CN107090090B - 改善含有卤化烯烃发泡剂的聚氨酯多元醇共混物的稳定性的方法 - Google Patents

改善含有卤化烯烃发泡剂的聚氨酯多元醇共混物的稳定性的方法 Download PDF

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CN107090090B
CN107090090B CN201710427382.XA CN201710427382A CN107090090B CN 107090090 B CN107090090 B CN 107090090B CN 201710427382 A CN201710427382 A CN 201710427382A CN 107090090 B CN107090090 B CN 107090090B
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B·B·陈
J·S·科斯塔
P·波内特
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Abstract

本发明是针对一种用于稳定化热固性泡沫共混物的方法，该热固性泡沫共混物包含具有可忽略(低或零)的臭氧消耗和低的全球变暖潜势的、基于不饱和的卤化氢烯烃的一种发泡剂，例如聚氨酯多元共混物，其中将一种或多种酯加入这些热固性泡沫共混物中。这些热固性泡沫共混物典型地包括：一种或多种多元醇；一种或多种表面活性剂；一种或多种催化剂；一种或多种阻燃剂；一种或多种有机酸抑制剂/稳定剂；一种或多种二氧化碳发生剂。出乎意料地发现将该一种或多种酯加入这些热固性泡沫共混物中产生了随着时间推移也稳定的共混物，并且所得的泡沫具有一种带有很少或没有泡沫塌陷的均匀孔隙结构。

Description

改善含有卤化烯烃发泡剂的聚氨酯多元醇共混物的稳定性的 方法
分案申请说明
本申请系申请日为2011年04月22日、国际申请号为PCT/US2011/033513、进入中国国家阶段后的国家申请号为201180021009.5、题为“改善含有卤化烯烃发泡剂的聚氨酯多元醇共混物的稳定性的方法”的发明专利申请的分案申请。
发明领域
本发明涉及用于稳定化结合有发泡剂例如HCFO 1233zd的热固性泡沫共混物的一种方法。这些热固性泡沫共混物可以包括聚氨酯多元醇共混物，这些共混物包括一种多元醇、一种表面活性剂、一种催化剂、一种阻燃剂、一种稳定剂/抑制剂、一种卤化的烯烃、一种二氧化碳发生剂以及一种稳定用酯。在这些共混物中添加该酯导致了这些共混物随着时间推移的稳定性，并且所得的泡沫具有一种带有很少或没有泡沫塌陷的均匀孔隙结构。
发明背景
用于臭氧层保护的蒙特利尔议定书命令逐步淘汰氯氟烃类(CFC)的使用。对臭氧层更“友好”的材料，诸如氢氟烃类(HFC)如HFC-134a，替代了氯氟烃类。后者的化合物已证明是温室气体，引起了全球变暖并且受关于气候变化的京都议定书所管辖。所出现的替代材料氢氟丙烯类被证明是环境可接受的，即具有零臭氧消耗潜势(ODP)以及可接受的低的全球变暖潜势(GWP)。
当前使用的用于热固性泡沫的发泡剂包括具有相对高的全球变暖潜势的HFC-134a、HFC-245fa、HFC-365mfc，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，正在寻找新的替代性的发泡剂。卤化的氢烯属材料(例如氢氟丙烯类和/或氢氯氟丙烯类)作为HFC的代替物已令人产生了兴趣。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为零或接近零的臭氧消耗特性。
US 2009/0099272 A1公开了“双组份体系、尤其是使用某些氢卤烯烃(包括HFO-1234ze和HFCO-1233zd)的那些的一个缺点在于B侧组合物的保质期。正常地，当通过将A和B组份放在一起来生产泡沫时，就可以得到很好的泡沫。然而，如果在用聚异氰酸酯处理之前，该多元醇预混料组合物已经老化，则泡沫的质量较低并且甚至可能在泡沫的形成过程中塌陷”。
发明概述
已经发现在结合有不饱和的卤化的氢烯烃发泡剂的热固性泡沫共混物(多元醇预混料B侧)中添加一种酯使的该共混物稳定并且延长了该预混料的保质期而且增强了所得泡沫的泡沫特性。本发明的目的是提供一种用于稳定化热固性泡沫共混物组合物如聚氨酯泡沫的方法，该方法提供了长的保质期以及增强的泡沫特性以便满足对低或零臭氧消耗潜势、更低的全球变暖潜势的要求并且展先出低的毒性。
附图简要说明
图1为根据实例2制备的泡沫的图片。
发明的详细描述
本发明涉及通过加入一种或多种酯来稳定化热固性泡沫共混物例如聚氨酯多元共混物的一种方法，这些共混物包含具有可忽略(低或零)的臭氧消耗和低的GWP的、基于不饱和的卤化的氢烯烃的一种发泡剂；一种或多种多元醇；一种或多种表面活性剂；一种或多种催化剂；一种或多种阻燃剂；一种或多种有机酸抑制剂/稳定剂；一种或多种二氧化碳发生剂。这些共混物出乎意料地随时间推移是稳定的，并且所得的泡沫具有一种带有很少或没有泡沫塌陷的均匀孔隙结构。
本发明的热固性泡沫共混物中的发泡剂包括一种不饱和的卤化的氢烯烃，如氢氟烯烃类(HFO)、氢氯氟烯烃类(HCFO)、氢氟烃类(HFC)、氢氟醚类(HFE)、以及其混合物，以及任选的烃类、醇类、醛类、酮类、醚类/二醚类或二氧化碳。
本发明的热固性泡沫共混物中的优选发泡剂是单独的或组合的氢氟烯烃或氢氯氟烯烃。优选的氢氟烯烃(HFO)发泡剂包含3、4、5、或6个碳原子，而且包括但不限于五氟丙烷类如1,2,3,3,3-五氟丙烯(HFO 1225ye)；四氟丙烯类如1,3,3,3-四氟丙烯(HFO 1234ze，E和Z异构体)、2,3,3,3-四氟丙烯(HFO 1234yf)、1,2,3,3-四氟丙烯(HFO1234ye)；三氟丙烯类如3,3,3-三氟丙烯(1243zf)；四氟丁烯类如(HFO 1345)；五氟丁烯异构体类如(HFO1354)；六氟丁烯异构体类如(HFO1336)；七氟丁烯异构体类如(HFO1327)；七氟戊烯异构体类如(HFO1447)；八氟戊烯异构体类如(HFO1438)；九氟戊烯异构体类如(HFO1429)。HCFO，例如1-氯-3,3,3-三氟丙烯(HCFO-1233zd)、2-氯-3,3,3-三氟丙烯(HCFO-1233xf)、HCFO1223、1,2-二氯-1,2-二氟乙烯(E和Z异构体)、3,3-二氯-3-氟丙烯、2-氯-1,1,1,4,4,4-六氟丁烯-2(E和Z异构体)、2-氯-1,1,1,3,4,4,4-七氟丁烯-2(E和Z异构体)。本发明的热固性泡沫共混物中的优选发泡剂包括标准沸点低于约60℃的不饱和的卤化的氢烯烃类。优选的氢氯氟烯烃发泡剂包括但不限于1-氯-3,3,3-三氟丙烯，E 1233zd和/或Z 1233zd。
本发明的热固性泡沫共混物中的这些发泡剂可以单独使用或与其他发泡剂结合使用，其他发泡剂包括但不限于：(a)氢氟烃类，包括但不限于二氟甲烷(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)烃类包括但不限于戊烷异构体类以及丁烷异构体类，(c)氢氟醚类(HFE)，如C4F9OCH3(HFE-7100)、C4F9OC2H5(HFE-7200)、CF3CF2OCH3(HFE-245cb2)、CF3CH2CHF2(HFE-245fa)、CF3CH2OCF3(HFE-236fa)、C3F7OCH3(HFE-7000)、2-三氟甲基-3-乙氧基十二氟己烷(HFE 7500)、1,1,1,2,3-六氟-4-(1,1,2,3,3,3-六氟丙氧基)-戊烷(HFE-7600)、1,1,1,2,2,3,5,5,5-十氟-3-甲氧基-4-(三氟甲基)戊烷(HFE-7300)、乙基九氟异丁基醚/乙基九氟丁基醚(HFE 8200)、CHF2OCHF2、CHF2-OCH2F、CH2F-OCH2F、CH2F-O-CH3、环-CF2CH2CF2-O、环-CF2CF2CH2-O、CHF2-CF2CHF2、CF3CF2-OCH2F、CHF2-O-CHFCF3、CHF2-OCF2CHF2、CH2F-O-CF2CHF2、CF3-O-CF2CH3、CHF2CHF-O-CHF2、CF3-O-CHFCH2F、CF3CHF-O-CH2F、CF3-O-CH2CHF2、CHF2-O-CH2CF3、CH2FCF2-O-CH2F、CHF2-O-CF2CH3、CHF2CF2-O-CH3(HFE254pc)、CH2F-O-CHFCH2F、CHF2-CHF-O-CH2F、CF3-O-CHFCH3、CF3CHF-O-CH3、CHF2-O-CH2CHF2、CF3-O-CH2CH2F、CF3CH2-O-CH2F、CF2HCF2CF2-O-CH3、CF3CHFCF2-O-CH3、CHF2CF2CF2-O-CH3、CHF2CF2CH2-OCHF2、CF3CF2CH2-O-CH3、CHF2CF2-O-CH2CH3、(CF3)2CF-O-CH3、(CF3)2CH-O-CHF2、(CF3)2CH-O-CH3、以及其混合物；(d)C1至C5醇类、C1至C4醛类、C1至C4酮类、C1至C4醚类和二醚类、以及二氧化碳。
本发明的这些热固性泡沫共混物包括一种或多种能够形成具有总体上蜂窝状结构的泡沫的组份以及一种或多种发泡剂。热固性组合物的实例包括聚氨酯和聚异氰脲酸酯泡沫组合物、以及还有酚醛泡沫组合物，优选柔性或刚性的低密度泡沫。
本发明还涉及由其中已添加有稳定量值的一种酯的一种热固性泡沫配方所制备的泡沫，优选闭孔泡沫。
本发明的发泡剂与酯的组合被形成和/或添加到该可发泡组合物中的顺序和方式一般不会影响本发明的操作性。例如,在聚氨酯泡沫的情况下，有可能的是该发泡剂与酯的组合的各种组份在引入发泡设备前是没被混合的，或者甚至是这些组分并没有被添加到发泡设备中的同一位置。因此，在某些实施方案中，可能希望以这些组分将在发泡设备中聚集到一起的方式引入该发泡剂与酯的组合的一种或多种组分。尽管如此，在某些实施方案中，将该发泡剂与酯的组合的这些组分提前组合、并且直接地或作为预混料的一部分一起引入该可发泡组合物中，然后进一步将该预混料加入该可发泡组合物的其他部分中。
在某些制备聚氨酯多元醇泡沫的实施方案中，该b-侧多元醇预混料可以包括多元醇类、基于硅的或不基于硅的表面活性剂类、基于胺的或不基于胺的催化剂类、阻燃剂类/遏制剂类、酸清除剂类、自由基清除剂类、填充剂类、以及其他必要的稳定剂类/抑制剂类。
示例性的多元醇包括：基于甘油的聚醚多元醇类，如Carpol GP-700、GP-725、GP-4000、GP-4520；基于胺的聚醚多元醇类，如Carpol TEAP-265和EDAP-770、Jeffol AD-310；基于蔗糖的聚醚多元醇，如Jeffol SD-360、SG-361、和SD-522、Voranol 490、Carpol SPA-357；基于曼尼希碱的聚醚多元醇，如Jeffol R-425X和R-470X；基于山梨糖醇的聚醚多元醇，如Jeffol S-490；芳香族的聚酯多元醇类，如Terate 2541和3510、Stepanpol PS-2352、Terol TR-925。
示例性的催化剂类包括：N,N-二甲基乙醇胺(DMEA)、N,N-二甲基环己胺(DMCHA)、双(N,N-二甲基氨基乙基)醚(BDMAFE)、N,N,N’,N’,N”-五甲基二亚乙基三胺(PDMAFE)、1,4-二氮杂二环[2,2,2]辛烷(DABCO)、2-(2-二甲基氨基乙氧基)乙醇(DMAFE)、2-((2-二甲基氨基乙氧基)-乙基甲基-氨基)乙醇、1-(双(3-二甲基氨基)丙基)氨基-2-丙醇、N,N’,N”-三(3-二甲基氨基丙基)六氢三嗪、二吗啉代二乙基醚(DMDEE)、N,N-二甲基苄胺、N,N,N’,N”,N”-五甲基二亚丙基三胺、N,N'-二乙基哌嗪。特别地，空间位阻的伯、仲或叔胺是有用的，例如，二环己基甲基胺、乙基二异丙胺、二甲基环己胺、二甲基异丙胺、甲基异丙基苄胺、甲基环戊基苄胺、异丙基-仲丁基-三氟乙胺、二乙基(α-苯乙基)胺、三正丙胺、二环己胺、叔丁基异丙胺、二叔丁胺、环己基叔丁胺、二仲丁胺、二环戊胺、二(α-三氟甲基乙基)胺、二(α-苯乙基)胺、三苯甲基胺、以及1,1-二乙基正丙胺。其他空间位阻胺包括：吗啉类、咪唑类、含醚的化合物，如二吗啉代二乙基醚、N-乙基吗啉、N-甲基吗啉、双(二甲基氨基乙基)醚、咪唑、N-甲基咪唑、1,2-二甲基咪唑、二吗啉代二甲基醚、N,N,N’,N’,N”,N”-五甲基二亚乙基三胺、N,N,N’,N’,N”,N”-五乙基二亚乙基三胺、N,N,N’,N’,N”,N”-五甲基二亚丙基三胺、双(二乙氨基乙基)醚、双(二甲基氨基丙基)醚、或其组合。
示例性的非胺催化剂包括：含有铋、铅、锡、锑、镉、钴、铁、钍、铝、汞、锌、镍、铈、钼、钛、钒、铜、锰、锆、镁、钙、钠、钾、锂或其组合的有机金属化合物，如辛酸亚锡、二月桂酸二丁基锡(DGTDL)、二丁基硫醇锡、丙酸苯汞、辛酸铅、乙酸/辛酸钾、乙酸镁、草酸氧钛、草酸氧钛钾、季铵甲酸盐类、三乙酰丙酮铁、以及其组合。
催化剂的使用水平典型地是该多元醇预混料的从约0.1ppm至6.00wt％的量值，优选从约0.5ppm至4wt％，更优选从约1ppm至2wt％。
示例性的表面活性剂类包括：聚硅氧烷聚氧化烯嵌段共聚物，如从高德施密特公司(Goldschmidt)可购得的B8404、B8407、B8409、B8462以及B8465；从空气产品公司(AirProducts)可购得的DC-193、DC-197、DC-5582、以及DC-5598；以及从迈图公司(Momentive)可购得的L-5130、L5180、L-5340、L-5440、L-6100、L-6900、L-6980、以及L6988。示例性的非有机硅表面活性剂包括：磺酸的盐类、脂肪酸的碱金属盐类、脂肪酸的铵盐类、油酸、硬脂酸、十二烷基苯二磺酸、二萘基甲二磺酸、蓖麻油酸、一种乙氧基化的烷基酚、一种乙氧基化的脂肪醇、一种石蜡油、一种蓖麻油酯、一种蓖麻油酸酯、土耳其红油、花生油、一种石蜡脂肪醇、或其组合。表面活性剂的使用水平典型地是多元醇预混料的从约0.4wt％至6wt％，优选地从约0.8wt％至4.5wt％，更优选从约1wt％至3wt％。
示例性的阻燃剂包括：三氯丙基磷酸酯(TCPP)、磷酸三乙酯(TEP)、乙基磷酸二乙酯(DEEP)、二乙基双(2-羟乙基)氨基甲基膦酸酯、基于溴化酸酐的酯、二溴代新戊二醇、溴化的聚醚多元醇、三聚氰胺、多磷酸铵、三水合铝(ATH)、三(1,3-二氯异丙基)磷酸酯、三(2-氯乙基)磷酸酯、三(2-氯异丙基)磷酸酯、氯烷基磷酸酯/低聚膦酸酯、低聚氯烷基磷酸酯、基于五溴二苯醚的溴化阻燃剂、甲基膦酸二甲酯、二乙基N,N-二(2-羟乙基)氨基甲基膦酸酯、低聚膦酸酯、以及其衍生物类。
在某些实施方案中，酸清除剂类、自由基清除剂类、以及其他稳定剂类/抑制剂类被包括在该预混料中。示例性的稳定剂/抑制剂类包括1,2-环氧丁烷；缩水甘油基甲基醚；环状萜烯类如消旋柠檬烯、l-柠檬烯、d-柠檬烯；1,2-环氧-2,2-甲基丙烷；硝基甲烷；二乙基羟基胺；α-甲基苯乙烯；异戊二烯；对甲氧基苯酚；间甲氧基苯酚；消旋柠檬烯氧化物；肼类；2,6-二叔丁基苯酚；氢醌；有机酸类如羧酸、二羧酸、膦酸、磺酸、氨基磺酸、异羟肟酸、甲酸、乙酸、丙酸、丁酸、己酸、异己酸、2-乙基己酸、辛酸、氰基乙酸、丙酮酸、苯甲酸、草酸、丙二酸、琥珀酸、己二酸、壬二酸、三氟乙酸、甲磺酸、苯磺酸、以及其组合。还可以包括其他的添加剂如助黏附剂类、防静电剂类、抗氧化剂类、填充剂类、水解剂类、润滑剂类、抗微生物剂类、颜料类、粘度改性剂类、抗紫外线剂类。这些添加剂的实例包括：位阻酚类；二苯胺类；苯并呋喃酮衍生物类；丁羟甲苯(BHT)；碳酸钙；硫酸钡；玻璃纤维类；碳纤维类；微球类；硅石类；三聚氰胺；炭黑；蜡类和皂类；锑、铜、以及砷的有机金属衍生物类；二氧化钛；氧化铬；氧化铁；乙二醇醚类；尼龙酸(AGS)二甲酯类；碳酸丙烯酯；以及二苯甲酮和苯并三唑化合物类。
在本发明中,将一种酯添加到一种热固性泡沫共混物中。发现这向该共混物提供了随时间推移的稳定性，同时延长了该预混料的保质期并且增强了所得泡沫的性能。本发明中所使用的酯具有化学式R-C(O)-O-R’，其中R和R’可以是CaHc-bGb，其中G是一种卤素如F、Cl、Br、I，a＝0至15，b＝0至31，并且c＝1至31，而且这些酯包括作为二羧酸、次膦酸、膦酸、磺酸、氨基磺酸、异羟肟酸、或其组合的产物的酯类。优选的酯是一种醇与一种酸的产物，该醇例如为甲醇、乙醇、乙二醇、二甘醇、丙醇、异丙醇、丁醇、异丁醇、戊醇、异戊醇、以及其混合物；该酸例如为甲酸、乙酸、丙酸、丁酸、己酸、异己酸、2-乙基己酸、辛酸、氰乙酸、丙酮酸、苯甲酸、草酸、三氟乙酸、草酸、丙二酸、琥珀酸、己二酸、壬二酸、三氟乙酸、甲磺酸、苯磺酸、以及其混合物。更优选的酯类是己酸烯丙酯、乙酸苄酯、甲酸苄酯、乙酸冰片酯、丁酸丁酯、乙酸乙酯、丙酸乙酯、丁酸乙酯、己酸乙酯、肉桂酸乙酯、甲酸乙酯、庚酸乙酯、异戊酸乙酯、乳酸乙酯、壬酸乙酯、戊酸乙酯、乙酸香叶酯、丁酸香叶酯、戊酸香叶酯、乙酸异丁酯、甲酸异丁酯、乙酸异戊酯、甲酸异戊酯、乙酸异丙酯、甲酸异丙酯、乙酸芳樟酯、丁酸芳樟酯、甲酸芳樟酯、乙酸甲酯、邻氨基苯甲酸甲酯、苯甲酸甲酯、丁酸甲酯、肉桂酸甲酯、甲酸甲酯、异丁酸甲酯、戊酸甲酯、丙酸甲酯、苯乙酸甲酯、水杨酸甲酯、辛酸壬酯、乙酸辛酯、丁酸辛酯、乙酸戊基酯/乙酸戊酯(amyl acetate/pentyl acetate)、丁酸戊酯/丁酸戊基酯(pentylbutyrate/amyl butyrate)、己酸戊酯/己酸戊基酯(pentyl hexanoate/amyl caproate)、戊酸戊酯/戊酸戊基酯(pentyl pentanoate/amyl valerate)、乙酸丙酯(propylethanoate)、异丁酸丙酯、丁酸松油醇酯(terpenyl butyrate)以及其混合物。最优选的酯是甲酸甲酯、甲酸乙酯、乙酸甲酯、甲酸异丙酯、甲酸异丁酯、甲酸异戊酯、苯甲酸甲酯、甲酸苄酯、乙酸乙酯以及其混合物。
通过本领域已知的方法，可以将该酯与该发泡剂组合地或与该发泡剂分开地添加到热固性泡沫共混物中。酯的典型量值是该热固性泡沫共混物的从约0.1wt％至10wt％，酯的优选量值是该热固性泡沫共混物的从0.2wt％至7wt％，酯的更优选的量值是热固性泡沫共混物的从约0.3wt％至5wt％。
实例
实例1
每个测试的配方(全部具有115的Iso指数)均包含：Rubinate M，从亨斯迈公司(Huntsman)可购得的一种聚合的亚甲基联苯二异氰酸酯(MDI)；Jeffol R-425-X，来自亨斯迈公司的一种多元醇；Voranol 490，来自陶氏化学公司(Dow Chemical)的一种多元醇；Stephan 2352，来自斯特凡公司(Stepan)的一种多元醇；来自罗地亚公司(Rhodia)的一种阻燃剂TCPP；来自赢创公司(Evonik Corp.)的一种表面活性剂B 8465；从空气产品公司可购得的Polycat 8和5(五甲基二亚乙基三胺，PMDETA)。总的发泡剂水平是20.0mls/g。表1概括了所测试的配方A、B以及C。
表1
Figure BDA0001316515700000091
Figure BDA0001316515700000101
用一台手动搅拌机将A-侧(MDI)与新制备的B-侧(多元醇、表面活性剂、催化剂类、发泡剂、以及添加剂类的混合物)进行混合，并且分配到一个容器中以形成一种自由起发的泡沫。允许所分配的材料在一个开放容器中膨胀。表2中概括了反应性、密度以及泡沫品质。
表2
Figure BDA0001316515700000102
如表2所示，新制的多元醇共混物产生了具有相似的自由起发密度和泡沫品质的泡沫。
实例2
然后将配方A、B、以及C的这些B-侧多元醇共混物在环境条件下老化9个月，按照与实例1相同的方式制备泡沫，将其结果概括在表3中。
表3
Figure BDA0001316515700000103
Figure BDA0001316515700000111
*由于很差的泡沫品质而无法测量
在图1中进一步展示了泡沫品质。
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，所预期的是，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，并且在此期望对这些权利要求进行相应的诠释。

Claims (2)

1.用于稳定化一种包含聚氨酯、聚异氰脲酸酯或酚醛以及卤化的烯烃泡沫形成剂1-氯-3,3,3-三氟丙烯的热固性泡沫共混物的预混料的方法，该方法包括将甲酸甲酯加入其中；其中，所述热固性泡沫共混物的预混料是选自下组，该组由以下各项组成：聚氨酯泡沫预混料类、聚异氰脲酸酯泡沫预混料类以及酚醛泡沫预混料类。
2.如权利要求1所述的方法，其中所述热固性泡沫共混物进一步包含一种表面活性剂、一种催化剂、一种阻燃剂、一种稳定剂/抑制剂以及一种二氧化碳发生剂。
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