CN108749216A - 一种加强型复合隔热材料及其制备方法 - Google Patents

一种加强型复合隔热材料及其制备方法 Download PDF

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CN108749216A
CN108749216A CN201810480194.8A CN201810480194A CN108749216A CN 108749216 A CN108749216 A CN 108749216A CN 201810480194 A CN201810480194 A CN 201810480194A CN 108749216 A CN108749216 A CN 108749216A
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张道静
裴作清
金伟浩
李守元
高勇
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Zhejiang PENGYUAN New Material Technology Group Co., Ltd
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Abstract

本发明提供了一种纳米复合隔热材料及其制备方法，其特征在于，包括依次设置的铝箔、改性PET膜、改性聚乙烯粘接膜、不锈钢网格、改性阻燃气囊、改性聚乙烯粘接膜、纤维网格、阻燃防炫聚丙烯薄膜；所述改性PET膜为SiC/聚多巴胺配合物改性的PET膜。本发明通过提高骨架的复合强度和减少空气流通路径，提高了铝箔气泡隔热材料的阻燃效果以及力学强度。

Description

一种加强型复合隔热材料及其制备方法
【技术领域】
本发明涉及保温材料领域，尤其涉及一种加强型复合隔热材料及其制备方法。
工业建筑和维持室内舒适温度所消耗的能量占到世界每年总能耗的30%以上，隔热材料的使用可以提高建筑物的能量利用率、降低能耗。然而，无机隔热材料的热导率普遍偏高，传统的有机隔热材料普遍易燃，而有机阻燃剂的使用则会对环境和人类健康造成危害。因此，防火性能良好的保温材料在现代建筑中的重要性体现了越来越明显，如何进一步改善保温材料的燃烧性能，使其达到A级的阻燃性能，已经成为研究热点。
铝箔气泡隔热材料是一种良好的绿色建筑隔热材料，一般采用多层的铝箔+气囊+铝箔的结构设计，质量轻、热传导低，但是其阻燃性能一般是通过添加磷系或者溴系阻燃剂进行改善，阻燃效果不够理想，达不到A级阻燃要求；同时，这种隔热材料的力学强度差，能单独承受的压力很低，层间易剥离，无法满足承压有一定要求的场合。
【发明内容】
本发明的目的之一在于提供一种加强型复合隔热材料，通过提高骨架的复合强度和减少空气流通路径，提高了铝箔气泡隔热材料的阻燃效果以及力学强度。本发明的另一目的在于提供上述加强型复合隔热材料的制备方法。
本发明的技术方案是：
一种加强型复合隔热材料，其特征在于，包括依次设置的铝箔、改性PET膜、改性聚乙烯粘接膜、不锈钢网格、改性阻燃气囊、改性聚乙烯粘接膜、纤维网格、阻燃防炫聚丙烯薄膜；所述改性PET膜为SiC/聚多巴胺配合物改性的PET膜。多巴胺在碱性环境中通过自由基聚合，形成聚多巴胺配合物；聚多巴胺配合物具有多个活性位点，能够吸附在SiC表面形成类球形自组装结构，同时仍然保留交联高分子的特性，能够PET发生交联，对PET膜进行改性，改性后的PET膜具有更好的强度和阻燃效果，并且与铝箔的粘合粘度更高，不易出现层状剥离。
进一步的，上述聚多巴胺配合物为Mo-PDA或者W-PDA。Mo-PDA指的是钼-聚多巴胺配合物，W-PDA指的是钨-聚多巴胺配合物，这两种金属-聚多巴胺配合物与SiC自组装形成规则结构的能力更强，且具有良好的高温性能和阻燃效果。
进一步的，上述SiC/聚多巴胺配合物的质量比为（5~10）：1，在该比例范围内，SiC/聚多巴胺配合物能够形成较为规则的类球形结构，在PET中形成均匀的分散效果。
进一步的，上述SiC/聚多巴胺配合物改性的PET膜通过以下方法制备：
a) 制备SiC/聚多巴胺配合物：将纳米SiC粉体分散在乙醇中，用氨水调节pH为10-11，加入Mo源或者W源，调节pH为9-9.5，再滴加98%的DA-HCl，搅拌6~8h，60~80℃干燥、收集；其中Mo或W与DA的摩尔比为1:1；
b)制备改性聚酯粒：取乙二醇单体及对苯二甲酸为聚合原料，加入制备的SiC/聚多巴胺配合物粉体0.005~0.1wt%，在催化剂作用下进行聚缩合反应，生成聚酯融熔体，通过精馏去除副产物后，再经过冷却、切粒制得改性聚酯粒；
c)进行聚酯膜加工：在270~290℃温度下，将改性聚酯粒挤出成改性PET膜。
进一步的，上述改性阻燃气囊为蜂窝状排列的六边形气囊。相较于横竖排列的气囊，蜂窝状排列的六边形气囊在平面上是紧密排列的，不存在空气流通的直接通道，能够有效降低燃烧的蔓延速度。
进一步的，上述纤维网格为尼龙纤维与碳纤维复合编织的网格。采用尼龙纤维和碳纤维的复合网格，能够大大提高材料的力学强度和阻燃效果。
进一步的，上述阻燃防炫聚丙烯薄膜为茂金属线性低密度聚乙烯膜。
进一步的，上述加强型复合隔热材料的制备方法，其特征在于，包含以下步骤：
a) 制备SiC/聚多巴胺配合物：将纳米SiC粉体分散在乙醇中，用氨水调节pH为10-11，加入Mo源或者W源，调节pH为9-9.5，再滴加98%的DA-HCl，搅拌6~8h，60~80℃干燥、收集；其中Mo或W与DA的摩尔比为1:1；
b)制备改性聚酯粒：取乙二醇单体及对苯二甲酸为聚合原料，加入制备的SiC/聚多巴胺配合物粉体0.005~0.1wt%，在催化剂作用下进行聚缩合反应，生成聚酯融熔体，通过精馏去除副产物后，再经过冷却、切粒制得改性聚酯粒；
c)进行聚酯膜加工：在270~290℃温度下，将改性聚酯粒挤出成改性PET膜；
d）制作改性阻燃气囊：在气囊复合机上挤出流延两层聚乙烯淋膜，分别用于复合和发泡，辊筒增设凹形蜂窝状排列的六边形通气孔，通过真空负压使一层聚乙烯淋膜生成凹泡，另一层热熔融膜贴附在其上形成封闭气囊，得到改性阻燃气囊；
e) 将铝箔、改性PET膜、改性聚乙烯粘接膜、不锈钢网格、改性阻燃气囊、改性聚乙烯粘接膜、纤维网格、阻燃防炫聚丙烯薄膜依次热压结合，形成多层结构的加强型复合隔热材料。
本发明具有以下有益的技术效果：
本发明通过SiC/聚多巴胺配合物改性的PET膜、不锈钢网格、蜂窝状排列的六边形改性阻燃气囊、尼龙和碳纤维复合网格，提高了整体材料的骨架的复合强度，减少空气流通路径，提高了铝箔气泡隔热材料的阻燃效果以及力学性能，整体结构的抗压强度≥1.6MPa，抗拉强度≥1.8 MPa，无法完整剥离铝箔，常温导热系数≤0.02W/m·K，燃烧氧指数达到70%以上，综合防火性能达到了国家标准GB/T8624-2012《建筑材料及制品燃烧性能》的A2级。
【具体实施方式】
以下结合具体实施例，对本发明做进一步描述。
以下所提供的实施例并非用以限制本发明所涵盖的范围，所描述的步骤也不是用以限制其执行顺序。本领域技术人员结合现有公知常识对本发明做显而易见的改进，亦落入本发明要求的保护范围之内。
实施例1
一种加强型复合隔热材料，包括依次设置的铝箔、改性PET膜、改性聚乙烯粘接膜、不锈钢网格、改性阻燃气囊、改性聚乙烯粘接膜、纤维网格、阻燃防炫聚丙烯薄膜；其中，铝箔为纯度≥99.99%的高镜面铝箔，改性PET膜为SiC/Mo-PDA改性的PET膜，改性阻燃气囊为蜂窝状排列的六边形气囊，纤维网格为尼龙纤维与碳纤维复合编织的网格，阻燃防炫聚丙烯薄膜为茂金属线性低密度聚乙烯膜。
上述加强型复合隔热材料的制备方法包含以下步骤：
a) 制备SiC/聚多巴胺配合物：将纳米SiC粉体分散在乙醇中，用氨水调节pH为10-11，加入H24Mo7N6O24·4H2O（四水合钼酸铵），调节pH为9-9.5，再滴加98%的DA-HCl（质量分数为98%的盐酸多巴胺），搅拌6~8h，60~80℃干燥、收集；其中Mo或W与DA的摩尔比为1:1，SiC/聚多巴胺配合物的质量比为5：1；
b)制备改性聚酯粒：取乙二醇单体及对苯二甲酸为聚合原料，加入制备的SiC/聚多巴胺配合物粉体0.005~0.1wt%，在催化剂作用下进行聚缩合反应，生成聚酯融熔体，通过精馏去除副产物后，再经过冷却、切粒制得改性聚酯粒；
c)进行聚酯膜加工：在270~290℃温度下，将改性聚酯粒挤出成改性PET膜。
d）制作改性阻燃气囊：在气囊复合机上挤出流延两层聚乙烯淋膜，分别用于复合和发泡，辊筒增设凹形蜂窝状排列的六边形通气孔，通过真空负压使一层聚乙烯淋膜生成凹泡，另一层热熔融膜贴附在其上形成封闭气囊，得到改性阻燃气囊；
e) 将铝箔、改性PET膜、改性聚乙烯粘接膜、不锈钢网格、改性阻燃气囊、改性聚乙烯粘接膜、纤维网格、阻燃防炫聚丙烯薄膜依次热压结合，形成多层结构的加强型复合隔热材料。
性能测试：
按GB/T2406.1-2008《塑料用氧指数法测定燃烧行为》检测，其氧指数为70~71；按GB/T8607-2007《建筑材料燃烧或分解的烟密度实验方法》测试，烟密度等级≤21；按GB/T8333-2008《硬质泡沫塑料燃烧性能实验方法垂直燃烧法》检测，其平均燃烧时间≤10s，平均燃烧高度≤17mm，热释放效率小于36.7W/g，导热系数0.016W/m·K。各项性能参数均大大高于国家标准，符合GB/T8624-2012的A2级要求，达到UL-94的V-0级标准。根据GB/T8813-2008测试强度，抗拉强度1.60MPa，抗压强度1.81MPa。
实施例2
一种加强型复合隔热材料，包括依次设置的铝箔、改性PET膜、改性聚乙烯粘接膜、不锈钢网格、改性阻燃气囊、改性聚乙烯粘接膜、纤维网格、阻燃防炫聚丙烯薄膜；其中，铝箔为纯度≥99.99%的高镜面铝箔，改性PET膜为SiC/W-PDA改性的PET膜，改性阻燃气囊为蜂窝状排列的六边形气囊，纤维网格为尼龙纤维与碳纤维复合编织的网格，阻燃防炫聚丙烯薄膜为茂金属线性低密度聚乙烯膜。
上述加强型复合隔热材料的制备方法包含以下步骤：
a) 制备SiC/聚多巴胺配合物：将纳米SiC粉体分散在乙醇中，用氨水调节pH为10-11，加入Na2WO4·2H2O（二水合钨酸钠），调节pH为9-9.5，再滴加98%的DA-HCl（质量分数为98%的盐酸多巴胺），搅拌6~8h，60~80℃干燥、收集；其中Mo或W与DA的摩尔比为1:1，SiC/聚多巴胺配合物的质量比为10：1；
b)制备改性聚酯粒：取乙二醇单体及对苯二甲酸为聚合原料，加入制备的SiC/聚多巴胺配合物粉体0.005~0.1wt%，在催化剂作用下进行聚缩合反应，生成聚酯融熔体，通过精馏去除副产物后，再经过冷却、切粒制得改性聚酯粒；
c)进行聚酯膜加工：在270~290℃温度下，将改性聚酯粒挤出成改性PET膜。
d）制作改性阻燃气囊：在气囊复合机上挤出流延两层聚乙烯淋膜，分别用于复合和发泡，辊筒增设凹形蜂窝状排列的六边形通气孔，通过真空负压使一层聚乙烯淋膜生成凹泡，另一层热熔融膜贴附在其上形成封闭气囊，得到改性阻燃气囊；
e) 将铝箔、改性PET膜、改性聚乙烯粘接膜、不锈钢网格、改性阻燃气囊、改性聚乙烯粘接膜、纤维网格、阻燃防炫聚丙烯薄膜依次热压结合，形成多层结构的加强型复合隔热材料。
性能测试：
按GB/T2406.1-2008《塑料用氧指数法测定燃烧行为》检测，其氧指数为70~71；按GB/T8607-2007《建筑材料燃烧或分解的烟密度实验方法》测试，烟密度等级≤21；按GB/T8333-2008《硬质泡沫塑料燃烧性能实验方法垂直燃烧法》检测，其平均燃烧时间≤10s，平均燃烧高度≤17mm，热释放效率小于33.7W/g，导热系数0.02W/m·K。各项性能参数均大大高于国家标准，符合GB/T8624-2012的A2级要求，达到UL-94的V-0级标准。根据GB/T8813-2008测试强度，抗拉强度1.60MPa，抗压强度1.81MPa。

Claims (9)

1.一种加强型复合隔热材料，其特征在于，包括依次设置的铝箔、改性PET膜、改性聚乙烯粘接膜、不锈钢网格、改性阻燃气囊、改性聚乙烯粘接膜、纤维网格、阻燃防炫聚丙烯薄膜；所述改性PET膜为SiC/聚多巴胺配合物改性的PET膜。
2.根据权利要求1所述的加强型复合隔热材料，其特征在于，所述聚多巴胺配合物为Mo-PDA或者W-PDA。
3.根据权利要求2所述的加强型复合隔热材料，其特征在于，所述SiC/聚多巴胺配合物的质量比为（5~10）：1。
4.根据权利要求1所述的加强型复合隔热材料，其特征在于，所述SiC/聚多巴胺配合物改性的PET膜通过以下方法制备：
a) 制备SiC/聚多巴胺配合物：将纳米SiC粉体分散在乙醇中，用氨水调节pH为10-11，加入Mo源或者W源，调节pH为9-9.5，再滴加98%的DA-HCl，搅拌6~8h，60~80℃干燥、收集；其中Mo或W与DA的摩尔比为1:1；
b)制备改性聚酯粒：取乙二醇单体及对苯二甲酸为聚合原料，加入制备的SiC/聚多巴胺配合物粉体0.005~0.1wt%，在催化剂作用下进行聚缩合反应，生成聚酯融熔体，通过精馏去除副产物后，再经过冷却、切粒制得改性聚酯粒；
c)进行聚酯膜加工：在270~290℃温度下，将改性聚酯粒挤出成改性PET膜。
5.根据权利要求1所述的加强型复合隔热材料，其特征在于，所述改性阻燃气囊为蜂窝状排列的六边形气囊。
6.根据权利要求1所述的加强型复合隔热材料，其特征在于，所述纤维网格为尼龙纤维与碳纤维复合编织的网格。
7.根据权利要求1所述的加强型复合隔热材料，其特征在于，所述阻燃防炫聚丙烯薄膜为茂金属线性低密度聚乙烯膜。
8.如权利要求1或2所述的加强型复合隔热材料的制备方法，其特征在于，包含以下步骤：
a) 制备SiC/聚多巴胺配合物：将纳米SiC粉体分散在乙醇中，用氨水调节pH为10-11，加入Mo源或者W源，调节pH为9-9.5，再滴加98%的DA-HCl，搅拌6~8h，60~80℃干燥、收集；其中Mo或W与DA的摩尔比为1:1；
b)制备改性聚酯粒：取乙二醇单体及对苯二甲酸为聚合原料，加入制备的SiC/聚多巴胺配合物粉体0.005~0.1wt%，在催化剂作用下进行聚缩合反应，生成聚酯融熔体，通过精馏去除副产物后，再经过冷却、切粒制得改性聚酯粒；
c)进行聚酯膜加工：在270~290℃温度下，将改性聚酯粒挤出成改性PET膜。
9.根据权利要求8所述的所述的加强型复合隔热材料的制备方法，其特征在于，包含以下步骤：
d）制作改性阻燃气囊：在气囊复合机上挤出流延两层聚乙烯淋膜，分别用于复合和发泡，辊筒增设凹形蜂窝状排列的六边形通气孔，通过真空负压使一层聚乙烯淋膜生成凹泡，另一层热熔融膜贴附在其上形成封闭气囊，得到改性阻燃气囊。
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