EP2614100A1 - Procédé de production d'alcools de polyester - Google Patents

Procédé de production d'alcools de polyester

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Publication number
EP2614100A1
EP2614100A1 EP11751906.6A EP11751906A EP2614100A1 EP 2614100 A1 EP2614100 A1 EP 2614100A1 EP 11751906 A EP11751906 A EP 11751906A EP 2614100 A1 EP2614100 A1 EP 2614100A1
Authority
EP
European Patent Office
Prior art keywords
acid
catalyst
temperature
phosphoric acid
reaction
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.)
Withdrawn
Application number
EP11751906.6A
Other languages
German (de)
English (en)
Inventor
Hermann Graf
Ulrike Mahn
Stefan Käshammer
Günter Scherr
Christian Nitschke
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
Priority to EP11751906.6A priority Critical patent/EP2614100A1/fr
Publication of EP2614100A1 publication Critical patent/EP2614100A1/fr
Withdrawn legal-status Critical Current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
    • 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
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • 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
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
    • 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
    • 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
    • C08G63/82—Preparation processes characterised by the catalyst used

Definitions

  • the invention relates to a process for the preparation of polyester alcohols based on polytetrahydrofuran and dicarboxylic acid and the use of these polyester alcohols for the production of polyurethane urea-based elastic fibers (Elastan, synonym: spandex) with a particularly flat hysteresis curve, in the literature as "Soft Elastan “or” Soft Spandex "referred.
  • Elastane fibers are for example in HJ. Koslowski, "Dictionary of Man-Made Fibers", 1st edition 1998, International Business Press Publishers GmbH, Frankfurt am Main, pp. 69ff.
  • polyester alcohols also known as polyesterols
  • polyesterols 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 polyurethane urea, which have a particularly flat hysteresis curve, requires a careful selection of the starting materials and the polycondensation technology to be carried out.
  • PUR polyurethane
  • the usual technology 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 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 evolution, if appropriate, other reaction components are added, temperature changes are made, and the beginning of the vacuum phase is shifted to the high-vacuum phase.
  • low-boiling components water, methanol
  • Polyurethane fibers are prepared from the polyester alcohols thus prepared by reacting with a diisocyanate to form an isocyanate-terminated prepolymer, and further reacting the resulting isocyanate-terminated prepolymer in a suitable solvent with a chain extender, optionally a chain stopper and optionally other additives to the polyurethane elastomer , produced.
  • the polyurethane elastomer is spun with removal of the solvent to form a fiber, which can be carried out in a widespread dry spinning process from a solution of the polyurethane elastomer, for example in dimethylacetamide, dimethylformamide or N-methylpyrrolidone.
  • a catalyst is used in the polycondensation of dicarboxylic acid and polyol, in particular polytetrahydrofuran, it is generally added in such a low concentration that it does not disturb the subsequent processing steps or after reaching the number average molecular weight Mn desired for the polyester alcohol by addition of Deactivation reagent, for example phosphoric acid, deactivated in order not to impair the subsequent reaction with diisocyanate to the prepolymer.
  • Deactivation reagent for example phosphoric acid
  • the aim is thus the production of a polyester polyalcohol with high functionality and at the same time low reactivity. It should be noted that an increase in the catalyst concentration for the purpose of shortening the runtime and resulting increase in functionality leads to an increase in the reactivity.
  • the invention accordingly provides a process for the preparation of polyester alcohols by condensation of polytetrahydrofuran with aromatic dicarboxylic acids and / or their anhydrides and / or their esters, preferably isophthalic acid, Phthalic acid and terephthalic acid, particularly preferably isophthalic acid in the presence of a transesterification catalyst in a multi-stage procedure at different pressure levels with at least one reaction stage at atmospheric pressure and at least one reaction stage under vacuum, is discharged from the reaction system in the distillate, characterized in that after the polycondensation to Deactivation of the catalyst phosphoric acid in a molar ratio of the catalyst to the phosphoric acid of 1: 1 to 1: 3.5 is used.
  • the molar ratio of catalyst to phosphoric acid is preferably 1: 1, 1 to 1: 2.4, more preferably 1: 1 to 1: 1.4.
  • transesterification catalysts examples include tetrabutyl orthotitanate, tetraisopropyl orthotitanate, dibutyltin laurate, dibutyltin oxide, tin octoate, tin chloride, tin oxide, potassium hydroxide, sodium methoxide, titanium zeolites, lipases or hydrolases immobilized on a support, preferably in a concentration of 3 to 100 ppm from 20 to 60 ppm, and more preferably from 40 to 50 ppm. Tetrabutyl orthotitanate is preferred as a catalyst.
  • concentration of the tetrabutyl orthotitanate in the solvent is from 0.1 to 15% by weight, preferably from 2 to 10%.
  • the use of solvent is not required.
  • 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.
  • polytetrahydrofuran is conventionally prepared in a manner known per se by polymerization of tetrahydrofuran - hereinafter referred to as THF - on suitable catalysts
  • THF tetrahydrofuran
  • suitable reagents such reagents being called chain terminators or "telogens”.
  • telogens chain terminators
  • functional groups can additionally be introduced at one or both ends of the polymer chain.
  • acetic anhydride or water are often used as telogens. The method is described, for example, in patent DE 19801462.
  • PTH F having average molecular weights of from 250 to 3000 daltons, more preferably an average molecular weight of from 250 to 2000, such as PTHF 250, PTHF 450, PTHF 650, PTHF 1800 and PTHF 2000 is preferably used in the process according to the invention.
  • PTHF 250, PTHF 450, PTHF 650, PTHF 1800 and PTHF 2000 is preferably used in the process according to the invention.
  • PTHF 250, PTHF 450, PTHF 650, PTHF 1800 and PTHF 2000 is preferably used in the process according to the invention.
  • PTHF 250, PTHF 450, PTHF 650, PTHF 1800 and PTHF 2000 is preferably used in the process according to the invention.
  • PTHF 250, PTHF 450, PTHF 650, PTHF 1800 and PTHF 2000 is preferably used in the process according to the invention.
  • PTHF 650, PTHF 1800 and PTHF 2000 is
  • aromatic dicarboxylic acids especially those having 2 to 12 carbon atoms, are used.
  • Suitable dicarboxylic acids are, for example: adipic acid, succinic acid, glutaric acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, maleic acid, fumaric acid, preferably adipic acid, phthalic acid, isophthalic acid, terephthalic acid and the isomeric naphthalenedicarboxylic acids.
  • the dicarboxylic acids can be used both individually and in admixture with each other. Instead of the dicarboxylic acids, the corresponding dicarboxylic acid derivatives, such as e.g.
  • Dicarboxylic acid esters of alcohols having 1 to 6 carbon atoms or dicarboxylic anhydrides are used.
  • dicarboxylic acid mixtures of succinic, glutaric and adipic acid in proportions of, for example, 20 to 35: 35 to 50: 20 to 32 parts by weight and adipic acid and in particular mixtures of phthalic and / or phthalic anhydride and adipic acid, mixtures of phthalic acid (Anhydride), isophthalic acid and adipic acid or dicarboxylic acid mixtures of succinic, glutaric and adipic acid and mixtures of terephthalic acid and adipic acid or dicarboxylic acid mixtures of succinic, glutaric and adipic acid.
  • aromatic carboxylic acids or mixtures containing aromatic carboxylic acids used. Isophthalic acid is particularly preferably used.
  • the reaction between polytetrahydrofuran and the aromatic dicarboxylic acid and / or its anhydride is carried out under Um- or esterification conditions.
  • the reaction mixture is heated while slowly raising the temperature, for example to a temperature of 150 to 250 ° C, then a vacuum of ⁇ 1013 to 5 hPa is applied, the resulting byproduct is removed by distillation.
  • polytetrahydrofuran is reacted with isophthalic acid in the presence of tetrabutyl orthotitanate in a multi-stage procedure at different pressure levels with at least one reaction stage at atmospheric pressure and at least one reaction stage under vacuum in the distillate is discharged from the reaction system, and in the reaction stage under normal pressure, the reaction mixture is heated in at least two phases, wherein the phases of heating are interrupted by at least one phase in which the temperature is kept constant.
  • 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 also 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 of 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 esterification conditions and can be carried out in a solvent. Preferably, no solvent is used in the reaction of polytetrahydrofuran and aromatic dicarboxylic acids.
  • the condensation of polytetrahydrofuran with aromatic dicarboxylic acids is advantageously carried out under an inert gas atmosphere.
  • inert gases e.g. Nitrogen, carbon dioxide or the noble gases are used, 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 orthotitanate, dibutyltin laurate, dibutyltin oxide, tin octoate, tin chloride, tin oxide, potassium hydroxide, sodium methoxide, titanium zeolites, lipases or hydrolases immobilized on carriers, preferably tetrabutyl orthotitanate, preferably 2 to 4 hours after reaching the temperature Tend and before applying the vacuum added.
  • tetrabutyl orthotitanate in polytetrahydrofuran having an average molecular weight of from 250 to 1000 daltons and / or 1,4-butanediol as a solvent.
  • concentration of titanium tetrabutyl orthotitanate 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. %.
  • solvent is not required.
  • the reaction stage under vacuum is preferably carried out at a pressure ⁇ 1013-2 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.
  • the process according to the invention leads to a marked improvement in the production of polyester alcohols, which show high functionality and low reactivity.
  • the average molecular weight Mn in terms of number average molecular weight, defined as the mass of all PTHF molecules divided by their amount in moles, is determined by the determination of 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 device has Anton Paar Drypoint membrane dryer, Haake DC10 thermostat (water temperature 30 ° C) PC with software Rheoplus / 32 V3.10 (connection via serial interface), compressed air connection (3bar cable).
  • 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).
  • 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 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 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.
  • the terminal double bond of the allyl group is titrated with mercuric acetate / alcoholic potassium hydroxide, i. by determining the unsaturation in milliequivalents per gram of polyol. Out of the unsatisfaction
  • 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 color number was determined in accordance with ASTM D 4890 EN or DIN ISO 6271.
  • the polymers freed from the solvent are left untreated in a LICO 200 liquid colorimeter from Fa. Long measured. Precision cuvettes type No. 100-QS (layer thickness 50 mm, Helma) are used.
  • the determination of the ester and carboxylic acid content of the starting materials was carried out by determining the "ester number" and To determine the acid value, all the carboxylic acids present were neutralized with an excess of potassium hydroxide and the remaining amount of potassium hydroxide was determined by volumetric titration with hydrochloric acid The quantity of potassium hydroxide remaining was determined by volumetric titration with hydrochloric acid, the ester number being the difference between the saponification number determined in this way and the acid number determined in advance, the ester number being 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.
  • the prepolymer was prepared isothermally at a temperature of 70 ° C.
  • the molar ratio of polyester alcohol to: 4,4'-diphenylmethane diisocyanate (MDI) was 1: 2; the batch size is 350g.
  • Polyesterol was placed in the reaction vessel at 70 ° C and stirred. An exact temperature maintenance of +/- 2 ° C is crucial
  • the diphenylmethane diisocyanate (4,4-MDI) was added to the polyesterol and 5, 10, 15, 20, 25, 30, 35, 40, 50, 60, 70 and 80min after addition of MDI samples are taken from the reaction mixture and the NCO- Content determined by titration.
  • NCO titration isocyanate content determination
  • a sample of the prepolymer was added in 30 ml of a mixture of dibutylamine and chlorobenzene in which the concentration of dibutylamine is 0.05 mol / l.
  • the blank value of the mixture was determined against 0.1 molar hydrochloric acid.
  • the mixture including the sample is stirred for 10 -15 min and then admixed with 50 ml of ethanol.
  • the unreacted dibutylamine is mixed with 0.1 molar hydrochloric acid. Taking into account the blank value, the NCO content can be calculated on the basis of the consumption.
  • the system Upon reaching the desired acid number, the system is cooled to 190 ° C. To deactivate the catalyst, 0.045 g (20 ppm, corresponding to a molar ratio of 1: 1, 18) of 85% strength by weight phosphoric acid was added. It was cooled to room temperature and the quality of the polyester alcohol was checked by iodine number, color number, OH number, acid number, viscosity and water content.
  • Viscosity [mPas, shear rate 100 [1 / s], 60 ° C] 2840
  • the system Upon reaching the desired acid number, the system is cooled to room temperature and the quality of the polyester alcohol was checked by iodine number, color number, OH number, acid number, viscosity and water content.
  • Iodine number [g / 100g] ⁇ 0.1
  • Viscosity [mPas, shear rate 100 [1 / s], 60 ° C] 2960
  • the prepolymer was prepared isothermally at 70 ° C.
  • the time decrease of the NCO concentration is shown in Figure 1 (Fig.1).
  • the significantly faster drop in the NCO concentration shows a considerably higher reactivity than in the example according to the invention.
  • This temperature was kept for 3h. Thereafter, it was heated to 205 ° C and held this temperature for 2h and then increased to 220 ° C. After this temperature temperature was maintained for 3 h, before the start of the vacuum phase, 2.25 (10 ppm) of tetrabutyl orthotitanate in the form of a 1 wt .-% solution in PTHF 650 were supplied. A vacuum of 20 mbar was applied. Distillation of water results in an acid number of less than 1 within 22 hours.
  • the system Upon reaching the desired acid number, the system is cooled to 190 ° C. There were added to deactivate the catalyst 0.0675g (30ppm, corresponding to a molar ratio of 1: 8.8) 85 wt .-% phosphoric acid. It was cooled to room temperature and the quality of the polyester alcohol was checked by iodine number, color number, OH number, acid number, viscosity and water content.
  • Viscosity [mPas, shear rate 100 [1 / s], 60 ° C] 3150
  • the prepolymer was prepared isothermally at 70 ° C.
  • the time decrease of the NCO concentration is shown in Figure 1.
  • the significantly faster drop in the NCO concentration shows a higher reactivity than in the example according to the invention.
  • Viscosity [mPas, shear rate 100 [1 / s], 60 ° C] 2920
  • the prepolymer was produced isothermally at 70 ° C.
  • the time decrease of the NCO concentration is shown in Figure 1.
  • the significantly faster drop in the NCO concentration shows a higher reactivity than in the example according to the invention.
  • polytetrahydrofuran 650 polytetrahydrofuran having an average molecular weight of 650 g / mol
  • the heating rate was set so that 180 ° C after 2 hours.
  • Viscosity [mPas, shear rate 100 [1 / s], 60 ° C] 2990
  • the time decrease of the NCO concentration is shown in Figure 1.
  • the significantly faster drop in the NCO concentration shows a higher reactivity than in the example according to the invention.

Abstract

L'invention concerne un procédé de production d'alcools de polyester par condensation de polytétrahydrofurane avec des acides dicarboxyliques aromatiques et/ou leurs anhydrides et/ou leurs esters, de préférence de l'acide isophtalique, de l'acide phtalique et de l'acide téréphtalique, en particulier de préférence de l'acide isophtalique en présence d'un catalyseur de transestérification dans un processus multiétape à des niveaux de pression différents comprenant au moins une étape de réaction à pression normale et au moins une étape de réaction sous vide dans laquelle le distillat est éclusé du système de réaction. L'invention est caractérisée en ce qu'après la polycondensation, de l'acide phosphorique est introduit dans un rapport molaire du catalyseur à l'acide phosphorique de 1:1 à 1:3,5 pour désactiver le catalyseur.
EP11751906.6A 2010-09-07 2011-09-05 Procédé de production d'alcools de polyester Withdrawn EP2614100A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP11751906.6A EP2614100A1 (fr) 2010-09-07 2011-09-05 Procédé de production d'alcools de polyester

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US38033810P 2010-09-07 2010-09-07
EP10175583 2010-09-07
PCT/EP2011/065253 WO2012031997A1 (fr) 2010-09-07 2011-09-05 Procédé de production d'alcools de polyester
EP11751906.6A EP2614100A1 (fr) 2010-09-07 2011-09-05 Procédé de production d'alcools de polyester

Publications (1)

Publication Number Publication Date
EP2614100A1 true EP2614100A1 (fr) 2013-07-17

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EP (1) EP2614100A1 (fr)
KR (1) KR20130114124A (fr)
CN (1) CN103080186A (fr)
WO (1) WO2012031997A1 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
PT3630869T (pt) 2017-05-31 2021-05-18 Basf Se Poliéster alifático-aromático com elevado índice de brancura
WO2019076582A1 (fr) * 2017-10-20 2019-04-25 Henkel Ag & Co. Kgaa Polyols de polyester à base d'acide phtalique à faible viscosité
CN113788949B (zh) * 2021-09-16 2022-08-12 北京化工大学 一种聚酯增塑剂的制备方法及其产品和应用

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1770823A1 (de) * 1968-07-09 1972-10-19 Hoechst Ag Thermoplastische Formmassen aus Blockcopolyestern
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
US20090182113A1 (en) * 2006-04-25 2009-07-16 Basf Se Segmented polyurethane elastomers with high elongation at tear

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2012031997A1 *

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KR20130114124A (ko) 2013-10-16
WO2012031997A1 (fr) 2012-03-15

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