CN104744721A - 氢氯氟烯烃的发泡剂组合物 - Google Patents

氢氯氟烯烃的发泡剂组合物 Download PDF

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CN104744721A
CN104744721A CN201510147758.2A CN201510147758A CN104744721A CN 104744721 A CN104744721 A CN 104744721A CN 201510147758 A CN201510147758 A CN 201510147758A CN 104744721 A CN104744721 A CN 104744721A
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B·B·陈
M·Y·艾尔希科
P·波内特
B·L·范霍恩
J·S·科斯塔
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Abstract

氢氯氟烯烃的发泡剂组合物。提供了一种用于热固性泡沫的聚合物发泡剂组合物,所述组合物包括氢氯氟烯烃1233zd和作为共发泡剂的二氧化碳,所述氢氯氟烯烃1233zd的97重量%或更多是氢氯氟烯烃1233zd的反式立体异构体。

Description

氢氯氟烯烃的发泡剂组合物
本发明专利申请是国际申请号为PCT/US2008/058600,国际申请日为2008年3月28日,进入中国国家阶段的申请号为200880010501.0,名称为“氢氯氟烯烃的发泡剂组合物”的发明专利申请的分案申请。
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,本发明涉及单独的氢氯氟烯烃(HCFO)HCFO-1233zd或在一个组合中在热固性泡沫的生产中作为一种发泡剂的用途。本发明的HCFO-1233zd占主导的是反式异构体。
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,该发泡剂具有可忽略的(低的或零)臭氧消耗和低的GWP。此类发泡剂包括氢氯氟烯烃(HCFO),单独的1-氯-3,3,3-三氟丙烯(HCFO-1233zd)或在一个组合中,该组合包括一种氢氟烯烃(HFO)、一种氢氯氟烯烃(HCFO)、一种氢氟烷(HFC)、一种烃、一种醇、一种醛、一种酮、一种醚/二醚或二氧化碳。本发明的HCFO-1233zd占主导的是HCFO-1233zd的反式异构体。
反式(E)和顺式(Z)展示如下:
氢氯氟烯烃(HCFO)HCFO-1233已被提议作为发泡剂,这类发泡剂表现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卤烯烃类的大气降解作用的一个结果。
通过混入一种多元醇类混合物中,占主导的氢氯氟烯烃HCFO-1233zd的反式异构体(单独的或在与HFO的组合中)可以作为用于热固性泡沫的一种发泡剂而使用。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。在环境温度下,HCFO 1233zd是一种液体,这允许了不同工业(特别是聚氨酯泡沫)所希望的处理上的减轻。优选的HFO组分典型地含有3或4个碳,并且包括但不局限于五氟丙烯,如1,2,3,3,3-五氟丙烯(HFO 1225ye);四氟丙烯,如1,3,3,3-四氟丙烯(HFO 1234ze)、2,3,3,3-四氟丙烯(HFO 1234yf)、1,2,3,3-四氟丙烯(HFO1234ye);三氟丙烯,如3,3,3-三氟丙烯(1243zf)。本发明优选的实施方案是正常沸点(低于大约60℃的不饱和的卤化的氢烯烃类的发泡剂组合物。
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(单独的HCFO-1233zd(反式异构体占主导)或在一个组合中)表现出良好的溶解性。本发明的HCFO-1233zd组分中大部分是反式异构体。在AMES中,发现反式异构体展现出比顺式异构体显著更低的遗传毒性。HCFO-1233zd的反式异构体与顺式异构体的一个优选的比率是低于该组合重量的大约30%的顺式异构体,并且优选低于大约10%的顺式异构体。最优选的比率是低于大约3%的顺式异构体。优选的发泡剂组合产生了具有所希望水平的绝缘值的泡沫。
本发明的HCFO-1233zd可以用于与其他发泡剂的组合中,包括但不局限于:(a)氢氟烷类,包括但不局限于二氟甲烷(HFC32);1,1,1,2,2-五氟乙烷(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)。(b)氢氟烯烃类,包括但不局限于:四氟丙烯类(HFO1234)、三氟丙烯类(HFO1243)、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的醚类和二醚类以及二氧化碳;(e)HCFO类,例如2-氯-3,3,3-三氟丙烯(HCFO-1233xf)以及二氯三氟丙烯(HCFO1223)。
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。
实例
实例1
每一个所测试的配制品(都具有114的ROH Iso Index)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 R-425-X(来自Huntsman的一种多元醇);Voranol 490(来自Dow Chemical的一种多元醇)、Terate 2541(来自Invista的一种多元醇)。Antiblaze 80是来自Rhodia的一种阻燃剂;Tegostab B 8404是来自Goldschmidt Chemical Corporation的一种表面活性剂。Polycat 8和5(五甲基二亚乙基三胺,PMDETA)从Air Products可得。总体发泡水平是24.5mls/g。表1概述了所测试配方的特性。
表1
用一台手动搅拌机将A侧(MDI)与B侧(多元醇、表面活性剂、催化剂、发泡剂、以及添加剂的混合物)进行混合,并且分配到一个容器中以形成一种自由发起的泡沫。当制作一种自由发起的泡沫时,被分配的物质允许在一个开放式容器中膨胀。所得到的泡沫具有26-秒的胶凝时间、以及41-秒的失粘时间、1.69lb(s)/ft3(lb/ft3)的自由发起密度。当制作一种模制的泡沫时,被分配的物质允许在一个封闭式容器中膨胀。在释放泡沫前,使模具保持封闭几分钟。在10°F与130°F之间对所得到的泡沫进行k-因数测量(ASTM C518)。在使用带锯机除去泡沫皮后的24小时内,获得初始的k-因数。更低的k-因数表明更好的绝缘值。表2概述了结果。
表2
实例2
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(都具有一个在110的ROH IsoIndex)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。NP9.5,来自Huntsman的一种增容剂。总体发泡剂水平是26.0mls/g。表3概述了本研究的配方。
表3配方
在10°F与130°F之间对所得到的泡沫进行k-因数测量(ASTM C518)。表4概述了结果。在使用带锯机除去泡沫皮后的48小时内,获得初始的k-因数。更低的k-因数表明更好的绝缘值。结果表明,使用反式HCFO1233zd发成的泡沫的k-因数优于使用HFO1234ze或HFC134a发成的泡沫。
表4泡沫的k-因数的比较
表5表明,在相同的发泡剂水平下,使用反式HCFCO1233zd发成的泡沫比使用HFO1234ze或HFC134a发成的泡沫显示出更低的密度以及更高的发泡效率。表5HFC134a与HCFO 1233zd(反式)泡沫的自由发起密度的比较
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 (9)

1.一种用于热固性泡沫的聚合物发泡剂组合物,所述组合物包括氢氯氟烯烃1233zd和作为共发泡剂的二氧化碳,所述氢氯氟烯烃1233zd的97重量%或更多是氢氯氟烯烃1233zd的反式立体异构体。
2.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。
3.如权利要求2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;1,1,1,2,2-五氟乙烷;1,1,1-三氟乙烷;1,1,2,2-四氟乙烷;1,1,1,2-四氟乙烷;1,1-二氟乙烷;1,1,1,2,3,3,3-七氟丙烷;1,1,1,3,3-五氟丙烷;1,1,1,3,3-五氟丁烷以及1,1,1,2,2,3,4,5,5,5-十氟戊烷。
4.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。
5.如权利要求4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;三氟丙烯类;四氟丁烯异构体类;五氟丁烯异构体类;六氟丁烯异构体类;七氟丁烯异构体类;七氟戊烯异构体类;八氟戊烯异构体类;以及九氟戊烯异构体类。
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添加剂,该组的构成为:烃类、C1至C5的醇类、C1至C4的醛类、C1至C4的酮类、C1至C4的醚类、二氧化碳、以及C1至C4的二醚类。
7.如权利要求6所述的聚合物发泡剂组合物,其中所述烃是选自下组,其构成为:戊烷异构体类以及丁烷异构体类。
8.如权利要求1所述的聚合物发泡剂组合物,进一步包括HCFC-1233zd之外的一种氢氯氟烯烃。
9.如权利要求4所述的聚合物发泡剂组合物,其中所述氢氟烯烃选自HFO-1234、HFO-1243、HFO-1354、HFO-1345、HFO-1336、HFO-1327、HFO-1447、HFO-1438和HFO1429。
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