CN109251296A - 一种多组分磷系复合无卤阻燃硬质聚氨酯泡沫材料 - Google Patents

一种多组分磷系复合无卤阻燃硬质聚氨酯泡沫材料 Download PDF

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CN109251296A
CN109251296A CN201811060492.8A CN201811060492A CN109251296A CN 109251296 A CN109251296 A CN 109251296A CN 201811060492 A CN201811060492 A CN 201811060492A CN 109251296 A CN109251296 A CN 109251296A
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钱立军
金尚林
王明昊
许博
辛菲
陈雅君
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Beijing Technology and Business University
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Abstract

本发明涉及一种多组分磷系复合无卤阻燃硬质聚氨酯泡沫材料，采用磷杂菲衍生物阻燃剂ABD、甲基膦酸二甲酯(DMMP)和可膨胀石墨(EG)为阻燃剂，将特定复配比例和添加比例的ABD/DMMP/EG复合阻燃剂加入聚氨酯泡沫中，制得一种多组分磷系复合无卤阻燃聚氨酯硬泡材料。本发明制得的复合无卤阻燃硬质聚氨酯泡沫材料的氧指数可达到30％以上，残炭产率由1.5％提升到23％以上，压缩强度由0.18Mpa提升到0.28Mpa以上；具有活性基团羟基的磷杂菲衍生物ABD含有一个羟基，能够与异氰酸酯反应连接于聚氨酯基体分子上，形成本质阻燃体系，使得该阻燃硬质聚氨酯泡沫的阻燃性能更加稳定；把聚氨酯泡沫材料放置在60℃烘箱30天，阻燃性能依然稳定。

Description

一种多组分磷系复合无卤阻燃硬质聚氨酯泡沫材料
技术领域
本发明涉及一种多组分磷系复合无卤阻燃硬质聚氨酯泡沫及其制备方法，主要应用于建筑保温材料领域。
背景技术
聚氨酯泡沫代表了种类繁多的热固性发泡材料，具有热导率低、保温性能优异、力学强度高、粘结性强，最重要的是其易于加工成型。因此，聚氨酯泡沫广泛地用于各领域，如建筑，石油管道，制冷等。但聚氨酯泡沫的阻燃性能较差，其氧指数(LOI)仅在16-18vol％之间，极其易燃，极大地限制了其应用，所以聚氨酯泡沫的阻燃研究引起越来越多的重视。
目前，硬质聚氨酯泡沫(RPUF)的阻燃方法有两种，使用添加型阻燃剂和反应型阻燃剂。添加型阻燃剂是在RPUF制备过程中添加含有卤素、磷、氮等阻燃元素的化合物或者具有阻燃效果的填料，这类阻燃剂不参与化学反应，选择范围广，成本低，但对泡沫的结构和性能影响较大。反应型阻燃剂是在多元醇的化学结构中引入含有阻燃功能的元素，通过化学反应使其成为RPUF分子链上的一部分，达到阻燃的目的，同时阻燃效果持久，对泡沫性能的负面影响也较小。卤素类阻燃剂燃烧后的产物对人员和环境的危害较大，所以无卤低烟阻燃剂是RPUF的发展方向。
专利申请号201610640190.2提出一种可膨胀石墨协同含磷阻燃剂的阻燃硬质聚氨酯泡沫材料，使用一种磷杂菲衍生物与可膨胀石墨复配，但是两种助剂的添加量很大，生产成本高，即使获得了好的阻燃性能，也不利于工业化生产。
本发明将两种磷系无卤阻燃剂按特定复配比例和添加比例和可膨胀石墨复配使用，其中一种是带有活性基团羟基的磷系无卤阻燃剂，在一个较低的阻燃剂添加量：18％以下，制备出一种具有多组分磷系复合无卤阻燃硬质聚氨酯泡沫材料，获得氧指数31％以上，高残炭产率，低密度，高压缩强度0.28Mpa，热稳定性好的硬质聚氨酯泡沫材料。
发明内容
本发明采用磷杂菲衍生物阻燃剂ABD、甲基膦酸二甲酯(DMMP)和可膨胀石墨(EG)为阻燃剂，将特定复配比例和添加比例的ABD/DMMP/EG复合阻燃剂加入聚氨酯泡沫中，制得一种多组分磷系复合无卤阻燃硬质聚氨酯泡材料。
其中，磷杂菲衍生物阻燃剂ABD分子结构式如下：
阻燃剂ABD具有一个羟基，能够与异氰酸酯反应成键连接于聚氨酯基体分子上，如下式，形成本质阻燃体系，使得该阻燃硬质聚氨酯泡沫中的阻燃剂本身更加稳定，不易迁移析出；
所述的阻燃剂ABD可采用丙烯醛(Acrolein)和9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物(DOPO)为原料，通过DOPO中的P-H键与丙烯醛中的醛基和双键同时进行加成反应制得。
本发明的制备方法如下：
硬质聚氨酯泡沫的制备：按重量份计，将ABD 5-10份、DMMP 15-25份按特定复配比例与80份聚醚多元醇混合，搅拌均匀后添加可膨胀石墨10-20份、发泡剂10-20份、泡沫稳定剂2～5份、催化剂3～5份。搅拌均匀，然后快速倒入异氰酸酯120-140份，搅拌均匀后倒入模具中进行发泡。
所述的聚醚多元醇包括：DSU-450L、DSU-450M、DSU-450K；所述的多异氰酸酯包括：MDI、TDI、PAPI；所述的催化剂包括：五甲基二亚乙烯三胺、N,N-二甲基环己胺、质量浓度30％的醋酸钾溶液；所述的发泡剂包括：水、HCFC-141b；所述的泡沫稳定剂是SD-622。
与现有技术相比，本发明具有如下优点和有益效果：
1.本发明的一种多组分磷系复合无卤阻燃硬质聚氨酯泡沫，将带有活性基团羟基的磷杂菲衍生物ABD和磷系无卤阻燃剂DMMP按照特定比例复配使用，制得的复合无卤硬质聚氨酯泡沫材料可获得氧指数30％以上，提高了在使用中的安全性；成炭性更好，450℃温度下，本发明中添加了ABD和DMMP的阻燃聚氨酯硬泡样品残炭产率>60％,明显高于不添加阻燃剂ABD和DMMP的聚氨酯样品的40％的残炭产率，也明显高于只添加了DMMP和可膨胀石墨阻燃剂的样品的42％的残炭产率，更高的残炭产率表明本发明阻燃聚氨酯硬泡能够减少可燃性气体释放，增强对火焰的阻隔效应，实现了更优异的阻燃效果；且具有高压缩强度，由不阻燃样品以及只添加DMMP和膨胀石墨的阻燃聚氨酯硬泡样品的0.18Mpa提升到0.28Mpa以上。且本发明中阻燃剂添加量较低，即通过添加较少的阻燃剂即可达到较好的阻燃效果。
2.具有活性基团羟基的磷杂菲衍生物ABD含有一个羟基，能够与异氰酸酯反应连接于聚氨酯基体分子上，形成本质阻燃体系，使得该阻燃硬质聚氨酯泡沫的阻燃性能更加稳定；把制得的聚氨酯泡沫材料放置在60℃烘箱30天，阻燃性能依然稳定。
具体实施方式
实施例
按重量份计，称取聚醚多元醇、异氰酸酯、可膨胀石墨、ABD、DMMP、141b发泡剂、泡沫稳定剂、催化剂。实施例的配方表如表1所示。
表1基于多组分磷系复合无卤阻燃硬质聚氨酯泡沫材料配方
原料编号 对比例1 实施例1 实施例2 实施例3 实施例4 实施例5
聚醚多元醇(份) 80 80 80 82 80 80
异氰酸酯(份) 120 120 120 130 130 140
可膨胀石墨(份) 10 10 15 15 15 17
DMMP(份) 0 25 15 20 25 24
ABD(份) 0 0 5 10 10 8
141b发泡剂(份) 10 10 10 16 16 20
泡沫稳定剂(份) 2 2 2 4 4 5
催化剂(份) 3 3 4 4 5 5
按照表1配方，将DMMP、ABD、可膨胀石墨、141b发泡剂、泡沫稳定剂、催化剂和聚醚多元醇在转速1000-2000r/min的条件下搅拌均匀；然后加入异氰酸酯，搅拌均匀倒入模具中进行发泡。
将制得的硬质聚氨酯泡沫进行切块制样，按照相应的标准进行性能测试，相关测试结果见表2。
表2复合无卤阻燃硬质聚氨酯泡沫的相关测试结果

Claims (7)

1.一种多组分磷系复合无卤阻燃硬质聚氨酯泡沫材料，其特征是：采用磷杂菲衍生物阻燃剂ABD、甲基膦酸二甲酯(DMMP)和可膨胀石墨(EG)为阻燃剂，加入聚氨酯泡沫中，制得一种多组分磷系复合无卤阻燃聚氨酯硬泡材料；其中ABD的化学结构为：
2.根据权利要求1所述的的一种多组分磷系复合无卤阻燃硬质聚氨酯泡沫材料，其特征在于，按重量份计，将ABD 5-10份、DMMP 15-25份与80份聚醚多元醇混合，搅拌均匀后添加可膨胀石墨10-20份、发泡剂10-20份、泡沫稳定剂2～5份、催化剂3～5份、异氰酸酯120-140份，搅拌均匀后倒入模具中进行发泡。
3.根据权利要求2所述的一种多组分磷系复合无卤阻燃硬质聚氨酯泡沫材料，其特征在于，所述的聚醚多元醇为DSU-450L、DSU-450M、DSU-450K中的一种或几种。
4.根据权利要求2所述的一种多组分磷系复合无卤阻燃硬质聚氨酯泡沫材料，其特征在于，所述的多异氰酸酯为MDI、TDI、PAPI中的一种或几种。
5.根据权利要求2所述的一种多组分磷系复合无卤阻燃硬质聚氨酯泡沫材料，其特征在于，所述的催化剂为五甲基二亚乙烯三胺、N,N-二甲基环己胺、质量浓度30％的醋酸钾溶液中的一种或几种。
6.根据权利要求2所述的一种多组分磷系复合无卤阻燃硬质聚氨酯泡沫材料，其特征在于，所述的发泡剂为水和HCFC-141b。
7.根据权利要求2所述的一种多组分磷系复合无卤阻燃硬质聚氨酯泡沫材料，其特征在于，所述的泡沫稳定剂为SD-622。
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