Processes for preparing a mixture that contains a polyoxyalkylene polyol

Abstract

The invention relates to processes for preparing a mixture that contains a polyoxyalkylene polyol, preferably a polyether polyol, to the mixtures obtainable by the process and to a mixture that contains a polyoxyalkylene polyol, preferably a polyether polyol and an alkoxylated oxoacid of phosphorus.

Description

[0001] Process for preparing a mixture containing a polyoxyalkylene polyol

[0002] The present invention relates to processes for producing a mixture comprising a polyoxyalkylene polyol, preferably a polyether polyol, the mixture obtainable by the process and a mixture comprising a polyoxyalkylene polyol, preferably a polyether polyol and an alkoxylated oxygen acid of phosphorus.

[0003] Polyoxyalkylene polyols suitable for the production of polyurethanes can be obtained using various manufacturing processes. Of industrial importance are, on the one hand, the base-catalyzed addition of alkylene oxides to H-functional starter compounds, and, on the other hand, the use of double metal cyanide compounds as catalysts ("DMC catalysts") for the addition of alkylene oxides to H-functional starter compounds. However, the production of short-chain polyoxyalkylene polyols with hydroxyl numbers (OH numbers) greater than approximately 300 mg KOH / g is hardly feasible with DMC catalysts, since these exhibit only low activity in the presence of high concentrations of hydroxyl groups or cannot be activated in the presence of high concentrations of hydroxyl groups.The addition of alkylene oxides to suitable starter compounds catalyzed by (Lewis) acids is of minor importance due to the tendency to form undesirable low-molecular-weight byproducts, particularly in the production of long-chain polyoxyalkylene polyols. Amines can generally be used as catalysts for the addition of alkylene oxides to starter compounds; heterocyclic amines such as imidazole and its derivatives have proven particularly suitable for this purpose. With these catalysts, OH numbers of at least about 200 mg KOH / g are accessible (equivalent molar mass approximately 280 g / mol). A disadvantage of using amine catalysts in many cases is that their residues remaining in the final product often impart undesirable reactivity to polyurethane systems.For the production of short-chain polyoxyalkylene polyols with high OH numbers of 400 mg KOH / g or higher, acid catalysis represents, in principle, a technically interesting alternative to base catalysis, since the tendency to form low-molecular-weight by-products is still relatively low in this hydroxyl number range. The authors consider the use of phosphorus oxygen acids, especially phosphoric acid itself, as catalysts to be particularly attractive in this context, as these are converted into their esters by alkoxylation, thus allowing the production of high-quality, short-chain polyoxyalkylene polyols that are free of catalyst residues or contain only small traces of catalyst without further processing steps.Presumably due to the advantageous fact that the catalytic activity of the phosphorus oxoacids is lost during alkylation, it proves extremely difficult to obtain polyols with OH numbers of less than 450 mg KOH / g using only a phosphorus oxoacid as catalysis, especially if the end products are not to contain excessively high levels of phosphorus oxoacid esters. The object of the present invention was therefore to provide a simple process for obtaining polyoxyalkylene polyols in the OH number range of 250 mg KOH / g to 600 mg KOH / g that contain no alkali or alkaline earth metal residues or any other catalyst residues that might influence subsequent foaming reactions, such as large concentrations of free amines. Furthermore, the process should be characterized by smooth uptake of the alkylene oxide.

[0004] The state of the art in the field of (Lewis) acid catalyzed processes, or processes that combine DMC and acid catalysis, is as follows:

[0005] EP 1125961 A1 discloses hydrophobic polyethers with more than 40% primary OH groups, which can be prepared exclusively from propylene oxide, i.e., without the use of ethylene oxide. The high content of primary OH groups is achieved by using Lewis acid catalysts based on boron and Al with phenyl radicals. B(C6Fs)3 and Al(C6p5)3 are particularly recommended. In the examples, very small amounts of catalyst are sufficient if the catalyst is added continuously to the starter with the alkylene oxide. In the examples, only long-chain polyols with maximum OH numbers of 56 mg KOH / g are produced. Prefabricated alkylene oxide adducts are used as starters for their preparation. A disadvantage of this disclosed process is the high moisture sensitivity of the tris(pentafluoro)phenylborane or tris(pentafluoro)phenylaluminum.The examples of EP 2415798 A1 also exclusively use the Lewis acid catalyst tris(pentafluoro)phenylborane, but here with the aim of obtaining long-chain polyethers with a relatively low content of unsaturated end groups while simultaneously using only small amounts of ethylene oxide.

[0006] Patent application WO 2016 / 064698 A1 discloses a two-step process for producing polyether polyols with a high content of primary OH groups, characterized in that in a first step (starting from a starter with a molecular weight < 1000 Da) an intermediate is obtained under DMC catalysis, a Lewis acid (preferably tris(pentafluorophenyl)borane) is added to this intermediate, and then epoxide is again added at a lower temperature than in the DMC-catalyzed step. The necessary deactivation of the DMC catalyst therefore apparently takes place by lowering the temperature. A disadvantage of this process is that it is unsuitable for the production of short-chain polyols (only polyethers with molecular weights greater than 2500 Da are produced) and again the use of the moisture-sensitive catalyst tris(pentafluorophenyl)borane.

[0007] The two patent applications WO 2017 / 194709 A1 and WO 2012084762 A1 disclose two-stage processes, each comprising a base-catalyzed and a DMC-catalyzed step, for obtaining polyether polyols with OH numbers > 200 mg KOH / g or those with OH numbers between 3 and 150 mg KOH / g. These processes utilize robust catalysts and do not require the removal of catalyst residues; the process claimed in WO 2017 / 194709 is also suitable for the production of typical short-chain rigid foam polyoxyalkylene polyols. However, a disadvantage is that the resulting polyoxyalkylene polyols are not completely free of alkali metal salts. The application WO 2012 / 134849 A1 discloses a reaction sequence consisting of a superacid-catalyzed reaction step followed by a DMC step, with the aim of obtaining short-chain polyoxyalkylene polyols with a low content of primary OH groups suitable for rigid foam applications without the need for further processing.The superacid is not separated prior to the DMC step, but can optionally be neutralized. A problem with the claimed process is the use of the highly aggressive superacid CF3SO3H. Furthermore, the work leading to the present invention surprisingly revealed that the neutralization method used in WO 2012 / 134849 A1 adversely affects the activity of the DMC catalyst.

[0008] Patent application WO 2005 / 118678 A1 describes a two-step process for the production of phosphorus-containing polyethers using DMC catalysis: The phosphorus-containing compounds, typically phosphorus oxygen acids and their partially esterified derivatives, are treated in a first step with 0.5–3 mol of alkylene oxide / OH group without catalyst. After the epoxide has reacted in this first step, the DMC catalyst is added and reacted further with epoxide using various methods until the target molecular weight is reached. It is emphasized that the process is characterized by the fact that no post-treatment of the precursor is required; instead, the precursor can be directly subjected to the DMC-catalyzed alkoxylation step. The target molecular weights of the process are in the range of long-chain polyoxyalkylene polyols.The advantage of neutralizing the residual acid number remaining in the intermediate after the first step, which is particularly evident in the production of short-chain polyoxyalkylene polyols using small amounts of DMC catalyst, was not recognized.

[0009] EP 2543689 claims a continuous process for producing polyethers, which is characterized in that in the first step of the reaction cascade a (Lewis) acid catalyzed step is carried out at a temperature below the typical activation temperature for DMC catalysts. In this step, an intermediate oligomeric polyol is obtained. The DMC catalyst can already be present in this first step. In the second step of the reaction cascade, the temperature is raised to values ​​typical for DMC-catalyzed alkylene oxide addition processes, and the finished polyol is obtained. The target molar masses of this process are also in the range of long-chain polyoxyalkylene polyols. The process engineering advantage of neutralizing the residual acid number remaining after step 1 was also not recognized by the authors.

[0010] Therefore, the current state of the art does not provide a process that provides access to short-chain polyoxyalkylene polyols in the OH number range of 300 to 600 mg KOH / g using active catalysts or catalyst amounts, in which catalyst residues do not have to be separated, no moisture-sensitive Lewis acids or aggressive superacids are used and in which neither alkali or alkaline earth metal residues nor large amounts of aminic catalyst residues remain in the polyoxyalkylene polyol.

[0011] The object of the present invention was therefore to eliminate the deficiencies of the processes described previously in the prior art. This object was surprisingly achieved by a process for preparing a mixture comprising a polyoxyalkylene polyol, preferably a polyether polyol, comprising the following steps: i. Providing a component (A) comprising a polyoxyalkylene polyol A1) having a calculated hydroxyl number (OHZAI) of 600 to 1060 mg KOH / g by a) reacting an H-functional starter compound (B) with an alkylene oxide (C) using a component (D), wherein component (D) contains a Brønsted acid, to form an intermediate (E); b) adding an amine (F) to the intermediate (E) obtained under ia) to form component (A) ii.Subsequent reaction of component (A) with an alkylene oxide (G) in the presence of a DMC catalyst (H) to form a mixture comprising the polyoxyalkylene polyol; wherein the reaction in step i.-a) takes place in the absence of a superacid, and wherein the calculated amount of Brönsted acid to be added according to step i.-a) is from 0.5 wt.% to 5.0 wt.%, preferably from 1.0 wt.% to 4.5 wt.%, and particularly preferably from 1.5 wt.% to 4.0 wt.%, based on the total mass of the intermediate (E).

[0012] The process according to the invention is also characterized by smooth uptake of the alkylene oxide in the alkoxylation stages i. and ii. In particular, the DMC catalyst used in stage ii. exhibits good activity even at low concentrations of a maximum of 150 ppm, based on the total batch mass, which is manifested by only a slight increase in pressure during the alkylene oxide addition phase. It has also been found that changing the reactor between the two alkoxylation stages also has a beneficial effect on the uptake of the epoxide in stage ii., which proceeds under DMC catalysis.

[0013] The method according to the invention is explained in more detail below, wherein embodiments according to the invention can be combined with one another in any desired manner and number, unless the contrary results from their technical content or is obvious to the person skilled in the art.

[0014] According to the invention, the mixture contains the polyoxyalkylene polyol, preferably the polyether polyol.

[0015] In the process according to the invention, polyoxyalkylene polyols are understood to mean addition products of one or more alkylene oxides and optionally one or more comonomers such as CO2 and / or cyclic anhydrides with one or more H-functional starter compounds in the presence of a catalyst such as the double metal cyanide (DMC) catalyst (H), wherein polyether polyols, polyether ester polyols, polycarbonate polyols, polyether carbonate polyols or polyether ester carbonate polyols are obtainable.

[0016] In a preferred embodiment of the process according to the invention, the polyoxyalkylene polyol is a polyether polyol, wherein the polyether polyol is obtainable by addition of one or more alkylene oxides to one or more H-functional starter compounds in the presence of a catalyst such as, for example, the double metal cyanide (DMC) catalyst (H).

[0017] According to the common technical definition, Bronsted acids are substances that can transfer protons to a second reaction partner, the so-called Bronsted base, typically in an aqueous medium at 25 °C.

[0018] In one embodiment of the process according to the invention or of the invention, the polyoxyalkylene polyol contained in the mixture has an equivalent mass of 93 to 225 g / mol, preferably of 93 to 190 g / mol.

[0019] The equivalent molar mass of materials containing active hydrogen atoms (H-functional starter compounds) is the total mass of the material containing active hydrogen atoms divided by the number of active hydrogen atoms. In the case of materials containing hydroxyl groups (such as polyoxyalkylene polyols), it is related to the OH number (OHN, hydroxyl number) as follows:

[0020] Equivalent molar mass = (56100 [mg / mol]) / (OHZ [mg KOH / g]) (I)

[0021] The equivalent molar mass of the polyoxyalkylene polyol is determined according to formula (I), whereby the OHM of the polyoxyalkylene polyol can be determined according to DIN 53240 or spectroscopically via NIR. The OHM of the polyoxyalkylene polyol is preferably determined according to DIN 53240-2 (2007).

[0022] The calculated OH number of the polyoxyalkylene polyol Al) (OHZAI) is determined according to formula (II): Equivalent molar mass = (56100 [mg / mol]) / (OHZAI [mg KOH / g]) (II)

[0023] OHZAI = ((Mass of the H-functional starter compound (B) used in step ia) x (OHZ of the H-functional starter compound (B) used in step ia)) / (Mass of the H-functional starter compound (B) used in step ia) + Mass of the alkylene oxide C used in step ia).

[0024] In one embodiment of the process according to the invention or of the invention, the polyether polyol contained in the mixture has an equivalent mass of 93 to 225 g / mol, preferably of 93 to 190 g / mol.

[0025] H-functional starter compounds (B) are used as starters in step ia). Such starters are compounds that contain at least one Zerewitinoff-active hydrogen atom, sometimes also referred to simply as "active hydrogen." A hydrogen bonded to N, O, or S is referred to as Zerewitinoff-active hydrogen if it yields methane by reaction with methylmagnesium iodide according to a process discovered by Zerewitinoff. Typical examples of compounds containing Zerewitinoff-active hydrogen are compounds that contain carboxyl, hydroxyl, amino, imino, or thiol groups as functional groups. In the present invention, the hydrogen atoms of the hydroxyl groups of the oxygen acids of phosphorus are also to be regarded as Zerewitinoff-active hydrogen atoms. Suitable H-functional starter compounds usually have functionalities of 1 to 35, preferably 1 to 8.Their equivalent molar masses are typically below 70 g / mol. In addition to the preferred hydroxy-functional starters, amino-functional starters can also be used. Examples of hydroxy-functional starter compounds are methanol, ethanol, 1-propanol, 2-propanol, the isomers of butanol, propylene glycol, ethylene glycol, diethylene glycol, dipropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, hexanediol, pentanediol, 3-methyl-1,5-pentanediol, glycerol, trimethylolpropane, pentaerythritol, sorbitol, sucrose, hydroquinone, pyrocatechol, resorcinol, 1,3,5-trihydroxybenzene, and methylol-containing condensates of formaldehyde and phenol or urea. Highly functional starter compounds based on hydrogenated starch hydrolysis products can also be used. Such are described, for example, in EP-A 1525244.Examples of amino-containing H-functional starter compounds are ammonia, ethanolamine, diethanolamine, triethanolamine, isopropanolamine, diisopropanolamine, ethylenediamine, hexamethylenediamine, aniline, the isomers of toluidine, the isomers of diaminotoluene, the isomers of diaminodiphenylmethane, and the higher-nuclear products obtained from the condensation of aniline with formaldehyde to diaminodiphenylmethane, as well as methylol-containing condensates of formaldehyde and melamine and Mannich bases. Ring-opening products of cyclic carboxylic acid anhydrides and polyols, which form very rapidly in situ after the two components combine, can also be used as starter compounds. Examples are ring-opening products of phthalic anhydride, succinic anhydride, maleic anhydride on the one hand and ethylene glycol, diethylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, glycerol, trimethylolpropane, pentaerythritol or sorbitol on the other hand.It is also possible to use mono- or polyfunctional carboxylic acids directly as starter compounds.

[0026] Furthermore, in addition to the aforementioned H-functional starter compounds (B), preformed alkylene oxide addition products of these starter compounds, i.e., polyoxyalkylene polyols preferably with OH numbers of > 600 to 1100 mg KOH / g, preferably 700 to 1000 mg KOH / g, can also be used to carry out step ia). It is also possible to use polyester polyols, preferably with OH numbers in the range of > 600 to, for example, 800 mg KOH / g, as (co-)starters in the process according to the invention with the aim of producing polyetheresters. Polyester polyols suitable for this purpose can be prepared, for example, from organic dicarboxylic acids and polyhydric alcohols, preferably diols, by known processes.

[0027] Furthermore, polycarbonate polyols, polyester carbonate polyols, or polyether carbonate polyols, preferably polycarbonate diols, polyester carbonate diols, or polyether carbonate diols, preferably each with OH numbers in the range from > 600 to, for example, 800 mg KOH / g, can be used as (co-)starters as H-functional starter compounds (B). These are prepared, for example, by reacting phosgene, dimethyl carbonate, diethyl carbonate, or diphenyl carbonate with di- or higher-functional alcohols or polyester polyols or polyether polyols.

[0028] To calculate the OHZAI according to formula (II), the number of -SH groups is used for starter compounds containing thiol groups, the number of =NH groups for starter compounds containing imino groups, the number of -COOH groups for starter compounds containing carboxyl groups and the number of hydrogen atoms bonded to amine nitrogen atoms for starter compounds containing amino groups.

[0029] In the process according to the invention, amino-free H-functional starter compounds containing hydroxy groups are preferably used as carriers of the active hydrogens, such as, for example, methanol, ethanol, 1-propanol, 2-propanol, the isomers of butanol, propylene glycol, ethylene glycol, diethylene glycol, dipropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, hexanediol, pentanediol, 3-methyl-1,5-pentanediol, glycerol, trimethylolpropane, pentaerythritol, sorbitol, sucrose, hydroquinone, pyrocatechol, resorcinol, 1,3,5-trihydroxybenzene, methylol-containing condensates of formaldehyde and phenol, and hydrogenated starch hydrolysis products. Mixtures of various H-functional starter compounds can also be used.

[0030] In one embodiment of the process according to the invention, the alkylene oxide (C) is one or more compounds and is selected from the group consisting of 1,2-epoxybutane, propylene oxide and ethylene oxide, preferably propylene oxide and ethylene oxide. If mixtures of ethylene oxide and propylene oxide are used in step i.-a), these preferably contain up to 50% by mass of ethylene oxide and more preferably up to 30% by mass of ethylene oxide, based on the total mass of the mixture of ethylene oxide and propylene oxide. Very particular preference is given to using propylene oxide alone. The alkylene oxides (C) can be fed to the reactor as individual components or as a mixture. It is also possible to feed a plurality of alkylene oxides (C) to the reactor one after the other, thus making it possible to produce polyoxyalkylene chains with a block structure. When metering in a plurality of alkylene oxides, it is possible to change the composition of the fed alkylene oxide stream continuously or instantaneously.

[0031] In one embodiment of the process according to the invention, component (D) consists of Brønsted acid.

[0032] In one embodiment of the process according to the invention, the Brönsted acid is an inorganic mineral acid. In the process according to the invention, the reaction takes place in the absence of a superacid such as trifluoromethanesulfonic acid (CF3SO3H). According to the general technical definition, superacids have a pKa value of less than minus three point zero (-3.0).

[0033] In one embodiment of the process according to the invention, the Brönsted acid is sulfuric acid and / or an oxyacid of phosphorus, preferably an oxyacid of phosphorus. Examples of oxyacids of phosphorus include orthophosphoric acid (phosphoric acid), phosphonic acid, or phosphinic acid. Furthermore, condensed phosphorus oxoacids, such as diphosphoric acid or diphosphonic acid, as well as cyclic metaphosphoric acids, can also be used. An overview of suitable phosphorus oxoacids is given, for example, in Holleman-Wiberg, Lehrbuch der Anorganischen Chemie, 91st - 100th improved and greatly expanded edition, Walter de Gruyter, Berlin, New York 1985, pp. 646 - 664.

[0034] In one embodiment of the process according to the invention, the oxygen acid of phosphorus has a structure according to formula (III):

[0035] (HO)a(H) bP(O)OH (III) with a = 0, 1 or 2 and b = 0, 1 or 2, where a + b = 2.

[0036] In a preferred embodiment of the process according to the invention, the oxygen acid of phosphorus is phosphinic acid (with a=0, b=2), phosphonic acid (with a=1, b=1) and / or phosphoric acid (orthophosphoric acid, with a=2, b=0), particularly preferably phosphoric acid (orthophosphoric acid). According to the invention, the calculated amount of Brönsted acid to be added in step i.-a) is from 0.5 wt.% to 5.0 wt.%, preferably from 1.0 wt.% to 4.5 wt.%, and particularly preferably from 1.5 wt.% to 4.0 wt.%, based on the total mass of the intermediate (E).

[0037] In one embodiment of the process according to the invention, the amount of amine (F) added in step i.-b) is such that >0.5 to <2.2, preferably >0.8 to <2.0, amine nitrogen equivalents are added per residual acid equivalent in intermediate (E) in step i.-b). The residual acid equivalent is determined using the ASTM D 7253 (2016) method. In one embodiment of the process according to the invention, the amine (F) is a tertiary amine, preferably a hydroxyl-containing tertiary amine.

[0038] In one embodiment of the process according to the invention, the tertiary amine, preferably the hydroxyl-containing tertiary amine, has a hydroxyl number of 300 mg KOH / g to 1200 mg, preferably of 350 mg KOH / g to 1000 mg KOH / g, particularly preferably of 400 mg KOH / g to 800 mg, wherein the hydroxyl number was determined by means of the method DIN 53240 -2 (2007).

[0039] In one embodiment of the process according to the invention, the tertiary amine is a hydroxyl-containing tertiary amine, and the hydroxyl-containing tertiary amine is obtainable, preferably obtained, by reacting ammonia, a primary amine such as methylamine, ethylamine, propylamine, isopropylamine, butylamine, sec-butylamine, N,N-dimethylaminopropylamine, a primary diamine such as ethylenediamine, 1,3-diaminopropane, hexamethylenediamine, tolylenediamine, a secondary amine such as dimethylamine, dibutylamine, diisopropylamine, diethanolamine, M-methylethanolamine, and / or a secondary diamine such as N,N'-dimethylaminopropylamine with an alkylene oxide (I).

[0040] In a further embodiment of the process according to the invention, the tertiary hydroxyl-containing amine is also obtainable, preferably also obtained by chain extension of tertiary alcohol amines such as triisopropanolamine and / or triethanolamine, with alkylene oxide (I) such as propylene oxide and / or ethylene oxide. In one embodiment of the process according to the invention, the alkylene oxide (G) is one or more compounds and is selected from the group consisting of 1,2-epoxybutane, propylene oxide and ethylene oxide. If mixtures of ethylene oxide and propylene oxide are used in step ii.), these preferably contain up to 50% by mass of ethylene oxide and more preferably up to 30% by mass of ethylene oxide, based on the total mass of the mixture of ethylene oxide and propylene oxide. Very particular preference is given to using propylene oxide alone. The alkylene oxides (G) can be fed to the reactor as individual components or as a mixture.It is also possible to feed several alkylene oxides (G) into the reactor sequentially, thus allowing the creation of polyoxyalkylene chains with a block structure. When feeding several alkylene oxides, it is possible to change the composition of the alkylene oxide feed stream continuously or instantaneously.

[0041] Further monomers copolymerizable with alkylene oxides (G) under DMC catalysis in step ii) according to the process according to the invention are, for example, aliphatic lactones, aromatic lactones, lactides, cyclic carbonates with preferably at least three optionally substituted methylene groups between the oxygen atoms of the carbonate group, aliphatic cyclic anhydrides, aromatic cyclic anhydrides and carbon dioxide.

[0042] Aliphatic or aromatic lactones are cyclic compounds containing an ester bond in the ring. Preferred compounds are 4-membered ring lactones such as ß-propiolactone, ß-butyrolactone, ß-isovalerolactone, ß-caprolactone, ß-isocaprolactone, ß-methyl-ß-valerolactone, 5-membered ring lactones, such as y-butyrolactone, y-valerolactone, 5-methylfuran-2(3H)-one, 5-methylidenedihydrofuran-2(3H)-one, 5-hydroxyfuran-2(5H)-one, 2-benzofuran-l(3H)-one and 6-methy-2-benzofuran-l(3H)-one, 6-membered ring lactones, such as 5-valerolactone, l,4-Dioxan-2-one, dihydrocoumarin, 1 H-isochromen-1-one, 8H-pyrano[3,4-b]pyridine-8-one, 1,4-dihydro-3H-isochromen-3-one, 7,8-dihydro-5H-pyrano[4,3-b]pyridine-5-one, 4-methyl-3,4-dihydro-lH-pyrano[3,4-b]pyridine-1-one, 6-Hydroxy-3,4-dihydro-1H-isochromen-1-one, 7-hydroxy-3,4-dihydro-2H-chromen-2-one, 3-Ethyl-lH-isochromen-l-one, 3-(hydroxymethyl)-lH-isochromen-l-one, 9- Hydroxy-1H,3H-benzo[de]isochromen-1-one, 6,7-dimethoxy-1,4-dihydro-3H-isochromen-3-one and 3-phenyl-3,4-dihydro-lH-isochromen-l-on, 7-gliedrige Ringlactone, wie 8-Caprolacton, 1,5- Dioxepan-2-on, 5-Methyloxepan-2-on, Oxepane-2,7-dion, thiepan-2-on, 5-Chlorooxepan-2-on, (4S)-4-(Propan-2-yl)oxepan-2-on, 7-Butyloxepan-2-on, 5-(4-Aminobuthyl)oxepan-2-on, 5- Phenyloxepan-2-on, 7-Hexyloxepan-2-on, (5S,7S)-5-Methyl-7-(propan-2-yl)oxepan-2-on, 4- Methyl-7-(propan-2-yl)oxepan-2-on, und höhergliedrige Ringlactone, wie (7E)-Oxacycloheptadec- 7-en-2-on.,

[0043] Lactides are cyclic compounds containing two or more ester bonds in the ring. Preferred compounds are glycolide (1,4-dioxane-2,5-dione), L-lactide (L-3,6-dimethyl-1,4-dioxane-2,5-dione), D-lactide, DL-lactide, mesolactide, and 3-methyl-1,4-dioxane-2,5-dione, 3-hexyl-6-methyl-1,4-dioxane-2,5-dione, and 3,6-di(but-3-en-1-yl)-1,4-dioxane-2,5-dione (each including optically active forms). L-lactide is particularly preferred. Compounds with at least three optionally substituted methylene groups between the oxygen atoms of the carbonate group are preferably used as cyclic carbonates.Bevorzugte Verbindungen sind Trimethylencarbonat, Neopentylglykolcarbonat (5,5-Dimethyl-l,3- dioxan-2-on), 2,2,4-Trimethyl-l,3-pentandiolcarbonat, 2,2-Dimethyl-l,3-butandiolcarbonat, 1,3- ButandioHcarbonat, 2-Methyl-l,3-propandiolcarbonat, 2,4-Pentandiolcarbonat, 2-Methyl-butan- 1,3-diolcarbonat, TMP-Monoallylethercarbonat, Pentaerythritdiallylethercarbonat, 5-(2- Hydroxyethyl)-l,3-dioxan-2-on, 5-[2-(Benzyloxy)ethyl]-l,3-dioxan-2-on, 4-Ethyl-l,3-dioxolan-2- on, l,3-Dioxolan-2-on, 5-Ethyl-5-methyl-l,3-dioxan-2-on, 5,5-Diethyl-l,3-dioxan-2-on, 5-Methyl- 5-propyl-l,3-dioxan-2-on, 5-(Phenylamino)-l,3-dioxan-2-on und 5,5-Dipropyl-l,3-dioxan-2-on. Besonders bevorzugt sind Trimethylencarbonat und Neopentylglykolcarbonat.

[0044] Cyclic carbonates with fewer than three optionally substituted methylene groups between the oxygen atoms of the carbonate group are not incorporated into the polymer chain or are incorporated only to a small extent under the conditions of the process according to the invention.

[0045] Cyclic anhydrides are cyclic compounds containing an anhydride group in the ring. Preferred compounds are succinic anhydride, maleic anhydride, phthalic anhydride, 1,2-cyclohexanedicarboxylic anhydride, diphenic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, norbornenedioic anhydride and their chlorination products, succinic anhydride, glutaric anhydride, diglycolic anhydride, 1,8-naphthalic anhydride, succinic anhydride, dodecenylsuccinic anhydride, tetradecenylsuccinic anhydride, hexadecenylsuccinic anhydride, octadecenylsuccinic anhydride, 3- and 4-nitrophthalic anhydride, tetrachlorophthalic anhydride, tetrabromophthalic anhydride, itaconic anhydride, dimethylmaleic anhydride, allylnorbornenedioic anhydride, 3-methylfuran-2,5-dione, 3-methyldihydrofuran-2,5-dione, Dihydro-2H-pyran-2,6(3H)-dione, 1,4-Dioxane-2,6-dione, 2H-pyran-2,4,6(3H,5H)-trione, 3-ethyldihydrofuran-2,5-dione, 3-

[0046] Methoxydihydrofuran-2,5-dione, 3-(prop-2-en-1-yl)dihydrofuran-2,5-dione, N-(2,5-dioxotetrahydrofuran-3-yl)formamide, and 3[(2E)-but-2-en-1-yl]dihydrofuran-2,5-dione. Succinic anhydride, maleic anhydride, and phthalic anhydride are particularly preferred.

[0047] Their use is further described in US-A 3538043, US-A 4500704, US-A 5032671, US-A 6646100, EP-A 222453 and WO-A 2008 / 013731.

[0048] In one embodiment of the process according to the invention, the DMC catalyst (H) is used in amounts of 30 to 150 ppm, based on the amount of component (A) and alkylene oxide (G).

[0049] DMC catalysts (H) suitable for the process according to the invention are known in principle from the prior art (see, for example, US-A 3,404,109, US-A 3,829,505, US-A 3,941,849, and US-A 5,158,922). DMC catalysts described, for example, in US-A 5,470,813, EP-A 700,949, EP-A 743,093, EP-A 761,708, WO 97 / 40086, WO 98 / 16310, and WO 00 / 47649 possess very high activity in the polymerization of alkylene oxides and enable the preparation of polyoxyalkylene polyols under optimal conditions at very low catalyst concentrations (100 ppm or less), so that separation of the catalyst from the finished product is generally no longer necessary. A typical example are the highly active DMC catalysts described in EP-A 700949, which contain a double metal cyanide compound (e.g. zinc hexacyanocobaltate(III)) and an organic complex ligand (e.g. tert.-butanol) or a polyoxyalkylene compound with a number-average molecular weight of > 500 g / mol. It is also possible to use the alkaline DMC catalysts disclosed in EP Application No. 10163170.3.

[0050] Cyanide-free metal salts suitable for the preparation of the double metal cyanide compound preferably have the general formula (IV),

[0051] M(X) n (IV) where

[0052] M is selected from the metal cations Zn 2+ , Fe 2+ , Ni 2+ , Mn 2+ , Co 2+ , Sr 2+ , Sn 2+ , Pb 2+ and, Cu 2+ , preferably M is Zn 2+ , Fe 2+ , Co 2+ or Ni 2+ ,

[0053] X is one or more (i.e. different) anions, preferably an anion selected from the group of halides (i.e. fluoride, chloride, bromide, iodide), hydroxide, sulfate, carbonate, cyanate, thiocyanate, isocyanate, isothiocyanate, carboxylate, oxalate and nitrate; n is 1 if X = sulfate, carbonate or oxalate and n is 2 if X = halide, hydroxide, cyanate, thiocyanate, isocyanate, isothiocyanate or nitrate, or suitable cyanide-free metal salts have the general formula (V),

[0054] M r (X)3(V) where

[0055] M is selected from the metal cations Fe 3+ , Al 3+ and Cr 3+ ,

[0056] X is one or more (i.e. different) anions, preferably an anion selected from the group of halides (i.e. fluoride, chloride, bromide, iodide), hydroxide, sulfate, carbonate, cyanate, thiocyanate, isocyanate, isothiocyanate, carboxylate, oxalate and nitrate; r is 2 if X = sulfate, carbonate or oxalate and r is 1 if X = halide, hydroxide, cyanate, thiocyanate, isocyanate, isothiocyanate, carboxylate or nitrate, or suitable cyanide-free metal salts have the general formula (VI),

[0057] M(X) S (VI) where

[0058] M is selected from the metal cations Mo 4+ , V 4+ and W 4+

[0059] X is one or more (i.e. different) anions, preferably an anion selected from the group of halides (i.e. fluoride, chloride, bromide, iodide), hydroxide, sulfate, carbonate, cyanate, thiocyanate, isocyanate, isothiocyanate, carboxylate, oxalate and nitrate; s is 2 if X = sulfate, carbonate or oxalate and s is 4 if X = halide, hydroxide, cyanate, thiocyanate, isocyanate, isothiocyanate, carboxylate or nitrate, or suitable cyanide-free metal salts have the general formula (VII),

[0060] M(X) t (VII) where

[0061] M is selected from the metal cations Mo 6+ and W 6+

[0062] X is one or more (i.e. different) anions, preferably an anion selected from the group of halides (i.e. fluoride, chloride, bromide, iodide), hydroxide, sulfate, carbonate, cyanate, thiocyanate, isocyanate, isothiocyanate, carboxylate, oxalate and nitrate; t is 3 if X = sulfate, carbonate or oxalate and t is 6 if X = halide, hydroxide, cyanate, thiocyanate, isocyanate, isothiocyanate, carboxylate or nitrate,

[0063] Examples of suitable cyanide-free metal salts are zinc chloride, zinc bromide, zinc iodide, zinc acetate, zinc acetylacetonate, zinc benzoate, zinc nitrate, iron(II) sulfate, iron(II) bromide, iron(II) chloride, cobalt(II) chloride, cobalt(II) thiocyanate, nickel(II) chloride, and nickel(II) nitrate. Mixtures of different metal salts can also be used.

[0064] Metal cyanide salts suitable for the preparation of the double metal cyanide compounds preferably have the general formula (VIII)

[0065] (Y) aM'(CN) b (A) c (VIII) where

[0066] M' is selected from one or more metal cations from the group consisting of Fe(II), Fe(III), Co(II), Co(III), Cr(II), Cr(III), Mn(II), Mn(III), Ir(III), Ni(II), Rh(III), Ru(II), V(IV) and V(V), preferably M' is one or more metal cations from the group consisting of Co(II), Co(III), Fe(II), Fe(III), Cr(III), Ir(III) and Ni(II),

[0067] Y is selected from one or more metal cations of the group consisting of alkali metal (ie Li + , N / a + , K + , Rb + , Cs + ) and alkaline earth metal (ie Be 2+ , Ca 2+ , Mg 2+ , Sr 2+ , Ba 2+ ),

[0068] A is selected from one or more anions of the group consisting of halides (i.e., fluoride, chloride, bromide, iodide), hydroxide, sulfate, carbonate, cyanate, thiocyanate, isocyanate, isothiocyanate, carboxylate, oxalate, or nitrate, and a, b, and c are integers, the values ​​for a, b, and c being chosen to ensure electroneutrality of the metal cyanide salt; a is preferably 1, 2, 3, or 4; b is preferably 4, 5, or 6; c is preferably 0.

[0069] Examples of suitable metal cyanide salts are potassium hexacyanocobaltate(III), potassium hexacyanoferrate(II), potassium hexacyanoferrate(III), calcium hexacyanocobaltate(III) and lithium hexacyanocobaltate(III).

[0070] Preferred double metal cyanide compounds contained in the DMC catalysts (H) according to the invention are compounds of the general formula (VIII)

[0071] M x [M' x ,(CN) y ] z(IX), wherein M is as defined in formula (IV) to (VII) and M' is as defined in formula (VIII), and x, x', y and z are integers and chosen so as to ensure electron neutrality of the double metal cyanide compound.

[0072] Preferably x = 3, x' = 1, y = 6 and z = 2,

[0073] M = Zn(II), Fe(II), Co(II) or Ni(II) and M' = Co(III), Fe(III), Cr(III) or Ir(III).

[0074] Examples of suitable double metal cyanide compounds are zinc hexacyanocobaltate(III), zinc hexacyanoiridate(III), zinc hexacyanoferrate(III), and cobalt(II) hexacyanocobaltate(III). Further examples of suitable double metal cyanide compounds can be found, for example, in US-A 5158922 (column 8, lines 29-66). Zinc hexacyanocobaltate(III) is particularly preferred.

[0075] The organic complex ligands added in the preparation of the DMC catalysts (H) are disclosed, for example, in US-A 5158922 (see in particular column 6, lines 9 to 65), US-A 3404109, US-A 829505, US-A 3941849, EP-A 700949, EP-A 761708, JP-A 4145123, US-A 5470813, EP-A 743093 and WO-A 97 / 40086. For example, water-soluble organic compounds containing heteroatoms, such as oxygen, nitrogen, phosphorus, or sulfur, which can form complexes with the double metal cyanide compound, are used as organic complex ligands. Preferred organic complex ligands are alcohols, aldehydes, ketones, ethers, esters, amides, ureas, nitriles, sulfides, and mixtures thereof. Particularly preferred organic complex ligands are aliphatic ethers (such as dimethoxyethane), water-soluble aliphatic alcohols (such as ethanol, isopropanol, n-butanol, isobutanol, sec.-Butanol, tert-butanol, 2-methyl-3-buten-2-ol and 2-methyl-3-butyn-2-ol), compounds that contain both aliphatic or cycloaliphatic ether groups and aliphatic hydroxyl groups (such as ethylene glycol mono-tert-butyl ether, diethylene glycol mono-tert-butyl ether, tripropylene glycol mono-methyl ether and 3-methyl-3-oxetane-methanol). Highly preferred organic complex ligands are selected from one or more compounds of the group consisting of dimethoxyethane, tert-butanol, 2-methyl-3-buten-2-ol, 2-methyl-3-butyn-2-ol, ethylene glycol mono-tert-butyl ether and 3-methyl-3-oxetane-methanol.Optionally, in the preparation of the DMC catalysts (H) according to the invention, one or more complexing components from the compound classes of polyoxyalkylene compounds, polyesters, polycarbonates, polyalkylene glycol sorbitan esters, polyalkylene glycol glycidyl ethers, polyacrylamide, poly(acrylamide-co-acrylic acid), polyacrylic acid, poly(acrylic acid-co-maleic acid), polyacrylonitrile, polyalkyl acrylates, polyalkyl methacrylates, polyvinyl methyl ether, polyvinyl ethyl ether, polyvinyl acetate, polyvinyl alcohol, poly-N-vinylpyrrolidone, poly(N-vinylpyrrolidone-co-acrylic acid), polyvinyl methyl ketone, poly(4-vinylphenol), poly(acrylic acid-co-styrene), oxazoline polymers, polyalkyleneimines, maleic acid and maleic anhydride copolymers, hydroxyethyl cellulose and polyacetals, or the glycidyl ethers, glycosides, carboxylic acid esters of polyhydric alcohols, bile acids or their salts, esters or amides, cyclodextrins, phosphorus compounds, α,β-unsaturated carboxylic acid esters or ionic surface orsurface-active compounds.

[0076] In the preparation of the DMC catalysts (H) according to the invention, the aqueous solutions of the metal salt (e.g., zinc chloride), used in a stoichiometric excess (at least 50 mol%) based on the metal cyanide salt (i.e., at least a molar ratio of cyanide-free metal salt to metal cyanide salt of 2.25 to 1.00), and of the metal cyanide salt (e.g., potassium hexacyanocobaltate) are preferably reacted in the first step in the presence of the organic complex ligand (e.g., tert-butanol), so that a suspension is formed which contains the double metal cyanide compound (e.g., zinc hexacyanocobaltate), water, excess cyanide-free metal salt, and the organic complex ligand. The organic complex ligand can be present in the aqueous solution of the cyanide-free metal salt and / or the metal cyanide salt, or it is added directly to the suspension obtained after precipitation of the double metal cyanide compound.It has proven advantageous to mix the aqueous solutions of the cyanide-free metal salt and the metal cyanide salt and the organic complexing ligand with vigorous stirring. Optionally, the suspension formed in the first step is then treated with another complexing component. The complexing component is preferably used in a mixture with water and the organic complexing ligand. A preferred method for carrying out the first step (i.e., preparing the suspension) is carried out using a mixing nozzle, particularly preferably using a jet disperser as described in WO-A 01 / 39883.

[0077] In the second step, the solid (i.e. the precursor of the catalyst according to the invention) is isolated from the suspension by known techniques such as centrifugation or filtration.

[0078] In a preferred embodiment for preparing the DMC catalyst (H), the isolated solid is subsequently washed in a third process step with an aqueous solution of the organic complex ligand (e.g., by resuspension and subsequent reisolation by filtration or centrifugation). In this way, for example, water-soluble by-products, such as potassium chloride, can be removed from the catalyst according to the invention. The amount of the organic complex ligand in the aqueous wash solution is preferably between 40 and 80% by mass, based on the total solution.

[0079] Optionally, in the third step, one or more further complex-forming components are added to the aqueous washing solution, preferably in the range between 0.5 and 5 mass%, based on the total solution.

[0080] It is also advantageous to wash the isolated solid more than once. For this purpose, the first washing step can be repeated, for example. However, it is preferable to use non-aqueous solutions for subsequent washing steps, e.g., a mixture of organic complexing ligand and another complexing component. The isolated and optionally washed solid is then dried, optionally after pulverization, at temperatures generally between 20 and 100 °C and at absolute pressures generally between 0.1 mbar and atmospheric pressure (1013 mbar).

[0081] A preferred process for isolating the DMC catalysts (H) according to the invention from the suspension by filtration, filter cake washing and drying is described in WO-A 01 / 80994.

[0082] In one embodiment of the process according to the invention, the alkylene oxide (I) usable for preparing the hydroxyl-containing tertiary amine (F) is one or more compounds and is selected from the group consisting of 1,2-epoxybutane, propylene oxide, and ethylene oxide, preferably ethylene oxide and propylene oxide, and particularly preferably propylene oxide. In one embodiment of the process according to the invention, the reaction in step i.-a) takes place in the absence of a superacid such as, for example, trifluoromethanesulfonic acid (CF3SO3H). According to the general technical definition, superacids have a pKa value of less than minus three point zero (-3.0). In a preferred embodiment of the process according to the invention, the reaction in step i.-a) takes place in the absence of trifluoromethanesulfonic acid.

[0083] In one embodiment of the process according to the invention, step i.-a) is carried out at a reaction temperature of less than 80°C, preferably from 30°C to 70°C, and particularly preferably from 35°C to 65°C. If step i.-a) is carried out at temperatures of 80°C or higher, side reactions are observed which lead to an increased content of volatile by-products in intermediate (E). The reaction temperature can, of course, be varied within the described limits during the alkylene oxide metering phase in step i.-a).

[0084] In one embodiment of the process according to the invention, in step i.-a), the total amount of component (D) containing the Brönsted acid is premixed with the H-functional starter compound (B) in the reactor before the addition of the alkylene oxide (C).

[0085] In a further embodiment of the process according to the invention, in step i.-a), a first portion of component (D) comprising the Brönsted acid is premixed with the H-functional starter compound (B) in the reactor before the addition of the alkylene oxide (C), and at least a second portion, but preferably the entire remaining amount of component (D) comprising the Brönsted acid is added separately to the first reactor at the same time as the addition of the alkylene oxide (C).

[0086] In variants of this embodiment of the process according to the invention, in step i.-a), the additions of the alkylene oxide (C) and the component (D) containing the Brönsted acid either end simultaneously or the addition of the alkylene oxide (C) ends before or after the complete addition of the component (D) containing the Brönsted acid.

[0087] The H-functional starter compound (B) initially introduced into the reactor together with (a portion of) the Brønsted acid, preferably the phosphorus oxyacid, is reacted in step i.-a) with one or more alkylene oxides (C) under an inert gas atmosphere at temperatures of less than 80 °C, preferably from 30 °C to 70 °C, and particularly preferably from 35 °C to 65 °C. The alkylene oxide (C) and also the alkylene oxide (G) in step ii.) are continuously fed to the reactor in the conventional manner such that the safety pressure limits of the reactor system used are not exceeded. In particular, when metering ethylene oxide-containing alkylene oxide mixtures or pure ethylene oxide, care must be taken to ensure that a sufficient inert gas partial pressure is maintained in the reactor during the start-up and metering phase. This can be adjusted, for example, using noble gases or nitrogen.

[0088] The alkylene oxides (C) or (G) in step i.-a) or step ii.) can be fed to the reactor in different ways: Dosing is possible into the gas phase or directly into the liquid phase, e.g., via a dip tube or a distributor ring located near the reactor bottom in a well-mixed zone. When dosing into the liquid phase, the dosing units should be designed to be self-emptying, for example, by installing the dosing holes on the underside of the distributor ring. Backflow of reaction medium into the alkylene oxide-carrying lines and dosing units or into the alkylene oxide storage tanks can advantageously be prevented by means of technical measures, for example, by installing check valves. If an alkylene oxide mixture is dosed in step i.-a) and / or step ii.), the respective alkylene oxides (C) or (G) can be fed to the reactor separately or as a mixture.Premixing of the alkylene oxides (C) and (G) can be achieved, for example, by a mixing unit located in the common metering line (“inline blending”). It has also proven effective to meter alkylene oxides (C) and (G) individually or premixed on the pump pressure side into a pumped circulation circuit, for example, via a heat exchanger. To ensure thorough mixing with the reaction medium, it is then advantageous to integrate a high-shear mixing unit into the alkylene oxide / reaction medium stream.

[0089] If a portion of the Brönsted acid, preferably the oxygen acid of phosphorus, is to be fed to the reactor in parallel with the alkylene oxide stream of the alkylene oxide (C), it is recommended not to bring the partial stream of the Brönsted acid, preferably the oxygen acid of phosphorus, into contact with the alkylene oxide stream of the alkylene oxide (C) outside the actual reaction zone in order to avoid uncontrolled and premature conversion of the alkylene oxide (C).

[0090] The temperature of the exothermic polymerization (alkylene oxide addition reaction) in steps i.- a) and ii) is maintained at or adjusted to the desired level by cooling. According to the state of the art for the design of polymerization reactors for exothermic reactions (e.g. Ullmann's Encyclopedia of Industrial Chemistry, Vol. B4, pp. 167ff, 5th Ed., 1992), such cooling is generally achieved via the reactor wall (e.g. double jacket, half-coil) and by means of additional heat exchanger surfaces arranged internally in the reactor and / or externally in the pumped circulation circuit, e.g. on cooling coils, cooling candles, plate-and-tube, or mixer heat exchangers. These should be designed so that effective cooling can be achieved even at the beginning of the dosing phase, i.e. when the fill level is low and / or when the reacting reactor contents may have a high viscosity.In general, thorough mixing of the reactor contents should be ensured in all reaction phases by designing and using commercially available stirring elements. Single- or multi-stage stirrers or stirrer types acting over a large area across the fill level are particularly suitable (see, for example, Handbook of Apparatus; Vulkan-Verlag Essen, 1st ed. (1990), pp. 188-208). Of particular technical relevance here is an average mixing energy input across the entire reactor contents, which generally lies in the range of 0.2 to 5 W / l, with correspondingly higher local power inputs in the area of ​​the stirring elements themselves and, if necessary, at lower fill levels. To achieve optimal stirring efficiency, combinations of baffles (e.g., flat or tubular baffles) and cooling coils (or cooling plugs) can be arranged in the reactor in accordance with the general state of the art; these can also extend across the vessel bottom.The stirring performance of the mixing unit can also be varied during the dosing phase depending on the fill level in order to ensure a particularly high energy input during critical reaction phases. For example, it can be advantageous to mix solid-containing dispersions, which may be present at the beginning of the reaction, for example, when using sucrose, particularly intensively. Furthermore, especially when using solid H-functional starter compounds, the choice of stirring unit should ensure sufficient dispersion of the solid in the reaction mixture. Bottom-running stirring stages and stirring elements particularly suitable for suspension are preferred. Furthermore, the stirrer geometry should contribute to reducing foaming of reaction products.Foaming of reaction mixtures can be observed, for example, after the end of the dosing and post-reaction phases when residual alkylene oxides are additionally removed under vacuum at absolute pressures in the range of 1 to 500 mbar. In such cases, agitators that achieve continuous mixing of the liquid surface have proven suitable. Depending on requirements, the agitator shaft has a bottom bearing and, if necessary, additional support bearings in the vessel. The agitator shaft can be driven from above or below (with a central or eccentric shaft arrangement). Alternatively, it is also possible to achieve the necessary mixing exclusively via a pumped circulation circuit guided by a heat exchanger or to operate this as an additional mixing component in addition to the agitator unit, with the reactor contents being pumped around as needed (typically 1 to 50 times per hour).The specific mixing power introduced by means of pumping, for example via an external heat exchanger or when returning to the reactor via a nozzle or injector, also amounts to values ​​of 0.2 to 5 W / E on average, whereby this is related to the volume of liquid in the reactor and the pumping circuit at the end of the reaction phase.

[0091] A wide variety of reactor types are suitable for carrying out the process according to the invention. Preference is given to using cylindrical vessels which have a height / diameter ratio of 1:1 to 10:1. Suitable reactor bottoms include, for example, spherical, dished, flat or conical bottoms. After the end of the alkylene oxide metering phase or a change in the composition of the metered alkylene oxide mixture in step i.-a) and / or step ii.), a post-reaction phase can follow in which the remaining alkylene oxide (C) and / or alkylene oxide (G) reacts. The end of such post-reaction phases is reached when no further pressure drop can be detected in the reaction vessel or the pressure drop rate falls below a certain threshold value, i.e. when the pressure decreases, for example, by less than 20 mbar / h.Traces of unreacted alkylene oxides (epoxides) can be removed after the reaction phase, if necessary, in a vacuum at an absolute pressure of 1 to 500 mbar.

[0092] According to the invention, in step i.-b) the amine (F) is added to the intermediate (E) obtained under ia) to form component (A).

[0093] Here, the amine (F) is added to the polyoxyalkylene polyol A1) obtained in step i.-a) either directly in the reaction vessel in which step ia) was carried out or in another mixing vessel.

[0094] In a preferred embodiment of the process according to the invention, step i.-b) is carried out in the first reactor in which the reaction of an H-functional starter compound (B) with an alkylene oxide (C) using a component (D) also takes place.

[0095] The amount of amine to be added in step i.-b) is determined based on the residual acid number determined on the intermediate product after step ia).

[0096] Preferably, the amount of amine (F) added in step i.-b) is such that > ​​0.5 to < 2.2, preferably > 0.8 to < 2.0, amine nitrogen equivalents are added per residual acid equivalent in intermediate (E) in step i.-b), the acid residue equivalent being determined using the ASTM D 7253 (2016) method.

[0097] For example, if an alkylene oxide addition product initiated with ethylenediamine is used as the amine (F), 1 mol of this alkylene oxide addition product can be used per remaining acid equivalent. The amine (F) can be mixed with the intermediate (E) obtained from step i.-a) at room temperature or elevated temperature. Preferably, step i.-b) is also carried out under a protective gas atmosphere.

[0098] If required, anti-aging agents or antioxidants can also be added to component (A) obtained according to step i.-b), for example if this component (A) is to be stored temporarily before its further reaction and no or insufficient amount of an antioxidant has been added after step ia).

[0099] According to the invention, in step ii.), component (A) obtained in step i.) is reacted with the alkylene oxide (G) in the presence of the DMC catalyst (H) to form the polyoxyalkylene polyol. Polyoxyalkylene polyols having a hydroxyl number (OH number) of > 250 mg KOH / g to 600 mg KOH / g, and particularly preferably of > 300 mg KOH / g to 600 mg KOH / g, are preferably obtained. Small amounts (1 to 500 ppm) of other organic or inorganic acids can also be added to component (A) prior to the addition of the DMC catalyst (H), as described, for example, in WO 99 / 14258, although this acid addition is less preferred in the present inventive process. The reaction of component (A) in step ii.) with the alkylene oxide (C) in the presence of the DMC catalyst (H) can, in principle, be carried out in the same reactor (first reactor) as the preparation of component (A) in step i.-a). However, it is preferred that step i.-a) and optionally step i.-b), preferably step i.-a) and step i.-b) are carried out in a first reactor and step ii) in a second reactor, wherein the first reactor is different from the second reactor. The DMC catalyst concentration calculated based on the amount of polyoxyalkylene polyol is in the range from 20 to 1000 ppm, preferably in the range from 30 to 400 ppm, more preferably in the range from 30 to 200 ppm, and most preferably in the range from 40 to 150 ppm.

[0100] The DMC-catalyzed reaction step ii.) can generally be carried out according to the same process engineering principles as the preparation of the precursor of component (A) in step i-1). Some process engineering features of the DMC-catalyzed reaction step ii.) will be discussed below.

[0101] In a preferred procedure, the reactor contents are first stripped with inert gas (nitrogen or a noble gas such as argon) in the presence of the DMC catalyst before step ii.) at temperatures of 60 to 150 °C, more preferably at temperatures of 90 to 140 °C, most preferably at temperatures of 100 to 130 °C for a period of preferably 10 to 60 minutes with stirring. Volatile constituents are removed by introducing inert gases into the liquid phase while simultaneously applying a vacuum at an absolute pressure of 5 to 500 mbar. The temperature can then be adjusted to the reaction temperature of the subsequent step, for example the activation and / or alkylene oxide addition step in step ii.), provided this is not identical to the stripping temperature. The final reaction temperature in step ii.) can also be set in the initial phase of alkylene oxide dosing, for example by utilizing the released reaction heat.

[0102] In a process step preceding the actual polymerization phase (alkylene oxide addition phase) by adding the alkylene oxide (G) in step ii.), the DMC catalyst (H) can first be activated separately by adding typically 2 to 20 mass % of the alkylene oxide (G), based on the amount of component A) used in step ii. The addition of the at least one alkylene oxide (G) can take place before, during, or after heating the reactor contents to the stripping or reaction temperature; it is preferably carried out after stripping. After interrupting the alkylene oxide metering of the alkylene oxide (G), after typically 2 to 20 mass % of the at least one alkylene oxide (G), based on the amount of component A) used in step ii), have been added, the activation of the DMC catalyst (H) is sometimes noticeable by an accelerated drop in reactor pressure, which indicates the onset of alkylene oxide conversion.The remaining portion of the total amount of at least one alkylene oxide (G) to be added to produce the desired polyoxyalkylene polyol (1) is then added to the reaction mixture, ie, after activation has taken place. In the process according to the invention, however, catalyst activation often occurs gradually, so that the interruption of the alkylene oxide metering is eliminated and the continuous metering of the alkylene oxide (G) can begin directly.

[0103] The reaction temperature to be selected in step ii) can be varied during the alkylene oxide metering phase. The reaction temperature is understood to be the time-averaged temperature prevailing in the reacting liquid during the alkylene oxide metering phase. It may prove advantageous to vary the reaction temperature in step ii), for example, by raising it towards the end of the alkylene oxide metering phase, in order to accelerate the alkylene oxide conversion in the final phase of the alkylene oxide metering and in the post-reaction phase. The reaction temperature usually remains constant during the alkylene oxide metering phase of step ii). In step ii), reaction temperatures are preferably selected in the range from 80 to 200 °C, but more preferably from 100 to 160 °C, and particularly preferably from 135 °C to 145 °C.Maintaining the reaction temperature range of 135 to 145 °C results in a relatively low pressure increase during the metering of the alkylene oxide (G) in step ii.). In step ii.), the at least one alkylene oxide (G) can also be fed into the reactor in the DMC-catalyzed reaction step in different ways: Dosing is possible in the gas phase or directly in the liquid phase, e.g., via a dip tube or a distributor ring located near the reactor bottom in a well-mixed zone. In DMC-catalyzed processes, dosing in the liquid phase is the preferred variant.

[0104] After the end of the alkylene oxide metering or before a change of the alkylene oxide in step ii.), post-reaction phases can follow, or post-reaction phases can be inserted, in which the decrease in the concentration of unreacted alkylene oxide can be quantified by monitoring the pressure. The end of such post-reaction phases is reached when no further pressure drop is detectable in the reaction vessel or the pressure drop rate falls below a certain threshold, i.e., the pressure decreases by less than 20 mbar / h, for example. If necessary, the reaction mixture can be completely freed of small amounts of unreacted alkylene oxides under vacuum, for example at an absolute pressure of 1 to 500 mbar, or by stripping after the end of the last post-reaction phase.Stripping removes volatile constituents, such as (residual) alkylene oxides, by introducing inert gases and / or steam into the liquid phase while simultaneously applying a vacuum (for example, by passing an inert gas through the liquid phase at an absolute pressure of 5 to 500 mbar). The removal of volatile constituents, such as unreacted alkylene oxides, either in a vacuum or by stripping, generally takes place at temperatures of 20 to 200 °C, preferably at 50 to 160 °C, and preferably at reaction temperature with stirring. Such stripping processes can also be carried out in so-called stripping columns, in which a stream of inert gas or steam is passed against the product stream. Stripping columns with packed beds or internals are preferably used for this purpose.Such stripping processes can also be carried out continuously, for example, by collecting the unstripped material in a buffer tank and continuously feeding it from there to the stripping column. After reaching constant pressure in the post-reaction phase and, if necessary, after removing volatile components by vacuum and / or stripping, the product can be discharged from the reactor.

[0105] Anti-aging agents such as antioxidants can optionally be added to the mixtures containing the polyoxyalkylene polyol prepared by the process according to the invention.

[0106] The DMC catalyst (H) preferably remains in the mixture containing the polyoxyalkylene polyol, preferably the mixture containing the polyether polyol, but it can also be separated off, for example by treatment with adsorbents. Processes for separating DMC catalysts are described, for example, in US-A 4,987,271, DE-A 3,132,258, EP-A 406,440, US-A 5,391,722, US-A 5,099,075, US-A 4,721,818, US-A 4,877,906, and EP-A 385,619.

[0107] According to the process according to the invention, it is also possible to change the composition of the alkylene oxide mixture not only within one of the two reaction steps, but also when changing from the acid-catalyzed (steps ia) and ib)) to the DMC-catalyzed alkylene oxide addition step (step ii)).

[0108] If different alkylene oxides (G) are used during the DMC-catalyzed alkylene oxide addition step in step ii.), they can be added either as a mixture or sequentially. In the latter case, the polyoxyalkylene chains, which continue to grow under DMC catalysis, acquire block structures. Often, pure ethylene oxide or mixtures of propylene oxide and ethylene oxide with a high ethylene oxide content are added as the end block, so that the polyoxyalkylene polyols produced have 40 to 100% primary OH end groups. When several alkylene oxides are added, it is possible to change the composition of the supplied alkylene oxide stream continuously or instantaneously.

[0109] In a preferred embodiment of the process according to the invention, steps i.-a) and i.-b) are carried out in a first reactor, and step ii) in a second reactor, wherein the first reactor is different from the second reactor. It has been found that such a reactor change leads to better activation of the DMC catalyst used in step ii.). Such improved DMC catalyst activation is manifested by a less pronounced pressure increase at the same epoxide feed rate in the initial phase of step ii.).

[0110] The invention further provides the intermediate (E) obtainable by the process according to the invention.

[0111] A further object of the invention is component (A) obtainable by the process according to the invention.

[0112] The invention further provides a component (A) comprising a polyoxyalkylene polyol A1) having a calculated hydroxyl number (OHZAI) of 600 to 1060 mg KOH and an alkoxylated phosphorus oxygen acid, the calculated phosphorus content being from 0.16 to 2.35 wt. % based on component (A). The polyoxyalkylene polyol A1) results from the reaction of the H-functional starter compound (B) with the alkylene oxide (C) in step i.). According to the invention, the alkoxylated phosphorus oxygen acid is understood to mean the reaction product of the phosphorus oxygen acid of the invention with the alkylene oxide (C) in step i.).

[0113] A further object of the invention is the mixture obtainable by the process according to the invention.

[0114] In a further embodiment of the process according to the invention, the molar mass of the polyoxyalkylene polyol obtained in step ii.) is at least 44 g / mol, preferably at least 58 g / mol, and very preferably at least 88 g / mol higher than the molar mass of component (A) obtained in step i.). In one embodiment of the invention, the polyoxyalkylene polyol present in the mixture has equivalent masses of 93 to 225 g / mol, preferably of 93 to 190 g / mol.

[0115] The invention further provides a mixture comprising a polyoxyalkylene polyol, preferably a polyether polyol with an equivalent mass of 93 to 225 g / mol, preferably 93 to 190 g / mol, and an alkoxylated phosphorus oxygen acid, wherein the calculated phosphorus content is from 0.065 to 1.287 wt. %, based on the mixture. According to the invention, the alkoxylated phosphorus oxygen acid in the present mixture is understood to mean the reaction product of the phosphorus oxygen acid according to the invention with the alkylene oxide (C) in step i.) and with the alkylene oxide (G) in step ii.).

[0116] The mixture according to the invention containing the polyoxyalkylene polyol according to the invention, preferably the mixture according to the invention containing the polyether polyol according to the invention, can be reacted alone or optionally in a mixture with further isocyanate-reactive components with organic polyisocyanates, optionally in the presence of blowing agents, in the presence of catalysts and optionally with further additives such as cell stabilizers, and thus serve as a component of solid or foamed polyurethanes, in particular flexible polyurethane foams such as flexible polyurethane block foam and flexible polyurethane molded foam.

[0117] Polyurethanes, preferably solid or foamed polyurethanes, in particular flexible polyurethane foams such as flexible polyurethane block foams and flexible polyurethane molded foams, comprising the mixture according to the invention comprising the polyoxyalkylene polyol according to the invention, preferably the mixture according to the invention comprising the polyether polyol according to the invention are also subject of the invention.

[0118] In a first embodiment, the invention comprises a process for producing a mixture comprising a polyoxyalkylene polyol, preferably a polyether polyol, comprising the following steps: i. Providing a component (A) comprising a polyoxyalkylene polyol A1) having a calculated hydroxyl number (OHZAI) of 600 to 1060 mg KOH / g by a) reacting an H-functional starter compound (B) with an alkylene oxide (C) using a component (D), wherein component (D) contains a Brønsted acid, to form an intermediate (E); b) adding an amine (F) to the intermediate (E) obtained under ia) to form component (A); ii. Subsequently reacting component (A) with an alkylene oxide (G) in the presence of a DMC catalyst (H) to give the mixture comprising the polyoxyalkylene polyol; wherein the reaction in step i.-a) takes place in the absence of a superacid, and wherein the reaction product obtained according to step i.-a) the calculated amount of Bronsted acid to be added is from 0.5 wt.% to 5.0 wt.%, preferably from 1.0 wt.% to 4.5 wt.% and particularly preferably from 1.5 wt.% to 4.0 wt.%, based on the total mass of the intermediate (E).

[0119] In a second embodiment, the invention comprises a process according to the first embodiment, wherein the polyoxyalkylene polyol present in the mixture has an equivalent mass of 93 to 225 g / mol, preferably of 93 to 190 g / mol.

[0120] In a third embodiment, the invention comprises a process according to the first or second embodiment, wherein the alkylene oxide (C) is one or more compounds and is selected from the group consisting of 1,2-epoxybutane, propylene oxide and ethylene oxide, preferably propylene oxide and ethylene oxide.

[0121] In a fourth embodiment, the invention comprises a process according to any one of the first to third embodiments, wherein the Brpnsted acid is an inorganic mineral acid.

[0122] In a fifth embodiment, the invention comprises a process according to the fourth embodiment, wherein the Brönsted acid is sulfuric acid and / or an oxygen acid of phosphorus, preferably an oxygen acid of phosphorus.

[0123] In a sixth embodiment, the invention comprises a process according to any one of the first to fifth embodiments, wherein the Brpnsted acid is an oxygen acid of phosphorus, preferably phosphinic acid, phosphonic acid and / or phosphoric acid (ortho-phosphoric acid), and particularly preferably phosphoric acid (ortho-phosphoric acid).

[0124] In a seventh embodiment, the invention comprises a process according to any one of the first to sixth embodiments, wherein in step i.-b) the amount of amine (F) added is such that > ​​0.5 to < 2.2, preferably > 0.8 to < 2.0, amine nitrogen equivalents are added per residual acid equivalent in intermediate (E) in step i.-b), wherein the acid residue equivalent is determined using the method disclosed in the description.

[0125] In an eighth embodiment, the invention comprises a process according to any one of the first to seventh embodiments, wherein the amine (F) is a tertiary amine, preferably a hydroxyl-containing tertiary amine.

[0126] In a ninth embodiment, the invention comprises a process according to the eighth embodiment, wherein the tertiary amine has a hydroxyl number of 300 mg KOH / g to 1200 mg, preferably of 350 mg KOH / g to 1000 mg KOH / g, particularly preferably of 400 mg KOH / g to 800 mg, wherein the hydroxyl number was determined by the method disclosed in the description. In a tenth embodiment, the invention comprises a process according to the eighth or ninth embodiment, wherein the tertiary amine is a hydroxyl-containing tertiary amine and the hydroxyl-containing tertiary amine is obtainable, or is preferably obtained, by reacting ammonia, a primary amine, a primary diamine, a secondary amine and / or a secondary diamine with an alkylene oxide (I) and / or by chain extension of tertiary alcohol amines with an alkylene oxide (I).

[0127] In an eleventh embodiment, the invention comprises a process according to any one of the first to tenth embodiments, wherein the alkylene oxide (G) is one or more compounds and is selected from the group consisting of 1,2-epoxybutane, propylene oxide and ethylene oxide

[0128] In a twelfth embodiment, the invention comprises a process according to any one of the first to eleventh embodiments, wherein the DMC catalyst (H) is used in amounts of 30 to 150 ppm, based on the amount of component (A) and alkylene oxide (G).

[0129] In a thirteenth embodiment, the invention comprises a process according to any one of the first to twelfth embodiments, wherein step i.-a) is carried out at a reaction temperature of less than 80°C, preferably from 30°C to 70°C and particularly preferably from 35°C to 65°C.

[0130] In a fourteenth embodiment, the invention comprises a process according to any one of the first to thirteenth embodiments, wherein step i.-a) and optionally step i.-b), preferably step i.-a) and step i.-b) are carried out in a first reactor and step ii) in a second reactor, wherein the first reactor is different from the second reactor.

[0131] In a fifteenth embodiment, the invention comprises a process according to any one of the first to fourteenth embodiments, wherein a first portion or the total amount of component (D) comprising the Brønsted acid is premixed with the H-functional starter compound (B) before the addition of the alkylene oxide (C), preferably in the first reactor.

[0132] In a sixteenth embodiment, the invention comprises a process according to any one of the first to fifteenth embodiments, wherein at least a second portion of component (D) comprising the Brpnsted acid is added separately to the first reactor at the same time as the addition of the alkylene oxide (C).

[0133] In a seventeenth embodiment, the invention comprises a process according to any one of the first to sixteenth embodiments, wherein the additions of the alkylene oxide (C) and the component (D) containing the Brpnsted acid either end simultaneously or the addition of the alkylene oxide (C) ends before or after the complete addition of the component (D) containing the Brpnsted acid.

[0134] In an eighteenth embodiment, the invention comprises a process according to any one of the first to seventeenth embodiments, wherein step ii) is carried out at a reaction temperature of 135°C to 145°C.

[0135] In a nineteenth embodiment, the invention comprises an intermediate (E) obtainable by a process according to any one of the first to eighteenth embodiments. In a twentieth embodiment, the invention comprises a component (A) obtainable by a process according to any one of the first to eighteenth embodiments.

[0136] In a twenty-first embodiment, the invention comprises a mixture obtainable by a process according to any of the first to eighteenth embodiments. In a twenty-second embodiment, the invention comprises a mixture according to the twenty-first embodiment, wherein the polyoxyalkylene polyol present in the mixture has equivalent masses of 93 to 225 g / mol, preferably of 93 to 190 g / mol.

[0137] In a twenty-third embodiment, the invention comprises a component (A) component (A) containing a polyoxyalkylene polyol A1) having a calculated hydroxyl number (OHZAI) of 600 to 1060 mg KOH and an alkoxylated oxygen acid of phosphorus, wherein the calculated phosphorus content is from 0.16 to 2.35 wt.% based on component (A).

[0138] In a twenty-fourth embodiment, the invention comprises a mixture comprising a polyoxyalkylene polyol, preferably a polyether polyol having an equivalent mass of 93 to 225 g / mol, preferably of 93 to 190 g / mol and an alkoxylated oxygen acid of phosphorus, wherein the calculated phosphorus content is from 0.065 to 1.287 wt.%, based on the mixture.

[0139] Examples

[0140] General:

[0141] Pressures are always absolute. Percentages are weight percentages unless otherwise stated.

[0142] Methods:

[0143] QH number, acid number and viscosity

[0144] The OH numbers (OHN) were determined according to DIN 53240-2 (2007), and the acid numbers were determined according to ASTM D 7253 (2016). Viscosities were determined using a rotational viscometer (Physica MCR 51, manufacturer: Anton Paar) according to DIN 53018.

[0145] Determination of the reaction temperature TB

[0146] The reaction temperature TR was determined using a thermocouple located in the bottom of the reactor. The reaction temperature TR is defined as the temperature of the reacting liquid.

[0147] Raw materials used

[0148] Catalyst for alkylene oxide addition (DMC catalyst):

[0149] Double metal cyanide catalyst containing zinc hexacyanocobaltate, tert-butanol, and polypropylene glycol with a number-average molecular weight of 1000 g / mol; described in WO-A 01 / 80994, Example 6.

[0150] IRGANQX® 1076:

[0151] Octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate. (BASF SE)

[0152] Qxophosphoric acid:

[0153] Orthophosphoric acid, 85 wt% in water (Fisher Scientific)

[0154] Neutralizing agent 1 (according to the invention):

[0155] A triethanolamine-started polyether based exclusively on propylene oxide with an OHZ of 495 mg KOH / g, corresponding to a molecular weight of 340 g / mol (Covestro)

[0156] Neutralizing agent 2 (according to the invention):

[0157] An ethylenediamine-started polyether based exclusively on propylene oxide, with an OHZ of 470 mg KOH / g, corresponding to a molecular weight of 477 g / mol (Covestro)

[0158] Neutralizing agent 3 (comparison):

[0159] Potassium carbonate (Acros) Preparation of precursors according to step ia)

[0160] Example A, according to the invention:

[0161] 2764.2 g of trimethylolpropane (TMP) and 255.2 g of an 85% solution of orthophosphoric acid in water were placed in a 10 l laboratory autoclave under a nitrogen atmosphere. Oxygen was removed during the heating phase to 100 °C by pressurizing the autoclave with nitrogen three times to an absolute pressure of 4 bar and then evacuating to approximately 40 mbar while stirring (mesh stirrer, 100 rpm). At 100 °C, the reactor contents were stripped below the liquid surface while stirring at 100 rpm over a period of 3 h while introducing 50 ml of N2. The stirrer speed was then increased to 450 rpm, and the reactor contents were cooled to 60 °C. Under these conditions, 3019 g of propylene oxide (PO) were metered into the gas space of the autoclave over a period of 5.1 hours. After a post-reaction time of 3.5 hours, the reactor contents were heated for a further 30 minutes at 60 °C under vacuum at a pressure of 30 mbar.After increasing to atmospheric pressure, 2.412 g of IRGANOX® 1076 were added to the reactor contents.

[0162] The measured OHN of the product was 616 mg KOH / g and the viscosity at 25 °C was 2315 mPas. 3.62 wt.% orthophosphoric acid was used, based on the batch mass. The calculated phosphorus content in the precursor according to Example A was 1.142 wt.%.

[0163] When repeating this approach, precursors with the following characteristics were obtained:

[0164] Example B, according to the invention:

[0165] Measured OHZ: 623.8 mg KOH / g; Acid number: 405 ppm KOH

[0166] Example C, according to the invention:

[0167] Measured OHZ: 624.9 mg KOH / g; Acid number: 420 ppm KOH

[0168] Example D, comparison:

[0169] 2633.2 g of TMP and 386.0 g of an 85% solution of orthophosphoric acid in water were placed in a 10 l laboratory autoclave under a nitrogen atmosphere. Oxygen was removed during the heating phase to 100 °C by pressurizing the autoclave with nitrogen three times to an absolute pressure of 4 bar and then evacuating to approximately 40 mbar while stirring (mesh stirrer, 100 rpm). At 100 °C, the reactor contents were stripped below the liquid surface while stirring at 100 rpm over a period of 3 hours while introducing 50 ml of N2. The stirrer speed was then increased to 450 rpm, and the reactor contents were cooled to 60 °C. Under these conditions, 3039.6 g of propylene oxide were metered into the gas space of the autoclave over a period of 5.1 hours. After a post-reaction time of 2.0 h, the reactor contents were heated for a period of 30 min at 60 °C in vacuum at a pressure of 35 mbar.After increasing the pressure to atmospheric pressure, 2.413 g of IRGANOX® 1076 were added to the reactor contents. The product's OHN was 619 mg KOH / g and its acid number was 5700 ppm KOH. 5.46 wt.% orthophosphoric acid was used, based on the batch mass. The calculated phosphorus content in the precursor according to Example D was 1.727 wt.%.

[0170] Manufacture of final products in accordance with steps ib) and ii

[0171] The results of the experiments for steps ib) and ii are summarized in Table 1.

[0172] Example 1, according to the invention:

[0173] 752.6 g of the precursor according to Example A and 0.51 g of neutralizing agent 1 were placed in a 2 l laboratory autoclave under a nitrogen atmosphere. The mixture was stirred at room temperature for 0.25 h (crossbar stirrer, 200 rpm). 0.124 g of DMC catalyst was then added, and the contents of the autoclave were stripped for 60 min at 130 °C while stirring at 200 rpm in a vacuum at a pressure of approximately 130 mbar while introducing 50 ml of nitrogen per minute via a distributor ring located below the liquid level. Thereafter, 447.5 g of propylene oxide were metered into the gas space of the autoclave at a constant metering rate over a period of 4.97 h, also at 130 °C but stirring at 800 rpm. Propylene oxide dosing started at a pressure of 0.044 bar. The maximum pressure of 3.29 bar was reached after 295 g of propylene oxide had been dosed.After a post-reaction time of 7.0 h, the mixture was heated for 0.5 h at 130 °C at an absolute pressure of 1 mbar, then cooled to 80 °C and 0.630 g of IRGANOX® 1076 was added. The OH number of the product was 395 mg KOH / g and the viscosity at 25 °C was 745 mPas. The calculated phosphorus content in the polyoxyalkylene polyol according to Example 1 was 0.716 wt. %.

[0174] Example 2, comparison:

[0175] 750.9 g of the precursor according to Example B were placed in a 2 l laboratory autoclave under a nitrogen atmosphere. 0.129 g of DMC catalyst was then added, and the contents of the autoclave were stripped for 45 minutes at 130 °C while stirring at 200 rpm (cross-beam stirrer) under vacuum at a pressure of approximately 120 mbar while introducing 50 ml of nitrogen per minute via a distributor ring located below the liquid level. Subsequently, 450.0 g of propylene oxide were metered into the gas space of the autoclave at a constant metering rate over a period of 5 hours, also at 130 °C but stirring at 800 rpm. The propylene oxide metering started at a pressure of 0.065 bar. The maximum pressure of 4.47 bar was reached after 234 g of propylene oxide had been metered. After a post-reaction time of 6.0 h, the mixture was heated for 0.5 h at 130 °C at an absolute pressure of 1 mbar, then cooled to 80 °C and 0.633 g of IRGANOX® 1076 was added.The OH number of the product was 394 mg KOH / g and the viscosity at 25 °C was 744 mPas. The calculated phosphorus content in the polyoxyalkylene polyol according to Example 2 was 0.714 wt. %. Example 3, inventive:

[0176] 750.0 g of the precursor according to Example B and 1.900 g of neutralizing agent 1 were placed in a 2 l laboratory autoclave under a nitrogen atmosphere. The mixture was stirred at room temperature for 0.25 h (crossbar stirrer, 200 rpm). 0.123 g of DMC catalyst was then added, and the contents of the autoclave were stripped for 60 min at 130 °C while stirring at 200 rpm in a vacuum at a pressure of approximately 125 mbar while introducing 50 ml of nitrogen per minute via a distributor ring located below the liquid level. Towards the end of the stripping time, the temperature was increased to 140 °C. Subsequently, 447.5 g of propylene oxide were metered into the gas space of the autoclave at a constant metering rate over a period of 5.03 h, also at 140 °C but with stirring at 800 rpm. Propylene oxide metering began at a pressure of 0.062 bar. The maximum pressure of 2.85 bar was reached after 245 g of propylene oxide had been metered.After a post-reaction time of 5.0 h, the mixture was heated for 0.5 h at 130 °C at an absolute pressure of 1 mbar, then cooled to 80 °C and 0.602 g of IRGANOX® 1076 was added. The OH number of the product was 397 mg KOH / g and the viscosity at 25 °C was 766 mPas. The calculated phosphorus content in the polyoxyalkylene polyol according to Example 3 was 0.714 wt. %.

[0177] Example 4, comparison:

[0178] 752.6 g of the precursor according to Example D and 26.03 g of neutralizing agent 1 were placed in a 2 l laboratory autoclave under a nitrogen atmosphere. The mixture was stirred at room temperature for 0.25 h (crossbar stirrer, 200 rpm). 0.120 g of DMC catalyst was then added, and the contents of the autoclave were stripped for 30 min at 130 °C while stirring at 200 rpm in a vacuum at a pressure of approximately 140 mbar while introducing 50 ml of nitrogen per minute via a distributor ring located below the liquid level. A total of 447.5 g of propylene oxide were then metered into the gas space of the autoclave, also at 130 °C, but stirring at 800 rpm. The propylene oxide metering began at a pressure of 0.044 bar. The dosing time alone was 5.08 h. Since a pressure of 5.5 bar was reached after 349.5 g of propylene oxide had been dosed, the propylene oxide dosing had to be continued for a period of 90 min.interrupted before the remaining amount of propylene oxide could be metered in. After a post-reaction time of 17.5 h, the mixture was heated for 0.5 h at 130 °C at an absolute pressure of 1 mbar, then cooled to 80 °C and 0.626 g of IRGANOX® 1076 was added. The OH number of the product was 405 mg KOH / g and the viscosity at 25 °C was 779 mPas. The calculated phosphorus content in the polyoxyalkylene polyol according to Example 4 was 1.060 wt. %.

[0179] Example 5, according to the invention:

[0180] In a 2 1 laboratory autoclave under nitrogen atmosphere, 750.2 g of the precursor according to

[0181] Example C and 1.363 g of neutralizing agent 2 were added. The mixture was stirred at room temperature for 0.25 h (crossbar stirrer, 200 rpm). 0.136 g of DMC catalyst was then added, and the contents of the autoclave were stripped for 60 min at 130 °C while stirring at 200 rpm in a vacuum at a pressure of approximately 140 mbar, while introducing 50 ml of nitrogen per minute through a distributor ring located below the liquid level. Subsequently, 451.8 g of propylene oxide were metered into the gas space of the autoclave at a constant metering rate over a period of 5.03 h, also at 130 °C, but stirring at 800 rpm. The propylene oxide metering started at a pressure of 0.050 bar. The maximum pressure of 2.72 bar was reached after 185 g of propylene oxide had been added. After a post-reaction time of 4.0 h, the mixture was heated for 0.5 h at 130 °C at an absolute pressure of 1 mbar, then cooled to 80 °C and 0.622 g of IRGANOX® 1076 was added.The OH number of the product was 394 mg KOH / g and the viscosity at 25 °C was 751 mPas. The calculated phosphorus content in the polyoxyalkylene polyol according to Example 5 was 0.712 wt.%.

[0182] Example 6, according to the invention:

[0183] 749.1 g of the precursor according to Example C and 2.707 g of neutralizing agent 2 were placed in a 2 l laboratory autoclave under a nitrogen atmosphere. The mixture was stirred at room temperature for 0.25 h (crossbar stirrer, 200 rpm). 0.131 g of DMC catalyst was then added, and the contents of the autoclave were stripped for 60 min at 130 °C while stirring at 200 rpm in a vacuum at a pressure of approximately 140 mbar while introducing 50 ml of nitrogen per minute through a distributor ring located below the liquid level. Thereafter, 451.1 g of propylene oxide were metered into the gas space of the autoclave at a constant metering rate over a period of 5.03 h, also at 130 °C but stirring at 800 rpm. Propylene oxide dosing started at a pressure of 0.048 bar. The maximum pressure of 2.60 bar was reached after 191 g of propylene oxide had been dosed.After a post-reaction time of 4.0 h, the mixture was heated for 0.5 h at 130 °C at an absolute pressure of 1 mbar, then cooled to 80 °C and 0.619 g of IRGANOX® 1076 was added. The OH number of the product was 393 mg KOH / g and the viscosity at 25 °C was 760 mPas. The calculated phosphorus content in the polyoxyalkylene polyol according to Example 6 was 0.711 wt. %.

[0184] Example 7, according to the invention:

[0185] 748.9 g of the precursor according to Example C and 1.881 g of neutralizing agent 1 were placed in a 2 l laboratory autoclave under a nitrogen atmosphere. The mixture was stirred at room temperature for 0.25 h (crossbar stirrer, 200 rpm). 0.063 g of DMC catalyst was then added, and the contents of the autoclave were stripped for 60 min at 130 °C while stirring at 200 rpm in a vacuum at a pressure of approximately 130 mbar while introducing 50 ml of nitrogen per minute via a distributor ring located below the liquid level. Thereafter, 451.1 g of propylene oxide were metered into the gas space of the autoclave at a constant metering rate over a period of 5.02 h, also at 130 °C, but stirring at 800 rpm. Propylene oxide dosing started at a pressure of 0.046 bar. The maximum pressure of 4.3 bar was reached after 365 g of propylene oxide had been dosed*.After a post-reaction time of 8.0 h, the mixture was heated for 0.5 h at 130 °C at an absolute pressure of 1 mbar, then cooled to 80 °C and 0.611 g of IRGANOX® 1076 was added. The OH number of the product was 396 mg KOH / g and the viscosity at 25 °C was 719 mPas. The calculated phosphorus content in the polyoxyalkylene polyol according to Example 7 was 0.712 wt. %.

[0186] *Halfing the amount of catalyst compared to Example 1 explains the higher pressure level.

[0187] Example 8, comparison:

[0188] 752.6 g of the precursor according to Example A and 0.106 g of neutralizing agent 3 were placed in a 2 l laboratory autoclave under a nitrogen atmosphere. The mixture was stirred at room temperature for 0.25 h (crossbar stirrer, 200 rpm). 0.121 g of DMC catalyst was then added, and the contents of the autoclave were stripped for 60 min at 130 °C while stirring at 200 rpm in a vacuum at a pressure of approximately 140 mbar while introducing 50 ml of nitrogen per minute via a distributor ring located below the liquid level. Thereafter, 447.5 g of propylene oxide were metered into the gas space of the autoclave at a constant metering rate over a period of 4.97 h, also at 130 °C but stirring at 800 rpm. Propylene oxide dosing started at a pressure of 0.045 bar. The maximum pressure of 4.01 bar was reached after 321 g of propylene oxide had been dosed.After a post-reaction time of 13.5 h, the mixture was heated for 0.5 h at 130 °C at an absolute pressure of 1 mbar, then cooled to 80 °C and 0.622 g of IRGANOX® 1076 was added. The OH number of the product was 396 mg KOH / g and the viscosity at 25 °C was 728 mPas. The calculated phosphorus content in the polyoxyalkylene polyol according to Example 8 was 0.716 wt. %.

[0189] Table 1

[0190] * Reaction temperature in step ii) = 140 °C

[0191] ** At 5.5 bar the epoxy dosing was interrupted

[0192] *** The amount of neutralizing agent 2 was doubled compared to Example 5. It can be seen that omitting the neutralization of the residual acid content in the reaction product obtained after step ia) leads to a poorer reaction course (higher pressure level during the epoxide metering); the same applies to the cases shown in which a precursor with a phosphoric acid content that is not high according to the invention was used or a neutralizing agent according to WO 2012134849 was used.

Claims

1. A process for producing a mixture containing a polyoxyalkylene polyol, preferably a polyether polyol, comprising the following steps: i. Providing a component (A) containing a polyoxyalkylene polyol A1) having a calculated hydroxyl number (OHZAI) of 600 to 1060 mg KOH / g by a) reacting an H-functional starter compound (B) with an alkylene oxide (C) using a component (D), wherein component (D) contains a Brønsted acid, to form an intermediate (E); b) adding an amine (F) to the intermediate (E) obtained under ia) to form component (A); ii. Subsequent reaction of component (A) with an alkylene oxide (G) in the presence of a DMC catalyst (H) to form the mixture containing the polyoxyalkylene polyol; wherein the reaction in step i.-a) takes place in the absence of a superacid, and wherein the calculated amount of Bronsted acid to be added according to step i.-a) is from 0.5 wt.% - 5.0 wt.%, preferably from 1.0 wt.-% to 4.5 wt.% and particularly preferably from 1.5 wt.% to 4.0 wt.% based on the total mass of the intermediate (E).

2. Process according to claim 1, wherein the polyoxyalkylene polyol contained in the mixture has an equivalent mass of 93 to 225 g / mol, preferably of 93 to 190 g / mol.

3. The process according to claim 1 or 2, wherein the Brpnsted acid is an oxygen acid of phosphorus, preferably phosphinic acid, phosphonic acid and / or phosphoric acid (ortho-phosphoric acid), and particularly preferably phosphoric acid (ortho-phosphoric acid).

4. The process according to any one of claims 1 to 4, wherein in step i.-b) the amount of amine (F) added is such that > ​​0.5 to < 2.2, preferably > 0.8 to < 2.0, amine nitrogen equivalents are added per residual acid equivalent in intermediate (E) in step i.-b), wherein the acid residue equivalent is determined using the method disclosed in the description.

5. The process according to any one of claims 1 to 5, wherein the amine (F) is a tertiary amine, preferably a hydroxyl-containing tertiary amine.

6. The process according to claim 6, wherein the tertiary amine has a hydroxyl number of 300 mg KOH / g to 1200 mg, preferably 350 mg KOH / g to 1000 mg KOH / g, particularly preferably 400 mg KOH / g to 800 mg, wherein the hydroxyl number was determined by the method disclosed in the description.

7. The process according to claim 5 or 6, wherein the tertiary amine is a hydroxyl-containing tertiary amine and the hydroxyl-containing tertiary amine is obtainable, preferably obtained is prepared by reacting ammonia, a primary amine, a primary diamine, a secondary amine and / or a secondary diamine with an alkylene oxide (I) and / or by chain extension of tertiary alcohol amines with an alkylene oxide (I).

8. The process according to any one of claims 1 to 7, wherein step i.-a) is carried out at a reaction temperature of less than 80°C, preferably from 30°C to 70°C and particularly preferably from 35°C to 65°C.

9. The process according to any one of claims 1 to 8, wherein step i.-a) and optionally step i.-b), preferably step i.-a) and step i.-b) are carried out in a first reactor and step ii) in a second reactor, wherein the first reactor is different from the second reactor.

10. The process according to any one of claims 1 to 9, wherein step ii) is carried out at a reaction temperature of 135°C to 145°C.

11. Intermediate (E) obtainable by a process according to any one of claims 1 to 10.

12. Component (A) obtainable by a process according to any one of claims 1 to 10.

13. A mixture obtainable by a process according to any one of claims 1 to 10.

14. Component (A) containing a polyoxyalkylene polyol A1) having a calculated hydroxyl number (OHZAI) of 600 to 1060 mg KOH and an alkoxylated oxygen acid of phosphorus, wherein the calculated phosphorus content is from 0.16 to 2.35 wt.% based on component (A).

15. Mixture containing a polyoxyalkylene polyol, preferably a polyether polyol having an equivalent mass of 93 to 225 g / mol, preferably 93 to 190 g / mol and an alkoxylated oxygen acid of phosphorus, wherein the calculated phosphorus content is from 0.065 to 1.287 wt. %, based on the mixture.

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