CN114536928B - 一种汽车衣帽架用环保阻燃高承载pu复合材料的制备方法 - Google Patents

一种汽车衣帽架用环保阻燃高承载pu复合材料的制备方法 Download PDF

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CN114536928B
CN114536928B CN202111644803.7A CN202111644803A CN114536928B CN 114536928 B CN114536928 B CN 114536928B CN 202111644803 A CN202111644803 A CN 202111644803A CN 114536928 B CN114536928 B CN 114536928B
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flame
retardant
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composite material
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刘国旺
方腾飞
楼娣
沈宇鹏
段鹏飞
周立
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Zhejiang Huajiang Technology Co ltd
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Abstract

本发明公开了一种汽车衣帽架用环保阻燃高承载PU复合材料的制备方法，PU复合材料是自下而上依次包括PET无纺布层、阻燃增强粘合层、阻燃PU泡沫芯层、阻燃增强粘合层和PET无纺布层热压复合成的复合板，与传统PP蜂窝或纸蜂窝衣帽架材料相比，PU泡沫复合板承载性能更为优异，因PU泡沫与增强层之间粘接涵盖整个表面，故粘结效果比蜂窝板更好，不易分层。成型后R角位置平整饱满，满足衣帽架的特殊造型要求。另外，PP蜂窝的耐高温性能较差，PU泡沫相较于PP蜂窝更好，不容易变形；纸蜂窝容易吸湿受潮，导致刚性强度变差，PU泡沫不易吸湿受潮影响刚性。

Description

一种汽车衣帽架用环保阻燃高承载PU复合材料的制备方法
技术领域
本发明涉及汽车衣帽架用复合材料技术领域，尤其是一种汽车衣帽架用环保阻燃高承载PU复合材料的制备方法。
背景技术
我国的汽车保有量持续增加，现已达到2亿辆左右，尤其是新能源汽车发展势头更是迅猛，但其对各汽车内饰件在阻燃方面的要求也更高，对内饰材料在阻燃方面提出了更高的要求。同时，环境污染和碳排放已被公认为当代社会所面临的严峻挑战，废旧PU泡沫大多是掩埋或焚烧处理，对环境极不友好。
目前汽车内饰件衣帽架零部件，其材料有PP蜂窝复合板、PU复合板、玻纤复合板等。专利CN 209208627 U公布了一种汽车衣帽架结构，自下到上依次为针刺PET无纺布层、PP玻纤层、PP蜂窝芯层、PP玻纤层和PET无纺布面层。PP蜂窝复合板模压成型后R角(造型弧面拐角)位置容易不平整，且耐高温性能较差，尤其在夏季炎热高温天气时，车内高温容易使其软化变形。而蜂窝芯与表面增强层之间的线状粘结，使其承载性能变差。该材料虽然易循环利用，但不阻燃。专利CN 110948951 A公布了一种用于汽车衣帽架的PU复合板材料，强调了轻质高强方面的性能，泡沫密度在45～55kg/m3之间，但该专利对PU泡沫的制备方法及阻燃性能等均未涉及，尤其是垂直燃烧性能和回收再生多元醇的循环再利用方面。
PU复合材料相较于PP蜂窝，其在吸音、承载方面表现更卓越。如今常规的汽车衣帽架材料大多为PP蜂窝或纸蜂窝复合材料，较少涉及使用PU复合材料，主要受限于材料阻燃性能差，不能循环利用，成本偏高，因此，研究其新的制备方法具有重大的现实意义。
发明内容
随着我国经济社会的快速全面发展，每年产生的PU泡沫废料也在成倍增长，已达到数百万吨每年，而人们对安全和环保方面的意识也日益提高，且国家政策要求在2030年前实现碳达峰。
本发明目的在于针对现有技术所存在的不足而提供一种环保、阻燃、高承载的汽车衣帽架用环保阻燃高承载PU复合材料的制备方法。
本发明是通过以下技术方案来实现的：
本发明公开了一种汽车衣帽架用环保阻燃高承载PU复合材料制备方法，PU复合材料是自下而上依次包括PET无纺布层、阻燃增强粘结层、阻燃PU泡沫芯层、阻燃增强粘结层和PET无纺布层热压复合成的复合板，包括如下步骤：
1)阻燃PU泡沫芯层的配方如下：
回收再生多元醇，其羟值为400±20mgKOH/g，回收再生多元醇的用量占发泡原液总质量的5～20％；
阻燃剂，用量占发泡原液总质量的0.5～3％；
阻燃PU泡沫芯层厚度介于6～20mm之间，其配方体系，利用PU泡沫降解回收得到的多元醇，再次重新用于PU发泡，PU泡沫的密度在40～60kg/m3之间，实现物料的循环利用；
2)PET无纺布层与阻燃增强粘结层的制备方法为：在复合机自下而上依次放卷PET无纺布，撒短切玻纤，撒胶粉和膨胀石墨，在180～200℃，0.3～0.8Mpa的条件下，以6～8m/min的速度进行热压复合并收卷；
3)将上述PET无纺布层+阻燃增强粘结层放卷，铺放阻燃PU泡沫层，放卷阻燃增强粘结层+PET无纺布层，在190～210℃，0.3～0.8Mpa条件下，以3～5m/min的速度进行热压复合。
作为进一步地改进，本发明所述的步骤1)中，PU泡沫密度优选为45～55kg/m3。
作为进一步地改进，本发明所述的步骤1)中，PU泡沫芯层厚度优选8～12mm。
作为进一步地改进，本发明所述的步骤1)中，回收再生多元醇用量优选占总量10～15％，阻燃剂用量优选占1～1.5％。
作为进一步地改进，本发明所述的步骤2)中，PET无纺布层的克重为50～120g/m2，阻燃增强粘结层的克重为400～800g/m2。
作为进一步地改进，本发明所述的PET无纺布层的克重优选为80～110g/m2，阻燃增强粘结层的克重优先为450～500g/m2。
作为进一步地改进，本发明所述的步骤2)中，所述的短切玻纤的长度在3～8cm，胶粉为PE或PP胶粉。
作为进一步地改进，本发明所述的步骤2)中，所述的短切玻纤的长度优选为4～6cm，胶粉优选为PP胶粉。
作为进一步地改进，本发明所述的步骤2)中，玻纤撒落量：胶粉和膨胀石墨量的比例为0.8～1.4∶1，胶粉：膨胀石墨的混匀比例为1～3∶1。
作为进一步地改进，本发明所述的步骤2)中，玻纤撒落量：胶粉和膨胀石墨量的比例为0.9～1.1∶1，胶粉：膨胀石墨的混匀比例为1.5～2∶1，胶粉和膨胀石墨的粒径优选均在80-200目。
本发明的有益效果如下：
本发明由于采用了上述技术方案，具有以下有益效果：
1、与传统PP蜂窝或纸蜂窝衣帽架材料相比，PU泡沫复合板承载性能更为优异，因PU泡沫与增强层之间粘接涵盖整个表面，故粘结效果比蜂窝板更好，不易分层。成型后R角位置平整饱满，满足衣帽架的特殊造型要求。另外，PP蜂窝的耐高温性能较差，PU泡沫相较于PP蜂窝更好，不容易变形；纸蜂窝容易吸湿受潮，导致刚性强度变差，PU泡沫不易吸湿受潮影响刚性。
2、本发明提出的添加阻燃剂和回收再生多元醇发泡，不仅可减少废泡沫焚烧处理产生的碳排放和有毒有害气体，还降低了PU泡沫的生产成本，且PU泡沫芯层比普通的PU泡沫阻燃效果佳，性价比高。
3、表面的增强层不仅增加了复合板的整体强度，且因膨胀石墨的添加，在复合材料的表面起到了阻燃作用，极大改善了材料的阻燃性能，特别适合用于新能源汽车，提高了驾乘的安全性。胶粉与膨胀石墨一起混合均匀作为粘结剂，不仅起到粘结作用，且透气性比使用胶膜更好，对改善衣帽架内饰件吸音也有一定的帮助。
附图说明
图1为汽车衣帽架用环保阻燃高承载PU复合材料结构；
图中，1为阻燃PU泡沫层，2为阻燃增强粘结层，3为PET无纺布层。
具体实施方式
下面结合说明书附图，通过具体实施例对本发明的技术方案做进一步的说明：
实施例1
(1)阻燃PU泡沫发泡，其中回收再生多元醇质量占比15％，4110聚醚占比19％，交联剂占比2.5％，亨斯迈ZR70催化剂占比0.05％，301阻燃剂占比1.5％，水占比0.9％，硅油表面活性剂占比0.6％，抗氧剂占比0.45％，MR100异氰占比60％，所得泡沫密度为55kg/m3，泡沫切片厚度8mm。
(2)PET无纺布层3与阻燃增强粘结层2的制备：在复合机自下而上依次放卷100g/m2的PET无纺布，5cm长的短切玻纤撒落量为200g/m2，PP胶粉和膨胀石墨事先混合均匀，洒落克重分别为140和60g/m2，在180℃，0.3MPa下以6m/min的速度进行热压复合，两侧修边裁切至需要的门幅并收卷。得到克重为500g/m2的表面阻燃增强粘结层2。
(3)将上述PET无纺布层3+阻燃增强粘结层2放卷，铺放阻燃PU泡沫层1，放卷阻燃增强粘结层2+PET无纺布层3，在复合机200℃，0.4MPa下以4m/min的速度进行热压复合，得到总克重为1440g/m2的PU泡沫复合板材。
实施例2
(1)阻燃PU泡沫发泡，其中回收再生多元醇质量占比10％，4110聚醚占比23.5％，交联剂占比2.5％，亨斯迈ZR70催化剂占比0.05％，301阻燃剂占比1.5％，水占比1.4％，硅油表面活性剂占比0.6％，抗氧剂占比0.45％，MR100异氰占比60％。所得泡沫密度为50kg/m3，泡沫切片厚度12mm。
(2)PET无纺布层3与阻燃增强粘结层2的制备：在复合机自下而上依次放卷100g/m2的PET无纺布，5cm长的短切玻纤撒落量为240g/m2，PE胶粉和膨胀石墨事先混合均匀，洒落克重分别为185和75g/m2，在190℃，0.5MPa下以7m/min的速度进行热压复合，两侧修边裁切至需要的门幅并收卷。得到克重为600g/m2的表面阻燃增强粘结层2。
(3)将上述PET无纺布层3+阻燃增强粘结层2放卷，铺放阻燃PU泡沫层1，放卷阻燃增强粘结层2+PET无纺布层3，在复合机200℃，0.4MPa下以4m/min的速度进行热压复合。得到总克重为1800g/m2的PU泡沫复合板材。
对比例1
(1)普通PU泡沫芯层，即未添加回收再生多元醇及阻燃剂，泡沫密度为55kg/m3，泡沫切片厚度8mm。
(2)PET无纺布层3与阻燃增强粘结层2的制备：在复合机自下而上依次放卷100g/m2的PET无纺布，5cm长的短切玻纤撒落量为200g/m2，PP胶膜100g/m2两层，在180℃，0.3MPa下以6m/min的速度进行热压复合，两侧修边裁切至需要的门幅并收卷。得到克重为500g/m2的表面阻燃增强粘结层2。
(3)将上述PET无纺布层3+阻燃增强粘结层2放卷，铺放阻燃PU泡沫层1，放卷阻燃增强粘结层2+PET无纺布层3，在复合机200℃，0.4MPa下以4m/min的速度进行热压复合。得到总克重为1440g/m2的PU泡沫复合板材。
对比例2
(1)玻纤增强层的制备：在复合机自下而上依次放卷5cm长的短切玻纤撒落量为210g/m2，PE胶膜100g/m2两层，在180℃，0.3MPa下以6m/min的速度进行热压复合，两侧修边裁切至需要的门幅并收卷，得到克重为410g/m2的玻纤增强层。
(2)将克重100g/m2的PET无纺布层3，410g/m2的增强层放卷，铺放一层厚度12mm，密度65kg/m3的PP蜂窝板，放卷410g/m2的增强层和克重100g/m2的PET无纺布层3，在复合机200℃，0.4MPa下以6m/min的速度进行热压复合。得到总克重为1800g/m2的PU泡沫复合板材。
根据GB8410-2016标准测试水平燃烧，GB 32086-2015标准测试垂直燃烧特性；按QC-G/SY-002测试透气性；承载的测试方法：样品大小1000*500mm，两边搭接，支撑的宽度为13mm，在中间150*150mm的区域施加50N和100N的力。具体水平燃烧、垂直燃烧和承载的测试对比数据如下表1：
表1样品数据对比
测试材料 厚度mm 克重g/m2 水平燃烧 垂直燃烧 透气性 50N下垂量 100N下垂量
实施例1 8.0 1440 A0 0mm/min 0.23cfm 0.2mm 0.3mm
实施例2 12.0 1800 A0 0mm/min 0.12cfm 0.1mm 0.2mm
对比例1 8.0 1440 27mm/min ＞100mm/min 0.02cfm 0.2mm 0.3mm
对比例2 12.0 1800 36mm/min ＞100mm/min 0.01cfm 0.6mm 1.0mm
从上表性能对比看，实施例1与对比例1，相同厚度和克重下，承载性能基本一致，但水平燃烧和垂直燃烧阻燃性能效果相差很大，实施例1明显阻燃效果更佳，透气性也是高于使用胶膜的对比例1。实施例2和对比例2，相同克重和厚度下，实施例2的承载性能明显高于对比例2，同样重量下的下垂量更小，同时透气性也高于对比例2。
另外，因添加了15％的价格更为实惠的回收多元醇，实施例1较对比例1还具有一定的成本优势。
本发明可改变为多种方式对本领域的技术人员是显而易见的，这样的改变不认为脱离本发明的范围，所有这样的对所述领域的技术人员显而易见的修改，将包括在本权利要求的范围之内。

Claims (7)

1.一种汽车衣帽架用环保阻燃高承载PU复合材料制备方法，其特征在于，PU复合材料是自下而上依次包括PET无纺布层（3）、阻燃增强粘接层（2）、阻燃PU泡沫芯层、阻燃增强粘接层（2）和PET无纺布层（3）热压复合成的复合板，包括如下步骤：
1）阻燃PU泡沫芯层的配方如下：
回收再生多元醇，其羟值为400±20mgKOH/g，回收再生多元醇的用量占发泡原液总质量的5~20%；
阻燃剂，用量占发泡原液总质量的0.5~3%；
所述的阻燃PU泡沫芯层厚度介于8~12mm之间，其配方体系，利用PU泡沫降解回收得到的多元醇，再次重新用于PU发泡，PU泡沫的密度在45~55kg/m3之间，实现物料的循环利用；
2）PET无纺布层（3）与阻燃增强粘接层（2）的制备方法为：在复合机自下而上依次放卷PET无纺布，撒短切玻纤，撒胶粉和膨胀石墨，在180~200℃，0.3~0.8Mpa的条件下，以6~8m/min的速度进行热压复合并收卷；所述的PET无纺布层（3）的克重为50~120g/m2，所述的阻燃增强粘接层（2）的克重为400~800g/m2；
3）将上述PET无纺布层（3）+阻燃增强粘接层（2）放卷，铺放阻燃PU泡沫层（1），放卷阻燃增强粘接层（2）+PET无纺布层（3），在190~210℃，0.3~0.8Mpa条件下，以3~5m/min的速度进行热压复合。
2.根据权利要求1所述的汽车衣帽架用环保阻燃高承载PU复合材料制备方法，其特征在于，所述的步骤1）中，回收再生多元醇用量占总量10~15%，阻燃剂用量占1~1.5%。
3.根据权利要求2所述的汽车衣帽架用环保阻燃高承载PU复合材料制备方法，其特征在于，所述的PET无纺布层（3）的克重为80~110g/m2，所述的阻燃增强粘接层（2）的克重优先为450~500g/m2。
4.根据权利要求1所述的汽车衣帽架用环保阻燃高承载PU复合材料制备方法，其特征在于，所述的步骤2）中，所述的短切玻纤的长度在3~8cm，所述的胶粉为PE或PP胶粉。
5.根据权利要求4所述的汽车衣帽架用环保阻燃高承载PU复合材料制备方法，其特征在于，所述的步骤2）中，所述的短切玻纤的长度为4~6cm，所述的胶粉为PP胶粉。
6.根据权利要求1或2或3或4或5所述的汽车衣帽架用环保阻燃高承载PU复合材料制备方法，其特征在于，所述的步骤2）中，玻纤撒落量：胶粉和膨胀石墨量的比例为0.8~1.4∶1，胶粉：膨胀石墨的混匀比例为1~3∶1。
7.根据权利要求6所述的汽车衣帽架用环保阻燃高承载PU复合材料制备方法，其特征在于，所述的步骤2）中，玻纤撒落量：胶粉和膨胀石墨量的比例为0.9~1.1∶1，胶粉：膨胀石墨的混匀比例为1.5~2∶1，所述的胶粉和膨胀石墨的粒径均在80-200目。
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