CN101646723A - 氢氯氟烯烃以及氢氟烯烃的发泡剂组合物 - Google Patents

氢氯氟烯烃以及氢氟烯烃的发泡剂组合物 Download PDF

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CN101646723A
CN101646723A CN200880010511A CN200880010511A CN101646723A CN 101646723 A CN101646723 A CN 101646723A CN 200880010511 A CN200880010511 A CN 200880010511A CN 200880010511 A CN200880010511 A CN 200880010511A CN 101646723 A CN101646723 A CN 101646723A
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B·B·陈
J·S·科斯塔
P·波内特
M·Y·艾尔希科
B·L·范霍恩
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Abstract

在此披露了一种用于热固性泡沫的发泡剂。该发泡剂是一种氢氟烯烃(HCFO)、优选HFCO－1234yf与一种氢氯氟烯烃(HCFO)的组合，该氢氯氟烯烃是优选是选自HCFO－1233zd、HCFO－1223、HCFO－1233xf以及它们的混合物中的一种。该发泡剂作为热固性泡沫生产中的一种发泡剂是有效的。

Description

氢氯氟烯烃以及氢氟烯烃的发泡剂组合物
发明领域
本发明涉及用于热固性泡沫的发泡剂。更具体地说，本发明涉及至少一种氢氟烯烃(例如HFO-1234yf)与至少一种氢氯氟烯烃(HCFO)(例如HCFO-1233zd、HCFO-1223、HCFO-1233xf以及它们的混合物)的组合作为一种发泡剂在热固性泡沫生产中的用途。
发明背景
用于臭氧层保护的蒙特利尔议定书(于1987年10月签署)命令逐步淘汰氯氟烃类(CFC)的使用。对臭氧层更“友好”的材料，例如氢氟烷类(HFC)(例如HFC-134a)取代了氯氟烃类。后者的化合物已证明是温室气体，温室气体引起全球变暖并且受关于气候变化的京都议定书(于1998年签署)所管辖。所出现的替代材料(氢氟丙烯类)表明是环境可接受的，即具有零臭氧消耗潜势(ODP)以及可接受的低全球变暖潜势(GWP)。
当前使用的用于热固性泡沫的发泡剂包括HFC-134a、HFC-245fa、HFC-365mfc(具有相对高的全球变暖潜势)，以及烃类(例如可燃的并且具有低能量效率的戊烷异构体类)。因此，正在寻找新的可替代的发泡剂。卤化的氢烯烃类物质(例如氢氟丙烯类和/或氢氯氟丙烯类)作为HFC的代替物已产生了的兴趣。这些材料在低层大气中的固有的化学不稳定性提供了所希望的低的全球变暖潜势以及零或接近零的臭氧消耗潜势。
本发明的目的是提供可充当用于热固性泡沫的发泡剂的新颖的组合物，该组合物提供了独特的特性来满足低的或零臭氧消耗潜势、更低的全球变暖潜势的需要并且显示出低的毒性。
发明内容
本发明涉及基于不饱和的卤化的氢烯烃的发泡剂的用途，此类发泡剂具有可忽略的(低的或零)臭氧消耗和低的全球变暖潜势。此类发泡剂包括至少一种氢氟烯烃(优选(HFO)HFO-1234yf)与至少一种氢氯氟烯烃(HCFO)(例如HCFO-1233zd、HCFO-1223、HCFO-1233xf以及它们的混合物)的组合。HFO-1234yf是2，3，3，3-四氟丙烯；HCFO 1223是二氯三氟丙烯；HCFO-1233zd是1-氯-3，3，3-三氟丙烯；HCFO1233xf是2-氯-3，3，3-三氟丙烯。该组合物可以进一步包括一种额外的氢氟烯烃(HFO)、一种氢氟烷、一种烃、一种醇、一种酯、一种醛、一种酮醚/二醚、二氧化碳以及它们的混合物。
氢氟烯烃(HFO)材料已被提议作为发泡剂，此类发泡剂显示出低的全球变暖潜势以及低的臭氧消耗值。低的全球变暖潜势以及低的臭氧消耗值是氢氟烯烃类的大气降解作用的一个结果。
通过在一种多元醇混合物中混合，该氢氟烯烃(优选HFO-1234yf)与一种氢氯氟烯烃(HCFO)(优先选自HCFO-1223、HCFO-1233zd、HCFO-1233xf以及它们的混合物)的组合可以作为一种发泡剂用于热固性泡沫。所生成的产物显示出优越的品质，包括减小的密度以及改进的k-因数。该发泡剂在热固性聚合物中溶解，并且提供了足以生产可接受的泡沫的一定程度的增塑作用。
在生产聚氨酯以及聚异氰脲酸酯泡沫中使用的多元醇混合物中，本发明优选的发泡剂组合物，氢氟烯烃(优选HFO-1234yf)与一种氢氯氟烯烃(HCFO)(优先选自HCFO-1223、HCFO-1233zd、HCFO-1233xf以及它们的混合物)的组合，显示出良好的溶解性。氢氟烯烃(优选HFO-1234yf)组分与一种氢氯氟烯烃(HCFO)(优先选自HCFO-1223、HCFO-1233zd、HCFO-1233xf以及它们的混合物)的组合的一个优选比率是大于约5wt％的氢氟烯烃。
本发明的氢氟烯烃(优选HFO-1234yf)与一种氢氯氟烯烃(HCFO)(优先选自HCFO-1223、HCFO-1233zd、HCFO-1233xf以及它们的混合物)的组合可以在与低的或零臭氧消耗值物质的组合中使用，这些物质包括但不局限于：(a)氢氟烷类，包括但不局限于二氟甲烷(HFC32)、1，1，1-三氟乙烷(143a)、1，1，1，2，2-五氟乙烷(HFC125)、1，1，2，2-四氟乙烷(HFC134)、1，1，1，2-四氟乙烷(HFC134a)、1，1-二氟乙烷(HFC152a)、1，1，1，2，3，3，3-七氟丙烷(HFC227ea)、1，1，1，3，3-五氟丙烷(HFC245fa)、1，1，1，3，3-五氟丁烷(HFC365mfc)以及1，1，1，2，2，3，4，5，5，5-十氟戊烷(HFC4310mee)。(b)另外的氢氟烯烃类(除HFO-1234yf之外)，包括但不局限于四氟丙烯类(例如HFO1234ze)、三氟丙烯类(HFO1243zf)、所有的四氟丁烯异构体类(HFO1354)、所有的五氟丁烯异构体类(HFO1345)、所有的六氟丁烯异构体类(HFO1336)、所有的七氟丁烯异构体类(HFO1327)、所有的七氟戊烯异构体类(HFO1447)、所有的八氟戊烯异构体类(HFO1438)、所有的九氟戊烯异构体类(HFO1429)；(c)烃类，包括但不局限于戊烷异构体类、丁烷异构体类；(d)C1至C5的醇类、C1至C4的醛类、C1至C4的酯类、C1至C4的酮类、C1至C4的醚类和二醚类以及二氧化碳。
根据本发明，本发明的可起泡的组合物总体而言包括能够形成泡沫(具有一种总体上多孔的结构)的一种或多种组分以及一种发泡剂，典型的是在一个组合中。在某些实施方案中，该一种或多种组分包括一种能够形成泡沫的热固性组合物和/或可起泡的组合物。热固性组合物的实例包括聚氨酯以及聚异氰脲酸酯泡沫组合物，以及还有酚类的泡沫组合物。在此类热固性泡沫的实施方案中，包括本发明的一种或多种组合物作为在一种可起泡的组合物中的一种发泡剂或发泡剂的一部分，或作为一种两部分或多部分的可起泡组合物的一部分，该可起泡组合物优选包括在适当的条件下能够反应和/或能够起泡以形成一种泡沫或多孔结构的一种或多种组分。
本发明还涉及从一种聚合物泡沫配制品制备的泡沫，并且优选闭孔泡沫，该聚合物泡沫配制品含有包括本发明的组合物的一种发泡剂。然而在其他的实施方案中，本发明提供了可起泡的组合物，这类组合物包括热固性泡沫，例如聚氨酯以及聚异氰脲酸酯泡沫，优选柔性或刚性的低密度泡沫。
本领域的那些普通技术人员将理解到，本发明的发泡剂组合形成和/或加入可起泡的组合物的顺序和方式总体上不影响本发明的可操作性。例如，在聚氨酯泡沫的情况下，有可能该发泡剂组合的不同组分(以及甚至本发明的组合物的多个组分)不在引入发泡设备之前混合，或者甚者这些组分不加入该发泡设备中的同一位置。因此，在某些实施方案中，可能希望在一台共混机中引入该发泡剂组合的一种或多种组分，预期这些组分将在该发泡设备中汇合到一起和/或以这种方式更有效地运作。尽管如此，在某些实施方案中，使该发泡剂组合中的一种或多种组分提前结合，并且一起引入该起泡组合物中(直接地或作为预混合料的一部分)，然后进一步加入该可起泡组合物的其他部分。
虽然在此参照特定的实施方案对本发明进行了展示和说明，但无意将所附的权利要求限制为所示的细节。相反，在此预期本领域的普通技术人员可对这些细节做出不同的变更，这些变更仍然会在所要求的主题的精神和范围之内，并且在此企望对这些权利要求进行相应的诠释。

Claims (11)

1.一种用于热固性泡沫的聚合物发泡剂组合物，包括(a)HFO-1234yf与(b)至少一种氢氯氟烯烃(HCFO)的组合。
2.如权利要求1所述的聚合物发泡剂组合物，其中所述氢氯氟烯烃是选自下组，其构成为：HCFO-1233zd、HCFO-1223、HCFO-1233xf以及它们的混合物，并且进一步地其中所述HFO-1234yf包括所述聚合物发泡剂组合物的大约5wt％或更多。
3.如权利要求2所述的聚合物发泡剂组合物，进一步包括一种氢氟烷。
4.如权利要求3所述的聚合物发泡剂组合物，其中所述氢氟烷是选自下组，其构成为：二氟甲烷(HFC32)、1，1，1，2，2-五氟乙烷(HFC125)、1，1，1-三氟乙烷(143a)、1，1，2，2-四氟乙烷(HFC134)、1，1，1，2-四氟乙烷(HFC134a)、1，1-二氟乙烷(HFC152a)、1，1，1，2，3，3，3-七氟丙烷(HFC227ea)、1，1，1，3，3-五氟丙烷(HFC245fa)、1，1，1，3，3-五氟丁烷(HFC365mfc)以及1，1，1，2，2，3，4，5，5，5-十氟戊烷(HFC4310mee)。
5.如权利要求2所述的聚合物发泡剂组合物，进一步包括选自下组的一种第二氢氟烯烃，该组的构成为：四氟丙烯类(HFO1234ze)、三氟丙烯类(HFO1243zf)、四氟丁烯异构体类(HFO1354)、五氟丁烯异构体类(HFO1345)、六氟丁烯异构体类(HFO1336)、七氟丁烯异构体类(HFO1327)、七氟戊烯异构体类(HFO1447)、八氟戊烯异构体类(HFO1438)以及九氟戊烯异构体类(HFO1429)。
6.如权利要求1所述的聚合物发泡剂组合物，进一步包括选自下组的一种组分，该组的构成为：一种第二氢氟烯烃(HFO)、一种氢氟烷、一种烃、一种醇、一种酯、一种醛、一种酮醚/二醚、二氧化碳以及它们的混合物。
7.一种聚氨酯泡沫的发泡方法，包括将多种聚合物泡沫类组分与一种泡沫发泡剂进行混合，该泡沫发泡剂包含(a)HFO-1234yf与(b)至少一种氢氯氟烯烃(HCFO)的组合。
8.如权利要求7所述的方法，其中所述氢氯氟烯烃是选自下组，其构成为：HCFO-1233zd、HCFO-1223、HCFO-1233xf以及混合物，并且进一步地其中所述HFO-1234yf包括所述聚合物发泡剂组合物的大约5wt％或更多。
9.如权利要求8所述的方法，其中所述聚合物发泡剂组合物进一步包括一种氢氟烷。
10.如权利要求9所述的方法，其中所述氢氟烷是选自下组，其构成为：二氟甲烷(HFC32)、1，1，1，2，2-五氟乙烷(HFC125)、1，1，1-三氟乙烷(HFC143a)、1，1，2，2-四氟乙烷(HFC134)、1，1，1，2-四氟乙烷(HFC134a)、1，1-二氟乙烷(HFC152a)、1，1，1，2，3，3，3-七氟丙烷(HFC227ea)、1，1，1，3，3-五氟丙烷(HFC245fa)、1，1，1，3，3-五氟丁烷(HFC365mfc)以及1，1，1，2，2，3，4，5，5，5-十氟戊烷(HFC4310mee)。
11.如权利要求8所述的方法，进一步包括选自下组的一种第二氢氟烯烃，该组的构成为：四氟丙烯类(HFO1234ze)、三氟丙烯类(HFO1243zf)、四氟丁烯异构体类(HFO1354)、五氟丁烯异构体类(HFO1345)、六氟丁烯异构体类(HFO1336)、七氟丁烯异构体类(HFO1327)、七氟戊烯异构体类(HFO1447)、八氟戊烯异构体类(HFP1438)以及九氟戊烯异构体类(HFP1429)。
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Application publication date: 20100210