Process for producing a hydroxyl-group terminated polyesterol

Abstract

The present invention relates to a particular process for producing a hydroxyl-group terminated polyesterol via a two-step polycondensation reaction, to the polyesterol obtained by way of this process, and to the use of these polyesterols for producing polyurethanes.

Description

[0001] Process for the preparation of a hydroxyl group-terminated polyesterol

[0002] The present invention relates to a specific process for producing a hydroxyl group-terminated polyesterol via a two-stage polycondensation reaction, the polyesterol obtained by this process, and the use of this polyesterol for producing polyurethanes.

[0003] Hydroxyl-terminated polyesterols are usually produced industrially via condensation reactions by reacting a polyol with a polycarboxylic acid, sometimes in the presence of catalysts, to form the polyesterol and water. The water must be removed from the reaction system. The reactant components are usually initially introduced into the reactor and subsequently converted to the product, whereby the reactor volume can usually only be partially utilized due to the formation of water. WO 2018 / 058016 A1 discloses a process for producing polyester polyols with a high proportion of renewable feedstocks from biological sources. The polyesterol is obtained by reacting biorenewable succinic acid with biorenewable 1,3-propanediol and biorenewable isosorbide.

[0004] The object of the present invention was to provide a process for producing hydroxyl-terminated polyesterols by means of a condensation reaction by reacting a polyol with a polycarboxylic acid and / or a cyclic carboxylic anhydride to form a polyesterol and water, wherein the polyesterol product has a lower acid number of less than 5.0 mgKOH / g, preferably less than 2.0 mgKOH / g, particularly preferably 1.0 mgKOH / g, which is comparably preferably lower than prior art polyesterol production processes for a defined reaction time. A further aspect is the reduction in the reaction time for producing the polyesterol product compared to the mostly single-step prior art production processes while maintaining, preferably improving, product properties, such as, for example, a low acid number of the polyesterol product.In particular, it is also the aim of the invention to maximize the production yield of the process according to the invention in the given reactor volume while minimizing the reaction time, provided that the product properties for the end application remain the same, such as the hydroxyl number, acid number, color number and / or reactivity.

[0005] This object was achieved according to the invention by a process for producing a hydroxyl group-terminated polyesterol comprising the condensation reaction of a polycarboxylic acid and / or a cyclic carboxylic acid anhydride, preferably a polycarboxylic acid, having m(COOH)-mol of carboxyl groups with a polyol having n(OH)-mol of free hydroxyl groups in a reactor comprising the following steps: i) reacting the polycarboxylic acid and / or the cyclic anhydride having m(COOH)-mol of carboxyl groups with a first portion T1 of the polyol having nl(OH)-mol of free hydroxyl groups within the reaction time t1 to form a carboxyl group-terminated polyester intermediate, ii) reacting the carboxyl group-terminated polyester intermediate with a second portion T2 of the polyol having n2(OH)-mol of free hydroxyl groups within the reaction time t2 to form the hydroxyl group-terminated polyesterol;wherein the molar ratio m(COOH) / nl(OH) is greater than 1.0 mol / mol, preferably from 1.05 mol / mol to 1.5 mol / mol and particularly preferably from 1.05 mol / mol to 1.3 mol / mol; wherein m(COOH) < n(OH), preferably m(COOH)+l.0 <n(OH), besonders bevorzugt m(COOH)+l,0 < n(OH) < m(COOH)+2,0 ist; wobei das in Schritt i) gebildete Wasser kontinuierlich oder stufenweise, bevorzugt kontinuierlich aus dem Reaktor entfernt wird; wobei in Schritt i) von 65 mol-% bis 95 mol-%, bevorzugt von 70 mol-% bis 90 mol-% und besonders bevorzugt von 75 mol-% bis 85 mol-% des Polyols bezogen auf die Summe der in Schritt i) und ii) zugegebenen Menge an Polyol zugegeben wird; und wobei die Reaktionszeit tl von 0,60 h / h bis 0,80 h / h, bevorzugt von 0,60 h / h bis 0,75 h / h bezogen auf die Summe der Reaktionszeiten tl und t2 beträgt, und wobei der Reaktordruck in Schritt ii) von 1,0- 10"; 3 bara to 0.55 bara.

[0006] According to the invention, a hydroxyl group-terminated polyesterol is understood to mean a hydroxyl group-terminated compound having at least two ester groups, preferably having at least two terminal hydroxyl groups, wherein the acid number of the polyesterol is less than 5.0 mg KOH / g, preferably less than 2.0 mg KOH / g, particularly preferably 1.0 mg KOH / g, wherein the acid number is determined by means of the method disclosed in the experimental section (measured acid number).

[0007] In one embodiment of the process according to the invention, the hydroxyl-terminated polyesterol has a calculated hydroxyl number of 10 mg KOH / g to 500 mg KOH / g, preferably of 10 mg KOH / g to 400 mg KOH / g and particularly preferably of 15 mg KOH / g to 350 mg.

[0008] According to the invention and in accordance with general technical knowledge, a condensation reaction is understood to mean the reaction of a polyol component having at least two free hydroxyl groups with a polycarboxylic acid and / or a cyclic carboxylic anhydride having at least two carboxyl groups to form the polyester(ol) and water. The carboxyl groups of the cyclic anhydride in the condensation reaction according to the invention can already be present in the molecular structure, as in the case of trimellitic anhydride, or result from the reaction with water and / or the free hydroxyl groups of the polyol, whereby the corresponding reaction forms two carboxyl groups per anhydride group.

[0009] According to the invention, a carboxyl group-terminated polyester intermediate is understood to be the reaction product of a polycarboxylic acid and / or a cyclic carboxylic acid anhydride having m(COOH)-mol carboxyl groups with a first portion TI of the polyol having nl(OH)-mol hydroxyl groups, wherein the molar ratio m(COOH) / nl(OH) is greater than 1.0 mol / mol, preferably from 1.05 mol / mol to 1.5 mol / mol, and particularly preferably from 1.05 mol / mol to 1.3 mol / mol.

[0010] According to the invention, the reaction time, both the reaction time t1 and the reaction time t2, is understood to mean the time below reaction temperature, comprising the metering of a reaction component to the reaction system and the reaction of the reaction components below the reaction temperature thereof. Basically, the invention assumes a condensation reaction between the polycarboxylic acid and / or the cyclic carboxylic anhydride with the polyol to form the carboxyl-terminated polyester intermediate in step i) and the hydroxyl-terminated polyesterol in step ii) starting at a reaction temperature of 150°C. According to the invention, the reaction temperature corresponds to the temperature of the reaction mixture in the reactor, with the temperature measurement being carried out using means customary to the person skilled in the art.

[0011] According to the invention, polycarboxylic acids are understood to mean compounds with two or more (free) carboxyl groups, where the polycarboxylic acid contains m(COOH)-mol of (free) carboxyl groups per molecule. In addition, monocarboxylic acids with only one (free) carboxyl group can also be used. Examples of corresponding monocarboxylic acids are oleic acid and ricinoleic acid. Derivatives of the aforementioned monocarboxylic acids, such as soybean oil or castor oil, can also be used, although this is not preferred according to the invention.

[0012] Polycarboxylic acids include, for example, saturated or unsaturated, linear or branched, aliphatic or cycloaliphatic polycarboxylic acids or optionally branched aromatic polycarboxylic acids having preferably up to 20, particularly preferably up to 10, carbon atoms (including the carbon atoms of the carboxylic acid groups), which may optionally contain heteroatoms from the group consisting of oxygen (regardless of the oxygen atoms of the acid groups), sulfur, nitrogen, and halogens. The polycarboxylic acids preferably contain two free carboxyl groups.

[0013] In one embodiment of the process according to the invention, the polycarboxylic acid is one or more compound(s) and is selected from the group consisting of terephthalic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, brassylic acid, tetradecanedioic acid, thapsiic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid and furandicarboxylic acid, preferably succinic acid, glutaric acid and adipic acid, particularly preferably adipic acid.

[0014] Polycarboxylic acids can be used individually or in mixtures in the process according to the invention.

[0015] According to the invention, cyclic anhydrides are understood to be compounds with at least one anhydride group, where this anhydride group is part of a cyclic ring structure, preferably five-membered or six-membered ring structures. Anhydrides can be formed by intramolecular dehydration of dicarboxylic acids, such as the dehydration of butanedioic acid to form butanedioic anhydride (succinic anhydride).

[0016] In one embodiment of the process according to the invention, the cyclic carboxylic anhydride is one or more compound(s) and is selected from the group consisting of succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, citric anhydride, cis-aconitic anhydride, 2-(2'-carboxyethyl)maleic anhydride, 1-methyl-2-(2'-carboxyethyl)maleic anhydride,

[0017] Phthalic anhydride and trimellitic anhydride, preferably succinic anhydride, maleic anhydride phthalic anhydride and trimellitic anhydride, particularly preferably phthalic anhydride.

[0018] Cyclic carboxylic anhydrides can be used individually or in mixtures in the process according to the invention.

[0019] As a result of the use of the cyclic carboxylic anhydride, the production yield in the given reactor volume is further increased.

[0020] According to the invention, polyols are understood to mean compounds with two or more free hydroxyl groups, wherein the polyol contains n(OH)-mol of free hydroxyl groups per molecule. In addition, monools with only one free hydroxyl group or compounds with one free hydroxyl group and one (free) carboxyl group can also be used, with ricinoleic acid, for example, containing one free hydroxyl group and one carboxyl group each, although the use of these compounds is not preferred according to the invention.

[0021] In one embodiment of the process according to the invention, the proportion of primary hydroxyl groups in the first subset TI of the polyol in step i) is at least 50%, preferably at least 60% and particularly preferably at least 75%, based on the sum of all hydroxyl groups in the first subset TI of the polyol.

[0022] In one embodiment of the process according to the invention, the polyol is one or more compound(s) and is selected from the group consisting of ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, dipropylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, 1,12-dodecanediol, neopentyl glycol, trimethylolpropane, triethylolpropane, castor oil and glycerin, preferably ethylene glycol, diethylene glycol, 1,2-propylene glycol, 1,4-butanediol, particularly preferably 1,4-butanediol and diethylene glycol.

[0023] Polyols can be used individually or as a mixture in the process according to the invention. In one embodiment of the process according to the invention, the polycondensation reaction, ie, step i) and / or ii), is carried out in the presence of a catalyst.

[0024] In a preferred embodiment of the process according to the invention, step ii) is carried out in the presence of a catalyst, wherein tin(II) salts, such as tin dichloride, tin dichloride dihydrate, tin(II) 2-ethylhexanoate, dibutyltin dilaurate; titanium alkoxylates, such as titanium tetrabutoxide, tetraisopropyl titanate; bismuth(III) neodecanoate; zinc(II) acetate; manganese(II) acetate or protonic acids, such as p-toluenesulfonic acid, may be mentioned. Furthermore, the condensation reaction according to the invention can also be catalyzed by enzymes, such as esterases and / or lipases, although corresponding enzymes are not preferred as catalysts according to the invention.

[0025] In one embodiment of the process according to the invention, the catalyst is one or more compound(s) and is selected from the group consisting of tin dichloride, tin dichloride dihydrate, tin(II) 2-ethylhexanoate, dibutyltin dilaurate, titanium tetrabutoxide, tetraisopropyl titanate; bismuth(III) neodecanoate; zinc(II) acetate and manganese(II) acetate.

[0026] In one embodiment of the process according to the invention, the catalyst is used in amounts of 1 ppm to 500 ppm, preferably 2 ppm to 200 ppm, and particularly preferably 5 ppm to 100 ppm, based on the amount of polyol and polycarboxylic acid used. In an alternative embodiment of the process according to the invention, the polycondensation reaction, ie, steps i) and / or ii), is carried out in the absence of a catalyst.

[0027] In one embodiment of the process according to the invention, step i) is carried out at a temperature, ie a reaction temperature step i), of 150 °C to 250 °C, preferably of 155 °C to 240 °C, and particularly preferably of 158 °C to 240 °C.

[0028] In one embodiment of the process according to the invention, step i) is carried out in a reaction time t1 of 30 min to 12 h, preferably of 30 min to 10 h, and particularly preferably of 60 min to 8 h.

[0029] In one embodiment of the method according to the invention, step i) comprises steps i-1) and i-2). In a preferred embodiment of the method according to the invention, step i) consists of steps i-1) and i-2), ie, no further step (method step) is performed in step i).

[0030] In one embodiment of the process according to the invention, the ratio SZ(calculated) / SZ(measured) of the calculated target acid number SZ(calculated) to the measured acid number SZ(measured) for the carboxy group-terminated polyester intermediate in step

[0031] 1) at least 0.45; preferably from 0.50 to 1.0, particularly preferably from 0.53 to 0.90 before the carboxyl group-terminated polyester intermediate is further reacted in step ii); wherein the measured acid number (AQ) was determined by the method disclosed in the experimental section; and wherein the calculated target acid number (AQ) was determined by the method disclosed in the experimental section.

[0032] In one embodiment of the process according to the invention, step i-1) is carried out at a reaction pressure which is greater than that in the subsequent step i-

[0033] 2). Preferably, the reaction pressure in step i-1) is from 1.0 to 103 bara to 1.0 bara, preferably from 300- I 0 3 bara to 1.0 bara and particularly preferably from 500- I 0 3 bara to 1.0 bara. Step i-1) is particularly preferably carried out at standard pressure or ambient pressure.

[0034] In one embodiment of the process according to the invention, step i) comprises steps i-1) and i-2), wherein step i-2) follows step i-1) in time and step i-2) comprises at least 90%, preferably at least 70% and particularly preferably 50% of the reaction time of step i), and wherein the reactor pressure in step i-2) is lower than in step i-1). In a preferred embodiment of the process according to the invention, the reactor pressure in step i-2) is 1.0-10" 3 bara to 1.0 bara, preferably from 1.0-10" 3 bara to 0.55 bara and particularly preferably from 1.0- 10" 3bara to 0.35 bara. In one embodiment of the process according to the invention, step ii) is carried out at the same temperature (reaction temperature) as step i). In a preferred embodiment of the process according to the invention, step ii) is carried out at a temperature of 150°C to 250°C, preferably from 155°C to 240°C, and particularly preferably from 160°C to 240°C.

[0035] In one embodiment of the process according to the invention, the reactor pressure at the beginning of step ii) is identical to the reaction pressure at the end of step i-2).

[0036] According to the invention, the reactor pressure in step ii) is from 1.0 to 10 3 bara to 0.55 bara, preferably from 1.0-10" 3 bara to 0.35 bara.

[0037] The invention further provides a carboxyl group-terminated polyester intermediate obtainable by the process according to the invention, wherein the ratio AN (calculated) / AN (measured) of the calculated target acid number AN (calculated) to the measured acid number AN (measured) for the carboxyl group-terminated polyester intermediate in step i) is at least 0.45; preferably from 0.50 to 1.0, particularly preferably from 0.53 to 0.90. The invention further provides a hydroxyl group-terminated polyesterol obtainable by the process according to the invention, wherein the hydroxyl group-terminated polyesterol has a calculated hydroxyl number of 10 mgKOH / g to 500 mgKOH / g, preferably from 10 mgKOH / g to 400 mgKOH / g and particularly preferably from 15 mgKOH / g to 350 mgKOH / g.

[0038] A further object of the invention is the use of the hydroxyl group-terminated polyesterol prepared by the process according to the invention or the hydroxyl group-terminated polyesterol obtainable by the process according to the invention for producing a polyurethane.

[0039] In a first embodiment, the invention relates to a process for producing a hydroxyl-terminated polyesterol comprising the condensation reaction of a polycarboxylic acid and / or a cyclic carboxylic anhydride, preferably a polycarboxylic acid, having m(COOH)-mol carboxyl groups with a polyol having n(OH)-mol free hydroxyl groups in a reactor comprising the following steps: i) reacting the polycarboxylic acid and / or the cyclic carboxylic anhydride having m(COOH)-mol carboxyl groups with a first portion TI of the polyol having nl(OH)-mol free hydroxyl groups within the reaction time t1 to form a carboxyl-terminated polyester intermediate, ii) reacting the carboxyl-terminated polyester intermediate with a second

[0040] Partial amount T2 of the polyol with n2(OH)-mol of free hydroxyl groups within the reaction time t2 to form the hydroxyl-terminated polyesterol; wherein the molar ratio m(COOH) / nl(OH) is greater than 1.0 mol / mol, preferably from 1.02 mol / mol to 1.5 mol / mol, and particularly preferably from 1.05 mol / mol to 1.3 mol / mol; wherein m(COOH) < n(OH), preferably m(COOH)+1.0 <n(OH), besonders bevorzugt m(COOH)+l,0 < n(OH) < m(COOH)+2,0 ist; wobei das in Schritt i) gebildete Wasser kontinuierlich oder stufenweise, bevorzugt kontinuierlich aus dem Reaktor entfernt wird; wobei in Schritt i) von 62 mol-% bis 95 mol-%, bevorzugt von 64 mol-% bis 90 mol-% und besonders bevorzugt von 75 mol-% bis 85 mol-% des Polyols bezogen auf die Summe der in Schritt i) und ii) zugegebenen Menge an Polyol zugegeben wird;and wherein the reaction time t1 is from 0.58 h / h to 0.95 h / h, preferably from 0.59 h / h to 0.90 h / h and particularly preferably from 0.60 h / h to 0.80 h / h and very particularly preferably from 0.60 h / h to 0.75 h / h, based on the sum of the reaction times t1 and t2;

[0041] In a second embodiment, the invention relates to a process according to the first embodiment, wherein the hydroxyl group-terminated polyesterol has a calculated hydroxyl number of 10 mg KOH / g to 500 mg KOH / g, preferably of 10 mg KOH / g to 400 mg KOH / g and particularly preferably of 15 mg KOH / g to 350 mg KOH / g.

[0042] In a third embodiment, the invention relates to a process according to the first or second embodiment, wherein the polycarboxylic acid is one or more compound(s) and is selected from the group consisting of terephthalic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, brassylic acid, tetradecanedioic acid, thapsiic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid and furandicarboxylic acid, preferably succinic acid, glutaric acid and adipic acid, particularly preferably adipic acid.

[0043] In a fourth embodiment, the invention relates to a process according to any one of the first to third embodiments, wherein the cyclic carboxylic anhydride is one or more compound(s) and is selected from the group consisting of succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, citric anhydride, cis-aconitic anhydride, 2-(2'-carboxyethyl)maleic anhydride, 1-methyl-2-(2'-carboxyethyl)maleic anhydride, phthalic anhydride and trimellitic anhydride, preferably succinic anhydride, maleic anhydride, phthalic anhydride and trimellitic anhydride, particularly preferably phthalic anhydride.

[0044] In a fifth embodiment, the invention relates to a process according to one of the first to fourth embodiments, wherein the proportion of primary hydroxyl groups of the first subset TI of the polyol in step i) is at least 50%, preferably at least 60% and particularly preferably at least 75%, based on the sum of all hydroxyl groups of the first subset TI of the polyol.

[0045] In a sixth embodiment, the invention relates to a process according to any one of the first to fifth embodiments, wherein the polyol is one or more compound(s) selected from the group consisting of ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, dipropylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, 1,12-dodecanediol, neopentyl glycol, trimethylolpropane, triethylolpropane, castor oil, and glycerin, preferably ethylene glycol, diethylene glycol, 1,2-propylene glycol, 1,4-butanediol, particularly preferably 1,4-butanediol and diethylene glycol. In a seventh embodiment, the invention relates to a process according to any one of the first to sixth embodiments, wherein the polycondensation reaction, i.e., step i) and / or ii), is carried out in the presence of a catalyst.

[0046] In an eighth embodiment, the invention relates to a process according to any one of the first to seventh embodiments, wherein step ii) is carried out in the presence of a catalyst.

[0047] In a ninth embodiment, the invention relates to a process according to the seventh or eighth embodiment, wherein the catalyst is one or more compounds and is selected from the group consisting of tin dichloride, tin dichloride dihydrate, tin(II) 2-ethylhexanoate, dibutyltin dilaurate; titanium tetrabutoxide, tetraisopropyl titanate; bismuth(III) neodecanoate; zinc(II) acetate; manganese(II) acetate and p-toluenesulfonic acid, preferably tin dichloride, tin dichloride dihydrate, tin(II) 2-ethylhexanoate, dibutyltin dilaurate, titanium tetrabutoxide, tetraisopropyl titanate; bismuth(III) neodecanoate; zinc(II) acetate and manganese(II) acetate.

[0048] In a tenth embodiment, the invention relates to a process according to any one of the seventh to ninth embodiments, wherein the catalyst is used in amounts of 1 ppm to 500 ppm, preferably 2 ppm to 200 ppm, and particularly preferably 5 ppm to 100 ppm, based on the amount of polyol and polycarboxylic acid used. In an eleventh embodiment, the invention relates to a process according to any one of the first to sixth embodiments, wherein the polycondensation reaction, ie, steps i) and / or ii), is carried out in the absence of a catalyst.

[0049] In a twelfth embodiment, the invention relates to a process according to any one of the first to twelfth embodiments, wherein step i) is carried out at a temperature, ie a reaction temperature step i), of 150 °C to 250 °C, preferably of 170 °C to 240 °C, and particularly preferably of 180 °C to 240 °C.

[0050] In a thirteenth embodiment, the invention relates to a method according to one of the first to twelfth embodiments, wherein

[0051] In a fourteenth embodiment, the invention relates to a process according to any one of the first to thirteenth embodiments, wherein step i) is carried out in a reaction time t1 of 30 min to 12 h, preferably of 30 min to 10 h, and particularly preferably of 60 min to 8 h.

[0052] In a fifteenth embodiment, the invention relates to a method according to one of the first to fourteenth embodiments, wherein step i) comprises steps i-1) and i-2), preferably step i) consists of steps i-1) and i-2).

[0053] In a sixteenth embodiment, the invention relates to a process according to any one of the first to fifteenth embodiments, wherein the ratio SZ(calculated) / SZ(measured) of the calculated target acid number SZ(calculated) to the measured acid number SZ(measured) for the carboxyl group-terminated polyester intermediate in step i) is at least 0.45; preferably from 0.50 to 1.0, particularly preferably from 0.53 to 0.90 before the carboxyl group-terminated polyester intermediate is further reacted in step ii); wherein the measured acid number SZ(measured) was determined by means of the method disclosed in the experimental section; and wherein the calculated target acid number SZ(calculated) was determined by means of the method disclosed in the experimental section

[0054] In a seventeenth embodiment, the invention relates to a process according to the fifteenth or sixteenth embodiment, wherein step i-1) is carried out at a reaction pressure which is greater than that in the subsequent step i-2).

[0055] In an eighteenth embodiment, the invention relates to a process according to any one of the fifteenth to seventeenth embodiments, wherein the reaction pressure in step i-1) is from 1.0 to 10" 3 bara to 1.0 bara, preferably from 300-10 bara to 1.0 bara, and particularly preferably from 500-10 bara to 1.0 bara. In a nineteenth embodiment, the invention relates to a process according to any one of the fifteenth to seventeenth embodiments, wherein step i-1) is carried out at standard pressure or ambient pressure.

[0056] In a twentieth embodiment, the invention relates to a process according to any one of the first to nineteenth embodiments, wherein step i) comprises steps i-1) and i-2), wherein step i-2) follows step i-1) in time and step i-2) comprises at least 90%, preferably at least 70% and particularly preferably 50% of the reaction time of step i), and wherein the reactor pressure in step i-2) is lower than in step i-1).

[0057] In a twenty-first embodiment, the invention relates to a process according to any one of the first to twenty-first embodiments, wherein step ii) is carried out at the same temperature (reaction temperature) as step i).

[0058] In a twenty-second embodiment, the invention relates to a method according to any one of the first to twelfth embodiments, wherein.

[0059] In a twenty-third embodiment, the invention relates to a process according to any one of the first to twenty-second embodiments, wherein step ii) is carried out at a temperature of 150°C to 250°C, preferably of 155°C to 240°C, and particularly preferably of 160°C to 240°C.

[0060] In a twenty-fourth embodiment, the invention relates to a process according to any one of the first to twenty-third embodiments, wherein the reactor pressure at the beginning of step ii) is identical to the reaction pressure at the end of step i-2).

[0061] In a twenty-fifth embodiment, the invention relates to a method according to one of the first to twenty-fourth embodiments, wherein

[0062] In a twenty-sixth embodiment, the invention relates to a process according to any one of the first to twelfth embodiments, wherein the reactor pressure in step ii) is from 1.0 to 10 3bara to 0.35 bara.

[0063] In a twenty-seventh embodiment, the invention relates to a carboxyl group-terminated polyester intermediate obtainable by the process according to the invention, wherein the ratio SZ (calculated) / SZ (measured) of the calculated target acid number SZ (calculated) to the measured acid number SZ (measured) for the carboxyl group-terminated polyester intermediate in step i) is at least 0.45; preferably from 0.50 to 1.0, particularly preferably from 0.53 to 0.90.

[0064] In a twenty-eighth embodiment, the invention relates to a hydroxyl-terminated polyesterol obtainable by the process according to the invention, wherein the hydroxyl-terminated polyesterol has a calculated hydroxyl number of 10 mg KOH / g to 500 mg KOH / g, preferably of 10 mg KOH / g to 400 mg KOH / g and particularly preferably of 15 mg KOH / g to 350 mg KOH / g.

[0065] In a twenty-ninth embodiment, the invention relates to the use of the hydroxyl-terminated polyesterol prepared by the process according to the invention or the hydroxyl-terminated polyesterol obtainable by the process according to the invention for producing a polyurethane.

[0066] 1. Methods and materials

[0067] 1.1 Raw materials used:

[0068] Adipic acid purity >99%

[0069] 1,4-Butanediol purity >99%

[0070] Ethylene glycol purity >99%

[0071] SnCl2-2H2O Purity >97.0%

[0072] Phthalic anhydride purity >99%

[0073] Diethylene glycol purity >99%

[0074] 1.2 Methods used

[0075] The analyses were carried out as follows:

[0076] Hydroxyl number: Blank value determination:

[0077] 20 mL of a phthalic anhydride-pyridine solution is placed in a 250 mL Erlenmeyer flask and refluxed for 50 minutes. Then, 50 mL of pyridine and water are added, and the solution is titrated against an aqueous 1M NaOH solution. The equivalence point is determined using a pH electrode.

[0078] Determination of the hydroxyl number of the analyte:

[0079] The sample is weighed into a 250 mL Erlenmeyer flask and mixed with 20 mL of a phthalic anhydride-pyridine solution. The mixture is then refluxed for 50 minutes. The mixture is then mixed with 50 mL of pyridine and water and titrated against an aqueous 1M NaOH solution. The equivalence point is determined using a pH electrode.

[0080] The sample weight is calculated as follows:

[0081] M(analyte) = molar mass of the analyte in g / mol

[0082] 56100 = Molar mass of KOH in mg KOH / mol = Hydroxyl functionality of the analyte

[0083] Hydroxyl number = in mgKOH / gv(blank value) = volume of the NaOH solution of the blank value determination at the equivalence point of the blank value measurement in mL v(NaOH) = volume of the NaOH solution at the equivalence point of the hydroxyl number determination of the analyte in mL c = concentration of sodium hydroxide solution, 1 mol / 1 t = titer of the sodium hydroxide solution

[0084] 56.1 = molar mass of KOH in g / mol m(weight) = weight of the analyte in g

[0085] Acid number measured: Weigh 3-5 g of sample substance into a 150 mL beaker and dissolve it in a 1:1 ethanol / chlorobenzene mixture. Then, add 5 drops of a saturated thymolphthalein / ethanol solution. For acid numbers > 25 mg KOH / g, titrate against an aqueous 1M NaOH solution until the color changes. For acid numbers < 25 mg KOH / g, titrate against an aqueous 0.1M NaOH solution until the color changes.

[0086] The acid number is calculated using the following equation:

[0087] ".. , , 56, l*c*t*V(NaOH)

[0088] Acid number (measured = - - - - m ßinwaage)

[0089] Acid number (measured) = in mg KOH / g

[0090] 56.1 = Molar mass of KOH in g / mol c = Concentration of sodium hydroxide solution in mol / 1 t = Titer of the corresponding NaOH solution

[0091] V(NaOH) = sodium hydroxide solution consumed during titration of the sample during color change in mL m(sample weight) = sample weight in g Acid number calculated: n(COOH) = Amount of acid groups used to

[0092] Start of i) or ii) in mol n(OH) = Amount of free hydroxyl groups used at the start of i) in mol

[0093] 56.1 = Molar mass of KOH in g / mol m(batch) = Total mass of the batch at time x m(yield) = mass of ester after the reaction in kg ti / t2 = reaction time in h

[0094] 2. Polyesterol synthesis

[0095] 2.1 Example 1: Two-step preparation process of a hydroxyl group-terminated polyesterol comprising the condensation reaction of a polycarboxylic acid with a polyol

[0096] In a first step (step i)), 1493.4 g of adipic acid and 843.7 g (83.8 mol% of the total hydroxyl amount from i) and ii)) of 1,4-butanediol are weighed into a 4 L, 4-neck flask equipped with a mechanical stirrer, heating mantle, bottom thermometer, nitrogen gas connection, diaphragm pump vacuum connection, and a 40 cm packed column with attached column head and intensive condenser. The mixture is heated to 160 °C within 40 minutes. 3.1 h after 150 °C was first exceeded as the bottom temperature, the acid number (measured) is 128 mg KOH / g, corresponding to a conversion of 84%. A vacuum is applied and reduced to 12 mbar within 1 h. After a further 1.75 h, the acid number (measured) of the carboxyl-terminated polyester intermediate is 83.0 mg KOH / g, corresponding to a conversion of 93%. A calculated acid number (measured) of 48.2 mg KOH / g is possible, which would correspond to a conversion of 100%.The batch containing the carboxyl-terminated polyester intermediate formed in step i) is cooled to room temperature. In the subsequent second step (step ii), 163.1 g of 1,4-butanediol (16.2 mol% of the total hydroxyl molar amount from i) and ii)) and 152.9 mg of 28% tin(II) chloride*2H2O in ethylene glycol (20 ppm of tin(II) chloride*2H2O based on the total batch amount) are added to the carboxyl-terminated polyester intermediate from step i). The acid number (calculated) at this point is 75.8 mg KOH / g, which corresponds to a conversion of the carboxyl-terminated polyester intermediate in step ii) of 0%. The mixture is heated to 220 °C within 20 minutes. After the bottom temperature exceeds 150 °C for the first time in step ii), it takes 10 minutes until 220 °C is reached in the bottom. The pressure is reduced to 250 mbar and adjusted to 15 mbar within 55 minutes. Acid number (measured): 13.9 mg KOH / g, conversion 82%.After a further 2.5 h, the acid number is 0.8 mg KOH / g (99% conversion), resulting in the hydroxyl group-terminated polyesterol.

[0097] 2.2 Example 2 (Comparison): Two-stage production process of a hydroxyl group-terminated polysterol comprising the condensation reaction of a polycarboxylic acid with a polyol

[0098] In a first step (step i)), 1493.4 g of adipic acid and 604.1 g (60.0 mol% of the total hydroxyl amount from i) and ii)) of 1,4-butanediol are weighed into a 4 L, 4-neck flask equipped with a mechanical stirrer, heating mantle, bottom thermometer, nitrogen gas connection, diaphragm pump vacuum connection, and a 40 cm packed column with attached column head and intensive condenser. The mixture is heated to 160 °C within 40 minutes. 3.1 h after 150 °C was first exceeded as the bottom temperature, the acid number (measured) is 238 mg KOH / g, corresponding to a conversion of 93%. A vacuum is applied and reduced to 12 mbar within 1 h. After a further 1.75 h, the acid number (measured) of the carboxyl-terminated polyester intermediate is 217 mg KOH / g, corresponding to a conversion of 98%. A theoretical acid number (measured) of 212.7 mg KOH / g is possible, which would correspond to a conversion of 100%.The mixture containing the carboxyl group-terminated polyester intermediate formed in step i) is cooled to room temperature.

[0099] In the subsequent second step (step ii), 402.7 g of 1,4-butanediol (40.0 mol% of the total hydroxyl amount from i) and ii)) and 152.9 mg of 28% tin(II) chloride*2H2O in ethylene glycol (20 ppm of tin(II) chloride*2H2O based on the total batch amount) are added to the carboxyl-terminated polyester intermediate from step i). The acid number (calculated) at this point is 178.3 mg KOH / g, which corresponds to a conversion of the carboxyl-terminated polyester intermediate in step ii) of 0%. The mixture is heated to 220 °C within 20 minutes. After the bottom temperature exceeds 150 °C for the first time in step ii), it takes 10 minutes until 220 °C is reached in the bottom. The pressure is reduced to 250 mbar and adjusted to 15 mbar within 55 minutes. Acid number (measured): 20.6 mg KOH / g, conversion 89%. After another 2.5 h, the acid number is 1.7 mg KOH / g (99% conversion).An acid number (measured) of 0.9 mg KOH / g (99% conversion) is present after a further 55 minutes, resulting in the hydroxyl group-terminated polyesterol.

[0100] 2.3 Example 3 (Comparison): One-step production process of a hydroxyl group-terminated polysterol comprising the condensation reaction of a polycarboxylic acid with a polyol

[0101] In a first step (step i)), 1493.4 g of adipic acid and 1006.8 g (100 mol% of the total hydroxyl content) of 1,4-butanediol are weighed into a 4 L, 4-neck flask equipped with a mechanical stirrer, heating mantle, bottom thermometer, nitrogen gas connection, diaphragm pump vacuum connection, and a 40 cm packed column with attached column head and intensive condenser. The mixture is heated to 160 °C within 40 minutes. 3.1 h after 150 °C was first exceeded as the bottom temperature, the acid number (measured) is 92 mg KOH / g, corresponding to a conversion of 82%. A vacuum is applied and reduced to 12 mbar within 1 h. After a further 1.75 h, the acid number (measured) of the carboxyl-terminated polyester intermediate is 32 mg KOH / g, corresponding to a conversion of 94%. A mathematically possible acid number (measured) of 0 mg KOH / g is possible, which would correspond to a conversion of 100%.The mixture containing the carboxyl group-terminated polyester intermediate formed in step i) is cooled to room temperature.

[0102] In the subsequent second step (step ii), 152.9 mg of tin(II) chloride*2H2O at 28% strength in ethylene glycol (20 ppm of tin(II) chloride*2H2O based on the total batch amount) are added to the carboxyl group-terminated polyester intermediate from step i). The mixture is heated to 220 °C within 20 minutes. After 150 °C is exceeded as the bottom temperature for the first time in step ii), it takes 10 minutes until 220 °C is reached in the bottom, the pressure is reduced to 250 mbar and adjusted to 15 mbar within 55 minutes. Acid number (measured): 7.3 mg KOH / g, conversion 99%. After a further 2.5 h, the acid number is 1.6 mg KOH / g (99% conversion). An acid number (measured) of 0.8 mg KOH / g (100% conversion) is present after a further 55 minutes, resulting in the hydroxyl group-terminated polyesterol.

[0103] 2.4 Example 4 (Comparison): Two-stage production process of a hydroxyl group-terminated polyesterol with a polyol

[0104] In a first step (step i)), 1493.4 g of adipic acid and 843.7 g (83.8 mol% of the total hydroxyl amount from i) and ii)) of 1,4-butanediol are weighed into a 4 L, 4-neck flask equipped with a mechanical stirrer, heating mantle, bottom thermometer, nitrogen gas connection, diaphragm pump vacuum connection, and a 40 cm packed column with attached column head and intensive condenser. The mixture is heated to 160 °C within 30 minutes. 3.1 h after 150 °C is first exceeded as the bottom temperature, vacuum is applied and reduced to 16 mbar within 1.5 h. After a further 0.5 h, the acid number (measured) of the carboxyl group-terminated polyester intermediate is 86.5 mg KOH / g, corresponding to a conversion of 92%. A calculated acid number (measured) of 48.2 mg KOH / g is possible, which would correspond to a conversion of 100%. The batch containing the carboxyl-terminated polyester intermediate formed in step i) is cooled to room temperature.

[0105] In the subsequent second step (step ii), 163.1 g of 1,4-butanediol (16.2 mol % of the total hydroxyl amount from i) and ii)) and 152.9 mg of 28% tin(II) chloride*2H2O in ethylene glycol (20 ppm of tin(II) chloride*2H2O based on the total batch amount) are added to the carboxyl-terminated polyester intermediate from step i). The acid number (calculated) at this point is 80.5 mg KOH / g, which corresponds to a conversion of the carboxyl-terminated polyester intermediate in step ii) of 0%. The mixture is heated to 220 °C within 35 minutes. After the bottom temperature exceeds 150 °C for the first time in step ii), it takes 15 minutes until 220 °C is reached in the bottom. The pressure is reduced to 250 mbar and adjusted to 15 mbar within 50 minutes. Acid number (measured): 17.0 mg KOH / g, conversion 79%. After another 2.5 h, the acid number is 2.6 mg KOH / g (97% conversion).An acid number (measured) of 0.8 mg KOH / g (99% conversion) is present after a further 1.58 hours, resulting in the hydroxyl group-terminated polyesterol.

[0106] 2.5 Example 5 (Comparison): Two-stage production process for a hydroxyl group-terminated polyesterol with a polyvol. In a first step (step i)), 1493.4 g of adipic acid and 843.7 g (83.8 mol% of the total hydroxyl amount from i) and ii)) of 1,4-butanediol are weighed into a 4 L, 4-neck flask equipped with a mechanical stirrer, heating mantle, bottom thermometer, nitrogen gas connection, diaphragm pump vacuum connection, and a 40 cm packed column with attached column head and intensive condenser. The mixture is heated to 160 °C within 25 minutes. 3.1 h after 150 °C was first exceeded as the bottom temperature, the acid number (measured) is 124 mg KOH / g, which corresponds to a conversion of 82%. A vacuum is applied and reduced to 14 mbar within 1 h. After a further 4.8 h, the acid number (measured) of the carboxyl-terminated polyester intermediate is 65.0 mg KOH / g, corresponding to a conversion of 96%.A calculated acid number (measured) of 48.2 mg KOH / g is possible, which would correspond to a conversion of 100%. The batch containing the carboxyl-terminated polyester intermediate formed in step i) is cooled to room temperature. In the subsequent second step (step ii), 163.1 g of 1,4-butanediol (16.2 mol% of the total hydroxyl amount from i) and ii)) and 152.9 mg of tin(II) chloride*2H2O at 28% in ethylene glycol (20 ppm of tin(II) chloride*2H2O based on the total batch amount) are added to the carboxyl-terminated polyester intermediate from step i). The acid number (calculated) at this point is 60.1 mg KOH / g, which corresponds to a conversion of the carboxyl-terminated polyester intermediate in step ii) of 0%. The mixture is heated to 220 °C within 30 minutes.After the bottom temperature exceeds 150 °C for the first time in step ii), it takes 10 minutes to reach 220 °C in the bottom. The pressure is reduced to 250 mbar and adjusted to 15 mbar within 55 minutes. Acid number (measured): 21.9 mg KOH / g, conversion 63.6%. After another 40 minutes, the acid number is 11.8 mg KOH / g (80.4% conversion), resulting in the hydroxyl-terminated polyesterol.

[0107] 2.6 Example 6 one terminated Polvesterol with a Polvol

[0108] In a first step (step i)), 1493.4 g of adipic acid and 843.7 g (83.8 mol% of the total hydroxyl amount from i) and ii)) of 1,4-butanediol are weighed into a 4 L, 4-neck flask equipped with a mechanical stirrer, heating mantle, bottom thermometer, nitrogen gas connection, diaphragm pump vacuum connection, and a 40 cm packed column with attached column head and intensive condenser. The mixture is heated to 160 °C within 40 minutes. 3.1 h after 150 °C was first exceeded as the bottom temperature, the acid number (measured) is 126 mg KOH / g, corresponding to a conversion of 81%. A vacuum is applied and reduced to 12 mbar within 1 h. After a further 1.75 h, the acid number (measured) of the carboxyl-terminated polyester intermediate is 89.0 mg KOH / g, corresponding to a conversion of 90%. A calculated acid number (measured) of 48.2 mg KOH / g is possible, which would correspond to a conversion of 100%.The batch containing the carboxyl-terminated polyester intermediate formed in step i) is cooled to room temperature. In the subsequent second step (step ii), 163.1 g of 1,4-butanediol (16.2 mol% of the total hydroxyl molar amount from i) and ii)) and 152.9 mg of 28% tin(II) chloride*2H2O in ethylene glycol (20 ppm of tin(II) chloride*2H2O based on the total batch amount) are added to the carboxyl-terminated polyester intermediate from step i). The acid number (calculated) at this time is 82 mg KOH / g, which corresponds to a conversion of the carboxyl-terminated polyester intermediate in step ii) of 0%. The mixture is heated to 220 °C within 30 minutes. After the bottom temperature exceeds 150 °C for the first time in step ii), it takes 10 minutes for the bottom temperature to reach 220 °C. After 5 hours at ambient pressure and 220 °C in the bottom, the acid number (measured) is 21.0 mg KOH / g, conversion 65.1%.

[0109]

[0110] 2.7 Example 7: Two-step preparation process of a hydroxyl group-terminated polyesterol comprising the condensation reaction of a polycarboxylic acid and a cyclic carboxylic acid anhydride with a polyol

[0111] In a first step (step i)), 961.1 g of phthalic anhydride, 334.0 g of adipic acid, 489.6 g of diethylene glycol, and 228.4 g of ethylene glycol (62 mol% of the total hydroxyl content from i) and ii)) are weighed into a 4 L, 4-neck flask equipped with a mechanical stirrer, heating mantle, bottom thermometer, nitrogen gas connection, diaphragm pump vacuum connection, and a 40 cm packed column with attached column head and intensive condenser. The mixture is heated to 160 °C within 20 minutes. 3.1 h after the bottom temperature exceeds 150 °C for the first time, a vacuum is applied and reduced to 20 mbar within 55 minutes. After a further 1.75 h, the acid number (measured) of the carboxyl-terminated polyester intermediate is 109 mg KOH / g, corresponding to a conversion of 83%. A theoretical acid number (measured) of 29.3 mg KOH / g is possible, which would correspond to a conversion of 100%.The mixture containing the carboxyl group-terminated polyester intermediate formed in step i) is cooled to room temperature.

[0112] In the subsequent second step (step ii), 318.4 g of ethylene glycol (38 mol% of the total hydroxyl amount from i) and ii)) and 152.9 mg of 28% tin(II) chloride*2H2O in ethylene glycol (20 ppm of tin(II) chloride*2H2O based on the total batch amount) are added to the carboxyl-terminated polyester intermediate from step i). The acid number (calculated) at this point is 93.3 mg KOH / g, which corresponds to a conversion of the carboxyl-terminated polyester intermediate in step ii) of 0%. The mixture is heated to 220 °C within 35 minutes. After the bottom temperature exceeds 150 °C for the first time in step ii), it takes 15 minutes until 220 °C is reached in the bottom. The pressure is reduced to 700 mbar and adjusted to 300 mbar within 1.33 h. Acid number (measured): 4.1 mg KOH / g, conversion 95.7%.After a further 35 minutes, an acid number of 1.7 mg KOH / g (98% conversion) is present, resulting in the hydroxyl group-terminated polyesterol.

[0113] 2.8 Example 8 one terminated polyesterol comprising the condensation reaction of a polycarboxylic acid and a cyclic carboxylic acid anhydride with a polyol

[0114] In a first step (step i)), 961.1 g of phthalic anhydride, 334.0 g of adipic acid, 489.6 g of diethylene glycol, and 228.4 g of ethylene glycol (62 mol% of the total hydroxyl content from i) and ii)) are weighed into a 4 L, 4-neck flask equipped with a mechanical stirrer, heating mantle, bottom thermometer, nitrogen gas connection, diaphragm pump vacuum connection, and a 40 cm packed column with attached column head and intensive condenser. The mixture is heated to 160 °C within 20 minutes. 3.1 h after the bottom temperature exceeds 150 °C for the first time, a vacuum is applied and reduced to 20 mbar within 60 minutes. After another 60 minutes, the acid number (measured) of the carboxyl-terminated polyester intermediate is 127 mg KOH / g, corresponding to a conversion of 80%. A theoretical acid number (measured) of 29.3 mg KOH / g is possible, which would correspond to a conversion of 100%.The mixture containing the carboxyl group-terminated polyester intermediate formed in step i) is cooled to room temperature.

[0115] In the subsequent second step (step ii), 318.4 g of ethylene glycol (38 mol% of the total hydroxyl amount from i) and ii)) and 152.9 mg of 28% tin(II) chloride*2H2O in ethylene glycol (20 ppm of tin(II) chloride*2H2O based on the total batch amount) are added to the carboxyl-terminated polyester intermediate from step i). The acid number (calculated) at this point is 108.8 mg KOH / g, which corresponds to a conversion of the carboxyl-terminated polyester intermediate in step ii) of 0%. The mixture is heated to 220 °C within 35 minutes. After the bottom temperature exceeds 150°C for the first time in step ii), it takes 15 minutes for the bottom temperature to reach 220°C. The pressure is then reduced to 700 mbar and adjusted to 300 mbar within 1.42 h. Acid number (measured): 7.0 mg KOH / g, conversion 94%.After a further 2.67 hours, an acid number of 1.8 mg KOH / g (98% conversion) is present, resulting in the hydroxyl group-terminated polyesterol.

[0116]

Claims

1. A process for producing a hydroxyl-terminated polyesterol comprising the condensation reaction of a polycarboxylic acid and / or a cyclic carboxylic anhydride, preferably a polycarboxylic acid, having m(COOH)-mol of carboxyl groups with a polyol having n(OH)-mol of free hydroxyl groups in a reactor comprising the following steps: i) reacting the polycarboxylic acid and / or the cyclic carboxylic anhydride having m(COOH)-mol of carboxyl groups with a first portion T1 of the polyol having nl(OH)-mol of free hydroxyl groups within the reaction time t1 to form a carboxyl-terminated polyester intermediate, ii) reacting the carboxyl-terminated polyester intermediate with a second portion T2 of the polyol having n2(OH)-mol of free hydroxyl groups within the reaction time t2 to form the hydroxyl-terminated polyesterol;wherein the molar ratio m(COOH) / nl(OH) is greater than 1.0 mol / mol, preferably from 1.02 mol / mol to 1.5 mol / mol, and particularly preferably from 1.05 mol / mol to 1.3 mol / mol; wherein m(COOH) < n(OH), preferably m(COOH)+l.0 <n(OH), besonders bevorzugt m(COOH)+l,0 < n(OH) < m(COOH)+2,0 ist; wobei das in Schritt i) gebildete Wasser kontinuierlich oder stufenweise, bevorzugt kontinuierlich aus dem Reaktor entfernt wird; wobei in Schritt i) von 62 mol-% bis 95 mol-%, bevorzugt von 64 mol-% bis 90 mol-% und besonders bevorzugt von 75 mol-% bis 85 mol-% des Polyols bezogen auf die Summe der in Schritt i) und ii) zugegebenen Menge an Polyol zugegeben wird; wobei die Reaktionszeit tl von 0,60 h / h bis 0,80 h / h und bevorzugt von 0,60 h / h bis 0,75 h / h bezogen auf die Summe der Reaktionszeiten tl und t2 beträgt; und wobei der Reaktordruck in Schritt ii) von 1,0- 10"; 3 bara to 0.55 bara.

2. The process according to claim 1, wherein the hydroxyl group-terminated polyesterol has a calculated hydroxyl number of 10 mg KOH / g to 500 mg KOH / g, preferably of 10 mg KOH / g to 400 mg KOH / g and particularly preferably from 15 mg KOH / g to 350 mg KOH / g.

3. The process according to claim 1 or 2, wherein the proportion of primary hydroxyl groups of the first subset TI of the polyol in step i) is at least 50%, preferably at least 60% and particularly preferably at least 75%, based on the sum of all hydroxyl groups of the first subset TI of the polyol.

4. The process according to any one of claims 1 to 3, wherein the polyol is one or more compound(s) selected from the group consisting of ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, dipropylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, 1,12-dodecanediol, neopentyl glycol, trimethylolpropane, triethylolpropane, castor oil and glycerin, preferably ethylene glycol, diethylene glycol, 1,2-propylene glycol, 1,4-butanediol, particularly preferably 1,4-butanediol and diethylene glycol.

5. A process according to any one of claims 1 to 4, wherein the polycarboxylic acid is one or more compounds selected from the group consisting of phthalic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, brassylic acid, tetradecanedioic acid, thapsiic acid, maleic acid, fumaric acid, Citraconic acid, mesaconic acid and furandicarboxylic acid, preferably succinic acid, glutaric acid and adipic acid, particularly preferably adipic acid.

6. A process according to any one of claims 1 to 5, wherein the cyclic carboxylic anhydride is one or more compounds and is selected from the group consisting of succinic anhydride, maleic anhydride, glutaric anhydride, Itaconic anhydride, citric anhydride, cis-aconitic anhydride, 2-(2'-carboxyethyl)maleic anhydride, 1-methyl-2-(2'-carboxyethyl)maleic anhydride, phthalic anhydride and trimellitic anhydride, preferably succinic anhydride, maleic anhydride, phthalic anhydride and trimellitic anhydride, particularly preferably phthalic anhydride.

7. A process according to any one of claims 1 to 6, wherein step i) is carried out at a temperature of 150 °C to 250 °C, preferably from 155 °C to 240 °C, and particularly preferably from 158 °C to 240 °C.

8. The process according to any one of claims 1 to 7, wherein step i) is carried out in a reaction time t1 of 30 min to 12 h, preferably of 30 min to 10 h, and particularly preferably of 60 min to 8 h.

9. The process according to any one of claims 1 to 8, wherein step i) comprises steps i-1) and i-2), wherein step i-1) follows step i-2) in time and step i-2) comprises at least 90%, preferably at least 70% and particularly preferably 50% of the reaction time t1 of step i), and wherein the reactor pressure in step i-2) is lower than in step i-1).

10. The process according to claim 9, wherein the reactor pressure in step i-2) is from 1.0 to 10" 3 bara to 1.0 bara, preferably from 1.0-10" 3 bara to 0.55 bara and particularly preferably from 1.0- 10" 3 bara to 0.35 bara.

11. The process according to any one of claims 1 to 10, wherein step ii) is carried out at a temperature of from 150°C to 250°C, preferably from 155°C to 240°C, and particularly preferably from 160°C to 240°C.

12. A process according to any one of claims 1 to 11, wherein the reactor pressure in step ii) is from 1.0 to 10 3 bara to 0.35 bara.

13. A process according to any one of claims 1 to 12, wherein step ii) is carried out in the presence of a catalyst.

14. Hydroxyl group-terminated polyesterol obtainable by the process according to any one of claims 1 to 12, wherein the hydroxyl group-terminated polyesterol has a calculated hydroxyl number of 10 mg KOH / g to 500 mg KOH / g, preferably of 10 mg KOH / g to 400 mg KOH / g and particularly preferably of 15 mg KOH / g to 350 mg KOH / g.

15. Use of the hydroxyl group-terminated polyesterol prepared by the process according to any one of claims 1 to 13 or of the hydroxyl group-terminated polyesterol according to 14 for producing a polyurethane.

Images