 1,4-Hexadiene, 4-methyl-1,4-hexadiene, 1,9-decadiene, 5-methylene-2-norbornene, 5-pentylene-2-nor Borbornene, 1,5-cyclooctadiene, 1,4-cyclooctadiene, and the like. Specifically, the ethylene propylene rubber may contain two or more kinds of diene monomers at the same time, such as 5-ethylidene-2-norbornene and 5-vinyl-2-norbornene. The functional group of the diene monomer can play the same role as the intrinsic co-crosslinking agent in the peroxide vulcanization, thereby improving the crosslinking efficiency. This helps to reduce the amount and residual amount of crosslinker and co-crosslinker required and the cost of adding them. The weight specific gravity of the diene monomer to the ethylene propylene rubber is preferably from 1% to 14%, more preferably from 3% to 10%, still more preferably from 4% to 7%.

In a preferred embodiment, the silica comprises at least one of precipitated silica and fumed silica.

In a preferred embodiment, the carbon black comprises at least one of N220, N330, N550, N660, N774, N990.

In a preferred embodiment, the crosslinking agent comprises at least one of a peroxide crosslinking agent and a sulfur, and the peroxide crosslinking agent is di-tert-butyl peroxide, dicumyl peroxide, Tert-butyl cumyl peroxide, 1,1-di-tert-butyl peroxide-3,3,5-trimethylcyclohexane, 2,5-dimethyl-2,5-di(tert-butyl) Base oxidized) hexane, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne-3, bis(tert-butylperoxyisopropyl)benzene, 2,5-di At least one of methyl-2,5-bis(benzoyl peroxy)hexane, tert-butyl peroxybenzoate, and t-butylperoxy-2-ethylhexyl carbonate.

In a preferred embodiment, the rubber composition further comprises an auxiliary component, the auxiliary component comprising: 0.2 to 20 parts of a co-crosslinking agent, 5 to 100 parts of a plasticizer, and a stabilizer 1 based on 100 parts by weight of the rubber matrix. ～3 parts, 2 to 10 parts of metal oxide, 1 to 10 parts of surface modifier, 0 to 3 parts of vulcanization accelerator, and 0 to 20 parts of binder.

In a preferred embodiment, the stabilizer comprises 2,2,4-trimethyl-1,2-dihydroquinoline (RD), 6-ethoxy-2,2,4-trimethyl-1 At least one of 2-dihydroquinoline (AW), 2-mercaptobenzimidazole (MB), and N-4 (anilinophenyl)maleimide (MC).

In a preferred embodiment, the co-crosslinking agent comprises triallyl cyanurate, triallyl isocyanurate, ethylene glycol dimethacrylate, ethyl dimethacrylate, and dimethyl Triethyl acrylate, triallyl trimellitate, trimethylolpropane trimethacrylate, ethylene glycol dimethacrylate, N, N'-m-phenylene bismaleimide At least one of N, N'-bis-indenyl acetonone, 1,2-polybutadiene, sulfur, and a metal salt of an unsaturated carboxylic acid.

In a preferred embodiment, the plasticizer is at least one of pine tar, motor oil, naphthenic oil, paraffin oil, coumarone, RX-80, stearic acid, paraffin wax, and liquid polyisobutylene. Among them, stearic acid can also act as an active agent in sulfur-sulfur-based systems, and can form soluble salts with some metal oxides, thereby increasing the activation of metal oxides on promoters. The rational use of plasticizers can increase the flexibility of the compound and the plasticity suitable for process operation. In order to increase the viscosity, it is also preferred to use an adhesion promoter such as pine tar, coumarone, RX-80, liquid polyisobutylene or the like.

In a preferred embodiment, the metal oxide is at least one of zinc oxide, magnesium oxide, and calcium oxide.

In a preferred embodiment, the surface modifier is polyethylene glycol, diphenyl silicon glycol, triethanolamine, vinyl tris(2-methoxyethoxy)silane having a molecular weight of 2000 or 3400 or 4000. (A-172), at least one of γ-glycidoxypropyltrimethoxysilane (A-187) and γ-mercaptopropyltrimethoxysilane (A-189).

In a preferred embodiment, the vulcanization accelerator comprises 2-thiol benzothiazole, dibenzothiazyl disulfide, tetramethylthiuram monosulfide, tetramethylthiuram disulfide, tetrazyl disulfide Kethiram, N-cyclohexyl-2-benzothiazolyl sulfenamide, N,N-dicyclohexyl-2-benzothiazolyl sulfenamide, bismaleimide, ethylene thiourea At least one of them.

In a preferred embodiment, the resorcinol donor may be selected from the group consisting of resorcinol (adhesive R), binder RS, binder RS-11, binder R-80, binder At least one of RL, binder binder PF, binder PE, binder RK, binder RH; the methylene donor may be selected from hexamethylenetetramine (HMTA), bonding At least one of the agent H-80, the binder A, the binder RA, the binder AB-30, the binder Rq, the binder RC, the binder CS963, and the binder CS964.

A preferred embodiment is that the adhesive may also be selected from a triazine adhesive, and the specific commercial grade may be selected from at least one of the adhesive TAR, the adhesive TZ, the adhesive AIR-1, and the adhesive AIR-101. One type, preferably at least one of the binder AIR-1 and the binder AIR-101, can partially replace the above-mentioned resorcinol donor binder, and has the advantages of good adhesion and relatively environmental protection. In an embodiment of the present invention, in order to improve the viscosity of the rubber compound, the rubber composition may further comprise a tackifier, wherein the plasticizer is pine tar, coumarone resin, RX-80, and liquid polyisobutylene. The role of the adhesive, wherein the liquid coumarone resin has a better viscosity-increasing effect than the solid coumarone resin, and the tackifier may also be selected from the group consisting of C5 petroleum resin, C9 petroleum resin, hydrogenated rosin, terpene resin, alkyl group. A commonly used tackifier such as a phenol resin, a modified alkyl phenol resin, or an alkyl phenol-acetylene resin, and the tackifier is generally not more than 30 parts by weight, further preferably not more than 10 parts by weight, based on 100 parts by weight of the rubber base. It is further preferably not more than 5 parts by weight.

The crosslinking agent, the co-crosslinking agent and the vulcanization accelerator involved in the rubber composition provided by the present invention all belong to a crosslinking system.

The rubber composition of the present invention may be present in the form of an uncrosslinked rubber compound, and may be present in the form of a vulcanized rubber after further crosslinking reaction. Vulcanized rubber can also be referred to simply as vulcanizate.

The present invention also provides a method for processing the above rubber composition, the processing method comprising the following steps: Step 1: setting the temperature of the internal mixer and the rotation speed of the rotor, first adding the rubber composition other than the crosslinking system in order of weight Mixing into an internal mixer;

Step 2: Then adding a crosslinking system, after being uniformly kneaded, discharging, to obtain a rubber mixture;

Step 3: The mixture is thinned on the open mill and then placed on the sheet to be vulcanized;

Step 4: then vulcanizing according to a vulcanization process;

Wherein, the crosslinking system comprises a crosslinking agent, and further comprises at least one of a crosslinking agent and a vulcanization accelerator. In order to improve the mechanical properties and compression set resistance of the vulcanizate, the vulcanization process may be further carried out by a two-stage vulcanization process. . .

The present invention provides an insulating material for high-strength wire and cable, and the rubber compound used comprises the above rubber composition.

The invention also provides a method for producing an insulating material for high-strength wire and cable, the production method comprising the following steps:

(1) Rubber mixing: set the temperature of the internal mixer and the rotor speed, add the rubber matrix pre-compression mixing; then add zinc oxide, stearic acid, surface modifier to mix; then add reinforcing filler and the remaining increase The plastic agent is mixed; then the cross-linking agent and the cross-linking agent are added to mix and disperse the glue, and the rubber compound is thinly passed on the open mill, and the lower piece is parked;

(2) Granulation: The rubber mixture is put into an extruder, extruded, sheared, and packaged.

The present invention also provides a waterproofing membrane comprising the above rubber composition.

The present invention also provides a method of waterproofing a coiled material, the method comprising the method of producing the waterproofing membrane comprising the following steps:

(1) Mixing: set the temperature of the internal mixer and the rotor speed, add the rubber matrix pre-compression mixing; then add zinc oxide, stearic acid, surface modifier and stabilizer to mix; then add reinforcing filler and The remaining plasticizer is mixed; then the cross-linking agent and the cross-linking agent are added to mix and disperse the glue; the block-shaped rubber is sent to the open mill for mixing and thinning until the surface of the rubber is smooth, and then the mixture is kneaded. Thin through, you can mix evenly the rubber pieces, cool the next piece, stack;

(2) hot refining: the uniformly mixed rubber flakes are subjected to hot refining on the open mill to control the roll temperature and the roll distance until the rubber piece is smooth and evenly formed;

(3) calendering: the rubber sheet which has been preliminarily rolled into a roll is placed on a calender, and the roll pitch is adjusted according to the thickness requirement of the finished product to obtain a semi-finished coil material meeting the requirements of the thickness specification of the finished product;

(4) Winding: According to the specification length requirements of the finished coil, the isolation liner layer is sandwiched, and the semi-finished coil is consolidated into a roll;

(5) vulcanization: the coiled material is placed in a nitrogen-filled vulcanization kettle for vulcanization;

(6) Rewinding: re-opening the vulcanized coil, taking out the release liner layer, and then rewinding and packaging into a product.

The present invention also provides a high temperature resistant conveyor belt, wherein at least one of the working surface covering rubber and the non-working surface covering rubber comprises the above rubber composition.

The invention also provides a method for producing a high temperature resistant conveyor belt, wherein the working surface covering rubber comprises a high temperature resistant conveyor belt of the above rubber composition, the composition and proportion of the working surface covering rubber are in parts, and the production method comprises the steps as follows:

(1) Rubber mixing process: firstly, the rubber composition except the crosslinking system is sequentially added to the internal mixer for mixing by weight, and then added to the crosslinking system, uniformly kneaded, and discharged to obtain a rubber compound. After the mixture is thinned on the open mill, the tablet is left, parked, and wait for vulcanization, wherein the crosslinking system comprises a crosslinking agent, and may further comprise at least one of a co-crosslinking agent and a vulcanization accelerator;

(2) Calendering process: The above mixing rubber is placed in a screw extruder for hot refining, and then supplied to a calender for calendering to be used, and the film thickness is controlled to be 4.5 to 12 mm when calendering. After being good, keep warm for use;

(3) Molding process: the film is closely attached to the preformed adhesive tape strip blank on the forming machine to form a strip of the high temperature resistant conveyor belt, and then rolled up for 4 hours and then vulcanized;

(4) Vulcanization process: the above-mentioned formed conveyor belt blank is placed in a flat vulcanizing machine for stage vulcanization, the vulcanization time of each plate is 25 to 30 minutes, the vulcanization pressure is 2.5 to 4 MPa, and the vulcanization temperature is 155 to 170 ° C. .

The present invention also provides a tire comprising at least one of the above-mentioned rubber composition for the rubber for the sidewall of the tire and the rubber for the tread.

The tire provided by the present invention is preferably used as a force tire or an agricultural machine tire. Among them, the force tire can be a bicycle tire, a trolley tire, an animal tire, an electric tire, and the like. Agricultural machinery tires can be used on tractors, combine harvesters, and other agricultural vehicles.

The rubber composition of the present invention can be used as a side wall rubber, and a tire can be produced by a usual method. That is, the rubber compound is subjected to extrusion processing in accordance with the sidewall shape of the tire design, and is molded together with other tire members by a usual method on a tire molding machine to form an unvulcanized tire, which is subjected to the unvulcanized tire in a vulcanizer. Heating and pressurizing to obtain a tire.

The rubber composition of the present invention can be used as a tread rubber, and the tire can be produced by a usual method, that is, the rubber compound is subjected to extrusion processing according to the tread shape of the tire design, and the tire is molded by a usual method and other tires. The components are molded together to form an unvulcanized tire. The unvulcanized tire is heated and pressurized in a vulcanizer to obtain a tire.

The steel wire or fiber skeleton used in the above tires is preferably a surface treated with a type which can be well bonded to a non-polar rubber. The surface treatment can be carried out by soaking the RFL impregnation system.

The invention has the beneficial effects of providing a new rubber composition, which partially or completely replaces ethylene propylene rubber with branched polyethylene, and applies it to a rubber product which is reinforced by silica and carbon black. Under the peroxide vulcanization system, good heat resistance, compression set resistance and mechanical strength are simultaneously obtained.

detailed description

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

In order to more clearly describe the embodiments of the present invention, the materials to which the present invention relates are defined below.

The crosslinking system contains a crosslinking agent, and may further contain at least one of a co-crosslinking agent and a vulcanization accelerator.

The Mooney viscosity ML (1+4) of the ethylene-propylene rubber used is preferably 20 to 50, more preferably 40 to 50, and preferably 4 to 60%.

The Mooney viscosity ML (1+4) of the ethylene propylene diene rubber used is preferably 20 to 100, more preferably 40 to 80, the ethylene content is preferably 55% to 75%, and the third monomer is 5-ethylene-2. - norbornene, 5-vinyl-2-norbornene or dicyclopentadiene, the third monomer content being from 1% to 7%.

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

The branched polyethylenes involved in the examples are characterized by a branching degree 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 ° C of 6 ~102.

The rubber composition provided by the invention comprises: a rubber base and a necessary component, and the rubber base further comprises: a content of branched polyethylene a: 0 < a ≤ 100 parts, a binary ethylene propylene rubber and an ethylene propylene diene rubber Content b: 0 ≤ b < 100 parts, the necessary components include: 1.5 to 10 parts of a crosslinking agent, 40 to 200 parts of a reinforcing filler, and the reinforcing filler contains carbon black, white carbon, calcium carbonate, talc Two or more of powder, calcined clay, magnesium silicate, magnesium carbonate, wherein when the reinforcing filler contains carbon black or white carbon, it contains 5 to 100 parts of carbon black, and contains white carbon black 5 to 60 parts, and the white carbon black in the reinforcing filler comprises at least one of precipitated silica and fumed silica, and the carbon black comprises at least one of N220, N330, N550, N660, N774, N990 . The crosslinking agent comprises at least one of a peroxide crosslinking agent and sulfur, wherein the peroxide crosslinking agent is di-tert-butyl peroxide, dicumyl peroxide, t-butyl cumyl 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)hexyne-3, bis(tert-butylperoxyisopropyl)benzene, 2,5-dimethyl-2,5-di At least one of (benzoyl peroxide) hexane, tert-butyl peroxybenzoate, and t-butylperoxy-2-ethylhexyl carbonate.

The white carbon black used in the examples of the present invention is a fumed silica or a precipitated silica, and for applications where transparency and electrical insulation are not critical, precipitated silica is preferred, and further preferably highly dispersed. Sex precipitated silica, unless otherwise specified, the ordinary precipitation method used in the examples is Solverodi zeosil142, and the highly dispersible silica is Solvay zeosil 165N. .

The rubber composition provided by the present invention may further comprise an auxiliary component comprising: 0.2 to 20 parts of a co-crosslinking agent, 5 to 100 parts of a plasticizer, 1 to 3 parts of a stabilizer, and 2 to 10 parts of a metal oxide. 1 to 10 parts of the surface modifier, 0 to 3 parts of the vulcanization accelerator, and 0 to 20 parts of the binder. Wherein the stabilizer comprises 2,2,4-trimethyl-1,2-dihydroquinoline polymer (RD), 6-ethoxy-2,2,4-trimethyl-1,2-di At least one of hydrogenated quinoline (AW) and 2-mercaptobenzimidazole (MB).

The co-crosslinking agent comprises triallyl cyanurate, triallyl isocyanurate, ethylene glycol dimethacrylate, ethyl dimethacrylate, triethylene glycol dimethacrylate, partial Triallyl trimellitate, trimethylolpropane trimethacrylate, ethylene glycol dimethacrylate, N,N'-m-phenylene bismaleimide, N,N'-double At least one of mercaptoacetone, 1,2-polybutadiene, sulfur, and a metal salt of an unsaturated carboxylic acid.

The unsaturated carboxylic acid metal salt contains at least one of zinc acrylate, zinc methacrylate, magnesium methacrylate, calcium methacrylate, and aluminum methacrylate. The plasticizer is at least one of pine tar, motor oil, naphthenic oil, paraffin oil, coumarone, RX-80, stearic acid, and paraffin wax.

The metal oxide is at least one of zinc oxide, magnesium oxide, and calcium oxide.

The surface modifier is polyethylene glycol, diphenyl silicon glycol, triethanolamine, vinyl tris(2-methoxyethoxy)silane (A-172), γ- having a molecular weight of 2000 or 3400 or 4000. At least one of glycidyloxypropyltrimethoxysilane (A-187) and γ-mercaptopropyltrimethoxysilane (A-189).

The vulcanization accelerator comprises 2-thiol benzothiazole, dibenzothiazole disulfide, tetramethylthiuram monosulfide, tetramethylthiuram disulfide, tetraethylthiuram disulfide, N-ring At least one of hexyl-2-benzothiazolylsulfenamide, N,N-dicyclohexyl-2-phenylthiazolylsulfenamide, bismaleimide, and ethylenethiourea.

The binder comprises at least one of a resorcinol donor, a methylene donor, and a triazine binder

The degree of branching of the branched polyethylene in the above rubber composition is measured by nuclear magnetic resonance spectroscopy, and the molar percentages of various branches are measured by nuclear magnetic carbon spectroscopy, as shown in the following table:

Rubber performance test method:

1. Hardness test: According to the national standard GB/T 531.1-2008, the test is carried out with a hardness tester, and the test temperature is room temperature;

2, tensile strength, elongation at break performance test: in accordance with the national standard GB/T528-2009, using an electronic tensile testing machine for testing, the tensile speed is 500mm / min, the test temperature is 23 ± 2 ° C, the sample is type 2 Dumbbell sample

3, tear strength test: in accordance with the national standard GB/T529-2008, using an electronic tensile test machine for testing, the tensile speed is 500mm / min, the test temperature is 23 ± 2 ° C, the sample is a rectangular sample;

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

5, Mooney viscosity test: in accordance with the national standard GB/T1232.1-2000, with Mooney viscosity meter for testing, the test temperature is 125 ° C, preheat 1 minute, test 4 minutes;

6, hot air accelerated aging test: in accordance with the national standard GB/T3512-2001, in the heat aging test chamber, the test conditions are 150 ° C × 72h;

7. Positive curing time Tc90 test: According to the national standard GB/T16584-1996, it is carried out in a rotorless vulcanizer, and the test temperature is 160 °C.

The vulcanization conditions of the following Examples 1 to 10 and Comparative Examples 1 and 2 were uniform: temperature: 160 ° C; pressure: 16 MPa; time was Tc90 + 2 min.

In order to more clearly illustrate the performance of the rubber composition, the present invention will be further described below in conjunction with specific embodiments.

Example 1:

The branched polyethylene used was numbered PER-5.

The processing steps of the rubber composition are as follows:

(1) Rubber mixing: set the temperature of the internal mixer to 90 ° C, the rotor speed is 50 rpm, add 50 parts of ethylene propylene diene rubber and 50 parts of branched polyethylene for 90 seconds; add 40 parts of carbon Black N550 and 10 parts of white carbon black were mixed for 3 minutes; then 3 parts of cross-linking agent dicumyl peroxide (DCP) was added, and the mixture was kneaded for 2 minutes and then discharged. The mixture was thinly spread on the open mill, and the roll was adjusted to obtain a sheet thickness of about 2.5 mm and parked for 20 hours.

(2) After the vulcanization, the test was carried out for 16 hours.

Example 2:

The branched polyethylene used was numbered PER-5.

The processing steps of the rubber composition are as follows:

(1) Rubber mixing: set the temperature of the internal mixer to 90 ° C, the rotor speed is 50 rpm, add 100 parts of branched polyethylene pre-pressed and kneaded for 90 seconds; add 40 parts of carbon black N550 and 10 parts of white carbon black , mixing for 3 minutes; then adding 3 parts of cross-linking agent dicumyl peroxide (DCP), mixing for 2 minutes and then discharging the glue. The mixture was thinly spread on the open mill, and the roll was adjusted to obtain a sheet thickness of about 2.5 mm and parked for 20 hours.

(2) After the vulcanization, the test was carried out for 16 hours.

Comparative Example 1:

The processing steps are as follows:

(1) Rubber mixing: set the temperature of the internal mixer to 90 ° C, the rotor speed is 50 rpm, add 100 parts of EPDM rubber for 90 seconds, and add 40 parts of carbon black N550 and 10 parts of white carbon. Black, kneaded for 3 minutes; then add 3 parts of cross-linking agent dicumyl peroxide (DCP), mix for 2 minutes and then drain. The mixture was thinly spread on the open mill, and the roll was adjusted to obtain a sheet thickness of about 2.5 mm and parked for 20 hours.

(2) After the vulcanization, the test was carried out for 16 hours.

Example 3:

The branched polyethylene used was numbered PER-9.

The processing steps of the rubber composition are as follows:

(1) Rubber mixing: set the temperature of the internal mixer to 90 ° C, the rotor speed to 50 rpm, add 90 parts of ethylene propylene diene rubber and 10 parts of branched polyethylene for 90 seconds; then add 5 parts Zinc oxide, 1 part stearic acid, 5 parts polyethylene glycol PEG4000 and 1 part antioxidant 2,2,4-trimethyl-1,2-dihydroquinoline polymer (RD), kneaded for 2 minutes; Then add 80 parts of carbon black N550, 20 parts of white carbon black, 20 parts of calcined clay, 20 parts of petrolatum and 30 parts of paraffin oil SUNPAR 2280, and knead for 3 minutes; then add 6 parts of cross-linking agent dicumyl peroxide (DCP) 2 parts of the co-crosslinking agent triallyl isocyanurate (TAIC) and 0.3 parts of the cross-linking agent sulfur, which were mixed for 2 minutes and then discharged. The mixture was thinly spread on the open mill, and the roll was adjusted to obtain a sheet thickness of about 2.5 mm and parked for 20 hours.

(2) After the vulcanization, the test was carried out for 16 hours.

Example 4:

The branched polyethylene used was numbered PER-8.

The processing steps of the rubber composition are as follows:

(1) Rubber mixing: set the temperature of the internal mixer to 90 ° C, the rotor speed is 50 rpm, add 20 parts of ethylene propylene diene rubber, 50 parts of ethylene propylene diene monomer and 30 parts of branched polyethylene pre-pressure mixing. 90 seconds; then add 5 parts of zinc oxide, 1 part of stearic acid, 5 parts of polyethylene glycol PEG4000, 1 part of antioxidant 2,2,4-trimethyl-1,2-dihydroquinoline ( RD) and 1 part of vinyltris(2-methoxyethoxy)silane (A-172), kneaded for 2 minutes; then add 80 parts of carbon black N550, 20 parts of white carbon black, 20 parts of calcined clay, 15 Vaseline and 30 paraffin oil SUNPAR2280, mixed for 3 minutes; then add 6 parts of cross-linking agent dicumyl peroxide (DCP), 2 parts of cross-linking agent triallyl isocyanurate (TAIC) and 0.2 parts of the crosslinking agent sulfur, and the rubber was discharged after 2 minutes of mixing. The mixture was thinly spread on the open mill, and the roll was adjusted to obtain a sheet thickness of about 2.5 mm and parked for 20 hours.

(2) After the vulcanization, the test was carried out for 16 hours.

Example 5:

The branched polyethylene used was numbered PER-6.

The processing steps of the rubber composition are as follows:

(1) Rubber mixing: set the temperature of the internal mixer to 90 ° C, the rotor speed to 50 rpm, add 30 parts of EPDM rubber and 70 parts of branched polyethylene for 90 seconds; then add 5 parts. Zinc oxide, 1 part stearic acid, 5 parts polyethylene glycol PEG4000 and 1 part antioxidant 2,2,4-trimethyl-1,2-dihydroquinoline polymer (RD), kneaded for 2 minutes; Then add 80 parts of carbon black N550, 20 parts of white carbon black, 20 parts of calcined clay, 15 parts of petrolatum and 30 parts of paraffin oil SUNPAR 2280, and knead for 3 minutes; then add 6 parts of cross-linking agent dicumyl peroxide (DCP) 2 parts of the co-crosslinking agent triallyl isocyanurate (TAIC) and 0.2 parts of the cross-linking agent sulfur, which were mixed for 2 minutes and then discharged. The mixture was thinly spread on the open mill, and the roll was adjusted to obtain a sheet thickness of about 2.5 mm and parked for 20 hours.

(2) After the vulcanization, the test was carried out for 16 hours.

Example 6

The branched polyethylene used was numbered PER-5.

The processing steps of the rubber composition are as follows:

(1) Rubber mixing: set the temperature of the internal mixer to 90 ° C, the rotor speed is 50 rpm, add 100 parts of branched polyethylene pre-pressed for 90 seconds; then add 5 parts of zinc oxide, 1 part of stearic acid 5 parts of polyethylene glycol PEG4000 and 1 part of antioxidant 2,2,4-trimethyl-1,2-dihydroquinoline polymer (RD), kneaded for 2 minutes; then add 80 parts of carbon black N550, 20 parts of white carbon black, 20 parts of calcined clay, 15 parts of petrolatum and 30 parts of paraffin oil SUNPAR 2280, mixed for 3 minutes; then added 6 parts of cross-linking agent dicumyl peroxide (DCP), 2 parts of cross-linking agent Allyl isocyanurate (TAIC) and 0.2 parts of the cross-linking agent sulfur were mixed and dispersed for 2 minutes. The mixture was thinly spread on the open mill, and the roll was adjusted to obtain a sheet thickness of about 2.5 mm and parked for 20 hours.

(2) After the vulcanization, the test was carried out for 16 hours.

Comparative Example 2:

The processing steps are as follows:

(1) Rubber mixing: set the temperature of the internal mixer to 90 ° C, the rotor speed is 50 rpm, add 100 parts of EPDM rubber for 90 seconds, and then add 5 parts of zinc oxide and 1 part of stearin. Acid, 5 parts of polyethylene glycol PEG4000 and 1 part of antioxidant 2,2,4-trimethyl-1,2-dihydroquinoline polymer (RD), kneaded for 2 minutes; then add 80 parts of carbon black N550 20 parts of white carbon black, 20 parts of calcined clay, 15 parts of petrolatum and 30 parts of paraffin oil SUNPAR 2280, mixed for 3 minutes; then added 6 parts of cross-linking agent dicumyl peroxide (DCP), 2 parts of cross-linking agent The triallyl isocyanurate (TAIC) and 0.2 parts of the cross-linking agent sulfur were mixed for 2 minutes and then discharged. The mixture was thinly spread on the open mill, and the roll was adjusted to obtain a sheet thickness of about 2.5 mm and parked for 20 hours.

(2) After the vulcanization, the test was carried out for 16 hours.

Performance test data analysis:

Performance test data analysis:

By comparison of Example 1, Example 2 and Comparative Example 1 and comparison of Examples 3 to 6 and Comparative Example 2, it can be found that the tensile strength of the obtained vulcanized rubber increases as the specific gravity of the branched polyethylene replaces the ethylene-propylene rubber increases. Both strength and tear strength are significantly improved, indicating that better mechanical properties can be obtained with a rubber composition containing branched polyethylene.

Example 7

The branched polyethylene used was numbered PER-5.

The processing steps of the rubber composition are as follows:

(1) Rubber mixing: set the temperature of the internal mixer to 90 ° C, the rotor speed to 50 rpm, and add 100 parts of branched polyethylene for pre-pressing and kneading for 90 seconds; then add 10 parts of zinc oxide and 2 parts of stearic acid. 3 parts of polyethylene glycol PEG4000, 1 part of antioxidant 2,2,4-trimethyl-1,2-dihydroquinoline polymer (RD) and 2 parts of vinyltris(2-methoxyethoxy) Silane (A-172), kneaded for 2 minutes; then add 100 parts of carbon black N550, 30 parts of silica, 30 parts of calcined clay, 40 parts of talc, 20 parts of petrolatum and 60 parts of paraffin oil SUNPAR 2280, mixed 3 minutes; then add 10 parts of cross-linking agent dicumyl peroxide (DCP), 2 parts of cross-linking agent triallyl isocyanurate (TAIC) and 8 parts of co-crosslinking agent 1,2-poly Butadiene, after 2 minutes of mixing, drained. The mixture was thinly spread on the open mill, and the roll was adjusted to obtain a sheet thickness of about 2.5 mm and parked for 20 hours.

(2) After the vulcanization, the test was carried out for 16 hours.

Example 8

The branched polyethylene used was numbered PER-4.

The processing steps of the rubber composition are as follows:

(1) Rubber mixing: set the temperature of the internal mixer to 90 ° C, the rotor speed is 50 rpm, add 100 parts of branched polyethylene pre-pressed for 90 seconds; then add 5 parts of zinc oxide, 1 part of stearic acid 5 parts of polyethylene glycol PEG4000, 1 part of antioxidant 2,2,4-trimethyl-1,2-dihydroquinoline polymer (RD) and 2 parts of vinyltris(2-methoxyethoxy) Silane (A-172), kneaded for 2 minutes; then add 20 parts of carbon black N550, 60 parts of silica, 40 parts of calcined clay, 15 parts of petrolatum and 30 parts of paraffin oil SUNPAR 2280, mix for 3 minutes; then join 8 parts of cross-linking agent dicumyl peroxide (DCP), 1 part of cross-linking agent triallyl isocyanurate (TAIC) and 6 parts of cross-linking agent 1,2-polybutadiene, mixed After 2 minutes of smelting, the glue is discharged. The mixture was thinly spread on the open mill, and the roll was adjusted to obtain a sheet thickness of about 2.5 mm and parked for 20 hours.

(2) After the vulcanization, the test was carried out for 16 hours.

Example 9

The branched polyethylenes used were numbered PER-2 and PER-6.

The processing steps of the rubber composition are as follows:

(1) Rubber mixing: set the temperature of the internal mixer to 90 ° C, the rotor rotation speed is 50 rpm, add 70 parts of PER-6 and 30 parts of PER-2 pre-pressure mixing for 90 seconds; then add 5 parts of zinc oxide, 1 part stearic acid, 2 parts polyethylene glycol PEG4000 and 1 part antioxidant 2,2,4-trimethyl-1,2-dihydroquinoline polymer (RD), kneaded for 2 minutes; then added 35 Parts carbon black N550, 5 parts white carbon black and 10 parts paraffin oil SUNPAR2280, mixed for 3 minutes; then add 1 part of cross-linking agent dicumyl peroxide (DCP), 0.3 parts of co-crosslinker triallyl Cyanurate (TAIC), 0.5 parts of cross-linking agent sulfur, 1 part of N-cyclohexyl-2-benzothiazole sulfenamide (CZ) and 0.8 parts of tetramethylthiuram disulfide (TMTD), mixed After 2 minutes of smelting, the glue is discharged. The mixture was thinly spread on the open mill, and the roll was adjusted to obtain a sheet thickness of about 2.5 mm and parked for 20 hours.

(2) After the vulcanization, the test was carried out for 16 hours.

Example 10:

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

The processing steps of the rubber composition are as follows:

(1) Rubber mixing: set the temperature of the internal mixer to 90 ° C, the rotor rotation speed is 50 rpm, add 80 parts of PER-7 and 20 parts of PER-1 pre-pressure mixing for 90 seconds; then add 10 parts of zinc oxide, 2 parts stearic acid, 2 parts polyethylene glycol PEG4000 and 1 part antioxidant 2,2,4-trimethyl-1,2-dihydroquinoline polymer (RD), kneaded for 2 minutes; then added 60 Parts carbon black N330, 20 parts white carbon black and 20 parts paraffin oil SUNPAR2280, mixed for 3 minutes; then add 4 parts of cross-linking agent di-tert-butyl diisopropylbenzene (BIPB), 1.5 parts of cross-linking agent Triallyl isocyanurate (TAIC) and 15 parts of zinc methacrylate were mixed for 2 minutes and then discharged. The mixture was thinly spread on the open mill, and the roll was adjusted to obtain a sheet thickness of about 2.5 mm and parked for 20 hours.

(2) After the vulcanization, the test was carried out for 16 hours.

The performance test data is as follows:

Test items	Example 7	Example 8	Example 9	Example 10
hardness	67	66	58	71
Tensile strength / MPa	15.4	13.2	18.2	20.2
Elongation at break %	368	539	522	489
Tear strength N/mm	37.2	42.1	35.8	49.7
After aging (150 ° C × 72h)
hardness	74	75	62	79
Tensile strength retention rate /%	75	83	81	89
Elongation at break elongation /%	72	79	78	87

In a specific embodiment of the present invention, there is also provided an application of a rubber composition for producing a rubber product comprising an insulating material for producing high-strength wire and cable, a waterproofing membrane, and a high-temperature resistant conveyor belt. The specific implementation application is as follows:

Example 11

An insulating material for high-strength wire and cable, the branched polyethylene is PER-3, and the processing steps are as follows:

(1) Rubber mixing: set the temperature of the internal mixer to 90 ° C, the rotor rotation speed is 50 rpm, and add 100 parts of branched polyethylene for pre-pressing and kneading for 90 seconds; then add 10 parts of zinc oxide and 1 part of stearic acid. 2 parts of polyethylene glycol PEG4000 and 2 parts of vinyl tris(2-methoxyethoxy)silane (A-172), kneaded for 2 minutes; then add 5 parts of carbon black N330, 45 parts of white carbon black, 2 parts of petrolatum and 15 parts of paraffin oil SUNPAR2280 were mixed for 3 minutes; then 4 parts of cross-linking agent dicumyl peroxide (DCP), 0.3 parts of cross-linking agent sulfur were added, and the mixture was mixed for 2 minutes and then discharged. The mixture was thinly spread on the open mill, and the roll was adjusted to obtain a sheet thickness of about 2.5 mm and parked for 20 hours.

(2) Granulation: The rubber mixture is put into an extruder, extruded, sheared and granulated, and packaged.

Among them, vulcanization and performance test, vulcanization process: steam vulcanization, 155 ° C × 40 minutes, immersed in water;

Performance test: hardness: 68; tensile strength: 19.1 MPa; elongation at break: 622%; volume resistivity: 3.8 × 10 ¹⁵ Ω · cm; 150 ° C × 72 h after hot air aging: hardness: 74; tensile strength Retention rate: 75%; elongation at break retention rate: 72%.

Example 12

A waterproof membrane material whose production process is as follows:

(1) Mixing: set the temperature of the internal mixer to 90 ° C, the rotor speed to 50 rpm, add 100 parts of branched polyethylene PER-5 pre-pressure mixing for 90 seconds; then add 5 parts of zinc oxide, 1 part of hard Fatty acid, 5 parts of polyethylene glycol PEG4000 and 1 part of antioxidant 2,2,4-trimethyl-1,2-dihydroquinoline polymer (RD), kneaded for 2 minutes; then add 80 parts of carbon black N550, 20 parts of white carbon black, 20 parts of calcined clay, 15 parts of petrolatum and 30 parts of paraffin oil SUNPAR 2280, mixed for 3 minutes; then added 6 parts of cross-linking agent dicumyl peroxide (DCP), 2 parts of cross-linking The triallyl isocyanurate (TAIC) and 0.2 parts of the cross-linking agent sulfur were mixed for 2 minutes and then discharged. The block rubber is fed into the open mill for mixing, the temperature of the control roller is between 85 and 95 ° C, and the roll distance is controlled to be less than 1 mm, and the thin pass is not less than four times until the surface of the rubber compound is smooth and shiny. Then turn the head and further mix it, make the thin pass no less than four times, adjust the roll distance to not more than 8mm, mix it three times, and obtain the evenly mixed rubber piece with the thickness below 8mm, and cool it to below 50 °C. Stacking

(2) Hot-smelting: the uniformly mixed rubber flakes are heat-treated on the open mill, the temperature of the control roll is between 85 and 95 ° C, and the roll distance is below 6 mm, until the rubber sheet is smooth and uniform, and then preliminaryly rolled;

(3) calendering: the rubber sheet which has been preliminarily rolled into a roll is placed on a calender, and the roll pitch is adjusted according to the thickness requirement of the finished product to obtain a semi-finished coil material meeting the requirements of the thickness specification of the finished product;

(4) Winding: According to the specification length requirements of the finished coil, the isolation liner layer is sandwiched, and the semi-finished coil is consolidated into a roll;

(5) vulcanization: the rolled material is placed in a nitrogen-containing vulcanization kettle for vulcanization treatment, the temperature of the vulcanization kettle is controlled between 155 and 165 ° C, the pressure is between 20 and 25 MPa, and the vulcanization is for 25 to 30 minutes;

(6) Rewinding: re-opening the vulcanized coil, taking out the release liner layer, and then rewinding and packaging into a product.

Example 13

The utility model relates to a high-temperature resistant conveyor belt, which comprises a working surface covering glue, a non-working surface covering glue, and a cored tensile canvas provided between the two, and the composition and proportion of the working surface covering glue are divided into parts. Number:

(1) Rubber mixing process:

One-stage mixing: set the internal temperature of the mixer to 90 ° C, the rotor speed to 50 rpm, add 80 parts of PER-7 and 20 parts of PER-1 pre-pressure mixing for 90 seconds; then add 10 parts of zinc oxide, 2 parts of hard Fatty acid, 2 parts of polyethylene glycol PEG4000 and 1 part of antioxidant 2,2,4-trimethyl-1,2-dihydroquinoline polymer (RD), kneaded for 2 minutes; then add 60 parts of carbon black N330, 20 parts of white carbon black, 2.5 parts of resorcinol (RS) and 20 parts of paraffin oil SUNPAR2280, mixing for 3 minutes, debinding; two-stage mixing: setting the internal temperature of the mixer to 90 ° C, the rotor speed is 50 Rpm, then add 2 parts of methylene donor RH, mix for two minutes; then add 4 parts of crosslinker di-tert-butylperoxydiisopropylbenzene (BIPB), 1.5 parts of cross-linker Propyl isocyanurate (TAIC) and 15 parts of zinc methacrylate were mixed for 2 minutes and then degreased.

(2) Calendering process:

The above rubber mixture is placed in a screw extruder for hot refining, and then supplied to a calender for calendering to be used. The thickness of the film is controlled to be 4.5 to 12 mm when the film is rolled. After being good, keep warm for use.

(3) Molding process:

The film is closely attached to the pre-formed adhesive canvas strip on the molding machine to form a strip of the high temperature resistant conveyor belt, and then vulcanized after being rolled up for 4 hours.

(4) Vulcanization process:

The formed conveyor belt blank was placed in a flat vulcanizing machine for stage vulcanization, and the vulcanization time per plate was 25 minutes, the vulcanization pressure was 3 MPa, and the vulcanization temperature was 160 °C.

Example 14

A bicycle tire, the processing steps of the sidewall rubber are as follows:

(1) Rubber mixing: set the temperature of the internal mixer to 90 ° C, the rotor speed to 50 rpm, add 100 parts of branched polyethylene PER-5 pre-pressure mixing for 90 seconds; then add 5 parts of zinc oxide, 1 part Stearic acid, 2 parts of polyethylene glycol PEG4000 and 2 parts of vinyltris(2-methoxyethoxy)silane (A-172), kneaded for 2 minutes; then added 40 parts of carbon black N330, 20 parts high Disperse silica and 10 parts of paraffin oil SUNPAR2280, mix for 3 minutes; then add 4 parts of cross-linking agent dicumyl peroxide (DCP), 1.5 parts of cross-linking agent N, N'-m-phenylene double horse The imide (HVA-2) and 0.3 parts of the co-crosslinking agent sulfur were kneaded for 2 minutes and then discharged. The rubber compound is opened on the open mill and then placed, parked and tested.

(2) Extrusion molding: The qualified rubber compound is extruded through an extruder to obtain a rubber member having a side wall shape to be used.

Example 15

A bicycle tire, the processing steps of the sidewall rubber are as follows:

(1) Rubber mixing: set the temperature of the internal mixer to 90 ° C, the rotor speed to 50 rpm, add 100 parts of branched polyethylene PER-12 pre-pressure mixing for 90 seconds; then add 5 parts of zinc oxide, 1 part Stearic acid, 2 parts of polyethylene glycol PEG4000 and 2 parts of vinyltris(2-methoxyethoxy)silane (A-172), kneaded for 2 minutes; then added 40 parts of carbon black N330, 20 parts high Disperse silica and 10 parts of paraffin oil SUNPAR2280, mix for 3 minutes; then add 4 parts of cross-linking agent dicumyl peroxide (DCP), 1.5 parts of cross-linking agent N, N'-m-phenylene double horse The imide (HVA-2) and 0.3 parts of the co-crosslinking agent sulfur were kneaded for 2 minutes and then discharged. The rubber compound is opened on the open mill and then placed, parked and tested.

(2) Extrusion molding: The qualified rubber compound is extruded through an extruder to obtain a rubber member having a side wall shape to be used.

Example 16:

A bicycle tire, the processing steps of the tread rubber are as follows:

(1) Rubber mixing: set the temperature of the internal mixer to 90 ° C, the rotor rotation speed is 50 rpm, add 80 parts of PER-7 and 20 parts of PER-1 pre-pressure mixing for 90 seconds; then add 10 parts of zinc oxide, 2 parts stearic acid, 2 parts polyethylene glycol PEG4000 and 1 part antioxidant 2,2,4-trimethyl-1,2-dihydroquinoline polymer (RD), kneaded for 2 minutes; then added 60 Part of carbon black N330, 20 parts of white carbon black and 15 parts of paraffin oil SUNPAR2280, mixing for 3 minutes; then add 4 parts of cross-linking agent di-tert-butylperoxydiisopropylbenzene (BIPB), 1.5 parts of cross-linking agent Triallyl isocyanurate (TAIC) and 15 parts of zinc methacrylate were mixed for 2 minutes and then discharged. The rubber compound is opened on the open mill and then placed, parked, and tested;

(2) Rolling the tested mixed rubber into a suitable thickness, and cutting the strip for use;

(3) Tread extrusion: using a cold feed extrusion process, extruding into a tread semi-finished product through an extruder.

Example 17

A bicycle tire, the processing steps of the tread rubber are as follows:

(1) Rubber mixing: set the temperature of the internal mixer to 90 ° C, the rotor speed to 50 rpm, add 70 parts of PER-11 and 30 parts of PER-3 pre-pressure mixing for 90 seconds; then add 10 parts of zinc oxide, 2 parts stearic acid, 2 parts of coumarone resin, 2 parts of modified alkyl phenolic resin TKM-K, 2 parts of polyethylene glycol PEG4000 and 1 part of antioxidant RD, kneaded for 2 minutes; then added 60 parts of carbon black N330, 20 parts of white carbon black and 20 parts of paraffin oil SUNPAR2280, mixed for 3 minutes; then add 4 parts of cross-linking agent di-tert-butylperoxydiisopropylbenzene (BIPB), 1.5 parts of cross-linking agent triene The base isocyanurate (TAIC) and 3 parts of zinc methacrylate were mixed for 2 minutes and then discharged. The rubber compound is opened on the open mill and then placed, parked, and tested;

(2) Rolling the tested mixed rubber into a suitable thickness, and cutting the strip for use;

(3) Tread extrusion: using a cold feed extrusion process, extruding into a tread semi-finished product through an extruder.

Example 18

The utility model relates to a high-temperature resistant conveyor belt, which comprises a working surface covering glue, a non-working surface covering glue, and a cored tensile body canvas provided between the two, the working surface covering glue composition and the mixing process as follows:

One-stage mixing: set the internal temperature of the mixer to 90 ° C, the rotor speed is 50 rpm, add 100 parts of PER-12 pre-pressure mixing for 90 seconds; then add 10 parts of zinc oxide, 2 parts of stearic acid, 2 parts of poly Ethylene glycol PEG4000 and 1 part antioxidant RD, kneaded for 2 minutes; then add 60 parts carbon black N330, 20 parts white carbon black, 5 parts triazine adhesive AIR-1, 1 part resorcinol (RS) And 20 parts of paraffin oil SUNPAR2280, mixing for 3 minutes, debinding; two-stage mixing: setting the temperature of the internal mixer to 90 ° C, the rotor speed is 50 rev / min, then adding 2 parts of methylene donor RH, mixing Two minutes; then add 4 parts of crosslinker di-tert-butylperoxydiisopropylbenzene (BIPB), 1.5 parts of co-crosslinker triallyl isocyanurate (TAIC) and 15 parts of zinc methacrylate After 2 minutes of mixing, the glue is discharged.

The remaining processing techniques are in accordance with Embodiment 13.

Example 19

A rubber for rubber metal shock absorbing parts, the composition and mixing process are as follows:

Set the internal temperature of the mixer to 100 ° C, the rotor speed to 50 rpm, add 40 parts of EPDM rubber (keltan 9565Q) and 60 parts of PER-10 pre-pressure mixing for 90 seconds; then add 5 parts of zinc oxide, 1 Stearic acid, 4 parts of binder RS, 2 parts of polyethylene glycol PEG4000 and 1 part of antioxidant RD, kneaded for 2 minutes; then add 60 parts of carbon black N330, 20 parts of white carbon black and 20 parts of paraffin oil SUNPAR2280 , mixing for 3 minutes; then adding 4 parts of binder RA-65 for 1 minute; then adding 4 parts of cross-linking agent di-tert-butylperoxydiisopropylbenzene (BIPB), 1 part of cross-linking agent Allyl isocyanurate (TAIC), 0.5 parts of sulfur and 3 parts of zinc methacrylate were mixed for 2 minutes and then discharged. The rubber compound is smelted on the open mill and then placed on the sheet and parked for use.

Claims (22)

1. A rubber composition comprising: a rubber matrix and a necessary component, the rubber matrix comprising: a content of branched polyethylene a: 0 < a ≤ 100 parts, a binary ethylene propylene rubber And the content of ethylene propylene diene monomer b: 0 ≤ b < 100 parts, the necessary components include: 1.5 to 10 parts of a crosslinking agent, 40 to 200 parts of a reinforcing filler, wherein the branched polyethylene contains ethylene a polymer having 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 ML (1+4) of 125 ° C not lower than 2, the reinforcing filler It comprises two or more kinds of carbon black, white carbon black, calcium carbonate, talc powder, calcined clay, magnesium silicate and magnesium carbonate, and contains 5 to 100 parts of carbon black and 5 to 60 parts of white carbon black.
2. The rubber composition according to claim 1, wherein the content of the branched polyethylene in the rubber matrix is 10: a ≤ 100 parts based on 100 parts by weight of the rubber base; the ethylene propylene rubber and the three The content of the ethylene propylene rubber b: 0 ≤ b ≤ 90 parts; the branched polyethylene is characterized by: it is an ethylene homopolymer, the degree of branching is 60 to 130 branches / 1000 carbon, and the weight average molecular weight is 66,000 ~ 518,000, Mooney viscosity ML (1 + 4) 125 ° C is 6 ~ 102.
3. The rubber composition according to claim 1, wherein the white carbon black comprises at least one of precipitated silica and fumed silica.
4. The rubber composition according to claim 1, wherein the carbon black comprises at least one of N220, N330, N550, N660, N774, and N990.
5. The rubber composition according to claim 1, wherein the crosslinking agent comprises at least one of a peroxide crosslinking agent and sulfur, and the peroxide crosslinking agent is di-tert-butyl peroxide. , dicumyl peroxide, tert-butyl cumyl 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)hexyne-3, bis(tert-butylperoxyperoxide) Of phenyl, 2,5-dimethyl-2,5-bis(benzoyl peroxy)hexane, tert-butyl peroxybenzoate, t-butylperoxy-2-ethylhexyl carbonate At least one.
6. The rubber composition according to claim 1, wherein the rubber composition further comprises an auxiliary component based on 100 parts by weight of the rubber base, the auxiliary component comprising: 0.2 to 20 parts by weight of the crosslinking agent, plasticizing 5 to 100 parts of the agent, 1 to 3 parts of the stabilizer, 2 to 10 parts of the metal oxide, 1 to 10 parts of the surface modifier, 0 to 3 parts of the vulcanization accelerator, and 0 to 20 parts of the binder.
7. The rubber composition according to claim 6, wherein the stabilizer comprises a 2,2,4-trimethyl-1,2-dihydroquinoline polymer, 6-ethoxy-2,2 At least one of 4-trimethyl-1,2-dihydroquinoline, 2-mercaptobenzimidazole, and N-4 (anilinophenyl)maleimide.
8. The rubber composition according to claim 6, wherein the co-crosslinking agent comprises triallyl cyanurate, triallyl isocyanurate, ethylene glycol dimethacrylate, Ethyl dimethacrylate, triethylene glycol dimethacrylate, triallyl trimellitate, trimethylolpropane trimethacrylate, ethylene glycol dimethacrylate, N, N'- At least one of m-phenylene bismaleimide, N,N'-bis-decylenedone, 1,2-polybutadiene, sulfur, and a metal salt of an unsaturated carboxylic acid, wherein the unsaturated The metal carboxylate salt contains at least one of zinc acrylate, zinc methacrylate, magnesium methacrylate, calcium methacrylate, and aluminum methacrylate.
9. The rubber composition according to claim 6, wherein the plasticizer is pine tar, motor oil, naphthenic oil, paraffin oil, coumarone, RX-80, stearic acid, paraffin, liquid polyisobutylene At least one of them.
10. The rubber composition according to claim 6, wherein the metal oxide is at least one of zinc oxide, magnesium oxide, and calcium oxide.
11. The rubber composition according to claim 6, wherein the surface modifier is polyethylene glycol having a molecular weight of 2000 or 3400 or 4000, diphenylsilyl glycol, triethanolamine, vinyl tris(2) At least one of -methoxyethoxy)silane, γ-glycidyloxypropyltrimethoxysilane, and γ-mercaptopropyltrimethoxysilane.
12. The rubber composition according to claim 6, wherein the vulcanization accelerator comprises 2-thiol benzothiazole, dibenzothiazyl disulfide, tetramethylthiuram monosulfide, and tetrasulfide disulfide. Kethiram, tetraethylthiuram disulfide, N-cyclohexyl-2-benzothiazolyl sulfenamide, N,N-dicyclohexyl-2-phenylthiazolyl sulfenamide, bismaleyl At least one of an imine and an ethylene thiourea.
13. The rubber composition according to claim 6, wherein the binder comprises at least one of a resorcinol donor and a methylene donor.
14. A method of processing the rubber composition according to any one of claims 1 to 13, characterized in that the processing method comprises the steps of:

    Step 1: setting the temperature of the internal mixer and the rotation speed of the rotor, firstly adding the rubber composition other than the crosslinking system to the internal mixer according to the weight portion for kneading;

    Step 2: adding a crosslinking system after being uniformly kneaded and discharging, to obtain a rubber mixture;

    Step 3: The mixture is thinned on the open mill and then placed under the sheet, and parked for vulcanization;

    Step 4: vulcanization according to a vulcanization process;

    Wherein, the crosslinking system comprises a crosslinking agent, and may further comprise at least one of a co-crosslinking agent and a vulcanization accelerator.
15. An insulating material for a high-strength electric wire and cable, characterized in that the rubber compound for an insulating material for a high-strength electric wire and cable includes the rubber composition according to any one of claims 1 to 13.
16. A method for producing the insulating material for high-strength electric wire and cable according to claim 15, wherein the production method comprises the following steps:

    (1) Rubber mixing: set the temperature of the internal mixer and the rotor speed, add the rubber matrix pre-compression mixing; then add zinc oxide, stearic acid, surface modifier to mix; then add reinforcing filler and the remaining increase The plastic agent is mixed; then the cross-linking agent and the cross-linking agent are added to mix and disperse the glue, and the rubber compound is thinly passed on the open mill, and the lower piece is parked;

    (2) Granulation: The rubber mixture is put into an extruder, extruded, sheared and granulated, and packaged.
17. A waterproofing membrane characterized by comprising the rubber composition according to any one of claims 1 to 13.
18. A method of producing the waterproofing membrane of claim 17, wherein the production method comprises the following steps:

    (1) Mixing: set the temperature of the internal mixer and the rotor speed, add the rubber matrix pre-compression mixing; then add zinc oxide, stearic acid, surface modifier and stabilizer to mix; then add reinforcing filler and The remaining plasticizer is mixed; then the cross-linking agent and the cross-linking agent are added to mix and disperse the glue; the block-shaped rubber is sent to the open mill for mixing and thinning until the surface of the rubber is smooth, and then the mixture is kneaded. Thin through, you can mix evenly the rubber pieces, cool the next piece, stack;

    (2) hot refining: the uniformly mixed rubber flakes are subjected to hot refining on the open mill to control the roll temperature and the roll distance until the rubber piece is smooth and evenly formed;

    (3) calendering: the rubber sheet which has been preliminarily rolled into a roll is placed on a calender, and the roll pitch is adjusted according to the thickness requirement of the finished product to obtain a semi-finished coil material meeting the requirements of the thickness specification of the finished product;

    (4) Winding: According to the specification length requirements of the finished coil, the isolation liner layer is sandwiched, and the semi-finished coil is consolidated into a roll;

    (5) vulcanization: the coiled material is placed in a nitrogen-filled vulcanization kettle for vulcanization;

    (6) Rewinding: re-opening the vulcanized coil, taking out the release liner layer, and then rewinding and packaging into a product.
19. A high temperature resistant conveyor belt, characterized in that at least one of the working surface covering rubber and the non-working surface covering rubber comprises the rubber composition according to any one of claims 1 to 13.
20. A method for producing the high temperature resistant conveyor belt according to claim 19, wherein the high temperature resistant conveyor belt comprises a working surface covering rubber and a non-working surface covering rubber, and the composition and proportion of the working surface covering rubber are The number of steps in the production method is as follows:

    (1) Rubber mixing process: firstly, the rubber composition except the crosslinking system is sequentially added to the internal mixer for mixing by weight, and then added to the crosslinking system, uniformly kneaded, and discharged to obtain a rubber compound. After the rubber compound is thinned on the open mill, the film is left, parked, and wait for vulcanization, wherein the crosslinking system comprises a crosslinking agent, and may further comprise at least one of a co-crosslinking agent and a vulcanization accelerator;

    (2) calendering process: the above mixture rubber is placed in a screw extruder for hot refining, and then supplied to a calender for calendering and discharging, and the heat preservation is used;

    (3) Molding process: the film is closely attached to the preformed adhesive tape strip blank on the forming machine to form a strip of the high temperature resistant conveyor belt, and then rolled up and then vulcanized;

    (4) Vulcanization process: the above-mentioned formed conveyor belt blank is placed in a flat vulcanizing machine for stage vulcanization, the vulcanization time of each plate is 25 to 30 minutes, the vulcanization pressure is 2.5 to 4 MPa, and the vulcanization temperature is 155 to 170 ° C. .
21. A tire characterized in that at least one of the compound for use in the side wall of the tire and the tread comprises the rubber composition according to any one of claims 1 to 13.
22. The tire according to claim 21, wherein the tire is a force tire and an agricultural machinery tire.