CN101652412A - 氢氟丙烯与氢氯氟烯烃的发泡剂组合物 - Google Patents

氢氟丙烯与氢氯氟烯烃的发泡剂组合物 Download PDF

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CN101652412A
CN101652412A CN200880010144A CN200880010144A CN101652412A CN 101652412 A CN101652412 A CN 101652412A CN 200880010144 A CN200880010144 A CN 200880010144A CN 200880010144 A CN200880010144 A CN 200880010144A CN 101652412 A CN101652412 A CN 101652412A
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B·B·陈
J·S·科斯塔
B·L·范霍恩
M·Y·艾尔希科
P·波内特
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Abstract

在此披露了一种用于热固性泡沫的发泡剂。该发泡剂是氢氟丙烯HFO-1243zf与一种氢氯氟烯烃(HCFO)的组合,该氢氯氟烯烃选自:HCFO-1233zd、HCFO-1233xf、HCFO-1223。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

氢氟丙烯与氢氯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,本发明涉及不饱和的卤化的氢烯烃(3,3,3-三氟丙烯(HFO-1243zf或TFP)与一种氢氯氟烯烃(HCFO)(选自HCFO-1233zd、HCFO-1233xf、HCFO-1223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。
美国专利5,205,956披露了在发泡剂配制品中使用化学式为CH2=CH-Cn-F(2n+1)的乙烯基氟代烷(其中n是从1到6的整数)取代CFC-11以及/或CFC-12。对于取代CFC-11和CFC-113而言,n优选是从3到6,并且对于取代CFC-12而言,n优选是从1到3。这些实例披露了更长的、更高沸点的乙烯基氟代烷(包括乙烯基全氟正丁烷以及乙烯基全氟正己烷)在发泡剂配制品中用于聚氨酯发泡。
美国专利4,085,073披露了包含氯氟甲烷、溴氯二氟甲烷、以及它们的混合物,单独地或与少量的其他种类的含碳卤素化合物一起作为发泡剂。该专利提及了TFP,连同一系列其他卤化的化合物一起作为可能的稀释剂。
GB 950,876披露了一种用于生产聚氨酯泡沫的方法。它描述了具有低于150℃(优选低于50℃)的沸点的任何合适的卤化的饱和或不饱和烃都可以用作发泡剂。TFP在所列的卤化的烃类之中,然而,实例都使用CFC-11作为发泡剂。
美国专利6,858,571以及WO 2004/037742披露了含有五氟丙烯(HFO-1225)以及一种第二流体的类共沸混合物组合物,该流体来自下组,其构成为:3,3,3-三氟丙烯(“HFO-1243zf”)、1,1-二氟乙烷(“HFC-152a”)、反式-1,3,3,3-四氟丙烯(“HFO-1234ze”),以及它们的两种或更多种的组合。提到了这些共沸混合物作为发泡剂的用途。
WO 2004/037913以及美国专利公布2004119047披露了HFO的一个通式,包括TFP但是传授了含有另外的氟的氟丙烯是优选的,确切地说是四氟丙烯以及五氟丙烯,并且甚至更优选的是HFO-1234ze、HFO-1234yf、以及HFO-1225ye、以及它们的任何立体异构体。在此没有披露使用TFP的任何优点。
美国专利公布2006243944披露了包括多种物质的组合的多种组合物,这些组合包括TFP与至少一种其他化合物(选自一个包括多种HFC以及烃类的特定的名单)的一个组合。描述了这些结合体对于多种用途是有用的,包括作为发泡剂的用途。
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,该发泡剂具有可忽略的(低的或零)臭氧消耗和低的GWP。此类发泡剂包括氢氟丙烯HFO-1243zf(3,3,3-三氟丙烯)与一种氢氯氟烯烃(HCFO)的组合,该氢氯氟烯烃是选自HCFO-1233zd(1-氯-3,3,3-三氟丙烯)、HCFO-1233xf(2-氯-3,3,3-三氟丙烯)、HCFO-1223(二氯三氟丙烯)以及它们的混合物。该组合物可以进-步包括一种不同的第二氢氟烯烃(HFO)、一种氢氟烷、一种烃、一种醇、一种醛、一种酯、一种酮醚/二醚或二氧化碳。
通过在一种多元醇类混合物中混合,HFO-1243zf与一种氢氯氟烯烃(HCFO)(选自HCFO-1233zd、HCFO-1233xf、HCFO-1223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容易溶解,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(HFO-1243zf与一种氢氯氟烯烃(HCFO)(选自HCFO-1233zd、HCFO-1233xf、HCFO-1223以及它们的混合物)的组合)表现出良好的溶解性。HFO-1243zf组分与一种氢氯氟烯烃(HCFO)(选自HCFO-1233zd、HCFO-1233xf、HCFO-1223以及它们的混合物)的组合的一个优选的比率是大于大约5wt%的HFO-1243zf。
氢氟丙烯HFO-1243zf与一种氢氯氟烯烃(HCFO)(选自HCFO-1233zd、HCFO-1233xf、HCFO-1223以及它们的混合物)的组合的本发明的组合物可以在与额外的低全球变暖潜势以及低的或零臭氧消耗值的物质的组合中使用,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)氢氟烯烃类,包括但不局限于:四氟丙烯类(HFO1234)、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的酮类、C1至C4的酯类、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,期望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。
实例
实例l
在以下实例中,除非另外指明,泡沫是由小型聚氨酯配料器制得。该配料器由两个承压的汽缸构成,一个用于A侧(MDI)并且另一个用于B侧(多元醇混合物)。可以通过调节器调节汽缸内的压力。将B侧的混合物进行预混合,并且然后装入承压的汽缸内。然后向B侧的汽缸内加入发泡剂并且充分混合。该汽缸与配有静态混合器的一个喷液枪相连。调节两个汽缸内的气压,这样可以实现所希望的A侧与B侧之比。每一个所测试的配制品(对ROH都具有110的Iso指数)都含有Rubinate M(从Huntsman可得的一种聚合物亚甲基联苯二异氰酸酯(MDI))、Jeffol SG-360和R-425-X(来自Huntsman的一种多元醇)、TEAP-265(来自Carpenter Company的一种多元醇)。从Evonik-Degussa可得的一种表面活性剂TegostabB 8465。Jeffcat TD33A和ZR-70是来自Huntsman的催化剂。来自Huntsman的一种增容剂NP 9.5。总体发泡剂水平是26.0mls/g。表l概述了本研究的配方。
表1:配方
Figure A20088001014400081
实例2
表2概述了不同种发泡剂的B侧的蒸气压。
表2:B侧蒸气压
Figure A20088001014400091
当加入一个少量的HCFO1233zd(占HCFO1233zd和HFO 1234zf总数的15.5mol%的HCFO1233zd)后,B侧蒸气压显著降低。
实例3
表3K-因数
Figure A20088001014400092
K-因数是泡沫的热绝缘的一个关键参数。k-因数越低,热绝缘就越好。如在表3中所示,当加入一个少量的HCFO1233zd(占HCFO1233zd和HFO1234zf总数的15.5mol%的HCFO1233zd)时,k-因数降低。在低温下,由15.5mol%的HCFO1233zd和84.5mol%的HFO 1243ze制得的泡沫的k-因数非常接近于甚至优于单独由HCFO 1233zd制得的泡沫的k-因数。对于器具的低温绝缘而言,这是非常有用的。
实例4
表4:自由发起密度
Figure A20088001014400101
表4表明,当加入一个少量的HCFO1233zd(占HCFO1233zd和HFO 1234zf总数的15.5mol%的HCFO1233zd)后,自由发起密度降低。自由发起密度越低,发泡效率越高,高的发泡效率能带来加工益处,诸如泡沫前体更好的可流动性。低的自由发起密度导致了更低的填充重量以及材料节省。
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 (14)

1.一种用于热固性泡沫的聚合物发泡剂组合物,包括一种氢氯氟烯烃与氢氟丙烯HFO-1243zf的组合,该氢氯氟烯烃选自下组,其构成为:HCFO-1233zd、HCFO-1223、HCFO-1233xf以及它们的混合物。
2.如权利要求1所述的聚合物发泡剂组合物,其中所述氢氟丙烯HFO-1243zf包括氢氟丙烯与氢氯氟烯烃的组合物的大约5wt%或更多。
3.如权利要求1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);1,1,1-三氟乙烷(HFC143a);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)。
5.如权利要求1所述的聚合物发泡剂组合物,进一步包括一种氢氟烯烃。
6.如权利要求5所述的聚合物发泡剂组合物,其中所述氢氟烯烃是选自下组,其构成为:四氟丙烯类(HFO1234)、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)、九氟戊烯异构体类(HFO1429)。
7.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、一种醛、一种酯、一种酮醚/二醚或二氧化碳。
8.一种聚氨酯泡沫的发泡方法,包括将多个聚合物泡沫组分与一种泡沫发泡剂进行混合,该泡沫发泡剂包括氢氟丙烯HFO-1243zf与一种氢氯氟烯烃(HCFO)的组合,该氢氯氟烯烃选自下组,其构成为:HCFO-1233zd、HCFO-1233xf、HCFO-1223以及它们的混合物。
9.如权利要求8所述的方法,其中所述氢氟丙烯HFO-1243zf包括氢氟丙烯与氢氯氟烯烃的组合物的大约5wt%或更多。
10.如权利要求8所述的方法,其中所述泡沫发泡剂进一步包括一种氢氟烷。
11.如权利要求10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)。
12.如权利要求8所述的方法,其中所述泡沫发泡剂进一步包括一种氢氟烯烃。
13.如权利要求12所述的方法,其中所述氢氟烯烃是选自下组,其构成为:1,1,1,2-四氟丙烯类(HFO1234)、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)。
14.如权利要求8所述的方法,其中所述发泡剂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、一种醛、一种酯、一种酮醚/二醚或二氧化碳。
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