EP3606974A1

EP3606974A1 - Flame-retardant phosphor-functional polyether carbonate polyols and method for production thereof

Info

Publication number: EP3606974A1
Application number: EP18713977.9A
Authority: EP
Inventors: Thomas Ernst Müller; Christoph Gürtler; Kai LAEMMERHOLD; Muhammad Afzal Subhani; Burkhard Koehler; Walter Leitner
Original assignee: Covestro Deutschland AG
Current assignee: Covestro Intellectual Property GmbH and Co KG
Priority date: 2017-04-05
Filing date: 2018-04-03
Publication date: 2020-02-12
Also published as: WO2018185069A1; US20200048402A1; EP3385295A1; CN110446734A; CN110446734B; US11098154B2

Abstract

The invention relates to a method for producing a phosphor-functional polyether carbonate polyol, wherein a polyether carbonate polyol having unsaturated groups is reacted with a phosphor-functional compound according to formula (Ia), formula (Ia), wherein X = O, S; R¹ and R² is selected from the group comprising C1-C22 alkyl, C1-C22 alkoxy, C1-C22 alkylsulfanyl, C6-C70 aryl, C6-C70 aryloxy, C6-C70 arylsulfanyl, C7-C70 aralkyl, C7-C70 aralkyloxy, C7-C70 aralkylsulfanyl, C7-C70 alkyl, C7-C70 alkylaryloxy, C7-C70 alkylarylsulfanyl, or wherein R¹ and R² are bridged directly and/or by means of heteroatoms and are selected from the group comprising C1-C22 alkylene, oxygen, sulfur, or NR⁵, wherein R⁵ is hydrogen, C1-C22 alkyl, C1-C22 acyl, C7-C22 aralkyl, or C6-C70 aryl radical.

Description

Flame-retardant phosphorus-functional polyethercarborate polyols and process for their preparation

The invention relates to a process for preparing a phosphorus-functional polyethercarbonate polyol, in which a polyethercarbonate polyol having unsaturated groups is reacted with a phosphorus-functional compound. The invention further relates to a phosphorus-functional polyethercarbonate polyol preparable by the process according to the invention and to the use thereof inter alia in the production of a phosphorus-functional polyurethane polymer.

In addition to tailor-made functionality, modern plastics should also increasingly take account of ecological considerations. This can, in addition to a general optimization of manufacturing processes, also by the use of greenhouse gases, such as carbon dioxide, can be achieved as synthesis building blocks for the construction of polymers. For example, by fixing carbon dioxide as a whole, a better process environmental balance can be obtained. This route is used in the production of polyether carbonates and has been the subject of intensive research for more than 40 years (eg Inoue et al., Copolymerization of Carbon Dioxide and Alkylene Oxide with Organometallic Compounds; Macromolecular Chemistry 130, 210-220, 1969). , In one possible preparation variant, polyether carbonates are obtained by a catalytic reaction of epoxides and carbon dioxide in the presence of H-functional starter substances (Scheme (I)), where R is an organic radical such as alkyl, alkylaryl or aryl, which may also each contain heteroatoms such as O, S, Si, etc., and wherein a, b and c are an integer, and wherein the product shown here in the scheme (I) for the polyethercarbonate polyol merely understood is to be that blocks with the structure shown in the polyether carbonate obtained in principle can find again, but the order, number and length of the blocks and the OH functionality of the starter can vary and is not limited to the polyether carbonate shown in Scheme (I).

Starter OH + (a +

As a further product, here an undesirable by-product, in addition to the polyether carbonate, a cyclic carbonate (for example, for R = CH3 propylene carbonate) is formed. In principle, it is possible to functionalize this type of polyethercarbonate polyols specifically for certain fields of application. For example, if it is desired that the polymer has certain flame retardant properties, this can be achieved by different routes. On the one hand, the flame retardancy of these polymers can be effected by adding low molecular weight or oligomeric phosphorus compounds. Also heterogeneous solids, such as (encapsulated) red phosphorus or melamine polyphosphate can be added at this point. A disadvantage, however, is that these flame retardant additives can degrade the mechanical and other physical properties of polymers. These negative effects are mentioned, for example, in US 20130046036 AI. Another strategy for preparing phosphorus-containing polyethercarbonate polyols is the use of phosphorus-containing monomers in the course of polyethercarbonate synthesis. Epoxides and cyclic anhydrides represent monomers which can be incorporated into the polymer chain of polyether carbonates. US 2008/0227884 describes, for example, the preparation of phosphorus-functional epoxides, for example by radical addition of 9,10-dihydro-9-oxa-10-phosphaphenanthren-10-oxide (DOPO) to allyl glycidyl ether and the use of the reaction product as a reactive flame retardant additive in epoxy resins , However, the use of such comonomers in the copolymerization of CO ₂ and epoxides using metal salts or complexes as catalysts has the disadvantage that the phosphorus functional epoxides can interact with the catalyst and thus the catalytic activity is impaired. It would therefore be desirable to provide the phosphorus functionality of the polyethercarbonate polyols only after the polymerization.

The object of the present invention is to provide an improved process for the production of flame-retardant polyethercarbonate polyols which does not entail any disadvantages with regard to the preparation of the polymers per se. This object is achieved according to the invention by a process for preparing a phosphorus-functional polyethercarbonate polyol in which a polyethercarbonate polyol having unsaturated groups is reacted with a phosphorus-functional compound of the formula (Ia),

where X = O, S,

R ¹ and R ^{2 are} selected from the group consisting of C 1 -C 22 alkyl, C 1 -C 22 alkoxy, C 1 -C 22 alkylsulfanyl C 6 -C 70 aryl, C 6 -C 70 aryloxy, C 6 -C 70 arylsulfanyl, C 7 -C 70 aralkyl, C7-C70 Aralkyloxy, C7-C70 aralkylsulfanyl, C7-C70 alkylaryl, C7-C70 alkylaryloxy, C7-C70 alkylarylsulfanyl, or wherein R ¹ and R ² are bridged directly and / or via heteroatoms and are selected from the group comprising C 1 -C 22 -alkylene, Oxygen, sulfur or NR ⁵ , wherein R ^{5 is} hydrogen, C 1 -C 22 alkyl, C 1 -C 22 acyl, C 7 -C 22 aralkyl or C 6 -C 70 aryl radical. The invention is based on the finding that the above-mentioned disadvantages of the prior art can be overcome by the subsequent functionalization of the polyethercarbonate polyol with a phosphorus-functional compound of the formula (Ia), since no softening effect by short-chain flame retardant additives occurs due to the solid incorporation into the polymer and no deactivation of the polymerization catalyst occurs because at the time of incorporation of the phosphorus-functional compound, the polymer chain of the polyethercarbonate is already built up. It has been found that the incorporation of double bonds into the polymer backbone of the polyethercarbonate polyol allows a comparatively simple addition of the phosphorus-functional compound.

Surprisingly, it has been found that this preparation process enables efficient and controlled functionalization of unsaturated polyethercarbonate polyols with phosphorus-functional compounds. The phosphorus groups are covalently bonded to the polymer backbone. This results in functionalized polyethercarbonate polyol having a defined phosphorus functionality. This is in contrast to polymers with phosphorus groups weakly bonded via ionic or van der Waals interactions whose content of phosphorus compound and its properties may change during storage or in subsequent reaction or purification steps. This is precluded by the covalent attachment of the phosphorus-containing group to the polymer backbone according to the process of the invention. Furthermore, this process allows a fast and controlled construction of the actual polyethercarbonate polyols, without having to fear an inactivation or modification of the catalyst required to build up the polyethercarbonate polyols by phosphorus-containing compounds.

Furthermore, a variable amount of phosphorus compounds can also be introduced into a polyethercarbonate polyol having defined functionality via the separate process control. This functionality can be selected depending on the requirements in the later application. In this way, differently modified products can be produced from a production batch of phosphorus-functional polyethercarbonate polyols. A further advantage can additionally result from the fact that not all unsaturated groups of the polyethercarbonate polyols have to be modified. As a result, further functional groups can be located on the polymer backbone after the phosphorus-functional modification, which can be used within further reaction steps. For example, this functionality can be used in the context of further crosslinking reactions. The obtained phosphorus-containing polyether carbonate polyols are also ecologically safe. The phosphorus-functional polyethercarbonate polyols obtainable by this process can initiate enhanced carbonification in the event of fire, forming a protective surface layer which ultimately reduces the amount of combustible material. Furthermore, additional release of gases can lead to the formation of a voluminous insulation layer which acts as a flame retardant. As a further possibility, the phosphorus-functional polyethercarbonate polyols or decomposition products formed therefrom in the gas phase can intercept free-radical species and thus inhibit the combustion process.

Embodiments and other aspects of the present invention will be described below. They can be combined with each other as long as the context does not clearly indicate the opposite.

In a preferred embodiment of the process, the phosphorus-functional compound (Ib) can comprise

in which

A, B, and C are independently selected from the group comprising a chemical bond, O, NH, N- (C 1 -C 10 alkyl), N- (C 6 -C 14 aryl), and

R ³ and R ^{4 are} independently selected from the group consisting of C 1 -C 10 alkyl, C 1 -C 10 alkoxy, C 6 -C 14 aryl, C 6 -C 14 aryloxy, C 9 -C 17 aralkyl and

m, n are independently 0, 1, 2, 3 or 4.

These compounds according to formula (Ib) with the listed substituent pattern have proven to be particularly suitable for addition to polyether carbonate polyols having unsaturated groups.

The available phosphorus-functional polyethercarbonate polyols show a very good flame-retardant effect with only a relatively small change in the other performance properties of the polymer. This may in particular apply to the viscosity of the phosphorus-functional polyethercarbonate polyol, which should be kept as low as possible within the scope of further reaction steps. The addition of this class of compounds with the presented substituent pattern of the polyethercarbonate polyol with unsaturated groups leads to phosphorus-functional polyether carbonate with only a slightly increased viscosity, which are particularly suitable for further crosslinking steps.

In a further embodiment of the process, the substituents R ³ and R ^{4 of} the formula (Ib) can be selected from the group comprising C 1 -C 8 -alkyl and C 1 -C -alkoxy and n, m independently of one another can be 0 or 1. These compounds with the listed substituent pattern can contribute to a significant flame retardant effect of the phosphorus functional polyether carbonate polyols without overly altering essential properties of the base polymer. This can apply in particular for further reactions with crosslinking reagents. Without being bound by theory, this may probably be due to the steric constraints of the relatively short chain residues R3 and R4.

In an additional aspect of the process, the phosphorus functional compound may include 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), diethylphosphite, phenyl P-phenylphosphinate (CAS Reg. 52744-21-5) and / or P-methyl-phosphinic acid butyl ester (CAS Reg. 6172-80-1). In particular, DOPO has been found in the context of the process of the invention for addition to polyether carbonate polyols having unsaturated groups as suitable. This reaction can be carried out extremely selectively and by-product-poor. The products obtainable by the process according to the invention exhibit reproducible and good flame-retardant action and, despite the phosphorus functionalization, can still be sufficiently converted into further, for example more highly crosslinked, polyoxyalkylene polymers.

Polyether carbonate polyols having unsaturated groups in the context of the invention are polyether carbonate polyols whose molecular structure contains one or more C 2 -C 5 double or triple bonds. These may also be conjugated with aromatic compounds not included. However, aromatic groups may be included in the molecular structure in addition to the unsaturated group.

Polyether carbonate polyols having unsaturated groups can be obtained, for example, by reacting a starter compound with one or more alkylene oxides, carbon dioxide, and one or more other monomers selected from the group consisting of alkylene oxides, cyclic anhydrides of dicarboxylic acids, lactones, lactides, cyclic 6-ring carbonates, and the like In that at least one of the other monomers used contains one or more C 2 -C double or triple bonds.

In a further embodiment of the process, the polyethercarbonate polyol having unsaturated groups may have a proportion of unsaturated comonomers within the polyethercarbonate polyol of greater than or equal to 0.1 mol% and less than or equal to 50 mol%. Preferably, the proportion of unsaturated comonomers within the Polyethercarbonatepolyols greater than or equal to 1 mol% and less than or equal to 40 mol%, more preferably greater than or equal to 5 mol% and less than or equal to 25 mol%. This number of possible binding sites of the phosphorus functional compounds to the polyethercarbonate polyol having unsaturated groups has been found to be particularly advantageous. On the one hand, it is possible to obtain phosphorus-functional polyethercarbonate polyols which can provide sufficient flame retardancy and, on the other hand, to avoid excessive changes in the polymer properties of the polyoxyalkylene polymer. This may in particular apply to the viscosity of the modified base polymer, which could increase too much with an even higher proportion of unsaturated comonomers. Smaller contents of unsaturated comonomers in the polyoxyalkylene polymer can lead to insufficient phosphorus functional functionalization of the polymer.

In a further embodiment of the process, the molar ratio of phosphorus-functional compounds to unsaturated groups of the polyethercarbonate polyol may be 10: 1 to 1: 1, preferably 2: 1 to 1: 1, very particularly preferably 1.25: 1 to 1: 1.25 , The phosphorus content of the phosphorus-functional polyether carbonate polyols obtained according to the process of the invention may be between 0.5 and 15% by weight, preferably between 1 and 10% by weight and more preferably between 1 and 4% by weight. This proportion of phosphorus can contribute to a sufficient flame retardant effect of the phosphorus-functional polyether carbonate polyols and the products produced therefrom. In a preferred embodiment of the invention, the process for preparing the polyethercarbonate polyol having unsaturated groups comprises the steps

(a) preparing an H-functional initiator compound and a DMC catalyst,

(ß) optionally dosing an epoxide,

(γ) adding (γΐ) at least one epoxide, as well as

(γ2) at least one epoxide, a cyclic anhydride of a dicarboxylic acid, a lactone, a lactide and / or a cyclic 6-ring carbonate which has a

Having double bond, and

(γ3) of carbon dioxide. Epoxides, cyclic anhydrides of a dicarboxylic acid, a lactone, a lactide and / or a cyclic 6-ring carbonate which have an unsaturated group are, for example, vinylcyclohexene oxide, cyclooctadiene monoepoxide, cyclododecatriene monoepoxide, Butadiene monoepoxide, isoprene monoepoxide, limonene oxide, 1,4-divinylbenzene monoepoxide, 1,3-divinylbenzene monoepoxide, glycidyl esters of unsaturated fatty acids (such as oleic acid, linoleic acid, conjuene fatty acid or linolenic acid) and / or partially epoxidized fats and oils (such as partially epoxidized soybean oil, linseed oil, rapeseed oil, palm oil or sunflower oil), maleic anhydride, norbornene diacid anhydride, dodecenyl succinic anhydride, tetradecene succinic anhydride, hexadecenyl succinic anhydride, octadecenyl succinic anhydride,

Itaconic anhydride, dimethylmaleic anhydride, allylnorbornene diacetic anhydride, TMP monoallyl ether carbonate, pentaerythritol diallyl ether carbonate and epoxides, cyclic anhydrides of a dicarboxylic acid, a lactone, a lactide and / or a cyclic 6-ring carbonate substituted with an allylglycidyl ether group.

It has surprisingly been found that this type of preparation leads to polyethercarbonate polyols having unsaturated groups which are particularly suitable in the context of the further phosphorus-functional modification. In particular, polyethercarbonate polyols having unsaturated side chains exhibit good reactivity and a particularly low viscosity, which, without being bound by theory, is caused by the reduction of intermolecular polymer-polymer interactions due to the incorporation of the unsaturated side chains. In particular, the terpolymerization with epoxides, wherein at least one of the epoxides carries a double bond and / or epoxides with cyclic anhydrides, has this effect and is, compared to a "simple" polymerization with only one monomer species having unsaturated groups, significantly more advantageous.

Preferably, before the reaction of the unsaturated groups with phosphorus-functional compounds, the terminal OH groups of the polyethercarbonate polyols are converted into a chemical group which does not react with phosphorus-functional groups. The customary methods are known to the person skilled in the art. For example, this can be done by reacting the OH groups with trialkylsiloxanes with elimination of alcohol. Suitable trialkylsiloxanes are, for example, trimethylsiloxane, triethylsiloxane. An alternative method is the reaction of the OH groups with alkylating reagents, such as trimethyloxonium salts, methyl sulfonate and methyl sulfate. This may allow further implementation of the OH groups of the polyethercarbonate polyols after removal of the protecting group. A preferred embodiment of the process involves the use of polyethercarbonate polyols having electron-rich double bonds, denoting double bonds substituted by + M or +1 substituents, such as alkyl or alkoxyalkyl or cyclohexyl groups. In general, electron-rich double bonds in the context of the invention are those which are more electron-rich than ethylene. Particularly preferred are allyl ethers or vinylcyclohexenes. The introduction of these double bonds into the backbone of the polyethercarbonate polyols can be effected by the use of one or more double bonds containing epoxides as a comonomer. Examples of suitable epoxides are allyl glycidyl ether, vinyl cyclohexene oxide, butadiene monoepoxide, isoprene monoepoxide or limonene oxide, with allyl glycidyl ether being preferred.

The introduction of electron-rich double bonds into the polyethercarbonate polyol polymer may also be accomplished by using one or more cyclic anhydrides of dicarboxylic acids containing electron-rich double bonds as a comonomer. Examples of suitable cyclic anhydrides are 4-cyclohexene-l, 2-dicarboxylic anhydride, 4-methyl-4-cyclohexene-1, 2-dicarboxylic anhydride, norbornene diacid anhydride, allylnorbornene diacid anhydride,

Dodecenylsuccinic anhydride, tetradecenylsuccinic anhydride, Hexadecenylbernsteinsäureanhydrid or Octadecenylbernsteinsäureanhydrid, wherein in the Alkenylbernsteinsäureanhydriden the double bond is no exo-double bond on the ring.

An alternative embodiment involves the use of polyethercarbonate polyols having electron-deficient double bonds, denoting double bonds substituted by -M or -I substituents, such as carbonyl groups. The introduction of such double bonds into the polyethercarbonate polyol polymer can preferably be carried out by using glycidyl esters of α, β-unsaturated acids, such as acrylic acid or methacrylic acid, as comonomer. In a preferred embodiment, the double bonds may also be introduced as a comonomer by the use of cyclic anhydrides bearing double bonds adjacent to a carbonyl group.

Polyether carbonate polyols can also be phosphorus-functionalized, which simultaneously carry electron-rich and low-double bonds. Mixtures of polyethercarbonate polyols with various unsaturated building blocks can also be used for the phosphorus functionalization. However, polyethercarbonate polyols or mixtures of polyethercarbonate polyols are preferred in which the molar content of electron-rich double bonds is greater than or equal to the content of electron-poor double bonds. Very particular preference is given to using polyethercarbonate polyols which contain only electron-rich double bonds. Especially for the introduction of phosphorus functional groups double bonds are preferred which have a free = CH 2 group. These so-called α-olefins usually show only a slight steric hindrance to the double bond and can be implemented relatively easily. Allyl glycidyl ethers or vinyl cyclohexene oxide are exemplified as comonomers useful epoxides which introduce such double bonds in the polyether carbonate polyol chain. Further, as monomers for synthesizing the polyethercarbonate polyol having unsaturated groups, alkylene oxides (epoxides) having 2-45 carbon atoms which do not carry a double bond can be used. The alkylene oxides having 2 to 45 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 -Pentene oxide, 2,3-pentenoxide, 2-methyl-l, 2-butene oxide, 3-methyl-l, 2-butene oxide, epoxides of C6-C22 α-olefins, such as 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-heptene oxide, 1-octene oxide, 1-nonene oxide, 1-decene oxide , 1-undecene oxide, 1-dodecene oxide, 4-methyl-l, 2-pentenoxide, cyclopentene oxide, cyclohexene oxide, cycloheptenoxide, cyclooctene oxide, styrene oxide, methylstyrene oxide, pinene oxide, mono- or poly-epoxidized fats as mono-, di- and triglycerides, epoxidized fatty acids , C1-C24 esters of epoxidized fatty acids, epichlorohydrin, glycidol, and derivatives of glycidol such as glycidyl ethers of C1-C22 alkanols, glycidyl esters of C1-C22 alkanecarboxylic acids. Examples of derivatives of glycidol are phenyl glycidyl ether, cresyl glycidyl ether, methyl glycidyl ether, ethyl glycidyl ether and 2-ethylhexyl glycidyl ether. The alkylene oxides used may preferably be ethylene oxide and / or propylene oxide, in particular propylene oxide.

Polyether carbonate polyols having unsaturated groups are exemplified in formula (II), wherein the product shown here in the formula (II) for the polyether carbonate is merely to be understood that blocks with the structure shown in principle can be found in the polyether carbonate obtained, the order, number and length of the blocks as well as the OH functionality of the initiator but can vary and is not limited to the polyethercarbonate polyol shown in formula (II), and

wherein R ^{6 is} C1-C43 alkyl, C7-C70 alkylaryl or C6-C70 aryl, wherein in each case also heteroatoms such as O, S, Si may be contained, and

wherein R ^{7 is} C1-C43 alkenyl, or C7-C70 alkenylaryl, wherein in each case also heteroatoms such as O, S, Si may be contained, and

where a and b are an integer and the ratio of a / b is 2: 1 to 1:20, in particular 1.5: 1 to 1:10, and

where c is zero or an integer, and the proportion of unsaturated comonomers within the polyethercarbonate polyol (c), based on the chemical groups present without starters (sum a + b + c), is greater than or equal to 0.1: 100 and less or equal to 50: 100 has. The proportion of unsaturated groups within the polyetherestercarbonatepolyol is preferably greater than or equal to 1: 100 and less than or equal to 40: 100, particularly preferably greater than or equal to 5: 100 and less than or equal to 25: 100.

Polyetherestercarbonatepolyole with unsaturated groups are exemplified in formula (IIa), wherein the product shown here in the formula (IIa) for the Polyetherestercarbonatpolyol only be understood that blocks with the structure shown in the resulting Polyetherestercarbonatpolyol can find in principle, the order, number and length of the blocks as well as the OH functionality of the initiator but may vary and is not limited to the Polyetherestercarbonatpolyol shown in formula (III), and

where d is an integer and the proportion of unsaturated comonomers within the Polyetherestercarbonatpolyol (d) based on the contained chemical groups without initiator (sum a + b + d) has a value of greater than or equal to 0.1: 100 and less than or equal 50: 100. The proportion of unsaturated groups within the polyethercarbonate polyol is preferably greater than or equal to 1: 100 and less than or equal to 40: 100, particularly preferably greater than or equal to 5: 100 and less than or equal to 25: 100.

A preferred embodiment of the process for preparing polyethercarbonate polyols having unsaturated groups which can be used according to the invention comprises the reaction of one or more H-functional starter compounds, one or more alkylene oxides, one or more comonomers and carbon dioxide in the presence of a DMC catalyst, where (a) an H Functional starter substance or a mixture of at least two H-functional starter substances presented and optionally water and / or other volatile compounds by elevated temperature and / or reduced pressure are removed ("first activation stage"), wherein the DMC catalyst of the H-functional Starter substance or the mixture of at least two H-functional starter substances before or after the first activation stage is added, (β) a partial amount (based on the total amount of epoxides / cyclic anhydrides used in steps (β) and (γ) of one or more epoxides is added to the mixture resulting from step (a) ("second activation stage") Optionally, the addition of a partial amount of epoxide in the presence of CO ₂ and / or inert gas (such as nitrogen or argon) may take place and multiple dosing is also possible (ie step (β) may be repeated, preferably one to three times be repeated, and

(γ) one or more epoxides / cyclic anhydrides, one or more comonomers and carbon dioxide are continuously added to the mixture resulting from step (β), the epoxides / cyclic anhydrides used for the terpolymerization being equal to or from those used in step (β) Epoxides are different ("polymerization").

To step (a):

The addition of the individual components in step (a) can be carried out simultaneously or sequentially in any order. Preferably, the DMC catalyst is initially introduced in step (a) and the H-functional initiator compound is added simultaneously or subsequently.

The subject of a preferred embodiment is a process, wherein in step (a)

(al) in a reactor, the DMC catalyst and one or more H-functional starter compounds are presented,

(a2) [first activation step] through the reactor at a temperature of 50 to 200 ° C, preferably from 80 to 160 ° C, more preferably from 125 to 135 ° C an inert gas (for example nitrogen or a noble gas such as argon), an inert gas Carbon dioxide mixture or carbon dioxide is passed and at the same time by removing the inert gas or carbon dioxide (for example with a pump) a reduced pressure (absolute) from 10 mbar to 800 mbar, preferably from 40 mbar to 200 mbar in the reactor. The subject of a further preferred embodiment is a process, wherein in step (a)

(al) the H-functional initiator compound or a mixture of at least two H-functional starter compounds, optionally under an inert gas atmosphere, under an atmosphere of inert gas-carbon dioxide mixture or under a pure carbon dioxide atmosphere, more preferably under an inert gas atmosphere, and (a2 ) [first activation stage] in the resulting mixture of DMC catalyst and one or more H-functional starter compounds at a temperature of 50 to 200 ° C, preferably from 80 to 160 ° C, particularly preferably from 125 to 135 ° C an inert gas, an inert gas Carbon dioxide mixture or carbon dioxide, more preferably an inert gas introduced and simultaneously by removing the inert gas or carbon dioxide (for example with a pump) a reduced pressure (absolute) from 10 mbar to 800 mbar, preferably from 40 mbar to 200 mbar in the reactor is set, wherein the double metal cyanide catalyst may be added to the H-functional starter substance or to the mixture of at least two H-functional starter substances in step (a1) or immediately thereafter in step (a2).

The DMC catalyst may be added in solid form or suspended in an H-functional initiator compound. If the DMC catalyst is added as a suspension, it is preferably added in step (a1) to the one or more H-functional starter compounds. To step (ß):

Step (β) of the second activation step can be carried out in the presence of CO ₂ and / or an inert gas. Preferably, step (β) is carried out under an atmosphere of an inert gas-carbon dioxide mixture (for example, nitrogen-carbon dioxide or argon-carbon dioxide) or a carbon dioxide atmosphere, more preferably under a carbon dioxide atmosphere. The setting of an inert gas-carbon dioxide atmosphere or a carbon dioxide atmosphere and the metering of one or more alkylene oxides can in principle be carried out in different ways. The admission pressure is preferably set by introducing carbon dioxide, the pressure being (absolute) 10 mbar to 100 bar, preferably 100 mbar to 50 bar and particularly preferably 500 mbar to 50 bar. The start of the dosage of the epoxide (s) / cyclic anhydrides can take place at any desired pre-selected form. As total pressure (absolute) of the atmosphere, a range of 10 mbar to 100 bar, preferably 100 mbar to 50 bar and further preferably 500 mbar to 50 bar is preferably set in step (ß). Optionally, during or after the metering of the epoxides / cyclic anhydrides, the pressure can be readjusted by introducing further carbon dioxide, the pressure being (absolute) 10 mbar to 100 bar, preferably 100 mbar to 50 bar and preferably 500 mbar to 50 bar.

In a preferred embodiment, the amount of one or more epoxides / cyclic anhydrides used in the activation in step (β) can be 0.1 to 25.0% by weight, preferably 1.0 to 20.0% by weight, more preferably 2 , 0 to 16.0% by weight, based on the amount of H-functional starter compound used in step (a). The epoxides / cyclic anhydrides can be added in one step or in stages in several aliquots.

In a preferred embodiment for the preparation of the polyether carbonate polyols having unsaturated groups, in the activation in step (β) a partial amount (based on the total amount of epoxides / cyclic anhydrides used in steps (β) and (γ)) of one or more Epoxides / cyclic anhydrides are added to the mixture resulting from step (a) [second activation step]. The addition of a Subset of epoxide / cyclic anhydride may optionally be in the presence of CO ₂ and / or inert gas. The step (β) can also be done several times. The DMC catalyst is preferably used in an amount such that the content of DMC catalyst in the resulting polyethercarbonate polyol is 10 to 10,000 ppm, more preferably 20 to 5000 ppm, and most preferably 50 to 500 ppm.

In the second activation step, the epoxide / cyclic anhydride may be added, for example, in one portion or within 1 to 15 minutes, preferably 5 to 10 minutes. The duration of the second activation step is preferably 15 to 240 minutes, more preferably 20 to 60 minutes. To step (γ):

The dosage of epoxide, cyclic anhydride and carbon dioxide can be simultaneous, alternate or sequential. It is also possible that the dosage of the total amount of carbon dioxide takes place at once and that only the epoxide and the cyclic anhydride is dosed simultaneously, alternately or sequentially. In a further embodiment of the invention, during the addition of the epoxides / cyclic anhydrides, the CC pressure is increased or decreased gradually or gradually or kept constant. Preferably, the total pressure is kept constant during the reaction by a subsequent addition of carbon dioxide. The dosage of the epoxide (s) / cyclic anhydrides and CO ₂ may be simultaneous, alternate or sequential to the carbon dioxide dosage. It is possible to dose the epoxide at a constant metering rate or to increase or decrease the metering rate continuously or stepwise or to add the epoxide in portions. Preferably, the epoxide and / or cyclic anhydride is added to the reaction mixture at a constant metering rate. If several epoxides and / or cyclic anhydrides are used within one stage for the synthesis of the polyether carbonate polyols, the epoxides and / or cyclic anhydrides can be added individually or as a mixture. The dosing of the epoxides and / or cyclic anhydrides can be carried out simultaneously, alternately or sequentially via separate doses (additions) or via one or more doses, wherein the alkylene oxides can be metered individually or as a mixture. By way of the type and / or sequence of metering of the epoxides, the cyclic anhydrides and / or the carbon dioxide, it is possible to synthesize random, alternating, blocky or gradient polyethercarbonate polyols.

Step (γ) can be carried out, for example, at temperatures of 60 to 150 ° C, preferably from 80 to 120 ° C, most preferably from 90 to 110 ° C. If temperatures below 60 ° C are set, the reaction stops. At temperatures above 150 ° C, the amount of unwanted by-products increases sharply. Preferably, an excess of carbon dioxide based on the calculated amount of carbon dioxide required is used in the polyethercarbonate polyol, since a carbon dioxide excess is advantageous due to the inertness of the carbon dioxide. The amount of carbon dioxide can be set by the total pressure. As the total pressure (absolute), the range of 0.01 to 120 bar, preferably 0.1 to 110 bar, more preferably from 1 to 100 bar for the copolymerization for the preparation of polyether carbonate has proven to be advantageous. It is possible to supply the carbon dioxide continuously or discontinuously to the reaction vessel. This depends on how fast the epoxides and the CO _{2 are} consumed and whether the product should optionally contain CC-free polyether blocks or blocks with different CO ₂ content. The concentration of carbon dioxide may also vary as the epoxides / cyclic anhydrides are added. Depending on the chosen reaction conditions, it is possible to introduce the CO ₂ in the gaseous, liquid or supercritical state into the reactor. CO ₂ can also be added to the reactor as a solid and then converted to the gaseous, dissolved, liquid and / or supercritical state under the chosen reaction conditions.

In step (γ), the carbon dioxide may be introduced into the mixture, for example

(i) gassing of the reaction mixture in the reactor from below,

(ii) use of a hollow shaft agitator,

(iii) a combination of the dosages according to (i) and (ii), and / or

(iv) Fumigation via the liquid surface by using multi-stage executed stirrers.

The gassing of the reaction mixture in the reactor according to (i) preferably takes place via a gassing ring, a gassing nozzle or via a gas inlet tube. The gassing ring is preferably an annular array or two or more annular arrays of gassing nozzles, which are preferably located at the bottom of the reactor and / or on the sidewall of the reactor.

The hollow shaft agitator according to (ii) is preferably a stirrer in which the gas is introduced into the reaction mixture via a hollow shaft of the stirrer. As a result of the rotation of the stirrer in the reaction mixture (ie during mixing), a negative pressure is created at the end of the agitator blade connected to the hollow shaft in such a way that the gas phase (containing CO ₂ and optionally unconsumed alkylene oxide) is sucked out of the gas space above the reaction mixture and is passed into the reaction mixture via the hollow shaft of the stirrer.

The gassing of the reaction mixture according to (i), (ii), (iii) or (iv) can be carried out in each case with freshly added carbon dioxide and / or combined with an extraction of the gas from the gas space over the reaction mixture and subsequent recompression of the gas. For example, the extracted from the gas space above the reaction mixture and compressed gas, optionally mixed with fresh carbon dioxide and / or epoxides / cyclic anhydrides, is recycled to the reaction mixture according to (i), (ii), (iii) and / or (iv).

Preferably, the pressure drop, which is formed by incorporation of the carbon dioxide and the epoxides in the terpolymerization in the reaction product, balanced over freshly metered carbon dioxide.

The introduction of the epoxides / cyclic anhydrides can take place separately or together with the CO ₂ both via the liquid surface or directly into the liquid phase. Preferably, the introduction of the epoxides / cyclic anhydrides takes place directly in the liquid phase, since this has the advantage that a rapid mixing of the introduced compounds with the liquid phase takes place and so local concentration peaks can be avoided. The liquid phase introduction may be via one or more inlet tubes, one or more nozzles, or one or more annular arrays of multiple dosing sites, preferably located at the bottom of the reactor and / or on the side wall of the reactor. The three steps (a), (β) and (γ) can be carried out in the same reactor or separately in different reactors. Particularly preferred reactor types are stirred tank, tubular reactor, and loop reactor. If the reaction steps (a), (β) and (γ) are carried out in different reactors, a different reactor type can be used for each step. Polyethercarbonatepolyols 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 circulating cooling surfaces is cooled. In semi-batch applications, where the product is not removed until after the end of the reaction, and in continuous use, where the product is continuously withdrawn, particular attention should be paid to the dosing rate of the epoxides. It should be adjusted so that despite the inhibiting effect of carbon dioxide, the epoxides / cyclic anhydrides can react quickly enough. The concentration of free epoxides / cyclic anhydrides in the reaction mixture during the second activation stage (step β) is preferably> 0 to 100% by weight, more preferably> 0 to 50% by weight, most preferably> 0 to 20% by weight (in each case based on the weight of the reaction mixture). The concentration of free epoxides / cyclic anhydrides in the reaction mixture during the reaction (step γ) is preferably> 0 to 40% by weight, more preferably> 0 to 25% by weight, most preferably> 0 to 15% by weight (in each case on the weight of the reaction mixture).

Another embodiment in the stirred tank for the copolymerization (step γ) is characterized in that one or more H-functional starter compounds during the Reaction continuously be metered into the reactor. When carrying out the process in semi-batch operation, the amount of H-functional starter compounds which are continuously metered into the reactor during the reaction, preferably at least 20 mol% equivalents, particularly preferably 70 to 95 mol% equivalents (in each case based on the total amount of H-functional starter compounds). In a continuous implementation of the method, the amount of H-functional starter compounds, which are continuously metered into the reactor during the reaction, preferably at least 80 mol% equivalents, particularly preferably 95 to 99.99 mol% equivalents (in each case based on the total amount on H-functional starter compounds). In a preferred embodiment, the catalyst-starter mixture activated according to steps (a) and (β) is further reacted in the same reactor with epoxides / cyclic anhydrides and carbon dioxide.

In a further preferred embodiment, the catalyst-starter mixture activated according to steps (a) and (β) is further reacted in another reaction vessel (for example a stirred tank, tubular reactor or loop reactor) with epoxides / cyclic anhydrides and carbon dioxide. In a further preferred embodiment, the catalyst-starter mixture prepared according to step (a) is reacted in another reaction vessel (for example a stirred tank, tubular reactor or loop reactor) according to steps (β) and (γ) with epoxides / cyclic anhydrides and carbon dioxide. When carrying out the reaction in a tube reactor, the catalyst-starter mixture prepared according to step (a) or the catalyst-starter mixture activated according to steps (a) and (β) and optionally further starters and epoxides / cyclic anhydrides and carbon dioxide are continuously passed through Pipe pumped. When using a catalyst-starter mixture prepared according to step (a), the second activation step according to step (β) in the first part of the tubular reactor and the terpolymerisation according to step (γ) in the second part of the tubular reactor can take place. The molar ratios of the reactants can vary depending on the desired polymer.

In a preferred embodiment, carbon dioxide is metered in its liquid or supercritical form to allow optimum miscibility of the components. The carbon dioxide can be introduced into the reactor at the inlet of the reactor and / or via metering points which are arranged along the reactor. A subset of the epoxides / cyclic anhydrides can be introduced at the entrance of the reactor. The residual amount of the epoxides / cyclic anhydrides is preferably introduced into the reactor via a plurality of metering points which are arranged along the reactor. Advantageously, mixing elements, such as those marketed by the company Ehrfeld Mikrotechnik BTS GmbH, for better mixing of the reactants installed, or mixer-heat exchanger elements, which at the same time improve the mixing and heat dissipation. Preference is given by the mixing elements metered CO ₂ and epoxides / cyclic anhydrides mixed with the reaction mixture. In an alternative embodiment, different volume elements of the reaction mixture are mixed together. Loop reactors can likewise be used for the preparation of the polyether carbonate polyols having unsaturated groups which can be used according to the invention. These generally include reactors with internal and / or external material recycling (possibly with heat exchange surfaces arranged in the circulation), such as, for example, a jet loop reactor, jet loop reactor or venturi loop reactor, which can also be operated continuously, or a tubular reactor designed in a loop shape suitable devices for the circulation of the reaction mixture or a loop of several series-connected tubular reactors or a plurality of stirred stirred kettles connected in series.

In order to realize a complete conversion, the reactor in which step (γ) is carried out can often be followed by a further kettle or a tube ("dwell") in which residual concentrations of free epoxides / cyclic anhydrides present after the reaction are consumed the pressure in this downstream reactor is at the same pressure as in the reactor in which the reaction step (γ) is carried out, but the pressure in the downstream reactor can also be chosen to be higher or lower The temperature in the downstream reactor is preferably from 10 to 150 ° C. and more preferably from 20 to 100 ° C. The reaction mixture contains at the end of the reaction mixture (γ) Post-reaction time or at the output of nachg eschalteten reactor preferably less than 0.05 wt.% Epoxide / cyclic anhydride. The after-reaction time or the residence time in the downstream reactor is preferably 10 minutes to 24 hours, more preferably 10 minutes to 3 hours.

Suitable H-functional starter compounds (starters) compounds with active for the alkoxylation H atoms can be used. 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 , is particularly preferred -OH. As H-functional starter substance, for example, one or more compounds can be selected from the group comprising monohydric or polyhydric alcohols, polyhydric amines, polyhydric thiols, amino alcohols, thioalcohols, hydroxyesters, polyetherpolyols, polyesterpolyols, polyesteretherpolyols, polyethercarbonatepolyols, polycarbonatepolyols, polycarbonates, polyethyleneimines, polyetheramines (eg so-called Jeffamine ^® from Huntsman like D-230, D-400, D-2000, T-403, T-3000, T-5000 or corresponding BASF products, such as Polyetheramine D230, D400, D200, T403, T5000), polytetrahydrofurans (eg PolyTHF ^® of BASF, such as PolyTHF ^® 250, 650S, 1000, 1000S, 1400, 1800, 2000), Polytetrahydrofuranamine (BASF product Polytetrahydrofuranamin 1700), Polyetherthiole, polyacrylate , Castor oil, the mono- or diglyceride 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. By way of example, it is at the C1-C23 alkyl fatty acid ester containing 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 compounds. As monofunctional alcohols may find use: 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, 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 monofunctional amines are: butylamine, ieri-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. As monofunctional carboxylic acids may be mentioned: 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.

As H-functional starter substances suitable polyhydric alcohols are, for example, dihydric alcohols (such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-propanediol, 1,4-butanediol, 1,4-butenediol, 1,4-butynediol, neopentyl glycol, 1 , 5-pentanediol, methylpentanediols (such as 3-methyl-1,5-pentanediol), 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, 1,12-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), as well as all modification products of these aforementioned alcohols with different amounts of ε-caprolactone. The H-functional starter substances may also be selected from the class of polyether polyols, in particular those having a molecular weight M _n in the range from 100 to 4000 g / mol. 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. Suitable polyether polyols made up of repeating propylene oxide and / or ethylene oxide units are, for example Desmophen ^® -, Acclaim ^® -, Arcol ^® -, Baycoll ^® -, Bayfill ^® -, Bayflex ^® - Baygal ^® -, PET ^® - and polyether polyols Bayer MaterialScience AG (such. as Desmophen ^® 3600Z, Desmophen ^® 1900U, Acclaim ^® polyol 2200 Acclaim ^® polyol 40001, Arcol ^® polyol 1004 Arcol ^® polyol 1010 Arcol ^® polyol 1030 Arcol ^® polyol 1070, Baycoll ^® BD 1110 Bayfill VPPU ^® 0789, Baygal ^® K55, PET ^® 1004 polyether ^® S180). Other suitable homo-polyethylene oxides are the BASF SE example Pluriol ^® E-marks suitable homo-polypropylene oxides such as the BASF SE Pluriol ^® P-marks suitable mixed copolymers of ethylene oxide and propylene oxide such as the Pluronic ^® PE or PLURIOL ^® RPE Brands of BASF SE.

The H-functional starter substances can also be selected from the substance class of the polyesterpolyols, in particular those having a molecular weight M _n in the range from 200 to 4500 g / mol. As polyester polyols at least difunctional polyesters can be used. Polyester polyols preferably consist of alternating acid and alcohol units. Examples of suitable acid components are 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 said acids and / or anhydrides. Examples of alcohol components are ethanediol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-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 polyethers are obtained which can likewise serve as starter substances for the preparation of the polyether carbonate polyols. Preference is given to using polyether polyols having M _n = 150 to 2000 g / mol for the preparation of the polyether carbonate polyols.

Furthermore, polycarbonate diols can be used as H-functional starter substances, in particular those having a molecular weight M _n in the range of 150 to 4500 g / mol, preferably 500 to 2500 g / mol, for example by reaction of phosgene, dimethyl carbonate, diethyl carbonate or diphenyl carbonate and difunctional alcohols or polyester polyols or polyether polyols. Find examples of polycarbonates for example, in EP-A 1,359,177th example, the Desmophen ^® C can types of Bayer MaterialScience AG are used as polycarbonate, such as Desmophen ^® C 1100 or Desmophen ^® C 2200th

In a further embodiment of the invention, polyether carbonate polyols and / or polyetherestercarbonate polyols can be used as H-functional starter substances. In particular, polyetherestercarbonatepolyols can be used. These polyetherestercarbonatepolyols used as H-functional starter substances can be prepared beforehand in a separate reaction step for this purpose.

The H-functional starter substances generally have an OH functionality (i.e., number of H atoms per molecule active for polymerization) of from 1 to 8, preferably from 2 to 6, and more preferably from 2 to 4. The H-functional starter substances are used either individually or as a mixture of at least two H-functional starter substances.

Preferred H-functional starter substances are alcohols having a composition of the general formula (III), HO- (CH ₂ ) _x -OH (III) where x is a number from 1 to 20, preferably an even number from 2 to 20. Examples of alcohols according to formula (III) are ethylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol and 1,12-dodecanediol. Further preferred H-functional starter substances are neopentyl glycol, trimethylolpropane, glycerol, pentaerythritol, reaction products of the alcohols of the formula (III) with ε-caprolactone, for example reaction products of trimethylolpropane with ε-caprolactone, reaction products of glycerol with ε-caprolactone, and reaction products of pentaerythritol with ε-caprolactone. Also preferred as H-functional starter compounds are water, diethylene glycol, dipropylene glycol, castor oil, sorbitol and polyether polyols composed of repeating polyalkylene oxide units. 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-l, 3-diol, neopentyl glycol, 1,6-hexanediol, diethylene glycol, dipropylene glycol, glycerol, trimethylolpropane, di- and trifunctional polyether polyols, wherein the polyether polyol from a di- or tri-H-functional starter compound and propylene oxide or a di- or tri-H-functional initiator compound, propylene oxide and ethylene oxide is constructed. The polyether polyols preferably have an OH functionality of 2 to 4 and a molecular weight M _n in the range of 62 to 4500 g / mol and in particular a molecular weight M _n in the range of 62 to 3000 g / mol. Double metal cyanide (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, which are described, for example, 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 a very high activity and allow the production of polyoxyalkylene polyols at very low catalyst concentrations. A typical example are 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, ieri butanol), also have a polyether having a number average molecular weight greater than 500 g / mol.

The inventively employable DMC catalysts are preferably obtained by

(1.) 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,

(2) wherein in the second step the solid is separated from the suspension obtained from (a) by known techniques (such as centrifugation or filtration),

(3) optionally, in a third step, washing the isolated solid with an aqueous solution of an organic complex ligand (e.g., by resuspending and then reisolating by filtration or centrifugation),

(4.) wherein then 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) is dried, and wherein in the first step or directly after the precipitation of the double metal cyanide compound (second step), one or more organic complexing ligands, preferably in excess (based on the double metal cyanide compound) and optionally further complexing components, are added.

The double metal cyanide compounds present in the DMC catalysts which can be used according to the invention are the reaction products of water-soluble metal salts and water-soluble metal cyanide salts. For example, an aqueous zinc chloride solution (preferably in excess, based on the metal cyanide salt) and potassium hexacyanocobaltate is mixed, and then dimethoxyethane (glyme) or tert-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 a composition of the general formula (IV),

M (X) _n (IV) 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, cyanide, isocyanate, 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 preferably have a composition of the general formula (V), M _r (X) ₃ (V) wherein

M is selected from the metal cations Fe ³⁺ , Al ³⁺ , Co ³⁺ and Cr ³⁺ ,

X comprises 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 = sulphate, carbonate or oxalate and

r is 1 when X = halide, hydroxide, carboxylate, cyanate, thiocyanate, isocyanate, isothiocyanate or nitrate, or suitable metal salts preferably have a composition according to the general formula (VI),

M (X) _S (VI) where

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

X comprises 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 ;

s is 2 if X = sulphate, carbonate or oxalate and s is 4 when X = halide, hydroxide, carboxylate, cyanate, thiocyanate, isocyanate, isothiocyanate or nitrate,

or suitable metal salts preferably have a composition of the general formula (VII), M (X) _t (VII) wherein

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

X comprises one or more (i.e., different) anions, preferably anions 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 = sulphate, 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 a composition of the general formula (VIII) (Y) _a M '(CN) b (A) _c (VIII) 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 anions of the group consisting of halides (ie 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 electron wire 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 which can be used according to the invention are compounds having compositions of the general formula (IX)

M _x [M ' _x , (CN) _y ] _z (IX) where M is as in the formulas (III) to (VI) and

M 'is as defined in formula (VII), 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) can be used with particular preference. The organic complexing ligands which can be 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, EP-A No. 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 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 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-oxetane-methanol). Highly preferred organic complexing ligands are selected from one or more compounds of the group consisting of dimethoxyethane, feri-butanol 2-methyl-3-buten-2-ol, 2-methyl-3-butyn-2-ol, Efhylenglykol mono-ieri-butylefher and 3-methyl-3-oxetan-methanol.

Optionally, one or more complex-forming component (s) from the compound classes of polyethers, polyesters, polycarbonates, polyalkylene glycol sorbitan esters, polyalkylene glycol glycidyl ethers, polyacrylamide, poly (acrylamide-co-acrylic acid), polyacrylic acid, poly (acrylic acid), are used in the preparation of the DMC catalysts which can be used according to the invention. 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 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, α, β-unsaturated carboxylic esters or ionic Surface bz w., surface-active compounds. In the preparation of the DMC catalysts which can be used according to the invention, the aqueous solutions of the metal salt (for example zinc chloride) are preferably used in the first step in a stoichiometric excess (at least 50 mol%) relative to the metal cyanide salt. This corresponds to at least a molar ratio of metal salt to metal cyanide salt of 2.25 to 1.00. The metal cyanide salt (e.g., potassium hexacyanocobaltate) is reacted in the presence of the organic complexing ligand (e.g., tert-butanol) to form a suspension containing the double metal cyanide compound (e.g., zinc hexacyanocobaltate), water, excess metal salt, and the organic complexing ligand.

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 use of a mixing nozzle, more preferably using a jet disperser as described, for example, in WO-A-01/39883.

In the second step, the isolation of the solid (ie, the precursor of the catalyst) from the suspension can be 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 (eg by resuspending 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 which can be used according to the invention. Preferably, the amount of the organic complex ligand in the aqueous washing solution is between 40 and 80% by weight, based on the total solution.

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

In addition, it is advantageous to wash the isolated solid more than once. Preferably, in a first washing step (3.-1) with an aqueous solution of the unsaturated alcohol washed (eg by resuspension and subsequent reisolation by filtration or centrifugation), in this way, for example, water-soluble by-products, such as potassium chloride, from the present invention Remove catalyst. Particularly preferably, the amount of the unsaturated alcohol in the aqueous washing solution is between 40 and 80% by weight, based on the total solution of the first washing step. In the further washing steps (3.-2), either the first washing step is repeated once or several times, preferably once to three times, or preferably a nonaqueous solution, such as e.g. a mixture or solution of unsaturated alcohol and further complexing component (preferably in the range between 0.5 and 5 wt.%, Based on the total amount of the washing solution of step (3.-2)), used as a washing solution and the solid so once or washed several times, preferably once to three times.

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

A preferred process for the isolation of the DMC catalysts which can be used according to the invention from the suspension by filtration, filter cake washing and drying is described in WO-A 01/80994. The unsaturated comonomers may be distributed randomly or in blocks in the polyethercarbonate polyols. Gradient polymers can also be used.

In a further aspect of the process, the reaction of the polyethercarbonate polyol with unsaturated groups takes place with the phosphorus-functional compound of the formula (Ia) at a temperature greater than or equal to 100 ° C. and less than or equal to 220 ° C. This temperature range has proved to be particularly suitable in the context of an efficient process management with a sufficient reaction rate. Advantageously, results from this reaction a final product without Katalysatorbeimischungen. Without being bound by theory, anionic addition of the phosphorus functional compound to the unsaturated groups of the polyethercarbonate polyol is likely to occur within this temperature range. Lower temperatures can lead to an only unsatisfactory reaction of the phosphorus-functional compound, whereas higher temperatures can lead to a reduced yield, due to the increase in side reactions.

In a further aspect of the process, the reaction of the polyethercarbonate polyol with unsaturated groups takes place with the phosphorus-functional compound of the formula (Ia) at a temperature greater than or equal to 0 ° C. and less than or equal to 100 ° C., and a compound selected from the group of the basic Catalysts are added. For example, basic catalysts can be used which are known to those skilled in the art for use within a Michael addition. Tertiary amines, such as, for example, diazabicyclooctane (DABCO), amidines, such as, for example, 1,6-diazabicyclo [5.4.0] undec-5-ene (BDU) or 1,8-diazabicyclo [5.4.0] undecarboxylic acid, may be used as basic catalysts. 7-ene (DBU), guanidines, such as triazabicyclodecene, N-methyl-triazabicyclodecen, -Butyl- triazabicyclodecen or tetramethylguanidine, pentamethylguanidine, and / or Phosphoriminbasen or Proazaphosphatrane be used as basic catalysts. It is also possible to use mixtures of different basic catalysts. The use of these catalysts in the specified temperature range leads to a rapid and low-by-product reaction of the phosphorus-functional compounds to the polyethercarbonate polyols having unsaturated groups.

In a further aspect of the process, the reaction of the polyethercarbonate polyol with unsaturated groups with the phosphorus-functional compound of the formula (Ia) takes place at a temperature greater than or equal to 0 ° C. and less than or equal to 100 ° C., and a compound selected from the group of photoinitiators , Peroxides, azo compounds, metal-activated peroxides and / or redox initiators. The reaction of the Polyethercarbonatpolyols with unsaturated groups with the phosphorus-functional compound can, for example, with

Initiators disclosed in T. Myers, N. Kirk-Othmer, Encyclopedia of Chemical Technology (5th Edition) (2005), 14, 274-311, or in JC Beevington, Macromolecular Chemistry, Macromolecular Symposia (1987), 10 (1), 89 .

Photoinitiators described in J.P. Fouassier, X. Allonas, J. Lalevee; C. Dietlin, Photochemistry and Photophysics of Polymer Materials (2010), 351-419,

metal-activated peroxides described in C. Sma, Applied Macromolecular Chemistry (1969), 9165-181 or US Pat Redox initiators used in GS Misra; UDN Bajpai Progress in Polymer Science (1982) 8 (1-2), 61-131

described are accelerated.

Preference is given to using photoinitiators. Photoinitiators which can be used according to the invention are e.g. Bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, diphenylmesitoyl-phosphine oxide, camphorquinone, isopropylthioxanthone, Michler's ketone, benzophenone, benzoin methyl ether, dimethoxyphenylacetophenone or 2,2-dimethyl-2-hydroxyacetophenone.

The radical initiators can be used in amounts of greater than or equal to 0.01% by weight and less than or equal to 2% by weight, based on the polyethercarbonate polyol. Redox initiators are a mixture of an oxidizing and a reducing substance. The phosphorus-functional compounds used for the functionalization can also take on the function of a reducing substance. Type II photoinitiators require the addition of a hydrogen donor, such as an amine or another phosphine compound, whereby the phosphorus functional compounds added to the unsaturated groups can also fulfill this function.

Furthermore, according to the invention, phosphorus-functional polyethercarbonate polyols are obtainable by the process according to the invention. The phosphorus-functional polyether carbonate polyols which can be prepared by the process according to the invention have a good flame-retardant action and, owing to their steric structure and the resulting viscosity, can be very readily obtained by further processes, such as e.g. a subsequent networking, further processing. The inventive phosphorus functional

Polyethercarbonatepolyols or their reaction products with isocyanates may also, if required, in addition to conventional external flame retardant additives, such as halogenated hydrocarbons, optionally with antimony trioxide synergist, (encapsulated) red phosphorus, monomeric or oligomeric phosphorus compounds, polyhedral oligomeric silsesquioxanes, other siloxanes, melamine isocyanurate, Melaminpolyphosphat, Cyclophosphazenen , Carbon nanotubes, fullerenes, montmorillonite or aluminum hydroxide. The addition of further additives, as described, for example, in Progress in Polymer Science 34 (2009) 1068-1133, is also possible. In one embodiment of the process, in a further process step, the phosphorus-functional polyether carbonate polyols can be crosslinked by adding di- or polyisocyanates. In one embodiment, mixtures of polyethercarbonate polyols and phosphorus functional polyethercarbonate polyols are reacted with one or more di- or polyisocyanates. In this case, preference is given to reacting at least one phosphorus-functional polyethercarbonate polyol with one or more di- or polyisocyanates. The Details of the reaction of polyols with diisocyanates or polyisocyanates are known to those skilled in polyurethane chemistry.

Furthermore, according to the invention, crosslinked phosphorus-functional polyethercarbonate polyol polymers are obtainable by the process according to the invention. The crosslinked phosphorus-functional polyethercarbonate polyol polymers are distinguished by reproducible mechanical properties and controllable reaction behavior, since the starting materials have a narrow and defined molecular weight distribution and the further crosslinking takes place only downstream. In this way, side reactions in the context of cross-linking of the polyether carbonate polyols can already be avoided as part of the phosphorus functionalization. Furthermore, the crosslinked phosphorus-functional polyethercarbonate polyol polymers show good flame-retardant properties without significant losses in the range of other quality criteria for crosslinked systems such as stiffness, mechanical strength, abrasion properties, elasticity or the like.

The phosphorus-functional polyether carbonate polyols obtainable by the process according to the invention can be used as flame-retardant adhesion promoters, filler activators or additives. Especially the combination according to the invention of the different functional groups in the polymer can lead due to the combination of hydrophilic and hydrophobic properties to a particularly good suitability to connect different polar interfaces with each other. Accordingly, the phosphorus-functional polyethercarbonate polyols which can be prepared according to the invention can be used particularly well in cases in which adhesion between different polar boundary surfaces is desired. Likewise, a better dispersion of fillers can be achieved by using the phosphorus-functional polyether carbonate polyols. This can contribute to a faster reaction in the context of crosslinking reactions and consequently to a more uniform end product. Furthermore, the crosslinked phosphorus-functional polyethercarbonatepolyol polymers obtainable by the process according to the invention can be used as flame-retardant coating, foam, sealant, thermoplastic, duromeric plastic, rubber. This use of the crosslinked phosphorus-functional polyethercarbonatepolyol polymers may be particularly advantageous, since the other process properties of the crosslinked phosphorus-functional polyethercarbonatepolyol polymers are only insignificantly impaired by the flame-retardant functionalization as a result of the selected process procedure. This is most likely due to a lower number of undesirable by-products in the synthesis of the polyether carbonate polyols having unsaturated groups, a more constant molecular weight distribution of the polyether carbonate polyols having unsaturated groups and a more controlled phosphorus functionalization. Likewise within the meaning of the invention are moldings comprising a flame-retardant layer comprising a flame-retardant, crosslinked phosphorus-functional polyether carbonate polyol polymer preparable by the process according to the invention. The crosslinked phosphorus-functional polyethercarbonatepolyol polymers prepared according to the invention can be particularly suitable for the construction of flame-retardant, mechanically stable layers on moldings, since the polyethercarbonatepolyols according to the invention can be easily and reproducibly placed on moldings and a crosslinking reaction with diisocyanates or polyisocyanates can be carried out simply and reproducibly.

With regard to further advantages and features of the above-described shaped body, reference is hereby explicitly made to the explanations in connection with the crosslinked phosphorus-functional polyether carbonate polyol polymers according to the invention and the process according to the invention. Also features of the invention and advantages of the phosphorus-functional polyether carbonate polyols according to the invention should also be applicable to the process according to the invention and the crosslinked phosphorus-functional polyether carbonate polyol polymers according to the invention and be regarded as disclosed and vice versa. The invention also includes all combinations of at least two features disclosed in the description and / or the claims.

Examples

Used H-functional starter substance (starter):

PET-1 difunctional poly (oxypropylene) polyol having an OH number of 112 mgKOH g

Used alkylene oxide, which carries no double bonds:

PO propylene oxide

Comonomer used:

MSA maleic anhydride containing electron-poor double bonds

AGE allyl glycidyl ether containing electron-rich double bonds

Phosphorus compound used:

DOPO 9,10-Dihydro-9-oxa-phosphaphenanthrene-10-oxide

Used radical starter:

Irgacure 819 bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide

The DMC catalyst was prepared according to Example 6 of WO-A 01/80994. The polymerization reactions were carried out in a 300 ml pressure reactor from Parr. The pressure reactor used in the examples had a height (inside) of 10.16 cm and an inner diameter of 6.35 cm. The reactor was equipped with an electric heating mantle (510 watts maximum heat output). The countercooling consisted of a U-shaped dip tube with 6 mm outer diameter, which protruded to 5 mm above the ground in the reactor and was flowed through with cooling water of about 10 ° C. The water flow was switched on and off via a solenoid valve. Furthermore, the reactor was equipped with an inlet tube and a thermo sensor with 1.6 mm diameter, which protrude to 3 mm above the ground in the reactor.

The heat output of the electric heating jacket during activation [first activation stage] averaged about 20% of the maximum heating capacity. Due to the regulation, the heating output fluctuated by + 5% of the maximum heating power. The occurrence of increased heat in the reactor, caused by the rapid reaction of propylene oxide during the activation of the catalyst [second activation stage] was observed via a reduced heat output of the heating mantle, switching on the countercooling and optionally a temperature rise in the reactor. The occurrence of heat buildup in the reactor caused by the continuous reaction of propylene oxide during the reaction [polymerization step] led to a lowering of the power of the heating jacket to about 8% of the maximum heating power. Due to the regulation, the heating output fluctuated by + 5% of the maximum heating power.

The hollow-shaft stirrer used in the examples was a hollow-shaft stirrer in which the gas was introduced into the reaction mixture via a hollow shaft of the stirrer. The mounted on the hollow shaft agitator had four arms, had a diameter of 35 mm and a height of 14 mm. At each end of the arm there were two gas outlets with a diameter of 3 mm. The rotation of the stirrer resulted in a negative pressure such that the gas (CO ₂ and optionally alkylene oxide) present above the reaction mixture was sucked off and introduced into the reaction mixture via the hollow shaft of the stirrer.

The impeller stirrer used in some examples was a skew-blade turbine in which a total of two stirring stages, each with four stirring blades (45 °), were mounted on the stirrer shaft at a distance of 7 mm, having a diameter of 35 mm and a height of 10 mm. a) In the case of the terpolymerization of propylene oxide, allyl glycidyl ether and CO ₂ , in addition to the cyclic propylene carbonate, the polyether carbonate polyol which contains polycarbonate units shown in formula (Xa), on the one hand,

and on the other hand, polyether units shown in formula (Xb).

When incorporating cyclic anhydrides into the polymer chain, this additionally contains ester groups.

The characterization of the reaction mixture was carried out by NMR spectroscopy and gel permeation chromatography.

The ratio of the amount of cyclic propylene carbonate to polyethercarbonate polyol (selectivity, ratio c / a) and the proportion of unreacted monomers (propylene oxide Rpo, allylglycidyl ether R _AG E in mol%) were determined by means of NMR spectroscopy. This was in each case one sample of the reaction mixture obtained after the reaction was dissolved in deuterated chloroform and measured on a Bruker spectrometer (AV400, 400 MHz).

Subsequently, the reaction mixture was diluted with dichloromethane (20 ml) and the solution passed through a falling film evaporator. The solution (0.1 kg in 3 h) ran down the inner wall of a 70 mm diameter, 200 mm long, externally heated tube at 120 ° C with the reaction mixture passing through three rotating rollers at a speed of 250 rpm with 10 mm diameter was evenly distributed as a thin film on the inner wall of the falling film evaporator. Inside the pipe, a pressure of 3 mbar was set by means of a pump. The reaction mixture, purified from light volatiles (unreacted epoxides, cyclic carbonate, solvent) was collected at the bottom of the heated tube in a receiver.

The molar ratio of carbonate groups to ether groups in the polyethercarbonate polyol (ratio a / b) and the molar fraction of the comonomers incorporated in the polymer were determined by means of λ NMR spectroscopy. A sample of the purified reaction mixture was in each case dissolved in deuterated chloroform and measured on a Bruker spectrometer (AV400, 400 MHz).

The relevant resonances in the ^ -NMR spectrum (relative to TMS = 0 ppm) used for integration are as follows:

Signal shift Designation Area corresponds to ppm number of H atoms

II 1.10 - 1.17 CEb group of polyether units 3

12 1.25 - 1.34 CE group of polycarbonate units 3

13 1.45 - 1.48 CEb group of the cyclic carbonate 3

14 2.95 - 3.00 CH groups of the free, not 1

reacted propylene oxide

15 5.83-5.94 CH group of in the polymer over the 1

Incorporation of allyl glycidyl ether

obtained double bond

16 6.22-6.29 CH group of in the polymer over the 2nd

Incorporation of maleic anhydride

obtained double bond

17 7.03 - 7.04 CH group for free, unreacted 2

Male acid anhy drid

18 2,59-2,66 & CH group of in the polymer 2

2.75-2.78 built DOPO

19 1.74-1.84 CH group of in the polymer 2

built-in DOPO

The molar ratio of the amount of cyclic propylene carbonate to carbonate units in the polyethercarbonate polyol or polyetherestercarbonate polyol (selectivity c / a) and the molar ratio of carbonate to ether groups in the polyethercarbonate polyol or polyetherestercarbonatepolyol (ab) and the proportions of unreacted propylene oxide ( in mol%) and maleic anhydride (in mol%).

Taking into account the relative intensities, the values were calculated as follows:

Molar ratio of the amount of cyclic propylene carbonate to carbonate units in the polyethercarbonate polyol or polyetherestercarbonate polyol (selectivity c / a): c / a = 13/12 (XI)

Molar ratio of carbonate groups to ether groups in the polyethercarbonate polyol or polyetherestercarbonate polyol (ab): a / b = 12 / II (XII) The molar fraction of unreacted propylene oxide (RPO in mol%) based on the sum of the amount of propylene oxide used in the activation and the copolymerization is calculated according to the formula:

RPO = [(14/1) / ((11/3) + (12/3) + (13/3) + (14/1))] x 100% (XIII) The information on the proportions A is given in Following on Polyetherestercarbonatpolyole obtained using maleic anhydride as a comonomer.

The molar proportion of unreacted maleic anhydride (RMSA in mol%) based on the sum of the amount of maleic anhydride used in the activation and copolymerization is calculated according to the formula: RMSA = [(16/2) / ((16/2) + (17/2))] x 100% (XIV)

Proportion of carbonate units in the repeating units of the polyetherestercarbonatepolyol:

AcaAonate = [(12/3) / ((11/3) + (12/3) + (16/2))] x 100% (XV)

Proportion of the double bonds resulting from the incorporation of the maleic anhydride in the repeating units of the polyetherestercarbonate polyol: ADoppeibi "du" g = [(16/2) / ((11/3) + (12/3) + (16/2))] x 100 % (XVI)

Proportion of DOPO units in the repeating units of the polyetherestercarbonatepolyol:

ADOPO = [(18/2) / ((11/3) + (12/3) + (18/2) + (16))] x 100% (XVII)

The statements on the proportions B refer in the following to polyether carbonate polyols obtained using allyl glycidyl ether as a comonomer. The proportion of carbonate units in the repeating units of the polyethercarbonate polyol:

B carbonate = [(12/3) / ((11/3) + (12/3) + (15/1))] x 100% (XVIII)

The proportion of the double bonds resulting from the incorporation of the allyl glycidyl ether in the repeating units of the polyethercarbonate polyol:

B _Do ppeibindung = [(15) / ((11/3) + (12/3) + (15/1))] x 100% (XIX) The proportion of DOPO units in the repeat units of the polyether carbonate polyol:

BDOPO = [(19/2) / ((11/3) + (12/3) + (19/2) + (15))] x 100% (XX) Preparation of Polyethercarboriatpolyole

Polyethercarbonate polyol A: terpolymerization of propylene oxide, maleic anhydride (9.5 mol%) and C0 ₂

[first activation step] A mixture of DMC catalyst (104 mg) and PET-1 (130 g) was placed in a 970 ml pressure reactor equipped with a gas introduction stirrer and passed through at 130 ° C. in a partial vacuum (50 mbar) for 30 minutes of argon was stirred through the reaction mixture.

[second activation level]

After pressing 15 bar CO2, with a slight drop in temperature was observed, and re-reaching a temperature of 130 ° C, 13.0 g of a monomer mixture (15 wt .-% maleic anhydride [corresponding to 9.5 mol%] dissolved in propylene oxide) with Aided by an HPLC pump (1 ml / min). The reaction mixture was stirred for 20 minutes at 130 ° C (800 rpm). The addition of 13.0 g of a monomer mixture was repeated a second and third time.

[Polymerization stage] After cooling to 100 ° C., a further 186.0 g of the monomer mixture (15% by weight of maleic anhydride, corresponding to 9.5 mol%) were metered in via an HPLC pump (6 ml / min), the CO 2 pressure remaining constant was kept at 15 bar. Subsequently, the reaction mixture was stirred at 100 ° C for a further 2 h. The reaction was stopped by cooling the reactor with ice-water. Product features:

The resulting mixture was free of the monomers used propylene oxide (Rpo = 0%) and maleic anhydride (RMS _A = 0%).

Selectivity c / a 0.04

a / b 0.27

Acarbonate in% 21.2

Aooppelbindung in% 5,7

Molecular weight M _n 4175

g / mol

Polydispersity 1,2

OH number in mgKOH / g 38.0 Example 1: Preparation of DOPO-Containing Polyethercarbonatepolyol

In a 250 ml two-necked flask, DOPO (12.01 g, 0.06 mol) and DBU (1.69 g, 0.01 mol) were dissolved in THF (40 mL). Subsequently, another solution of polyethercarbonate polyol A (50.0 g) in THF (130 mL) was prepared. This Polyethercarbonatpolyol solution was transferred by means of a dropping funnel in the two-necked flask. The reaction mixture was stirred for one hour. Subsequently, the solvent was removed under reduced pressure.

Product features:

Preparation of the Polyurethanes EXAMPLE 2 Preparation of a Polyurethane from Phosphorus-containing Polyethercarbonate Polyol

For the preparation of phosphorus-containing polyurethane (Sample PU-1), the DOPO-containing polyethercarbonate polyol from Example 1 (8.2 g) was mixed with an equimolar amount of aliphatic polyisocyanate (HDI trimer, Desmodur N3300, 1.0 g) and 1000 ppm dibutyltin laurate added. The sample was cured on a planar metal plate. Subsequently, the phosphorus-thin polyurethane sample (1.5 g, 20 × 15 × 2 mm) was exposed to a flame for 10 seconds to check the flame resistance

Example 3 (Cf.): Production of a polyurethane from Polyethercarbonatpolyol

For the preparation of polyurethane without phosphorus (sample PU-2), the polyether carbonate polyol A (7.4 g) was treated with an equimolar amount of aliphatic polyisocyanate (HDI trimer, Desmodur N3300, 1.0 g) and 1000 ppm dibutyltin laurate. The sample was cured on a planar metal plate. Subsequently, the polyurethane sample (1.5 g, 20 × 15 × 2 mm) was exposed to a flame for 10 seconds to check the flame resistance Results of the flame test

The results from the flame test are given for the polyurethane sample from Example 2 and the polyurethane sample from Comparative Example 3 in the table below. The stated phosphorus content refers to the polyurethane sample.

Comparative Example

comparison

The comparison of the results from Example 2 with Comparative Example 3 shows that the Phosphorhai term polyurethane sample has a much higher flame resistance.

Preparation of Polyethercarboriatpolyole

Polyethercarbonate polyol B: terpolymerization of propylene oxide, allyl glycidyl ether (9.5 mol%) and C0 ₂

[first activation step] A mixture of DMC catalyst (48 mg) and PET-1 (80 g) was placed in a 970 ml pressure reactor equipped with a gas introduction stirrer and passed through at 130 ° C. in a partial vacuum (50 mbar) for 30 minutes of argon was stirred through the reaction mixture.

[second activation level]

After pressing on 15 bar of CO2, whereby a slight decrease in temperature was observed, and re-reaching a temperature of 130 ° C., 8.0 g of a monomer mixture (16.7% by weight of allylglycidyl ether [corresponding to 9.5 mol%] dissolved in propylene oxide) metered by means of an HPLC pump (1 ml / min). The reaction mixture was stirred for 20 minutes at 130 ° C (800 rpm). The addition of 8.0 g of a monomer mixture was repeated a second and third time.

[Polymerization stage] After cooling to 100 ° C., a further 136.0 g of the monomer mixture (16.7% by weight of allyl glycidyl ether, corresponding to 9.5 mol%) were metered in via an HPLC pump (1 ml / min), the CO ₂ Pressure was kept constant at 15 bar. Subsequently, the reaction mixture was stirred at 100 ° C for a further 2 h. The reaction was stopped by cooling the reactor with ice water.

Product properties: The resulting mixture was free from the monomers used, propylene oxide and allyl glycidyl ether.

Selectivity c / a 0.07

a / b 0.19

B carbonate in% 14.9

B double bond in% 5.5

Molecular weight in M _n 4678

g / mol

Polydispersity 1.4

OH number in mg _K oH / g 36.3 Example 4: Preparation of DOPO-Containing Polyethercarbonatepolyol

The polyethercarbonate polyol B (10.0 g) and DOPO (2.2 g) were mixed and heated to 120 ° C. After complete dissolution of the DOPO, the temperature was controlled at 80 ° C. Subsequently, the photoinitiator Irgacure 819 (100 mg) was added to the reaction mixture. The solution was irradiated with UV light for 2 minutes (22 W / cm ² ). The product prepared was analyzed by NMR spectroscopy and GPC.

Product features:

Preparation of the Polyurethanes EXAMPLE 5 Preparation of a Polyurethane from Phosphorus-containing Polyethercarbonate Polyol

For the preparation of phosphorus-containing polyurethane (PU-3), the DOPO-containing polyethercarbonate polyol from Example 4 (9.3 g) was mixed with an equimolar amount of aliphatic polyisocyanate (HDI trimer, Desmodur N3300, 1.0 g) and 1000 ppm dibutyltin laurate , The sample was cured on a planar metal plate. Subsequently, the phosphorus-containing polyurethane sample (1.5 g, 20 × 15 × 2 mm) was exposed to a flame for 10 seconds to check the flame resistance

Example 6 (Cf.): Production of a polyurethane from Polyethercarbonatpolyol

For the preparation of polyurethane without phosphorus (PU-4), the polyether carbonate polyol B (7.7 g) was treated with an equimolar amount of aliphatic polyisocyanate (HDI trimer, Desmodur N3300, 1.0 g) and 1000 ppm dibutyltin laurate. The sample was cured on a planar metal plate. Subsequently, the polyurethane sample (1.5 g, 20 × 15 × 2 mm) was exposed to a flame for 10 seconds to check the flame resistance. Results of the flame test

The results from the flame test are given for the polyurethane sample from Example 5 and the polyurethane sample from Comparative Example 6 in the table below. The stated phosphorus content refers to the polyurethane sample.

5 Cf. Comparative Example

comparison

The comparison of the results from Example 5 with Comparative Example 6 shows that the phosphorus-containing polyurethane sample has a much higher flame resistance.

Claims

claims

Process for the preparation of a phosphorus-functional polyethercarbonate polyol, in which polyethercarbonate polyol having unsaturated groups with a phosphorus-functional

Compound according to formula (Ia) is reacted,

X = O, S means;

R ¹ and R ^{2 are} selected from the group consisting of C 1 -C 22 alkyl, C 1 -C 22 alkoxy, C 1 -C 22 alkylsulfanyl C 6 -C 70 aryl, C 6 -C 70 aryloxy, C 6 -C 70 arylsulfanyl, C 7 -C 70 aralkyl, C 7 -C 70 aralkyloxy, C7-C70 aralkylsulfanyl, C7-C70 alkylaryl, C7-C70 alkylaryloxy, C7-

C70 alkylarylsulfanyl, or wherein

R ¹ and R ² are bridged together directly and / or via heteroatoms and are selected from the group comprising C1-C22 alkylene, oxygen, sulfur or NR ⁵ , wherein

R ^{5 is} hydrogen, C 1 -C 22 alkyl, C 1 -C 22 acyl, C 7 -C 22 aralkyl or C 6 -C 70 aryl. 2. The method according to claim 1, characterized in that the phosphorus-functional

Compound of formula (Ia) is a compound of formula (Ib)

in which

n, m are independently 0, 1,

2, 3 or 4 are.

3. The method according to claim 2, characterized in that

R ³ and R ^{4 are} selected from the group consisting of C 1 -C 8 alkyl and C 1 -C 8 alkoxy and n, m are independently 0 or 1.

4. The method according to any one of the preceding claims, characterized in that the phosphorus-functional compound is 9,10-dihydro-9-oxa-10-phosphaphenanthren-10-oxide and / or P-methyl-phosphinic acid butyl ester.

5. The method according to any one of the preceding claims, characterized in that the polyether carbonate polyol having unsaturated groups is selected from Polyethercarbonatpolyolen with unsaturated groups or Polyetherestercarbonatpolyolen with unsaturated groups.

6. The method according to any one of claims 1 to 5, characterized in that the Polyethercarbonatpolyol was obtained with unsaturated groups by reacting a starter compound with one or more alkylene oxides, carbon dioxide and one or more other monomers selected from the group of alkylene oxides, the cyclic anhydrides of Dicarboxylic acids, the lactones, lactides, cyclic 6-ring carbonates under the

In that at least one of the other monomers used contains one or more C-C double or triple bonds

7. The method according to any one of the preceding claims, characterized in that the phosphorus content of the phosphorus-functional polyether carbonate is between 0.5 and 15 wt .-%.

8. The method according to any one of the preceding claims, characterized in that the polyethercarbonate polyol is prepared with unsaturated groups by a process comprising the following steps:

(a) preparing an H-functional initiator compound and a DMC catalyst,

(ß) optionally dosing an epoxide,

(γ) metering

(γΐ) at least one epoxide, as well

(γ2) at least one epoxide, a cyclic anhydride of a dicarboxylic acid, a lactone, a lactide and / or a cyclic 6-ring carbonate having a double bond, and /

(γ3) of carbon dioxide.

9. The method according to any one of the preceding claims, characterized in that the reaction of the Polyethercarbonatpolyols with unsaturated groups with the Phosphorofunctional compound according to formula (Ia) is carried out at a temperature greater than or equal to 100 ° C and less than or equal to 220 ° C.

10. The method according to any one of claims 1 to 8, characterized in that the reaction of the Polyethercarbonatpolyols with unsaturated groups with the phosphorus-functional compound of formula (Ia) at a temperature greater than or equal to 0 ° C and less than or equal to 100 ° C and at the implementation

a compound selected from the group of basic catalysts or

a compound selected from the group of photoinitiators, peroxides, azo compounds, metal-activated peroxides and / or redox initiators

is added.

11. A phosphorus-functional polyethercarbonate polyol obtainable by a process according to any one of claims 1 to 10.

12. A process for preparing a phosphorus-functional polyurethane polymer, characterized in that at least one phosphorus-functional polyethercarbonate polyol according to claim 11 is reacted with one or more di- or polyisocyanates.

13. A phosphorus-functional polyurethane polymer obtainable by a process according to claim 12.

14. Use of a phosphorus-functional polyethercarbonate polyol according to claim 11 or a phosphorus-functional polyurethane polymer according to claim 13 as a flame-retardant adhesion promoter, filler activator or as a flameproofing agent or as a flame retardant

Coating, foam, sealant, thermoplastic, thermosetting plastic or rubber.

15. Shaped body comprising a flame retardant layer comprising a phosphorus-functional polyurethane polymer according to claim 13.