CN101896525B - 包含卤代烯烃发泡剂的聚氨酯泡沫多元醇预混物的稳定 - Google Patents

包含卤代烯烃发泡剂的聚氨酯泡沫多元醇预混物的稳定 Download PDF

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CN101896525B
CN101896525B CN200880121281.9A CN200880121281A CN101896525B CN 101896525 B CN101896525 B CN 101896525B CN 200880121281 A CN200880121281 A CN 200880121281A CN 101896525 B CN101896525 B CN 101896525B
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D·J·威廉斯
M·范德皮伊
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Honeywell International Inc
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Abstract

本发明提供聚氨酯和聚异氰脲酸酯泡沫及其制备方法。更具体地说，本发明涉及开孔聚氨酯和聚异氰脲酸酯泡沫及其制备方法。所述泡沫的特征在于均匀细孔结构和很小或没有泡沫结构破坏。所述泡沫用多元醇预混组合物制备，该多元醇预混组合物包括氢卤烯烃发泡剂、多元醇、硅氧烷表面活性剂和为胺和有机酸加合物的催化剂的组合。

Description

包含卤代烯烃发泡剂的聚氨酯泡沫多元醇预混物的稳定
相关申请的交叉引用
本申请要求2007年10月12日提交的同时待审临时专利申请60/979,427的权益，所述申请通过引用结合到本文中。
发明背景
发明领域
本发明涉及聚氨酯和聚异氰脲酸酯泡沫及其制备方法。更具体地说，本发明涉及硬质聚氨酯和聚异氰脲酸酯泡沫及其制备方法，所述泡沫的特征在于均匀细孔结构和很小或没有泡沫结构破坏。泡沫用有机多异氰酸酯和多元醇预混组合物制备，所述预混组合物包括发泡剂(优选为氢卤烯烃)、多元醇、硅氧烷表面活性剂和催化剂(此催化剂为胺和有机酸的加合物)的组合。
相关技术描述
已知为低密度、硬质聚氨酯或聚异氰脲酸酯泡沫的一类泡沫广泛用于隔热应用，包括屋面系统、建筑板材、建筑包层隔热、冰箱和冷冻机。硬质聚氨酯泡沫的大规模商业认同的关键因素一直是它们提供良好性能平衡的能力。已知硬质聚氨酯和聚异氰脲酸酯泡沫提供显著的隔热、极佳的耐火性和在合理低密度的优良结构性能。泡沫工业过去已使用液体碳氟化合物发泡剂，因为它们容易在加工条件使用。碳氟化合物不仅由于其挥发性作为发泡剂，而且包封或夹杂于硬质泡沫的闭孔结构中，并且是硬质聚氨酯泡沫低导热性的主要贡献者。碳氟化合物作为优选的工业膨胀剂或发泡剂用于隔热泡沫应用部分基于与产生的泡沫相关的所得k因数。k因数定义为其中垂直跨材料两个表面有1°F差的热能在1小时内传导通过1平方英尺1英寸厚均匀材料的转移速率。由于闭孔聚氨酯类型泡沫的应用部分基于它们的隔热性，因此，鉴别产生较低k因数泡沫的材料是有利的。
本领域已知在发泡剂、催化剂、表面活性剂和任选的其它成分存在下，通过多异氰酸酯与多元醇反应制备硬质聚氨酯和聚异氰脲酸酯泡沫。发泡剂包括烃、碳氟化合物(fluorocarbon)、碳氯化合物(chlorocarbon)、碳氟氯化合物(fluorochlorocarbon)、卤代烃、醚、酯、醛、酮或CO2产生物质。热在多异氰酸酯与多元醇反应时产生，并使液体混合物中所含的发泡剂挥发，从而在其中形成泡。随着聚合反应进行，液体混合物变成多孔固体，使发泡剂残留在泡沫的孔中。如果在发泡组合物中不使用表面活性剂，则泡简单地通过液体混合物，而不形成泡沫或不形成具有大、不规则孔的泡沫，使其没有什么用处。优选的发泡剂具有低全球变暖潜势。在这些发泡剂中包括氢卤烯烃，其中氢氟烯烃(HFOs)中的反-1，3，3，3-四氟丙烯(HFO-1234ze)和氢氯氟烯烃(HFCOs)中的1-氯-3，3，3-三氟丙烯(HFCO-1233zd)特别有用。制备1，3，3，3-四氟丙烯的方法公开于美国专利7,230,146和7,189,884。制备1-氯-3，3，3-三氟丙烯的方法公开于美国专利6,844,475和6,403,847。
在很多应用中，很方便在预混制剂中提供用于聚氨酯或聚异氰脲酸酯泡沫的组分。最一般将泡沫制剂预混成两种组分。多异氰酸酯和任选的异氰酸酯相容性原料构成第一组分，一般称为“A”组分。多元醇或多元醇的混合物、表面活性剂、催化剂、发泡剂和其它异氰酸酯反应性和非反应性成分构成第二组分，一般称为“B”组分。因此，通过A组分和B组分结合，通过用于少量制剂的手混合，和优选机械混合技术，可容易制备聚氨酯或聚异氰脲酸酯泡沫，以形成块、板、层压材料、现浇板和其它物品、喷施泡沫、泡等。可任选将其它成分加到混合头或反应部位，如阻燃剂、着色剂、辅助发泡剂和其它多元醇。然而，最方便将它们全部加入一个B组分。
双组分系统，尤其是使用包括HFO-1234ze和HFCO-1233zd的某些氢卤烯烃的双组分系统，缺点是B组合物的保存期限。一般在通过A组分和B组分的结合制备泡沫时得到良好的泡沫。然而，如果多元醇预混组合物在用多异氰酸酯处理前老化，则泡沫为低品质，并且可能甚至在形成泡沫期间结构破坏。
现已发现，问题的根源在于某些胺催化剂与包括HFO-1234ze和HFCO-1233zd的某些氢卤烯烃的反应，导致发泡剂部分分解。已发现，在发泡剂分解后，聚硅氧烷表面活性剂(如果存在)的分子量不利改变，产生不良泡沫结构。
虽然可通过分离发泡剂、表面活性剂和催化剂解决此问题，例如将发泡剂、胺催化剂或表面活性剂加入到多异氰酸酯(“A”组分)，或者用不同于“A”或“B”组分的单独物流引入发泡剂、胺催化剂或表面活性剂，但优选的解决方法是不需要重新配制或改变制备泡沫的方式。现已发现，为胺和有机酸的加合物的催化剂具有对某些发泡剂较低的反应性，这些发泡剂如氢卤烯烃，包括反-HFO-1234ze和HFCO-1233zd，使得即使多元醇混合物老化也能制备优良品质的泡沫。
发明详述
本发明提供一种多元醇预混组合物，所述多元醇预混组合物包括发泡剂、多元醇、硅氧烷表面活性剂和催化剂的组合，所述催化剂为胺和有机酸的加合物，其中发泡剂包括氢卤烯烃和任选的烃、碳氟化合物、碳氯化合物、碳氟氯化合物、卤代烃、CO2生物质或其组合。
本发明还提供一种制备聚氨酯或聚异氰脲酸酯泡沫的方法，所述方法包括使有机多异氰酸酯与多元醇预混组合物反应。
发泡剂组分包括氢卤烯烃(优选包括至少反-HFO-1234ze和HFCO-1233zd之一)和任选的烃、碳氟化合物、碳氯化合物、碳氟氯化合物、卤代烃、醚、氟代醚、酯、醛、酮、CO2产生物质或其组合。
氢卤烯烃优选包括至少一种含3至4个碳原子和至少一个碳-碳双键的卤烯烃，如氟烯烃或氯烯烃。优选的氢卤烯烃非排他性地包括三氟丙烯、四氟丙烯(如HFO-1234)、五氟丙烯(如HFO-1225)、三氟氯丙烯(如HFO-1233)、二氟氯丙烯、三氟氯丙烯、四氟氯丙烯及其组合。更优选本发明的化合物为四氟丙烯、五氟丙烯和其中不饱和末端碳具有不多于一个F或Cl取代基的三氟氯丙烯化合物。包括1，3，3，3-四氟丙烯(HFO-1234ze)、1，1，3，3-四氟丙烯、1，2，3，3，3-五氟丙烯(HFO-1225ye)、1，1，1-三氟丙烯、1，1，1，3，3-五氟丙烯(HFO-1225zc)、1，1，1，3，3，3-六氟丁-2-烯、1，1，2，3，3-五氟丙烯(HFO-1225yc)、1，1，1，2，3-五氟丙烯(HFO-1225yez)、1-氯-3，3，3-三氟丙烯(HFCO-1233zd)、1，1，1，4，4，4-六氟丁-2-烯或其组合，以及各个这些化合物的任何和所有结构同分异构体、几何异构体或立体异构体。
优选的氢卤烯烃具有不大于150，更优选不大于100，甚至更优选不大于75的全球变暖潜势(GWP)。本文所用“GWP”相对于二氧化碳经100年时间范围测定，定义于“The Scientific Assessment ofOzone Depletion，2002，a report of the World MeteorologicalAssociation′s Global Ozone Research and Monitoring Project”(臭氧损耗科学评估，2002，世界气象组织全球臭氧研究和监测计划报告)，其通过引用结合到本文中。优选的氢卤烯烃也优选具有不大于0.05，更优选不大于0.02，甚至更优选约0的臭氧损耗潜势(ODP)。本文所用“ODP”定义于“The Scientific Assessment of Ozone Depletion，2002，A report of the World Meteorological Association′s Global OzoneResearch and Monitoring Project”(臭氧损耗科学评估，2002，世界气象组织全球臭氧研究和监测计划报告)，其通过引用结合到本文中。
优选的任选发泡剂非排他性包括水，甲酸，在与异氰酸酯反应时产生CO2的有机酸，烃；醚，卤代醚；五氟丁烷；五氟丙烷；六氟丙烷；七氟丙烷；反-1，2-二氯乙烯；甲酸甲酯；1-氯-1，2，2，2-四氟乙烷；1，1-二氯-1-氟乙烷；1，1，1，2-四氟乙烷；1，1，2，2-四氟乙烷；1-氯-1，1-二氟乙烷；1，1，1，3，3-五氟丁烷；1，1，1，2，3，3，3-七氟丙烷；三氯氟甲烷；二氯二氟甲烷；1，1，1，3，3，3-六氟丙烷；1，1，1，2，3，3-六氟丙烷；二氟甲烷；二氟乙烷；1，1，1，3，3-五氟丙烷；1，1-二氟乙烷；异丁烷；正戊烷；异戊烷；环戊烷或其组合。发泡剂组分通常存在于多元醇预混组合物中的量以多元醇预混组合物重量计为约1％重量至约30％重量，优选约3％重量至约25％重量，更优选约5％重量至约25％重量。在氢卤烯烃和任选的发泡剂两者均存在时，氢卤烯烃组分通常存在于发泡剂组分中的量以发泡剂组分重量计为约5％重量至约90％重量，优选约7％重量至约80％重量，更优选约10％重量至约70％重量，任选的发泡剂通常存在于发泡剂组分中的量以发泡剂组分重量计为约95％重量至约10％重量，优选约93％重量至约20％重量，更优选约90％重量至约30％重量。
多元醇组分，包括多元醇的混合物，可以为任何以已知方式与异氰酸酯在制备聚氨酯或聚异氰脲酸酯泡沫中反应的多元醇。有用的多元醇包括一种或多种含蔗糖的多元醇；酚，含酚醛的多元醇；含葡萄糖的多元醇；含山梨糖醇的多元醇；含甲基葡糖苷的多元醇；芳族聚醚多元醇；甘油；乙二醇；二乙二醇；丙二醇；聚醚多元醇与乙烯基聚合物的接枝共聚物；聚醚多元醇与聚脲的共聚物；一种或多种(b)缩合的一种或多种(a)：
(a)甘油、乙二醇、二乙二醇、三羟甲基丙烷、乙二胺、季戊四醇、豆油、卵磷脂、妥尔油、棕榈油、蓖麻油；
(b)环氧乙烷、环氧丙烷、环氧乙烷和环氧丙烷的混合物或其组合。多元醇组分通常存在于多元醇预混组合物中的量以多元醇预混组合物重量计为约60％重量至约95％重量，优选约65％重量至约95％重量，更优选约70％重量至约90％重量。
多元醇预混组合物接下来包含硅氧烷表面活性剂。硅氧烷表面活性剂用于从混合物形成泡沫，也用于控制泡沫的泡大小，以便得到所需孔结构的泡沫。优选需要其中具有均匀大小的小泡或孔的泡沫，因为它具有最合乎需要的物理性能，如压缩强度和导热性。另外，至关重要的是具有在形成前或泡沫隆起期间不破坏的稳定孔的泡沫。
用于制备聚氨酯或聚异氰脲酸酯泡沫的硅氧烷表面活性剂可以本领域的技术人员已知几种商品名获得。已发现这些物质可应用于允许形成均匀孔和最大气体残留的多种制剂，以得到极低密度泡沫结构。优选的硅氧烷表面活性剂包括聚硅氧烷聚氧化烯嵌段共聚物。用于本发明的一些代表性硅氧烷表面活性剂为Momentive的L-5130、L-5180、L-5340、L-5440、L-6100、L-6900、L-6980和L-6988；AirProducts DC-193、DC-197、DC-5582和DC-5598；以及来自Goldschmidt AG of Essen，Germany的B-8404、B-8407、B-8409和B-8462。其它的公开于美国专利2,834,748、2,917,480、2,846,458和4,147,847。硅氧烷表面活性剂组分通常存在于多元醇预混组合物中的量以多元醇预混组合物重量计为约0.5％重量至约5.0％重量，优选约1.0％重量至约4.0％重量，更优选约1.5％重量至约3.0％重量。
多元醇预混组合物可任选包含非硅氧烷表面活性剂，如非硅氧烷非离子表面活性剂。这种表面活性剂可包括乙氧基化烷基酚、乙氧基化脂肪醇、石蜡油、蓖麻油酯、蓖麻油酸酯、土耳其红油、花生油、石蜡和脂肪醇。优选的非硅氧烷非离子表面活性剂为LK-443，可市售获自Air Products Corporation。在使用非硅氧烷非离子表面活性剂时，其通常存在于多元醇预混组合物中的量以多元醇预混组合物重量计为约0.25％重量至约3.0％重量，优选约0.5％重量至约2.5％重量，更优选约0.75％重量至约2.0％重量。
本发明的多元醇预混组合物接下来包含催化剂，这种催化剂为胺和有机酸的加合物。在一个实施方案中，胺具有式R1R2N-[A-NR3]nR4，其中R1、R2、R3和R4分别独立为H、C1至C8烷基、C1至C8烯基、C1至C8醇基或C1至C8醚基，或者R1和R2一起形成C5至C7环烷基、C5至C7环烯基、C5至C7杂环烷基或C5至C7杂环烯基；A为C1至C5烷基、C1至C5烯基或醚；n为0、1、2或3。
优选胺为空间位阻胺。可使用伯胺、仲胺或叔胺。可用的叔胺催化剂非排他性包括二环己基甲基胺、乙基二异丙基胺、二甲基环己基胺、二甲基异丙基胺、甲基异丙基苄基胺、甲基环戊基苄基胺、异丙基-仲丁基-三氟乙基胺、二乙基-(α-苯基乙基)胺、三正丙基胺或其组合。可用的仲胺催化剂非排他性包括二环己基胺、叔丁基异丙基胺、二叔丁基胺、环己基叔丁基胺、二仲丁基胺、二环戊基胺、二-(α-三氟甲基乙基)胺、二-(α-苯基乙基)胺或其组合。
可用的伯胺催化剂非排他性包括三苯甲基胺和1，1-二乙基-正丙基胺。
其它可用的胺包括吗啉、咪唑、含醚化合物等。这些包括：
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(二乙基氨基乙基)醚
双(二甲基氨基丙基)醚。
可用的有机酸非排他性包括羧酸、二羧酸、次膦酸、膦酸、磺酸、磺酸、氨基磺酸、异羟肟酸或其组合。这些有机酸的实例非排他性包括甲酸、乙酸、丙酸、丁酸、己酸、异己酸(isocaprotic)、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、苯磺酸等及其混合物。优选组包括乙酸、己酸(caprotic)、异己酸和2-乙基己酸及其组合。酸与胺反应生成一种加合物催化剂，所述加合物催化剂与单独为胺的催化剂相比具有对某些发泡剂较低的反应性，如氢卤烯烃，包括HFO-1234ze和HFCO-1233zd。在多元醇预混组合物中加入所得加合物之前通过使胺和有机酸预反应生成加合物。在通常情况下，为了完全与胺反应，使足够的有机酸与选择的胺反应。这通常为所述胺的量的至少化学计量有机酸。或者，在发泡剂引入多元醇预混物之前，分别将胺和有机酸加入到多元醇，原位形成加合物。
胺-有机酸加合物催化剂通常存在于多元醇预混组合物中的量以多元醇预混组合物重量计为约0.2％重量至约8.0％重量，优选约0.4％重量至约7.0％重量，更优选约0.7％重量至约6.0％重量。
多元醇预混组合物可任选进一步包含非胺催化剂。适合的非胺催化剂可包括含铋、铅、锡、钛、锑、铀、镉、钴、钍、铝、汞、锌、镍、铈、钼、钒、铜、锰、锆、钠、钾或其组合的有机金属化合物。这些有机金属化合物非排他性包括硝酸铋、2-乙基己酸铅、苯甲酸铅、氯化铁、三氯化锑、羟基乙酸锑、羧酸的亚锡盐、羧酸的锌盐、羧酸的二烷基锡盐、乙酸钾、辛酸钾、2-乙基己酸钾、氨基乙酸盐、羧酸季铵盐、羧酸碱金属盐和N-(2-羟基-5-壬基苯酚)甲基-N-甲基氨基乙酸盐、2-乙基己酸锡(II)、二月桂酸二丁基锡或其组合。在使用任选的非胺催化剂时，它通常存在于多元醇预混组合物中的量以多元醇预混组合物重量计为约0.01％重量至约2.5％重量，优选约0.05％重量至约2.25％重量，更优选约0.10％重量至约2.00％重量。虽然这些为一般量，但金属催化剂的量可在宽范围变化，适合量可很容易由本领域的技术人员决定。
用本文所述组合物制备聚氨酯或聚异氰脲酸酯泡沫可按照可利用的本领域熟知的任何方法，参见Saunders和Frisch，Volumes I and IIPolyurethanes Chemistry and technology，1962，John Wiley and Sons，New York，N.Y.或Gum，Reese，Ulrich，Reaction Polymers，1992，Oxford University Press，New York，N.Y.或Klempner和Sendijarevic，Polymeric Foams and Foam Technology，2004，Hanser GardnerPublications，Cincinnati，OH。通常，通过混合异氰酸酯、多元醇预混组合物和其它物质如任选的阻燃剂、着色剂或其它添加剂，制备聚氨酯或聚异氰脲酸酯泡沫。这些泡沫可以为硬质、软质或半硬质，并且可具有闭孔结构、开孔结构或开孔和闭孔的混合结构。
在很多应用中可方便在预混制剂中提供用于聚氨酯或聚异氰脲酸酯泡沫的组分。最一般将泡沫制剂预混成两种组分。异氰酸酯和任选的其它异氰酸酯相容性原料构成第一组分，一般称为“A”组分。多元醇混合物组合物，包括表面活性剂、催化剂、发泡剂和任选的其它成分，构成第二组分，一般称为“B”组分。在任何指定应用中，“B”组分可并非包含全部以上所列组分，例如一些制剂省去阻燃剂，如果阻燃性不是需要的泡沫性能。因此，通过A组分和B组分结合，通过用于少量制剂的手混合，和优选机械混合技术，很容易制备聚氨酯或聚异氰脲酸酯泡沫，以形成块、板、层压材料、现浇板和其它物品、喷施泡沫、泡等。可任选将其它成分作为物流加到混合头或反应部位，如阻燃剂、着色剂、辅助发泡剂、水和甚至其它多元醇。然而，最方便如上所述将它们全部加入一个B组分。
通过使上述有机多异氰酸酯和多元醇预混组合物反应，可形成适用于形成聚氨酯或聚异氰脲酸酯泡沫的可发泡组合物。可在聚氨酯或聚异氰脲酸酯泡沫合成中利用任何有机多异氰酸酯，包括脂族和芳族多异氰酸酯。适合的有机多异氰酸酯包括在聚氨酯化学领域熟知的脂族、脂环族、芳脂族、芳族和杂环族异氰酸酯。这些例如描述于美国专利4,868,224、3,401,190、3,454,606、3,277,138、3,492,330、3,001,973、3,394,164、3,124.605和3,201,372。芳族多异氰酸酯为优选的一类。
代表性有机多异氰酸酯相应于式：
R(NCO)z
其中R为脂族、芳烷基、芳族或其混合的多价有机基团，z为相应于R的化合价的整数，并且为至少2。本文涵盖的代表性有机多异氰酸酯包括例如芳族二异氰酸酯，如2，4-甲苯二异氰酸酯、2，6-甲苯二异氰酸酯、2，4-和2，6-甲苯二异氰酸酯的混合物、粗甲苯二异氰酸酯、亚甲基二苯基二异氰酸酯、粗亚甲基二苯基二异氰酸酯等；芳族三异氰酸酯，如4，4′，4″-三苯基甲烷三异氰酸酯、2，4，6-甲苯三异氰酸酯；芳族四异氰酸酯，如4，4′-二甲基二苯基甲烷-2，2′5，5′-四异氰酸酯等；芳基烷基多异氰酸酯，如苯二亚甲基二异氰酸酯；脂族多异氰酸酯，如1，6-己二异氰酸酯、赖氨酸二异氰酸酯甲基酯等；及其混合物。其它有机多异氰酸酯包括多亚甲基多苯基异氰酸酯、氢化的亚甲基二苯基异氰酸酯、间苯二异氰酸酯、萘-1，5-二异氰酸酯、1-甲氧基苯-2，4-二异氰酸酯、4，4′-联苯二异氰酸酯、3，3′-二甲氧基-4，4′-联苯二异氰酸酯、3，3′-二甲基-4，4′-联苯二异氰酸酯和3，3′-二甲基二苯基甲烷-4，4′-二异氰酸酯；典型的脂族多异氰酸酯为亚烷基二异氰酸酯，如1，3-亚丙基二异氰酸酯、1，4-亚丁基二异氰酸酯和1，6-亚己基二异氰酸酯、异佛尔烯二异氰酸酯、4，4’-亚甲基双(环己基异氰酸酯)等；典型的芳族多异氰酸酯包括间和对苯二异氰酸酯、多亚甲基多苯基异氰酸酯、2，4-和2，6-甲苯二异氰酸酯、联甲氧基苯胺二异氰酸酯、二甲基联苯二异氰酸酯、萘-1，4-二异氰酸酯、双(4-异氰酸基苯基)甲烷、双(2-甲基-4-异氰酸基苯基)甲烷等。优选的多异氰酸酯为多亚甲基多苯基异氰酸酯。具体地说，混合物包含约30至约85％重量的亚甲基双(苯基异氰酸酯)，混合物的剩余部分包含官能度高于2的多亚甲基多苯基多异氰酸酯。这些多异氰酸酯通过在本领域已知的常规方法制备。在本发明中，多异氰酸酯和多元醇以产生约0.9至约5.0的NCO/OH化学计量比的量使用。在本发明中，NCO/OH当量比为优选约1.0或更大和约3.0或更小，理想范围为约1.1至约2.5。尤其适合的有机多异氰酸酯包括多亚甲基多苯基异氰酸酯、亚甲基双(苯基异氰酸酯)、甲苯二异氰酸酯或其组合。
在聚异氰脲酸酯泡沫的制备中，为了使混合物与过量A组分转化成聚异氰脲酸酯-聚氨酯泡沫，使用三聚催化剂。所用三聚催化剂可以为本领域的技术人员已知的任何催化剂，包括但不限于氨基乙酸盐、叔胺三聚催化剂、羧酸季铵盐和羧酸碱金属盐及各种类型催化剂的混合物。其中优选类别的物质为乙酸钾、辛酸钾和N-(2-羟基-5-壬基苯酚)甲基-N-甲基氨基乙酸盐。
也可加入常规阻燃剂，优选以不大于反应剂重量约20％重量的量加入。任选的阻燃剂包括磷酸三(2-氯乙基)酯、磷酸三(2-氯丙基)酯、磷酸三(2，3-二溴丙基)酯、磷酸三(1，3-二氯丙基)酯、磷酸三(2-氯异丙基)酯、磷酸三甲苯酯、磷酸三(2，2-二氯异丙基)酯、N，N-双(2-羟基乙基)氨基甲基膦酸二乙酯、甲基膦酸二甲酯、磷酸三(2，3-二溴丙基)酯、磷酸三(1，3-二氯丙基)酯和亚乙基二磷酸四(2-氯乙基)酯、磷酸三乙酯、磷酸二铵、各种卤化的芳族化合物、氧化锑，三水合铝、聚氯乙烯、三聚氰胺等。其它任选的成分可包括0至约7％水，水与异氰酸酯化学反应产生二氧化碳。此二氧化碳作为辅助发泡剂。甲酸也通过与异氰酸酯反应产生二氧化碳，并任选加入到“B”组分。
除了前述成分外，可在泡沫制备物中包含其它成分，如染料、填料、颜料等。可向混合物加入分散剂和孔稳定剂。所用常规填料包括例如硅酸铝、硅酸钙、硅酸镁、碳酸钙、硫酸钡、硫酸钙、玻璃纤维、炭黑和二氧化硅。如果使用，填料一般以每100份多元醇约5份至100份的量存在。可使用的颜料可以为任何常规颜料，例如二氧化钛、氧化锌、氧化铁、氧化锑、铬绿、铬黄、铁蓝黄土、钼橙，和有机颜料，如对位红、联苯胺黄、甲苯胺红、调色剂和酞菁。
制造的聚氨酯或聚异氰脲酸酯泡沫的密度可以为约0.5磅/立方英尺至约60磅/立方英尺，优选约1.0至20.0磅/立方英尺，最优选约1.5至6.0磅/立方英尺。所得密度为在A和/或B组分中存在或在制造泡沫时加入的多少本发明公开的发泡剂或发泡剂混合物加上辅助发泡剂(如水或其它助发泡剂)的量的函数。这些泡沫可以为硬质、软质或半硬质泡沫，并且可具有闭孔结构、开孔结构或开孔和闭孔的混合结构。这些泡沫用于多种熟知的应用，包括但不限于隔热、缓冲、漂浮、包装、粘合、空隙填充、工艺和装饰及冲击吸收。
以下非限制实施例用于说明本发明。
实施例1
为了确定酸对产生氟离子的作用，将20mL甲醇、0.28g水、1.01g三乙胺、0.35g Niax L6900、1.78g 1，3，3，3-四氟丙烯和1.16g 4-甲基戊酸(相对于三乙胺的1摩尔当量)的试验混合物在玻璃耐压瓶中于120°F加热70小时。在加热阶段结束，分析液相的氟化物。氟化物含量小于4-甲基戊酸不存在下生成的量的十分之一。
实施例2(比较性实施例)
多元醇(B组分)制剂由100重量份多元醇混合物、1.5重量份NiaxL6900硅氧烷表面活性剂、1.5重量份水、1.2重量份N，N，N’，N’，N”，N”-五甲基二亚乙基三胺(Air Products and Chemicals作为Polycat 5销售)催化剂、5.6重量份顺-1，3，3，3-四氟丙烯、0.7重量份反-1，3，3，3-四氟丙烯和1.7重量份1，1，1，3，3-五氟丙烷发泡剂组成。全部B组分组合物，在新制备并与120.0重量份Lupranate M20S多异氰酸酯混合时，产生具有规则细孔结构的优良品质泡沫。泡沫反应性典型用于现浇泡沫，胶凝时间78秒。然后使全部B组合物(112.2份)在120°F老化62小时，接着与120.0份M20S Iso多异氰酸酯混合，以制备泡沫。泡沫外观很差，并且全部瘪泡。由于瘪泡，凝胶时间不能确定。在老化期间注意到显著变黄。
实施例3-(泡沫试验)
多元醇(B组分)制剂由100重量份多元醇混合物、1.5重量份NiaxL6900硅氧烷表面活性剂、1.5重量份水、1.2重量份N，N，N’，N’，N”，N”-五甲基二亚乙基三胺(Air Products and Chemicals作为Polycat 5销售)催化剂、2.4重量份异己酸和5.6重量份顺-1，3，3，3-四氟丙烯、0.7重量份反-1，3，3，3-四氟丙烯及1.7重量份1，1，1，3，3-五氟丙烷发泡剂组成。全部B组分组合物，在新制备并与120.0重量份Lupranate M20S多异氰酸酯混合时，产生具有规则细孔结构的优良品质泡沫。泡沫反应性典型用于现浇泡沫，胶凝时间105秒。然后使全部B组合物(114.6份)在120°F老化62小时，接着与120.0份M20S Iso多异氰酸酯混合，以制备泡沫。泡沫外观正常，没有瘪泡。胶凝时间为150秒。在老化期间注意到有些变黄。
虽然已关于优选的实施方案特别展示和描述了本发明，但本领域的普通技术人员很容易理解，可在不脱离本发明的精神和范围下进行各种变化和改进。权利要求旨在解释为覆盖所公开的实施方案、以上讨论的那些替代及其所有等同部分。

Claims (19)

1.一种多元醇预混组合物，所述多元醇预混组合物包含发泡剂、多元醇、硅氧烷表面活性剂和催化剂的组合，所述催化剂为胺和有机酸的加合物，其中发泡剂包括氢卤烯烃和任选的烃、卤代烃、在与异氰酸酯反应时产生CO2的有机酸或其组合。
2.权利要求1的多元醇预混组合物，其中卤代烃选自碳氟化合物、碳氯化合物和碳氟氯化合物。
3.权利要求1的多元醇预混组合物，其中胺具有式R1R2N-[A-NR3]nR4，其中R1、R2、R3和R4分别独立为H、C1至C8烷基、C1至C8烯基、C1至C8醇基或C1至C8醚基，或者R1和R2一起形成C5至C7环烷基、C5至C7环烯基、C5至C7杂环烷基或C5至C7杂环烯基；A为C1至C5烷基、C1至C5烯基或醚；n为0、1、2或3。
4.权利要求1的多元醇预混组合物，其中所述形成加合物的有机酸包括羧酸、次膦酸、膦酸、磺酸、氨基磺酸、异羟肟酸或其组合。
5.权利要求1的多元醇预混组合物，其中所述形成加合物的有机酸包括二羧酸。
6.权利要求1的多元醇预混组合物，其中氢卤烯烃包括至少一种四氟丙烯和／或氯三氟丙烯。
7.权利要求1的多元醇预混组合物，其中氢卤烯烃包括1，3，3，3-四氟丙烯、2，3，3，3-四氟丙烯、1-氯-3，3，3-三氟丙烯或其结构同分异构体或立体异构体或其组合。
8.权利要求1的多元醇预混组合物，其中发泡剂包括甲酸，五氟丁烷；五氟丙烷；六氟丙烷；七氟丙烷；反-1，2-二氯乙烯；1-氯-1，2，2，2-四氟乙烷；1，1-二氯-1-氟乙烷；1，1，1，2-四氟乙烷；1-氯-1，1-二氟乙烷；三氯氟甲烷；二氯二氟甲烷；二氟甲烷；二氟乙烷；异丁烷；正戊烷；异戊烷；环戊烷或其组合。
9.权利要求1的多元醇预混组合物，其中发泡剂包括1，1，1，3，3-五氟丁烷；1，1，1，3，3-五氟丙烷；或其组合。
10.权利要求1的多元醇预混组合物，其中硅氧烷表面活性剂包括聚硅氧烷聚氧化烯嵌段共聚物。
11.权利要求1的多元醇预混组合物，所述多元醇预混组合物进一步包含非硅氧烷非离子表面活性剂。
12.权利要求1的多元醇预混组合物，其中胺包括环己基二甲基胺、二环己基甲基胺、乙基二异丙基胺、二甲基异丙基胺、甲基异丙基苄基胺、甲基环戊基苄基胺、异丙基-仲丁基-三氟乙基胺、二乙基-(α-苯基乙基)胺、三正丙基胺、二环己基胺、叔丁基异丙基胺、二叔丁基胺、环己基叔丁基胺、二仲丁基胺、二环戊基胺、二-(α-三氟甲基乙基)胺、二-(α-苯基乙基)胺或其组合。
13.权利要求1的多元醇预混组合物，所述多元醇预混组合物进一步包含催化剂，所述催化剂包括含铋、铅、锡、钛、钴、锌、镍、锰、锆、钾、钠或其组合的有机金属化合物。
14.权利要求1的多元醇预混组合物，所述多元醇预混组合物进一步包含催化剂，所述催化剂包括硝酸铋、2-乙基己酸铅、苯甲酸铅、氯化铁、三氯化锑、羟基乙酸锑、羧酸的亚锡盐、羧酸的锌盐、羧酸的二烷基锡盐、氨基乙酸盐、叔胺三聚催化剂、羧酸季铵盐、羧酸碱金属盐、乙酸钾、辛酸钾、2-乙基己酸钾、N-(2-羟基-5-壬基苯酚)甲基-N-甲基氨基乙酸盐、2-乙基己酸锡(II)、二月桂酸二丁基锡或其组合。
15.一种形成多元醇预混组合物的方法，所述方法包括混合发泡剂、多元醇、硅氧烷表面活性剂和催化剂，所述催化剂为胺和有机酸的加合物，其中发泡剂包括四氟丙烯和／或氯三氟丙烯和任选的烃、卤代烃、在与异氰酸酯反应时产生CO2的有机酸或其组合。
16.权利要求15的方法，其中卤代烃包括1，1，1，3，3-五氟丙烷。
17.一种可发泡组合物，所述可发泡组合物包括有机多异氰酸酯和权利要求1的多元醇预混组合物的混合物。
18.一种制备聚氨酯或聚异氰脲酸酯泡沫的方法，所述方法包括使有机多异氰酸酯与权利要求1的多元醇预混组合物反应。
19.一种泡沫，所述泡沫根据权利要求18的方法制备。
CN200880121281.9A 2007-10-12 2008-10-06 包含卤代烯烃发泡剂的聚氨酯泡沫多元醇预混物的稳定 Active CN101896525B (zh)

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