High-strength wear-resistant plastic material and preparation method thereof

Abstract

The invention relates to the technical field of polyethylene, and discloses a high-strength wear-resistant plastic material and a preparation method thereof.The high-strength wear-resistant plastic material is obtained by mixing and vulcanizing 50-70 parts of polyethylene resin, 3-8 parts of polybutadiene grafted polysiloxane, 6.2-10.7 parts of filler, 30-50 parts of silicone rubber and the like. The polybutadiene grafted polysiloxane plays a role in compatibilizing the polyethylene and the silicone rubber, the interfacial compatibility of the polyethylene and the silicone rubber is improved, the tensile strength and the impact strength of the plastic material are remarkably improved, the compatibility of the silicone rubber and the polyethylene is very good, the silicone rubber is uniformly dispersed in a polyethylene matrix, the frictional wear loss of the polyethylene is reduced, and the service life of the plastic material is prolonged. And the wear resistance is improved.

Description

Technical Field

[0001] The present invention relates to the technical field of polyethylene, in particular to a high-strength wear-resistant plastic material and a preparation method thereof. Background Art

[0002] Polyethylene is a high-performance thermoplastic resin. It is odorless, non-toxic, has excellent low-temperature resistance, and boasts excellent toughness. It is primarily used in the manufacture of films, containers, building materials, pipes, and other materials. However, polyethylene suffers from low mechanical strength and poor wear resistance, limiting its practical application. Silicone rubber exhibits excellent high-temperature resistance, wear resistance, weather resistance, and mechanical properties. When blended with polyethylene, polyvinyl chloride, polystyrene, polycarbonate, and other materials, it can produce high-performance plastic composites.

[0003] Due to the significant structural differences between silicone rubber and polyethylene, their compatibility is poor. Mixing the two can affect the composite's performance. Patent publication CN102702598B discloses a 150°C-resistant, halogen-free, flame-retardant polyolefin cable material and its preparation method. High-density polyethylene, ethylene-octene copolymer, silicone rubber, and a PE-g-MAH compatibilizer are extruded and granulated to produce a polyethylene cable material with excellent temperature resistance. However, this polyethylene material lacks good wear resistance. Summary of the Invention

[0004] The technical problem solved by the present invention is to improve the compatibility of polyethylene and silicone rubber and enhance the mechanical strength and wear resistance of polyethylene plastic.

[0005] The technical solution of the present invention is: a high-strength wear-resistant plastic material and a preparation method thereof. The preparation method comprises the following steps: adding 50-70 parts by weight of polyethylene resin, 3-8 parts of polybutadiene grafted polysiloxane, 6.2-10.7 parts of filler, 1.3-1.6 parts of additives, and 0.15-0.22 parts of antioxidant to an open mill for mixing; then adding 30-50 parts of silicone rubber for secondary mixing; and finally adding 1.1-1.4 parts of vulcanizing agent for vulcanization to obtain the high-strength wear-resistant plastic material.

[0006] Preferably, the filler includes calcium carbonate and zinc oxide.

[0007] Preferably, the auxiliary agent includes stearic acid and polyethylene wax.

[0008] Preferably, the antioxidant includes antioxidant 1010 and antioxidant 168.

[0009] Preferably, the vulcanizing agent comprises dicumyl peroxide.

[0010] Preferably, the temperature during mixing is 80-90° C., and the time is 15-30 min; the secondary temperature is 120-135° C., and the time is 10-20 min.

[0011] Preferably, the vulcanization temperature is 170-180° C. and the vulcanization time is 15-25 minutes.

[0012] Preferably, the preparation method of polybutadiene grafted polysiloxane comprises:

[0013] (1) Add 100 parts by weight of aminopropyl polydimethylsiloxane and 3.2-4.6 parts of mercaptoacetic acid to N,N-dimethylacetamide, stir, add 4.1-5.8 parts of N-hydroxysuccinimide and 6.8-9.6 parts of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, react at 20-35°C for 6-10 hours, filter, distill the filtrate under reduced pressure, wash with methanol, and dry to obtain mercaptopolysiloxane. The preparation reaction formula is:

[0014]

[0015] (2) Add 100 parts of mercaptopolysiloxane and 120-260 parts of polybutadiene to N,N-dimethylacetamide by weight, stir, add 0.23-0.28 parts of benzoin dimethyl ether, irradiate under ultraviolet light for 2-3 hours, add ethanol to the solution, filter, wash the solid with ethanol, and dry to obtain polybutadiene-grafted polysiloxane.

[0016] The present invention has the following beneficial technical effects: The present invention conducts an addition reaction between the terminal mercapto groups of mercaptopolysiloxane and the alkenyl groups in the polybutadiene main chain to obtain polybutadiene-grafted polysiloxane, which is then mixed with polyethylene, silicone rubber, fillers, a vulcanizing agent, and the like, and subjected to high-temperature vulcanization to obtain a high-strength, wear-resistant plastic material. The alkenyl groups of polybutadiene and the mercapto groups of polysiloxane undergo an addition reaction, whereby the alkenyl C=C double bond generates a C-C single bond, forming a saturated polyolefin molecular chain having a molecular chain structure more similar to that of the polyethylene molecular chain. Furthermore, the polybutadiene side chain introduces a polysiloxane structure similar to that of silicone rubber, allowing the polybutadiene-grafted polysiloxane to act as a compatibilizer for polyethylene and silicone rubber. As a compatibilizer, it improves the interfacial compatibility between polyethylene and silicone rubber, significantly improving the tensile strength and impact strength of the plastic material. Furthermore, the silicone rubber has excellent compatibility with polyethylene and is uniformly dispersed in the polyethylene matrix, reducing the friction and wear of the polyethylene and improving wear resistance. DETAILED DESCRIPTION

[0017] Embodiments of the present invention are described in detail below. The embodiments described below are exemplary and are only used to explain the present invention, and are not to be construed as limiting the present invention. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those generally understood by those skilled in the art of the present invention. The terms used herein in the specification of the present invention are only for the purpose of describing specific embodiments and are not intended to limit the present invention.

[0018] The following polyethylene, model LL6201XR, was sourced from Dongguan Xinrui New Materials Co., Ltd. Polybutadiene, model RB830, was sourced from Dongguan Xinrui New Materials Co., Ltd. Silicone rubber, model CHN-ROLL-40U, was sourced from Guangzhou Zhongxiang Trading Co., Ltd. Aminopropyl polydimethylsiloxane, molecular weight approximately 3500, was sourced from Hubei Dali Chemical Co., Ltd.

[0019] Example 1:

[0020] (1) To 3 L of N,N-dimethylacetamide, 200 g of aminopropyl polydimethylsiloxane and 7.7 g of mercaptoacetic acid were added, and after stirring, 10.2 g of N-hydroxysuccinimide and 16.5 g of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride were added. The mixture was reacted at 20°C for 10 h. After filtering, the filtrate was distilled under reduced pressure, washed with methanol, and dried to obtain mercaptopolysiloxane.

[0021] (2) Add 200 g of mercaptopolysiloxane and 240 g of polybutadiene to 3 L of N,N-dimethylacetamide, stir, add 0.46 g of benzoin dimethyl ether, and irradiate under a UV light source (power 40 W, wavelength between 315-380 nm) to react for 3 h. Add ethanol to the solution, filter, wash the solid with ethanol, and dry to obtain polybutadiene-grafted polysiloxane.

[0022] (3) 7 kg polyethylene resin, 0.3 kg polybutadiene grafted polysiloxane, 1 kg calcium carbonate, 20 g zinc oxide, 60 g stearic acid, 70 g polyethylene wax, and 22 g antioxidant 1010 were added to an open mill and mixed at 85 ° C for 30 min. Then, 3 kg silicone rubber was added and mixed at 120 ° C for 20 min. Finally, 110 g diisopropylbenzene peroxide was added and vulcanized at 180 ° C for 15 min to obtain a high-strength wear-resistant plastic material.

[0023] Example 2:

[0024] (1) To 2.5 L of N,N-dimethylacetamide, 200 g of aminopropyl polydimethylsiloxane and 9.2 g of mercaptoacetic acid were added, and after stirring, 11.6 g of N-hydroxysuccinimide and 19.2 g of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride were added. The mixture was reacted at 25° C. for 6 h. After filtering, the filtrate was distilled under reduced pressure, washed with methanol, and dried to obtain mercaptopolysiloxane.

[0025] (2) Add 200 g of mercaptopolysiloxane and 520 g of polybutadiene to 4 L of N,N-dimethylacetamide, stir, add 0.56 g of benzoin dimethyl ether, and irradiate under a UV light source (power 40 W, wavelength between 315-380 nm) to react for 3 h. Add ethanol to the solution, filter, wash the solid with ethanol, and dry to obtain polybutadiene-grafted polysiloxane.

[0026] (3) 6 kg polyethylene resin, 0.57 kg polybutadiene grafted polysiloxane, 0.8 kg calcium carbonate, 40 g zinc oxide, 80 g stearic acid, 50 g polyethylene wax, and 15 g antioxidant 168 were added to an open mill and mixed at 80 ° C for 30 min. Then, 4 kg silicone rubber was added and mixed at 135 ° C for 10 min. Finally, 126 g diisopropylbenzene peroxide was added and vulcanized at 170 ° C for 20 min to obtain a high-strength wear-resistant plastic material.

[0027] Example 3:

[0028] (1) To 2.5 L of N,N-dimethylacetamide, 200 g of aminopropyl polydimethylsiloxane and 6.4 g of mercaptoacetic acid were added, and after stirring, 8.2 g of N-hydroxysuccinimide and 13.6 g of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride were added. The mixture was reacted at 35° C. for 6 h. After filtering, the filtrate was distilled under reduced pressure, washed with methanol, and dried to obtain mercaptopolysiloxane.

[0029] (2) Add 200 g of mercaptopolysiloxane and 360 g of polybutadiene to 3 L of N,N-dimethylacetamide, stir, add 0.5 g of benzoin dimethyl ether, and irradiate under a UV light source (power 50 W, wavelength between 315-380 nm) to react for 2 h. Add ethanol to the solution, filter, wash the solid with ethanol, and dry to obtain polybutadiene-grafted polysiloxane.

[0030] (3) 5 kg polyethylene resin, 0.8 kg polybutadiene grafted polysiloxane, 0.6 kg calcium carbonate, 70 g zinc oxide, 90 g stearic acid, 70 g polyethylene wax, and 17 g antioxidant 168 were added to an open mill and mixed at 90 ° C for 15 min. Then, 5 kg silicone rubber was added and mixed at 130 ° C for 20 min. Finally, 140 g diisopropylbenzene peroxide was added and vulcanized at 170 ° C for 25 min to obtain a high-strength wear-resistant plastic material.

[0031] Comparative Example 1:

[0032] (1) 7 kg of polyethylene resin, 1 kg of calcium carbonate, 20 g of zinc oxide, 60 g of stearic acid, 70 g of polyethylene wax, and 22 g of antioxidant 1010 were added to an open mill and mixed at 85°C for 30 min. Then, 3 kg of silicone rubber was added and mixed at 120°C for 20 min. Finally, 110 g of diisopropylbenzene peroxide was added and vulcanized at 180°C for 15 min to obtain a plastic material.

[0033] Comparative Example 2:

[0034] (1) 7 kg polyethylene resin, 0.3 kg polybutadiene, 1 kg calcium carbonate, 20 g zinc oxide, 60 g stearic acid, 70 g polyethylene wax, and 22 g antioxidant 1010 were added to an open mill and mixed at 85°C for 30 min. Then, 3 kg silicone rubber was added and mixed at 120°C for 20 min. Finally, 110 g diisopropylbenzene peroxide was added and vulcanized at 180°C for 15 min to obtain a plastic material.

[0035] Comparative Example 3

[0036] (1) 7 kg of polyethylene resin, 0.3 kg of mercaptopolysiloxane, 1 kg of calcium carbonate, 20 g of zinc oxide, 60 g of stearic acid, 70 g of polyethylene wax, and 22 g of antioxidant 1010 were added to an open mill and mixed at 85 ° C for 30 min. Then, 3 kg of silicone rubber was added and mixed at 120 ° C for 20 min. Finally, 110 g of diisopropylbenzene peroxide was added and vulcanized at 180 ° C for 15 min to obtain a plastic material.

[0037] Comparative Example 4

[0038] (1) 200 g of mercaptopolysiloxane and 240 g of polybutadiene were stirred and mixed to obtain a polybutadiene-polysiloxane blend.

[0039] (2) 7 kg of polyethylene resin, 0.3 kg of polybutadiene-polysiloxane blend, 1 kg of calcium carbonate, 20 g of zinc oxide, 60 g of stearic acid, 70 g of polyethylene wax, and 22 g of antioxidant 1010 were added to an open mill and mixed at 85°C for 30 min. Then, 3 kg of silicone rubber was added and mixed at 120°C for 20 min. Finally, 110 g of diisopropylbenzene peroxide was added and vulcanized at 180°C for 15 min to obtain a plastic material.

[0040] Table 1 Properties of plastic materials

[0041]

[0042] Comparative Example 1: Polyethylene, silicone rubber, and fillers were mixed and then vulcanized at high temperature. The resulting plastic material had low tensile strength, elongation at break, and impact strength, and exhibited high wear, resulting in poor mechanical strength and wear resistance. This was primarily due to the poor compatibility between polyethylene and silicone rubber, which severely affected the mechanical properties of the plastic material.

[0043] In each embodiment, polybutadiene-grafted polysiloxane is added, wherein the alkenyl group of polybutadiene reacts with the mercapto group of polysiloxane to form a C-C single bond through the alkenyl C=C double bond, thereby forming a saturated polyolefin molecular chain having a molecular chain structure more similar to that of the polyethylene molecular chain. In addition, the polybutadiene side chain introduces a polysiloxane structure similar to that of silicone rubber, so that the polybutadiene-grafted polysiloxane plays the role of compatibilizing polyethylene and silicone rubber. As a compatibilizer, it improves the interfacial compatibility between polyethylene and silicone rubber, thereby making the plastic material have better mechanical properties, improved tensile strength and impact strength, and the addition of silicone rubber is beneficial to improving the wear resistance of polyethylene and reducing friction wear.

[0044] In Comparative Example 2, polybutadiene was added, which has poor compatibility with silicone rubber and is difficult to play the role of compatibilizing polyethylene and silicone rubber, resulting in poor mechanical strength and wear resistance of the plastic material.

[0045] Comparative Example 3 adds mercaptopolysiloxane, which has poor compatibility with polyethylene and is difficult to play the role of compatibilizing polyethylene and silicone rubber, resulting in poor mechanical strength and wear resistance of the plastic material.

[0046] In Comparative Example 4, a polybutadiene-polysiloxane blend was added, and the performance of the material was slightly improved. This may be because a small amount of mercaptopolysiloxane reacted with polybutadiene under high-temperature mixing and vulcanization. However, the compatibilization was poor, and the tensile strength, impact strength and other properties were lower than those in Example 1.

[0047] The above-described embodiments merely illustrate several implementations of the present invention, and while their descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the patent. It should be noted that a person skilled in the art would be able to make numerous variations and improvements without departing from the spirit of the present invention, all of which fall within the scope of protection of the present invention. Therefore, the scope of protection of the patent for this invention shall be determined by the appended claims.

Claims

1. A method for preparing a high-strength wear-resistant plastic material, characterized in that: The preparation method comprises: adding 50-70 parts by weight of polyethylene resin, 3-8 parts of polybutadiene grafted polysiloxane, 6.2-10.7 parts of filler, 1.3-1.6 parts of auxiliary agent, and 0.15-0.22 parts of antioxidant into an open mill for mixing; then adding 30-50 parts of silicone rubber, mixing for a second time, and finally adding 1.1-1.4 parts of vulcanizing agent for vulcanization to obtain a high-strength and wear-resistant plastic material.

2. The method for preparing a high-strength wear-resistant plastic material according to claim 1, characterized in that: The filler includes any one or a combination of calcium carbonate and zinc oxide.

3. The method for preparing a high-strength wear-resistant plastic material according to claim 1, characterized in that: The auxiliary agent includes any one or a combination of stearic acid and polyethylene wax.

4. The method for preparing a high-strength wear-resistant plastic material according to claim 1, characterized in that: The antioxidant includes any one or a combination of antioxidant 1010 and antioxidant 168; the vulcanizing agent includes dicumyl peroxide.

5. The method for preparing a high-strength wear-resistant plastic material according to claim 1, characterized in that: The temperature during the mixing is 80-90° C., and the time is 15-30 minutes; the temperature of the second mixing is 120-135° C., and the time is 10-20 minutes.

6. The method for preparing a high-strength wear-resistant plastic material according to claim 1, characterized in that: The vulcanization temperature is 170-180° C. and the vulcanization time is 15-25 minutes.

7. The method for preparing a high-strength wear-resistant plastic material according to claim 1, characterized in that: The preparation method of the polybutadiene grafted polysiloxane comprises: (1) Adding aminopropyl polydimethylsiloxane and mercaptoacetic acid to N,N-dimethylacetamide, stirring, adding N-hydroxysuccinimide and 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, reacting at 20-35° C. for 6-10 hours, filtering, and distilling the filtrate under reduced pressure, washing the product, and drying to obtain mercaptopolysiloxane; (2) Add mercaptopolysiloxane and polybutadiene to N,N-dimethylacetamide, stir, add benzoin dimethyl ether, irradiate under ultraviolet light source to react for 2-3 hours, add ethanol to the solution, filter, wash the solid, and dry to obtain polybutadiene-grafted polysiloxane.

8. The method for preparing a high-strength wear-resistant plastic material according to claim 7, characterized in that: By weight, the amount of aminopropyl polydimethylsiloxane used is 100 parts, and the amount of thioglycolic acid is 3.2-4.6 parts. After stirring, 4.1-5.8 parts of N-hydroxysuccinimide and 6.8-9.6 parts of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride are added.

9. The method for preparing a high-strength wear-resistant plastic material according to claim 7, characterized in that: In parts by weight, the amount of the mercaptopolysiloxane is 100 parts, the amount of polybutadiene is 120-260 parts, and the amount of benzoin dimethyl ether is 0.23-0.28 parts.

10. A high-strength wear-resistant plastic material obtained by the preparation method according to any one of claims 1 to 9.

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