CN1090198C - 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

Info

Publication number
CN1090198C
CN1090198C CN96107163A CN96107163A CN1090198C CN 1090198 C CN1090198 C CN 1090198C CN 96107163 A CN96107163 A CN 96107163A CN 96107163 A CN96107163 A CN 96107163A CN 1090198 C CN1090198 C CN 1090198C
Authority
CN
China
Prior art keywords
polyvalent alcohol
ethylene oxide
capped
described method
weight
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
CN96107163A
Other languages
English (en)
Other versions
CN1150582A (zh
Inventor
J·F·帕佐斯
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Lyondell Chemical Technology LP
Original Assignee
Arco Chemical Technology LP
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Arco Chemical Technology LP filed Critical Arco Chemical Technology LP
Publication of CN1150582A publication Critical patent/CN1150582A/zh
Application granted granted Critical
Publication of CN1090198C publication Critical patent/CN1090198C/zh
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2642—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the catalyst used
    • C08G65/2645—Metals or compounds thereof, e.g. salts
    • C08G65/2663—Metal cyanide catalysts, i.e. DMC's
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4833—Polyethers containing oxyethylene units
    • C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
    • C08G18/4841—Polyethers containing oxyethylene units and other oxyalkylene units containing oxyethylene end groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4866—Polyethers having a low unsaturation value
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
    • C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
    • C08G65/2609—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aliphatic hydroxyl groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2642—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the catalyst used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/04—Preparatory processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • C08G69/28—Preparatory processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/02—Polyalkylene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2101/00—Manufacture of cellular products
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2190/00—Compositions for sealing or packing joints
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C08L2666/14—Macromolecular compounds according to C08L59/00 - C08L87/00; Derivatives thereof
    • C08L2666/22—Macromolecular compounds not provided for in C08L2666/16 - C08L2666/20

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。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，人们不能够通过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：
a)将由双金属氰化物(DMC)催化剂制成并含有活性双金属氰化物催化剂的第一多元醇与由碱性催化剂制成并含有用于制成第二多元醇的碱性催化剂的第二多元醇共混，碱性催化剂的用量为多元醇共混物重量的0.05-2％重量；和
b)可选地首先使所得的多元醇共混物与另一氧化烯反应之后在不需预先对所得到的多元醇共混物中的水或醇进行汽提的情况下，将所得到的多元醇共混物与环氧乙烷反应，以生成环氧乙烷封端的多元醇。
我惊讶地发现，根据本发明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)和高伯羟基含理的多元醇的方法。
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。
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0.02meq/g，更优选低于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。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20-1800mg KOH/g的范围内，更优选在30-500mg KOH/g的范围内。第二多元醇的数均分子量通常在76-8000的范围内，更优选在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10-90％(重量)第一多元醇和10-90％(重量)第二多元醇。更优选的情况是共混物含有30-70％(重量)第一多元醇和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，需要具有至少5％，如50-95％(重量)、优选具有至少70％，如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号中。反应温度通常在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。
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。
下述实施例用来阐述本发明。
                     实施例1
将聚氧化丙烯三醇(247g)投入1升的Parr反应器中，所述聚氧化丙烯三醇的羟基值为21.5mg KOH/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1480kPa(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。

Claims (9)

1.制备环氧乙烷封端的多元醇的方法，所述方法包括：
(a)将由双金属氰化物的催化作用制成并含有活性双金属氰化物催化剂的第一多元醇与由碱性催化剂作用制成并含有碱性催化剂的第二多元醇共混，碱性催化剂的用量为多元醇共混物重量的0.05-2％；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，在不需于乙氧基化之前从多元醇中间体中将水或醇汽提出来的情况下，与环氧乙烷反应，以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.权利要求1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1所述的方法，其特征在于多元醇混合物含有10-90％(重量)第一多元醇和10-90％(重量)第二多元醇。
6.权利要求5所述的方法，其特征在于多元醇混合物含有30-70％(重量)第一多元醇和30-70％(重量)第二多元醇。
7.权利要求1-6的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，是在环氧乙烷封端的多元醇的量的5-30％(重量)范围内。
8.权利要求1-6的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50％伯羟基端基。
9.权利要求8所述的方法，其特征在于环氧乙烷封端的多元醇具有至少70％伯羟基端基。
CN96107163A 1995-06-21 1996-06-21 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 Expired - Lifetime CN1090198C (zh)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US493,372 1995-06-21
US493372 1995-06-21
US08/493,372 US5563221A (en) 1995-06-21 1995-06-21 Process for making ethylene oxide-capped polyols from double metal cyanide-catalyzed polyols

Publications (2)

Publication Number Publication Date
CN1150582A CN1150582A (zh) 1997-05-28
CN1090198C true CN1090198C (zh) 2002-09-04

Family

ID=23959967

Family Applications (1)

Application Number Title Priority Date Filing Date
CN96107163A Expired - Lifetime CN1090198C (zh) 1995-06-21 1996-06-21 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

Country Status (19)

Country Link
US (1) US5563221A (zh)
EP (1) EP0750001B1 (zh)
JP (1) JP3247612B2 (zh)
KR (1) KR100451872B1 (zh)
CN (1) CN1090198C (zh)
AR (1) AR002561A1 (zh)
AT (1) ATE199094T1 (zh)
AU (1) AU694874B2 (zh)
BR (1) BR9602829A (zh)
CA (1) CA2177871C (zh)
DE (1) DE69611743T2 (zh)
DK (1) DK0750001T3 (zh)
ES (1) ES2153938T3 (zh)
GR (1) GR3035686T3 (zh)
HU (1) HU217692B (zh)
MX (1) MX9602435A (zh)
RO (1) RO117101B1 (zh)
TW (1) TW322470B (zh)
ZA (1) ZA965263B (zh)

Families Citing this family (34)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5700847A (en) * 1995-12-04 1997-12-23 Arco Chemical Technology, L.P. Molded polyurethane foam with enhanced physical properties
US5691441A (en) * 1996-10-11 1997-11-25 Arco Chemical Technology, L.P. Spandex elastomers
US5723563A (en) * 1996-10-11 1998-03-03 Arco Chemical Technology, L.P. Spandex elastomers
US5708118A (en) * 1996-10-11 1998-01-13 Arco Chemical Technology, L.P. Spandex elastomers
US6008263A (en) * 1998-04-03 1999-12-28 Lyondell Chemical Worldwide, Inc. Molded and slab polyurethane foam prepared from double metal cyanide complex-catalyzed polyoxyalkylene polyols and polyols suitable for the preparation thereof
US6063309A (en) * 1998-07-13 2000-05-16 Arco Chemical Technology L.P. Dispersion polyols for hypersoft polyurethane foam
DE19918727A1 (de) 1999-04-24 2000-10-26 Bayer Ag Langkettige Polyetherpolyole mit hohem Anteil primärer OH-Gruppen
US6642423B2 (en) 1999-07-09 2003-11-04 Dow Global Technologies, Inc. Polymerization of ethylene oxide using metal cyanide catalysts
ATE323119T1 (de) 1999-07-09 2006-04-15 Dow Global Technologies Inc Polymerisierung von ethylenoxid mit der verwendung von metallcyanidkatalysatoren
DE19944762A1 (de) * 1999-09-17 2001-03-22 Basf Ag Verfahren zur Herstellung von Blockweichschaumpolyolen
WO2001083107A2 (en) 2000-04-28 2001-11-08 Synuthane International, Inc. Double metal cyanide catalysts containing polyglycol ether complexing agents
US6462133B2 (en) * 2000-05-19 2002-10-08 Dow Global Technologies, Inc. Polymerizing alkylene oxide with phospazen (IUM) crosslinked polymer
US6344494B1 (en) 2000-05-24 2002-02-05 Basf Corporation Use of low unsaturated polyether polyols in slabstock foam applications
US6201035B1 (en) 2000-05-24 2001-03-13 Basf Corporation Use of low unsaturated polyether polyols in high resilience slabstock foam applications
TW591046B (en) * 2000-10-23 2004-06-11 Huntsman Int Llc High performance sealant formulations based on MDI prepolymers
US6835801B2 (en) * 2002-07-19 2004-12-28 Bayer Antwerp, N.V. Activated starter mixtures and the processes related thereto
US20040064001A1 (en) * 2002-09-30 2004-04-01 Stephan Ehlers Processes for preparing ethylene oxide-capped polyols
KR20050084970A (ko) * 2002-11-07 2005-08-29 다우 글로벌 테크놀로지스 인크. 중합가능한 착화제를 사용해 금속 시안화물 촉매를제조하는 방법
AU2004220072A1 (en) 2003-03-07 2004-09-23 Dow Global Technologies Inc. Continuous process and system of producing polyether polyols
DE10324998A1 (de) * 2003-06-03 2004-12-23 Basf Ag Herstellung von Polyetheralkoholen unter Verwendung der DMC-Katalyse
US6884826B2 (en) * 2003-06-09 2005-04-26 Bayer Antwerp, N.V. Process for preparing double metal cyanide catalyzed polyols
US20050014979A1 (en) * 2003-07-08 2005-01-20 Eleveld Michiel Barend Preparation of an alkoxylate composition using a double metal cyanide catalyst
US7005552B2 (en) * 2003-11-03 2006-02-28 Bayer Materialscience Llc Single reactor synthesis of KOH-capped polyols based on DMC-synthesized intermediates
US7186867B2 (en) 2004-04-21 2007-03-06 Basf Aktiengesellschaft Process for preparing reactive polyether polyols having an ethylene oxide end block
DE102004047524A1 (de) * 2004-09-28 2006-03-30 Basf Ag Verfahren zur Herstellung von Polyurethan-Weichschaumstoffen
DE102006006696A1 (de) * 2006-02-14 2007-08-23 Clariant International Limited Polyalkylenglykol-Schmiermittelbasisöle mit enger Molmassenverteilung
DE102008002091A1 (de) 2007-05-31 2008-12-11 Basf Se Verfahren zur Herstellung von Monoalkylenglykolmonoethern
SG185102A1 (en) 2010-04-30 2012-12-28 Basf Se Polyether polyols, process for preparing polyether polyols and their use for producing polyurethanes
US9115246B2 (en) 2010-04-30 2015-08-25 Basf Se Polyether polyols, process for preparing polyether polyols and their use for producing polyurethanes
JP5937609B2 (ja) * 2010-11-18 2016-06-22 ダウ グローバル テクノロジーズ エルエルシー 難燃性軟質ポリウレタンフォーム
JP2014527093A (ja) * 2011-06-29 2014-10-09 ダウ グローバル テクノロジーズ エルエルシー 熱的に安定な難燃性可撓性ポリウレタンフォーム
US9035105B2 (en) 2012-07-20 2015-05-19 Bayer Materialscience Llc Process for the in situ production of polyether polyols based on renewable materials and their use in the production of flexible polyurethane foams
US9051412B2 (en) * 2013-03-14 2015-06-09 Bayer Materialscience Llc Base-catalyzed, long chain, active polyethers from short chain DMC-catalyzed starters
US20230147479A1 (en) 2021-11-05 2023-05-11 Covestro Llc Processes and production plants for producing polyols

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4355188A (en) * 1980-10-16 1982-10-19 The General Tire & Rubber Company Method for treating polypropylene ether and poly-1,2-butylene ether polyols
US4721818A (en) * 1987-03-20 1988-01-26 Atlantic Richfield Company Purification of polyols prepared using double metal cyanide complex catalysts
EP0370705A2 (en) * 1988-11-25 1990-05-30 ARCO Chemical Technology, L.P. Purification of polyols prepared using double metal cyanide complex catalysts
WO1991018909A1 (en) * 1990-03-30 1991-12-12 Olin Corporation Process for removing double metal cyanide complex catalyst residues from catalyst-residue containing polyols

Family Cites Families (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3427256A (en) * 1963-02-14 1969-02-11 Gen Tire & Rubber Co Double metal cyanide complex compounds
US3427335A (en) * 1963-02-14 1969-02-11 Gen Tire & Rubber Co Double metal cyanides complexed with an acyclic aliphatic saturated monoether,an ester and a cyclic ether and methods for making the same
DE1222261B (de) * 1963-04-20 1966-08-04 Bayer Ag Verfahren zur Herstellung von Polyaethern durch Polymerisation von Alkylenoxyden
US3317508A (en) * 1964-11-09 1967-05-02 Union Carbide Corp Process for making alkylene oxidepolyol adducts
US3823145A (en) * 1968-07-26 1974-07-09 Basf Wyandotte Corp Removal of impurities from polyols
US3715402A (en) * 1969-08-08 1973-02-06 Basf Wyandotte Corp Removal of catalysts from polyols
US3829505A (en) * 1970-02-24 1974-08-13 Gen Tire & Rubber Co Polyethers and method for making the same
US3941849A (en) * 1972-07-07 1976-03-02 The General Tire & Rubber Company Polyethers and method for making the same
AU551979B2 (en) * 1982-03-31 1986-05-15 Shell Internationale Research Maatschappij B.V. Epoxy polymerisation catalysts
AU552988B2 (en) * 1982-03-31 1986-06-26 Shell Internationale Research Maatschappij B.V. Polymerizing epoxides and catalyst suspensions for this
US4495081A (en) * 1982-07-13 1985-01-22 The Dow Chemical Company Compositions containing polyether polyols and aliphatic primary amines
US4687851A (en) * 1985-08-15 1987-08-18 The Dow Chemical Company Polyurethane elastomers prepared from high equivalent weight polyahls
US5144093A (en) * 1991-04-29 1992-09-01 Olin Corporation Process for purifying and end-capping polyols made using double metal cyanide catalysts
US5235114A (en) * 1991-04-29 1993-08-10 Olin Corporation Process for purifying and end-capping polyols made using double metal cyanide catalysts
US5158922A (en) * 1992-02-04 1992-10-27 Arco Chemical Technology, L.P. Process for preparing metal cyanide complex catalyst

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4355188A (en) * 1980-10-16 1982-10-19 The General Tire & Rubber Company Method for treating polypropylene ether and poly-1,2-butylene ether polyols
US4721818A (en) * 1987-03-20 1988-01-26 Atlantic Richfield Company Purification of polyols prepared using double metal cyanide complex catalysts
EP0370705A2 (en) * 1988-11-25 1990-05-30 ARCO Chemical Technology, L.P. Purification of polyols prepared using double metal cyanide complex catalysts
WO1991018909A1 (en) * 1990-03-30 1991-12-12 Olin Corporation Process for removing double metal cyanide complex catalyst residues from catalyst-residue containing polyols

Also Published As

Publication number Publication date
HU217692B (hu) 2000-03-28
EP0750001A3 (en) 1997-07-23
KR970001292A (ko) 1997-01-24
RO117101B1 (ro) 2001-10-30
CN1150582A (zh) 1997-05-28
HUP9601691A3 (en) 1997-12-29
CA2177871C (en) 2009-07-28
AR002561A1 (es) 1998-03-25
MX9602435A (es) 1997-02-28
BR9602829A (pt) 1998-10-06
ATE199094T1 (de) 2001-02-15
CA2177871A1 (en) 1996-12-22
KR100451872B1 (ko) 2004-12-04
HU9601691D0 (en) 1996-08-28
HUP9601691A2 (en) 1997-04-28
EP0750001B1 (en) 2001-02-07
DE69611743T2 (de) 2001-05-31
JP3247612B2 (ja) 2002-01-21
AU5605796A (en) 1997-01-09
DE69611743D1 (de) 2001-03-15
GR3035686T3 (en) 2001-06-29
ZA965263B (en) 1997-01-09
DK0750001T3 (da) 2001-03-19
EP0750001A2 (en) 1996-12-27
JPH093186A (ja) 1997-01-07
AU694874B2 (en) 1998-07-30
US5563221A (en) 1996-10-08
ES2153938T3 (es) 2001-03-16
TW322470B (zh) 1997-12-11

Similar Documents

Publication Publication Date Title
CN1090198C (zh) 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
KR101173690B1 (ko) Ｄｍｃ-합성된 중간체에 기초한 ｋｏｈ-캡핑된 폴리올의단일 반응기 제조 방법
US5777177A (en) Preparation of double metal cyanide-catalyzed polyols by continuous addition of starter
CN101851329A (zh) 在双金属氰化物催化工艺中起始物进料流的酸化
CA2443117C (en) Processes for preparing ethylene oxide-capped polyols
KR20010024062A (ko) 이중 금속 시안화물 촉매에 의한 글리세린의 직접폴리옥시알킬화 반응
WO1992019578A1 (en) Process for purifying and end-capping polyols made using double metal cyanide catalysts
JP2003503516A5 (zh)
CA2140499C (en) Method for purifying polyether polyols made with double metal cyanide catalysts
US5235114A (en) Process for purifying and end-capping polyols made using double metal cyanide catalysts
CN110790916A (zh) 一种低气味聚醚多元醇的制备方法
CA2119630A1 (en) Productive process for making conventional and low-unsaturation polyether polyols
CN1487000A (zh) 活性起始混合物及相关方法
AU679134B2 (en) Process for purifying polyols
EP1448663B1 (en) Process for the alkoxylation of organic compounds
JPH06199980A (ja) プレポリマーの製造方法
MXPA94008230A (es) Procedimiento para la purificacion de polioles.

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CX01 Expiry of patent term

Granted publication date: 20020904

EXPY Termination of patent right or utility model