CN116462877A - High-strength wear-resistant engineering plastic and preparation method thereof - Google Patents

High-strength wear-resistant engineering plastic and preparation method thereof Download PDF

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CN116462877A
CN116462877A CN202310345516.9A CN202310345516A CN116462877A CN 116462877 A CN116462877 A CN 116462877A CN 202310345516 A CN202310345516 A CN 202310345516A CN 116462877 A CN116462877 A CN 116462877A
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CN116462877B (en
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赵兴乐
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Guangdong Taflon Material Technology Co ltd
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Changzhou Yiguan Plastic Products Co ltd
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Abstract

The invention discloses high-strength wear-resistant engineering plastic and a preparation method thereof, and relates to the technical field of plastics. The high-strength wear-resistant engineering plastic is prepared by extruding modified polyamide and plasticizer and coating wear-resistant paint; the modified polyamide is prepared by reacting furyl polyamide with quaternized polyphenyl ether; the furyl polyamide is prepared by reacting polyethylene glycol difuranate with poly (p-benzoyl dodecandiamine), so as to form polyamide with long chain of bisamide structure and furyl, and enhance the heat resistance and strength of engineering plastics; the wear-resistant coating comprises epoxy polyamide and filler; epoxy polyamide is prepared by adding soybean protein into polyamine polyamide with epoxy group; after the wear-resistant coating is coated, the epoxy polyamide reacts with the modified polyamide and is solidified on the surface of the modified polyamide, so that the wear resistance of the engineering plastic is enhanced.

Description

High-strength wear-resistant engineering plastic and preparation method thereof
Technical Field
The invention relates to the technical field of plastics, in particular to a high-strength wear-resistant engineering plastic and a preparation method thereof.
Background
Engineering plastics can be divided into general engineering plastics and special engineering plastics. The former is mainly used for five general engineering plastics including polyamide, polycarbonate, polyoxymethylene, modified polyphenyl ether and thermoplastic polyester; the latter is mainly engineering plastics with heat resistance of more than 150 ℃, and the main varieties include polyimide, polyphenylene sulfide, polysulfones, aromatic polyamides, polyarylates, polyphenyl esters, polyaryletherketones, liquid crystal polymers, fluororesin and the like.
The polyamide engineering plastic with single component often has the defects of insufficient strength or poor wear resistance, so the invention researches and prepares the high-strength wear-resistant engineering plastic which can ensure heat resistance and has high strength and wear resistance.
Disclosure of Invention
The invention aims to provide high-strength wear-resistant engineering plastic and a preparation method thereof, so as to solve the problems in the background technology.
In order to solve the technical problems, the invention provides the following technical scheme: the high-strength wear-resistant engineering plastic is prepared by extruding modified polyamide and plasticizer and then coating wear-resistant paint.
Preferably, the modified polyamide is prepared by reacting furan-based polyamide with quaternized polyphenylene ether.
Preferably, the furyl polyamide is prepared by reacting polyethylene furan dicarboxylate with poly (p-phenylene diformyl) dodecandiamine; the quaternized polyphenyl ether is prepared by reacting azidated polyphenyl ether, methyl hydroxybenzoate and aminopropanol.
Preferably, the wear resistant coating comprises an epoxy polyamide and a filler; the epoxy polyamide is prepared by adding soybean protein into polyamine polyamide with epoxy groups; the filler is nano alumina; the plasticizer is epoxidized soybean oil.
Preferably, the preparation method of the high-strength wear-resistant engineering plastic comprises the following specific steps:
(1) Mixing polyethylene furandicarboxylate and poly (p-benzoyl) dodecandiamine according to a mass ratio of 1:1.05-1:1.25, placing the mixture into a reaction device, adding a catalyst butyl titanate with the mass of 0.03-0.05 times of the polyethylene furandicarboxylate, heating to 90-93 ℃ under a nitrogen atmosphere, reacting for 10-30 min, heating to 130-150 ℃, sealing and vacuumizing to the maximum vacuum degree of ester, continuously heating to 200-210 ℃, reacting for 1-2 h, heating to 220-230 ℃, and continuously reacting for 1-2 h to obtain the furyl polyamide;
(2) Mixing the azido polyphenyl ether, N-methylpyrrolidone and quaternized polyphenyl ether precursor according to the mass ratio of 3:15:0.2-3:20:0.5, stirring uniformly, adding copper bromide with the mass of 0.005-0.008 times of the azido polyphenyl ether and pentamethyl diethylenetriamine with the mass of 0.05-0.08 times of the azido polyphenyl ether, freezing, vacuum and thawing for 3 times, heating to 80-83 ℃, stirring at 100-200 rpm for reacting for 90-100 h, cooling to room temperature, precipitating with isopropanol and anhydrous diethyl ether with the volume ratio of 3:7, and finally vacuum drying at 60 ℃ to obtain the quaternized polyphenyl ether;
(3) Mixing furan-based polyamide and quaternized polyphenyl ether Afather mass part 1:1.05-1:1.25, placing the mixture into a reaction device, adding butyl titanate serving as a catalyst with the weight 0.03-0.05 times that of furan-based polyamide, heating to 90-93 ℃ under a nitrogen atmosphere, reacting for 10-30 min, heating to 130-150 ℃, sealing and vacuumizing to the maximum vacuum degree, continuously heating to 200-210 ℃, reacting for 1-2 h, heating to 220-230 ℃, and continuously reacting for 1-2 h to obtain modified polyamide;
(4) Mixing the modified polyamide and the plasticizer, placing the mixture in a plasticator, plasticating for 3-5 min at the temperature of 120-140 ℃, and then extruding and granulating the mixture by an injection molding machine to obtain an engineering plastic matrix;
(5) Mixing epoxy polyamide and filler according to the mass ratio of 10:0.3-20:0.5, and uniformly stirring to obtain the wear-resistant coating; and (3) coating the wear-resistant coating on the surface of the engineering plastic matrix, and standing and curing for 3-7 d to prepare the high-strength wear-resistant engineering plastic.
Preferably, in the step (1): the preparation method of the polyethylene furandicarboxylate comprises the following steps: terephthalic acid, 2, 5-furandicarboxylic acid, hexanediol and tetrabutyl titanate are mixed according to the mass ratio of 2:1:3:0.2-2:2:3:0.2, the temperature is raised to 120-130 ℃, stirring reaction is carried out for 8-12 h at 100-200 rpm, and then vacuum drying is carried out for 12h at 90-100 ℃ to obtain the polyethylene furandicarboxylic acid glycol ester.
Preferably, in the step (2): the preparation method of the quaternized polyphenyl ether precursor comprises the following steps: mixing sodium hydride and tetrahydrofuran according to a mass ratio of 1:20-1:30, stirring for 1-2 hours in an ice bath, heating to room temperature for continuous reaction for 1-2 hours, adding tetrahydrofuran solution of 3-bromopropyne with a mass fraction of 20-30% of that of sodium hydride, which is 2.3-2.5 times of that of sodium hydride, continuously reacting for 12-16 hours, transferring into the ice bath, dropwise adding ammonium chloride until no gas is generated, extracting with dichloromethane, drying, dispersing in methanol with a mass of 20-30 times of that of sodium hydride again, stirring uniformly, adding methyl iodide with a mass of 15-18 times of that of sodium hydride, refluxing for reaction for 70-76 hours, adding ethyl acetate with a mass of 200-300 times of that of sodium hydride for precipitation, and finally drying at 70-80 ℃ for 24 hours to obtain the quaternized polyphenyl ether precursor.
Preferably, in the step (4): the mass ratio of the modified polyamide to the plasticizer is 10:0.5-15:0.8.
Preferably, in the step (5): the preparation method of the epoxy polyamide comprises the following steps: mixing adipic acid and diethylenetriamine according to a mass ratio of 1:1.05-1:1.15, heating to 110-120 ℃, stirring at 100-200 rpm for reaction for 20-30 min, heating to 180-190 ℃, continuing to react for 2-3 h, cooling to room temperature, then dripping epichlorohydrin with the mass of 0.9-1.1 times of adipic acid and soy protein with the mass of 0.1-0.3 times of adipic acid at a rate of 3-5 ml/min, heating to 50-60 ℃, continuing to react for 2-3 h, and regulating pH to 3-4 with sulfuric acid to obtain the epoxy polyamide.
Preferably, in the step (5): the thickness of the wear-resistant paint is 0.03-0.08 mu m.
Compared with the prior art, the invention has the following beneficial effects:
the high-strength wear-resistant engineering plastic is prepared by extruding modified polyamide and plasticizer and coating wear-resistant paint;
the modified polyamide is prepared by reacting furyl polyamide with quaternized polyphenyl ether; the furyl polyamide is prepared by reacting polyethylene glycol difuranate with poly (p-benzoyl dodecandiamine), so as to form polyamide with long chain of bisamide structure and furyl, and enhance the heat resistance of engineering plastics; the quaternized polyphenyl ether is prepared by reacting azidated polyphenyl ether, methyl hydroxybenzoate and aminopropanol, and the quaternized polyphenyl ether is introduced onto furan-based polyamide to form furan quaternary ammonium salt, and is crosslinked in polyamide with long chain of a bisamide structure, so that the crosslinking density is improved, and the strength of engineering plastics is enhanced;
the wear-resistant coating comprises epoxy polyamide and filler; epoxy polyamide is prepared by adding soybean protein into polyamine polyamide with epoxy group; the polyamine polyamide and the amino groups of the soybean protein are bonded with each other, and are crosslinked into a relatively stable molecule with a network structure, and meanwhile, the active groups are simultaneously branched to generate a large number of azetidinium groups, the azetidinium groups can be crosslinked with the active groups, hydrophilic groups exposed outside the soybean protein are crosslinked into a stable three-dimensional space network structure and are connected to the surface of the modified polyamide, and after the wear-resistant coating is coated, the epoxy polyamide reacts with the modified polyamide and is solidified on the surface of the modified polyamide, so that the wear resistance of engineering plastics is further enhanced.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In order to more clearly illustrate the method provided by the invention, the following examples are used for describing the method for testing each index of the high-strength abrasion-resistant engineering plastics prepared in the examples and comparative examples as follows:
placing the high-strength wear-resistant engineering plastics prepared in the examples and the comparative examples into a hot press, and preparing engineering plastic plates with the same size under the same conditions for testing;
heat resistance: and carrying out thermogravimetric analysis test on the engineering plastic plate, and recording the initial decomposition temperature.
Intensity: the engineering plastic plate was subjected to elongation at break test with reference to GB 1040.
Abrasion resistance: and (5) carrying out abrasion test on the engineering plastic plate, and recording the abrasion loss.
Example 1
(1) Mixing terephthalic acid, 2, 5-furandicarboxylic acid, hexanediol and tetrabutyl titanate according to the mass ratio of 2:1:3:0.2, heating to 120 ℃, stirring at 100rpm for reaction for 8 hours, and then vacuum drying at 90 ℃ for 12 hours to prepare the polyethylene furandicarboxylic acid glycol ester; mixing polyethylene furan dicarboxylate and poly (p-phenylene diformyl) dodecandiamine according to a mass ratio of 1:1.05, placing the mixture into a reaction device, adding a catalyst butyl titanate with the mass of 0.03 times of the polyethylene furan diformyl, heating to 90 ℃ under a nitrogen atmosphere, reacting for 10min, heating to 130 ℃, sealing and vacuumizing to the maximum vacuum degree, continuously heating to 200 ℃, reacting for 1h, heating to 220 ℃, and continuously reacting for 1h to obtain furan-based polyamide;
(2) Mixing sodium hydride and tetrahydrofuran according to a mass ratio of 1:20, stirring for 1h in an ice bath, heating to room temperature for continuous reaction for 1h, then adding a tetrahydrofuran solution of which the mass fraction is 20% and of which the mass is 2.3 times that of sodium hydride, continuously reacting for 12h, transferring into the ice bath, dripping ammonium chloride until no gas is generated, extracting with dichloromethane, drying, dispersing in methanol of which the mass is 20 times that of sodium hydride again, stirring uniformly, adding methyl iodide of which the mass is 15 times that of sodium hydride, refluxing for reaction for 70h, adding ethyl acetate of which the mass is 200 times that of sodium hydride for precipitation, and finally drying at 70 ℃ for 24h to obtain the quaternized polyphenyl ether precursor; mixing the azido polyphenyl ether, N-methylpyrrolidone and quaternized polyphenyl ether precursor according to the mass ratio of 3:15:0.2, adding copper bromide with the mass of 0.005 times of the azido polyphenyl ether and pentamethyl diethylenetriamine with the mass of 0.05 times of the azido polyphenyl ether after uniformly stirring, freezing, vacuum and thawing for 3 times, heating to 80 ℃, stirring and reacting for 90 hours at 100rpm, cooling to room temperature, precipitating with isopropanol and anhydrous diethyl ether with the volume ratio of 3:7, and finally vacuum drying at 60 ℃ to obtain the quaternized polyphenyl ether;
(3) Mixing furan-based polyamide and quaternized polyphenyl ether (PAD) in a mass part of 1:1.05, placing the mixture into a reaction device, adding butyl titanate serving as a catalyst with the mass 0.03 times that of furan-based polyamide, heating to 90 ℃ under a nitrogen atmosphere, reacting for 10min, heating to 130 ℃, sealing and vacuumizing to the maximum vacuum degree of ester, continuously heating to 200 ℃, reacting for 1h, heating to 220 ℃, and continuously reacting for 1h to obtain modified polyamide;
(4) Mixing the modified polyamide and the plasticizer epoxy soybean oil according to the mass ratio of 10:0.5, placing the mixture into a plasticator, plasticating the mixture for 3min at the temperature of 120 ℃, and then extruding and granulating the mixture by an injection molding machine to obtain an engineering plastic matrix;
(5) Mixing adipic acid and diethylenetriamine according to a mass ratio of 1:1.05, heating to 110 ℃, stirring at 100rpm for reaction for 20min, heating to 180 ℃, continuing to react for 2h, cooling to room temperature, then dripping epichlorohydrin with an amount of 0.9 times of the mass of adipic acid and soybean protein with an amount of 0.1 time of the mass of adipic acid at a rate of 3ml/min, heating to 50 ℃, continuing to react for 2h, and regulating pH to 3 with sulfuric acid to obtain epoxy polyamide; mixing epoxy polyamide and filler nano alumina according to the mass ratio of 10:0.3, and uniformly stirring to obtain the wear-resistant coating; and (3) coating the wear-resistant coating on the surface of an engineering plastic matrix, wherein the thickness of the wear-resistant coating is 0.03 mu m, and standing and curing for 3d to prepare the high-strength wear-resistant engineering plastic.
Example 2
(1) Terephthalic acid, 2, 5-furandicarboxylic acid, hexanediol and tetrabutyl titanate are mixed according to the mass ratio of 2:1.5:3:0.2, the temperature is raised to 125 ℃, the mixture is stirred and reacted for 10 hours at 150rpm, and then the mixture is dried in vacuum for 12 hours at 95 ℃ to prepare the polyethylene furandicarboxylic acid glycol ester; mixing polyethylene furan dicarboxylate and poly (p-phenylene diformyl) dodecandiamine according to a mass ratio of 1:1.15, placing the mixture into a reaction device, adding a catalyst butyl titanate with the mass of 0.04 times of the polyethylene furan diformate, heating to 92 ℃ under a nitrogen atmosphere, reacting for 20min, heating to 140 ℃, sealing and vacuumizing to the maximum vacuum degree, continuously heating to 205 ℃, reacting for 1.5h, heating to 225 ℃ and continuously reacting for 1.5h to obtain furan-based polyamide;
(2) Mixing sodium hydride and tetrahydrofuran according to a mass ratio of 1:25, stirring for 1.5 hours in an ice bath, heating to room temperature for continuous reaction for 1.5 hours, then adding a tetrahydrofuran solution of which the mass fraction is 25% and of which the mass is 2.4 times that of sodium hydride, continuously reacting for 14 hours, transferring into the ice bath, dropwise adding ammonium chloride until no gas is generated, extracting with methylene chloride, drying, dispersing in methanol of which the mass is 25 times that of sodium hydride again, stirring uniformly, adding methyl iodide of which the mass is 16 times that of sodium hydride, refluxing for 73 hours, adding ethyl acetate of which the mass is 250 times that of sodium hydride for precipitation, and finally drying at 75 ℃ for 24 hours to obtain a quaternized polyphenyl ether precursor; mixing the azido polyphenyl ether, N-methylpyrrolidone and quaternized polyphenyl ether precursor according to the mass ratio of 3:18:0.3, adding copper bromide with the mass of 0.007 times of the azido polyphenyl ether and pentamethyl diethylenetriamine with the mass of 0.07 times of the azido polyphenyl ether after uniformly stirring, freezing, vacuum and thawing for 3 times, heating to 82 ℃, stirring and reacting for 95 hours at 150rpm, cooling to room temperature, precipitating with isopropanol and anhydrous diethyl ether with the volume ratio of 3:7, and finally vacuum drying at 60 ℃ to obtain the quaternized polyphenyl ether;
(3) Mixing furyl polyamide and quaternized polyphenyl ether A/D1.15 in a reaction device, adding butyl titanate serving as a catalyst with the mass 0.04 times that of the furyl polyamide, heating to 92 ℃ under nitrogen atmosphere, reacting for 20min, heating to 140 ℃, sealing and vacuumizing to the maximum vacuum degree, continuously heating to 205 ℃, reacting for 1.5h, heating to 225 ℃ and continuously reacting for 1.5h to obtain modified polyamide;
(4) Mixing the modified polyamide and the plasticizer epoxy soybean oil according to the mass ratio of 13:0.6, placing the mixture into a plasticator, plasticating for 4min at the temperature of 130 ℃, and then extruding and granulating the mixture by an injection molding machine to obtain an engineering plastic matrix;
(5) Mixing adipic acid and diethylenetriamine according to a mass ratio of 1:1.1, heating to 115 ℃, stirring at 150rpm for reaction for 25min, heating to 185 ℃, continuing to react for 2.5h, cooling to room temperature, then dripping epichlorohydrin with an amount which is 1 time of the mass of the adipic acid and soybean protein with an amount which is 0.2 time of the mass of the adipic acid at a rate of 4ml/min, heating to 54 ℃, continuing to react for 2.5h, and regulating pH to 3.5 by sulfuric acid to obtain epoxy polyamide; mixing epoxy polyamide and filler nano alumina according to a mass ratio of 15:0.4, and uniformly stirring to obtain the wear-resistant coating; and (3) coating the wear-resistant coating on the surface of an engineering plastic matrix, wherein the thickness of the wear-resistant coating is 0.05 mu m, and standing and curing for 5 days to prepare the high-strength wear-resistant engineering plastic.
Example 3
(1) Terephthalic acid, 2, 5-furandicarboxylic acid, hexanediol and tetrabutyl titanate are mixed according to the mass ratio of 2:2:3:0.2, the temperature is raised to 130 ℃, stirring is carried out for reaction for 12 hours at 1200rpm, and then vacuum drying is carried out for 12 hours at 100 ℃ to prepare the polyethylene furandicarboxylic acid glycol ester; mixing polyethylene furan dicarboxylate and poly (p-phenylene diformyl) dodecandiamine according to a mass ratio of 1:1.25, placing the mixture into a reaction device, adding a catalyst butyl titanate with the mass of 0.05 times of the polyethylene furan diformyl, heating to 93 ℃ under a nitrogen atmosphere, reacting for 30min, heating to 150 ℃, sealing and vacuumizing to the maximum vacuum degree, continuously heating to 210 ℃, reacting for 2h, heating to 230 ℃, and continuously reacting for 2h to obtain the furyl polyamide;
(2) Mixing sodium hydride and tetrahydrofuran according to a mass ratio of 1:30, stirring for 2 hours in an ice bath, heating to room temperature for continuous reaction for 2 hours, then adding a tetrahydrofuran solution of which the mass fraction is 30% and of which the mass is 2.5 times that of sodium hydride, continuously reacting for 16 hours, transferring into the ice bath, dripping ammonium chloride until no gas is generated, extracting with methylene dichloride, drying, dispersing in methanol of which the mass is 20-30 times that of sodium hydride again, stirring uniformly, adding methyl iodide of which the mass is 18 times that of sodium hydride, refluxing for reaction for 76 hours, adding ethyl acetate of which the mass is 300 times that of sodium hydride for precipitation, and finally drying at 80 ℃ for 24 hours to obtain a quaternized polyphenyl ether precursor; mixing the azido polyphenyl ether, N-methylpyrrolidone and quaternized polyphenyl ether precursor according to the mass ratio of 3:20:0.5, adding copper bromide with the mass of 0.008 times of the azido polyphenyl ether and pentamethyl diethylenetriamine with the mass of 0.08 times of the azido polyphenyl ether after uniformly stirring, freezing, vacuum and thawing for 3 times, heating to 83 ℃, stirring and reacting for 100 hours at 200rpm, cooling to room temperature, precipitating with isopropanol and anhydrous diethyl ether with the volume ratio of 3:7, and finally vacuum drying at 60 ℃ to obtain the quaternized polyphenyl ether;
(3) Mixing furan-based polyamide and quaternized polyphenyl ether (PAD) with the mass part of 1:1.25, placing the mixture into a reaction device, adding butyl titanate serving as a catalyst with the mass 0.05 times that of furan-based polyamide, heating to 93 ℃ under nitrogen atmosphere, reacting for 30min, heating to 150 ℃, sealing and vacuumizing to the maximum vacuum degree of ester, continuously heating to 210 ℃, reacting for 2h, heating to 230 ℃, and continuously reacting for 2h to obtain modified polyamide;
(4) Mixing the modified polyamide and the plasticizer epoxy soybean oil according to the mass ratio of 15:0.8, placing the mixture into a plasticator, plasticating the mixture for 5 minutes at the temperature of 140 ℃, and then extruding and granulating the mixture by an injection molding machine to obtain an engineering plastic matrix;
(5) Mixing adipic acid and diethylenetriamine according to a mass ratio of 1:1.15, heating to 120 ℃, stirring at 200rpm for reaction for 30min, heating to 190 ℃, continuing to react for 3h, cooling to room temperature, then dropwise adding epichlorohydrin with the mass of 1.1 times of that of adipic acid and soybean protein with the mass of 0.3 times of that of adipic acid at a rate of 5ml/min, heating to 60 ℃, continuing to react for 3h, and regulating pH to 4 by sulfuric acid to obtain epoxy polyamide; mixing epoxy polyamide and filler nano alumina according to a mass ratio of 20:0.5, and uniformly stirring to obtain the wear-resistant coating; and (3) coating the wear-resistant coating on the surface of an engineering plastic matrix, wherein the thickness of the wear-resistant coating is 0.08 mu m, and standing and curing for 7d to prepare the high-strength wear-resistant engineering plastic.
Comparative example 1
(1) Terephthalic acid, 2, 5-furandicarboxylic acid, hexanediol and tetrabutyl titanate are mixed according to the mass ratio of 2:1.5:3:0.2, the temperature is raised to 125 ℃, the mixture is stirred and reacted for 10 hours at 150rpm, and then the mixture is dried in vacuum for 12 hours at 95 ℃ to prepare the polyethylene furandicarboxylic acid glycol ester; mixing polyethylene furan dicarboxylate and poly (p-phenylene diformyl) dodecandiamine according to a mass ratio of 1:1.15, placing the mixture into a reaction device, adding a catalyst butyl titanate with the mass of 0.04 times of the polyethylene furan diformate, heating to 92 ℃ under a nitrogen atmosphere, reacting for 20min, heating to 140 ℃, sealing and vacuumizing to the maximum vacuum degree, continuously heating to 205 ℃, reacting for 1.5h, heating to 225 ℃ and continuously reacting for 1.5h to obtain furan-based polyamide;
(2) Mixing furan-based polyamide and plasticizer epoxy soybean oil according to a mass ratio of 13:0.6, placing into a plasticator, plasticating for 4min at 130 ℃, and then extruding and granulating by an injection molding machine to obtain an engineering plastic matrix;
(3) Mixing adipic acid and diethylenetriamine according to a mass ratio of 1:1.1, heating to 115 ℃, stirring at 150rpm for reaction for 25min, heating to 185 ℃, continuing to react for 2.5h, cooling to room temperature, then dripping epichlorohydrin with an amount which is 1 time of the mass of the adipic acid and soybean protein with an amount which is 0.2 time of the mass of the adipic acid at a rate of 4ml/min, heating to 54 ℃, continuing to react for 2.5h, and regulating pH to 3.5 by sulfuric acid to obtain epoxy polyamide; mixing epoxy polyamide and filler nano alumina according to a mass ratio of 15:0.4, and uniformly stirring to obtain the wear-resistant coating; and (3) coating the wear-resistant coating on the surface of an engineering plastic matrix, wherein the thickness of the wear-resistant coating is 0.05 mu m, and standing and curing for 5 days to prepare the high-strength wear-resistant engineering plastic.
Comparative example 2
(1) Mixing sodium hydride and tetrahydrofuran according to a mass ratio of 1:25, stirring for 1.5 hours in an ice bath, heating to room temperature for continuous reaction for 1.5 hours, then adding a tetrahydrofuran solution of which the mass fraction is 25% and of which the mass is 2.4 times that of sodium hydride, continuously reacting for 14 hours, transferring into the ice bath, dropwise adding ammonium chloride until no gas is generated, extracting with methylene chloride, drying, dispersing in methanol of which the mass is 25 times that of sodium hydride again, stirring uniformly, adding methyl iodide of which the mass is 16 times that of sodium hydride, refluxing for 73 hours, adding ethyl acetate of which the mass is 250 times that of sodium hydride for precipitation, and finally drying at 75 ℃ for 24 hours to obtain a quaternized polyphenyl ether precursor; mixing the azido polyphenyl ether, N-methylpyrrolidone and quaternized polyphenyl ether precursor according to the mass ratio of 3:18:0.3, adding copper bromide with the mass of 0.007 times of the azido polyphenyl ether and pentamethyl diethylenetriamine with the mass of 0.07 times of the azido polyphenyl ether after uniformly stirring, freezing, vacuum and thawing for 3 times, heating to 82 ℃, stirring and reacting for 95 hours at 150rpm, cooling to room temperature, precipitating with isopropanol and anhydrous diethyl ether with the volume ratio of 3:7, and finally vacuum drying at 60 ℃ to obtain the quaternized polyphenyl ether;
(2) Mixing polyamide and quaternized polyphenyl ether (PAE) with the mass part of 1:1.15, placing the mixture into a reaction device, adding butyl titanate serving as a catalyst with the mass of 0.04 times that of furan-based polyamide, heating to 92 ℃ under nitrogen atmosphere, reacting for 20min, heating to 140 ℃, sealing and vacuumizing the maximum vacuum degree of ester, continuously heating to 205 ℃, reacting for 1.5h, heating to 225 ℃ and continuously reacting for 1.5h to obtain modified polyamide;
(3) Mixing the modified polyamide and the plasticizer epoxy soybean oil according to the mass ratio of 13:0.6, placing the mixture into a plasticator, plasticating for 4min at the temperature of 130 ℃, and then extruding and granulating the mixture by an injection molding machine to obtain an engineering plastic matrix;
(4) Mixing adipic acid and diethylenetriamine according to a mass ratio of 1:1.1, heating to 115 ℃, stirring at 150rpm for reaction for 25min, heating to 185 ℃, continuing to react for 2.5h, cooling to room temperature, then dripping epichlorohydrin with an amount which is 1 time of the mass of the adipic acid and soybean protein with an amount which is 0.2 time of the mass of the adipic acid at a rate of 4ml/min, heating to 54 ℃, continuing to react for 2.5h, and regulating pH to 3.5 by sulfuric acid to obtain epoxy polyamide; mixing epoxy polyamide and filler nano alumina according to a mass ratio of 15:0.4, and uniformly stirring to obtain the wear-resistant coating; and (3) coating the wear-resistant coating on the surface of an engineering plastic matrix, wherein the thickness of the wear-resistant coating is 0.05 mu m, and standing and curing for 5 days to prepare the high-strength wear-resistant engineering plastic.
Comparative example 3
(1) Terephthalic acid, 2, 5-furandicarboxylic acid, hexanediol and tetrabutyl titanate are mixed according to the mass ratio of 2:1.5:3:0.2, the temperature is raised to 125 ℃, the mixture is stirred and reacted for 10 hours at 150rpm, and then the mixture is dried in vacuum for 12 hours at 95 ℃ to prepare the polyethylene furandicarboxylic acid glycol ester; mixing polyethylene furan dicarboxylate and poly (p-phenylene diformyl) dodecandiamine according to a mass ratio of 1:1.15, placing the mixture into a reaction device, adding a catalyst butyl titanate with the mass of 0.04 times of the polyethylene furan diformate, heating to 92 ℃ under a nitrogen atmosphere, reacting for 20min, heating to 140 ℃, sealing and vacuumizing to the maximum vacuum degree, continuously heating to 205 ℃, reacting for 1.5h, heating to 225 ℃ and continuously reacting for 1.5h to obtain furan-based polyamide;
(2) Mixing sodium hydride and tetrahydrofuran according to a mass ratio of 1:25, stirring for 1.5 hours in an ice bath, heating to room temperature for continuous reaction for 1.5 hours, then adding a tetrahydrofuran solution of which the mass fraction is 25% and of which the mass is 2.4 times that of sodium hydride, continuously reacting for 14 hours, transferring into the ice bath, dropwise adding ammonium chloride until no gas is generated, extracting with methylene chloride, drying, dispersing in methanol of which the mass is 25 times that of sodium hydride again, stirring uniformly, adding methyl iodide of which the mass is 16 times that of sodium hydride, refluxing for 73 hours, adding ethyl acetate of which the mass is 250 times that of sodium hydride for precipitation, and finally drying at 75 ℃ for 24 hours to obtain a quaternized polyphenyl ether precursor; mixing the azido polyphenyl ether, N-methylpyrrolidone and quaternized polyphenyl ether precursor according to the mass ratio of 3:18:0.3, adding copper bromide with the mass of 0.007 times of the azido polyphenyl ether and pentamethyl diethylenetriamine with the mass of 0.07 times of the azido polyphenyl ether after uniformly stirring, freezing, vacuum and thawing for 3 times, heating to 82 ℃, stirring and reacting for 95 hours at 150rpm, cooling to room temperature, precipitating with isopropanol and anhydrous diethyl ether with the volume ratio of 3:7, and finally vacuum drying at 60 ℃ to obtain the quaternized polyphenyl ether;
(3) Mixing furyl polyamide and quaternized polyphenyl ether A/D1.15 in a reaction device, adding butyl titanate serving as a catalyst with the mass 0.04 times that of the furyl polyamide, heating to 92 ℃ under nitrogen atmosphere, reacting for 20min, heating to 140 ℃, sealing and vacuumizing to the maximum vacuum degree, continuously heating to 205 ℃, reacting for 1.5h, heating to 225 ℃ and continuously reacting for 1.5h to obtain modified polyamide;
(4) Mixing the modified polyamide and the plasticizer epoxy soybean oil according to the mass ratio of 13:0.6, placing the mixture into a plasticator, plasticating for 4min at the temperature of 130 ℃, and then extruding and granulating the mixture by an injection molding machine to obtain an engineering plastic matrix;
(5) Mixing adipic acid and diethylenetriamine according to a mass ratio of 1:1.1, heating to 115 ℃, stirring at 150rpm for reaction for 25min, heating to 185 ℃, continuing to react for 2.5h, cooling to room temperature, heating to 54 ℃, continuing to react for 2.5h, and regulating pH to 3.5 with sulfuric acid to obtain polyamide; mixing polyamide and filler nano alumina according to a mass ratio of 15:0.4, and uniformly stirring to obtain the wear-resistant coating; and (3) coating the wear-resistant coating on the surface of an engineering plastic matrix, wherein the thickness of the wear-resistant coating is 0.05 mu m, and standing and curing for 5 days to prepare the high-strength wear-resistant engineering plastic.
Comparative example 4
(1) Terephthalic acid, 2, 5-furandicarboxylic acid, hexanediol and tetrabutyl titanate are mixed according to the mass ratio of 2:1.5:3:0.2, the temperature is raised to 125 ℃, the mixture is stirred and reacted for 10 hours at 150rpm, and then the mixture is dried in vacuum for 12 hours at 95 ℃ to prepare the polyethylene furandicarboxylic acid glycol ester; mixing polyethylene furan dicarboxylate and poly (p-phenylene diformyl) dodecandiamine according to a mass ratio of 1:1.15, placing the mixture into a reaction device, adding a catalyst butyl titanate with the mass of 0.04 times of the polyethylene furan diformate, heating to 92 ℃ under a nitrogen atmosphere, reacting for 20min, heating to 140 ℃, sealing and vacuumizing to the maximum vacuum degree, continuously heating to 205 ℃, reacting for 1.5h, heating to 225 ℃ and continuously reacting for 1.5h to obtain furan-based polyamide;
(2) Mixing sodium hydride and tetrahydrofuran according to a mass ratio of 1:25, stirring for 1.5 hours in an ice bath, heating to room temperature for continuous reaction for 1.5 hours, then adding a tetrahydrofuran solution of which the mass fraction is 25% and of which the mass is 2.4 times that of sodium hydride, continuously reacting for 14 hours, transferring into the ice bath, dropwise adding ammonium chloride until no gas is generated, extracting with methylene chloride, drying, dispersing in methanol of which the mass is 25 times that of sodium hydride again, stirring uniformly, adding methyl iodide of which the mass is 16 times that of sodium hydride, refluxing for 73 hours, adding ethyl acetate of which the mass is 250 times that of sodium hydride for precipitation, and finally drying at 75 ℃ for 24 hours to obtain a quaternized polyphenyl ether precursor; mixing the azido polyphenyl ether, N-methylpyrrolidone and quaternized polyphenyl ether precursor according to the mass ratio of 3:18:0.3, adding copper bromide with the mass of 0.007 times of the azido polyphenyl ether and pentamethyl diethylenetriamine with the mass of 0.07 times of the azido polyphenyl ether after uniformly stirring, freezing, vacuum and thawing for 3 times, heating to 82 ℃, stirring and reacting for 95 hours at 150rpm, cooling to room temperature, precipitating with isopropanol and anhydrous diethyl ether with the volume ratio of 3:7, and finally vacuum drying at 60 ℃ to obtain the quaternized polyphenyl ether;
(3) Mixing furyl polyamide and quaternized polyphenyl ether A/D1.15 in a reaction device, adding butyl titanate serving as a catalyst with the mass 0.04 times that of the furyl polyamide, heating to 92 ℃ under nitrogen atmosphere, reacting for 20min, heating to 140 ℃, sealing and vacuumizing to the maximum vacuum degree, continuously heating to 205 ℃, reacting for 1.5h, heating to 225 ℃ and continuously reacting for 1.5h to obtain modified polyamide;
(4) Mixing the modified polyamide and the plasticizer epoxy soybean oil according to the mass ratio of 13:0.6, placing the mixture into a plasticator, plasticating for 4min at the temperature of 130 ℃, and then extruding and granulating the mixture by an injection molding machine to obtain the engineering plastic.
Effect example
The following table 1 gives the results of performance analysis of high strength abrasion resistant engineering plastics using examples 1 to 3 of the present invention and comparative examples 1 to 4:
TABLE 1
As is evident from comparison of the experimental data of examples in Table 1 with comparative examples, the high-strength abrasion-resistant engineering plastics prepared in examples 1, 2 and 3 are superior in heat resistance, strength and abrasion resistance.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are, therefore, to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.

Claims (10)

1. The high-strength wear-resistant engineering plastic is characterized by being prepared by extruding modified polyamide and plasticizer and then coating wear-resistant paint.
2. The high strength abrasion resistant engineering plastic according to claim 1, wherein the modified polyamide is prepared by reacting furan based polyamide with quaternized polyphenylene ether.
3. The high-strength wear-resistant engineering plastic according to claim 2, wherein the furyl polyamide is prepared by reacting polyethylene furandicarboxylate with poly (p-phenylene diformyl dodecandiamine); the quaternized polyphenyl ether is prepared by reacting azidated polyphenyl ether, methyl hydroxybenzoate and aminopropanol.
4. A high strength wear resistant engineering plastic according to claim 1, wherein said wear resistant coating comprises epoxy polyamide and filler; the epoxy polyamide is prepared by adding soybean protein into polyamine polyamide with epoxy groups; the filler is nano alumina; the plasticizer is epoxidized soybean oil.
5. The preparation method of the high-strength wear-resistant engineering plastic is characterized by comprising the following specific steps of:
(1) Mixing polyethylene furandicarboxylate and poly (p-benzoyl) dodecandiamine according to a mass ratio of 1:1.05-1:1.25, placing the mixture into a reaction device, adding a catalyst butyl titanate with the mass of 0.03-0.05 times of the polyethylene furandicarboxylate, heating to 90-93 ℃ under a nitrogen atmosphere, reacting for 10-30 min, heating to 130-150 ℃, sealing and vacuumizing to the maximum vacuum degree of ester, continuously heating to 200-210 ℃, reacting for 1-2 h, heating to 220-230 ℃, and continuously reacting for 1-2 h to obtain the furyl polyamide;
(2) Mixing the azido polyphenyl ether, N-methylpyrrolidone and quaternized polyphenyl ether precursor according to the mass ratio of 3:15:0.2-3:20:0.5, stirring uniformly, adding copper bromide with the mass of 0.005-0.008 times of the azido polyphenyl ether and pentamethyl diethylenetriamine with the mass of 0.05-0.08 times of the azido polyphenyl ether, freezing, vacuum and thawing for 3 times, heating to 80-83 ℃, stirring at 100-200 rpm for reacting for 90-100 h, cooling to room temperature, precipitating with isopropanol and anhydrous diethyl ether with the volume ratio of 3:7, and finally vacuum drying at 60 ℃ to obtain the quaternized polyphenyl ether;
(3) Mixing furan-based polyamide and quaternized polyphenyl ether Afather mass part 1:1.05-1:1.25, placing the mixture into a reaction device, adding butyl titanate serving as a catalyst with the weight 0.03-0.05 times that of furan-based polyamide, heating to 90-93 ℃ under a nitrogen atmosphere, reacting for 10-30 min, heating to 130-150 ℃, sealing and vacuumizing to the maximum vacuum degree, continuously heating to 200-210 ℃, reacting for 1-2 h, heating to 220-230 ℃, and continuously reacting for 1-2 h to obtain modified polyamide;
(4) Mixing the modified polyamide and the plasticizer, placing the mixture in a plasticator, plasticating for 3-5 min at the temperature of 120-140 ℃, and then extruding and granulating the mixture by an injection molding machine to obtain an engineering plastic matrix;
(5) Mixing epoxy polyamide and filler according to the mass ratio of 10:0.3-20:0.5, and uniformly stirring to obtain the wear-resistant coating; and (3) coating the wear-resistant coating on the surface of the engineering plastic matrix, and standing and curing for 3-7 d to prepare the high-strength wear-resistant engineering plastic.
6. The method for producing a high-strength abrasion-resistant engineering plastic according to claim 5, wherein in the step (1): the preparation method of the polyethylene furandicarboxylate comprises the following steps: terephthalic acid, 2, 5-furandicarboxylic acid, hexanediol and tetrabutyl titanate are mixed according to the mass ratio of 2:1:3:0.2-2:2:3:0.2, the temperature is raised to 120-130 ℃, stirring reaction is carried out for 8-12 h at 100-200 rpm, and then vacuum drying is carried out for 12h at 90-100 ℃ to obtain the polyethylene furandicarboxylic acid glycol ester.
7. The method for producing a high-strength abrasion-resistant engineering plastic according to claim 5, wherein in the step (2): the preparation method of the quaternized polyphenyl ether precursor comprises the following steps: mixing sodium hydride and tetrahydrofuran according to a mass ratio of 1:20-1:30, stirring for 1-2 hours in an ice bath, heating to room temperature for continuous reaction for 1-2 hours, adding tetrahydrofuran solution of 3-bromopropyne with a mass fraction of 20-30% of that of sodium hydride, which is 2.3-2.5 times of that of sodium hydride, continuously reacting for 12-16 hours, transferring into the ice bath, dropwise adding ammonium chloride until no gas is generated, extracting with dichloromethane, drying, dispersing in methanol with a mass of 20-30 times of that of sodium hydride again, stirring uniformly, adding methyl iodide with a mass of 15-18 times of that of sodium hydride, refluxing for reaction for 70-76 hours, adding ethyl acetate with a mass of 200-300 times of that of sodium hydride for precipitation, and finally drying at 70-80 ℃ for 24 hours to obtain the quaternized polyphenyl ether precursor.
8. The method for producing a high-strength abrasion-resistant engineering plastic according to claim 5, wherein in the step (4): the mass ratio of the modified polyamide to the plasticizer is 10:0.5-15:0.8.
9. The method for producing a high-strength abrasion-resistant engineering plastic according to claim 5, wherein in the step (5): the preparation method of the epoxy polyamide comprises the following steps: mixing adipic acid and diethylenetriamine according to a mass ratio of 1:1.05-1:1.15, heating to 110-120 ℃, stirring at 100-200 rpm for reaction for 20-30 min, heating to 180-190 ℃, continuing to react for 2-3 h, cooling to room temperature, then dripping epichlorohydrin with the mass of 0.9-1.1 times of adipic acid and soy protein with the mass of 0.1-0.3 times of adipic acid at a rate of 3-5 ml/min, heating to 50-60 ℃, continuing to react for 2-3 h, and regulating pH to 3-4 with sulfuric acid to obtain the epoxy polyamide.
10. The method for producing a high-strength abrasion-resistant engineering plastic according to claim 5, wherein in the step (5): the thickness of the wear-resistant paint is 0.03-0.08 mu m.
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