WO2011110528A1 - Procédé de production de polyols à l'aide d'une catalyse basique - Google Patents

Procédé de production de polyols à l'aide d'une catalyse basique Download PDF

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Publication number
WO2011110528A1
WO2011110528A1 PCT/EP2011/053394 EP2011053394W WO2011110528A1 WO 2011110528 A1 WO2011110528 A1 WO 2011110528A1 EP 2011053394 W EP2011053394 W EP 2011053394W WO 2011110528 A1 WO2011110528 A1 WO 2011110528A1
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ppm
value
determined
exceed
acid
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PCT/EP2011/053394
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German (de)
English (en)
Inventor
Thomas Ostrowski
Anne-Kathrin Merten
Achim LÖFFLER
Hermann Graf
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Basf Se
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Publication of WO2011110528A1 publication Critical patent/WO2011110528A1/fr

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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
    • C08G65/02—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
    • C08G65/2696—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 process or apparatus 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
    • 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
    • C08G18/4829—Polyethers containing at least three hydroxy 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
    • C08G65/2645—Metals or compounds thereof, e.g. salts
    • C08G65/2648—Alkali metals or compounds thereof

Definitions

  • the invention relates to a process for the preparation of polyether alcohols (polyetherols) by catalyzed addition of alkylene oxides to solid starter substances, primarily sucrose, and the use of these polyether alcohols for the preparation of polyurethanes (PUR), in particular PUR foams.
  • polyether alcohols polyetherols
  • PUR polyurethanes
  • alkylene oxides are usually carried out using catalysts.
  • catalysts mainly basic, and in particular alkaline catalysts are used in the art.
  • Basic compounds such as alkali and alkaline earth hydroxides are among the standard catalysts in the preparation of polyether alcohols; Potassium hydroxide (KOH) is the most widely used.
  • alkylene oxide starting materials for the preparation of polyether alcohols are propylene oxide (PO) and / or ethylene oxide (EO).
  • PO propylene oxide
  • EO ethylene oxide
  • Disturbances in the process can occur if the at least one alkylene oxide used, in particular propylene oxide (PO) and / or ethylene oxide (EO), has too high a content of by-products (impurities). Impurities can also by the starting substances, eg. For example, alcohols may be added to the process. however, the present disclosure is particularly concerned with impurities in the alkylene oxide starting materials, such as e.g. EO and PO.
  • Allyl alcohol which can be formed by rearrangement of the PO, acts as a monofunctional starter and lowers the functionality of the polyol. Deviations in OH number and viscosity are the result, as well as deviations in the properties of the polyurethanes produced therefrom.
  • Water as a ubiquitous impurity acts as a bifunctional starter and alters functionality, with consequences as indicated for allyl alcohol.
  • Acid can be present as a mineral acid (for example as hydrochloric acid in the case of PO from the epichlorohydrin process) and / or as an organic carboxylic acid (in the case of PO from the SM / PO or MTBE / PO process).
  • Mineral acid deactivates the basic catalysts used in polyol synthesis, especially when treated with tert.
  • Amine catalysts are co-catalysed, as they are less active compared to the (alkaline) alkali metal hydroxides.
  • Carboxylic acids act similarly, but additionally as monofunctional ler starter.
  • the primary alkoxylated carboxylic acid can be saponified again by the basic catalyst in the presence of traces of water so that diols are formed with release of the carboxylic acid, leading to altered functionality.
  • Acetic acid therefore has almost the same effect as the equivalent amount of water.
  • Carbon dioxide reacts with the basic catalyst to form inorganic carbonates and partly deactivates it.
  • base carbonates form cyclic carbonates with zero functionality.
  • the resulting polyol then does not have the intended functionality, and the OH number is too high, since the carbon dioxide consumes propylene oxide, which is then not available for the chain structure.
  • the object of the invention was thus to improve the basic catalyzed preparation process for polyols with at least one alkylene oxide, such as propylene oxide and / or ethylene oxide, as starting materials so that the above-mentioned problems are avoided; In this case, particular attention was paid to the KOH-catalyzed process.
  • alkylene oxide such as propylene oxide and / or ethylene oxide
  • Figure 1 shows an example of the OH number of a polyol as a function of the content of allyl alcohol in PO.
  • Figure 2 shows an example of the viscosity of a polyol as a function of the content of allyl alcohol in PO.
  • alkoxylations are carried out only with (at least) one alkylene oxide, in particular PO and / or EO, whose added content (s) of the following impurities do not exceed the following defined threshold values:
  • ⁇ content of allyl alcohol which is determined by gas chromatography, of ⁇ 2500 ppm, preferably ⁇ 1700 ppm, particularly preferably ⁇ 1000 ppm
  • ⁇ Content of water determined by Karl Fischer titration, of ⁇ 1700 ppm, preferably of ⁇ 500 ppm, more preferably ⁇ 200 ppm ⁇ content of the acid, in the form of mineral acid and / or organic acid, expressed by the acid-base titration and calculated specific for acetic acid content of ⁇ 100 ppm, preferably ⁇ 40 ppm, particularly preferably ⁇ 20 ppm
  • Carbon dioxide which is determined by KOH titration, of ⁇ 500 ppm, preferably ⁇ 200 ppm, more preferably ⁇ 100 ppm
  • the invention accordingly provides a process for the base-catalyzed preparation of polyetherols, characterized in that at least one alkylene oxide, in particular propylene oxide (PO) and / or ethylene oxide (EO), is used whose or their added contents a) are expressed on aldehydes the contents determined by gas chromatography or by titration with the bisulfite method and calculated for propionaldehyde, the value of 300 ppm and
  • the process according to the invention for preparing polyetherols in the presence of basic catalysts is preferably carried out using a propylene oxide (PO) and / or an ethylene oxide (EO) whose added contents of aldehydes, expressed by gas chromatography or titrimetry with the bisulfite Determined and propionaldehyde calculated levels, do not exceed the value of 120 ppm.
  • PO propylene oxide
  • EO ethylene oxide
  • the process is carried out such that a propylene oxide (PO) and / or an ethylene oxide (EO) is used whose added contents of allyl alcohol are determined by gas chromatography , do not exceed the value of 1000 ppm.
  • the process is carried out such that a propylene oxide (PO) and / or an ethylene oxide (EO) is used whose added contents of water, determined by Fischer titration, the value of 500 ppm, preferably not exceed 200 ppm.
  • the process is carried out such that a propylene oxide (PO) and / or an ethylene oxide (EO) is used whose added contents of acid, expressed by the Acid-base titration determined and calculated for acetic acid contents, the value of 40 ppm not exceed.
  • a propylene oxide (PO) and / or an ethylene oxide (EO) is used whose added contents of acid, expressed by the Acid-base titration determined and calculated for acetic acid contents, the value of 40 ppm not exceed.
  • the process is carried out such that a propylene oxide (PO) and / or an ethylene oxide (EO) is used, whose added contents of carbon dioxide, which are carbonated by Titration, do not exceed the value of 200 ppm.
  • a propylene oxide (PO) and / or an ethylene oxide (EO) is used, whose added contents of carbon dioxide, which are carbonated by Titration, do not exceed the value of 200 ppm.
  • the process is carried out so that only EO is used and wherein the content of water, determined by Karl Fischer titration, the value of 70 ppm, preferred Does not exceed 50 ppm.
  • the analyzes of the respective contaminants were carried out as follows:
  • a) mono- and polyhydric alcohols having functionality F 1-8, for example MEG (monoethylene glycol), DEG (diethylene glycol), TEG (trietylene glycol), PEG (polyethylene glycol); MPG (monopropylene glycol), DPG (dipropylene glycol), TPG (tripropylene glycol), PPG (polypropylene glycol); PTHF (polytetrahydrofuran), glycerol, glycerol alkoxilate with molecular weight ⁇ 10000, TMP (trimethylolpropane), TME, (trimethylolethane), NPG (neopentyl glycol), allyl alcohol alkoxylate with molecular weight ⁇ 1000, sugars and sugar derivatives such as sucrose or sorbitol, bisphenol A, Bisphenol F, pentaerythritol, degraded starch, water, mixtures thereof;
  • hydroxycarboxylic acids hydroxyaldehydes, hydroxyketones; Tridecanol N and polymers thereof; Esters of acrylic acid and methacrylic acid with difunctional alcohols such as HEA (hydroxyethyl acrylate), HPA (hydroxypropyl acrylate), HEMA (hydroxyethylmethyl acrylate), HPMA (hydroxypropyl methacrylate), vinyl ethers such as HBVE (hydroxybutyl vinyl ether); isoprenol; polyester polyols; lower alkoxylates of the abovementioned starters, in particular sucrose, sorbitol; polyesterols,
  • the starters can be submitted to the beginning of the reaction or possibly also added during the process.
  • the alkylene oxides used are preferably selected from the group comprising ethylene oxide and propylene oxide.
  • the basic catalysts are preferably selected from the group comprising alkali metal hydroxides and alkaline earth metal hydroxides and the mono-, di- or trihydric amines; particularly preferred is potassium hydroxide.
  • the process can be carried out as a random or as a block copolymerization using different alkylene oxides.
  • EO / PO Mixtures are randomly polymerized by EO and PO are fed as a mixture, or polymerized in blocks by first pure PO and then pure EO is closed or vice versa.
  • the inventive method can be carried out in a stirred tank, wherein the stirred tank can be equipped with at least one internal and / or at least one external heat exchanger.
  • the addition of the total amount of the catalyst can be carried out at the beginning of the reaction or in portions over the reaction time. Likewise, it is possible to proceed with the starter substance (s).
  • the process according to the invention can be carried out as a batch, semibatch or continuous process.
  • the reaction of the starting substance with the alkylene oxides is carried out at the customary pressures in the range between 0.1 and 1.0 MPa and the usual temperatures in the range between 80 and 160 ° C.
  • the dosing of the alkylene oxides is usually followed by a post-reaction phase to completely react the alkylene oxides.
  • the Rohpolyetheralkohol thus obtained is freed of unreacted alkylene oxide and volatile compounds by distillation or stripping, preferably under vacuum, dehydrated and worked up by acid neutralization and separation of the resulting salts. If amines are used as catalysts, they can remain in the polyol.
  • the subject of the process according to the invention for the preparation of polyetherols in the presence of basic catalysts are also the polyetherols which can be prepared using the process according to the invention.
  • polyether alcohols which can be prepared by the process according to the invention can preferably be reacted with polyisocyanates to give polyurethanes.
  • polyether alcohols according to the invention in the production of polyurethanes allows accurate prediction of the properties of the final product, since the polyether alcohols according to the invention due to the absence of undesirable side reactions with impurities or impurities in the production process have well-defined and predictable properties. Thus, the tailor-made production of polyurethanes with certain properties is possible. In addition, only when using the polyether alcohols according to the invention some desired in polyurethanes specifications such. B. the lowest possible color can be achieved.
  • the use of the polyetherols which can be prepared according to the invention for adjusting PUR (polyurethane) foams is particularly preferred.
  • OH number and the viscosity are determined by standard methods which are familiar to the person skilled in the art.
  • pure propylene oxide a propylene oxide which contains impurities or impurities only up to the following upper limits:
  • Viscosity 960 mPa * s / 25 ° C
  • Viscosity 840 mPa * s / 25 ° C
  • the maximum permitted amount of allyl alcohol was determined.
  • the reason for this was the requirement that the OH number and viscosity should be within the limits of measuring accuracy should not deviate from the comparative batch without contamination.
  • the measurement accuracy for the OH number was one unit (ie 1 mg KOH / g), for the viscosity ⁇ 3% of the measured value (rotational viscometer, at 660 mPa * s therefore about 20 mPa * s). This resulted in the maximum amount of 500 ppm.
  • Figure 1 shows the curve for the OH number
  • Figure 2 for the viscosity
  • the maximum permissible quantity was determined as described in B). The amount was thus 500 ppm.
  • Acetic acid acetic acid pure PO OH number [mg viscosity [ppm] [g] [g] KOH / g] [mPa * s / 25 ° C]

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  • 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 a pour objet un procédé de production de polyéthérols en présence de catalyseurs basiques, caractérisé en ce que de l'oxyde de propylène (PO) et/ou de l'oxyde d'éthylène (EO) sont utilisés, dont : • les teneurs ajoutées en aldéhydes, exprimées par les teneurs déterminées par chromatographie gazeuse ou par titrimétrie avec la méthode du bisulfite et calculées pour le propionaldéhyde, ne dépassent pas la valeur de 300 ppm et • les teneurs ajoutées en alcool allylique, qui sont déterminées par chromatographie gazeuse, ne dépassent pas la valeur de 2 500 ppm et • les teneurs ajoutées en eau, déterminées par dosage de Karl-Fischer, ne dépassent pas la valeur de 1 700 ppm et • les teneurs ajoutées en acide, exprimées par les teneurs déterminées au moyen d'un dosage acido-basique et calculées pour l'acide acétique ne dépassent pas la valeur de 100 ppm et • les teneurs ajoutées en dioxyde de carbone, qui sont déterminées par dosage du KOH, ne dépassent pas la valeur de 500 ppm.
PCT/EP2011/053394 2010-03-09 2011-03-07 Procédé de production de polyols à l'aide d'une catalyse basique WO2011110528A1 (fr)

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EP10155878.1 2010-03-09
EP10155878 2010-03-09

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106248807A (zh) * 2015-06-10 2016-12-21 中国石油天然气股份有限公司 丙烯氧化反应液相产物中乙酸含量的分析方法
CN111430797A (zh) * 2020-04-03 2020-07-17 河南华瑞高新材料有限公司 一种处理再利用水、酸含量高的锂离子电池电解液的方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5133839A (en) * 1991-07-25 1992-07-28 Arco Chemical Technology, L.P. Lower alkylene oxide purification
WO2004076528A1 (fr) * 2003-02-26 2004-09-10 Shell Internationale Research Maatschappij B.V. Procede de preparation de polyether polyols
EP1498414A1 (fr) * 2002-02-15 2005-01-19 Sumitomo Chemical Company, Limited Procede de purification d'oxyde de propylene
WO2005040248A1 (fr) * 2003-10-10 2005-05-06 Shell Internationale Research Maatschappij B.V. Procede de preparation d'un polyol polyether

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5133839A (en) * 1991-07-25 1992-07-28 Arco Chemical Technology, L.P. Lower alkylene oxide purification
EP1498414A1 (fr) * 2002-02-15 2005-01-19 Sumitomo Chemical Company, Limited Procede de purification d'oxyde de propylene
WO2004076528A1 (fr) * 2003-02-26 2004-09-10 Shell Internationale Research Maatschappij B.V. Procede de preparation de polyether polyols
WO2005040248A1 (fr) * 2003-10-10 2005-05-06 Shell Internationale Research Maatschappij B.V. Procede de preparation d'un polyol polyether

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
ALDEHYD-GEHALT: "Method. d. Org. Chemie Bd. 2, Analyt. Method.", vol. 2, 1953, THIEME VERL., article "Disulfit-Methode: Houben-Weyl", pages: 463,464
DR. A. HÖCHTLEN: "POLYURETHANE", 1983
M. LONESCU: "Chemistry and Technology of Polyols for Polyurethanes", RAPRA TECHNOLOGY, 2005
M. SZYCHER: "Szycher's Handbook of Polyurethanes", 1993, CRC PRESS
VON DR. R. VIEWEG: "Polyurethane", vol. VII, 1966, CARL-HANSER-VERLAG, article "Kunststoffhandbuch"

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106248807A (zh) * 2015-06-10 2016-12-21 中国石油天然气股份有限公司 丙烯氧化反应液相产物中乙酸含量的分析方法
CN106248807B (zh) * 2015-06-10 2019-03-12 中国石油天然气股份有限公司 丙烯氧化反应液相产物中乙酸含量的分析方法
CN111430797A (zh) * 2020-04-03 2020-07-17 河南华瑞高新材料有限公司 一种处理再利用水、酸含量高的锂离子电池电解液的方法

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