EP3728397A1

EP3728397A1 - Method for producing polyetherester polyols

Info

Publication number: EP3728397A1
Application number: EP18814632.8A
Authority: EP
Inventors: Markus MEURESCH; Aurel Wolf; Christoph Gürtler
Original assignee: Covestro Deutschland AG
Current assignee: Covestro Deutschland AG
Priority date: 2017-12-19
Filing date: 2018-12-12
Publication date: 2020-10-28
Also published as: CN111479846A; US20200317860A1; WO2019121205A1; EP3502162A1

Abstract

A subject of the invention is a method for producing a polyetherester polyol by addition of alkylene oxide and lactone to H-functional starter substance in the presence of a double metal cyanide catalyst, wherein a suspension medium containing no H-functional groups is first initially charged in a reactor, and an H-functional starter substance is subsequently continuously metered in to the reactor during the reaction, and wherein the lactone is a 4-membered cyclic lactone. A further subject is also the polyetherester polyol obtainable according to the method according to the invention, and also polyurethanes which can be produced therefrom.

Description

Process for the preparation of polyetherester polyols

The invention relates to a process for the preparation of a polyetherester polyol by addition of alkylene oxide and lactone to H-functional starter substance in the presence of a double metal cyanide catalyst, wherein initially a suspension agent containing no H-functional groups is introduced into a reactor, then an H functional starter substance is metered continuously into the reactor during the reaction, and wherein the lactone is a 4-membered ring lactone. A further subject is also the polyetherester polyol and obtainable by the process according to the invention and polyurethanes obtainable therefrom.

WO2012022048 discloses a process for preparing polyetherester polyols by reacting an H-functional starter substance with alkylene oxides and lactones in the presence of hybrid catalyst systems having a lactone content of 20% by weight, said systems comprising a double metal cyanide catalyst (DMC catalyst) and another copolymer. Catalyst, such as titanium alcoholate exist. The use of pure double metal cyanide catalysts leads in the opinion of the authors to cloudy or layered polyol products, which is due to inhomogeneities of the polyol compositions. The latter inhomogeneities lead, after reaction of the polyol component with polyisocyanates in the resulting polyurethane elastomer, to a poorer swelling behavior for polyetherester polyols prepared with double metal cyanide catalysts without co-catalyst compared to those with co-catalyst.

No. 5,032,671 discloses a process for preparing polyetherester polyols by reacting an H-functional starter substance with alkylene oxides and lactones in the presence of a double metal cyanide catalyst. In this case, oligomeric, H-functional starter substances are introduced together with the DMC catalyst in the reactor and metered in a mixture of alkylene oxides and lactones in so-called semi-batch mode 20 h, resulting in reaction times of 20 h and the maximum theoretical ester group content in the resulting copolymer 20 wt .-% scam.

It was therefore an object of the present invention to provide a simple and time-efficient process for the preparation of polyetheresterpolyols. In this case as far as possible commercially available catalysts in the field of polyol synthesis are to be used to obtain homogeneous, single-phase polyol product compositions, and to avoid inhomogeneities, such as turbidity or even separation processes, which complicates the proliferation, such as in the formation of polyurethanes. In particular, it was also subject of the present invention to increase the ester group content in the polyester polyol over the methods known in the art.

Surprisingly, it has been found that the object according to the invention is achieved by a process for preparing a polyetherester polyol by addition of alkylene oxide and lactone to H-functional starter substance in the presence of a double metal cyanide catalyst, wherein

(A) a suspending agent containing no H-functional groups is introduced into a reactor

(g) H-functional starter substance is metered continuously into the reactor during the reaction, and wherein the lactone is a 4-membered ring lactone.

In the method according to the invention, a suspending agent which does not contain any H-functional groups is initially introduced into the reactor. Subsequently, the amount of DMC catalyst required for the polyaddition, which is preferably not activated, is added to the reactor. The order of addition is not critical. It is also possible first to fill the DMC catalyst and then the suspending agent into the reactor. Alternatively, it is also possible first to suspend the DMC catalyst in the inert suspension medium and then to fill the suspension into the reactor. By means of the suspending agent, a sufficient heat exchange surface with the reactor wall or cooling elements installed in the reactor is made available, so that the released heat of reaction can be dissipated very well. In addition, the suspension agent provides heat capacity in the event of a cooling failure, so that the temperature in this case can be kept below the decomposition temperature of the reaction mixture.

The suspending agents used according to the invention contain no H-functional groups. Suitable suspending agents are all polar aprotic, weakly polar aprotic and nonpolar aprotic solvents, which each contain no H-functional groups. As suspending agent, it is also possible to use a mixture of two or more of these suspending agents. By way of example, the following polar aprotic solvents may be mentioned at this point: 4-methyl-2-oxo-1,3-dioxolane (also referred to below as cyclic propylene carbonate or cPC), 1,3-dioxolan-2-one (hereinafter also as cyclic ethylene carbonate or cEC), acetone, methyl ethyl ketone, acetonitrile, nitromethane, dimethyl sulfoxide, sulfolane, dimethylformamide, dimethylacetamide and V-methylpyrrolidone. The group of nonpolar and weakly polar aprotic solvents include, for example, ethers, such as dioxane, diethyl ether, methyl tert-butyl ether and tetrahydrofuran, esters, such as ethyl acetate and butyl acetate, hydrocarbons, such as pentane, n-hexane, benzene and alkylated Benzene derivatives (eg toluene, xylene, ethylbenzene) and chlorinated hydrocarbons, such as, for example, chloroform, chlorobenzene, dichlorobenzene and carbon tetrachloride. Preferred suspending agents are 4-methyl-2-oxo-1,3-dioxolane, 1,3-dioxolan-2-one, toluene, xylene, ethylbenzene, chlorobenzene and dichlorobenzene, and mixtures of two or more of these suspending agents, more preferably 4 -Methyl 2-oxo-l, 3-dioxolane and 1,3-dioxolan-2-one or a mixture of 4-methyl-2-oxo-l, 3-dioxolane and l, 3-dioxolan-2-one.

To step (q):

Preferably, in step (a), a suspending agent which does not contain any H-functional groups is initially charged together with DMC catalyst in the reactor, and no H-functional starter substance is initially introduced into the reactor. Alternatively, in step (a), a suspending agent which does not contain any H-functional groups and additionally a subset of the H-functional starter substance (s) and, if appropriate, DMC catalyst may also be initially charged in the reactor.

The DMC catalyst is preferably used in an amount such that the content of DMC catalyst in the resulting reaction product is 10 to 10,000 ppm, more preferably 20 to 5,000 ppm, and most preferably 50 to 2,000 ppm. In a preferred embodiment, the resulting mixture from suspension medium and DMC catalyst at a temperature of 90 to 150 ° C, more preferably from 100 to 40 ° C, an inert gas (for example, argon or nitrogen) and simultaneously introduced a reduced pressure (absolute) of 10 mbar to 800 mbar, especially preferably applied from 50 mbar to 200 mbar.

In an alternative preferred embodiment, the resulting mixture of suspending agent and DMC catalyst at a temperature of 90 to 150 ° C, more preferably from 100 to l40 ° C at least once, preferably three times with 1.5 bar to 10 bar (absolute), particularly preferably from 3 bar to 6 bar (absolute) of an inert gas (for example argon or nitrogen) is applied and then the overpressure is subsequently reduced to approximately 1 bar (absolute).

The DMC catalyst may be added in solid form or as a suspension in a suspending agent or in a mixture of at least two suspending agents. In a further preferred embodiment, in step (a)

(aI) the suspending agent or a mixture of at least two suspending agents submitted and (A-II) the temperature of the suspension medium or of the mixture of at least two suspending agents to 50 to 200 ° C, preferably 80 to l60 ° C, more preferably 100 to l40 ° C brought and / or the pressure in the reactor to less than 500 mbar , preferably 5 mbar to 100 mbar, wherein optionally an inert gas stream (for example of argon or nitrogen) is passed through the reactor,

wherein the double metal cyanide catalyst is added to the suspending agent or to the mixture of at least two suspending agents in step (a-I) or immediately thereafter in step (a-II), and

wherein the suspending agent does not contain H-functional groups.

To step (ß):

Step (β) serves to activate the DMC catalyst. This step may optionally be carried out under an inert gas atmosphere. Activation for the purposes of this invention is a step in which a partial amount of alkylene oxide or a mixture of alkylene oxide and lactone, at temperatures of 90 to 150 ° C to the DMC catalyst suspension is added and then the addition of the alkylene oxide or a mixture of Alkylene oxide compound and lactone is interrupted, wherein due to a subsequent exothermic chemical reaction, a heat generation, which can lead to a hotspot, and due to the reaction of alkylene oxide or a mixture of alkylene oxide and lactone, a pressure drop is observed in the reactor. The step of activation is the period from the addition of the subset of alkylene oxide compound or a mixture of alkylene oxide compound and lactone to the DMC catalyst until the evolution of heat occurs. Optionally, the partial amount of alkylene oxide compound or of a mixture of alkylene oxide compound and lactone can be added to the DMC catalyst in several steps and then the addition of the alkylene oxide compound or a mixture of alkylene oxide compound and lactone is interrupted in each case. In this case, the activation step comprises the time from the addition of the first aliquot of alkylene oxide compound or a mixture of alkylene oxide compound and lactone to the DMC catalyst until the evolution of heat after addition of the last aliquot of alkylene oxide or mixture of alkylene oxide and lactone occurs. In general, the activation step may be preceded by a step of drying the DMC catalyst and optionally the H-functional initiator substance at elevated temperature and / or reduced pressure, optionally with passage of an inert gas through the reaction mixture.

The metered addition of one or more alkylene oxides or a mixture of alkylene oxide compound and lactone can in principle be carried out in different ways. The start of dosing may be off out of vacuum or on a pre-selected form. The pre-pressure is preferably by introducing an inert gas (such as nitrogen or argon), wherein the pressure (absolute) is 5 mbar to 100 bar, preferably 10 mbar to 50 bar and preferably 20 mbar to 50 bar.

In a preferred embodiment, the amount of one or more alkylene oxides or a mixture of alkylene oxide compound and lactone used in the activation in step (β) is 0.1 to 25.0% by weight, preferably 1.0 to 20.0% by weight. %, particularly preferably 2.0 to 16.0% by weight (based on the amount of suspending agent used in step (a)). The alkylene oxide or a mixture of alkylene oxide compound and lactone can be added in one step or in portions in several portions. Preferably, after adding a partial amount of alkylene oxide compound or a mixture of alkylene oxide compound and lactone, the addition of the alkylene oxide compound or a mixture of alkylene oxide compound and lactone is stopped until the evolution of heat occurs, and then the next portion of alkylene oxide compound or a mixture of alkylene oxide compound and lactone is added.

To step (g):

The dosage of one or more H-functional starter substance (s), a mixture of alkylene oxide compound and lactone can be carried out simultaneously or sequentially (in portions), for example, the amount of H-functional starter substances and / or the metered in step (g) amount of a mixture be added at once or continuously from alkylene oxide compound and lactone. As used herein, the term "continuous" may be defined as a mode of adding a reactant so as to maintain a copolymerization effective concentration of the reactant, i. For example, the metering can be carried out at a constant metering rate, at a varying metering rate or in portions.

It is possible to meter the mixture of alkylene oxide compound and lactone at a constant metering rate or to gradually increase or decrease the metering rate or to add the mixture of alkylene oxide compound and lactone and / or further alkylene oxide compound and / or lactone in portions. Preferably, the alkylene oxide or a mixture of alkylene oxide compound and lactone is added to the reaction mixture at a constant metering rate. If several alkylene oxides and / or lactones are used for the synthesis of the polyether ester polyols, then the alkylene oxides and / or lactones can be metered individually or as a mixture. The metering of the alkylene oxide compound, of the lactone or of the H-functional starter substances can be carried out simultaneously or sequentially via separate doses (additions) or via one or more doses, the alkylene oxides, lactones or the H-functional starters being functional starter substances can be dosed individually or as a mixture. About the type and / or order of the dosage of the H-functional starter substances, the alkylene oxides and / or the lactone, it is possible to synthesize random, alternating, block-like or gradient-like polyetheresterpolyols.

In a preferred embodiment, in step (g) the dosage of the one or more H-functional starter substance (s) is terminated prior to the addition of the alkylene oxide.

A preferred embodiment of the method according to the invention is characterized inter alia by the fact that in step (g) the total amount of the one or more H-functional starter substance (s) is added. This addition can be carried out at a constant metering rate, at a varying metering rate or in portions.

For the process according to the invention, it has further been found that the copolymerization (step (g)) for the preparation of the polyetheresterpolyols advantageously at 50 to 150 ° C, preferably at 60 to 45 ° C, more preferably at 70 to 40 ° C and most preferably is carried out at 90 to 130 ° C. When temperatures are set below 50 ° C, the reaction generally becomes very slow. At temperatures above 150 ° C, the amount of unwanted by-products increases sharply.

The dosage of the alkylene oxide, the H-functional starter substance and the DMC catalyst can be carried out via separate or common metering. In a preferred embodiment, the alkylene oxide and the H-functional starter substance are fed via separate metering continuously to the reaction mixture. This addition of the one or more H-functional starter substance (s) can be carried out as a continuous metered addition to the reactor or in portions.

The steps (a), (β) and (g) can be carried out in the same reactor or separately in different reactors. Particularly preferred reactor types are: tubular reactors, stirred tanks, loop reactors.

Polyetheresterpolyole can be prepared in a stirred tank, wherein the stirred tank depending on the embodiment and operation over the reactor jacket, inside and / or located in a pumped circulation cooling surfaces is cooled. Both in the semi-batch application, in which the product is removed only after the end of the reaction, as well as in the continuous application, in which the product is removed continuously, pay particular attention to the metering rate of the alkylene oxide. The concentration of free Alkylene oxides in the reaction mixture during the activation step (step β) is preferably> 0 to 100 wt .-%, more preferably> 0 to 50 wt%, most preferably> 0 to 20 wt .-% (each based on the weight of the reaction mixture ). The concentration of free alkylene oxides in the reaction mixture during the reaction (step g) is preferably> 0 to 40 wt .-%, particularly preferably> 0 to 25 wt .-%, most preferably> 0 to 15 wt .-% (in each case on the weight of the reaction mixture).

In a preferred embodiment, the activated DMC catalyst-suspending agent mixture resulting from steps (a) and (β) in the same reactor is further treated with one or more alkylene oxide (s), one or more starter substance (s) and one or more lactones implemented. In another preferred embodiment, the activated DMC catalyst-suspending agent mixture resulting from steps (a) and (β) in another reaction vessel (for example a stirred tank, tubular reactor or loop reactor) is further reacted with alkylene oxides, one or more starter substance (s). and one or more lactone (s) implemented.

When carrying out the reaction in a tubular reactor, the activated catalyst-suspending agent mixture resulting from steps (a) and (β), one or more H-functional starter substance (s), one or more alkylene oxide (s) and one or more lactone (s) ) continuously pumped through a pipe. The molar ratios of the reactants vary depending on the desired polymer. Advantageously, mixing elements for better mixing of the reactants are incorporated, as they are marketed for example by the company Ehrfeld Mikrotechnik BTS GmbH, or mixer-heat exchanger elements, which improve the mixing and heat dissipation simultaneously.

Loop reactors may also be used to prepare polyetherester polyols. This generally includes reactants with material recycling, such as a jet loop reactor, which can also be operated continuously, or a loop-shaped tubular reactor with suitable devices for the circulation of the reaction mixture or a loop of several series-connected tubular reactors. The use of a loop reactor is particularly advantageous because backmixing can be realized so that the concentration of free alkylene oxides in the reaction mixture in the optimum range, preferably in the range> 0 to 40 wt .-%, particularly preferably> 0 to 25 Wt .-%, most preferably> 0 to 15 wt .-% (in each case based on the weight of the reaction mixture) can be maintained. Preferably, the polyetherester polyols are prepared in a continuous process comprising both continuous copolymerization and continuous addition of the one or more H-functional starter substance (s).

The invention therefore also provides a process wherein, in step (g), one or more H-functional starter substance (s), one or more alkylene oxide (s), one or more lactone (s) are reacted and DMC catalyst ("copolymerization") are metered continuously into the reactor and wherein the resulting reaction mixture (containing the reaction product) is continuously removed from the reactor. Preferably, in step (g), the DMC catalyst suspended in H-functional starter substance is added continuously.

For example, for the continuous process for preparing the polyetherester polyols according to steps (a) and (b), an activated DMC catalyst-suspending agent mixture is prepared, then according to step (g)

(gΐ) in each case a partial amount of one or more H-functional starter substance (s), one or more alkylene oxide (s) and one or more lactone (s) reacted metered to initiate the copolymerization, and

(g2) while the progress of the copolymerization, the remaining amount of DMC catalyst, one or more starter substance (s) and alkylene oxide (s) and one or more lactone (s) continuously metered in, while simultaneously resulting reaction mixture is continuously removed from the reactor ,

In step (g), the DMC catalyst is preferably added suspended in the H-functional starter substance, the amount preferably being selected such that the content of DMC catalyst in the resulting reaction product is 10 to 10,000 ppm, more preferably 20 to 5,000 ppm and most preferably 50 to 2000 ppm.

Preferably, steps (a) and (b) are carried out in a first reactor, and then the resulting reaction mixture is transferred to a second reactor for the copolymerization according to step (g). However, it is also possible to carry out the steps (a), (β) and (g) in a reactor.

It has also been found that the process of the present invention can be used to make large quantities of the polyetherester polyol product using initially a DMC catalyst activated according to steps (a) and (β) in a suspending agent and during the copolymerization ( g) the DMC catalyst is added without prior activation. Thus, a particularly advantageous feature of the preferred embodiment of the present invention is the ability to use "fresh" DMC catalysts without activation for the portion of DMC catalyst that is added continuously in step (g). Activation of DMC catalysts, analogous to step (b), not only involves additional operator attention, which increases manufacturing costs, but also requires a pressure reaction vessel, which also increases the capital cost of constructing a corresponding production facility. Here, "fresh" catalyst is defined as unactivated DMC catalyst in solid form or in the form of a slurry in a starter substance or suspending agent. The ability of the present process to utilize fresh, unactivated DMC catalyst in step (g) enables significant savings in the commercial production of polyetherester polyols and is a preferred embodiment of the present invention.

As used herein, the term "continuous" may be defined as the mode of addition of a relevant catalyst or reactants to maintain a substantially continuous effective concentration of the DMC catalyst or reactant. The catalyst feed may be genuinely continuous or at relatively closely spaced increments. Likewise, continuous starter addition may be truly continuous or in increments. It would not depart from the present process to incrementally add a DMC catalyst or reactant such that the concentration of added materials drops substantially to zero for some time prior to the next incremental addition. However, it is preferred that the DMC catalyst concentration be maintained at substantially the same concentration during most of the course of the continuous reaction and that starter substance be present during the major part of the copolymerization process. An incremental addition of DMC catalyst and / or reactant that does not materially affect the nature of the product is still "continuous" in the sense that the term is used herein. For example, it is feasible to provide a feedback loop in which a portion of the reacting mixture is returned to a previous point in the process, thereby smoothing out discontinuities caused by incremental additions.

Step foej

Optionally, in step (d) the reaction mixture continuously removed in step (g), which generally contains a content of from 0.05% by weight to 10% by weight of alkylene oxide and / or lactone, can be transferred to a post-reactor, in which, by means of an after-reaction, the content of free alkylene oxide is reduced to less than 0.05% by weight in the reaction mixture. As a secondary reactor can serve, for example, a tubular reactor, a loop reactor or a stirred tank.

Preferably, the pressure in this post reactor is at the same pressure as in the reactor in which the reaction step (g) is carried out. However, the pressure in the downstream reactor can also be selected higher or lower and the downstream reactor operated at atmospheric pressure or a slight overpressure. The temperature in the downstream reactor is preferably 50 to 150 ° C and more preferably 80 to 140 ° C.

The polyetheresterpolyols obtained according to the invention have, for example, a functionality of at least 1, preferably from 1 to 8, particularly preferably from 1 to 6 and very particularly preferably from 2 to 4. The molecular weight is preferably from 400 to 10,000 g / mol and more preferably from 500 to 6,000 g / mol.

In general, alkylene oxides (epoxides) having 2-24 carbon atoms can be used for the process according to the invention. The alkylene oxides having 2-24 carbon atoms are, for example, one or more compounds selected from the group consisting of ethylene oxide, propylene oxide, 1-butene oxide, 2,3-butene oxide, 2-methyl-1,2-propene oxide (isobutene oxide), 1-pentoxide, 2,3-pentenoxide, 2-methyl-l, 2-butene oxide, 3-methyl-l, 2-butene oxide, 1-hexene oxide, 2,3-hexene oxide, 3,4-hexene oxide, 2-methyl l, 2-pentenoxide, 4-methyl-l, 2-pentenoxide, 2-ethyl-l, 2-butene oxide, 1-epoxide, 1-octene oxide, 1-nonoxide, 1-decene oxide, 1-undecenoxide, 1-dodecene oxide, 4-methyl-l, 2-pentenoxide, butadiene monoxide, isoprene monoxide, cyclopentene oxide, cyclohexene oxide, cycloheptenoxide, cyclooctene oxide, styrene oxide, methylstyrene oxide, pinene oxide, mono- or multiply epoxidized fats as mono-, di- and triglycerides, epoxidized fatty acids, C 1 -C24 - esters of epoxidized fatty acids, epichlorohydrin, glycidol, and derivatives of glycidol such as methyl glycidyl ether, ethyl glycidyl ether, 2-ethylhexyl glycidyl ether, allyl glycidyl ether , Glycidyl methacrylate and epoxy-functional alkyloxysilanes such as 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropyltripropoxysilane, 3-glycidyloxypropyl-methyl-dimethoxysilane, 3-glycidyloxypropyl-ethyldiethoxysilane, 3-glycidyloxypropyltriisopropoxysilane. The alkylene oxides used are preferably ethylene oxide and / or propylene oxide, in particular propylene oxide.

As a suitable H-functional starter substance ("starter") can be used compounds having active for the alkoxylation H atoms having a molecular weight of 18 to 4500 g / mol, preferably from 62 to 500 g / mol and particularly preferably from 62 to 250 g / mol. The ability to use a low molecular weight starter is a distinct advantage versus the use of oligomeric initiators made by a prior oxyalkylation. In particular, economics achieved by omitting a separate oxyalkylation process are achieved.

For the alkoxylation active groups having active H atoms are, for example, -OH, -NH 2 (primary amines), -NH- (secondary amines), -SH and -CO 2 H, preferred are -OH and -NH 2, more preferably -OH. As H-functional starter substance, for example, one or more compounds selected from the group consisting of mono- or polyhydric alcohols, polyhydric amines, polyhydric thiols, amino alcohols, thio alcohols, hydroxy esters, polyether polyols, polyester polyols, polyester ether polyols,

Polyether carbonate polyols, polycarbonate polyols, polycarbonates, polyethyleneimines, polyetheramines, polytetrahydrofurans (z. B. PolyTHF ^® of BASF), Polytetrahydrofuranamine, Polyetherthiole, polyacrylate polyols, castor oil, the mono- or di-glyceride of ricinoleic acid, monoglycerides of fatty acids, chemically modified mono-, di- and or triglycerides of fatty acids, and C1-C24 alkyl fatty acid esters containing on average at least 2 OH groups per molecule used. By way of example, it is at the C1-C24 alkyl fatty acid esters that contain on average at least 2 OH groups per molecule to commercial products such as Lupranol Balance ^® (Fa. BASF AG), Merginol ^® grades (Fa. Hobum Oleochemicals GmbH), Sovermol ^® grades (Messrs. Cognis Germany GmbH & Co. KG) and Soyol ^® TM types (Fa. USSC Co.).

Alcohols, amines, thiols and carboxylic acids can be used as monofunctional starter substances. The following may be used as mono-functional alcohols: methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, tert-butanol, 3-buten-1-ol, 3-butyn-1-ol, 2 Methyl-3-buten-2-ol, 2-methyl-3-butyn-2-ol, propargyl alcohol, 2-methyl-2-propanol, 1-tert-butoxy-2-propanol, 1-pentanol, 2-pentanol, 3-pentanol, 1-hexanol, 2-hexanol, 3-hexanol, 1-heptanol, 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 3-octanol, 4-octanol, phenol, 2-hydroxybiphenyl, 3-hydroxybiphenyl, 4-hydroxybiphenyl, 2-hydroxypyridine, 3-hydroxypyridine, 4-hydroxypyridine. Suitable mono-functional amines are: butylamine, tert-butylamine, pentylamine, hexylamine, aniline, aziridine, pyrrolidine, piperidine, morpholine. As monofunctional thiols can be used: ethanethiol, 1 -propanethiol, 2-propanethiol, 1-butanethiol, 3-methyl-l-butanethiol, 2-butene-1-thiol, thiophenol. The following may be mentioned as mono-functional carboxylic acids: formic acid, acetic acid, propionic acid, butyric acid, fatty acids such as stearic acid, palmitic acid, oleic acid, linoleic acid, linolenic acid, benzoic acid, acrylic acid.

Polyhydric alcohols which are suitable as H-functional starter substances are, for example, dihydric alcohols (for example ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-propanediol, 1,4-butanediol, 1,4-butenediol, 1,4-butynediol, neopentylglycol, 1, 5-pentanediol, methylpentanediols (such as 3-methyl-l, 5-pentanediol), 1, 6-hexanediol, l, 8-octanediol, l, l0-decanediol, l, l2-dodecanediol, bis (hydroxymethyl) cyclohexanes (such as, for example, 1,4-bis (hydroxymethyl) cyclohexane), triethylene glycol, tetraethylene glycol, polyethylene glycols, dipropylene glycol, tripropylene glycol, polypropylene glycols, dibutylene glycol and polybutylene glycols); trihydric alcohols (such as trimethylolpropane, glycerol, trishydroxyethyl isocyanurate, castor oil); tetrahydric alcohols (such as pentaerythritol); Polyalcohols (such as sorbitol, hexitol, sucrose, starch, starch hydrolysates, cellulose, cellulose hydrolysates, hydroxy-functionalized fats and oils, in particular castor oil).

The H-functional starter substances may also be selected from the class of polyether polyols having a molecular weight M _n in the range of 58 to 4500 g / mol and a functionality of 2 to 3. Preference is given to polyether polyols which are composed of repeating ethylene oxide and propylene oxide units, preferably with a proportion of 35 to 100% propylene oxide units, more preferably with a proportion of 50 to 100% propylene oxide units. These may be random copolymers, gradient copolymers, alternating or block copolymers of ethylene oxide and propylene oxide.

The H-functional starter substances can also be selected from the substance class of the polyesterpolyols. Polyester polyols used are at least difunctional polyesters. Polyester polyols preferably consist of alternating acid and alcohol units. As acid components z. For example, succinic acid, maleic acid, maleic anhydride, adipic acid, phthalic anhydride, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride or mixtures of the acids and / or anhydrides mentioned. As alcohol components z. B. ethanediol, 1,2-propanediol, l, 3-propanediol, 1, 4-butanediol, l, 5-pentanediol, neopentyl glycol, l, 6-hexanediol, 1,4-bis (hydroxymethyl) cyclohexane, diethylene glycol, Dipropylene glycol, trimethylolpropane, glycerol, pentaerythritol or mixtures of the alcohols mentioned. If divalent or polyhydric polyether polyols are used as the alcohol component, polyester polyester polyols are obtained which can likewise serve as starter substances for the preparation of the polyetherester polyols.

In a further embodiment of the invention, polyether carbonate polyols can be used as H-functional starter substances. These polyether carbonate polyols used as H-functional starter substances are prepared beforehand in a separate reaction step for this purpose. The H-functional starter substances generally have a functionality (ie number of H atoms active per molecule for the polymerization) of from 1 to 8, preferably from 2 or 3. The H-functional starter substances are used either individually or as a mixture of at least two H-functional starter substances.

Particularly preferably, the H-functional starter substances are one or more compounds selected from the group consisting of ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 2-methylpropane-1,3-diol, neopentyl glycol, 1,6-hexanediol, 1,8-octanediol, diethylene glycol, dipropylene glycol, glycerol, trimethylolpropane, pentaerythritol, sorbitol and polyether polyols having a molecular weight Mn in the range from 150 to 4500 g / mol and a functionality of 2 to 3.

The polyether carbonate polyols are prepared by catalytic addition of carbon dioxide and alkylene oxides to H-functional starter substances. For the purposes of the invention, "H-functional" means the number of H atoms active for the alkoxylation per molecule of the starter substance.

Furthermore, it is possible to use polycarbonate diols as H-functional starter compounds, in particular those having a molecular weight Mn in the range from 150 to 4500 g / mol, preferably 500 to 2500 g / mol, for example by reacting phosgene, dimethyl carbonate, diethyl carbonate or diphenyl carbonate and difunctional Alcohols or polyester polyols or polyether polyols are produced. Examples of polycarbonates can be found e.g. in EP-A 1359177. For example, as the polycarbonate diols, the Desmophen® C

Types of Covestro AG may be used, e.g. Desmophen® C 1100 or Desmophen® C 2200.

In a further embodiment of the invention, polyether carbonate polyols (for example Cardyon® polyols from Covestro), polycarbonate polyols (for example Converge® polyols from Novomer / Saudi Aramco, NEOSPOL polyols from Repsol etc.) and / or polyetherestercarbonate polyols can be used as H-functional Starter compounds are used. In particular, polyether carbonate polyols, polycarbonate polyols and / or polyetherestercarbonate polyols can be obtained by reacting alkylene oxides, preferably ethylene oxide, propylene oxide or mixtures thereof, optionally further co-monomers with CO 2 in the presence of a further H-functional starter compound and using catalysts. These catalysts comprise double metal cyanide catalysts (DMC catalysts) and / or metal complex catalysts, for example based on the metals zinc and / or cobalt, for example zinc glutarate catalysts (described, for example, in MH Chisholm et al., Macromolecules 2002, 35, 6494). , so-called zinc diiminate catalysts (described, for example, in SD Allen, J. Am. Chem. Soc., 2002, 124, 14284) and so-called cobalt-salen catalysts (described, for example, in US 7,304,172 B2, US 2012/0165549 A1) and / or manganese-salen complexes. An overview of the known catalysts for the copolymerization of alkylene oxides and CO 2 are, for example, Chemical Communications 47 (2011) 141-163. By using different catalyst systems, reaction conditions and / or reaction sequences, the formation of random, alternating, block-like or gradient-like polyethercarbonate polyols, polycarbonate polyols and / or polyetherestercarbonate polyols takes place. These polyethercarbonate polyols, polycarbonate polyols and / or polyetherestercarbonate polyols used as H-functional starter compounds can be prepared beforehand in a separate reaction step for this purpose.

In a preferred embodiment of the process, the 4-membered ring lactone is one or more compound (s) selected from the group consisting of propiolactone, β-butyrolactone, β-isovalerolactone, β-caprolactone, β-isocaprolactone, β-methyl-β-valerolactone , Diketene, preferably propiolactone and .beta.-butyrolactone, and more preferably propiolactone.

DMC catalysts for use in the homopolymerization of alkylene oxides are in principle known in the art (see eg US-A 3 404 109, US-A 3 829 505, US-A 3 941 849 and US-A 5 158 922) , DMC catalysts, e.g. in US Pat. No. 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 have very high activity and make possible the preparation of polyether carbonate polyols at very low catalyst concentrations, so that a separation of the catalyst from the finished product ia is no longer necessary. A typical example is the highly active DMC catalysts described in EP-A 700 949 which, in addition to a double metal cyanide compound (eg zinc hexacyanocobaltate (III)) and an organic complex ligand (eg tert-butanol), also have a polyether having a number-average molecular weight greater than 500 g / mol.

The DMC catalysts of the invention are preferably obtained by

(I) in the first step, an aqueous solution of a metal salt with the aqueous solution of a

Metal cyanide salt in the presence of one or more organic complexing ligands, e.g. an ether or alcohol,

(ii) wherein in the second step the solid from the suspension obtained from (i) by known

Techniques (such as centrifugation or filtration) is separated,

(iii) optionally wherein, in a third step, the isolated solid is washed with an aqueous solution of an organic complex ligand (eg by resuspending and subsequent reisolation by filtration or centrifugation), (iv) subsequently drying the resulting solid, optionally after pulverization, at temperatures of generally 20-120 ° C. and at pressures of generally 0.1 mbar to atmospheric pressure (1013 mbar),

and wherein in the first step or immediately after the precipitation of the double metal cyanide compound (second step) one or more organic complex ligands, preferably in excess (based on the double metal cyanide compound) and optionally further complex-forming components are added.

The double metal cyanide compounds contained in the DMC catalysts according to the invention are the reaction products of water-soluble metal salts and water-soluble metal cyanide salts.

For example, an aqueous solution of zinc chloride (preferably in excess, based on the metal cyanide salt such as, for example, potassium hexacyanocobaltate) and potassium hexacyanocobaltate is mixed and then dimethoxyethane (glyme) or butanol (preferably in excess, based on zinc hexacyanocobaltate) is added to the suspension formed.

Metal salts suitable for preparing the double metal cyanide compounds preferably have the general formula (II)

M (X) _n (II) where

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 Zn ²⁺ , Fe ²⁺ , Co ²⁺ or Ni ²⁺ ,

X are one or more (ie different) anions, preferably an anion selected from the group of halides (ie 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 when X = halide, hydroxide, carboxylate, cyanate, thiocyanate, isocyanate, isothiocyanate or nitrate, or suitable metal salts have the general formula (III), M _G (C) ₃ (III) wherein

M is selected from the metal cations Fe ³⁺ , Al ³⁺ , Co ³⁺ and Cr ³⁺ , X are one or more (ie different) anions, preferably an anion selected from the group of halides (ie fluoride, chloride, bromide, iodide), hydroxide, sulfate, carbonate, cyanate, thiocyanate, isocyanate, isothiocyanate, carboxylate, oxalate and nitrate ;

r is 2 when X = sulfate, carbonate or oxalate and

r is 1 when X = halide, hydroxide, carboxylate, cyanate, thiocyanate, isocyanate, isothiocyanate or nitrate, or suitable metal salts have the general formula (IV),

M (X) _S (IV) where

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

s is 2 if X = sulfate, carbonate or oxalate and

s is 4 when X = halide, hydroxide, carboxylate, cyanate, thiocyanate, isocyanate, isothiocyanate or nitrate, or suitable metal salts have the general formula (V),

M (X) _t (V) where

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

t is 3 when X = sulfate, carbonate or oxalate and

t is 6 when X = halide, hydroxide, carboxylate, cyanate, thiocyanate, isocyanate, isothiocyanate or nitrate,

Examples of suitable 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, iron (III) chloride, cobalt (II) chloride, Cobalt (II) thiocyanate, nickel (II) chloride and nickel (II) nitrate. It is also possible to use mixtures of different metal salts. Metal cyanide salts suitable for preparing the double metal cyanide compounds preferably have the general formula (VI)

(Y) _a M '(CN) _b (A) _c (VI) where

M 'is selected from one or more metal cations of 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 of the group consisting of Co (II), Co (III), Fe (II), Fe (III), Cr (III), Ir (III) and Ni (II)

Y is selected from one or more metal cations of the group consisting of alkali metal (ie Li ⁺ , Na ⁺ , K ⁺ , Rb ⁺ ) and alkaline earth metal (ie Be ²⁺ , Mg ²⁺ , Ca ²⁺ , Sr ²⁺ , Ba ²⁺ )

A is selected from one or more of the group consisting of halides (i.e., fluoride, chloride, bromide, iodide), hydroxide, sulfate, carbonate, cyanate, thiocyanate, isocyanate, isothiocyanate, carboxylate, azide, oxalate or nitrate, and

a, b and c are integer numbers, with the values for a, b and c chosen to give the electroneutrality of the metal cyanide salt; a is preferably 1, 2, 3 or 4; b is preferably 4, 5 or 6; c preferably has the value 0.

Examples of suitable metal cyanide salts are sodium hexacyanocobaltate (III), potassium hexacyanocapaltate (III), potassium hexacyanoferrate (II), potassium hexacyanoferrate (III), calcium hexacyanocobaltate (III) and lithium hexacyanocobaltate (III).

Preferred double metal cyanide compounds which are contained in the DMC catalysts according to the invention are compounds of the general formula (VII)

M _x [M ' _x , (CN) _y ] _z (VII) wherein M is as in formula (II) to (V) and

M 'is as defined in formula (VI), and

x, x ', y and z are integers and chosen so that the electron neutrality of the double metal cyanide compound is given.

Preferably

x = 3, x '= 1, y = 6 and z = 2,

M = Zn (II), Fe (II), Co (II) or Ni (II) and

M '= Co (III), Fe (III), Cr (III) or Ir (III). Examples of suitable double metal cyanide compounds a) 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 Pat. No. 5,158,922 (column 8, lines 29-66). Zinc hexacyanocobaltate (III) is particularly preferably used.

The organic complex ligands added in the preparation of the DMC catalysts are described, for example, in US Pat. No. 5,158,922 (see in particular column 6, lines 9 to 65), US Pat. No. 3,404,109, US Pat. No. 3,829,505, US Pat. No. 3,941,849 and EP-A-700,949 EP-A 761 708, JP 4 145 123, US 5 470 813, EP-A 743 093 and WO-A 97/40086). For example, water-soluble, organic compounds having 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 complexing 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 containing both aliphatic or cycloaliphatic ether groups as well as 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-oxetan-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-oxetan-methanol.

Optionally, in the preparation of the DMC catalysts according to the invention, one or more complex-forming component (s) from the classes of polyethers, polyesters, polycarbonates, Polyalkylenglykolsorbitanester, Polyalkylenglykolglycidylether, 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-acrylic acid). styrene), oxazoline polymers, polyalkyleneimines, maleic and maleic anhydride copolymers, hydroxyethylcellulose and polyacetals, or the glycidyl ethers, glycosides, carboxylic esters of polyhydric alcohols, bile acids or their salts, esters or amides, cyclodextrins, phosphorus compounds, a, b-unsaturated carboxylic esters or ionic surfactants. or border area henaktiven compounds used. In the preparation of the DMC catalysts according to the invention, preference is given in the first step to the aqueous solutions of the metal salt (eg zinc chloride) used in stoichiometric excess (at least 50 mol%) based on metal cyanide salt (ie at least one molar ratio of metal salt to metal cyanide salt of 2, 25 to 1.00) and the metal cyanide salt (eg, potassium hexacyanocobaltate) in the presence of the organic complexing ligand (eg, tert-butanol) to form a suspension containing the double metal cyanide compound (eg, zinc hexacyanocobaltate), water, excess metal salt, and den contains organic complex ligands.

The organic complex ligand can be present in the aqueous solution of the 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 to be advantageous to mix the aqueous solutions of the metal salt and the metal cyanide salt, and the organic complex ligand with vigorous stirring. Optionally, the suspension formed in the first step is subsequently treated with a further complex-forming component. The complex-forming component is preferably used in a mixture with water and organic complex ligands. A preferred method of carrying out the first step (i.e., the preparation of the suspension) is by using a mixing nozzle, more preferably using a jet disperser as described in WO-A-01/39883.

In the second step, the isolation of the solid (i.e., the precursor of the inventive catalyst) from the suspension is accomplished by known techniques such as centrifugation or filtration.

In a preferred embodiment, the isolated solid is then 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. Preferably, the amount of the organic complex ligand in the aqueous washing solution is between 40 and 80 wt .-%, based on the total solution.

Optionally, in the third step, the aqueous washing solution further complex-forming component, preferably in the range between 0.5 and 5 wt .-%, based on the total solution added.

In addition, it is advantageous to wash the isolated solid more than once. Preferably, in a first washing step (iii-1) with an aqueous solution of the unsaturated alcohol washed (eg by resuspension and subsequent reisolation by filtration or centrifugation) to remove in this way, for example, water-soluble by-products, such as potassium chloride, from the catalyst according to the invention. More preferably, the amount of the unsaturated alcohol in the aqueous washing solution is from 40 to 80% by weight based on the total solution of the first washing step. In the further washing steps (iii-2), either the first washing step is repeated one or more times, preferably once to three times is repeated, or preferably, a non-aqueous solution, such as a mixture or solution of unsaturated alcohol and further complex-forming component (preferably in the range between 0.5 and 5 wt .-%, based on the total amount of the washing solution of step (iii) 2)), used as a washing solution and the solid so washed once or several times, preferably once to three times.

The isolated and optionally washed solid is then, optionally after pulverization, at temperatures of generally 20 - 100 ° C and at pressures of generally 0.1 mbar to atmospheric pressure (1013 mbar) dried.

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

The polyetherester polyols obtainable by the process according to the invention have a low content of by-products and can be processed without problems, in particular by reaction with di- and / or polyisocyanates to form polyurethanes, in particular flexible polyurethane foams. For polyurethane applications, polyetherester polyols are preferably used which are based on an H-functional starter substance having a functionality of at least 2. In addition, the polyetherester polyols obtainable by the process according to the invention can be used in applications such as washing and cleaning agent formulations, drilling fluids, fuel additives, ionic and nonionic surfactants, lubricants, process chemicals for paper or textile production or cosmetic formulations. It is known to the person skilled in the art that, depending on the particular field of application, the polyetherester polyols to be used have to fulfill certain substance properties such as, for example, molecular weight, viscosity, functionality and / or hydroxyl number.

The polyisocyanate may be an aliphatic or aromatic di- or polyisocyanate. Examples are 1, 4-butylene diisocyanate, l, 5-pentane diisocyanate, l, 6-hexamethylene diisocyanate (HD1) or their dimers, trimers, pentamers, heptamers or nonamers or mixtures thereof, Isophorone diisocyanate (IPDI), 2,2,4- and / or 2,4,4-trimethylhexamethylene diisocyanate, the isomeric bis (4,4'-isocyanatocyclohexyl) methanes or mixtures thereof of any isomer content, 1,4-cyclohexylene diisocyanate, 1,4 Phenylene diisocyanate, 2,4- and / or 2,6-tolylene diisocyanate (TDI), l, 5-naphthylene diisocyanate, 2,2'- and / or 2,4'- and / or 4,4'-diphenylmethane diisocyanate (MDI) and / or higher homologues (polymeric MDI), 1,3- and / or 1,4-bis (2-isocyanato-prop-2-yl) -benzene (TMXDI), 1,3-bis (isocyanatomethyl) benzene ( XDI), and alkyl 2,6-diisocyanatohexanoate (lysine diisocyanates) with Cl to C6 alkyl groups. Preference is given here to an isocyanate from the diphenylmethane diisocyanate series.

In addition to the abovementioned polyisocyanates, modified diisocyanates containing uretdione, isocyanurate, urethane, carbodiimide, uretonimine, allophanate, biuret, amide, iminooxadiazinedione and / or oxadiazinetrione structure as well as unmodified polyisocyanate having more than 2 NCO can also be proportionally added. Groups per molecule such as 4-isocyanatomethyl-l, 8-octane diisocyanate (nonane triisocyanate) or triphenylmethane-4,4 ', 4 "triisocyanate are used.

In a first embodiment, the invention relates to a process for preparing a polyetherester polyol by addition of alkylene oxide and lactone to H-functional starter substance in the presence of a double metal cyanide catalyst, characterized in that

(a) a suspending agent containing no H-functional groups is placed in a reactor, and

(g) H-functional starter substance is metered continuously into the reactor during the reaction and wherein the lactone is a 4-membered ring lactone.

In a second embodiment, the invention relates to a process according to the first embodiment, wherein in step (a) a suspending agent which does not contain H-functional groups is introduced into the reactor, and thereby no H-functional starter substance is introduced into the reactor.

In a third embodiment, the invention relates to a method according to the first embodiment, wherein in step (a) a suspending agent which does not contain H-functional groups, and additionally a subset of the H-functional starter substance is introduced into the reactor.

In a fourth embodiment, the invention relates to a process according to one of the first to third embodiments, wherein in step (a) a suspending agent which does not contain H-functional groups, together with DMC catalyst is introduced into the reactor. In a fifth embodiment, the invention relates to a method according to the fourth embodiment, wherein subsequent to step (a)

(ß) is added to the mixture of step (a) a portion of alkylene oxide or a mixture of alkylene oxide and lactone at temperatures of 90 to l50 ° C, and then the addition of the alkylene oxide compound is interrupted.

In a sixth embodiment, the invention relates to a process according to the embodiment, wherein in step (β) a mixture of alkylene oxide and lactone is added and the proportion of the lactone 1 wt .-% to 80 wt .-%, preferably 3 wt .-% to 60 wt .-% and particularly preferably 22 wt .-% to 40 wt .-% based on the total mass of metered alkylene oxide and lactone in step (ß).

In a seventh embodiment, the invention relates to a process according to one of the first to sixth embodiments, wherein in step (g) H-functional starter substance, alkylene oxide and lactone are continuously metered ("copolymerization").

In an eighth embodiment, the invention relates to a method according to any one of the first to sixth embodiments, wherein in step (g) the dosage of the H-functional starter substance is terminated in time prior to the addition of the alkylene oxide.

In a ninth embodiment, the invention relates to a process according to the eighth embodiment, wherein in step (g) a mixture of alkylene oxide and lactone is added and the proportion of lactone 1 wt .-% to 80 wt .-%, preferably 3 wt .-% to 60 wt .-% and particularly preferably 22 wt .-% to 40 wt .-% based on the total mass of metered alkylene oxide and lactone in step (g).

In a tenth embodiment, the invention relates to a method according to any one of the first to ninth embodiments, wherein the 4-membered ring lactone is one or more compound (s) selected from the group consisting of propiolactone, β-butyrolactone, β-isovalerolactone, β -Caprolactone, ß-isocaprolactone, ß-methyl-ß-valerolactone, diketene preferably propiolactone and ß-butyrolactone.

In an eleventh embodiment, the invention relates to a process according to any one of the eighth to tenth embodiments, wherein in step (g) DMC catalyst is continuously metered into the reactor and the resulting reaction mixture is continuously removed from the reactor. In a twelfth embodiment, the invention relates to a process according to the eighth embodiment, wherein the DMC catalyst suspended in H-functional starter substance is added continuously. In the thirteenth embodiment, the invention relates to a process according to the eleventh or twelfth embodiment, wherein (d) the reaction mixture continuously removed in step (g) in a content of 0.05 wt .-% to 10 wt .-% alkylene oxide in a post-reactor is, in which by means of a post-reaction, the content of free alkylene oxide is reduced to less than 0.05 wt .-% in the reaction mixture. In a fourteenth embodiment, the invention relates to a process according to any one of the first to thirteenth embodiments, wherein in step (a) a suspending agent is one or more compounds and is selected from the group consisting of 4-methyl-2-oxo 1, 3-dioxolane, 1,3-dioxolan-2-one, acetone, methyl ethyl ketone, acetonitrile, nitromethane, dimethyl sulfoxide, sulfolane, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dioxane, diethyl ether, methyl tert-butyl ether, tetrahydrofuran, Ethyl acetate, butyl acetate, pentane, n-hexane, benzene, toluene, xylene, ethylbenzene, chloroform, chlorobenzene, dichlorobenzene and tetra-''-carbon is used. In a fifteenth embodiment, the invention relates to a method of the fourteenth embodiment, wherein the suspending agent is one or more compound (s) selected from the group consisting of 4-methyl-2-oxo-1,3-dioxolane and 1.3 - Dioxolan-2-one or a mixture of 4-methyl-2-oxo-l, 3-dioxolane and l, 3-dioxolan-2-one is used. In a sixteenth embodiment, the invention relates to a method according to any of the first to fifteenth embodiments, wherein the H-functional starter suspension agent is one or more compounds selected from the group consisting of ethylene glycol, propylene glycol, 1,3-propanediol , 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 2-methylpropan-1,3-diol, neopentyl glycol, 1,6-elexanediol, 1,8-octanediol, diethylene glycol, dipropylene glycol, glycerol, trimethylolpropane , Pentaerythritol, sorbitol and polyether polyols having a molecular weight Mn in the range of 150 to 4500 g / mol and a functionality of 2 to 3. In a seventeenth embodiment, the invention relates to a process according to the sixteenth embodiment, wherein the H-functional starter substance suspension agent is a compound or more compound (s) and is selected from the group consisting of ethylene glycol, propylene glycol, trimethylolpropane and glycerol.

In an eighteenth embodiment, the invention relates to a process according to any of the first to seventeenth embodiments, wherein the DMC catalyst is used in an amount such that the content of DMC catalyst in the resulting reaction product is 10 to 10,000 ppm, more preferably 20 to 5,000 ppm and most preferably 50 to 2000 ppm

In a nineteenth embodiment, the invention relates to a polyetherester polyol obtainable according to at least one of the first to eighteenth embodiments.

In a twentieth embodiment, the invention relates to a process for the preparation of polyurethanes obtainable by reacting

i) Polyetheresterpolyolen according to one of the nineteenth embodiment with

ii) polyisocyanates

In a twenty-first embodiment, the invention relates to a process for the preparation of polyurethanes according to the twentieth embodiment, wherein the polyisocyanate is one or more compound (s) selected from the group consisting of 1,4-butylene diisocyanate, 1,5-pentane diisocyanate, 1 , 6-hexamethylene diisocyanate (HDI) or their dimers, trimers, pentamers, heptamers or nonamers or mixtures thereof, isophorone diisocyanate (IPDI), 2,2,4- and / or 2,4,4-trimethylhexamethylene diisocyanate, the isomeric bis (4 , 4'-isocyanatocyclohexyl) methanes or mixtures thereof any isomer content, 1, 4-cyclohexylene diisocyanate, 1, 4-phenylene diisocyanate, 2,4- and / or 2,6-toluene diisocyanate (TDI), l, 5-naphthylene diisocyanate, 2.2 'and / or 2,4'- and / or 4,4'-diphenylmethane diisocyanate (MDI) and / or higher homologs (polymeric MDI), 1,3- and / or 1,4-bis (2-isocyanato) prop-2-yl) benzene (TMXDI), 1,3-bis (isocyanatomethyl) benzene (XDI), and alkyl 2,6-diisocyanatohexane oate (lysine diisocyanates) with CI to C6-alkyl groups.

In a twenty-second embodiment, the invention relates to a process for the preparation of polyurethanes according to the twenty-first embodiment, wherein the polyisocyanate is one or more compound (s) selected from the group consisting of 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate (TDI ), 2,2'-diphenylmethane diisocyanate 2,4'-diphenylmethane diisocyanate 4,4'-diphenylmethane diisocyanate (MDI). Examples

Starting materials used Propylene glycol (purity> 99.5%, Sigma-Aldrich Chemie GmbH)

Propylene oxide (purity> 99.5%, Sigma-Aldrich Chemie GmbH) β-propiolactone (97%, Acros Organics BVBA) β-butyrolactone (purity 98%, Sigma-Aldrich Chemie GmbH) e-caprolactone (purity 97%, sigma Aldrich Chemie GmbH) DMC catalyst prepared according to Example 6 in WO 01/80994 A1 was used as the DMC catalyst in all the examples.

Description of the methods:

Gel Permeation Chromatography (GPC): Measurements were taken on an Agilent 1200 Series (G1311A Bin Pump, G1313A ALS, G1362A RID), detection via RID; eluent:

Tetrahydrofuran (GPC grade), flow rate 1.0 mL / min at 40 ° C column temperature; Column combination: 2 x PSS SDV guard column 100 Ä (5 pm), 2 * PSS SDV 1000 Ä (5 mih). For calibration, the ReadyCal Kit Poly (styrene) low was used in the range Mp = 266 - 66000 Da of "PSS Polymer Standards Service". The program package "PSS WinGPC Unity" was used as the measurement recording and evaluation software.

'H-NMR

The composition of the polymer was determined by means of * H-NMR (Broker, DPX 400, 400 MHz, pulse program zg30, waiting time D1: 10 s, 64 scans). Each sample was dissolved in deuterated chloroform. The relevant resonances in the H-NMR (relative to TMS = 0 ppm) and the assignment of the surface integrals (A) are as follows:

• cyclic propylene carbonate (cPC), solvent, with resonance at 4.5 ppm, area integral corresponds to one H atom; • monomeric propylene oxide (PO), which is not fully reacted, with resonance at 2.4 or 2.8 ppm, area integral corresponds to one H atom;

• polypropylene oxide (PPO), PO homopolymer, with resonances at 1.0 to 1.2 ppm, area integral minus proportion of PPL-PPO bond (1.5 * A (PPL-PPO)) corresponds to 3 H atoms;

• Polypropiolactone (PPL-PPL) with resonance at 4.4 ppm, area integral corresponds to 2 H atoms;

• Polypropiolactone (PPL-PPO) with resonance at 2.6 ppm, area integral minus 2 H atoms from the PPL-PPL repeat unit corresponds to 2 H atoms; · Beta-butyrolactone (BL) with resonance at 1.6 ppm, area integral minus 3 H atoms of cPC corresponds to 3 H atoms;

• Beta-propiolactone (PL) with resonance at 4.28 and 3.54, area integral corresponds to 2 H atoms;

• Polybutyrolactone (PBL-PBL) with resonance at 2, 4-2, 7 ppm, area integral corresponds to 2 H atoms;

• Polypropiolactone (PBL-PPO) with resonance at 2.4 ppm, area integral corresponds to 2 H atoms;

• epsilon-caprolactone (CL) with resonance at 4.3 ppm, area integral corresponds to 2 H atoms;

Polycaprolactone (PCL) with resonance at 2.3 ppm, area integral corresponds to 2 H atoms;

This results in the mole fractions (x) of the respective components: x (cPC) = A (4.5 ppm) x (PO) = A (2.75 ppm) or A (2.4 ppm) x (PPO) = A (1.0-1.2 ppm) / 3 x (PPL-PPL) = A (PPL-PPL) / 2 x (PPL-PPO) = A (PPL-PPO) / 2 x (BL) = A (BL) / 3 x (PL) = A (PL) / 2 x (PBL-PBL) = A (PBL-PBL) / 2 x (PBL-PPO) = A (PBL-PPO) / 2 x (CL) = A (CL) / 2 x (PCL) = A ( PCL) / 2

The percentage molar fraction is calculated by dividing the molar fraction (x) of the respective component by the sum of the molar fractions contained in the sample. In addition, the proportion by weight is calculated by multiplying the mole fractions (x) by the corresponding molar masses and dividing by the sum of the parts by weight contained. The following molecular weights (g / mol) are used to convert the proportions by weight: cPC = 102, PO and PPO = 58, BL = 86, PL = 72, CL = PCL = 114, PPL-PPO = 130, PBL-PPO = 144, PCL-PPO = 172.

Example 1 Preparation of Polyetheresterpolyol with presentation of cPC as suspending agent and continuous dosing of propylene glycol as H-functional starter substance and ß-propiolactone as lactone

Step a:

100 mg of dried DMC catalyst, which was not activated, in 50.0 g of 4-methyl-2-oxo-l, 3-dioxolane (hereinafter also referred to as cyclic propylene carbonate or cPC) in a 0.3 L pressure reactor with Gas metering suspended. The reactor was closed and rendered inert by applying it three times with 20 bar N 2 and then releasing it to 5 bar.

Step ß:

In the reactor, an amount of 10 g of a mixture of β-propiolactone (10% by weight) in propylene oxide was added all at once at 130 ° C., 500 rpm and at a pressure of 5 bar, which was adjusted with nitrogen , The start of the reaction went through a Temperature peak ("hotspot") and by a drop in pressure on the output pressure noticeable. The process was carried out twice in total.

Step g:

After activation, 76.20 g of a mixture of β-propiolactone (30% by weight) in propylene oxide at 1 g / min and simultaneously 38.05 g of a mixture of propylene glycol (10% by weight) in propylene carbonate with 1 g / min simultaneously metered into the reactor. After the addition has ended, the mixture is stirred at 130 ° C. until the exothermic reaction has subsided and until the pressure remains constant. The average molecular weight (determined by gel permeation chromatography) are given in Table 1.

Example 2 Preparation of Polyetheresterpolyol with presentation of cPC as suspending agent and continuous metering of propylene glycol as H-functional starter substance and ß-butyrolactone as lactone

The preparation of the polyetherester polyol was carried out in accordance with Example 1, with a mixture of β-butyrolactone (30% by weight) in propylene oxide being used in step β and g. The results are shown in Table 1.

Example 3 (comparison): Preparation of polyetherester polyol with presentation of cPC as suspending agent and continuous metering of propylene glycol as H-functional starter substance and e-caprolactone as lactone

In accordance with Example 1, the preparation of the polyetherester polyol was carried out, wherein in step ß and g, a mixture of e-capro lactone (30 wt .-%) was used in propylene oxide. The results are shown in Table 1.

Example 4 Preparation of polyetherester polyol with the introduction of cPC as suspending agent and continuous metering of propylene glycol as H-functional starter substance and β-propiolactone as lactone

The preparation of the polyetherester polyol was carried out in accordance with Example 1, with a mixture of β-propiolactone (5% by weight) in propylene oxide being used in step β and g. The results are shown in Table 1. Example 5 Preparation of polyetherester polyol with presentation of cPC as suspending agent and continuous metering of propylene glycol as H-functional starter substance and β-propiolactone as lactone

The preparation of the polyetherester polyol was carried out in accordance with Example 1, wherein in step β and g, a mixture of β-propiolactone (10 wt .-%) was used in propylene oxide. The results are shown in Table 1.

Example 6 (Comparison): Preparation of polyetherester polyol with presentation of propylene glycol as H-functional starter substance and β-propiolactone as lactone

Step a:

100 mg of dried DMC catalyst which was not activated was dissolved in 50 g of 4-methyl-2-oxo-1,3-dioxolane (hereinafter also referred to as cyclic propylene carbonate or cPC) and 3.805 g of monopropylene glycol (MPG) in a 0 , 3 L pressure reactor with gas dosing suspended. The reactor was closed and rendered inert by applying it three times with 20 bar N 2 and then releasing it to 5 bar.

Step ß:

In the reactor, an amount of 10 g of a mixture of β-propiolactone (10% by weight) in propylene oxide was added all at once at 130 ° C., 500 rpm and at a pressure of 5 bar, which was adjusted with nitrogen , After the addition of the propylene oxide, there was no reaction that would have been noticeable by a temperature increase and a pressure drop in the reactor. Adding a second subset PO (10 g) did not result in the onset of a reaction. The polyester ether polyol could not be prepared in this way.

Table 1: conversion of the lactone and molecular weight of the polyetheresterpolyols

a) calculated lactone content in step (ß) / (g) based on the sum of lactone and alkylene oxide in wt .-% in step (ß) / (g).

Table 1 summarizes the results for the preparation of polyetherester polyols. Polyetherester polyols were prepared via the process of the invention by copolymerization of an alkylene oxide with a lactone by adding 5% by weight (entry 4), 10% by weight (entry 5) and 30% by weight (entry 1) of lactone. The results illustrate that the 4-ring lactones have an improved incorporation rate and conversion rate over the prior art and over higher lactones such as e-caprolactone (Comparative Example 3) due to the continuous metering of the H-functional starter substance. Submission of the H-functional starter substance resulted in that no polyetherester polyol (Comparative Example 6) could be obtained.

Claims

claims

1. A process for the preparation of a polyetherester polyol by addition of alkylene oxide and lactone to H-functional starter substance in the presence of a double metal cyanide catalyst, characterized in that

(a) a suspending agent containing no H-functional groups is placed in a reactor;

(g) H-functional starter substance is metered continuously into the reactor during the reaction, and

wherein the lactone is a 4-membered ring lactone.

2. The method according to claim 1, wherein in step (a) a suspending agent which contains no H-functional groups is introduced into the reactor, and thereby no H-functional starter substance is introduced into the reactor.

3. The method according to claim 1, wherein in step (a) a suspension agent containing no H-functional groups, and additionally a subset of the H-functional starter substance in the reactor is presented.

4. The method according to any one of claims 1 to 3, wherein in step (a) a suspending agent which does not contain H-functional groups, together with DMC catalyst is introduced into the reactor.

5. The method according to claim 4, wherein subsequent to step (a)

6. The method according to claim 5, wherein in step (ß) a mixture of alkylene oxide and lactone is added and the proportion of the lactone 1 wt .-% to 80 wt .-%, preferably 3 wt .-% to 60 wt .-% and particularly preferably 22 wt .-% to 40 wt .-% based on the total mass of metered alkylene oxide and lactone in step (ß).

7. The method according to any one of claims 1 to 6, wherein in step (g) H-functional starter substance, alkylene oxide and lactone are continuously metered ("copolymerization").

A method according to any one of claims 1 to 7, wherein in step (g) the dosage of the H-functional starter substance is terminated in time prior to the addition of the alkylene oxide.

9. The method according to claim 8, wherein in step (g) a mixture of alkylene oxide and lactone is added and the proportion of the lactone 1 wt .-% to 80 wt .-%, preferably 3

Wt .-% to 60 wt .-% and particularly preferably 22 wt .-% to 40 wt .-% based on the total mass of metered alkylene oxide and lactone in step (g).

10. The method according to any one of claims 1 to 9, wherein the 4-membered ring lactone is one or more compound (s) and is selected from the group consisting of

Propiolactone, β-butyrolactone, β-isovalerolactone, β-caprolactone, β-isocaprolactone, β-methyl-β-valerolactone, diketene preferably propiolactone and β-butyrolactone and particularly preferably propiolactone.

11. Polyetheresterpolyol obtainable according to at least one of claims 1 to 10.

12. Process for the preparation of polyurethanes obtainable by reaction of

i) Polyetheresterpolyols according to claim 11 with

ii) polyisocyanates.