CN103261253B - 使用脂族二醇增链剂和仲胺的混合物制备的聚氨酯弹性体 - Google Patents
使用脂族二醇增链剂和仲胺的混合物制备的聚氨酯弹性体 Download PDFInfo
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- CN103261253B CN103261253B CN201180059005.6A CN201180059005A CN103261253B CN 103261253 B CN103261253 B CN 103261253B CN 201180059005 A CN201180059005 A CN 201180059005A CN 103261253 B CN103261253 B CN 103261253B
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Abstract
聚氨酯弹性体通过使包含如下物质的反应混合物固化形成:至少一种多异氰酸酯,至少一种多元醇,脂族二醇增链剂,和少量可以不具有或具有一个或多个羟基的仲氨基化合物。反应用金属催化剂催化。在某些实施方式中,催化剂是有机锆催化剂,有机钛催化剂或基于叔胺的催化剂。在那些情况下存在仲胺化合物可提供良好的表面外观和良好的物理性质。
Description
相关申请的交叉引用
本申请要求2010年12月7日提交的美国临时专利申请61/420,385的优先权。
技术领域
本发明涉及制备流延聚氨酯弹性体(cast polyurethane elastomers)的方法。
背景技术
聚氨酯弹性体通过使高当量多元醇和增链剂物质与多异氰酸酯化合物反应制备。将起始原料混合,通常进行脱气,并转移至其中使弹性体固化的模具中,通常其中施加热量。部分或全部高当量多元醇可以与多异氰酸酯在初始步骤中预反应,形成异氰酸酯封端的预聚物或准预聚物。然后使这样的预聚物与增链剂和任选的剩余部分的高当量多元醇在模塑步骤过程中反应。
开模时间(Open time)在流延弹性体法中是非常重要的。一旦将起始原料混合,则必须使它们保持未固化的可流动状态至多几分钟以允许混合物脱气(在大多数情况下)并转移进模具。如果反应进行得过快,那么模具可能未完全填满,和/或流线或其它缺陷会出现在部件中。这可导致高废品率。
但是,一旦模具被填满,则期望快速固化,从而减少循环时间和使模具利用率最大化。
聚氨酯流延弹性体通常可以按特征划分为聚氨酯类型和聚氨酯-脲类型。两种类型之间的差异涉及用于制备弹性体的增链剂的类型。聚氨酯类型使用二醇增链剂制备,而聚氨酯-脲类型使用二胺增链剂制备。大多数二胺增链剂对异氰酸酯的反应性远大于二醇增链剂对异氰酸酯的反应性。大多数二胺增链的体系具有的开模时间往往对于流延弹性体法而言过短。一些二胺例如亚甲基二(2-氯苯胺)提供长的开模时间,但是与亚甲基二(2-氯苯胺)有关的工人暴露问题使该法成为不期望的选择问题。而且,聚氨酯-脲弹性体的性质通常不能匹配聚氨酯弹性体的那些性质。
流延弹性体法通常选择有机汞化合物作为催化剂。有机汞催化剂提供特性的重要组合,这是用其它催化剂体系极难再现的。这些有机汞催化剂提供非常需要的固化模式,其中先是长的开模时间,然后是快速的固化。有机汞催化剂的第二个特性是它们可制得具有非常需要的物理性质和机械性能的聚氨酯弹性体。
有机汞催化剂的第三个特性涉及完成的聚氨酯产品的外观。有机汞催化剂往往制得具有高度均匀表面外观的弹性体,甚至当聚氨酯体系包含大量增链剂时也是如此。
期望找到有机汞催化剂的替代品。这样的替换催化剂体系理想地将会提供有机汞催化剂的特性,包括所需的固化模式,产品中良好的性质展现,和良好的表面外观。
不幸的是,几乎没有催化剂可成功地模拟有机汞催化剂的性能。几乎没有其它催化剂提供所需的反应模式。可提供类似于有机汞催化剂的反应模式的极少催化剂是某些有机锆催化剂,有机钛催化剂和某些叔胺催化剂。但是,当流延聚氨酯体系包含大量增链剂时,使用这些催化剂制备的流延弹性体通常表现出的表面外观的特征在于存在不连续的透明或半透明的区域连同不连续的不透明区域。这样的外观对于消费者而言通常是表面装饰上(cosmetically)无法接受的,也产生高废品率。在某些情况下,机械性质也可能遭受损害。
期望提供流延弹性体法,其提供可接受的开模时间,然后是快速的固化,并且制得具有可接受物理性质和可接受表面外观的弹性体。也期望在避免使用含汞的催化剂的同时实现这些结果。
发明内容
一方面,本发明是制备无孔或微孔聚氨酯弹性体的方法,包括:1)形成包含以下物质的反应混合物:a)一种或多种羟基当量为约30至约100的脂族二醇,b)一种或多种分子量为200或更少的仲胺化合物,以及c-1)和c-2)中的至少一种,其中c-1)包括一种或多种异氰酸酯含量为至少15重量%的有机多异氰酸酯和一种或多种羟基当量为至少250的多元醇,c-2)包括一种或多种异氰酸酯含量小于15%的异氰酸酯封端的预聚物或准预聚物,所述预聚物或准预聚物在有机多异氰酸酯与一种或多种羟基当量为至少250的多元醇的反应中形成,和2)在催化剂的存在下使所述反应混合物固化形成所述聚氨酯弹性体,其中:
A)所述反应混合物包含至多0.25重量%的化学发泡剂;
B)所述仲胺化合物包含1至4个仲氨基,不含伯氨基,且包含0至3个羟基,条件是仲氨基和羟基的总数为1至4;
3)组分a)与组分b)的重量比为60:40至95:5;
4)所述聚氨酯弹性体的硬链段含量为30至60重量%;和
5)异氰酸酯指数为70至125。
具体实施方式
"无孔"弹性体基本上没有由在固化步骤中存在的气体产生的泡孔或其它空隙。无孔弹性体的堆积密度通常为至少0.9g/cc和/或空隙体积为5%或更少。针对本发明的目的,"微孔"弹性体通过在少量发泡剂存在下进行固化步骤制备。"微孔"弹性体的堆积密度为至少0.4g/cc,更通常为0.5至0.9g/cc,和/或空隙体积为5至60%。
根据本发明制备的弹性体的物理性质往往近似于由具有相同硬链段含量、但是未使用仲胺组分(组分b)制备的相同聚氨酯弹性体表现出的那些物理性质。令人惊讶地,这些弹性体也表现出高度均匀的表面外观,其中即使有也是极少透明或半透明的区域散布在不透明的区域之中。甚至当反应体系中不存在有机汞催化剂时,也可见这种期望的表面外观。甚至当有机锆、有机钛或叔胺催化剂替代有机汞催化剂使用时,也可以制得具有良好表面外观的弹性体。
组分a)是一种或多种脂族二醇,其羟基当量为30至约100,优选为31至60。这种类型的物质通常称为"增链剂"。"脂族二醇"表示恰好具有两个羟基的化合物,其中每个羟基键接于脂族(或脂环族)碳原子。代表性的增链剂包括乙二醇,二甘醇,三甘醇,1,2-丙二醇,1,3-丙二醇,1,4-丁二醇,1,6-己二醇,新戊二醇,一缩二丙二醇,二缩三丙二醇和环己烷二甲醇。可以使用两种或更多种羟基当量为30至100的脂族二醇。
组分a)适当地占反应混合物的反应性组分(即,异氰酸酯和异氰酸酯反应性物质)的至少5重量%,并且可以占其多达25重量%。在一些实施方式中,组分a)将占反应混合物的反应性组分的6至15重量%或6.5至12重量%。
组分b)是一种或多种下述化合物,其分子量为至多200,包含1至4个仲氨基,不含伯氨基,且包含0至3个羟基。仲氨基和羟基的总数为1至4。组分b)化合物应该不含除仲氨基和羟基之外的基团,这些基团对异氰酸酯具有反应性。优选的组分b)化合物具有一个或两个仲氨基,0至2个羟基,和总数为1至3、特别是1至2个仲氨基和羟基。
二烷基胺和取代的二烷基胺是适宜的组分b)物质。烷基可以彼此相同或不同,并且每个烷基可以包含至多约10个碳原子,条件是二烷基胺的分子量不大于200。烷基各自优选地具有1至3个原子,并且优选为甲基,乙基或丙基。烷基可以取代有在固化反应条件下没有反应性的取代基。这样的取代基的实例包括卤素(特别是氯),芳基,硝基,醚,酯,苯基,烷基取代的苯基等。可用的具体二烷基胺包括,例如,二甲基胺,二乙基胺,二异丙基胺,甲基乙基胺,二苄基胺等。
二(芳基)胺(例如二苯基胺)和单芳基单烷基胺(例如甲基苯基胺或乙基苯基胺)也可用作组分b)物质。芳基可以是单环类型或多环类型,条件是化合物的分子量为200或更低。多环类型可以是稠合的或桥连结构。二(芳基)胺中的芳基可以彼此相同或不同。单芳基单烷基胺的烷基可以包含至多10个碳原子,优选为至多4个碳原子。这些化合物的芳基和/或烷基可以按照关于二烷基胺所描述的进行取代。
也可使用在环结构中包含一个或多个仲氮原子的脂环族化合物。这些包括,例如,哌啶,吗啉,哌嗪等。环结构上的碳原子可以按照上述取代。
二烷醇胺例如二乙醇胺和二异丙醇胺也是有用的组分b)物质。类似地,使用二胺(如乙二胺)与每摩尔二胺约3摩尔的环氧烷烃(例如环氧乙烷和/或环氧丙烷)的反应产物。这些反应产物每分子平均具有一个仲胺基团和三个羟基。
单烷基单链烷醇胺也是有用的组分b)物质。烷基可以包含1至10个碳原子,优选为1至3个碳原子,更优选为1或2个碳原子。烷醇基团可以包含2至10个碳原子,优选为2至4个碳原子,更优选为2个碳原子。烷基或烷醇基团可以按照之前描述的取代。适宜的单烷基单链烷醇胺包括,例如下述化合物,如2-(甲基氨基)乙醇,2-(乙基氨基)乙醇,2-(丙基氨基)乙醇,1-甲基-2-(甲基氨基)乙醇,1-甲基-2-(乙基氨基)乙醇,1-甲基-2-(丙基氨基)乙醇,1-乙基-2-(甲基氨基)乙醇,1-乙基-2-(乙基氨基)乙醇,1-乙基-2-(丙基氨基)乙醇,N-羟基乙基苄胺,N-羟基丙基苄胺等。
组分a)和b)在反应混合物中存在的重量比为至少60:40(60份组分a)比40份组分b))至多达95:5。优选的比率为70:30至95:5。在一些实施方式中,该比率可以为80:20至95:5。
反应混合物优选地包含至多5重量%的交联剂,优选地包含至多2重量%的交联剂,仍更优选地包含至多0.25重量%的交联剂。交联剂表示具有至少三个异氰酸酯反应性基团且分子量为250或更少/异氰酸酯反应性基团的异氰酸酯反应性化合物。反应混合物优选地包含至多1重量%的包含一个或多个伯胺基的化合物,更优选地包含至多0.25重量%的包含一个或多个伯胺基的化合物。
反应混合物包含至少一种有机多异氰酸酯。在某些实施方式(c-1)中,有机多异氰酸酯的异氰酸酯含量为15重量%或更多,且反应混合物还包含至少一种羟基当量为至少250的多元醇。在其它实施方式(c-2)中,有机多异氰酸酯是或包括异氰酸酯含量小于15%的一种或多种异氰酸酯封端的预聚物或准预聚物,所述预聚物或准预聚物在有机多异氰酸酯与一种或多种羟基当量为至少250的多元醇的反应中形成。在后一种(c-2)情况下,没必要使反应混合物进一步包含羟基当量为至少250的多元醇,除非是需要将弹性体的硬链段含量限定在30至60的范围内。这两种类型的实施方式近似地对应于用于制备聚氨酯弹性体的熟知的"一步"法和"两步"法。
适宜的有机多异氰酸酯每分子平均包含至少1.5个异氰酸酯基团,优选为至少1.8个异氰酸酯基团,或至少2.0个异氰酸酯基团。有机多异氰酸酯可以每分子包含多至8个异氰酸酯基团,但是通常每分子包含至多约4个异氰酸酯基团,优选为至多3.5个异氰酸酯基团或至多2.5个异氰酸酯基团。有机多异氰酸酯可以包含少至约15重量%的异氰酸酯基团,或可以包含少至约50重量%的异氰酸酯基团。其优选地包含至少25重量%的异氰酸酯基团。异氰酸酯基团可以键接于芳族碳原子,脂族或脂环族碳原子。
有用的多异氰酸酯的实例包括间苯二异氰酸酯,甲苯-2,4-二异氰酸酯,甲苯-2,6-二异氰酸酯,六亚甲基-1,6-二异氰酸酯,四亚甲基-1,4-二异氰酸酯,环己烷-1,4-二异氰酸酯,六氢甲苯二异氰酸酯,萘-1,5-二异氰酸酯,甲氧基苯基-2,4-二异氰酸酯,二苯基甲烷-4,4'-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,3,3'-二甲基二苯基甲烷-4,4'-二异氰酸酯,4,4',4"-三苯基甲烷三异氰酸酯,聚亚甲基聚苯基异氰酸酯(PMDI),甲苯-2,4,6-三异氰酸酯和4,4'-二甲基二苯基甲烷-2,2',5,5'-四异氰酸酯。二苯基甲烷-4,4’-二异氰酸酯,二苯基甲烷-2,4’-二异氰酸酯及其混合物通常在本申请称为MDI。甲苯-2,4-二异氰酸酯,甲苯-2,6-二异氰酸酯及其混合物通常称为TDI。
可以改性任何前述异氰酸酯以包括氨基甲酸酯、脲、缩二脲、碳化二亚胺、脲基甲酸酯、脲酮亚胺(uretonimines)、异氰脲酸酯、酰胺等连接基。这些类型的改性的异氰酸酯的实例包括各种包含氨基甲酸酯基团和/或脲基团的预聚物,其中的一些在下文详细描述,和所谓的“液体MDI”产物等。
当需要光稳定性时,脂族多异氰酸酯是优选的。在其它情况下,通常使用TDI、MDI或MDI衍生物。MDI可以是2,2’-异构体,2,4’-异构体或4,4’-异构体,其中4,4’-异构体,或4,4’-异构体和2,4’-异构体的混合物是优选的。MDI的“衍生物”是下述MDI,已将其改性以包括氨基甲酸酯、脲、缩二脲、碳化二亚胺、脲酮亚胺等连接基,并且其异氰酸酯含量为至少15重量%,优选为至少25重量%。
组分c-1)或c-2)的多元醇的羟基当量为至少250。"多元醇"表示物质每分子平均具有至少1.8个羟基。多元醇物质可以每分子平均包含至多8个羟基。其优选地每分子包含2至4个羟基,更优选为2至3个羟基。羟基当量优选为至少500,更优选为500至3000,仍更优选为750至2100。
可以使用两种或更多种多元醇的混合物,每种多元醇每分子具有至少1.8个羟基且羟基当量为至少250。
羟基当量为250或更多的适宜的多元醇的实例包括羟基官能的丙烯酸酯聚合物和共聚物,羟基官能的聚丁二烯聚合物,聚醚多元醇,聚酯多元醇,胺封端的聚醚,以及基于植物油或动物脂肪的各种多元醇。聚醚多元醇在这些之中是优选的。
有用的聚醚多元醇包括,例如,环氧丙烷、环氧乙烷、1,2-环氧丁烷、四氢呋喃的聚合物,其嵌段和/或无规共聚物等。特别有用的是聚(环氧丙烷)均聚物;环氧丙烷和环氧乙烷的无规共聚物,其中氧亚乙基(oxyethylene)含量为,例如,约1至约30重量%;环氧乙烷-封端的聚(环氧丙烷)聚合物,其包含70至100%的伯羟基;和环氧丙烷和环氧乙烷的环氧乙烷封端的无规共聚物,其中氧亚乙基含量为约1至约30重量%。聚醚多元醇可以包含低末端不饱和度(例如,小于0.02meq/g或小于0.01meq/g),例如使用所谓双金属氰化物(DMC)催化剂制备的那些,例如描述于美国专利3,278,457,3,278,458,3,278,459,3,404,109,3,427,256,3,427,334,3,427,335,5,470,813和5,627,120的那些。也可以使用各种类型的聚合物多元醇。聚合物多元醇包括聚合物粒子在多元醇(通常为聚醚多元醇)中的分散体,所述聚合物粒子例如聚脲,聚氨酯-脲,聚苯乙烯,聚丙烯腈和聚苯乙烯-共聚-丙烯腈聚合物粒子。适宜的聚合物多元醇描述于美国专利4,581,418和4,574,137。
有用的聚酯多元醇包括多元醇(优选为二醇)与多羧酸或它们的酐(优选为二羧酸或二羧酸酐)的反应产物。多羧酸或酐可以是脂族的,脂环族的,芳族的和/或杂环的,并且可以由例如卤素原子取代。多羧酸可以是不饱和的。这些多羧酸的实例包括琥珀酸,己二酸,对苯二甲酸,间苯二甲酸,偏苯三甲酸酐,邻苯二甲酸酐,马来酸,马来酸酐和富马酸。用于制备聚酯多元醇的多元醇的当量优选为150或更少,并且包括乙二醇,1,2-丙二醇和1,3-丙二醇,1,4-丁二醇和2,3-丁二醇,1,6-己二醇,1,8-辛二醇,新戊二醇,环己烷二甲醇,2-甲基-1,3-丙二醇,甘油,三羟甲基丙烷,1,2,6-己三醇,1,2,4-丁三醇,三羟甲基乙烷,季戊四醇,对环己二醇,甘露醇,山梨糖醇,甲基糖苷,二甘醇,三甘醇,四甘醇,一缩二丙二醇,一缩二丁二醇等。可使用聚己内酯多元醇。也可以使用各种类型的聚合物多元醇。
基于植物油和/或动物脂肪的多元醇包括,例如,蓖麻油,包含羟甲基的多元醇,如描述于WO2004/096882和WO2004/096883,包含酰胺基团的多元醇,如描述于WO2007/019063,羟基酯取代的脂肪酸酯,如描述于WO2007/019051,“吹制”大豆油,如描述于美国公开的专利申请2002/0121328,2002/0119321和2002/0090488,低聚的植物油或动物脂肪,如描述于WO06/116456,包含羟基的纤维素-木质素物质,包含羟基的改性淀粉以及各种类型的可再生资源多元醇,如描述于Ionescu,Chemistry and Technology ofPolyols for Polyurethanes,Rapra Publishers2005。
包含异氰酸酯的化合物与异氰酸酯反应性化合物的比率通常表示为"异氰酸酯指数",其针对本发明的目的表示异氰酸酯基团与由异氰酸酯反应性物质提供的异氰酸酯反应性基团的比率乘以100。异氰酸酯指数为至少70,并且可以为至多125。异氰酸酯指数可以为至少80,至少90或至少95,并且可以为至多115或至多约110。
也选择各成分的类型和比例,使得聚氨酯弹性体的硬链段含量为30至60重量%,优选为35至50重量%。针对本发明的目的,"硬链段含量"是由多异氰酸酯和增链剂(即,组分a)物质)贡献的聚氨酯弹性体的重量分数,由方程I表示:
在方程1中,%HS是基于重量的%硬链段含量。Wiso是或存在于反应混合物中或用于(在c-2情况下)制备异氰酸酯封端的预聚物或准预聚物的异氰酸酯含量为15%或更多的多异氰酸酯的重量。Wiso不包括在c-2情况下用于制备预聚物或准预聚物的羟基当量为250或更多的任何多元醇的重量。Wa是用于制备弹性体的增链剂(即,组分a)物质)的重量。Wt是用于制备弹性体(包括组分a)和b)物质和组分c-1)和/或c-2)物质,视情况而定)的全部多异氰酸酯和异氰酸酯反应性物质的总重量。Wt包括催化剂的重量。Wt不包括可能存在于反应混合物的发泡剂、填料或增强剂,或者不会反应形成部分聚氨酯聚合物结构的其它成分的重量。在其中组分a)、b)和c-1)和/或c-2)是仅有的反应性组分的简单情况下,硬链段含量可以表示为:
其中%HS和Wiso如前所述,Wa是组分a)的重量,Wb是组分b)的重量,Wcat是催化剂的重量,Wp是存在于反应混合物和/或在c-2)情况下用于形成预聚物或准预聚物的羟基当量为250或更多的全部多元醇的重量。
弹性体如下制备:形成包含组分a)、b)和c-1)或c-2)的至少一种的反应混合物,并在含金属的催化剂存在下使混合物固化。包括c-1)物质的方法通常称为"一步"法;包括c-2)物质的方法通常称为"预聚物"法或"两步"法。
在一步法中,反应混合物包含如前所述的组分a),b)和c-1),连同催化剂和可能存在的任何任选的成分。在两步法中,反应混合物包含组分a)、b)和c-2),连同催化剂和可能存在的任何任选的成分。在两步法情况下的反应混合物可以进一步包括一种或多种当量为250或更多的多元醇。
如前所述,预聚物或准预聚物c-2)是至少一种异氰酸酯含量为至少15重量%、优选为至少25重量%的有机多异氰酸酯与一种或多种羟基当量为至少250的多元醇的反应产物。"预聚物"表示每当量多元醇上的羟基约1摩尔多异氰酸酯的反应产物;所得预聚物包含多元醇和至多少量(至多10重量%)未反应的多异氰酸酯化合物的异氰酸酯封端的加合物。预聚物的异氰酸酯含量可以为0.5至约10重量%,优选为0.5至5重量%。"准预聚物"表示每当量由多元醇提供的羟基多于1摩尔多异氰酸酯的反应产物。所得准预聚物主要为多元醇和多异氰酸酯和一定量(通常为10至50重量%)未反应的多异氰酸酯化合物的异氰酸酯封端的加合物的混合物。在任一种情况下,可以发生多元醇分子的部分偶联,制得少量较高分子量物质。预聚物或准预聚物c-2)物质应该每分子平均包含约1.9至约4.0个异氰酸酯基团,优选为2.0至3.5个异氰酸酯基团,更优选为2.0至3.0个异氰酸酯基团。
除了前述成分之外,低(至多300)分子量二醇也可用于制备准预聚物。该低分子量二醇的分子量优选为62至200。低分子量二醇的实例包括乙二醇,1,2-丙二醇或1,3-丙二醇,二甘醇,一缩二丙二醇,三甘醇,二缩三丙二醇,环己烷二甲醇等。如果使用,该物质通常以小量使用。如果用于制备预聚物或准预聚物,可以使用1且至多25重量份的预聚物或准预聚物/100重量份的当量为250或更多的多元醇。在计算硬链段含量时,该低分子量二醇作为增链剂(即,方程I中组分Wa部份)计算。
反应混合物在含金属的催化剂或叔胺催化剂存在下固化。金属催化剂的实例包括,例如,金属的金属螯合物,金属如Be,Mg,Al,Zn,Cd,Pd,Ti,Zr,Sn,As,Bi,Cr,Mo,Mn,Fe,Co和Ni。螯合剂可以是,例如,乙酰丙酮,苯甲酰丙酮,三氟乙酰丙酮,乙酰乙酸乙酯等。也可使用强酸的酸性金属盐。这些的实例包括氯化铁,氯化锡,氯化亚锡,三氯化锑,硝酸铋和氯化铋。另一类有用的金属催化剂包括各种金属的醇盐或酚盐,例如Ti(OR)4,Sn(OR)4和Al(OR)3,其中R是烷基或芳基,以及醇盐与羧酸、β-二酮和2-(N,N-二烷基氨基)醇的反应产物。再另一类有用的金属催化剂包括碱土金属,Bi,Pb,Sn或Al的羧酸盐。四价锡化合物,和三价或五价铋,锑或砷化合物也是有用的金属催化剂。
其它适宜的催化剂包括铜或锌催化剂络合物,其包含至少一个与多配位基配体相连的铜原子或锌原子,所述配体包含至少一个含氮的配位位点。多配位基配体包含至少两个配位位点,该配位位点由至少一个原子、优选为2至3个原子隔开。配位位点可以,例如,形成与铜离子的共价键、配位键或离子键。配位位点中的至少一个包含氮。含氮的配位位点可以是,例如,氨基,烯氨基或亚氨基。一些特别有用类型的配体化合物包含至少一个羟基或羰基和至少一个氨基、烯氨基或亚氨基,其中氨基、烯氨基或亚氨基位于羟基键接的碳的α-位或β-位或在羰基碳的α-位或β-位,视情况而定。这些类型的配体包括:(A)α-氨基醇;(B)α-亚氨基醇,(C)β-氨基醇或烯醇,(D)β-亚氨基醇或烯醇,(E)β-烯氨基醇和(F)β-氨基酮或β-烯氨基酮或酯化合物。其它特别有用类型的配体化合物是(G)β-二酮酰亚胺化物化合物和(H)β-二胺化合物。配体类型(A)-(H)中的任何一种也可以包含另外的配位位点。当与催化剂中的铜或锌离子连接时,这些配体通常呈相应的阴离子形式,其中氢原子从羟基撤出(形成醇化物)和/或从氨基撤出(形成胺化物)。
适宜的叔胺催化剂包括酸封端的类型,其中酸基团是,例如,具有1至18个碳原子的链烷酸,或酚类化合物。这种酸封端的胺催化剂的实例包括,例如,甲酸-封端的二(二甲基氨基乙基)醚,甲酸-封端的三亚乙基二胺,2-乙基己酸-封端的1,8-二氮杂双环-5,4,0-十一碳烯-7,苯酚-封端的1,8-二氮杂双环-5,4,0-十一碳烯-7和甲酸-封端的1,8-二氮杂双环-5,4,0-十一碳烯-7,以及其它酸封端的叔胺化合物。
可以使用含汞的催化剂,但是这不是优选的并且可以省略。含汞的催化剂具有以下优点,提供慢的初始固化,然后是快速固化;这样的催化剂提供长的开模时间与合理的短脱模时间。
本发明在以下方面是特别有益的,催化剂是无汞催化剂,例如有机锆和/或有机钛催化剂或叔胺催化剂。这些催化剂通常提供类似于含汞的催化剂所提供的有益的固化分布,但是,在常规流延弹性体法中,其中该方法包括大量增链剂(例如占反应混合物的反应性组分的5重量%或更多)且不包括组分b)物质,通常形成具有差的表面外观的弹性体,这种表面外观是表面装饰所不能接受的。已经出乎意料地发现,该问题通过将少量组分b)物质加入到反应混合物中得以克服。当组分b)存在时弹性体具有视觉上均匀的表面外观,甚至当使用不含汞的催化剂例如有机锆催化剂、有机钛催化剂和/或叔胺催化剂时也是如此。而且,已经发现存在组分b)物质对弹性体的物理性质具有极小或不具有不利影响。
催化剂的适当量为0.001至5份每100份存在于反应混合物的反应性物质,但是该含量可以根据具体的聚合工艺和存在的具体反应物变化。优选的量为0.05至2重量份每100重量份的反应性物质。
多种另外的物质可以存在于反应混合物。这些物质包括物理发泡剂;填料;颜料和/或着色剂;干燥剂;增强剂;生物灭杀剂;防腐剂;抗氧化剂;阻燃剂等。
如果期望形成多孔或微孔弹性体,那么可以存在物理发泡剂。但是,化学发泡剂例如水应该存在,如果存在,应该仅以小量存在,不超过反应混合物中反应性物质的0.25重量%。物理发泡剂包括在标准条件下为气体的物质,例如空气,氮气,氩气等。在将反应混合物转移至模具并固化之前,通常将气体发泡剂驱赶进反应混合物。在固化反应条件下挥发的液体和超临界气体也是有用的发泡剂。这些的实例包括各种低沸点氯氟烃,氟碳化合物,烃等。氟碳化合物和烃在物理发泡剂中是优选的,因为它们具有低或零全球变暖效应和臭氧消耗作用。通常将液体和超临界气体混合进反应混合物(或其一些组分)并在固化反应过程中挥发。
发泡剂的量可以广泛变化,这取决于使用的特定发泡剂和所得聚合物的所需密度。如果存在,选择发泡剂的量以制得无孔或微孔弹性体。
也可以存在一种或多种填料。填料可以帮助按有益方式改性组合物的流变学性质,减少成本和赋予泡沫体以有益的物理性质。适宜的填料包括颗粒状无机和有机材料,这些材料在形成聚氨酯的反应过程中所遇温度下是稳定的并且不会熔融。适宜的填料的实例包括高岭土,蒙脱土,碳酸钙,硅灰石,滑石,高熔点热塑性材料,飞灰,炭黑,二氧化钛,氧化铁,氧化铬,偶氮/重氮染料,酞菁染料,二嗪,胶态二氧化硅等。填料可以赋予触变性质。蒸气沉积二氧化硅是这样的填料的实例。当存在时,填料有利地占聚合物重量的约0.5至约30%,特别是约0.5至约10%。
前述填料中的一些也可以赋予聚合物以颜色。这些的实例包括二氧化钛,氧化铁,氧化铬和炭黑。其它着色剂例如偶氮/重氮染料、酞菁染料和二嗪也可使用。
也可以存在增强剂。增强剂的形式为颗粒和/或纤维,其纵横比(最长尺寸与最短尺寸的比率)为至少3,优选为至少10。增强剂的实例包括云母薄片,纤维玻璃,碳纤维,硼或其它陶瓷纤维,金属纤维,玻璃薄片等。增强剂可以形成垫层或其它预成型的块体(masses)。
为制备弹性体,通常将起始原料按可产生异氰酸酯指数为至少70至约125的比率混合。优选的异氰酸酯指数为90至115,更优选的指数为95至110。
通常认为固化条件不是关键的,条件是该混合物充分固化。通常将反应混合物转移至模具中并在模具中至少部分固化。各组分或混合物可以在引入到模具之前预加热。可以预加热模具。通常需要在高温使混合物固化;由于该原因,填充的模具通常在烘箱或其它适当的设备中加热。模具温度可以为40至90°C。固化时间可以为少至1分钟至60分钟或更多。在至少达到所得弹性体可在没有永久损伤或永久变形情况下从模具取出的程度的固化之后,部件可以脱模。如果必要,可以在高温使部件后固化以完成固化。
弹性体当然会呈现模具内腔的形状;因此设计模具以制备具有所需外部形状和尺寸的部件。可以制备多种弹性体部件,包括垫圈,套管,轮,带,海运弹性体,工程弹性体等。但是,鞋底是特别有用的应用。鞋底可以是,例如,鞋底夹层,鞋内底,和外底,或者实现两种或更多种这些功能的整合鞋底。
提供以下实施例说明本发明但不意图限制本发明的范围。除非另有指出,否则所有的份和百分比均基于重量。
实施例
实施例1–5和对比样品A和B
弹性体实施例1-5和对比样品A和B根据以下通用规程制备:
将包含1重量%分子筛糊剂的6000分子量、标称三官能的环氧乙烷封端的聚(环氧丙烷)(VoranolTMCP6001,得自The Dow Chemical Company),1,4-丁二醇和仲胺化合物(如果使用)按以下表1中所示的比例共混。仲胺化合物是二乙醇胺(DEOA),2-(甲基氨基)乙醇(MAE),2-(乙基胺)乙醇(EAE),2-(丙基胺)乙醇(PAE)和二乙基胺(DEA)。然后使用高速混合机将共混物与催化剂按照表1所示混合。催化剂是有机汞催化剂(Thorcat535,得自Thor Chemicals)或有机钛催化剂(SC2210,得自Johnson Matthey)。所得多元醇混合物在室温保持至少30分钟,然后与改性的MDI在高速混合机上共混90秒,所述改性的MDI的异氰酸酯含量为26.3重量%,且每分子平均具有2.1个异氰酸酯基团(ISONATETMM340,得自The Dow Chemical Company)。所得反应混合物保持另一分钟,然后将其倒入80°C的敞开模具中并使其固化。消粘时间(TFT)通过用手轻拍固化混合物的表面评价。脱模时间评价为在倾倒之后当弹性体可以在没有永久变形或撕裂情况下从模具取出时的时间。在脱模之后,弹性体在80°C后固化约16小时,物理性质根据ASTM D1708测量。物理性质测试的结果如表1所示。
后固化的试验样片的表面外观通过视觉检查评价。对比样品A(使用汞催化剂制备)的表面品质规定为"1"(非常好,其具有最少或没有不透明区域散布有半透明区域)等级,将其设定为基准,与其它的相比较。表面品质的等级分为1至5,其中数字越高,表示表面品质越差。视觉检查的结果如表1所示。
表1
对比样品A说明使用有机汞催化剂获得的性质;其用作其它实验的性能基准。对比样品B显示用有机钛催化剂代替有机汞催化剂的效果。有机钛催化剂比汞催化剂快一点。尽管可以见到性质方面有一些损失,但是认为对比样品B的物理性质是可接受的。但是,表面是表面装饰上所不能接受的。该表面具有大片区域散布有半透明和不透明聚合物。
实施例1-5显示添加仲胺化合物的效果。在这些实施例中,1,4-丁二醇的量相对于对比样品降低,以获得相等的硬链段含量。认为在这组实验中各硬链段含量之间的差异是无关紧要的,硬度差异也是如此。与对比样品B(其使用相同催化剂制备)相比,实施例1至5各自具有远好得多的表面外观。实施例2,3和5实际上具有的表面外观与在实施例1中使用有机汞催化剂获得的那些相等。对物理性质存在极小或没有不利影响,在一些情况下(实施例3,4和5),确定模量增加。
实施例6-8和对比样品C
多元醇共混物6-8和C由表2所示的组分制备。多元醇与前面实施例中描述的多元醇相同,所不同的是其不包含分子筛糊剂。两种弹性体由这些母料的每一种使用关于前面实施例描述的通用方法制备。这些弹性体分别称为实施例6-1,6-2,7-1,7-2,8-1,8-2和对比样品C-1和C-2。相应多元醇共混物的量和多异氰酸酯的量描述于表3。在脱模之后,弹性体在80°C后固化约1小时,物理性质根据ASTM D1708测量。测得的性质作为实施例6-8和对比样品C记录于表4。
表2-多元醇共混物组合物
表3–弹性体配制物
表4-弹性体性质
如表4中的数据所示,存在仲胺化合物导致表面外观的极大改善,同时对物理性质具有极小或没有不利影响。
Claims (9)
1.制备无孔或微孔聚氨酯弹性体的方法,包括:1)形成包含以下物质的反应混合物:a)一种或多种羟基当量为30至100的脂族二醇,b)一种或多种分子量为200或更少的仲胺化合物,以及c-1)和c-2)中的至少一种,其中c-1)包括一种或多种异氰酸酯含量为至少15重量%的有机多异氰酸酯和一种或多种羟基当量为至少250的多元醇,c-2)包括一种或多种异氰酸酯含量小于15%的异氰酸酯封端的预聚物或准预聚物,所述预聚物或准预聚物在有机多异氰酸酯与一种或多种羟基当量为至少250的多元醇的反应中形成,和2)在催化剂的存在下使所述反应混合物固化形成所述聚氨酯弹性体,所述催化剂为至少一种有机锆化合物或有机钛化合物,其中:
A)所述反应混合物包含至多0.25重量%的化学发泡剂;
B)所述仲胺化合物包含一个或两个仲氨基,不含伯氨基,且仲氨基和羟基的总数为1至2;
3)组分a)与组分b)的重量比为60:40至95:5;
4)所述聚氨酯弹性体的硬链段含量为30至60重量%;和
5)异氰酸酯指数为70至125。
2.权利要求1的方法,其中组分b)是二烷基胺,取代的二烷基胺,二(芳基)胺,在环结构中包含一个或多个仲氮原子的脂环族化合物,单烷基单链烷醇胺,或前述物质中两种或更多种的混合物。
3.权利要求2的方法,其中组分b)是二甲基胺,二乙基胺,二异丙基胺,甲基乙基胺,二苄基胺,或它们的任何两种或更多种的混合物。
4.权利要求2的方法,其中组分b)是2-(甲基氨基)乙醇,2-(乙基氨基)乙醇,2-(丙基氨基)乙醇,1-甲基-2-(甲基氨基)乙醇,1-甲基-2-(乙基氨基)乙醇,1-甲基-2-(丙基氨基)乙醇,1-乙基-2-(甲基氨基)乙醇,1-乙基-2-(乙基氨基)乙醇,1-乙基-2-(丙基氨基)乙醇,N-羟基乙基苄胺,N-羟基丙基苄胺,或前述物质中两种或更多种的混合物。
5.前述权利要求中任一项的方法,其中组分a)占所述反应混合物中反应性物质重量的6至15%。
6.前述权利要求1-4中任一项的方法,其中组分a)和b)存在的重量比为80:20至95:5。
7.前述权利要求1-4中任一项的方法,其中所述反应混合物不包括含汞的催化剂。
8.前述权利要求1-4中任一项的方法,其中所述催化剂包括至少一种基于叔胺的催化剂。
9.前述权利要求1-4中任一项的方法,其中所述反应混合物包含少于0.5重量%的交联剂和少于0.25重量%的包含一个或多个伯氨基的化合物。
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