CN115536801B - 一种保冷高阻燃喷涂型硬质聚氨酯泡沫及其制备方法 - Google Patents

一种保冷高阻燃喷涂型硬质聚氨酯泡沫及其制备方法 Download PDF

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CN115536801B
CN115536801B CN202211178124.XA CN202211178124A CN115536801B CN 115536801 B CN115536801 B CN 115536801B CN 202211178124 A CN202211178124 A CN 202211178124A CN 115536801 B CN115536801 B CN 115536801B
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信延垒
任丽
任洁洁
吴菲
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Shanghai Yumo Energy Saving Technology Co ltd
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Abstract

本发明涉及一种保冷高阻燃喷涂型硬质聚氨酯泡沫及其制备方法，由组分A和组分B经聚氨酯喷涂机器喷涂制得，其中组分A组成有：多元醇主体、有机硅表面活性剂、催化剂、水、物理发泡剂、阻燃剂；所述的多元醇主体为由曼尼希聚醚多元醇a，含氮、磷元素改性的聚酯多元醇b，芳香族聚酯多元醇c按质量比20‑30：30‑50：30‑50混合而成；组分B为多苯基多亚甲基多异氰酸酯。制得的聚氨酯泡沫不仅能满足用于超低温保冷的要求，还具有较高的阻燃性能，达到了DIN4102B1级阻燃要求，提高了罐体聚氨酯保温材料的安全性和适用性。

Description

一种保冷高阻燃喷涂型硬质聚氨酯泡沫及其制备方法
技术领域
本发明涉及一种超低温保冷高阻燃喷涂型硬质聚氨酯泡沫及其制备方法，属于有机材料合成技术领域。
背景技术
聚氨酯泡沫作为保温性能优异的材料已经被广泛地用于LNG、LPG、LEG运输船舶罐体的保冷。目前，罐体聚氨酯保温材料的阻燃等级为DIN 4102 B2，保温泡沫具有一定防火性能；专利CN 107090074A公开了一种玻纤增强硬质聚氨酯保温材料，密的阻燃性能也仅为DIN 4102 B2或者B3级别；但是，当液仓表面进行焊接施工或者热切割等作业时，上千摄氏度高温的焊渣或者附属件会掉落到液仓表面保温泡沫的表面，破坏并引燃保温层，容易由局部引发整体火灾出现，存在严重的安全隐患。据行业内信息，2015年韩国三星重工造船厂出现过LNG船舶维修期间，滴落的焊渣引燃保温泡沫造成了重大火灾事故。
因此，LNG、LPG、LEG等保冷领域需要阻燃性能更加优异的硬质聚氨酯泡沫，兼具超低温下具有良好的尺寸稳定性、机械性能和较高的阻燃性能。
发明内容
本发明的目的是克服现有技术不足，而提供一种保冷高阻燃喷涂型硬质聚氨酯泡沫及其制备方法。制得的聚氨酯泡沫不仅能满足用于超低温保冷的要求，还具有较高的阻燃性能，达到了DIN 4102 B1级阻燃要求，提高了罐体聚氨酯保温材料的安全性和适用性。
本发明采取的技术方案为：
一种保冷高阻燃喷涂型硬质聚氨酯泡沫，由组分A和组分B经聚氨酯喷涂机器喷涂制得，其中组分A的重量份比组成如下：多元醇主体100份、有机硅表面活性剂1-5份、催化剂2-10份、水0.5-3份、物理发泡剂10-30份、阻燃剂10-20份；所述的多元醇主体为由曼尼希聚醚多元醇a，含氮、磷元素改性的聚酯多元醇b，芳香族聚酯多元醇c按质量比20-30：30-50：30-50混合而成；
组分B为多苯基多亚甲基多异氰酸酯；
组分A与组分B的质量比例为100：100。
所述的曼尼希聚醚多元醇a，粘度为4000-30000mPa.s(25℃)，羟值为300-600mgKOH/g，官能度为4.5-5.5；所述的含氮、磷元素改性的聚酯多元醇b，粘度为4000-20000mPa.s(25℃)，羟值为250-350mgKOH/g，官能度为2.2；所述的芳香族聚酯多元醇c，粘度为10000-15000mPa.s(25℃)，羟值为150-250mgKOH/g，官能度为2.0。
所述的曼尼希聚醚多元醇a为壬基苯酚、多聚甲醛、二乙醇胺按照一定比例和环氧丙烷、环氧乙烷聚合而成，进一步优选佳化化学的Pruanol 3778。
所述的含氮、磷元素改性的聚酯多元醇b，优选南京康塑德化工公司的CF6255和斯泰潘公司的PS-3158中的一种或两种，更优选PS-3158。
所述的芳香族聚酯多元醇c为苯酐、间苯二甲酸、对苯二甲酸中的一种或多种与乙二醇、丙二醇、丁二醇、双酚A中的一种或多种缩合而成，优选苯酐与乙二醇、双酚A的混合物缩合；更优选淄博瑞诺新材料股份有限公司的聚酯多元醇PS-3175。
所述的阻燃剂为TCPP(三(2-氯丙基)磷酸酯)、TCEP(三(2-氯乙基)磷酸酯)、TEP(磷酸三乙酯)、DMMP(甲基膦酸二甲酯)中的一种或几种，较佳的为TCPP与TEP混合物，优选质量比为1：1。
所述的催化剂为发泡型催化剂五甲基二乙烯三胺、二吗啉二乙基醚、双(二甲氨基乙基)醚，凝胶型催化剂N,N-二甲基环己胺、三乙烯二胺，三聚型催化剂N,N’N”-三(二甲胺基丙基)-六氢化三嗪、2,4,6-三(二甲胺基甲基)苯酚、季铵盐、可溶性钾盐、可溶性钠盐中的一种或多种，进一步优选发泡型催化剂、凝胶型催化剂、三聚型催化剂三者复配。
所述的有机硅表面活性剂，可以选用上海麦豪化工科技有限公司的S系列产品、赢创集团的B系列产品、迈图高新材料的L系列产品及江苏美思德化学股份有限公司的AK系列产品，进一步优选上海麦豪化工科技有限公司的S-193。
所述的水优选为去离子水。
所述的物理发泡剂为五氟丙烷(HFC-245fa)、五氟丁烷(HFC-365mfc)、一氯三氟丙烯(HFO-1233zd)、六氟丁烯(FEA-1100)中的一种或几种。
上述保冷高阻燃喷涂型硬质聚氨酯泡沫的制备方法，包括步骤如下：
(1)组分A的制备：将各原料组分在具有安全装置的混合釜中搅拌均匀混合，混合时间0.5-1小时，静置0.5-1小时消泡后，放出即得组分A；
(2)将组分A和组分B经聚氨酯喷涂机器喷涂在相应的基材表面制备而成。
喷涂设备优选美国固瑞克A系、E系或H系，进一步优选H系喷涂机；按照喷涂施工工艺员熟知的操作，管路加热温度设定35-45℃，管路压力设定1200-1800psi。
本发明优势在于：
1)采用高官能度曼尼希聚醚多元醇，保证泡沫获得足够的交联度，使泡沫具有良好的尺寸稳定性和机械性能；
2)采用氮磷元素改性聚酯多元醇和磷、氯复合的阻燃剂体系，提高泡沫的阻燃性；
3)采用的聚醚多元醇和聚酯多元醇都含有大量的苯环结构，提高了制得泡沫的机械性能和热稳定性，以及泡沫燃烧过程中的结碳性能，提高泡沫的阻燃性能；
4)采用了零臭氧消耗的环保发泡为物理发泡剂。
本发明制得的聚氨酯泡沫达到了DIN 4102 B1级阻燃要求，依据DIN 4102-15：1990和DIN4102-16：2015难燃性测试测得到烟气温度最大值仅为173.5℃，燃烧剩余长度35cm；依据DIN 4102-1：1998第6.2.5可燃性测试测得最大火焰高度5cm，续燃时间0s，烟气情况少量；同时，泡沫的抗压强度、线性尺寸变化率、导热系数等性能达到船级社对聚氨酯材料超低温保冷技术要求。制得的聚氨酯泡沫不仅能满足用于超低温保冷的要求，还具有较高的阻燃性能。
具体实施方式
为了能够详细地理解本发明的技术特征和内容，以下结合实施例对本发明做进一步说明。
以下实施例中所用到的原料来源如下：
曼尼希聚醚多元醇a：Pruanol 3778，羟值520-540mgKOH/g，粘度12000-17000mPa.s，购于佳化化学股份有限公司；
含氮、磷元素改性的聚酯多元醇b：PS-3158，羟值280-310mgKOH/g，粘度7000-8000mPa.s，购于斯泰潘南京化学有限公司；
芳香族聚酯多元醇c：PS-3175，羟值175-195mgKOH/g，粘度10000-12000mPa.s，购于淄博瑞诺新材料股份有限公司；
有机硅表面活性剂S-193购于上海麦豪化工科技有限公司；
聚氨酯复合催化剂五甲基二乙烯三胺(PC5)、三乙烯二胺(A33)和异辛酸钾(K-15)购于EVONIK；
阻燃剂TCPP购于江苏法力克化工有限公司；
阻燃剂TEP购于张家港雅瑞化工有限公司；
物理发泡剂HFC-245fa购于中化蓝天霍尼韦尔新材料有限公司；
多苯基多亚甲基多异氰酸酯：PM200，NCO含量31.5％，粘度200-250mPa.s，购于万华化学。
实施例1
一种保冷高阻燃喷涂型硬质聚氨酯泡沫，由组分A和组分B经聚氨酯喷涂机器喷涂制得，
其中组分A组成如下：曼尼希聚醚多元醇a，含氮、磷元素改性的聚酯多元醇b，芳香族聚酯多元醇c、有机硅表面活性剂，催化剂，水，物理发泡剂，阻燃剂；组分B为多苯基多亚甲基多异氰酸酯；
具体重量份比组成见表1。
制备方法：将组分A各原料在具有安全装置的搅拌速度为500rpm的混合釜中均匀混合，混合时最好在不锈钢混合釜内进行，混合时间1小时，静置1小时消泡后，放出即得组分A。将组分A和组分B经聚氨酯高压喷涂机器喷涂在干燥的木板或者水泥板上制备聚氨酯泡沫。泡沫熟化48小时后测试各项性能。
实施例2-6
一种保冷高阻燃喷涂型硬质聚氨酯泡沫，由组分A和组分B反应制得，具体组成如下表1，制备方法同实施例1。
制备保冷高阻燃喷涂型硬质聚氨酯泡沫实施例1-6的配方如下表1。
表1
Figure BDA0003860059510000041
硬质聚氨酯泡沫的性能测试采用以下标准：
泡沫密度采用ASTM D1622，抗压强度采用ASTM D1621，闭孔率采用ASTM D6226，导热系数采用ASTM C518，线性热膨胀系数采用ASTM E831-14，难燃性测试采用DIN 4102-15和DIN 4102-16，可燃性测试采用DIN 4102-1，燃烧性能分级采用DIN 4102-1。各实施例制得的硬质聚氨酯泡沫的性能如下表2所示。
表2
Figure BDA0003860059510000051
经测试，实施例1-6所制备的硬质聚氨酯泡沫材料能具有良好的机械性能、低导热系数，且泡沫的燃烧性能达到了DIN 4102 B1级要求。同时将实施例1制备的硬质聚氨酯泡沫送SGS进行三方检测，测试结果显示泡沫的燃烧性能达到DIN 4102 B1级，测试报告编号：AJFS2010009199FF_CN(中文版)、AJFS2010009199FF(英文板)。本发明制备的硬质聚氨酯泡沫可用于超低温保冷领域，且具有优异的阻燃性能。
上述虽然对本发明的具体实施方式进行了描述，但并非对本发明保护范围的限制，所属领域技术人员应该明白，在本发明的技术方案的基础上，本领域技术人员不需要付出创造性劳动即可做出的各种修改或变形仍在本发明的保护范围以内。

Claims (8)

1.一种保冷高阻燃喷涂型硬质聚氨酯泡沫，其特征是，由组分A和组分B经聚氨酯喷涂机器喷涂制得，其中组分A的重量份比组成如下：多元醇主体100份、有机硅表面活性剂1-5份、催化剂2-10份、水0.5-3份、物理发泡剂10-30份、阻燃剂10-20份；所述的多元醇主体为由曼尼希聚醚多元醇a，含氮、磷元素改性的聚酯多元醇b，芳香族聚酯多元醇c按质量比20-30：30-50：30-50混合而成；所述的曼尼希聚醚多元醇a，粘度为25℃时4000-30000mPa.s，羟值为300-600mgKOH/g，官能度为4.5-5.5；所述的含氮、磷元素改性的聚酯多元醇b，粘度为25℃时4000-20000mPa.s，羟值为250-350mgKOH/g，官能度为2.2；所述的聚酯多元醇c，粘度为25℃时10000-15000mPa.s，羟值为150-250mgKOH/g，官能度为2.0；所述的催化剂为发泡型催化剂、凝胶型催化剂、三聚型催化剂三者复配；
组分B为多苯基多亚甲基多异氰酸酯；
组分A与组分B的质量比例为100：100。
2.根据权利要求1所述的一种保冷高阻燃喷涂型硬质聚氨酯泡沫，其特征是，所述的含氮、磷元素改性的聚酯多元醇b选自南京康塑德化工公司的CF6255和斯泰潘公司的PS-3158的一种或两种。
3.根据权利要求1所述的一种保冷高阻燃喷涂型硬质聚氨酯泡沫，其特征是，所述的芳香族聚酯多元醇为苯酐、间苯二甲酸、对苯二甲酸中的一种或多种与乙二醇、丙二醇、丁二醇、双酚A中的一种或多种缩合而成。
4.根据权利要求1所述的一种保冷高阻燃喷涂型硬质聚氨酯泡沫，其特征是，所述的阻燃剂为TCPP(三(2-氯丙基)磷酸酯)、TCEP(三(2-氯乙基)磷酸酯)、TEP(磷酸三乙酯)、DMMP(甲基膦酸二甲酯)中的一种或几种。
5.根据权利要求4所述的一种保冷高阻燃喷涂型硬质聚氨酯泡沫，其特征是，所述的阻燃剂为TCPP与TEP按质量比1：1的混合物。
6.根据权利要求1所述的一种保冷高阻燃喷涂型硬质聚氨酯泡沫，其特征是，所述的发泡型催化剂选自五甲基二乙烯三胺、二吗啉二乙基醚、双(二甲氨基乙基)醚，凝胶型催化剂选自N,N-二甲基环己胺、三乙烯二胺，三聚型催化剂选自N,N’N”-三(二甲胺基丙基)-六氢化三嗪、2,4,6-三(二甲胺基甲基)苯酚、季铵盐、可溶性钾盐、可溶性钠盐。
7.根据权利要求1所述的一种保冷高阻燃喷涂型硬质聚氨酯泡沫，其特征是，所述的物理发泡剂为五氟丙烷、五氟丁烷、一氯三氟丙烯、六氟丁烯中的一种或几种。
8.权利要求1-7任一项所述的一种保冷高阻燃喷涂型硬质聚氨酯泡沫的制备方法，其特征是，包括步骤如下：
(1)组分A的制备：将各原料组分在具有安全装置的混合釜中搅拌均匀混合，混合时间0.5-1小时，静置0.5-1小时消泡后，放出即得组分A；
(2)将组分A和组分B经聚氨酯喷涂机器喷涂在相应的基材表面制备而成。
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CN116426202B (zh) * 2023-03-24 2023-09-26 中国铁道科学研究院集团有限公司 一种寒区隧道用喷涂聚氨酯保温材料及应用和其施工方法
CN116515069B (zh) * 2023-04-10 2023-11-14 天长市伯士的环保新材料有限公司 一种聚氨酯硬泡原料组合物和聚氨酯硬泡及其制备方法
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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011016854A (ja) * 2009-06-11 2011-01-27 Dic Corp 硬質ポリウレタンフォーム用ポリオール組成物及び硬質ポリウレタンフォームの製造方法
JP2011157528A (ja) * 2010-02-03 2011-08-18 Toyo Tire & Rubber Co Ltd 硬質ポリウレタンフォーム用ポリオール組成物および硬質ポリウレタンフォームの製造方法
CN103923294A (zh) * 2013-01-10 2014-07-16 上海联合气雾制品灌装有限公司 单组份阻燃聚氨酯泡沫填缝剂的制备
CN105820369A (zh) * 2011-02-21 2016-08-03 霍尼韦尔国际公司 用于含有卤代烯烃发泡剂的聚氨酯泡沫多元醇预混合料的催化剂
CN108164737A (zh) * 2017-12-27 2018-06-15 上海东大聚氨酯有限公司 一种组合聚醚、聚氨酯原料组合物、聚氨酯泡沫及其制备方法
CN109400839A (zh) * 2018-10-16 2019-03-01 上海东大聚氨酯有限公司 一种阻燃组合聚醚、阻燃聚异氰脲酸酯泡沫及其制备方法
CN111909339A (zh) * 2020-08-10 2020-11-10 万华化学（烟台）容威聚氨酯有限公司 烷烃类发泡b1级阻燃聚氨酯硬质泡沫及其制备方法
CN112239531A (zh) * 2020-10-10 2021-01-19 上海东大聚氨酯有限公司 全水组合聚醚、源自其的高阻燃lng用聚氨酯块泡及其制备方法

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011016854A (ja) * 2009-06-11 2011-01-27 Dic Corp 硬質ポリウレタンフォーム用ポリオール組成物及び硬質ポリウレタンフォームの製造方法
JP2011157528A (ja) * 2010-02-03 2011-08-18 Toyo Tire & Rubber Co Ltd 硬質ポリウレタンフォーム用ポリオール組成物および硬質ポリウレタンフォームの製造方法
CN105820369A (zh) * 2011-02-21 2016-08-03 霍尼韦尔国际公司 用于含有卤代烯烃发泡剂的聚氨酯泡沫多元醇预混合料的催化剂
CN103923294A (zh) * 2013-01-10 2014-07-16 上海联合气雾制品灌装有限公司 单组份阻燃聚氨酯泡沫填缝剂的制备
CN108164737A (zh) * 2017-12-27 2018-06-15 上海东大聚氨酯有限公司 一种组合聚醚、聚氨酯原料组合物、聚氨酯泡沫及其制备方法
CN109400839A (zh) * 2018-10-16 2019-03-01 上海东大聚氨酯有限公司 一种阻燃组合聚醚、阻燃聚异氰脲酸酯泡沫及其制备方法
CN111909339A (zh) * 2020-08-10 2020-11-10 万华化学（烟台）容威聚氨酯有限公司 烷烃类发泡b1级阻燃聚氨酯硬质泡沫及其制备方法
CN112239531A (zh) * 2020-10-10 2021-01-19 上海东大聚氨酯有限公司 全水组合聚醚、源自其的高阻燃lng用聚氨酯块泡及其制备方法
WO2022073403A1 (zh) * 2020-10-10 2022-04-14 上海东大聚氨酯有限公司 全水组合聚醚、源自其的高阻燃lng用聚氨酯块泡及其制备方法

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