CN103709355B - 用于超低温lng储罐储保冷的改性聚氨酯喷涂组合料及其制备方法 - Google Patents

用于超低温lng储罐储保冷的改性聚氨酯喷涂组合料及其制备方法 Download PDF

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CN103709355B
CN103709355B CN201310714031.9A CN201310714031A CN103709355B CN 103709355 B CN103709355 B CN 103709355B CN 201310714031 A CN201310714031 A CN 201310714031A CN 103709355 B CN103709355 B CN 103709355B
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宁晓龙
徐业峰
李欣
李明友
马海晶
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Shandong Inov New Material Co Ltd
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Abstract

本发明涉及用于超低温LNG储罐保冷的改性聚氨酯喷涂组合料及其制备方法。该组合料由组分A和组分B按重量比1:1~1.05组成,其中,组分A由聚醚多元醇A、聚醚多元醇B、改性聚酯多元醇、泡沫稳定剂A、泡沫稳定剂B、化学发泡剂、物理发泡剂、催化剂、阻燃剂和其他助剂组成;组分B为多次甲基多苯基多异氰酸酯。制备方法为,将上述组分A中的组分依次加入反应釜中,在常温下搅拌0.5~1小时充分混合;将组分A与组分B按A:B=1:1~1.05的重量比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。本发明所制备的泡沫有极强的低温尺寸稳定性,在深冷环境中不产生收缩裂缝,得到完美的深冷保冷效果,特别适合用于LNG储罐保冷施工。

Description

用于超低温LNG储罐储保冷的改性聚氨酯喷涂组合料及其制备方法
技术领域
本发明属于化学合成领域,具体涉及一种用于超低温LNG储罐储保冷的改性聚氨酯喷涂组合料及其制备方法。
背景技术
随着液化天然气(LNG)开采及应用的快速发展,液化气体(+90℃—-196℃)储罐的深冷保冷成为人们急需解决的问题。目前国内LNG储罐保冷大多采用膨胀珍珠岩抽真空的深冷技术,且罐体容积多在40m3以内,若遇大容量深冷容器,则抽真空基本无法实现。同时,由于膨胀珍珠岩易吸潮,一旦保温层真空被破坏,易在保温层内部形成结冰现象。聚氨酯喷涂硬泡产品具有优异的理化性能和便捷的加工工艺,适宜在各种异形表面制作保温层,导热系数低,保冷作用良好,同时具有优异的防水性能,吸水力很小,特别适合作为储罐保温材料,常用于罐体保温保冷。
但是,常规的聚氨酯硬泡材料只能用于一般罐体保温,当其置于深冷环境中时,其气孔耐压差以及材料尺寸稳定性较差,易产生收缩裂纹,无法保证长期处于安全、正常的使用状态。因此,必须在传统的硬质聚氨酯泡沫基础上进行改性,获得超低温LNG储罐用喷涂型改性聚氨酯组合料。
发明内容
为解决上述技术问题,本发明提供了一种用于超低温LNG储罐储保冷的改性聚氨酯喷涂组合料,其制得的聚氨酯泡沫在保证导热系数低、性能稳定、强度高的同时,还具有极强的低温尺寸稳定性;同时本发明还提供了制备该组合料的方法。
本发明所述的超低温LNG储罐用喷涂型改性聚氨酯组合料,由组分A和组分B组成,组分A与组分B的重量比为1:1~1.05;
其中:
所述组分A由以下组分组成:聚醚多元醇A、30~38%,聚醚多元醇B、10~18%,特种聚酯多元醇、3~10%,泡沫稳定剂A、0.5~1.5%,泡沫稳定剂B、0.5~1.5%,化学发泡剂、0.5~1.0%,物理发泡剂、10~20%,催化剂、0.5~1.5%,阻燃剂、15~18%,其他助剂%、0.5~2;以上各数值为各组分在组分A中所占的重量百分数;
所述组分B为多次甲基多苯基多异氰酸酯。
上述组合料的制备方法,包括以下步骤:
(1)、准备原料:按上述组合料的组分及重量比准备原料:
组分A:聚醚多元醇A、30~38%,聚醚多元醇B、10~18%,特种聚酯多元醇、3~10%,泡沫稳定剂A、0.5~1.5%,泡沫稳定剂B、0.5~1.5%,化学发泡剂、0.5~1.0%,物理发泡剂、10~20%,催化剂、0.5~1.5%,阻燃剂、15~18%,其他助剂、0.5~2%;以上各数值为各组分在组分A中所占的重量百分数;
组分B:多次甲基多苯基多异氰酸酯;
组分A与组分B的重量比为1:1~1.05;
(2)、制备组分A:按照步骤(1)中组分及重量比,将称量好的聚醚多元醇A、聚醚多元醇B、特种聚酯多元醇、泡沫稳定剂A、泡沫稳定剂B、化学发泡剂、催化剂、阻燃剂、物理发泡剂和其他助剂,依次加入反应釜中,在常温下搅拌0.5~1小时,充分混合;
(3)、按照步骤(1)中组分及重量比,将组分B称量备用;
(4)、使用时,将组分A与组分B按A:B=1:1~1.05的重量比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。
所述的组分A中:聚醚多元醇A为羟值为300~400mgKOH/g的聚醚多元醇,优选山东蓝星东大公司450L;聚醚多元醇B为4.5~5官能度,数均分子量为500~700的聚醚多元醇;优选山东淄博诺立化工有限公司DZ102C;聚酯多元醇为本公司(山东一诺威新材料公司)自制的2官能度,数均分子量为300~330的新型低酸值特种聚酯多元醇TE-B503;物理发泡剂为一氟二氯乙烷(141b)。
所述的泡沫稳定剂A为非水解硅碳类表面活性剂,优选B-8545(赢创公司市售产品)。泡沫稳定剂B为非硅酮类表面活性剂LK-443(空气化工公司市售产品)。
所述的化学发泡剂为水,优选去离子水。
所述的催化剂为三乙烯二胺、N,N,N’,N”,N”-五甲基二亚乙基三胺、1,3,5-三(二甲氨基丙基)-六氢化三嗪或二月桂酸二丁基锡中的三种或四种。
所述的所述阻燃剂为TCPP(三(2-氯丙基)磷酸酯)、DMMP(甲基膦酸二甲酯)、APP(聚磷酸铵)或三聚氰胺中的一种或多种。
所述的其他助剂为色浆、颜料或抗氧化剂中的一种或多种。
本发明的有益效果在于:
1、组分A采用了本公司自产的新型低酸值特种聚酯多元醇TE-B503,此种聚酯多元醇具有极低的分子量分布,制得的组合聚醚经高压喷涂发泡制备硬泡聚氨酯具有更加优异的低温尺寸稳定性和更高的泡沫强度。
2、组分A所使用的泡沫稳定剂B为非硅酮类表面活性剂,此类表面活性剂用于喷涂型硬质聚氨酯泡沫可以形成非常圆的泡孔结构,从而提供极高的气孔耐压差和尺寸稳定性,特别适于用于深冷环境。
3、此法制得的改性聚氨酯组合料通过现场喷涂的工艺施工,施工方法便捷高效,可以适用于各种复杂形状和狭小部位的腔体空间,且无需过多的维修及在机械损伤后修复便捷,特别适用于大容量超低温LNG储罐。
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、制备组分A,200kg:分别称量聚醚多元醇A:450L(山东蓝星东大公司)、76kg,聚醚多元醇B:DZ102C(山东淄博诺立化工有限公司)、20kg,特种聚酯多元醇:TE-B503(本公司自产)、17kg,泡沫稳定剂A:B-8545(赢创公司)、1kg,泡沫稳定剂B:LK-443(空气化工)、2kg,去离子水、1.1kg,催化剂选用N,N,N’,N”,N”-五甲基二亚乙基三胺、三乙烯二胺、1,3,5-三(二甲氨基丙基)-六氢化三嗪和二月桂酸二丁基锡的混合物,重量分别为1.5kg、0.8kg、0.4kg和0.2kg,物理发泡剂一氟二氯乙烷(141b)、40kg,阻燃剂TCPP、36kg,绿色浆、4kg。
将称量好的聚醚多元醇A、聚醚多元醇B、特种聚酯多元醇、泡沫稳定剂A、泡沫稳定剂B、化学发泡剂、催化剂、阻燃剂、物理发泡剂和其他助剂,依次加入反应釜中,在常温下搅拌0.5小时,充分混合。
2、组分B聚合二苯基甲烷二异氰酸酯、200kg。
3、将组分A与组分B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,制得聚氨酯硬泡保温材料,制得的产品质量指标见表1。
实施例2
1、制备组分A,200kg:分别称量聚醚多元醇A:450L(山东蓝星东大公司)、60kg,聚醚多元醇B:DZ102C(山东淄博诺立化工有限公司)、36kg,特种聚酯多元醇:TE-B503(本公司自产)、20kg,泡沫稳定剂A:B-8545(赢创公司)、1kg,泡沫稳定剂B:LK-443(空气化工)、2kg,去离子水、2kg,催化剂选用N,N,N’,N”,N”-五甲基二亚乙基三胺、1,3,5-三(二甲氨基丙基)-六氢化三嗪和二月桂酸二丁基锡的混合物,重量分别为1.6kg、1.0kg和0.4kg,物理发泡剂一氟二氯乙烷(141b)、40kg,阻燃剂APP(聚磷酸铵)、32kg,抗氧剂、1kg,绿色浆、3kg。
将称量好的聚醚多元醇A、聚醚多元醇B、特种聚酯多元醇、泡沫稳定剂A、泡沫稳定剂B、化学发泡剂、催化剂、阻燃剂、物理发泡剂和其他助剂,依次加入反应釜中,在常温下搅拌0.5小时,充分混合。
2、组分B聚合二苯基甲烷二异氰酸酯、210kg。
3、将组分A与组分B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,制得聚氨酯硬泡保温材料,制得的产品质量指标见表1。
实施例3
1、制备组分A,200kg:分别称量聚醚多元醇A:450L(山东蓝星东大公司)、75kg,聚醚多元醇B:DZ102C(山东淄博诺立化工有限公司)、35kg,特种聚酯多元醇:B503(本公司自产)、20kg,泡沫稳定剂A:B8532(赢创公司)、1kg,泡沫稳定剂B:LK-443(空气化工)、2kg,去离子水、1.8kg,催化剂选用N,N,N’,N”,N”-五甲基二亚乙基三胺、三乙烯二胺、1,3,5-三(二甲氨基丙基)-六氢化三嗪和二月桂酸二丁基锡的混合物,重量分别为1.3kg、1.1kg、0.5kg和0.1kg,物理发泡剂一氟二氯乙烷(141b)、25kg,阻燃剂TCPP20kg,阻燃剂DMMP15kg,抗氧剂、2.2kg。
将称量好的聚醚多元醇A、聚醚多元醇B、特种聚酯多元醇、泡沫稳定剂A、泡沫稳定剂B、化学发泡剂、催化剂、阻燃剂、物理发泡剂和其他助剂,依次加入反应釜中,在常温下搅拌1小时,充分混合。
2、组分B聚合二苯基甲烷二异氰酸酯、200kg。
3、将组分A与组分B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,制得聚氨酯硬泡保温材料,制得的产品质量指标见表1。
表1为实施例1~3的泡沫产品质量检测数据。
表1:实施例1~3的泡沫产品质量检测数据
由上表可知:组合聚醚产品制得的聚氨酯泡沫导热系数低,强度高,闭孔率极高,阻燃性能优,同时具有极强的低温尺寸稳定性。

Claims (8)

1.一种超低温LNG储罐储保冷用改性聚氨酯喷涂组合料,其特征在于,由组分A和组分B组成,组分A与组分B的重量比为1:1~1.05,其中,
所述组分A由以下组分组成:聚醚多元醇A、30~38%,聚醚多元醇B、10~18%,聚酯多元醇、3~10%,泡沫稳定剂A、0.5~1.5%,泡沫稳定剂B、0.5~1.5%,化学发泡剂、0.5~1.0%,物理发泡剂、10~20%,催化剂、0.5~1.5%,阻燃剂、15~18%,其他助剂、0.5~2%;以上各数值为各组分在组分A中所占的重量百分数;
其中组分A中:所述聚醚多元醇A为羟值为300~400mgKOH/g的聚醚多元醇;聚醚多元醇B为4.5~5官能度,数均分子量为500~700的聚醚多元醇;聚酯多元醇为2官能度,数均分子量为300~330的聚酯多元醇TE-B503;
所述泡沫稳定剂A为非水解硅碳类表面活性剂;
所述泡沫稳定剂B为非硅酮类表面活性剂;
所述物理发泡剂为一氟二氯乙烷;
所述组分B为多次甲基多苯基多异氰酸酯。
2.根据权利要求1所述的改性聚氨酯喷涂组合料,其特征在于,所述化学发泡剂为水。
3.根据权利要求1所述的改性聚氨酯喷涂组合料,其特征在于,所述催化剂为三乙烯二胺、N,N,N’,N”,N”-五甲基二亚乙基三胺、1,3,5-三(二甲氨基丙基)-六氢化三嗪或二月桂酸二丁基锡中的三种或四种。
4.根据权利要求1所述的改性聚氨酯喷涂组合料,其特征在于,所述阻燃剂为三(2-氯丙基)磷酸酯、甲基膦酸二甲酯、磷酸铵或三聚氰胺中的一种或多种。
5.一种超低温LNG储罐储保冷用改性聚氨酯喷涂组合料的制备方法,其特征在于,包括以下步骤:
(1)、按以下组分准备原料:
组分A:聚醚多元醇A、30~38%,聚醚多元醇B、10~18%,聚酯多元醇、3~10%,泡沫稳定剂A、0.5~1.5%,泡沫稳定剂B、0.5~1.5%,化学发泡剂、0.5~1.0%,物理发泡剂、10~20%,催化剂、0.5~1.5%,阻燃剂、15~18%,其他助剂、0.5~2%;以上各数值为各组分在组分A中所占的重量百分数;
其中:
聚醚多元醇A为羟值为300~400mgKOH/g的聚醚多元醇;
聚醚多元醇B为4.5~5官能度,数均分子量为500~700的聚醚多元醇;
聚酯多元醇为2官能度,数均分子量为300~330的聚酯多元醇TE-B503;
泡沫稳定剂A为非水解硅碳类表面活性剂;
泡沫稳定剂B为非硅酮类表面活性剂;
物理发泡剂为一氟二氯乙烷;
组分B:多次甲基多苯基多异氰酸酯;
组分A与组分B的重量比为1:1~1.05;
(2)、制备组分A:按照步骤(1)中组分及重量比,将称量好的聚醚多元醇A、聚醚多元醇B、聚酯多元醇、泡沫稳定剂A、泡沫稳定剂B、化学发泡剂、催化剂、阻燃剂、物理发泡剂和其他助剂,依次加入反应釜中,在常温下搅拌0.5~1小时,充分混合;
(3)、按照步骤(1)中组分及重量比,将组分B称量备用;
(4)、使用时,将组分A与组分B混合即可。
6.根据权利要求5所述的改性聚氨酯喷涂组合料的制备方法,其特征在于,所述化学发泡剂为水。
7.根据权利要求5所述的改性聚氨酯喷涂组合料的制备方法,其特征在于,所述催化剂为三乙烯二胺、N,N,N’,N”,N”-五甲基二亚乙基三胺、1,3,5-三(二甲氨基丙基)-六氢化三嗪或二月桂酸二丁基锡中的三种或四种。
8.根据权利要求5所述的改性聚氨酯喷涂组合料的制备方法,其特征在于,所述阻燃剂为三(2-氯丙基)磷酸酯、甲基膦酸二甲酯、磷酸铵或三聚氰胺中的一种或多种。
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