WO2018130187A1 - Rubber composite, processing method, applications, and method for manufacturing high-strength rubber products - Google Patents

Abstract

A rubber composite, a processing method, products applying the rubber composite, and a manufacturing method. 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 comprises : a crosslinking agent 1-10 parts and unsaturated metal carboxylate 5-50 parts. The beneficial effects are such that the rubber composite is applicable in rubber products such as insulating gloves, a heat-resistant conveyor belt, and a rubber tube, and the rubber products have great mechanical performance.

Description

Rubber composition and processing method and application thereof, and method for producing high-strength rubber product Technical field

The invention belongs to the technical field of rubber, and particularly relates to a rubber composition with high mechanical strength and a processing method thereof, and a high-strength rubber product using the rubber composition and a production method thereof.

technical background

Sulfur vulcanization and peroxide vulcanization are the two most commonly used vulcanization processes for ethylene propylene rubber. In the production process of ethylene-propylene rubber products, in order to obtain good resilience, electrical insulation, heat aging resistance, a peroxide-based vulcanization system is often used. However, the mechanical strength of peroxide-cured ethylene-propylene rubber is lower than that of sulfur-vulcanized ethylene-propylene rubber. Unsaturated carboxylic acid metal salts such as zinc acrylate and zinc methacrylate can be used as a co-crosslinking agent for peroxide vulcanization to improve the vulcanization rate and crosslinking efficiency, and can also be used as a reinforcing filler for rubber when the amount is high. Improve the mechanical strength of rubber. At present, an unsaturated carboxylic acid metal salt is often added to an ethylene-propylene rubber product having high mechanical strength requirements. However, due to the weak strength of the ethylene-propylene rubber under the peroxide vulcanization system, this also limits the application range of the ethylene-propylene rubber product reinforced with the unsaturated carboxylic acid metal salt to some extent. In the case where the content of the unsaturated carboxylic acid metal salt is large, the compression set resistance is also deteriorated to some extent.

Therefore, how to further improve the aging resistance, mechanical strength and some functional indexes (such as compression set resistance) of ethylene propylene rubber in the presence of unsaturated carboxylic acid metal salts is a technical problem to be solved.

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. Chain length, large steric hindrance, difficulty in radical reaction, resulting in difficulty in crosslinking, affecting processing efficiency and product performance, such as compression set resistance is unsatisfactory.

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

The object of the present invention is to solve the above problems and provide a novel rubber composition, which is partially or completely replaced with ethylene-propylene rubber with a branching degree of not less than 50 branches/1000 carbons, and continues to use peroxidation. The main-based vulcanization system, and the addition of unsaturated carboxylic acid metal salts to assist cross-linking and reinforcement, so that the rubber has better mechanical strength.

In order to achieve the above object, the present invention adopts the following technical solution: a rubber composition comprising: a rubber matrix and an essential component, the rubber matrix comprising: a content of branched polyethylene a: 0 < a ≤ 100 parts; The content of the ethylene propylene rubber and the ethylene propylene diene rubber is b: 0 ≤ b < 100 parts; the essential component comprises: 1 to 10 parts of the crosslinking agent, and the unsaturated carboxylic acid metal salt, based on 100 parts by weight of the rubber matrix. 5 to 50 parts, wherein the branching degree of the branched polyethylene is not less than 50 branches/1000 carbons, the weight average molecular weight is not less than 50,000, and the Mooney viscosity ML (1+4) is not lower than 125 °C. 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 invention and the prior art ethylene dipropylene rubber or the conventional ethylene-α-olefin copolymer.

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

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

Compared with ethylene propylene rubber, when the branched polyethylene has an appropriate number of secondary branched structures, the cross-linking point of the branched polyethylene 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, including tear strength. On the other hand, better cross-linking ability can effectively increase the cross-linking density, and the molecular weight distribution of the branched polyethylene is close to 2, which is narrower than that of the general ethylene-propylene rubber, so that it is also expected to obtain better compression set resistance.

A further technical solution is that, in 100 parts by weight, the content of branched polyethylene in the rubber matrix is a: 10 ≤ a ≤ 100 parts; the content of binary ethylene propylene rubber and ethylene propylene diene rubber is b: 0 ≤ b ≤90 parts; the branched polyethylene is an ethylene homopolymer having a degree of branching of 60 to 130 branches/1000 carbons, a weight average molecular weight of 66,000 to 518,000, and a Mooney viscosity ML (1+4) ) 125 ° C is 6 ~ 102;

A further technical solution is that, in 100 parts by weight, the content of branched polyethylene in the rubber matrix is a: 10 ≤ a ≤ 100 parts; the content of binary ethylene propylene rubber and ethylene propylene diene rubber is b: 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.

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

A further technical solution is that, in 100 parts by weight of the rubber matrix, the content of the branched polyethylene is: 10 ≤ a ≤ 100 parts; the content of the binary ethylene propylene rubber and the ethylene propylene diene rubber is b: 0 ≤ b ≤ 90 The branched polyethylene is an ethylene homopolymer having a degree of branching of 80 to 105 branches/1000 carbons, a weight average molecular weight of 268,000 to 356,000, and a Mooney viscosity of ML (1+4) 125. °C is 42-80.

A further technical solution is that 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 further technical solution, the crosslinking agent comprises at least one of a peroxide crosslinking agent and a sulfur, and the peroxide crosslinking agent comprises 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.

A further technical solution is that the content of the crosslinking agent is from 1.5 to 6 parts based on 100 parts by weight of the rubber matrix.

According to a further aspect of the invention, the unsaturated carboxylic acid metal salt comprises at least one of zinc acrylate, zinc methacrylate, magnesium methacrylate, calcium methacrylate, and aluminum methacrylate.

A further technical solution is that the content of the unsaturated carboxylic acid metal salt is 5 to 30 parts based on 100 parts by weight of the rubber matrix.

According to a further technical proposal, the rubber composition further comprises an auxiliary component, wherein the auxiliary component is in parts by weight, based on 100 parts by weight of the rubber matrix, and comprises: a co-crosslinking agent other than the unsaturated carboxylic acid metal salt 0.2 to 10 The reinforcing filler is 10 to 150 parts, the plasticizer is 5 to 80 parts, the stabilizer is 1 to 3 parts, the metal oxide is 2 to 20 parts, and the vulcanization accelerator is 0 to 3 parts.

A further technical solution is that the co-crosslinking agent comprises triallyl cyanurate, triallyl isocyanurate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, Triallyl trimellitate, trimethylolpropane trimethacrylate, N,N'-m-phenylene bismaleimide, N,N'-bis-indenylacetone, 1,2- At least one of polybutadiene and sulfur.

In a further technical solution, the reinforcing filler comprises at least one of carbon black, white carbon, calcium carbonate, talc, calcined clay, and magnesium carbonate.

According to a further technical solution, the plasticizer comprises at least one of pine tar, engine oil, naphthenic oil, paraffin oil, coumarone, RX-80, stearic acid, paraffin, liquid ethylene propylene rubber, and liquid polyisobutylene. Kind. 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 further technical solution, the stabilizer comprises 2,2,4-trimethyl-1,2-dihydroquinoline polymer (RD), 6-ethoxy-2,2,4-trimethyl At least one of -1,2-dihydroquinoline (AW), 2-mercaptobenzimidazole (MB), and N-4 (anilinophenyl)maleimide (MC).

In a further technical solution, the metal oxide comprises at least one of zinc oxide, magnesium oxide, and calcium oxide.

According to a further technical proposal, the vulcanization accelerator comprises 2-thiol benzothiazole, dibenzothiazyl disulfide, tetramethyl thiuram monosulfide, tetramethyl thiuram disulfide, tetrazyl disulfide Kethiram, N-cyclohexyl-2-benzothiazolyl sulfenamide, N,N-dicyclohexyl-2-benzothiazolyl sulfenamide, bismaleimide, ethylene thiourea At least one of them.

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 of processing the above rubber composition, the processing method comprising the steps of:

(1) Rubber kneading: First, the rubber composition other than the cross-linking system is sequentially added to the internal mixer according to the parts by weight for kneading, and then added to the cross-linking system, uniformly kneaded, and discharged to obtain a rubber compound. The rubber compound is thinned on the open mill, and then the film is left to be vulcanized, wherein the crosslinking system comprises a crosslinking agent, and may further comprise at least one of a crosslinking agent and a vulcanization accelerator;

(2) Vulcanization: The rubber compound is filled into the cavity of the mold, and after being vulcanized by vulcanization on a flat vulcanizer, the vulcanized rubber is obtained by demolding.

The present invention also provides an application for the production of insulating gloves using the above rubber composition, the production steps of which include the following:

(1) Rubber kneading: First, the rubber composition other than the cross-linking system is sequentially added to an internal mixer for kneading, and then added to a cross-linking system, which is uniformly kneaded and discharged to obtain a kneaded rubber. The mixture is thinned on the open mill and then discharged, and is parked 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) Cut piece: After parking the film for a period of time, the piece is formed according to the size of the mold cavity;

(3) Vulcanization: The formed film is filled into the cavity of the mold, and the mold is placed on a flat vulcanizing machine for pressure vulcanization, then cooled and demolded, and trimmed to obtain a rubber insulated glove.

The present invention also provides an application for producing a hose using the above rubber composition, and the production method thereof comprises the following steps:

(1) Rubber kneading: First, the rubber composition other than the cross-linking system is sequentially added to the internal mixer for mixing by weight, and then added to the cross-linking system, uniformly kneaded, and discharged to obtain a rubber compound. The rubber compound is thinned on the open mill, and then the film is left to be vulcanized, wherein the crosslinking system comprises a crosslinking agent, and may further comprise at least one of a crosslinking agent and a vulcanization accelerator;

(2) Extrusion and molding: a cold feed extruder is used to extrude the rubber layer on the mandrel to obtain a tube blank, which is cooled by steam vulcanization, de-core, trimmed, inspected, and stored in a warehouse to obtain a hose.

The present invention also provides an application of the above rubber composition, which can be used for producing a conveyor belt, wherein at least one of the working surface covering rubber and the non-working surface covering rubber comprises the above rubber composition, and the production method comprises the following steps:

(1) Rubber kneading process: First, the rubber composition other than the cross-linking system is sequentially added to an internal mixer in terms of parts by weight for kneading, and then added to a cross-linking system, which is uniformly kneaded and discharged to obtain a kneaded rubber. The mixture is thinned on the open mill and then placed on the sheet to be vulcanized. 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 and heat preservation for use;

(3) Molding process: the film is closely attached to the pre-formed adhesive canvas strip blank on the forming machine to form a strip of high temperature resistant conveyor belt, and then rolled up for waiting for vulcanization;

(4) placing the formed conveyor belt blank into a flat vulcanizing machine for segmental vulcanization;

(5) After the vulcanization is finished, it is trimmed, inspected, and then packaged into the warehouse.

The present invention also provides an application of the above rubber composition, which can be used for producing a conveyor belt, wherein the rubber used for the adhesive layer comprises the above rubber composition, and the rubber composition preferably comprises a tackifier, and the production method thereof comprises the following steps:

(1) Rubber kneading process: First, the rubber composition other than the cross-linking system is sequentially added to an internal mixer in terms of parts by weight for kneading, and then added to a cross-linking system, which is uniformly kneaded and discharged to obtain a kneaded rubber. The mixture is thinned on the open mill and then discharged, and is parked 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) Adhesive glue: the rubber compound and the cloth layer are finished at a normal temperature by a double roll or a four roll calender to complete the bonding of the adhesive glue and the canvas layer to obtain a rubberized canvas strip;

(3) Molding process: the formed adhesive tape canvas blank and the cover film are closely attached together on the molding machine to form a strip of the high temperature resistant conveyor belt, and then rolled up to be vulcanized;

(4) placing the formed conveyor belt blank into a flat vulcanizing machine for segmental vulcanization,

(5) After the vulcanization is finished, it is trimmed, inspected, and then packaged into the warehouse.

The present invention also provides an application of the above rubber composition, which can be used for producing a shock absorbing member, which can be a rubber shock absorbing member, and can also be rubber because the rubber composition has good bonding property with metal. Metal composite shock absorber.

The beneficial effects of the invention are: since the branch of the ethylene-propylene rubber is substantially methyl, the branched polyethylene has more branches in the molecular structure, and the branch length has a certain distribution, and the branched polyethylene has An appropriate number of secondary branched structures. During the peroxide crosslinking process, the crosslinking point of the branched polyethylene can be generated on the tertiary chain of the main chain or on the branched tertiary carbon of the secondary structure, so Compared with ethylene-propylene rubber, the rubber network formed by cross-linking of branched polyethylene has a richer CC connecting segment length between the main chains, which can effectively avoid stress concentration and facilitate better mechanics. Performance, including tear strength. On the other hand, the compression set property is related to the molecular weight distribution of the rubber material, and the rubber having a narrow molecular weight distribution has a relatively low compression set. The molecular weight distribution of ethylene propylene rubber is mostly between 3 and 5, and the highest is 8 to 9. The molecular weight distribution of a small amount of ethylene propylene rubber is close to 2 and convenient for processing, but the cost is high. Since the molecular weight distribution of the branched polyethylene is generally lower than 2.5, which is significantly smaller than the molecular weight distribution of the ordinary ethylene propylene rubber, the rubber composition of the present invention has a lower compression set after vulcanization, and can be compensated to some extent. The adverse effect of the unsaturated carboxylic acid metal salt on the compression set resistance of the compound. In summary, the rubber composition provided by the present invention can obtain a rubber product having high mechanical strength and good compression set resistance.

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 Mooney viscosity ML (1+4) of the ethylene propylene rubber used is preferably 20 to 50 at 125 ° C, and the ethylene content is preferably 45% to 60%.

The Mooney viscosity ML (1+4) of the ethylene propylene diene rubber used is preferably 20 to 100, more preferably 30 to 80, the ethylene content is preferably 50 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 selected branched polyethylene is 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 to 102. . Among them, the degree of branching is measured by nuclear magnetic resonance spectroscopy, and the molar percentages of various branches are measured by nuclear magnetic carbon spectroscopy.

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. Mooney viscosity test: According to the national standard GB/T1232.1-2000, the test is carried out with a Mooney viscometer. The test temperature is 125 ° C, preheating for 1 minute, testing for 4 minutes;

4, 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;

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

6, compression permanent deformation test: in accordance with the national standard GB/T7759-1996, using a compression permanent deformation device for testing, type B, the compression is 25%, the test temperature is 70 ° C;

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 170 °C.

The vulcanization conditions of the following Examples 1 to 12 and Comparative Examples 1 and 2 were as follows: temperature: 170 ° C; pressure: 16 MPa; time was Tc90 + 1 min.

Example 1:

The branched polyethylene used was numbered PER-6.

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 70 parts of EPDM rubber and 30 parts of branched polyethylene for 90 seconds; then in the rubber compound 35 parts of zinc methacrylate was added and kneaded for 4 minutes; finally, 6 parts of cross-linking agent dicumyl peroxide (DCP) was added, and after 2 minutes of mixing, the rubber was discharged, and the mixture was placed at a roll temperature of 60 ° C. The thin open on the open mill, the sheet with a thickness of about 2.5mm, 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 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; then in the rubber compound Add 50 parts of zinc methacrylate, mix for 4 minutes; finally add 10 parts of cross-linking agent dicumyl peroxide (DCP), mix for 2 minutes, then drain the glue, the mixture is at a roll temperature of 60 ° C. The thin open on the open mill, the sheet with a thickness of about 2.5mm, 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-5.

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 to pre-press and knead for 90 seconds; then add 35 parts of zinc methacrylate to the rubber compound. , mixing for 4 minutes; finally adding 5 parts of cross-linking agent dicumyl peroxide (DCP), mixing for 2 minutes, then discharging the glue, and the mixture is thinned on an open mill with a roll temperature of 60 ° C to obtain 2.5. A sheet of about mm thickness is 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 to 50 rpm, add 100 parts of EPDM rubber for 90 seconds, and then add 35 parts of methacrylic acid to the compound. Zinc, kneading for 4 minutes; finally adding 5 parts of cross-linking agent dicumyl peroxide (DCP), mixing for 2 minutes, then discharging the glue, and the mixture is thinned on an open mill with a roll temperature of 60 ° C. A sheet of thickness of about 2.5 mm is parked for 20 hours.

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

The test data of Examples 1-3 and Comparative Example 1 are as follows:

Test items	Example 1	Example 2	Example 3	Comparative Example 1
hardness	71	75	69	70
Tensile strength / MPa	16.7	16.9	17.5	13.2
Elongation at break %	312	279	349	307
Tear strength N/mm	57	59	62	52
Compression set (70 ° C × 22h)	16	17	13	19

Example 4:

The branched polyethylene used was numbered PER-9.

The processing steps are as follows:

(1) Rubber mixing: set the temperature of the mixer to 90 ° C, the rotor speed is 50 rpm, add 90 parts of EPDM rubber and 10 parts of branched polyethylene for 90 seconds; then add 6 parts. Zinc oxide, 1 part stearic acid and 8 parts zinc methacrylate, kneaded for 2 minutes; then add 50 parts of carbon black N550 to the compound, knead for 3 minutes; finally add 4 parts of cross-linking agent diisopropyl peroxide Benzene (DCP), 1 part of triallyl isocyanurate (TAIC) and 0.3 parts of sulfur, after 2 minutes of mixing, the rubber was discharged, and the mixture was thinned on an open mill with a roll temperature of 60 ° C to obtain A sheet of thickness of about 2.5 mm is 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 are as follows:

(1) Rubber mixing: set the temperature of the internal mixer to 90 ° C, the rotor speed is 50 rpm, add 30 parts of EPDM rubber and 70 parts of branched polyethylene for 90 seconds; then add 6 parts. Zinc oxide, 1 part stearic acid and 5 parts zinc methacrylate, kneaded for 2 minutes; then add 50 parts of carbon black N550 to the compound, knead for 3 minutes; finally add 1 part of cross-linking agent diisopropyl peroxide Benzene (DCP), 0.5 parts of sulfur, 1.5 parts of 2-mercaptobenzimidazole and 1.5 parts of N-cyclohexyl-2-benzothiazolyl sulfenamide, after 3 minutes of mixing, the rubber is discharged, and the rubber is mixed at the roll temperature. It was thin on the 60 ° C open mill, and a sheet having a thickness of about 2.5 mm was obtained 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-4.

The processing steps 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 pre-pressed for 90 seconds; then add 6 parts of zinc oxide and 1 part of stearic acid. And 8 parts of zinc methacrylate, mixing for 2 minutes; then adding 50 parts of carbon black N550 to the compound, mixing for 3 minutes; finally adding 4 parts of cross-linking agent dicumyl peroxide (DCP), 1 part three Allyl isocyanurate (TAIC) and 0.3 parts of sulfur were mixed for 2 minutes, and the rubber was drained. The mixture was thinned on an open mill with a roll temperature of 60 ° C to obtain a sheet having a thickness of about 2.5 mm. 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 to 50 rpm, add 100 parts of EPDM rubber for 90 seconds, and then add 6 parts of zinc oxide and 1 part of stearin. Acid and 8 parts of zinc methacrylate, kneaded for 2 minutes; then add 50 parts of carbon black N550 to the compound, mix for 3 minutes; finally add 4 parts of cross-linking agent dicumyl peroxide (DCP), 1 part Triallyl isocyanurate (TAIC) and 0.3 parts of sulfur, after 2 minutes of mixing, the rubber was discharged, and the rubber mixture was thinly passed through an open mill having a roll temperature of 60 ° C to obtain a sheet having a thickness of about 2.5 mm. Park for 20 hours.

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

The test data of Examples 4 to 6 and Comparative Example 2 are as follows:

Example 7

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

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, 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, 1 part stearic acid and 1 part antioxidant 2,2,4-trimethyl-1,2-dihydroquinoline polymer (RD), kneaded for 2 minutes; then add 30 parts of methacrylic acid to the compound Zinc, 50 parts of carbon black N330 and 15 parts of paraffin oil SUNPAR 2280, mixed for 3 minutes; finally added 4 parts of cross-linking agent dicumyl peroxide (DCP), 1.5 parts of triallyl isocyanurate (TAIC) And 0.3 parts of sulfur, after 2 minutes of kneading, the rubber was discharged, and the rubber mixture was thinly passed through an open mill having a roll temperature of 60 ° C to obtain a sheet having a thickness of about 2.5 mm, and was left for 20 hours.

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

Example 8

The branched polyethylene used was numbered PER-8.

The processing steps are as follows:

(1) Rubber mixing: set the temperature of the internal mixer to 90 ° C, the rotor speed to 50 rpm, add 80 parts of EPDM rubber and 20 parts of PER-8 pre-pressure mixing for 90 seconds; then add 10 parts of oxidation. Zinc, 1 part stearic acid, 1 part antioxidant RD and 1 part 2-mercaptobenzimidazole (MB), kneaded for 2 minutes; then 30 parts of zinc methacrylate, 60 parts of carbon black N330 and then added to the compound 20 paraffin oil SUNPAR 2280, mixed for 3 minutes; finally added 3 parts of cross-linking agent dicumyl peroxide (DCP), 1 part triallyl isocyanurate (TAIC) and 9 parts of cross-linking agent 1,2-polybutadiene, after 2 minutes of kneading, the rubber was discharged, and the kneaded rubber was thinly passed through an open mill having a roll temperature of 60 ° C to obtain a sheet having a thickness of about 2.5 mm, and was left to stand for 20 hours.

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

Example 9

The branched polyethylene used was numbered PER-7.

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 20 parts of ethylene propylene diene rubber, 50 parts of ethylene propylene diene monomer and 30 parts of PER-7 pre-pressure mixing. 90 seconds; then add 5 parts of zinc oxide, 1 part of stearic acid, 1 part of antioxidant RD and 1 part of N-4 (anilinophenyl) maleimide (MC), knead for 2 minutes; then in the glue Add 20 parts of zinc methacrylate, 50 parts of carbon black N330 and 10 parts of liquid polyisobutylene (number average molecular weight of 1200), mix for 3 minutes; finally add 3 parts of cross-linking agent dicumyl peroxide (DCP) And 1 part of N, N'-m-phenylene bismaleimide (HVA-2), after 2 minutes of mixing, the rubber was discharged, and the mixture was thinned on an open mill with a roll temperature of 60 ° C to obtain 2.5. A sheet of about mm thickness is parked for 20 hours.

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

Example 10:

The branched polyethylene used was numbered PER-3.

The processing steps are as follows:

(1) Rubber mixing: set the temperature of the internal mixer to 90 ° C, the rotor speed to 50 rpm, add 20 parts of ethylene propylene diene rubber, 30 parts of EPDM rubber and 50 parts of PER-3 pre-pressure mixing 90 seconds; then add 20 parts of zinc oxide, 2 parts of stearic acid, 1 part of antioxidant RD and 1 part of 2-mercaptobenzimidazole (MB), knead for 2 minutes; then add 30 parts of methacrylic acid to the compound Zinc, 80 parts of carbon black N330 and 20 parts of paraffin oil SUNPAR 2280, mixing for 3 minutes; finally adding 1 part of cross-linking agent dicumyl peroxide (DCP), mixing for 2 minutes, then discharging the glue, the glue is The sheet was rolled on a mill with a roll temperature of 60 ° C to obtain a sheet having a thickness of about 2.5 mm and parked for 20 hours.

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

Example 11

The branched polyethylene used was numbered PER-5.

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 PER-5 pre-pressure mixing for 90 seconds; then add 15 parts of zinc oxide, 2 parts of stearic acid, 1 part of antioxidant RD, kneaded for 2 minutes; then add 25 parts of zinc methacrylate, 60 parts of carbon black N330 and 15 parts of paraffin oil SUNPAR 2280 to the compound, mix for 3 minutes; finally add 4 parts of cross-linking agent Dicumyl oxide (DCP) and 1.5 parts of N, N'-m-phenylene bismaleimide (HVA-2), after 2 minutes of mixing, the rubber is discharged, and the mixture is at a roll temperature of 60 ° C. The thin open on the open mill, the sheet with a thickness of about 2.5mm, and parked for 20 hours.

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

Example 12

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

The processing steps 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 PER-2 and 70 parts of PER-6 pre-pressure mixing for 90 seconds; then add 10 parts of zinc oxide, 2 parts of stearic acid, 1 part of antioxidant RD, mixing for 2 minutes; then adding 15 parts of zinc methacrylate, 50 parts of carbon black N330 and 15 parts of paraffin oil SUNPAR 2280 to the compound, mixing for 3 minutes; 3 parts of cross-linking agent dicumyl peroxide (DCP) and 1 part of triallyl isocyanurate (TAIC), after 2 minutes of mixing, the rubber was discharged, and the mixture was opened at a roll temperature of 60 ° C. Thin on the refiner, a sheet with a thickness of about 2.5 mm, and parked for 20 hours.

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

The test data of Examples 7 to 12 are as follows:

Example 13

A light-colored pure rubber pipe produced by using the rubber composition provided by the present invention, the production method comprising the following steps:

(1) Rubber mixing:

Set the temperature of the 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 35 parts of zinc methacrylate to the compound, mix 4 In the end, 5 parts of cross-linking agent dicumyl peroxide (DCP) was added, and after 2 minutes of mixing, the rubber was drained, and the mixture was thinly passed on an open mill with a roll temperature of 60 ° C to obtain a thickness of about 2.5 mm. Sheet, park for 20 hours.

(2) Extrusion and molding:

The 60mm cold feed extruder is equipped with a T-type head. At 90 °C, the rubber layer is extruded on the mandrel to obtain the tube blank, which is cooled, de-core, trimmed, inspected and stored after being vulcanized. Among them, the vulcanization process is steam vulcanization at 160 ° C, steam pressure 0.6 MPa, time 30 minutes.

Example 14

An insulating glove produced by using the rubber composition provided by the present invention, the production method comprising the following steps:

(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-4 pre-pressure mixing for 90 seconds; then add 6 parts of zinc oxide, 1 part of stearic acid and 8 parts of A Zinc acrylate, kneaded for 2 minutes; then add 50 parts of carbon black N550 to the compound, mix for 3 minutes; finally add 4 parts of cross-linking agent dicumyl peroxide (DCP), 1 part of triallyl Cyanurate (TAIC) and 0.3 parts of sulfur were mixed for 2 minutes, and the rubber was drained. The mixture was thinned on an open mill with a roll temperature of 60 ° C to obtain a sheet having a thickness of about 2.5 mm, and allowed to stand for 20 hours.

(2) Cut piece: After parking the film for a period of time, the piece is formed according to the size of the mold cavity;

(3) Apply the release agent to the mold and preheat it to 150 ° C, then put the three pieces of the film cut in step 2 into the mold, and put the mold into the vulcanizer, pressurize to 20 MPa, heat preservation and pressure curing 5 min, then take out the mold, cool to ambient temperature and then open the mold. Finally, the insulating gloves obtained after the mold opening are dried for 24 hours, and the insulated gloves are obtained.

Example 15

A high temperature resistant conveyor belt using the rubber composition provided by the present invention as a working surface covering glue, the production method comprising the following steps:

The high temperature resistant conveyor belt of the embodiment is provided with a cored tensile canvas between the working surface covering glue and the non-working surface covering glue, and they are made into a solid whole by molding and vulcanization process.

The composition and ratio of the working surface covering glue described in this embodiment are in parts:

Rubber mixing process: set the temperature of the internal mixer to 90 ° C, the rotor speed is 50 rpm, add 100 parts of PER-5 pre-pressure mixing for 90 seconds; then add 15 parts of zinc oxide, 2 parts of stearic acid, 1 part Anti-aging agent RD, mixing for 2 minutes; then adding 25 parts of zinc methacrylate, 60 parts of carbon black N330 and 15 parts of paraffin oil SUNPAR 2280 to the compound, mixing for 3 minutes; finally adding 4 parts of cross-linking agent peroxide Cumene (DCP) and 1.5 parts of N,N'-m-phenylene bismaleimide (HVA-2) were mixed for 2 minutes and then discharged.

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.

Molding process: The film is closely attached to the preformed adhesive canvas strip to form a strip of the high temperature resistant conveyor belt, and then rolled up for 4 hours and then vulcanized.

Vulcanization process: The above-mentioned formed conveyor belt blanks are placed in a flat vulcanizing machine for stage vulcanization, each of which has a vulcanization time of 25 minutes, a vulcanization pressure of 3 kg/cm ² and a vulcanization temperature of 160 ° C.

Trimming and inspection: After the vulcanization is finished, it is trimmed, inspected, and then packaged into the warehouse.

Example 16:

A high-temperature resistant conveyor belt using the rubber composition provided by the present invention as an adhesive layer, the production method comprising the following steps:

The high temperature resistant conveyor belt of the embodiment is provided with a rubberized canvas as a tensile layer between the working surface covering rubber and the non-working surface covering rubber, and they are made into a solid whole through molding and vulcanization processes.

The composition and ratio of the adhesive layer rubber for the appliqué canvas according to the embodiment are in parts:

(1) Rubber mixing:

Set the temperature of the internal mixer to 90 ° C, the rotor speed to 50 rpm, add 100 parts of PER-4 pre-pressure mixing for 90 seconds; then add 5 parts of nano zinc oxide, 1 part of stearic acid, 1 part of antioxidant RD and 1 part of N-4 (anilinophenyl)maleimide (MC), kneaded for 2 minutes; then add 15 parts of zinc methacrylate, 20 parts of carbon black N330, 30 parts of highly dispersed white carbon in the compound Black and 15 parts of liquid polyisobutylene (number average molecular weight of 1200), mixing for 3 minutes; finally adding 3 parts of cross-linking agent dicumyl peroxide (DCP) and 1 part of N, N'-m-phenylene double horse Imide (HVA-2), after 2 minutes of kneading, the rubber was discharged, and the rubber mixture was thinly passed on an open mill with a roll temperature of 60 ° C, and the lower piece was left for 20 hours;

(2) Adhesive:

The rubber compound and the cloth layer are pasted at a normal temperature by a double roll or a four roll calender to complete the bonding of the adhesive glue and the canvas layer to obtain a rubberized canvas strip;

(3) Molding process:

The formed adhesive canvas strip and the cover film are closely attached together on a molding machine to form a strip of a high temperature resistant conveyor belt, and then rolled up for 4 hours and then vulcanized.

(4) Vulcanization process:

The formed conveyor belt blanks were placed in a flat vulcanizing machine for stage vulcanization, each of which had a vulcanization time of 25 minutes, a vulcanization pressure of 3 kg/cm2, and a vulcanization temperature of 160 °C.

(5) Trimming and inspection:

After the vulcanization is finished, it is trimmed, inspected, and then packaged into the warehouse.

Example 17

An insulating glove produced by using the rubber composition provided by the present invention, the production method comprising the following steps:

(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-11 pre-pressure mixing for 90 seconds; then add 6 parts of zinc oxide, 1 part of stearic acid and 8 parts of A Zinc acrylate, kneaded for 2 minutes; then add 50 parts of carbon black N550 and 10 parts of paraffin oil to the compound, mix for 3 minutes; finally add 4 parts of cross-linking agent dicumyl peroxide (DCP), 1 part Triallyl isocyanurate (TAIC) and 0.3 parts of sulfur, after 2 minutes of mixing, the rubber was discharged, and the rubber mixture was thinly passed through an open mill having a roll temperature of 60 ° C to obtain a sheet having a thickness of about 2.5 mm. Park for 20 hours.

The rest of the production process is in accordance with Example 14. The rubber composition of the present embodiment was molded into a test sample by molding, and the test performance was as follows:

Hardness: 66; tensile strength: 25.9 MPa; elongation at break: 512%; tear strength 61 N/mm; 50 kV power frequency withstand voltage for 1 minute without breakdown without flashover.

Example 18

A high temperature resistant conveyor belt using the rubber composition provided by the invention as a working surface covering glue, the composition and mixing process of the working surface covering glue is as follows:

Set the temperature of the internal mixer to 90 ° C, the rotor speed to 50 rpm, add 100 parts of PER-12 pre-pressure mixing for 90 seconds; then add 5 parts of zinc oxide, 1 part of stearic acid, 1 part of antioxidant RD, 1 An antioxidant MB, 2 parts of coumarone resin and 2 parts of RX-80 resin were mixed for 2 minutes; then 25 parts of zinc methacrylate, 60 parts of carbon black N330 and 20 parts of paraffin oil SUNPAR 2280 were added to the compound. Mixing for 3 minutes; finally adding 4 parts of cross-linking agent dicumyl peroxide (DCP) and 1.5 parts of N, N'-m-phenylene bismaleimide (HVA-2), mixing for 2 minutes gum. The rest of the processing techniques are in accordance with Example 15.

Example 19

A high temperature resistant conveyor belt using the rubber composition provided by the present invention as an adhesive layer rubber, and the composition and mixing process of the adhesive layer rubber for the adhesive canvas are as follows:

Set the temperature of the internal mixer to 90 ° C, the rotor speed to 50 rpm, add 100 parts of PER-12 pre-pressure mixing for 90 seconds; then add 5 parts of nano zinc oxide, 1 part of stearic acid, 1 part of antioxidant RD and 2 parts of modified alkyl phenolic resin TKM-K, kneaded for 2 minutes; then add 15 parts of zinc methacrylate, 20 parts of carbon black N330, 30 parts of highly dispersed white carbon black, 2 parts of binder RS in the compound And 15 parts of paraffin oil, mixing for 3 minutes; finally adding 2 parts of binder RH, 3 parts of cross-linking dicumyl peroxide (DCP) and 1 part of N, N'-m-phenylene bismalemide Amine (HVA-2), after 2 minutes of mixing, the rubber is discharged, and the rubber mixture is thinly passed on an open mill with a roll temperature of 60 ° C, and the lower piece is left for 20 hours;

Example 20

The processing steps of a rubber metal shock absorbing member are as follows:

(1) Rubber mixing: set the temperature of the internal mixer to 100 ° C, the rotor speed to 50 rpm, add 100 parts of PER-10 and 15 parts of paraffin oil SUNPAR 2280 pre-pressed and kneaded for 90 seconds; then add 5 parts of zinc oxide, 1 part stearic acid, 2 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, 10 parts of methyl Zinc acrylate and 15 parts paraffin oil SUNPAR2280, mixed for 3 minutes; then add 3 parts of binder RA-65, knead for 1 minute; then add 4 parts of cross-linking agent di-tert-butylperoxydiisopropylbenzene (BIPB 1 part of a co-crosslinking agent, triallyl isocyanurate (TAIC), and 0.3 parts of sulfur, which 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.

(2) Vulcanization process: the rubber material and the surface-treated and coated metal parts are laminated according to the process requirements, and then loaded into the preheated mold, and then vulcanized into a flat vulcanizing machine, and the vulcanization temperature is 160. °C, steam pressure 0.6MPa, time is 25 minutes.

(3) Trimming finishing, inspection, and obtaining finished products.

The damper member of the embodiment can be used for a high temperature portion such as an engine and an exhaust pipe.

Claims (21)

1. A rubber composition comprising: a rubber matrix and an essential component, the rubber matrix comprising: a branched polyethylene having a content of a: 0 < a ≤ 100 parts; The content of rubber and ethylene propylene diene rubber is b: 0 ≤ b < 100 parts; the essential components include: 1 to 10 parts of a crosslinking agent, and 5 to 50 parts of an unsaturated carboxylic acid metal salt, based on 100 parts by weight of the rubber matrix. The branched polyethylene comprises an ethylene homopolymer having a degree of branching of not less than 50 branches/1000 carbons, a weight average molecular weight of not less than 50,000, and a Mooney viscosity of ML (1+4) of 125 ° C. Not less than 2.
2. The rubber composition according to claim 1, wherein the content of the branched polyethylene in the rubber matrix is 10: a ≤ 100 parts in terms of 100 parts by weight; the ethylene propylene rubber and the ternary The content of ethylene propylene rubber is b: 0 ≤ b ≤ 90 parts; the branched polyethylene is an ethylene homopolymer having a branching degree of 60 to 130 branches/1000 carbons and a weight average molecular weight of 66,000 to 51.8. Million, Mooney viscosity ML (1 + 4) 125 ° C is 6 ~ 10.
3. A rubber composition according to claim 1, wherein said crosslinking agent comprises at least one of a peroxide crosslinking agent and sulfur, and said peroxide crosslinking agent comprises di-tert-butyl group. Peroxide, dicumyl peroxide, tert-butyl cumyl peroxide, 1,1-di-tert-butyl peroxide-3,3,5-trimethylcyclohexane, 2,5-di Methyl-2,5-di(tert-butylperoxy)hexane, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne-3, bis(tert-butylperoxide) Isopropyl)benzene, 2,5-dimethyl-2,5-bis(benzoyl peroxy)hexane, tert-butyl peroxybenzoate, tert-butylperoxy-2-ethylhexyl carbonate At least one of them.
4. The rubber composition according to claim 1, wherein the unsaturated carboxylic acid metal salt comprises zinc acrylate, zinc methacrylate, magnesium methacrylate, calcium methacrylate or aluminum methacrylate. At least one.
5. A rubber composition according to claim 1, wherein said rubber composition further comprises an auxiliary component in terms of 100 parts by weight of the rubber base, said auxiliary component in parts by weight, comprising: in addition to unsaturated 0.2 to 10 parts of a crosslinking agent other than a metal carboxylate, 10 to 150 parts of a reinforcing filler, 5 to 80 parts of a plasticizer, 1 to 3 parts of a stabilizer, 2 to 20 parts of a metal oxide, and a vulcanization accelerator 0 to 3 servings.
6. A rubber composition according to claim 5, wherein the co-crosslinking agent comprises triallyl cyanurate, triallyl isocyanurate, ethylene glycol dimethacrylate Ester, triethylene glycol dimethacrylate, triallyl trimellitate, trimethylolpropane trimethacrylate, N,N'-m-phenylene bismaleimide, N,N' - at least one of bis-indenyl acetonide, 1,2-polybutadiene and sulphur.
7. The rubber composition according to claim 5, wherein the reinforcing filler comprises at least one of carbon black, white carbon, calcium carbonate, talc, calcined clay, and magnesium carbonate.
8. A rubber composition according to claim 5, wherein said plasticizer comprises pine tar, motor oil, naphthenic oil, paraffin oil, coumarone, RX-80, stearic acid, paraffin, liquid At least one of ethylene propylene rubber and liquid polyisobutylene.
9. A rubber composition according to claim 5, wherein said stabilizer comprises 2,2,4-trimethyl-1,2-dihydroquinoline (RD), 6-ethoxy -2,2,4-trimethyl-1,2-dihydroquinoline (AW), 2-mercaptobenzimidazole (MB), N-4 (anilinophenyl) maleimide (MC At least one of them.
10. A rubber composition according to claim 5, wherein said metal oxide contains at least one of zinc oxide, magnesium oxide and calcium oxide.
11. The rubber composition according to claim 5, wherein the vulcanization accelerator comprises 2-thiol benzothiazole, dibenzothiazole disulfide, tetramethylthiuram monosulfide, and disulfide. Tetramethylthiuram, tetraethylthiuram disulfide, N-cyclohexyl-2-benzothiazolyl sulfenamide, N,N-dicyclohexyl-2-phenylthiazolyl sulfenamide, double horse At least one of imide and ethylene thiourea.
12. A method of processing the rubber composition according to any one of claims 1 to 11, characterized in that the processing method comprises the steps of:

    (1) Rubber kneading: First, the rubber composition other than the cross-linking system is sequentially added to the internal mixer for mixing by weight, and then added to the cross-linking system, uniformly kneaded, and discharged to obtain a rubber compound. The rubber compound is thinned on the open mill, and then the film is left to be vulcanized, wherein the crosslinking system comprises a crosslinking agent, and may further comprise at least one of a crosslinking agent and a vulcanization accelerator;

    (2) Vulcanization: The rubber compound is filled into the cavity of the mold, and after being vulcanized by vulcanization on a flat vulcanizer, the vulcanized rubber is obtained by demolding.
13. An insulating glove, characterized in that the rubber compound used in the insulating glove comprises the rubber composition according to any one of claims 1 to 11.
14. A method of producing the insulating glove according to claim 13, wherein the production method comprises the following steps:

    (1) Rubber kneading: First, the rubber composition other than the cross-linking system is sequentially added to an internal mixer for kneading, and then added to a cross-linking system, which is uniformly kneaded and discharged to obtain a kneaded rubber. The mixture is thinned on the open mill and then discharged, and is parked for vulcanization, wherein the crosslinking system comprises a crosslinking agent, and may further comprise at least one of a crosslinking agent and a vulcanization accelerator;

    (2) Cut piece: After parking the film for a period of time, the piece is formed according to the size of the mold cavity;

    (3) Vulcanization: The formed film is filled into the cavity of the mold, and the mold is placed on a flat vulcanizing machine to be pressure vulcanized, cooled and demolded, and trimmed to obtain a rubber insulated glove.
15. A hose characterized in that the rubber composition comprises the rubber composition according to any one of claims 1 to 11.
16. A method of producing the hose of claim 15 wherein the production method comprises the steps of:

    (1) Rubber kneading: First, the rubber composition other than the cross-linking system is sequentially added to the internal mixer for mixing by weight, and then added to the cross-linking system, uniformly kneaded, and discharged to obtain a rubber compound. The rubber compound is thinned on the open mill, and then the film is left to be vulcanized, wherein the crosslinking system comprises a crosslinking agent, and may further comprise at least one of a crosslinking agent and a vulcanization accelerator;

    (2) Extrusion and molding: a cold feed extruder is used to extrude the rubber layer on the mandrel to obtain a tube blank, which is cooled by steam vulcanization, de-core, trimmed, inspected, and stored in a warehouse to obtain a hose.
17. A 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 11.
18. A method of producing a conveyor belt according to claim 17, wherein the production method comprises the following steps:

    (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. The mixture is thinned on the open mill and then discharged, and is parked 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 and heat preservation for use;

    (3) Molding process: the film is closely attached to the pre-formed adhesive canvas strip blank on the forming machine to form a strip of high temperature resistant conveyor belt, and then rolled up for waiting for vulcanization;

    (4) placing the formed conveyor belt blank into a flat vulcanizing machine for segmental vulcanization;

    (5) After the vulcanization is finished, it is trimmed, inspected, and then packaged into the warehouse.
19. A conveyor belt characterized in that the rubber used for the adhesive layer of the conveyor belt comprises the rubber composition according to any one of claims 1 to 11.
20. A method of producing a conveyor belt according to claim 19, characterized in that the production method comprises the following steps:

    (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. The mixture is thinned on the open mill and then discharged, and is parked 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) Adhesive: The rubber mixture and the cloth layer are finished at a normal temperature by a double-roll or a four-roll calender to bond the adhesive to the canvas layer to obtain a rubberized canvas strip;

    (3) Molding process: the formed adhesive tape canvas blank and the cover film are closely attached together on the molding machine to form a strip of the high temperature resistant conveyor belt, which is rolled up and then vulcanized;

    (4) placing the formed conveyor belt blank into a flat vulcanizing machine for segmental vulcanization;

    (5) After vulcanization, it is trimmed, inspected, and then packaged into the warehouse.
21. A shock absorbing member characterized in that the shock absorbing member is a rubber shock absorbing member or a rubber metal composite shock absorbing member, and the rubber used comprises the rubber composition according to any one of claims 1 to 11.