CN104311788B - 聚异氰脲酸酯改性高阻燃聚氨酯喷涂材料及其制备方法 - Google Patents

聚异氰脲酸酯改性高阻燃聚氨酯喷涂材料及其制备方法 Download PDF

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CN104311788B
CN104311788B CN201410597542.1A CN201410597542A CN104311788B CN 104311788 B CN104311788 B CN 104311788B CN 201410597542 A CN201410597542 A CN 201410597542A CN 104311788 B CN104311788 B CN 104311788B
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尚伟
由明
孙萌萌
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Shandong Run Yi Jin New Material Polytron Technologies Inc
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Abstract

本发明的目的是提供一种聚异氰脲酸酯改性高阻燃聚氨酯喷涂材料及其制备方法，该材料由A、B组分聚合而成，其中：A组份含聚醚多元醇4110、聚醚多元醇403、聚酯多元醇3152 LA、聚酯多元醇6320、水、泡沫稳定剂、复合胺类催化剂、复合碱金属盐类催化剂、复合阻燃剂和发泡剂，B组分为多苯基多亚甲基多异氰酸酯；在聚合过程中主要通过催化剂的选择与优化，在聚氨酯结构中引入异氰脲酸酯基团的方法提高了所制备的聚氨酯泡沫的耐热性和耐火焰贯穿性，同时也具有燃烧发烟量低的特点，该聚氨酯泡沫阻燃性能达到B1级。

Description

聚异氰脲酸酯改性高阻燃聚氨酯喷涂材料及其制备方法
技术领域
本发明涉及一种聚异氰脲酸酯改性高阻燃聚氨酯喷涂材料，属于聚氨酯泡沫材料领域。
背景技术
随着节能减排工作取得积极进展，聚氨酯材料的应用技术得到了广泛推广，对其阻燃性能的要求也越来越高，特别是GB20286-2006《公共场所阻燃制品及组件燃烧性能要求及标识》和GB8624-2006《建筑材料燃烧性能分级方法》的颁布实施后，聚氨酯泡沫材料在防火领域面临的挑战日渐严峻。聚氨酯作为一种高分子材料具有优良的保温性能但所具有的特殊结构决定了其易燃的特点，为一种易燃材料，极限氧指数只有17左右。又由于聚氨酯泡沫材料表面积大且导热系数低，其燃烧开始后不易自熄。为提高聚氨酯泡沫材料的阻燃性能，传统的做法是单一提高配方中阻燃剂的含量，虽然取得了一定效果，但是应用于建筑保温领域特别是公共场所保温场合时仍达不到国家防火要求或即使达到防火要求但烟密度和烟毒性不达标。
聚氨酯泡沫材料与火源接触时，当温度升高达到其分解温度后开始释放易燃气体，易燃气体接触空气后开始燃烧，燃烧放出的热量又进一步加速聚氨酯材料的分解，这样一直周而复始的循环下去直至聚氨酯材料燃烧完毕。
聚氨酯材料阻燃化方法有以下几种：
(1)引入反应性阻燃剂。此方法主要是在制备聚氨酯原料聚醚多元醇中引入诸如磷、卤素等阻燃元素，此方法虽然有所进展但效果仍不理想。
(2)加入添加型阻燃剂。在制备聚氨酯材料配方中加入无反应活性但具有阻燃作用的物质，该物质均匀的分布于聚氨酯泡沫体中。
(3)防火涂层法。在成型的泡沫体表面涂覆防火涂层以达到阻燃的目的，该法虽然取得了一定效果，但不属于聚氨酯本身的阻燃化方法。
(4)引入阻燃结构。在聚氨酯分子结构中引入异氰脲酸酯、恶唑烷酮、碳化二亚胺等具有阻燃功能的基团。
(5)浸渍法。将聚氨酯泡沫体浸渍到含有阻燃物质的溶液中，然后干燥，使阻燃物均匀的涂敷在泡沫体系中。由于喷涂用聚氨酯泡沫材料闭孔滤高，浸渍液很难渗透到聚氨酯体系内部，且该方法工艺复杂，因此该法效果较不理想。
发明内容
本发明的目的是提供一种聚异氰脲酸酯改性高阻燃聚氨酯喷涂材料，该喷涂材料通过配方优化和对催化剂的选择，有较好的耐热性和耐火焰贯穿性，本发明同时还提供其制备方法。
本发明所述的聚异氰脲酸酯改性高阻燃聚氨酯喷涂材料由A、B组分组成，其中：
所述A组份的原料以重量份配置为：
所述B组分为多苯基多亚甲基多异氰酸酯。
进一步地，聚酯多元醇3152LA和聚酯多元醇6320来自南京金陵斯泰潘化学有限公司。
进一步地，泡沫稳定剂优选迈图公司的Niax*Silicone L-6952。
进一步地，复合胺类催化剂选取美国气体化工产品公司的Polycat 5、Polycat 41和Dabco PT303，三者之间重量比为2:1.5:1。
进一步地，复合碱金属盐类催化剂选取美国气体化工产品公司的Polycat 46、DabcoK-15和青岛瑞诺化工有限公司的RAYNOL PC-3932，三者之间的重量比为1-1.5:0.5-1:2～4。
进一步地，复合阻燃剂为TDCPP与DMMP，二者的重量比为0.5-1.5:1。
进一步地，所述的发泡剂优选发泡剂141B。
进一步地，A、B组分的重量比为1:1.5。
本发明所述的聚异氰脲酸酯改性高阻燃聚氨酯喷涂材料的制备方法，包括以下步骤：
(1)制备A组份料：
将称量好的聚醚多元醇4110、聚醚多元醇403、聚酯多元醇3152LA、聚酯多元醇6320、水、泡沫稳定剂、复合胺类催化剂、复合碱金属盐类催化剂、复合阻燃剂、发泡剂装入混合釜中，在常温下搅拌均匀，取样检测合格后，即可装桶；
(2)使用时，将A、B组份料按A:B＝1:1.5的重量比由两个泵打入喷枪，混合后喷涂。
提高聚氨酯喷涂材料的阻燃性需通过配方优化添加阻燃剂及引入阻燃结构。本发明除了 添加复合阻燃剂外，还通过催化剂的选择与优化，将异氰脲酸酯基团引入到聚氨酯结构中，提高了聚氨酯喷涂材料的阻燃性。
引入异氰脲酸酯结构的原理是在三聚催化剂的作用下-NCO之间发生三聚反应生产异氰脲酸酯环结构，本发明通过三聚催化剂的选择与优化使得聚氨酯结构形成过程中同时生成大量的聚异氰脲酸酯，同时兼顾了发泡与凝胶反应间的平衡，生成的泡沫体泡孔结构优良。
本发明的有益效果：
(1)本发明通过三聚催化剂的选择与优化，在聚氨酯结构中引入异氰脲酸酯基团，提高聚氨酯喷涂材料耐热性和耐火焰贯穿性，同时该喷涂材料具有燃烧发烟量低的特点，满足B1级防火等级要求。
(2)采用本发明制备方法生成的泡沫体泡孔结构优良，并克服了异氰脲酸酯结构所带来的材料脆性，使得所制备的泡沫体同时具有良好的力学性能。
具体实施方式
以下结合实施例对本发明做进一步说明，但本发明的保护范围包括而不仅限于此。
实施例1
制备A组份料163公斤，分别称量：聚醚多元醇4110 30公斤，聚醚多元醇403 15公斤，聚酯多元醇3152LA 30公斤，聚酯多元醇6320 25公斤，水1公斤，泡沫稳定剂Niax*Silicone L-69522公斤，复合胺类催化剂3公斤(Polycat 5、Polycat 41和Dabco PT303，三者之间重量比为2:1.5:1)，复合碱金属盐类催化剂2公斤(Polycat 46、Dabco K-15和RAYNOL PC-3932，三者之间的重量比为1:1:2)，复合阻燃剂25公斤(TDCPP与DMMP重量比为1:1)，发泡剂141B 30公斤。将称量好的聚醚多元醇和聚酯多元醇装入混合釜中于常温下搅拌均匀，取样检测合格后，即可装桶。
使用时将A、B组份料按A:B＝1:1.5的重量比由两个泵打入喷枪混合后喷涂，所制备的泡沫部分性能指标如下：
模塑芯密度： 47kg/m3
导热系数： 0.0191W/m·K
阻燃性能： B1级
实施例2
制备A组份料174公斤，分别称量：聚醚多元醇4110 30公斤，聚醚多元醇403 10公斤，聚酯多元醇3152LA 30公斤，聚酯多元醇6320 30公斤，水1公斤，泡沫稳定剂Niax*Silicone L-6952 2公斤，复合胺类催化剂4公斤(Polycat 5、Polycat 41和Dabco PT303，三者之间重量比为2:1.5:1)，复合碱金属盐类催化剂2公斤(Polycat 46、Dabco K-15和RAYNOL PC-3932，三者之间的重量比为1:1:2)，复合阻燃剂30公斤(TDCPP与DMMP重量比为1:1)，发泡剂141B 35公斤。将称量好的聚醚多元醇和聚酯多元醇装入混合釜中于常温下搅拌均匀，取样检测合格后，即可装桶。
使用时将A、B组份料按A:B＝1:1.5的重量比由两个泵打入喷枪混合后喷涂，所制备的泡沫部分性能指标如下：
模塑芯密度： 42kg/m3
导热系数： 0.0193W/m·K
阻燃性能： B1级
实施例3
制备A组份料196公斤，分别称量：聚醚多元醇4110 35公斤，聚醚多元醇403 10公斤，聚酯多元醇3152LA 25公斤，聚酯多元醇6320 30公斤，水1.5公斤，泡沫稳定剂Niax*Silicone L-6952 2.5公斤，复合胺类催化剂4公斤(Polycat 5、Polycat 41和DabcoPT303，三者之间重量比为2:1.5:1)，复合碱金属盐类催化剂3公斤(Polycat 46、Dabco K-15和RAYNOL PC-3932，三者之间的重量比为1:1:2)，复合阻燃剂40公斤(TDCPP与DMMP重量比为0.5:1)，发泡剂141B 45公斤。将称量好的聚醚多元醇和聚酯多元醇装入混合釜中于常温下搅拌均匀，取样检测合格后，即可装桶。
使用时将A、B组份料按A:B＝1:1.5的重量比由两个泵打入喷枪混合后喷涂，所制备的泡沫部分性能指标如下：
模塑芯密度： 32kg/m3
导热系数： 0.0192W/m·K
阻燃性能： B1级 。

Claims (5)

1.一种聚异氰脲酸酯改性高阻燃聚氨酯喷涂材料，由A、B组分组成，其特征在于：
A组份以重量份配置为：
聚醚多元醇4110： 10-40
聚醚多元醇403： 5-20
聚酯多元醇3152 LA： 10-40
聚酯多元醇6320： 10-30
水： 1-2
泡沫稳定剂： 1-3
复合胺类催化剂： 1-4
复合碱金属盐类催化剂： 1-3
复合阻燃剂： 5-40
发泡剂： 10-50
B组分为多苯基多亚甲基多异氰酸酯；
复合胺类催化剂采用Polycat 5、Polycat 41和Dabco PT303，三者之间重量比为2:1.5:1；
复合碱金属盐类催化剂采用Polycat 46、Dabco K-15和RAYNOL PC-3932，三者之间的重量比为1-1.5:0.5-1:2-4；
A、B组分的重量比为1:1.5。
2.根据权利要求1所述的聚异氰脲酸酯改性高阻燃聚氨酯喷涂材料，其特征在于：泡沫稳定剂采用Niax* Silicone L-6952。
3.根据权利要求1所述的聚异氰脲酸酯改性高阻燃聚氨酯喷涂材料，其特征在于：复合阻燃剂采用TDCPP与DMMP，二者的重量比为0.5-1.5:1。
4.根据权利要求1所述的聚异氰脲酸酯改性高阻燃聚氨酯喷涂材料，其特征在于：发泡剂采用141B。
5.一种权利要求1-4任一所述的聚异氰脲酸酯改性高阻燃聚氨酯喷涂材料的制备方法，其特征在于：包括以下步骤：
（1）制备A组份料：
将称量好的聚醚多元醇4110、聚醚多元醇403、聚酯多元醇3152LA、聚酯多元醇6320、水、泡沫稳定剂、复合胺类催化剂、复合碱金属盐类催化剂、复合阻燃剂、发泡剂装入混合釜中，在常温下搅拌均匀，即可装桶；
（2）使用时，将A、B组份料按A:B=1:1.5的重量比由两个泵打入喷枪，混合后喷涂。
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