CN104130368A - 一种阻燃聚氨酯浇注硬质泡沫塑料板材 - Google Patents

一种阻燃聚氨酯浇注硬质泡沫塑料板材 Download PDF

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CN104130368A
CN104130368A CN201410347900.3A CN201410347900A CN104130368A CN 104130368 A CN104130368 A CN 104130368A CN 201410347900 A CN201410347900 A CN 201410347900A CN 104130368 A CN104130368 A CN 104130368A
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flame retardant
glycol
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王磊
窦忠山
王炳凯
王耀西
余郁
潘振勇
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浇注硬质泡沫塑料板材,属于聚氨酯硬质泡沫塑料板材领域。该板材由异氰酸酯组分与多元醇组分聚合而成,异氰酸酯组分与多元醇组分质量比为(140-200):100。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%、10-30%、22-52%。其可以使用聚氨酯浇注机或者电动、气动搅拌等设备把异氰酸酯组分和多元醇组分均匀混合后浇注成型,该板材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。

Description

一种阻燃聚氨酯浇注硬质泡沫塑料板材
技术领域
本发明涉及一种阻燃聚氨酯浇注硬质泡沫塑料板材。
背景技术
聚氨酯硬质泡沫塑料(硬泡)是由硬泡聚醚多元醇(聚氨酯硬泡组合聚醚又称白料),与聚合MDI(又称黑料)反应制备的。主要用于制备硬质聚氨酯泡沫塑料,广泛应用于冰箱、冷库、喷涂、太阳能、热力管线、建筑等领域。
聚氨酯硬质泡沫塑料具有优异的的物理与隔热保温性能:
1、导热系数低于岩棉、玻璃棉、聚苯板、挤塑板等建筑保温隔热材料,节电效率高;
2、重量轻,降低载荷;
3、具优良的防水性能,保温、防水合二为一;
4、设计简单、效率高、进度快、质量好、寿命长;
5、聚氨酯是惰性材料,与酸和碱都不发生反应,且不是虫类以及啮齿类动物的食物源,可保持材料性质及保温性能恒定。
聚氨酯硬泡的成型工艺一般分为喷涂和浇注两种;喷涂是使用聚氨酯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。最突出的特点是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浇注发泡,不需模具。
浇注是使用聚氨酯浇注机或者是电动、气动搅拌等设备把异氰酸酯组分和多元醇组分均匀混合后浇注到模具中,经过在模具中保温保压一段时间后取出得到硬泡制品。对比喷涂有以下主要优点:
1、可以工厂连续化生产,产品质量容易控制;
2、生产不受温度、风力等气候影响,一年四季均可进行;
3、相比喷涂,材料飞溅损耗少,对施工环境污染少;
4、可以生产需要较厚结皮、形状复杂的各种板材或线条;
5、异氰酸酯组分和多元醇组分混合比例可以调整范围比较灵活。
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、玻璃棉、膨胀珍珠岩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。
发明内容
本发明的目的在于:解决聚氨酯浇注硬泡板材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浇注硬质泡沫塑料板材。
本发明的技术解决方案是:
一种阻燃聚氨酯浇注硬质泡沫塑料板材,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质量比为(140-200):100;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10-30%;所述助剂占多元醇组分总重量的22-52%。
一种阻燃聚氨酯浇注硬质泡沫塑料板材的另一种配方:异氰酸酯组分与多元醇组分质量比为(140-200):100;多元醇组分包括聚酯多元醇、带羟基的反应型阻燃剂、助剂,这些原料占多元醇组分总质量的百分比为:聚酯多元醇6-57%,带羟基的反应型阻燃剂12-57%,助剂22-52%;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70-90%,无机微粒10-30%。
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。例如南京金陵斯泰潘化学有限公司生产的牌号为PS-3152的聚酯多元醇,江苏富盛新材料有限公司生产的牌号为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与蔗糖加环氧乙烷和/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:
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,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 Corporationin USA)。
上述无机微粒指不燃无机物,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。使用电动、气动搅拌等混合设备时候对无机微粒粒径没有要求,使用低压、高压聚氨酯浇注机等混合设备时候无机微粒小于500目并相应调整原料滤网孔径,优先采用气缸计量泵或齿轮泵或者柱塞计量泵的高压浇注机混合。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为不含羟基,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只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30%;所述无机微粒还可以同时添加到异氰酸酯组分中,添加到异氰酸酯组分中时添加量不超过多元醇组分总质量的30%。
上述双组份原料中还可以添加占有多元醇组分总质量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。
本发明为了增加聚氨酯浇注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;最后使用不燃物无机微粒,添加到异氰酸酯组分或者多元醇组分中,增加阻燃性能。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。
本发明的一种阻燃聚氨酯浇注硬质泡沫塑料板材,其最终制品的形状取决于生产中使用模具的形状,可以使用不同的模具生产各种不同花纹、造型、尺寸的阻燃聚氨酯浇注硬质泡沫塑料制品。比如如果使用球型模具,可以得到球型的阻燃聚氨酯浇注硬质泡沫塑料制品。
本发明的制备上述阻燃聚氨酯浇注硬质泡沫塑料板材的生产方法为:使用聚氨酯浇注机或者电动搅拌设备或者气动搅拌设备把异氰酸酯组分和多元醇组分均匀混合后浇注到模具中,在模具中保温保压一段时间后取出得到硬泡制品。
本发明的有益效果是:
(1)本发明的阻燃聚氨酯浇注硬质泡沫塑料板材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浇注硬质泡沫塑料板材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。
具体实施方式
下面结合实施例进一步说明本发明的实施方案,但是本发明不限于所列出的实施例,还应包括在本发明所要求的权利范围内其它任何公知的改变。
实施例1
异氰酸酯组分与多元醇组分质量比为140:100。
多元醇组分:
异氰酸酯组分选用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)90wt%,氢氧化铝微粒(320目)10wt%;
生产步骤:
(1)把4*1.2*0.6尺寸块泡模具涂好脱模剂;
(2)将多元醇组分预混合,机械搅拌5min以上;
(3)将步骤(2)所得物与异氰酸酯组分通过箱泡机(河北香河巨龙泡沫机械有限公司)充分混合,浇注140kg到模具中;
(4)合模,等待12小时,块泡充分熟化后取出;
(5)使用平切机把块泡切割成2-20cm厚度板材即可。
所制的板材颜色为均匀灰色,各种性能如下:
达到国标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
异氰酸酯组分与多元醇组分质量比为160:100;
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)82wt%,氢氧化镁微粒(200目)18wt%;
生产步骤:
(1)把1.2*0.6*0.03m尺寸板材模具使用循环水加热到45℃,并且涂好脱模剂;
(2)将多元醇组分预混合,机械搅拌0.5min以上;
(3)将步骤(2)所得物与异氰酸酯组分通过电动、气动搅拌手工搅拌充分混合,浇注1270g到模具中;
(4)立即合上板材模具,等待20min板材充分熟化后取出。
达到国标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
异氰酸酯组分与多元醇组分质量比为160:100;
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);
生产步骤:
(1)把聚氨酯板材连续生产线压机加热到55℃;
(2)然后把上下两面卷材预热、并引到压机内部;
(3)将多元醇组分预混合,机械搅拌10min以上;
(4)开动压机;
(5)将步骤(3)所得物与异氰酸酯组分通过低压浇注机(镇江奥力聚氨酯机械有限公司)混合,均匀浇注到下卷材面上;
(6)调整压机走速,保持在4-6m/min,连续生产。
所制的板材颜色为均匀淡黄色,各种物理性能如下:
实施例4
异氰酸酯组分与多元醇组分质量比为140:100。
多元醇组分:
异氰酸酯组分选用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(320目)20wt%;
生产步骤:
(1)把4*1.2*0.6尺寸块泡模具涂好脱模剂;
(2)将多元醇组分预混合,机械搅拌5min以上;
(3)将步骤(2)所得物与异氰酸酯组分通过箱泡机(河北香河巨龙泡沫机械有限公司)充分混合,浇注140kg到模具中;
(4)合模,等待12小时,块泡充分熟化后取出;
(5)使用平切机把块泡切割成2-20cm厚度板材即可。
所制的板材颜色为均匀灰色,各种性能如下:
达到国标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5
异氰酸酯组分与多元醇组分质量比为160:100;
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)70wt%,氢氧化镁微粒(200目)30wt%;
生产步骤:
(1)把1.2*0.6*0.03m尺寸板材模具使用循环水加热到45℃,并且涂好脱模剂;
(2)将多元醇组分预混合,机械搅拌0.5min以上;
(3)将步骤(2)所得物与异氰酸酯组分通过电动、气动搅拌手工搅拌充分混合,浇注1270g到模具中;
(4)立即合上板材模具,等待20min板材充分熟化后取出。
所制的板材颜色为均匀灰色,各种性能如下:
达到国标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。
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。此板材可以方便地用于建筑物外墙、屋顶、地面等保温领域的硬质聚氨酯泡沫领域。

Claims (10)

1.一种阻燃聚氨酯浇注硬质泡沫塑料板材,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质量比为(140-200):100;
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,这些原料占多元醇组分总质量的百分比为:聚酯多元醇5-40%,带羟基的反应型阻燃剂10-40%,无机微粒10-30%,助剂22-52%。
2.根据权利要求1所述的阻燃聚氨酯浇注硬质泡沫塑料板材,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和乙二醇、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所述的阻燃聚氨酯浇注硬质泡沫塑料板材,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所述的阻燃聚氨酯浇注硬质泡沫塑料板材,其特征在于:所述带羟基的反应型阻燃剂含有含有卤元素、磷元素、氮元素中的至少一种元素;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的任一种;
曼尼烯多元醇为酚类、甲醛、二乙醇胺和环氧丙烷聚合而成的多元醇;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;
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;
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。
5.根据权利要求4所述的阻燃聚氨酯浇注硬质泡沫塑料板材,其特征在于:所述无机微粒包括氢氧化铝、氢氧化镁、碳酸钙、三氧化二锑、硼酸锌微粒中的至少一种。
6.根据权利要求5所述的阻燃聚氨酯浇注硬质泡沫塑料板材,其特征在于:
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;
所述异氰酸酯组分为多亚甲基多苯基多异氰酸酯。
7.根据权利要求6所述的阻燃聚氨酯浇注硬质泡沫塑料板材,其特征在于:所述无机微粒还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30%。
8.根据权利要求7所述的阻燃聚氨酯浇注硬质泡沫塑料板材,其特征在于:所述多元醇组分或者异氰酸酯组分中还包括占多元醇组分总质量0.1-2%的色浆。
9.一种阻燃聚氨酯浇注硬质泡沫塑料板材,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质量比为(140-200):100;
所述多元醇组分包括聚酯多元醇、带羟基的反应型阻燃剂、助剂,这些原料占多元醇组分总质量的百分比为:聚酯多元醇6-57%,带羟基的反应型阻燃剂12-57%,助剂22-52%;
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70-90%,无机微粒10-30%。
10.根据权利要求9所述的阻燃聚氨酯喷涂硬质泡沫塑料,其特征在于:所述带羟基的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。
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