[go: up one dir, main page]

WO1995015997A1 - Procede de finition pour polyethers a terminaison hydroxyle - Google Patents

Procede de finition pour polyethers a terminaison hydroxyle Download PDF

Info

Publication number
WO1995015997A1
WO1995015997A1 PCT/US1994/013312 US9413312W WO9515997A1 WO 1995015997 A1 WO1995015997 A1 WO 1995015997A1 US 9413312 W US9413312 W US 9413312W WO 9515997 A1 WO9515997 A1 WO 9515997A1
Authority
WO
WIPO (PCT)
Prior art keywords
polyether
sulphonic acid
hydroxyl
metal ion
acid ester
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/US1994/013312
Other languages
English (en)
Inventor
Inge M. Rouwenhorst
Pieter J. Platteeuw
Christiaan J. Hiensch
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.)
Dow Chemical Co
Original Assignee
Dow Chemical Co
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 Dow Chemical Co filed Critical Dow Chemical Co
Priority to AU14082/95A priority Critical patent/AU1408295A/en
Publication of WO1995015997A1 publication Critical patent/WO1995015997A1/fr
Anticipated expiration legal-status Critical
Ceased 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
    • C08G65/30—Post-polymerisation treatment, e.g. recovery, purification, drying

Definitions

  • This invention relates to a finishing process for hydroxyl-terminated polyethers and the reduction of residual basicity therein due to the presence of Periodic Group la or Ila metal ions.
  • Hydroxyl-terminated polyethers are generally prepared by reacting an alkylene oxide with an initiator containing one or more active hydrogen atoms in the presence of a catalyst which usually remains in the polyether.
  • the catalysts are basic substances including tertiary amines, or alkali and alkaline earth metal compounds such as, for example, potassium hydroxide or sodium hydroxide.
  • the finishing of polyethers can be effected by alternative means which avoid the need to subsequently remove material from the treated polyether by, for example, using ion exchange resins.
  • Japanese Patent J61043629 discloses the finishing of hydroxyl-terminated polyethers with water and certain cationic resins.
  • U.S. Patent 3,271 ,462 discloses the use of a mercury activated sulfonated polystyrene ion exchange resin for such purpose.
  • these methods suffers certain disadvantages in that acidic ion exchange resins, particularly sulfonic acid ion exchange resins, are known to release acids into organic compounds. Acids can be detrimental in certain formulations when forming polyurethanes from the so-treated polyether.
  • a source of fouling can be, for example, propionaldehyde produced by acid hydrolysis of propenyl adducts that may be present in the polyether. Propionaldehyde also imparts an undesirable odor to the polyether, and if present when preparing a polyurethane foam may cause undesirable discoloration or scorching of the foam.
  • the present invention provides a process for finishing crude hydroxyl-terminated polyethers containing Group la and Group Ila metal ions without requiring the subsequent removal of metal salts prior to the use of the polyether in end applications such as, for example, the preparation of polyurethane polymer.
  • this invention is a hydroxyl-terminated polyether composition having an equivalent weight of from 50 to 50000 characterized in that it further comprises: a) from 5 to 5000 ppm of polyether, of a metal sulphonate salt where the metal is from Group la or Group Ila of the Periodic Table; and b) from 1 to 5000 ppm of polyether, an aliphatic alcohol.
  • this invention is a process for obtaining a hydroxyl-terminated polyether composition having an equivalent weight of from 50 to 50000 and containing from 5 to 5000 ppm of polyether of a metal sulphonate salt and from 1 to 5000 ppm of polyether of an aliphatic alcohol characterized in that a crude hydroxyl-terminated polyether containing a Group la or Ila metal ion is treated with an organic sulphonic acid ester.
  • the sulphonic acid ester treatment of the metal ion in the polyether provides for a finished polyether readily usable in polyurethane applications.
  • the finishing process is a mild, noncorrosive, process and essentially does not result in any unnecessary formation of aldehyde by hydrolysis of unsaturated substances that may be present in the polyether.
  • the present invention is applicable to a wide range of commonly and conventionally known hydroxyl-terminated polyethers including polyalkylene ethers having at least one hydroxyl group and preferably polyoxyalkylene polyethers having a plurality of hydroxyl groups.
  • polyethers may be prepared by reacting alkylene oxide(s) with an active hydrogen-containing initiator, typically an alcohol or amine, in the presence of a metal ion of the Periodic Group la or Ila or mixtures thereof. If the polyether is to be suitable for end applications the metal ion present in the polyether, and conferring basicity to it, requires treatment to render it neutral.
  • such treatment comprises contacting under reaction conditions the polyether with an organic sulphonic acid ester.
  • Sulphonic acid esters are preferred over carboxylic acid esters such as, for example, ethyl acetate, as the metal sulphonate salts formed during the treatment are usually of better compatibility with the intended end applications.
  • Use of, for example, ethyl acetate would result in a metal acetate content in the polyether which may not be compatible with polyurethane applications.
  • Suitable organic sulphonic acid esters for use in this invention include those which are preferably liquid at room temperature and are the ester of an aliphatic alcohol with an organic sulphonic acid that can be an aliphatic, but preferably is an aromatic, sulphonic acid.
  • the aliphatic alcohol advantageously is a C 1 .6 alcohol such as propanol, butanol, pentanol, or hexanol, and especially methanol or ethanol.
  • the organic sulphonic acid when an aromatic acid, advantageously includes benzene sulphonic acid, an alkylbenzene sulphonic acid or an alkylnaphthalene sulphonic acid.
  • alkylbenzene- and alkylnaphthalene sulphonic acids are preferably monoalkyl adducts where advantageously the alkyl radical is a straight chain or branched chain containing from 1 12 carbon atoms including, for example, methyl, ethyl, propyl, isopropyl, nonyl, decyl, undecyl or dodecyl moities.
  • the preferred aromatic sulphonic acids are methylbenzene- and ethylbenzene sulphonic acid.
  • the sulphonic acid esters employed include the methyl or ethyl ester of methyl or ethylbenzene sulphonic acid with most preferred being the commercially available methyl ester of methylbenzene sulphonic acid.
  • the amount of ester used is sufficient to substantially or completely treat the free basicity content of the polyether due to the presence of the metal ion.
  • the polyether to be treated may contain the metal ion in an amount up to 5000 ppm of polyether, but usually in from 5 to 1000, more usually in from 5 to 200, and yet more usually from 5 to 100 ppm of polyether.
  • Treatment with the sulphonic acid ester results in the formation of the corresponding metal sulphonate salt and the aliphatic alcohol corresponding to alkyl moiety of the ester.
  • the ester is present in an amount of from 0.95 to 1.5, preferably from 0.97 to 1.2, and more preferably from 0.99 to 1.05 equivalent per equivalent of metal ion to be treated.
  • the term "equivalent” is understood to mean equivalent per unity of oxidation; i.e. one mole of a metal 2+ ion will require treatment with from 2 X (0.95 to 1.5) equivalents of ester.
  • Use of amounts of sulphonic acid ester in excess of this provide a finished hydroxyl-terminated polyether with an unnecessarily high sulphonic acid ester content which on storage could be susceptible to hydrolysis, liberating an acid.
  • An acid content of hydroxyl-terminated polyethers can be disadvantageous in, for example, polyurethane end applications.
  • the sulphonic acid ester is contacted with the polyether advantageously at a temperature of from 60°C to 150°C, preferably from 80°C to 130°C, and more preferably from 90°C to 125 C C typically for a period of from 15 to 600, and preferably from 30 to 300 minutes.
  • a temperature of from 60°C to 150°C preferably from 80°C to 130°C, and more preferably from 90°C to 125 C C typically for a period of from 15 to 600, and preferably from 30 to 300 minutes.
  • the basicity of the polyether can be monitored by standard acid-base titration techniques to assess the time required to obtain a polyether having little or no free basicity.
  • the actual time required will depend on the metal ion content of the polyether but frequently need not be longer than 60 minutes.
  • the treatment may be effected at ambient pressures but it is found advantageous to conduct the treatment at above ambient pressures in an essentially oxygen-free environment.
  • Such environment can be provided by displacing all air/oxygen as might be present with, for example, nitrogen.
  • the process will be operated at a pressure of up to 5 bar, but more preferably from 1.5 to 3.5 bars.
  • Exclusion of air/oxygen minimizes any potential oxidation of the polyether while it is being treated with the sulphonic acid ester at the elevated temperature.
  • the polyether advantageously has a water content of less than 2, preferably less than 1, and more preferably less than 0.8 percent based on total weight of polyether and water.
  • the present invention is applicable to treatment of various hydroxyl-terminated polyethers including polyalkylene ethers having at least one hydroxyl group and preferably polyoxyalkylene polyethers having a plurality of hydroxyl groups which are obtained by reacting an alkylene oxide with an initiator in the presence of a substance comprising a Group la or Ila metal.
  • alkylene oxides suitable for the preparation of polyethers include ethylene oxide, propylene oxide, butylene oxide, amylene oxide, glycidyl ethers such as t-butyl glycidyl ether, phenyl glycidyl ether, styrene oxide and epihalohydrins such as epichlorohydrin, epibromohydrin, 3,3-dichloropropylene oxide, 3-chloro-1,2- epoxypropane, 3-chloro-1,2-epoxybutane and 3,4-dichloro-1,2-epoxyutane.
  • the polyethers are prepared from alkylene oxides having from two to four carbon atoms such as ethylene oxide, propylene oxide, and butylene oxide or mixtures thereof.
  • Illustrative alcohols suitable for initiating formation of a hydroxyl-terminated polyether include polyalcohols such as ethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, 1,5-pentane diol, 1,7-heptane diol, 1,1,1-trimethylolpropane, glycerine, 1,1,1- trimethylolethane, hexane-1,2,6-triol, ⁇ -methyl glucoside, pentaerythritol, erythritol, sorbitol, glucose, sucrose, fructose or maltose.
  • polyalcohols such as ethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, 1,5-pentane diol, 1,7-heptane diol, 1,1,1-trimethylolpropane, glycerine, 1,1,1- trimethylolethane, hexane-1
  • monoalcohols such as those having from 1 to 18 carbon atoms including methanol, ethanol, isomers of propyl alcohol, isomers of butyl alcohol, and monoalkylethers of diols; and aromatic alcohols such as phenols and compounds derived from phenols such as (4,4'-hydroxyphenyl)2,2-propane, alkylphenols such as dodecylphenol, octylphenol, decylphenol and mixtures thereof.
  • monoalcohols such as those having from 1 to 18 carbon atoms including methanol, ethanol, isomers of propyl alcohol, isomers of butyl alcohol, and monoalkylethers of diols
  • aromatic alcohols such as phenols and compounds derived from phenols such as (4,4'-hydroxyphenyl)2,2-propane, alkylphenols such as dodecylphenol, octylphenol, decylphenol and mixtures thereof.
  • Illustrative of amines suitable for initiating formation of a hydroxyl-terminated polyether by reaction with alkylene oxide include aliphatic and aromatic mono- and polyamines, optionally having substituents such as alkyl, carboxyl or carboalkoxy groups.
  • Exemplary aromatic amines include aniline, o-chloroaniline, p-phenylene diamine, 1,5- diaminonaphthalene, methylene dianiline, toluene diamine and the condensation products of aniline with formaldehyde.
  • Exemplary aliphatic amines include methylamine, triisopropanolamine, isopropanolamine, diethanolamine, triethanolamine, ethylenediamine, propylenediamine, butylenediamine, and mixtures of two or more thereof.
  • Amine initiators for polyether adducts are disclosed in, for example, U.S. Patent 4,358,547.
  • catalysts promoting the reacting of alkylene oxide with initiator are used in the preparation of the hydroxyl-terminated polyether.
  • Conventional catalysts include Periodic Group la or Ila alkali or alkaline earth metals or their corresponding hydroxides and alkoxides, Lewis acids, protonic acids or coordination compounds.
  • Preferred catalysts are hydroxides and alkoxides of Group la metals including cesium, sodium, potassium, and Group Ila metals including barium or strontium. Potassium hydroxide is more preferred.
  • the resulting polyethers have an average of from 1 to 8 hydroxyl groups per molecule and an equivalent weight ranging from 50 and up to 50000, preferably from 500 to 10000.
  • the polyether adduct contains from 2 to 8, and preferably from 2 to 4 hydroxyl groups per molecule; the equivalent weight is advantageously from 50 to 5000, preferably from 500 to 4000, and more preferably from 1000 to 3000.
  • this invention pertains to the sulphonic acid ester treatment of a hydroxyl-terminated polyether having a hydroxyl equivalent weight of from 500 to 4000 and being obtained by reacting an initiator containing from 2 to 4 active hydrogen atoms per molecule with an alkylene oxide comprising propylene oxide and optionally ethylene oxide or butylene oxide, in the presence of the metal ion which is sodium, potassium, cesium, barium or strontium.
  • the use of the sulphonic acid ester is particularly well suited to these polyethers providing for finished products not requiring any subsequent removal of metal salts.
  • the metal alkyl sulphonate salt formed during the finishing process remains in the polyether and is present in an amount commensurate with that of the metal ion.
  • the alcohol formed during the finishing process remains in the polyether and is present in an amount commensurate with that of the metal ion.
  • this alcohol content can be reduced by application of reduced pressure.
  • the hydroxyl-terminated polyethers finished in accordance with disclosed process are characterized as being a composition comprising the hydroxyl-terminated polyether, metal sulphonate salt and an alcohol.
  • the amount of metal sulphonate salt and alcohol present will not exceed the equivalent mole concentration of metal ion which has been treated with the sulphonic acid ester.
  • the metal salt is present in from 5 to 1000, more typically in from 5 to 200, and yet more typically in from 5 to 100 ppm of polyether; the alcohol being present in similar amounts unless having been reduced in amount by application of reduced pressure.
  • the amount of alcohol present may be as low as 1, and typically is from 1 to 50, preferably from 1 to 20, ppm of polyether.
  • the hydroxyl-terminated polyethers finished in accordance with disclosed process can be further characterized in that they are substantially free of aldehyde such as, for example, propionaldehyde.
  • aldehyde such as, for example, propionaldehyde.
  • Hydroxyl-terminated polyethers particularly polyether polyols finished according to the above-described process are eminently suitable for the preparation of polyurethane polymer, and especially flexible polyurethane foam as used for cushioning and upholstery applications.
  • Example 1 A crude glycerine-initiated polyoxyethylene-oxypropylene triol (PO/EO weight ratio 87: 13, mixed feed) having a molecular weight of 3000, equivalent weight of 1000, is prepared using conventional methods and using potassium hydroxide to catalyze the alkoxylation reaction. An extraction is conducted to remove potassium hydroxide resulting in a crude polyether containing 100 ppm potassium hydroxide, or alternatively 70 ppm potassium and having a water content of 0.3 wt% .
  • PO/EO weight ratio 87: 13 mixed feed
  • toluene sulphonic acid methyl ester available from Merck, purity 985% in an amount to provide for a 10 mole percent excess relative to the potassium hydroxide. After maintaining the mixture at these conditions for 3 hours, the treated polyol is cooled to room temperature to provide the finished polyether.
  • the residual basicity is reduced to a near zero amount and the polyether now has essentially a neutral pH without loss of unsaturation and the concomitant formation of propionaldehyde.
  • Polyurethane Foam is prepared under handmix conditions according to the formulation given below from the polyethers of Example 1 and Comparative Example 2.
  • a similar foam is prepared from an equivalent polyether polyol (Polyether 3) in which the potassium content has been removed by magnesium silicate adsorption.

Landscapes

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

Abstract

L'invention concerne un procédé de finition de polyéthers à terminaison hydroxyle contenant un ion métal de groupe Ia ou IIa par mise en contact desdits polyéthers avec un ester d'acide sulfonique organique. Les conditions peu agressives du procédé permettent de minimiser la formation de sous-produits indésirables. Ce procédé offre l'avantage écologique et économique de ne pas nécessiter l'extraction et l'élimination des produits ou sous-produits. Lesdits polyéthers finis conviennent parfaitement à des applications de finition dont la préparation des polymères polyuréthanne.
PCT/US1994/013312 1993-12-06 1994-11-15 Procede de finition pour polyethers a terminaison hydroxyle Ceased WO1995015997A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU14082/95A AU1408295A (en) 1993-12-06 1994-11-15 A finishing process for hydroxyl-terminated polyethers

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US16341193A 1993-12-06 1993-12-06
US08/163,411 1993-12-06

Publications (1)

Publication Number Publication Date
WO1995015997A1 true WO1995015997A1 (fr) 1995-06-15

Family

ID=22589916

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1994/013312 Ceased WO1995015997A1 (fr) 1993-12-06 1994-11-15 Procede de finition pour polyethers a terminaison hydroxyle

Country Status (2)

Country Link
AU (1) AU1408295A (fr)
WO (1) WO1995015997A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6969775B2 (en) * 2002-09-19 2005-11-29 The Texas A&M University System Method of producing organic compounds in presence of oxyethylene ether catalyst and in a solvent minimized environment

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS51101099A (ja) * 1975-03-03 1976-09-07 Sanyo Chemical Ind Ltd Horieeteruhorioorunoseiho
JPS6343950A (ja) * 1986-08-12 1988-02-25 Hodogaya Chem Co Ltd ポリエ−テル重合体の熱安定化方法
JPS63308059A (ja) * 1987-06-10 1988-12-15 Toray Ind Inc 帯電防止性を有するポリエステル組成物
JPH04218555A (ja) * 1990-12-13 1992-08-10 Sumitomo Dow Ltd 制電性熱可塑性樹脂組成物

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS51101099A (ja) * 1975-03-03 1976-09-07 Sanyo Chemical Ind Ltd Horieeteruhorioorunoseiho
JPS6343950A (ja) * 1986-08-12 1988-02-25 Hodogaya Chem Co Ltd ポリエ−テル重合体の熱安定化方法
JPS63308059A (ja) * 1987-06-10 1988-12-15 Toray Ind Inc 帯電防止性を有するポリエステル組成物
JPH04218555A (ja) * 1990-12-13 1992-08-10 Sumitomo Dow Ltd 制電性熱可塑性樹脂組成物

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Derwent World Patents Index; AN 76-80091X *
DATABASE WPI Derwent World Patents Index; AN 88-094524(14) *
DATABASE WPI Derwent World Patents Index; AN 89-035356(05) *
DATABASE WPI Derwent World Patents Index; AN 92-312557(38) *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6969775B2 (en) * 2002-09-19 2005-11-29 The Texas A&M University System Method of producing organic compounds in presence of oxyethylene ether catalyst and in a solvent minimized environment

Also Published As

Publication number Publication date
AU1408295A (en) 1995-06-27

Similar Documents

Publication Publication Date Title
US5010187A (en) Production of polyether polyols with reduced unsaturation
US5114619A (en) Production of polyether polyols with reduced unsaturation
EP0383333B1 (fr) Méthode de purification d'un alcool polyoxyalkylénique
RU2089564C1 (ru) Способ получения гидроксифункциональных полиэфиров
KR101173690B1 (ko) Ｄｍｃ-합성된 중간체에 기초한 ｋｏｈ-캡핑된 폴리올의단일 반응기 제조 방법
PL191179B1 (pl) Sposób bezpośredniego polioksyalkilowania startera o niskiej masie cząsteczkowej czułego na kwas w obecności kompleksowego dwumetalowego katalizatora cyjankowego
EP0406440A1 (fr) Production de polyether
EP1212370B1 (fr) Procede de preparation de polyethers
EP0026544A1 (fr) Procédé pour la préparation de sels basiques de barium
EP0369487B1 (fr) Procédé de préparation de polyétherpolyols à insaturation réduite
US5070125A (en) Production of polyether polyols with reduced unsaturation
US5698746A (en) Process for preparing low unsaturation polyether polyols
WO1995015997A1 (fr) Procede de finition pour polyethers a terminaison hydroxyle
JP2989625B2 (ja) ポリエーテル類の製造方法
EP0541244A1 (fr) Elimination de catalyseurs d'alkoxylates d'alcools au moyen d'argiles acides
KR100265869B1 (ko) 폴리올 중의 불포화도를 감소시키는 방법
JP3085740B2 (ja) ポリエーテル類の製造方法
JP2841525B2 (ja) ポリエーテル類の製造方法
JP2745664B2 (ja) ポリエーテル類の製造方法
EP0832147B1 (fr) Procede de preparation de polyols polyether a faible insaturation
JP2830171B2 (ja) ポリエーテル類の製造方法
US11572440B2 (en) Methods for purifying polyols containing oxyalkylene units to reduce 2-methyl-2-pentenal content
EP0876418B1 (fr) Procede de preparation de polyols de polyether a faible insaturation
JP2855705B2 (ja) ポリエーテル類の製造方法
JPH0696635B2 (ja) ポリエーテル類の精製方法

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AU BR CA CN JP KR NO

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FR GB GR IE IT LU MC NL PT SE

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
122 Ep: pct application non-entry in european phase
NENP Non-entry into the national phase

Ref country code: CA