CN1233703C - Method for preparing high-cohesiveness thermoplastic cross-linked rubber - Google Patents

Abstract

The preparation method of high-adhesive thermoplastic vulcanizate of the present invention relates to a method for preparing thermoplastic vulcanizate by dynamic full vulcanization technology, and its operation steps are as follows: (1) rubber and plastics are premixed with tackifier: first mix part of rubber and all Plastic and tackifier are premixed, the amount of rubber involved in the premixing accounts for 20% to 60% of the total weight of the rubber in the thermoplastic vulcanizate to be prepared, and the amount of tackifier is 2% to 4% of the total weight of the thermoplastic vulcanizate to be prepared. %, the tackifier is the condensation product of polyisobutylene or butylphenol and acetylene; (2) Preparation of rubber masterbatch: mix the remaining rubber with filler, softener, aging agent and processing aid to form masterbatch (3) Dynamic vulcanization: dynamic vulcanization of the premix prepared in the previous two steps, rubber masterbatch, vulcanizing agent, and accelerator; (4) late oil filling: add 20% of the plastic weight content of oil, and continue to mix evenly , that is to obtain a thermoplastic vulcanizate with high adhesion and excellent comprehensive properties.

Description

Preparation method of high-adhesion thermoplastic vulcanizate

Technical field The present invention relates to a method for preparing high-adhesive thermoplastic vulcanizate by dynamic full vulcanization technology. The preparation method proposed on the basis of the existing formula for preparing thermoplastic vulcanizate by melt blending method can prepare high-adhesive A thermoplastic vulcanizate with excellent comprehensive properties.

Background technology The dynamic full vulcanization technology is to mix rubber into the thermoplastic resin matrix, and at the same time of mixing with the cross-linking agent, it can completely produce chemical cross-linking of the rubber "in situ", and under the action of high-speed mixing and shearing, the cross-linking The rubber is crushed into a large number of micron-sized particles and dispersed in a continuous thermoplastic resin matrix to form thermoplastic vulcanizate (TPV for short). The rubber that can be selected for preparing TPV usually includes: EPDM rubber, butyl rubber, trans isoprene rubber, natural rubber, butadiene rubber, styrene butadiene rubber, ethylene-vinyl acetate copolymer, acrylate rubber, chlorinated polystyrene Vinyl, Neoprene, Nitrile or mixtures thereof. Thermoplastic resin matrix plastics usually include polypropylene, polyethylene, polystyrene, acrylonitrile-butadiene-styrene terpolymer, styrene-acrylonitrile copolymer, polymethyl methacrylate, polyterephthalic acid Butylene Glycol Esters, Nylon, Polycarbonate or mixtures thereof. Dynamic full vulcanization technology can be used to prepare thermoplastic vulcanizates with a rubber-to-plastic ratio of 90/10 to 10/90. Full vulcanization means that the crosslinking density of the rubber is at least 7×10-5mol/mL or 97% of the rubber is crosslinked. TPV not only has excellent comprehensive performance, but also has the processing characteristics of thermoplastic materials, and is gradually replacing traditional rubber in many fields. The main reason for the rapid development of thermoplastic vulcanizate is that it has the advantages of thermoplastic plastics in processing and molding. Compared with thermosetting rubber, it has higher production efficiency and can be recycled and reused. It has elastic properties comparable to vulcanized rubber. As early as the early 1980s, there was a typical industrial production of EPDM/PPTPV in foreign countries.

The typical preparation method of TPV is: put the plastic into the high-temperature mixer to pre-melt, then add the rubber and mix together, then add additives, fillers and softeners in turn, mix well, and finally add vulcanizing agent and accelerator for dynamic vulcanization. The preparation process of blended thermoplastic vulcanizate is introduced in the review paper "Kinetic Model of Dynamic Vulcanization" (Polym.Mater.sci.Eng1998, 79 102-103). The preparation process can be roughly classified into two categories. Melt blending method, this type is also the most common preparation technology currently used in industrial production abroad. This preparation technology mainly has two specific processes. The difference between the two processes lies in the way of adding the vulcanizing agent. One is that the vulcanizing agent is added after the rubber and plastics, fillers and softeners are uniformly mixed, and the other is that the vulcanizing agent is mixed Vulcanizing agents, fillers and softeners are added to the rubber in advance, and then mixed with plastics for dynamic vulcanization. The second type is the solution polymerization method, which is still in the experimental stage.

As we all know, to a certain extent, dynamic vulcanization technology is not very suitable for the preparation of thermoplastic vulcanizates with low hardness and high fluidity, because low hardness TPV is generally obtained by increasing the rubber phase content, a large number of elastomer particles, easy to form a network structure , as the rubber content increases, the elasticity of the material increases, and the prepared material becomes difficult to extrude, or even cannot be extruded. The key to the performance of blended thermoplastic vulcanizates lies in the control methods and means of the morphology structure and the particle size of the rubber phase. Since TPV contains a large number of cross-linked rubber particles, these rubber particles are easy to form a network structure, thereby affecting the fluidity of TPV. If the content of the rubber phase is reduced, the fluidity will increase, but the hardness and compression deformation of TPV will also increase, that is, the elasticity will decrease. Therefore, there is a contradiction between the elasticity and fluidity of TPV, and it has always been a difficult point to prepare TPV with high flow and high elasticity. The traditional approach is generally to solve this problem by changing the formula or adopting more advanced processing equipment.

In recent years, domestic and foreign researches in this field have mainly focused on the combination of raw materials. For example, American Advanced Elastomer Systems Co., Ltd. [AES. Composition" (Chinese Patent Application No. 99807124.2) discloses that the melt flow rate of the polypropylene composition is in the range of about 0.5 to about 5 dg/min, and its molecular weight distribution Mw/Mn is from greater than 5.5 to the highest about 20 , the prepared thermoplastic elastomer can improve processing performance while maintaining excellent physical properties. "Thermoplastic vulcanizates from isobutylene rubber and either EPDM or a conjugated diene rubber" (US Patent No. 5,621,045) discloses that in order to improve the overall performance of TPV, a three-component blending method is proposed. There are two rubber components in the blend, such as The combination of isobutylene rubber and ethylene propylene rubber or natural rubber, ternary blending is beneficial to improve the overall performance of the blend, and to a certain extent can improve the bonding performance of the material. "Thermoplastic elastomers based upon chlorinated polyethylene and a crystalline olefin polymer" (US Patent No. 4,978,716) proposes a multi-component blending method. The blend has two kinds of plastics, such as chlorinated polyethylene and polypropylene, and the multi-component plastic phase contributes to Improve the crystallinity and fluidity of the plastic phase to prepare TPV with excellent performance. "Modification of thermoplastic vulcanizates with athermoplastic random copolymer of ethylene" (US Patent No. 6,399,710) proposes the use of random copolymers as the continuous phase of plastics. The invention believes that random copolymers are beneficial to improve the elongation at break of the material. Although the combination of the above raw materials can improve the bonding performance of TPV to a certain extent, the bonding effect of the material is still not ideal according to the feedback information from the manufacturers using TPV. The reason why thermoplastic vulcanizates bond poorly with other rubber materials is mainly because the continuous phase of thermoplastic vulcanizates is plastic, and it is well known that plastic and rubber have poor bonding properties. According to the results of laboratory testing of the peel strength of foreign TPV materials available in the laboratory, the inventor's adhesive performance is not ideal. For example, the TPV of Santoprene64A-80A of AES company has a peel strength of only 1.6-2.5KN/m (the test method adopts GB532-91 to test on an electronic rubber tensile machine, T-shaped 180°peel, and the tensile speed is 100mm/min). SUMMARY OF THE INVENTION The object of the present invention is to propose a method for preparing a thermoplastic vulcanizate with high bonding performance. The method is to add a tackifier in the premixing stage of part of the rubber and plastic, so that the tackifier can be evenly dispersed in the two phases of rubber and plastic and participate in the dynamic vulcanization process, so that the rubber phase and the plastic phase can have better bonding. performance. Studies have shown that within a certain amount of tackifier, the bonding performance of TPV and other materials can be greatly improved without reducing other properties of TPV. This method not only enables the thermoplastic vulcanizate to have excellent high bonding performance, but also has high fluidity, low compression deformation and low hardness at the same time.

The traditional melt blending method to prepare thermoplastic vulcanizate is to first melt the plastic and mix it with rubber, then add additives, fillers, softeners and mix evenly, and finally add vulcanizing agent and accelerator for dynamic vulcanization. The technical scheme that the present invention adopts comprises following four steps:

1) Premixing of rubber, plastic and tackifier: first mix part of the rubber and all the plastic and tackifier evenly above the melting point of the plastic, and the amount of rubber involved in the premixing accounts for the total weight of the rubber in the thermoplastic vulcanizate to be prepared The amount of tackifier is 20% to 60% of the total weight of the thermoplastic vulcanizate to be prepared, and the tackifier is polyisobutylene or the condensation product of butylphenol and acetylene;

2) The remaining rubber is prepared into a masterbatch: the rubber remaining in the previous step, fillers, softeners, aging agents, and processing aids are mixed into a masterbatch;

3) dynamic vulcanization: the premix of rubber, plastics and tackifier prepared in the last two steps, rubber masterbatch and vulcanizing agent, accelerator are carried out dynamic vulcanization;

4) Late oil filling: In the late stage or after the dynamic vulcanization is completed, add 20% of the plastic weight content of oil and continue to mix evenly. After the above four steps, a thermoplastic vulcanizate with high viscosity, high fluidity, low compression deformation and low hardness can be obtained.

The rubber used in the present invention is the commonly used rubber of known thermoplastic vulcanizates, such as: EPDM rubber, butyl rubber, trans isoprene rubber, natural rubber, trans isoprene rubber, butadiene rubber, styrene butadiene rubber, Ethylene-vinyl acetate copolymer, acrylate rubber, chlorinated polyethylene rubber, neoprene, nitrile rubber or mixtures thereof. The used plastics of the present invention are commonly used plastics of known thermoplastic vulcanizates, such as: polyethylene, polypropylene, polystyrene, acrylonitrile-butadiene-styrene terpolymer, styrene-acrylonitrile copolymer, polystyrene Methyl methacrylate, polybutylene terephthalate, nylon, polycarbonate or mixtures thereof.

The oil used for oil extension in the later stage of the present invention is the oil commonly used in known thermoplastic vulcanizates, for example: naphthenic oil, paraffin oil, petrolatum or their mixtures. The type of oil used for post-oil extension is the same as or different from the commonly used softeners for known thermoplastic vulcanizates.

The present invention mainly adopts two technologies: one is the premixing of part of rubber and plastics with the tackifier; the other is the post-oil filling technology.

The rubber-plastic premixing technology makes the pre-mixing of plastic and part of rubber and tackifier very uniform. After further adding rubber, all rubber, plastic and tackifier will form a uniform phase in a short time. Because the entire dynamic vulcanization process is very short, this technology can effectively avoid the disadvantages of the traditional dynamic vulcanization technology that the rubber and tackifier cannot be fully mixed evenly, and it also avoids some traditional methods in order to increase the uniformity of rubber and plastic mixing. Deliberately prolonging the premixing time has caused the disadvantage of a large amount of migration of fillers and various ingredients into the plastic phase. The uniform mixing of rubber, plastic and tackifier is very important for the successful realization of phase inversion in the next dynamic vulcanization process and obtaining fine particles uniformly covered by the plastic phase, and fine rubber particles are important for improving the fluidity of TPV And flexibility is also a must.

Post-oil filling technology refers to adding oil equivalent to 20% of the plastic content in the late stage of dynamic vulcanization. This part of oil can be carried out after dynamic vulcanization is completed, or it can be directly oil-filled to the finished TPV. In this way, a small part of the oil energy will penetrate into the rubber particles, and most will remain in the plastic phase. Experiments have proved that as long as the filled oil has sufficient compatibility with plastics and the amount is not too much, it can significantly reduce the hardness and compression deformation of TPV, and can improve fluidity. The reason is to achieve the purpose of reducing the compression set of TPV and improving the fluidity by plasticizing and compatibilizing the molecules of the plastic phase.

The present invention is except existing known commonly used rubber and plastics, and other fillers, auxiliary agent are also commonly used, and softening agent is for example: naphthenic oil, paraffin oil or vaseline etc.; Filler is for example: white carbon black, carbon black, silica , clay, etc.; vulcanizing agents such as: organic peroxides, sulfur, phenolic resins, etc.; other additives such as: stearic acid, antioxidants, etc.

The formula used in the present invention is an existing, known thermoplastic vulcanizate formula. On the basis of not changing the original formula and the conventional equipment (open mill, internal mixer or screw extruder), only the tackifier is added. This component adopts the uniformly dispersed thickening method of the present invention to prepare thermoplastic vulcanizate with high bonding performance.

The tackifier that the present invention adopts mainly contains two kinds, and one is polyisobutylene, such as No. 2 polyisobutylene produced with Xinjiang Xinfeng Co., Ltd., according to this product introduction, it mainly has the purposes of following five aspects: 1) It can be used to produce three series of dispersants. 2) Used as an adhesion aid to improve the bonding performance of thermosetting rubber and fiber, as well as modifiers such as rubber, paraffin, asphalt, etc. 3) Used as high-voltage cable protection ointment, component of electrical insulating resin, insulating pressure-sensitive adhesive, insulating tape, industrial transformer oil, etc. 4) Used as gap filling and sealing material. 5) Used as a food additive. In the field of rubber, polyisobutylene can be used as a tackifier, but it is mainly used to improve the bonding performance of thermosetting rubber semi-finished products and skeleton materials such as fibers, and the dosage is generally about 4% of the rubber dosage. In the field of thermoplastic vulcanizates, traditionally, there has never been a method of adding tackifiers to improve the bonding properties of plastic and rubber matrix materials, and there has never been a report on the use of polyisobutylene to improve the bonding properties of thermoplastic vulcanizates and rubber. . The second is the KORESIN resin of BASF in Germany, which is a condensate of butylphenol and acetylene, and is used as a tackifier to improve the adhesion of tires in the rubber industry. The dosage range is generally 2 to 5%.

The present invention cleverly introduces a tackifier into the continuous phase plastic through the rubber-plastic premixing stage by adding a tackifier, thereby improving the bonding performance of thermoplastic vulcanizates. This method has not been reported in the field of thermoplastic vulcanizates. . The reason why the present invention adds the tackifier in the rubber and plastic premixing stage is mainly to consider that adding the tackifier in the rubber and plastic premixing stage can make the tackifier more evenly dispersed in the two phases of rubber and plastics, so that the tackifier can play a role Very good effect, so that both the dispersed phase rubber and the continuous phase plastic have better bonding performance. The peel strength of the thermoplastic vulcanizate prepared by the method of the present invention can reach 5.2KN/m, which is the highest level of the current thermoplastic vulcanizate, and is much better than the bonding performance of commercially available TPV materials (generally lower than 2.5KN/m) . If the tackifier is added in the traditional masterbatch method, the tackifier can only stay in the rubber phase, and cannot make the plastic have better bonding performance; if the tackifier is added in the dynamic vulcanization process, then it will It affects the dynamic vulcanization process, making other properties of the prepared material not ideal. The performance of the thermoplastic vulcanizate prepared by adopting the present invention is compared with that prepared by the traditional technology, and the thermoplastic vulcanizate prepared by the technology of the present invention is much higher than that obtained by the traditional technical method in terms of bonding performance (expressed in the peel strength of the material) To prepare vulcanized rubber, the peel strength of commercially available TPV materials is generally not higher than 2.5KN/m. The TPV prepared by this technology has other properties (such as: compression deformation can be as low as 26%, hardness can be as low as 60 Shore degrees, The peel strength can reach 5.2KN/m under the premise that the tensile strength can reach more than ten Mpa), and the bonding performance has been improved by nearly two times.

Detailed ways

Table 1 lists the properties of the thermoplastic vulcanizates prepared in the examples and comparative examples of the present invention.

Example 1 Preparation of EPDM/polypropylene (EPDM/PP) blended thermoplastic vulcanizate with a rubber-to-plastic ratio of 60/40. The tackifier polyisobutylene involved in premixing accounts for the total amount of the prepared thermoplastic vulcanizate formula. 2% of weight), the tackifier is No. 2 polyisobutylene produced by Xinjiang Xinfeng Co., Ltd.

The operation steps are as follows:

1) Mix 24 grams of EPDM rubber, 80 grams of polypropylene plastic, 0.8 grams of antioxidant 1010 and 8.1 grams of polyisobutylene tackifier in a double-roller masticator at 170 ° C for about 3 minutes and set aside .

2) Put the remaining 96 grams of EPDM rubber into the open mill at room temperature, adjust the appropriate roller distance, and add 1.2 grams of stearic acid and 48 grams of white carbon black in small quantities according to the rubber mixing method. Make 6 triangular bags, add 120 grams of combined oil (naphthenic oil and vaseline, and use a weight ratio of 1: 1), make 6 triangular bags, make rubber masterbatch, and set aside.

3) Put the rubber-plastic premix and rubber masterbatch prepared in the previous two steps into a 180°C double-roller plasticizer in turn, with a roller distance of 0.5mm. After 30 seconds, add 14.2 grams of tert-octyl phenolic resin, mix for 30 seconds, and finally Add 2.8 grams of stannous chloride for dynamic vulcanization for 15 minutes.

4) Add 16 grams of combined oil (naphthenic oil and vaseline, combined with a weight ratio of 1:1), and continue mixing until uniform, to obtain an EPDM/PP blended thermoplastic vulcanizate with a rubber-to-plastic ratio of 60/40. Performance see table 1

Example 2 Preparation of butyl rubber/polypropylene (IIR/PP) blended thermoplastic vulcanizate with a rubber-to-plastic ratio of 70/30, the tackifier KORESIN resin participating in the premixing accounts for 30% of the total weight of the prepared thermoplastic vulcanizate formula 3%, the tackifier is the condensate of butylphenol and acetylene KORESIN resin from BASF, Germany.

1) Mix 56 grams of butyl rubber, 60 grams of polypropylene plastic, 0.6 grams of antioxidant 1010 and 12.8 grams of KORESIN resin tackifier in a mixer at 170 ° C for about 3 minutes and set aside;

2) Put the remaining 84 grams of butyl rubber into the open mill at room temperature, adjust the appropriate roller distance, and add 1.4 grams of stearic acid and 56 grams of white carbon black in small quantities and several times according to the mixing method of rubber, and beat 6 triangle bags, then add 140 grams of paraffin oil, make 6 triangle bags to make rubber masterbatch, set aside;

3) Put the rubber-plastic premix and rubber masterbatch prepared in the previous two steps into a 180°C double-roller plasticizer in turn, with a roller distance of 0.5mm. After 30 seconds, add 14.0 grams of tert-octyl phenolic resin, mix for 30 seconds, and finally Add 2.8 grams of stannous chloride for dynamic vulcanization for 15 minutes;

4) Add 12 grams of combined oil (naphthenic oil and petrolatum, combined with a weight ratio of 1:1), and continue mixing until uniform. That is, an IIR/PP blended thermoplastic vulcanizate with a rubber-to-plastic ratio of 70/30 was obtained. The properties are shown in Table 1. It can be seen from the performance table that even if different types of thermoplastic vulcanization and different types of tackifiers are used, as long as the vulcanized rubber is prepared by the technology of the present invention, the purpose of high adhesion can be achieved.

Example 3 Preparation of natural rubber/polyethylene (NR/PE) blended thermoplastic vulcanizate with a rubber-to-plastic ratio of 50/50 (participating in the premixed tackifier and tackifier polyisobutylene, accounting for the prepared thermoplastic vulcanizate 4% of the total weight of the recipe)

1) Mix 60 grams of natural rubber, 100 grams of polyethylene plastic, 1.0 grams of antioxidant 1010 and 14.8 grams of polyisobutylene tackifier in a mixer at 170 ° C for about 3 minutes and set aside;

2) Put the remaining 40 grams of natural rubber into the normal temperature open mill, adjust the appropriate roller distance, and add 1.0 grams of stearic acid and 40 grams of white carbon black in small quantities according to the mixing method of rubber, and beat 6 1 triangle bag, then add 100 grams of paraffin oil, make 6 triangle bags to make rubber masterbatch, set aside;

3) Put the rubber-plastic premix and rubber masterbatch prepared in the previous two steps into a 180°C double-roller plasticizer in turn, with a roller distance of 0.5mm. After 30 seconds, add 10.0 grams of tert-octyl phenolic resin, mix for 30 seconds, and finally Add 2.0 grams of stannous chloride for dynamic vulcanization for 15 minutes;

4) Add 20 grams of combined oil (naphthenic oil and vaseline, combined with a weight ratio of 1:1), and continue mixing until uniform. That is, a NR/PE blended thermoplastic vulcanizate with a rubber-to-plastic ratio of 50/50 was obtained. The properties are shown in Table 1. It can be seen from the performance table that even if the ratio of rubber to plastic is different and different types of thermoplastic vulcanizates, as long as the vulcanizates prepared by the technology of the present invention can achieve the purpose of high adhesion.

Comparative Example 1 Traditional dynamic vulcanization technology prepared EPDM/PP (EPDM/PP) blended thermoplastic vulcanizate with a rubber-to-plastic ratio of 60/40 (the composition and dosage of the formula are the same as in Example 1)

1) Put the whole amount of plastic and antioxidant 1010 into a double-drum plastic mixer at 170°C until the plasticization is uniform, about 2 minutes.

2) Put the whole amount of EPDM rubber into the plastic plasticized in the first step, mix until uniform, and then add 8.1 grams of polyisobutylene tackifier.

3) After the rubber, plastic and tackifier in the previous step are mixed evenly, add white carbon black and oil several times in batches. until well mixed. Then adjust the roller distance to 0.5mm, add tert-octyl phenolic resin, mix for 30 seconds, and finally add stannous chloride for dynamic vulcanization for 15 minutes; the properties are shown in Table 1. It can be seen from the comparison between Table 1 and Example 1 that with the same formula, the vulcanizate prepared by traditional technology

It is not as good as the vulcanized rubber prepared by the technology of the present invention in bonding performance. Comparative Example 2 A butyl rubber/polypropylene (IIR/PP) blended thermoplastic vulcanizate with a rubber-to-plastic ratio of 70/30 was prepared. (method is the same as Example 2, except that no tackifier is used in the formula) From Table 1 and Example 2, it can be seen that the addition of tackifier can greatly improve the tackiness of the material.

Table 1 Hardness (Shore A) 100% elongation (MPa) Tensile strength (MPa) Elongation(%) Tear strength (KN/m) Tensile set (%) Compression set (%)100℃×22h Peel strengthKN/m Example 1 68 3.0 12.1 420 34.6 20 30 4.9 Example 2 60 2.4 9.6 380 30.0 16 26 5.1 Example 3 80 5.1 16.1 430 48.0 16 38 5.2 Comparative example 1 73 3.6 12.4 410 34.8 20 40 1.3 Comparative example 2 60 2.3 9.5 380 30.0 16 26 1.3

Claims (4)

1. the preparation method of a high-adhesion thermoplastic sulfurized rubber, first with melt-blending process with plastics fusion in advance and rubber mix, add auxiliary agent, filler, tenderizer again and mix, add vulcanizing agent and promotor at last and carry out dynamic vulcanization, it is characterized in that operation steps is as follows:

(1) rubber and plastics and tackifier premix: earlier with part rubber with all plastics and tackifier mix being higher than under the plastics fusing point, the rubber consumption that participates in premix accounts for the 20%-60% of rubber gross weight in the thermoplastic sulfurized rubber that will prepare, the tackifier consumption is thermoplastic sulfurized rubber gross weight 2%-4%, and tackifier are the condenses of polyisobutene or butylphenol and acetylene;

(2) preparation of rubber rubber master batch: become rubber master batch with the remaining rubber of previous step and filler, tenderizer, aging agent, processing aid are mixing;

(3) dynamic vulcanization: will go up the pre-composition of rubber, plastics and tackifier of two step preparations and rubber rubber master batch and vulcanizing agent, promotor and carry out dynamic vulcanization;

(4) later stage is oil-filled: in the dynamic vulcanization later stage or after finishing, add 20% oil of plastics weight content, continue to mix, promptly obtain commixed type high-adhesion thermoplastic sulfurized rubber.

2. the preparation method of thermoplastic sulfurized rubber according to claim 1, it is characterized in that: rubber is terpolymer EP rubber, isoprene-isobutylene rubber, natural rubber, trans-isoprene, cis-1,4-polybutadiene rubber, styrene-butadiene rubber(SBR), ethene-acetate ethylene copolymer, acrylic elastomer, chlorinated polyethylene rubber, chloroprene rubber, paracril or their mixture.

3. the preparation method of thermoplastic sulfurized rubber according to claim 1, it is characterized in that: plastics are polyethylene, polypropylene, polystyrene, acrylonitrile-butadiene-styrene terpolymer, vinylbenzene-acrylonitrile copolymer, polymethylmethacrylate, polybutylene terephthalate, nylon, polycarbonate or their mixture.

4. the preparation method of thermoplastic sulfurized rubber according to claim 1, it is characterized in that: the later stage, oil-filled used oil was naphthenic oil, paraffin oil, Vaseline or their mixture.