CN113968057A - 一种阻燃人造革及其制备方法 - Google Patents

一种阻燃人造革及其制备方法 Download PDF

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CN113968057A
CN113968057A CN202111309345.1A CN202111309345A CN113968057A CN 113968057 A CN113968057 A CN 113968057A CN 202111309345 A CN202111309345 A CN 202111309345A CN 113968057 A CN113968057 A CN 113968057A
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flame
retardant
artificial leather
pvc resin
surface layer
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陆勤中
赵建明
朱家顺
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Kunshan Achilles New Material Technology Co ltd
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Abstract

本申请公开了一种阻燃人造革及其制备方法。阻燃人造革包括贴合的阻燃基布和阻燃PVC树脂面层；阻燃PVC树脂面层由以下原料制成：PVC树脂、复合阻燃剂、防水剂、填料和偶联剂；复合阻燃剂为二氧化硅包覆硼酸锌协同石墨烯和增强阻燃剂，增强阻燃剂为P‑N系、卤‑锑系或Mg‑Al系阻燃剂。本申请阻燃人造革的制备方法：将原料混合，压延成型得到阻燃PVC树脂面层；将基布浸泡在氮磷阻燃剂溶液中，干燥并冷却得到阻燃基布；将阻燃PVC树脂面层与阻燃基布贴合、压花，并对阻燃基布表面进行阻燃处理，对阻燃PVC树脂面层表面涂覆聚偏氟乙烯涂料，冷却后得到阻燃人造革。本申请的复合阻燃剂具有协同效应，故所得到的阻燃人造革具有良好的阻燃性、耐磨性、抗菌性和力学性能。

Description

一种阻燃人造革及其制备方法
技术领域
本申请涉及人造革技术领域，更具体地说，它涉及一种阻燃人造革及其制备方法。
背景技术
皮革是由天然蛋白质纤维在三维空间紧密编织构成的，其表面有一种特殊的粒面层，具有自然的粒纹和光泽，手感舒适。皮革按制造方式分为真皮、再生皮和人造革。其中人造革也叫仿皮或胶料，是PVC和PU等人造材料的总称。它是在纺织布或无纺布上，由各种不同配方的PVC和PU等发泡或覆膜加工制作而成，可以根据不同强度、耐磨度、耐寒度和色彩、光泽、花纹图案等要求加工制成，具有花色品种繁多、防水性能好、边幅整齐、利用率高和价格相对真皮便宜的特点，因而人造革被广泛应用在汽车、家具、家居等领域。
因人造革材料多为易燃品，这样给人们生活及财产带来了极大的隐患；并且限制了人造革在一些防火等级要求较高的特殊区域的使用，如公共场所、商业场所、娱乐等人员密集型场所。
针对上述中的相关技术，发明人认为人造革存在阻燃性差的问题，因此限制了其使用与发展。
发明内容
为了提高人造革的阻燃性，本申请提供一种阻燃人造革及其制备方法。
第一方面，本申请提供的一种阻燃人造革，采用如下的技术方案：
一种阻燃人造革，包括贴合在一起的阻燃基布和阻燃PVC树脂面层；
所述阻燃PVC树脂面层由包括以下重量份的原料制成：PVC树脂60-80份、复合阻燃剂10-50份、防水剂5-7份、填料5-10份和偶联剂1-3份；
所述复合阻燃剂包括重量比为1：(1-4)的二氧化硅包覆硼酸锌协同石墨烯和增强阻燃剂，所述增强阻燃剂为P-N系、卤-锑系或Mg-Al系阻燃剂。
通过采用上述技术方案，由于硼酸锌是一种低熔点玻璃体，对新生炭中的空洞和裂缝具有封闭作用，因而硼酸锌对PVC聚合物有一定的阻燃作用；纳米二氧化硅添加到PVC复合材料中，可以使PVC材料表面更加致密，加上纳米颗粒的高强度，使PVC材料的耐磨性大大提高；利用纳米二氧化硅包覆硼酸锌，构成核-壳结构，具有协同阻燃增效作用；且纳米二氧化硅能够降低硼酸锌的表面极性，增加硼酸锌与PVC材料的表面相容性，从而提高阻燃PVC树脂面层的阻燃效果和热稳定性；由于石墨烯是一种二维晶体，受热膨胀，膨胀后的石墨烯与PVC聚合物混合时，在火焰的作用下，可在PVC聚合物表面生成坚韧的炭层，起到阻燃作用；同时细菌在锋利的纳米级二维材料上游走瞬间就被割破细胞壁而死亡，因而石墨烯具有良好的阻燃性和抗菌性；二氧化硅包覆硼酸锌后再与石墨烯复配，形成的二氧化硅包覆硼酸锌协同石墨烯具有良好的阻燃性同时兼具优良的耐磨性和抗菌性。
P-N系、卤-锑系或Mg-Al系阻燃剂作为复合阻燃剂具有显著的协同效应，其与二氧化硅包覆硼酸锌协同石墨烯在一定比例下复配后形成的复合阻燃剂进一步提高了PVC复合材料的阻燃性。
优选的，所述二氧化硅包覆硼酸锌协同石墨烯多功能助剂颗粒的制备方法如下：
S1，将硼酸溶于水中，加入氧化锌，边混合边加入氨水；再加入十二烷基苯磺酸钠，混合后，经过滤，烘干得到硼酸锌；
S2，将所述硼酸锌加入水中，再加入氨水得到混合液，将所述混合液加入含有正硅酸四乙酯和无水乙醇的混合液中，混合过滤后用无水乙醇洗涤，烘干得到二氧化硅包覆硼酸锌；
S3，将所述二氧化硅包覆硼酸锌分散于水中，超声震荡后加入石墨烯，混合洗涤后烘干得到二氧化硅包覆硼酸锌协同石墨烯；
通过采用上述技术方案，制备方法简单，且制备出的二氧化硅包覆硼酸锌协同石墨烯具有阻燃效果佳、抗菌性好且耐磨性优良，同时具有良好的加工性能和力学性能。
优选的，所述原料还包括3-5重量份的热稳定剂。
通过采用上述技术方案，热稳定剂可有效地阻止、减少甚至基本停止PVC材料的降解，从而延长PVC材料的使用寿命。
优选的，所述原料还包括1-3重量份的邻苯二甲酸酯类。
通过采用上述技术方案，邻苯二甲酸酯类作为PVC材料的增塑剂，可进一步提高阻燃PVC树脂面层的力学性能。
优选的，所述原料还包括0.5-2重量份的抗氧化剂。
通过采用上述技术方案，抗氧化剂可以捕获活性的游离基，生成非活性游离基，或者能够分解PVC聚合物在氧化过程中产生的过氧化物，使链锁反应终止，延缓PVC聚合物的氧化过程，从而使PVC聚合物能顺利进行加工，并延长使用寿命。
优选的，所述阻燃PVC树脂面层设有聚偏氟乙烯涂层。
通过采用上述技术方案，聚偏氟乙烯具有最强韧性、低摩擦系数、耐腐蚀性强、耐老化性、耐气候，耐辐照性能好等特点，其涂覆在阻燃PVC树脂面层的表面，从而赋予阻燃PVC树脂面层更多优异性能。
第二方面，本申请提供一种阻燃人造革的制备方法，采用如下的技术方案：
阻燃PVC树脂面层：将相应重量的原料进行混合，压延成型；
阻燃基布：将基布浸泡在氮磷阻燃剂溶液中，干燥并冷却得到；
合成：将所述阻燃PVC树脂面层与阻燃基布贴合、压花；并对阻燃基布背向阻燃PVC树脂面层的一面进行阻燃处理，对阻燃PVC树脂面层背向阻燃基布的一面涂覆浓度为1-45％聚偏氟乙烯涂料，冷却后得到所需人造革。
通过上述技术方案，本制备方法通过二氧化硅包覆硼酸锌协同石墨烯颗粒对PVC树脂进行阻燃；基布浸泡在阻燃剂溶液中为一次阻燃，且其一面阻燃处理为二次阻燃，进而实现层层阻燃的效果，形成的人造革具有优异的阻燃性能；
聚偏氟乙烯具有一定的疏水性，再加上压花致使阻燃PVC面层的表面具有微观粗糙结构，因而聚偏氟乙烯层可以提高水滴的静态接触角，截流更多气体，使液滴不易渗入粗糙结构，减少了粉尘、雨水在其表面的附着力，从而使水滴能够滚动带走阻燃PVC树脂面层表面的灰尘颗粒，实现了良好的长效抗污性。
综上可知，本制备方法通过对人造革进行层层阻燃处理，再进行疏水处理的特点，从而制备出的人造革具有优异的阻燃性和抗菌性。
优选的，所述原料混合时采用加热混合的方式，其中加热温度为110-130℃，混合时间为2-4min。
优选的，所述基布的初始温度为60-90℃。
通过采用上述技术方案，优化了基布的初始温度，原料混合时的加热温度和混合时间，有利于更好地制备阻燃PVC树脂面层。
优选的，所述阻燃处理为：在阻燃基布背向阻燃PVC树脂面层的一面喷涂含5-8％三聚氰胺磷酸酯阻燃剂的聚氨酯溶液。
通过采用上述技术方案，在含羟基的聚氨酯聚合物中添加三聚氰胺磷酸酯，使聚氨酯具有良好的阻燃效果，再将聚氨酯溶液喷涂在基布表面，使基布表面具有良好的阻燃性。
综上所述，本申请具有以下有益效果：
1、由于本申请通过制备出的二氧化硅包覆硼酸锌协同石墨烯具有良好的阻燃性、抗菌性和耐磨性，其与P-N系、卤-锑系或Mg-Al系阻燃剂复配后形成的复合阻燃剂使得阻燃PVC树脂面层具有优异的阻燃性，同时具有良好的抗菌性和耐磨性；
2、本申请中选用聚偏氟乙烯涂覆阻燃PVC树脂面层表面，聚偏氟乙烯具有一定的疏水性，在压花的作用下，使得阻燃人造革具有长效的抗污能力；
3、本申请将基布浸泡在氮磷阻燃剂中，且将基布的表面用含有三聚氰胺磷酸酯阻燃剂的聚氨酯溶液进行涂覆，再与阻燃PVC树脂面层贴合后制得的人造革具有层层阻燃的效果，从而提高了人造革整体的阻燃性。
具体实施方式
以下结合实施例对本申请作进一步详细说明。
实施例中所用的相关原材料中：
填料选择碳酸钙；热稳定剂选择钡锌稳定剂；抗氧剂选择BASF抗氧剂；防水剂选择羟基硅油；偶联剂选择KH550；以上选择不仅限于此。P-N系阻燃剂细度为200-1200目；卤-锑系阻燃剂牌号为：1327-33-9；Mg-Al系阻燃剂牌号为11097-59-9。
制备例
本制备例制备了一种二氧化硅包覆硼酸锌协同石墨烯，具体方法如下：
S1，硼酸锌的制备：将3.72g硼酸溶于去离子水中，加入1.3g氧化锌，边混合边加入0.5ml氨水形成混合液，在混合液中加入1g十二烷基苯磺酸钠，升温至45℃水浴混合2h后过滤，60℃烘干得到硼酸锌；
S2，二氧化硅包覆硼酸锌的制备：在20ml无水乙醇中加入1ml正硅酸四乙酯形成混合液1；将1.12g硼酸锌加入到4ml去离子水中，然后加入0.2ml氨水形成混合液2；将混合液2缓慢加入到混合液1中，持续混合4h，过滤，用无水乙醇洗涤，70℃烘干，得到二氧化硅包覆硼酸锌；
S3，二氧化硅包覆硼酸锌协同石墨烯的制备：将10g二氧化硅包覆硼酸锌分散到去离子水中，超声震荡30min，然后加入2g石墨烯，混合1h，洗涤，60℃下烘干得到二氧化硅包覆硼酸锌协同石墨烯。
实施例
实施例1-16
如表1所述，实施例1-16的主要区别在于PVC树脂面层的原料配比不同。
以下以实施例1为例进行说明。本申请实施例公开了一种阻燃人造革，包括贴合在一起的阻燃基布和阻燃PVC树脂面层。
其中阻燃PVC树脂面层以PVC树脂60kg、二氧化硅包覆硼酸锌协同石墨烯5kg、P-N系阻燃剂5kg、羟基硅油5kg、碳酸钙5kg和KH5501kg为原料制备而成；其中二氧化硅包覆硼酸锌协同石墨烯采用制备例所得。
本申请实施例还公开了一种阻燃人造革的制备方法：包括以下步骤：
阻燃PVC树脂面层的制备：按配方称取原料并置于高速分散混合机，在混合温度为110℃条件下，混合4min，使原料充分混合，形成混合料；将混合料排入密炼机中进行混练，在温度为140℃的条件下，混练5min，然后排出至开放式练胶机上，在130℃的条件下进行塑化15min后，输送至压延机中压延成型，其中压延机作业温度为180℃，生产速度为30m/min；
阻燃基布的制备：将基布预热至60℃并浸泡在氮磷阻燃剂溶液中30s拿出，经烘干、冷却得到；
合成：将阻燃PVC树脂面层与阻燃基布进行压延贴合后送入发泡机加热发泡、压花，发泡机作业温度为190℃；对阻燃基布背向阻燃PVC树脂面层的一面用喷枪喷涂含有5％三聚氰胺磷酸酯阻燃剂的聚氨酯溶液，其中喷枪压力为0.4Mpa,喷涂时间为2min；对阻燃PVC树脂面层背向阻燃基布的一面用喷枪喷涂涂浓度为1％的聚偏氟乙烯涂料，喷枪压力为0.6Mpa,喷涂时间为45S；冷却定型得到阻燃人造革。(在此需要说明的是，三聚氰胺磷酸阻燃剂的浓度为5-8％均可，聚偏氟乙烯涂料的浓度为1-45％均可)
表1实施例1-16中阻燃PVC树脂面层各原料配比
Figure BDA0003341343950000081
实施例17
本实施例与实施例15不同的是，将P-N系阻燃剂替换为卤-锑系阻燃剂。
实施例18
本实施例与实施例15不同的是，将P-N系阻燃剂替换为Mg-Al系阻燃剂。
实施例19
本实施例与实施例15不同的是，制备方法中，原料混合时的加热温度为130℃，混合时间为2min；基布的初始温度为90℃。
对比例
对比例1
本对比例与实施例5不同之处在于，将二氧化硅包覆硼酸锌协同石墨烯替换为P-N系阻燃剂。
对比例2
本对比例与实施例5不同之处在于，将P-N系阻燃剂替换为二氧化硅包覆硼酸锌协同石墨烯。
对比例3
本对比例与实施例5不同之处在于，将二氧化硅包覆硼酸锌协同石墨烯替换为硼酸锌。
对比例4
本对比例与实施例5不同之处在于，将二氧化硅包覆硼酸锌协同石墨烯替换为石墨烯1kg、硼酸锌3kg和纳米二氧化硅1kg。
对比例5
本实施例与实施例5不同之处在于，制备方法中，阻燃基布背向阻燃PVC树脂面层的一面不进行阻燃处理。
对比例6
本实施例与实施例5不同之处在于，制备方法中，阻燃PVC树脂面层背向阻燃基布的一面不涂覆聚偏氟乙烯涂料。
性能检测试验
采用相同重量的由实施例1-19获得的阻燃人造革作为试验样1-19，采用与试验样相同重量的由对比例1-6获得的阻燃人造革作为对照样1-6。对试验样和对照样进行性能检测，结果如表2。
一、力学性能
力学性能试验在温度为25℃、湿度为50％的条件下进行的，试验如下：
根据GB/T38612-2020，对相应的试验样、对照样进行拉伸及断裂伸长率的测定，记录数据并分析，其中伸长速度为200mm/min。
根据GB8808-1988，对相应的试验样、对照样进行剥离强度试验，记录数据并分析，其中试验尺寸为A法，宽度15mm，长度200mm。
二、阻燃性能
根据ASTMD2863-2000，对相应的试验样、对照样在规定的试验条件下，在氧氮混合气流中，测定刚好能维持材料燃烧的以体积百分数表示的最低氧浓度进行测试，记录数据并分析，其中试样类型为Ⅱ(尺寸为80×10×10mm)。
三、耐磨性能
根据QB/T2726-2005，对相应的试验样、对照样进行测试，记录数据并分析，其中试样的旋转速度为60r/min，试样为直径为106mm的圆形试样。
四、抗菌性能
根据2002年中华人民共和国卫生部颁布的《消毒技术规范》抑菌环实验要求，将对应的试验样和对照样所得抗菌非天然革剪成直径为22mm大小的圆样进行测试，采用大肠杆菌为供试菌种，通过抑菌环方法进行评价，判定了各试验样和对照样的抗菌性能，其中，当抑菌环宽度大于7毫米，判为有抑菌作用。
表2性能检测数据表
Figure BDA0003341343950000111
Figure BDA0003341343950000121
参照表2，结合实施例2和4-6和对比例1-4，可以看出，随着复合阻燃剂含量的不断增加，试样的阻燃性能不断提高；当二氧化硅包覆硼酸锌协同石墨烯替换为P-N系阻燃剂时，试样的阻燃性、耐磨性和抗菌性均下降；当P-N系阻燃剂替换为二氧化硅包覆硼酸锌协同石墨烯时，试样的阻燃性下降而耐磨性和抗菌性有所提高；以上说明P-N系阻燃剂和二氧化硅包覆硼酸锌协同石墨烯复配形成的复合阻燃剂提高了试样的阻燃性；当二氧化硅包覆硼酸锌协同石墨烯替换为硼酸锌时，试样的阻燃性有所下降，耐磨性和抗菌性下降的尤为严重；当硼酸锌、纳米二氧化硅和石墨烯不做处理一起加入阻燃PVC树脂面层时，试样的阻燃性、耐磨性和抗菌性均有所下降，故二氧化硅包覆硼酸锌协同石墨烯的功效优于硼酸锌、纳米二氧化硅和石墨烯不做处理时的功效。
参照表2，结合实施例5和对比例5和6，可以看出，当阻燃基布背向阻燃PVC树脂面层的一面不进行阻燃处理时，试样整体的阻燃性有所下降；当阻燃PVC树脂面层背向阻燃基布的一面涂覆聚偏氟乙烯涂料时，试样的抗菌性能下降。
参照表2，结合实施例1-3，可以看出，随着PVC树脂的不断加入，试样的力学性能有一定的提高作用；当试样中PVC树脂含量的不断增加，试样的阻燃性、耐磨性和抗菌性能呈下降趋势。
参照表2，结合实施例5和7，可以看出，随着作为防水剂的羟基硅油含量的增加，试样的力学性能变化不大，试样的阻燃性、耐磨性和抗菌性有所下降。
参照表2，结合实施例5和8，可以看出，随着作为填料的碳酸钙含量的增加，试样的力学性能变化不大，试样的阻燃性、耐磨性和抗菌性有所下降。
参照表2，结合实施例5、9和10，可以看出，随着作为偶联剂的KH550的含量的不断增加，试样的力学性能有所提高，试样的阻燃性、耐磨性和抗菌性均呈下降趋势。
参照表2，结合实施例11-16可以看出，加入适量的钡锌稳定剂、邻苯二甲酸酯类和BASF氧化剂，试样均具有优异的力学性能、阻燃性能耐磨性和抗菌性。
参照表2，结合实施例15、17和18可以看出，当P-N系阻燃剂替换为卤-锑系或Mg-Al系阻燃剂时，试样仍然具有优异的阻燃性、耐磨性、抗菌性和力学性能。
本具体实施例仅仅是对本申请的解释，其并不是对本申请的限制，本领域技术人员在阅读完本说明书后可以根据需要对本实施例做出没有创造性贡献的修改，但只要在本申请的权利要求范围内都受到专利法的保护。

Claims (10)

1.一种阻燃人造革，其特征在于，包括贴合在一起的阻燃基布和阻燃PVC树脂面层；
所述阻燃PVC树脂面层由包括以下重量份的原料制成：PVC树脂60-80份、复合阻燃剂10-50份、防水剂5-7份、填料5-10份和偶联剂1-3份；
所述复合阻燃剂包括重量比为1：（1-4）的二氧化硅包覆硼酸锌协同石墨烯和增强阻燃剂，所述增强阻燃剂为P-N系、卤-锑系或Mg-Al系阻燃剂。
2.根据权利要求1所述的一种阻燃人造革，其特征在于：所述二氧化硅包覆硼酸锌协同石墨烯的制备方法如下：
S1，将硼酸溶于水中，加入氧化锌，边混合边加入氨水；再加入十二烷基苯磺酸钠，混合后，经过滤，烘干得到硼酸锌；
S2，将所述硼酸锌加入水中，再加入氨水得到混合液，将所述混合液加入含有正硅酸四乙酯和无水乙醇的混合液中，混合过滤后用无水乙醇洗涤，烘干得到二氧化硅包覆硼酸锌；
S3，将所述二氧化硅包覆硼酸锌分散于水中，超声震荡后加入石墨烯，混合洗涤后烘干得到二氧化硅包覆硼酸锌协同石墨烯。
3.根据权利要求1所述的一种阻燃人造革，其特征在于：所述原料还包括3-5重量份的热稳定剂。
4.根据权利要求3所述的一种阻燃人造革，其特征在于：所述原料还包括1-3重量份的邻苯二甲酸酯类。
5.根据权利要求4所述的一种阻燃人造革，其特征在于：所述原料还包括0.5-2重量份的抗氧化剂。
6.根据权利要求1所述的一种阻燃人造革，其特征在于：所述阻燃PVC树脂面层设有聚偏氟乙烯涂层。
7.权利要求1-6中任意一项所述的阻燃人造革的制备方法，其特征在于：包括以下步骤：
阻燃PVC树脂面层：将相应重量的原料进行混合，压延成型；
阻燃基布：将基布浸泡在氮磷阻燃剂溶液中，干燥并冷却得到；
合成：将所述阻燃PVC树脂面层与阻燃基布贴合、压花；并对阻燃基布背向阻燃PVC树脂面层的一面进行阻燃处理，对阻燃PVC树脂面层背向阻燃基布的一面涂覆浓度为1-45%聚偏氟乙烯涂料，冷却后得到所需人造革。
8.根据权利要求7所述的一种阻燃人造革的制备方法，其特征在于：所述原料混合时采用加热混合的方式，其中加热温度为110-130℃，混合时间为2-4min。
9.根据权利要求7所述的一种阻燃人造革的制备方法：其特征在于：所述基布的初始温度为60-90℃。
10.根据权利要求7所述的一种阻燃人造革的制备方法，其特征在于：所述阻燃处理为：在阻燃基布背向阻燃PVC树脂面层的一面喷涂含5-8%三聚氰胺磷酸酯阻燃剂的聚氨酯溶液。
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005015942A (ja) * 2003-06-25 2005-01-20 Okamoto Ind Inc 難燃性合成樹脂レザー
KR100755893B1 (ko) * 2006-10-18 2007-09-06 주식회사위드 합성피혁용 비할로겐계 난연제 조성물
CN106003931A (zh) * 2016-05-26 2016-10-12 浙江明士达新材料有限公司 一种长效抗污膜结构复合篷盖材料
CN111204107A (zh) * 2019-12-27 2020-05-29 昆山阿基里斯新材料科技有限公司 一种高阻燃高防水人造革的制备方法
CN111363383A (zh) * 2020-04-22 2020-07-03 福州大学 一种二氧化硅包覆硼酸锌协同石墨烯多功能助剂及其制备方法和应用

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005015942A (ja) * 2003-06-25 2005-01-20 Okamoto Ind Inc 難燃性合成樹脂レザー
KR100755893B1 (ko) * 2006-10-18 2007-09-06 주식회사위드 합성피혁용 비할로겐계 난연제 조성물
CN106003931A (zh) * 2016-05-26 2016-10-12 浙江明士达新材料有限公司 一种长效抗污膜结构复合篷盖材料
CN111204107A (zh) * 2019-12-27 2020-05-29 昆山阿基里斯新材料科技有限公司 一种高阻燃高防水人造革的制备方法
CN111363383A (zh) * 2020-04-22 2020-07-03 福州大学 一种二氧化硅包覆硼酸锌协同石墨烯多功能助剂及其制备方法和应用

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
李建军: "《塑料配方设计》", 31 May 2019, 中国轻工业出版社, pages: 229 - 242 *
欧育湘: "《阻燃高分子材料》", 31 January 2001, 国防工业出版社, pages: 97 - 100 *
钱立军: "《高分子材料助剂》", 31 August 2020, 中国轻工业出版社, pages: 133 - 135 *

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