CN1040446C - 聚氨酯前体组合物及其用途 - Google Patents
聚氨酯前体组合物及其用途 Download PDFInfo
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- CN1040446C CN1040446C CN93118086A CN93118086A CN1040446C CN 1040446 C CN1040446 C CN 1040446C CN 93118086 A CN93118086 A CN 93118086A CN 93118086 A CN93118086 A CN 93118086A CN 1040446 C CN1040446 C CN 1040446C
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- agent
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- microns
- porous plastics
- polyurethane
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Classifications
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Abstract
本发明公开了一种在穿孔剂存在下得到的含有孔泡窗的微孔聚合物,穿孔剂为临界表面自由能小于23mJ/m2的物质。按本发明得到的微孔聚合物有细泡孔结构及高的尺寸稳定性和热绝缘性。本发明还涉及例如在作为穿孔剂的颗粒聚四氟乙烯或沸点至少为130℃的液体多氟或全氟碳化合物存在下制备的硬质聚氨酯泡沫塑料。
Description
本发明涉及一种聚氨酯前体组合物和一种含有孔泡窗的微孔聚合物,更具体地是微孔聚氨酯聚合物的制备方法。
各种微孔聚合物如聚乙烯、聚苯乙烯或聚氨酯在包括显著的热绝缘材料在内的许多应用场合中都有价值。在这种情况下,这样的泡沫塑料表现出有吸引力的尺寸稳定性以及相对稳定的热绝缘性能是特别有利的。这两个特性主要由泡沫塑料的微孔结构以及泡孔空洞中的气体组成决定。泡孔结构越细一般使泡沫塑料得到更好的绝缘性质。但是,当泡孔变细时,即平均直径变小时,泡沫塑料的压缩强度和尺寸稳定性常常变坏。当泡孔空洞含有可能冷凝或者可能从泡孔扩散出来的气体时,对尺寸稳定性变差的敏感性最大。上述任何一种现象都会使泡孔内的部分气体压力下降,引起泡沫塑料的尺寸稳定性变差。提到的扩散出泡孔空间特别是聚氨酯泡孔空洞的泡孔气体的例子是二氧化碳。二氧化碳作为许多普遍使用的、被认为对臭氧层有损害的物理发泡剂的替代品,用来制备微孔聚合物特别是聚氨酯微孔聚合物现在是十分有好处的。
为了支持这一发展趋势,有必要开发一种制备有吸引力的尺寸稳定性和热绝缘性的微孔聚合物的改进方法。特别是对聚氨酯泡沫塑料来说,需要一种能使用例如水产生的二氧化碳又能得到具有工业上可接受的尺寸稳定性和热绝缘性能的泡沫塑料。
从泡沫塑料形态和细泡孔聚合物形成的一般认识出发,可认识到随着平均泡孔尺寸减小,泡沫塑料的闭孔含量变得更重要。泡孔由许多支柱和角限定的许多泡窗区构成。所谓“闭孔”,一般理解为泡窗区完全被一层薄膜封闭,因而得到隔离的泡孔空洞。高的闭孔含量常常使泡沫塑料的尺寸稳定性变差。
尺寸稳定性问题的一个可能的解决办法是生产一种有开孔结构的泡沫塑料。该结构是一个或多个泡窗完全打开,而不被薄膜封闭。这样的开孔不会因部分压力损失而受到损害而引起尺寸稳定性变差。有开孔结构的发泡聚合物可通过发泡聚合物制备后经压榨使泡窗破裂的方法制备。这一方法只可用于弹性体型聚合物,因为压榨硬质微孔聚合物会造成永久性变形和损坏。为了在硬质聚合物中产生开放的泡孔,需要在制备过程中使用泡孔开孔剂。这样的泡孔开孔剂一般是高沸点液体,如高分子量的聚氧化烯加合物。但是,伴随使用这样的泡孔开孔剂产生的缺点是,这些泡孔开孔剂通常促使具有大泡孔结构的聚合物生成,因而其热绝缘性变得不具吸引力。
因此,有必要得到一种具有与尺寸稳定性有关的“开孔特性”而又保持细泡孔结构的泡沫塑料。为此,研究了制备含有孔泡窗的泡沫塑料的概念。所谓“有孔”可理解为泡孔窗仍有一层与支柱和角相连的膜,而这样的膜内有空洞,即“针孔”或孔。因此,需要找到能产生有孔泡孔膜又不特别产生开孔结构的物质。从理论考虑出发,必须找到能促使局部破坏在泡孔膜内形成“针孔”的物质。再从理论考虑出发,最有可能促使局部破坏的物质是那些与微孔聚合物几乎没有相互作用(物理作用或化学作用)的物质。所提到的与其周围环境几乎没有相互作用的物质例如包括聚四氟乙烯,常称为“PTFE”。
欧洲专利EP-224945-A公开了一种在每100份多元醇有25~60份重粒径为25微米或25微米以下的颗粒PTFE存在下制备的聚氨酯泡沫塑料。美国专利3753933公开了一种在每100份多元醇仅有9份重较大尺寸的PTFE颗粒存在下聚氨酯发泡法。但是应当指出,在聚氨酯发泡过程中使用大颗粒,由于粘度限制而不易加工或/和得到有不希望的开孔结构的泡沫塑料。
第一方面,本发明涉及一种含有孔泡窗的微孔聚合物,其中该聚合物在穿孔剂存在下制备,其特征在于,穿孔剂的用量按聚合物总重量计为0.01~1.0%(重量),它是临界表面自由能小于23mJ/m2的物质,而且它为固体时其平均粒径为20微米或20微米以下,它或为液体时,其沸点高于聚合物制备过程中遇到的最高温度。
第二方面,本发明涉及一种含有聚氨酯前体和穿孔剂的聚氨酯前体组合物,聚氨酯前体是聚异氰酸酯或含有能与异氰酸酯反应的氢原子的物质,穿孔剂的特征在于,穿孔剂的用量按前体和穿孔剂的总重量计为0.01~2.0%(重量),所述的穿孔剂是临界表面自由能小于23mJ/m2,且为固体时平均粒径为20微米或20微米以下,或为液体时沸点高于130℃。
第三方面,本发明涉及一种通过使有机聚异氰酸酯与每一分子含有一个或多个可与异氰酸酯反应的氢原子的物质在有如下特征的发泡剂和穿孔剂存在下反应,制备含有孔泡窗的微孔聚氨酯聚合物的方法:
a)发泡剂含有能得到密度为10~150千克/米3的聚合物所需发泡剂总量的至少50%(摩尔)的水;
b)穿孔剂的用量按有机聚异氰酸酯和每一分子含有一个或多个能与异氰酸酯反应的氢原子的物质的总重量计为0.01~1.0%(重量),它是临界表面自由能小于23mJ/m2且为固体时平均粒径为20微米或20微米以下,或为液体时常压下沸点至少130℃的物质。
按照本发明,含有孔泡窗的微孔聚合物用下法制备,该法使用经选择的颗粒固体或液体穿孔剂。该聚合物可为热塑性聚合物或热固性聚合物,例如包括聚乙烯、聚苯乙烯、聚酯、聚醚、聚酰胺、酚醛树脂,特别是聚氨酯。在聚氨酯聚合物的情况下,当制备软质、半硬质、特别是硬质聚氨酯泡沫塑料时,本发明特别有价值。
穿孔剂是在制备微孔聚合物的条件下在化学上是惰性的物质,其临界表面自由能小于23,优选小于20,更优选小于18.5mJ/m2。使用有更高临界表面自由能的物质通常不能得到有孔泡窗。在1983年CRC出版公司A、F、M、Barton编辑出版的“CRCHandbook of Solubility Parameters and other CohesionParameters”(ISBN 0-8493-3295-8)第425页及以后几页提供了临界表面自由能的解释。在液体穿孔剂的情况下,应当理解,临界表面自由能与温度有关,当温度升高通常临界表面自由能下降。因此,本发明适用的液体穿孔剂是在升高的工艺温度下其临界表面自由能小于23mJ/m2的那些穿孔剂,优选的是在室温下其临界表面自由能小于23mJ/m2的那些穿孔剂。
为固体时,穿孔剂的粒度与覆盖泡窗区的薄膜厚度相当。通常,平均粒度小于20微米,优选小于15微米,更优选小于10微米,最优选小于3微米。就平均粒度为10微米来说,其粒度分布最好是至少90%的颗粒的粒度为10微米或10微米以下;就平均粒度为3微米或3微米以下来说,至少90%的颗粒的粒度小于6微米以及至少10%的颗粒的粒度小于1微米。这样的粒度和粒度分布可用传统的激光非剪切技术测定,使用诸如Malvern激光衍射分析仪的仪器。如果颗粒的比表面积至少为3米2/克则更好,优选至少为4.5米2/克,更优选至少为6.5米2/克(用氪吸附法测定)。适用的固体颗粒穿孔剂的例子包括氟化的聚合物,包括临界表面自由能为22mJ/m2的聚三氟乙烯;临界表面自由能为16.2mJ/m2的聚六氟丙烯;临界表面自由能为10.6mJ/m2的聚甲基丙烯酸1,1-二氢全氟辛基酯,特别是临界表面自由能为18.5mJ/m2的聚四氟乙烯。适用于本发明的颗粒PTFE可商购,包括可从ICI公司购买的商品名为FLUOROGLIDE的产品,如FL1710和FL1200以及可从Dupont公司购买的商品名为TEFLON的产品,包括TEFLON MP1100、TEFLON M1200、MP1300和MP1500。
为液体时,穿孔剂在常压下的沸点最好高于在制备微孔聚合物过程遇到的最高工艺温度。如果该液体穿孔剂的沸点明显低于最高工艺温度,它将不起穿孔剂的作用而起发泡剂的作用。所谓“明显低于”应理解为其沸点至少比最高工艺温度低10℃。该沸点最好至少比最高工艺温度低20℃。对于热塑性聚合物的挤塑工艺来说,典型的工艺温度至少为100℃或100℃以上。另一方面,这样的工艺可为反应模工艺,如在制备热固性聚合物,特别是聚氨酯中采用的工艺。因此,适用的液体穿孔剂包括常压沸点至少100℃(优选至少130℃、更优选至少150℃和最优选至少175℃)以及不溶或仅少量溶于该聚合物或其前体的物质。适用的液体穿孔剂包括有机多氟化合物特别是全氟碳化合物,它们的平均分子量最好至少350,优选至少400。适用的液体穿孔剂的例子包括3M公司以商标FLOURIERT销售的氟化的有机化合物(包括FC-104、FC-75、FC-40、FC-43、FC-70、FC-5312和FC-71)以及Rhone-Poulenc公司以商标FLUTEC销售的物质(包括PP3、PP6、PP7、PP10、PP11、PP24和PP25)。这样的液体穿孔剂的临界表面自由能常温下为9~16mJ/m2。
穿孔剂为固体时,其用量按微孔聚合物的总重计为0.05~0.75%(重量),更优选的是0.05~0.5%(重量)。穿孔剂为液体时,其用量为0.01~0.6%(重量),优选0.01~0.5%(重量),最优选0.01~0.2%(重量)。在本发明中,使用液体穿孔剂优于固体穿孔剂,因为当制备微孔聚合物时,液体穿孔剂更容易引入工艺中。另外,为了得到相同的技术效果,可使用的液体穿孔剂比固体穿孔剂少。也可使用固体穿孔剂和液体穿孔剂组合。
在一优选的实施方案中,本发明涉及微孔聚氨酯聚合物。微孔聚氨酯聚合物一般可通过在反应条件下,在所述的穿孔剂以及发泡剂存在下聚氨酯前体材料(包括聚异氰酸酯)和含有一个或多个能与异氰酸酯反应的氢原子的物质接触来得到。含有能与异氰酸酯反应的氢原子的物质包括醇类、聚酯多元醇、聚醚多元醇以及伯或仲胺基端封的聚醚或其混合物。穿孔剂可独立地加到反应混合物中或与聚氨酯前体预掺混。当与聚氨酯前体预掺混时,穿孔剂的用量在用其他反应物稀释后应得到含有已提到的穿孔剂数量的微孔聚合物。通常,聚氨酯前体混合时穿孔剂的用量按聚氨酯前体和存在的穿孔剂的总重量计为0.01~2%(重量)优选0.01~1.5%(重量),更优选0.01~1.0%(重量)。
适用的聚异氰酸酯包括芳族聚异氰酸酯、脂族聚异氰酸酯和环脂族聚异氰酸酯以其混合物。粗聚异氰酸酯也可用于本发明,如用甲苯二胺混合物的光气化作用得到的粗甲苯二异氰酸脂或用粗亚甲基二苯基胺的光气化作用得到的粗二苯基甲烷二异氰酸酯。美国专利3215652公开了优选的聚异氰酸酯。特别优选的是亚甲基桥连的多苯基聚异氰酸酯及其与粗二苯基甲烷二异氰酸酯的混合物,由于它们能使聚氨酯交联。当制备聚氨酯泡沫塑料时存在的聚异氰酸酯的数量应得到在多元醇中存在的每一异氰酸酯反应原子有0.6~3.0个异氰酸酯基以及任何水可存在。异氰酸酯的数量最好是能得到每一异氰酸酯反应原子有0.7(更优选0.8)至2(更优选至1.6)个异氰酸酯基。
适用的多元醇包括传统用于制备硬质聚氨酯泡沫塑料的那些多元醇,它们的平均羟基当量重通常为50~700,优选70~500,更优选70~300。另外,这样的多元醇通常每一分子含有2~8个(优选3~8个,更优选3~6个)羟基。适用的多元醇的例子是如美国专利4394491更全面描述的聚醚多元醇。这样的聚醚多元醇的例子包括可商购的商标为VORANOL的那些多元醇,包括VORANOL202、VORANOL360、VORANOL370、VORANOL446、VORANOL490、VORANOL575、VORANOL640、VORANOL800,所有的都由Dow化学公司销售。另外优选的多元醇包括曼期尼缩合的烯化氧衍生物(如美国专利3297597、4137265和4383102中提出的)和氨基-烷基哌嗪引发的聚醚多元醇(如美国专利4704410和4704411描述的)。当要求显示能变性的发泡工艺时,一组适用于本发明的聚酯多元醇包括在室温下基本上是固体的那些多元醇。最好是,聚酯多元醇的熔点为50~115℃,优选55~100℃。这样的聚酯多元醇的平均分子量通常为2000~6000,优选从2500(更优选从3000)至5000(更优选至4500)。这样的聚酯多元醇的例子是可以从Huls公司购买的DynacollTM7360,一种分子量为3500,熔点为60℃的聚六亚甲基己二酸多元醇。
当按本发明制备微孔聚合物时,优选的是,有发泡剂。发泡剂的用量应得到总密度一般为10~150,优选10~100,更优选15~80千克/米3的微孔聚合物。适用的发泡剂例如包括烷烃(如环戊烷、戊烷、环己烷、己烷)或含卤素化合物(如全氟碳、氟碳化合物和含氢的氟氯碳化合物),这些化合物的例子包括Refrigerant21、Refigerant22、Refigerant123、Refrigerant123a、Refrigerant124、Refrigerant124a、Refrigerant133(全异构体)、Refrigerant134、Refrigerant141b、Refrigerant142、Refrigerant151。其中,最优选的是Refrigerant123(全异构体)、Refrigerant141b和Refrigerant142(全异构体),因为它们都能商购,此外被认为有较低的臭氧耗竭潜力。其他适用的发泡剂还包括胺/二氧化碳络合物,如美国专利4735970和4500656提出的。
当制备聚氨酯泡沫塑料时,发泡剂最好含有水。水与聚异氰酸酯反应原位产生新生的二氧化碳,引起反应物质膨胀,使密度下降。通常,水的数量要提供得到所述的密度的聚氨酯发泡需要的至少50%,优选至少75%一直到100%(摩尔)。在一个本发明高度优选的实施方案中,聚氨酯发泡剂基本上由水组成。为此,通常存在的水的数量为每100份重多元醇有0.5~15份,优选从2.0(更优选从3.0)一直到10(更优选一直到8)份水。
当制备聚氨酯时其他成份也可存在。这些其他成分是催化剂、表面活性剂、着色剂、抗氧化剂、增强剂、填充剂、抗静电剂和阻燃剂。适用的阻燃剂包括含磷物质,如磷酸三(氯烷基)酯和磷酸三烷基酯(例如磷酸三乙酯)和含氮物质(例如密胺)。
最好存在用于含活性氢化合物与聚异氰酸酯反应的一种或多种催化剂。适用的催化剂包括叔胺化合物和有机金属化合物。例证性叔胺催化剂包括三亚乙基二胺、N-甲基吗啉、五甲基二亚乙基三胺、四甲基亚乙基二胺、1-甲基-4-二甲基氨基乙基哌嗪、3-甲氧基-N-二甲基丙胺、N-乙基吗啉、二乙基乙醇胺、N-可可吗啉(N-cocomorpholine),N,N-二甲基-N′,N′-二甲基异丙基丙二胺、N,N-二乙基-3-二乙基氨基丙胺和二甲基苄胺。例证性有机金属催化剂包括有机汞、有机铅、有机铁和有机锡催化剂,其中有机锡催化剂是优选的。适用的催化剂包括氯化亚锡、羧酸的锡盐如二-2-乙基己酸二丁基锡,以及其他有机金属化合物如美国专利2846408公开的。用于聚异氰酸酯的三聚和聚异氰酸酯聚合物的生成的催化剂如碱金属烷氧化物、碱金属羧酸盐、或季铵化合物在这里也可以使用。当使用这些催化剂时,所用的催化剂数量要足以提高聚合反应的速率。准确的数量必须用实验确定,但通常每100份多元醇有0.01~3.0份重催化剂,取决于催化剂的类型和活性。
使用少量表面活性剂来使发泡反应混合物在它固化前一直稳定通常是高度优选的。这样的表面活性剂最好是液体或固体有机硅表面活性剂。其他较优选的表面活性剂包括直链醇的聚乙二醇醚、长链烷基酸硫酸酯的叔胺或烷醇胺盐、烷基磺酸酯和烷基芳基磺酸、这样的表面活性剂的用量应是以使发泡的反应混合物对瘪泡和不均匀大泡孔的形成是稳定的。为此,通常每100份重多元醇有0.1~5份表面活性剂是足够的。所需表面活性剂的最佳数量需通过实验确定。但是,应注意随着表面活性剂的增加,穿孔剂的操作效率下降。
按照所公开的方法得到的泡沫塑料显示了有吸引力的尺寸稳定性和热绝缘稳定性。有足以减少或克服收缩倾向的有孔泡窗含量产生泡沫塑料的尺寸稳定性。目前,申请者不知道除用光学显微镜技术观测外是否还有方便的定量测定有孔泡窗含量的方法。传统的空气流动技术(如用于测定泡沫塑料的开孔泡孔含量,如试验方法ASTM D 2856)不能提供一种可靠的测定方法。借其细泡孔结构给予泡沫塑料有吸引力的热绝缘性。泡沫塑料的平均泡孔尺寸最好小于400(优选小于350,更优选小于300)微米。
本发明的聚氨酯泡沫塑料对建筑工业具有价值,在建筑工业中,有吸引力的尺寸稳定性和热绝缘性的隔热厚板材是十分需要的。本发明也可用于生产半硬质应用场合的聚氨酯泡沫塑料如密封泡沫塑料应用场合。
本发明通过下文给出的实施例进行说明,但不把这些实施例作为对本发明的限制。除非另加说明,所有的数量为份重。
实施例1
按照表1给出的配方制备泡沫塑料1~4和对比泡沫塑料A。这里给出的泡沫塑料物理性质按下面提到的试验方法测定:压缩强度-DIN 53421;尺寸稳定性-DIN53431和热导率-ASTMC518。
多元醇A含有(份重):
41.3份NIA×APP315,一种可从UCC公司购买的聚酯多元醇;
25.8份1×OL B251,一种可从Solvay Cie公司购买的含卤素聚醚多元醇
6.2份VORANOL RN 482,一种可从DOW化学公司购买的山梨醇开始的聚醚多元醇;
5.2份VORANOL RA640,一种可从DOW化学公司购买的乙二胺开始的聚醚多元醇;
2.1份甘油;
15.4份磷酸三乙酯(TEP);
5.0份可从DSM公司购买的密胺,平均粒度10微米;
4.0份含硅表面活性剂掺混物,从DOW Coring公司购买的表面活性剂DC193和从Th.Goldschmidt公司购买的表面活性剂Tegostal B-8418重量比1∶3;
4.7份含重量比为17∶5.5∶1的从DOW化学公司购买的专买胺化合物VORANOLC-52,二甲氨基环己烷(DMCHA)和从UCC公司购买的专买胺化合物NIAX A1的催化剂混合物;
2.1份水;
3.0份从Rhone-Poulenc购买的FLUTECPPI,为全氟己烷;
11.8份异戊烷。
穿孔剂
TEFLON*MP1100颗粒PTFE,平均粒度3微米,>90%的颗粒的平均粒度小于6微米和至少10%颗粒的平均粒度<1微米,平均表面积8米2/克。
TEFLON*MP1200颗粒PTFE,平均粒度3微米,平均表面积3米2/克。
TEFLON*MP1300颗粒PTFE,平均粒度15微米,平均表面积3米2/克。
TEFLON*MP1500颗粒PTFE,平均粒度20微米,平均表面积3米2/克。
多元醇A与可从DOW化学公司购买的粗多苯基多亚甲基聚异氰酸酯VORANATEM220反应。聚异氰酸酯的数量要能得到异氰酸酯反应指数为1.6。该体系的反应性通过测量其乳白时间(CT)、胶凝时间(G.T.)和不粘时间(Y.F.T.)进行进行观测。
与不含穿孔剂的对比泡沫塑料A相比,泡沫塑料1~4表明低温尺寸稳定性改善。泡沫塑料1~4还表明在有较小平均粒度的穿孔剂存在下制备的泡沫塑料的需要性。
实施例2(泡沫塑料5)
重复实施例1的方法,以下除外。TEFLON30-N,一种含有60%(重量)平均粒度为20微米的固体的颗粒聚四氟乙烯的水分散液用作穿孔剂。用多元醇B(聚酯多元醇NIAX APP315)和多元醇C(一种羟基当量重为300的酚-醛树脂开始的聚氧化烯多元醇)的掺混物代替多元醇A。选择多元醇B和C,得到在正常情况下对收缩特别敏感的泡沫塑料。该泡沫塑料的物理性质列入表2。
表2列出的结果说明,固体穿孔剂作为含水分散液可方便地引入发泡过程。
实施例3(泡沫塑料6~9和对比泡沫塑料B)
重复实施例2的方法,只是在这地情况中穿孔剂是(1)TEFLON MP1500和(2)TEFLON MP1100。对比泡沫塑料B在粒度为10微米和临界表面自由能为39mJ/m2的颗粒淀粉存在下制备。该泡沫塑料的物理性质列入表3。
表3列出的结果说明,使用不同数量的不同穿孔剂得到不同的尺寸稳定性。对比泡沫塑料B说明颗粒淀粉不能使泡沫塑料得到相同程度的尺寸稳定性,甚至当使用较多的数量时。
实施例4
重复实施例2的方法,只是在这一情况下穿孔剂是从3M公司购买的FLUORINERT L-9901,它是沸点为215℃的C15~C18全氟化的化合物的混合物。对比泡沫塑料C和D在FLOURINERTFC104(从3M公司购买的)存在下制备,它是沸点为101℃和临界表面自由能为10mJ/m2的全氟碳化合物。FLUORINERT FC104的沸点比观测到的最高工艺温度160℃低。泡沫塑料10、11和对比泡沫塑料C和D的物理性质列入表4。
表4的结果说明,临界表面自由能小于23mJ/m2、沸点明显低于最高工艺温度的物质不能得到与按本发明的穿孔剂存在下制备的泡沫塑料相同的尺寸稳定性。
表1
份重 | 泡沫塑料1 | 泡沫塑料2 | 泡沫塑料3 | 泡沫塑料4 | 泡沫塑料A* |
多元醇A | 126.6 | 126.6 | 126.6 | 126.6 | 126.6 |
聚异氰酸酯 | 169 | 169 | 169 | 169 | 169 |
TEFLONTM MP 1100 | 1.0 | / | / | / | / |
TEFLONTM MP 1200 | / | 1.0 | / | / | / |
TEFLONTM MP 1300 | / | / | 1.0 | / | / |
TEFLONTM MP 1500 | / | / | / | 1.0 | / |
粒度(μm)表面积(m2/g) | 38 | 33 | 151 | 201 | / |
CT./G.T../T.F.T.(秒) | 11/40/57 | 11/41/55 | 10/39/51 | 11/40/58 | 11/38/51 |
密度(kg/m3) | 29.4 | 29.1 | 29.0 | 28.6 | 29.8 |
泡孔直径(microns) | 393 | 256 | 387 | 360 | 348 |
压缩强度(i)与起发平行(kPa)(ii)与起发垂直 | 16051 | 14743.5 | 15450 | 14744 | 15446 |
导热率(i)初期(mW/M.K)(ii)老化4天后 | 23.428.2 | 22.625.4 | 23.325.5 | 23.025.0 | 22.525.0 |
聚合物中穿孔剂的重量百分数 | 0.34 | 0.34 | 0.34 | 0.34 | 0 |
尺寸稳定性(%体积变化)(i)-30℃(ii)+110℃ | -0.6-0.6 | -1.8-0.6 | -1.8-1.8 | -2.8-3.6 | -12.7+0.2 |
*不是本发明的实施例
表2
份重 | 泡沫塑料 |
多元醇B | 50 |
多元醇C | 50 |
DMCHA | 0.5 |
NIAXA1 | 0.2 |
表面活性剂 DC-193 | 2.0 |
水 | 4.3 |
穿孔剂 | 0.83 |
Voranate M 220 | 150 |
C.T./G.T./T.F.T.(秒) | 15/52/66 |
密度 (kg/m3) | 27.9 |
压缩强度(i)与起发平行(kpa)(ii)与起发垂直 | 172115 |
热导率,初期 (mW/M.K) | 29.3 |
聚合物中穿孔剂的重量百分数 | 0.2 |
尺寸稳定性(%体积变化)(i)-30℃(ii)+110℃ | -0.6-1.2 |
表3
份重 | 泡沫塑料6 | 泡沫塑料7 | 泡沫塑料8 | 泡沫塑料9 | 泡沫塑料B* |
多元醇B | 50 | 50 | 50 | 50 | 50 |
多元醇C | 50 | 50 | 50 | 50 | 50 |
DMCHA | 0.6 | 0.6 | 0.6 | 0.6 | 1 |
NIAXA1 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 |
表面活性剂DC-193 | 2 | 2 | 2 | 2 | 2 |
水 | 4.6 | 4.6 | 4.6 | 4.6 | 4.6 |
穿孔剂1 | 0.5 | / | 0.1 | / | / |
穿孔剂2 | / | 0.5 | / | 0.1 | / |
淀粉 | / | / | / | / | 1 |
Voranate M220 | 150 | 150 | 150 | 150 | 150 |
C.T./G.T./T.F.T.(秒) | 15/49/60 | 16/50/66 | 16/47/58 | 17/50/63 | 14/38/48 |
密度(kg/m3) | 26.2 | 26.1 | 26.1 | 26.0 | 27.1 |
压缩强度(i)与起发平行(kpa)(ii)与起发垂直 | 14472 | 17369 | 12849 | 14154 | 14994 |
热导率初期(mW/M.K) | 24.7 | 26.1 | 24.5 | 24.1 | 23.8 |
聚合物中穿孔剂的重量百分数 | 0.2 | 0.2 | 0.04 | 0.04 | 0.4 |
尺寸稳定性(%体积变化)(i)-30℃(ii)+110℃ | -0.6-43.6 | -0.6-9.4 | -1.0-57.6 | -1.0-57.9 | -1.2-74.2 |
*不是本发明的实施例
表4
份重 | 泡沫塑料10 | 泡沫塑料11 | 泡沫塑料C* | 泡沫塑料D* |
多元醇B | 50 | 50 | 50 | 50 |
多元醇C | 50 | 50 | 50 | 50 |
DMCHA | 0.6 | 0.6 | 0.6 | 0.6 |
NIAXA1 | 0.2 | 0.2 | 0.2 | 0.2 |
表面活性剂DC-193 | 2 | 2 | 2 | 2 |
水 | 4.6 | 4.6 | 4.6 | 4.6 |
穿孔剂 | 0.5 | 0.1 | / | / |
FC 104 | / | / | 0.5 | 0.1 |
Voranate M220 | 150 | 150 | 150 | 150 |
C.T./G.T./T.F.T.(秒) | 15/43/56 | 15/47/67 | 16/45/58 | 16/49/62 |
密度(kg/m3) | 26.9 | 26.3 | 25.7 | 26.0 |
压缩强度(i)与起发平行(kpa)(ii)与起发垂直 | 181114 | 212101 | 16464 | 18060 |
热导率初期(mW/M.K) | 27.1 | 26.5 | 24.0 | 24.3 |
聚合物中穿孔剂的重量百分数 | 0.2 | 0.04 | 0.2 | 0.04 |
尺寸稳定性(%体积变化)(i)-30℃(ii)+110℃ | -0.4-1.2 | -0.2-0.4 | -1.0-75.9 | -0.6-77.9 |
*不是本发明的实施例
Claims (4)
1.一种含有聚氨酯前体和穿孔剂的聚氨酯前体组合物,聚氨酯前体是聚异氰酸酯或含有能与异氰酸酯反应的氢原子的物质,其特征在于,穿孔剂的用量按前体和穿孔剂的总重量计为0.01-2.0%(重量),以及所述的穿孔剂是临界表面自由能小于23mJ/m2的物质,它为固体时平均粒径为20微米或20微米以下,或它为液体时沸点高于130℃。
2.按照权利要求1的聚氨酯前体组合物,其中所述的固体穿孔剂是颗粒聚四氟乙烯,所述的液体穿孔剂是不溶于或少量溶于该前体的有机多氟或全氟碳化合物。
3.按照权利要求1的聚氨酯前体组合物,其中含有能与异氰酸酯反应的氢原子的前体物质是聚醚多元醇、聚酯多元醇、氨基封端的聚醚及其混合物。
4.一种制备含有孔泡窗的微孔聚氨酯聚合物的方法,该方法使有机聚异氰酸酯与每分子含有一个或多个能与异氰酸酯反应的氢原子的物质在发泡剂和穿孔剂存在下反应,其特征在于:
a)发泡剂含水,其数量提供密度为10-150千克/米3的聚合物的总发泡需要量的至少50%(摩尔)。
b)穿孔剂的数量按有机聚异氰酸酯和一分子含有一个或多个能与异氰酸酯反应的氢原子的物质的总重量计为0.01-1.0%(重量),其临界表面自由能小于23mJ/m2,它为固体时平均粒径为20微米或20微米以下,或为液体时在常压下的沸点至少为130℃。
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- 1993-09-02 JP JP6509062A patent/JPH08503720A/ja active Pending
- 1993-09-02 DK DK93921327T patent/DK0662100T3/da active
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- 1993-09-02 DE DE69331276T patent/DE69331276T2/de not_active Expired - Fee Related
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- 1993-09-02 BR BR9307122A patent/BR9307122A/pt not_active IP Right Cessation
- 1993-09-02 WO PCT/US1993/008308 patent/WO1994007942A1/en active IP Right Grant
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- 1993-09-27 TW TW082107964A patent/TW294690B/zh active
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Also Published As
Publication number | Publication date |
---|---|
FI951456A0 (fi) | 1995-03-27 |
CA2144658C (en) | 2000-05-30 |
NO951157D0 (no) | 1995-03-27 |
CN1203242A (zh) | 1998-12-30 |
AU4845993A (en) | 1994-04-26 |
EP0662100B1 (en) | 2001-12-05 |
WO1994007942A1 (en) | 1994-04-14 |
US5312846A (en) | 1994-05-17 |
AU666971B2 (en) | 1996-02-29 |
FI951456A (fi) | 1995-03-27 |
TW294690B (zh) | 1997-01-01 |
NO951157L (no) | 1995-03-27 |
KR950703599A (ko) | 1995-09-20 |
US5250579A (en) | 1993-10-05 |
CO4290304A1 (es) | 1996-04-17 |
CN1086226A (zh) | 1994-05-04 |
KR100294568B1 (ko) | 2001-09-17 |
MX9305940A (es) | 1994-04-29 |
DK0662100T3 (da) | 2002-02-25 |
ATE210164T1 (de) | 2001-12-15 |
US5281632A (en) | 1994-01-25 |
BR9307122A (pt) | 1999-03-30 |
CA2144658A1 (en) | 1994-04-14 |
ES2164670T3 (es) | 2002-03-01 |
DE69331276D1 (de) | 2002-01-17 |
EP0662100A1 (en) | 1995-07-12 |
JPH08503720A (ja) | 1996-04-23 |
DE69331276T2 (de) | 2002-06-13 |
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