High-performance composite material with anti-aging property and injection molding process thereof

Abstract

The present application relates to the technical field of high polymer, in particular to a kind of anti-aging high-performance composite material and its injection molding process.The acidized spirocyclic phosphate is prepared by adding phosphorus oxychloride, pentaerythritol and formic acid.A kind of composite flame retardant is prepared by mixing reaction of acidized spirocyclic phosphate, phosphorus heteroheptacyclo-acrylamide double bond derivative, phosphorus heteroheptacyclo-allyloxy double bond derivative and phosphorus hetero-link-benzenediol diallyl double bond derivative.Then, high-performance composite material is obtained by adding polypropylene, acrylonitrile-butadiene-styrene copolymer, compatibilizer, inorganic filler, antioxidant, anti-aging agent, composite flame retardant and lubricant, and by melt extrusion and granulation.The high-performance composite material is injection molded to obtain finished product.The finished product prepared by the present application has good flame retardancy, anti-aging property and mechanical property, so it has wide application prospect in the technical field of high polymer.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of high polymers, in particular to an anti-aging high-performance composite material and its injection molding process. BACKGROUND

[0002] High-performance composite materials have important application value in modern industry and daily life, especially in meeting the multifunctional demands of high strength, wear resistance, anti-aging, flame retardance, etc. High-performance composite materials realize the comprehensive performance improvement of materials through the synergistic effect of polypropylene, ABS, inorganic fillers, compatibilizers, etc. Such materials not only have excellent mechanical properties, such as high strength and high toughness, but also can maintain stability in extreme environments such as high temperature and high pressure. For example, in the field of automobile manufacturing, high-performance composite materials can be used to manufacture lightweight parts, reduce the weight of the whole vehicle, and improve fuel efficiency; in the field of home appliances, their wear resistance and anti-aging performance can prolong the service life of products and reduce resource waste. By meeting the stringent requirements of industry on material performance, this composite material promotes the technological progress and industrial upgrading of related industries. The wide application of high-performance composite materials promotes the development of high-value-added products. For example, in the field of electronics and electrical appliances, such materials can be used to manufacture high-durability housings to protect internal precision components. In addition, through optimization of the formula and processing technology, high-performance composite materials can also realize customized production to meet the special needs of different industries and scenarios, thereby bringing greater market competitiveness and economic benefits to enterprises.

[0003] In many application scenarios, the flame retardance of materials is crucial. For example, in the fields of building materials, electronics and electrical appliances, automobile manufacturing, etc., if materials do not have good flame retardance when exposed to high temperature or flame environment, they are prone to cause fire, resulting in serious casualties and property losses. By adding flame retardants to the composite material, the burning rate of the material can be significantly reduced, and even self-extinguishing can be achieved, thereby effectively inhibiting the spread of flames in the early stage of fire. This not only gains valuable time for personnel evacuation and fire fighting, but also greatly improves the safety performance of products. In addition, in outdoor or high-temperature environments, materials are easily affected by factors such as oxygen, ultraviolet light, and moisture, leading to oxidative degradation, resulting in problems such as mechanical property decline, surface cracking, or discoloration. For example, automobile parts, outdoor building materials, and solar cell panels, etc. If the anti-oxidation and anti-aging performance is insufficient during long-term use, it will accelerate the aging of the material, increase the frequency of maintenance and replacement, and thus increase the use cost. By adding antioxidants and anti-aging agents, the composite material can effectively resist the erosion of environmental factors, maintain long-term mechanical properties and appearance quality, and prolong its service life.

[0004] In order to overcome the defects of the prior art, the present application provides an anti-aging high-performance composite material and its injection molding process. SUMMARY

[0005] The present application aims to provide an anti-aging high-performance composite material and its injection molding process to solve the problems in the prior art.

[0006] To solve the above technical problems, the present application provides the following technical solutions:

[0007] An anti-aging high-performance composite material, comprising polypropylene, acrylonitrile-butadiene-styrene copolymer, compatibilizer, inorganic filler, antioxidant, anti-aging agent, composite flame retardant and lubricant.

[0008] More preferably, the content of each component of the high-performance composite material is as follows: 60-80 parts by mass of polypropylene, 20-30 parts by mass of acrylonitrile-butadiene-styrene copolymer, 3-4 parts by mass of compatibilizer, 8-10 parts by mass of inorganic filler, 0.4-0.6 parts by mass of antioxidant, 0.6-1.0 parts by mass of anti-aging agent, 15-20 parts by mass of composite flame retardant and 0.8-1.0 parts by mass of lubricant.

[0009] An injection molding process for an anti-aging high-performance composite material, comprising the following steps:

[0010] Step one: under a nitrogen environment, mix phosphorus oxychloride and pentaerythritol uniformly and heat to 85-95℃ for 30-40min, then heat to 120-130℃ for 9-10h of continuous reaction, after the reaction is completed, cool, wash, distill and vacuum dry to obtain chlorinated spirocyclic phosphate; under a nitrogen environment, slowly drop formic acid into the chlorinated spirocyclic phosphate at 35-45℃, the drop time is 1.0-1.5h, after the reaction is completed, wash and vacuum dry to obtain acidified spirocyclic phosphate;

[0011] Step two: under a nitrogen environment, mix the acidified spirocyclic phosphate and N,N-dimethylformamide, fully dissolve at 70-80℃, then add phosphorus hetero-fused-allyl acrylamide double bond derivative, phosphorus hetero-fused-allyloxy double bond derivative and phosphorus hetero-fused-hydroquinone diallyl double bond derivative, continue to react for 55-75h, after the reaction is completed, wash, centrifuge and dry to obtain the composite flame retardant;

[0012] Step three: mix polypropylene, acrylonitrile-butadiene-styrene copolymer, compatibilizer, inorganic filler, antioxidant, anti-aging agent, composite flame retardant and lubricant uniformly, then put them into a double-screw extruder for melt extrusion and granulation to obtain the high-performance composite material; the high-performance composite material is subjected to injection molding to obtain the finished product.

[0013] More preferably, in step one, the reaction molar ratio of phosphorus oxychloride to pentaerythritol is (0.4-0.5):0.1; the reaction molar ratio of chlorinated spirocyclic phosphate to formic acid is 1:(2.5-3.0).

[0014] More preferably, in step two, the molar ratio of the acidified spirocyclic phosphate, phosphaphenanthrene-acrylamide double bond derivative, phosphaphenanthrene-allyloxy double bond derivative, and phosphacalix-benzene diol diallyl double bond derivative in the preparation of the composite flame retardant is (5-6):2:1:(2-3).

[0015] More preferably, the preparation process of the phosphaphenanthrene-acrylamide double bond derivative is as follows: 9,10-dihydro-9-oxo-10-phosphaphenanthrene-10-oxide, triethylamine, and dichloromethane are uniformly mixed, then N-(2-hydroxyethyl) acrylamide is added and the temperature is lowered to 0-4℃, then carbon tetrachloride is added and reacted for 14-16h, after the reaction is completed, dilution, extraction, drying, filtration, and reduced pressure distillation are performed to obtain the phosphaphenanthrene-acrylamide double bond derivative; the molar ratio of 9,10-dihydro-9-oxo-10-phosphaphenanthrene-10-oxide and N-(2-hydroxyethyl) acrylamide is 1:(1.2-1.3).

[0016] More preferably, the preparation process of the phosphaphenanthrene-allyloxy double bond derivative is as follows: 9,10-dihydro-9-oxo-10-phosphaphenanthrene-10-oxide is dissolved at 135-145℃, then 1-allyloxy-2,3-epoxypropane and triphenylphosphine catalyst are added, and the reaction is continuously stirred under a nitrogen environment for 12-14h to obtain the phosphaphenanthrene-allyloxy double bond derivative; the molar ratio of 9,10-dihydro-9-oxo-10-phosphaphenanthrene-10-oxide and 1-allyloxy-2,3-epoxypropane is 1:(1.2-1.3).

[0017] More preferably, the preparation process of the phosphacalix-benzene diol diallyl double bond derivative is as follows: 5',5-diallyl-2,2'-biphenyldiol, triethylamine, and toluene are uniformly mixed, then benzene phosphonic dichloride is added dropwise, after the dropwise addition is completed, the temperature is raised to 70-75℃ and the reaction is continuously performed for 12-14h, after the reaction is completed, washing, distillation of the solvent, standing, and vacuum drying are performed to obtain the phosphacalix-benzene diol diallyl double bond derivative; the molar ratio of 5',5-diallyl-2,2'-biphenyldiol and benzene phosphonic dichloride is 1:

[0018] (1.2-1.3).

[0019] More preferably, the compatibilizer is ethylene-maleic anhydride copolymer, the inorganic filler is calcium carbonate, and the lubricant is zinc stearate.

[0020] More preferably, in step three, the extrusion temperature of the melt extrusion is 250-270℃ and the screw rotation speed is 400-450r / min.

[0021] The beneficial effects of the present application are as follows:

[0022] The application is characterized in that, in step two, a phosphaphenanthrene-acrylamide double bond derivative is prepared by adding 9,10-dihydro-9-oxo-10-phosphaphenanthrene-10-oxide, N-(2-hydroxyethyl) acrylamide, triethylamine, dichloromethane; in the process, 9,10-dihydro-9-oxo-10-phosphaphenanthrene-10-oxide reacts with N-(2-hydroxyethyl) acrylamide under the action of carbon tetrachloride to prepare a phosphaphenanthrene-acrylamide double bond derivative containing flame-retardant nitrogen and phosphorus; a phosphaphenanthrene-allyloxy double bond derivative is prepared by adding 9,10-dihydro-9-oxo-10-phosphaphenanthrene-10-oxide, 1-allyloxy-2,3-epoxypropane, triphenylphosphine catalyst; in the process, 9,10-dihydro-9-oxo-10-phosphaphenanthrene-10-oxide and 1-allyloxy-2,3-epoxypropane undergo ring-opening reaction to prepare a phosphaphenanthrene-allyloxy double bond derivative containing flame-retardant phosphorus; a phosphorus-linked-benzene diol diallyl double bond derivative is prepared by adding 5',5-diallyl-2,2'-diphenyl diol, phenyl phosphinic dichloride, triethylamine, toluene; in the process, 5',5-diallyl-2,2'-diphenyl diol and phenyl phosphinic dichloride undergo nucleophilic substitution reaction to prepare a phosphorus-linked-benzene diol diallyl double bond derivative containing flame-retardant phosphorus.

[0023] In step one, acidified spirocyclic phosphate containing multiple active P-H bonds is prepared by adding phosphorus oxychloride, pentaerythritol, formic acid; in step two, the acidified spirocyclic phosphate containing multiple active P-H bonds is mixed with the phosphaphenanthrene-acrylamide double bond derivative, the phosphaphenanthrene-allyloxy double bond derivative, and the phosphorus-linked-benzene diol diallyl double bond derivative to undergo addition reaction and prepare a multi-crosslinked network composite flame retardant.

[0024] The application is characterized in that, in step three, high-performance composite materials are prepared by adding polypropylene, acrylonitrile-butadiene-styrene copolymer, compatibilizer, inorganic filler, antioxidant, anti-aging agent, composite flame retardant, and lubricant, and then melt extruding and granulating; the high-performance composite materials are injection molded to obtain finished products; and the finished products prepared by the application have good flame retardancy, anti-aging property, and mechanical property, thus having wide application prospects in the field of high polymer technology. DETAILED DESCRIPTION

[0025] The technical solutions in the present application will be described clearly and completely below in combination with the embodiments of the present application. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all the other embodiments obtained by those skilled in the art without creative work fall within the scope of protection of the present application.

[0026] Raw material sources:

[0027] Polypropylene, provided by Shanghai Shunshi Plastic Co., Ltd., model Y16; acrylonitrile-butadiene-styrene copolymer, provided by Shanghai Kaijin Chemical Co., Ltd., model ABSPA777D; ethylene-maleic anhydride copolymer, provided by Shanghai Wanluj Plastic Co., Ltd., model E400; anti-aging agent, provided by Guangzhou Yino Chemical Technology Co., Ltd., model 3808; antioxidant, provided by Nanjing Milan New Material Co., Ltd., specifically antioxidant 168.

[0028] Example 1: Step one: under the nitrogen environment, mix phosphorus oxychloride and pentaerythritol uniformly and heat to 95℃ for 40 min, then heat to 130℃ for 10 h of continuous reaction, after the reaction is completed, cool, wash, distill, and vacuum dry to obtain chlorinated spirocyclic phosphonate; under the nitrogen environment, slowly drop formic acid into the chlorinated spirocyclic phosphonate at 45℃, the drop time is 1.5 h, after the reaction is completed, wash, and vacuum dry to obtain acidified spirocyclic phosphonate; the reaction molar ratio of phosphorus oxychloride and pentaerythritol is 0.45:0.1; the reaction molar ratio of chlorinated spirocyclic phosphonate and formic acid is 1:2.7;

[0029] Step two: mix 9,10-dihydro-9-oxo-10-phosphaphenanthrene-10-oxide, triethylamine, dichloromethane uniformly, then add N-(2-hydroxyethyl) acrylamide and cool to 4℃, then add carbon tetrachloride for 16 h of reaction, after the reaction is completed, dilute, extract, dry, filter, and reduce pressure distill to obtain phosphaphenanthrene-acrylamide double bond derivative; the reaction molar ratio of 9,10-dihydro-9-oxo-10-phosphaphenanthrene-10-oxide and N-(2-hydroxyethyl) acrylamide is 1:1.2;

[0030] Dissolve 9,10-dihydro-9-oxo-10-phosphaphenanthrene-10-oxide at 145℃, then add 1-allyloxy-2,3-epoxypropane, triphenylphosphine catalyst, and continuously stir for 14 h of reaction under the nitrogen environment to obtain phosphaphenanthrene-allyloxy double bond derivative; the reaction molar ratio of 9,10-dihydro-9-oxo-10-phosphaphenanthrene-10-oxide and 1-allyloxy-2,3-epoxypropane is 1:1.2;

[0031] Mixing 5', 5-diallyl-2, 2'-diphenylol, triethylamine, toluene uniformly, then adding phenyl phosphinic dichloride dropwise, after the end of dropwise adding, warming to 75℃ for 14h, after the reaction is completed, washing, distilling solvent, standing, vacuum drying, obtaining phosphin-phenol diallyl double bond derivative; the reaction molar ratio of 5', 5-diallyl-2, 2'-diphenylol and phenyl phosphinic dichloride is 1:1.2;

[0032] Mixing acidified spirocyclic phosphate and N, N-dimethylformamide under nitrogen environment, after fully dissolving at 80℃, adding phosphin-phenyl acrylamide double bond derivative, phosphin-phenyl allyloxy double bond derivative, phosphin-phenol diallyl double bond derivative, continuing to react for 75h, after the reaction is completed, washing, centrifuging, drying, obtaining composite flame retardant; the reaction molar ratio of acidified spirocyclic phosphate, phosphin-phenyl acrylamide double bond derivative, phosphin-phenyl allyloxy double bond derivative, phosphin-phenol diallyl double bond derivative is 5.5:2:1:2.5;

[0033] Step three: mixing 70g polypropylene, 25g acrylonitrile-butadiene-styrene copolymer, 3g ethylene-maleic anhydride copolymer, 8g calcium carbonate, 0.4g antioxidant, 0.6g anti-aging agent, 18g composite flame retardant and 1g zinc stearate uniformly, then putting into double screw extruder, melt extruding, granulating, obtaining high performance composite material; the high performance composite material is injection molded, obtaining finished product; the extrusion temperature of melt extruding is 270℃, the screw rotation speed is 450r / min.

[0034] Example 2: step one: mixing phosphorus oxychloride and pentaerythritol uniformly under nitrogen environment, warming to 90℃ for 35min, then warming to 125℃ for 9.5h, after the reaction is completed, cooling, washing, distilling, vacuum drying, obtaining chlorinated spirocyclic phosphate; under nitrogen environment, slowly adding formic acid to chlorinated spirocyclic phosphate at 40℃, the dropwise adding time is 1.2h, after the reaction is completed, washing, vacuum drying, obtaining acidified spirocyclic phosphate; the reaction molar ratio of phosphorus oxychloride and pentaerythritol is 0.45:0.1; the reaction molar ratio of chlorinated spirocyclic phosphate and formic acid is 1:2.7;

[0035] Step two: mixing 9, 10-dihydro-9-oxo-10-phosphaphenanthrene-10-oxide, triethylamine, dichloromethane uniformly, then adding N-(2-hydroxyethyl) acrylamide and cooling to 2℃, then adding carbon tetrachloride for 15h, after the reaction is completed, diluting, extracting, drying, filtering, reducing pressure distilling, obtaining phosphin-phenyl acrylamide double bond derivative; the reaction molar ratio of 9, 10-dihydro-9-oxo-10-phosphaphenanthrene-10-oxide and N-(2-hydroxyethyl) acrylamide is 1:1.2;

[0036] Dissolve 9,10-dihydro-9-oxo-10-phosphaphenanthrene-10-oxide at 140℃, then add 1-allyloxy-2,3-epoxypropane and triphenylphosphine catalyst, continuously stir the reaction under nitrogen for 13h to obtain phosphaphenanthrene-allyloxy double bond derivative; the molar ratio of 9,10-dihydro-9-oxo-10-phosphaphenanthrene-10-oxide and 1-allyloxy-2,3-epoxypropane is 1:1.2;

[0037] Mix 5',5-diallyl-2,2'-biphenyldiol, triethylamine and toluene uniformly, then add benzene phosphonic dichloride dropwise, after the dropwise addition is completed, warm to 73℃ for 13h, after the reaction is completed, wash, distill the solvent, stand, vacuum dry to obtain phosphorus-linked-biphenyldiol diallyl double bond derivative; the molar ratio of 5',5-diallyl-2,2'-biphenyldiol and benzene phosphonic dichloride is 1:1.2;

[0038] Mix acidified spirocyclic phosphate and N,N-dimethylformamide under nitrogen, fully dissolve at 70-80℃, then add phosphaphenanthrene-acrylamide double bond derivative, phosphaphenanthrene-allyloxy double bond derivative, phosphorus-linked-biphenyldiol diallyl double bond derivative, continuously react for 65h, after the reaction is completed, wash, centrifuge, dry to obtain a composite flame retardant; the molar ratio of acidified spirocyclic phosphate, phosphaphenanthrene-acrylamide double bond derivative, phosphaphenanthrene-allyloxy double bond derivative, phosphorus-linked-biphenyldiol diallyl double bond derivative is 5.5:2:1:2.5;

[0039] Step three: mix 70g of polypropylene, 25g of acrylonitrile-butadiene-styrene copolymer, 3g of ethylene-maleic anhydride copolymer, 8g of calcium carbonate, 0.4g of antioxidant, 0.6g of anti-aging agent, 18g of composite flame retardant and 1g of zinc stearate uniformly, then put them into a double screw extruder to melt extrude and pelletize to obtain a high-performance composite material; the high-performance composite material is injection molded to obtain a finished product; the extrusion temperature of the melt extrusion is 260℃, and the screw rotation speed is 425r / min.

[0040] Example 3: Step one: mix phosphorus oxychloride and pentaerythritol uniformly under nitrogen, warm to 85℃ for 30min, then warm to 120℃ for 9h, after the reaction is completed, cool, wash, distill, vacuum dry to obtain chlorinated spirocyclic phosphate; under nitrogen, slowly drop formic acid into chlorinated spirocyclic phosphate at 35℃ for 1h, after the reaction is completed, wash, vacuum dry to obtain acidified spirocyclic phosphate; the molar ratio of phosphorus oxychloride and pentaerythritol is 0.45:0.1; the molar ratio of chlorinated spirocyclic phosphate and formic acid is 1:2.7;

[0041] Step two: 9, 10-dihydro-9-oxo-10-phosphaphenanthrene-10-oxide, triethylamine, dichloromethane are mixed uniformly, then N- (2-hydroxyethyl) acrylamide is added and cooled to 0℃, then carbon tetrachloride is added and reacted for 14h, after the reaction is completed, dilution, extraction, drying, filtration, and reduced pressure distillation are performed to obtain a phosphaphenanthrene-acrylamide double bond derivative; wherein the molar ratio of 9, 10-dihydro-9-oxo-10-phosphaphenanthrene-10-oxide and N- (2-hydroxyethyl) acrylamide is 1: 1.2;

[0042] 9, 10-dihydro-9-oxo-10-phosphaphenanthrene-10-oxide is dissolved at 135℃, then 1-allyloxy-2, 3-epoxypropane and triphenylphosphine catalyst are added, and the reaction is continuously stirred under a nitrogen environment for 12h to obtain a phosphaphenanthrene-allyloxy double bond derivative; wherein the molar ratio of 9, 10-dihydro-9-oxo-10-phosphaphenanthrene-10-oxide and 1-allyloxy-2, 3-epoxypropane is 1: 1.2;

[0043] 5', 5-diallyl-2, 2'-diphenylol, triethylamine, toluene are mixed uniformly, then benzene phosphonic dichloride is added dropwise, after the dropwise addition is completed, the temperature is raised to 70℃ and the reaction is continuously performed for 12h, after the reaction is completed, washing, distillation of solvent, standing, and vacuum drying are performed to obtain a phosphorus-linked-diphenol diallyl double bond derivative; wherein the molar ratio of 5', 5-diallyl-2, 2'-diphenylol and benzene phosphonic dichloride is 1: 1.2;

[0044] Under a nitrogen environment, acidified spirocyclic phosphate and N, N-dimethylformamide are mixed and fully dissolved at 70℃, then phosphaphenanthrene-acrylamide double bond derivative, phosphaphenanthrene-allyloxy double bond derivative, and phosphorus-linked-diphenol diallyl double bond derivative are added, and the reaction is continuously performed for 55h, after the reaction is completed, washing, centrifugation, and drying are performed to obtain a composite flame retardant; wherein the molar ratio of acidified spirocyclic phosphate, phosphaphenanthrene-acrylamide double bond derivative, phosphaphenanthrene-allyloxy double bond derivative, and phosphorus-linked-diphenol diallyl double bond derivative is 5.5: 2: 1: 2.5;

[0045] Step three: 70g of polypropylene, 25g of acrylonitrile-butadiene-styrene copolymer, 3g of ethylene-maleic anhydride copolymer, 8g of calcium carbonate, 0.4g of antioxidant, 0.6g of anti-aging agent, 18g of composite flame retardant, and 1g of zinc stearate are uniformly stirred, then are put into a double screw extruder to perform melt extrusion and granulation to obtain a high-performance composite material; the high-performance composite material is subjected to injection molding to obtain a finished product; the extrusion temperature of the melt extrusion is 250℃, and the screw rotation speed is 400r / min.

[0046] Comparative Example 1: In the preparation of the composite flame retardant, the reaction molar ratio of acidified spirocyclic phosphate, phosphine-propenamide double bond derivative, phosphine-allyloxy double bond derivative, phosphine-benzene diol diallyl double bond derivative is adjusted to 1:2:1:1, and the rest is the same as Example 1. The specific steps are as follows: Step one: under the nitrogen environment, mix phosphorus oxychloride and pentaerythritol uniformly and heat to 95°C for 40 min, then heat to 130°C for 10 h of continuous reaction. After the reaction is completed, cool, wash, distill, and vacuum dry to obtain chlorinated spirocyclic phosphate. Under the nitrogen environment, slowly drop formic acid into chlorinated spirocyclic phosphate at 45°C, with a drop time of 1.5 h. After the reaction is completed, wash and vacuum dry to obtain acidified spirocyclic phosphate. The reaction molar ratio of phosphorus oxychloride and pentaerythritol is 0.45:0.1. The reaction molar ratio of chlorinated spirocyclic phosphate and formic acid is 1:2.7.

[0047] Step two: mix 9,10-dihydro-9-oxo-10-phosphaphenanthrene-10-oxide, triethylamine, dichloromethane uniformly, then add N-(2-hydroxyethyl) acrylamide and cool to 4°C, then add carbon tetrachloride and react for 16 h. After the reaction is completed, dilute, extract, dry, filter, and distill under reduced pressure to obtain a phosphine-propenamide double bond derivative. The reaction molar ratio of 9,10-dihydro-9-oxo-10-phosphaphenanthrene-10-oxide and N-(2-hydroxyethyl) acrylamide is 1:1.2.

[0048] Dissolve 9,10-dihydro-9-oxo-10-phosphaphenanthrene-10-oxide at 145°C, then add 1-allyloxy-2,3-epoxypropane and triphenylphosphine catalyst, and continuously stir under the nitrogen environment for 14 h to obtain a phosphine-allyloxy double bond derivative. The reaction molar ratio of 9,10-dihydro-9-oxo-10-phosphaphenanthrene-10-oxide and 1-allyloxy-2,3-epoxypropane is 1:1.2.

[0049] Mix 5',5-diallyl-2,2'-biphenyldiol, triethylamine, and toluene uniformly, then drop benzene phosphonic dichloride. After the drop is completed, heat to 75°C for 14 h of continuous reaction. After the reaction is completed, wash, distill the solvent, stand, and vacuum dry to obtain a phosphine-benzene diol diallyl double bond derivative. The reaction molar ratio of 5',5-diallyl-2,2'-biphenyldiol and benzene phosphonic dichloride is 1:1.2.

[0050] The acidified spirocyclic phosphate and N,N-dimethylformamide are mixed under a nitrogen environment, and after being fully dissolved at 80℃, a phosphaphenanthrene-propenamide double bond derivative, a phosphaphenanthrene-allyloxy double bond derivative, and a phosphacalix-benzene diol diallyl double bond derivative are added, and the reaction is continuously carried out for 75 hours; after the reaction is completed, washing, centrifugation, and drying are performed to obtain the composite flame retardant; wherein the molar ratio of the acidified spirocyclic phosphate, the phosphaphenanthrene-propenamide double bond derivative, the phosphaphenanthrene-allyloxy double bond derivative, and the phosphacalix-benzene diol diallyl double bond derivative is 1:2:1:1.

[0051] Step three: 70g of polypropylene, 25g of acrylonitrile-butadiene-styrene copolymer, 3g of ethylene-maleic anhydride copolymer, 8g of calcium carbonate, 0.4g of antioxidant, 0.6g of anti-aging agent, 18g of composite flame retardant, and 1g of zinc stearate are uniformly stirred, and then are put into a double-screw extruder to perform melt extrusion and granulation, thereby obtaining a high-performance composite material; the high-performance composite material is subjected to injection molding to obtain a finished product; the extrusion temperature of the melt extrusion is 270℃, and the screw rotation speed is 450r / min.

[0052] Comparative Example 2: The preparation steps of the composite flame retardant are removed, and the remaining steps are the same as those in Example 1, and the specific steps are as follows: Step one: 70g of polypropylene, 25g of acrylonitrile-butadiene-styrene copolymer, 3g of ethylene-maleic anhydride copolymer, 8g of calcium carbonate, 0.4g of antioxidant, 0.6g of anti-aging agent, and 1g of zinc stearate are uniformly stirred, and then are put into a double-screw extruder to perform melt extrusion and granulation, thereby obtaining a high-performance composite material; the high-performance composite material is subjected to injection molding to obtain a finished product; the extrusion temperature of the melt extrusion is 270℃, and the screw rotation speed is 450r / min.

[0053] Detection test:

[0054] Limiting oxygen index test: the high-performance composite material prepared in the present application is tested according to the ISO 4589-2 standard, and the sample size is 100.0×6.5×3.2mm 3 , and the sample is measured five times by an oxygen index tester and the average value is taken.

[0055] Vertical burning grade test: the high-performance composite material prepared in the present application is tested according to the ISO 9773-1998 standard, and the sample size is 100.0×13.0×1.6mm 3 , and the sample is subjected to UL-94 test by a horizontal and vertical burning tester, and the sample is continuously ignited for 10s, and the test is performed five times to evaluate the burning grade of the sample.

[0056] Mechanical property test: the high-performance composite material prepared in the application is tested according to GB / T 1039-1992 standard, the stress-strain curve of the sample is recorded by using the instrument tensile testing machine, and the tensile rate is set to 10 mm / min. The tensile strength of the sample is measured five times and the average value of the obtained results is taken as the tensile strength of the corresponding sample. The results are as follows:

[0057] limiting oxygen index / % vertical burning rating Tensile strength MPa ]]> Example 1 33.5 V-0 34.3 Example 2 33.2 V-0 34.1 Example 3 33.1 V-0 33.8 Comparative Example 1 31.1 V-0 31.6 Comparative Example 2 17.5 V-1 26.5

[0058] Conclusion: the amount of examples 1-3 is unchanged, only the reaction parameters are modified. According to the experimental data, the performance of the sample does not change significantly.

[0059] Comparative example 1: when preparing the composite flame retardant, the molar ratio of acidified spirocyclic phosphate, phosphine-allyl acrylamide double bond derivative, phosphine-allyloxy double bond derivative, and phosphine-phenol diallyl double bond derivative is adjusted to 1:2:1:1, and the rest is the same as example 1. According to the experimental data, compared with example 1, the limiting oxygen index is reduced to 31.1%, the vertical burning grade is changed to V-0, and the tensile strength is reduced to 31.6 MPa. The analysis reason is that the optimal reaction molar ratio of acidified spirocyclic phosphate, phosphine-allyl acrylamide double bond derivative, phosphine-allyloxy double bond derivative, and phosphine-phenol diallyl double bond derivative in the application is (5-6):2:1:(2-3). Within this range, the flame-retardant components can cross-link with each other to prepare a high-efficiency composite flame retardant. Therefore, after adjusting the reaction ratio to 1:2:1:1 in comparative example 1, the components do not react uniformly, so the flame-retardant performance is reduced, and the tensile strength also decreases.

[0060] Comparative example 2: the preparation steps of the composite flame retardant are removed, and the rest is the same as example 1. According to the experimental data, compared with example 1, the limiting oxygen index is reduced to 17.5%, the vertical burning grade is changed to V-1, and the tensile strength is reduced to 26.5 MPa. The analysis reason is that the composite flame retardant prepared in the application contains a large amount of flame-retardant elements nitrogen and phosphorus and a multiple cross-linked network structure, so nitrogen and phosphorus can synergistically act through different mechanisms to improve the flame-retardant effect. Therefore, after removing the composite flame retardant, the flame-retardant performance is reduced. In addition, the multiple cross-linked network structure of the composite flame retardant can enhance the mechanical properties of the material and improve the tensile strength, so after removing the composite flame retardant, the tensile strength will decrease.

[0061] It is to be noted that, in the present text, relational terms such as first and second and the like can be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Moreover, the terms "comprises", "comprising", or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but can include other elements not expressly listed or inherent to such process, method, article, or apparatus.

[0062] Finally, it should be noted that the above-mentioned only constitutes preferred embodiments of the present application and is not intended to limit the present application. Although the present application has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications, equivalent substitutions, improvements and the like of the technical solutions described in the foregoing embodiments can still be made. Any modifications, equivalent substitutions, improvements and the like made within the spirit and principles of the present application shall be included in the scope of protection of the present application.

Claims

1. A process for injection molding of high performance composites with anti-aging properties, characterized in that: Comprising the following steps: Step one: under the nitrogen environment, mix phosphorus oxychloride and pentaerythritol uniformly and heat to 85-95℃ for 30-40min, then heat to 120-130℃ for 9-10h, after the reaction, cool, wash, distill, vacuum dry to obtain chlorinated spirocyclic phosphate; under the nitrogen environment, slowly drop formic acid into chlorinated spirocyclic phosphate at 35-45℃, the drop time is 1.0-1.5h, after the reaction, wash, vacuum dry to obtain acidified spirocyclic phosphate; the reaction molar ratio of phosphorus oxychloride and pentaerythritol is (0.4-0.5):0.1; the reaction molar ratio of chlorinated spirocyclic phosphate and formic acid is 1:(2.5-3.0); Step two: under the nitrogen environment, mix acidified spirocyclic phosphate and N,N-dimethylformamide, dissolve at 70-80℃, then add phosphorus aza-allyl amide double bond derivative, phosphorus aza-allyl oxy double bond derivative, phosphorus aza-benzene diol diallyl double bond derivative, continue to react for 55-75h, after the reaction, wash, centrifuge, dry to obtain the composite flame retardant; The preparation process of phosphorus aza-allyl amide double bond derivative is: mix 9,10-dihydro-9-oxo-10-phosphaphenanthrene-10-oxide, triethylamine, dichloromethane uniformly, then add N-(2-hydroxyethyl) acrylamide and cool to 0-4℃, then add carbon tetrachloride and react for 14-16h, after the reaction, dilute, extract, dry, filter, reduce pressure distillation to obtain phosphorus aza-allyl amide double bond derivative; the reaction molar ratio of 9,10-dihydro-9-oxo-10-phosphaphenanthrene-10-oxide and N-(2-hydroxyethyl) acrylamide is 1:(1.2-1.3); The preparation process of phosphorus aza-allyl oxy double bond derivative is: dissolve 9,10-dihydro-9-oxo-10-phosphaphenanthrene-10-oxide at 135-145℃, then add 1-allyloxy-2,3-epoxypropane, triphenylphosphine catalyst, continue to stir under the nitrogen environment for 12-14h to obtain phosphorus aza-allyl oxy double bond derivative; the reaction molar ratio of 9,10-dihydro-9-oxo-10-phosphaphenanthrene-10-oxide and 1-allyloxy-2,3-epoxypropane is 1:(1.2-1.3); The preparation process of phosphorus aza-benzene diol diallyl double bond derivative is: mix 5',5-diallyl-2,2'-biphenyldiol, triethylamine, toluene uniformly, then drop benzene phosphonic dichloride, after the drop, heat to 70-75℃ for 12-14h, after the reaction, wash, distill solvent, stand, vacuum dry to obtain phosphorus aza-benzene diol diallyl double bond derivative; the reaction molar ratio of 5',5-diallyl-2,2'-biphenyldiol and benzene phosphonic dichloride is 1:(1.2-1.3); Step three: the polypropylene, acrylonitrile-butadiene-styrene copolymer, compatibilizer, inorganic filler, antioxidant, anti-aging agent, composite flame retardant and lubricant are stirred uniformly, then put into a double screw extruder to melt extrude and granulate, obtaining the high performance composite material; the high performance composite material is injection molded to obtain the finished product; The content of each component of the high performance composite material is: 60-80 parts of polypropylene, 20-30 parts of acrylonitrile-butadiene-styrene copolymer, 3-4 parts of compatibilizer, 8-10 parts of inorganic filler, 0.4-0.6 parts of antioxidant, 0.6-1.0 parts of anti-aging agent, 15-20 parts of composite flame retardant and 0.8-1.0 parts of lubricant.

2. A process for injection molding of high performance composites with anti-aging properties according to claim 1, characterized in that: In step two, when preparing the composite flame retardant, the reaction molar ratio of acidified spirocyclic phosphate, phosphine- acrylamide double bond derivative, phosphine- allyloxy double bond derivative and phosphine- benzoquinone diallyl double bond derivative is (5-6): 2: 1: (2-3).

3. The process for injection molding of high performance composites with anti-aging properties according to claim 1, characterized in that: The compatibilizer is ethylene-maleic anhydride copolymer, the inorganic filler is calcium carbonate and the lubricant is zinc stearate.

4. The process for injection molding of high performance composites with anti-aging properties according to claim 1, characterized in that: In step three, the extrusion temperature of the melt extrusion is 250-270℃ and the screw rotation speed is 400-450 r / min.

5. A high performance composite material prepared based on the process of claim 1.