CN110358321A - 一种环保型高韧性阻燃塑料基复合板材及其制备方法 - Google Patents

一种环保型高韧性阻燃塑料基复合板材及其制备方法 Download PDF

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CN110358321A
CN110358321A CN201910694396.7A CN201910694396A CN110358321A CN 110358321 A CN110358321 A CN 110358321A CN 201910694396 A CN201910694396 A CN 201910694396A CN 110358321 A CN110358321 A CN 110358321A
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composite board
base composite
plastics base
waste
flame retardant
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陈永清
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Zhejiang Mutual New Material Technology Co Ltd
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Abstract

本发明涉及建筑材料领域，公开了一种环保型高韧性阻燃塑料基复合板材及其制备方法，塑料基复合板材包括两层玻纤网、位于玻纤网之间的填充层以及位于两层玻纤网远离填充层一侧的固化层，填充层和固化层的原料以质量分数计包括10‑60%粉煤灰，30‑70%废旧回收塑料粉，2‑10%废旧轮胎橡胶粉，5‑10%阻燃剂改性纳米填料，余量为助剂，助剂包括初级发泡剂和二级发泡剂、偶联剂、粘结剂、润滑剂、丙烯酸酯和偶氮二异丁腈。填充层和固化层由双螺杆挤出机制得，并通过三辊碾压机复合定型。本发明采用废旧材料制作塑料基复合板材，并添加阻燃剂改性的纳米填料，实现了废物利用，同时提高了板材的韧性和阻燃性能。

Description

一种环保型高韧性阻燃塑料基复合板材及其制备方法
技术领域
本发明涉及建筑材料领域，尤其是涉及一种环保型高韧性阻燃塑料基复合板材及其制备方法。
背景技术
塑料基复合板材，是近年来新兴的一种环保型建筑装饰材料，是以聚乙烯、聚丙烯、聚氯乙烯等塑料原材料作为粘结剂，与木屑、锯末、秸秆等植物纤维、加工助剂经高温高压熔融挤出混合而成的新型材料，与其他材料相比，其具有良好的强度性能、耐水性能、可塑性强、可刨、可锯，广泛用于家具和建筑用品及室外、室内板材等方面。
现有技术中制备塑料基复合板材时一般使用木屑作为填充材料，例如，在中国专利文献上公开的“一种以废旧塑料为主要原料制成的板材及制备方法”，其公告号CN100503734，所用原料按重量比为：废旧塑料20-50份，粉煤灰0.8-2份，轻质碳酸钙0.8-2份，木屑4-11份，塑料助剂0.4-1份。
但使用木材作为填充材料，生产出的板材阻燃性、防水性都较差，限制了板材的使用，且木材属于宝贵的自然资源，二次利用率低，不利于环境保护。
发明内容
本发明是为了克服现有技术中使用木材作为生产塑料基复合板材时的填充材料，生产出的板材阻燃性、防水性、耐高温性都较差，限制了板材的使用，且木材属于宝贵的自然资源，二次利用率低，不利于环境保护的问题，提供一种环保型高韧性阻燃塑料基复合板材及其制备方法，使用回收的废旧塑料和粉煤灰作为主要材料，利用粉煤灰和由阻燃剂改性的纳米填料填充和改性塑料，制作出一种新型塑料基复合板材，该板材具有高韧性和良好的阻燃性，且原材料都使用回收材料，经济环保。
为了实现上述目的，本发明采用以下技术方案：
一种环保型高韧性阻燃塑料基复合板材，其特征是，包括两层玻纤网、位于两层玻纤网之间的填充层以及分别位于两层玻纤网远离填充层一侧的固化层，所述填充层和固化层的原料以质量分数计包括10-60％粉煤灰，30-70％废旧回收塑料粉，2-10％废旧轮胎橡胶粉，5-10％阻燃剂改性纳米填料，余量为助剂，所述助剂包括发泡温度不同的初级发泡剂和二级发泡剂、偶联剂、粘结剂、润滑剂、丙烯酸酯和偶氮二异丁腈。
本发明采用废旧回收塑料为原料制作塑料基复合板材，并用粉煤灰代替木屑作为塑料基复合板材的填充材料，粉煤灰是煤炭在1000℃以上经高温燃烧后残留下来的富含二氧化硅、三氧化二铝、氧化钙等物质的固体废弃物，用粉煤灰及废旧塑料和废旧轮胎加工制成塑料基复合板材，不仅及时解决了这些废弃物对环境的污染问题，并且可以使制作出的板材具有良好的耐高低温性、防水性、阻燃性和导热性等特性；同时，在板材中加入回收的废旧轮胎橡胶粉，可以增加板材的韧性和握钉率，实现了废物利用，降低了生产成本的同时提高了板材的使用性能。
使用无机纳米填料对塑料基复合板材进行填充改性，可以大大提高板材的耐磨性、力学强度和韧性，是现有技术中常用的提高板材性能的手段。但由于纳米填料粒径小，比表面积大，表面能大，因此填充纳米填料很容易发生团聚，从而影响板材性能的提高。本发明将大分子的有机阻燃剂接枝在纳米填料表面，制成阻燃剂改性的纳米填料，降低纳米填料的表面自由能，增大空间位阻，提高了纳米材料的分散性及与塑料基体间的相容性的同时，还增强了材料的阻燃性能，使得制备出的塑料基复合板材具有高韧性和良好的阻燃性能，扩展了其应用领域。
由于塑料为有机高聚合物，而粉煤灰为无机材料，二者之间不相融，因此不能直接将粉煤灰添加在塑料里，本发明为了使粉煤灰能有效分散在塑料中，使板材获得优良的性能，使用偶联剂来增强粉煤灰与塑料基体的亲和性。偶联剂是一种具有有两性结构的有机物，具有一个以上与无机粉体表面作用的基团和一个以上与有机聚合物亲合的基团，其分子中的一部分基团可以与粉煤灰表面发生官能团反应，另一基团可与塑料基体发生化学反应或物理缠绕，从而将两种性质差异很大的材料牢固结合，使粉煤灰和塑料基体之间建立起具有特殊功能的“分子桥”，从而使粉煤灰有效均匀地分散在塑料中，成功得到综合性能良好的粉煤灰填充的塑料基复合板材。同时，本发明还在原料中加入丙烯酸酯和偶氮二异丁腈，制备时，在引发剂偶氮二异丁腈的作用下可以引发丙烯酸酯的聚合接枝反应，使聚丙烯酸酯接枝在粉煤灰表面，与偶联剂一起对粉煤灰表面进行改性，使粉煤灰能更好的分散在塑料中，提高了板材的综合性能。
同时，本发明中还添加了发泡温度不同的初级发泡剂和二级发泡剂，使制作出的板材为发泡板材，减轻了板材的重量，并使板材具有良好的隔音、减震和保温性能。本发明经研究发现，使用发泡温度的两级发泡剂在不同温度下进行两次发泡，与传统的只使用一种发泡剂相比，能有效降低板材的密度，并显著提高板材的尺寸稳定性。
在板材中设置两层玻纤网，可以显著提高板材的抗冲击性和尺寸稳定性；在助剂中添加粘结剂和润滑剂可以提高各组分间的粘结性和原料的脱模性能，使制作出的板材具有良好的综合性能。
作为优选，阻燃剂改性纳米填料的制备方法如下：
A)将质量比为1：(0.5-1)的粉煤灰和Na2CO3混合均匀后在800-900℃下烧结1-2h；
B)将烧结产物在3-5mol/L的HCl溶液中酸浸1-2h；
C)过滤后将滤液在100℃下恒温陈化1-2h，过滤后将产物洗涤、干燥后得到纳米填料粉体；
D)将摩尔比为1：(0.5-1.5)的DOPO和乙烯基三甲氧基硅烷加入甲苯中，在70-90℃氮气保护下溶解；
E)完全溶解后逐滴加入偶氮二异丁腈的甲苯溶液，使得加入的偶氮二异丁腈与DOPO的质量比为1：(145-150)，反应12-24h后蒸发除去甲苯，得到改性DOPO；
F)将质量比为(1-2):1的纳米填料粉体和改性DOPO分散在无水乙醇中，70-80℃氮气保护下回流反应12-24h，过滤并将产物洗涤、干燥后得到所述阻燃剂改性纳米填料。
本发明利用粉煤灰制取纳米填料粉体，并在纳米填料粉体上接枝阻燃剂DOPO，实现了废物回收利用，减少了环境污染，提高了纳米填料粉体在塑料基体中的分散性和相容性的同时还能提高板材的阻燃性能。
步骤A)中将粉煤灰与Na2CO3混合烧结，生成NaAlSiO4；经过步骤B)的酸浸后，NaAlSiO4与HCl发生如下反应：
NaAlSiO4+4HCl→H4SiO4+AlCl3+NaCl
H4SiO4→H2SiO3+H2O
H2SiO3+mH2O→SiO2·(m+1)H2O
再经过步骤C)的陈化，使体系由溶胶向凝胶转变，成功分离出纳米填料。经过步骤D)和E)，用偶联剂乙烯基三甲氧基硅烷改性阻燃剂DOPO，然后再经过步骤F)将改性后的阻燃剂DOPO接枝在制得的纳米填料表面，制得了具有良好的分散性和阻燃性，并且与塑料基体具有良好相容性的阻燃剂改性纳米填料，将其添加在板材中可以大大提高板材的韧性和阻燃性能。
作为优选，助剂中各成分在原料中的质量分数为：初级发泡剂2-8‰，二级发泡剂2-15‰，偶联剂1-9‰，粘结剂2-17‰，润滑剂7-15‰，丙烯酸酯2-18‰，偶氮二异丁腈3-13‰。采用合适的助剂添加量，可以有效对粉煤灰进行改性，并使制作出的板材具有良好的综合性能。
作为优选，初级发泡剂为十二烷基硫酸钠，二级发泡剂为偶氮二甲酰胺，偶联剂为KH792，粘结剂为马来酸酐接枝聚丙烯，润滑剂为十八烷酸。十二烷基硫酸钠在100℃以下可以发泡，而偶氮二甲酰胺在160℃左右发泡，因此可以有效实现二次发泡，降低板材密度，提高板材尺寸稳定性。
作为优选，填充层的厚度为3-15mm，固化层的厚度为1-3mm。在此厚度范围内可以保证塑料基复合板材具有良好的力学性能。
作为优选，玻纤网的规格为70-300g/m2。使用此规格的玻纤网可以有效提高板材的抗冲击性能和尺寸稳定性。
本发明还提供了一种上述环保型高韧性阻燃塑料基复合板材的制备方法，包括如下步骤：
(1)将废旧回收塑料和废旧轮胎洗净并粉碎，得到废旧回收塑料粉和废旧轮胎橡胶粉；
(2)将粉煤灰、废旧回收塑料粉、废旧轮胎橡胶粉、阻燃剂改性纳米填料及助剂放入高速混合机搅拌均匀；
(3)将搅拌均匀的原料放入双螺杆挤出机，挤出后分别得到填充层和固化层；
(4)在填充层上下两侧敷上玻纤网，与上下两层固化层一起通过三辊碾压机定型后得到所述粉煤灰填充的塑料基复合板材。
采用双螺杆挤出机制作填充层和固化层，再通过三辊碾压机将填充层、玻纤网和固化层复合定型，制备方法简单，操作便捷，便于生产。
作为优选，步骤(1)中废旧回收塑料粉和废旧轮胎橡胶粉的粒径≤0.1mm。保证制备出的板材具有良好的力学性能和韧性。
作为优选，步骤(3)中双螺杆挤出机的熔融挤出温度为140-260℃。在此温度下各组分能充分熔融、反应并挤出成型，制得的板材具有良好的性能。
因此，本发明具有如下有益效果：
(1)采用废旧回收塑料和废旧轮胎为原料制作塑料基复合板材，并用粉煤灰代替木屑作为塑料基复合板材的填充材料，不仅及时解决了这些废弃物对环境的污染问题，并且可以使制作出的板材具有良好的耐高低温性、防水性、阻燃性和导热性，实现了废物利用，降低了生产成本的同时提高了板材的使用性能；
(2)利用粉煤灰制取纳米填料，并在纳米填料上接枝阻燃剂DOPO，制得了具有良好的分散性和阻燃性，并且与塑料基体具有良好相容性的阻燃剂改性纳米填料，将其添加在板材中可以大大提高板材的韧性和阻燃性能；
(3)添加了发泡温度不同的初级发泡剂和二级发泡剂，使制作出的板材为发泡板材，减轻了板材的重量，并使板材具有良好的隔音、减震和保温性能。使用发泡温度的两级发泡剂在不同温度下进行两次发泡，与传统的只使用一种发泡剂相比，有效降低了板材的密度，并显著提高了板材的尺寸稳定性。
附图说明
图1是本发明中的塑料基复合板材的一种分解结构示意图。
图中：1玻纤网、2填充层、3固化层。
具体实施方式
下面结合附图与具体实施方式对本发明做进一步的描述。
本发明各实施例和对比例中按照如下方法制备环保型高韧性阻燃塑料基复合板材：
(1)将废旧回收塑料和废旧轮胎洗净并粉碎，得到废旧回收塑料粉和废旧轮胎橡胶粉；
(2)将粉煤灰、废旧回收塑料粉、废旧轮胎橡胶粉、阻燃剂改性纳米填料及助剂放入高速混合机搅拌均匀；
(3)将搅拌均匀的原料放入双螺杆挤出机，挤出后分别得到填充层和固化层；
(4)在填充层上下两侧敷上玻纤网，与上下两层固化层一起通过三辊碾压机定型后得到所述粉煤灰填充的塑料基复合板材。
制得的粉煤灰填充的塑料基复合板材如图1所示，包括两层玻纤网1、位于两层玻纤网之间的填充层2以及分别位于两层玻纤网远离填充层一侧的固化层3。
各原料的比例及制备条件如下。
实施例1：
粉煤灰40％，粒径为0.1mm的废旧回收塑料粉40％，粒径为0.1mm的废旧轮胎橡胶粉4％，阻燃剂改性纳米填料10％，助剂6％，助剂包括十二烷基硫酸钠5‰，偶氮二甲酰胺10‰，KH792 5‰，马来酸酐接枝聚丙烯10‰，十八烷酸10‰，丙烯酸酯10‰，偶氮二异丁腈10‰。
步骤(3)中双螺杆挤出机的熔融挤出温度为160℃，填充层厚度15mm，固化层厚度2.5mm，玻纤网规格100g/m2。
阻燃剂改性纳米填料的制备：将质量比为1:0.8的粉煤灰和Na2CO3混合均匀后在850℃下烧结1.5h；将烧结产物在4mol/L的HCl溶液中酸浸1.5h；过滤后将滤液在100℃下恒温陈化1.5h，过滤后将产物洗涤，80℃下真空干燥后得到纳米填料粉体；将摩尔比为1:1的DOPO和乙烯基三甲氧基硅烷加入甲苯中，在80℃氮气保护下溶解；完全溶解后逐滴加入偶氮二异丁腈的甲苯溶液，使得加入的偶氮二异丁腈与DOPO的质量比为1:148，反应20h后旋蒸除去甲苯，得到改性DOPO；将质量比为1:1的纳米填料粉体和改性DOPO分散在无水乙醇中，75℃氮气保护下回流反应20h，过滤并将产物洗涤，80℃下干燥后得到所述阻燃剂改性纳米填料。
实施例2：
粉煤灰60％，粒径为20μm的废旧回收塑料粉30％，粒径为20μm的废旧轮胎橡胶粉2％，阻燃剂改性纳米填料5％，助剂3％，助剂包括十二烷基硫酸钠2‰，偶氮二甲酰胺13‰，KH7921‰，马来酸酐接枝聚丙烯2‰，十八烷酸7‰，丙烯酸酯2‰，偶氮二异丁腈3‰。
步骤(3)中双螺杆挤出机的熔融挤出温度为140℃，填充层厚度3mm，固化层厚度3mm，玻纤网规格300g/m2。
阻燃剂改性纳米填料的制备：将质量比为1:0.5的粉煤灰和Na2CO3混合均匀后在800℃下烧结2h；将烧结产物在3mol/L的HCl溶液中酸浸1h；过滤后将滤液在100℃下恒温陈化1h，过滤后将产物洗涤，80℃下真空干燥后得到纳米填料粉体；将摩尔比为1:0.5的DOPO和乙烯基三甲氧基硅烷加入甲苯中，在70℃氮气保护下溶解；完全溶解后逐滴加入偶氮二异丁腈的甲苯溶液，使得加入的偶氮二异丁腈与DOPO的质量比为1:145，反应12h后旋蒸除去甲苯，得到改性DOPO；将质量比为1.5:1的纳米填料粉体和改性DOPO分散在无水乙醇中，70℃氮气保护下回流反应12h，过滤并将产物洗涤，80℃下干燥后得到所述阻燃剂改性纳米填料。
实施例3：
粉煤灰20％，粒径为0.1mm的废旧回收塑料粉60％，粒径为0.1mm的废旧轮胎橡胶粉2％，阻燃剂改性纳米填料9.8％，助剂8.2％，助剂包括十二烷基硫酸钠8‰，偶氮二甲酰胺2‰，KH792 9‰，马来酸酐接枝聚丙烯17‰，十八烷酸15‰，丙烯酸酯18‰，偶氮二异丁腈13‰。
步骤(3)中双螺杆挤出机的熔融挤出温度为260℃，填充层厚度10mm，固化层厚度1mm，玻纤网规格70g/m2。
阻燃剂改性纳米填料的制备：将质量比为1:1的粉煤灰和Na2CO3混合均匀后在900℃下烧结1h；将烧结产物在5mol/L的HCl溶液中酸浸2h；过滤后将滤液在100℃下恒温陈化2h，过滤后将产物洗涤，80℃下真空干燥后得到纳米填料粉体；将摩尔比为1:1.5的DOPO和乙烯基三甲氧基硅烷加入甲苯中，在90℃氮气保护下溶解；完全溶解后逐滴加入偶氮二异丁腈的甲苯溶液，使得加入的偶氮二异丁腈与DOPO的质量比为1:150，反应24h后旋蒸除去甲苯，得到改性DOPO；将质量比为2:1的纳米填料粉体和改性DOPO分散在无水乙醇中，80℃氮气保护下回流反应24h，过滤并将产物洗涤，80℃下干燥后得到所述阻燃剂改性纳米填料。
实施例4：
粉煤灰10％，粒径为0.1mm的废旧回收塑料粉70％，粒径为0.1mm的废旧轮胎橡胶粉10％，阻燃剂改性纳米填料7％，助剂3％，助剂包括十二烷基硫酸钠2‰，偶氮二甲酰胺13‰，KH7921‰，马来酸酐接枝聚丙烯2‰，十八烷酸7‰，丙烯酸酯2‰，偶氮二异丁腈3‰。
步骤(3)中双螺杆挤出机的熔融挤出温度为160℃，填充层厚度15mm，固化层厚度2.5mm，玻纤网规格100g/m2。
阻燃剂改性纳米填料的制备：将质量比为1:0.8的粉煤灰和Na2CO3混合均匀后在850℃下烧结1.5h；将烧结产物在4mol/L的HCl溶液中酸浸1.5h；过滤后将滤液在100℃下恒温陈化1.5h，过滤后将产物洗涤，80℃下真空干燥后得到纳米填料粉体；将摩尔比为1:1的DOPO和乙烯基三甲氧基硅烷加入甲苯中，在80℃氮气保护下溶解；完全溶解后逐滴加入偶氮二异丁腈的甲苯溶液，使得加入的偶氮二异丁腈与DOPO的质量比为1:148，反应20h后旋蒸除去甲苯，得到改性DOPO；将质量比为1:1的纳米填料粉体和改性DOPO分散在无水乙醇中，75℃氮气保护下回流反应20h，过滤并将产物洗涤，80℃下干燥后得到所述阻燃剂改性纳米填料。
对比例1：
对比例1与实施例1的区别在于，将阻燃剂改性纳米填料替换为玻璃纤维，其余均与实施例1中相同。
对比例2：
对比例2与实施例1的区别在于，不对纳米填料进行改性，用粉煤灰制得的纳米填料粉体代替阻燃剂改性纳米填料作为原料直接加入，其他均与实施例1中相同。
将上述实施例和对比例中制得的塑料基复合板材切割成面积为50cm*50cm的试样，测试其性能，结果如表1所示。
表1：塑料基复合板材测试结果。
从表1中可以看出，实施例1-4中按照本发明中的方法制得的塑料基复合板材抗压性能、抗冲击性能和阻燃性能良好。对比例1中用玻璃纤维代替阻燃剂改性纳米填料，板材的力学性能、韧性和阻燃性均比实施例1中降低；对比例2中不对纳米填料进行改性，制得的板材的力学性能、韧性和阻燃性也明显降低，证明不经改性的纳米填料在塑料基体中的分散性较差，不能提高板材的力学性能。

Claims (9)

1.一种环保型高韧性阻燃塑料基复合板材，其特征是，包括两层玻纤网、位于两层玻纤网之间的填充层以及分别位于两层玻纤网远离填充层一侧的固化层，所述填充层和固化层的原料以质量分数计包括10-60%粉煤灰，30-70%废旧回收塑料粉，2-10%废旧轮胎橡胶粉，5-10%阻燃剂改性纳米填料，余量为助剂，所述助剂包括发泡温度不同的初级发泡剂和二级发泡剂、偶联剂、粘结剂、润滑剂、丙烯酸酯和偶氮二异丁腈。
2.根据权利要求1所述的一种环保型高韧性阻燃塑料基复合板材，其特征是，所述阻燃剂改性纳米填料的制备方法如下：
A）将质量比为1：（0.5-1）的粉煤灰和Na2CO3混合均匀后在800-900℃下烧结1-2h；
B）将烧结产物在3-5mol/L的HCl溶液中酸浸1-2h；
C）过滤后将滤液在100℃下恒温陈化1-2h，过滤后将产物洗涤、干燥后得到纳米填料粉体；
D）将摩尔比为1：（0.5-1.5）的DOPO和乙烯基三甲氧基硅烷加入甲苯中，在70-90℃氮气保护下溶解；
E）完全溶解后逐滴加入偶氮二异丁腈的甲苯溶液，使得加入的偶氮二异丁腈与DOPO的质量比为1：（145-150），反应12-24h后蒸发除去甲苯，得到改性DOPO；
F）将质量比为（1-2）:1的纳米填料粉体和改性DOPO分散在无水乙醇中，70-80℃氮气保护下回流反应12-24h，过滤并将产物洗涤、干燥后得到所述阻燃剂改性纳米填料。
3.根据权利要求1或2所述的一种环保型高韧性阻燃塑料基复合板材，其特征是，所述助剂中各成分在原料中的质量分数为：初级发泡剂2-8‰，二级发泡剂2-15‰，偶联剂1-9‰，粘结剂2-17‰，润滑剂7-15‰，丙烯酸酯2-18‰，偶氮二异丁腈3-13‰。
4.根据权利要求1或2所述的一种环保型高韧性阻燃塑料基复合板材，其特征是，所述初级发泡剂为十二烷基硫酸钠，所述二级发泡剂为偶氮二甲酰胺，所述偶联剂为KH792，所述粘结剂为马来酸酐接枝聚丙烯，所述润滑剂为十八烷酸。
5.根据权利要求1所述的一种环保型高韧性阻燃塑料基复合板材，其特征是，所述填充层的厚度为3-15mm，所述固化层的厚度为1-3mm。
6.根据权利要求1所述的一种环保型高韧性阻燃塑料基复合板材，其特征是，所述玻纤网的规格为70-300g/m2。
7.如权利要求1或2所述的一种环保型高韧性阻燃塑料基复合板材的制备方法，其特征是，包括如下步骤：
（1）将废旧回收塑料和废旧轮胎洗净并粉碎，得到废旧回收塑料粉和废旧轮胎橡胶粉；
（2）将粉煤灰、废旧回收塑料粉、废旧轮胎橡胶粉、阻燃剂改性纳米填料及助剂放入高速混合机搅拌均匀；
（3）将搅拌均匀的原料放入双螺杆挤出机，挤出后分别得到填充层和固化层；
（4）在填充层上下两侧敷上玻纤网，与上下两层固化层一起通过三辊碾压机定型后得到所述粉煤灰填充的塑料基复合板材。
8.根据权利要求8所述的一种环保型高韧性阻燃塑料基复合板材的制备方法，其特征是，步骤（1）中废旧回收塑料粉和废旧轮胎橡胶粉的粒径≤0.1mm。
9.根据权利要求8所述的一种环保型高韧性阻燃塑料基复合板材的制备方法，其特征是，步骤（3）中双螺杆挤出机的熔融挤出温度为140-260℃。
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