WO2020011005A1

WO2020011005A1 - Chlorine-containing rubber composition, and application thereof and preparation method therefor

Info

Publication number: WO2020011005A1
Application number: PCT/CN2019/092644
Authority: WO
Inventors: 徐涛; 傅智盛; 吴安洋
Original assignee: 杭州星庐科技有限公司
Priority date: 2018-07-13
Filing date: 2019-06-25
Publication date: 2020-01-16
Also published as: CN110713666B; CN110713666A

Abstract

A chlorine-containing rubber composition, a processing method, and an application. The rubber composition is characterized by comprising a rubber matrix and a compounding component. In parts by weight, per 100 parts by weight of the rubber matrix comprises: a parts of chlorine-containing branched polyethylene (CBPE), wherein 5≤a≤100 parts; b parts of chlorinated polyethylene rubber (CM), wherein 0≤b≤95; and c parts of chlorosulfonated polyethylene rubber (CSM), wherein 0≤c≤95. The mass fraction of chlorine in the chlorine-containing branched polyethylene is not less than 10%, and a branched polyethylene raw material used for preparing the chlorine-containing branched polyethylene comprises an ethylene homopolymer having a degree of branching of not less than 50 branches/1000 carbons. The compounding component comprises a vulcanization system. The provided rubber composition has a better comprehensive performance in physical and mechanical properties and processing properties, and thus the chlorine-containing rubber composition has a better overall performance.

Description

[Name of invention formulated by ISA according to Rule 37.2] 氯 Chlorine-containing rubber composition and application and preparation method thereof

Technical field

The invention belongs to the technical field of rubber, and particularly relates to a chlorine-containing rubber composition, a processing method and application thereof, and also relates to a method for preparing a chlorine-containing rubber composition and processing it into a compound rubber.

Background technique

The chlorinated polyethylene rubber in the prior art is a polar special rubber with excellent oil resistance, flame resistance and chemical stability. Mainly used in wire and cable, hose, conveyor belt, rubber dam, car inner tube, elevator handrail and other fields.

The raw material for preparing chlorinated polyethylene is generally high-density polyethylene. The variety and performance of the raw material will affect the processing properties and physical and mechanical properties of the prepared chlorinated polyethylene. Among them, the molecular weight of the raw material has a significant effect on the performance of chlorinated polyethylene. Chlorinated polyethylene raw rubber and vulcanized rubber products made from high-molecular-weight high-density polyethylene raw materials have higher physical and mechanical properties, but the processing fluidity is not good, and the processing is difficult. The prepared chlorinated polyethylene has good processing fluidity and easy processing, but the physical and mechanical properties are reduced. Therefore, it is difficult for the chlorinated polyethylene rubber in the prior art to have both good physical and mechanical properties and processing properties. This contradiction obviously limits the application and development of chlorinated polyethylene rubber.

In addition, because sufficient chlorine content is needed to fully destroy the crystalline structure of polyethylene and obtain elasticity, the mass fraction of chlorine in chlorinated polyethylene is generally above 25%, and more commonly it is above 30%. Restricting the production and application of chlorinated polyethylene rubber with a wider range of chlorine content, also restricts the development of the chlorinated polyethylene rubber industry.

Chlorosulfonated polyethylene rubber is a product with similar structure and performance to chlorinated polyethylene rubber. It also has excellent oil resistance, flame resistance, chemical stability and other characteristics, but also faces the same technical difficulties as the chlorinated polyethylene rubber. : It is difficult to have both good physical and mechanical properties and processability, and the range of chlorine content is also limited. Generally, it is required to be above 25%.

Summary of the invention

In view of the problems existing in the prior art, the present invention provides a new type of chlorine-containing rubber composition, which improves the comprehensive performance of physical and mechanical properties and processability, and can have good rubber in a wider range of chlorine content. elasticity. The rubber matrix of the rubber composition provided by the present invention uses a branched polyethylene having a branching degree of not less than 55 branches / 1000 carbons as a raw material to replace part or all of the chlorine-containing branched polyethylene (CBPE). Chlorinated polyethylene rubber (CM) or chlorosulfonated polyethylene rubber (CSM). The invention also provides a processing method of the rubber composition and its application in the fields of electric wires and cables, rubber hoses, tapes, waterproof coils, seals and the like.

The technical solution of the present invention is to provide a chlorine-containing rubber composition, which includes: a rubber matrix and a compounding component. In terms of parts by weight, each 100 parts by weight of the rubber matrix includes: chlorine-containing branched polyethylene (CBPE). Content a: 5≤a≤100 parts, content of chlorinated polyethylene rubber (CM) b: 0≤b≤95 parts, content of chlorosulfonated polyethylene rubber (CSM) c: 0≤c≤95 parts, The chlorine element in the chlorine-containing branched polyethylene has a mass fraction of not less than 10%. The branched polyethylene raw material used for preparing the chlorine-containing branched polyethylene includes an ethylene homopolymer, and the degree of branching of the ethylene homopolymer is not low. At 50 branches / 1000 carbons; the complex component comprises a vulcanization system.

In the prior art, "branched polyethylene" refers not only to branched ethylene homopolymers, but also to branched saturated vinyl copolymers, such as ethylene-α-olefin copolymers, which can be POE, the branched polyethylene according to the present invention may include both branched ethylene homopolymer and POE. Since the raw material cost of the branched ethylene homopolymer is relatively low, a better choice is to include a high proportion of branched polyethylene or Only branched ethylene homopolymer is included. The preferred technical solution of the present invention is that the branched polyethylene only contains branched ethylene homopolymer.

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

The branched polyethylene used in the present invention is a type of ethylene homopolymer with a degree of branching of not less than 50 branches / 1000 carbons, and can be called Branched Polyethylene or Branched PE. At present, its synthesis method mainly consists of a late transition metal catalyst. Based on the "chain walking mechanism" obtained by catalytic homopolymerization of ethylene, a preferred late transition metal catalyst may be one of (α-diimide) nickel / palladium catalysts. The essence of the chain walking mechanism is that post-transition metal catalysts, such as (α-diimide) nickel / palladium catalysts, are more likely to undergo β-hydrogen elimination reactions and reinsertion reactions in the process of catalyzing olefin polymerization, resulting in branching. Such branched polyethylenes may have different numbers of carbon atoms based on the branches of the main chain, and specifically may have 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, which is more suitable for industrial applications. Therefore, the present invention preferably uses the (α-diimide) nickel catalyst to catalyze the polymerization of ethylene. Of polyethylene.

Because the branched polyethylene used in the present invention has a rich branched chain structure, compared with commonly used high-density polyethylene or low-density polyethylene, at the same molecular weight, it has a lower Mooney viscosity and better processing performance; Under the same Mooney viscosity or processing difficulty, it has higher molecular weight and better physical and mechanical properties. The rubber composition provided by the present invention can have good comprehensive performance in terms of processability and physical and mechanical properties. A further technical solution is that the branched polyethylene raw material used in the present invention has a degree of branching of not less than 50 branches / 1000 carbons and a weight average molecular weight of not less than 66,000; the degree of branching is further preferably 60 to 130 The weight average molecular weight of the branched chains / 1000 carbons is more preferably 66,000 to 518,000; the degree of branching is more preferably 70 to 120 branched chains / 1000 carbons, and the weight average molecular weight is further preferably 82,000 to 436,000.

Because the branched polyethylene used in the present invention has a rich branched structure and has a low degree of crystallinity or tends to be zero, it can have good elasticity without being chlorinated (sulfonated) or only with a lower degree of chlorinated (sulfonated). Therefore, using branched polyethylene as a raw material, a chlorine-containing branched polyethylene having a wider chlorine content range than the chloro (sulfonated) polyethylene in the prior art can be prepared. In a further technical solution, the chlorine element mass fraction of the chlorine-containing branched polyethylene used in the present invention is 10% to 51.3%, more preferably 14.8% to 45.7%, and still more preferably 19.7% to 45.5%.

The synthesis process of chlorinated branched polyethylene can be divided into the following three categories: solution chlorination process, aqueous suspension process and solid-phase chlorination process. Among them, the more mature is the solution chlorination process. The solvent used may be selected from carbon tetrachloride, chloroform, chlorobenzene, trichloroethylene, tetrachloroethylene, etc. or a mixed solvent thereof, and the initiator used may be selected from benzyl peroxide. Acyl, azobisisobutyronitrile, and the like are chlorinated by passing chlorine gas into a solution containing branched polyethylene and an initiator. The reaction temperature is preferably 40 to 120 ° C, and the reaction time is set according to the requirements of the chlorine content. The preparation of chlorosulfonated branched polyethylene requires further sulfur dioxide and chlorine gas for chlorosulfonation reaction after proper chlorination.

A further technical solution is the chlorine-containing rubber composition of the present invention, the vulcanization system of which is selected from the group consisting of peroxide vulcanization system, thiourea vulcanization system, thiadiazole vulcanization system, triazole dimercaptoamine salt vulcanization system and radiation vulcanization system. At least one.

The peroxide vulcanization system includes a peroxide cross-linking agent and a cross-linking assistant. A further technical solution is that the amount of the peroxide cross-linking agent is 1 to 10 parts based on 100 parts by weight of the rubber matrix, and the cross-linking aid is assisted. The dosage of the agent is 0.2-10 parts. Among them, peroxide crosslinking agents include di-t-butyl peroxide, di-cumyl peroxide, t-butylcumyl peroxide, 1,1-di-tert-butyl peroxide-3,3,5- Trimethylcyclohexane, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane, 2,5-dimethyl-2,5-bis (t-butylperoxy) Hexyne-3, bis (tert-butylisopropylperoxy) benzene (BIBP), 2,5-dimethyl-2,5-bis (benzoylperoxy) hexane, tert-butyl peroxide Ester, at least one of t-butylperoxy-2-ethylhexyl carbonate, and the cross-linking aid includes triallyl cyanurate, triallyl isocyanurate, ethylene glycol dimethyl Acrylate, ethyl dimethacrylate, triethylene glycol dimethacrylate, triallyl trimellitate, trimethylolpropane trimethacrylate, ethylene glycol dimethacrylate, N At least one of N, N'-m-phenylenebismaleimide, N, N'-bisfurylene acetone, 1,2-polybutadiene, p-quinonedioxime, sulfur, and unsaturated carboxylic acid metal salt One type, the unsaturated carboxylic acid metal salt comprises zinc acrylate, zinc methacrylate, magnesium methacrylate, calcium methacrylate, At least one of aluminum acrylate. Adding an appropriate amount of unsaturated carboxylic acid metal salt such as zinc methacrylate can effectively improve the physical and mechanical properties of the vulcanizate, especially the tensile strength.

The thiourea vulcanization system is generally composed of thiourea and a small amount of sulfur. Among them, the thiourea can be selected from ethylthiourea or ethylenethiourea. Based on 100 parts by weight of the rubber matrix, a suitable amount of thiourea ranges from 2 to 8 , 0.5 to 2 parts of sulfur.

Thiadiazole vulcanization system consists of cross-linking agents and accelerators. The cross-linking agents are mainly thiadiazole derivative cross-linking agents. Commonly used are ECHO.A, ECHO., TDD, PT75, TDDS, etc. Common accelerators are Vanax 808, EataAccelDH, NC, Accel 903, BF, etc. And mix with a certain amount of acid absorbent, such as highly active magnesium oxide or ultra-fine magnesium hydroxide.

Triazole dimercaptoamine salt vulcanization system is a single substance, which integrates the effective groups of thiadiazole vulcanizing agent with n-butyraldehyde and aniline condensate accelerator, and overcomes the cross-linking of thiadiazole and accelerator to rubber. Later, the irregular distribution of the bonds has the disadvantage that the rubber cross-linked body becomes a stable structure. Compared to the thiadiazole system, the salt also changed the pH of the system due to the introduction of special groups, changing from strong acidity to neutrality, changing the adverse effects of acidic fillers on the system, making the rubber more chemically crosslinked. active. Therefore, the crosslinked rubber in this system has a qualitative improvement in physical or chemical properties. It is suitable for low-temperature, non-pressure and low-pressure vulcanization process conditions. The vulcanization speed is fast and the amount of addition is small. It does not decompose at the vulcanization temperature, does not produce odor, and is environmentally friendly and non-toxic. Typical products are: vulcanizing agent FSH, cross-linking agent TEHC.

The main component of the radiation vulcanization sensitization system is a radiation sensitizer, which can be selected from triallyl cyanurate, triallyl isocyanurate, ethylene glycol dimethacrylate, triethyl dimethacrylate Diesters, trimethylolpropane trimethacrylate, and the like. The radiation sensitization system is particularly suitable for the application fields of wires and cables that require electrical insulation performance.

In a further technical solution, the chlorine-containing rubber composition of the present invention is based on 100 parts by weight of a rubber matrix, and the compounding component further includes 10 to 200 parts of a reinforcing filler, 3 to 80 parts of a plasticizer, and a metal oxide. 1 to 20 parts, stabilizers 1 to 15 parts, antioxidants 0 to 2 parts, flame retardants 0 to 120 parts, surface modifiers 0 to 15 parts, adhesives 0 to 20 parts, foaming agents 0 to 20 Serving.

A further technical solution is that the reinforcing filler includes carbon black, white carbon black, calcium carbonate, calcined clay, talc, magnesium silicate, aluminum silicate, magnesium carbonate, titanium dioxide, montmorillonite, short fibers, At least one of kaolin and bentonite.

A further technical solution is that the plasticizer comprises pine tar, motor oil, naphthenic oil, paraffin oil, aromatic oil, liquid polyisobutylene, coomarone, RX-80, stearic acid, paraffin, chlorinated paraffin, Dioctyl dioctate, dioctyl sebacate, epoxy soybean oil, dibutyl phthalate, dioctyl phthalate, diisodecyl phthalate, ditridecyl phthalate At least one of an alkyl ester and trioctyl metaphthalate. In order to improve the viscosity, a plasticizer having a thickening effect, such as pine tar, coomarone, RX-80, liquid polyisobutylene, and the like can also be preferably used. In order to improve cold resistance, dioctyl adipate, dioctyl sebacate, dioctyl phthalate, and the like can be preferably used. Epoxidized soybean oil stabilizes the rubber matrix.

A further technical solution is that the metal oxide includes at least one of zinc oxide, magnesium oxide, aluminum oxide, lead oxide, and calcium oxide. Metal oxides can assist in crosslinking and absorb hydrogen chloride.

In a further technical solution, the stabilizer includes at least one of a basic lead salt compound, a metal soap compound, an organic tin compound, an epoxy compound, a phosphite compound, and a polyhydric alcohol compound. Among them, the basic lead salt compound is selected from lead stearate, lead dititanate, lead silicate, lead phthalate, and the like.

A further technical solution is that the antioxidant comprises 2,2,4-trimethyl-1,2-dihydroquinoline polymer (RD), 6-ethoxy-2,2,4-trimethyl -1,2-dihydroquinoline (AW), 2-mercaptobenzimidazole (MB), N-phenyl-N'-cyclohexyl-p-phenylenediamine (4010), N-isopropyl-N'- At least one of phenyl-p-phenylenediamine (4010NA) and N- (1,3-dimethyl) butyl-N'-phenyl-p-phenylenediamine (4020).

A further technical solution is that the flame retardant comprises pentaerythritol, ammonium polyphosphate, triethyl phosphate, aluminum hydroxide, magnesium hydroxide, zinc borate, antimony trioxide, zinc stearate, titanate, ten At least one of brominated diphenyl ether, hydroxide modified with silane coupling agent, and red phosphorus. The hydroxides modified by aluminum hydroxide, magnesium hydroxide, and silane coupling agent are nano-alumina, nano-magnesium hydroxide, nano-hydroxides modified by silane coupling agent, and the red phosphorus is microcapsules. Red phosphorus.

A further technical solution is that the surface modifier comprises at least one of polyethylene glycol, diphenylsilicon glycol, triethanolamine, a silane coupling agent, and a titanate coupling agent.

In a further technical solution, the adhesive includes at least one of a resorcinol donor, a methylene donor, an organic cobalt salt, a maleic anhydride butadiene resin, and a liquid natural rubber.

A further technical solution is that the chlorine-containing branched polyethylene used in the present invention further contains sulfur element, and the mass percentage content of the sulfur element is 0 to 4%. The synthetic process is to perform chlorosulfonation after chlorinating the branched polyethylene.

In order to improve the electrical insulation properties of the rubber composition, an appropriate amount of branched polyethylene, ethylene-propylene rubber, ethylene-propylene rubber, ethylene butene copolymer, ethylene octene copolymer, etc. may be used in combination in the rubber matrix of the present invention. In order to improve compatibility, an appropriate amount of branched polyethylene with low chlorine content, ethylene dipropylene rubber, ethylene dipropylene rubber, ethylene butene copolymer, ethylene octene copolymer, etc. may also be used in combination. The chlorine content is preferably at 10% or less.

A further technical solution is that, based on 100 parts by weight of the rubber matrix, the rubber matrix further comprises 0 to 70 parts of an auxiliary elastomer, the auxiliary elastomer is selected from the group consisting of branched polyethylene, ethylene-propylene rubber, and ethylene-propylene propylene Rubber, ethylene butene copolymer, ethylene octene copolymer or chlorinated branched polyethylene, chlorinated ethylene-propylene rubber, chlorinated ethylene-propylene rubber, chlorinated ethylene butene copolymer with a chlorine content of less than 10% And at least one of a chlorinated ethylene octene copolymer.

Because branched polyethylene has an advantage in synthesis cost, a further technical solution is that, based on 100 parts by weight of a rubber matrix, the rubber matrix also contains 0 to 70 parts of branched polyethylene or chlorine containing less than 10% chlorine. In order to have good oil resistance or flame retardancy, the branched polyethylene is preferably 0 to 40 parts of branched polyethylene or chlorine-containing branched polyethylene having a chlorine content of 10% or less, in which the branched polyethylene is branched. The degree is 60 to 130 branches / 1000 carbons.

The chlorine-containing rubber composition of the present invention may exist in the form of an uncrosslinked kneaded rubber, and may further exist in the form of a vulcanized rubber after a further crosslinking reaction occurs. Vulcanized rubber can also be referred to simply as vulcanized rubber.

The present invention also provides a method for processing the above-mentioned chlorine-containing rubber composition into a kneading compound, which is a reverse order kneading method, which includes the following steps:

(1) Set the mixer temperature and rotor speed;

(2) Put the components in the compounding system other than the vulcanization system into the mixer in the order of dry additives and liquid additives;

(3) Put the rubber matrix component into the mixer;

(4) After the mixing power is stable, the vulcanization system is put into operation and the rubber is discharged after mixing;

(5) After turning on the open mill or the multi-roller calender, lowering the sheet, lowering the temperature, and stopping for 24 hours, the sheet is returned to the refining sheet.

After the film is released, the sample preparation and performance testing are performed according to the test standards.

The present invention also provides a sheath material for electric wires and cables, and the rubber composition used therein comprises the above-mentioned chlorine-containing rubber composition.

The invention also provides a wire and cable, which comprises a sheath layer, and the rubber composition used for the sheath layer comprises the above-mentioned chlorine-containing rubber composition. Common electric wires and cables can be selected from twin-core parallel wires, three-core parallel wires, or rubber-sheathed flexible cables mainly composed of air-conditioning wires. Further, the electric wires and cables can be selected from mining cables, marine cables, household electrical appliances, Flexible cables for electrical equipment, flame-retardant rubber sheathed wires for construction, automobile ignition wires, electric welding machine cables, etc., can also be selected from wire and cable used in other occasions where flame retardancy, oil resistance and weather resistance are required, such as cranes, elevators Medium- and heavy-duty rubber-sheathed flat cables used in power stations and coal rail cars for power stations.

The present invention also provides a wire and cable, and the rubber composition used for the insulation layer thereof comprises the above-mentioned chlorine-containing rubber composition. Common electric wires and cables can be selected from twin-core parallel wires, three-core parallel wires, or rubber-sheathed flexible cables with air-conditioning wires as the main body. Further, the electric wires and cables are mainly selected from medium and low voltage electric wires and cables. Specifically, it can be a medium-sized rubber-sheathed flexible cable.

The invention also provides a single-layer rubber hose, and the rubber used therein comprises the above-mentioned chlorine-containing rubber composition. The hose may be selected from a water delivery hose, an oil delivery hose, an acid (alkali) delivery hose, and the like.

The present invention also provides a rubber tube including an inner rubber layer and an outer rubber layer. At least one of the inner rubber layer and the outer rubber layer includes the above-mentioned chlorine-containing rubber composition. The hose is selected from a fuel hose, a steering power hose, an air conditioning hose, a brake hose, an automatic transmission cooling system hose, a carburetor hose, an air hose, an air jet control hose, a wire and cable jacket hose, etc., among which the fuel hose, carburetor hose The outer rubber of the air hose and the air jet control hose contains at least one of the above-mentioned chlorine-containing rubber composition, the air-conditioning hose, the steering power hose, and the automatic transmission cooling system hose, the inner and outer rubber layers of the wire and cable sheathing hose. One layer contains the above-mentioned chlorine-containing rubber composition.

The present invention also provides a rubber tube including an inner rubber layer, a middle rubber layer, and an outer rubber layer. At least one of the inner rubber layer, the middle rubber layer, and the outer rubber layer includes the above-mentioned chlorine-containing rubber composition. The hose can be selected from oil-absorbing hoses, hydraulic hoses, and the like, such as automobile brake hoses and mining hydraulic hoses.

The present invention further provides a rubber hose assembly matching the above rubber hose, and the rubber composition used for the outer rubber layer thereof comprises the above-mentioned chlorine-containing rubber composition.

The present invention also provides a waterproofing membrane, and the rubber used therein comprises the above-mentioned chlorine-containing rubber composition.

The present invention also provides a conveyor belt, including working surface covering rubber and non-working surface covering rubber. At least one of the working surface covering rubber and the non-working surface covering rubber includes the above-mentioned chlorine-containing rubber composition. The conveyor belt is preferably an oil-resistant conveyor belt or a flame-resistant conveyor belt. The flame-resistant conveyor belt is suitable for underground coal mine operations or other occasions requiring flame retardancy.

The invention also provides a canvas core conveyor belt. The rubber used in the adhesive layer contains the rubber composition. The canvas used is cotton canvas, vinylon canvas, nylon canvas, polyester canvas, straight-weft polyester-nylon canvas, aramid. Any kind of canvas. A further technical solution is that each 100 parts by weight of rubber used in at least one layer of working surface covering rubber and non-working surface covering rubber of the conveyor belt contains 5 to 100 parts by weight of branched polyethylene or chlorinated branched polyethylene. .

The adhesive rubber used for the canvas core conveyor belt or the rubber composition used for the adhesive core rubber used for the rope core conveyor belt may further include 2 to 5 parts of short fibers for improving the modulus and improving the overall modulus distribution of the conveyor belt. The staple fiber is preferably a product having a pretreated surface and a good blending property with non-polar rubber.

The invention also provides a rope core conveyor belt. The rubber used for bonding the core rubber contains the rubber composition. The rope core used is a steel wire rope core or a polymer rope core. The polymer rope core may be selected from an aramid rope core, an ultra-high Molecular weight polyethylene fiber core and so on. A further technical solution is that each 100 parts by weight of rubber used in at least one layer of working surface covering rubber and non-working surface covering rubber of the conveyor belt contains 5 to 100 parts by weight of branched polyethylene or chlorinated branched polyethylene. .

The invention also provides a conveyor belt, which has a buffer rubber between the covering rubber and the adhesive rubber, and the rubber used for the buffer rubber comprises the above rubber composition. A further technical solution is that each 100 parts by weight of rubber used in at least one layer of working surface covering rubber and non-working surface covering rubber of the conveyor belt contains 5 to 100 parts by weight of branched polyethylene or chlorinated branched polyethylene. .

The present invention also provides a power transmission belt, which includes a main body having a certain length including a buffer rubber layer and a compression rubber layer, and at least one of the buffer rubber layer and the compression rubber layer uses rubber containing the above-mentioned chlorine-containing rubber composition. The buffer rubber layer may use the same rubber base as the compression rubber layer, and the buffer rubber layer may contain or not include the above short fibers. In order to improve the adhesion performance, it is preferable not to include short fibers.

The load-bearing core wire in the buffer rubber layer is preferably of a variety having high strength and low elongation, and may specifically be selected from polyester fibers, aramid fibers, glass fibers, ultra-high molecular weight polyethylene fibers, and the like, and the polyester fibers may be selected from polymer fibers. Aramid fibers, polybutylene terephthalate fibers, polyethylene terephthalate fibers, polytrimethylene terephthalate fibers, polyethylene naphthalate fibers, and the like. The above-mentioned load-bearing core wire is preferably subjected to an adhesion treatment to improve the adhesion performance between the load-bearing core wire and the rubber. The adhesion treatment can be performed by immersing the load-bearing core wire in a treatment solution such as resorcinol formaldehyde latex (PFL impregnating solution) and heating and drying. .

The power transmission belt provided by the present invention also includes a reinforcing fabric, which is generally located on the outer side of the buffer rubber layer. It can use cotton, polyester, aramid, polyamide, ultra-high molecular weight polyethylene fibers, etc. As the reinforcing fabric, a rubber canvas coated with a rubber composition and subjected to RFL treatment is preferably used as a woven or satin-woven fabric.

A further technical solution for the power transmission belt is: based on 100 parts by weight of the rubber matrix, the compressed rubber layer further comprises 10 to 80 parts by weight of a solid lubricant, wherein the solid lubricant includes graphite, mica, molybdenum disulfide, and polytetrafluoroethylene At least one of these is more preferably 10 to 60 parts by weight.

Transmission belts produced using the rubber composition provided by the present invention as compression layer rubber materials also include, but are not limited to, the following types: cloth-covered ordinary V-belts, cloth-covered narrow V-belts, cloth-covered combination belts, and cloth-covered agricultural machinery belts , Hexagonal belt, Trimmed V-belt, Trimmed narrow V-belt, Trimmed V-belt, Trimmed mechanical V-belt, Trimmed industrial V-belt, Motorcycle V-belt, Multi Wedge belt etc.

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

The present invention also provides a timing belt, and the rubber used comprises the above-mentioned chlorine-containing rubber composition.

The present invention also provides a rubber roller whose rubber comprises the above-mentioned chlorine-containing rubber composition. The rubber roller is suitable for occasions requiring oil resistance.

The present invention also provides a sealing member using rubber including the above-mentioned chlorine-containing rubber composition.

The present invention also provides an elevator handrail, the rubber used comprises the above-mentioned chlorine-containing rubber composition.

The beneficial effects of the present invention are: compared with the existing chloro (sulfonated) branched polyethylene, first, the chlorinated branched polyethylene used in the present invention has better comprehensive performance in physical mechanical properties and processability, Thus, the chlorine-containing rubber composition provided by the present invention is given better overall performance. Secondly, it can have rubber elasticity at a lower chlorine content, so that it can have better electrical insulation performance and is more suitable for the field of wire and cable insulation.

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. Some non-essential improvements and adjustments made by those skilled in the art based on the content of the present invention still belong to the protection scope of the present invention. .

The branched polyethylene raw material used for preparing the chlorine-containing branched polyethylene is characterized in that the degree of branching is preferably 50 to 130 branches / 1000 carbons and the weight average molecular weight is preferably 6.6 × 10 ⁴ to 53.4 × 10 ⁴ g / mol, Mooney viscosity ML (1 + 4) is preferably 6 to 105 at 125 ° C. Among them, the degree of branching was measured by nuclear magnetic hydrogen spectroscopy, and the mole percent content of various branch chains was measured by nuclear magnetic carbon spectroscopy.

The branched polyethylene raw material is further preferably from the following table:

The chlorination method of chlorinated branched polyethylene used is to pass chlorine gas into a carbon tetrachloride solution containing branched polyethylene and azobisisobutyronitrile initiator, and control different reaction temperatures and times to obtain various Chlorinated branched polyethylene (CPER) with chlorine content. Further, a method for preparing chlorosulfonated branched polyethylene is to first pass chlorine gas into a carbon tetrachloride solution containing branched polyethylene and azobisisobutyronitrile, perform appropriate chlorination, and then simultaneously pass chlorine gas. It is chlorosulfonated with sulfur dioxide to obtain chlorosulfonated branched polyethylene (CSPER).

The chlorine-containing branched polyethylene used in the examples of the present invention is preferably from the following table:

The properties of the commercially available chlorinated polyethylene rubber or chlorosulfonated polyethylene rubber used in the examples of the present invention are as follows:

Rubber performance test method:

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

2. Tensile strength and elongation at break performance test: According to the national standard GB / T528-2009, the test is performed with an electronic tensile tester, the tensile speed is 500mm / min, the test temperature is 23 ± 2 ℃, and the sample is type 2 Dumbbell-shaped specimen

3. Tear strength test: According to the national standard GB / T529-2008, the test is performed with an electronic tensile tester, the tensile speed is 500mm / min, the test temperature is 23 ± 2 ℃, and the sample is a right-angled sample;

4. Compression permanent deformation test: According to the national standard GB / T7759-1996, the test is performed with a compression permanent deformation device, type B, the compression amount is 25%;

5. Mooney viscosity test: According to the national standard GB / T1232.1-2000, use Mooney viscometer to test, set the test temperature according to the actual conditions, preheat for 1 minute, and test for 4 minutes;

6. Hot air accelerated aging test: According to the national standard GB / T3512-2001, conducted in a thermal aging test box, the temperature and time are set according to the actual conditions;

7. Volume resistivity test: According to the national standard GB / T1692-2008, use a high resistance meter for testing;

8. Oxygen index test: tested according to national standard GB / T2046.2-2009.

Comparative Example 1 and Examples 1-9:

The rubber composition formula components of Comparative Example 1 and Examples 1 to 9 are shown in Table 1: (which lists the weight parts of each component used per 100 weight parts of the rubber matrix)

Table 1

The mixing process of Comparative Example 1 and Examples 1-9 is as follows:

Set the starting temperature of the mixer to 85 ° C and the rotation speed to 40 rpm, add all the dry additives and liquid additives except BIBP and TAIC, and mix for 3 minutes, then add the rubber matrix, and wait for the mixing power to stabilize After that, add BIBP and TAIC, mix for 1 minute, and then discharge the glue. Then on the open mill, thin pass, lower the tablet, cool, and park for 24 hours to return the tablet.

Each test is performed in accordance with the standard sample preparation and testing. The vulcanization method is compression vulcanization, the vulcanization temperature is 170 ° C., the pressure is 16 MPa, the time is Tc90 + 1min, and the test is performed after being left for 16 hours. The performance data of each test sample is shown in Table 2:

Table 2

Data analysis: By comparing Examples 5-9 with Comparative Example 1, it can be found that the physical and mechanical properties of the rubber composition are significantly improved while maintaining the original flame retardancy.

The rubber compositions of Examples 1 to 9 can be used as flame retardant sheathing material for electric wires or rubber sheathed flexible cables. The production process is to make the rubber composition into a compound rubber and cold-feed it on a continuous vulcanization rubber extruder. It is then cured through a vulcanization tube.

Comparative Example 2 and Examples 10-12:

The rubber composition formula components of Comparative Example 2 and Examples 10 to 12 are shown in Table 3: (which lists the weight parts of each component used per 100 weight parts of the rubber base)

The mixing process of Comparative Example 2 and Examples 10-13 is as follows:

Set the starting temperature of the mixer to 85 ° C and the rotation speed to 40 rpm, add all the dry additives and liquid additives, mix for 3 minutes, and then add the rubber matrix. After the mixing power is stable, drain the rubber, and then On the open mill, the thin pass, the next sheet, cooling, and parking for 24 hours return to the refining sheet.

Each test is performed in accordance with the standard sample preparation and testing. Cross-linking by irradiation in normal temperature and air, the electron beam energy used for the irradiation is 1.0 MeV, the beam intensity is 1.0 mA, the irradiation dose is 100 kGy, and various tests are performed after being left for 16 hours. The performance data of each test sample is shown in Table 4:

Table 4

性能performance	对照例2Comparative Example 2	实施例10Example 10	实施例11Example 11	实施例12Example 12	实施例13Example 13
拉伸强度/MPaTensile strength / MPa	10.310.3	12.112.1	13.713.7	15.215.2	13.413.4
断裂伸长率/％Elongation at break /%	261261	284284	302302	323323	312312
体积电阻率/Ω·cmVolume resistivity / Ω · cm	6.5×10 ¹⁴ 6.5 × 10 ¹⁴	7.2×10 ¹⁴ 7.2 × 10 ¹⁴	8.4×10 ¹⁴ 8.4 × 10 ¹⁴	8.9×10 ¹⁴ 8.9 × 10 ¹⁴	10.3×10 ¹⁴ 10.3 × 10 ¹⁴

Data analysis: By comparing Examples 11 to 13 and Comparative Example 2, it can be found that under the same irradiation conditions, the rubber composition provided by the present invention can perform better in terms of physical and mechanical properties and electrical insulation. This is partly due to the fact that chlorinated branched polyethylene can maintain good elasticity at lower chlorine levels.

The rubber compositions of Examples 10 to 13 can be used as insulation materials for electric wires or rubber-sheathed flexible cables. The production process is to make the rubber composition into a compound rubber and then cold-feed it on a continuous vulcanization rubber extruder to obtain an insulated core. Then, the insulating layer is formed by cross-linking with one irradiation or cross-linking with two irradiations.

Comparative Example 3 and Examples 14 to 19:

The rubber composition formula components of Comparative Example 3 and Examples 14 to 19 are shown in Table 5: (which lists the weight parts of each component used per 100 weight parts of the rubber base)

table 5

The mixing process of Comparative Example 3 and Examples 14-19 is as follows:

Each test is performed in accordance with the standard sample preparation and testing. The vulcanization method is compression vulcanization, the vulcanization temperature is 170 ° C., the pressure is 16 MPa, the time is Tc90 + 1min, and the test is performed after being left for 16 hours. The performance data of each test sample is shown in Table 6:

Data analysis: By comparing Examples 16 to 19 and Comparative Example 3, it can be found that under the same processing conditions, the rubber composition provided by the present invention can perform better in terms of physical and mechanical properties and electrical insulation. Partly due to the chlorine-containing branched polyethylene can maintain good elasticity at lower chlorine content.

The rubber composition of Examples 14 to 19 can be used as an insulation material for electric wires or rubber sheathed flexible cables. The production process is to make the rubber composition into a compound rubber and cold-feed it on a continuous vulcanization rubber extruder to obtain an insulated wire core. , And then vulcanized by a high-temperature vulcanization tube to form an insulating layer.

Comparative Example 4 and Examples 20 to 25:

The rubber composition formula components of Comparative Example 4 and Examples 20 to 25 are shown in Table 7: (which lists the weight parts of each component used per 100 weight parts of the rubber matrix)

Table 7

The mixing process of Comparative Example 4 and Examples 20, 21, 24, and 25 is as follows:

Set the starting temperature of the mixer to 85 ° C and the speed of 40 rpm, add all the dry additives and liquid additives except DCP and TAIC, and mix for 3 minutes, then add the rubber matrix, and wait for the mixing power to stabilize After that, DCP and TAIC are added, and the mixture is discharged after mixing for 1 minute. Then, on the open mill, thin pass, lower the tablet, cool, and park for 24 hours to return the tablet.

The mixing process of Example 22 is as follows: set the starting temperature of the internal mixer to 85 ° C and the rotation speed of 40 rpm, add all the dry additives and liquid additives except TDD and NC, mix for 3 minutes, and then Add the rubber matrix. After the mixing power is stable, add TDD and NC, and then discharge the rubber after mixing for 1 minute. Then, on the open mill, thin pass, lower the tablet, cool, and park for 24 hours to return the tablet.

The mixing process of Example 23 is as follows: the starting temperature of the internal mixer is set to 85 ° C, the rotation speed is 40 rpm, and all the dry additives and liquid additives except sulfur and DE-TU are added successively, and the mixing is performed for 3 minutes. Then, add the rubber matrix, and then discharge the rubber after the mixing power is stable. Add sulfur and DE-TU to the open mill with a roller temperature of 70 ° C, and make three triangular packages. Refined tablets.

Each test is performed in accordance with the standard sample preparation and testing. The vulcanization method is compression vulcanization, the vulcanization temperature is 165 ° C, the pressure is 16 MPa, the time is Tc90 + 1min, and the test is performed after standing for 16 hours. The vulcanization time of the compressed permanent deformation sample is Tc90 + 5min. The performance data of each test sample is shown in Table 8:

Table 8

Data analysis: By comparing Examples 20 and 21 with Comparative Example 4, it can be found that under the same processing conditions, the rubber composition provided by the present invention can perform better in terms of mechanical strength and compression set resistance. This is partly due to the higher molecular weight and narrower molecular weight distribution of branched polyethylene.

The rubber compositions of Examples 20 to 25 can be used as a raw material for an outer rubber layer of an automobile fuel hose, an air hose, and a brake hose, and can also be used as a raw material for an inner rubber layer or an outer rubber layer of a power steering hose.

Examples 26-28:

The rubber composition formula components of Examples 26 to 28 are shown in Table 9: (which lists the weight parts of each component used per 100 weight parts of the rubber base)

Table 9

The mixing process of Examples 26-28 is as follows:

Each test is performed in accordance with the standard sample preparation and testing. The vulcanization method is compression vulcanization, the vulcanization temperature is 165 ° C, the pressure is 16 MPa, the time is Tc90 + 1min, and the test is performed after being left for 16 hours. The performance data of each test sample is shown in Table 10:

Table 10

性能performance	实施例26Example 26	实施例27Example 27	实施例28Example 28
拉伸强度/MPaTensile strength / MPa	16.516.5	17.217.2	21.421.4
断裂伸长率/％Elongation at break /%	479479	462462	513513
氧指数/％Oxygen Index/%	37.837.8	38.138.1	38.238.2

The rubber compositions of Examples 26 to 28 can be used as a raw material for a cover rubber of a flame-retardant conveyor belt.

Example 29:

A rubber sheath for electric wires uses the rubber composition in Example 6 as a raw material. The production process is that the rubber composition is made into a compound rubber and cold-fed on a continuous vulcanizing rubber extruder. The screw has a length to diameter ratio of 16: 1 and is vulcanized with a vulcanizing tube. The effective length of the vulcanizing tube is 48 m, the length of the cooling water tube is 12 m, the steam pressure is 1.7 to 2.0 MPa, and the extrusion speed is 65 to 75 m / min.

Example 30:

A cable sheath adopts the rubber composition in Example 7 as a raw material. The production process is that the rubber composition is made into a compound rubber and cold-fed on a continuous vulcanization rubber extruder. The screw of the extruder is extruded. The aspect ratio is 16: 1. The vulcanization tube is vulcanized. The effective length of the vulcanization tube is 48m, the length of the cooling water tube is 12m, the steam pressure is 1.7 ～ 2.0MPa, and the extrusion speed is 65 ～ 75m / min.

Example 31:

A medium-sized rubber-sheathed flexible cable whose insulation layer uses the rubber composition in Example 12. The compounded rubber of the rubber composition is extruded in a cold-feed extruder, and is wound after the spark machine high-pressure test. The first irradiation cross-linking was carried out, and the cable was extruded into the sheath and then subjected to the second irradiation. The total radiation dose of the insulating layer was about 100 kGy. The finished product is obtained after inspection.

Embodiment 32:

An electric wire whose insulation layer uses the rubber composition in Example 10, and the compounded rubber of the rubber composition is extruded in a cold-feed extruder, which is taken up after a high-pressure test on a spark machine, and then irradiated. Cross-linking, the total irradiation dose is 100kGy, and the finished product is obtained after inspection.

Example 33:

A cable production method. The continuous high-temperature vulcanization manufacturing process is as follows: First, the rubber composition in Example 18 is used as an insulating material to be extruded and coated on a conductor to form an insulating layer, and then vulcanized into a high-temperature vulcanized tube. After passing the inspection, the cable is formed, and then the rubber sheath is extruded, and then it is vulcanized and printed on the high-temperature vulcanization pipe to obtain the finished cable.

Example 34:

A method for producing a wire. The continuous high-temperature vulcanization manufacturing process is as follows: First, the rubber composition in Example 14 is extruded and coated on a conductor by an extruder to form an insulating layer, and is vulcanized into a high-temperature vulcanization pipe. The finished product is obtained after inspection.

Example 35:

A brake hose includes an inner rubber layer, a first braided layer, a middle braided layer, a second braided layer, and an outer rubber layer. The outer rubber layer uses the rubber composition in Example 21. The production method includes the following steps:

60mm cold feeding extruder equipped with T-type head, extruding the inner rubber layer on the core rod at 90 ℃, then weaving with vinylon, then extruding the middle rubber layer, then weaving with vinylon, and The outer rubber layer is extruded to obtain a tube blank. The vulcanization process is steam vulcanization at 160 ° C, a steam pressure of 0.6 MPa, and a time of 30 minutes. After the vulcanization process, it is cooled, cored, trimmed, inspected, and stored.

Example 36:

A fuel hose includes an inner rubber layer, a reinforcing layer, and an outer rubber layer. The outer rubber layer uses the rubber composition in Example 25. The production method includes the following steps:

Extrusion and molding: use a cold-feed extruder to extrude the inner rubber layer, then knit the fiber-reinforced layer on the inner rubber layer, and then squeeze the outer rubber layer to obtain the tube blank. After cutting, insert the core rod into the tube blank. High-temperature steam vulcanization is used, after the temperature is 165 ° C and the steam pressure is 1 MPa, after 25 minutes of vulcanization, it is cooled, cored, trimmed, inspected, and stored.

Example 37:

A flame-retardant steel wire core conveyor belt uses the rubber composition in Example 28 as the covering rubber. The production method includes the following steps:

(1) Kneading and calendering: The rubber composition covering the rubber is kneaded and heated by a screw extruder, and then fed to a calender to be rolled out for use. The film thickness is controlled to be 4.5 to 12 mm when rolling out. Keep it warm after use.

(2) Molding process:

The film on the molding machine and the pre-formed glued canvas tape blank are closely adhered together to form a tape blank of a high temperature resistant conveyor belt, and then rolled up for 4 hours before vulcanization.

(3) Vulcanization process:

The formed conveyer belt blank is put into a flat plate vulcanizing machine for partial vulcanization. The vulcanizing time of each plate is 25 minutes, the vulcanizing pressure is 3 MPa, and the vulcanizing temperature is 160 ° C.

(4) Trimming and inspection:

After vulcanization is finished, it is trimmed, inspected, and then packed and stored.

Example 38:

A flame retardant steel wire core conveyor belt adopts the rubber composition provided by the present invention in its covering rubber and adhesive core rubber, and the production process is as follows:

(1) Rubber mixing process:

The covering rubber uses the rubber composition in Example 26 and is kneaded in accordance with the kneading process of Example 26;

The rubber composition formula of the core rubber is: 80 parts of 17 # CPER, 20 parts of 23 # CSPER, 4 parts of BIBP, 2.5 parts of TAIC, 1 part of stearic acid, 8 parts of magnesium oxide, 3 parts of zinc oxide, 35 parts Carbon black N330, 15 parts of white carbon black, 4 parts of binder RF, 4 parts of binder RA, 2 parts of cobalt borylate, 10 parts of chlorinated paraffin, 1 part of calcium stearate, 1 part of zinc stearate , 2 parts of antioxidant RD, 5 parts of coomarone resin, 8 parts of antimony oxide, 12 parts of zinc borate, 15 parts of aluminum hydroxide. The mixing method is to set the starting temperature of the mixer to 85 ° C and the rotation speed to 40 rpm, and then add all the dry additives and liquid additives except BIBP and TAIC, mix for 3 minutes, and then add the rubber matrix. After the mixing power is stable, BIBP and TAIC are added, and the rubber is discharged after 1 minute of mixing. Then, on the open mill, thin pass, lower the tablet, cool, and stop for 24 hours to return the tablet.

(2) Calendering process:

The above mixed rubber is put into a screw extruder to be hot-melted, and then supplied to a calender to be rolled out for use. The film thickness is controlled to be 4.5 to 12 mm when rolling out. Keep it warm after use.

(3) Molding process:

The film is used as a cover glue on the molding machine and the preformed canvas tape blank containing the adhesive core is closely adhered together to form a tape blank of a conveyor belt, and then rolled up for 4 hours and then vulcanized.

(4) Vulcanization process:

The formed conveyer belt blank is put into a flat vulcanizing machine to perform partial vulcanization. The vulcanizing time of each plate is 25 minutes, the vulcanizing pressure is 2.5 MPa, and the vulcanizing temperature is 160 ° C.

(5) Trimming and inspection:

Example 39:

A waterproof coil material has the following processing steps:

(1) Mixing: The rubber composition in Example 21 was used, the starting temperature of the internal mixer was set to 85 ° C, the rotation speed was 40 rpm, and all dry additives and liquid additives except DCP and TAIC were added successively. , Mix for 3 minutes, then add the rubber matrix. After the mixing power is stable, add DCP and TAIC, and discharge after 1 minute of mixing. Feed the block rubber compound into the open kneader, control the roller temperature between 85 and 95 ° C, and control the roller distance to be less than 1mm, and to pass through no less than four times, until the surface of the compound is smooth, uniform and shiny. Then turn around and knead again, make the pass through no less than four times, adjust the roll distance to no more than 8mm, and knead three times to obtain a uniformly mixed rubber flake with a thickness of less than 8mm. Stacked

(2) Hot smelting: hot smelting of the evenly-mixed rubber flakes on an open mill, controlling the roll temperature between 85 and 95 ° C, and the roll distance below 6 mm, until the rubber sheet is smooth and uniform, and then rolls into a roll;

(3) Calendering: Put the rubber sheet that has been preliminarily rolled into the calender on the calender, adjust the roll pitch according to the thickness requirements of the finished product, and obtain a semi-finished coil that meets the requirements of the finished product thickness specification;

(4) Rewinding: According to the specifications and length requirements of the finished coil, a spacer liner is interposed, and the semi-finished coil is arranged into a roll;

(5) Vulcanization: Put the rolled coil into a nitrogen-filled vulcanization kettle for vulcanization treatment, and control the temperature of the vulcanization kettle between 155-165 ° C, the pressure between 20-25MPa, and vulcanization for 25-30 minutes;

(6) Rewinding: re-open the vulcanized coil, remove the release liner, and then rewind and pack the product.

Example 40:

The production and processing steps of a rubber roller are as follows:

(1) Mixing: The rubber composition in Example 25 was used, the internal temperature of the internal mixer was set to 85 ° C, the rotation speed was 40 rpm, and all the dry additives and liquid additives except BIBP and TAIC were added successively. After mixing for 3 minutes, add the rubber matrix. After the mixing power is stable, add BIBP and TAIC. After mixing for 1 minute, discharge the rubber. Then, on the open kneader, thinly pass, load, cool, and park for 24 hours.

(2) Wrapping: Put the compounded rubber into the screw extruder, and extrude the film of the thickness and width required by the process. After the film is uniform, start the rotary wrapping machine and wind the film on the prepared metal roller core. , Wrapping the rubber layer by layer until the thickness of the single side of the rubber bag reaches the specified thickness, and then winding 2 to 3 layers of nylon water cloth on the rubber surface to obtain the rubber roller after the rubber bag is completed.

(3) The vulcanization tank is vulcanized. The rubberized roller is sent to the vulcanization tank. After closing the tank door, steam is vulcanized into the vulcanization tank. When the steam is vented, the compressed air valve is opened, and the compressed air is passed to vulcanize. The pressure in the tank reaches 4.5 to 5 atmospheres within 0.5 hours; the vulcanization procedure is: first warm up to 70-80 ° C and hold for 2 hours; then heat up to 100-110 ° C and hold for 0.5 hours; then heat up to 120-130 ° C and hold 0.5 hour; heat up to 135 ～ 140 ℃, and keep for 8-10 hours. When the vulcanization is over, open the exhaust valve, the pressure drops, and when the pressure gauge pointer reaches zero, open the safety pin, wait for the steam to flow out of the pin hole, open the vulcanization tank halfway, let the temperature drop, and wait until the temperature in the tank is lower than 60 ℃ or When it is equivalent to room temperature, pull out the rubber roller;

(4) The vulcanized rubber roller is rough processed on a lathe, and then finished on a grinder, and inspected to obtain a finished product.

Embodiment 41:

A high-temperature-resistant V-ribbed belt uses a rubber composition provided by the present invention as a buffer layer. The production and processing steps are as follows:

1. Mixing:

(1) Compression of compressed layer rubber: Set the mixer temperature to 85 ° C, the rotor speed to 40 rpm, add 10 parts of magnesium oxide, 3 parts of zinc oxide, 45 parts of carbon black N330, 1 part of stearic acid, 1 part of calcium stearate, 1 part of zinc stearate, 1 part of antioxidant RD and 60 parts of nylon short fiber with a length of 1mm, knead for 1 minute, and then add 5 parts of paraffin oil SUNPAR2280 and 5 parts of dioctyl sebacate Knead with 5 parts of Gumalon resin for 2 minutes, and then add 100% of chlorinated branched polyethylene CPER-6. After the mixing power is stable, add 4 parts of BIBP and 2.5 parts of TAIC, and discharge after 1 minute of mixing. The kneaded rubber was thin-passed on an open mill with a roller temperature of 80 ° C. and thin-passed 7 times at a roll distance of 0.5 mm to fully orient the short fibers. The roll distance was enlarged to obtain a sheet of about 2.5 mm in thickness and left for 20 hours. .

(2) Buffer layer rubber mixing: set the mixer temperature to 85 ° C, the rotor speed to 40 rpm, add 10 parts of magnesium oxide, 3 parts of zinc oxide, 45 parts of carbon black N330, 1 part of stearic acid, 1 part calcium stearate, 1 part zinc stearate and 1 part antioxidant RD and mix for 1 minute, then add 5 parts of paraffin oil SUNPAR2280, 5 parts of dioctyl sebacate and 5 parts of coumarone resin and mix 2 Minutes, then add 100% chlorine-containing branched polyethylene CPER-6. After the mixing power is stable, add 4 parts of BIBP, 2.5 parts of TAIC, 10 parts of zinc methacrylate, and 0.3 parts of sulfur. After mixing for 1 minute, drain the rubber.

2. Forming: Adopt reverse forming method. Hang the optical mold on the molding machine first, clean the mold, apply a small amount of release agent, and after it volatilizes, cover the top of the multi-wedge belt cloth with the optical mold, and then apply cushioning rubber to correct the tension of the rope and flaten the winding. After the strong layer is wrapped with buffer rubber, finally wedge rubber is wrapped to the outer circumference required by the molding process to obtain a strip.

3. Vulcanization: The strip is sent to the vulcanization section for vulcanization. The vulcanization temperature is 160 ° C, the internal pressure is 0.45 to 0.55 MPa, the external pressure is 1.0 to 1.2 MPa, and the vulcanization time is 30 minutes.

4. Post-treatment: After the vulcanization is completed, the mold is cooled and demolded, and the tape cylinder is sent to the cutting process, and cut according to the required width. Grind the back, wedge, and pass the inspection after trimming to get the finished product.

Example 42:

A molded oil-resistant seal adopts the rubber composition in Example 21 and kneads using the kneading process in Example 21. The kneaded rubber is extruded and injected into a mold cavity. The vulcanization temperature is 165 ° C and the vulcanization is performed. The pressure is 20 MPa, and the curing time is 20 minutes. After the curing is completed, the mold is cooled, and the mold is trimmed, inspected, and stored.

Although preferred embodiments of the invention are described herein, these embodiments are provided as examples only. It should be understood that variations of the embodiments of the invention described herein may also be used to implement the invention. Those of ordinary skill in the art will appreciate that many variations, changes, and substitutions may occur without departing from the scope of the invention. It should be understood that the protection scope of various aspects of the present invention is determined by the claims, and the methods and structures within these claims and their equivalent methods and structures are all within the scope covered by the claims.

Claims

A chlorine-containing rubber composition, characterized in that the chlorine-containing rubber composition includes: a rubber base and a compounding component, and the 100 parts by weight of the rubber base comprises, by weight parts, a chlorine-containing branched polyethylene ( CBPE) content a: 5 ≤ a ≤ 100 parts, chlorinated polyethylene rubber (CM) content b: 0 ≤ b ≤ 95 parts, chlorosulfonated polyethylene rubber (CSM) content c: 0 ≤ c ≤ 95 Parts, wherein the chlorine element in the chlorine-containing branched polyethylene has a mass fraction of not less than 10%, and the branched polyethylene raw material used for preparing the chlorine-containing branched polyethylene includes an ethylene homopolymer; and the compounding component includes a vulcanization system.
The chlorine-containing rubber composition according to claim 1, wherein the degree of branching of the ethylene homopolymer raw material is not less than 50 branches / 1000 carbons, and the chlorine of the chlorine-containing branched polyethylene is Elemental mass fraction is 10% to 50%.
The chlorine-containing rubber composition according to claim 2, wherein a mass fraction of chlorine element of the chlorine-containing branched polyethylene is 15% to 45%.
The chlorine-containing rubber composition according to claim 1, wherein a raw material used for preparing the chlorine-containing branched polyethylene is an ethylene homopolymer, and the degree of branching of the ethylene homopolymer is 60 to 130 branches / 1,000 carbons with a weight average molecular weight of 66,000 to 518,000.
The chlorine-containing rubber composition according to claim 1, wherein the curing system is selected from the group consisting of a peroxide curing system, a thiourea curing system, a thiadiazole curing system, a triazole dimercaptoamine salt curing system, and radiation. At least one of a sulfur-sensitized system.
The chlorine-containing rubber composition according to claim 5, wherein the peroxide vulcanization system comprises a peroxide crosslinking agent and a co-crosslinking agent, and the peroxide is based on 100 parts by weight of a rubber matrix. The amount of cross-linking agent is 1 to 10 parts, and the amount of cross-linking aid is 0.2 to 10 parts.
The chlorine-containing rubber composition according to claim 6, wherein the peroxide crosslinking agent comprises di-t-butyl peroxide, di-cumyl peroxide, t-butyl-cumyl peroxide, 1,1-di-tert-butylperoxide-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-butylperisopropyl) benzene, 2,5-dimethyl-2,5-di ( At least one of benzoyl peroxide) hexane, tert-butyl peroxybenzoate, tert-butyl peroxy-2-ethylhexyl carbonate, and the cross-linking aid includes triallyl cyanurate, Triallyl isocyanurate, ethylene glycol dimethacrylate, ethyl dimethacrylate, triethylene dimethacrylate, triallyl trimellitate, trihydroxytrimethacrylate Methyl propane ester, ethylene glycol dimethacrylate, N, N'-m-phenylene bismaleimide, N, N'-bisfurfurylacetone, 1,2-polybutadiene, At least one of quinone dioxime, sulfur, and unsaturated carboxylic acid metal salt, the unsaturated carboxylic acid metal salt comprising zinc acrylate Zinc methacrylate, magnesium methacrylate, calcium methacrylate, methacrylic acid, at least one aluminum.
The chlorine-containing rubber composition according to claim 1, wherein the compounding component further comprises 10 to 200 parts of a reinforcing filler, 3 to 80 parts of a plasticizer, and metal based on 100 parts by weight of a rubber matrix. 1 to 20 parts of oxides, 1 to 15 parts of stabilizers, 0 to 2 parts of antioxidants, 0 to 120 parts of flame retardants, 0 to 15 parts of surface modifiers, 0 to 20 parts of adhesives, and 0 blowing agents ~ 20 servings.
The chlorine-containing rubber composition according to claim 8, wherein the reinforcing filler comprises carbon black, white carbon black, calcium carbonate, calcined clay, talc, magnesium silicate, aluminum silicate, magnesium carbonate , Titanium dioxide, montmorillonite, short fiber, kaolin, bentonite.
The chlorine-containing rubber composition according to claim 8, wherein the plasticizer comprises pine tar, motor oil, naphthenic oil, paraffin oil, aromatic oil, liquid polyisobutylene, coumarone, RX-80, Stearic acid, paraffin, chlorinated paraffin, dioctyl adipate, dioctyl sebacate, epoxy soybean oil, dibutyl phthalate, dioctyl phthalate, diphthalate At least one of isodecyl ester, ditridecyl phthalate, and trioctyl metaphthalate.
The chlorine-containing rubber composition according to claim 8, wherein the metal oxide comprises at least one of zinc oxide, magnesium oxide, aluminum oxide, lead oxide, and calcium oxide.
The chlorine-containing rubber composition according to claim 8, wherein the stabilizer comprises a basic lead salt compound, a metal soap compound, an organotin compound, an epoxy compound, a phosphite compound, At least one of polyol compounds.
The chlorine-containing rubber composition according to claim 8, wherein the antioxidant comprises 2,2,4-trimethyl-1,2-dihydroquinoline polymer (RD), 6-ethoxy -2,2,4-trimethyl-1,2-dihydroquinoline (AW), 2-mercaptobenzimidazole (MB), N-phenyl-N'-cyclohexyl-p-phenylenediamine (4010 ), N-isopropyl-N'-phenyl-p-phenylenediamine (4010NA), N- (1,3-dimethyl) butyl-N'-phenyl-p-phenylenediamine (4020) One.
The chlorine-containing rubber composition according to claim 8, wherein the flame retardant comprises pentaerythritol, ammonium polyphosphate, triethyl phosphate, aluminum hydroxide, magnesium hydroxide, zinc borate, and antimony trioxide. At least one of zinc stearate, titanate, decabromodiphenyl ether, silane coupling agent-modified hydroxide, and red phosphorus.
The chlorine-containing rubber composition according to claim 8, wherein the surface modifier comprises polyethylene glycol, diphenylsilicondiol, triethanolamine, a silane coupling agent, and a titanate coupling agent At least one of.
The chlorine-containing rubber composition according to claim 8, wherein the adhesive comprises a resorcinol donor, a methylene donor, an organic cobalt salt, a maleic anhydride butadiene resin, and a liquid natural At least one of rubber.
The chlorine-containing rubber composition according to claim 1, wherein the chlorine-containing branched polyethylene further contains a sulfur element, and a mass percentage content of the sulfur element is 0 to 4%.
The chlorine-containing rubber composition according to claim 1, wherein, based on 100 parts by weight of the rubber matrix, the rubber matrix further comprises 0 to 70 parts of an auxiliary elastomer, the auxiliary elastomer being selected from branched polyethylene , Ethylene propylene diene rubber, ethylene propylene diene rubber, ethylene butene copolymer, ethylene octene copolymer or chlorinated branched polyethylene with chlorine content below 10%, chlorinated ethylene propylene rubber, chlorinated tertiary At least one of ethylene-propylene rubber, chlorinated ethylene butene copolymer, and chlorinated ethylene octene copolymer.
The chlorine-containing rubber composition according to claim 18, characterized in that, based on 100 parts by weight of the rubber matrix, the rubber matrix further comprises 0 to 70 parts of branched polyethylene or a chlorine-containing branch having a chlorine content of 10% or less. The branched polyethylene has a branching degree of 60 to 130 branches / 1000 carbons.
A wire and cable sheathing material, characterized in that the rubber composition used comprises the chlorine-containing rubber composition according to any one of claims 1 to 19.
A wire and cable comprising a sheath layer, characterized in that the rubber composition used for the sheath layer comprises the chlorine-containing rubber composition according to any one of claims 1 to 19.
A wire and cable insulation material, characterized in that the rubber composition used comprises the chlorine-containing rubber composition according to any one of claims 1 to 19.
A wire and cable, characterized in that the rubber composition used for the insulation layer comprises the chlorine-containing rubber composition according to any one of claims 1 to 19.
A single-layer rubber hose, characterized in that the rubber used comprises the chlorine-containing rubber composition according to any one of claims 1 to 19.
A rubber tube comprising an inner rubber layer and an outer rubber layer, wherein at least one of the inner rubber layer and the outer rubber layer comprises the chlorine-containing rubber composition according to claim 1.
A rubber tube comprising an inner rubber layer, a middle rubber layer, and an outer rubber layer, characterized in that at least one of the inner rubber layer, the middle rubber layer and the outer rubber layer comprises any one of claims 1-19. Chlorine rubber composition.
A waterproof membrane, characterized in that the rubber material used comprises the chlorine-containing rubber composition according to any one of claims 1 to 19.
A conveyor belt comprising a working surface covering rubber and a non-working surface covering rubber, characterized in that at least one of the working surface covering rubber and the non-working surface covering rubber contains the chlorine-containing compound according to any one of claims 1 to 19 Rubber composition.
A canvas core conveyor belt, characterized in that there is an adhesive layer between the cover rubber and the dipped canvas of the canvas core conveyor belt, wherein the rubber used for the adhesive layer comprises the rubber composition according to any one of claims 1 to 19. The canvas is any one of cotton canvas, vinylon canvas, nylon canvas, polyester canvas, straight-weft polyester-nylon canvas, and aramid canvas.
A rope core conveyor belt, characterized in that the rubber used for bonding the core rubber of the rope core conveyor belt comprises the rubber composition according to any one of claims 1 to 19, and the rope core is a steel wire rope core or a polymer rope core .
A conveyor belt having a buffer rubber between a covering rubber and an adhesive rubber, characterized in that the rubber used for the buffer rubber comprises the rubber composition according to any one of claims 1 to 19.
A power transmission belt comprising: a main body having a certain length including a buffer rubber layer and a compression rubber layer, characterized in that the rubber used in at least one of the buffer rubber layer and the compression rubber layer includes any one of claims 1 to 19 The chlorine-containing rubber composition is described.
A rubber roller, characterized in that the rubber used comprises the chlorine-containing rubber composition according to any one of claims 1 to 19.
A seal, characterized in that the rubber used comprises the chlorine-containing rubber composition according to any one of claims 1 to 19.
An elevator handrail, characterized in that the rubber used comprises the chlorine-containing rubber composition according to any one of claims 1 to 19.
A method for preparing a chlorine-containing rubber composition for processing into a kneaded rubber, characterized in that the kneading adopts a reverse-order kneading method.