A high-strength, wear-resistant composite plastic with high auxiliary material content and its preparation method

Abstract

This invention discloses a high-strength, wear-resistant composite plastic with high auxiliary material content and its preparation method, belonging to the field of plastic processing technology. It addresses the technical problem that the wear resistance and strength of existing composite plastics need further improvement. The invention comprises the following components by weight: 40-50 parts plastic matrix, 15-20 parts modified plasticizer, 10-15 parts modified filler, 3-5 parts stabilizer, 3-5 parts antioxidant, 3-5 parts ultraviolet absorber, and 3-5 parts lubricant. In the preparation of the composite plastic, the modified plasticizer absorbs harmful gases generated by resin pyrolysis and hybridizes resin segments. Furthermore, during combustion, the flame-retardant groups in the modified filler promote carbonization, enhancing the flame-retardant ability of the material. The coupling agent component improves the compatibility between the auxiliary materials, ultimately resulting in a high-strength, wear-resistant, tensile-resistant, and flame-retardant environmentally friendly composite plastic.

Description

Technical Field

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

[0002] The development of high-strength, wear-resistant plastics with high filler content began with basic research and early applications of reinforcing materials in the mid-20th century. In the 1970s and 80s, formulation optimization became crucial, leading to the development of high-filler plastics. The addition of large amounts of fillers such as mineral powders and glass fibers significantly improved the mechanical properties of plastics. From the 1990s to the early 21st century, research shifted to the application of high-performance fillers, such as the introduction of nanomaterials, which significantly enhanced the strength, wear resistance, and thermal stability of plastics. Simultaneously, advanced processing technologies, such as high-precision injection molding and extrusion molding, further improved product quality. In the 21st century, the focus has shifted to the development of functional and smart materials, including self-healing materials and high-strength, wear-resistant plastics with antibacterial properties. These innovations meet more demanding application requirements. Furthermore, environmental protection and sustainability have become important trends, driving research into recyclable materials and bio-based plastics. These materials perform comparably to traditional materials while reducing environmental impact.

[0003] The prior art CN108795082A discloses a high-strength plastic comprising the following raw materials in parts by weight: 66-88 parts monomer resin, 5-6 parts plasticizer, 0.8-1.6 parts heat stabilizer, 3.5-5.5 parts toughening agent, 6-18 parts calcium carbonate, and 12-26 parts carbon black, which gives the plastic high strength, expands the application range of the plastic, has high strength and high toughness, and extends the service life of the plastic.

[0004] While the aforementioned disclosure aims to enhance plastic performance by improving the plastic formulation ratio, the low content of toughening agent during processing limits the potential for improving the strength and toughness of the plastic. Furthermore, the monomer resin or inorganic materials calcium carbonate and carbon black were not modified during processing. Due to their high polarity, the compatibility between the materials is low, thereby reducing the strength of the plastic. In other words, the strength of the plastic products obtained by optimizing the formulation ratio needs to be further improved.

[0005] To address this technical deficiency, a solution is proposed. Summary of the Invention

[0006] The purpose of this invention is to provide a high-strength wear-resistant composite plastic with high auxiliary material content and its preparation method, in order to solve the technical problem that the wear resistance and strength of composite plastics in the prior art need to be further improved.

[0007] The objective of this invention can be achieved through the following technical solution: a high-strength wear-resistant composite plastic with high auxiliary material content, comprising the following components in parts by weight: 40-50 parts plastic matrix, 30-40 parts modified plasticizer, 20-30 parts modified filler, 5-8 parts stabilizer, 5-8 parts antioxidant, 5-8 parts ultraviolet absorber and 5-8 parts lubricant;

[0008] The preparation method of the modified plasticizer includes the following steps:

[0009] A1. Modified polyester, cyanuric acid, 0.5-2.0 wt% sodium hydroxide solution and N,N-dimethylformamide are added to a reaction vessel. The temperature of the reaction vessel is raised to 60-80℃ and the reaction is maintained for 4-6 hours. The extended chain polyester is obtained after post-treatment.

[0010] The reaction equation for preparing chain-extended polyesters is as follows:

[0011]

[0012] In the formula:

[0013] The principle of preparing chain-extended polyester is as follows: under alkaline conditions, the carboxyl groups of the modified polyester and the hydroxyl groups of cyanuric acid undergo an esterification reaction to form polyester intercalated organic chain segments. After the reaction, the molecular structure of the modified polyester is effectively extended, and finally, chain-extended polyester with enhanced properties is generated.

[0014] A2. Add extended chain polyester, 3-(2,3-epoxypropoxy)propyltrimethoxysilane, triethylamine and N,N-dimethylformamide to a reaction vessel, raise the temperature of the reaction vessel to 50-60℃, keep the reaction at this temperature for 1-2 hours, and then perform post-treatment to obtain end-capped polyester.

[0015] The reaction equation for preparing end-capped polyester is as follows:

[0016]

[0017] In the formula:

[0018] The principle of preparing end-capped polyester is as follows: under the catalysis of triethylamine, the epoxy group on 3-(2,3-epoxypropoxy)propyltrimethoxysilane and the carboxyl group on the chain extended polyester undergo a ring-opening reaction, which end-capsulates the chain extended polyester to form a silane coupling agent crosslinked end-capped polyester.

[0019] A3. Add the capped polyester, formic acid, hydrogen peroxide and N,N-dimethylformamide to the reactor and stir. Raise the temperature of the reactor to 50-60℃ and keep it at that temperature for 30-40 minutes. Then, perform post-treatment to obtain the modified plasticizer.

[0020] The reaction equation for preparing the modified plasticizer is as follows:

[0021]

[0022] In the formula:

[0023] The reaction principle for preparing modified plasticizers is as follows: formic acid and hydrogen peroxide form peroxy acid in the system. Its excellent oxidizing properties cause the carbon-carbon double bonds in the capped polyester to cyclize, forming epoxy groups, thus obtaining modified plasticizers.

[0024] Further, in step A1, the ratio of the modified polyester, cyanuric acid, 0.5-2.0 wt% sodium hydroxide solution, and N,N-dimethylformamide is 2-4 g:2-4 g:15-20 mL:15-20 mL; in step A2, the ratio of the extended-chain polyester, 3-(2,3-epoxypropoxy)propyltrimethoxysilane, triethylamine, and N,N-dimethylformamide is 8-10 g:2-4 g:0.5-0.8 g:40-60 mL; in step A3, the stirring speed is 80-120 rpm, and the ratio of the capped polyester, formic acid, hydrogen peroxide, and N,N-dimethylformamide is 8-10 g:1-2 g:1-2 g:30-40 mL.

[0025] Further, in step A1, the post-processing operation is as follows: after the reactor is cooled to room temperature, the reaction solution is added to a rotary evaporator with a water bath temperature of 80-100℃, and distilled under reduced pressure until no liquid is collected, to obtain extended-chain polyester; in step A2, the post-processing operation is as follows: after the reactor is cooled to room temperature, the reaction solution is added to a rotary evaporator with a water bath temperature of 80-100℃, and distilled under reduced pressure until no liquid is collected, to obtain end-capped polyester; in step A3, the post-processing operation is as follows: after the reactor is cooled to room temperature, the reaction solution is added to a rotary evaporator with a water bath temperature of 80-100℃, and distilled under reduced pressure until no liquid is collected, to obtain modified plasticizer.

[0026] Further, in step A1, the modified polyester is prepared by adding 4,4'-stilbene dicarboxylic acid, 1,5-hexadien-3,4-diol, dichlorobenzene and 98.0 wt% concentrated sulfuric acid into a reaction vessel, raising the temperature of the reaction vessel to 150-170℃, maintaining the temperature for 12-16 hours, and then performing post-treatment to obtain the modified polyester.

[0027] The reaction equation for synthesizing modified polyester is as follows:

[0028]

[0029] In the formula:

[0030] The principle of the synthesis of modified polyester is as follows: at high temperature, 4,4'-stilbene dicarboxylic acid and 1,5-hexadien-3,4-diol undergo free radical polymerization under the catalysis of concentrated sulfuric acid. By controlling the amount of both, a modified polyester with carboxyl groups as end groups is obtained.

[0031] Furthermore, the ratio of 4,4'-stilbene dicarboxylic acid, 1,5-hexadien-3,4-diol, dichlorobenzene, and 98.0 wt% concentrated sulfuric acid is 2-4 g: 1-2 g: 20-30 mL: 0.1-0.2 g. The post-treatment includes: after cooling the reaction vessel to room temperature, adding the reaction solution to a rotary evaporator with a water bath temperature of 80-100°C, and distilling under reduced pressure until no liquid is collected to obtain the modified polyester.

[0032] Furthermore, the preparation method of the modified filler includes the following steps:

[0033] B1. Graphene oxide, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, triethylamine and ethanol are added to a reaction vessel and stirred. The temperature of the reaction vessel is raised to 50-60℃ and stirred for 1-2 hours. Modified graphene is obtained by post-treatment.

[0034] Reaction principle: A large number of active functional groups such as hydroxyl groups on graphene oxide react with the phosphorus-hydrogen bonds of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, causing 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide to crosslink on the surface and inside of graphene oxide, ultimately yielding modified graphene.

[0035] B2. Modified graphene, 3-aminopropyltriethoxysilane, zinc chloride and N,N-dimethylformamide are added to a reaction vessel. The temperature of the reaction vessel is raised to 50-60℃ and the reaction is maintained for 30-40 minutes. The modified filler is then obtained through post-treatment.

[0036] Reaction principle: A large number of active functional groups on the modified graphene, such as carboxyl groups, react with the amino groups of 3-aminopropyltriethoxysilane to form amide bonds. 3-aminopropyltriethoxysilane then crosslinks with the modified graphene through amide bonds, ultimately yielding the modified filler.

[0037] Further, in step B1, the stirring rate is 80-120 rpm, and the ratio of graphene oxide, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, triethylamine and ethanol is 5-8 g: 2-3 g: 0.5-0.6 g: 25-35 mL; in step B2, the ratio of modified graphene, 3-aminopropyltriethoxysilane, zinc chloride and N,N-dimethylformamide is 8-10 g: 2-4 g: 0.5-0.8 g: 40-50 mL.

[0038] Further, in step B1, the post-processing includes: after the reactor temperature is reduced to room temperature, the reaction solution is filtered to collect the filter cake, the filter cake is washed with deionized water 3-5 times, and the filter cake is placed in a drying oven at 80°C and vacuum dried until the filter cake reaches constant weight to obtain modified graphene; in step B2, the post-processing includes: after the reactor temperature is reduced to room temperature, the reaction solution is filtered to collect the filter cake, the filter cake is washed with deionized water 3-5 times, and the filter cake is placed in a drying oven at 80°C and vacuum dried until the filter cake reaches constant weight to obtain modified filler.

[0039] Furthermore, the preparation method of graphene oxide is as follows: multilayer graphene and 98.0 wt% sulfuric acid are added to a reaction vessel at a temperature of 0-5℃ and stirred. After stirring for 10-15 min, sodium chlorate is added to the reaction vessel. The reaction vessel temperature is maintained at 0-5℃ for 2-4 h. The pH of the reaction system is adjusted to 7 using saturated sodium hydroxide solution. After post-treatment, multilayer graphene oxide is obtained.

[0040] Reaction principle: Partial sulfation of multilayer graphene makes the graphene structure more active, creating conditions for oxidation reaction. Sodium chlorate decomposes under acidic conditions to generate chloric acid and oxygen. The strong oxidizing effect of chloric acid can oxidize the carbon layer of graphene oxide to produce graphene oxide, which contains various oxygen functional groups, such as epoxy groups, carboxyl groups and hydroxyl groups.

[0041] Furthermore, the ratio of the multilayer graphene, 98.0 wt% sulfuric acid, and sodium chlorate is 5-8 g: 30-40 g: 3-5 g, the stirring rate is 80-120 rpm, and the post-treatment includes: after the temperature of the reaction vessel is raised to room temperature, the reaction solution is filtered to collect the filter cake, the filter cake is washed with deionized water 3-5 times, and the filter cake is placed in a drying oven at 80°C and vacuum dried until the filter cake reaches a constant weight to obtain oxidized multilayer graphene.

[0042] This invention also proposes a method for preparing a high-strength, wear-resistant composite plastic with high auxiliary material content, comprising the following steps:

[0043] S1. The plastic matrix, modified plasticizer, modified filler, stabilizer, antioxidant, ultraviolet absorber and lubricant are mixed evenly to obtain the mixture;

[0044] S2. The mixture is added to a twin-screw extruder. The temperature of the eight temperature zones of the twin-screw extruder from the feed port to the discharge port is 180℃, 185℃, 185℃, 190℃, 190℃, 200℃, and 200℃ respectively. The main speed of the twin-screw extruder is 80-120 rpm and the pressure is 100-150 bar. After melt extrusion, a composite plastic precursor is obtained.

[0045] S3. Transfer the plastic precursor to a chamber filled with water vapor, process for 6-8 hours, cool down and discharge to obtain composite plastic.

[0046] Furthermore, the plastic matrix is ​​one or more of polytetrafluoroethylene, polyvinylidene fluoride, and polyvinylidene fluoride; the stabilizer is one or more of zinc diester stabilizer, calcium-zinc heat stabilizer HX-10, and lead-free calcium-zinc stabilizer LX-800; the antioxidant is one or two of butylated hydroxyanisole and butylated hydroxybenzoic acid; the ultraviolet absorber is UV-531; and the lubricant is one or more of magnesium stearate, calcium stearate, zinc stearate, and polyethylene wax.

[0047] The present invention has the following beneficial effects:

[0048] 1. In the process of preparing a high-strength, wear-resistant composite plastic with high auxiliary material content, this invention selects to add a large amount of modified plasticizer and modified filler to the resin to improve the strength of the composite plastic. The modified plasticizer and modified filler obtained after modification are modified with crosslinking agent groups, which improve the crosslinking ability inside the composite plastic while improving the strength of the composite plastic, thus significantly improving the wear resistance of the composite plastic. In the combustion process, the two work together. The flame-retardant chain segments modified by the modified auxiliary material decompose at high temperature, which promotes the carbonization of triazine rings in the modified plasticizer, forming a flame-retardant layer and working together with the graphene oxide component in the modified filler to improve the flame retardancy of the composite plastic. Finally, a high-strength, wear-resistant, tensile-resistant, and flame-retardant composite plastic with high auxiliary material content is obtained.

[0049] 2. In the process of preparing a high-strength, wear-resistant composite plastic with high auxiliary material content, this invention first prepares a modified polyester with olefin double bonds and benzene ring structures. After chain extension with cyanuric acid, a chain-extended polyester with a triazine ring as the core is formed. Then, after end-capping with 3-(2,3-epoxypropoxy)propyltrimethoxysilane, a silane coupling agent-terminated polyester is obtained. Finally, after peroxy acid oxidation, a modified plasticizer with a large number of epoxy groups is obtained. During the processing to obtain the composite plastic, the modified plasticizer reduces the glass content of the material by embedding itself into the resin chain segments. The glass transition temperature increases its flexibility and fluidity; the large number of benzene ring structures in the modified plasticizer enhances the strength and wear resistance of the plastic, and the silane coupling agent, as a terminating group, further enhances its crosslinking ability with inorganic materials, significantly improving the wear resistance and tensile strength of the composite plastic; furthermore, the large number of epoxy groups in the modified plasticizer absorbs the harmful gases released by the resin during the processing of the composite plastic, and at the same time forms free radical polymerization with the resin to form a more complex spatial structure of the resin chain segments, thereby significantly improving the strength and tensile strength of the resin.

[0050] 3. In the process of preparing a high-strength, wear-resistant composite plastic with high auxiliary material content, this invention modifies and oxidizes multilayer graphene, then crosslinks it with 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, and further modifies it with a silane coupling agent to obtain a modified filler. The modified graphene, as the base material of the modified filler, has an excellent specific surface area, allowing for a wider contact surface with the resin material and other auxiliary materials, enhancing the bonding ability of the remaining organic materials. Simultaneously, its excellent physical properties further improve the strength of the composite plastic, and its rich hierarchical structure also endows it with excellent impact resistance, further enhancing the strength of the composite plastic. After oxidation and silane coupling agent modification, the compatibility of multilayer graphene with organic materials is further improved, further enhancing its crosslinking ability with the resin material, thus further improving the wear resistance of the composite plastic. During processing, the numerous active functional groups of the oxidized graphene react with the free radicals generated by the pyrolysis of the resin, further improving the adhesion between the modified filler and the resin material, significantly enhancing the strength and wear resistance of the composite plastic. Detailed Implementation

[0051] The technical solution of the present invention will be clearly and completely described below with reference to the embodiments. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0052] Example 1

[0053] This embodiment provides a method for preparing a high-strength, wear-resistant composite plastic with high auxiliary material content, including the following steps:

[0054] S1. Preparation of modified plasticizers

[0055] Weigh out 12.0g of 4,4'-stilbene dicarboxylic acid, 6.0g of 1,5-hexadien-3,4-diol, 75.0mL of dichlorobenzene and 0.6g of 98.0wt% concentrated sulfuric acid and add them to a reaction vessel. Raise the temperature of the reaction vessel to 150℃ and keep it at that temperature for 12h. After the reaction vessel is cooled to room temperature, add the reaction solution to a rotary evaporator with a water bath temperature of 80℃ and distill under reduced pressure until no liquid is collected to obtain the modified polyester.

[0056] Weigh out 12.0g of modified polyester, 12.0g of cyanuric acid, 50.0mL of 0.5wt% sodium hydroxide solution and 45.0mL of N,N-dimethylformamide and add them to the reaction vessel. Raise the temperature of the reaction vessel to 60℃ and keep it at that temperature for 4h. After the reaction vessel is cooled to room temperature, add the reaction solution to a rotary evaporator with a water bath temperature of 80℃ and distill under reduced pressure until no liquid is collected to obtain extended chain polyester.

[0057] Weigh out 24.0g of extended-chain polyester, 9.0g of 3-(2,3-epoxypropoxy)propyltrimethoxysilane, 1.8g of triethylamine and 120.0mL of N,N-dimethylformamide and add them to the reaction vessel. Raise the temperature of the reaction vessel to 50℃ and keep it at that temperature for 1h. After the reaction vessel is cooled to room temperature, add the reaction solution to a rotary evaporator with a water bath temperature of 80℃ and distill under reduced pressure until no liquid is collected to obtain the end-capped polyester.

[0058] Weigh out 27.0g of end-capped polyester, 6.0g of formic acid, 6.0g of hydrogen peroxide, and 90.0mL of N,N-dimethylformamide and add them to a reaction vessel. Stir at 80rpm and raise the temperature of the reaction vessel to 50℃. After stirring at this temperature for 30min, cool the reaction vessel to room temperature and add the reaction solution to a rotary evaporator with a water bath temperature of 80℃. Distill under reduced pressure until no liquid is collected to obtain the modified plasticizer.

[0059] S2. Preparation of modified fillers

[0060] Weigh 18.0g of multilayer graphene and 96.0g of 98.0wt% sulfuric acid and add them to a reaction vessel at 5℃. Stir at 80rpm and keep stirring for 10min. Then add 12.0g of sodium chlorate to the reaction vessel. Keep the reaction vessel at 5℃ and react for 2h. Adjust the pH of the reaction system to 7 using saturated sodium hydroxide solution. After the reaction vessel temperature is raised to room temperature, filter the reaction solution and collect the filter cake. Wash the filter cake three times with deionized water. Place the filter cake in a drying oven at 80℃ and vacuum dry it until the filter cake reaches constant weight to obtain oxidized multilayer graphene.

[0061] Weigh out 18.0g of graphene oxide, 9.0g of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 1.5g of triethylamine and 75.0mL of ethanol and add them to the reaction vessel. Stir the mixture and raise the temperature of the reaction vessel to 50℃. Keep the mixture at this temperature and stir for 1 hour. After the temperature of the reaction vessel is lowered to room temperature, filter the reaction solution and collect the filter cake. Wash the filter cake three times with deionized water and place it in a drying oven at 80℃ to dry it under vacuum until the filter cake reaches a constant weight to obtain modified graphene.

[0062] Weigh out 24.0g of modified graphene, 9.0g of 3-aminopropyltriethoxysilane, 1.8g of zinc chloride, and 120.0mL of N,N-dimethylformamide and add them to the reaction vessel. Raise the temperature of the reaction vessel to 50℃ and keep it at that temperature for 30min. After the temperature of the reaction vessel is lowered to room temperature, filter the reaction solution and collect the filter cake. Wash the filter cake three times with deionized water and place it in a drying oven at 80℃ to vacuum dry until the filter cake reaches a constant weight to obtain the modified filler.

[0063] S3. Preparation of composite plastics

[0064] Weigh out 45.0g of polyvinyl fluoride, 16.0g of modified plasticizer, 12.0g of modified filler, 3.6g of zinc diester stabilizer, 3.6g of butylated hydroxyanisole, 3.6g of UV-531 and 3.6g of polyethylene wax, and mix them evenly to obtain a mixture.

[0065] The mixture is added to a twin-screw extruder. The temperature of the eight temperature zones of the twin-screw extruder from the feed port to the discharge port is 180℃, 185℃, 185℃, 190℃, 190℃, 200℃, and 200℃ respectively. The main speed of the twin-screw extruder is 80 rpm and the pressure is 100 bar. After melt extrusion, a composite plastic precursor is obtained.

[0066] The plastic precursor was transferred to a chamber filled with water vapor and treated for 6 hours. After cooling, the material was discharged to obtain the composite plastic.

[0067] Example 2

[0068] This embodiment provides a method for preparing a high-strength, wear-resistant composite plastic with high auxiliary material content, including the following steps:

[0069] S1. Preparation of modified plasticizers

[0070] Weigh out 12.0g of 4,4'-stilbene dicarboxylic acid, 5.4g of 1,5-hexadien-3,4-diol, 72.0mL of dichlorobenzene and 0.6g of 98.0wt% concentrated sulfuric acid and add them to the reaction vessel. Raise the temperature of the reaction vessel to 170℃ and keep it at that temperature for 16h. After the reaction vessel is cooled to room temperature, add the reaction solution to a rotary evaporator with a water bath temperature of 100℃ and distill under reduced pressure until no liquid is collected to obtain the modified polyester.

[0071] Weigh out 12.0g of modified polyester, 9.0g of cyanuric acid, 54.0mL of 2.0wt% sodium hydroxide solution and 60.0mL of N,N-dimethylformamide and add them to the reaction vessel. Raise the temperature of the reaction vessel to 80℃ and keep it at that temperature for 6h. After the reaction vessel is cooled to room temperature, add the reaction solution to a rotary evaporator with a water bath temperature of 100℃ and distill under reduced pressure until no liquid is collected to obtain extended chain polyester.

[0072] Weigh out 27.0g of extended-chain polyester, 12.0g of 3-(2,3-epoxypropoxy)propyltrimethoxysilane, 2.1g of triethylamine and 120.0mL of N,N-dimethylformamide and add them to the reaction vessel. Raise the temperature of the reaction vessel to 60℃ and keep it at that temperature for 2h. After the reaction vessel is cooled to room temperature, add the reaction solution to a rotary evaporator with a water bath temperature of 100℃ and distill under reduced pressure until no liquid is collected to obtain the end-capped polyester.

[0073] Weigh out 24.0g of end-capped polyester, 6.0g of formic acid, 6.0g of hydrogen peroxide, and 36.0mL of N,N-dimethylformamide and add them to a reaction vessel. Stir at 120rpm and raise the temperature of the reaction vessel to 60℃. After stirring at this temperature for 40min, cool the reaction vessel to room temperature and add the reaction solution to a rotary evaporator with a water bath temperature of 100℃. Distill under reduced pressure until no liquid is collected to obtain the modified plasticizer.

[0074] S2. Preparation of modified fillers

[0075] Weigh 18.0g of multilayer graphene and 96.0g of 98.0wt% sulfuric acid and add them to a reaction vessel at 3℃. Stir at 120rpm and keep stirring for 15min. Then add 12.0g of sodium chlorate to the reaction vessel. Keep the reaction vessel at 3℃ and react for 4h. Adjust the pH of the reaction system to 7 using saturated sodium hydroxide solution. After the reaction vessel temperature is raised to room temperature, filter the reaction solution and collect the filter cake. Wash the filter cake 5 times with deionized water. Place the filter cake in a drying oven at 80℃ and vacuum dry it until the filter cake reaches constant weight to obtain oxidized multilayer graphene.

[0076] Weigh out 18.0g of graphene oxide, 7.2g of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 1.5g of triethylamine and 75.0mL of ethanol and add them to the reaction vessel. Stir the mixture and raise the temperature of the reaction vessel to 60℃. Keep the mixture at this temperature and stir for 2 hours. After the temperature of the reaction vessel is lowered to room temperature, filter the reaction solution and collect the filter cake. Wash the filter cake 5 times with deionized water and place it in a drying oven at 80℃ to vacuum dry until the filter cake reaches a constant weight to obtain modified graphene.

[0077] Weigh out 24.0g of modified graphene, 6.0g of 3-aminopropyltriethoxysilane, 1.8g of zinc chloride, and 120.0mL of N,N-dimethylformamide and add them to the reaction vessel. Raise the temperature of the reaction vessel to 60℃ and keep it at that temperature for 40min. After the temperature of the reaction vessel is lowered to room temperature, filter the reaction solution and collect the filter cake. Wash the filter cake 5 times with deionized water and place it in a drying oven at 80℃ to vacuum dry until the filter cake reaches a constant weight to obtain the modified filler.

[0078] S3. Preparation of composite plastics

[0079] Weigh out 48.0g of polyvinyl fluoride, 16.0g of modified plasticizer, 12.0g of modified filler, 3.6g of zinc diester stabilizer, 4.8g of butylated hydroxyanisole, 4.8g of UV-531 and 3.6g of polyethylene wax, and mix them evenly to obtain a mixture.

[0080] The mixture is added to a twin-screw extruder. The temperature of the eight temperature zones of the twin-screw extruder from the feed port to the discharge port is 180℃, 185℃, 185℃, 190℃, 190℃, 200℃, and 200℃ respectively. The main motor speed of the twin-screw extruder is 120 rpm and the pressure is 150 bar. After melt extrusion, a composite plastic precursor is obtained.

[0081] The plastic precursor was transferred to a chamber filled with water vapor and treated for 8 hours. After cooling, the material was discharged to obtain the composite plastic.

[0082] Example 3

[0083] This embodiment provides a method for preparing a high-strength, wear-resistant composite plastic with high auxiliary material content, including the following steps:

[0084] S1. Preparation of modified plasticizers

[0085] Weigh out 10.8g of 4,4'-stilbene dicarboxylic acid, 5.4g of 1,5-hexadien-3,4-diol, 72.0mL of dichlorobenzene and 0.6g of 98.0wt% concentrated sulfuric acid and add them to the reaction vessel. Raise the temperature of the reaction vessel to 160℃ and keep it at that temperature for 14h. After the reaction vessel is cooled to room temperature, add the reaction solution to a rotary evaporator with a water bath temperature of 90℃ and distill under reduced pressure until no liquid is collected to obtain the modified polyester.

[0086] Weigh out 7.2g of modified polyester, 10.8g of cyanuric acid, 45.0mL of 1.0wt% sodium hydroxide solution and 45.0mL of N,N-dimethylformamide and add them to the reaction vessel. Raise the temperature of the reaction vessel to 70℃ and keep it at that temperature for 5h. After the reaction vessel is cooled to room temperature, add the reaction solution to a rotary evaporator with a water bath temperature of 90℃ and distill under reduced pressure until no liquid is collected to obtain extended chain polyester.

[0087] Weigh out 27.0g of extended-chain polyester, 9.0g of 3-(2,3-epoxypropoxy)propyltrimethoxysilane, 1.8g of triethylamine and 120.0mL of N,N-dimethylformamide and add them to the reaction vessel. Raise the temperature of the reaction vessel to 55℃ and keep it at that temperature for 2h. After the reaction vessel is cooled to room temperature, add the reaction solution to a rotary evaporator with a water bath temperature of 90℃ and distill under reduced pressure until no liquid is collected to obtain the end-capped polyester.

[0088] Weigh out 27.0g of end-capped polyester, 6.0g of formic acid, 6.0g of hydrogen peroxide and N,N-dimethylformamide and add them to the reaction vessel. Stir at 100rpm and raise the temperature of the reaction vessel to 55℃. After stirring at this temperature for 35min, cool the reaction vessel to room temperature and add the reaction solution to a rotary evaporator with a water bath temperature of 90℃. Distill under reduced pressure until no liquid is collected to obtain the modified plasticizer.

[0089] S2. Preparation of modified fillers

[0090] Weigh 18.0g of multilayer graphene and 90.0g of 98.0wt% sulfuric acid and add them to a reaction vessel at 0℃. Stir at 100rpm and keep stirring for 12min. Then add 15.0g of sodium chlorate to the reaction vessel. Keep the reaction vessel at 0℃ for 3h. Adjust the pH of the reaction system to 7 using saturated sodium hydroxide solution. After the reaction vessel temperature is raised to room temperature, filter the reaction solution and collect the filter cake. Wash the filter cake 4 times with deionized water. Place the filter cake in a drying oven at 80℃ and vacuum dry it until the filter cake reaches constant weight to obtain oxidized multilayer graphene.

[0091] Weigh out 18.0g of graphene oxide, 9.0g of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 1.8g of triethylamine and 75.0mL of ethanol and add them to the reaction vessel. Stir the mixture and raise the temperature of the reaction vessel to 55℃. Keep the mixture at this temperature and stir for 2 hours. After the temperature of the reaction vessel is lowered to room temperature, filter the reaction solution and collect the filter cake. Wash the filter cake four times with deionized water and place it in a drying oven at 80℃ to dry it under vacuum until the filter cake reaches a constant weight to obtain modified graphene.

[0092] Weigh out 27.0g of modified graphene, 9.0g of 3-aminopropyltriethoxysilane, 2.4g of zinc chloride, and 120.0mL of N,N-dimethylformamide and add them to the reaction vessel. Raise the temperature of the reaction vessel to 55℃ and keep it at that temperature for 35min. After the temperature of the reaction vessel is lowered to room temperature, filter the reaction solution and collect the filter cake. Wash the filter cake four times with deionized water and place it in a drying oven at 80℃ to vacuum dry until the filter cake reaches a constant weight to obtain the modified filler.

[0093] S3. Preparation of composite plastics

[0094] Weigh out 50.0g of polyvinyl fluoride, 18.0g of modified plasticizer, 12.0g of modified filler, 3.6g of zinc diester stabilizer, 4.8g of butylated hydroxyanisole, 3.6g of UV-531 and 4.8g of polyethylene wax and mix them evenly to obtain a mixture.

[0095] The mixture is added to a twin-screw extruder. The temperature of the eight temperature zones of the twin-screw extruder from the feed port to the discharge port is 180℃, 185℃, 185℃, 190℃, 190℃, 200℃, and 200℃ respectively. The main motor speed of the twin-screw extruder is 100 rpm and the pressure is 125 bar. After melt extrusion, a composite plastic precursor is obtained.

[0096] The plastic precursor was transferred to a chamber filled with water vapor and treated for 7 hours. After cooling, the material was discharged to obtain the composite plastic.

[0097] Comparative Example 1

[0098] The difference between this comparative example and Example 3 is that step S1 is omitted. In step S3, the composition of the mixture is 50.0g polyvinyl fluoride, 6.0g modified plasticizer, 4.0g modified filler, 1.2g zinc diester stabilizer, 1.6g butylated hydroxyanisole, 1.2g UV-531 and 1.6g polyethylene wax.

[0099] Comparative Example 2

[0100] The difference between this comparative example and Example 3 is that step S2 is omitted, and in step S3, multilayer graphene is used to replace the modified filler in an equal amount.

[0101] Comparative Example 3

[0102] The difference between this comparative example and Example 3 is that the step of preparing the modified filler in step S2 is omitted, and in step S3, the modified filler is replaced by an equal amount of modified graphene.

[0103] Performance testing:

[0104] The volumetric abrasion of the composite plastics prepared in Examples 1-3 and Comparative Examples 1-3 was tested in accordance with the standard GB / T 9867-2008 "Determination of abrasion resistance of vulcanized rubber or thermoplastic rubber (rotary roller abrasion tester method)".

[0105] The tensile strength of the composite plastics prepared in Examples 1-3 and Comparative Examples 1-3 was tested in accordance with the standard GB / T 528-2009 "Determination of tensile stress-strain properties of vulcanized rubber or thermoplastic rubber".

[0106] The cantilever beam impact strength of the composite plastics prepared in Examples 1-3 and Comparative Examples 1-3 was tested in accordance with the standard GB / T 1843-2008 "Determination of cantilever beam impact strength of plastics".

[0107] The vertical flammability ratings of the composite plastics prepared in Examples 1-3 and Comparative Examples 1-3 were tested in accordance with the standard GB / T 2408-2021 "Determination of flammability of plastics - Horizontal and Vertical Methods".

[0108] The limiting oxygen index of the composite plastics prepared in Examples 1-3 and Comparative Examples 1-3 was tested in accordance with the standard GB / T 26526-2011 "Determination of Combustion Behavior by Oxygen Index Method for Plastics - Part 2: Room Temperature Test".

[0109] The release of acidic gases during the preparation of composite plastics in Examples 1-3 and Comparative Examples 1-3 was tested in accordance with the standard GB / T 2917.1-2002 "Determination of the release of hydrogen chloride and any other acidic products at high temperature from blends and products mainly composed of vinyl chloride homopolymers and copolymers". The specific data are shown in Table 1.

[0110] Table 1 - Performance test data of each sample

[0111]

[0112] Data Analysis:

[0113] Comparative analysis of the data in Table 1 above shows that the volumetric wear of the composite plastic prepared by this invention is 39 mm. 3 The tensile strength is 90.5 MPa, and the cantilever beam impact strength is 64.5 kJ·m. -2 The vertical burning rating was V-0, the limiting oxygen index was 45.2%, and the Congo red test paper color change time was 852s. All data were better than the comparative example. By comparing the data of Example 3 and Comparative Example 1, it can be found that modifying the auxiliary materials and increasing their content helps to improve the performance of composite plastics.

[0114] By comparing the data of Example 3 with those of Comparative Examples 2 and 3, it can be found that the modified polyester prepared by the present invention, after chain extension, end-capping and peroxy acid oxidation, has improved the crosslinking ability of inorganic materials and plastics by the silane coupling agent in its molecular chain segments, and improved the wear resistance of the composite plastic. Moreover, the epoxy groups generated after peroxy acid oxidation react with the free reaction generated by the cracking of polyvinyl fluoride, which captures harmful gases and crosslinks with the polyvinyl fluoride chain segments to enhance the spatial complexity of the polyvinyl fluoride chain segments, thus significantly enhancing the tensile strength of polyvinyl fluoride. The triazine groups inside, which act as chain extenders, are catalyzed by the acidic substances generated by the decomposition of flame retardant groups in the modified filler at high temperature, further enhancing the flame retardant ability of the composite plastic.

[0115] Modified fillers obtained by crosslinking multilayer graphene through oxidation, flame retardant crosslinking, and silane coupling agent crosslinking, in synergy with modified plasticizers, enhance the strength and flame retardant properties of composite plastics, ultimately producing a high-strength composite plastic that is wear-resistant, tensile-resistant, flame-retardant, and environmentally friendly.

[0116] The above description is merely an example and illustration of the structure of the present invention. Those skilled in the art can make various modifications or additions to the specific embodiments described, or use similar methods to replace them, as long as they do not deviate from the structure of the invention or exceed the scope defined in the claims, all of which should fall within the protection scope of the present invention.

[0117] In the description of this specification, references to terms such as "an embodiment," "example," "specific example," etc., indicate that a specific feature, structure, material, or characteristic described in connection with that embodiment or example is included in at least one embodiment or example of the invention. In this specification, illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples.

[0118] The preferred embodiments of the present invention disclosed above are merely illustrative of the invention. These preferred embodiments do not exhaustively describe all details, nor do they limit the invention to specific implementations. Clearly, many modifications and variations can be made based on the content of this specification. This specification selects and specifically describes these embodiments to better explain the principles and practical applications of the invention, thereby enabling those skilled in the art to better understand and utilize the invention. The invention is limited only by the claims and their full scope and equivalents.

Claims

1. A high-strength, wear-resistant composite plastic with high auxiliary material content, characterized in that, It comprises the following components in parts by weight: 40-50 parts plastic matrix, 15-20 parts modified plasticizer, 10-15 parts modified filler, 3-5 parts stabilizer, 3-5 parts antioxidant, 3-5 parts ultraviolet absorber and 3-5 parts lubricant; The preparation method of the modified plasticizer includes the following steps: A1. Modified polyester, cyanuric acid, 0.5-2.0 wt% sodium hydroxide solution and N,N-dimethylformamide are added to a reaction vessel. The temperature of the reaction vessel is raised to 60-80℃ and the reaction is maintained for 4-6 hours. The extended chain polyester is obtained after post-treatment. A2. Add extended chain polyester, 3-(2,3-epoxypropoxy)propyltrimethoxysilane, triethylamine and N,N-dimethylformamide to a reaction vessel, raise the temperature of the reaction vessel to 50-60℃, keep the reaction at this temperature for 1-2 hours, and then perform post-treatment to obtain end-capped polyester. A3. Add the capped polyester, formic acid, hydrogen peroxide and N,N-dimethylformamide to the reaction vessel and stir. Raise the temperature of the reaction vessel to 50-60℃, keep it at the temperature and stir for 30-40 minutes, and then perform post-treatment to obtain the modified plasticizer. The method for preparing the modified filler includes the following steps: B1. Graphene oxide, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, triethylamine and ethanol are added to a reaction vessel and stirred. The temperature of the reaction vessel is raised to 50-60℃ and stirred for 1-2 hours. Modified graphene is obtained by post-treatment. B2. Modified graphene, 3-aminopropyltriethoxysilane, zinc chloride and N,N-dimethylformamide are added to the reactor. The reactor temperature is raised to 50-60℃ and the reaction is maintained for 30-40 minutes. The modified filler is obtained after post-treatment. In step B1, the stirring rate is 80-120 rpm, and the ratio of graphene oxide, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, triethylamine, and ethanol is 5-8 g: 2-3 g: 0.5-0.6 g: 25-35 mL; in step B2, the ratio of modified graphene, 3-aminopropyltriethoxysilane, zinc chloride, and N,N-dimethylformamide is 8-10 g: 2-4 g: 0.5-0.8 g: 40-50 mL. The preparation method of the graphene oxide is as follows: multilayer graphene and 98.0 wt% sulfuric acid are added to a reaction vessel at a temperature of 0-5℃ and stirred. After stirring for 10-15 min, sodium chlorate is added to the reaction vessel. The reaction vessel temperature is maintained at 0-5℃ for 2-4 h. The pH of the reaction system is adjusted to 7 using saturated sodium hydroxide solution. After post-treatment, multilayer graphene oxide is obtained.

2. The high-strength, wear-resistant composite plastic with high auxiliary material content according to claim 1, characterized in that, In step A1, the ratio of the modified polyester, cyanuric acid, 0.5-2.0 wt% sodium hydroxide solution, and N,N-dimethylformamide is 2-4 g:2-4 g:15-20 mL:15-20 mL; in step A2, the ratio of the extended-chain polyester, 3-(2,3-epoxypropoxy)propyltrimethoxysilane, triethylamine, and N,N-dimethylformamide is 8-10 g:2-4 g:0.5-0.8 g:40-60 mL; in step A3, the stirring speed is 80-120 rpm, and the ratio of the capped polyester, formic acid, hydrogen peroxide, and N,N-dimethylformamide is 8-10 g:1-2 g:1-2 g:30-40 mL.

3. The high-strength, wear-resistant composite plastic with high auxiliary material content according to claim 1, characterized in that, In step A1, the modified polyester is prepared by adding 4,4'-stilbene dicarboxylic acid, 1,5-hexadiene-3,4-diol, dichlorobenzene and 98.0 wt% concentrated sulfuric acid into a reaction vessel, raising the temperature of the reaction vessel to 150-170℃, maintaining the temperature for 12-16 hours, and then performing post-treatment to obtain the modified polyester.

4. The high-strength, wear-resistant composite plastic with high auxiliary material content according to claim 3, characterized in that, The ratio of 4,4'-stilbene dicarboxylic acid, 1,5-hexadien-3,4-diol, dichlorobenzene, and 98.0 wt% concentrated sulfuric acid is 2-4 g: 1-2 g: 20-30 mL: 0.1-0.2 g. The post-treatment includes: after the reaction vessel is cooled to room temperature, the reaction solution is added to a rotary evaporator with a water bath temperature of 80-100℃, and the solution is distilled under reduced pressure until no liquid is collected, thus obtaining the modified polyester.

5. The high-strength, wear-resistant composite plastic with high auxiliary material content according to claim 1, characterized in that, The ratio of multilayer graphene, 98.0wt% sulfuric acid, and sodium chlorate is 5-8g:30-40g:3-5g. The stirring rate is 80-120rpm. The post-treatment includes: after the reactor temperature is raised to room temperature, the reaction solution is filtered to collect the filter cake, the filter cake is washed with deionized water 3-5 times, and the filter cake is placed in a drying oven at 80℃ and vacuum dried until the filter cake reaches a constant weight to obtain oxidized multilayer graphene.

6. A method for preparing a high-strength, wear-resistant composite plastic with high auxiliary material content according to any one of claims 1-5, characterized in that, Includes the following steps: S1. The plastic matrix, modified plasticizer, modified filler, stabilizer, antioxidant, ultraviolet absorber and lubricant are mixed evenly to obtain a mixture; S2. The mixture is added to a twin-screw extruder. The temperature of the eight temperature zones of the twin-screw extruder from the feed port to the discharge port is 180℃, 185℃, 185℃, 190℃, 190℃, 200℃, and 200℃ respectively. The main speed of the twin-screw extruder is 80-120 rpm and the pressure is 100-150 bar. After melt extrusion, a composite plastic precursor is obtained. S3. Transfer the plastic precursor to a chamber filled with water vapor, process for 6-8 hours, cool down and discharge to obtain composite plastic.

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