A method for preparing antistatic and wear-resistant rubber tire material

Abstract

The present invention relates to the technical field of rubber tire materials, and discloses a method for preparing an antistatic wear-resistant rubber tire material, wherein carboxyl-terminated nitrile rubber, graphene oxide, epoxidized polyester fiber, and a catalyst are added to an internal mixer, and natural rubber, zinc oxide, accelerator CZ, antioxidant RD, paraffin, stearic acid, and carbon black are added after mixing, sulfur is added after mixing, thin pass, lower sheet, and vulcanization are performed to obtain an antistatic wear-resistant rubber tire material. The carboxyl group on the surface of graphene oxide and the carboxyl-terminated nitrile rubber react with the epoxy group of the epoxidized polyester fiber, so that the graphene oxide, the polyester fiber, and the nitrile rubber undergo chemical bonding to form an organic-inorganic hybrid reinforcement system, which has a good reinforcing effect on natural rubber, and the graphene is evenly dispersed in the rubber tire material matrix to form a continuous conductive network, which reduces the volume resistivity and improves the electrical conductivity and antistatic performance.

Description

Technical Field

[0001] The invention relates to the technical field of rubber tire materials, in particular to a method for preparing an antistatic and wear-resistant rubber tire material. Background Art

[0002] Tires are important parts of vehicles such as cars, which can support the body and buffer external impacts. Common tires are natural rubber, butyl rubber, butadiene rubber, etc. Natural rubber has high mechanical strength, good elasticity, low crystallinity, and is cheap and easy to obtain. Improving the wear resistance and antistatic properties of natural rubber materials and expanding the practical application of natural rubber in high-performance tires and other materials are research hotspots.

[0003] By using natural rubber with nitrile rubber, butadiene rubber, silicone rubber, etc., a rubber composite material with excellent performance can be obtained. Modifying natural rubber with nanomaterials and polymer fibers can improve the mechanical properties of rubber materials. Graphene, as a nanomaterial with excellent performance, is widely used in rubber and other materials. The difficulty of research is to modify the surface of graphene, improve its dispersibility, and improve its compatibility with materials. Polyester fiber is a synthetic fiber with high wear resistance, high strength, and high fracture performance. Adding it to rubber, plastic and other materials can improve the wear resistance and other properties of the material. Summary of the invention

[0004] In view of the deficiencies in the prior art, the present invention provides a method for preparing an antistatic and wear-resistant rubber tire material, which solves the problem that natural rubber tire materials have poor antistatic performance and poor wear resistance.

[0005] Technical solution: A method for preparing an antistatic and wear-resistant rubber tire material is as follows:

[0006] (1) Spinning the epoxy-modified PET polyester in a melt spinning machine and stretching it in a drawing machine to obtain epoxidized polyester fibers.

[0007] (2) Add 10-25 parts by weight of carboxyl-terminated nitrile rubber, 0.5-5 parts by weight of graphene oxide, 1-8 parts by weight of epoxidized polyester fiber, and 0.02-0.08 parts by weight of a catalyst into an internal mixer, mix at 100-120° C. for 20-30 minutes, then add 75-90 parts by weight of natural rubber, 3-4.5 parts by weight of zinc oxide, 1.2-1.5 parts by weight of an accelerator CZ, 0.8-1 parts by weight of an antioxidant RD, 0.6-1 parts by weight of paraffin wax, 3.2-4 parts by weight of stearic acid, and 20-30 parts by weight of carbon black, mix for 5-10 minutes, then add 1.7-2.3 parts by weight of sulfur, thin pass and sheet in a double-roll open mill, and finally vulcanize in a flat vulcanizer at a temperature of 150-155° C. for 20-30 minutes to obtain an antistatic and wear-resistant rubber tire material.

[0008] Furthermore, in (1), the temperature of zones 1-4 of the melt spinning machine is 270-295° C., the melt pressure is 25-30 MPa, and the spinning rate is 2200-2800 m / min.

[0009] Furthermore, in (1), the temperature of the hot plate of the drawing machine is 85-90°C, the temperature of the hot plate is 185-190°C, and the drawing ratio is 2-2.5.

[0010] Furthermore, the catalyst is triethylamine, N,N-dimethylaniline or N,N-dimethylbenzylamine.

[0011] Furthermore, the preparation method of epoxy-modified PET polyester is as follows: add 100 parts by weight of polyethylene terephthalate to 1,1,2,2-tetrachloroethane, stir and dissolve, then add 2-2.6 parts by weight of dianhydride compound and 0.12-0.16 parts by weight of 4-dimethylaminopyridine, react at 50-65° C. for 12-18 hours, cool to room temperature, add 3.4-4.2 parts by weight of glycidol, 9.6-10.4 parts by weight of N,N-dicyclohexylcarbodiimide, and add 0.42-0.48 parts by weight of 4-dimethylaminopyridine, react for 24-48 hours, add acetone for precipitation, filter, wash with acetone and ethanol, and dry to obtain epoxy-modified PET polyester.

[0012] Furthermore, the dianhydride compound is 4,4'-biphenyl ether dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride or 3,3',4,4'-benzophenonetetracarboxylic dianhydride.

[0013] Technical effect: The present invention uses dianhydride monomers such as 3,3',4,4'-biphenyltetracarboxylic dianhydride as a cross-linking agent, which reacts with the terminal hydroxyl groups of polyethylene terephthalate to generate carboxyl groups, which then undergo esterification reaction with glycidol to obtain epoxidized polyester fibers, and then undergoes melt spinning to obtain epoxidized polyester fibers.

[0014] The present invention uses natural rubber and carboxyl-terminated nitrile rubber as the base rubber of the rubber tire material, adds zinc oxide, antioxidant, sulfur and other additives, and adds graphene oxide and epoxidized polyester fiber as reinforcing agents; in the high-temperature mixing process, under the action of catalysts such as N, N-dimethylbenzylamine, the carboxyl groups on the surface of graphene oxide and the carboxyl groups of the carboxyl-terminated nitrile rubber react with the epoxy groups of the epoxidized polyester fiber, so that the graphene oxide, the polyester fiber and the nitrile rubber undergo chemical bonding to form an organic-inorganic hybrid reinforcement system, which has a good reinforcing effect on natural rubber and is conducive to enhancing the mechanical strength, wear resistance and other properties of the rubber tire material. At the same time, the surface of graphene oxide modifies the organic polymer molecular chains such as nitrile rubber and polyester fiber, which is conducive to improving the dispersibility of graphene oxide, enhancing the compatibility between graphene and natural rubber, further improving the reinforcing effect of graphene oxide, and significantly improving the mechanical properties of the rubber tire material. At the same time, the graphene is uniformly dispersed in the rubber tire material matrix to form a continuous conductive network, reduce the volume resistivity, and improve the conductivity and antistatic properties. DETAILED DESCRIPTION

[0015] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0016] Example 1

[0017] (1) Add 50g of polyethylene terephthalate to 1200mL of 1,1,2,2-tetrachloroethane, stir and dissolve, then add 1.3g of 3,3',4,4'-biphenyltetracarboxylic anhydride and 0.08g of 4-dimethylaminopyridine (DMAP), react at 55°C for 18h, cool to room temperature, add 2.1g of glycidol, 0.2g of N,N-dicyclohexylcarbodiimide (DCC), and 0.24g of 4-dimethylaminopyridine, react for 48h, add acetone for precipitation, filter, wash with acetone and ethanol, and dry to obtain epoxy-modified PET polyester. The preparation reaction formula is:

[0018]

[0019] (2) Spinning the epoxy-modified PET polyester in a melt spinning machine, with the temperatures of zones 1-4 being 270°C, 285°C, 285°C, and 295°C, the melt pressure being 30 MPa, and the spinning rate being 2200 m / min; then stretching in a stretching machine, controlling the hot plate temperature to 90°C, the hot plate temperature to 195°C, and the stretching ratio to 2.3; and obtaining epoxidized polyester fibers.

[0020] (3) Add 200 g of carboxyl-terminated nitrile rubber, 5 g of graphene oxide, 10 g of epoxidized polyester fiber, and 0.2 g of catalyst N,N-dimethylbenzylamine into an internal mixer, mix at 100° C. for 30 min, then add 800 g of natural rubber, 38 g of zinc oxide, 12 g of accelerator CZ, 10 g of antioxidant RD, 7 g of paraffin, 32 g of stearic acid, and 300 g of carbon black, mix for 5 min, then add 19 g of sulfur, thin through and sheet in a double-roll open mill, and finally vulcanize in a flat vulcanizer at a temperature of 150° C. for 30 min to obtain an antistatic and wear-resistant rubber tire material.

[0021] Example 2

[0022] (1) Add 50 g of polyethylene terephthalate to 1000 mL of 1,1,2,2-tetrachloroethane, stir to dissolve, add 1.2 4,4'-biphenyl ether dianhydride and 0.07 g of 4-dimethylaminopyridine, react at 65° C. for 12 h, cool to room temperature, add 1.9 g of glycidol, 5 g of N,N-dicyclohexylcarbodiimide, and 0.22 g of 4-dimethylaminopyridine, react for 24 h, add acetone for precipitation, filter, wash with acetone and ethanol, and dry to obtain epoxy-modified PET polyester.

[0023] (2) Spinning the epoxy-modified PET polyester in a melt spinning machine, with the temperatures of zones 1-4 being 270°C, 285°C, 285°C, and 295°C, the melt pressure being 25 MPa, and the spinning rate being 2200 m / min; then stretching in a stretching machine, controlling the hot plate temperature to 85°C, the hot plate temperature to 190°C, and the stretching ratio to 2; and obtaining epoxidized polyester fibers.

[0024] (3) Add 100 g of carboxyl-terminated nitrile rubber, 20 g of graphene oxide, 30 g of epoxidized polyester fiber, and 0.43 g of catalyst N,N-dimethylaniline into an internal mixer, mix at 120° C. for 20 min, then add 900 g of natural rubber, 30 g of zinc oxide, 13 g of accelerator CZ, 10 g of antioxidant RD, 7 g of paraffin, 40 g of stearic acid, and 250 g of carbon black, mix for 10 min, then add 17 g of sulfur, thin through and sheet in a double-roll open mill, and finally vulcanize in a flat vulcanizer at a temperature of 155° C. for 25 min to obtain an antistatic and wear-resistant rubber tire material.

[0025] Example 3

[0026] (1) Add 50 g of polyethylene terephthalate to 800 mL of 1,1,2,2-tetrachloroethane, stir to dissolve, add 1 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride and 0.06 g of 4-dimethylaminopyridine, react at 60° C. for 12 h, cool to room temperature, add 1.7 g of glycidol, 4.8 g of N,N-dicyclohexylcarbodiimide, and 0.21 g of 4-dimethylaminopyridine, react for 24 h, add acetone for precipitation, filter, wash with acetone and ethanol, and dry to obtain epoxy-modified PET polyester.

[0027] (2) Spinning the epoxy-modified PET polyester in a melt spinning machine, with the temperatures of zones 1-4 being 270°C, 285°C, 285°C, and 295°C, the melt pressure being 25 MPa, and the spinning rate being 2500 m / min; then stretching in a stretching machine, controlling the hot plate temperature to be 90°C, the hot plate temperature to be 190°C, and the stretching ratio to be 2; and obtaining epoxidized polyester fibers.

[0028] (3) Add 250g of terminal carboxyl nitrile rubber, 35g of graphene oxide, 55g of epoxidized polyester fiber, and 0.64g of catalyst triethylamine into an internal mixer, mix at 120°C for 20min, then add 750g of natural rubber, 45g of zinc oxide, 12g of accelerator CZ, 10g of antioxidant RD, 6g of paraffin, 37g of stearic acid, and 200g of carbon black, mix for 5min, then add 23g of sulfur, thin through and sheet in a double-roll open mill, and finally vulcanize in a flat vulcanizer at a temperature of 150°C for 20min to obtain an antistatic and wear-resistant rubber tire material.

[0029] Example 4

[0030] (1) Add 50 g of polyethylene terephthalate to 1200 mL of 1,1,2,2-tetrachloroethane, stir to dissolve, add 1.3 g of 3,3',4,4'-benzophenonetetracarboxylic dianhydride and 0.08 g of 4-dimethylaminopyridine, react at 50° C. for 18 h, cool to room temperature, add 2 g of glycidol, 5.2 g of N,N-dicyclohexylcarbodiimide, and 0.22 g of 4-dimethylaminopyridine, react for 36 h, add acetone for precipitation, filter, wash with acetone and ethanol, and dry to obtain epoxy-modified PET polyester.

[0031] (2) The epoxy-modified PET polyester is spun in a melt spinning machine, with the temperatures of zones 1-4 being 270°C, 285°C, 285°C, and 295°C, the melt pressure being 25 MPa, and the spinning rate being 2800 m / min; then the fiber is stretched in a stretching machine, with the hot plate temperature controlled at 85°C, the hot plate temperature at 190°C, and the stretch ratio being 2.5; and the epoxidized polyester fiber is obtained.

[0032] (3) Add 150g of carboxyl-terminated nitrile rubber, 50g of graphene oxide, 0g of epoxidized polyester fiber, and 0.8g of catalyst N,N-dimethylbenzylamine into an internal mixer, mix at 110°C for 20min, then add 850g of natural rubber, 40g of zinc oxide, 15g of accelerator CZ, 8g of antioxidant RD, 10g of paraffin, 32g of stearic acid, and 200g of carbon black, mix for 8min, then add 20g of sulfur, thin through and sheet in a double-roll open mill, and finally vulcanize in a flat vulcanizer at a temperature of 150°C for 30min to obtain an antistatic and wear-resistant rubber tire material.

[0033] Comparative Example 1

[0034] (1) Add 200g of carboxyl-terminated nitrile rubber and 0.2g of catalyst N,N-dimethylbenzylamine into an internal mixer, mix at 100°C for 30min, then add 800g of natural rubber, 38g of zinc oxide, 12g of accelerator CZ, 10g of antioxidant RD, 7g of paraffin, 32g of stearic acid, and 300g of carbon black, mix for 5min, then add 19g of sulfur, thin through and sheet in a double-roll open mill, and finally vulcanize in a flat vulcanizer at a temperature of 150°C for 30min to obtain an antistatic and wear-resistant rubber tire material.

[0035] Comparative Example 2

[0036] (1) Add 200g of carboxyl-terminated nitrile rubber, 10g of epoxidized polyester fiber, and 0.2g of catalyst N,N-dimethylbenzylamine into an internal mixer, mix at 100°C for 30min, then add 800g of natural rubber, 38g of zinc oxide, 12g of accelerator CZ, 10g of antioxidant RD, 7g of paraffin, 32g of stearic acid, and 300g of carbon black, mix for 5min, then add 19g of sulfur, thin through and sheet in a double-roll open mill, and finally vulcanize in a flat vulcanizer at a temperature of 150°C for 30min to obtain an antistatic and wear-resistant rubber tire material.

[0037] Comparative Example 3

[0038] (1) Add 200g of carboxyl-terminated nitrile rubber, 5g of graphene oxide, and 0.2g of catalyst N,N-dimethylbenzylamine into an internal mixer, mix at 100°C for 30min, then add 800g of natural rubber, 38g of zinc oxide, 12g of accelerator CZ, 10g of antioxidant RD, 7g of paraffin, 32g of stearic acid, and 300g of carbon black, mix for 5min, then add 19g of sulfur, thin through and sheet in a double-roll open mill, and finally vulcanize in a flat vulcanizer at a temperature of 150°C for 30min to obtain an antistatic and wear-resistant rubber tire material.

[0039] Comparative Example 4

[0040] (1) Spinning polyethylene terephthalate in a melt spinning machine, with the temperatures of zones 1-4 being 270°C, 285°C, 285°C, and 295°C, the melt pressure being 30 MPa, and the spinning rate being 2200 m / min; then stretching in a stretching machine, controlling the hot plate temperature to be 90°C, the hot plate temperature to be 195°C, and the stretch ratio to be 2.3; and obtaining polyester fiber.

[0041] (2) Add 200 g of carboxyl-terminated nitrile rubber, 5 g of graphene oxide, 10 g of polyester fiber, and 0.2 g of catalyst N,N-dimethylbenzylamine into an internal mixer, mix at 100° C. for 30 min, then add 800 g of natural rubber, 38 g of zinc oxide, 12 g of accelerator CZ, 10 g of antioxidant RD, 7 g of paraffin, 32 g of stearic acid, and 300 g of carbon black, mix for 5 min, then add 19 g of sulfur, thin through and sheet in a double-roll open mill, and finally vulcanize in a flat vulcanizer at a temperature of 150° C. for 30 min to obtain an antistatic and wear-resistant rubber tire material.

[0042] The tensile properties were tested according to GB / T528-2009, the tear strength was tested according to GB / T 529-2009, and the abrasion resistance was tested according to GB / T 1689-2014.

[0043] The volume resistivity of rubber tire materials was tested using a volume surface resistivity tester. The test results are shown in the table below.

[0044]

[0045] As can be seen from the above table, the antistatic wear-resistant rubber tire material of Comparative Example 1 does not contain graphene oxide and epoxidized polyester fiber, and its tensile strength and elongation at break are only 13.8 MPa and 528.4%, and its tear strength is only 63.56 kN / m. The Akron wear loss is relatively large, which is 0.225 cm 3 , the volume resistivity is relatively large, which is 1.65×10 14 Ω·cm, poor mechanical properties, poor wear resistance, poor conductivity and antistatic properties.

[0046] The antistatic and wear-resistant rubber tire materials of Examples 1-4 are added with graphene oxide and epoxidized polyester fibers. During the high-temperature mixing process, under the action of catalysts such as N,N-dimethylbenzylamine, the carboxyl groups on the surface of the graphene oxide and the carboxyl groups of the carboxyl-terminated nitrile rubber react with the epoxy groups of the epoxidized polyester fibers, so that the graphene oxide, polyester fibers and nitrile rubber are chemically bonded to form an organic-inorganic hybrid reinforcement system, which has a good reinforcement effect on natural rubber and is beneficial to enhancing the mechanical strength, wear resistance and other properties of the rubber tire material.

[0047] In addition, the surface of graphene oxide is modified with nitrile rubber and polyester fiber, which is beneficial to improve the dispersibility of graphene oxide, enhance the compatibility between graphene and natural rubber, further improve the reinforcing effect of graphene oxide, significantly improve the mechanical properties, reduce the volume resistivity, and improve the conductivity and antistatic properties.

[0048] Compared with Example 1, Comparative Example 2 does not add graphene oxide, and the tensile strength and other properties of the rubber tire material are lower than those of Example 1, and the Akron abrasion loss and volume resistivity are large, and the conductivity and antistatic properties are poor.

[0049] Comparative Example 3 does not add epoxidized polyester fiber, and the polyester fiber added to Comparative Example 4 does not contain epoxy groups. Both cannot react with graphene oxide and terminal carboxyl nitrile rubber, and no organic-inorganic hybrid reinforcement system is formed. The mechanical properties of the rubber tire materials of the two are low, and the dispersion of graphene oxide is not good, the compatibility with natural rubber is poor, and the reinforcement effect is not good. The Akron abrasion loss and volume resistivity are higher than those of Comparative Example 1, and the conductivity and antistatic properties are not good.

[0050] The above are only preferred embodiments of the present invention and are not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A method for preparing an antistatic and wear-resistant rubber tire material, characterized in that: The preparation method is: (1) spinning epoxy-modified PET polyester in a melt spinning machine and drawing it in a drawing machine to obtain epoxidized polyester fiber; (2) Add 10-25 parts by weight of carboxyl-terminated nitrile rubber, 0.5-5 parts by weight of graphene oxide, 1-8 parts by weight of epoxidized polyester fiber, and 0.02-0.08 parts by weight of a catalyst into an internal mixer, mix at 100-120° C. for 20-30 minutes, then add 75-90 parts by weight of natural rubber, 3-4.5 parts by weight of zinc oxide, 1.2-1.5 parts by weight of an accelerator CZ, 0.8-1 parts by weight of an antioxidant RD, 0.6-1 parts by weight of paraffin wax, 3.2-4 parts by weight of stearic acid, and 20-30 parts by weight of carbon black, mix for 5-10 minutes, then add 1.7-2.3 parts by weight of sulfur, thin pass and sheet in a double-roll open mill, and finally vulcanize in a flat vulcanizer at a temperature of 150-155° C. for 20-30 minutes to obtain an antistatic and wear-resistant rubber tire material.

2. The method for preparing the antistatic wear-resistant rubber tire material according to claim 1, characterized in that: In the above (1), the temperature of zones 1-4 of the melt spinning machine is 270-295° C., the melt pressure is 25-30 MPa, and the spinning rate is 2200-2800 m / min.

3. The method for preparing the antistatic wear-resistant rubber tire material according to claim 1, characterized in that: In the above (1), the temperature of the hot plate of the drawing machine is 85-90°C, the temperature of the hot plate is 185-190°C, and the drawing ratio is 2-2.

5.

4. The method for preparing the antistatic wear-resistant rubber tire material according to claim 1, characterized in that: The catalyst is triethylamine, N,N-dimethylaniline or N,N-dimethylbenzylamine.

5. The method for preparing the antistatic wear-resistant rubber tire material according to claim 1, characterized in that: The preparation method of the epoxy-modified PET polyester comprises the following steps: adding polyethylene terephthalate to 1,1,2,2-tetrachloroethane, stirring and dissolving, adding a dianhydride compound and 4-dimethylaminopyridine, carrying out a primary reaction, cooling to room temperature, adding glycidol and N,N-dicyclohexylcarbodiimide, adding 4-dimethylaminopyridine, carrying out a secondary reaction, adding acetone for precipitation, filtering, washing with acetone and ethanol, and drying to obtain the epoxy-modified PET polyester.

6. The method for preparing the antistatic wear-resistant rubber tire material according to claim 5, characterized in that: The primary reaction is carried out at 50-65°C for 12-18 hours.

7. The method for preparing the antistatic wear-resistant rubber tire material according to claim 5, characterized in that: The secondary reaction was carried out at room temperature for 24-48 h.

8. The method for preparing the antistatic wear-resistant rubber tire material according to claim 5, characterized in that: The mass ratio of the polyethylene terephthalate, the dianhydride compound, 4-dimethylaminopyridine, glycidol, N,N-dicyclohexylcarbodiimide, and the added 4-dimethylaminopyridine is 100:(2-2.6):(0.12-0.16):(3.4-4.2):(9.6-10.4):(0.42-0.48).

9. The method for preparing the antistatic wear-resistant rubber tire material according to claim 5, characterized in that: The dianhydride compound is 4,4'-biphenyl ether dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride or 3,3',4,4'-benzophenonetetracarboxylic dianhydride.

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