CN103641981B - 连续式生产聚氨酯板材用高阻燃组合聚醚及其制备方法 - Google Patents

连续式生产聚氨酯板材用高阻燃组合聚醚及其制备方法 Download PDF

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CN103641981B
CN103641981B CN201310714032.3A CN201310714032A CN103641981B CN 103641981 B CN103641981 B CN 103641981B CN 201310714032 A CN201310714032 A CN 201310714032A CN 103641981 B CN103641981 B CN 103641981B
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李欣
徐业峰
李明友
宁晓龙
马海晶
张佳佳
朱文静
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Shandong Inov New Material Co Ltd
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Abstract

本发明属于高分子领域，具体涉及一种连续式生产聚氨酯板材用高阻燃组合聚醚。采用阻燃聚酯多元醇、聚醚多元醇、交联剂和多种催化剂等原料复配制备得到高阻燃组合聚醚，应用于连续式生产B1级高阻燃聚氨酯板材中。本发明大大提高了生产效率，综合生产成本降低。克服了以往连续式生产B1级高阻燃板材容易造成的开裂、收缩严重、二次发泡的难点，采用本发明制备的组合聚醚生产的板材泡孔细腻，无开裂，收缩率维持在1.5%以下，且产品质量稳定，密度分布均匀，导热系数低，泡沫强度高，板面平整。本发明还提供其制备方法，工艺简单，易操作，挥发低，无三废，产品质量稳定，生产成本低，生产效率高。

Description

连续式生产聚氨酯板材用高阻燃组合聚醚及其制备方法
技术领域
本发明属于高分子领域，具体涉及一种连续式生产聚氨酯板材用高阻燃组合聚醚及其制备方法。
背景技术
目前，国家对建筑板材等行业阻燃要求越来越高，而连续式生产聚氨酯板材行业对B1级高阻燃领域还未涉及。目前建筑用车间板材、冷库一般用间歇式工艺生产高阻燃要求泡沫。优点是设备投资少，可以控制开模时间，保证高阻燃板材完全熟化后开模，不会产生内部开裂的现象。但是缺点相当明显，第一、生产效率低；第二、对聚氨酯组合料流动性要求相当高；第三、产品密度分布不均、导热系数高，质量不稳定。而连续式生产，效率高，质量稳定，综合生产成本低。但是，目前连续式生产高阻燃板材由于三聚反应缓慢，受连续线线长的限制，不能有足够长时间进行三聚反应，熟化，于是，下线后会形成泡沫开裂、三聚反应不彻底而造成的二次发泡，造成板面不平整、收缩的现象。
发明内容
本发明的目的是提供一种连续式生产聚氨酯板材用高阻燃组合聚醚，采用本发明制备的组合聚醚生产的板材泡孔细腻，无开裂，收缩率维持在1.5%以下。本发明还提供其制备方法，工艺简单，易操作，挥发低，无三废，产品质量稳定，生产成本低，生产效率高。
本发明所述的连续式生产聚氨酯板材用高阻燃组合聚醚，由组分A和组分B组成，其中：
组分A由以下重量份数的原料组成：
组分B为聚合二苯基甲烷二异氰酸酯。
其中：所述的阻燃聚酯多元醇A为官能度2、分子量为400～-500的聚酯多元醇；
所述的聚醚多元醇B为官能度4.3、分子量为550～650的聚醚多元醇。
交联剂为官能度3、分子量为130～180的交联剂。交联剂优先选用三乙醇胺。
泡沫稳定剂为非水解硅碳类表面活性剂。泡沫稳定剂优先选用B8545(赢创集团公司市售产品)。
化学发泡剂为去离子水。
催化剂为叔胺类催化剂和有机金属催化剂的混合物。其中：叔胺类催化剂为五甲基二亚乙基三胺、N,N二甲基环己胺、N,N二甲基苄胺或六氢三嗪中的一种或几种以任意比例混合；叔胺类催化剂优选五甲基二亚乙基三胺、N,N二甲基环己胺、N,N二甲基苄胺和六氢三嗪的混合物。有机金属催化剂为异辛酸钾或醋酸钾中的一种或两种以任意比例混合；有机金属催化剂优选为异辛酸钾和醋酸钾的混合物。
所述的物理发泡剂为HCFC-141b（1,1-二氯-1-氟代乙烷）。
所述的阻燃剂为添加型阻燃剂，三（2-氯丙基）磷酸酯TCPP。
所述的连续式生产聚氨酯板材用高阻燃组合聚醚的制备方法，包括以下步骤：
（1）组分A制备方法：将阻燃聚酯多元醇A、聚醚多元醇B、交联剂、稳定剂、化学发泡剂、催化剂、阻燃剂和物理发泡剂依次混合，常温搅拌1～2小时，得到组分A；
（2）组分B为聚合二苯基甲烷二异氰酸酯，市购；
（3）将组分A、B按组分A:组分B=100:185-200的重量配比混合，制备得到产品。
采用本发明制备得到的组合聚醚与异氰酸酯反应，连续式生产制得高阻燃泡沫。在达到B1级阻燃的前提下，无开裂现象，泡沫收缩率在1.5%以下，并且密度分布均匀、导热系数低、强度高、性能稳定，在节能降耗方面将会起到积极的催进作用；同时生产效率高、耗能低，大大降低了综合生产成本。
综上所述，本发明具有以下优点：
（1）本发明采用阻燃聚酯多元醇、聚醚多元醇、交联剂和多种催化剂等原料复配制备得到高阻燃组合聚醚，应用于连续式生产B1级高阻燃聚氨酯板材中。
（2）本发明大大提高了生产效率，综合生产成本降低。
（3）A组分料是在常温下进行，既节约能源又减少供能设备和繁琐的操作。
（4）A组份料利用HCFC-141b为物理发泡剂，保持泡沫性能稳定。
（5）克服了以往连续式生产B1级高阻燃板材容易造成的开裂、收缩严重、二次发泡的难点，采用本发明制备的组合聚醚生产的板材泡孔细腻，无开裂，收缩率维持在1.5%以下，且产品质量稳定，密度分布均匀，导热系数低，泡沫强度高，板面平整。
（6）本发明提供的制备方法，工艺简单，易操作，挥发低，无三废，产品质量稳定，生产成本低，生产效率高。采用本发明制备的组合聚醚生产的板材，也是在常温、常压下进行，工艺简单，易操作。
（7）本发明制备得到的产品各项指标达到国标的要求，经检测采用此组合聚醚所生产的B1级高阻燃泡沫的质量指标，可以达到：
性能完全达到了GB/T21558-2008建筑绝热用硬质聚氨酯泡沫塑料的标准、GB/T8624-2012建筑材料及制品燃烧性能B1级的要求。
具体实施方式
下面结合实施例对本发明做进一步说明。
实施例1
制备组分A，分别称量：阻燃聚酯多元醇A（2官能度，分子量为440）40公斤，聚醚多元醇B（4.3官能度，分子量为600）9.3公斤，交联剂三乙醇胺7.5公斤，B85451.4公斤（赢创市售），催化剂五甲基二亚乙烯三胺0.1公斤，N,N二甲基环己胺0.3公斤，N,N二甲基苄胺0.6公斤，六氢三嗪0.6公斤，异辛酸钾1.1公斤，醋酸钾0.8公斤，去离子水1.1公斤，HCFC-141b14.2公斤,三（2-氯丙基）磷酸酯23公斤。将称量好的阻燃聚酯多元醇A、聚醚多元醇B、交联剂、泡沫稳定剂、化学发泡剂、催化剂、物理发泡剂和阻燃剂，依次加入反应釜中，在常温下搅拌2小时，取出进行检验，满足工艺参数，发泡，即得A组份合格产品，从反应釜中取出装桶入库。
组分B为聚合二苯基甲烷二异氰酸酯，市购；
将组分A、B按组分A:组分B=100:195的重量配比混合，制备得到连续式生产聚氨酯板材用高阻燃组合聚醚泡沫，经检测产品质量指标：
实施例2
制备组分A，分别称量：阻燃聚酯多元醇A（2官能度，分子量为400）50公斤，聚醚多元醇B（4.3官能度，分子量为550）7.0公斤，交联剂三乙醇胺2.3公斤，B85452.0公斤（赢创市售），催化剂五甲基二亚乙烯三胺0.5公斤，N,N二甲基环己胺0.2公斤，异辛酸钾0.4公斤，醋酸钾0.9公斤，去离子水0.8公斤，HCFC-141b10.0公斤,三（2-氯丙基）磷酸酯15.0公斤。将称量好的阻燃聚酯多元醇A、聚醚多元醇B、交联剂、泡沫稳定剂、化学发泡剂、催化剂、物理发泡剂和阻燃剂，依次加入反应釜中，在常温下搅拌2小时，取出进行检验，满足工艺参数，发出泡沫，即得A组份合格产品，从反应釜中取出装桶入库。
组分B为聚合二苯基甲烷二异氰酸酯，市购；
将组分A、B按组分A:组分B=100:200的重量配比混合，制备得到连续式生产聚氨酯板材用高阻燃组合聚醚泡沫，经检测产品质量指标：
实施例3
制备组分A，分别称量：阻燃聚酯多元醇A（2官能度，分子量为500）43公斤，聚醚多元醇B（4.3官能度，分子量为650）15.0公斤，交联剂三乙醇胺3.2公斤，B85451.4公斤（赢创市售），催化剂五甲基二亚乙烯三胺0.1公斤，N,N二甲基苄胺0.6公斤，六氢三嗪0.7公斤，异辛酸钾1.0公斤，去离子水2.5公斤，HCFC-141b20.0公斤,三（2-氯丙基）磷酸酯30.0公斤。将称量好的阻燃聚酯多元醇A、聚醚多元醇B、交联剂、泡沫稳定剂、化学发泡剂、催化剂、物理发泡剂和阻燃剂，依次加入反应釜中，在常温下搅拌2小时，取出进行检验，满足工艺参数，发出泡沫，即得A组份合格产品，从反应釜中取出装桶入库。
组分B为聚合二苯基甲烷二异氰酸酯，市购；
将组分A、B按组分A:组分B=100:185的重量配比混合，制备得到连续式生产聚氨酯板材用高阻燃组合聚醚泡沫，经检测产品质量指标：

Claims (6)

1.一种连续式生产聚氨酯板材用高阻燃泡沫，其特征在于：由组分A和组分B组成，其中：
组分A由以下重量份数的原料组成：
阻燃聚酯多元醇A     40~50份；
聚醚多元醇B          5~15份；
交联剂                2~ 8份；
泡沫稳定剂           1.0~2.0份；
化学发泡剂          0.8~2.5份；
催化剂              2.0~4.0份；
物理发泡剂           10~20份；
阻燃剂               15~30份；
组分B为聚合二苯基甲烷二异氰酸酯；
其中：所述的阻燃聚酯多元醇A为官能度2、分子量为400~500的聚酯多元醇；
所述的聚醚多元醇B为官能度4.3、分子量为550~650的聚醚多元醇；
催化剂为叔胺类催化剂和有机金属催化剂的混合物；
叔胺类催化剂为五甲基二亚乙基三胺、N,N二甲基环己胺、N,N二甲基苄胺或六氢三嗪中的一种或几种以任意比例混合；
有机金属催化剂为异辛酸钾或醋酸钾中的一种或两种以任意比例混合；
阻燃剂为三（2-氯丙基）磷酸酯。
2.根据权利要求1所述的连续式生产聚氨酯板材用高阻燃泡沫，其特征在于：交联剂为官能度3、分子量为130~180的交联剂。
3.根据权利要求1所述的连续式生产聚氨酯板材用高阻燃泡沫，其特征在于：泡沫稳定剂为非水解硅碳类表面活性剂。
4.根据权利要求1所述的连续式生产聚氨酯板材用高阻燃泡沫，其特征在于：化学发泡剂为去离子水。
5.根据权利要求1所述的连续式生产聚氨酯板材用高阻燃泡沫，其特征在于：物理发泡剂为1,1-二氯-1-氟代乙烷。
6.一种根据权利要求1-5任一所述的连续式生产聚氨酯板材用高阻燃泡沫的制备方法，其特征在于：包括以下步骤：
（1）组分A制备方法：将阻燃聚酯多元醇A、聚醚多元醇B、交联剂、稳定剂、化学发泡剂、催化剂、阻燃剂和物理发泡剂依次混合，常温搅拌1~2小时，得到组分A；
（2）组分B为聚合二苯基甲烷二异氰酸酯；
（3）将组分A、B按组分A:组分B=100:185-200的重量配比混合，制备得到产品。
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