CN104119498B - 一种阻燃聚氨酯喷涂硬质泡沫塑料 - Google Patents

一种阻燃聚氨酯喷涂硬质泡沫塑料 Download PDF

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CN104119498B
CN104119498B CN201410347295.XA CN201410347295A CN104119498B CN 104119498 B CN104119498 B CN 104119498B CN 201410347295 A CN201410347295 A CN 201410347295A CN 104119498 B CN104119498 B CN 104119498B
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王磊
潘振勇
王炳凯
王耀西
余郁
窦忠山
李坤
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Wanhua Energysav Science and Technology Group Co Ltd
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Abstract

本发明涉及一种阻燃聚氨酯喷涂硬质泡沫塑料，属于硬质泡沫塑料领域。硬质泡沫塑料由异氰酸酯组分与多元醇组分按照体积比1:1聚合；其中的多元醇组分包括聚酯多元醇、反应型阻燃剂、无机微粒以及助剂，四者分别占多元醇组分总重量的10‑40％、5‑40％、10‑20％、24‑50％。其可以使用聚氨酯高压喷涂机喷涂成型，具有优异的阻燃性能。这种聚氨酯喷涂硬质泡沫塑料可以满足国标GB8624‑2012《建筑材料及制品燃烧性能分级》平板状建筑材料及制品的燃烧性能等级和分级判据中难燃材料B级要求，适用于对阻燃要求高的建筑墙体、屋面、地面保温等应用领域。

Description

一种阻燃聚氨酯喷涂硬质泡沫塑料
技术领域
本发明涉及一种硬质泡沫塑料，特别是一种阻燃聚氨酯喷涂硬质沫塑料。
背景技术
目前，世界建筑保温节能所采用的主要材料包括无机和有机材料两大类。无机材料主要有膨胀珍珠岩、玻璃棉、岩棉等；有机材料主要为聚苯乙烯泡沫、酚醛泡沫和聚氨酯硬泡，其中按加工方式聚苯乙烯材料又分为模塑型聚苯乙烯(EPS)和挤塑型聚苯乙烯(XPS)。
岩棉等无机材料具有不燃特性，但导热系数大，保温性能差，施工困难，资源有限，只在对防火有特殊要求时采用；EPS、XPS泡沫板价格便宜，施工方便，国内外仍在大量使用，但其为热塑性材料，受热熔融滴液，形成空腔，防火性能差，尤其在高层建筑和公共建筑方面，某些国外保险公司对使用EPS、XPS板保温的建筑采取不承保的方式加以限制；酚醛泡沫物性较差，极易粉化，应用也逐渐受限；聚氨酯硬泡材料导热系小，保温效果好，受热不熔，可以做到阻燃性能良好，施工方便，可采用喷涂、浇注和板材粘贴等方式，安全可靠，已开始被国外所广泛采用。
聚氨酯喷涂硬泡是指使用聚氨酯高压喷涂机将聚氨酯双组份原料直接以细小的雾状液滴形式喷出，涂布在物体表面上，物料快速发泡膨胀并固化，形成与基体形状一致的聚氨酯硬泡保温层。有以下主要优点：
1、对于各种形状的基材，不论是平面、立面还是顶面都可以直接实施喷涂发泡，不需模具。
2、喷涂发泡成型的保温层无接缝，绝热效果好；
3、液体原料直接喷涂在物体表面上发泡固化，与基材粘结力好；
4、固化速度快，生产施工效率高。
但是聚氨酯硬泡毕竟属于有机物，其本身的阻燃性能相对于岩棉等无机材料还有很大差距，随着有机保温材料火灾事故的多次发生，人们对其阻燃指标要求也越来越严格。
国标GB8624-2012《建筑材料及制品燃烧性能分级》中对平板状建筑材料及制品的燃烧性能等级和分级判据中难燃材料B级要求：
目前B级阻燃还很少有人达到，特别是其中GB/T20284单体燃烧试验要求：燃烧增长速率指数小于120W/s的要求几乎没有人能够达到。
提高聚氨酯硬泡阻燃等级常用的方法之一是增加双组份原料异氰酸酯组分与多元醇组分中异氰酸酯组分的比例，以增加聚氨酯硬泡反应体系的指数得到聚异氰脲酸酯(PIR)改性泡沫。但是聚氨酯高压喷涂机基本上都是按照异氰酸酯组分与多元醇组分双组份原料体积比一比一进行喷涂施工的，这就进一步增加了聚氨酯喷涂硬泡的阻燃等级提高的难度。
发明内容
本发明的目的在于解决聚氨酯喷涂硬泡在阻燃方面的不足之处，提供一种满足国标GB8624-2012《建筑材料及制品燃烧性能分级》平板状建筑材料及制品的燃烧性能等级和分级判据中难燃材料B级要求的阻燃聚氨酯喷涂硬质泡沫塑料。
本发明的技术解决方案是:
一种阻燃聚氨酯喷涂硬质泡沫塑料，由异氰酸酯组分与多元醇组分聚合而成，其特殊之处在于：
所述异氰酸酯组分与多元醇组分的体积比1:1；所述多元醇组分包括聚酯多元醇、带羟基的反应型阻燃剂、无机微粒和助剂；所述反应型阻燃剂占多元醇组分总重量的10-40％；所述聚酯多元醇占多元醇组分总重量的5-40％；所述无机微粒占多元醇组分总重量的10-20％；所述助剂占多元醇组分总重量的24-50％。
上述异氰酸酯组分与多元醇组分的体积比为1:1，符合目前主流聚氨酯高压喷涂机的混合比例为双组份体积比1:1的要求。
一种阻燃聚氨酯喷涂硬质泡沫塑料的另一种配方：异氰酸酯组分与多元醇组分的体积比1:1；多元醇组分包括聚酯多元醇、带羟基的反应型阻燃剂以及助剂；它们占多元醇组分总重量的百分比为:聚酯多元醇6-50％，带羟基的反应型阻燃剂12-50％，助剂24-50％；异氰酸酯组分包括多亚甲基多苯基多异氰酸酯以及无机微粒，占异氰酸酯组分总重量的百分比为:多亚甲基多苯基多异氰酸酯80-90％，无机微粒10-20％。
上述聚酯多元醇是由苯酐、苯二甲酸中的至少一种与乙二醇、丙二醇、丁二醇、戊二醇、己二醇、一缩二乙二醇、一缩二丙二醇、丙三醇、己三醇、三羟甲基丙烷、六羟甲基三聚氰胺中的至少一种缩聚得到的聚酯多元醇；例如江苏富盛新材料有限公司生产的牌号为CF-6320、CF-6255的聚酯多元醇；本发明选用高苯环含量的聚酯多元醇，没有使用常规的二甘醇或者甘油与蔗糖或者乙二胺加环氧乙烷和/或环氧丙烷聚合而成的聚醚多元醇，其原理是减少硬泡中易燃-CH2-链段的含量，增加苯环含量，苯环在燃烧中容易形成碳化保护层，有保护泡沫内部免受火焰攻击的作用。而且我们实验中发现，硬泡中易燃-CH2-链段含量越少，苯环含量越高，越有利于碳化保护层的形成，阻燃效果越好。
上述助剂包括物理发泡剂、泡沫表面活性剂、催化剂、液体有机阻燃剂和水；助剂中各组分的质量用量占多元醇组分总质量的百分比为：
物理发泡剂10-20％；泡沫表面活性剂0.5-1％；催化剂3-8％；液体有机阻燃剂10-20％；水0.5-1％。
上述反应型阻燃剂为含有羟基的化合物，并且含有卤元素、磷元素、氮元素中的至少一种元素。反应型阻燃剂含有可以与异氰酸酯反应的羟基，和不含羟基的液体有机阻燃剂相比，不仅起到阻燃作用，而且没有增塑作用。含有2个以上羟基的反应型阻燃剂还可以增加硬泡交联度，代替常规的二甘醇或者甘油与蔗糖或者乙二胺加环氧乙烷和/或环氧丙烷聚合而成的聚醚多元醇，不仅得到较高的泡沫强度，还可以减少硬泡中易燃-CH2-链段的含量。
上述反应型阻燃剂为曼尼烯多元醇或者含氮/磷/卤素聚醚多元醇或者四溴苯酐二醇。曼尼烯多元醇为酚类、甲醛、二乙醇胺聚合得到的的多元醇；所述的酚类为苯酚、对苯二酚、丙基酚、丁基酚、戊基酚、庚基酚、辛基酚、壬基酚和癸基酚中的至少一种，如R2470M(万华容威聚氨酯有限公司)；含氮/磷/卤素聚醚多元醇是以含氮/磷/卤素羟基化合物加环氧乙烷和/或环氧丙烷和/或环氧氯丙烷聚合而成的分子中含有氮/磷/卤素的聚醚多元醇，如Fr-130(万华容威聚氨酯有限公司)；四溴苯酐二醇为四溴邻苯二甲酸或四溴苯酐与乙二醇、丙二醇、丁二醇、戊二醇、己二醇、一缩二乙二醇、一缩二丙二醇中的至少一种缩聚得到的聚酯多元醇，如Saytex RB-79(美国雅宝公司Albemarle Corporation in USA)。
上述无机微粒指粒径小于500目的不燃无机物，比如氢氧化铝、氢氧化镁、碳酸钙、三氧化二锑、硼酸锌微粒中的至少一种，优选氢氧化铝；无机微粒不仅本身具有阻燃作用，而且和含有卤、磷、氮元素的反应型阻燃剂和液体有机阻燃剂具有很好的阻燃协同效应，能够泡沫燃烧中容易形成的碳化保护层一起保护泡沫内部免受火焰攻击。
上述液体有机阻燃剂不含羟基，为磷酸酯和/或卤代磷酸酯类有机化合物，优选甲基磷酸二甲酯、三(2-氯丙基)磷酸酯、三(2-氯乙基)磷酸酯和乙基磷酸二乙酯中的至少一种。
上述泡沫表面活性剂为硅油，硅油为聚二甲基硅氧烷，硅油可以采用迈图高新材料集团生产的牌号为L6950的硅油或者江苏美思德化学股份有限公司生产的牌号为AK8803的硅油；
上述催化剂为叔胺类催化剂和有机金属盐类催化剂；所述的叔胺类催化剂包括五甲基二乙烯三胺、N,N-二甲基环己胺、三乙烯二胺、三乙胺、1,4-二甲基哌嗪、N,N-二甲基苄胺和双二甲胺基乙基醚中的至少一种，所述的有机金属盐类催化剂包括异辛酸钾、甲酸季铵盐、醋酸钾、二月桂酸二丁基锡、辛酸亚锡、二醋酸二丁基锡和油酸钾中的至少一种；
上述物理发泡剂为1,1-二氯-1-氟乙烷、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至少一种；
上述异氰酸酯组分为多亚甲基多苯基多异氰酸酯，该多亚甲基多苯基多异氰酸酯优选万华化学集团股份有限公司生产的牌号为PM-200的多亚甲基多苯基多异氰酸酯。
上述无机微粒还可以单独添加到异氰酸酯组分中，添加量不超过多元醇组分总质量的20％。无机微粒也可以同时添加到异氰酸酯组分中，添加量不超过多元醇组分总质量的20％。
上述双组份原料中还可以添加占多元醇组分总质量0.1-2％的色浆，可以任意添加到异氰酸酯组分或者多元醇组分中。所述色浆可以采用宝美施化工(上海)有限公司生产的牌号为126-3M1665、036-2M1941的色浆，或者采用广州市墨克化工有限公司生产的牌号为P89855、P89750、P89856色浆中的至少一种。
本发明的一种阻燃聚氨酯喷涂硬质泡沫塑料的生产施工方法为：使用聚氨酯高压喷涂机把异氰酸酯组分以及多元醇组分进行混合并均匀喷涂到大坝等需要保温建筑的表面。
本发明为了增加聚氨酯喷涂硬质泡沫塑料的阻燃性，从三方面入手：一方面减少硬泡中易燃-CH2-链段的含量，没有使用常规的二甘醇或者甘油或者乙二胺与蔗糖加环氧乙烷和/或环氧丙烷聚合而成的聚醚多元醇；另一方面使用含有磷溴阻燃元素的反应型阻燃剂与高苯环含量的聚酯多元醇；最后使用粒径小于500目的不燃物无机微粒，添加到异氰酸酯组分或者多元醇组分中，不仅能够增加阻燃性能，而且能够调节双组份的体积配比，实现双组份原料混合施工比例为体积比1:1；通过这三方面，我们得到了可以满足国标GB8624-2012《建筑材料及制品燃烧性能分级》中对平板状建筑材料及制品的燃烧性能等级和分级判据中难燃材料B级要求：
本发明的有益效果是：
(1)本发明的阻燃聚氨酯喷涂硬质泡沫塑料，使用聚氨酯高压喷涂机双组份1:1喷涂成型，具有优异的阻燃性能：可以满足国标GB8624-2012《建筑材料及制品燃烧性能分级》平板状建筑材料及制品的燃烧性能等级和分级判据中难燃材料B级要求。
(2)本发明的阻燃聚氨酯喷涂硬质泡沫塑料，适用于建筑保温等对阻燃要求高的建筑墙体、屋面、地面保温等应用领域。
具体实施方式
以下给出本发明的具体实施方式，用来对本发明做进一步的说明。
实施例1
多元醇组分：
异氰酸酯组分：多亚甲基多苯基多异氰酸酯PM-200(万华化学集团股份有限公司)；
异氰酸酯组分与多元醇组分体积比为1:1；
设备：H25喷涂机(美国Graco公司)。
生产步骤：
(1)把喷涂机两组分提料泵分别插到对应原料桶中、打开电源及空压机等准备工作；
(2)设定喷涂机原料及管线加热温度50℃；
(3)使用喷枪把原料喷在基材上，喷涂5层以上完成8cm厚度泡沫；
所制的泡沫颜色为均匀灰色，性能如下：
测得的阻燃性能指标满足国标GB8624-2012《建筑材料及制品燃烧性能分级》平板状建筑材料及制品的燃烧性能等级和分级判据中难燃材料B级要求。
实施例2
多元醇组分：
异氰酸酯组分：多亚甲基多苯基多异氰酸酯PM-200(万华化学集团股份有限公司)80wt％，氢氧化铝微粒(800目)20wt％；
设备：H25喷涂机(美国Graco公司)；
异氰酸酯组分与多元醇组分体积比为1:1；
生产步骤：
(1)把喷涂机两组分提料泵分别插到对应原料桶中、打开电源及空压机等准备工作；
(2)设定喷涂机原料及管线加热温度50℃；
(3)使用喷枪把原料喷在基材上，喷涂5层以上完成8cm厚度泡沫；
所制的泡沫颜色为均匀淡黄色，性能如下：
测得的阻燃性能指标满足国标GB8624-2012《建筑材料及制品燃烧性能分级》平板状建筑材料及制品的燃烧性能等级和分级判据中难燃材料B级要求。
实施例3
多元醇组分：
异氰酸酯组分：多亚甲基多苯基多异氰酸酯PM-200(万华化学集团股份有限公司)88wt％，氢氧化铝微粒(800目)10wt％；色浆036-2M1941(宝美施化工(上海)有限公司)2wt％；
异氰酸酯组分与多元醇组分体积比为1:1；
设备：H25喷涂机(美国Graco公司)
生产步骤：
(1)把喷涂机两组分提料泵分别插到对应原料桶中、打开电源及空压机等准备工作；
(2)设定喷涂机原料及管线加热温度50℃；
(3)使用喷枪把原料喷在基材上，喷涂5层以上完成8cm厚度泡沫；
所制的泡沫颜色为均匀灰色，性能如下：
实施例四
多元醇组分：
种类 牌号与厂家/名称 质量份数
反应型阻燃剂 RB-79(美国雅宝公司) 50
聚酯多元醇 CF-6320(江苏富盛新材料有限公司) 6
物理发泡剂 1,1-二氯-1-氟乙烷 18.8
硅油 L6950(迈图高新材料集团) 0.8
水 蒸馏水或者市政自来水 0.6
催化剂 三乙烯二胺 2.5
催化剂 二月桂酸二丁基锡 0.6
催化剂 醋酸钾 0.6
液体有机阻燃剂 乙基磷酸二乙酯 20
色浆 036-2M1941(宝美施化工(上海)有限公 0.1
司)
合计： 100
异氰酸酯组分：多亚甲基多苯基多异氰酸酯PM-200(万华化学集团股份有限公司)85wt％，氢氧化铝微粒(800目)15wt％；
异氰酸酯组分与多元醇组分体积比为1:1。
生产设备及步骤同实施例三，
所制的泡沫颜色为均匀灰色，性能如下：
实施例五
多元醇组分：
异氰酸酯组分：多亚甲基多苯基多异氰酸酯PM-200(万华化学集团股份有限公司)80wt％，氢氧化铝微粒(800目)20wt％；
异氰酸酯组分与多元醇组分体积比为1:1。
生产设备及步骤同实施例三，
所制的泡沫颜色为均匀灰色，性能如下：
以上实施例的产品具有较高的抗压强度和优异的阻燃性能，阻燃水平达到GB/T8624-2012中B级阻燃要求。此原料可以方便地用于建筑物外墙等保温领域的硬质聚氨酯泡沫领域。

Claims (5)

1.一种阻燃聚氨酯喷涂硬质泡沫塑料，由异氰酸酯组分与多元醇组分聚合而成，其特征在于：
所述异氰酸酯组分与多元醇组分的体积比1:1；
所述多元醇组分由聚酯多元醇、带羟基的反应型阻燃剂、无机微粒和助剂组成；它们占多元醇组分总重量的百分比为，聚酯多元醇5-40％，带羟基的反应型阻燃剂10-40％，无机微粒10-20％，助剂24-50％；
所述异氰酸酯组分包括多亚甲基多苯基多异氰酸酯以及无机微粒，占异氰酸酯组分总重量的百分比为:多亚甲基多苯基多异氰酸酯80-90％，无机微粒10-20％；
所述无机微粒指粒径小于500目的不燃无机物，为氢氧化铝、氢氧化镁、碳酸钙、三氧化二锑、硼酸锌微粒中的至少一种；
所述反应型阻燃剂为曼尼烯多元醇或者含氮/磷/卤素聚醚多元醇或者四溴苯酐二醇中的至少一种。
2.根据权利要求1所述的阻燃聚氨酯喷涂硬质泡沫塑料，其特征在于：所述聚酯多元醇是由苯酐、苯二甲酸中的至少一种与乙二醇、丙二醇、丁二醇、戊二醇、己二醇、一缩二乙二醇、一缩二丙二醇、丙三醇、己三醇、三羟甲基丙烷、六羟甲基三聚氰胺中的至少一种缩聚得到的聚酯多元醇。
3.根据权利要求1或2所述的阻燃聚氨酯喷涂硬质泡沫塑料，其特征在于：所述助剂包括物理发泡剂、泡沫表面活性剂、催化剂、液体有机阻燃剂和水；助剂中各组分的质量用量占多元醇组分总质量的百分比为：
4.根据权利要求3所述的阻燃聚氨酯喷涂硬质泡沫塑料，其特征在于：
所述物理发泡剂为1,1-二氯-1-氟乙烷、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至少一种；
所述泡沫表面活性剂为硅油，硅油为聚二甲基硅氧烷；
所述催化剂为叔胺类催化剂和有机金属盐类催化剂；所述的叔胺类催化剂包括五甲基二乙烯三胺、N,N-二甲基环己胺、三乙烯二胺、三乙胺、1,4-二甲基哌嗪、N,N-二甲基苄胺和双二甲胺基乙基醚中的至少一种，所述的有机金属盐类催化剂包括异辛酸钾、甲酸季铵盐、醋酸钾、二月桂酸二丁基锡、辛酸亚锡、二醋酸二丁基锡和油酸钾中的至少一种；
所述液体有机阻燃剂不含羟基，为磷酸酯和/或卤代磷酸酯类有机化合物；
所述异氰酸酯组分为多亚甲基多苯基多异氰酸酯。
5.根据权利要求4所述的阻燃聚氨酯喷涂硬质泡沫塑料，其特征在于：所述多元醇组分或者异氰酸酯组分中还可以添加占多元醇组分总质量0.1-2％的色浆。
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