WO2012032006A1 - Procédé de production de polyester-alcools - Google Patents

Procédé de production de polyester-alcools Download PDF

Info

Publication number
WO2012032006A1
WO2012032006A1 PCT/EP2011/065297 EP2011065297W WO2012032006A1 WO 2012032006 A1 WO2012032006 A1 WO 2012032006A1 EP 2011065297 W EP2011065297 W EP 2011065297W WO 2012032006 A1 WO2012032006 A1 WO 2012032006A1
Authority
WO
WIPO (PCT)
Prior art keywords
temperature
acid
reaction
heating
polytetrahydrofuran
Prior art date
Application number
PCT/EP2011/065297
Other languages
German (de)
English (en)
Inventor
Gerlinde Tischer
Ulrike Mahn
Stefan Käshammer
Hermann Graf
Christian Seitz
Christian Nitschke
Dieter Rodewald
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 WO2012032006A1 publication Critical patent/WO2012032006A1/fr

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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/66—Polyesters containing oxygen in the form of ether groups
    • C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/672—Dicarboxylic acids and dihydroxy compounds
    • 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
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4244—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups
    • C08G18/4247—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups derived from polyols containing at least one ether group and polycarboxylic acids
    • C08G18/4252—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups derived from polyols containing at least one ether group and polycarboxylic acids derived from polyols containing polyether groups and polycarboxylic acids
    • 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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes

Definitions

  • the invention relates to a process for the preparation of polyester alcohols based on polytetrahydrofuran and aromatic dicarboxylic acids such as isophthalic acid and the use of these polyester alcohols for the production of polyurethane urea-based elastic fibers (elastane, synonym: spandex) with a particularly flat hysteresis curve, in the literature as "soft elastane or soft spandex.
  • Elastast fibers are for example HJ. Koslowski, "Dictionary of Man-Made Fibers", 1st edition 1998, International Business Press Publishers GmbH, Frankfurt am Main, ISBN 3-87150-583-8, described on page 69ff.
  • polyester alcohols also called polyester polyols
  • polyester polyols by polycondensation reactions of polybasic carboxylic acids with polyhydric alcohols or polyols has been described many times.
  • the plastic handbook Volume VII, Polyurethane, Carl-Hanser-Verlag, Kunststoff, 1st edition 1966, edited by Dr. med. R Vieweg and dr. A. Höchtlen, as well as 2nd edition 1983 and the 3rd revised edition 1993, edited by Dr. med. G. Oertel.
  • polyesterols in particular for the production of polyurethane (PUR) products), in particular of elastic fibers based on polyurethaneurea, which have a particularly flat hysteresis curve, requires careful selection of the starting materials and the polycondensation technology to be carried out.
  • the usual technology is e.g. described in DE-A-2904184, the addition of the reaction components to the start of the synthesis with a suitable catalyst with simultaneous increase in temperature and pressure reduction. The temperatures and the vacuum are then further changed during the synthesis.
  • reaction products In the polycondensation with several acids or alcohols, it is also possible to add individual reaction products only in the course of the reaction. It is usually condensed under atmospheric pressure or a slight vacuum until the removal of the low-boiling components (water, methanol). At the end of the low-boiling point development, other reaction components are optionally added, temperature changes are made, and the beginning of the vacuum phase to the high-vacuum phase postponed.
  • low-boiling components water, methanol
  • Polyester alcohols based on polytetrahydrofuran and isophthalic acid are known per se, e.g. from WO 2007/122124.
  • the aim is to ensure the highest possible functionality of the polyester alcohols. Too low a functionality results in the polyurethane produced therefrom too low molecular weight, which in turn leads to insufficient mechanical properties, since they are positively correlated with the molecular weight.
  • polyester alcohols are generally obtained by condensation of polytetrahydrofuran and isophthalic inadequate functionality.
  • functionality is meant the so-called end group functionality of the polyester alcohol. If all ends of the polyester alcohol molecules carry an OH group, the functionality is 2.000. In the reaction of polyester alcohols with diisocyanates, the higher the functionality of the polyester alcohols, the higher are the chain lengths of the prepolymers.
  • polyesterol object of this invention Since, in the preparation of the polyesterol object of this invention, side reactions occur during the polycondensation resulting in polyester polymer chains having an allyl group at one end and a hydroxyl group at the other end, the functionality of the polyester alcohols becomes higher than the iodine number determined according to DIN 53241-1. This provision is also common in the polyetherols.
  • polyester polyalcohols based on polytetrahydrofuran and aromatic dicarboxylic acids, with which these polyesterols can be prepared simply and economically with high functionality.
  • the object could be achieved by a driving regime at the normal pressure stage of the process for producing polyester alcohols, in which the reaction mixture of the aromatic dicarboxylic acid and / or its anhydrides and polytetrahydrofuran in at least two reaction sections, i. two temperature ramps, which are interrupted by a phase of constant temperature, a temperature plateau.
  • the invention accordingly provides a process for the preparation of polyester alcohols by condensation of polytetrahydrofuran with aromatic carboxylic acids and / or their anhydrides, preferably isophthalic acid, phthalic acid.
  • Terephthalic acid and its anhydrides particularly preferably isophthalic acid, in the presence of a transesterification catalyst such as titanium tetrabutyl orthotitanate, tetraisopropyl orthotitanate, dibutyltin laurate, dibutyltin oxide, tin octoate, tin chloride, tin oxide, sulfuric acid, paratoluenesulphonic acid, potassium hydroxide, sodium methoxide, titanium.
  • a transesterification catalyst such as titanium tetrabutyl orthotitanate, tetraisopropyl orthotitanate, dibutyltin laurate, dibutyltin oxide, tin octoate, tin chloride
  • carrier preferably of tetrabutyl orthotitanate (balance)
  • the polyester alcohols prepared according to the invention from isophthalic acid and polytetrahydrofuran preferably have an iodine value to DIN 53241 -1 of ⁇ 0.5 g 12 / 100g, preferably ⁇ 0.2 g 12 / 100g and particularly preferably ⁇ 0.1 g 12 / 100g ,
  • the functionality of the polyester alcohols produced according to the invention is thus at least 1.94, preferably> 1.976, and particularly preferably> 1.988.
  • the temperature Ti in the first phase, can be achieved by continuous heating (temperature ramp) or this temperature ramp can be interrupted by at least one phase of constant temperature delta Ti (temperature plateau), wherein delta Ti is preferably 1 to 10 ° C. lower than T
  • This second phase can be achieved by continuous heating to the final temperature of the reaction stage at normal pressure T en d or interrupted by at least one phase constant temperature delta T2 (temperature plateau), wherein delta T 2 is preferably 1 to 20 ° C lower than
  • the temperature between the phases of heating to the final temperature of the reaction stage at atmospheric pressure is preferably kept constant twice, corresponding to two temperature plateaus.
  • the temperature is kept constant between the phases of heating preferably twice for 0.5 to 10 hours (hours), preferably for 1 to 5 hours, particularly preferably for 1 to 4 hours.
  • the reaction step under atmospheric pressure corresponds to the time of the heating to T s, and is preferably in a total time of 2 to 15 hours, particularly preferably from 2.5 to 8 hours.
  • the preparation of the polyester alcohols is carried out under Um- or Verest fürsbedingun- conditions and can be done in a solvent.
  • no solvent is used in the reaction of polytetrahydrofuran and aromatic dicarboxylic acids.
  • the condensation of polytetrahydrofuran with aromatic dicarboxylic acids, preferably isophthalic acid, phthalic acid and terephthalic acid, particularly preferably isophthalic acid is advantageously carried out under an inert gas atmosphere. Nitrogen, carbon dioxide or the noble gases can serve as inert gases, for example nitrogen is preferred. Due to the inert gas atmosphere, the oxygen content in the reactor should be reduced to less than 0.1% by volume.
  • the transesterification catalyst used is, for example, tetrabutyl orthotitanate, tetraisopropyl lorthotitanate, dibutyltin laurate, dibutyltin oxide, tin octoate, tin chloride, tin oxide, sulfuric acid, para-toluenesulphonic acid, potassium hydroxide, sodium methoxide, titanium zeolites, lipases or hydrolases immobilized on a support, preferably tetrabutyl orthotitanate, preferably 2 to 4 h after reaching the temperature Te and before applying the vacuum added.
  • concentration of the titanium tetrabutoxide in the solvent is from 1 to 15% by weight, preferably from 2 to 10% by weight and more preferably from 5 to 10% by weight.
  • the reaction stage under vacuum is preferably at a pressure ⁇ 1013 to
  • 2 mbar preferably at 2 to 100 mbar, more preferably at 2 to 50 mbar.
  • the reaction step under vacuum is preferably carried out in a total time of 2 to 15 hours, more preferably 2.5 to 8 hours.
  • aromatic dicarboxylic acids and / or their anhydrides preferably isophthalic acid.
  • PTHF Polytetrahydrofuran
  • telogens chain terminators
  • functional groups can be additionally introduced at one or both ends of the polymer chain.
  • acetic anhydride or water are often used as telogens 19801462 described.
  • PTHF having average molecular weights of from 250 to 3,000 daltons, particularly preferably an average molecular weight of from 250 to 2,000 such as PTHF 250, PTHF 450, PTHF 650, PTHF 1800 and PTHF 2000 is preferably used in the process according to the invention.
  • average molecular weight or “average molecular weight” is understood to mean the number average M n of the molecular weight of the polymers, the determination of which is carried out, for example, by wet-chemical OH number determination.
  • the aromatic dicarboxylic acid used is an aromatic dicarboxylic acid, preferably isophthalic acid, phthalic acid and terephthalic acid, particularly preferably isophthalic acid.
  • isophthalic acid is advantageously polycondensed with polytetrahydrofuran in a molar ratio of 1: 0.9 to 1: 0.5, preferably 1: 0.8 to 1: 0.7, particularly preferably 1: 0.75.
  • inorganic acid in a molar ratio of the catalyst to the phosphoric acid of 1: 1 to 1: 3.5, preferably from 1: 1, 1 to 1: 2.4, particularly preferably 1 .1 to 1: 1, 4 are used.
  • the inorganic acid used is preferably phosphoric acid.
  • polyester alcohols prepared by the process according to the invention can be reacted, for example by reaction with polyisocyanates and downstream with di- and mono-amines to polyurethane urea-based elastic fibers (also known as elastane or spandex fibers) having a particularly flat hysteresis curve.
  • polyurethane urea-based elastic fibers also known as elastane or spandex fibers
  • the process according to the invention leads to a marked improvement in the preparation of polyester alcohols from aromatic dicarboxylic acids, preferably isophthalic acid, phthalic acid and terephthalic acid, particularly preferably isophthalic acid and polytetrahydrofuran.
  • aromatic dicarboxylic acids preferably isophthalic acid, phthalic acid and terephthalic acid, particularly preferably isophthalic acid and polytetrahydrofuran.
  • the polyester alcohols can be produced easily and economically with high functionality.
  • the average molecular weight Mn in the form of the number average molecular weight, defined as the mass of all PTHF molecules divided by their amount in moles, is determined by determining the hydroxyl number in polytetrahydrofuran.
  • the hydroxyl number is understood as meaning that amount of potassium hydroxide in mg which is equivalent to the amount of acetic acid bound in the acetylation of 1 g of substance.
  • the hydroxyl number is determined by the esterification of the hydroxyl groups present with an excess of acetic anhydride.
  • the iodine value was determined by the Kaufmann method (DGF unit method C-V 11 b).
  • the iodine number is a measure of the content of unsaturated carbon-carbon double bonds. The determination is based on the ability of halogens (here bromine) to add to the double bonds. It is determined by the back titration of the unused amount of halogen. It is expressed in g iodine / 100 g substance.
  • the determination of the content of hydroxyl groups was carried out as a determination of the "OH number" according to DIN 53240-2
  • all OH groups were reacted with an excess of acetylating reagent (acetic anhydride) and the excess acid equivalents were measured by volumetric titration with potassium hydroxide.
  • the OH number is understood to be the amount of potassium hydroxide in mg which is equivalent to the amount of acetic acid bound in the acetylation of 1 g of substance. Determination of the functionality of iodine number and OH number
  • the determination of the water content was carried out by Karl Fischer titration. For this purpose, 1 to 3 ml of the sample solution were injected into a machine for determining the water content according to the Karl Fischer method (Metrohm Karl Fischer Coulometer KF756). The measurement was carried out by coulometric method and is based on the Karl Fischer reaction, the water-mediated reaction of iodine with sulfur dioxide.
  • the polymers freed of the solvent are left untreated in a LICO 200 liquid color measuring instrument from Dr. med. Long measured. Precision cuvettes type No. 100-QS (layer thickness 50 mm, Helma) are used. Determination of the acid number (DIN EN 12634)
  • the determination of the ester and carboxylic acid contents of the starting materials (of the carboxy groups present in the mixture) was carried out by determining the "ester number" and the "acid number" by methods known to the person skilled in the art.
  • To determine the acid number all carboxylic acids were neutralized with an excess of potassium hydroxide and the remaining amount of potassium hydroxide was determined by volumetric titration with hydrochloric acid.
  • To determine the saponification number all the esters present were saponified with an excess of ethanolic potassium hydroxide. The remaining amount of potassium hydroxide was determined by volumetric titration with hydrochloric acid.
  • the ester number results from the difference between the saponification number determined in this way and the previously determined acid number.
  • the ester number 5 is understood to mean that amount of potassium hydroxide in mg which is equivalent to the amount of acetic acid bound in the acetylation of 1 g of substance.
  • the device features Anton Paar Drypoint membrane dryer, Haake DC10 thermostat (water temperature 30 ° C) PC with software Rheoplus / 32 V3.10
  • the liquid to be tested is located in the measuring gap of the viscometer between the cone: Anton Paar CP50-1 and the plate: Anton Paar Peltier P-PTD 200 (distance cone plate: 0.05mm), one of which with the Angular velocity Ü rotates (rotor) and the other rests (stator). (Timing: 15 measuring points with 5 seconds (s) measuring point duration (The device needs 2.5 s to adjust the respective shear rate.) For the next 2.5 s, raw measured values are acquired every 2 ms via the torque sensor (1250 values), shear rate: Ramp 10-100 1 / s logarithmic, measuring temperature: 60 ° C, trimming position: 0.06mm, measuring position: 0.05mm).
  • the 15 measuring points are at the shear rates 10; 1 1, 8; 13.9; 16.4; 19.3; 22.8; 26.8; 31, 6; 37.3; 43.9; 51, 8; 61, 1; 72; 84.8; 100 [1 / s], where the value given here is assigned to the shear rate of 100 [1 / s].
  • the quantities of isophthalic acid and polytetrahydrofuran 650 indicated in Table 1 were successively degassed three times in a flask which was capable of heating, stirring and distilling 650, rendered inert with nitrogen and then heated to 180 ° C. under atmospheric pressure.
  • the heating rate was set so that 180 ° C after 2 hours.
  • the polycondensation began. This temperature was kept for 3h. It was then heated to 205 ° C and held this temperature for 2h and then increased to T en d. After this temperature was maintained for 3 hours, before the start of the vacuum phase, titanium tetrabutylate in the form of a 1 wt .-% solution in PTHF 650 were supplied. A vacuum of 20 mbar was applied. Under distillation of water, an acid number less than 1 is achieved within time 1.
  • the system Upon reaching the desired acid number, the system is cooled to 190 ° C. 0.01 1 g (5 ppm) of 85% strength by weight phosphoric acid was added to deactivate the catalyst. It was cooled to room temperature and tested for iodine number, color number, OH number, acid number, viscosity and water content. The following values were determined:
  • Viscosity [mPas, shear rate 100 [1 / s], 60 ° C] 2910
  • the system Upon reaching the desired acid number, the system is cooled to 190 ° C. 0.018 g (8 ppm) of 85% strength by weight phosphoric acid was added to deactivate the catalyst. It was cooled to room temperature and tested for iodine number, color number, OH number, acid number, viscosity and water content. The following values were determined: iodine number [g / 100g] 0.7
  • Viscosity [mPas, shear rate 100 [1 / s], 60 ° C] 2950
  • the system Upon reaching the desired acid number, the system is cooled to 190 ° C. 0.045 g (20 ppm) of 85% strength by weight phosphoric acid was added to deactivate the catalyst. It was cooled to room temperature and tested for iodine number, color number, OH number, acid number, viscosity and water content. The following values were determined:
  • Viscosity [mPas, shear rate 100 [1 / s], 60 ° C] 2918

Abstract

La présente invention concerne un procédé de production de polyester-alcools par condensation de polytétrahydrofurane avec des acides dicarboxyliques aromatiques et/ou leurs anhydrides en présence d'un catalyseur de transestérification selon un mode de fonctionnement en plusieurs étapes à différents niveaux de pression, comprenant au moins une étape réactionnelle à la pression normale et au moins une étape réactionnelle sous vide dans laquelle le distillat est évacué du système réactionnel. Dans l'étape réactionnelle sous pression normale, le mélange réactionnel est chauffé en au moins deux phases, les phases de chauffage étant entrecoupées d'au moins une phase pendant laquelle la température est maintenue constante.
PCT/EP2011/065297 2010-09-07 2011-09-05 Procédé de production de polyester-alcools WO2012032006A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US38035010P 2010-09-07 2010-09-07
US61/380,350 2010-09-07
EP10175595 2010-09-07
EP10175595.7 2010-09-07

Publications (1)

Publication Number Publication Date
WO2012032006A1 true WO2012032006A1 (fr) 2012-03-15

Family

ID=45810148

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2011/065297 WO2012032006A1 (fr) 2010-09-07 2011-09-05 Procédé de production de polyester-alcools

Country Status (1)

Country Link
WO (1) WO2012032006A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016000949A1 (fr) * 2014-07-01 2016-01-07 Basf Coatings Gmbh Produits de réaction à base de polyéther et peintures de base aqueuses contenant lesdits produits de réaction

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1495583A1 (de) * 1961-10-16 1969-04-03 Eastman Kodak Co Verfahren zur Herstellung von elastischem Polyester
DE1770823A1 (de) * 1968-07-09 1972-10-19 Hoechst Ag Thermoplastische Formmassen aus Blockcopolyestern
DE2556149A1 (de) * 1974-12-14 1976-06-16 Teijin Ltd Weiche transparente polyester
DE2904184A1 (de) 1978-03-17 1979-09-20 Gaf Corp Formmasse und die daraus hergestellten spritzguss-formkoerper
DE19801462A1 (de) 1998-01-16 1999-07-22 Basf Ag Katalysator und Verfahren zur Herstellung von Polytetrahydrofuran
WO2007122124A1 (fr) 2006-04-25 2007-11-01 Basf Se Élastomère polyuréthane segmente présentant une résistance accrue a la déchirure

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1495583A1 (de) * 1961-10-16 1969-04-03 Eastman Kodak Co Verfahren zur Herstellung von elastischem Polyester
DE1770823A1 (de) * 1968-07-09 1972-10-19 Hoechst Ag Thermoplastische Formmassen aus Blockcopolyestern
DE2556149A1 (de) * 1974-12-14 1976-06-16 Teijin Ltd Weiche transparente polyester
DE2904184A1 (de) 1978-03-17 1979-09-20 Gaf Corp Formmasse und die daraus hergestellten spritzguss-formkoerper
DE19801462A1 (de) 1998-01-16 1999-07-22 Basf Ag Katalysator und Verfahren zur Herstellung von Polytetrahydrofuran
WO2007122124A1 (fr) 2006-04-25 2007-11-01 Basf Se Élastomère polyuréthane segmente présentant une résistance accrue a la déchirure

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
"Kunststoffhandbuch , Band VII, Polyurethane", vol. VII, 1966, CARL- HANSER-VERLAG
"KUNSTSTOFFHANDBUCH POLYURETHANE", 1983
"KUNSTSTOFFHANDBUCH POLYURETHANE", 1993
H.J. KOSLOWSKI: "Dictionary of Man-Made Fibers", 1998, INTERNATIONAL BUSINESS PRESS PUBLISHERS GMBH, pages: 69FF
N. BARKSBY, G.L. ALLEN, POLYURETHANE WORLD CONGRESS, 1993, pages 445 - 450

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016000949A1 (fr) * 2014-07-01 2016-01-07 Basf Coatings Gmbh Produits de réaction à base de polyéther et peintures de base aqueuses contenant lesdits produits de réaction
US10093814B2 (en) 2014-07-01 2018-10-09 Basf Coatings Gmbh Polyether-based reaction products and aqueous basecoat materials comprising said products

Similar Documents

Publication Publication Date Title
KR101797124B1 (ko) 이량체 지방산 잔기에 기반을 둔 폴리올 및 대응하는 폴리우레탄
EP3717535B1 (fr) Polyester contenant des imides
DE69722010T2 (de) Polyetherpolyol und verfahren zur herstellung von formbaren polyester daraus
EP2513189A1 (fr) Procédé de préparation de polyols de polyester, polyols de polyester préparés à l'aide de ces derniers et polyuréthanes obtenus à partir de ces derniers
EP2352774B1 (fr) Procédé pour produire des polyester-polyols en limitant les rejets de dioxane
WO1994021702A1 (fr) Polyol pour resine de coulee en isocyanate et revetements
EP2490728A1 (fr) Hydrogel biodégradable
WO2012031997A1 (fr) Procédé de production d'alcools de polyester
CN101466768B (zh) 制备聚四氢呋喃或四氢呋喃共聚物的方法
WO2012032006A1 (fr) Procédé de production de polyester-alcools
US20120059142A1 (en) Preparing polyester alcohols
US20120059143A1 (en) Preparing polyester alcohols
KR20160061371A (ko) 공중합체 폴리올
DE60205565T2 (de) Verfahren zur Herstellung vom Copolyesterharz
DE4336534B4 (de) Blockcopolyether über Oxonium-Kupplung von Poly(tetramethylenether)glycolen
DE2555882B2 (de) Verfahren zur Herstellung von Polycarbonaten mit endständigen Hydroxylgruppen
EP1654243A1 (fr) Procede d'obtention d'oligomeres de polytetrahydrofurane ou de copolymeres de tetrahydrofurane
WO2009030619A1 (fr) Procédé de dépolymérisation de mono et/ou de diesters de mélanges contenant du polytétrahydrofurane
WO2010142399A1 (fr) Procédé pour produire des polyester-polyols en limitant les rejets de dioxane
KR0121996B1 (ko) 생분해성을 갖는 지방족 폴리에스테르 수지조성물 및 그 제조방법
WO2022253685A1 (fr) Mousses rigides de pur/pir, procédé de synthèse d'un polyol pour la production de mousses rigides de pur/pir, et procédé de production de mousses rigides de pur/pir
EP4201973A1 (fr) Prépolymère comprenant une séquence de polyoxyméthylène et son procédé de production
WO2004081081A1 (fr) Procede de production de polyesterols a reactivite reduite
WO2002074819A1 (fr) Copolymeres oligomeres d'alcool vinylique
DE10112365A1 (de) Oligomere Vinylacetat/Vinylalkohol-Copolymere

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 11751610

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 11751610

Country of ref document: EP

Kind code of ref document: A1