CN103554558B - A kind of preparation method utilizing hydroxyethyl methylacrylate rubber modified graft copolymer potter's clay to strengthen native rubber composite material - Google Patents

Abstract

The invention relates to a preparation method of using hydroxyethyl methacrylate rubber to graft modified pottery clay to reinforce natural rubber composite materials. Specifically, adding pottery clay, an appropriate amount of coupling agent, anionic surfactant, milky methyl alcohol into deionized water Hydroxyethyl acrylate rubber is dispersed by ultrasonic stirring to prepare a clay emulsion dispersion; at the same time, an appropriate amount of non-ionic surfactant is used to stabilize the milky natural rubber, and then the clay emulsion dispersion is evenly mixed into the milky natural rubber, and added dropwise Initiate the crosslinking agent to obtain the hydroxyethyl methacrylate rubber graft modified clay-natural rubber composite material in the latex state; the composite material is further processed by standard Chinese rubber conventional processing techniques such as coagulation, tableting, washing, and drying to obtain The hydroxyethyl methacrylate rubber graft modified pottery clay-natural rubber composite material in a dry state; the pottery clay-natural rubber composite material prepared by the invention has good performance.

Description

A kind of preparation method of using hydroxyethyl methacrylate rubber graft modified pottery clay to strengthen natural rubber composite material

technical field

The invention relates to a preparation method of a natural rubber composite material, in particular to a preparation method of a hydroxyethyl methacrylate rubber graft modified clay reinforced natural rubber composite material, and belongs to the technical field of rubber composite material production.

Background technique

Natural rubber (NR) is an important polymer material, which is not only a traditional material, but also a It is an important part of contemporary high-tech materials, and plays an irreplaceable role in the pillar industries of the national economy such as the automobile industry and high-tech fields such as electronic information, biotechnology, and aerospace. As we all know, if the vast majority of rubber is not reinforced, its comprehensive performance cannot meet the application purpose. In order to improve the tensile strength, tear strength and wear resistance of rubber, improve the processing technology and reduce the cost, reinforcing agents are usually added to the rubber.

Pottery clay refers to clay that contains iron and has yellowish brown, grayish white, red purple and other hues, and has good plasticity. It is mainly used for firing exterior walls, floor tiles, pottery, etc. The mineral composition is mainly montmorillonite and kaolin. It is the mineral filler with the largest amount in the rubber industry, accounting for about 59% of the total mineral filler, and its main components are crystalline compounds of alumina and silica. Adding clay to the rubber has a great influence on the properties of the rubber, which can reduce the shrinkage of the rubber and make the surface of the rubber smooth; it can improve the tensile strength, constant elongation stress and wear resistance of the rubber.

As early as 1954, the Vietnam Rubber Research Institute discovered that clay was added to rubber to produce composite materials. First, the clay was in a state of water suspension, and then mixed with freshly collected fresh latex, so that after the cement was coagulated and processed, it formed A masterbatch consisting of clay and natural rubber with good material properties. However, due to the inactive silicate surface layer of clay, its interface strength with natural rubber is not high, and its reinforcing performance on rubber is not high. Therefore, people have been exploring ways to enhance the interaction between clay surfaces and natural rubber. It can be seen from the crystal structure of the clay that there are a large number of hydroxyl (-OH) hydrophilic groups on the surface of the clay, so a variety of crosslinking agents can chemically react with the hydroxyl groups on the surface of the clay to modify the clay. The chemical modification of the clay surface can not only increase the wettability of the clay and rubber, but also produce a stronger interaction between the clay and the rubber, thus becoming the most effective method to improve the reinforcing performance of the clay. At present, the common methods for preparing rubber/modified clay composites include solution method, melt method and in-situ method.

Solution method: Dissolve the rubber in a solvent first, disperse the nano clay in ethanol, pour the required amount of clay dispersion into the rubber solution, and stir the mixture for 2 hours. Add vulcanizing agent to the solution while stirring, and mold and vulcanize the casting sample at 160°C to obtain a composite material.

Melt method: use a CSI mixing extruder to mix the modified nano-clay with SEBS, and the mixing temperature is 205°C. The extruded and granulated pellets were molded into a thin film of about 0.5 mm on a hydraulic plate, with a pressure of 5 MPa, a temperature of 210° C., and a time of 3 min. Thereafter, it was cooled to room temperature under pressure. Get the composite material.

In situ method: In situ polymer-clay composites were prepared from unmodified clay (CloisiteNA) and organically modified clay (Cloisite 10A) in a two-step process: monomers were inserted into the clay structure followed by free radical bulk polymerization. Mix the required amount of pottery clay with 30g of pure monomer first, and leave it for 24 hours to insert the monomer into the pottery clay structure. Afterwards, add benzoyl peroxide to the monomer clay mixture by 0.06% of the monomer mass, and stir for 1 h. Polymerization was carried out at 80° C. for 30 min in a nitrogen inert atmosphere. Get the composite material.

Although the dispersibility of the above-mentioned modified clay in the rubber matrix has been improved to a certain extent, because they are not fully cross-linked with the rubber molecular chain in the rubber, they only play a semi-reinforcing role, resulting in clay The reinforcing effect on natural rubber is still not obvious enough, so the tensile strength of the modified clay/NR composite material prepared by the above method only fluctuates in the range of 20-25Mpa.

Therefore, it is also necessary to provide a method that can significantly improve the dispersibility of the modified clay in the rubber matrix and enable the modified clay to cross-link with the rubber molecular chain in the rubber matrix, and simplify the process flow for producing rubber products. The preparation method of the high-performance modified clay natural rubber composite material which is beneficial to the automatic control of the processing process, energy saving and environmental protection is expected by the industry.

Contents of the invention

The purpose of the present invention is to solve the problem that the pottery clay has a poor reinforcing effect on rubber after being treated with traditional modifiers. By adopting hydroxyethyl methacrylate rubber latex with strong polarity and active hydroxyl groups to graft and modify the pottery clay, Utilizing the excellent compatibility between hydroxyethyl methacrylate rubber latex and natural latex, the dispersion effect of clay in natural latex is improved, and the reinforcing effect of clay on natural rubber is improved.

For realizing the above-mentioned purpose of the invention, the technical scheme that the present invention takes is as follows:

A kind of preparation method utilizing hydroxyethyl methacrylate rubber graft modified pottery clay to strengthen natural rubber composite material, comprises the steps:

Add clay and an appropriate amount of coupling agent and anionic surfactant in deionized water, stir and ultrasonically disperse, then add an appropriate amount of milky hydroxyethyl methacrylate rubber, continue to use stirring and ultrasonic dispersion to prepare clay emulsion dispersion; The appropriate amount of non-ionic surfactant is used to stabilize the milky natural rubber, and then the above-mentioned clay emulsion dispersion is evenly mixed into the milky natural rubber under the condition of constant stirring, and at the same time, it is added dropwise under the condition of a water bath at 50~70°C to initiate cross-linking agent, to obtain the hydroxyethyl methacrylate rubber graft modified clay-natural rubber composite material in the latex state; the composite material is further processed by standard Chinese rubber conventional processing techniques such as coagulation, pressing, washing, and drying to obtain dry Hydroxyethyl methacrylate rubber graft modified clay-natural rubber composites in gel state.

Described potter's clay, coupling agent, anionic surfactant, emulsified hydroxyethyl methacrylate rubber, nonionic surfactant, emulsified natural rubber in dry rubber, the part that initiates cross-linking agent in dry rubber parts by weight, the same below) is:

Clay: 10~60 parts; Coupling agent: 2~4 parts; Anionic surfactant: 0.3~0.5 parts; Milky hydroxyethyl methacrylate rubber calculated as dry rubber: 5~40 parts; Nonionic surfactant : 0.3~0.5 parts; emulsified natural rubber based on dry rubber: 100 parts; initiator crosslinking agent: 1~3 parts.

A kind of preparation method utilizing hydroxyethyl methacrylate rubber graft modified pottery clay to strengthen natural rubber composite material, comprises the steps:

(1) Preparation of modified clay emulsion dispersion:

Add ethanol to clay, ultrasonically disperse while stirring, then add 2~4 parts of coupling agent hydrolyzed by ethanol and 0.3~0.5 parts of anionic surfactant, and react at 35℃~90℃ for 1~2 hours , and then add milky hydroxyethyl methacrylate rubber, and react for 1 to 2 hours under the condition of temperature of 70 ℃ ~ 90 ℃, while stirring and ultrasonic dispersion, to make hydroxyethyl methacrylate rubber graft modification clay emulsion dispersion;

(2) Preparation of clay-natural rubber composites in latex state:

Use 0.3~0.5 parts of nonionic surfactant to stabilize 100 parts of concentrated natural rubber latex with a total solid content of 60% based on dry rubber, and mix the above clay emulsion dispersion evenly into the stable concentrated natural latex under constant stirring. In latex, then add initiating cross-linking agent, stir and react for 1 to 2 hours at a temperature of 70°C to 90°C, and obtain hydroxyethyl methacrylate rubber graft modified clay-natural rubber composite material in latex state ;

(3) Preparation of clay-natural rubber composites in dry state:

Through coagulation, tableting, washing, and drying, the hydroxyethyl methacrylate rubber grafted modified clay-natural rubber compound in the dry state is obtained, and the hydroxyethyl methacrylate rubber is grafted on the rubber mixer in a conventional manner. The modified clay-natural rubber compound is properly masticated, and then the initiator crosslinking agent, paraffin base oil and rubber processing aid are added in sequence, and mixed evenly to prepare the clay-natural rubber composite material.

A kind of preparation method utilizing hydroxyethyl methacrylate rubber graft modified pottery clay to strengthen natural rubber composite material, comprises the steps:

(1) Preparation of modified clay emulsion dispersion:

Add ethanol to clay, ultrasonically disperse while stirring, then add 2~4 parts of coupling agent hydrolyzed by ethanol and 0.3~0.5 parts of anionic surfactant, and react at 35℃~90℃ for 1~2 hours , and then add milky hydroxyethyl methacrylate rubber, and react for 1 to 2 hours under the condition of temperature of 70 ℃ ~ 90 ℃, while stirring and ultrasonic dispersion, to make hydroxyethyl methacrylate rubber graft modification clay emulsion dispersion;

(2) Preparation of clay-natural rubber composites in dry state:

The clay emulsion dispersion is coagulated, pressed, washed, and dried to obtain the hydroxyethyl methacrylate rubber graft modified clay in the dry state, and then the hydroxyethyl methacrylate rubber in the dry state is grafted and modified The natural rubber in the state of clay and dry rubber is plasticized and homogenized on the rubber mixer in a conventional way. After homogenization, the initiator crosslinking agent, paraffin base oil and rubber processing aids are added in sequence, and mixed evenly to make a dry rubber state. Clay-natural rubber composites modified by grafting of hydroxyethyl methacrylate rubber.

The potter's clay described above is wet potter's clay that has been infiltrated by an appropriate amount of ethanol and then rinsed with deionized water. The particle size is 30-60 nm, and the potter's clay content is more than or equal to 90%.

The coupling agent can be selected from isopropyl tris(dioctyl pyrophosphate acyloxy) titanate or isopropyl tristearate titanate titanate or isopropyl trioleate acyloxytitanium acid ester, preferably isopropyl titanate tristearate titanate.

The anionic surfactant may be sodium hexametaphosphate or sodium dodecylbenzenesulfonate or potassium oleate, preferably sodium dodecylbenzenesulfonate.

The milky hydroxyethyl methacrylate rubber can be selected from the milky hydroxyethyl methacrylate rubber prepared by grafting and copolymerizing natural rubber with hydroxyethyl methacrylate, or by natural rubber latex with hydroxyethyl methacrylate Hydroxyethyl methacrylate latex prepared by ester graft copolymerization or hydroxyethyl methacrylate graft copolymerization prepared from concentrated natural latex with a graft rate of 5-50% and a total solid content of 20-25%. Hydroxyethyl methacrylate latex, preferably the hydroxyethyl methacrylate latex of 5-50% graft ratio prepared by concentrated natural rubber latex by graft copolymerization, and total solid content of 20-25%.

The nonionic surfactant can be selected from fatty alcohol polyoxyethylene ether or sorbitol polyoxyethylene ether or nonylphenol polyoxyethylene ether, preferably fatty alcohol polyoxyethylene ether.

The milky natural rubber can be selected from natural rubber latex or concentrated natural rubber latex of Hevea brasiliensis or concentrated natural rubber latex with a total solid content of 60% through centrifugal concentration, preferably concentrated natural rubber latex with a total solid content of 60% through centrifugal concentration. latex.

The cross-linking agent can be selected from peroxides such as tert-butyl hydroperoxide, ammonium persulfate or potassium persulfate, preferably ammonium persulfate.

A kind of preparation method utilizing hydroxyethyl methacrylate rubber graft modified pottery clay to strengthen natural rubber composite material, comprises the steps:

Weigh 10~60 parts of pottery clay, add ethanol just enough to soak it, rinse it with deionized water, then add 2~4 parts of isopropyl titanate tristearate titanate and 0.3~0.5 parts of dodecylbenzene Sodium sulfonate and 100 parts of deionized water, stirred and ultrasonically dispersed for 20 to 40 minutes, then added 5 to 40 parts of hydroxyethyl methacrylate with a graft rate of 5 to 50% based on dry glue and a total solid content of 20 to 25%. Ester rubber latex, continue to use stirring and ultrasonic dispersion for 20 to 40 minutes to prepare clay emulsion dispersion; at the same time, use 0.3 to 0.5 parts of fatty alcohol polyoxyethylene ether to 100 parts of concentrated natural rubber latex with a total solid content of 60% based on dry rubber. Stable, mix the above-mentioned clay emulsion dispersion into the stable concentrated natural rubber latex evenly under the condition of constant stirring, then add 1~3 parts of ammonium persulfate dropwise, after stirring evenly, get hydroxyethyl methacrylate in latex state Rubber graft modified clay-natural rubber composite material; the composite material is further subjected to standard Chinese rubber processing techniques such as coagulation, tableting, washing, and drying to obtain hydroxyethyl methacrylate rubber graft modification in a dry state Clay-natural rubber composite.

The prepared hydroxyethyl methacrylate rubber graft modified clay-natural rubber composite material can adopt conventional vulcanization system, such as effective vulcanization system, semi-effective vulcanization system, peroxide vulcanization system, etc. to make pre-vulcanized latex, according to Various latex products can be produced by dipping process; it can also be mixed and vulcanized by conventional processing technology to produce various dry rubber products.

The beneficial effects of the present invention are:

(1) Using hydroxyethyl methacrylate rubber latex prepared by graft copolymerization of hydroxyethyl methacrylate and natural rubber latex as the dispersion compatibilizer between clay and natural rubber latex, using hydroxyethyl methacrylate The excellent compatibility between rubber latex and natural rubber latex and the active hydroxyl group connect clay bridges to the cross-linked network of rubber, which significantly improves the dispersion effect of clay in natural rubber, thus realizing the relationship between clay and natural rubber. The strong combination between them prepared high-performance clay-natural rubber composites.

(2) Vulcanization of the hydroxyethyl methacrylate rubber graft modified clay-natural rubber composite material prepared by the present invention

The tensile strength of the film can reach 25~28MPa, the elongation at break can reach 800~960%, and the 300% modulus stress can reach 3.5~6.5MPa.

Detailed ways

The present invention will be further described in detail by examples below, and these examples are only used to illustrate the present invention, and do not limit the scope of the present invention.

Example 1

Weigh 10 parts of clay with a particle size of about 20nm, add ethanol that just soaks it and rinse it with deionized water, then add 3 parts of isopropyl titanate tristearate titanate and 0.4 parts of dodecylbenzene Sodium sulfonate and 100 parts of deionized water, stirred and ultrasonically dispersed for 30 minutes, then added 5 parts of hydroxyethyl methacrylate rubber latex with a graft rate of 5% and a total solid content of 25% based on dry rubber, and continued to use stirring ultrasonic Disperse for 30 minutes to prepare clay emulsion dispersion; simultaneously adopt 0.5 part of fatty alcohol polyoxyethylene ether to stabilize 100 parts of concentrated natural rubber latex with total solid content of 60% based on dry glue, and mix above-mentioned clay emulsion under constant stirring condition The dispersion is evenly mixed into the stable concentrated natural rubber latex, then 1.5 parts of ammonium persulfate is added dropwise, and the reaction is stirred for 1 hour at a temperature of 70°C to obtain hydroxyethyl methacrylate rubber grafted clay in latex state- Natural rubber composite material, adding 1.5 parts of sulfur, 0.6 parts of zinc oxide, 0.6 parts of zinc diethyldithiocarbamate (ZDC), 0.5 parts of zinc ethyl-phenyldithiocarbamate (PX) , 0.5 parts of 2,6-di-tert-butyl-4-methylphenol (anti-264), vulcanized in a water bath at 60°C for 1.5 hours, the tensile strength of the vulcanized film obtained was 26.6MPa, and the elongation at break was 910%. The 300% modulus stress is 4.8 Mpa.

Example 2

Weigh 60 parts of pottery clay with a particle size of about 60 nm, add ethanol that just soaks it and rinse it with deionized water, then add 4 parts of isopropyl titanate tristearate titanate and 0.5 parts of dodecyl Sodium benzenesulfonate and 100 parts of deionized water were stirred and ultrasonically dispersed for 30 minutes, and then 30 parts of hydroxyethyl methacrylate rubber latex with a grafting rate of 50% and a total solid content of 20% were added in terms of dry glue, and continued to use stirring ultrasonic Disperse for 30 minutes to prepare clay emulsion dispersion; simultaneously adopt 0.5 part of fatty alcohol polyoxyethylene ether to stabilize 100 parts of concentrated natural rubber latex with total solid content of 60% based on dry glue, and mix above-mentioned clay emulsion under constant stirring condition The dispersion is evenly mixed into the stable concentrated natural rubber latex, and after being evenly stirred, it is coagulated with acetic acid, pressed into tablets, washed, and dried to make a dry gel-like hydroxyethyl methacrylate rubber grafted clay-natural rubber compound. Add 3.0 parts of ammonium persulfate, 3.5 parts of sulfur, 6.0 parts of zinc oxide, 1.0 parts of stearic acid, 1.3 parts of benzothiazole disulfide (promoter DM) in the above-mentioned dry rubber-like composite material successively on the open rubber mixing machine. ), 0.7 parts of 2,6-di-tert-butyl-4-methylphenol (anti-264), vulcanized at 160°C for 20 minutes after mixing evenly. The obtained vulcanized rubber sheet had a tensile strength of 26.9 MPa, an elongation at break of 850%, and a 300% modulus of 6.4 MPa.

Example 3

Weigh 30 parts of pottery clay with a particle size of about 50 nm, add ethanol that just soaks it and rinse it with deionized water, then add 2 parts of isopropyl titanate tristearate titanate and 0.3 parts of dodecyl Sodium benzenesulfonate and 100 parts of deionized water were stirred and ultrasonically dispersed for 30 minutes, then 20 parts of hydroxyethyl methacrylate rubber latex with a graft rate of 30% and a total solid content of 20% were added in terms of dry glue, and the stirring method was continued. After ultrasonic dispersion for 30 minutes, ethanol was used for coagulation, tableting, washing, and drying to make dry colloidal hydroxyethyl methacrylate rubber grafted clay; then 100 parts of dry natural rubber and The above-mentioned dry colloidal hydroxyethyl methacrylate rubber grafted clay was blended, and then 2.0 parts of ammonium persulfate, 3.5 parts of sulfur, 6.0 parts of zinc oxide, 1.0 parts of stearic acid, 1.3 parts of benzo disulfide were added successively. Thiazole (accelerator DM), 0.5 parts of 2,6-di-tert-butyl-4-methylphenol (anti-264), after mixing evenly, vulcanize at 160°C for 20 minutes. The obtained vulcanized rubber sheet had a tensile strength of 25.8 MPa, an elongation at break of 870%, and a 300% modulus of 5.8 MPa.

Example 4

Weigh 20 parts of pottery clay with a particle size of about 40nm, add ethanol that just soaks it and rinse it with deionized water, then add 3 parts of isopropyl titanate tristearate titanate and 0.4 parts of dodecylbenzene Sodium sulfonate and 100 parts of deionized water, stirred and ultrasonically dispersed for 30 minutes, then added 5 parts of hydroxyethyl methacrylate rubber latex with a graft rate of 20% and a total solid content of 25% based on dry rubber, and continued to use stirring ultrasonic Disperse for 30 minutes to prepare clay emulsion dispersion; simultaneously adopt 0.5 part of fatty alcohol polyoxyethylene ether to stabilize 100 parts of concentrated natural rubber latex with total solid content of 60% based on dry glue, and mix above-mentioned clay emulsion under constant stirring condition The dispersion is uniformly mixed into the stable concentrated natural rubber latex, then 1.5 parts of ammonium persulfate is added dropwise, and the temperature is 90°C, and the reaction is stirred for 2 hours to obtain hydroxyethyl methacrylate rubber grafted clay in latex state- Natural rubber composite material, adding 1.5 parts of sulfur, 0.6 parts of zinc oxide, 0.6 parts of zinc diethyldithiocarbamate (ZDC), 0.5 parts of zinc ethyl-phenyldithiocarbamate (PX) , 0.5 parts of 2,6-di-tert-butyl-4-methylphenol (anti-264), vulcanized in a water bath at 60°C for 1.5 hours, the tensile strength of the vulcanized film obtained was 27.2MPa, and the elongation at break was 940%. The 300% modulus stress is 4.6 Mpa.

Example 5

Weigh 50 parts of pottery clay with a particle size of about 50 nm, add ethanol that just soaks it and rinse it with deionized water, then add 2 parts of isopropyl titanate tristearate titanate and 0.3 parts of dodecyl Sodium benzenesulfonate and 100 parts of deionized water were stirred and ultrasonically dispersed for 30 minutes, then 20 parts of hydroxyethyl methacrylate rubber latex with a graft rate of 40% and a total solid content of 25% were added in terms of dry glue, and the stirring method was continued. After ultrasonic dispersion for 30 minutes, ethanol was used for coagulation, tableting, washing, and drying to make dry colloidal hydroxyethyl methacrylate rubber grafted clay; then 100 parts of dry natural rubber and The above-mentioned dry colloidal hydroxyethyl methacrylate rubber grafted clay was blended, and then 2.0 parts of ammonium persulfate, 3.5 parts of sulfur, 6.0 parts of zinc oxide, 1.0 parts of stearic acid, 1.3 parts of benzo disulfide were added successively. Thiazole (accelerator DM), 0.5 parts of 2,6-di-tert-butyl-4-methylphenol (anti-264), after mixing evenly, vulcanize at 160°C for 20 minutes. The obtained vulcanized rubber sheet had a tensile strength of 26.5 MPa, an elongation at break of 850%, and a 300% modulus of 6.2 MPa.

Claims (11)

1. a kind of preparation method utilizing hydroxyethyl methacrylate rubber graft modification potter's clay to strengthen natural rubber composite material, is characterized in that: comprise the steps: Add clay and an appropriate amount of coupling agent and anionic surfactant in deionized water, stir and ultrasonically disperse, then add an appropriate amount of milky hydroxyethyl methacrylate rubber, continue to use stirring and ultrasonic dispersion to prepare clay emulsion dispersion; The non-ionic surfactant stabilizes an appropriate amount of milky natural rubber, and then mixes the above-mentioned clay emulsion dispersion into the milky natural rubber evenly under the condition of constant stirring, and at the same time drips it under the condition of 50~70 ℃ water bath to trigger exchange. Combined agent to obtain the hydroxyethyl methacrylate rubber graft modified clay-natural rubber composite material in the latex state; the composite material is further passed through the standard Chinese rubber conventional processing technology of solidification, pressing, washing, and drying to obtain the dry rubber state The hydroxyethyl methacrylate rubber graft modified clay-natural rubber composite material; The milky hydroxyethyl methacrylate rubber is the milky hydroxyethyl methacrylate rubber prepared by grafting and copolymerizing natural rubber with hydroxyethyl methacrylate, or it is prepared from natural rubber latex by grafting with hydroxyethyl methacrylate. Hydroxyethyl methacrylate latex prepared by graft copolymerization or methacrylate with a graft rate of 5-50% and a total solid content of 20-25% prepared from concentrated natural rubber latex by graft copolymerization with hydroxyethyl methacrylate Hydroxyethyl acrylate latex; The milky natural rubber is the natural rubber latex of Hevea brasiliensis or the concentrated natural rubber latex that is centrifuged and concentrated, and the total solid content is 60%. 2. the preparation method utilizing hydroxyethyl methacrylate rubber graft modification clay to strengthen natural rubber composite material according to claim 1, is characterized in that: described clay, coupling agent, anionic surfactant, with Emulsified hydroxyethyl methacrylate rubber in dry rubber, nonionic surfactant, emulsion natural rubber in dry rubber, and the part that initiates cross-linking agent are calculated in parts by weight: Clay: 10~60 parts; Coupling agent: 2~4 parts; Anionic surfactant: 0.3~0.5 parts; Milky hydroxyethyl methacrylate rubber calculated as dry rubber: 5~40 parts; Nonionic surfactant : 0.3~0.5 parts; emulsified natural rubber based on dry rubber: 100 parts; initiator crosslinking agent: 1~3 parts. 3. a preparation method utilizing hydroxyethyl methacrylate rubber graft modified pottery clay to strengthen natural rubber composite material, is characterized in that: comprise the steps: (1) Preparation of modified clay emulsion dispersion: Add ethanol to clay, ultrasonically disperse while stirring, then add 2~4 parts of coupling agent hydrolyzed by ethanol and 0.3~0.5 parts of anionic surfactant, and react at 35℃~90℃ for 1~2 hours , and then add milky hydroxyethyl methacrylate rubber, and react for 1 to 2 hours under the condition of temperature of 70 ℃ ~ 90 ℃, while stirring and ultrasonic dispersion, to make hydroxyethyl methacrylate rubber graft modification clay emulsion dispersion; (2) Preparation of clay-natural rubber composites in latex state: Use 0.3~0.5 parts of nonionic surfactant to stabilize 100 parts of concentrated natural rubber latex with a total solid content of 60% based on dry rubber, and mix the above clay emulsion dispersion evenly into the stable concentrated natural latex under constant stirring. In latex, then add initiating cross-linking agent, stir and react for 1 to 2 hours at a temperature of 70°C to 90°C, and obtain hydroxyethyl methacrylate rubber graft modified clay-natural rubber composite material in latex state ; (3) Preparation of clay-natural rubber composites in dry state: Through coagulation, tableting, washing, and drying, the hydroxyethyl methacrylate rubber grafted modified clay-natural rubber compound in the dry state is obtained, and the hydroxyethyl methacrylate rubber is grafted on the rubber mixer in a conventional manner. The modified pottery clay-natural rubber compound is properly masticated, and then the initiator crosslinking agent, paraffin base oil and rubber processing aid are added in sequence, and the compound is uniformly mixed to make the pottery clay-natural rubber composite material; The milky hydroxyethyl methacrylate rubber is the milky hydroxyethyl methacrylate rubber prepared by grafting and copolymerizing natural rubber with hydroxyethyl methacrylate, or it is prepared from natural rubber latex by grafting with hydroxyethyl methacrylate. Hydroxyethyl methacrylate latex prepared by graft copolymerization or methacrylate with a graft rate of 5-50% and a total solid content of 20-25% prepared from concentrated natural rubber latex by graft copolymerization with hydroxyethyl methacrylate Hydroxyethyl acrylate latex. 4. a preparation method utilizing hydroxyethyl methacrylate rubber graft modified pottery clay to strengthen natural rubber composite material, is characterized in that: comprise the steps: (1) Preparation of modified clay emulsion dispersion: Add ethanol to clay, ultrasonically disperse while stirring, then add 2~4 parts of coupling agent hydrolyzed by ethanol and 0.3~0.5 parts of anionic surfactant, and react at 35℃~90℃ for 1~2 hours , and then add milky hydroxyethyl methacrylate rubber, and react for 1 to 2 hours under the condition of temperature of 70 ℃ ~ 90 ℃, while stirring and ultrasonic dispersion, and made hydroxyethyl methacrylate rubber graft modified Sexual clay emulsion dispersion; (2) Preparation of clay-natural rubber composites in dry state: The clay emulsion dispersion is coagulated, pressed, washed, and dried to obtain the hydroxyethyl methacrylate rubber graft modified clay in the dry state, and then the hydroxyethyl methacrylate rubber in the dry state is grafted and modified The natural rubber in the state of clay and dry rubber is plasticized and homogenized on the rubber mixer in a conventional way. After homogenization, the initiator crosslinking agent, paraffin base oil and rubber processing aids are added in sequence, and mixed evenly to make a dry rubber state. The hydroxyethyl methacrylate rubber graft modified clay-natural rubber composite material; The milky hydroxyethyl methacrylate rubber is the milky hydroxyethyl methacrylate rubber prepared by grafting and copolymerizing natural rubber with hydroxyethyl methacrylate, or it is prepared from natural rubber latex by grafting with hydroxyethyl methacrylate. Hydroxyethyl methacrylate latex prepared by graft copolymerization or methacrylate with a graft rate of 5-50% and a total solid content of 20-25% prepared from concentrated natural rubber latex by graft copolymerization with hydroxyethyl methacrylate Hydroxyethyl acrylate latex. 5. according to claim 1, 3 or 4, utilize hydroxyethyl methacrylate rubber graft modification potter's clay to strengthen the preparation method of natural rubber composite material, it is characterized in that: described potter's clay, just pass through proper amount of ethanol Wet pottery clay rinsed with deionized water after infiltration, particle size is 30-60nm, pottery clay content ≥ 90%. 6. according to claim 1, 3 or 4 described preparation methods utilizing hydroxyethyl methacrylate rubber graft modified pottery clay to strengthen natural rubber composite material, it is characterized in that: described coupling agent is isopropyl three (Dioctyl pyrophosphate acyloxy) titanate or isopropyl tristearate titanate or isopropyl trioleate acyl titanate. 7. according to claim 1, 3 or 4 described preparation methods utilizing hydroxyethyl methacrylate rubber graft modification potter's clay to strengthen natural rubber composite material, it is characterized in that: described anion surfactant is hexametaphosphoric acid Sodium or sodium dodecylbenzenesulfonate or potassium oleate. 8. according to the preparation method of claim 1, 3 or 4 described utilizing hydroxyethyl methacrylate rubber graft modification potter's clay to strengthen natural rubber composite material, it is characterized in that: described nonionic surfactant is fatty alcohol Polyoxyethylene ether or sorbitol ethoxylate or nonylphenol ethoxylate. 9. according to claim 1, 3 or 4 described preparation methods utilizing hydroxyethyl methacrylate rubber graft modified pottery clay to strengthen natural rubber composite material, it is characterized in that: described initiating crosslinking agent is tert-butyl Hydrogen peroxide, ammonium persulfate, or potassium persulfate. 10. A preparation method utilizing hydroxyethyl methacrylate rubber graft modified pottery clay to strengthen natural rubber composite material, is characterized in that: comprises the steps: Weigh 10~60 parts of pottery clay, add ethanol just enough to soak it, rinse it with deionized water, then add 2~4 parts of isopropyl titanate tristearate titanate and 0.3~0.5 parts of dodecylbenzene Sodium sulfonate and 100 parts of deionized water, stirred and ultrasonically dispersed for 20 to 40 minutes, then added 5 to 40 parts of hydroxyethyl methacrylate with a graft rate of 5 to 50% based on dry glue and a total solid content of 20 to 25%. Ester rubber latex, continue to use stirring and ultrasonic dispersion for 20 to 40 minutes to prepare clay emulsion dispersion; at the same time, use 0.3 to 0.5 parts of fatty alcohol polyoxyethylene ether to 100 parts of concentrated natural rubber latex with a total solid content of 60% based on dry rubber. Stable, mix the above-mentioned clay emulsion dispersion into the stable concentrated natural rubber latex evenly under the condition of constant stirring, then add 1~3 parts of ammonium persulfate dropwise, after stirring evenly, get hydroxyethyl methacrylate in latex state Rubber graft modified clay-natural rubber composite material; the composite material is further processed through solidification, tableting, washing, and drying standard Chinese rubber conventional processing technology to obtain hydroxyethyl methacrylate rubber graft modified clay in a dry state - natural rubber composites; The milky hydroxyethyl methacrylate rubber is the milky hydroxyethyl methacrylate rubber prepared by grafting and copolymerizing natural rubber with hydroxyethyl methacrylate, or it is prepared from natural rubber latex by grafting with hydroxyethyl methacrylate. Hydroxyethyl methacrylate latex prepared by graft copolymerization or methacrylate with a graft rate of 5-50% and a total solid content of 20-25% prepared from concentrated natural rubber latex by graft copolymerization with hydroxyethyl methacrylate Hydroxyethyl acrylate latex. 11. according to claim 1,3,4 or 10, utilize the preparation method of hydroxyethyl methacrylate rubber graft modification potter's clay to strengthen natural rubber composite material, it is characterized in that: the hydroxyethyl methacrylate prepared Ester rubber graft modified clay-natural rubber composite material adopts effective vulcanization system, semi-effective vulcanization system and peroxide vulcanization system to make pre-vulcanized latex, and produces various latex products according to the dipping process; or adopts conventional processing technology for mixing Vulcanization, production of various dry rubber products.