CN104151517A - 一种高阻燃聚氨酯改性的聚异氰脲酸酯硬泡外墙保温材料及其制备方法 - Google Patents
一种高阻燃聚氨酯改性的聚异氰脲酸酯硬泡外墙保温材料及其制备方法 Download PDFInfo
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Abstract
本发明提供了一种高阻燃聚氨酯改性的聚异氰脲酸酯硬泡外墙保温材料,是由黑料和白料按照质量比1.5-1.8:1发泡制备而得;其中:所述黑料为异氰酸酯类;所述白料由如下重量份的组分组成:结构型阻燃聚醚多元醇20-30份,聚醚多元醇40-60份,聚酯多元醇40-60份,胺类催化剂5-15份,三聚催化剂1-5份,稳定剂1-5份,无卤阻燃剂5-10份,复合无机阻燃剂5-10份,疏水性有机改性粘土3-5份,发泡剂5-10份。本发明产品同时具有较高的阻燃性和良好的力学性能,燃烧性能能够达到不燃级(A级);采用的阻燃剂毒性低,不挥发,热稳定性好,不析出,阻燃效果持久,使得本发明产品具有更高的安全性。
Description
技术领域
本发明属于外墙保温材料技术领域,具体涉及一种高阻燃聚氨酯改性的聚异氰脲酸酯硬泡外墙保温材料及其制备方法。
背景技术
我国建筑节能领域目前大规模使用的有机保温材料主要有EPS(聚苯乙烯泡沫)、PS(挤塑聚苯乙烯泡沫)和PU(聚氨酯泡沫),均属易燃有机保温材料,其优点是质轻、保温、隔热性好;缺点是防火安全性差、易老化、易燃烧且燃烧分解产生大量有毒烟雾,导致频繁引发建筑火灾事故。而在上述有机保温材料中,又以PU(聚氨酯泡沫)的应用更为广泛。
随着GB20286-2012“公共场所阻燃制品及组件燃烧性能要求及标示”和GB8624-2012“建筑材料燃烧性能分级方法”的颁布实施,聚氨酯在防火性能方面面临巨大的挑战。因此具有较高阻燃性能的聚氨酯硬泡保温材料将会得到越来越广泛的重视和应用。
目前,提高聚氨酯泡沫阻燃性的途径主要有两种:(1) 在配方中添加含氯、溴、磷等元素的阻燃剂;(2) 对聚氨酯进行改性处理。 采用添加阻燃剂的办法可将硬泡聚氨酯的氧指数提高到26左右, 国内企业应用复合阻燃剂的方法,成功地研制出氧指数为28的硬泡聚氨酯体系, 达到GB8624-2006 规定中的B1难燃级的硬泡聚氨酯。但其缺点是制成的组合聚醚保质期较短,大量阻燃剂的使用,影响了泡沫的硬度和发泡工艺,制成的保温板尺寸稳定性较差,不利于大规模推广使用。
也有采用高阻燃树脂对组合聚醚进行改性,以期在提高阻燃性的同时保持其优异的力学性能。然而改性所用的热固性酚醛树脂虽然绝热耐热性能好,但其力学性能存在较大缺陷,因此,制成的酚醛树脂和溴化环氧树脂混合白料存在着水分含量较高,尺寸不稳定,所得聚氨酯泡沫硬度不够的问题。
发明内容
本发明的目的在于针对现有技术存在的问题,提供一种高阻燃聚氨酯改性的聚异氰脲酸酯硬泡外墙保温材料。该聚氨酯硬泡材料具有优异的阻燃性能,同时还具有良好的压缩强度和尺寸稳定性。
本发明的另一目的在于提供上述高阻燃聚氨酯改性的异氰酸酯硬泡外墙保温材料的制备方法。
为此,本发明采用如下技术方案:
一种高阻燃聚氨酯改性的聚异氰脲酸酯硬泡外墙保温材料,由黑料和白料按照质量比1.5-1.8:1发泡制备而得;其中:
所述黑料为异氰酸酯类;
所述白料由如下重量份的组分组成:结构型阻燃聚醚多元醇20-30份,聚醚多元醇40-60份,聚酯多元醇40-60份,胺类催化剂5-15份,三聚催化剂1-5份,稳定剂1-5份,无卤阻燃剂5-10份,复合无机阻燃剂5-10份, 疏水性有机改性粘土3-5份,发泡剂5-10份。
所述异氰酸酯类优选甲苯二异氰酸酯(TDI)、 聚合二苯基甲烷二异氰酸酯(MDI)、多亚甲基多异氰酸酯(PAPI)中的一种或者两种以上。
所述结构型阻燃聚醚多元醇是由磷酸三苯酯、二乙醇胺和醛溶液按10-20:10-20:5-10的质量比在0-10℃下先进行反应合成含氮磷结构的起始剂,然后起始剂与环氧己烷按10-20:1-5的质量比在室温下反应制得。
所述聚醚多元醇选自聚氧化丙烯多元醇、聚四氢呋喃多元醇、四氢呋喃-氧化丙烯共聚多元醇中的一种或者两种以上。
所述聚酯多元醇选自脂肪族聚酯多元醇、芳香族聚酯多元醇或脂环族聚酯多元醇中的一种或两种以上。
所述胺类催化剂选自脂肪族胺类催化剂、脂环族胺类催化剂、醇胺类催化剂、芳香族胺类催化剂中的一种或两种以上。
其中,所述脂肪族胺类催化剂选自N,N-二甲基环己胺、双(2-二甲氨基乙基)醚、N,N,N,,N,-四甲基亚烷基二胺、三乙胺、三乙烯二胺、N,N-二甲基苄胺中的一种或两种以上;
所述脂环族胺类催化剂选自固胺、N-乙基吗啉、NMM、N,N,-二乙基哌嗪中的一种或两种以上;
所述醇胺类催化剂选自三乙醇胺和/或DMEA;
所述芳香族胺类催化剂选自吡啶和/或N,N-二甲基吡啶。
所述三聚催化剂选用2,4,6-三(二甲胺基甲基)苯酚(简称DMP—30)。
所述稳定剂为有机硅泡沫稳定剂,优选泡沫稳定剂AK-8805。
所述无卤阻燃剂为有机磷系阻燃剂,优选磷酸三(2-氯乙基)酯、甲基膦酸二甲酯、三(2,3-二溴丙基)聚异氰酸酯中一种或者两种以上。上述无卤阻燃剂与聚氨酯体系相溶性好,加入后体系能保持长时间的稳定性,并且对聚氨酯硬泡本身的力学性能影响较好,在聚氨酯硬泡系统中使用阻燃抑烟效果较好。
所述复合无机阻燃剂是由微细粒的三聚氰胺、聚磷酸铵和红磷按5-10:5-10:1-5的质量比混合而成。
所述有机改性粘土为微米级。
一种高阻燃聚氨酯改性的聚异氰脲酸酯硬泡外墙保温材料的制备方法,是在室温下,先将结构型阻燃聚醚多元醇、聚醚多元醇、聚酯多元醇、胺类催化剂、三聚催化剂、稳定剂、无卤阻燃剂均匀混合得到起始白料,发泡前半小时加入复合无机阻燃剂、有机改性粘土和发泡剂,混合均匀后即得白料;然后将黑料和白料按照质量比1.5-1.8:1混合,充分搅拌后发泡即得。
所述搅拌时间为10-20s,搅拌速度为1500-2000r/min。
本发明从影响硬泡聚氨酯泡沫阻燃效果的两个主要方面同时入手,一方面,引入微细粒的复合无机阻燃剂和微米级的有机改性粘土,在多元醇中形成了一个稳定的触变分散体系。而且复合无机阻燃剂和有机改性粘土的优越性在于毒性低,不挥发,热稳定性好,不析出,阻燃效果持久。
另一方面,在异氰酸酯即所述黑料中加入2,4,6—三(二甲胺基甲基)苯酚(DMP—30),使得异氰酸酯基团发生三聚反应,形成六元杂环, 最终能够使合成的聚氨酯改性的聚异氰脲酸酯硬质泡沫材料具有良好的阻燃性和耐热性能。
同时在组合聚醚体系中引入了结构型阻燃聚醚多元醇,使得泡沫的压缩强度、尺寸稳定性和氧指数均有明显提高。其原因在于,结构型阻燃聚醚分子链上带有刚性链段,且能参与聚氨酯凝胶反应,对泡沫交联有相当的贡献,对最终硬泡产品的压缩强度提高非常明显,使产品在较低密度下可表现出高的压缩强度。
综上,本发明的有益效果在于:本发明产品同时具有较高的阻燃性和良好的力学性能,燃烧性能能够达到不燃级(A级);采用的阻燃剂毒性低,不挥发,热稳定性好,不析出,阻燃效果持久,使得本发明产品具有更高的安全性。
具体实施方式
实施例1
一种高阻燃聚氨酯改性的聚异氰脲酸酯硬泡外墙保温材料,由黑料和白料按照质量比1.5:1发泡制备而得;
所述黑料选用甲苯二异氰酸酯(TDI);
所述白料由如下重量份的组分组成:结构型阻燃聚醚多元醇25份,聚醚多元醇40份,聚酯多元醇50份,胺类催化剂5份,三聚催化剂3份,稳定剂1份,无卤阻燃剂5份,复合无机阻燃剂10份, 疏水性有机改性粘土3份,发泡剂5份。
所述结构型阻燃聚醚多元醇是由磷酸三苯酯、二乙醇胺和甲醛溶液按10: 20:5的质量比在0-10℃下先进行反应合成含氮磷结构的起始剂,然后起始剂与环氧己烷按10:3的质量比在室温下反应制得。
所述聚醚多元醇由20份聚氧化丙烯多元醇和20份聚四氢呋喃多元醇构成;所述聚酯多元醇选用聚酯400A;所述胺类催化剂选用三乙醇胺;所述三聚催化剂选用2,4,6-三(二甲胺基甲基)苯酚;所述稳定剂选用AK-8805;所述无卤阻燃剂选用磷酸三(2-氯乙基)酯;所述复合无机阻燃剂由微细粒的三聚氰胺、聚磷酸铵和红磷按5:8:3的质量比混合而成。
所述硬泡保温材料的制备方法为:室温下,先将结构型阻燃聚醚多元醇、聚醚多元醇、聚酯多元醇、胺类催化剂、三聚催化剂、稳定剂、无卤阻燃剂均匀混合得到起始白料,发泡前半小时加入复合无机阻燃剂、有机改性粘土和发泡剂,混合均匀后即得白料;然后将黑料和白料按要求混合,充分搅拌后发泡即得;具体搅拌时间为10s,搅拌速度为1800r/min。
实施例2
一种高阻燃聚氨酯改性的聚异氰脲酸酯硬泡外墙保温材料,由黑料和白料按照质量比1.6:1发泡制备而得;
所述黑料选用聚合二苯基甲烷二异氰酸酯;
所述白料由如下重量份的组分组成:结构型阻燃聚醚多元醇20份,聚醚多元醇60份,聚酯多元醇40份,胺类催化剂10份,三聚催化剂5份,稳定剂5份,无卤阻燃剂10份,复合无机阻燃剂8份, 疏水性有机改性粘土4份,发泡剂10份。
所述结构型阻燃聚醚多元醇是由磷酸三苯酯、二乙醇胺和乙醛溶液按15: 10:10的质量比在0-10℃下先进行反应合成含氮磷结构的起始剂,然后起始剂与环氧己烷按15:5的质量比在室温下反应制得。
所述聚醚多元醇选用四氢呋喃-氧化丙烯共聚多元醇;所述聚酯多元醇选用聚酯400A;所述胺类催化剂选自N,N-二甲基环己胺;所述三聚催化剂选用2,4,6-三(二甲胺基甲基)苯酚;所述稳定剂选用AK-8805;所述无卤阻燃剂选用甲基膦酸二甲酯;所述复合无机阻燃剂由微细粒的三聚氰胺、聚磷酸铵和红磷按8:5:5的质量比混合而成。
实施例2制备方法同实施例1。
实施例3
一种高阻燃聚氨酯改性的聚异氰脲酸酯硬泡外墙保温材料,由黑料和白料按照质量比1.7:1发泡制备而得;
所述黑料选用多亚甲基多异氰酸酯;
所述白料由如下重量份的组分组成:结构型阻燃聚醚多元醇30份,聚醚多元醇50份,聚酯多元醇55份,胺类催化剂15份,三聚催化剂1份,稳定剂3份,无卤阻燃剂8份,复合无机阻燃剂5份, 疏水性有机改性粘土5份,发泡剂8份。
所述结构型阻燃聚醚多元醇是由磷酸三苯酯、二乙醇胺和甲醛溶液按20: 15:8的质量比在0-10℃下先进行反应合成含氮磷结构的起始剂,然后起始剂与环氧己烷按20:5的质量比在室温下反应制得。
所述聚醚多元醇选用聚四氢呋喃多元醇;所述聚酯多元醇选用聚酯400A;所述胺类催化剂选用固胺;所述三聚催化剂选用2,4,6-三(二甲胺基甲基)苯酚;所述稳定剂选用AK-8805;所述无卤阻燃剂选用三(2.3二溴丙基)聚异氰酸酯;所述复合无机阻燃剂由微细粒的三聚氰胺、聚磷酸铵和红磷按10:8:3的质量比混合而成。
实施例3制备方法同实施例1。
实施例4
一种高阻燃聚氨酯改性的聚异氰脲酸酯硬泡外墙保温材料,由黑料和白料按照质量比1.8:1发泡制备而得;
所述黑料选用多亚甲基多异氰酸酯;
所述白料由如下重量份的组分组成:结构型阻燃聚醚多元醇25份,聚醚多元醇45份,聚酯多元醇60份,胺类催化剂10份,三聚催化剂2份,稳定剂2份,无卤阻燃剂8份,复合无机阻燃剂5份, 疏水性有机改性粘土5份,发泡剂5份。
所述结构型阻燃聚醚多元醇是由磷酸三苯酯、二乙醇胺和甲醛溶液按20: 10:10的质量比在0-10℃下先进行反应合成含氮磷结构的起始剂,然后起始剂与环氧己烷按20:3的质量比在室温下反应制得。
所述聚醚多元醇选用聚四氢呋喃多元醇;所述聚酯多元醇选用聚酯400A;所述胺类催化剂选用DMEA;所述三聚催化剂选用2,4,6-三(二甲胺基甲基)苯酚;所述稳定剂选用AK-8805;所述无卤阻燃剂选用甲基膦酸二甲酯;所述复合无机阻燃剂由微细粒的三聚氰胺、聚磷酸铵和红磷按5:10:1的质量比混合而成。
实施例3制备方法同实施例1。
上述实施例硬泡保温材料的阻燃性能测试结果如表1所示:
上述实施例硬泡保温材料的力学性能测试结果如表2所示:
由表1检验结果,依据GB8624-2012判定可知,本发明实施例制备的硬泡保温材料的阻燃性能均达到不燃A级,具有优异的阻燃性能。根据表2结果可知,本发明硬泡保温材料同时还具有良好的力学性能。
Claims (10)
1. 一种高阻燃聚氨酯改性的聚异氰脲酸酯硬泡外墙保温材料,其特征在于,由黑料和白料按照质量比1.5-1.8:1发泡制备而得;其中:
所述黑料为异氰酸酯类;
所述白料由如下重量份的组分组成:结构型阻燃聚醚多元醇20-30份,聚醚多元醇40-60份,聚酯多元醇40-60份,胺类催化剂5-15份,三聚催化剂1-5份,稳定剂1-5份,无卤阻燃剂5-10份,复合无机阻燃剂5-10份, 疏水性有机改性粘土3-5份,发泡剂5-10份。
2.根据权利要求1所述的一种高阻燃聚氨酯改性的聚异氰脲酸酯硬泡外墙保温材料,其特征在于,所述异氰酸酯类优选甲苯二异氰酸酯、 聚合二苯基甲烷二异氰酸酯、多亚甲基多异氰酸酯中的一种或者两种以上。
3.根据权利要求1所述的一种高阻燃聚氨酯改性的聚异氰脲酸酯硬泡外墙保温材料,其特征在于,所述结构型阻燃聚醚多元醇是由磷酸三苯酯、二乙醇胺和醛溶液按10-20:10-20:5-10的质量比在0-10℃下先进行反应合成含氮磷结构的起始剂,然后起始剂与环氧己烷按10-20:1-5的质量比在室温下反应制得。
4.根据权利要求1所述的一种高阻燃聚氨酯改性的聚异氰脲酸酯硬泡外墙保温材料,其特征在于,所述聚醚多元醇选自聚氧化丙烯多元醇、聚四氢呋喃多元醇、四氢呋喃-氧化丙烯共聚多元醇中的一种或者两种以上。
5.根据权利要求1所述的一种高阻燃聚氨酯改性的聚异氰脲酸酯硬泡外墙保温材料,其特征在于,所述聚酯多元醇选自脂肪族聚酯多元醇、芳香族聚酯多元醇或脂环族聚酯多元醇中的一种或两种以上。
6.根据权利要求1所述的一种高阻燃聚氨酯改性的聚异氰脲酸酯硬泡外墙保温材料,其特征在于,所述胺类催化剂选自脂肪族胺类催化剂、脂环族胺类催化剂、醇胺类催化剂、芳香族胺类催化剂中的一种或两种以上。
7.根据权利要求1所述的一种高阻燃聚氨酯改性的聚异氰脲酸酯硬泡外墙保温材料,其特征在于,所述三聚催化剂选用2,4,6-三(二甲胺基甲基)苯酚。
8.根据权利要求1所述的一种高阻燃聚氨酯改性的聚异氰脲酸酯硬泡外墙保温材料,其特征在于,所述无卤阻燃剂为有机磷系阻燃剂,优选磷酸三(2-氯乙基)酯、甲基膦酸二甲酯、三(2,3-二溴丙基)聚异氰酸酯中一种或者两种以上。
9.根据权利要求1所述的一种高阻燃聚氨酯改性的聚异氰脲酸酯硬泡外墙保温材料,其特征在于,所述复合无机阻燃剂是由微细粒的三聚氰胺、聚磷酸铵和红磷按5-10:5-10:1-5的质量比混合而成。
10.一种权利要求1所述高阻燃聚氨酯改性的聚异氰脲酸酯硬泡外墙保温材料的制备方法,其特征在于,是在室温下,先将结构型阻燃聚醚多元醇、聚醚多元醇、聚酯多元醇、胺类催化剂、三聚催化剂、稳定剂、无卤阻燃剂均匀混合得到起始白料,发泡前半小时加入复合无机阻燃剂、有机改性粘土和发泡剂,混合均匀后即得白料;然后将黑料和白料按照质量比1.5-1.8:1混合,充分搅拌后发泡即得。
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