技术领域Technical field
本发明涉及PET材料技术领域，具体为一种用于线圈骨架的耐高温阻燃PET材料及其制备方法。The invention relates to the technical field of PET materials, specifically a high-temperature resistant flame-retardant PET material used for coil frames and a preparation method thereof.
背景技术Background technique
PET是聚对苯二甲酸乙二醇酯，是目前应用广泛的高分子材料之一，PET材料具有优良的物理机械性能、电绝缘性性能、耐摩擦、抗疲劳，在高温高频下依旧能保持良好的电性能，是一种良好的可以应用于制备线圈骨架的材料。但是由于纯PET材料易燃，一旦燃烧火焰传播速度快且不易熄灭，存在巨大的安全隐患，因此，增强PET耐高温阻燃性能，使其能适用于线圈骨架的应用，具有很好的发展前景。PET is polyethylene terephthalate. It is one of the most widely used polymer materials. PET material has excellent physical and mechanical properties, electrical insulation properties, friction resistance, and fatigue resistance. It can still perform under high temperature and high frequency. It maintains good electrical properties and is a good material that can be used to prepare coil bobbins. However, since pure PET material is flammable, once the burning flame spreads quickly and is not easy to extinguish, it poses a huge safety hazard. Therefore, enhancing the high temperature flame retardant properties of PET to make it suitable for coil bobbin applications has good development prospects. .
为了解决上述问题，本发明提供了一种用于线圈骨架的耐高温阻燃PET材料及其制备方法。In order to solve the above problems, the present invention provides a high-temperature resistant flame-retardant PET material for coil frames and a preparation method thereof.
发明内容Contents of the invention
本发明的目的在于提供一种用于线圈骨架的耐高温阻燃PET材料及其制备方法，以解决上述背景技术中提出的问题。The purpose of the present invention is to provide a high-temperature resistant flame-retardant PET material for coil bobbins and a preparation method thereof, so as to solve the problems raised in the above background technology.
为了解决上述技术问题，本发明提供如下技术方案：In order to solve the above technical problems, the present invention provides the following technical solutions:
一种用于线圈骨架的耐高温阻燃PET材料的制备方法，包括以下步骤：A method for preparing high-temperature resistant flame-retardant PET material for coil frames, including the following steps:
步骤一：取氨基化氧化石墨烯、N,N-二甲基甲酰胺，超声50-70min，加入接枝钼酸铵的二氧化硅，在60-68℃下反应1-2h，过滤，洗涤，干燥，得到负载二氧化硅的氧化石墨烯；Step 1: Take aminated graphene oxide and N,N-dimethylformamide, ultrasonic for 50-70 minutes, add silica grafted with ammonium molybdate, react at 60-68°C for 1-2 hours, filter and wash. , dry to obtain silica-loaded graphene oxide;
步骤二：取聚对苯二甲酸乙二醇酯、乙烯-甲基丙烯酸共聚物、聚乙二醇、硬脂酸钠、滑石粉、超支化聚磷酰胺、负载二氧化硅的氧化石墨烯、乙撑双硬脂酰胺、扩链剂、抗氧剂、增强剂，混合均匀，在200-290℃下熔融挤出，造粒，制得用于线圈骨架的耐高温阻燃PET材料。Step 2: Take polyethylene terephthalate, ethylene-methacrylic acid copolymer, polyethylene glycol, sodium stearate, talc, hyperbranched polyphosphamide, silica-loaded graphene oxide, Ethylene bisstearamide, chain extender, antioxidant, and reinforcing agent are mixed evenly, melted and extruded at 200-290°C, and granulated to produce a high-temperature flame-retardant PET material for coil skeletons.
较为优化地，所述增强剂为玄武岩纤维、玻璃纤维、硫酸钙晶须、碳纤维中的一种或几种。Preferably, the reinforcing agent is one or more of basalt fiber, glass fiber, calcium sulfate whisker, and carbon fiber.
较为优化地，所述抗氧剂为抗氧剂1010、抗氧剂168的一种或几种。Preferably, the antioxidant is one or more of antioxidant 1010 and antioxidant 168.
较为优化地，所述PET材料包括以下成分，按照重量计，50-80份聚对苯二甲酸乙二醇酯、5-8份乙烯-甲基丙烯酸共聚物、2-4份聚乙二醇、1-3份硬脂酸钠、0.5-1份滑石粉、6-12份超支化聚磷酰胺、3-8份负载二氧化硅的氧化石墨烯、0.5-1份乙撑双硬脂酰胺、0.5-1份扩链剂、0.5-1份抗氧剂、10-30份增强剂。Preferably, the PET material includes the following components: 50-80 parts by weight of polyethylene terephthalate, 5-8 parts of ethylene-methacrylic acid copolymer, and 2-4 parts of polyethylene glycol. , 1-3 parts sodium stearate, 0.5-1 part talc, 6-12 parts hyperbranched polyphosphoramide, 3-8 parts silica-loaded graphene oxide, 0.5-1 part ethylene bisstearamide , 0.5-1 part chain extender, 0.5-1 part antioxidant, 10-30 parts enhancer.
较为优化地，步骤二中，超支化聚磷酰胺、负载二氧化硅的氧化石墨烯的质量比为2:（1-1.2）。More optimally, in step two, the mass ratio of hyperbranched polyphosphoramide and silica-loaded graphene oxide is 2: (1-1.2).
较为优化地，步骤一中，氨基化氧化石墨烯的制备方法为：包括以下步骤：Preferably, in step one, the preparation method of aminated graphene oxide includes the following steps:
S1：取氧化石墨烯、次磷酸、去离子水，在75-85℃下反应4.5-5.5h，超声分散50-70min，离心，洗涤，冻干，得到含磷的氧化石墨烯；S1: Take graphene oxide, hypophosphorous acid, and deionized water, react at 75-85°C for 4.5-5.5 hours, ultrasonically disperse for 50-70 minutes, centrifuge, wash, and freeze-dry to obtain phosphorus-containing graphene oxide;
S2：取乙醇、对苯二胺，搅拌均匀，得到混合溶液，取含磷的氧化石墨烯、去离子水，超声分散，加入混合溶液，在80-85℃下反应22-24h，过滤，洗涤，干燥，得到氨基化氧化石墨烯。S2: Take ethanol and p-phenylenediamine, stir evenly to obtain a mixed solution, take phosphorus-containing graphene oxide and deionized water, disperse it ultrasonically, add the mixed solution, react at 80-85°C for 22-24 hours, filter and wash , dried to obtain aminated graphene oxide.
较为优化地，步骤一中，接枝钼酸铵的二氧化硅的制备方法为：包括以下步骤：Preferably, in step one, the preparation method of silica grafted with ammonium molybdate includes the following steps:
步骤A：取KH560、去离子水、乙醇混合，超声分散，得到混合液；取二氧化硅、去离子水、乙醇混合，超声分散，升温至68-72℃，滴加混合液，保温反应10-13h，冷却，过滤，烘干，得到改性二氧化硅；Step A: Mix KH560, deionized water and ethanol, and disperse with ultrasound to obtain a mixed solution; mix silica, deionized water, and ethanol with ultrasound, disperse with ultrasound, raise the temperature to 68-72°C, add the mixture dropwise, and keep warm for 10 seconds. -13h, cool, filter, and dry to obtain modified silica;
步骤B：取钼酸铵、去离子水搅拌均匀，加入改性二氧化硅，在84-88℃下搅拌反应，过滤，烘干，得到接枝钼酸铵的二氧化硅；Step B: Stir ammonium molybdate and deionized water evenly, add modified silica, stir and react at 84-88°C, filter, and dry to obtain silica grafted with ammonium molybdate;
所述钼酸铵、去离子水、改性二氧化硅的质量比为（3-5）：（15-20）：1。The mass ratio of ammonium molybdate, deionized water and modified silica is (3-5): (15-20): 1.
较为优化地，步骤二中，超支化聚磷酰胺的制备方法为：取三氯氧磷、乙腈，搅拌均匀，得到溶液A；取4,4-二氨基二苯甲烷、三乙胺、乙腈，搅拌均匀，降温至3-6℃，加入溶液A，反应1-2h，升温至45-52℃，反应22-24h，过滤，洗涤，干燥，得到超支化聚磷酰胺。More optimally, in step two, the preparation method of hyperbranched polyphosphoramide is: take phosphorus oxychloride and acetonitrile, stir evenly to obtain solution A; take 4,4-diaminodiphenylmethane, triethylamine, and acetonitrile, Stir evenly, lower the temperature to 3-6°C, add solution A, react for 1-2 hours, raise the temperature to 45-52°C, react for 22-24 hours, filter, wash, and dry to obtain hyperbranched polyphosphoramide.
较为优化地，步骤一中，氨基化氧化石墨烯、接枝钼酸铵的二氧化硅的质量比为1：（10-20）。More optimally, in step one, the mass ratio of aminated graphene oxide and grafted ammonium molybdate silica is 1: (10-20).
与现有技术相比，本发明所达到的有益效果是：Compared with the prior art, the beneficial effects achieved by the present invention are:
（1）PET是一种易燃材料，燃烧时会产生浓烟和有毒气体，会对环境造成污染，威胁施工人员的身体健康。制备接枝钼酸铵的二氧化硅，二氧化硅具有良好的绝热性能以及热稳定性能，添加二氧化硅可以增强PET材料的阻燃性，使用KH560对二氧化硅进行环氧改性，通过改性二氧化硅上的环氧基团与钼酸铵上的氨基进行开环反应，在二氧化硅上接枝钼酸铵，提高PET材料的抑烟性能以及阻燃性。(1) PET is a flammable material that produces thick smoke and toxic gases when burned, polluting the environment and threatening the health of construction workers. Prepare silica grafted with ammonium molybdate. Silica has good thermal insulation properties and thermal stability. Adding silica can enhance the flame retardancy of PET materials. Use KH560 to epoxy modify the silica. The epoxy group on the modified silica undergoes a ring-opening reaction with the amino group on the ammonium molybdate, and the ammonium molybdate is grafted on the silica to improve the smoke suppression performance and flame retardancy of the PET material.
使用次磷酸对氧化石墨烯进行磷改性，增强了含磷的氧化石墨烯的阻燃性能。将氧化石墨烯、对苯二胺混合，氨基对氧化石墨烯上的环氧基团开环，在氧化石墨烯接枝了氨基。Phosphorus modification of graphene oxide using hypophosphorous acid enhances the flame retardant properties of phosphorus-containing graphene oxide. Graphene oxide and p-phenylenediamine are mixed, the amino group opens the ring of the epoxy group on the graphene oxide, and the amino group is grafted on the graphene oxide.
控制所述钼酸铵、去离子水、改性二氧化硅的质量比为（3-5）：（15-20）：1，在后续与氨基化氧化石墨烯混合负载时，改性二氧化硅表面的环氧基、氨基能够与氧化石墨烯表面的氨基、含氧基团通过化学接枝、氢键等相互作用，加大接枝钼酸铵的二氧化硅的负载量，并且使负载二氧化硅的氧化石墨烯不易团聚，在体系中分散地更均匀。Control the mass ratio of ammonium molybdate, deionized water, and modified silica to (3-5): (15-20): 1. When subsequently mixed with aminated graphene oxide for loading, the modified silica The epoxy groups and amino groups on the silicon surface can interact with the amino groups and oxygen-containing groups on the surface of graphene oxide through chemical grafting, hydrogen bonding, etc., increasing the loading capacity of the silica grafted with ammonium molybdate, and making the loading Silica graphene oxide is not easy to agglomerate and is more evenly dispersed in the system.
控制氨基化氧化石墨烯与接枝钼酸铵的二氧化硅的质量比为1：（10-20），此时PET材料的阻燃、机械性能最佳。Control the mass ratio of aminated graphene oxide to silica grafted with ammonium molybdate to 1: (10-20). At this time, the flame retardant and mechanical properties of the PET material are optimal.
（2）使用4,4-二氨基二苯甲烷、磷化合物制备超支化聚磷酰胺，超支化聚磷酰胺是一种三维分子结构，外部有大量活性基团，可以PET材料组份交联反应形成网络结构，改善机械性能。(2) Use 4,4-diaminodiphenylmethane and phosphorus compounds to prepare hyperbranched polyphosphoramide. Hyperbranched polyphosphoramide is a three-dimensional molecular structure with a large number of active groups on the outside, which can cross-link the components of PET materials. Form a network structure and improve mechanical properties.
使用超支化聚磷酰胺与负载二氧化硅的氧化石墨烯复配。将超支化聚磷酰胺作为膨胀型阻燃剂和负载二氧化硅的氧化石墨烯协同作用，使得阻燃效果进一步提高，并且无卤无毒，环境友好。Hyperbranched polyphosphoramide is compounded with silica-loaded graphene oxide. The synergy between hyperbranched polyphosphoramide as an intumescent flame retardant and silica-loaded graphene oxide further improves the flame retardant effect, and is halogen-free, non-toxic, and environmentally friendly.
当超支化聚磷酰胺与负载二氧化硅的氧化石墨烯的质量比为2:（1-1.2）时，PET材料的极限氧指数可达30.5。此时，形成的残炭致密，可以有效隔绝内部可燃性气体与外部氧气进行交换，阻燃性能优异。When the mass ratio of hyperbranched polyphosphamide to silica-loaded graphene oxide is 2: (1-1.2), the limiting oxygen index of PET material can reach 30.5. At this time, the carbon residue formed is dense, which can effectively isolate the exchange of internal flammable gases with external oxygen, and has excellent flame retardant properties.
具体实施方式Detailed ways
下面将对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。The technical solutions in the embodiments of the present invention will be described clearly and completely below. Obviously, the described embodiments are only some of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts fall within the scope of protection of the present invention.
实施例1Example 1
步骤一：氨基化氧化石墨烯的制备：Step 1: Preparation of aminated graphene oxide:
取1g氧化石墨烯、16g次磷酸、300ml去离子水，在80℃下反应5h，超声分散60min，离心，洗涤，冻干，得到含磷的氧化石墨烯。Take 1g graphene oxide, 16g hypophosphorous acid, and 300 ml deionized water, react at 80°C for 5 hours, ultrasonically disperse for 60 minutes, centrifuge, wash, and freeze-dry to obtain phosphorus-containing graphene oxide.
取30mL乙醇、1.5g对苯二胺，搅拌均匀，得到混合溶液，取1g含磷的氧化石墨烯、100mL去离子水，超声分散，加入混合溶液，在83℃下反应23h，过滤，洗涤，干燥，得到氨基化氧化石墨烯。Take 30 mL of ethanol and 1.5 g of p-phenylenediamine, stir evenly to obtain a mixed solution, take 1 g of phosphorus-containing graphene oxide and 100 mL of deionized water, disperse with ultrasound, add the mixed solution, react at 83°C for 23 hours, filter, and wash. After drying, aminated graphene oxide is obtained.
步骤二：超支化聚磷酰胺的制备：Step 2: Preparation of hyperbranched polyphosphoramide:
取1.8g三氯氧磷、50mL乙腈，搅拌均匀，得到溶液A；取3.4g4,4-二氨基二苯甲烷、3.5g三乙胺、300mL乙腈，搅拌均匀，降温至4℃，加入溶液A，反应1.5h，升温至47℃，反应23h，过滤，洗涤，干燥，得到超支化聚磷酰胺。Take 1.8g phosphorus oxychloride and 50mL acetonitrile, stir evenly to obtain solution A; take 3.4g 4,4-diaminodiphenylmethane, 3.5g triethylamine, and 300mL acetonitrile, stir evenly, cool to 4°C, and add solution A. , react for 1.5h, raise the temperature to 47°C, react for 23h, filter, wash and dry to obtain hyperbranched polyphosphoramide.
步骤三：接枝钼酸铵的二氧化硅的制备：Step 3: Preparation of silica grafted with ammonium molybdate:
取4.5mLKH560、30mL去离子水、70mL乙醇，超声分散，得到混合液；取3g二氧化硅、30mL去离子水、70mL乙醇，超声分散，升温至70℃，滴加混合液，保温12h，冷却，过滤，烘干，得到改性二氧化硅。Take 4.5mLKH560, 30mL deionized water, and 70mL ethanol, disperse with ultrasonic to obtain a mixed solution; take 3g silica, 30mL deionized water, and 70mL ethanol, disperse with ultrasonic, raise the temperature to 70°C, add the mixed solution dropwise, keep it warm for 12 hours, and cool. , filter and dry to obtain modified silica.
取12g钼酸铵、51g去离子水搅拌均匀，加入3g改性二氧化硅，在86℃下搅拌均匀，过滤，烘干，得到接枝钼酸铵的二氧化硅。Take 12g ammonium molybdate and 51g deionized water and stir evenly, add 3g modified silica, stir evenly at 86°C, filter, and dry to obtain silica grafted with ammonium molybdate.
所述钼酸铵、去离子水、改性二氧化硅的质量比为4：17：1。The mass ratio of ammonium molybdate, deionized water, and modified silica is 4:17:1.
步骤四：负载二氧化硅的氧化石墨烯的制备：Step 4: Preparation of silica-loaded graphene oxide:
取1g氨基化氧化石墨烯、150mLN,N-二甲基甲酰胺，超声60min，加入15g接枝钼酸铵的二氧化硅，在64℃下反应1.5h，过滤，洗涤，干燥，得到负载二氧化硅的氧化石墨烯。Take 1g of aminated graphene oxide and 150mL of N,N-dimethylformamide, ultrasonic for 60 minutes, add 15g of silica grafted with ammonium molybdate, react at 64°C for 1.5h, filter, wash, and dry to obtain the loaded dimethylformamide. Graphene oxide of silicon oxide.
所述氨基化氧化石墨烯与接枝钼酸铵的二氧化硅的质量比为1：15。The mass ratio of the aminated graphene oxide to the silica grafted with ammonium molybdate is 1:15.
步骤五：取聚对苯二甲酸乙二醇酯、乙烯-甲基丙烯酸共聚物、聚乙二醇、硬脂酸钠、滑石粉、超支化聚磷酰胺、负载二氧化硅的氧化石墨烯、乙撑双硬脂酰胺、扩链剂ADR-4368CS、抗氧剂1010、玻璃纤维，混合均匀，在200-290下熔融挤出，造粒，制得用于线圈骨架的耐高温阻燃PET材料。Step 5: Take polyethylene terephthalate, ethylene-methacrylic acid copolymer, polyethylene glycol, sodium stearate, talc, hyperbranched polyphosphamide, silica-loaded graphene oxide, Ethylene bisstearamide, chain extender ADR-4368CS, antioxidant 1010, and glass fiber are mixed evenly, melted and extruded at 200-290, and granulated to produce a high-temperature flame-retardant PET material for coil skeletons. .
所述PET材料包括以下成分，按照重量计，70份聚对苯二甲酸乙二醇酯、7份乙烯-甲基丙烯酸共聚物、3份聚乙二醇、2份硬脂酸钠、0.7份滑石粉、9份超支化聚磷酰胺、4.95份负载二氧化硅的氧化石墨烯、0.8份乙撑双硬脂酰胺、0.7份扩链剂ADR-4368CS、0.7份抗氧剂1010、20份玻璃纤维。The PET material includes the following ingredients, by weight, 70 parts of polyethylene terephthalate, 7 parts of ethylene-methacrylic acid copolymer, 3 parts of polyethylene glycol, 2 parts of sodium stearate, 0.7 parts Talc, 9 parts of hyperbranched polyphosphoramide, 4.95 parts of silica-loaded graphene oxide, 0.8 parts of ethylene bisstearamide, 0.7 parts of chain extender ADR-4368CS, 0.7 parts of antioxidant 1010, 20 parts of glass fiber.
所述超支化聚磷酰胺、负载二氧化硅的氧化石墨烯的质量比为2:1.1。The mass ratio of the hyperbranched polyphosphoramide and silica-loaded graphene oxide is 2:1.1.
实施例2Example 2
步骤一：氨基化氧化石墨烯的制备：Step 1: Preparation of aminated graphene oxide:
取1g氧化石墨烯、16g次磷酸、300ml去离子水，在75℃下反应4.5h，超声分散50min，离心，洗涤，冻干，得到含磷的氧化石墨烯。Take 1g graphene oxide, 16g hypophosphorous acid, and 300 ml deionized water, react at 75°C for 4.5 hours, ultrasonically disperse for 50 minutes, centrifuge, wash, and freeze-dry to obtain phosphorus-containing graphene oxide.
取30mL乙醇、1.5g对苯二胺，搅拌均匀，得到混合溶液，取1g含磷的氧化石墨烯、100mL去离子水，超声分散，加入混合溶液，在80℃下反应22h，过滤，洗涤，干燥，得到氨基化氧化石墨烯。Take 30 mL of ethanol and 1.5 g of p-phenylenediamine, stir evenly to obtain a mixed solution, take 1 g of phosphorus-containing graphene oxide and 100 mL of deionized water, disperse with ultrasound, add the mixed solution, react at 80°C for 22 hours, filter, and wash. After drying, aminated graphene oxide is obtained.
步骤二：超支化聚磷酰胺的制备：Step 2: Preparation of hyperbranched polyphosphoramide:
取1.8g三氯氧磷、50mL乙腈，搅拌均匀，得到溶液A；取3.4g4,4-二氨基二苯甲烷、3.5g三乙胺、300mL乙腈，搅拌均匀，降温至3℃，加入溶液A，反应1h，升温至45℃，反应22h，过滤，洗涤，干燥，得到超支化聚磷酰胺。Take 1.8g phosphorus oxychloride and 50mL acetonitrile, stir evenly to obtain solution A; take 3.4g 4,4-diaminodiphenylmethane, 3.5g triethylamine, 300mL acetonitrile, stir evenly, cool to 3°C, and add solution A , react for 1 hour, raise the temperature to 45°C, react for 22 hours, filter, wash and dry to obtain hyperbranched polyphosphoramide.
步骤三：接枝钼酸铵的二氧化硅的制备：Step 3: Preparation of silica grafted with ammonium molybdate:
取4.5mLKH560、30mL去离子水、70mL乙醇，超声分散，得到混合液；取3g二氧化硅、30mL去离子水、70mL乙醇，超声分散，升温至68℃，滴加混合液，保温10h，冷却，过滤，烘干，得到改性二氧化硅。Take 4.5mLKH560, 30mL deionized water, and 70mL ethanol, disperse with ultrasonic to obtain a mixed solution; take 3g silica, 30mL deionized water, and 70mL ethanol, disperse with ultrasonic, raise the temperature to 68°C, add the mixed solution dropwise, keep it warm for 10 hours, and cool. , filter and dry to obtain modified silica.
取9g钼酸铵、45g去离子水搅拌均匀，加入3g改性二氧化硅，在84℃下搅拌均匀，过滤，烘干，得到接枝钼酸铵的二氧化硅。Take 9g ammonium molybdate and 45g deionized water and stir evenly, add 3g modified silica, stir evenly at 84°C, filter, and dry to obtain silica grafted with ammonium molybdate.
所述钼酸铵、去离子水、改性二氧化硅的质量比为3：15：1。The mass ratio of ammonium molybdate, deionized water, and modified silica is 3:15:1.
步骤四：负载二氧化硅的氧化石墨烯的制备：Step 4: Preparation of silica-loaded graphene oxide:
取1g氨基化氧化石墨烯、150mLN,N-二甲基甲酰胺，超声50min，加入10g接枝钼酸铵的二氧化硅，在60℃下反应1h，过滤，洗涤，干燥，得到负载二氧化硅的氧化石墨烯。Take 1g of aminated graphene oxide and 150mL of N,N-dimethylformamide, ultrasonic for 50 minutes, add 10g of silica grafted with ammonium molybdate, react at 60°C for 1 hour, filter, wash, and dry to obtain loaded dioxide. Graphene oxide on silicon.
氨基化氧化石墨烯与接枝钼酸铵的二氧化硅的质量比为1：10。The mass ratio of aminated graphene oxide to silica grafted with ammonium molybdate is 1:10.
步骤五：取聚对苯二甲酸乙二醇酯、乙烯-甲基丙烯酸共聚物、聚乙二醇、硬脂酸钠、滑石粉、超支化聚磷酰胺、负载二氧化硅的氧化石墨烯、乙撑双硬脂酰胺、扩链剂ADR-4368CS、抗氧剂168、玄武岩纤维，混合均匀，在200-290℃下熔融挤出，造粒，制得用于线圈骨架的耐高温阻燃PET材料。Step 5: Take polyethylene terephthalate, ethylene-methacrylic acid copolymer, polyethylene glycol, sodium stearate, talc, hyperbranched polyphosphamide, silica-loaded graphene oxide, Ethylene bis stearamide, chain extender ADR-4368CS, antioxidant 168, and basalt fiber are mixed evenly, melted and extruded at 200-290°C, and granulated to produce high-temperature resistant flame-retardant PET for coil skeletons Material.
所述PET材料包括以下成分，按照重量计，50份聚对苯二甲酸乙二醇酯、5份乙烯-甲基丙烯酸共聚物、2份聚乙二醇、1份硬脂酸钠、0.5份滑石粉、6份超支化聚磷酰胺、3份负载二氧化硅的氧化石墨烯、0.5份乙撑双硬脂酰胺、0.5份扩链剂ADR-4368CS、0.5份抗氧剂168、10份玄武岩纤维。The PET material includes the following ingredients, by weight, 50 parts of polyethylene terephthalate, 5 parts of ethylene-methacrylic acid copolymer, 2 parts of polyethylene glycol, 1 part of sodium stearate, 0.5 parts Talc, 6 parts of hyperbranched polyphosphamide, 3 parts of silica-loaded graphene oxide, 0.5 parts of ethylene bisstearamide, 0.5 parts of chain extender ADR-4368CS, 0.5 parts of antioxidant 168, 10 parts of basalt fiber.
所述超支化聚磷酰胺、负载二氧化硅的氧化石墨烯的质量比为2:1。The mass ratio of the hyperbranched polyphosphoramide to silica-loaded graphene oxide is 2:1.
实施例3Example 3
步骤一：氨基化氧化石墨烯的制备：Step 1: Preparation of aminated graphene oxide:
取1g氧化石墨烯、16g次磷酸、300ml去离子水，在85℃下反应5.5h，超声分散70min，离心，洗涤，冻干，得到含磷的氧化石墨烯。Take 1g graphene oxide, 16g hypophosphorous acid, and 300 ml deionized water, react at 85°C for 5.5 hours, ultrasonically disperse for 70 minutes, centrifuge, wash, and freeze-dry to obtain phosphorus-containing graphene oxide.
取30mL乙醇、1.5g对苯二胺，搅拌均匀，得到混合溶液，取1g含磷的氧化石墨烯、100mL去离子水，超声分散，加入混合溶液，在85℃下反应24h，过滤，洗涤，干燥，得到氨基化氧化石墨烯。Take 30mL of ethanol and 1.5g of p-phenylenediamine, stir evenly to obtain a mixed solution, take 1g of phosphorus-containing graphene oxide and 100mL of deionized water, disperse with ultrasound, add the mixed solution, react at 85°C for 24 hours, filter, and wash. After drying, aminated graphene oxide is obtained.
步骤二：超支化聚磷酰胺的制备：Step 2: Preparation of hyperbranched polyphosphoramide:
取1.8g三氯氧磷、50mL乙腈，搅拌均匀，得到溶液A；取3.4g4,4-二氨基二苯甲烷、3.5g三乙胺、300mL乙腈，搅拌均匀，降温至6℃，加入溶液A，反应2h，升温至52℃，反应24h，过滤，洗涤，干燥，得到超支化聚磷酰胺。Take 1.8g phosphorus oxychloride and 50mL acetonitrile, stir evenly to obtain solution A; take 3.4g 4,4-diaminodiphenylmethane, 3.5g triethylamine, 300mL acetonitrile, stir evenly, cool to 6°C, and add solution A , react for 2 hours, raise the temperature to 52°C, react for 24 hours, filter, wash and dry to obtain hyperbranched polyphosphoramide.
步骤三：接枝钼酸铵的二氧化硅的制备：Step 3: Preparation of silica grafted with ammonium molybdate:
取4.5mLKH560、30mL去离子水、70mL乙醇，超声分散，得到混合液；取3g二氧化硅、30mL去离子水、70mL乙醇，超声分散，升温至72℃，滴加混合液，保温13h，冷却，过滤，烘干，得到改性二氧化硅。Take 4.5mLKH560, 30mL deionized water, and 70mL ethanol, disperse with ultrasonic to obtain a mixed solution; take 3g silica, 30mL deionized water, and 70mL ethanol, disperse with ultrasonic, raise the temperature to 72°C, add the mixed solution dropwise, keep warm for 13 hours, and cool. , filter and dry to obtain modified silica.
取15g钼酸铵、60g去离子水搅拌均匀，加入3g改性二氧化硅，在88℃下搅拌均匀，过滤，烘干，得到接枝钼酸铵的二氧化硅。Take 15g ammonium molybdate and 60g deionized water and stir evenly, add 3g modified silica, stir evenly at 88°C, filter, and dry to obtain silica grafted with ammonium molybdate.
所述钼酸铵、去离子水、改性二氧化硅的质量比为5：20：1。The mass ratio of ammonium molybdate, deionized water, and modified silica is 5:20:1.
步骤四：负载二氧化硅的氧化石墨烯的制备：Step 4: Preparation of silica-loaded graphene oxide:
取1g氨基化氧化石墨烯、150mLN,N-二甲基甲酰胺，超声70min，加入20g接枝钼酸铵的二氧化硅，在68℃下反应2h，过滤，洗涤，干燥，得到负载二氧化硅的氧化石墨烯。Take 1g of aminated graphene oxide and 150mL of N,N-dimethylformamide, ultrasonic for 70 minutes, add 20g of silica grafted with ammonium molybdate, react at 68°C for 2 hours, filter, wash, and dry to obtain loaded dioxide. Graphene oxide on silicon.
氨基化氧化石墨烯与接枝钼酸铵的二氧化硅的质量比为1：20。The mass ratio of aminated graphene oxide to silica grafted with ammonium molybdate is 1:20.
步骤五：取聚对苯二甲酸乙二醇酯、乙烯-甲基丙烯酸共聚物、聚乙二醇、硬脂酸钠、滑石粉、超支化聚磷酰胺、负载二氧化硅的氧化石墨烯、乙撑双硬脂酰胺、扩链剂ADR-4368CS、抗氧剂168、玻璃纤维，混合均匀，在200-290℃下熔融挤出，造粒，制得用于线圈骨架的耐高温阻燃PET材料。Step 5: Take polyethylene terephthalate, ethylene-methacrylic acid copolymer, polyethylene glycol, sodium stearate, talc, hyperbranched polyphosphamide, silica-loaded graphene oxide, Ethylene bisstearamide, chain extender ADR-4368CS, antioxidant 168, and glass fiber are mixed evenly, melted and extruded at 200-290°C, and granulated to produce high-temperature flame-retardant PET for coil skeletons. Material.
所述PET材料包括以下成分，按照重量计，80份聚对苯二甲酸乙二醇酯、8份乙烯-甲基丙烯酸共聚物、4份聚乙二醇、3份硬脂酸钠、1份滑石粉、12份超支化聚磷酰胺、7.2份负载二氧化硅的氧化石墨烯、1份乙撑双硬脂酰胺、1份扩链剂ADR-4368CS、1份抗氧剂168、30份玻璃纤维。The PET material includes the following ingredients, by weight, 80 parts polyethylene terephthalate, 8 parts ethylene-methacrylic acid copolymer, 4 parts polyethylene glycol, 3 parts sodium stearate, 1 part Talc, 12 parts of hyperbranched polyphosphoramide, 7.2 parts of silica-loaded graphene oxide, 1 part of ethylene bisstearamide, 1 part of chain extender ADR-4368CS, 1 part of antioxidant 168, 30 parts of glass fiber.
所述超支化聚磷酰胺、负载二氧化硅的氧化石墨烯的质量比为2:1.2。The mass ratio of the hyperbranched polyphosphoramide and silica-loaded graphene oxide is 2:1.2.
实施例4：不对氧化石墨烯进行氨基化处理，其余与实施例1相同。Example 4: The graphene oxide is not subjected to amination treatment, and the rest is the same as Example 1.
具体改变步骤为：The specific change steps are:
步骤一：含磷的氧化石墨烯的制备：Step 1: Preparation of phosphorus-containing graphene oxide:
取1g氧化石墨烯、16g次磷酸、300ml去离子水，在80℃下反应5h，超声分散60min，离心，洗涤，冻干，得到含磷的氧化石墨烯。Take 1g graphene oxide, 16g hypophosphorous acid, and 300 ml deionized water, react at 80°C for 5 hours, ultrasonically disperse for 60 minutes, centrifuge, wash, and freeze-dry to obtain phosphorus-containing graphene oxide.
步骤二、步骤三与实施例1相同。Step two and step three are the same as in Example 1.
步骤四：负载二氧化硅的氧化石墨烯的制备：Step 4: Preparation of silica-loaded graphene oxide:
取1g含磷的氧化石墨烯、150mLN,N-二甲基甲酰胺，超声60min，加入15g接枝钼酸铵的二氧化硅，在64℃下反应1.5h，过滤，洗涤，干燥，得到负载二氧化硅的氧化石墨烯。Take 1g of phosphorus-containing graphene oxide and 150mL of N,N-dimethylformamide, ultrasonic for 60 minutes, add 15g of silica grafted with ammonium molybdate, react at 64°C for 1.5h, filter, wash, and dry to obtain the load. Graphene oxide from silicon dioxide.
步骤五：取聚对苯二甲酸乙二醇酯、乙烯-甲基丙烯酸共聚物、聚乙二醇、硬脂酸钠、滑石粉、超支化聚磷酰胺、负载二氧化硅的氧化石墨烯、乙撑双硬脂酰胺、扩链剂ADR-4368CS、抗氧剂1010、玻璃纤维，混合均匀，在200-290下熔融挤出，造粒，制得用于线圈骨架的耐高温阻燃PET材料。Step 5: Take polyethylene terephthalate, ethylene-methacrylic acid copolymer, polyethylene glycol, sodium stearate, talc, hyperbranched polyphosphamide, silica-loaded graphene oxide, Ethylene bisstearamide, chain extender ADR-4368CS, antioxidant 1010, and glass fiber are mixed evenly, melted and extruded at 200-290, and granulated to produce a high-temperature flame-retardant PET material for coil skeletons. .
所述PET材料包括以下成分，按照重量计，70份聚对苯二甲酸乙二醇酯、7份乙烯-甲基丙烯酸共聚物、3份聚乙二醇、2份硬脂酸钠、0.7份滑石粉、9份超支化聚磷酰胺、4.95份负载二氧化硅的氧化石墨烯、0.8份乙撑双硬脂酰胺、0.7份扩链剂ADR-4368CS、0.7份抗氧剂1010、20份玻璃纤维。The PET material includes the following ingredients, by weight, 70 parts of polyethylene terephthalate, 7 parts of ethylene-methacrylic acid copolymer, 3 parts of polyethylene glycol, 2 parts of sodium stearate, 0.7 parts Talc, 9 parts of hyperbranched polyphosphoramide, 4.95 parts of silica-loaded graphene oxide, 0.8 parts of ethylene bisstearamide, 0.7 parts of chain extender ADR-4368CS, 0.7 parts of antioxidant 1010, 20 parts of glass fiber.
实施例5：不在二氧化硅上接枝钼酸铵，其余与实施例1相同。Example 5: Do not graft ammonium molybdate on silica, and the rest is the same as Example 1.
具体改变步骤为：The specific change steps are:
步骤一、步骤二与实施例1相同。Step 1 and step 2 are the same as in Example 1.
步骤三：二氧化硅的制备：Step 3: Preparation of silica:
取4.5mLKH560、30mL去离子水、70mL乙醇，超声分散，得到混合液；取3g二氧化硅、30mL去离子水、70mL乙醇，超声分散，升温至70℃，滴加混合液，保温12h，冷却，过滤，烘干，得到改性二氧化硅。Take 4.5mLKH560, 30mL deionized water, and 70mL ethanol, disperse with ultrasonic to obtain a mixed solution; take 3g silica, 30mL deionized water, and 70mL ethanol, disperse with ultrasonic, raise the temperature to 70°C, add the mixed solution dropwise, keep it warm for 12 hours, and cool. , filter and dry to obtain modified silica.
步骤四：负载二氧化硅的氧化石墨烯的制备：Step 4: Preparation of silica-loaded graphene oxide:
取1g氨基化氧化石墨烯、150mLN,N-二甲基甲酰胺，超声60min，加入15g改性二氧化硅，在64℃下反应1.5h，过滤，洗涤，干燥，得到负载二氧化硅的氧化石墨烯。Take 1g of aminated graphene oxide and 150mL of N,N-dimethylformamide, ultrasonic for 60 minutes, add 15g of modified silica, react at 64°C for 1.5h, filter, wash, and dry to obtain the oxidation of loaded silica. Graphene.
步骤五：取聚对苯二甲酸乙二醇酯、乙烯-甲基丙烯酸共聚物、聚乙二醇、硬脂酸钠、滑石粉、超支化聚磷酰胺、负载二氧化硅的氧化石墨烯、乙撑双硬脂酰胺、扩链剂ADR-4368CS、抗氧剂1010、玻璃纤维，混合均匀，在200-290下熔融挤出，造粒，制得用于线圈骨架的耐高温阻燃PET材料。Step 5: Take polyethylene terephthalate, ethylene-methacrylic acid copolymer, polyethylene glycol, sodium stearate, talc, hyperbranched polyphosphamide, silica-loaded graphene oxide, Ethylene bisstearamide, chain extender ADR-4368CS, antioxidant 1010, and glass fiber are mixed evenly, melted and extruded at 200-290, and granulated to produce a high-temperature flame-retardant PET material for coil skeletons. .
所述PET材料包括以下成分，按照重量计，70份聚对苯二甲酸乙二醇酯、7份乙烯-甲基丙烯酸共聚物、3份聚乙二醇、2份硬脂酸钠、0.7份滑石粉、9份超支化聚磷酰胺、4.95份负载二氧化硅的氧化石墨烯、0.8份乙撑双硬脂酰胺、0.7份扩链剂ADR-4368CS、0.7份抗氧剂1010、20份玻璃纤维。The PET material includes the following ingredients, by weight, 70 parts of polyethylene terephthalate, 7 parts of ethylene-methacrylic acid copolymer, 3 parts of polyethylene glycol, 2 parts of sodium stearate, 0.7 parts Talc, 9 parts of hyperbranched polyphosphoramide, 4.95 parts of silica-loaded graphene oxide, 0.8 parts of ethylene bisstearamide, 0.7 parts of chain extender ADR-4368CS, 0.7 parts of antioxidant 1010, 20 parts of glass fiber.
实施例6：不添加超支化聚磷酰胺，其余与实施例1相同。Example 6: No hyperbranched polyphosphoramide is added, and the rest is the same as Example 1.
具体改变步骤为：The specific change steps are:
步骤五：取聚对苯二甲酸乙二醇酯、乙烯-甲基丙烯酸共聚物、聚乙二醇、硬脂酸钠、滑石粉、负载二氧化硅的氧化石墨烯、乙撑双硬脂酰胺、扩链剂ADR-4368CS、抗氧剂1010、玻璃纤维，混合均匀，在200-290下熔融挤出，造粒，制得用于线圈骨架的耐高温阻燃PET材料。Step 5: Take polyethylene terephthalate, ethylene-methacrylic acid copolymer, polyethylene glycol, sodium stearate, talc, silica-loaded graphene oxide, and ethylene bisstearamide , chain extender ADR-4368CS, antioxidant 1010, and glass fiber, mix them evenly, melt and extrud at 200-290, and pelletize to prepare a high-temperature flame-retardant PET material for coil skeletons.
所述PET材料包括以下成分，按照重量计，70份聚对苯二甲酸乙二醇酯、7份乙烯-甲基丙烯酸共聚物、3份聚乙二醇、2份硬脂酸钠、0.7份滑石粉、4.95份负载二氧化硅的氧化石墨烯、0.8份乙撑双硬脂酰胺、0.7份扩链剂ADR-4368CS、0.7份抗氧剂1010、20份玻璃纤维。The PET material includes the following ingredients, by weight, 70 parts of polyethylene terephthalate, 7 parts of ethylene-methacrylic acid copolymer, 3 parts of polyethylene glycol, 2 parts of sodium stearate, 0.7 parts Talcum powder, 4.95 parts of silica-loaded graphene oxide, 0.8 parts of ethylene bisstearamide, 0.7 parts of chain extender ADR-4368CS, 0.7 parts of antioxidant 1010, 20 parts of glass fiber.
实施例7：不对氧化石墨烯进行磷改性，其余与实施例1相同。Example 7: Graphene oxide is not modified with phosphorus, and the rest is the same as Example 1.
具体改变步骤为：The specific change steps are:
步骤一：氨基化氧化石墨烯的制备：Step 1: Preparation of aminated graphene oxide:
取30mL乙醇、1.5g对苯二胺，搅拌均匀，得到混合溶液，取1g氧化石墨烯、100mL去离子水，超声分散，加入混合溶液，在83℃下反应23h，过滤，洗涤，干燥，得到氨基化氧化石墨烯。Take 30mL ethanol and 1.5g p-phenylenediamine, stir evenly to obtain a mixed solution, take 1g graphene oxide and 100mL deionized water, disperse it ultrasonically, add the mixed solution, react at 83°C for 23 hours, filter, wash, and dry to obtain Aminated graphene oxide.
步骤二、步骤三、步骤四与实施例1相同。Step 2, step 3 and step 4 are the same as in Example 1.
步骤五：取聚对苯二甲酸乙二醇酯、乙烯-甲基丙烯酸共聚物、聚乙二醇、硬脂酸钠、滑石粉、超支化聚磷酰胺、负载二氧化硅的氧化石墨烯、乙撑双硬脂酰胺、扩链剂ADR-4368CS、抗氧剂1010、玻璃纤维，混合均匀，在200-290下熔融挤出，造粒，制得用于线圈骨架的耐高温阻燃PET材料。Step 5: Take polyethylene terephthalate, ethylene-methacrylic acid copolymer, polyethylene glycol, sodium stearate, talc, hyperbranched polyphosphamide, silica-loaded graphene oxide, Ethylene bisstearamide, chain extender ADR-4368CS, antioxidant 1010, and glass fiber are mixed evenly, melted and extruded at 200-290, and granulated to produce a high-temperature flame-retardant PET material for coil skeletons. .
所述PET材料包括以下成分，按照重量计，70份聚对苯二甲酸乙二醇酯、7份乙烯-甲基丙烯酸共聚物、3份聚乙二醇、2份硬脂酸钠、0.7份滑石粉、9份超支化聚磷酰胺、4.95份负载二氧化硅的氧化石墨烯、0.8份乙撑双硬脂酰胺、0.7份扩链剂ADR-4368CS、0.7份抗氧剂1010、20份玻璃纤维。The PET material includes the following ingredients, by weight, 70 parts of polyethylene terephthalate, 7 parts of ethylene-methacrylic acid copolymer, 3 parts of polyethylene glycol, 2 parts of sodium stearate, 0.7 parts Talc, 9 parts of hyperbranched polyphosphoramide, 4.95 parts of silica-loaded graphene oxide, 0.8 parts of ethylene bisstearamide, 0.7 parts of chain extender ADR-4368CS, 0.7 parts of antioxidant 1010, 20 parts of glass fiber.
实施例8：超支化聚磷酰胺、负载二氧化硅的氧化石墨烯的质量比为2:0.7，其余与实施例1相同。Example 8: The mass ratio of hyperbranched polyphosphoramide and silica-loaded graphene oxide is 2:0.7, and the rest is the same as Example 1.
实施例9：钼酸铵、去离子水、改性二氧化硅的质量比为7：20：1。Example 9: The mass ratio of ammonium molybdate, deionized water, and modified silica is 7:20:1.
实验：experiment:
取实施例1至实施例9制备得到的PET材料在280℃下注塑，制备成130mm×13mm×3mm的样品，进行性能测试。根据GB1040-92测试PET材料的拉伸强度。根据GB/T 2406-1993测试PET材料阻燃性能。根据ISO5659-2：2017，测试PET材料抑烟性能，得到的数据如下表所示。The PET materials prepared in Examples 1 to 9 were injection molded at 280° C. to prepare samples of 130 mm × 13 mm × 3 mm, and performance tests were performed. Test the tensile strength of PET materials according to GB1040-92. Test the flame retardant performance of PET materials according to GB/T 2406-1993. According to ISO5659-2:2017, the smoke suppression performance of PET materials was tested, and the data obtained are as shown in the table below.
结论：由表上数据可知，实施例4不对氧化石墨烯进行氨基化处理，接枝钼酸铵的二氧化硅的负载量变少，阻燃性能以及抑烟性能受到了影响。实施例5不在二氧化硅上接枝钼酸铵，抑烟性能较差。实施例6不添加超支化聚磷酰胺，负载二氧化硅的氧化石墨烯单独作用，阻燃性能下降。实施例7不对氧化石墨烯进行磷改性，阻燃性能下降。实施例8超支化聚磷酰胺、负载二氧化硅的氧化石墨烯的质量比为2:0.7，性能有所下降。Conclusion: It can be seen from the data in the table that in Example 4, the graphene oxide is not amination treated, the loading amount of silica grafted with ammonium molybdate is reduced, and the flame retardant performance and smoke suppression performance are affected. Example 5 does not graft ammonium molybdate on silica, and the smoke suppression performance is poor. In Example 6, no hyperbranched polyphosphoramide is added, and the graphene oxide loaded with silica acts alone, and the flame retardant performance decreases. In Example 7, the graphene oxide is not modified with phosphorus, and the flame retardant performance decreases. In Example 8, the mass ratio of hyperbranched polyphosphoramide to silica-loaded graphene oxide is 2:0.7, and the performance has declined.
最后应说明的是：以上所述仅为本发明的优选实施例而已，并不用于限制本发明，尽管参照前述实施例对本发明进行了详细的说明，对于本领域的技术人员来说，其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分技术特征进行等同替换。凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。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, for those skilled in the art, it is still The technical solutions described in the foregoing embodiments may be modified, or some of the technical features may be equivalently replaced. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention shall be included in the protection scope of the present invention.
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211266027.6ACN117285798A (en) | 2022-10-17 | 2022-10-17 | High-temperature-resistant flame-retardant PET material for coil frameworks and preparation method thereof |
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211266027.6ACN117285798A (en) | 2022-10-17 | 2022-10-17 | High-temperature-resistant flame-retardant PET material for coil frameworks and preparation method thereof |
| Publication Number | Publication Date |
|---|---|
| CN117285798Atrue CN117285798A (en) | 2023-12-26 |
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211266027.6APendingCN117285798A (en) | 2022-10-17 | 2022-10-17 | High-temperature-resistant flame-retardant PET material for coil frameworks and preparation method thereof |
| Country | Link |
|---|---|
| CN (1) | CN117285798A (en) |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101415758A (en)* | 2006-01-27 | 2009-04-22 | 沙伯基础创新塑料知识产权有限公司 | Molding compositions containing fillers and modified polybutylene terephthalate (PBT) random copolymers derived from polyethylene terephthalated (PET) |
| CN107245228A (en)* | 2017-06-22 | 2017-10-13 | 魏科峰 | A preparation method of flame-retardant and anti-melt-dripping polyester material and flame-retardant and anti-melt-dripping polyester material |
| CN108149337A (en)* | 2017-12-05 | 2018-06-12 | 上海帕吉索纳米技术有限公司 | A kind of graphene Jinlun-6 fireproof fiber and preparation method thereof |
| CN110982233A (en)* | 2019-12-27 | 2020-04-10 | 福州大学 | High-barrier RGO-SiO2PET protective film and preparation method thereof |
| WO2022068621A1 (en)* | 2020-09-30 | 2022-04-07 | 黎明职业大学 | Halogen-free flame-retardant reinforced pet composite material and preparation method therefor |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101415758A (en)* | 2006-01-27 | 2009-04-22 | 沙伯基础创新塑料知识产权有限公司 | Molding compositions containing fillers and modified polybutylene terephthalate (PBT) random copolymers derived from polyethylene terephthalated (PET) |
| CN107245228A (en)* | 2017-06-22 | 2017-10-13 | 魏科峰 | A preparation method of flame-retardant and anti-melt-dripping polyester material and flame-retardant and anti-melt-dripping polyester material |
| CN108149337A (en)* | 2017-12-05 | 2018-06-12 | 上海帕吉索纳米技术有限公司 | A kind of graphene Jinlun-6 fireproof fiber and preparation method thereof |
| CN110982233A (en)* | 2019-12-27 | 2020-04-10 | 福州大学 | High-barrier RGO-SiO2PET protective film and preparation method thereof |
| WO2022068621A1 (en)* | 2020-09-30 | 2022-04-07 | 黎明职业大学 | Halogen-free flame-retardant reinforced pet composite material and preparation method therefor |
| Title |
|---|
| 胡晋: "超支化聚磷酰胺和二氧化硅负载三氧化二铁的合成及其在聚丙烯阻燃中的应用", 《中国优秀硕士学位论文全文数据库工程科技I辑》, no. 8, 15 August 2021 (2021-08-15), pages 016 - 364* |
| Publication | Publication Date | Title |
|---|---|---|
| Long et al. | Boosting safety and performance of lithium-ion battery enabled by cooperation of thermotolerant fire-retardant composite membrane and nonflammable electrolyte | |
| CN110878155B (en) | Halogen-free flame-retardant external insulation material for nuclear power station cable and preparation method thereof | |
| CN119060441B (en) | A reinforced halogen-free flame-retardant cable and preparation method thereof | |
| CN114702769B (en) | Reinforced flame-retardant microcapsule composite material and preparation method thereof | |
| CN110862620A (en) | Halogen-free flame retardant filling material for nuclear power plant cables and preparation method thereof | |
| CN118420998A (en) | Flame-retardant photovoltaic cable | |
| CN101891896B (en) | Expansible fire retardant containing fluorine-phosphorus-nitrogen oligomer and preparation method thereof | |
| CN118772510A (en) | Flame retardant and smoke suppression insulating cable material and preparation method thereof | |
| CN118562291A (en) | A pressure-resistant shell polymer material for LED lamp and preparation method thereof | |
| CN117285798A (en) | High-temperature-resistant flame-retardant PET material for coil frameworks and preparation method thereof | |
| CN117844087B (en) | Polyethylene material with efficient flame retardant property and preparation method thereof | |
| CN118336162B (en) | Modified coating for lithium battery diaphragm and lithium battery diaphragm | |
| CN112064353B (en) | Degradable flame retardant plant fiber nonwoven fabric and preparation method thereof | |
| CN112029157B (en) | Anti-dripping composite intumescent flame retardant and preparation method and application thereof | |
| CN117511032A (en) | A kind of high flame retardant and low smoke cloth wire and its preparation process | |
| CN118388775A (en) | A method for preparing modified nanocellulose | |
| CN118638348A (en) | A hybrid core-shell ferroferric oxide with both flame retardancy and electromagnetic wave absorption functions and a composite material thereof and a preparation method thereof | |
| CN108774472A (en) | A kind of FFC wire rod hot melt adhesive films of flame-retardant and anti-dripping and preparation method thereof | |
| CN114773707B (en) | Beta-cyclodextrin microcapsule ammonium polyphosphate intumescent flame-retardant low-density polyethylene and preparation method thereof | |
| CN118546461A (en) | Polypropylene composite plastic for logistics packaging box and production method thereof | |
| CN114709030B (en) | Preparation method of B1-level wire cable | |
| CN115521503B (en) | Flame-retardant additive and preparation method and application thereof | |
| CN118581619B (en) | Flame-retardant fabric with electromagnetic shielding performance and preparation method thereof | |
| CN112038511A (en) | Surface-encapsulated silica aerogel felt product for buffering and vibration reduction of electric vehicle lithium-ion power battery and its manufacturing method | |
| CN105694193B (en) | A kind of isolated fire-retardant cable |
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication | Application publication date:20231226 |