CN110804149A - Lng液货围护系统用增强型聚氨酯保温材料及其制备方法 - Google Patents

Lng液货围护系统用增强型聚氨酯保温材料及其制备方法 Download PDF

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CN110804149A
CN110804149A CN201911110206.9A CN201911110206A CN110804149A CN 110804149 A CN110804149 A CN 110804149A CN 201911110206 A CN201911110206 A CN 201911110206A CN 110804149 A CN110804149 A CN 110804149A
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insulation material
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曹恒
沈琦
朱红飞
范金和
吴华兵
马建青
孙剑
邢秀桃
林沫
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Abstract

本发明公开了一种LNG液货围护系统用增强型聚氨酯保温材料,包括聚醚多元醇、聚酯多元醇、二氧化硅气凝胶玻璃纤维复合毡、多亚甲基多苯基多异氰酸酯、表面活性剂、复配催化剂和物理发泡剂。本发明还公开了此种保温材料的制备方法。本发明在配方中使用了二氧化硅气凝胶玻璃纤维复合毡,相比其它的增强型聚氨酯硬泡材料,本发明能在‑173℃超低温环境使用并维持高强度和低导热,产品密度在150‑250kg/m3,在20℃条件下,产品导热系数小于23.1mw/m·k,闭孔率大于96%。

Description

LNG液货围护系统用增强型聚氨酯保温材料及其制备方法
技术领域
本发明涉及一种聚氨酯保温材料,特别是一种LNG液货围护系统用增强型聚氨酯保温材料及其制备方法。
背景技术
液化天然气是公认的最清洁能源,随着我国对环境保护的日益重视,对液化天然气的需求正日益剧增。液化天然气的存贮和运输需要用到在超低温环境下保持高绝热性、高强度及高稳定性的保温材料。
普通的聚氨酯材料具有绝佳的保温性能,然而它在超低温下会发生严重收缩无法保持其在常温下的力学强度。通常可以采用与廉价的玻纤进行复合来增强聚氨酯材料在低温下的力学性能和尺寸稳定性,并通过加入一定的阻燃剂来提高聚氨酯的阻燃等级。
专利2007101441393(公开号CN101235128A)公开一种使用连续纤维增强的密度在400-800kg/m3的聚氨酯泡沫材料,但材料适用于“承载结构材料”,并不能用于超低温环境下的保温。
专利2006101282439(公开号CN101191010A)公开了连续纤维增强的聚氨酯泡沫材料,但材料同样无法用作超低温保温材料。
专利200610058849X(公开号CN1834130A)公开了一种密度在115-135kg/m3压缩强度在1.4-1.7MPa的保温材料,但专利对材料的保温性能并没有给出详细的导热系数,且未知该材料在低温下的力学性能如何。
专利2010101347270(公开号CN101781395A)公开了一种密度在40-80kg/m3的短玻纤增强的聚氨酯保温材料,然而该材料密度偏低,无法达到液货舱承压区域所需的力学性能。
专利2013102559538(公开号CN103382263B)发明公开了一种环保型发泡剂生产聚氨酯硬质泡沫的方法,该方法可以克服预混料的储存不稳定问题,又不会对催化剂的使用产生限制,但该专利所涉及产品为常温下使用的密度在50kg/m3以下的聚氨酯硬泡材料。
专利2016100894643(公开号CN107090074A)公开了一种以连续玻纤毡为增强材料的高阻燃型玻纤增强硬质聚氨酯超低温保温材料及其制法,但该专利产品密度为110-140kg/m3,密度偏低,无法满足LNG液货舱承压区域所需的力学性能。
专利2016100963709(公开号CN107099018A)公开了一种环保型发泡剂生产的耐超低温无卤阻燃玻纤增强型硬质聚氨酯保温材料及其制备方法,但该专利产品密度为110-130kg/m3,同样无法达到LNG液货舱承压区域所需的力学性能。
综上所述,目前尚未见到密度在150-250kg/m3之间,可应用于LNG液货围护系统用增强型聚氨酯保温材料的报道。
发明内容
发明目的:二氧化硅气凝胶玻璃纤维复合毡具有较低的导热系数(低于0.018mw/mk),同时可以起到增强聚氨酯硬泡力学性能的作用,本发明将可以解决现有技术无法实现的密度在150-250kg/m3之间的可应用于LNG液货围护系统用增强型聚氨酯保温材料的问题。
技术方案:为实现上述目的,本发明采用的技术方案为:
一种LNG液货围护系统用增强型聚氨酯保温材料,其特征在于:按照重量份数包括:
(a)聚醚多元醇20-80份;
(b)聚酯多元醇20-80份;
(c)二氧化硅气凝胶玻璃纤维复合毡20-35份;
(d)多亚甲基多苯基多异氰酸酯100-130份;
(e)表面活性剂1-2.2份;
(f)复配催化剂0.2-0.8份;
(g)物理发泡剂11-12份。
进一步地,按照重量份数包括:
(a)聚醚多元醇40-60份;
(b)聚酯多元醇30-50份;
(c)二氧化硅气凝胶玻璃纤维复合20-35份;
(d)多亚甲基多苯基多异氰酸酯100-110份;
(e)表面活性剂1-2份;
(f)复配催化剂0.2-0.3份;
(g)物理发泡剂11-12份。
进一步地,聚醚多元醇的羟值在400-600mgKOH/g,粘度在2500-4500mPa·S,官能度为4-7,水份含量小于0.07%。
进一步地,所述聚酯多元醇的羟值在300-500mgKOH/g,粘度在500-2500mPa·S,官能度为2-4,水份含量小于0.07%。
进一步地,所述二氧化硅气凝胶玻璃纤维复合毡的密度在150-200kg/m3,导热系数在15-20mw/m·k。
进一步地,所述多亚甲基多苯基多异氰酸酯的异氰酸根含量为30-35wt%,粘度为150-300mPa·S,官能度为2-3。
进一步地,所述的表面活性剂为聚醚改性的有机硅化合物,所用催化剂为二甲基环胺、二月桂酸二丁基锡和甲酸的复配物。
进一步地,所述的物理发泡剂为HFC365,HFC245,环戊烷,三氟丙烯或六氟丁烯的一种或者其中两种的混合物。
一种LNG液货围护系统用增强型聚氨酯保温材料的制备方法,将5-10卷二氧化硅气凝胶玻璃纤维复合毡整齐重叠好后送入连续泡沫板生产线,各组分由原料储罐经管道进入高压发泡机高速搅拌混合均匀后浇筑在气凝胶玻璃纤维复合毡上,液体原料彻底浸润复合毡后开始发泡,到达切割工位后对连续泡沫进行切割分段,待材料熟化48小时进行测试。
有益效果:本发明与现有技术相比:
本发明提供的一种LNG液货围护系统用增强型聚氨酯保温材料,能够保证LNG在陆上储罐中的安全存储。
附图说明
图1为本发明的产品的结构示意图;
图2为对比例1产品的结构示意图。
具体实施方式
下面结合实施例和附图对本发明进行进一步地描述。
如图1所示为本发明的产品结构示意图,其中的灰色部分为二氧化硅气凝胶玻璃纤维复合毡,白色部分代表聚氨酯树脂基体,如图2所示为对比例的产品结构示意图,其中的黑色网格代表二维玻纤毡,白色部分代表聚氨酯树脂基体。
本申请采用的聚醚多元醇的羟值在400-600mgKOH/g,优选450-550mgKOH/g,粘度在2500-4500mPa·S(25℃,即常温下),优选3000-3500mPa·S,官能度为4-7,优选5-6,水份含量小于0.07%,,优选0.04-0.05%。
本申请采用的聚酯多元醇的羟值在300-500mgKOH/g,优选400-450mgKOH/g,粘度在500-2500mPa·S(25℃),优选500-1000mPa·S,官能度为2-4,优选2-3,水份含量小于0.07%,优选0.04-0.05%。
本申请采用的二氧化硅气凝胶玻璃纤维复合毡的密度在150-200kg/m3,优选170-190kg/m3的产品,导热系数在15-20mw/m·k,优选15-16mw/m·k的产品。
本申请采用的多亚甲基多苯基多异氰酸酯(PMDI)的异氰酸根含量为30-35wt%,优选30-32wt%,粘度为150-300mPa·S(25℃),优选150-250mPa·S(25℃),官能度为2-3。
本申请采用的表面活性剂为聚醚改性的有机硅化合物,所述催化剂为二甲基环胺、二月桂酸二丁基锡和甲酸的复配物。
本申请采用的物理发泡剂为HFC365,HFC245,环戊烷,三氟丙烯或六氟丁烯的一种或者其中两种的混合物,优选HFC245与HCFO-1233zd(三氟丙烯)的质量比为5:5的混合物。
制备方法是将5-10卷二氧化硅气凝胶玻璃纤维复合毡整齐重叠好后送入连续泡沫板生产线,各组分由原料储罐经管道进入高压发泡机高速搅拌混合均匀后浇筑在气凝胶玻璃纤维复合毡上,液体原料彻底浸润复合毡后开始发泡,到达切割工位后对连续泡沫进行切割分段,待材料熟化48小时进行测试。
实施例1~7及对比例1~2均采用相同的上述标准,具体的差别仅在于组分的变化。
实施例1
一种LNG液货围护系统用增强型聚氨酯保温材料,按照重量份数包括:
(a)聚醚多元醇80份;
(b)聚酯多元醇20份;
(c)二氧化硅气凝胶玻璃纤维复合毡10份;
(d)多亚甲基多苯基多异氰酸酯130份;
(e)表面活性剂1份;
(f)复配催化剂0.2份;
(g)HFC2456份和HFO-1336mmz 5份。
实施例2
一种LNG液货围护系统用增强型聚氨酯保温材料,按照重量份数包括:
(a)聚醚多元醇70份;
(b)聚酯多元醇30份;
(c)二氧化硅气凝胶玻璃纤维复合毡15份;
(d)多亚甲基多苯基多异氰酸酯125份;
(e)表面活性剂1.2份;
(f)复配催化剂0.3份;
(g)HFC2455份和HFO-1336mmz 6份。
实施例3
一种LNG液货围护系统用增强型聚氨酯保温材料,按照重量份数包括:
(a)聚醚多元醇60份;
(b)聚酯多元醇40份;
(c)二氧化硅气凝胶玻璃纤维复合毡20份;
(d)多亚甲基多苯基多异氰酸酯120份;
(e)表面活性剂1.4份;
(f)复配催化剂0.4份;
(g)HFC2454份和HFO-1336mmz 7份。
实施例4
一种LNG液货围护系统用增强型聚氨酯保温材料,按照重量份数包括:
(a)聚醚多元醇50份;
(b)聚酯多元醇50份;
(c)二氧化硅气凝胶玻璃纤维复合毡25份;
(d)多亚甲基多苯基多异氰酸酯115份;
(e)表面活性剂1.6份;
(f)复配催化剂0.5份;
(g)HFC2453份和HFO-1336mmz 8份。
实施例5
一种LNG液货围护系统用增强型聚氨酯保温材料,按照重量份数包括:
(a)聚醚多元醇40份;
(b)聚酯多元醇60份;
(c)二氧化硅气凝胶玻璃纤维复合毡20份;
(d)多亚甲基多苯基多异氰酸酯110份;
(e)表面活性剂1.8份;
(f)复配催化剂0.6份;
(g)HFC2452份和HFO-1336mmz 9份。
实施例6
一种LNG液货围护系统用增强型聚氨酯保温材料,按照重量份数包括:
(a)聚醚多元醇30份;
(b)聚酯多元醇70份;
(c)二氧化硅气凝胶玻璃纤维复合毡15份;
(d)多亚甲基多苯基多异氰酸酯105份;
(e)表面活性剂2.0份;
(f)复配催化剂0.7份;
(g)HFC2451份和HFO-1336mmz 10份。
实施例7
一种LNG液货围护系统用增强型聚氨酯保温材料,按照重量份数包括:
(a)聚醚多元醇20份;
(b)聚酯多元醇80份;
(c)二氧化硅气凝胶玻璃纤维复合毡10份;
(d)多亚甲基多苯基多异氰酸酯100份;
(e)表面活性剂2.2份;
(f)复配催化剂0.8份;
(g)HFO-1336mmz 12份。
对比例1
一种聚氨酯保温材料,按照重量份数包括:
(a)聚醚多元醇50份;
(b)聚酯多元醇50份;
(c)多亚甲基多苯基多异氰酸酯115份;
(d)表面活性剂1.5份;
(e)复配催化剂0.3份;
(f)HFC2455份和HFO-1336mmz 6份。
对比例2
一种聚氨酯保温材料,按照重量份数包括:
(a)聚醚多元醇60份;
(b)聚酯多元醇50份;
(c)多亚甲基多苯基多异氰酸酯120份;
(d)表面活性剂1.3份;
(e)复配催化剂0.5份;
(f)HFC2457份和HFO-1336mmz 4份。
整理实施例1-7以及对比例1和2的组分对比,如下表:
表1、实施例1-7以及对比例1-2的原料质量分数比
Figure BDA0002272483920000061
上述实施例制备所得复合发泡材料的性能评估如下:
产品密度:将模具中的泡沫取出,除去表皮并切割成立方体,按照GB/T6343-2009进行测试。
导热系数:将发泡材料切割成长300mm,宽300mm,厚度为30mm的样品,在20℃条件下进行测试。
闭孔率:将发泡材料切割成30mm×30mm×50mm的样品,按照GB/T10799-1989在20℃条件下进行测试。
压缩强度:将发泡材料切割成50mm×50mm×50mm的样品,按照GB/T8813-2008在20℃条件下进行测试。
拉伸强度:将发泡材料切割成如图1所示的样品,按照BS ISO 1926-2005在-170度条件下进行测试。
实际测试结果如下表:
表2实施例1-7及对比例1-2的性能测试结果
Figure BDA0002272483920000071
从结果可以看出,本发明在配方中使用了二氧化硅气凝胶玻璃纤维复合毡,相比现有的聚氨酯泡沫生产技术,所制备材料能在-173℃超低温环境使用并维持高强度和低导热,产品密度在150-250kg/m3,在20℃条件下,产品导热系数小于23.1mw/m.k,闭孔率大于96%。

Claims (9)

1.一种LNG液货围护系统用增强型聚氨酯保温材料,其特征在于:按照重量份数包括:
(a)聚醚多元醇20-80份;
(b)聚酯多元醇20-80份;
(c)二氧化硅气凝胶玻璃纤维复合毡20-35份;
(d)多亚甲基多苯基多异氰酸酯100-130份;
(e)表面活性剂1-2.2份;
(f)复配催化剂0.2-0.8份;
(g)物理发泡剂11-12份。
2.根据权利要求1所述的LNG液货围护系统用增强型聚氨酯保温材料,其特征在于:按照重量份数包括:
(a)聚醚多元醇40-60份;
(b)聚酯多元醇30-50份;
(c)二氧化硅气凝胶玻璃纤维复合20-35份;
(d)多亚甲基多苯基多异氰酸酯100-110份;
(e)表面活性剂1-2份;
(f)复配催化剂0.2-0.3份;
(g)物理发泡剂11-12份。
3.根据权利要求1或2所述的LNG液货围护系统用增强型聚氨酯保温材料,其特征在于:聚醚多元醇的羟值在400-600mgKOH/g,粘度在2500-4500mPa·S,官能度为4-7,水份含量小于0.07%。
4.根据权利要求1或2所述的LNG液货围护系统用增强型聚氨酯保温材料,其特征在于:所述聚酯多元醇的羟值在300-500mgKOH/g,粘度在500-2500mPa·S,官能度为2-4,水份含量小于0.07%。
5.根据权利要求1或2所述的LNG液货围护系统用增强型聚氨酯保温材料,其特征在于:所述二氧化硅气凝胶玻璃纤维复合毡的密度在150-200kg/m3,导热系数在15-20mw/m·k。
6.根据权利要求1或2所述的LNG液货围护系统用增强型聚氨酯保温材料,其特征在于:所述多亚甲基多苯基多异氰酸酯的异氰酸根含量为30-35wt%,粘度为150-300mPa·S,官能度为2-3。
7.根据权利要求1或2所述的LNG液货围护系统用增强型聚氨酯保温材料,其特征在于:所述的表面活性剂为聚醚改性的有机硅化合物,所用催化剂为二甲基环胺、二月桂酸二丁基锡和甲酸的复配物。
8.根据权利要求1或2所述的LNG液货围护系统用增强型聚氨酯保温材料,其特征在于:所述的物理发泡剂为HFC365,HFC245,环戊烷,三氟丙烯或六氟丁烯的一种或者其中两种的混合物。
9.一种如权利要求1所述的LNG液货围护系统用增强型聚氨酯保温材料的制备方法,其特征在于:将5-10卷二氧化硅气凝胶玻璃纤维复合毡整齐重叠好后送入连续泡沫板生产线,各组分由原料储罐经管道进入高压发泡机高速搅拌混合均匀后浇筑在气凝胶玻璃纤维复合毡上,液体原料彻底浸润复合毡后开始发泡,到达切割工位后对连续泡沫进行切割分段,待材料熟化48小时进行测试。
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