CN105924942A - 一种高强度高阻燃聚氨酯复合保温板 - Google Patents

一种高强度高阻燃聚氨酯复合保温板 Download PDF

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CN105924942A
CN105924942A CN201610269387.XA CN201610269387A CN105924942A CN 105924942 A CN105924942 A CN 105924942A CN 201610269387 A CN201610269387 A CN 201610269387A CN 105924942 A CN105924942 A CN 105924942A
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夏正忠
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ANHUI GUANGYAN NEW MATERIAL TECHNOLOGY Co Ltd
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Abstract

本发明公开了一种高强度高阻燃聚氨酯复合保温板，包括两层背衬层和位于两层背衬层之间的聚氨酯保温层，聚氨酯保温层采用高性能聚氨酯泡沫材料制成，高性能聚氨酯泡沫材料的原料由A组分和B组分组成，且A组分与B组分的重量比为2:1.2‑2.3；A组分的原料包括：聚醚多元醇、五甲基二乙烯三胺、三羟甲基丙烷、季戊四醇、聚乙二醇、有机铋类催化剂、环己烷、水、有机硅泡孔稳定剂、氨基改性碳纳米管、膨胀珍珠岩、空心玻璃微珠、晶须硅、纳米氢氧化铝、磷酸三氯乙酯、焦磷酸哌嗪、磷酰胺类阻燃剂、环氧树脂、聚氯乙烯；B组分的原料包括：二苯甲烷二异氰酸酯、六亚甲基二异氰酸酯。

Description

一种高强度高阻燃聚氨酯复合保温板
技术领域
本发明涉及聚氨酯板材技术领域，尤其涉及一种高强度高阻燃聚氨酯复合保温板。
背景技术
聚氨酯复合保温板是由两层防水彩色涂层钢板或其它金属作面板，中间注入阻燃型聚氨酯硬质泡沫复合而成，是当今世界公认的最佳隔热保温材料，可用于大型工业厂房、仓库、展览馆、体育馆、冷库、净化车间等各种建筑的屋面和墙体，集保温、隔热、承重、防水于一体，且具有色彩丰富、造型美观的特点，目前将逐步在国内的保温材料市场内占领主导地位。但是用于保温板的聚氨酯硬质泡沫具有多孔结构，使得其比一般的塑料更易被引燃，并在燃烧过程中伴随释放氰化氢、CO、NO等大量毒性气体，造成很大的潜在危害，再加上其强度不是很高，限制了其应用范围。
发明内容
基于背景技术存在的技术问题，本发明提出了一种高强度高阻燃聚氨酯复合保温板，其强度高，耐热性和阻燃性能优异，使用寿命长。
本发明提出的一种高强度高阻燃聚氨酯复合保温板，包括两层背衬层和位于两层背衬层之间的聚氨酯保温层，所述聚氨酯保温层采用高性能聚氨酯泡沫材料制成，所述高性能聚氨酯泡沫材料的原料由A组分和B组分组成，且A组分与B组分的重量比为2:1.2-2.3；
其中，所述A组分的原料按重量份包括：聚醚多元醇20-50份、五甲基二乙烯三胺0.5-2份、三羟甲基丙烷3-12份、季戊四醇2-10份、聚乙二醇3-15份、有机铋类催化剂0.1-1份、环己烷0.5-2份、水0.5-2份、有机硅泡孔稳定剂1-5份、氨基改性碳纳米管1-5份、膨胀珍珠岩5-15份、空心玻璃微珠5-20份、晶须硅3-15份、纳米氢氧化铝2-10份、磷酸三氯乙酯3-10份、焦磷酸哌嗪5-15份、磷酰胺类阻燃剂5-15份、环氧树脂5-20份、聚氯乙烯3-20份；
所述B组分的原料按重量份包括：二苯甲烷二异氰酸酯10-25份、六亚甲基二异氰酸酯25-50份。
优选地，所述A组分的原料按重量份包括：聚醚多元醇32-40份、五甲基二乙烯三胺1.2-1.7份、三羟甲基丙烷5.6-7.3份、季戊四醇6.2-7份、聚乙二醇5.8-8份、有机铋类催化剂0.53-0.62份、环己烷1.1-1.5份、水1-1.3份、有机硅泡孔稳定剂1.2-1.6份、氨基改性碳纳米管3.2-4份、膨胀珍珠岩8-11份、空心玻璃微珠10-15份、晶须硅5.8-10份、纳米氢氧化铝5.3-7.5份、磷酸三氯乙酯5.9-7.3份、焦磷酸哌嗪8.6-10份、磷酰胺类阻燃剂8-13份、环氧树脂10-14份、聚氯乙烯8-15份。
优选地，所述A组分的原料按重量份包括：聚醚多元醇37份、五甲基二乙烯三胺1.5份、三羟甲基丙烷6份、季戊四醇6.5份、聚乙二醇7份、有机铋类催化剂0.6份、环己烷1.3份、水1.2份、有机硅泡孔稳定剂1.5份、氨基改性碳纳米管3.8份、膨胀珍珠岩10份、空心玻璃微珠12份、晶须硅8份、纳米氢氧化铝6.2份、磷酸三氯乙酯7份、焦磷酸哌嗪9份、磷酰胺类阻燃剂12份、环氧树脂13份、聚氯乙烯12份。
优选地，所述聚醚多元醇的羟值为70-120mgKOH/g。
优选地，所述聚乙二醇为聚乙二醇20000、聚乙二醇6000按重量比为2-5:1-3的混合物；所述聚乙二醇选择了聚乙二醇20000、聚乙二醇6000按重量比为2-5:1-3的混合物，使聚氨酯在体系中提高聚氨酯柔韧性的同时保持了优异的强度。
优选地，所述有机铋类催化剂为异辛酸铋、新癸酸铋、环烷酸铋中的一种或者多种的混合物。
优选地，所述磷酰胺类阻燃剂按照以下工艺进行制备：按重量份将2-10份亚磷酸二苯酯、3-15份四氯化碳和15-30份四氢呋喃混合均匀，然后冷却至0-5℃，在氮气的保护下加入100份质量分数为5-12％的苄胺的四氢呋喃溶液，然后搅拌反应5-10h，反应结束后经过滤、蒸馏、干燥得到所述磷酰胺类阻燃剂；在磷酰胺类阻燃剂的制备过程中，以亚磷酸二苯酯和苄胺为原料，通过控制反应的条件，使亚磷酸二苯酯中的氢原子与苄胺中的氨基发生了反应，得到了磷酰胺类阻燃剂，一方面，因含有P-N原子，显著提高了泡沫材料的阻燃性，另一方面，因引入了多个苯环结构，显著改善了泡沫材料的刚性和耐热性。
优选地，所述环氧树脂为四溴双酚A环氧树脂。
本发明所述高性能聚氨酯泡沫材料可以按照常规的聚氨酯硬质泡沫材料制备工艺制备而成。
本发明中，以聚醚多元醇、二苯甲烷二异氰酸酯、六亚甲基二异氰酸酯为聚氨酯的单体材料，赋予泡沫材料优异的强度、耐热性和耐老化性，同时加入了环氧树脂对体系进行改性，一方面，聚氨酯相和环氧树脂相穿插缠结，另一方面，两者交联接枝，形成了交联互穿网络结构，与聚乙二醇配合后，使得泡沫材料的压缩强度和冲击强度达到最优，并显著提高了聚氨酯泡沫材料的热稳定性；聚氯乙烯加入体系中，与氨基改性碳纳米管、膨胀珍珠岩、空心玻璃微珠、晶须硅、纳米氢氧化铝配合后，具有增强孔壁结构，增强支撑强度的作用，改善了填料体系与聚氨酯相的协调作用，显著提高了泡沫材料的力学性能；以环己烷和水复配作为发泡体系，得到的泡沫材料的孔壁结构具有较好的完整性，且泡孔尺寸更加均匀，显著提高了泡沫材料的压缩强度和压缩模量；磷酰胺类阻燃剂具有较低的挥发度和良好的热稳定性，将其加入阻燃剂中，与体系具有良好的相容性，与氨基改性碳纳米管、膨胀珍珠岩、空心玻璃微珠、晶须硅、纳米氢氧化铝份、磷酸三氯乙酯、焦磷酸哌嗪、聚氯乙烯和季戊四醇配合后实现了多种阻燃作用协同增效效应，显著提高了泡沫材料的阻燃性能。
具体实施方式
下面，通过具体实施例对本发明的技术方案进行详细说明。
实施例1
本发明提出的一种高强度高阻燃聚氨酯复合保温板，包括两层背衬层和位于两层背衬层之间的聚氨酯保温层，所述聚氨酯保温层采用高性能聚氨酯泡沫材料制成，所述高性能聚氨酯泡沫材料的原料由A组分和B组分组成，且A组分与B组分的重量比为2:2.3；
其中，所述A组分的原料按重量份包括：聚醚多元醇20份、五甲基二乙烯三胺2份、三羟甲基丙烷12份、季戊四醇2份、聚乙二醇15份、有机铋类催化剂0.1份、环己烷2份、水0.5份、有机硅泡孔稳定剂5份、氨基改性碳纳米管1份、膨胀珍珠岩15份、空心玻璃微珠5份、晶须硅15份、纳米氢氧化铝2份、磷酸三氯乙酯10份、焦磷酸哌嗪5份、磷酰胺类阻燃剂15份、环氧树脂5份、聚氯乙烯20份；
所述B组分的原料按重量份包括：二苯甲烷二异氰酸酯10份、六亚甲基二异氰酸酯50份。
实施例2
本发明提出的一种高强度高阻燃聚氨酯复合保温板，包括两层背衬层和位于两层背衬层之间的聚氨酯保温层，所述聚氨酯保温层采用高性能聚氨酯泡沫材料制成，所述高性能聚氨酯泡沫材料的原料由A组分和B组分组成，且A组分与B组分的重量比为2:1.2；
其中，所述A组分的原料按重量份包括：聚醚多元醇50份、五甲基二乙烯三胺0.5份、三羟甲基丙烷3份、季戊四醇10份、聚乙二醇3份、有机铋类催化剂1份、环己烷0.5份、水2份、有机硅泡孔稳定剂1份、氨基改性碳纳米管5份、膨胀珍珠岩5份、空心玻璃微珠20份、晶须硅3份、纳米氢氧化铝10份、磷酸三氯乙酯3份、焦磷酸哌嗪15份、磷酰胺类阻燃剂5份、环氧树脂20份、聚氯乙烯3份；
所述B组分的原料按重量份包括：二苯甲烷二异氰酸酯25份、六亚甲基二异氰酸酯25份。
实施例3
本发明提出的一种高强度高阻燃聚氨酯复合保温板，包括两层背衬层和位于两层背衬层之间的聚氨酯保温层，所述聚氨酯保温层采用高性能聚氨酯泡沫材料制成，所述高性能聚氨酯泡沫材料的原料由A组分和B组分组成，且A组分与B组分的重量比为2:1.5；
其中，所述A组分的原料按重量份包括：聚醚多元醇40份、五甲基二乙烯三胺1.7份、三羟甲基丙烷5.6份、季戊四醇7份、聚乙二醇5.8份、异辛酸铋0.2份、新癸酸铋0.2份、环烷酸铋0.22份、环己烷1.1份、水1.3份、有机硅泡孔稳定剂1.2份、氨基改性碳纳米管4份、膨胀珍珠岩8份、空心玻璃微珠15份、晶须硅5.8份、纳米氢氧化铝7.5份、磷酸三氯乙酯5.9份、焦磷酸哌嗪10份、磷酰胺类阻燃剂8份、环氧树脂14份、聚氯乙烯8份；
所述聚醚多元醇的羟值为120mgKOH/g；
所述聚乙二醇为聚乙二醇20000、聚乙二醇6000按重量比为3:2的混合物；
所述磷酰胺类阻燃剂按照以下工艺进行制备：按重量份将10份亚磷酸二苯酯、3份四氯化碳和30份四氢呋喃混合均匀，然后冷却至0℃，在氮气的保护下加入100份质量分数为12％的苄胺的四氢呋喃溶液，然后搅拌反应5h，反应结束后经过滤、蒸馏、干燥得到所述磷酰胺类阻燃剂；
所述B组分的原料按重量份包括：二苯甲烷二异氰酸酯14份、六亚甲基二异氰酸酯40份。
实施例4
本发明提出的一种高强度高阻燃聚氨酯复合保温板，包括两层背衬层和位于两层背衬层之间的聚氨酯保温层，所述聚氨酯保温层采用高性能聚氨酯泡沫材料制成，所述高性能聚氨酯泡沫材料的原料由A组分和B组分组成，且A组分与B组分的重量比为2:2；
其中，所述A组分的原料按重量份包括：聚醚多元醇32份、五甲基二乙烯三胺1.2份、三羟甲基丙烷7.3份、季戊四醇6.2份、聚乙二醇8份、新癸酸铋0.3份、环烷酸铋0.23份、环己烷1.5份、水1份、有机硅泡孔稳定剂1.6份、氨基改性碳纳米管3.2份、膨胀珍珠岩11份、空心玻璃微珠10份、晶须硅10份、纳米氢氧化铝5.3份、磷酸三氯乙酯7.3份、焦磷酸哌嗪8.6份、磷酰胺类阻燃剂13份、环氧树脂10份、聚氯乙烯15份；
所述聚醚多元醇的羟值为70mgKOH/g；
所述聚乙二醇为聚乙二醇20000、聚乙二醇6000按重量比为2:3的混合物；
所述磷酰胺类阻燃剂按照以下工艺进行制备：按重量份将2份亚磷酸二苯酯、15份四氯化碳和15份四氢呋喃混合均匀，然后冷却至5℃，在氮气的保护下加入100份质量分数为5％的苄胺的四氢呋喃溶液，然后搅拌反应10h，反应结束后经过滤、蒸馏、干燥得到所述磷酰胺类阻燃剂；
所述B组分的原料按重量份包括：二苯甲烷二异氰酸酯22份、六亚甲基二异氰酸酯32份。
实施例5
本发明提出的一种高强度高阻燃聚氨酯复合保温板，包括两层背衬层和位于两层背衬层之间的聚氨酯保温层，所述聚氨酯保温层采用高性能聚氨酯泡沫材料制成，所述高性能聚氨酯泡沫材料的原料由A组分和B组分组成，且A组分与B组分的重量比为2:1.8；
其中，所述A组分的原料按重量份包括：聚醚多元醇37份、五甲基二乙烯三胺1.5份、三羟甲基丙烷6份、季戊四醇6.5份、聚乙二醇7份、异辛酸铋0.6份、环己烷1.3份、水1.2份、有机硅泡孔稳定剂1.5份、氨基改性碳纳米管3.8份、膨胀珍珠岩10份、空心玻璃微珠12份、晶须硅8份、纳米氢氧化铝6.2份、磷酸三氯乙酯7份、焦磷酸哌嗪9份、磷酰胺类阻燃剂12份、环氧树脂13份、聚氯乙烯12份；
所述聚醚多元醇的羟值为100mgKOH/g；
所述聚乙二醇为聚乙二醇20000、聚乙二醇6000按重量比为5:1的混合物；
所述磷酰胺类阻燃剂按照以下工艺进行制备：按重量份将7份亚磷酸二苯酯、12份四氯化碳和22份四氢呋喃混合均匀，然后冷却至4℃，在氮气的保护下加入100份质量分数为10％的苄胺的四氢呋喃溶液，然后搅拌反应8.5h，反应结束后经过滤、蒸馏、干燥得到所述磷酰胺类阻燃剂；
所述B组分的原料按重量份包括：二苯甲烷二异氰酸酯21份、六亚甲基二异氰酸酯35份。
以上所述，仅为本发明较佳的具体实施方式，但本发明的保护范围并不局限于此，任何熟悉本技术领域的技术人员在本发明揭露的技术范围内，根据本发明的技术方案及其发明构思加以等同替换或改变，都应涵盖在本发明的保护范围之内。

Claims (8)

1.一种高强度高阻燃聚氨酯复合保温板，包括两层背衬层和位于两层背衬层之间的聚氨酯保温层，其特征在于，所述聚氨酯保温层采用高性能聚氨酯泡沫材料制成，所述高性能聚氨酯泡沫材料的原料由A组分和B组分组成，且A组分与B组分的重量比为2:1.2-2.3；
其中，所述A组分的原料按重量份包括：聚醚多元醇20-50份、五甲基二乙烯三胺0.5-2份、三羟甲基丙烷3-12份、季戊四醇2-10份、聚乙二醇3-15份、有机铋类催化剂0.1-1份、环己烷0.5-2份、水0.5-2份、有机硅泡孔稳定剂1-5份、氨基改性碳纳米管1-5份、膨胀珍珠岩5-15份、空心玻璃微珠5-20份、晶须硅3-15份、纳米氢氧化铝2-10份、磷酸三氯乙酯3-10份、焦磷酸哌嗪5-15份、磷酰胺类阻燃剂5-15份、环氧树脂5-20份、聚氯乙烯3-20份；
所述B组分的原料按重量份包括：二苯甲烷二异氰酸酯10-25份、六亚甲基二异氰酸酯25-50份。
2.根据权利要求1所述高强度高阻燃聚氨酯复合保温板，其特征在于，所述A组分的原料按重量份包括：聚醚多元醇32-40份、五甲基二乙烯三胺1.2-1.7份、三羟甲基丙烷5.6-7.3份、季戊四醇6.2-7份、聚乙二醇5.8-8份、有机铋类催化剂0.53-0.62份、环己烷1.1-1.5份、水1-1.3份、有机硅泡孔稳定剂1.2-1.6份、氨基改性碳纳米管3.2-4份、膨胀珍珠岩8-11份、空心玻璃微珠10-15份、晶须硅5.8-10份、纳米氢氧化铝5.3-7.5份、磷酸三氯乙酯5.9-7.3份、焦磷酸哌嗪8.6-10份、磷酰胺类阻燃剂8-13份、环氧树脂10-14份、聚氯乙烯8-15份。
3.根据权利要求1或2所述高强度高阻燃聚氨酯复合保温板，其特征在于，所述A组分的原料按重量份包括：聚醚多元醇37份、五甲基二乙烯三胺1.5份、三羟甲基丙烷6份、季戊四醇6.5份、聚乙二醇7份、有机铋类催化剂0.6份、环己烷1.3份、水1.2份、有机硅泡孔稳定剂1.5份、氨基改性碳纳米管3.8份、膨胀珍珠岩10份、空心玻璃微珠12份、晶须硅8份、纳米氢氧化铝6.2份、磷酸三氯乙酯7份、焦磷酸哌嗪9份、磷酰胺类阻燃剂12份、环氧树脂13份、聚氯乙烯12份。
4.根据权利要求1-3中任一项所述高强度高阻燃聚氨酯复合保温板，其特征在于，所述聚醚多元醇的羟值为70-120mgKOH/g。
5.根据权利要求1-4中任一项所述高强度高阻燃聚氨酯复合保温板，其特征在于，所述聚乙二醇为聚乙二醇20000、聚乙二醇6000按重量比为2-5:1-3的混合物。
6.根据权利要求1-5中任一项所述高强度高阻燃聚氨酯复合保温板，其特征在于，所述有机铋类催化剂为异辛酸铋、新癸酸铋、环烷酸铋中的一种或者多种的混合物。
7.根据权利要求1-6中任一项所述高强度高阻燃聚氨酯复合保温板，其特征在于，所述磷酰胺类阻燃剂按照以下工艺进行制备：按重量份将2-10份亚磷酸二苯酯、3-15份四氯化碳和15-30份四氢呋喃混合均匀，然后冷却至0-5℃，在氮气的保护下加入100份质量分数为5-12％的苄胺的四氢呋喃溶液，然后搅拌反应5-10h，反应结束后经过滤、蒸馏、干燥得到所述磷酰胺类阻燃剂。
8.根据权利要求1-7中任一项所述高强度高阻燃聚氨酯复合保温板，其特征在于，所述环氧树脂为四溴双酚A环氧树脂。
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CN109469217A (zh) * 2018-10-09 2019-03-15 绍兴臣工新材料科技有限公司 一种高强度复合保温板及其制备方法
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CN109469217A (zh) * 2018-10-09 2019-03-15 绍兴臣工新材料科技有限公司 一种高强度复合保温板及其制备方法
CN109401280A (zh) * 2018-10-10 2019-03-01 苏州市雄林新材料科技有限公司 一种tpu幻彩膜及其制备方法
CN109593226A (zh) * 2018-11-16 2019-04-09 山东省海洋化工科学研究院 一种低收缩率阻燃聚氨酯硬质泡沫材料的配方及其制备泡沫材料的方法
CN113462080A (zh) * 2021-08-05 2021-10-01 华东理工大学 一种聚丙烯阻燃结构件的选择性激光烧结成型工艺
CN116410643A (zh) * 2022-09-30 2023-07-11 国网浙江省电力有限公司开化县供电公司 一种具有阻燃性能的绝缘电线夹头

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