CN1150582A - 从双金属氰化物催化的多元醇制备环氧乙烷封端的多元醇的方法 - Google Patents

从双金属氰化物催化的多元醇制备环氧乙烷封端的多元醇的方法 Download PDF

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CN1150582A
CN1150582A CN96107163A CN96107163A CN1150582A CN 1150582 A CN1150582 A CN 1150582A CN 96107163 A CN96107163 A CN 96107163A CN 96107163 A CN96107163 A CN 96107163A CN 1150582 A CN1150582 A CN 1150582A
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J·F·帕佐斯
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Abstract

制备高伯羟基含量、低不饱和度多元醇的方法，包括将通过双金属氰化物(DMC)催化制得的多元醇与通过碱性催化制得的多元醇共混；将该多元醇共混物与环氧乙烷反应产生环氧乙烷封端的多元醇。该方法克服了常规的从DMC催化的多元醇制备环氧乙烷封端的多元醇的再催化方法中存在的问题。

Description

从双金属氰化物催化的多元醇制备 环氧乙烷封端的多元醇的方法
本发明涉及具有高伯羟基含量的聚醚多元醇的方法。具体地说，本发明是从双金属氰化物催化制得的多元醇制备环氧乙烷封端的多元醇的方法。
长期以来，由于环氧乙烷封端的多元醇的伯羟基具有对多异氰酸酯的很好的反应性而在聚氨酯工业中很有价值。环氧乙烷封端的多元醇通常是分两步制备的。首先在碱性催化剂(通常是氢氧化钾)存在下将环氧丙烷(或者环氧丙烷与环氧乙烷的混合物)聚合生成主要含有或者仅含有仲羟基的多元醇。第二步，将环氧乙烷加到含有催化剂的混合物中，以使得一些或者大多数仲羟基转化为伯羟基。该方法通常对于丙氧化和乙氧化都使用相同的催化剂(通常为KOH)。
用双金属氰化物(DMC)催化剂如六氰基钴酸锌来制备聚醚多元醇有许多优点。可以制得比KOH多元醇低得多的不饱和度的多元醇。用低不饱和度多元醇制备性能得到提高的聚氨酯的优点已有许多文献描述。DMC催化剂还具有异常的活性，能有效地生产多元醇。目前已知的最好的DMC催化剂具有足以在很低的浓度下使用的活性，常常使得多元醇的后续纯化成为不必要。
尽管用DMC催化剂来制备聚醚多元醇有许多优点，但还有一个重要的缺点：不能用DMC催化剂直接制备环氧乙烷封端的多元醇。换句话说，人门不能够通过DMC催化然后简单地加入环氧乙烷将多元醇封端(用KOH进行)来制备氧化丙烯多元醇。当环氧乙烷被加到由DMC催化剂制备的聚氧化丙烯多元醇中时，所得产物是多相混合物，其组成为：(1)占大部分的未反应聚氧化丙烯多元醇；和(2)少部分高度乙氧基化的聚氧化丙烯多元醇和/或聚氧化乙烯。
从DMC催化的多元醇制备环氧乙烷封端的多元醇常规方法包括再催化(recatalysis)，参见例如美国专利第4355188和4721818号。第一步，通过DMC催化制得氧化丙烯多元醇(或者EO-PO无规共聚物)。第二步，加入碱性催化剂例如碱金属、碱金属氢化物、碱金属醇盐、碱金属氢氧化物等。碱性催化剂使DMC催化剂失活。一般来说，必须随后将多元醇汽提以除去随碱性催化剂引入的水或醇(即使是微量的)。最后，加入环氧乙烷，用氧化乙烯单元将多元醇封端。
再催化法有一些重要的缺点。首先许多碱性催化剂(特别是碱金属和碱金属氢化物)是高活性的、对潮湿敏感性的，并且难以安全地操作。其次，需要特制的反应器来进行碱催化的环氧乙烷封端，因为即使微量的残留碱也会使DMC催化剂中毒。因而，用于碱催化的环氧乙烷封端的反应器必须在在同一反应器中进行另一DMC催化的反应之前彻底洗涤。对于大规模生产来说，这是不现实的，因此需要特制的仅用于环氧乙烷封端的反应器。再次，将多元醇汽提以除去水或乙醇是耗时、费能的，而且通常给出不规则的结果。不完全的汽提会得到含有聚环氧乙烷(微量水或醇与环氧乙烷的反应产物)的、浑浊的多元醇，浑浊的多元醇在商业上是不合需要的。
人们需要一种改进的由DMC催化的多元醇制备环氧乙烷封端的多元醇的方法。该方法最好克服再催化的需要。它将避免高活性潮湿敏感性乙氧基化催化剂，并且可以免除了在添加环氧乙烷之前从多元醇中间体中将水或醇汽提的步骤。优选的方法不需要仅为环氧乙烷封端而特制的反应器。理想的方法应当易于实施，并且提供制备具有高伯羟基含量的、低不饱和度的多元醇的途径。
本发明是一种从双金属氰化物催化的多元醇制备环氧乙烷封端的多元醇的方法。该方法包括将含有活性双金属氰化物(DMC)催化剂的第一多元醇与含有碱性催化剂的第二多元醇共混。然后使所得多元醇共混物与环氧乙烷反应，制得环氧乙烷封端的多元醇。
我惊讶地发现，不能直接乙氧基化的DMC催化的多元醇可通过下述方法成功地加以封端：首先将它们与含碱多元醇共混，然后将环氧乙烷加到该多元醇共混物中。本发明的方法克服了对环氧乙烷封端的DMC多元醇的再催化方法的一些关键缺陷。第一点，本发明不需要使用任何反应性金属或金属氢化物；用来制备第二多元醇的碱性催化剂(通常是氢氧化钾)催化乙氧基化。第二点，因为用来将多元醇共混物乙氧基化的反应器也可用来制备共混物的碱催化的多元醇成分，不需要仅为环氧乙烷封端而特制的反应器。第三点，也是最重要的一点，本发明的方法无需在乙氧基化之前从多元醇中间体中将水或醇汽提出来。
本发明提供一种简单而有效的制备具有较低的不饱和度(这是因为它们是部分地通过DMC催化制备的)和高伯羟基含量的多元醇的方法。
本发明是通过将多元醇共混物乙氧基化来制备环氧乙烷封端的多元醇的方法。该多元醇共混物包括含有活性双金属氰化物催化剂的第一多元醇和含有碱性催化剂的第二多元醇。该多元醇共混物与环氧乙烷反应产生环氧乙烷封端的多元醇。
第一多元醇是用双金属氰化物(DMC)催化剂制备的。一般来说，可以使用任何已知的DMC催化剂。适宜的DMC催化剂是本领域公知的。催化剂及其制备方法在美国专利第3427256,3427335,3829505,4477589和5158922号(其内容通过引用结合入本文中)中有详尽的描述。优选六氰基钴酸锌催化剂。最近研制出了高活性DMC催化剂(参见例如共同未决的EP-A-0654302所述)，这些催化剂可以方便地用来制备第一多元醇。
第一多元醇通常是用本领域公知的方法制备的。在DMC催化剂的存在下将杂环单体(通常是环氧化物)与含活泼氢引发剂(一般是低分子量多元醇)反应产生第一多元醇。适宜的杂环单体、含活泼氢引发剂和用DMC催化剂制备聚醚多元醇的方法可参见美国专利第3829505，3941849,4355188和4472560号(其内容通过引用结合到本文中)。
第一多元醇是任何可用DMC催化剂制备的聚醚多元醇。优选的第一多元醇是聚氧化丙烯多元醇和环氧丙烷和环氧乙烷的无规共聚物。第一多元醇的标称官能度优选为2-8，更优选2-3。第一多元醇的羟基值通常在大约5-500mg KOH/g的范围内，更优选在大约10-100mgKOH/g的范围内。第一多元醇的数均分子量通常在大约200-25000的范围内，更优选在大约500-10000的范围内。第一多元醇通常具有低的不饱和度，一般低于大约0.04meq/g，优选低于大约0.02meq/g，更优选低于大约0.01meq/g。
将第一多元醇与第二多元醇共混。第二多元醇是用碱性催化剂通过本领域技术人员公知的制备常规聚醚多元醇的方法制备的。在碱性催化剂的存在下将杂环单体(通常是环氧化物)与含活泼氢引发剂(一般是低分子量多元醇)反应产生第二多元醇。适宜的杂环单体、含活泼氢引发剂、碱性催化剂和用碱性催化剂制备聚醚的方法可参见美国专利第4495081,4687851,3317508和3445525号(其内容通过引用结合到本文中)。第二聚醚最好是以碱金属氢氧化物(例如氢氧化钾)为碱性催化剂制备的。
第二多元醇是任何可用碱性催化制备的聚醚多元醇。优选的第二多元醇是聚氧化丙烯多元醇、环氧丙烷与环氧乙烷的无规共聚物和环氧乙烷封端的多元醇。第二多元醇的标称官能度优选为2-8，更优选2-3。第二多元醇的羟基值通常在大约20-1800mg KOH/g的范围内，更优选在大约30-500mg KOH/g的范围内。第二多元醇的数均分子量通常在大约76-8000的范围内，更优选在大约500-6000的范围内。
第一和第二多元醇可通过任何适当的设备共混到一起。多元醇最好是相溶性的。一般来说，多元醇无需具有相同或相似的官能度、羟基值或分子量。对于某些应用而言，使用特性差异很大的第一和第二多元醇可能是有利的。另一方面，将具有大致相同的羟基值的多元醇共混常常是有利的，这样可以简化配置聚氨酯的过程。
第一和第二多元醇在共混物中的相对用量可以在很宽的范围内变化。一般来说，在共混物中优选使用大约10-90％(重量)第一多元醇和大约10-90％(重量)第二多元醇。更优选的情况是共混物含有大约30-70％(重量)第一多元醇和大约30-70％(重量)第二多元醇。
当这两种多元醇共混在一起时，在第二多元醇中的一些碱性催化剂使得第一多元醇中的DMC催化剂减活化。剩下的碱性催化剂用来催化多元醇共混物的乙氧基化。碱性催化剂(一般为KOH)在多元醇共混物中的用量在大约0.05-2％(重量)的范围内，这对于环氧乙烷封端步骤已经足够了。更优选的范围是大约0.1-1.0％(重量)。
在本发明方法的第二步骤中，多元醇共混物与环氧乙烷反应生成环氧乙烷封端的多元醇。用来将多元醇封端的环氧乙烷(EO)的用量取决于许多因素，包括所限的聚醚的氧化乙烯含量，所限的伯羟基含量，多元醇分子量和官能度和其它因素。一般来说，基于环氧乙烷封端的多元醇的用量计，EO的用量在大约5-30％(重量)的范围内。
本发明的方法被用来制备具有高伯羟基含量的聚醚多元醇。对于具体用途，所需伯羟基的比例有所变化。一般来说，需要具有大约50-95％(重量)、优选大约70-90％(重量)伯羟基含量的产品。这些产品可以用本发明的方法制备。
乙氧基化步骤通常是通过将第一和第二多元醇的共混物加热至所需反应温度并向混合物中逐渐加入环氧乙烷来进行的。该项技术基本上与当前用碱性催化剂用环氧乙烷将多元醇封端的做法相同。适宜的方法被描述于例如美国专利第4355188号(其内容通过引用结合到本文中)中。反应温度通常在大约50-220℃的范围内。加完EO后，通常在相同或较高的温度下继续反应以完成聚合作用。
在乙氧基化之后，通常将环氧乙烷封端的产品纯化以除去催化剂残余物。可以使用任何适当的纯化多元醇的手段，包括用离子交换树脂处理、水洗或者用诸如硅酸镁之类的吸附剂处理。关于纯化环氧乙烷封端的多元醇的适当方法可参见美国专利第3715402,3823145,4721818和4355188号(其内容通过引用结合到本文中)。
本发明方法制备的聚醚多元醇具有高的伯羟基含量。这一特点使得它们对于需要“反应性”多元醇的聚氨酯很有价值。同时，该多元醇比仅用碱性催化剂制备的多元醇的不饱和度低得多。在需要很低的不饱和度时，便可简单地增加共混物中DMC催化的多元醇的相对比例。低不饱和度多元醇(例如用本发明方法制备的多元醇)为聚氨酯提供了许多公认的好处，包括提高拉伸性能和降低压缩变定。
以前人们可以获得高伯羟基含量、低不饱和度多元醇，但仅仅是通过再催化方法获得的，而该方法需要在乙氧基化之前预先汽提。即使汽提得好，再催化方法也常常给出浑浊的多元醇。本发明的方法可以惊人地给出具有高伯羟基含量和低不饱和度的多元醇。此外，本发明的方法可以给出不浑浊的产品，而无需汽提步骤。
本发明的方法制备的多元醇对于制备聚氨酯泡沫塑料、弹性体、密封剂、涂料和粘合剂特别有用。该多元醇对于模塑聚氨酯泡沫塑料的制造特别有价值，模塑聚氨酯泡沫塑料是在较低温度下制造的，并且需要高的伯羟基含量以便具有足够的反应性。
下述实施例仅用来阐述本发明。本领域技术人员将认识到在本发明的实质和权利要求范围内还有许多变异的方法。
     实施例1
将聚氧化丙烯三醇(247g)投入l升的Parr反应器中，所述聚氧化丙烯三醇的羟基值为21.5mgKOH/g，不饱和度为0.008meq/g，含有25ppm活性六氰基钴酸锌催化剂。再向反应器中投入通过KOH催化剂制备的、甘油衍生的粗制聚氧化丙烯三醇(134g)，其羟基值为41.5mgKOH/g，不饱和度为0.046meq/g，KOH含量为0.71％(重量)。
将多元醇混合物加热至117℃，加入环氧丙烷(20g)。45分钟后，将温度升到125℃，在125℃保温90分钟。向反应器中吹入氮气，直至反应器中压力达大约20磅/平方英寸(表压)。以1g/min的速率加入环氧乙烷(100g)，在加入环氧乙烷后，将混合物于125℃再保温1小时。使产物(491g)通过活化的苯乙烯/二乙烯基苯阳离子交换树脂进行提纯。
提纯的多元醇的羟基值为33mg KOH/g，不饱和度为0.017meq/g，环氧乙烷含量为20.5％(重量)，伯羟基含量为80％。产物毫不浑浊，并可保持数个月的清澈。
上述实施例仅是为了说明本发明。下面的权利要求书定义了本发明的范围。

Claims (12)

1.制备环氧乙烷封端的多元醇的方法，所述方法包括：
(a)将含有活性双金属氰化物催化剂的第一多元醇与含有碱性催化剂的第二多元醇共混；和
(b)可选地在首先使所得多元醇共混物与另一氧化烯反应后，将所得多元醇混合物与环氧乙烷反应，产生环氧乙烷封端的多元醇。
2.权利要求1所述的方法，其特征在于第一多元醇选自聚氧化丙烯多元醇和环氧丙烷与环氧乙烷的无规共聚物。
3.权利要求1或2所述的方法，其特征在于第一多元醇含有六氰基钴酸锌催化剂。
4.上述任一项权利要求所述的方法，其特征在于第二多元醇含有碱金属氢氧化物催化剂。
5.权利要求4所述的方法，其特征在于第二多元醇含有氢氧化钾催化剂。
6.上述任一项权利要求所述的方法，其特征在于多元醇混合物含有大约10-90％(重量)第一多元醇和大约10-90％(重量)第二多元醇。
7.权利要求6所述的方法，其特征在于多元醇混合物含有大约30-70％(重量)第一多元醇和大约30-70％(重量)第二多元醇。
8.上述任一项权利要求所述的方法，其特征在于多元醇混合物含有大约0.05-2％(重量)碱性催化剂。
9.上述任一项权利要求所述的方法，其特征在于：在步骤(b)中，环氧乙烷的用量在环氧乙烷封端的多元醇的量的大约5-30％(重量)范围内。
10.上述任一项权利要求所述的方法，其特征在于环氧乙烷封端的多元醇具有至少大约50％伯羟基端基。
11.权利要求1-9中任一项所述的方法，其特征在于环氧乙烷封端的多元醇具有至少大约70％伯羟基端基。
12.权利要求1所述的方法，它包括：
(a)将含有活性六氰基钴酸锌催化剂的第一多元醇与含有碱金属氢氧化物催化剂的第二多元醇共混；和
(b)将所得多元醇共混物与环氧乙烷反应，产生环氧乙烷封端的多元醇；
其中第一多元醇选自聚氧化丙烯多元醇和环氧乙烷与环氧丙烷的无规共聚物；
其中多元醇共混物含有大约10-90％(重量)第一多元醇和大约10-90％(重量)第二多元醇；
其中在步骤(b)中，环氧乙烷的用量在环氧乙烷封端的多元醇的量的大约5-30％(重量)范围内；
其中环氧乙烷封端的多元醇具有至少大约70％伯羟基端基。
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