CN105330809B - 用于冷库喷涂的聚氨酯组合料及其制备方法 - Google Patents

用于冷库喷涂的聚氨酯组合料及其制备方法 Download PDF

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CN105330809B
CN105330809B CN201510835026.2A CN201510835026A CN105330809B CN 105330809 B CN105330809 B CN 105330809B CN 201510835026 A CN201510835026 A CN 201510835026A CN 105330809 B CN105330809 B CN 105330809B
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徐业峰
周生鹏
殷晓峰
朱文静
张佳佳
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Shandong Inov New Material Co Ltd
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Abstract

本发明属于化学合成技术领域,具体涉及一种用于冷库喷涂的聚氨酯组合料及其制备方法。用于冷库喷涂的聚氨酯组合料由A组分和B组分组成,A组分:聚醚多元醇Ⅰ、聚醚多元醇Ⅱ、聚酯多元醇Ⅰ、聚酯多元醇Ⅱ、扩链剂、泡沫稳定剂、发泡剂、催化剂、阻燃剂、水,B组分:多亚甲基多苯基多异氰酸酯。本发明制备过程和施工过程中都可以在常温常压下操作,施工时气味小,室内施工,发泡时不会对工人造成损害;制得的聚氨酯喷涂泡沫材料阻燃性能极佳,防火级别达到B1级,通过保温系统复合可以达到A级阻燃标准。

Description

用于冷库喷涂的聚氨酯组合料及其制备方法
技术领域
本发明属于化学合成技术领域,具体涉及一种用于冷库喷涂的聚氨酯组合料及其制备方法。
背景技术
冷库是发展冷藏业的基础设施,也是在低温条件下贮藏货物的建筑群。
自从1955年我国建立起第一座储藏肉制品冷库以来,冷库在我国发展势头迅猛,截止到2015年,我国冷库总容量已突破800万吨,随着社会发展,冷库的需求量也更加旺盛,以2014年为例,全国在建或计划建设万吨级以上冷库52个,总储存量达446万吨。
但是随着冷库的迅猛发展,冷库施工安全和使用安全也越来越突显重要。如2014年11月17日-山东寿光一正常使用冷库发生火灾,造成18死13伤。2015年7月4日,北京市通州区驹桥大松垡村一在建冷库发生火情,冷库失火一人身亡。起火原因虽然有很多,但是易燃保温材料助长冷库火势,是造成严重后果的推手。
现在冷库保温一般使用聚氨酯或者聚苯板作为主要的保温材料,然而由于技术以及成本限制,以往使用的聚氨酯和聚苯板保温很难达到难燃级别,勉强使用高阻燃聚氨酯也会因为其过高气味以及对人体的伤害而不能大面积普及。使用聚苯板一方面阻燃效果难以保证,另一方面聚苯板在接口以及门柱边角施工留下的边封也难以保证保温效果,这为我们以后冷库的发展埋下了重大隐患。
发明内容
本发明的目的是提供一种用于冷库喷涂的聚氨酯组合料,其制得的聚氨酯硬泡材料环保、绝热性好、闭孔率高同时还可以防水防潮,同时可以达到B1级标准,气味性小,对人体几乎无害,可以在冷库施工中大面积普及;本发明同时提供了用于冷库喷涂的聚氨酯组合料的制备方法,科学合理、简单易行。
本发明所述的用于冷库喷涂的聚氨酯组合料,由A组分和B组分组成,A组分和B组分的重量比为1:1-1.05,其中,
A组分由如下重量百分比的原料制成:
B组分为多亚甲基多苯基多异氰酸酯。
所述的聚醚多元醇Ⅰ为3-8官能度,数均分子量为300-1200的聚醚多元醇;优选为YNW-210(一诺威新材料有限公司生产)。
所述的聚醚多元醇Ⅱ为4官能度,数均分子量为500-700的磷碳结构聚醚多元醇,聚醚多元醇Ⅱ中磷的质量分数为8-12%;优选为YNW-501F(山东一诺威新材料有限公司生产)。
所述的聚酯多元醇Ⅰ为粘度2000-2500mpa.s/25℃,官能度为2-3的低酸值苯酐聚酯多元醇;优选为B503(山东一诺威股份有限公司生产)。
所述的聚酯多元醇Ⅱ为粘度2000-3000mpa.s/25℃,官能度为2-3的低酸值苯酐聚酯多元醇;优选为B175(山东一诺威股份有限公司生产)。
所述的扩链剂为数均分子量在100-200的醇氨类物质,优选1,1’,1”-氮基-2-三丙醇(TIPA),更优选石家庄海森化工有限公司醇胺含量97%以上。
所述的泡沫稳定剂为硅-碳键耐水解型聚硅氧烷-聚醚共聚物,优选B8545(赢创德固赛)。
所述的发泡剂为1,1,1,3,3-五氟丁烷(HFC-365mfc)和反式-1-氯-3,3,3-三氯丙烯(LBA)的混合物,1,1,1,3,3-五氟丁烷与反式-1-氯-3,3,3-三氯丙烯的重量比为80:20。当1,1,1,3,3-五氟丁烷/反式-1-氯-3,3,3-三氯丙烯以80:20混合时,混合物无闪点,室温下为液体,为不可燃的混合发泡剂,热导率(25℃)为18.2,故用其所生产的组合聚醚属于无氟型组合聚醚,具有绿色环保的特点。采用1,1,1,3,3-五氟丁烷/反式-1-氯-3,3,3-三氯丙烯型发泡剂的冷库用聚氨酯硬泡材料,在达到绿色环保效果的同时,在比强度、粘结性、低温尺寸稳定性、阻燃性、闭孔率等方面都达到国际先进水平。
所述的催化剂为N,N-二甲基环己胺、双(2-二甲氨基乙基)醚、三亚乙基二胺、N,N,N',N'-四甲基亚乙基二胺、三乙胺、N-乙基吗啡啉、N-甲基吗啡啉、N,N-二甲基苄胺、N,N,N',N”,N”-五甲基二亚乙基三胺、N,N'-二乙基哌嗪、N,N'-二乙基-2-甲基哌嗪或二月桂酸二丁基锡中的一种或多种。
所述的阻燃剂为三(2-氯丙基)磷酸酯(TCPP)、甲基膦酸二甲酯(DMMP)、聚磷酸铵(APP)、三聚氰胺或三(2-羧乙基)膦(TCEP)中的一种或多种。
所述的多亚甲基多苯基多异氰酸酯优选为万华牌号PM200或拜耳牌号44V20。
本发明所述的用于冷库喷涂的聚氨酯组合料的制备方法,步骤如下:
(1)A组分的制备:将聚醚多元醇Ⅰ、聚醚多元醇Ⅱ、聚酯多元醇Ⅰ和聚酯多元醇Ⅱ加入反应釜中搅拌,加入扩链剂、泡沫稳定剂、发泡剂、催化剂、阻燃剂和水,在常温下搅拌0.5-1.5小时,充分混合;
(2)B组分的制备:将多亚甲基多苯基多异氰酸酯称量备用。
使用时,将A组分与B组分通过高压喷涂机均匀混合,雾化发泡,泡沫迅速成型熟化,制得产品。
本发明与现有技术相比,具有如下有益效果:
1、在冷库中,制得的聚氨酯喷涂泡沫材料阻燃性能极佳,防火级别达到B1级,通过保温系统复合可以达到A级阻燃标准。泡沫性能完全能够达到国标GB/T 10294-2008、JC/T998-2006的标准要求。发生火灾,可以有效的遏制火势的发展。
2、制备过程和施工过程中都可以在常温常压下操作,施工时气味小,室内施工,发泡时不会对工人造成损害。
3、采用LBA(反式-1-氯-3,3,3-三氯丙烯)发泡剂,在大气中的存在时间只有26天,ODP为0,比传统的发泡剂毒性更低,对臭氧层无伤害。
4、施工方便,对于复杂的管线、墙角可以无缝喷涂,保温效果好。喷涂样板测试导热系数为18.6,远低于行业水平。
5、与传统的高阻燃聚氨酯相比,本产品添加型阻燃剂量少,所生成的泡沫性质稳定,泡孔细腻,导热系数低,强度高。
6、生成的聚氨酯制品为微泡闭孔结构,而且表面能形成一层结皮,能有效的隔热防潮。
具体实施方式
以下结合实施例对本发明做进一步描述。
实施例1
(1)A组分的制备:
A组分原料组成见表1。
表1 实施例1中A组分原料组成
1,1,1,3,3-五氟丁烷与反式-1-氯-3,3,3-三氯丙烯的质量比为80:20。
将称量好的上述原料加入反应釜中,在常温下搅拌0.5小时,充分混合。
(2)B组分的制备:称量多亚甲基多苯基多异氰酸酯100kg。
(3)将A组分与B组分按照重量比1:1通过高压喷涂机均匀混合,雾化发泡,泡沫迅速成型熟化,其中自由泡密度38.6kg/m3,发泡速度控制在乳白时间3-4秒,凝胶时间8-10秒,制得聚氨酯硬泡材料,制得的产品质量指标见表4。
实施例2
(1)A组分的制备:
A组分原料组成见表2。
表2 实施例2中A组分原料组成
1,1,1,3,3-五氟丁烷与反式-1-氯-3,3,3-三氯丙烯的质量比为80:20。
将称量好的上述原料加入反应釜中,在常温下搅拌0.5小时,充分混合。
(2)B组分的制备:称量多亚甲基多苯基多异氰酸酯100kg。
(3)将A组分与B组分按照重量比1:1通过高压喷涂机均匀混合,雾化发泡,泡沫迅速成型熟化,其中自由泡密度37.2kg/m3,发泡速度控制在乳白时间3-4秒,凝胶时间8-10秒,制得聚氨酯硬泡材料,制得的产品质量指标见表4。
实施例3
(1)A组分的制备:
A组分原料组成见表3。
表3 实施例3中A组分原料组成
1,1,1,3,3-五氟丁烷与反式-1-氯-3,3,3-三氯丙烯的质量比为80:20。
将称量好的上述原料加入反应釜中,在常温下搅拌1小时,充分混合。
(2)B组分的制备:称量多亚甲基多苯基多异氰酸酯105kg。
(3)将A组分与B组分按照重量比1:1.05通过高压喷涂机均匀混合,雾化发泡,泡沫迅速成型熟化,其中自由泡密度36.0kg/m3,发泡速度控制在乳白时间3-4秒,凝胶时间8-10秒,制得聚氨酯硬泡材料,制得的产品质量指标见表4。
表4 实施例1-3的泡沫产品质量检测数据
由表4可知:组合聚醚产品对臭氧层无破坏,环保性能优异;制得的聚氨酯泡沫导热系数低,密闭性好,阻燃性能优异、产品稳定性好。

Claims (7)

1.一种用于冷库喷涂的聚氨酯组合料,由A组分和B组分组成,其特征在于A 组分和B组分的重量比为1:1-1.05,其中,
A组分由如下重量百分比的原料制成:
聚醚多元醇Ⅰ 10-15﹪
聚醚多元醇Ⅱ 15-20﹪
聚酯多元醇Ⅰ 15-20﹪
聚酯多元醇Ⅱ 10-15﹪
扩链剂 6-10﹪
泡沫稳定剂 1-1.5﹪
发泡剂 13-25﹪
催化剂 2.5-4.5﹪
阻燃剂 10-15﹪
水 1.5-5.0﹪;
B组分为多亚甲基多苯基多异氰酸酯;
所述的聚醚多元醇Ⅰ为3-8官能度,数均分子量为300-1200的聚醚多元醇;
所述的聚醚多元醇Ⅱ为4官能度,数均分子量为500-700的磷碳结构聚醚多元醇,聚醚多元醇Ⅱ中磷的质量分数为8-12%;
所述的聚酯多元醇Ⅰ为粘度2000-2500mpa.s/25℃,官能度为2-3的低酸值苯酐聚酯多元醇;聚酯多元醇Ⅱ为粘度2000-3000mpa.s/25℃,官能度为2-3的低酸值苯酐聚酯多元醇。
2.根据权利要求1所述的用于冷库喷涂的聚氨酯组合料,其特征在于所述的扩链剂为数均分子量在100-200的醇氨类物质。
3.根据权利要求1所述的用于冷库喷涂的聚氨酯组合料,其特征在于所述的泡沫稳定剂为硅-碳键耐水解型聚硅氧烷-聚醚共聚物。
4.根据权利要求1所述的用于冷库喷涂的聚氨酯组合料,其特征在于所述的发泡剂为1,1,1,3,3-五氟丁烷和反式-1-氯-3,3,3-三氯丙烯的混合物,1,1,1,3,3-五氟丁烷与反式-1-氯-3,3,3-三氯丙烯的重量比为80:20。
5.根据权利要求1所述的用于冷库喷涂的聚氨酯组合料,其特征在于所述的催化剂为N,N-二甲基环己胺、双(2-二甲氨基乙基)醚、三亚乙基二胺、N,N,N',N'-四甲基亚乙基二胺、三乙胺、N-乙基吗啡啉、N-甲基吗啡啉、N,N-二甲基苄胺、N,N,N',N'',N''-五甲基二亚乙基三胺、N,N'-二乙基哌嗪、N,N'-二乙基-2-甲基哌嗪或二月桂酸二丁基锡中的一种或多种。
6.根据权利要求1所述的用于冷库喷涂的聚氨酯组合料,其特征在于所述的阻燃剂为三(2-氯丙基)磷酸酯、甲基膦酸二甲酯、聚磷酸铵、三聚氰胺或三(2-羧乙基)膦中的一种或多种。
7.一种权利要求1-6任一所述的用于冷库喷涂的聚氨酯组合料的制备方法,其特征在于步骤如下:
(1)A组分的制备:将聚醚多元醇Ⅰ、聚醚多元醇Ⅱ、聚酯多元醇Ⅰ和聚酯多元醇Ⅱ加入反应釜中搅拌,加入扩链剂、泡沫稳定剂、发泡剂、催化剂、阻燃剂和水,在常温下搅拌0.5-1.5小时,充分混合;
(2)B 组分的制备:将多亚甲基多苯基多异氰酸酯称量备用。
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