CN104892889B - 一种硬质阻燃聚氨酯泡沫 - Google Patents

一种硬质阻燃聚氨酯泡沫 Download PDF

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CN104892889B
CN104892889B CN201510364061.0A CN201510364061A CN104892889B CN 104892889 B CN104892889 B CN 104892889B CN 201510364061 A CN201510364061 A CN 201510364061A CN 104892889 B CN104892889 B CN 104892889B
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杨秀莲
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Chengde Sheng Jin Wei insulation material Co., Ltd.
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Abstract

本发明提供了一种硬质阻燃氨酯泡沫及其制备方法和用途。该聚氨酯泡沫通过包含多异氰酸酯、聚合物多元醇、扩链剂、催化剂、阻燃剂、发泡剂的组合物制得，其中，上述阻燃剂是有机磷类阻燃剂和无机阻燃剂的复配组合物。该硬质聚氨酯泡沫既优异的阻燃性能，还具备更低的烟气释放速率，可以大大提高火灾受困人员的存活几率。

Description

一种硬质阻燃聚氨酯泡沫
技术领域
本发明涉及一种硬质阻燃聚氨酯泡沫，其制备方法和用途。
背景技术
硬质聚氨酯泡沫是在发泡剂、催化剂和泡沫稳定剂等存在的情况下，由多元醇和多异氰酸酯反应制得。由于硬质聚氨酯泡沫重量轻、绝热性好等特点，所以广泛用于城市供热管道、冷藏设备等领域。近年来，随着建筑业节能材料在我国的渗入发展，硬质聚氨酯泡沫各种优良的性能被建筑行业的人士看好，该材料逐渐用于建筑屋面、墙体等建筑领域。但是未经阻燃处理的硬质聚氨酯泡沫的阻燃性能不足，还达不到建筑材料的防火阻燃要求。
从而人们纷纷需求提高硬质聚氨酯泡沫的阻燃性能的方法。添加阻燃剂是本领域常见的一种方法。常见的阻燃剂有卤系阻燃剂、氮系阻燃剂、磷系阻燃剂和无机阻燃剂。经过近十年的发展，硬质聚氨酯泡沫的阻燃性能已经达到了实际应用的要求，满足UL-94 V0的阻燃标准。根据近几年的火灾现场分析，火灾受困人员被大火直接烧死的只是很少的一部分，绝大部分遇难人员是因为火灾中释放大量烟气，中毒昏迷和致死。因此，目前急需寻求在达到所需要的阻燃性能的前提下，能够减少有毒烟气排放的建筑保温材料。
发明详述
本发明提供一种阻燃性能好且低烟气排放的硬质阻燃聚氨酯泡沫。
在本发明的一个技术方案中，提供了一种硬质阻燃聚氨酯泡沫，其由包含多异氰酸酯、聚合物多元醇、扩链剂、催化剂、发泡剂、阻燃剂的组合物制得，阻燃剂的量占整个组合物重量的25-45wt％。
本发明所使用的多异氰酸酯可以是本领域常见的各种多异氰酸酯，如六亚甲基二异氰酸酯、甲苯二异氰酸酯、二苯基甲烷二异氰酸酯，异佛尔酮二异氰酸酯等，和/或上述二异氰酸酯的三聚体或多聚体。
上述聚合物多元醇是聚醚多元醇和/或聚酯多元醇。优选，具有300-600的羟值和3.0以上的官能度。
在本发明中，扩链剂是含有多个异氰酸酯反应性基团的小分子化合物，如乙二醇、丙二醇、丁二醇、二甘醇等。
上述阻燃剂为有机磷类阻燃剂和无机阻燃剂的复配组合物，两者的质量比是60-90∶10-40。其中，无机阻燃剂是氧化锌、沸石和硼酸锌三种化合物的复配，粒径范围是20-1500nm。氧化锌、沸石和硼酸锌之间的质量比是10-25∶50-80∶10-25。
优选，氧化锌的粒径是20-200nm，优选50-100nm；沸石的粒径是800-1500nm，优选1100-1350nm；硼酸锌的粒径是100-950nm，优选400-700nm。
优选，沸石的比表面积是600-800m2/g，孔隙率≥50％。
本发明所使用的有机磷类阻燃剂是本领域常见的各种有机磷类阻燃剂，如磷酸三甲酯、磷酸三苯酯、双酚A双(二苯基)磷酸酯、9，10-二氢-9-氧杂-10-磷杂菲-10-氧化物(DOPO)、1，3-亚苯基磷酸四(2，6-二甲苯基)酯等。优选，有机磷类阻燃剂在加料前是颗粒形式，其粒径小于10mm、优选小于5mm和特别优选小于2mm。
在本发明中，催化剂选自叔胺类催化剂和金属盐类催化剂等本领域技术人员常用的催化剂。例如，叔胺是三亚乙基二胺、三乙胺、环己胺等；金属盐是乙酸钾、异辛酸钾、油酸钾、辛酸亚锡、二月桂酸二丁基锡等。
发泡剂可以是化学发泡剂或物理发泡剂，如CO2、水、异丁烷、环戊烷、正戊烷、异戊烷、二氯甲烷、氟利昂、HFC-134a、HCFC-141b等。
在本发明的组合物中，还可以根据需要加入其他常用的添加剂，如泡沫稳定剂、增韧剂、增强剂、相容剂、抗氧剂、抗紫外剂等。
本发明还提供了一种硬质阻燃聚氨酯泡沫的制备方法，其包含以下步骤
(1)将包含聚合物多元醇、扩链剂、发泡剂、硼酸锌和有机磷类阻燃剂的组合物混合均匀，得到A组分；
(2)将包含多异氰酸酯、催化剂、氧化锌和沸石组合物混合均匀，得到B组分；
(3)将A组分和B组分混合，进行聚合、发泡得到硬质聚氨酯泡沫。
本发明还提供一种将本发明的硬质聚氨酯泡沫用于建筑保温材料等各种保温材料的用途。
本发明还提供一种建筑保温材料，该材料包含本发明的硬质聚氨酯泡沫。
实施例
下面通过实施例对本发明进一步详细描述，但并不限制本发明。
本发明的实施例用到以下原料：
多异氰酸酯：具有2.7-2.8的平均官能度的多苯基多亚甲基多异氰酸酯(PAPI)；
多元醇；
多元醇：聚氧化丙烯多元醇，具有480-520的羟值和5.5的官能度；
扩链剂：乙二醇；
催化剂：二月桂酸二丁基锡(DBTDL)；
有机磷类阻燃剂：双酚A双(二苯基)磷酸酯；
氧化锌1：粒径80nm；
氧化锌2：粒径100nm；
沸石：粒径1100nm，比表面积700m2/g，孔隙率60％；
硼酸锌1：粒径400nm；
硼酸锌2：粒径700nm；
发泡剂：环戊烷；
泡沫稳定剂：硅油。
将不同量的多元醇、扩链剂、硼酸锌、有机磷类阻燃剂、发泡剂和泡沫稳定剂加入到反应器中，室温下超声混合120分钟。然后，将多异氰酸酯、催化剂、氧化锌和沸石加入到上述反应器中，加热至180℃，搅拌至开始发泡，到入50-60℃的模具中进行固化。具体见表1。
表1
对实施例1-4和对比例1-4中的产品进行性能测试，具体结果见表2。
表2
从表2的结果可以看出，实施例1-4和对比例1-4的聚氨酯泡沫均达到UL-94 V-0的阻燃性能，但是实施例1-4的烟气释放速率相对于对比例1-4大大降低。这在火灾中，大大提高了火灾受困人员的存活几率。

Claims (9)

1.一种硬质阻燃聚氨酯泡沫，其由包含多异氰酸酯、聚合物多元醇、扩链剂、催化剂、发泡剂、阻燃剂的组合物制得，阻燃剂的量占整个组合物重量的25-45wt％，其特征在于：上述阻燃剂为有机磷类阻燃剂和无机阻燃剂的复配组合物，其中，无机阻燃剂是氧化锌、沸石和硼酸锌三种化合物的复配，粒径范围是20-1500nm，氧化锌、沸石和硼酸锌的用量分别是5重量份、15重量份和6重量份，上述有机磷类阻燃剂为双酚A双(二苯基)磷酸酯，其用量为16重量份。
2.一种权利要求1中所述的硬质阻燃聚氨酯泡沫，上述聚合物多元醇是聚醚多元醇和/或聚酯多元醇。
3.一种权利要求1中所述的硬质阻燃聚氨酯泡沫，其特征在于：上述沸石的比表面积是600-800m2/g，孔隙率≥50％。
4.一种权利要求1中所述的硬质阻燃聚氨酯泡沫，其特征在于：氧化锌的粒径是20-200nm。
5.一种权利要求1中所述的硬质阻燃聚氨酯泡沫，其特征在于：沸石的粒径是800-1500nm。
6.一种权利要求1中所述的硬质阻燃聚氨酯泡沫，其特征在于：硼酸锌的粒径是100-950nm。
7.一种制备权利要求1-6的硬质阻燃聚氨酯泡沫的方法，其包含以下步骤
(1)将包含聚合物多元醇、扩链剂、发泡剂、硼酸锌和有机磷类阻燃剂混合均匀，得到A组分；
(2)将包含多异氰酸酯、催化剂、氧化锌和沸石混合均匀，得到B组分；
(3)将A组分和B组分混合，进行聚合、发泡得到硬质聚氨酯泡沫。
8.一种建筑保温材料，包含权利要求1-6中的硬质聚氨酯泡沫。
9.一种权利要求1-5中的硬质聚氨酯泡沫的用途，将其用于建筑保温材料。
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CN106084177A (zh) * 2016-07-29 2016-11-09 苏州荣昌复合材料有限公司 一种环保阻燃型硬质聚氨酯结构泡沫塑料及其应用
CN106279634A (zh) * 2016-09-06 2017-01-04 南京大学 一种建筑用高强度阻燃硬质聚氨酯保温材料及其制备方法
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CN110272560A (zh) * 2019-05-06 2019-09-24 什邡市太丰新型阻燃剂有限责任公司 一种新型无卤阻燃聚氨酯硬质泡沫及其制备方法
CN112724351B (zh) * 2020-12-25 2022-07-15 山东一诺威新材料有限公司 真空绝热板用高开孔阻燃型聚氨酯泡沫芯材及其制备方法

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