CN1052016C - 纯化多醇的方法 - Google Patents

纯化多醇的方法 Download PDF

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CN1052016C
CN1052016C CN94194470A CN94194470A CN1052016C CN 1052016 C CN1052016 C CN 1052016C CN 94194470 A CN94194470 A CN 94194470A CN 94194470 A CN94194470 A CN 94194470A CN 1052016 C CN1052016 C CN 1052016C
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alcohol
many
extract compounds
polyoxyalkylene
list
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CN1137279A (zh
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P·M·G·戈格比尔
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HENTZMAN ICI CHEMICAL PRODUCT CO Ltd
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Imperial Chemical Industries Ltd
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    • 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
    • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
    • C08G65/46—Post-polymerisation treatment, e.g. recovery, purification, drying
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/34—Separation; Purification; Stabilisation; Use of additives
    • C07C41/38—Separation; Purification; Stabilisation; Use of additives by liquid-liquid treatment
    • 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
    • C08G65/30—Post-polymerisation treatment, e.g. recovery, purification, drying

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Polyethers (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Extraction Or Liquid Replacement (AREA)

Abstract

降低聚氧化亚烷基单醇或多醇中金属离子和/或金属化合物含量的方法，该聚氧化亚烷基单醇或多醇的数均分子量约500-25000，方法是使该单醇或多醇与一种萃取化合物接触，该萃取化合物是数均分子量至多为500的多醇或多醇混合物和与该聚氧化亚烷基单醇或多醇不相混溶，使萃取化合物与聚氧化亚烷基单醇或多醇混合，使萃取化合物与聚氧化亚烷基单醇或多醇分离和除去萃取化合物。

Description

纯化多醇的方法
本发明涉及制备具有金属离子和/或金属化合物低含量的聚氧化亚烷基单醇或多醇的方法。
已知通过引发剂的烷氧基化制备聚氧化亚烷基单醇或多醇的方法中，该引发剂有至少一个反应性氢原子，尤其是至少一个羟基，可以使用象KOH，NaOH和CsOH的催化剂。
令人惊异地，已发现：在制备这些聚氧化亚烷基单醇或多醇之后，可以用某些低分子量多醇萃取来降低这些催化剂的含量。
因此，本发明涉及降低聚氧化亚烷基单醇或多醇中金属离子和/或金属化合物含量的方法，该单醇或多醇的数均分子量约为500-25000，此方法是：
使该单醇或多醇与一种萃取化合物接触，该萃取化合物是数均分子量至多为500(优选至多为250)且与该聚氧化亚烷基单醇或多醇不相混溶；
使该萃取化合物与聚氧化亚烷基单醇或多醇混合；
使该萃取化合物与聚氧化亚烷基单醇或多醇分离；和
除去萃取化合物。
聚氧化亚烷基多醇优选的标称平均官能度为2-8，更优选为2-6，和优选的数均分子量为1000-10000。聚氧化亚烷基单醇优选的数均分子量为1000-10000。
在含有金属如K，Na，Cs，Ba，Sr的烷氧化催化剂，例如KOH，NaOH和CsOH存在下，通过具有至少两个反应性氢原子的引发剂的烷氧化来制备这种聚氧化亚烷基多醇。尤其是经常使用K，Na和Cs的化合物。催化剂的用量一般范围在以所制多醇的量为基计算的100-50000ppm金属，优选范围在500-30000ppm金属。上述用量范围也适用于单醇，条件是所用的引发剂只含有一个反应性氢原子，如甲醇，乙醇，丙醇和烯丙醇及其混合物。
制备多醇的引发剂可选自常规使用的那些引发剂诸如：乙二醇，二甘醇，丙二醇，二丙二醇，丁二醇，丙三醇，三羟甲基丙烷，季戊四醇，蔗糖，山梨醇，甘胺，乙醇胺，二乙醇胺，三乙醇胺，甲苯二胺，二苯甲烷二胺和二乙甲苯二胺。也可以使用引发剂的混合物。
烷氧化可以用常规使用的环氧烷来进行，如环氧乙烷，环氧丙烷，环氧丁烷及其混合物。
该单醇或多醇可以是：均聚物，无规共聚物，嵌段共聚物和无规-嵌段共聚物。
萃取化合物优选选自：乙二醇，二甘醇，三甘醇，四甘醇，丙三醇和丁二醇及其混合物；更优选为乙二醇，二甘醇及其混合物。
本文所称“不相混溶”是意指：在室温下如果萃取化合物至多只有30重％可溶解在聚氧化亚烷基单醇或多醇中就视作不相混溶的萃取化合物。
按常规的萃取方法进行萃取。可以采用批次或连续方式进行萃取。若以批次操作，可进行一次或多次，优选1-5次，更优选1或2次。
萃取方法可以在室温下进行，也可以在升温下进行，但条件是施加温度要低于施加条件下萃取化合物的沸点和低于聚氧化亚烷基多醇在该施加条件下会造成分解的温度。优选的温度范围是75-250℃。一旦此或多醇与该萃取化合物合并它们就进行混合。可以在一般条件下混合，也可在高剪切条件下进行混合。萃取化合物的用量范围很宽。优选地，萃取化合物与单醇或多醇的重量比至少为0.25∶1，更优选为0.3-5∶1。
如果说多醇含有不饱和成分，正如以环氧丙烷为基的多醇的情况，则可以通过上述的萃取将这样的不饱和物部分除去。在萃取化合物中的金属如果需要可以回收。
下述实例将进一步说明本发明。
一种EO/PO多醇，其分子量6000，不饱和值0.068meg/g(乙酸汞法)和标称官能度为3和15％(重量)EO(tipped)。它是这样制备：使用0.2重量％的KOH(该多醇一次制成含有1400ppm的K+)。该多醇中加入二甘醇(多醇/二甘醇的重量比为1∶1)在室温下进行萃取，接着混合和加热至200℃约20分钟。然后此混合物在200℃保持2小时，再在室温下保持静置15小时。两层形成后进行分离。然后对多醇进行真空抽提(200℃，0.2kPa(2毫巴)，8小时，N2气流下)，以除去残留的二甘醇。
这样得到的多醇(顶层)含有3ppm K+(原子吸收分析)和不饱和值为0.047meg/g(乙酸汞法)。

Claims (8)

1.降低聚氧化亚烷基单醇或多醇中金属离子和/或金属化合物含量的方法，该单醇或多醇的数均分子量为500-25000，此方法是：
使该单醇或多醇与一种萃取化合物接触，该萃取化合物是数均分子量至多为500和与该聚氧化亚烷基单醇或多醇不相混溶的一种多元醇或多元醇混合物；
使该萃取化合物与该聚氧化亚烷基单醇或多醇混合；
使萃取化合物与聚氧化亚烷基单醇或多醇分离；和
除去萃取化合物。
2.权利要求1的方法，其特征在于在萃取化合物加入之前该聚氧化亚烷基单醇或多醇含有100-50000ppm的金属离子。
3.权利要求1或2的方法，其特征在于以连续的方式实施该方法。
4.权利要求1或2的方法，其特征在于1次或两次批次实施该方法。
5.权利要求1的方法，其特征在于该萃取化合物选自：乙二醇，二甘醇，三甘醇，四甘醇，丙三醇和丁二醇，及其混合物。
6.权利要求1的方法，其特征在于该萃取化合物选自：乙二醇和二甘醇及其混合物。
7.权利要求1的方法，其特征在于在萃取化合物加入之前该聚氧化亚烷基单醇或多醇含有Na，K和/或Cs离子和/或其化合物。
8.权利要求1的方法，其特征在于萃取化合物的数均分子量至多为250。
CN94194470A 1993-12-13 1994-11-17 纯化多醇的方法 Expired - Fee Related CN1052016C (zh)

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GB9325468.8 1993-12-13
GB939325468A GB9325468D0 (en) 1993-12-13 1993-12-13 Process for purifying polyols

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EP (1) EP0734407B1 (zh)
JP (1) JPH09506644A (zh)
KR (1) KR960706521A (zh)
CN (1) CN1052016C (zh)
AU (1) AU679134B2 (zh)
CA (1) CA2175191A1 (zh)
DE (1) DE69407622T2 (zh)
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GB (1) GB9325468D0 (zh)
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US6291797B1 (en) 1996-08-13 2001-09-18 Nippon Sheet Glass Co., Ltd. Laser machining method for glass substrate, diffraction type optical device fabricated by the machining method, and method of manufacturing optical device
KR19980059285A (ko) * 1996-12-31 1998-10-07 박영구 반응 혼합물로부터 폴리올 화합물을 분리 정제하는 방법
CA2280854A1 (en) 1997-02-25 1998-08-27 Exxonmobil Chemical Patents, Inc. Heat sealable films
US5962749A (en) * 1997-12-24 1999-10-05 Bayer Corporation Process for the removal of alkalinity in the manufacture of polyether polyols and the reuse of this alkalinity in the manufacture of polyether polyols
US6806348B2 (en) 2003-02-11 2004-10-19 Basf Corporation Process for removing and regenerating a double metal cyanide (DMC) catalyst from a polymer polyol
CN1321099C (zh) * 2005-09-28 2007-06-13 蓝仁水 从稀水溶液中浓缩低级多元醇的工艺方法
US10150837B2 (en) 2016-06-23 2018-12-11 Covestro Llc Processes for removing water from a polyether polyol
CN109575268A (zh) 2018-11-02 2019-04-05 佳化化学（滨州）有限公司 一种聚醚多元醇的精制方法及精制装置

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EP0236995A2 (de) * 1986-03-11 1987-09-16 BASF Aktiengesellschaft Verfahren zur Einengung der Molkulargewichtsverteilung von Polytetrahydrofuran und von Copolymerisaten aus Tetrahydrofuran und Alkylenoxiden
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HK1004607A1 (zh) 1998-11-27
DE69407622D1 (de) 1998-02-05
EP0734407A1 (en) 1996-10-02
EP0734407B1 (en) 1997-12-29
JPH09506644A (ja) 1997-06-30
CA2175191A1 (en) 1995-06-22
AU8144394A (en) 1995-07-03
CN1137279A (zh) 1996-12-04
MY111426A (en) 2000-04-29
GB9325468D0 (en) 1994-02-16
WO1995016724A1 (en) 1995-06-22
ES2111385T3 (es) 1998-03-01
DE69407622T2 (de) 1998-04-23
AU679134B2 (en) 1997-06-19
US5449841A (en) 1995-09-12
KR960706521A (ko) 1996-12-09

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