Anti-aging high-performance composite material and injection molding process thereof

Abstract

The invention relates to the technical field of macromolecules, in particular to an anti-aging high-performance composite material and an injection molding process thereof. According to the invention, phosphorus oxychloride, pentaerythritol and formic acid are added to prepare the acidified spirocyclic phosphate. And mixing the acidified spirocyclic phosphate with a phosphaphenanthrene-acrylamide double-bond derivative, a phosphaphenanthrene-allyloxy double-bond derivative and a phosphalinkage-benzenediol diallyl double-bond derivative, and carrying out a reaction so as to prepare the composite flame retardant. Polypropylene, an acrylonitrile-butadiene-styrene copolymer, a compatilizer, an inorganic filler, an antioxidant, an anti-aging agent, a composite flame retardant and a lubricant are added, melt extrusion and granulation are performed, and the high-performance composite material is obtained. And performing injection molding on the high-performance composite material to obtain a finished product. The finished product prepared by the invention has good flame retardance, aging resistance and mechanical properties, so that the finished product has a wide application prospect in the technical field of macromolecules.

Description

Technical Field

[0001] The present invention relates to the field of polymer technology, and specifically to a high-performance composite material with anti-aging properties and its injection molding process. Background Art

[0002] High-performance composite materials have important application values in modern industry and daily life, especially in meeting multi-functional requirements such as high strength, wear resistance, anti-aging, and flame retardancy. High-performance composite materials achieve the improvement of the comprehensive performance of materials through the synergistic effect of multiple components such as polypropylene, ABS, inorganic fillers, and compatibilizers. This material not only has excellent mechanical properties such as high strength and high toughness, but also can maintain stability under extreme environments such as high temperature and high pressure. For example, in the field of automotive manufacturing, high-performance composite materials can be used to manufacture lightweight components, reduce the weight of the whole vehicle, and improve fuel efficiency; in the field of household appliances, its wear resistance and anti-aging properties can extend the service life of products and reduce resource waste. By meeting the strict requirements of the industry for material properties, 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 electronic and electrical appliances, this material can be used to manufacture highly durable casings to protect internal precision components. In addition, by optimizing the formulation and processing technology, high-performance composite materials can also achieve customized production to meet the special needs of different industries and scenarios, thus bringing greater market competitiveness and economic benefits to enterprises.

[0003] In many application scenarios, the flame retardancy of materials is crucial. For example, in the fields of building materials, electronic and electrical appliances, and automotive manufacturing, once the material is exposed to a high-temperature or flame environment, if it does not have good flame retardancy, it is extremely easy to cause a fire, resulting in serious casualties and property losses. By adding flame retardants to the composite material, the combustion rate of the material can be significantly reduced, and even self-extinguishing can be achieved, thereby effectively suppressing the spread of flames in the initial stage of a fire. This not only buys precious 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 rays, and moisture, resulting in oxidative degradation, leading to problems such as a decrease in mechanical properties, surface cracking, or discoloration. For example, automotive parts, outdoor building materials, and solar panels, etc., during long-term use, if the antioxidant and anti-aging properties are insufficient, it will accelerate the aging of the material, increase the frequency of maintenance and replacement, and thus drive up 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 extend its service life.

[0004] In order to overcome the defects of the prior art, the present invention provides a high-performance composite material with anti-aging properties and its injection molding process. Summary of the Invention

[0005] The object of the present invention is to provide a high-performance composite material with anti-aging properties and its injection molding process to solve the problems in the prior art.

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

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

[0008] Preferably, the contents of the components of the high-performance composite material are as follows: in parts by mass, 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.

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

[0010] Step 1: Under a nitrogen atmosphere, phosphorus oxychloride and pentaerythritol are mixed evenly and heated to 85 - 95 °C and maintained for 30 - 40 min, then heated to 120 - 130 °C and continuously reacted for 9 - 10 h. After the reaction is completed, it is cooled, washed, distilled, and vacuum dried to obtain chlorinated spirophosphate; under a nitrogen atmosphere, formic acid is slowly added dropwise to chlorinated spirophosphate at 35 - 45 °C, and the dropping time is 1.0 - 1.5 h. After the reaction is completed, it is washed and vacuum dried to obtain acidified spirophosphate;

[0011] Step 2: Under a nitrogen atmosphere, acidified spirophosphate and N,N-dimethylformamide are mixed, fully dissolved at 70 - 80 °C, and then phosphaphenanthrene-acrylamide double bond derivative, phosphaphenanthrene-allyloxy double bond derivative, and phosphaphenylene-biphenol diallyl double bond derivative are added, and the reaction continues for 55 - 75 h. After the reaction is completed, it is washed, centrifuged, and dried to obtain a composite flame retardant;

[0012] Step 3: After polypropylene, acrylonitrile-butadiene-styrene copolymer, compatibilizer, inorganic filler, antioxidant, anti-aging agent, composite flame retardant and lubricant are stirred evenly, they are put into a twin-screw extruder for melt extrusion and granulation to obtain a high-performance composite material; the high-performance composite material is injection molded to obtain a finished product.

[0013] Preferably, in Step 1, the reaction molar ratio of phosphorus oxychloride to pentaerythritol is (0.4 - 0.5):0.1; the reaction molar ratio of chlorinated spirophosphate to formic acid is 1:(2.5 - 3.0).

[0014] Preferably, in step two, when preparing the composite flame retardant, the reaction molar ratio of the acidified spiro phosphate, the phosphaphenanthrene-acrylamide double bond derivative, the phosphaphenanthrene-allyloxy double bond derivative, and the phosphaphenylene-biphenol diallyl double bond derivative is (5-6):2:1:(2-3).

[0015] Preferably, the preparation process of the phosphaphenanthrene-acrylamide double bond derivative is as follows: Mix 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, triethylamine, and dichloromethane evenly, then add N-(2-hydroxyethyl)acrylamide and cool down to 0-4°C, and then add carbon tetrachloride and react for 14-16 hours. After the reaction, dilute, extract, dry, filter, and distill under reduced pressure to obtain the phosphaphenanthrene-acrylamide double bond derivative; the reaction molar ratio of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and N-(2-hydroxyethyl)acrylamide is 1:(1.2-1.3).

[0016] Preferably, the preparation process of the phosphaphenanthrene-allyloxy double bond derivative is as follows: Dissolve 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide at 135-145°C, then add 1-allyloxy-2,3-epoxypropane and triphenylphosphine catalyst, and continuously stir and react for 12-14 hours under a nitrogen atmosphere to obtain the phosphaphenanthrene-allyloxy double bond derivative; the reaction molar ratio of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and 1-allyloxy-2,3-epoxypropane is 1:(1.2-1.3).

[0017] Preferably, the preparation process of the phosphaphenylene-biphenol diallyl double bond derivative is as follows: Mix 5',5-diallyl-2,2'-biphenol, triethylamine, and toluene evenly, then dropwise add benzenephosphonic dichloride. After the dropping is completed, heat up to 70-75°C and continuously react for 12-14 hours. After the reaction, wash, distill the solvent, stand, and dry under vacuum to obtain the phosphaphenylene-biphenol diallyl double bond derivative; the reaction molar ratio of 5',5-diallyl-2,2'-biphenol and benzenephosphonic dichloride is 1:

[0018] (1.2-1.3).

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

[0020] Preferably, in step three, the extrusion temperature of the melt extrusion is 250-270°C, and the screw speed is 400-450 r / min.

[0021] The beneficial effects of the present invention:

[0022] The characteristics of the present invention are as follows. In step two, by adding 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, N-(2-hydroxyethyl)acrylamide, triethylamine, and dichloromethane, a phosphaphenanthrene-acrylamide double bond derivative is prepared. In this process, 9,10-dihydro-9-oxa-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. By adding 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 1-allyloxy-2,3-epoxypropane, and triphenylphosphine catalyst, a phosphaphenanthrene-allyloxy double bond derivative is prepared. In this process, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and 1-allyloxy-2,3-epoxypropane undergo a ring-opening reaction to prepare a phosphaphenanthrene-allyloxy double bond derivative containing flame-retardant phosphorus. By adding 5',5-diallyl-2,2'-biphenol, phenylphosphonic dichloride, triethylamine, and toluene, a phosphaphenylene-biphenol diallyl double bond derivative is prepared. In this process, 5',5-diallyl-2,2'-biphenol and phenylphosphonic dichloride undergo a nucleophilic substitution reaction to prepare a phosphaphenylene-biphenol diallyl double bond derivative containing flame-retardant phosphorus.

[0023] In step one, phosphorylated spirocyclic phosphate is prepared by adding phosphorus oxychloride, pentaerythritol, and formic acid. The phosphorylated spirocyclic phosphate contains multiple active P-H bonds. In step two, the phosphorylated spirocyclic phosphate with multiple active P-H bonds is mixed with the phosphaphenanthrene-acrylamide double bond derivative, the phosphaphenanthrene-allyloxy double bond derivative, and the phosphaphenylene-biphenol diallyl double bond derivative to undergo an addition reaction, thereby preparing a multi-crosslinked network composite flame retardant. The composite flame retardant prepared by the present invention contains a large amount of flame-retardant elements nitrogen and phosphorus and a multiple multi-crosslinked network structure. Therefore, nitrogen and phosphorus can synergistically act through different mechanisms to improve the flame retardant effect. For example, phosphorus can form phosphoramide through chemical reactions, and the latter further promotes the formation of a carbonized layer; while nitrogen can decompose to generate non-combustible gases, reducing the oxygen concentration. In addition, the multiple multi-crosslinked network structure can enhance the mechanical properties of the material, such as tensile strength, impact strength, etc., so that the flame retardant can improve the flame retardant performance without sacrificing the basic mechanical properties of the material.

[0024] The characteristics of the present invention are as follows. In step three, by adding polypropylene, acrylonitrile-butadiene-styrene copolymer, compatibilizer, inorganic filler, antioxidant, anti-aging agent, composite flame retardant, and lubricant, and through melt extrusion and granulation, a high-performance composite material is obtained; the high-performance composite material is injection molded to obtain the finished product. In summary, the finished product prepared by the present invention has good flame retardancy, anti-aging property, and mechanical properties, and thus has broad application prospects in the field of polymer technology. Detailed implementation mode

[0025] The following will combine the embodiments of the present invention to clearly and completely describe the technical solutions in the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all embodiments. Based on the embodiments in the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts belong to the scope of protection of the present invention.

[0026] Raw material source:

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

[0028] Example 1: Step 1: Under a nitrogen atmosphere, phosphorus oxychloride and pentaerythritol are mixed evenly and heated to 95°C and maintained for 40 min, then heated to 130°C and reacted continuously for 10 h. After the reaction is completed, it is cooled, washed, distilled, and vacuum dried to obtain chlorinated spiro phosphate ester; under a nitrogen atmosphere, formic acid is slowly added dropwise to the chlorinated spiro phosphate ester at 45°C, and the dropping time is 1.5 h. After the reaction is completed, it is washed and vacuum dried to obtain acidified spiro phosphate ester; the reaction molar ratio of phosphorus oxychloride to pentaerythritol is 0.45:0.1; the reaction molar ratio of chlorinated spiro phosphate ester to formic acid is 1:2.7;

[0029] Step 2: 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, triethylamine, and dichloromethane are mixed evenly, then N-(2-hydroxyethyl)acrylamide is added and the temperature is lowered to 4°C, and then carbon tetrachloride is added and reacted for 16 h. After the reaction is completed, it is diluted, extracted, dried, filtered, and distilled under reduced pressure to obtain a phosphaphenanthrene-acrylamide double bond derivative; the reaction molar ratio of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide to N-(2-hydroxyethyl)acrylamide is 1:1.2;

[0030] 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is dissolved at 145°C, then 1-allyloxy-2,3-epoxypropane and triphenylphosphine catalyst are added, and the reaction is continuously stirred under a nitrogen atmosphere for 14 h to obtain a phosphaphenanthrene-allyloxy double bond derivative; the reaction molar ratio of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide to 1-allyloxy-2,3-epoxypropane is 1:1.2;

[0031] Mix 5',5-diallyl-2,2'-biphenyldiol, triethylamine, and toluene evenly, then dropwise add phenylphosphonic dichloride. After the addition is completed, raise the temperature to 75 °C and continue the reaction for 14 h. After the reaction is completed, wash, distill the solvent, let it stand, and dry under vacuum to obtain a phosphaphenanthrene-biphenyldiol diallyl double bond derivative; the reaction molar ratio of 5',5-diallyl-2,2'-biphenyldiol to phenylphosphonic dichloride is 1:1.2;

[0032] Under a nitrogen atmosphere, mix acidified spirocyclic phosphate and N,N-dimethylformamide, fully dissolve at 80 °C, then add phosphaphenanthrene-acrylamide double bond derivative, phosphaphenanthrene-allyloxy double bond derivative, and phosphaphenanthrene-biphenyldiol diallyl double bond derivative, and continue the reaction for 75 h. After the reaction is completed, wash, centrifuge, and dry to obtain a composite flame retardant; the reaction molar ratio of acidified spirocyclic phosphate, phosphaphenanthrene-acrylamide double bond derivative, phosphaphenanthrene-allyloxy double bond derivative, and phosphaphenanthrene-biphenyldiol diallyl double bond derivative is 5.5:2:1:2.5;

[0033] Step 3: Stir 70 g of polypropylene, 25 g of acrylonitrile-butadiene-styrene copolymer, 3 g of ethylene-maleic anhydride copolymer, 8 g of calcium carbonate, 0.4 g of antioxidant, 0.6 g of anti-aging agent, 18 g of composite flame retardant, and 1 g of zinc stearate evenly, then put them into a twin-screw extruder for melt extrusion and pelletizing to obtain a high-performance composite material; injection mold the high-performance composite material to obtain a finished product; the extrusion temperature for the melt extrusion is 270 °C, and the screw speed is 450 r / min.

[0034] Example 2: Step 1: Under a nitrogen atmosphere, mix phosphorus oxychloride and pentaerythritol evenly and raise the temperature to 90 °C and keep it for 35 min, then raise the temperature to 125 °C and continue the reaction for 9.5 h. After the reaction is completed, cool, wash, distill, and dry under vacuum to obtain chlorinated spirocyclic phosphate; under a nitrogen atmosphere, slowly drop formic acid into chlorinated spirocyclic phosphate at 40 °C, and the dropping time is 1.2 h. After the reaction is completed, wash and dry under vacuum to obtain acidified spirocyclic phosphate; the reaction molar ratio of phosphorus oxychloride to pentaerythritol is 0.45:0.1; the reaction molar ratio of chlorinated spirocyclic phosphate to formic acid is 1:2.7;

[0035] Step 2: Mix 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, triethylamine, and dichloromethane evenly, then add N-(2-hydroxyethyl)acrylamide and cool down to 2 °C, then add carbon tetrachloride and react for 15 h. After the reaction is completed, dilute, extract, dry, filter, and distill under reduced pressure to obtain a phosphaphenanthrene-acrylamide double bond derivative; the reaction molar ratio of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide to N-(2-hydroxyethyl)acrylamide is 1:1.2;

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

[0037] Mix 5',5-diallyl-2,2'-biphenol, triethylamine, and toluene evenly, then dropwise add phenylphosphonic dichloride. After the addition is completed, raise the temperature to 73 °C and continuously react for 13 h. After the reaction is completed, wash, distill the solvent, let it stand, and dry in vacuum to obtain a phosphaphenylene-biphenol diallyl double bond derivative; the reaction molar ratio of 5',5-diallyl-2,2'-biphenol to phenylphosphonic dichloride is 1:1.2;

[0038] Under a nitrogen atmosphere, mix acidified spirocyclic phosphate and N,N-dimethylformamide, fully dissolve at 70 - 80 °C, then add phosphaphenanthrene-acrylamide double bond derivative, phosphaphenanthrene-allyloxy double bond derivative, and phosphaphenylene-biphenol diallyl double bond derivative, and continuously react for 65 h. After the reaction is completed, wash, centrifuge, and dry to obtain a composite flame retardant; the reaction molar ratio of acidified spirocyclic phosphate, phosphaphenanthrene-acrylamide double bond derivative, phosphaphenanthrene-allyloxy double bond derivative, and phosphaphenylene-biphenol diallyl double bond derivative is 5.5:2:1:2.5;

[0039] Step 3: Stir 70 g of polypropylene, 25 g of acrylonitrile-butadiene-styrene copolymer, 3 g of ethylene-maleic anhydride copolymer, 8 g of calcium carbonate, 0.4 g of antioxidant, 0.6 g of anti-aging agent, 18 g of composite flame retardant, and 1 g of zinc stearate evenly, then put them into a twin-screw extruder for melt extrusion and pelletizing to obtain a high-performance composite material; injection mold the high-performance composite material to obtain the finished product; the extrusion temperature for the melt extrusion is 260 °C, and the screw speed is 425 r / min.

[0040] Example 3: Step 1: Under a nitrogen atmosphere, mix phosphorus oxychloride and pentaerythritol evenly and raise the temperature to 85 °C and keep it for 30 min, then raise the temperature to 120 °C and continuously react for 9 h. After the reaction is completed, cool, wash, distill, and dry in vacuum to obtain chlorinated spirocyclic phosphate; under a nitrogen atmosphere, slowly drop formic acid into chlorinated spirocyclic phosphate at 35 °C, and the dropping time is 1 h. After the reaction is completed, wash and dry in vacuum to obtain acidified spirocyclic phosphate; the reaction molar ratio of phosphorus oxychloride to pentaerythritol is 0.45:0.1; the reaction molar ratio of chlorinated spirocyclic phosphate to formic acid is 1:2.7;

[0041] Step 2: Mix 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, triethylamine, and dichloromethane evenly, then add N-(2-hydroxyethyl)acrylamide and cool down to 0 °C, then add carbon tetrachloride and react for 14 h. After the reaction, dilute, extract, dry, filter, and distill under reduced pressure to obtain a phosphaphenanthrene-acrylamide double bond derivative; the reaction molar ratio of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide to N-(2-hydroxyethyl)acrylamide is 1:1.2;

[0042] Dissolve 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide at 135 °C, then add 1-allyloxy-2,3-epoxypropane and triphenylphosphine catalyst, and continuously stir and react for 12 h under a nitrogen environment to obtain a phosphaphenanthrene-allyloxy double bond derivative; the reaction molar ratio of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide to 1-allyloxy-2,3-epoxypropane is 1:1.2;

[0043] Mix 5',5-diallyl-2,2'-biphenol, triethylamine, and toluene evenly, then dropwise add phenylphosphonic dichloride. After the addition, raise the temperature to 70 °C and continuously react for 12 h. After the reaction, wash, distill the solvent, let it stand, and dry under vacuum to obtain a phosphaphenylene-biphenol diallyl double bond derivative; the reaction molar ratio of 5',5-diallyl-2,2'-biphenol to phenylphosphonic dichloride is 1:1.2;

[0044] Under a nitrogen environment, mix acidified spirophosphate and N,N-dimethylformamide, fully dissolve at 70 °C, then add the phosphaphenanthrene-acrylamide double bond derivative, phosphaphenanthrene-allyloxy double bond derivative, and phosphaphenylene-biphenol diallyl double bond derivative, and continuously react for 55 h. After the reaction, wash, centrifuge, and dry to obtain a composite flame retardant; the reaction molar ratio of acidified spirophosphate, phosphaphenanthrene-acrylamide double bond derivative, phosphaphenanthrene-allyloxy double bond derivative, and phosphaphenylene-biphenol diallyl double bond derivative is 5.5:2:1:2.5;

[0045] Step 3: Stir 70 g of polypropylene, 25 g of acrylonitrile-butadiene-styrene copolymer, 3 g of ethylene-maleic anhydride copolymer, 8 g of calcium carbonate, 0.4 g of antioxidant, 0.6 g of anti-aging agent, 18 g of composite flame retardant, and 1 g of zinc stearate evenly, then put them into a twin-screw extruder for melt extrusion and pelletizing to obtain a high-performance composite material; injection mold the high-performance composite material to obtain the finished product; the extrusion temperature for the melt extrusion is 250 °C, and the screw speed is 400 r / min.

[0046] Comparative Example 1: When preparing the composite flame retardant, the reaction molar ratio of acidified spirophosphate, phosphaphenanthrene-acrylamide double bond derivative, phosphaphenanthrene-allyloxy double bond derivative, and phosphaphenylene-biphenol diallyl double bond derivative was adjusted to 1:2:1:1, and the rest was the same as in Example 1. The specific steps are as follows: Step 1: Under a nitrogen atmosphere, phosphorus oxychloride and pentaerythritol were mixed evenly and heated to 95 °C and maintained for 40 min, then heated to 130 °C and reacted for 10 h. After the reaction, it was cooled, washed, distilled, and vacuum dried to obtain chlorinated spirophosphate; under a nitrogen atmosphere, formic acid was slowly added dropwise to chlorinated spirophosphate at 45 °C, and the dropping time was 1.5 h. After the reaction, it was washed and vacuum dried to obtain acidified spirophosphate; the reaction molar ratio of phosphorus oxychloride and pentaerythritol was 0.45:0.1; the reaction molar ratio of chlorinated spirophosphate and formic acid was 1:2.7;

[0047] Step 2: 9,10-Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, triethylamine, and dichloromethane were mixed evenly, then N-(2-hydroxyethyl)acrylamide was added and the temperature was lowered to 4 °C, and then carbon tetrachloride was added and reacted for 16 h. After the reaction, it was diluted, extracted, dried, filtered, and distilled under reduced pressure to obtain a phosphaphenanthrene-acrylamide double bond derivative; the reaction molar ratio of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and N-(2-hydroxyethyl)acrylamide was 1:1.2;

[0048] 9,10-Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide was dissolved at 145 °C, then 1-allyloxy-2,3-epoxypropane and triphenylphosphine catalyst were added, and the reaction was continuously stirred under a nitrogen atmosphere for 14 h to obtain a phosphaphenanthrene-allyloxy double bond derivative; the reaction molar ratio of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and 1-allyloxy-2,3-epoxypropane was 1:1.2;

[0049] 5',5-Diallyl-2,2'-biphenol, triethylamine, and toluene were mixed evenly, then benzenephosphonic dichloride was added dropwise. After the addition, the temperature was raised to 75 °C and reacted for 14 h. After the reaction, it was washed, the solvent was distilled off, allowed to stand, and vacuum dried to obtain a phosphaphenylene-biphenol diallyl double bond derivative; the reaction molar ratio of 5',5-diallyl-2,2'-biphenol and benzenephosphonic dichloride was 1:1.2;

[0050] Under a nitrogen atmosphere, acidified spirophosphate and N,N-dimethylformamide were mixed and fully dissolved at 80 °C. Then, a phosphaphenanthrene-acrylamide double bond derivative, a phosphaphenanthrene-allyloxy double bond derivative, and a phosphaphenanthrene-biphenol diallyl double bond derivative were added, and the reaction was continued for 75 h. After the reaction, washing, centrifugation, and drying were performed to obtain a composite flame retardant; the reaction molar ratio of acidified spirophosphate, phosphaphenanthrene-acrylamide double bond derivative, phosphaphenanthrene-allyloxy double bond derivative, and phosphaphenanthrene-biphenol diallyl double bond derivative was 1:2:1:1;

[0051] Step 3: 70 g of polypropylene, 25 g of acrylonitrile-butadiene-styrene copolymer, 3 g of ethylene-maleic anhydride copolymer, 8 g of calcium carbonate, 0.4 g of antioxidant, 0.6 g of anti-aging agent, 18 g of composite flame retardant, and 1 g of zinc stearate were stirred evenly and then put into a twin-screw extruder for melt extrusion and pelletizing to obtain a high-performance composite material; the high-performance composite material was injection molded to obtain a finished product; the extrusion temperature for the melt extrusion was 270 °C, and the screw speed was 450 r / min.

[0052] Comparative Example 2: The preparation step of the composite flame retardant was removed, and the rest was the same as in Example 1. The specific steps were as follows: Step 1: 70 g of polypropylene, 25 g of acrylonitrile-butadiene-styrene copolymer, 3 g of ethylene-maleic anhydride copolymer, 8 g of calcium carbonate, 0.4 g of antioxidant, 0.6 g of anti-aging agent, and 1 g of zinc stearate were stirred evenly and then put into a twin-screw extruder for melt extrusion and pelletizing to obtain a high-performance composite material; the high-performance composite material was injection molded to obtain a finished product; the extrusion temperature for the melt extrusion was 270 °C, and the screw speed was 450 r / min.

[0053] Detection test:

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

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

[0056] Mechanical property test: The high-performance composite material prepared by the present invention was tested according to the standard of GB / T 1039-1992. A universal mechanical testing machine was used to record the stress-strain curve of the sample, and the tensile rate was set at 10 mm / min. The specimen was measured five times and the average value of the obtained results was taken as the tensile strength of the corresponding specimen. The results are shown in the following table:

[0057] Limiting oxygen index / % Vertical burning rating <![CDATA[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 dosages in Examples 1 to 3 remain unchanged, and only some reaction parameters are modified. It can be seen from the experimental data that there are no obvious fluctuations in the properties of the specimens.

[0059] Comparative Example 1: When preparing the composite flame retardant, the reaction molar ratio of acidified spirocyclic phosphate, phosphaphenanthrene-acrylamide double bond derivative, phosphaphenanthrene-allyloxy double bond derivative, and phosphaphenylene-biphenol diallyl double bond derivative was adjusted to 1:2:1:1, and the rest was the same as in Example 1. It can be seen from the experimental data that compared with Example 1, the limiting oxygen index decreased to 31.1%, the vertical burning grade became V-0, and the tensile strength decreased to 31.6 MPa. The reason for the analysis is that the present invention sets the preferred reaction molar ratio of acidified spirocyclic phosphate, phosphaphenanthrene-acrylamide double bond derivative, phosphaphenanthrene-allyloxy double bond derivative, and phosphaphenylene-biphenol diallyl double bond derivative as (5-6):2:1:(2-3). Within this range, each flame retardant component can crosslink with each other to prepare an efficient composite flame retardant. Therefore, in Comparative Example 1, after adjusting the reaction ratio to 1:2:1:1, the reaction of each component is uneven, so the flame retardant performance decreases and the tensile strength also decreases.

[0060] Comparative Example 2: The preparation step of the composite flame retardant was removed, and the rest was the same as in Example 1. It can be seen from the experimental data that compared with Example 1, the limiting oxygen index decreased to 17.5%, the vertical burning grade became V-1, and the tensile strength decreased to 26.5 MPa. The reason for the analysis is that the composite flame retardant prepared by the present invention contains a large amount of flame retardant elements nitrogen, phosphorus and a multiple crosslinked network structure. Therefore, nitrogen and phosphorus can act synergistically through different mechanisms to improve the flame retardant effect. So after removing the composite flame retardant, the flame retardant performance decreases; in addition, the multiple crosslinked network structure of the composite flame retardant can enhance the mechanical properties of the material and improve the tensile strength. Therefore, after removing the composite flame retardant, the tensile strength will decrease.

[0061] It should be noted that in this text, relational terms such as first and second are only used to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any actual relationship or order between these entities or operations. Moreover, the terms "comprising", "including" or any other variant thereof are intended to cover non-exclusive inclusion, so that a process, method, article or device comprising a series of elements not only includes those elements, but also includes other elements not expressly listed, or also includes elements inherent to such process, method, article or device.

[0062] Finally, it should be noted that the above are only preferred embodiments of the present invention and are not intended to limit the present invention. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments, or perform equivalent replacements for some of the technical features. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Claims

1. A high-performance composite material with anti-aging properties, characterized in that: The invention comprises polypropylene, acrylonitrile-butadiene-styrene copolymer, a compatibilizer, an inorganic filler, an antioxidant, an anti-aging agent, a composite flame retardant and a lubricant.

2. The high-performance composite material with anti-aging properties according to claim 1, characterized in that: The contents of the components of the high-performance composite material are as follows: by mass: 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.

3. An injection molding process for high-performance composite materials with anti-aging properties, characterized in that: The following steps are involved: Step 1: Under a nitrogen environment, phosphorus oxychloride and pentaerythritol are mixed evenly and heated to 85-95°C for 30-40 minutes, and then heated to 120-130°C for continuous reaction for 9-10 hours. After the reaction is completed, the mixture is cooled, washed, distilled, and vacuum dried to obtain chlorinated spirocyclic phosphate; Under a nitrogen environment, formic acid is slowly added dropwise to the chlorinated spirocyclic phosphate at 35-45°C for 1.0-1.5 hours. After the reaction is completed, the mixture is washed and vacuum dried to obtain acidified spirocyclic phosphate; Step 2: In a nitrogen environment, the acidified spirocyclic phosphate and N,N-dimethylformamide are mixed, and after being fully dissolved at 70-80°C, a phosphaphenanthrene-acrylamide double bond derivative, a phosphaphenanthrene-allyloxy double bond derivative, and a phosphabiphenyl-diphenol diallyl double bond derivative are added, and the reaction is continued for 55-75 hours. After the reaction is completed, the composite flame retardant is obtained by washing, centrifuging, and drying; Step 3: After uniformly mixing polypropylene, acrylonitrile-butadiene-styrene copolymer, compatibilizer, inorganic filler, antioxidant, anti-aging agent, composite flame retardant and lubricant, the mixture is put into a twin-screw extruder for melt extrusion and granulation to obtain a high-performance composite material; the high-performance composite material is injection molded to obtain a finished product.

4. The injection molding process of the high-performance composite material with anti-aging properties according to claim 3, characterized in that: In step 1, 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).

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

6. The injection molding process of the high-performance composite material with anti-aging properties according to claim 5, characterized in that: The preparation process of the phosphaphenanthrene-acrylamide double bond derivative is as follows: 9,10-dihydro-9-oxygen-10-phosphaphenanthrene-10-oxide, triethylamine and dichloromethane are uniformly mixed, N-(2-hydroxyethyl)acrylamide is added and the temperature is lowered to 0-4°C, carbon tetrachloride is added and reacted for 14-16 hours, and after the reaction is completed, the phosphaphenanthrene-acrylamide double bond derivative is obtained by dilution, extraction, drying, filtration and reduced pressure distillation; wherein the reaction molar ratio of 9,10-dihydro-9-oxygen-10-phosphaphenanthrene-10-oxide and N-(2-hydroxyethyl)acrylamide is 1:(1.2-1.3).

7. The injection molding process of the high-performance composite material with anti-aging properties according to claim 5, characterized in that: The preparation process of the phosphaphenanthrene-allyloxy double bond derivative is as follows: dissolve 9,10-dihydro-9-oxygen-10-phosphaphenanthrene-10-oxide at 135-145°C, add 1-allyloxy-2,3-propylene oxide and triphenylphosphine catalyst, and continue stirring the reaction for 12-14 hours under a nitrogen environment to obtain the phosphaphenanthrene-allyloxy double bond derivative; wherein the reaction molar ratio of 9,10-dihydro-9-oxygen-10-phosphaphenanthrene-10-oxide to 1-allyloxy-2,3-propylene oxide is 1:(1.2-1.3).

8. The injection molding process of the high-performance composite material with anti-aging properties according to claim 5, characterized in that: The preparation process of the phosphabiphenyl-diphenylphenol diallyl double bond derivative is as follows: 5',5-diallyl-2,2'-biphenyl, triethylamine and toluene are uniformly mixed, and then phenylphosphonic acid dichloride is added dropwise. After the addition is completed, the temperature is raised to 70-75°C and the reaction is continued for 12-14 hours. After the reaction is completed, the phosphabiphenyl-diphenylphenol diallyl double bond derivative is obtained by washing, distilling the solvent, standing and vacuum drying; wherein the reaction molar ratio of 5',5-diallyl-2,2'-biphenyl and phenylphosphonic acid dichloride is 1:(1.2-1.3).

9. The injection molding process of the high-performance composite material with anti-aging properties according to claim 8, characterized in that: The compatibilizer is ethylene-maleic anhydride copolymer, the inorganic filler is calcium carbonate, and the lubricant is zinc stearate.

10. The injection molding process of the high-performance composite material with anti-aging properties according to claim 3, characterized in that: In step three, the extrusion temperature of the melt extrusion is 250-270° C., and the screw speed is 400-450 r / min.