CN105384902A - 一种建筑保温用新型环保阻燃聚氨酯材料 - Google Patents
一种建筑保温用新型环保阻燃聚氨酯材料 Download PDFInfo
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Abstract
本发明涉及一种建筑保温用环保阻燃聚氨酯材料,其包括多异氰酸酯、聚醚多元醇、扩链剂、催化剂、发泡剂、阻燃剂,其中发泡剂为物理发泡剂和化学发泡剂,物理发泡剂为HFC-245fa和HFC-365mfc,化学发泡剂为水,阻燃剂包括有机硅阻燃剂和膨胀型阻燃剂,有机硅阻燃剂包括含有9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物的聚倍半硅氧烷,膨胀型阻燃剂为以多聚磷酸/二氨基双酚A/三聚氰胺为原料的膨胀型阻燃剂。本发明的产品可用于建筑保温领域,具有阻燃性能好、对环境污染小、适于喷涂工艺等特点。
Description
技术领域
本发明涉及一种建筑保温用新型环保阻燃聚氨酯材料,属于建筑工业用高分子材料领域。
背景技术
聚氨酯由多元醇和多异氰酸酯反应制得,利用不同原料带来的不同结构和性能,可制成从液体到固体、从软质到硬质的涂料、粘合剂、塑料、纤维、橡胶等各种不同性能和类型的制品,应用十分广泛且增长迅速。聚氨酯硬质泡沫塑料是聚氨酯制品中重要的组成部分,与其它泡沫塑料相比,具有原料丰富、制备工艺简便、综合性能优良、使用范围广泛等优势。尤其是其极低的导热系数,可达到0.022-0.025W/K·m,使其成为现今使用效果最好的保温隔热材料。
为达到外墙和屋顶对保温隔热的要求必须在结构中采用低传热的材料,传统的围护结构材料很难达到隔热保温要求。硬质聚氨酯泡沫塑料是目前性能最好的建筑保温材料,与聚苯乙烯泡沫塑料等其它材料相比,其拥有导热系数更低、与无机材料粘接性更好、施工方式多样化、在自然条件下的稳定性及耐久性更好的优点。虽然聚氨酯硬泡目前价格大大高于PS塑料,但聚氨酯在整个外墙保温体系的应用中可以利用其自身粘合以及运输方便等特点,使得很多产品综合成本接近于PS泡沫。从长远角度看,节能所带来的利益大于使用聚氨酯硬泡时建筑成本的提高。国际发达国家的建筑节能保温材料中,聚氨酯占据75%的市场份额,而我国建筑保温材料中目前只有约10%采用聚氨酯泡沫。与发达国家消费结构相比,国内聚氨酯硬泡在建筑领域的发展空间巨大。
聚氨酯硬泡属易燃材料,且燃烧过程中放出HCN、CO等有毒气体,给灭火及火场逃生都带来很大的困难,所以聚氨酯泡沫的阻燃研究(尤其是用于建筑行业时)一直是聚氨酯材料改性的热点。央视大火、上海大火等重大灾害更加强了人们对建筑外墙保温材料阻燃性能的研究。近年来国内外相继开发出了许多阻燃方法,如南京红宝丽的申请CN101508939A通过使用具有结构阻燃能力的蓖麻油聚醚多元醇来达到阻燃目的,拜尔公司的申请CN1082062A、苏普雷斯塔的申请CN101395209A等则外添加阻燃剂来阻燃。由于卤原子的环境污染问题,近年来无卤阻燃是主流的研究方向。
聚氨酯硬泡发泡剂主要分为化学发泡剂和物理发泡剂。化学发泡剂主要是水,其臭氧破坏效应ODP值为零,而且工艺简便,对设备的要求低,但全水发泡体系有组合聚醚粘度较大,泡沫尺寸稳定性较低、因产生大量脲键而使泡沫粉化且导热系数上升等缺点。物理发泡剂中,氟里昂是理想的发泡剂,但氯氟烃对大气臭氧层有严重的破坏作用。
另外,聚氨酯外墙保温层通常采用喷涂方式进行生产,这易受大风、下雨、下雪等外界条件影响,尤其是对于高阻燃聚氨酯建筑外墙产品,由于添加了较大量的阻燃剂,喷涂的生产方式常难以达到实际应用要求。
发明内容
针对以上现有技术中存在的问题,本发明提供了一种建筑保温用新型环保阻燃聚氨酯材料,其具有阻燃性能好、环境污染小的优点,且适用于连续喷涂施工方式。
本发明还提供了一种建筑保温用新型环保阻燃聚氨酯材料的制备方法。
本发明解决其技术问题所采用的技术方案是:一种聚氨酯组合物,包括多异氰酸酯、聚醚多元醇、扩链剂、催化剂、发泡剂、阻燃剂,其特征在于,其中所述阻燃剂包括有机硅阻燃剂和膨胀型阻燃剂。
在所述聚氨酯组合物中,所述多异氰酸酯为本领域常用的多异氰酸酯,如甲苯二异氰酸酯TDI、二苯基甲烷二异氰酸酯MDI、多亚甲基多苯基多异氰酸酯PAPI、异佛尔酮二异氰酸酯IPDI、六亚甲基二异氰酸酯HDI、氢化MDI等,优选其中的一种或多种的混合物。
在所述聚氨酯组合物中,所述聚醚多元醇的数均分子量为500-3000,羟值为20-250mgKOH/g,优选一种以上的聚醚多元醇混合使用。
在所述聚氨酯组合物中,所述扩链剂为直链二元醇、直链二元胺等,如乙二醇、1,3丙二醇、1,4-丁二醇、乙二胺,优选一种以上的扩链剂混合使用。
在所述聚氨酯组合物中,所述催化剂可为锡类催化剂,如二月桂酸二丁基锡、辛酸亚锡等,也可为胺类催化剂,如三乙胺、三乙醇胺、三亚甲基二胺等,优选锡类催化剂与胺类催化剂共用,二者重量比为锡类催化剂:胺类催化剂=1:0.5-1.2。
在所述聚氨酯组合物中,所述发泡剂可包括物理发泡剂和化学发泡剂,物理发泡剂为无氯氟利昂HFC-245fa、HFC-365mfc等,化学发泡剂为水,优选物理发泡剂与化学发泡剂共用,二者重量比为物理发泡剂:化学发泡剂=1:0.4-1。
在所述聚氨酯组合物中,所述有机硅阻燃剂优选包括含有9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物(DOPO)的聚倍半硅氧烷(POSS)的阻燃剂,膨胀型阻燃剂优选以多聚磷酸/二氨基双酚A/三聚氰胺为原料的膨胀型阻燃剂。
在所述聚氨酯组合物中,还可进一步包括泡沫稳定剂,如硅类泡沫稳定剂。
在所述聚氨酯组合物中,各组分以重量份计的用量分别为90-100份聚醚多元醇、10-15份扩链剂、0.2-1份催化剂、3-7份发泡剂、7-10份有机硅阻燃剂、10-15份膨胀型阻燃剂,多异氰酸酯以NCO/OH为0.98-1.1的量存在;
优选95-100份聚醚多元醇、12-15份扩链剂、0.5-0.8份催化剂、5-7份发泡剂、8-10份有机硅阻燃剂、10-12份膨胀型阻燃剂。
在本发明的聚氨酯组合物中,发明人通过长期的研究和大量的试验,获得了组合物的优化配方,组合物中各组分通过相互协同作用,使得制品具有优良的综合性能。其中,有机硅阻燃剂在制品燃烧时有向制品表面迁移的倾向,同时迅速聚集成炭,从而阻止进一步的燃烧。膨胀型阻燃剂在制品燃烧时会在制品表面形成一层均匀的炭质泡沫层,起到隔热、隔氧、抑烟、防滴的作用,且低烟、低毒,无腐蚀性气体产生。另外,本发明的有机硅阻燃剂和膨胀型阻燃剂中均含磷,可进一步提高材料的阻燃性能。
本发明中,通过将物理发泡剂和化学发泡剂共用,实现了良好的发泡效果,既能获得满足需求的发泡倍率,又没有因使用水作发泡剂而使泡沫性能劣化。同时,将有机锡类催化剂与胺类催化剂共用,可将发泡速度控制在合理区间内,使泡沫基体的固化与泡孔体积增长相配合,适用于建筑外墙喷涂保温材料的连续施工,提高了生产效率。
由上述本发明的聚氨酯组合物可制得建筑保温用新型环保阻燃聚氨酯材料,具体制备方法为:按配方准备相应重量的各组分,将除多异氰酸酯之外的组分充分搅拌混合,再加入多异氰酸酯,混合反应,得到产品。
与现有技术相比,本发明所得建筑保温用新型环保阻燃聚氨酯材料的优点为:
(1)采用对环境几乎无污染的发泡剂和无卤的阻燃体系,实现环保的目的;
(2)通过选用特定的阻燃体系,获得具有高阻燃性能的产品;
(3)通过催化剂、发泡剂等反应原料的配合,实现迅速发泡与固化,适用于喷涂工艺,提高了生产效率。
具体实施方式
为了加深对本发明的理解,下面将结合实施例对本发明作进一步详述。
实施例1
制备聚氨酯组合物,其中以重量份数计,组合物包括75份聚醚多元醇A,其数均分子量为500,羟值为224mgKOH/g,20份聚醚多元醇B,其数均分子量为2000,羟值为56mgKOH/g,12份1,4-丁二醇,0.5份二月桂酸二丁基锡,0.3份三亚甲基二胺,2份HFC-245fa,2份HFC-365mfc,2份水,0.5份硅类泡沫稳定剂,10份含有DOPO的POSS,10份以多聚磷酸/二氨基双酚A/三聚氰胺为原料的膨胀型阻燃剂,多异氰酸酯为PAPI,以NCO/OH为1.05的量存在。上述原料混合反应得到制品,测试其各项性能。
实施例2
制备聚氨酯组合物,其中以重量份数计,组合物包括75份聚醚多元醇A,其数均分子量为500,羟值为224mgKOH/g,20份聚醚多元醇B,其数均分子量为2000,羟值为56mgKOH/g,12份1,4-丁二醇,0.4份二月桂酸二丁基锡,0.4份三亚甲基二胺,2份HFC-245fa,2.5份HFC-365mfc,2.5份水,0.5份硅类泡沫稳定剂,8份含有DOPO的POSS,12份以多聚磷酸/二氨基双酚A/三聚氰胺为原料的膨胀型阻燃剂,多异氰酸酯为PAPI,以NCO/OH为1.05的量存在。上述原料混合反应得到制品,测试其各项性能。
对比例1
制备聚氨酯组合物,其中以重量份数计,组合物包括75份聚醚多元醇A,其数均分子量为500,羟值为224mgKOH/g,20份聚醚多元醇B,其数均分子量为2000,羟值为56mgKOH/g,12份1,4-丁二醇,0.5份二月桂酸二丁基锡,0.3份三亚甲基二胺,6份水,0.5份硅类泡沫稳定剂,10份含有DOPO的POSS,10份以多聚磷酸/二氨基双酚A/三聚氰胺为原料的膨胀型阻燃剂,多异氰酸酯为PAPI,以NCO/OH为1.05的量存在。上述原料混合反应得到制品,测试其各项性能。
对比例2
制备聚氨酯组合物,其中以重量份数计,组合物包括75份聚醚多元醇A,其数均分子量为500,羟值为224mgKOH/g,20份聚醚多元醇B,其数均分子量为2000,羟值为56mgKOH/g,12份1,4-丁二醇,1份三亚甲基二胺,2份HFC-245fa,2份HFC-365mfc,2份水,0.5份硅类泡沫稳定剂,10份含有DOPO的POSS,10份以多聚磷酸/二氨基双酚A/三聚氰胺为原料的膨胀型阻燃剂,多异氰酸酯为PAPI,以NCO/OH为1.05的量存在。上述原料混合反应得到制品,测试其各项性能。
对比例3
制备聚氨酯组合物,其中以重量份数计,组合物包括75份聚醚多元醇A,其数均分子量为500,羟值为224mgKOH/g,20份聚醚多元醇B,其数均分子量为2000,羟值为56mgKOH/g,12份1,4-丁二醇,0.5份二月桂酸二丁基锡,0.3份三亚甲基二胺,2份HFC-245fa,2份HFC-365mfc,2份水,0.5份硅类泡沫稳定剂,30份磷酸三苯酯,多异氰酸酯为PAPI,以NCO/OH为1.05的量存在。上述原料混合反应得到制品,测试其各项性能。
对比例4
制备聚氨酯组合物,其中以重量份数计,组合物包括75份聚醚多元醇A,其数均分子量为500,羟值为224mgKOH/g,20份聚醚多元醇B,其数均分子量为2000,羟值为56mgKOH/g,12份1,4-丁二醇,0.5份二月桂酸二丁基锡,0.3份三亚甲基二胺,2份HFC-245fa,2份HFC-365mfc,2份水,0.5份硅类泡沫稳定剂,25份十溴联苯醚,10份三氧化二锑,多异氰酸酯为PAPI,以NCO/OH为1.05的量存在。上述原料混合反应得到制品,测试其各项性能。
实施例1-2(EX1-EX2)及对比例1-4(CEX1-CEX4)的性能测试结果如表1所示,其中均使用聚氨酯领域通用的测试方法。
表1
性能 | EX1 | EX2 | CEX1 | CEX2 | CEX3 | CEX4 |
固化时间(s) | 41 | 42 | 45 | 120 | 45 | 50 |
导热系数(W/K·m) | 0.024 | 0.023 | 0.039 | 0.037 | 0.026 | 0.030 |
氧指数 | 31 | 31 | 30 | 30 | 25 | 25 |
阻燃级别UL-94 | V0 | V0 | V0 | V0 | V1 | V1 |
喷涂工艺 | 适用 | 适用 | 发泡倍率小 | 混合液流延 | 混合液流延 | 混合液流延 |
由实施例1-2和对比例1-4的对比可以看出,符合本申请限定的范围的实施例1和2,所得聚氨酯泡沫材料具有优异的阻燃性能、保温性能和施工性质,且对环境的污染小。而对比例1中只使用水作发泡剂,导热系数高,发泡倍率小,难以满足建筑保温的要求。对比例2仅使用胺类催化剂,发泡和固化速度慢,不适用于喷涂工艺。对比例3仅使用磷系阻燃剂,对比例4使用含卤阻燃剂,阻燃效果比本发明差,且为达到一定的阻燃效果,阻燃剂添加量大,改变了反应体系的粘度,影响了喷涂工艺的正常进行。
需要强调的是,本发明所述的实施例是说明性的,而不是限定性的。因此,本发明并不限于具体实施方式中所述的实施例,任何熟悉本领域的技术人员在本发明所揭露的技术范围内,可不经过创造性劳动想到的变化或替换,都应涵盖在本发明的保护范围之内。
Claims (10)
1.一种聚氨酯组合物,包括多异氰酸酯、聚醚多元醇、扩链剂、催化剂、发泡剂、阻燃剂,其特征在于,其中所述阻燃剂包括有机硅阻燃剂和膨胀型阻燃剂。
2.根据权利要求1所述的聚氨酯组合物,其中所述多异氰酸酯为TDI、MDI、PAPI、IPDI、HDI、氢化MDI中的一种或多种的混合物,所述聚醚多元醇的数均分子量为500-3000,羟值为20-250mgKOH/g。
3.根据权利要求1-2中任一项所述的聚氨酯组合物,其中所述扩链剂为乙二醇、1,3丙二醇、1,4-丁二醇、乙二胺中的一种或多种的混合物。
4.根据权利要求1-3中任一项所述的聚氨酯组合物,其中所述催化剂为锡类催化剂和胺类催化剂,锡类催化剂为二月桂酸二丁基锡、辛酸亚锡和一种或多种的混合物,胺类催化剂为三乙胺、三乙醇胺、三亚甲基二胺的一种或多种的混合的,锡类催化剂与胺类催化剂的重量比为1:0.5-1.2。
5.根据权利要求1-4中任一项所述的聚氨酯组合物,其中所述发泡剂为物理发泡剂和化学发泡剂,物理发泡剂为HFC-245fa和HFC-365mfc,化学发泡剂为水,物理发泡剂与化学发泡剂的重量比为1:0.4-1。
6.根据权利要求1-5中任一项所述的聚氨酯组合物,其中所述有机硅阻燃剂包括含有9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物的聚倍半硅氧烷,膨胀型阻燃剂为以多聚磷酸/二氨基双酚A/三聚氰胺为原料的膨胀型阻燃剂。
7.根据权利要求1-6中任一项所述的聚氨酯组合物,其中各组分以重量份计的用量分别为90-100份聚醚多元醇、10-15份扩链剂、0.2-1份催化剂、3-7份发泡剂、7-10份有机硅阻燃剂、10-15份膨胀型阻燃剂,多异氰酸酯以NCO/OH为0.98-1.1的量存在;
优选95-100份聚醚多元醇、12-15份扩链剂、0.5-0.8份催化剂、5-7份发泡剂、8-10份有机硅阻燃剂、10-12份膨胀型阻燃剂。
8.根据权利要求1-7中任一项所述的聚氨酯组合物,其中还包括硅类泡沫稳定剂。
9.一种建筑保温用环保阻燃聚氨酯材料的制备方法,其特征在于,根据权利要求1-8中任一项的聚氨酯组合物准备相应重量的各组分,将除多异氰酸酯之外的组分充分搅拌混合,再加入多异氰酸酯,混合反应,得到建筑保温用环保阻燃聚氨酯材料。
10.由权利要求1-8中任一项所述的聚氨酯组合物得到的聚氨酯材料和根据权利要求9的制备方法得到的聚氨酯材料。
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