High-strength wear-resistant plastic material and method for producing same

Abstract

The application relates to the technical field of polyethylene, and discloses a high-strength wear-resistant plastic material and a preparation method thereof, wherein 50-70 parts of polyethylene resin, 3-8 parts of polybutadiene grafted polysiloxane, 6.2-10.7 parts of fillers, 30-50 parts of silicone rubber and the like are mixed and vulcanized to obtain the high-strength wear-resistant plastic material. The polybutadiene grafted polysiloxane plays a role in compatibilizing the polyethylene and the silicone rubber, improves the interfacial compatibility of the polyethylene and the silicone rubber, significantly improves the tensile strength and impact strength of the plastic material, the compatibility of the silicone rubber and the polyethylene is good, the silicone rubber is uniformly dispersed in the polyethylene matrix, the friction and wear loss of the polyethylene is reduced, and the wear resistance is improved.

Description

Technical Field

[0001] This invention relates to the field of polyethylene technology, specifically to a high-strength wear-resistant plastic material and its preparation method. Background Technology

[0002] Polyethylene is a high-performance thermoplastic resin that is odorless, non-toxic, has good low-temperature resistance, and excellent toughness. It is mainly used to manufacture films, containers, building materials, and pipes. However, polyethylene has relatively low mechanical strength and poor abrasion resistance, which limits its practical applications. Silicone rubber, on the other hand, has excellent high-temperature resistance, abrasion resistance, weather resistance, and mechanical properties. Blending it with polyethylene, polyvinyl chloride, polystyrene, and polycarbonate can produce high-performance plastic composite materials.

[0003] Due to the significant structural differences between silicone rubber and polyethylene, their compatibility is very poor. Mixing the two will affect the performance of the composite material. Patent publication number CN102702598B discloses a halogen-free flame-retardant polyolefin cable material resistant to 150℃ and its preparation method. High-density polyethylene, ethylene-octene copolymer, silicone rubber, PE-g-MAH compatibilizer, etc. are extruded and granulated to obtain a polyethylene cable material with excellent temperature resistance. However, this polyethylene material does not have good wear resistance. Summary of the Invention

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

[0005] The technical solution of this invention is: a high-strength wear-resistant plastic material and its preparation method. The preparation method is as follows: by weight, 50-70 parts 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 are added to a two-roll mill for mixing, then 30-50 parts of silicone rubber are added for a second mixing, and finally 1.1-1.4 parts of vulcanizing agent are added for vulcanization to obtain the high-strength wear-resistant plastic material.

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

[0007] Preferably, the additives include stearic acid and polyethylene wax.

[0008] Preferably, the antioxidants include antioxidant 1010 and antioxidant 168.

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

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

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

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

[0013] (1) By weight, add 100 parts of aminopropyl polydimethylsiloxane and 3.2-4.6 parts of mercaptoacetic acid to N,N-dimethylacetamide, stir, then 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℃ for 6-10 h. After filtration, distill under reduced pressure, wash with methanol, and dry to obtain mercaptopolysiloxane. The preparation reaction formula is:

[0014]

[0015] (2) By weight, add 100 parts of mercaptopolysiloxane and 120-260 parts of polybutadiene to N,N-dimethylacetamide, 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 beneficial technical effects of this invention are as follows: This invention involves an addition reaction between the terminal thiol group of a mercaptopolysiloxane and the alkenyl group in the main chain of polybutadiene to obtain a polybutadiene-grafted polysiloxane. This grafted polysiloxane is then mixed with polyethylene, silicone rubber, fillers, vulcanizing agents, etc., and vulcanized at high temperature to obtain a high-strength, wear-resistant plastic material. The addition reaction between the alkenyl group of polybutadiene and the thiol group of the polysiloxane transforms the C=C double bond of the alkenyl group into a C-C single bond, forming a saturated polyolefin molecular chain with a molecular chain structure more similar to that of polyethylene. Furthermore, the introduction of a polysiloxane structure similar to that of silicone rubber into the side chain of polybutadiene allows the polybutadiene-grafted polysiloxane to act as a compatibilizer for both polyethylene and silicone rubber. This improves the interfacial compatibility between polyethylene and silicone rubber, significantly increasing the tensile strength and impact strength of the plastic material. Additionally, the silicone rubber exhibits excellent compatibility with polyethylene, is uniformly dispersed within the polyethylene matrix, reducing the amount of frictional wear in polyethylene and improving its wear resistance. Detailed Implementation

[0017] The embodiments of the present invention are described in detail below. These embodiments are exemplary and are only used to explain the present invention, and should not be construed as limiting the present invention. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. The terminology used herein in the specification of the present invention is for the purpose of describing particular embodiments only and is not intended to limit the present invention.

[0018] The following polyethylene grade LL6201XR is sourced from Dongguan Xinrui New Materials Co., Ltd. The polybutadiene grade RB830 is also sourced from Dongguan Xinrui New Materials Co., Ltd. The silicone rubber grade CHN-ROLL-40U is sourced from Guangzhou Zhongxiang Trading Co., Ltd. The aminopropyl polydimethylsiloxane, with a molecular weight of approximately 3500, is sourced from Hubei Dali Chemical Co., Ltd.

[0019] Example 1:

[0020] (1) Add 200g of aminopropyl polydimethylsiloxane and 7.7g of mercaptoacetic acid to 3L of N,N-dimethylacetamide, stir, add 10.2g of N-hydroxysuccinimide and 16.5g of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, react at 20℃ for 10h, filter, distill under reduced pressure, wash with methanol, and dry to obtain mercaptopolysiloxane.

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

[0022] (3) Add 7kg polyethylene resin, 0.3kg polybutadiene-grafted polysiloxane, 1kg calcium carbonate, 20g zinc oxide, 60g stearic acid, 70g polyethylene wax, and 22g antioxidant 1010 to a two-roll mill and mix at 85℃ for 30min. Then add 3kg silicone rubber and mix at 120℃ for 20min. Finally add 110g dicumyl peroxide and vulcanize at 180℃ for 15min to obtain a high-strength wear-resistant plastic material.

[0023] Example 2:

[0024] (1) Add 200g of aminopropyl polydimethylsiloxane and 9.2g of mercaptoacetic acid to 2.5L of N,N-dimethylacetamide, stir, add 11.6g of N-hydroxysuccinimide and 19.2g of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, react at 25℃ for 6h, filter, distill under reduced pressure, wash with methanol, and dry to obtain mercaptopolysiloxane.

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

[0026] (3) Add 6 kg of polyethylene resin, 0.57 kg of polybutadiene-grafted polysiloxane, 0.8 kg of calcium carbonate, 40 g of zinc oxide, 80 g of stearic acid, 50 g of polyethylene wax, and 15 g of antioxidant 168 to a two-roll mill and mix at 80°C for 30 min. Then add 4 kg of silicone rubber and mix at 135°C for 10 min. Finally add 126 g of dicumyl peroxide and vulcanize at 170°C for 20 min to obtain a high-strength wear-resistant plastic material.

[0027] Example 3:

[0028] (1) Add 200g of aminopropyl polydimethylsiloxane and 6.4g of mercaptoacetic acid to 2.5L of N,N-dimethylacetamide, stir, add 8.2g of N-hydroxysuccinimide and 13.6g of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, react at 35℃ for 6h, filter, distill under reduced pressure, wash with methanol, and dry to obtain mercaptopolysiloxane.

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

[0030] (3) Add 5kg of polyethylene resin, 0.8kg of polybutadiene-grafted polysiloxane, 0.6kg of calcium carbonate, 70g of zinc oxide, 90g of stearic acid, 70g of polyethylene wax, and 17g of antioxidant 168 to a two-roll mill and mix at 90°C for 15 minutes. Then add 5kg of silicone rubber and mix at 130°C for 20 minutes. Finally, add 140g of dicumyl peroxide and vulcanize at 170°C for 25 minutes to obtain a high-strength wear-resistant plastic material.

[0031] Comparative Example 1:

[0032] (1) Add 7kg polyethylene resin, 1kg calcium carbonate, 20g zinc oxide, 60g stearic acid, 70g polyethylene wax and 22g antioxidant 1010 to a two-roll mill and mix at 85℃ for 30min. Then add 3kg silicone rubber and mix at 120℃ for 20min. Finally add 110g dicumyl peroxide and vulcanize at 180℃ for 15min to obtain plastic material.

[0033] Comparative Example 2:

[0034] (1) Add 7kg polyethylene resin, 0.3kg polybutadiene, 1kg calcium carbonate, 20g zinc oxide, 60g stearic acid, 70g polyethylene wax, and 22g antioxidant 1010 to a two-roll mill and mix at 85°C for 30 minutes. Then add 3kg silicone rubber and mix at 120°C for 20 minutes. Finally, add 110g dicumyl peroxide and vulcanize at 180°C for 15 minutes to obtain the plastic material.

[0035] Comparative Example 3

[0036] (1) Add 7kg polyethylene resin, 0.3kg mercaptopolysiloxane, 1kg calcium carbonate, 20g zinc oxide, 60g stearic acid, 70g polyethylene wax, and 22g antioxidant 1010 to a two-roll mill and mix at 85°C for 30 minutes. Then add 3kg silicone rubber and mix at 120°C for 20 minutes. Finally, add 110g dicumyl peroxide and vulcanize at 180°C for 15 minutes to obtain the plastic material.

[0037] Comparative Example 4

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

[0039] (2) Add 7kg polyethylene resin, 0.3kg polybutadiene-polysiloxane blend, 1kg calcium carbonate, 20g zinc oxide, 60g stearic acid, 70g polyethylene wax, and 22g antioxidant 1010 to a two-roll mill and mix at 85℃ for 30min. Then add 3kg silicone rubber and mix at 120℃ for 20min. Finally add 110g dicumyl peroxide and vulcanize at 180℃ for 15min to obtain plastic material.

[0040] Table 1 Properties of Plastic Materials

[0041]

[0042] Comparative Example 1 involved mixing polyethylene, silicone rubber, and fillers, followed by high-temperature vulcanization. The resulting plastic material exhibited low tensile strength, elongation at break, and impact strength, along with high wear resistance, indicating poor mechanical strength and abrasion resistance. This was primarily due to the poor compatibility between polyethylene and silicone rubber, which severely impacted the mechanical properties of the plastic material.

[0043] In each embodiment, polybutadiene-grafted polysiloxane was added. The alkenyl group of polybutadiene undergoes an addition reaction with the mercapto group of polysiloxane, and the alkenyl C=C double bond is converted into a C-C single bond to form a saturated polyolefin molecular chain, which has a molecular chain structure more similar to that of polyethylene. Furthermore, the polybutadiene side chain introduces a polysiloxane structure similar to that of silicone rubber, so that the polybutadiene-grafted polysiloxane acts as a compatibilizer for polyethylene and silicone rubber. As a compatibilizer, it improves the interfacial compatibility between polyethylene and silicone rubber, thereby giving the plastic material better mechanical properties, improving tensile strength and impact strength. In addition, the addition of silicone rubber is beneficial to improving the wear resistance of polyethylene and reducing friction and wear.

[0044] Comparative Example 2 included polybutadiene, which has poor compatibility with silicone rubber and is difficult to compatibilize polyethylene and silicone rubber, resulting in poor mechanical strength and wear resistance of the plastic material.

[0045] In Comparative Example 3, mercaptopolysiloxane was added. It has poor compatibility with polyethylene and is difficult to compatibilize polyethylene and silicone rubber, resulting in poor mechanical strength and wear resistance of the plastic material.

[0046] Comparative Example 4 incorporated a polybutadiene-polysiloxane blend, which slightly improved the material's performance. This may be because a small amount of mercaptopolysiloxane and polybutadiene reacted during 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 embodiments described above are merely illustrative of several implementations of the present invention, and while the descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the invention patent. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of the present invention, and these all fall within the protection scope of the present invention. Therefore, the protection scope of this invention patent should 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 is as follows: by weight, 50-70 parts 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 are added to an open mill for mixing, then 30-50 parts of silicone rubber are added for secondary mixing, and finally 1.1-1.4 parts of vulcanizing agent are added for vulcanization to obtain a high-strength wear-resistant plastic material; Methods for preparing polybutadiene-grafted polysiloxanes include: (1) Add aminopropyl polydimethylsiloxane and mercaptoacetic acid to N,N-dimethylacetamide, stir, add N-hydroxysuccinimide and 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, react at 20-35℃ for 6-10h, filter, distill the filtrate under reduced pressure, wash the product, dry, and obtain mercaptopolysiloxane; (2) Add mercaptopolysiloxane and polybutadiene to N,N-dimethylacetamide, stir, add benzoin dimethyl ether, irradiate under ultraviolet light source for 2-3 hours, add ethanol to the solution, filter, wash the solid, dry, and obtain polybutadiene-grafted polysiloxane. By weight, the amount of aminopropyl polydimethylsiloxane is 100 parts, mercaptoacetic acid is 3.2-4.6 parts, and after stirring, N-hydroxysuccinimide is added in the amount of 4.1-5.8 parts and 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride in the amount of 6.8-9.6 parts; The amount of mercaptopolysiloxane used, by weight, is 100 parts, polybutadiene is 120-260 parts, and dimethyl benzoate is 0.23-0.28 parts; The additives include any one or a combination of stearic acid and polyethylene wax.

2. The method for preparing the 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 the 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.

4. The method for preparing the high-strength wear-resistant plastic material according to claim 1, characterized in that, The mixing temperature is 80-90℃ and the time is 15-30 min; the secondary mixing temperature is 120-135℃ and the time is 10-20 min.

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

6. A high-strength wear-resistant plastic material obtained by the preparation method according to any one of claims 1-5.

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