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WO2010072769A1 - Procédé de production de copolymères à blocs polyéther - Google Patents

Procédé de production de copolymères à blocs polyéther Download PDF

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Publication number
WO2010072769A1
WO2010072769A1 PCT/EP2009/067758 EP2009067758W WO2010072769A1 WO 2010072769 A1 WO2010072769 A1 WO 2010072769A1 EP 2009067758 W EP2009067758 W EP 2009067758W WO 2010072769 A1 WO2010072769 A1 WO 2010072769A1
Authority
WO
WIPO (PCT)
Prior art keywords
polyol
iii
polyoxyalkylene
starter
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.)
Ceased
Application number
PCT/EP2009/067758
Other languages
German (de)
English (en)
Inventor
Ulrich Steinbrenner
Sophia Ebert
Tobias Habeck
Paul Klingelhoefer
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.)
BASF SE
Original Assignee
BASF SE
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 BASF SE filed Critical BASF SE
Publication of WO2010072769A1 publication Critical patent/WO2010072769A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G2650/28—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
    • C08G2650/58—Ethylene oxide or propylene oxide copolymers, e.g. pluronics

Definitions

  • multimetal cyanide catalysts dimetal cyanide catalysts and DMC catalysts are used synonymously.
  • the C2-C6 polyols carry at least 2, preferably 2 to 8, in particular 2 to 6 and particularly preferably 2 or 3 OH groups on the carbon skeleton of the compound.
  • the hydrophobic polyoxyalkylene skeletons have terminal Cs-C ⁇ -oxyalkylene units whose terminal oxygen atoms carry the terminal hydroxy (polyoxyethylene) groups of the polyoxyalkylene block copolymers prepared according to the invention.
  • M 1 and M 2 may be the same or different.
  • a and X may be the same or different.
  • Preferred for use in step a) of the process according to the invention is a double metal cyanide compound of the formula A, wherein M 1 is selected from Zn 2+ , Fe 2+ , Co 2+ and Ni 2+ , especially Zn 2+ .
  • M 1 is selected from Zn 2+ , Fe 2+ , Co 2+ and Ni 2+ , especially Zn 2+ .
  • M 2 is selected from Co 2+ , Co 3+ , Fe 2+ , Fe 3+ , Cr 3+ and Rh 3+ , especially Co 3+ .
  • a double metal cyanide compound of the formula A wherein A is cyanide.
  • crystalline DMC compounds Preference is given to using crystalline DMC compounds.
  • a Zn-Co type crystalline DMC compound is used as the catalyst containing zinc acetate as the metal salt component. Such compounds crystallize in monoclinic structure and have a platelet-shaped habit.
  • step a) of the process according to the invention is a multimetal cyanide catalyst, as described in WO 2006/117364.
  • the multimetal cyanide catalyst used in step a) is then specially selected from catalysts which contain at least one bimetallic cyanide compound of the general formula (D)
  • M 2 is a metal ion selected from the group consisting of Sr (I), Mg (II), Zn (II), Fe (II), Fe (III), Co (III), Cr (III), Mn (II), Mn (II I), Ir (III), Rh (III), Ru (II), V (IV), V (V), Co (II), Cr (II), Ti (IV)
  • X is a non-cyanide group which forms a coordinate bond to M 1 selected from the group consisting of carbonyl, cyanate, isocyanate, nitrite, thiocyanate and nitrosyl, a, b, r, t are integers such as are chosen that the electroneutrality condition is met.
  • r is 4 to 6.
  • t is 0 to 2.
  • the reaction of at least one C 2 -C 6 -epoxide in the presence of at least one multimetal cyanide catalyst, at least one continuously added starter Sk, selected from C 2 -C 8 -polymers and / or C 2 -C 6 -olefin oligomers, and optionally at least one initially introduced polyol Starter S v is carried out by customary methods known to the person skilled in the art and in apparatuses customary therefor, in particular in those which are equipped for working under pressure.
  • the polyoxyalkylene polyols obtained in step a) of the process according to the invention usually have 2 to 8, preferably 2 to 3 and in particular 2 hydroxyl groups.
  • step b) of the process according to the invention at elevated temperatures, preferably at temperatures of 40 ° C to 250 ° C, more preferably from 80 ° C to 200 ° C and in particular from 100 0 C to 150 0 C, fürbowen.
  • the ethylene oxide is added to the mixture of polyoxyalkylene polyol and base at a pressure greater than or equal to the vapor pressure of ethylene oxide at the selected reaction temperature.
  • the ethoxylation is carried out without addition of a solvent, d. H. in substance.
  • the alkoxylation may also be carried out in the presence of a solvent inert under the ethoxy curing conditions.
  • Suitable inert solvents are aliphatic and aromatic hydrocarbons, such as toluene or hexane, or ethers, such as tetrahydrofuran.
  • the inventive method is particularly suitable for the preparation of polyoxyalkylene block copolymers, wherein the proportion of hydroxy (polyoxyethylene) groups, based on the total weight of the polyoxyalkylene block copolymer prepared, 5 to 85 wt .-% and in particular 20 to 80 parts by weight. % is.
  • the inventive method is particularly suitable for the preparation of polyoxyalkylene block copolymers, wherein the hydrophobic polyoxyalkylene skeleton of the polyoxyalkylene block copolymer produced a molecular weight of at least 1500 g / mol, preferably at least 3000 g / mol, more preferably at least 6000 g / mol and most preferably at least 8000 g / mol.
  • the upper limit of the molecular weight is usually not critical.
  • the molecular weight of the hydrophobic polyoxyalkylene skeleton will not exceed 100,000 g / mol, preferably 50,000 g / mol and more preferably 30,000 g / mol.
  • the ratio of ethylene oxide to propylene oxide (EO / PO ratio) and the ratio of primary to secondary OH groups was determined by means of 1 H-NMR (according to the method of J. Loccufier et al., Polymer Bulletin 1991, 27, 201-204).
  • a sample of the polymer to be investigated was derivatized with trichloroacetyl isocyanate (TAI).
  • TAI trichloroacetyl isocyanate
  • the hydroxy functions are converted into carbamic acid esters.
  • the signals of the esterified primary alcohols have a shift of about 4.4 ppm, those of the esterified secondary alcohols of about 5.2 ppm.
  • Methylene and methine protons are in the range of 3.0 to 4.0 ppm.
  • the signal of the methyl groups from the propylene oxide appears at 1.2 ppm. From the signal at 4.2 ppm (all primary alcohols esterified with TAI) in 1 H NMR, the OH number can be calculated. Higher OH numbers than expected can be attributed to the presence of polyethylene glycols.
  • the proportion of ethylene oxide was calculated from the integral of the signals at 3.0 to 4.0 ppm minus the 3 protons for the methine protons and methylene protons from the propylene oxide.
  • the signal at 4.2 ppm was used. Substituting this in relation to the signals for propylene and ethylene oxide, the OH number can be calculated.

Landscapes

  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Toxicology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyethers (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

La présente invention concerne un procédé de production d'un copolymère à blocs polyoxyalkylène constitué d'une structure de base polyoxyalkylène hydrophobe et de groupes terminaux hydroxy (polyoxyéthylène).
PCT/EP2009/067758 2008-12-23 2009-12-22 Procédé de production de copolymères à blocs polyéther Ceased WO2010072769A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP08172792.7 2008-12-23
EP08172792 2008-12-23

Publications (1)

Publication Number Publication Date
WO2010072769A1 true WO2010072769A1 (fr) 2010-07-01

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2009/067758 Ceased WO2010072769A1 (fr) 2008-12-23 2009-12-22 Procédé de production de copolymères à blocs polyéther

Country Status (3)

Country Link
AR (1) AR074880A1 (fr)
TW (1) TW201033248A (fr)
WO (1) WO2010072769A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012093039A1 (fr) 2011-01-07 2012-07-12 Omya Development Ag Procédé de blanchiment superficiel à base d'une suspension aqueuse de substances minérales
US8492326B2 (en) 2010-06-28 2013-07-23 Basf Se Alkoxylates and use thereof
CN112358608A (zh) * 2020-10-29 2021-02-12 江苏利宏科技发展有限公司 一种聚醚多元醇制备方法
WO2021109557A1 (fr) * 2019-12-06 2021-06-10 浙江皇马科技股份有限公司 Procédé de synthèse d'un polyéther pour matériau d'étanchéité à faible module

Citations (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1992016484A1 (fr) 1991-03-19 1992-10-01 Cytrx Corporation Copolymeres de polyoxypropylene/polyoxyethylene presentant une activite biologique amelioree
US5158922A (en) 1992-02-04 1992-10-27 Arco Chemical Technology, L.P. Process for preparing metal cyanide complex catalyst
WO1996004932A1 (fr) 1994-08-09 1996-02-22 Cytrx Corporation Nouvel adjuvant de vaccin et nouveau vaccin
WO1997029146A1 (fr) 1996-02-07 1997-08-14 Arco Chemical Technology, L.P. Preparation de polyols catalyses au moyen d'un catalyseur double metal au cyanure impliquant l'addition en continu d'initiateur
WO1999016775A1 (fr) 1997-09-29 1999-04-08 Basf Aktiengesellschaft Complexes cyanures a metaux multiples s'utilisant comme catalyseurs
WO1999019063A1 (fr) 1997-10-13 1999-04-22 Bayer Aktiengesellschaft Catalyseurs cristallins de cyanure de metaux composites pour preparer des polyols de polyether
WO2000074845A1 (fr) 1999-06-02 2000-12-14 Basf Aktiengesellschaft Composes a base de cyanure polymetallique, leur procede de production et leur utilisation
WO2001016209A1 (fr) 1999-08-31 2001-03-08 Basf Aktiengesellschaft Alcools de polyether
WO2001064772A1 (fr) 2000-02-29 2001-09-07 Basf Aktiengesellschaft Procede de production de composes du type des cyanures polymetalliques
DE10117273A1 (de) 2001-04-06 2002-10-17 Basf Ag Verfahren zur Herstellung von Hydroxyalkylcarbonsäureestern
EP1403301A1 (fr) * 2002-09-30 2004-03-31 Bayer MaterialScience AG Procédé pour la préparation de polyols ayant des groupes terminaux à partir d'oxyde d'éthylène
WO2006002807A1 (fr) 2004-06-30 2006-01-12 Basf Aktiengesellschaft Procede de production d'alcools de polyether
WO2006094979A2 (fr) 2005-03-10 2006-09-14 Basf Aktiengesellschaft Procede de fabrication de catalyseurs dmc
DE102005020347A1 (de) 2005-05-02 2006-11-09 Basf Ag Verfahren zur Herstellung von Doppelmetallcyanidkomplex-Katalysatoren
WO2007082596A1 (fr) 2005-12-02 2007-07-26 Basf Se Procédé de fabrication de composes de cyanures multimétalliques

Patent Citations (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1992016484A1 (fr) 1991-03-19 1992-10-01 Cytrx Corporation Copolymeres de polyoxypropylene/polyoxyethylene presentant une activite biologique amelioree
US5158922A (en) 1992-02-04 1992-10-27 Arco Chemical Technology, L.P. Process for preparing metal cyanide complex catalyst
EP1181937A2 (fr) 1994-08-09 2002-02-27 Cytrx Corporation Vaccin contenant des acides nucléiquées et adjuvant de vaccin
WO1996004932A1 (fr) 1994-08-09 1996-02-22 Cytrx Corporation Nouvel adjuvant de vaccin et nouveau vaccin
WO1997029146A1 (fr) 1996-02-07 1997-08-14 Arco Chemical Technology, L.P. Preparation de polyols catalyses au moyen d'un catalyseur double metal au cyanure impliquant l'addition en continu d'initiateur
WO1999016775A1 (fr) 1997-09-29 1999-04-08 Basf Aktiengesellschaft Complexes cyanures a metaux multiples s'utilisant comme catalyseurs
WO1999019063A1 (fr) 1997-10-13 1999-04-22 Bayer Aktiengesellschaft Catalyseurs cristallins de cyanure de metaux composites pour preparer des polyols de polyether
WO2000074845A1 (fr) 1999-06-02 2000-12-14 Basf Aktiengesellschaft Composes a base de cyanure polymetallique, leur procede de production et leur utilisation
WO2001016209A1 (fr) 1999-08-31 2001-03-08 Basf Aktiengesellschaft Alcools de polyether
WO2001064772A1 (fr) 2000-02-29 2001-09-07 Basf Aktiengesellschaft Procede de production de composes du type des cyanures polymetalliques
DE10117273A1 (de) 2001-04-06 2002-10-17 Basf Ag Verfahren zur Herstellung von Hydroxyalkylcarbonsäureestern
EP1403301A1 (fr) * 2002-09-30 2004-03-31 Bayer MaterialScience AG Procédé pour la préparation de polyols ayant des groupes terminaux à partir d'oxyde d'éthylène
WO2006002807A1 (fr) 2004-06-30 2006-01-12 Basf Aktiengesellschaft Procede de production d'alcools de polyether
WO2006094979A2 (fr) 2005-03-10 2006-09-14 Basf Aktiengesellschaft Procede de fabrication de catalyseurs dmc
DE102005020347A1 (de) 2005-05-02 2006-11-09 Basf Ag Verfahren zur Herstellung von Doppelmetallcyanidkomplex-Katalysatoren
WO2006117364A2 (fr) 2005-05-02 2006-11-09 Basf Aktiengesellschaft Procede de production de catalyseurs a base de complexes bimetalliques a pont cyanure
WO2007082596A1 (fr) 2005-12-02 2007-07-26 Basf Se Procédé de fabrication de composes de cyanures multimétalliques

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
J. LOCCUFIER ET AL., POLYMER BULLETIN, vol. 27, 1991, pages 201 - 204

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8492326B2 (en) 2010-06-28 2013-07-23 Basf Se Alkoxylates and use thereof
WO2012093039A1 (fr) 2011-01-07 2012-07-12 Omya Development Ag Procédé de blanchiment superficiel à base d'une suspension aqueuse de substances minérales
WO2012092986A1 (fr) 2011-01-07 2012-07-12 Omya Development Ag Procédé de blanchiment de la surface d'une boue minérale à base d'eau
WO2021109557A1 (fr) * 2019-12-06 2021-06-10 浙江皇马科技股份有限公司 Procédé de synthèse d'un polyéther pour matériau d'étanchéité à faible module
CN112358608A (zh) * 2020-10-29 2021-02-12 江苏利宏科技发展有限公司 一种聚醚多元醇制备方法

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TW201033248A (en) 2010-09-16
AR074880A1 (es) 2011-02-16

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