CN105669931A - 一种低烟密度高阻燃无卤聚氨酯泡沫材料及其制备方法 - Google Patents

一种低烟密度高阻燃无卤聚氨酯泡沫材料及其制备方法 Download PDF

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CN105669931A
CN105669931A CN201610051661.6A CN201610051661A CN105669931A CN 105669931 A CN105669931 A CN 105669931A CN 201610051661 A CN201610051661 A CN 201610051661A CN 105669931 A CN105669931 A CN 105669931A
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沈遒
毕生
陈玲霞
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Suzhou Inoac New Polymers Co Ltd
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Abstract

本发明提供一种低烟密度高阻燃无卤聚氨酯泡沫材料，包括A组份和B组份；A组份为异氰酸酯，B组份为组合白料。本发明不含卤素，总热释放量和最大热释放速率低，能够确保聚氨酯泡沫在燃烧时，在保证阻燃等级的前提下，拥有比传统阻燃聚氨酯泡沫塑料更低的烟密度等级。

Description

一种低烟密度高阻燃无卤聚氨酯泡沫材料及其制备方法
技术领域
本发明属于聚氨酯泡沫塑料领域，具体涉及一种低烟密度高阻燃无卤聚氨酯泡沫材料。
背景技术
硬质聚氨酯泡沫塑料因其极其出色的保温性能和施工便利性广泛地应用于建筑保温领域。但聚氨酯泡沫塑料极易燃烧，这又在一定程度上限制了其在建筑上的应用。近年来，提高聚氨酯泡沫塑料的阻燃性能成为行业一致的发展方向。
目前，主流的提高聚氨酯泡沫塑料燃烧性能的方法是向聚氨酯配方中添加阻燃剂，主要为含有卤素的添加型阻燃剂和含有卤素的反应性阻燃聚醚。例如：TCPP，TCEP以及万华化学的FR130，雅宝材料的RB～79等溴系阻燃聚醚。
向聚氨酯泡沫中添加含有卤素的阻燃剂会带来聚氨酯泡沫塑料阻燃性能的迅速提高，这样的聚氨酯泡沫塑料在燃烧时，含有卤素的阻燃剂会分解生成不燃的卤化氢气体，从而阻止燃烧，同时，卤元素会捕捉高分子链分解生成的自由基，抑制分解反应，提高聚氨酯泡沫的热稳定性。
然而，添加含有卤素阻燃剂的聚氨酯泡沫材料，在燃烧时，阻燃剂降解时会生成大量的有毒烟雾和刺激性气体，在发生火灾特别是室内火灾时，含有卤素阻燃剂的聚氨酯泡沫材料燃烧产生的极高烟密度会显著降低建筑的安全性和人员逃生几率。
发明内容
为解决以上问题，本发明提供一种低烟密度高阻燃无卤聚氨酯泡沫材料，不含卤素，能够在保证阻燃等级的前提下，拥有比传统阻燃聚氨酯泡沫塑料更低的烟密度等级。
为实现上述目的，本发明的技术方案是，一种低烟密度高阻燃无卤聚氨酯泡沫材料，其特征在于，所述低烟密度高阻燃无卤聚氨酯泡沫材料包括A组份和B组份；
A组份为异氰酸酯，B组份为组合白料；A组份与B组份的质量比为：1.2～1.5；
按照质量百分比，B组份中各成份的含量为：
其中，所述B组份中，多元醇组合物包含：
羟值为200～500，官能度为2～4的聚酯多元醇1为30～50wt％；
羟值为150～300，官能度为3～8的聚醚多元醇2为50～70wt％。
其中，所述B组份中的阻燃剂由无机阻燃剂以及有机阻燃剂组成；无机阻燃剂由氧化镁、氢氧化铝、磷酸铵、有机蒙脱土中的一种或几种构成；有机阻燃剂由DMMP、TEP中的至少一种构成。
其中，所述的聚酯多元醇1是由酸\酐和多元醇缩合而成的聚酯多元醇；所述的酸酐为邻苯二甲酸\酐、对苯二甲酸酸\酐、间苯二甲酸酸\酐、己二酸酸\酐中的一种或多种；所述的多元醇为乙二醇、丙二醇、二甘醇、一缩二丙二醇、丁二醇、甘油、三羟甲基丙烷和山梨醇中的一种或多种。
其中，所述的酸\酐优选邻苯二甲酸酐、对苯二甲酸酐中的一种或两种。
其中，所述的多元醇优选二甘醇和一缩二丙二醇中的一种或两种。
其中，所述聚醚多元醇2中的磷含量为聚醚多元醇2质量的15～25wt％；所述聚醚多元醇2是由甲基磷酸甲酯、磷酸三乙酯、乙基磷酸二乙酯中的一种或多种与二甘醇、环氧丙烷、环氧丙烷、甘油中的一种或多种聚合而成的阻燃聚醚多元醇。
其中，所述的阻燃聚醚多元醇为北京东方美龙化工科技有限公司的DM1301和DM2008中的至少一种。
其中，所述催化剂为叔胺类催化剂和/或有机盐类催化剂。
其中，所述的叔胺类催化剂为五甲基二乙烯三胺、N，N～二甲基环己胺、三乙烯二胺、三乙胺、1，4二甲基哌嗪中的一种或多种。
其中，所述有机盐类催化剂为异辛酸钾、甲酸季铵盐、醋酸钾、辛酸亚锡、二醋酸二丁基锡中的一种或多种。
其中，所述发泡剂为甲酸甲酯、1，1，1，3，3-五氟丙烷、1，1，1，3，3-五氟丁烷和1，1，1，2-四氟丁烷中的一种或多种。
其中，所述A组份为多亚甲基多苯基异氰酸酯。
其中，所述的A组份优选HUNTSMAN公司5005牌号、BASF公司M20S牌号和烟台万华公司PM400牌号中的一种或多种。
其中，所述的泡沫稳定剂为含聚硅氧烷的泡沫稳定剂，其能够在泡沫形成过程中降低混合物的表面张力，促进形成规整的泡沫结构。
其中，所述泡沫稳定剂优选美思德硅油8805、空气化工硅油LK221。
本发明还提供一种低烟密度高阻燃无卤聚氨酯泡沫材料的制备方法，包括以下步骤：
1)将多元醇组合物、水、阻燃剂、催化剂、泡沫稳定剂、发泡剂按照比例混合制得B组份；
2)将B组份和A组份异氰酸酯按质量比1∶1.2～1∶1.5混合，使用电动搅拌机10～15S，注入铝制模具中，锁闭模具，将模具温度升高至40～60℃，熟化30mins后取出样块，得到低烟密度高阻燃无卤聚氨酯泡沫材料。
本发明制备的聚氨酯泡沫塑料，使用锥形量热仪测试其总热释放量和最大热释放速率，分别为24～30MJ/m2和77～120kw/m2。烟密度等级SDR在3～15。
本发明采用无卤素添加型阻燃剂和反应型无卤阻燃聚醚多元醇以及无卤发泡剂，整个体系中不含卤素，总热释放量和最大热释放速率低，能够确保聚氨酯泡沫在燃烧时，在保证阻燃等级的前提下，拥有比传统阻燃聚氨酯泡沫塑料更低的烟密度等级。
附图说明
图1是实施例1～5的总热释放量。
图2是实施例1～5的热释放速率。
具体实施方式
下面的实施例将对本发明所提供的方法予以进一步的说明，但本发明不限于所列出的实施例，还应包括在本发明所要求的权利范围内其他任何公知的改变。
实施例
使用原料：
聚酯多元醇：江苏富盛化工材料的聚酯多元醇，牌号为CF6200，CF6300；
阻燃聚醚多元醇：北京东方美龙化工的阻燃聚醚多元醇，牌号为DM2008，DM1301；
阻燃剂组合物：氢氧化铝，TEP，DMMP，有机蒙脱土，氧化镁；
水：蒸馏水；
泡沫稳定剂：江苏美思德的硅油AK8805，空气化工的硅油LK221；
催化剂：三乙烯二胺，N，N二甲基环己胺，异辛酸钾；
发泡剂：甲酸甲酯，甲缩醛，HFC～245fa；
多亚甲基多苯基异氰酸酯：烟台万华聚氨酯的PM400，美国亨斯曼公司的5005，德国BASF公司的M20S。
表1实施例1～5制备产品的含量配方
注：表中原料皆以质量份额计算
实施例5为最优选方案。
实施例均按以下方法制备：将各原料按表1中所给的份额投入容器内搅拌均匀，将该组合聚醚与多苯基多亚甲基多异氰酸酯按组合聚醚∶异氰酸酯＝1∶1.2～1.5的重量比进行高速混合反应，制成低烟密度高阻燃无卤聚氨酯硬质泡沫材料。
将制备的低烟密度高阻燃无卤聚氨酯泡沫材料进行性能测试，测试标准如下，测试结果见图1，图2和表2。
烟密度等级GB/T8627-2007
热释放量速率ASTME1354-94
总热释放ASTME1354-94
表2实施例制品技术性能测试结果
总热释放量 最大热释放速率 烟密度
实施例1 35.49MJ/m2 131.74Kw/m2 11
实施例2 30.39MJ/m2 125.69Kw/m2 9
实施例3 25.44MJ/m2 112.56Kw/m2 12
实施例4 25.25MJ/m2 118.26Kw/m2 8
实施例5 24.35MJ/m2 77.78Kw/m2 5
从表1，表2和图2的数据可知，实施例1～5的热释放量小，热释放速率低，并具有较低的烟密度等级。其中实施例5具有尤其出色的热释放速率。
本发明不含卤素，总热释放量和最大热释放速率低，能够确保聚氨酯泡沫在燃烧时，在保证阻燃等级的前提下，拥有比传统阻燃聚氨酯泡沫塑料更低的烟密度等级，可以方便的用于建筑内部的保温聚氨酯领域。

Claims (10)

1.一种低烟密度高阻燃无卤聚氨酯泡沫材料，其特征在于，所述低烟密度高阻燃无卤聚氨酯泡沫材料包括A组份和B组份；
A组份为异氰酸酯，B组份为组合白料；A组份与B组份的质量比为：1.2～1.5；
按照质量百分比，B组份中各成份的含量为：
2.如权利要求1所述的低烟密度高阻燃无卤聚氨酯泡沫材料，其特征在于，所述B组份中，多元醇组合物包含：
羟值为200～500，官能度为2～4的聚酯多元醇1为30～50wt％；
羟值为150～300，官能度为3～8的聚醚多元醇2为50～70wt％。
3.如权利要求1所述的低烟密度高阻燃无卤聚氨酯泡沫材料，其特征在于，所述B组份中的阻燃剂由无机阻燃剂以及有机阻燃剂组成；
其中无机阻燃剂由氧化镁、氢氧化铝、磷酸铵、有机蒙脱土中的一种或几种构成；
有机阻燃剂由DMMP、TEP中的至少一种构成。
4.如权利要求2中所述的低烟密度高阻燃无卤聚氨酯泡沫材料，其特征在于，所述的聚酯多元醇1是由酸\酐和多元醇缩合而成的聚酯多元醇；所述的酸酐为邻苯二甲酸\酐、对苯二甲酸\酐、间苯二甲酸\酐、己二酸\酐中的一种或多种；所述的多元醇为乙二醇、丙二醇、二甘醇、一缩二丙二醇、丁二醇、甘油、三羟甲基丙烷和山梨醇中的一种或多种。
5.如权利要求2所述的低烟密度高阻燃无卤聚氨酯泡沫材料，其特征在于，所述聚醚多元醇2中的磷含量为聚醚多元醇2质量的15～25wt％；所述聚醚多元醇2是由甲基磷酸甲酯、磷酸三乙酯、乙基磷酸二乙酯中的一种或多种与二甘醇、环氧丙烷、环氧丙烷、甘油中的一种或多种聚合而成的阻燃聚醚多元醇。
6.如权利要求1所述的低烟密度高阻燃无卤聚氨酯泡沫材料，其特征在于，所述催化剂为叔胺类催化剂和/或有机盐类催化剂。
7.如权利要求1所述的低烟密度高阻燃无卤聚氨酯泡沫材料，其特征在于，所述发泡剂为甲酸甲酯、1，1，1，3，3-五氟丙烷、1，1，1，3，3-五氟丁烷和1，1，1，2-四氟丁烷中的一种或多种。
8.如权利要求1所述的低烟密度高阻燃无卤聚氨酯泡沫材料，其特征在于，所述A组份为多亚甲基多苯基异氰酸酯。
9.如权利要求1所述的低烟密度高阻燃无卤聚氨酯泡沫材料，其特征在于，所述的泡沫稳定剂为含聚硅氧烷的泡沫稳定剂。
10.如权利要求1～9任一所述的低烟密度高阻燃无卤聚氨酯泡沫材料聚氨酯泡沫材料的制备方法，其特征在于，包括以下步骤：
1)将多元醇组合物、水、阻燃剂、催化剂、泡沫稳定剂、发泡剂按照比例混合制得B组份；
2)将B组份和A组份按质量比1∶1.2～1∶1.5混合，使用电动搅拌机10～15s，注入铝制模具中，锁闭模具，将模具温度升高至40～60℃，熟化30mins后取出样块，得到低烟密度高阻燃无卤聚氨酯泡沫材料。
CN201610051661.6A 2016-01-26 2016-01-26 一种低烟密度高阻燃无卤聚氨酯泡沫材料及其制备方法 Pending CN105669931A (zh)

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