High-wear-resistance plastic particles and preparation method thereof

Abstract

The invention relates to high-wear-resistance plastic particles and a preparation method thereof, and belongs to the technical field of high polymer materials. The high-wear-resistance plastic particles comprise the following components in parts by weight: 60-80 parts of polyphenylene sulfide, 1-4 parts of a lubricant, 0.1-0.5 part of an antioxidant, 20-40 parts of glass fibers, 1-4 parts of a modified flame retardant and 5-15 parts of a high-temperature-resistant toughening agent, the high-wear-resistance plastic particle prepared by the invention not only has a good flame-retardant effect, but also has excellent high-temperature-resistant and toughening effects.

Description

Technical Field

[0001] The present invention belongs to the technical field of polymer materials, and particularly relates to a highly wear-resistant plastic particle and a preparation method thereof. Background Art

[0002] Polyphenylene sulfide (PPS), as a special engineering plastic with excellent comprehensive properties, is a polymer composed of alternating benzene rings and sulfur atoms. It has high rigidity and regularity, and also has characteristics such as corrosion resistance, aging resistance, balanced physical and mechanical properties, good dimensional stability, and excellent electrical properties, showing outstanding advantages in various harsh environments.

[0003] However, with the rapid progress of science and technology and the booming development of industry, traditional highly wear-resistant PPS plastic particles have poor heat resistance, are prone to oxidation and deformation at high temperatures, and are brittle, thus limiting their application in high-temperature fields; in addition, although PPS has certain flame retardancy, with the improvement of actual application requirements, its own flame retardancy no longer meets the needs. Therefore, researching and developing highly wear-resistant plastic particles with excellent properties has important practical significance and application value. Summary of the Invention

[0004] In order to solve the above technical problems, the present invention provides a highly wear-resistant plastic particle and a preparation method thereof.

[0005] The object of the present invention can be achieved by the following technical solutions: A highly wear-resistant plastic particle and a preparation method thereof, comprising the following raw materials in parts by weight: 60 - 80 parts of polyphenylene sulfide, 1 - 4 parts of lubricant, 0.1 - 0.5 part of antioxidant, 20 - 40 parts of glass fiber, 1 - 4 parts of modified flame retardant, 5 - 15 parts of high-temperature toughening agent; The lubricant is ethylene bisstearamide; The antioxidant is antioxidant 1098.

[0006] The modified flame retardant is prepared by the following method: Step A1: Add diethylene glycol dimethyl ether and pentaerythritol to a three-necked round-bottom flask equipped with a stirrer, thermometer, dropping funnel, reflux condenser, and hydrogen chloride absorption device. Under the condition of an ice-water bath, dropwise add methyltrichlorosilane, slowly raise the temperature to 60 - 70 °C, keep the temperature for 1 - 2 h, then raise the temperature to 140 - 160 °C, keep the temperature for 3 - 5 h, carry out reduced-pressure distillation, cool to room temperature, and wash to obtain a compound; Further, the dosage ratio of diethylene glycol dimethyl ether, pentaerythritol, and methyltrichlorosilane is 50 mL: 0.1 - 0.2 mol: 0.1 - 0.2 mol; First, react the hydroxyl group of pentaerythritol with the chlorine atom of methyltrichlorosilane to obtain a compound; Step A2: Mix the compound, dichloroethane, aluminum chloride, and cetylpyridinium chloride. While under an ice-water bath, dropwise add p-styrenesulfonyl chloride. After the addition is complete, raise the temperature to 70 °C and reflux for 2 h. Then perform vacuum distillation, cool, filter, wash, and dry to obtain the pre-product; Further, the dosage ratio of the compound, dichloroethane, aluminum chloride, cetylpyridinium chloride, and p-styrenesulfonyl chloride is 0.1 - 0.2 mol : 50 mL : 0.05 - 0.06 mol : 0.01 mol : 0.1 - 0.2 mol; Secondly, react the hydroxyl group of the compound with the chlorine atom of p-styrenesulfonyl chloride to obtain the pre-product; Step A3: Mix 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, N,N-dimethylformamide, and the pre-product, stir at 140 °C for 9 h, filter, wash, and vacuum dry at 60 °C for 24 h to obtain the modified flame retardant; Further, the dosage ratio of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, N,N-dimethylformamide, and the pre-product is 0.01 - 0.02 mol : 40 - 60 mL : 0.01 - 0.02 mol; Finally, react the carbon-carbon double bond of the pre-product with 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide to obtain the modified flame retardant.

[0007] The high-temperature resistant toughening agent is prepared by the following method: Step B1: Mix toluene, maleic anhydride, and N,N-dimethylformamide and stir for 30 min. Add p-aminophenol and react at 40 - 50 °C for 2 h. Then add p-toluenesulfonic acid, raise the temperature to 110 °C, and reflux for 4.0 h. Wash, filter by suction, and vacuum dry to obtain the intermediate; Further, the dosage ratio of toluene, maleic anhydride, N,N-dimethylformamide, p-aminophenol, and p-toluenesulfonic acid is 5 - 20 mL : 0.01 - 0.02 mol : 2 - 6 mL : 0.01 - 0.02 mol : 1 - 5 g; First, react the amino group of p-aminophenol with maleic anhydride to form the intermediate; Step B2: Mix the intermediate and dibutyltin dilaurate evenly, perform an oil bath at 60 °C, stir at 100 r / min for 10 min, then add isophorone diisocyanate, raise the temperature to 80 - 85 °C, stir at 400 - 500 r / min for 30 min, cool, wash, filter, and dry to obtain the high-temperature resistant toughening agent; Further, the dosage ratio of the intermediate, dibutyltin dilaurate, and isophorone diisocyanate is 0.02 - 0.04 mol : 1 - 5 mL : 0.01 - 0.02 mol; Finally, a high-temperature resistant toughening agent is prepared by reacting the hydroxyl group of the intermediate with the isocyanate group of isophorone diisocyanate.

[0008] A preparation method of high wear-resistant plastic particles specifically includes the following steps: S1. Put polyphenylene sulfide, lubricant, antioxidant, glass fiber, modified flame retardant and high-temperature resistant toughening agent into a high-speed mixer and stir and mix evenly at a temperature of 70-90°C, stir at 200-400 r / min for 1-3 h to obtain a mixed material; S2: Put the mixed material into a twin-screw extruder for extrusion molding and cooling, dry at 75-85°C for 1-3 h and then pelletize to obtain high wear-resistant plastic particles.

[0009] The beneficial effects of the present invention: The high wear-resistant plastic particles of the present invention have good flame retardant effect, and at the same time have excellent high-temperature resistance and toughening effect, and prolong the service life.

[0010] The modified flame retardant prepared by the present invention realizes efficient flame retardancy through a multi-component synergistic mechanism. During the pyrolysis process, the siloxane group migrates to the surface of the material to form a continuous and dense Si-O-C char layer, forming a heat-insulating and oxygen-barrier barrier to inhibit flame propagation; the benzenesulfonyl group decomposes at high temperature to generate sulfuric acid substances, catalyze the matrix to dehydrate and carbonize and release non-combustible gases, induce the carbon layer to expand to form a porous heat-insulating structure, reduce the heat release rate of the material, and significantly improve the flame retardant performance. At the same time, the formed sulfonate structure not only enhances the flame retardant efficiency, but also improves the compatibility with the matrix; in addition, the phosphorus-nitrogen flame retardant 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, as a phosphaphenanthrene compound with high thermal stability, promotes the formation of a dense and continuous carbon layer during combustion, further isolating oxygen and heat exchange, and synergistically retarding fire with the phosphorus-oxygen double bond, prolonging its service life; in addition, the modified flame retardant prepared by the present invention is halogen-free, which helps to reduce environmental pollution and damage to the ecosystem, is harmless to human health, and realizes sustainable development.

[0011] In the high-temperature resistant toughening agent prepared by the present invention, the maleimide group has high stability. Due to the dipole moment perpendicular to the main axis of the molecular chain, the intermolecular force is significantly enhanced, thereby increasing the glass transition temperature and melting point of the material, and imparting rigidity and heat resistance to the molecular chain. In addition, the maleimide group has high compatibility with the polyphenylene sulfide matrix and can form a cross-linked network structure. When impacted, the cross-linked network can effectively disperse stress and reduce the propagation of cracks, thereby enhancing the impact resistance of the material; in addition, the formed urethane bond imparts a unique toughening effect to the material, which can inhibit the stress concentration at the crack tip, promote crack deflection or bifurcation, and avoid brittle fracture. At the same time, when subjected to external force, the sacrificial bond in the urethane bond will break to prevent local stress concentration during the stretching process, thereby promoting molecular chain orientation. As the deformation intensifies, these broken sacrificial bonds are reconnected through dynamic recombination and continuously break and recombine during subsequent stretching, thereby inhibiting brittle fracture and enhancing the toughness of the material. Detailed implementation mode

[0012] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.

[0013] Example 1: A preparation method of high wear-resistant plastic particles specifically includes the following steps: S1. Weigh the raw materials by weight: 60 parts of polyphenylene sulfide, 1 part of lubricant, 0.1 part of antioxidant, 20 parts of glass fiber, 1 part of modified flame retardant (prepared in this example), and 5 parts of high-temperature resistant toughening agent (prepared in this example); put the polyphenylene sulfide, ethylene bisstearamide, antioxidant 1098, glass fiber, modified flame retardant, and high-temperature resistant toughening agent into a high-speed mixer and stir to mix evenly at a temperature of 70°C and a stirring speed of 200 r / min for 1 h to obtain a mixed material; S2: Put the mixed material into a twin-screw extruder for extrusion molding and cooling, dry at 75°C for 1 h, and then pelletize to obtain high wear-resistant plastic particles; The modified flame retardant is prepared by the following method: Step A1: Add 50 mL of diethylene glycol dimethyl ether and 0.1 mol of pentaerythritol to a three-necked round-bottom flask equipped with a stirrer, thermometer, dropping funnel, reflux condenser, and hydrogen chloride absorption device. Under the condition of an ice-water bath, drop 0.1 mol of methyltrichlorosilane, slowly heat up to 60°C, keep the temperature for reaction for 1-2 h, then heat up to 140°C, keep the temperature for reaction for 3 h, carry out vacuum distillation, cool to room temperature, and wash to obtain a compound; Step A2: Mix 0.1 mol of the compound, 50 mL of dichloroethane, 0.05 mol of aluminum chloride, and 0.01 mol of cetylpyridinium chloride. Under an ice-water bath, add dropwise 0.1 mol of p-styrenesulfonyl chloride. After the addition is complete, raise the temperature to 70 °C and reflux for 2 h. Then perform vacuum distillation, cool, filter, wash, and dry to obtain the pre-product; Step A3: Mix 0.01 mol of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 40 mL of N,N-dimethylformamide, and 0.01 mol of the pre-product. Stir at 140 °C for 9 h, filter, wash, and dry under vacuum at 60 °C for 24 h to obtain the modified flame retardant; The high-temperature resistant toughening agent is prepared by the following method: Step B1: Mix 5 mL of toluene, 0.01 mol of maleic anhydride, and 2 mL of dimethylformamide and stir for 30 min. Add 0.01 mol of p-aminophenol and react at 40 °C for 2 h. Then add 1 - 5 g of p-toluenesulfonic acid, raise the temperature to 110 °C, and reflux for 4.0 h. Wash, filter by suction, and dry under vacuum to obtain the intermediate; Step B2: Mix 0.02 mol of the intermediate and 1 mL of dibutyltin dilaurate evenly. Heat in an oil bath at 60 °C and stir at 100 r / min for 10 min. Then add 0.01 mol of isophorone diisocyanate, raise the temperature to 80 °C, and stir at 400 r / min for 30 min. Cool, wash, filter, and dry to obtain the high-temperature resistant toughening agent.

[0014] Example 2: A method for preparing high wear-resistant plastic particles, specifically including the following steps: S1. Weigh the raw materials by weight parts: 70 parts of polyphenylene sulfide, 2.5 parts of lubricant, 0.3 part of antioxidant, 30 parts of glass fiber, 2.5 parts of modified flame retardant (prepared in this example), and 10 parts of high-temperature resistant toughening agent (prepared in this example); Put polyphenylene sulfide, ethylene bisstearamide, antioxidant 1098, glass fiber, modified flame retardant, and high-temperature resistant toughening agent into a high-speed mixer and stir to mix evenly at a temperature of 80 °C and a stirring speed of 300 r / min for 2 h to obtain a mixed material; S2: Place the mixed material into a twin-screw extruder for extrusion molding and cooling. Dry at 80 °C for 2 h and then pelletize to obtain high wear-resistant plastic particles; The modified flame retardant is prepared by the following method: Step A1: Add 50 mL of diethylene glycol dimethyl ether and 0.15 mol of pentaerythritol into a three-necked round-bottom flask equipped with a stirrer, a thermometer, a dropping funnel, a reflux condenser and a hydrogen chloride absorption device. Under the condition of an ice-water bath, dropwise add 0.15 mol of methyltrichlorosilane, slowly heat up to 65 °C, keep the temperature for reaction for 1.5 h, then heat up to 150 °C, keep the temperature for reaction for 4 h, carry out vacuum distillation, cool to room temperature, wash, and obtain the compound; Step A2: Mix 0.15 mol of the compound, 50 mL of dichloroethane, 0.055 mol of aluminum chloride and 0.01 mol of cetylpyridinium chloride, under the ice-water bath, dropwise add 0.15 mol of p-styrenesulfonyl chloride. After the dropping is completed, heat up to 70 °C, carry out reflux reaction for 2 h, carry out vacuum distillation, cool and filter, wash, and dry to obtain the pre-product; Step A3: Mix 0.015 mol of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 50 mL of N,N-dimethylformamide and 0.015 mol of the pre-product, stir at 140 °C for 9 h, filter and wash, and vacuum dry at 60 °C for 24 h to obtain the modified flame retardant; The high-temperature resistant toughening agent is prepared by the following method: Step B1: Mix 12.5 mL of toluene, 0.015 mol of maleic anhydride and 4 mL of dimethylformamide and stir for 30 min, add 0.015 mol of p-aminophenol, react at 45 °C for 2 h, then add 3 g of p-toluenesulfonic acid, heat up to 110 °C, carry out reflux reaction for 4.0 h, wash, carry out suction filtration, and vacuum dry to obtain the intermediate; Step B2: Mix 0.03 mol of the intermediate and 3 mL of dibutyltin dilaurate evenly, carry out oil bath at 60 °C, stir at 100 r / min for 10 min, then add 0.015 mol of isophorone diisocyanate, heat up to 82 °C, stir at 450 r / min for 30 min, cool, wash, filter, and dry to obtain the high-temperature resistant toughening agent.

[0015] Example 3: A preparation method of high wear-resistant plastic particles, specifically including the following steps: S1. Weigh the raw materials by weight parts, 80 parts of polyphenylene sulfide, 4 parts of lubricant, 0.5 part of antioxidant, 40 parts of glass fiber, 4 parts of modified flame retardant (prepared by this example), 15 parts of high-temperature resistant toughening agent (prepared by this example); put polyphenylene sulfide, ethylene bisstearamide, antioxidant 1098, glass fiber, modified flame retardant and high-temperature resistant toughening agent into a high-speed mixer and stir and mix evenly, the temperature is 90 °C, stir at 400 r / min for 3 h to obtain the mixed material; S2: Put the mixed material into a twin-screw extruder for extrusion molding and cooling, dry at 85 °C for 3 h and then pelletize to obtain high wear-resistant plastic particles; The modified flame retardant is prepared by the following method: Step A1: Add 50 mL of diethylene glycol dimethyl ether and 0.2 mol of pentaerythritol into a three-necked round-bottom flask equipped with a stirrer, a thermometer, a dropping funnel, a reflux condenser and a hydrogen chloride absorption device. Under the condition of an ice-water bath, dropwise add 0.2 mol of methyltrichlorosilane, slowly heat up to 70 °C, keep the temperature for reaction for 2 h, then heat up to 160 °C, keep the temperature for reaction for 5 h, carry out vacuum distillation, cool to room temperature, wash, and obtain a compound. Step A2: Mix 0.2 mol of the compound, 50 mL of dichloroethane, 0.06 mol of aluminum chloride and 0.01 mol of cetylpyridinium chloride, under an ice-water bath, dropwise add 0.2 mol of p-styrenesulfonyl chloride. After the dropping is completed, heat up to 70 °C and carry out reflux reaction for 2 h, carry out vacuum distillation, cool and filter, wash, and dry to obtain a pre-product. Step A3: Mix 0.02 mol of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 60 mL of N,N-dimethylformamide and 0.02 mol of the pre-product, stir at 140 °C for 9 h, filter, wash, and vacuum dry at 60 °C for 24 h to obtain the modified flame retardant. The high-temperature resistant toughening agent is prepared by the following method: Step B1: Mix 20 mL of toluene, 0.02 mol of maleic anhydride and 6 mL of dimethylformamide, stir for 30 min, add 0.02 mol of p-aminophenol, react at 50 °C for 2 h, then add 5 g of p-toluenesulfonic acid, heat up to 110 °C, carry out reflux reaction for 4.0 h, wash, filter by suction, and vacuum dry to obtain an intermediate. Step B2: Mix 0.04 mol of the intermediate and 5 mL of dibutyltin dilaurate evenly, carry out an oil bath at 60 °C, stir at 100 r / min for 10 min, then add 0.02 mol of isophorone diisocyanate, heat up to 85 °C, stir at 500 r / min for 30 min, cool, wash, filter, and dry to obtain the high-temperature resistant toughening agent.

[0016] Comparative Example 1: This comparative example is a kind of high wear-resistant plastic particles. The difference from Example 3 is that magnesium hydroxide in an equal amount is used to replace the modified flame retardant prepared in Example 3, and the rest are the same.

[0017] Comparative Example 2: This comparative example is a kind of high wear-resistant plastic particles. The difference from Example 3 is that sodium sulfide in an equal amount is used to replace the high-temperature resistant toughening agent prepared in Example 3, and the rest are the same.

[0018] Performance test: The high wear-resistant plastic particles prepared in Examples 1-3 and Comparative Examples 1-2 were cut into standard test sizes, and the flame retardant performance was tested according to the standard UL-94; the tensile strength was tested according to the standard ASTM D-638; they were placed in an oven at 220 °C for 8 h, and the elongation at break was tested according to the standard GB / T 1040.1-2018; the test results are shown in Table 1 below: Table 1

[0019] It can be seen from the data tested in Table 1 that the high wear-resistant plastic particles prepared by the present invention have good flame retardant and high temperature resistance effects. It can also be seen from Table 1 that the high wear-resistant plastic particles prepared by the present invention have good tensile strength and extended service life.

[0020] The above content is only an example and illustration of the concept of the present invention. Those skilled in the art of this technology can make various modifications or supplements to the described specific embodiments or use similar methods for substitution, as long as they do not deviate from the concept of the invention or exceed the scope defined by this claim book, they should all fall within the protection scope of the present invention.

Claims

1. A preparation method of high wear-resistant plastic particles, characterized in that, Specifically, it includes the following steps: S1. Weigh the raw materials by weight parts. Put 60 - 80 parts of polyphenylene sulfide, 1 - 4 parts of lubricant, 0.1 - 0.5 parts of antioxidant, 20 - 40 parts of glass fiber, 1 - 4 parts of modified flame retardant, and 5 - 15 parts of high - temperature resistant toughening agent into a high - speed mixer for stirring and mixing evenly. The temperature is 70 - 90°C, and stir at 200 - 400 r / min for 1 - 3 h to obtain a mixed material; S2: Put the mixed material into a twin - screw extruder for extrusion molding and cooling. After drying at 75 - 85°C for 1 - 3 h, pelletize to obtain high - wear - resistant plastic particles; The modified flame retardant is prepared by the following method: Step A1: Add diglyme and pentaerythritol to a three - necked round - bottom flask equipped with a stirrer, thermometer, dropping funnel, reflux condenser, and hydrogen chloride absorption device. Under the condition of an ice - water bath, dropwise add methyltrichlorosilane, slowly raise the temperature to 60 - 70°C, keep the temperature for reaction for 1 - 2 h, then raise the temperature to 140 - 160°C, keep the temperature for reaction for 3 - 5 h, carry out vacuum distillation, cool to room temperature, and wash to obtain a compound; Step A2: Mix the compound, dichloroethane, aluminum chloride, and cetylpyridinium chloride. Under the ice - water bath, dropwise add p - styrenesulfonyl chloride. After the addition is completed, raise the temperature to 70°C and carry out reflux reaction for 2 h. Carry out vacuum distillation, cool and filter, wash, and dry to obtain a pre - product; Step A3: Mix 9,10 - dihydro - 9 - oxa - 10 - phosphaphenanthrene - 10 - oxide, N,N - dimethylformamide, and the pre - product, stir at 140°C for 9 h, filter and wash, and vacuum dry at 60°C for 24 h to obtain the modified flame retardant.

2. The preparation method of a highly wear-resistant plastic particle according to claim 1, characterized in that, In step A1, the dosage ratio of diglyme, pentaerythritol, and methyltrichlorosilane is 50 mL: 0.1 - 0.2 mol: 0.1 - 0.2 mol.

3. The preparation method of a highly wear-resistant plastic particle according to claim 1, characterized in that, In step A2, the dosage ratio of the compound, dichloroethane, aluminum chloride, cetylpyridinium chloride, and p - styrenesulfonyl chloride is 0.1 - 0.2 mol: 50 mL: 0.05 - 0.06 mol: 0.01 mol: 0.1 - 0.2 mol.

4. The preparation method of a highly wear-resistant plastic particle according to claim 1, wherein, In step A3, the dosage ratio of 9,10 - dihydro - 9 - oxa - 10 - phosphaphenanthrene - 10 - oxide, N,N - dimethylformamide, and the pre - product is 0.01 - 0.02 mol: 40 - 60 mL: 0.01 - 0.02 mol.

5. The preparation method of a highly wear-resistant plastic particle according to claim 1, characterized in that, The high - temperature resistant toughening agent is prepared by the following method: Step B1: Mix toluene, maleic anhydride, and N,N - dimethylformamide and stir for 30 min. Add p - aminophenol, react at 40 - 50°C for 2 h, then add p - toluenesulfonic acid, raise the temperature to 110°C, and carry out reflux reaction for 4.0 h. Wash, filter by suction, and vacuum dry to obtain an intermediate; Step B2: Mix the intermediate and dibutyltin dilaurate evenly, carry out an oil bath at 60°C, stir at 100 r / min for 10 min, then add isophorone diisocyanate, raise the temperature to 80 - 85°C, stir at 400 - 500 r / min for 30 min, cool, wash, filter, and dry to obtain the high - temperature resistant toughening agent.

6. The preparation method of a highly wear-resistant plastic particle according to claim 5, wherein, In step B1, the dosage ratio of toluene, maleic anhydride, dimethylformamide, p-aminophenol, and p-toluenesulfonic acid is 5 - 20 mL: 0.01 - 0.02 mol: 2 - 6 mL: 0.01 - 0.02 mol: 1 - 5 g.

7. The preparation method of a highly wear-resistant plastic particle according to claim 5, characterized in that, In step B2, the dosage ratio of the intermediate, dibutyltin dilaurate, and isophorone diisocyanate is 0.02 - 0.04 mol: 1 - 5 mL: 0.01 - 0.02 mol.

8. The preparation method of a highly wear-resistant plastic particle according to claim 1, characterized in that, The lubricant is ethylene bis-stearamide, and the antioxidant is antioxidant 1098.

9. A highly wear-resistant plastic particle, characterized in that, Prepared according to the preparation method described in any one of claims 1 - 8.

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