CN109666116B - 一种高强度冷藏车厢硬质聚氨酯 - Google Patents

一种高强度冷藏车厢硬质聚氨酯 Download PDF

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CN109666116B
CN109666116B CN201811612939.8A CN201811612939A CN109666116B CN 109666116 B CN109666116 B CN 109666116B CN 201811612939 A CN201811612939 A CN 201811612939A CN 109666116 B CN109666116 B CN 109666116B
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王宏
谭汉辉
毕沛炳
王碧莹
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Guangzhou Baier Airport Cold Chain Logistics Center Co ltd
GUANGZHOU BAIER COLD-CHAIN POLYURETHANE TECHNOLOGY CO LTD
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Abstract

一种高强度冷藏车厢硬质聚氨酯，由A组份和B组份组成，两者重量比为1:1.2‑1.5，B组份为多亚甲基多苯基异氰酸酯，A组份包括如下重量百分比的原料：聚醚多元醇Ⅰ为35‑45%，聚醚多元醇Ⅱ为5‑15%，聚醚多元醇Ⅲ为5‑10%，聚酯多元醇Ⅰ为5‑15%，泡沫稳定剂为1.5‑2.5%，催化剂为0.5‑2%，水为1.0‑2.5%，发泡剂为5‑25%，阻燃剂为10‑15%；其中：聚醚多元醇Ⅰ官能度为4‑7，数均分子量为500‑800；聚醚多元醇Ⅱ官能度为4‑6，数均分子量为500‑700；聚醚多元醇Ⅲ官能度为3.5‑5，数均分子量为400‑600；聚酯多元醇Ⅰ官能度2‑3，数均分子量300‑500；多亚甲基多苯基异氰酸酯25℃下粘度为350‑500mPa.s。采用上述配方制得的聚氨酯强度高且保温效果好。

Description

一种高强度冷藏车厢硬质聚氨酯
技术领域
本发明涉及聚氨酯，尤其是一种高强度冷藏车厢硬质聚氨酯。
背景技术
冷藏车的冷藏厢体，一般由玻璃钢板材外层、聚氨酯保温中间层以及玻璃钢板材内层，由于玻璃钢板材本身强度有限，这就要求硬质聚氨酯不仅要保温效果好，还需要具有较好的强度，否则，在车厢承重大或者通过叉车搬运过程中，容易造成冷藏厢体的损坏，造成经济损失，另外聚氨酯保温中间层直接影响冷藏厢体的使用寿命。
见专利号为CN201510542073.8的中国发明专利，公开了一种组合聚醚、聚氨酯原料组合物、泡沫及制备方法和应用，其主要应用于冷柜、冰箱冷藏以及集装箱等领域，其在拥有较低的导热系数的情况下，压缩强度为208至215 kPa之间，强度有待进一步提高。
发明内容
本发明目的是提供一种高强度冷藏车厢硬质聚氨酯，为达到上述目的，本发明采用如下技术方案：
一种高强度冷藏车厢硬质聚氨酯，由A组份和B组份组成，两者重量比为1:1.2-1.5，B组份为多亚甲基多苯基异氰酸酯，A组份包括如下重量百分比的原料：聚醚多元醇Ⅰ为35-45%，聚醚多元醇Ⅱ为5-15%，聚醚多元醇Ⅲ为5-10%，聚酯多元醇Ⅰ为5-15%，泡沫稳定剂为1.5-2.5%，催化剂为0.5-2%，水为1.0-2.5%，发泡剂为5-25%，阻燃剂为10-15%；其中：
所述聚醚多元醇Ⅰ是官能度为4-7，数均分子量为500-800，羟值为435-465mgKOH/g，25℃下粘度为16000-19000mPa.s的聚醚多元醇；所述聚醚多元醇Ⅱ是官能度为4-6，数均分子量为500-700，羟值为440-470mgKOH/g，25℃下粘度为13000-17000mPa.s的山梨醇聚醚多元醇；所述聚醚多元醇Ⅲ是官能度为3.5-5，数均分子量为400-600，羟值为385-415mgKOH/g，25℃下粘度为11000-15000mPa.s的甲苯二胺聚醚多元醇；所述聚酯多元醇Ⅰ官能度2-3，数均分子量300-500的聚酯多元醇；所述多亚甲基多苯基异氰酸酯25℃下粘度为350-500mPa.s。
进一步的，所述聚醚多元醇Ⅰ为河北亚东化工集团有限公司生产的聚醚多元醇YD8315，所述聚醚多元醇Ⅱ为河北亚东化工集团有限公司生产的山梨醇聚醚多元醇YD600，所述聚醚多元醇Ⅲ为河北亚东化工集团有限公司生产的甲苯二胺聚醚多元醇YD401P，所述聚酯多元醇Ⅰ为南京金陵斯泰潘化学有限公司生产的聚酯多元醇PS4027。
进一步的，B组份所述多亚甲基多苯基异氰酸酯为万华化学集团股份有限公司生产的多亚甲基多苯基异氰酸酯PM400。
进一步的，所述泡沫稳定剂为赢创德固赛有限公司生产的硅碳键耐水解型聚硅氧烷-聚醚共聚物B8545。
进一步的，所述催化剂为N,N-二甲基环己胺、三乙烯二胺、二甲基乙醇胺、三乙醇胺、N,N-二甲基苄胺、五甲基二亚乙基三胺、1,3,5-三（二甲氨基丙基）六氢三嗪以及2,4,6-（二甲氨基甲基）苯酚一种或多种。
进一步的，所述催化剂为五甲基二亚乙基三胺、N,N-二甲基环己胺以及1,3,5-三（二甲氨基丙基）六氢三嗪三种复配使用。
进一步的，所述发泡剂为1，1，1，3，3-五氟丁烷（HFC-365mfc）、1，1，1，3，3-五氟丙烷（HFC-245fa）、反式-1-氯-3,3,3-三氟丙烯（LBA）、环戊烷、异戊烷以及正戊烷中的一种或多种。
进一步的，所述发泡剂为1，1，1，3，3-五氟丁烷（HFC-365mfc）和1，1，1，3，3-五氟丙烷（HFC-245fa）按93:7的比例复配使用。
进一步的，所述阻燃剂为三（2-氯丙基）磷酸酯（TCPP）、甲基膦酸二甲酯（DMMP）以及磷酸三乙酯（TEP）中的一种或多种。
作为一个优选的方案，A组分中，所述聚醚多元醇Ⅰ为聚醚多元醇YD8315，所述聚醚多元醇Ⅱ为山梨醇聚醚多元醇YD600，所述聚醚多元醇Ⅲ为甲苯二胺聚醚多元醇YD401P，所述聚酯多元醇Ⅰ为聚酯多元醇PS4027，所述泡沫稳定剂为硅碳键耐水解型聚硅氧烷-聚醚共聚物B8545，所述催化剂为五甲基二亚乙基三胺、N,N-二甲基环己胺以及1,3,5-三（二甲氨基丙基）六氢三嗪三种复配使用，所述发泡剂为1，1，1，3，3-五氟丁烷（HFC-365mfc）和1，1，1，3，3-五氟丙烷（HFC-245fa）两种按93:7的比例复配使用，所述阻燃剂为三（2-氯丙基）磷酸酯（TCPP）；B组份中所述多亚甲基多苯基异氰酸酯为多亚甲基多苯基异氰酸酯PM400；
A组分中各原料重量百分比如下：
聚醚多元醇YD8315为42.2%，山梨醇聚醚多元醇YD600为5%，苯二胺聚醚多元醇YD401P为10%，聚酯多元醇PS4027为10%，泡沫稳定剂B8545为2%，催化剂五甲基二亚乙基三胺为0.2%，催化剂N,N-二甲基环己胺为0.4%，催化剂1,3,5-三（二甲氨基丙基）六氢三嗪为0.3%，水为1.4%，发泡剂为18%，阻燃剂三（2-氯丙基）磷酸酯（TCPP）为10.5%。
采用上述技术方案，压缩强度可以达到280kPa以上，强度高，导热系数低，能很好的适用于大型冷藏厢，具有很好的冷藏效果。
具体实施方式
一种高强度冷藏车厢硬质聚氨酯，由A组份和B组份组成，两者重量比为1:1.2-1.5，B组份为多亚甲基多苯基异氰酸酯，A组份包括如下重量百分比的原料：聚醚多元醇Ⅰ为35-45%，聚醚多元醇Ⅱ为5-15%，聚醚多元醇Ⅲ为5-10%，聚酯多元醇Ⅰ为5-15%，泡沫稳定剂为1.5-2.5%，催化剂为0.5-2%，水为1.0-2.5%，发泡剂为5-25%，阻燃剂为10-15%；其中：
聚醚多元醇Ⅰ是官能度为4-7，数均分子量为500-800，羟值为435-465mgKOH/g，25℃下粘度为16000-19000mPa.s的聚醚多元醇；聚醚多元醇Ⅱ是官能度为4-6，数均分子量为500-700，羟值为440-470mgKOH/g，25℃下粘度为13000-17000mPa.s的山梨醇聚醚多元醇；聚醚多元醇Ⅲ是官能度为3.5-5，数均分子量为400-600，羟值为385-415mgKOH/g，25℃下粘度为11000-15000mPa.s的甲苯二胺聚醚多元醇；聚酯多元醇Ⅰ官能度2-3，数均分子量300-500的聚酯多元醇；多亚甲基多苯基异氰酸酯25℃下粘度为350-500mPa.s。
催化剂为N,N-二甲基环己胺、三乙烯二胺、二甲基乙醇胺、三乙醇胺、N,N-二甲基苄胺、五甲基二亚乙基三胺、1,3,5-三（二甲氨基丙基）六氢三嗪以及2,4,6-（二甲氨基甲基）苯酚一种或多种。
发泡剂为1，1，1，3，3-五氟丁烷（HFC-365mfc）、1，1，1，3，3-五氟丙烷（HFC-245fa）、反式-1-氯-3,3,3-三氟丙烯（LBA）、环戊烷、异戊烷以及正戊烷中的一种或多种。
阻燃剂为三（2-氯丙基）磷酸酯（TCPP）、甲基膦酸二甲酯（DMMP）以及磷酸三乙酯（TEP）中的一种或多种。
作为优选的实施例：
A组分如下：
聚醚多元醇Ⅰ为河北亚东化工集团有限公司生产的聚醚多元醇YD8315，聚醚多元醇Ⅱ为河北亚东化工集团有限公司生产的山梨醇聚醚多元醇YD600，聚醚多元醇Ⅲ为河北亚东化工集团有限公司生产的甲苯二胺聚醚多元醇YD401P，聚酯多元醇Ⅰ为南京金陵斯泰潘化学有限公司生产的聚酯多元醇PS4027。
泡沫稳定剂为赢创德固赛有限公司生产的硅碳键耐水解型聚硅氧烷-聚醚共聚物B8545。催化剂为五甲基二亚乙基三胺（PC5）、N,N-二甲基环己胺（PC8）以及1,3,5-三（二甲氨基丙基）六氢三嗪（PC41）三种复配使用。发泡剂为1，1，1，3，3-五氟丁烷（HFC-365mfc）和1，1，1，3，3-五氟丙烷（HFC-245fa）两种按93:7的比例复配使用，阻燃剂为三（2-氯丙基）磷酸酯（TCPP）。
B组份多亚甲基多苯基异氰酸酯为万华化学集团股份有限公司生产的多亚甲基多苯基异氰酸酯PM400。
针对上述优选的实施例，按照不同的配比，具体成分配比和性能如下：
下表为组份和含量表，表中所记录数据为该组分重量占总重量百分比。
Figure 973324DEST_PATH_IMAGE001
将上述制得的聚氨酯与多亚甲基多苯基异氰酸酯PM400按照重量比1:1.25在原料温度22℃下，用高压发泡机注入模具进行发泡，模具温度40℃，自模具合模开始计时，1小时后开模，制得高强度冷厢车厢聚氨酯硬泡。聚氨酯硬质泡沫开模后在常温下熟化24h后测试相关性能。
Figure 156044DEST_PATH_IMAGE002
由表上参数可知，该法制得的聚氨酯硬质泡沫强度均高于250kPa，可达280 kPa以上，远高于市场上传统的泡沫板，如背景技术所述的聚氨酯硬质泡沫。属于使用方便，生产效率高，环保的高性能产品，能很好的适用于大型冷藏厢，且具有良好的冷藏效果，另一方面，上述原料市场皆有售，方便采购。同时聚氨酯的配方具有极大的可调性，可以通过不同组份的调整来制备不同密度不同性能的泡沫板材，通用性强。
以上仅为本发明的优选实施例而已，并不用于限制本发明，对于本领域的技术人员来说，本发明可以有各种更改、组合和变化。凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的权利要求范围之内。

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1.一种高强度冷藏车厢硬质聚氨酯，其特征在于：由A组份和B组份组成，两者重量比为1:1.2-1.5，B组份为多亚甲基多苯基异氰酸酯，A组份包括如下重量百分比的原料：聚醚多元醇YD8315为42.2%，山梨醇聚醚多元醇YD600为5%，苯二胺聚醚多元醇YD401P为10%，聚酯多元醇PS4027为10%，泡沫稳定剂B8545为2%，催化剂五甲基二亚乙基三胺为0.2%，催化剂N,N-二甲基环己胺为0.4%，催化剂1,3,5-三（二甲氨基丙基）六氢三嗪为0.3%，水为1.4%，发泡剂为18%，阻燃剂三（2-氯丙基）磷酸酯（TCPP）为10.5%；
所述发泡剂为1，1，1，3，3-五氟丁烷（HFC-365mfc）和1，1，1，3，3-五氟丙烷（HFC-245fa）两种按93:7的比例复配使用；
B组份中所述多亚甲基多苯基异氰酸酯为多亚甲基多苯基异氰酸酯PM400。
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