CN108045050A - 一种低voc泡沫夹心轻质高强无卤阻燃复合材料及其制备方法 - Google Patents
一种低voc泡沫夹心轻质高强无卤阻燃复合材料及其制备方法 Download PDFInfo
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Abstract
本发明涉及复合材料领域,为解决目前车辆内饰存在的问题,本发明提供一种低VOC泡沫夹心轻质高强无卤阻燃复合材料,以无卤阻燃连续纤维增强聚丙烯复合材料板材层作为上下壳层,无卤阻燃聚丙烯泡沫层作为芯层,呈三明治结构,通过对产品结构和配方进行了优化,尤其是解决了玻纤增强热塑性树脂和聚丙烯泡沫的无卤阻燃问题,使得本发明产品同时兼有高强度、使用寿命长、低VOC、可回收、无卤阻燃、轻量化、易施工等优点,从而完全能满足车辆地板、车辆侧顶板、模块化建筑装饰板等场合。
Description
技术领域
本发明涉及复合材料领域,具体涉及一种三明治结构的低VOC泡沫夹心轻质高强无卤阻燃复合材料及其制备方法。
背景技术
随环保意识和舒适性要求不断提高,车辆内饰的安全环保性及可回收性越来越受到人们的重视,交通工具轻量化、防火安全与低VOC、低气味和可回收利用的矛盾日益突出,为推动交通工具用材料的绿色发展,TB/T 3237-2010《动车组用内装材料阻燃技术条件》、GB/T 27630-2011《乘用车内空气质量评价指南》、工业和信息化部发布2015年第38号公告-《汽车有害物质和可回收利用率管理要求》、GB/T30512-2014《汽车禁用物质要求》、TJ/T1095-2016《营运客车内饰材料阻燃特性》等国内安全环保法规相继出台。
含溴(Br)、氯(Cl)等卤素的阻燃剂防火效果良好,被广泛应用于车辆内饰材料中。但含溴、氯阻燃剂的卤素阻燃材料在燃烧过程中会产生大量的烟雾毒性,对眼和呼吸道粘膜有强烈的刺激作用和皮肤、粘膜的刺激或灼伤,不利于人员的逃生。同时卤素阻燃材料使用后如果未能进行有效的分类而混入生活垃圾进行焚烧处理,会成为PM 2.5和地下水环境污染的来源之一。因此,车辆内饰材料的环保阻燃技术升级迫在眉睫。车辆地板作为内饰中面积最大的承力部件,在高强、环保、减重及使用寿命长等方面有着更高的要求,轻量化、低VOC、可再生汽车材料是未来的发展趋势。
车辆用地板经历了从木板、到竹胶板再到现在的夹心复合材料地板的变革,得到的地板整体质量轻,耐腐蚀性较好,强度也较高。夹心复合材料按照材料可分为铝塑型、热固型和全热塑型三种,其中铝塑型和热固型复合材料有较好的强度和防火性能,但后期回收困难。全热塑性夹心复合材料设计时可采用同一树脂基材,以聚丙烯、聚酰胺或热塑性聚酯树脂为主,通过热压工艺将芯层与面层结合,不需胶黏剂,产品可挥发分少,可回收,工序绿色环保,其技术方案按照夹心层的不同,主要分为两大类:
1、蜂窝夹心复合结构,具有代表性的专利为CN201310109036.9,本发明公开了一种三明治复合材料板材及其制造方法,表层为热塑性玻璃纤维板,芯层为聚丙烯蜂窝板,使用热熔胶胶膜粘接,材质环保。但蜂窝夹心结构在安装过程中存在重大问题,需要对螺钉安装部位进行特殊处理,以保证足够的握钉力,施工工艺复杂,大批量生产困难。
2、纤维毡夹心复合结构,具有代表性的专利有CN201620259309.7,本实用新型公开了一种客车地板,面层由多层单向连续玻璃纤维增强热塑性树脂预浸片和/或玻璃纤维织物增强热塑性树脂预浸片复合而成,面层厚度为0.5-2mm。芯材是以聚丙烯、聚酰胺或热塑性聚酯为基体,以玻璃纤维毡为增强体的热塑性轻质复合材料板材,密度为200-600kg/m3,厚度为4-15mm。复合后整体厚度为6-20mm,密度400-800kg/m3。产品强度和耐久性更好,重量轻,可吸收噪音,而且无需使用胶黏剂便可直接通过热压工艺与面层结合,减少了喷胶工序,制备绿色环保。但存在阻燃和环保回收问题。
发明内容
为解决上述存在问题,本发明提供一种低VOC泡沫夹心轻质高强无卤阻燃复合材料,具有高强度、使用寿命长、低VOC、可回收、无卤阻燃、轻量化、易施工等优点。
本发明还提供了一种上述复合板材的制备方法,工艺简单。
为了实现上述目的,本发明采用以下技术方案:一种低VOC泡沫夹心轻质高强无卤阻燃复合材料以无卤阻燃连续纤维增强聚丙烯复合材料板材层作为上下壳层,无卤阻燃聚丙烯泡沫层作为芯层,呈三明治结构,如图1所示,其厚度为10-12mm。复合材料为从上往下依次为:无卤阻燃连续纤维增强聚丙烯复合材料板材层、无卤阻燃聚丙烯泡沫层、和无卤阻燃连续纤维增强聚丙烯复合材料板材层构成的复合三明治结构。
所述的复合材料密度780-860Kg/m3,静曲强度纵向>60MPa,静曲强度横向>40MPa,弹性模量纵横向>6000MPa,冲击韧性>45KJ/m2,力学性能好;阻燃性能LOI≥30%,阻燃等级达到TB/T 3237-2010 B级和GB 8624 B1等级,低烟、低毒;环保性能为不含卤素,TVOC≤50μ gc/g,气味等级≤3级,使用过程中不会释放对人体有害的有毒气体。
所述无卤阻燃连续纤维增强聚丙烯复合材料板材层由以下质量份的原料构成:100份聚丙烯树脂A,180-270份连续纤维,18-23份马来酸酐接枝聚丙烯,40-90份无卤阻燃剂,0.5-1.0份助剂。
所述无卤阻燃聚丙烯泡沫层由以下质量份的原料构成:100份聚丙烯树脂B,17-22份无卤阻燃剂,0.5-1.5份助剂。
作为优选,所述的聚丙烯树脂A选自熔融指数40-150g/10min的均聚、共聚聚丙烯中的一种或几种,所述聚丙烯树脂B选自熔融指数≤2.0g/10min的高熔体强度均聚聚丙烯。
作为优选,所述的连续纤维选自玻璃纤维和玄武岩纤维中的一种或几种,其中,所述玻璃纤维为直径12-20μm的无碱连续玻璃纤维,所述玄武岩纤维直径为硅烷表面处理、直径7-13μm。
作为优选,所述的马来酸酐接枝聚丙烯的接枝率为0.9-1.3%,熔融指数为20g/10min-100g/10min。
作为优选,无卤阻燃剂选自聚磷酸三聚氰胺、三聚氰胺氰尿酸盐、JLS-PNA220(申请人工业化产品)中的一种或多种
作为优选,所述的助剂选自润滑剂、抗氧化剂中的一种或多种。更优选,润滑剂选自乙撑双硬脂酰胺、季戊四醇硬脂酸酯、硬脂酸钙中的一种或多种。
本发明所述的一种低VOC泡沫夹心轻质高强无卤阻燃复合材料的制备工艺为以下步骤:
(1)将无卤阻燃连续纤维增强聚丙烯复合材料板材层各原料按配比混合后经熔融浸渍,得到无卤阻燃连续纤维增强聚丙烯预浸带,以0°/90°/0°/90°/0°或0°/90°/0°/90°的方式进行铺层后,通过辊压热复合成无卤阻燃连续纤维增强聚丙烯复合材料板材层,所述的无卤阻燃连续纤维增强聚丙烯复合材料板材层厚度为1.40-1.75mm;
(2)将无卤阻燃聚丙烯泡沫层原料按配比熔融混合后,注入二氧化碳发泡剂发泡,得到无卤阻燃聚丙烯泡沫层,二氧化碳用量为无卤阻燃聚丙烯泡沫层总质量的0.5-5%,厚度为7-10mm;
(3)将无卤阻燃连续纤维增强聚丙烯复合材料板材层作为上下壳层,无卤阻燃聚丙烯泡沫层作为芯层,通过热压成型为三明治结构复合材料,厚度为10-12mm。
本发明无卤阻燃三明治结构复合材料,所有树脂均为聚丙烯,回收方便;采用二氧化碳发泡剂发泡的芯层,结构均匀性好,握钉力好;防火阻燃,阻燃性能LOI大于30%,阻燃等级能达到TB/T 3237-2010 B级,低VOC、轻量化、可回收,满足密闭空间和人流量密集场所的安全要求,可替代竹胶地板、蜂窝地板等、纤维毡复合板、酚醛多层复合等材料应用于车辆地板、车辆侧顶板、模块化建筑装饰板等场合。
与现有技术相比,本发明的有益效果是:
①、对产品的结构和配方进行了优化改进,尤其是解决了玻纤增强热塑性树脂和聚丙烯泡沫的无卤阻燃问题,使得本发明产品同时兼有高强度、使用寿命长、低VOC、可回收、无卤阻燃、轻量化、易施工等优点,从而完全能满足车辆地板、车辆侧顶板、模块化建筑装饰板等场合;
②、提供了一种低VOC泡沫夹心轻质高强无卤阻燃三明治结构复合材料的制备方法,直接采用热压复合工艺即可得到三明治结构复合材料,步骤简单,生产过程环保,可操作性强,适合工业化生产。
附图说明
图1为本发明一种低VOC泡沫夹心轻质高强无卤阻燃复合材料结构示意图;
其中,1:无卤阻燃连续纤维增强聚丙烯复合材料板材层,2:无卤阻燃聚丙烯泡沫层。
具体实施方式
下面结合附图和具体实施方式对本发明做进一步的说明,实施例中所用原料均可市购或采用常规方法制备。
实施例中抗氧化剂由抗氧剂1010(四[β-(3,5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯)、抗氧剂1076(β-(3,5-二叔丁基-4-羟基苯基)丙酸正十八碳醇酯)、抗氧剂168(亚磷酸三(2,4-二叔丁基苯)酯)组成,质量比例为抗氧剂1010∶抗氧剂1076∶抗氧剂168=1∶1∶1。
实施例中市购的聚丙烯树脂A中均聚或共聚聚丙烯的熔融指数40-150g/10min,聚丙烯树脂B中市购的均聚聚丙烯的熔融指数≤2.0g/10min。
实施例中市购的马来酸酐接枝聚丙烯的接枝率为0.9-1.3%,熔融指数为20g/10min-100g/10min。
实施例中市购的玻璃纤维为直径12-20μm的无碱连续玻璃纤维,市购的玄武岩纤维直径为硅烷表面处理、直径7-13μm。
实施例1-5:
(1)按照表1计量各原料后,将表面层原料作为无卤阻燃连续纤维增强聚丙烯复合材料板材层原料混合后经熔融浸渍,得到无卤阻燃连续纤维增强聚丙烯预浸带。将连续玻璃纤维增强聚丙烯树脂预浸带,以0°/90°/0°/90°/0°的方式进行铺层后,通过压辊热压复合成板材,单层厚度在1.75mm,得到无卤阻燃连续纤维增强聚丙烯复合材料板材作为上、下壳层;
(2)按照表1计量各原料后,将芯层原料熔融混合后,注入4%二氧化碳发泡剂发泡,得到厚度在9-10mm无卤阻燃聚丙烯泡沫芯层;
(3)将(1)得到的无卤阻燃连续纤维增强聚丙烯复合材料板材作为上下壳层和(2)得到的无卤阻燃聚丙烯泡沫做为芯层,通过辊压热复合成型得到低VOC泡沫夹心轻质高强无卤阻燃三明治结构复合材料1-5,厚度为12mm,结构如图1所示。
实施例6
(1)按照表1计量各原料后,将表面层原料作为无卤阻燃连续纤维增强聚丙烯复合材料板材层原料混合后经熔融浸渍,得到无卤阻燃连续纤维增强聚丙烯预浸带。将连续玻璃纤维增强聚丙烯树脂预浸带,以0°/90°/0°/90°的方式进行铺层后,通过压辊热压复合成板材,得到的无卤阻燃连续纤维增强聚丙烯复合材料板材厚度为1.40mm,作为上、下壳层;
(2)芯层原料熔融混合后,注入2%二氧化碳发泡剂发泡,得到厚度7.5-8mm无卤阻燃聚丙烯泡沫芯层;
(3)将(1)得到的无卤阻燃连续纤维增强聚丙烯复合材料板材作为上下壳层和(2)得到的无卤阻燃聚丙烯泡沫做为芯层,通过辊压热复合成型得到低VOC泡沫夹心轻质高强无卤阻燃三明治结构复合材料6,厚度为10mm,结构如图1所示。
表1各实施例中低VOC泡沫夹心轻质高强无卤阻燃三明治结构复合材料的原料配比
测试例
实施例1-6制得的低VOC泡沫夹心轻质高强无卤阻燃三明治结构复合材料1-6性能如表2所示。
表2各实施例得到的低VOC泡沫夹心轻质高强无卤阻燃三明治结构复合材料性能
从表2可以看出,各实施例得到的低VOC泡沫夹心轻质高强无卤阻燃三明治结构复合材料兼具高强度、低VOC、无卤阻燃、轻量化等优点,完全能满足车辆地板、车辆侧顶板、模块化建筑装饰板等场合的性能要求。
以上所述的实施例只是本发明的一种较佳的方案,并非对本发明作任何形式上的限制,在不超出权利要求所记载的技术方案的前提下还有其它的变体及改型。
Claims (10)
1.一种低VOC泡沫夹心轻质高强无卤阻燃复合材料,其特征在于,所述的复合材料以无卤阻燃连续纤维增强聚丙烯复合材料板材层作为上下壳层,无卤阻燃聚丙烯泡沫层作为芯层,呈三明治结构,其厚度为10-12mm。
2.根据权利要求1所述的一种低VOC泡沫夹心轻质高强无卤阻燃复合材料,其特征在于,所述的复合材料密度780-860Kg/m3,静曲强度纵向>60MPa,静曲强度横向>40MPa,弹性模量纵横向>6000MPa,冲击韧性>45KJ/m2,阻燃性能LOI≥30%, TVOC≤50μgc/g,气味等级≤3级。
3.根据权利要求1所述的一种低VOC泡沫夹心轻质高强无卤阻燃复合材料,其特征在于,无卤阻燃连续纤维增强聚丙烯复合材料板材层由以下质量份的原料构成:100份聚丙烯树脂A,180-270份连续纤维,18-23份马来酸酐接枝聚丙烯,40-90份无卤阻燃剂,0.5-1.0份助剂。
4.根据权利要求1所述的一种低VOC泡沫夹心轻质高强无卤阻燃复合材料,其特征在于,所述无卤阻燃聚丙烯泡沫层由以下质量份的原料构成:100份聚丙烯树脂B,17-22份无卤阻燃剂,0.5-1.5份助剂。
5.根据权利要求3或4所述的一种低VOC泡沫夹心轻质高强无卤阻燃复合材料,其特征在于,所述的聚丙烯树脂A选自熔融指数40-150g/10min的均聚、共聚聚丙烯中的一种或几种,所述聚丙烯树脂B选自熔融指数≤2.0 g/10min的均聚聚丙烯。
6.根据权利要求3所述的一种低VOC泡沫夹心轻质高强无卤阻燃复合材料,其特征在于,所述的连续纤维选自玻璃纤维,玄武岩纤维和碳纤维中的一种或几种。
7.根据权利要求3所述的一种低VOC泡沫夹心轻质高强无卤阻燃复合材料,其特征在于,所述的马来酸酐接枝聚丙烯的接枝率为0.9-1.3%,熔融指数为20g/10min-100g/10min。
8.根据权利要求3或4所述的一种低VOC泡沫夹心轻质高强无卤阻燃复合材料,其特征在于,无卤阻燃剂选自聚磷酸三聚氰胺、三聚氰胺氰尿酸盐、JLS-PNA220中的一种或多种。
9.根据权利要求3或4所述的一种低VOC泡沫夹心轻质高强无卤阻燃复合材料,其特征在于,所述的助剂选自润滑剂、抗氧化剂中的一种或多种。
10.一种如权利要求1至9中任一项所述的一种低VOC泡沫夹心轻质高强无卤阻燃复合材料的制备工艺,其特征在于,所述的制备工艺为以下步骤:
(a)将无卤阻燃连续纤维增强聚丙烯复合材料板材层各原料按配比混合后经熔融浸渍,得到无卤阻燃连续纤维增强聚丙烯预浸带,以0°/90°/0°/90°/0°或0°/90°/0°/90°的方式进行铺层后,通过辊压热复合成无卤阻燃连续纤维增强聚丙烯复合材料板材层;厚度为1.40-1.75mm;
(b)将无卤阻燃聚丙烯泡沫层原料按配比熔融混合后,注入二氧化碳发泡剂发泡,得到无卤阻燃聚丙烯泡沫层,二氧化碳用量为无卤阻燃聚丙烯泡沫层总质量的0.5-5%,厚度为7-10 mm;
(c)将无卤阻燃连续纤维增强聚丙烯复合材料板材层作为上下壳层,无卤阻燃聚丙烯泡沫层作为芯层,通过热压成型为三明治结构复合材料,总厚度为10-12mm。
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