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CN104877105B - 一种聚氨酯硬泡组合料及其制备方法 - Google Patents

一种聚氨酯硬泡组合料及其制备方法 Download PDF

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CN104877105B
CN104877105B CN201510226941.1A CN201510226941A CN104877105B CN 104877105 B CN104877105 B CN 104877105B CN 201510226941 A CN201510226941 A CN 201510226941A CN 104877105 B CN104877105 B CN 104877105B
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李同续
周鹏
赵修文
董火成
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Liming Research Institute of Chemical Industry Co Ltd
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Abstract

本发明公开了一种聚氨酯硬泡组合料及其制备方法，本发明聚氨酯硬泡组合料由A、B两组分组成，A组分：聚醚多元醇A40～60份，聚酯多元醇B5～10份，植物油多元醇15～30份，表面活性剂1.0～2.0份，催化剂：0.8～2.2份，水2.0～3.0份，发泡剂HFC‑365mfc/227ea10～20份；B组分：多亚甲基多苯基多异氰酸酯；A/B＝1/1。所述聚醚多元醇A为4～6官能度、数均分子量300～1000的聚氧化丙烯多元醇；聚酯多元醇B为2官能度、分子量为300～700的苯酐聚酯多元醇；所述植物油多元醇C为羟值为200～500的环氧大豆油多元醇。本发明组合料所得泡沫导热系数低，压缩强度大，尺寸稳定性好，成本低。

Description

一种聚氨酯硬泡组合料及其制备方法
技术领域
本发明涉及聚氨酯领域，特别涉及太阳能热水器用聚氨酯硬泡组合料。
背景技术
聚氨酯硬泡因其保温性能优异，被广泛应用于填充太阳能热水器水箱的夹层腔体。
太阳能热水器行业90％以上的聚氨酯泡沫保温采用了HCFC-141b。随着《蒙特利尔公约》第三阶段的实施，将加快HCFC-141b的淘汰。目前，在太阳能热水器领域还没有一种适宜的替代路线，开展新一代替代技术迫在眉睫。
目前潜在的HCFC-141b替代路线主要是全水发泡、烷烃类发泡剂和氢氟烃(HFCs)类发泡剂三大类。
由于全水发泡中C02的气相导热系数(λ)值较高(λ＝16.3mW/(m·K))，以水为发泡剂制得的聚氨酯硬泡制品，导热系数有25％左右的上升，为达到同样的保温性能，全水发泡的泡沫需要更大的用量，消耗更多的异氰酸酯，替代成本较高，在经济上不合算。而戊烷类发泡剂是一类易燃的挥发性有机化合物，它们的爆炸极限下限很低，生产中易发生爆炸。若由HCFC-141b等发泡生产线转换到戊烷发泡，为保证安全生产，需对现有计量、贮存及发泡设备进行较大的改进，增加复杂的安全处理设施，操作工艺需严格控制，以保证安全生产。因而安全、设备成本、运行管理成本较HCFC-141b发泡体系的高。目前HFC-365/227的价格较高，且HFC-365/227的分子量比比HCFC-141b大，相同质量的发泡剂，HFC-365/227的物质的量比HCFC-141b的小，欲达到与HCFC-141b相同的发泡密度，做为发泡剂的HFC-365/227需添加更多的量，其成本高，业界人士难以接受；若以水来替代部分HFC-365/227，又会引起异氰酸酯使用量的增加，而异氰酸酯的价格通常是高于组合聚醚的。
专利CN101787203B公开了一种采用五氟丁烷(HFC-365mfc)为发泡剂的 太阳能热水器用组合料及制备方法，以五氟丁烷代替HCFC-141b制得满足太阳能热水器用组合料，但导热系数较高，由于完全使用HFC-365mfc为发泡剂，成本较高。
专利CN101555312B公开了一种性能改进的硬质泡沫塑料及其制备方法。使用环戊烷与HFC-365mfc、HFC-245fa和全氟烷烃的混合物做为发泡剂，以降低泡沫的导热系数，但从实施例看出其导热系数不低于0.0182W/m·K。
专利CN102167901B公开了一种聚氨酯硬质泡沫组合聚醚，以环戊烷和HFC-365/227的混合物为发泡剂，所得泡沫导热系数在18.5～19.5mW/m·K。
发明内容
本发明要解决的第一个技术问题是提供一种聚氨酯硬泡组合料，该组合料所得泡沫导热系数低，成本低。
本发明要解决的第二个技术问题是提供一种该聚氨酯硬泡组合料的制备方法。
本发明聚氨酯硬泡组合料由A、B两组分组成，以重量份计包括：
A组分：
聚醚多元醇A：40～60份
聚酯多元醇B：5～10份
植物油多元醇：15～30份
表面活性剂：1.0～2.0份
催化剂：0.8～2.2份
水：2.0～3.0份
发泡剂HFC-365mfc/227ea：10～20份
B组分：
多亚甲基多苯基多异氰酸酯
A/B＝1/1
其中，所述的A组分中聚醚多元醇A为4～6官能度、数均分子量300～1000的聚氧化丙烯多元醇；聚酯多元醇B为2官能度、分子量为300～700的苯酐聚酯多元醇；所述植物油多元醇C为羟值为200～500的环氧大豆油多元醇。
所述的A组分中催化剂包括胺类和/或金属类催化剂，优选N，N-二甲基环己胺、五甲基二乙烯三胺、N，N-二甲基苄胺、1，3，5-三(二甲基氨基丙基)六氢三嗪，双(2-二甲氨基乙基)醚、三乙烯二胺、有机锡、有机铋或有机锌化合物的一种或几种的任意组合。
所述的发泡剂为1，1，1，3，3-五氟丁烷(HFC-365mfc)和1，1，1-2-3，3，3-七氟丙烷(HFC-227ea)以93∶7或83∶17组成的混合物。
所述的表面活性剂有利于稳定发泡反应混合物。任何合适的表面活性剂均可用于本发明，包括硅氧烷/环氧乙烷/环氧丙烷共聚物。可用于本发明的表面活性剂的例子包括可从美国空气化工产品公司(Air Products and Chemicals，Inc)、赢创德固赛公司(Evonik Degussa GmbH)、迈图高新材料集团公司(Momentive Performance MaterialsInc.)、南京美思德公司等制造商购得的表面活性剂，优选AK-8801，AK-8808，AK-8818，AK-8811，AK-8832(南京美思德公司)，L-5346、L-6900、L-6840、L-5511、L-5566(迈图高新材料集团公司)，B8460、B8545、B84805(赢创德固赛公司)，DC5598、DC5357(美国空气化工产品公司)。
所述的B组分原料中的多异氰酸酯为多亚甲基多苯基多异氰酸酯，包括聚合MDI、液化改性MDI等，优选烟台万华公司的PM-200，8002，Huntsman公司的5005S，Bayer公司的44V20，BASF公司的M20S。
所述的聚氨酯硬泡组合料的制备方法，包括以下步骤：
A组分的制备：将聚醚多元醇A、聚酯多元醇B、植物油多元醇C、催化剂、表面活性剂、水和发泡剂按比例投入反应釜中，室温下搅拌混合1～2小时，密 封包装；
B组分为聚合二苯基甲烷二异氰酸酯，直接装桶。
本发明相对于现有技术具有以下效果和优点：
(1)本发明组合料所得泡沫导热系数低，压缩强度大，尺寸稳定性好。
(2)不用环戊烷，选用水与HFC-365mfc/227ea为发泡剂，通过提高水用量，减少HFC-365mfc/227ea的用量，降低成本。
(3)在配方中引入低羟值、价格低廉的环氧大豆油多元醇，减少石油基聚醚多元醇的使用，在不增加异氰酸酯消耗的情况下，降低整个组合聚醚的成本。
具体实施方式
下面结合实施例对本发明做进一步详细的描述，但是本发明的实施方式不限于此。
实施例1
A组分的制备：
将准确计量的聚醚多元醇A(官能度4.5，分子量670)56份、聚酯多元醇B(2官能度，数均分子量350)5份、环氧大豆油多元醇(羟值450)15份，催化剂三乙烯二胺0.05份，五甲基二乙烯三胺0.3份，N，N-二甲基环己胺0.65份(空气化工产品公司)、表面活性剂AK-8808(南京美思德公司)1份、发泡剂HFC-365mfc/227ea(83∶17)(索尔维公司)20份，水2份，投入反应釜中，搅拌混合2h出料，密封包装；
将A、B组分料按A∶B＝100∶100重量配比混合反应，制得泡沫，检测产品质量。
模塑芯密度：36.2kg/m3
压缩强度：223kPa
导热系数：17.6mW·(m·K)-1
尺寸稳定性：
-20℃，24h：0.012％
70℃，24h：0.021％
闭孔率：94％
实施例2
A组分的制备：
将准确计量的聚醚多元醇A(官能度4.3，分子量500)50份、聚酯多元醇B(2官能度，数均分子量500)7份、植物油多元醇C(羟值310)20份，催化剂五甲基二乙烯三胺(美国空气化工产品公司)0.3份，N，N-二甲基苄胺(美国空气化工产品公司)0.5份，1，3，5-三(二甲基氨基丙基)六氢三嗪(美国空气化工产品公司)0.2份，N，N-二甲基环己胺(美国空气化工产品公司)1份、表面活性剂AK-8801(南京美思德)1.5份、发泡剂HFC-365/227(索尔维公司)(93∶7)17份，水2.5份，投入反应釜中，搅拌混合2小时后出料、密封包装；
将A、B组分料按A∶B＝100∶100重量配比混合反应，制得泡沫，检测产品质量。
模塑芯密度：36.8kg/m3
压缩强度：216kPa
导热系数：18.0mW·(m·K)-1
尺寸稳定性：
-20℃，24h：0.168％
70℃，24h：0.146％
闭孔率：94％
实施例3
A组分的制备：
将准确计量的聚醚多元醇A(官能度5.2，分子量850)44份、聚酯多元醇B(2官能度，分子量670)10份、植物油多元醇C(羟值210)30份，催化剂N，N-二甲基环己胺0.8份(美国空气化工产品公司)，N，N-二甲基苄胺(美国空气化工产品公司)0.4份，双(2-二甲氨基乙基)醚0.2份(美国空气化工产品公司)、表面活性剂L-5466(迈图高新材料集团公司)1.6份、发泡剂HFC-365mfc/227ea(索尔维公司)(83∶17)10份，水3份，投入反应釜中，搅拌混合2小时后出料、密封包装；
将A、B组分料按A∶B＝100∶100重量配比混合反应，制得泡沫，检测产品质量。
模塑芯密度：37.1kg/m3
压缩强度：207kPa
导热系数：17.8mW·(m·K)-1
尺寸稳定性：
-20℃，24h：0.227％
70℃，24h：0.353％
闭孔率：92％。

Claims (7)

1.一种聚氨酯硬泡组合料，以重量份计包括：
A组分：
聚醚多元醇A：40～60份
聚酯多元醇B：5～10份
植物油多元醇C：15～30份
表面活性剂：1.0～2.0份
催化剂：0.8～2.2份
水：2.0～3.0份
发泡剂HFC-365mfc/227ea：10～20份
B组分：
多亚甲基多苯基多异氰酸酯
A/B＝1/1；
所述的A组分中聚醚多元醇A为4～6官能度、分子量300～1000的聚氧化丙烯多元醇；聚酯多元醇B为2官能度、分子量为300～700的苯酐聚酯多元醇；所述植物油多元醇C为羟值为200～500的环氧大豆油多元醇。
2.根据权利要求1所述的聚氨酯硬泡组合料，所述的A组分中催化剂是指胺类和/或金属类催化剂。
3.根据权利要求1所述的聚氨酯硬泡组合料，所述的A组分中催化剂是指N，N-二甲基环己胺、五甲基二乙烯三胺、N，N-二甲基苄胺、1，3，5-三(二甲基氨基丙基)六氢三嗪，双(2-二甲氨基乙基)醚、三乙烯二胺、有机锡、有机铋或有机锌化合物的一种或几种的任意组合。
4.根据权利要求1所述的聚氨酯硬泡组合料，所述的发泡剂为1，1，1，3，3-五氟丁烷(HFC-365mfc)和1，1，1-2-3，3，3-七氟丙烷(HFC-227ea)以93∶7或83∶17组成的混合物。
5.根据权利要求1所述的聚氨酯硬泡组合料，所述表面活性剂为南京美思德公司的AK-8801、AK-8808、AK-8818、AK-8811、AK-8832；迈图高新材料集团公司的L-5346、L-6900、L-6840、L-5511、L-5566；赢创德固赛公司的B8460、B8545、B84805；美国空气化工产品公司DC5598、DC5357产品。
6.根据权利要求1所述的聚氨酯硬泡组合料，所述的B组分是指烟台万华公司的PM-200、PM-8002、Huntsman公司的5005S。
7.一种制备权利要求1～6之一所述的聚氨酯硬泡组合料的方法，包括以下步骤：
A组分的制备：将聚醚多元醇A、聚酯多元醇B、植物油多元醇C、催化剂、表面活性剂、水和发泡剂按比例投入反应釜中，室温下搅拌混合1～2小时，密封包装；
B组分为聚合二苯基甲烷二异氰酸酯，直接装桶。
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