EP3824013A1 - Polyéthers ou carbonates de polyéther à fonction hétérocycle et leur procédé de préparation - Google Patents

Polyéthers ou carbonates de polyéther à fonction hétérocycle et leur procédé de préparation

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Publication number
EP3824013A1
EP3824013A1 EP19737776.5A EP19737776A EP3824013A1 EP 3824013 A1 EP3824013 A1 EP 3824013A1 EP 19737776 A EP19737776 A EP 19737776A EP 3824013 A1 EP3824013 A1 EP 3824013A1
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EP
European Patent Office
Prior art keywords
formula
anhydride
polyoxyalkylene polyol
functional
heterocycle
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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EP19737776.5A
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German (de)
English (en)
Inventor
Daniela Cozzula
Burkhard KÖHLER
Muhammad Afzal Subhani
Piotr PUTAJ
Walter Leitner
Thomas Ernst MÜLLER
Christoph Gürtler
Volker Marker
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Covestro Intellectual Property GmbH and Co KG
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Covestro Intellectual Property GmbH and Co KG
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Publication of EP3824013A1 publication Critical patent/EP3824013A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/333—Polymers modified by chemical after-treatment with organic compounds containing nitrogen
    • C08G65/33303—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing amino group
    • C08G65/33317—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing amino group heterocyclic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/334—Polymers modified by chemical after-treatment with organic compounds containing sulfur
    • C08G65/3344—Polymers modified by chemical after-treatment with organic compounds containing sulfur containing oxygen in addition to sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/02—Aliphatic polycarbonates
    • C08G64/0208—Aliphatic polycarbonates saturated
    • C08G64/0225—Aliphatic polycarbonates saturated containing atoms other than carbon, hydrogen or oxygen
    • C08G64/0241—Aliphatic polycarbonates saturated containing atoms other than carbon, hydrogen or oxygen containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/02—Aliphatic polycarbonates
    • C08G64/0208—Aliphatic polycarbonates saturated
    • C08G64/0225—Aliphatic polycarbonates saturated containing atoms other than carbon, hydrogen or oxygen
    • C08G64/025—Aliphatic polycarbonates saturated containing atoms other than carbon, hydrogen or oxygen containing sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/20—General preparatory processes
    • C08G64/32—General preparatory processes using carbon dioxide
    • C08G64/34—General preparatory processes using carbon dioxide and cyclic ethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/42—Chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2642—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the catalyst used
    • C08G65/2645—Metals or compounds thereof, e.g. salts
    • C08G65/2663—Metal cyanide catalysts, i.e. DMC's
    • C—CHEMISTRY; METALLURGY
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    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/333—Polymers modified by chemical after-treatment with organic compounds containing nitrogen
    • C08G65/3332—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing carboxamide group
    • C08G65/33327—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing carboxamide group cyclic
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/334—Polymers modified by chemical after-treatment with organic compounds containing sulfur
    • C08G65/3342—Polymers modified by chemical after-treatment with organic compounds containing sulfur having sulfur bound to carbon and hydrogen
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2101/00—Manufacture of cellular products
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2150/00—Compositions for coatings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2170/00—Compositions for adhesives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2190/00—Compositions for sealing or packing joints
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G2650/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterized by the type of post-polymerisation functionalisation
    • C08G2650/20—Cross-linking

Definitions

  • the invention relates to a process for the preparation of a heterocycle-functional polyoxyalkylene polyol, in which a polyoxyalkylene polyol having unsaturated groups is reacted with a heterocyclic compound.
  • the invention further relates to a heterocycle-functional polyoxyalkylene polyol which can be prepared by the process according to the invention and to its use, inter alia, in the production of a heterocycle-functional polyurethane polymer.
  • polyether carbonate polyols specifically for certain areas of application.
  • the reaction of polyols with isocyanates is catalyzed by aminic compounds which, after the reaction, remain in the polyurethane as low molecular weight substances but gradually diffuse out of the polymer. It would therefore be desirable to chemically bind the compounds that catalyze the polyurethane reaction to the polyol.
  • Other heterocycles, such as furans offer the possibility of subsequent crosslinking with formaldehyde resins, furfuryl alcohol, air drying or the Diels-Alder reaction. It would therefore be desirable to subsequently functionalize polyols with furan rings.
  • Heterocycles also reduce the heat of combustion of polymers or increase the amount of residual carbon in pyrolysis. It is desirable to chemically bind such compounds that reduce the heat of combustion or increase the carbonization residue to the polyol.
  • Complex formation can be used to load polymers with catalytically active metal ions or to coordinate coordinate the polymers. To do this, a substituent that acts as a ligand, e.g. a heterocycle to which the polymer is chemically attached. For this reason, too, it is desirable to chemically bind effective heterocycles to the polyol as ligands. Adhesion to metal surfaces or to metallic fillers can also be improved by complex ligands coupled to the polymer matrix. This can also be associated with improved corrosion protection if polyurethanes containing heterocycle-functional polyoxyalkylenes are used for coating metals.
  • heterocyclic compounds interfere with polyoxyalkylene synthesis through interaction or deactivation of the catalyst, for example the double metal cyanide catalyst. It may therefore be advantageous to chemically attach the heterocycle after the synthesis of the poloxyalkylene polyol.
  • the reaction of unsaturated polyoxyalkylenes with mercapto compounds is known in principle, but only open-chain mercaptans have been added to the electron-rich double bonds by the mechanism of radical addition.
  • the addition of BOC-cytein, BOC-cysteine amine and mercaptoacetic acid to a copolycarbonate containing allyl glycidyl ether as an unsaturated monomer has been described in Angewandte Chemie International Edition (2015) 54 (35) 10206-10210.
  • the object of the present invention is to provide an improved process for the preparation of heterocycle-functional polyoxyalkylene polyols which does not entail any disadvantages with regard to the preparation of the polymers themselves.
  • XI, Yl and Zl have the meaning given under formula Ha for X, Y and Z and Ch for an oxygen atom, a sulfur atom or an NH or NR group, where R is a Cl-C22 alkyl radical, a C7-C17 aralkyl - or arylalkyl radical or a C6-C16 aryl radical, stand or of the formula (Ile),
  • Chl and Ch2 have the meaning given under formula IIb for Ch and Rl and R2 are hydrogen, a C1-C22 alkyl radical, a C7-C17 aralkyl or arylalkyl radical or a C6-C16 aryl radical or members of a 5-, 6- or Can be 7-rings or of the formula (Ild),
  • Ch3 and Ch4 have the meaning given under formula IIb for Ch and R3 and R4 are hydrogen, a C1-C22 alkyl radical, a C7-C17 aralkyl or arylalkyl radical or a C6-C16 aryl radical or members of a 5-, 6- or Can be 7-rings or of the formula (Ile),
  • Ch5 and R6 are hydrogen, a C1-C22 alkyl radical, a C7-C17 aralkyl or arylalkyl radical or a C6-C16 aryl radical or members of a 5-, 6- or 7- Can be rings and R7 represents hydrogen, a C1-C22 alkyl radical, a C7-C17 aralkyl or arylalkyl radical, a C6-C16 aryl radical or an aldehyde group.
  • the invention is based on the knowledge that the subsequent functionalization of the polyoxyalkylene polyol with a heterocycle compound of the formula (Ia) can overcome the aforementioned disadvantages from the prior art, since due to the fixed incorporation into the polymer there is no softening effect due to low molecular weight heterocycles and there is also no deactivation of the polymerization catalyst since the polymer chain of the polyoxyalkylene polyol has already been built up at the time the heterocyclic compound is incorporated. It has been found that the incorporation of double bonds in the main polymer structure of the polyoxyalkylene polyol allows a relatively simple addition of the heterocyclic compound.
  • this production process enables an efficient and controlled functionalization of unsaturated polyoxyalkylene polyols with heterocyclic compounds.
  • the heterocycles are covalently bound to the polymer structure. This results in functionalized polyoxyalkylene polyol with a defined heterocycle functionality. This is in contrast to polymers with heterocycles which are weakly bound via ionic or van der Waals interactions, the content of heterocycles and their properties can change during storage or in subsequent reaction or purification steps. This is precluded by the covalent attachment of the heterocycles to the polymer structure in accordance with the method according to the invention. Furthermore, this process procedure enables the actual polyoxyalkylene polyols to be built up quickly and in a controlled manner without having to fear inactivation or modification of the catalyst required for the construction of the polyoxyalkylene polyols by heterocyclic compounds.
  • a variable amount of heterocylene can also be introduced into a polyoxyalkylene polyol with 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 heterocycle-functional polyoxyalkylene polyols.
  • Another advantage can also result from the fact that not all unsaturated groups of the polyoxyalkylene polyols have to be modified. This can result in further modifications after the heterocycle-functional modification Functional groups are on the polymer backbone, which can be used in further implementation steps. For example, this functionality can be used in the context of further crosslinking reactions.
  • the heterocycle-containing polyoxyalkylene polyols obtained are also ecologically harmless.
  • the heterocycle-functional polyoxyalkylene polyols obtainable by this process can initiate increased carbonification in the event of a fire, as a result of which a protective surface layer is formed, which ultimately reduces the amount of combustible material. They also reduce the heat of combustion of the polymer. Furthermore, additional release of gases can lead to the formation of a voluminous insulation layer, which has a flame-retardant effect.
  • the heterocycle-functional polyoxyalkylene polyols or decomposition products formed therefrom can trap radical species in the gas phase and thus inhibit the combustion process.
  • such heterocycle-functional polyoxyalkylene polyols are self-catalytic in relation to the further reaction with isocyanates to give polyurethanes. These polyurethanes or the heterocycle-functional polyoxyalkylene polyols themselves can serve as polymeric ligands for metal ions, which can improve flame retardancy or can be used to produce catalysts.
  • the heterocyclic compound of the formula (I) is one or more compound (s) and is selected from the group consisting of furfurylthiol, 4-methyl-triazole-3-thiol, 4-methyl-4H -l, 2,4-triazole-3-thiol, imidazole and 2,5-pyrrolidinedione.
  • polyoxyalkylene polyols with unsaturated groups examples include polyether polyols with unsaturated groups, polyether carbonate polyols with unsaturated groups, polyether ester polyols with unsaturated groups, polyether ester carbonate polyols with unsaturated groups.
  • Preferred polyoxyalkylene polyols with unsaturated groups are polyether ester carbonate polyols with unsaturated groups.
  • Preferred polyether carbonate polyols are compounds of the formula (III), and the product for the polyether carbonate polyol shown here in Scheme (III) is only to be understood such that blocks with the structure shown can in principle be found in the polyether carbonate polyol obtained, the order, number and length the blocks and the OH functionality of the starter can vary, however, and is not limited to the polyether carbonate polyol shown in scheme (III), and Formula (III), where R8 is C1-C43 alkyl, CI-CIO alkylaryl or C6-C70 aryl, where heteroatoms such as O, S, Si may also be present, and where a and b are an integer and the ratio from a / b 2: 1 to 1:20, in particular 1.5: 1 to 1:10.
  • the polyoxyalkylene polyol with unsaturated groups can have a proportion of unsaturated comonomers within the polyoxyalkylene polyol of greater than or equal to 0.1 mol% and less than or equal to 50 mol%.
  • This number of possible binding sites of the heterocyclic compounds to the polyoxyalkylene polyol with unsaturated groups has proven to be particularly advantageous.
  • heterocycle-functional polyoxyalkylene polyols can be obtained which can provide adequate flame protection, and on the other hand excessive changes in the polymer properties of the polyol are avoided. This can go in particular for the viscosity of the modified base polymer, which could increase too much with an even higher proportion of unsaturated comonomers. Smaller levels of unsaturated comonomers in the polyoxyalkylene polymer can lead to insufficient functionalization of the polymer.
  • the molar ratio of heterocyclic compounds to unsaturated groups of the polyoxyalkylene polyol can be 10: 1 to 1: 1, preferably 2: 1 to 1: 1, very particularly preferably 1.25: 1 to 1: 1.
  • the method for producing the polyoxyalkylene polyol with unsaturated groups comprises the steps
  • Lactones a lactide and / or a cyclic carbonate which has a double bond, and / or (g3) of carbon dioxide.
  • Epoxides, cyclic anhydrides of a dicarboxylic acid, a lactone, a lactide and / or a cyclic carbonate which have a double bond are one or more compounds selected from the group consisting of vinylcyclohexene oxide, cyclooctadiene monoepoxide, cyclododecatriene monoepoxide, butadiene monoepoxide, isoprenone monoepoxide , 1,4-divinylbenzene monoepoxide, 1,3-di vinylbenzene monoepoxide, glycidyl ester 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, ita
  • the terminal OH groups of the polyoxyalkylene polyols are converted into a chemical group which does not react with phosphorus-functional groups.
  • the methods used for this are known to the person skilled in the art. For example, this can be done by reacting the OH groups with silylating reagents such as bistrimethylsilylacetamide, hexamethyldisilazane or trimethylchlorosilane, with trialkylsiloxanes with the elimination of alcohol or by acetylation with acylating reagents such as acetic anhydride or trifluoroacetic anhydride.
  • An alternative method is the reaction of the OH groups with alkylation reagents, such as trimethyloxonium salts, methyl sulfonate and methyl sulfate. This can enable further implementation options on the OH groups of the polyoxyalkylene polyols after removal of the protective group.
  • alkylation reagents such as trimethyloxonium salts, methyl sulfonate and methyl sulfate.
  • a preferred embodiment of the process includes the use of polyoxyalkylene polyols with electron-rich double bonds, which denotes double bonds which are substituted by + M or +1 substituents, such as alkyl or alkoxyalkyl or cyclohexyl groups.
  • electron-rich double bonds are generally those which are more electron-rich than ethylene. Allyl ethers or vinylcyclohexenes are particularly preferred.
  • Epoxides which can be used in accordance with the invention are, for example, allyl glycidyl ether, vinylcyclohexene oxide, butadiene monoepoxide, 1,3- and 1,4-cyclohexadiene monooxide, isoprene monoepoxide or limonene oxide, allyl glycidyl ether being preferred.
  • the introduction of electron-rich double bonds into the polyoxyalkylene polyol polymer can also be carried out by cyclic anhydrides with electron-rich double bonds, such as 4-cyclohexene-1, 2-dicarboxylic acid anhydride, 4-methyl-4-cyclohexene-1, 2-dicarboxylic acid anhydride,
  • Norbornedioic anhydride allylnorbornene anhydride, dodecenylsuccinic anhydride, tetradecenylsuccinic anhydride, hexadecenylsuccinic anhydride or octadecenylsuccinic anhydride, with the alkenylsuccinic anhydride
  • Double bond is not an exo double bond on the ring.
  • Epoxides that introduce such double bonds into the polyoxyalkylene polyol chain are Epoxides that introduce such double bonds into the polyoxyalkylene polyol chain.
  • Electron-rich double bonds are particularly suitable for the radical addition of mercapto groups.
  • An alternative embodiment involves the use of polyoxyalkylene polyols with electron-deficient double bonds, which denotes double bonds which are substituted by -M or -I substituents, such as carbonyl groups.
  • Such double bonds can preferably be introduced into the polyoxyalkylene polyol polymer by using glycidyl esters a, b-unsaturated acids, such as acrylic acid or methacrylic acid, as comonomers in the copolymerization with CO2.
  • the double bonds can also be introduced as comonomers in the copolymerization with epoxides and CO2 by using cyclic anhydrides which carry double bonds in the vicinity of a carbonyl group.
  • Maleic anhydride and itaconic anhydride are particularly preferred for this purpose.
  • Only polyoxyalkylenes with electron-deficient double bonds are suitable for the addition of NH groups carrying NH groups according to the aza-Michael addition mechanism, but heterocycles carrying mercapto groups can also be used according to the Thia-Michael Addition can be added.
  • the reactions by the Michael addition mechanism are catalyzed with basic compounds.
  • Polyoxyalkylene polyols can also be functionalized with heterocycles which simultaneously carry electron-rich and electron-deficient double bonds. Mixtures of polyoxyalkylene polyols with various unsaturated building blocks can also be used for the functionalization with heterocycles.
  • alkylene oxides having 2-45 carbon atoms which do not have a double bond
  • the alkylene oxides having 2 to 45 carbon atoms are, for example, one or more compounds selected from the group comprising ethylene oxide, propylene oxide, 1-butene oxide, 2,3-butene oxide, 2-methyl-1,2-propene oxide (isobutene oxide), 1 Pentene oxide, 2,3-pentene oxide, 2-methyl-l, 2-butene oxide, 3-methyl-l, 2-butene oxide, epoxides of C6-C22 a-olefins, such as 1-hexene oxide, 2,3-hexene oxide, 3 , 4-hexene oxide, 2-methyl-1, 2-pentene oxide, 4-methyl-1, 2-pentene oxide, 2-ethyl-1, 2-butene oxide, 1-heptene oxide, 1-octene
  • Examples of derivatives of glycidol are phenyl glycidyl ether, cresyl glycidyl ether, methyl glycidyl ether, ethyl glycidyl ether and 2-ethylhexyl glycidyl ether.
  • Ethylene oxide and / or propylene oxide, in particular propylene oxide, can preferably be used as alkylene oxides.
  • a preferred embodiment for the process according to the invention for the production of polyoxyalkylene polyols with unsaturated groups includes 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
  • step (g) one or more epoxides / cyclic anhydrides, one or more comonomers and carbon dioxide are continuously metered into the mixture resulting from step ( ⁇ ), the epoxides / cyclic anhydrides used for the terpolymerization being the same as or those used in step ( ⁇ ) Epoxides are different ("polymerization stage").
  • step (a) The individual components in step (a) can be added simultaneously or in succession in any order, preferably in step (a) the DMC catalyst is initially introduced and the H-functional starter compound is added simultaneously or subsequently.
  • a preferred embodiment relates to a method, wherein in step (a)
  • 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 a reduced pressure (absolute) of 10 mbar to 800 mbar, preferably from 40 mbar to 200 mbar, is set in the reactor by removing the inert gas or carbon dioxide (for example with a pump).
  • Another preferred embodiment relates to a method, wherein in step (a)
  • the H-functional starter compound or a mixture of at least two H-functional starter compounds if appropriate under an inert gas atmosphere, under an atmosphere of an inert gas / carbon dioxide mixture or under a pure carbon dioxide atmosphere, particularly preferably under an inert gas atmosphere, and (a2) [first activation stage] into the resulting mixture of DMC catalyst and one or more H-functional starter compounds at a temperature from 50 to 200 ° C., preferably from 80 to 160 ° C., particularly preferably from 125 to 135 ° C.
  • an inert gas / carbon dioxide mixture or carbon dioxide particularly preferably an inert gas
  • a reduced pressure absolute
  • 10 mbar to 800 mbar preferably from 40 mbar to 200 mbar
  • the double metal cyanide catalyst being able to be added to the H-functional starter substance or the mixture of at least two H-functional starter substances in step (a1) or immediately thereafter in step (a2).
  • the DMC catalyst can be added in solid form or suspended in an H-functional starter compound. If the DMC catalyst is added as a suspension, it is preferably added to the one or more H-functional starter compounds in step (a1).
  • the step ( ⁇ ) of the second activation stage can take place in the presence of CO2 and / or an inert gas.
  • Step ( ⁇ ) is preferably 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, particularly 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 dosing of the epoxide (s) / cyclic anhydrides can be started at any pre-selected form.
  • the total pressure (absolute) of the atmosphere is preferably set in a range from 10 mbar to 100 bar, preferably 100 mbar to 50 bar and further preferably 500 mbar to 50 bar. If necessary, the pressure can be adjusted during or after the dosing of the epoxides / cyclic anhydrides 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.
  • the amount of one or more epoxides / cyclic anhydrides used in the activation in step ( ⁇ ) can be 0.1 to 25.0% by weight, preferably 1.0 to 20.0% by weight, particularly preferably 2 , 0 to 16.0% by weight, based on the amount of H-functional starter compound used in step (a).
  • the epoxides / cyclic anhydrides can be added in one step or stepwise in several portions.
  • a portion (based on the total amount of the amount of epoxides / cyclic anhydrides used in steps ( ⁇ ) and (g) used in steps ( ⁇ ) and (g)) can be one or more during the activation in step ( ⁇ )
  • Epoxides / cyclic anhydrides are added to the mixture resulting from step (a) [second activation stage].
  • a partial amount of epoxy / cyclic anhydride can optionally be added in the presence of CO2 and / or inert gas.
  • the step (ß) can also be carried out several times.
  • the DMC catalyst is preferably used in an amount such that the DMC catalyst content in the resulting polyoxyalkylene polyol is 10 to 10,000 ppm, particularly preferably 20 to 5000 ppm and most preferably 50 to 500 ppm.
  • the epoxide / cyclic anhydride can 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, particularly preferably 20 to 60 minutes.
  • the dosing of epoxides and of cyclic anhydride can be carried out simultaneously, alternately or sequentially. It is possible to dose epoxy at a constant dosing rate or to increase or decrease the dosing rate continuously or step by step or to add the epoxy in portions.
  • the epoxide / cyclic anhydride is preferably added to the reaction mixture at a constant metering rate. If several epoxides / cyclic anhydrides are used in one step for the synthesis of the polyoxyalkylene polyols, the epoxides / cyclic anhydrides can be metered in individually or as a mixture.
  • the epoxides / cyclic anhydrides can be dosed simultaneously, alternately or sequentially via separate doses (additions) or via one or more doses, the alkylene oxides being able to be dosed individually or as a mixture.
  • the type and / or sequence of metering the epoxides and / or cyclic anhydrides makes it possible to synthesize statistical, alternating, block-like or gradient-like polyoxyalkylene polyols.
  • Step (g) can be carried out, for example, at temperatures from 60 to 150 ° C., preferably from 80 to 120 ° C., very particularly preferably from 90 to 105 ° C. If temperatures below 60 ° C are set, the reaction stops. At temperatures above 150 ° C, the amount of unwanted by-products increases sharply.
  • step (g) is carried out with the addition of epoxide, cyclic anhydride and carbon dioxide; here is used as a polyoxyalkylene polyol Obtained polyether carbonate polyol.
  • Epoxy, cyclic anhydride and carbon dioxide can be metered in simultaneously, alternately or sequentially, with the total amount of carbon dioxide being metered in all at once or over the reaction time. It is possible to increase or decrease the CCE pressure gradually or gradually or to keep it constant during the addition of the epoxides / cyclic anhydrides. The total pressure is preferably kept constant during the reaction by adding carbon dioxide.
  • the epoxide / cyclic anhydrides and the CO2 can be metered in simultaneously, alternately or sequentially to the carbon dioxide metering. 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.
  • the epoxide / cyclic anhydride is preferably added to the reaction mixture at a constant metering rate. If several epoxides / cyclic anhydrides are used in one step for the synthesis of the polyether carbonate polyols, the epoxides / cyclic anhydrides can be metered in individually or as a mixture.
  • the epoxides / cyclic anhydrides can be dosed simultaneously, alternately or sequentially via separate doses (additions) or via one or more doses, the alkylene oxides being able to be dosed individually or as a mixture.
  • the type and / or sequence of metering the epoxides / cyclic anhydrides and / or the carbon dioxide makes it possible to synthesize statistical, alternating, block-like or gradient-like polyether carbonate polyols.
  • An excess of carbon dioxide based on the calculated amount of carbon dioxide required in the polyether carbonate polyol is preferably used, since an excess of carbon dioxide is advantageous due to the inertness of the carbon dioxide.
  • the amount of carbon dioxide can be determined via the total pressure. As a total pressure (absolute), the range from 0.01 to 120 bar, preferably 0.1 to 110 bar, particularly preferably from 1 to 100 bar has proven advantageous for the copolymerization for the preparation of the polyether carbonate polyols. It is possible to supply the carbon dioxide to the reaction vessel continuously or batchwise. This depends on how quickly the epoxies and CO2 are consumed and whether the product should contain CCE-free polyether blocks or blocks with different CO2 contents.
  • the concentration of carbon dioxide can also vary with the addition of the epoxides / cyclic anhydrides. Depending on the selected reaction conditions, it is possible to introduce the CO2 into the reactor in the gaseous, liquid or supercritical state. CO2 can also be added to the reactor as a solid and then change to the gaseous, dissolved, liquid and / or supercritical state under the chosen reaction conditions. In step (g), the carbon dioxide can be introduced into the mixture, for example
  • the reaction mixture is gassed in the reactor according to (i) preferably via a gassing ring, a gassing nozzle or a gas inlet pipe.
  • the gassing ring is preferably an annular arrangement or two or more annular arrangements of gassing nozzles, which are preferably arranged on the bottom of the reactor and / or on the side wall of the reactor.
  • the hollow shaft stirrer according to (ii) is preferably a stirrer in which the gas is introduced into the reaction mixture via a hollow shaft of the stirrer.
  • the rotation of the stirrer in the reaction mixture creates a suppression at the end of the impeller connected to the hollow shaft such that the gas phase (containing CO 2 and possibly unused 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 reaction mixture according to (i), (ii), (iii) or (iv) can be gassed in each case with freshly metered in carbon dioxide and / or combined with an extraction of the gas from the gas space above the reaction mixture and subsequent recompression of the gas.
  • the gas extracted and compressed from the gas space above the reaction mixture optionally mixed with fresh carbon dioxide and / or epoxides / cyclic anhydrides, is reintroduced into the reaction mixture according to (i), (ii), (iii) and / or (iv) ,
  • the pressure drop which arises from the incorporation of the carbon dioxide and the epoxides in the terpolymerization into the reaction product is preferably compensated for by means of freshly metered in 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.
  • the introduction of the epoxides / cyclic anhydrides preferably takes place directly into the liquid phase, since this has the advantage that the introduced compounds are rapidly mixed with the liquid phase and local concentration peaks can thus be avoided.
  • the introduction into the liquid phase can be via one or more inlet pipes, one or more nozzles or one or several annular arrangements of multiple dosing points, which are preferably arranged on the bottom of the reactor and / or on the side wall of the reactor.
  • the three steps (a), ( ⁇ ) and (g) can be carried out in the same reactor or in each case separately in different reactors.
  • Particularly preferred reactor types are stirred tanks, tubular reactors and loop reactors. If reaction steps (a), ( ⁇ ) and (g) are carried out in different reactors, a different type of reactor can be used for each step.
  • Polyoxyalkylene polyols can be produced in a stirred tank, the stirred tank depending on the embodiment and mode of operation being cooled via the reactor jacket, internal cooling surfaces and / or cooling surfaces located in a pumping circuit. Both in the semi-batch application, in which the product is only removed after the end of the reaction, and in the continuous application, in which the product is continuously removed, particular attention should be paid to the metering rate of the epoxides. It should be set so that, despite the inhibiting effect of carbon dioxide, the epoxides / cyclic anhydrides can react sufficiently quickly.
  • the concentration of free epoxides / cyclic anhydrides in the reaction mixture during the second activation stage (step ⁇ ) is preferably> 0 to 100% by weight, particularly preferably> 0 to 50% by weight, most preferably> 0 to 20% by weight (each based on the weight of the reaction mixture).
  • the concentration of free epoxides / cyclic anhydrides in the reaction mixture during the reaction (step g) is preferably> 0 to 40% by weight, particularly preferably> 0 to 25% by weight, most preferably> 0 to 15% by weight (in each case based on the weight of the reaction mixture).
  • step g Another embodiment in the stirred tank for the copolymerization (step g) is characterized in that one or more H-functional starter compounds are metered continuously into the reactor during the reaction.
  • the amount of H-functional starter compounds which are metered continuously into the reactor during the reaction is 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).
  • the amount of the H-functional starter compounds which are metered continuously into the reactor during the reaction is 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 connections).
  • the catalyst / starter mixture activated according to steps (a) and ( ⁇ ) is reacted further in the same reactor with epoxides / cyclic anhydrides and carbon dioxide.
  • the catalyst / starter mixture activated according to steps (a) and ( ⁇ ) is further reacted with epoxides / cyclic anhydrides and carbon dioxide in another reaction vessel (for example a stirred tank, tubular reactor or loop reactor).
  • the catalyst / starter mixture prepared according to step (a) is reacted with epoxides / cyclic anhydrides and carbon dioxide in another reaction vessel (for example a stirred kettle, tubular reactor or loop reactor) according to steps ( ⁇ ) and (g).
  • the catalyst-starter mixture prepared according to step (a) or the catalyst-starter mixture activated according to steps (a) and ( ⁇ ) and optionally further starters as well as epoxides / cyclic anhydrides and carbon dioxide are continuously passed through Pumped pipe.
  • the second activation stage according to step ( ⁇ ) can take place in the first part of the tubular reactor and the terpolymerization according to step (g) in the second part of the tubular reactor.
  • the molar ratios of the reactants can vary depending on the desired polymer.
  • carbon dioxide is metered in in its liquid or supercritical form in order to enable optimal 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 inlet of the reactor.
  • the remaining amount of the epoxides / cyclic anhydrides is preferably introduced into the reactor via a plurality of metering points which are arranged along the reactor.
  • Mixing elements such as those sold by Ehrfeld Mikrotechnik BTS GmbH, for example, are advantageously installed for better mixing of the reactants, or mixer-heat exchanger elements which simultaneously improve mixing and heat dissipation.
  • CO 2 and epoxides / cyclic anhydrides metered in by the mixing elements are preferably mixed with the reaction mixture. In an alternative embodiment, different volume elements of the reaction mixture are mixed together.
  • Loop reactors can also be used to produce the polyoxyalkylene polyols with unsaturated groups that can be used according to the invention. This includes in General reactors with internal and / or external material recycling (possibly with heat exchanger surfaces arranged in a circuit), such as a jet loop reactor, jet loop reactor or venturi loop reactor, which can also be operated continuously, or a loop-shaped tubular reactor with suitable devices for the circulation of the reaction mixture or a loop of several tubular reactors connected in series or several stirred kettles connected in series.
  • the reactor in which step (g) is carried out can often be followed by a further boiler or a tube (“indwelling tube”) in which residual concentrations of free epoxides / cyclic anhydrides which are present after the reaction react.
  • the pressure in this downstream reactor is preferably at the same pressure as in the reaction apparatus in which the reaction step (g) is carried out. However, the pressure in the downstream reactor can also be selected to be higher or lower. In a further preferred embodiment, all or part of the carbon dioxide is discharged after the reaction step (g) and the downstream reactor is operated at normal pressure or a slight excess pressure.
  • the temperature in the downstream reactor is preferably 10 to 150 ° C and particularly preferably 20 to 100 ° C.
  • the reaction mixture preferably contains less than 0.05% by weight of epoxide / cyclic anhydride.
  • the post-reaction time or the residence time in the downstream reactor is preferably 10 minutes to 24 hours, particularly preferably 10 minutes to 3 hours.
  • Suitable H-functional starter compounds are compounds with H atoms active for the alkoxylation.
  • Groups with active H atoms which are active for the alkoxylation are, for example, -OH, -NH2 (primary amines), -NH- (secondary amines), -SH and -CO2H, -OH and -NH2 are preferred, and -OH is particularly preferred.
  • one or more compounds can be selected from the group comprising mono- or polyhydric alcohols, polyhydric amines, polyhydric thiols, amino alcohols, thio alcohols, hydroxy esters, polyether polyols, polyester polyols, polyester ether polyols, polyether carbonate polyols, polycarbonate polyols, polycarbonates,
  • Polyethyleneimines such as so-called Jeffamine ® from Huntsman, such as D230, D400, D-2000, T-403, T-3000, T-5000 or corresponding BASF products, such as polyetheramine D230, D400, D200 , T403, T5000), polytetrahydrofurans (e.g.
  • PolyTHF ® from BASF such as PolyTHF ® 250, 650S, 1000, 1000S, 1400, 1800, 2000), polytetrahydrofuranamines (BASF product polytetrahydrofuranamine 1700), polyether thiols, polyacrylate polyols, 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, which contain an average of at least 2 OH groups per molecule.
  • Alcohols, amines, thiols and carboxylic acids can be used as monofunctional starter compounds.
  • the following can be used as monofunctional alcohols: methanol, ethanol, l-propanol, 2-propanol, l-butanol, 2-butanol, tert-butanol, 3-buten-l-ol, 3-butyn-l-ol, 2-methyl -3-buten-2-ol, 2-methyl-3-butyn-2-ol, propargyl alcohol, 2-methyl-2-propanol, l-tert-butoxy-2-propanol, l-pentanol, 2-pentanol, 3 -Pentanol, l-hexanol, 2-hexanol, 3-hexanol, 1-heptanol, 2-heptanol, 3-heptanol, l-octanol, 2-octanol, 3-octanol, 4-oc
  • Possible monofunctional amines are: butylamine, / tvY-butylamine, pentylamine, hexylamine, aniline, aziridine, pyrrolidine, piperidine, morpholine.
  • the following monofunctional thiols can be used: ethanethiol, l-propanethiol, 2-propanethiol, l-butanethiol, 3-methyl-l-butanethiol, 2-butene-l-thiol, thiophenol.
  • monofunctional carboxylic acids formic acid, acetic acid, propionic acid, butyric acid, fatty acids such as stearic acid, palmitic acid, oleic acid, linoleic acid, linolenic acid, benzoic acid, acrylic acid.
  • Polyhydric alcohols suitable as H-functional starter substances are, for example, dihydric alcohols (such as, for example, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-propanediol, 1,4-butanediol, 1,4-butenediol, 1,4-butynediol, neopentyl glycol, l , 5-pentantanediol, methylpentanediols (such as 3-methyl-l, 5-pentanediol), l, 6-hexanediol; l, 8-octanediol, l, lO-decanediol, l, l2-dodecanediol, bis- (hydroxymethyl) - cyclohexanes (such as 1,4-bis (hydroxymethyl) cyclohexane), triethylene glycol, tetraethylene glycol,
  • the H-functional starter substances can also be selected from the substance class of the polyether polyols, in particular those with a molecular weight M n in the range from 100 to 4000 g / mol.
  • Preferred are polyether polyols which consist of repeating ethylene oxide and Propylene oxide units are constructed, preferably with a proportion of 35 to 100% propylene oxide units, particularly preferably with a proportion of 50 to 100% propylene oxide units.
  • These can be statistical 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).
  • suitable homo-polyethylene oxides are, for example, the Pluriol ® E brands from BASF SE
  • suitable homo-polypropylene oxides are, for example, the Pluriol ® P brands from BASF SE
  • suitable mixed copolymers of ethylene oxide and propylene oxide are, for example, 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 polyester polyols, in particular those with a molecular weight M n in the range from 200 to 4500 g / mol.
  • At least difunctional polyesters can be used as polyester polyols.
  • Polyester polyols preferably consist of alternating acid and alcohol units. Examples of acid components which can be used 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 the acids mentioned and / or.
  • polycarbonate diols can be used as H-functional starter substances, in particular those with a molecular weight M n in the range from 150 to 4500 g / mol, preferably 500 to 2500 g / mol, which can be obtained, for example, by reacting phosgene, dimethyl carbonate, diethyl carbonate or diphenyl carbonate and difunctional alcohols or polyester polyols or polyether polyols.
  • polycarbonates such as can be found in EP-A 1,359,177th example, as polycarbonate, the Desmophen ® C- Types from Bayer MaterialScience AG are used, such as Desmophen ® C 1100 or Desmophen ® C 2200.
  • polyether carbonate polyols and / or polyether ester carbonate polyols can be used as H-functional starter substances.
  • polyether ester carbonate polyols can be used.
  • These polyether ester carbonate polyols used as H-functional starter substances can be prepared beforehand in a separate reaction step.
  • the H-functional starter substances generally have an OH functionality (i.e. the number of H atoms active for the polymerization per molecule) from 1 to 8, preferably from 2 to 6 and particularly 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 with a composition according to the general formula (II),
  • alcohols according to formula (II) are ethylene glycol, 1, 4-butanediol, l, 6-hexanediol, l, 8-octanediol, 1.10 decanediol and l, l2-dodecanediol.
  • H-functional starter substances are neopentyl glycol, trimethylolpropane, glycerol, pentaerythritol, reaction products of the alcohols according to formula (V) with e-caprolactone, for example reaction products of trimethylolpropane with e-caprolactone, reaction products of glycerol with e-caprolactone with, and reaction products with e-caprolactone.
  • Water, diethylene glycol, dipropylene glycol, castor oil, sorbitol and polyether polyols, composed of repeating polyalkylene oxide units, are furthermore preferably used as H-functional starter compounds.
  • the H-functional starter substances are particularly preferably 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, neopentylglycol, l, 6-hexanediol, diethylene glycol, dipropylene glycol, glycerol, trimethylolpropane, di- and trifunctional polyether polyols, the polyether polyol consisting of a di- or tri-H-functional starter compound and propylene oxide or a di- or tri-H-functional starter compound, propylene oxide and ethylene oxide.
  • the polyether polyols preferably have an OH functionality of 2 to 4 and a molecular weight M n in the range from 62 to 4500 g / mol and in particular a molecular weight M n in the range from 62 to 3000 g / mol.
  • Double metal cyanide (DMC) catalysts for use in the homopolymerization of alkylene oxides are known in principle from the prior art (see, for example, US Pat. Nos. 3,404,109, 3,829,505, 3,941,849 and 5) 158 922).
  • DMC catalysts which are described for example in US-A 5 470 813, EP-A 700 949, EP-A 743 093, EP-A 761 708, WO 97/40086, WO 98/16310 and WO 00/47649 a very high activity and enable the production of polyoxyalkylene polyols at very low catalyst concentrations.
  • a typical example is the highly active DMC catalysts described in EP-A 700 949, which, in addition to a double metal cyanide compound (for example zinc hexacyanocobaltate (III)) and an organic complex ligand (for example / er / butanol), also have a larger polyether with a number average molecular weight contained as 500 g / mol.
  • a double metal cyanide compound for example zinc hexacyanocobaltate (III)
  • organic complex ligand for example / er / butanol
  • the DMC catalysts which can be used according to the invention are preferably obtained by:
  • the isolated solid is optionally washed with an aqueous solution of an organic complex ligand (e.g. by resuspending and then isolating again by filtration or centrifugation),
  • the solid obtained optionally after pulverization, at temperatures of generally 20-120 ° C. and at pressures of generally 0.1 mbar to normal pressure (1013 mbar), and wherein in the first step or immediately after the precipitation of the double metal cyanide compound (second step) one or more organic complex ligands, preferably in excess (based on the double metal cyanide compound) and optionally further complex-forming components are added.
  • the double metal cyanide compounds contained in the DMC catalysts which can be used according to the invention are the reaction products of water-soluble metal salts and water-soluble metal cyanide salts.
  • an aqueous zinc chloride solution preferably in excess based on the metal cyanide salt
  • potassium hexacyanocobaltate are 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 the preparation of the double metal cyanide compounds preferably have a composition of the general formula (IV)
  • 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+ , M Zn 2+ is preferred, Fe 2+ , Co 2+ or Ni 2+ ,
  • X are one or more (ie different) anions, preferably an anion selected from the group consisting of the halides (ie fluoride, chloride, bromide, iodide), hydroxide, sulfate, carbonate, cyanide, isocyanate, isocyanate, isothiocyanate, carboxylate, oxalate and nitrate ;
  • 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 consisting of the halides (i.e. fluoride, chloride, bromide, iodide), hydroxide, sulfate, carbonate, cyanate, thiocyanate isocyanate, isothiocyanate, carboxylate, oxalate and nitrate;
  • 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 the halides (ie fluoride, chloride, bromide, iodide), hydroxide, sulfate, carbonate, Cyanate, thiocyanate, isocyanate, isothiocyanate, carboxylate, oxalate and nitrate;
  • halides ie fluoride, chloride, bromide, iodide
  • hydroxide sulfate
  • carbonate Cyanate, thiocyanate, isocyanate, isothiocyanate, carboxylate, oxalate and nitrate
  • 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 the halides (i.e. fluoride, chloride, bromide, iodide), hydroxide, sulfate, carbonate, cyanate, thiocyanate, isocyanate, isothiocyanate, carboxylate, oxalate and nitrate;
  • halides i.e. fluoride, chloride, bromide, iodide
  • hydroxide sulfate
  • carbonate cyanate
  • thiocyanate thiocyanate
  • isocyanate isothiocyanate
  • carboxylate oxalate and nitrate
  • metal salts examples include 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. Mixtures of different metal salts can also be used.
  • Metal cyanide salts suitable for the preparation of the double metal cyanide compounds preferably have a composition of the general formula (VIII)
  • M ' is selected from one or more metal cations from the group consisting of Fe (II), Fe (III), Co (II), Co (III), Cr (II), Cr (III), Mn (II), Mn ( III), Ir (III), Ni (II), Rh (III), Ru (II), V (IV) and V (V), M 'is preferably one or more metal cations from the group consisting of Co (II), Co (III), Fe (II), Fe (III), Cr (III), Ir (III) and Ni (II),
  • Y is selected from one or more metal cations from 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 from the group consisting of halides (ie fluoride, chloride, bromide, iodide), hydroxide, sulfate, carbonate, cyanate, thiocyanate, isocyanate, iso- thiocyanate, carboxylate, azide, oxalate or nitrate and a, b and c are integer numbers, the values for a, b and c being chosen so that the electroneutrality of the metal cyanide salt is given; a is preferably 1, 2, 3 or 4; b is preferably 4, 5 or 6; c preferably has the value 0.
  • suitable metal cyanide salts are sodium hexacyanocobaltate (III), potassium hexacyano cobaltate (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)
  • x, x ’, y and z are integers and chosen so that the electron neutrality of the double metal cyanide compound is given.
  • M Zn (II), Fe (II), Co (II) or Ni (II) and
  • M ’ Co (III), Fe (III), Cr (III) or Ir (III).
  • suitable double metal cyanide compounds a) are zinc hexacyanocobaltate (III), zinc hexacyanoiridate (III), zinc hexacyanoferrate (III) and cobalt (II) hexacyanocobaltate (III).
  • suitable double metal cyanide compounds are e.g. US 5 158 922 (column 8, lines 29-66).
  • Zinc hexacyanocobaltate (III) can be used particularly preferably.
  • organic complex 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 700 949, EP-A 761 708, JP 4 145 123, US 5 470 813, EP-A 743 093 and WO-A 97/40086).
  • water-soluble, organic compounds with 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, iso-butanol, sec-butanol, tert-butanol, 2-methyl-3-buten-2-ol and 2- Methyl-3-butyn-2-ol), compounds which contain both aliphatic or cycloaliphatic ether groups and aliphatic hydroxyl groups (such as, for example, ethylene glycol mono-tert-butyl ether, diethylene glycol mono-tert-butyl ether, tripropylene glycol mono-methyl ether and 3 methyl-3-oxetane-methanol).
  • Highly preferred organic complex ligands are selected from one or more compounds from the group consisting of dimethoxyethane, ter / butanol, 2-methyl-3-buten-2-ol, 2-methyl-3-butyn-2-ol, ethylene glycol mono- / er / butyl ether and 3-methyl-3-oxetane-methanol.
  • 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 optionally used in the production of the DMC catalysts which can be used according to the invention.
  • polyacrylonitrile polyalkyl acrylates, polyalkyl methacrylates, polyvinyl methyl ether, polyvinyl ethyl ether, polyvinyl acetate, polyvinyl alcohol, poly-N-vinyl pyrrolidone, poly (N-vinyl pyrrolidone-co-acrylic acid), polyvinyl methyl ketone, poly (4-vinylphenol), poly (acrylic acid) -co-styrene)
  • Oxazoline polymers polyalkyleneimines, maleic and maleic anhydride copolymers, hydroxyethyl cellulose and polyacetals, or the glycidyl ethers, glycosides, carboxylic acid esters of polyhydric alcohols, bile acids or their salts, esters or amides, cyclodextrins, phosphorus compounds, a, b-unsaturated carboxylic acid esters or surface active compounds or ionic surfaces used.
  • the aqueous solutions of the metal salt are preferably used in the first step in a stoichiometric excess (at least 50 mol%), based on the metal cyanide salt, in the preparation of the DMC catalysts which can be used according to the invention.
  • the metal cyanide salt e.g. potassium hexacyanocobaltate
  • the organic complex ligand e.g. tert-butanol
  • 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 ligands with vigorous stirring.
  • the first step is optional formed suspension then treated with another complex-forming component.
  • the complex-forming component is preferably used in a mixture with water and organic complex ligands.
  • a preferred method for carrying out the first step is carried out using a mixing nozzle, particularly preferably using a jet disperser, as described, for example, in WO-A 01/39883.
  • the solid i.e. the catalyst precursor
  • the solid can be isolated from the suspension by known techniques such as centrifugation or filtration.
  • the isolated solid is then washed in a third process step with an aqueous solution of the organic complex ligand (e.g. by resuspending and then isolating again by filtration or centrifugation).
  • an aqueous solution of the organic complex ligand e.g. by resuspending and then isolating again by filtration or centrifugation.
  • water-soluble by-products such as potassium chloride
  • the amount of the organic complex ligand in the aqueous washing solution is preferably between 40 and 80% by weight, based on the total solution.
  • a further complex-forming component preferably in the range between 0.5 and 5% by weight, based on the total solution, is added to the aqueous washing solution in the third step.
  • washing is preferably carried out with an aqueous solution of the unsaturated alcohol (for example by resuspending and then isolating again by filtration or centrifugation), in order in this way, for example, to use water-soluble by-products, such as potassium chloride, from the product which can be used according to the invention Remove catalyst.
  • the amount of unsaturated alcohol in the aqueous washing solution is particularly preferably between 40 and 80% by weight, based on the total solution of the first washing step.
  • either the first washing step is repeated once or several times, preferably once to three times, or preferably a non-aqueous solution, such as a mixture or solution of unsaturated alcohol and other complex-forming component (preferably in A range between 0.5 and 5% by weight, based on the total amount of the washing solution of step (3.-2), is used as the washing solution and the solid is thus washed once or several times, preferably once to three times.
  • a non-aqueous solution such as a mixture or solution of unsaturated alcohol and other complex-forming component (preferably in A range between 0.5 and 5% by weight, based on the total amount of the washing solution of step (3.-2)
  • the isolated and optionally washed solid can then, optionally after pulverization, be dried at temperatures of 20-100 ° C. and at pressures from 0.1 mbar to normal pressure (1013 mbar).
  • the unsaturated comonomers can be distributed randomly or in blocks in the polyoxyalkylene polyols. Gradient polymers can also be used.
  • the reaction of the polyoxyalkylene polyol with unsaturated groups with the heterocyclic compound of the formula (I) takes place at a temperature greater than or equal to 100 ° C. and less than or equal to 220 ° C.
  • This temperature range has proven to be particularly suitable in the context of efficient process management with a sufficient reaction rate.
  • This reaction procedure advantageously results in an end product without catalyst additions.
  • anionic addition of the heterocyclic compound to the unsaturated groups of the polyoxyalkylene polyol is likely to occur within this temperature range. Lower temperatures can lead to an unsatisfactory conversion of the heterocyclic compound, whereas higher temperatures can lead to a reduced yield due to the increase in side reactions.
  • the reaction of the polyoxyalkylene polyol with unsaturated groups with the heterocyclic compound of the formula (I) takes place at a temperature greater than or equal to 0 ° C. and less than or equal to 100 ° C. in the presence of a basic catalyst.
  • a basic catalyst can be used which are known to the person skilled in the art for use within a Michael addition.
  • Preferred basic catalysts are tertiary amines, such as, for example, diazabicyclooctane (DABCO), amidines, such as, for example, 1,5-diazabicyclo [5.4.0] undec-5-ene (BDU) or 1,8-diazabicyclo [5.4.0] undec- 7-ene (DBU), guanidines such as triazabicyclodecen, N-methyl-triazabicyclodecen, N-butyl-triazabicyclodecen or tetramethylguanidine, pentamethylguanidine, and / or phosphorimine bases or proazaphosphatranes can be used as basic catalysts. Mixtures of different basic catalysts can also be used.
  • DABCO diazabicyclooctane
  • amidines such as, for example, 1,5-diazabicyclo [5.4.0] undec-5-ene (BDU) or 1,8-diazabicyclo [5.4.0] undec- 7
  • the reaction can also take place in a solvent, dipolar aprotic solvents such as acetonitrile, propionitrile, benzonitrile, DMA, DMF or NMP, or protic solvents such as methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-butanol, isobutanol or tert-butyl alcohol are preferred. Solvents containing nitrile groups are particularly preferred.
  • the reaction of the polyoxyalkylene polyol with unsaturated groups with the heterocyclic compound of the formula (I) is carried out at a temperature greater than or equal to 0 ° C. and less than or equal to 100 ° C. in the presence of one or more compounds the group consisting of photoinitiators, peroxides, azo compounds, metal-activated peroxides and / or redox initiators.
  • the reaction of the polyoxyalkylene polyol with unsaturated groups with the phosphorus functional compound can, for example, with
  • Photoinitiators are preferably used. 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.
  • Bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide diphenylmesitoyl phosphine oxide
  • camphorquinone isopropylthioxanthone
  • Michler's ketone Michler's ketone
  • benzophenone benzoin methyl ether
  • dimethoxyphenylacetophenone 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 polyoxyalkylene polyol.
  • Redox initiators are a mixture of an oxidizing and a reducing substance.
  • the heterocyclic compounds used for the functionalization can also take on the function of a reducing substance if they contain a mercapto group or another reducing group.
  • Photoinitiators of type II require the addition of a hydrogen donor, such as an amine or another mercaptan, where also the heterocyclic compounds which are added to the unsaturated groups can fulfill this function if they contain a group suitable as a hydrogen donor.
  • heterocycle-functional polyoxyalkylene polyols are obtainable by the process according to the invention.
  • the heterocycle-functional polyoxyalkylene polyols which can be prepared by the process according to the invention have a good flame-retardant effect and, owing to their steric structure and the viscosity resulting therefrom, can be used very well within other processes, such as e.g. a subsequent networking process.
  • polyoxyalkylene polyols or their reaction products with isocyanates can, if necessary, be used with conventional external flame retardants, such as halogenated hydrocarbons, optionally with antimony trioxide as a synergist, (encapsulated) red phosphorus, monomeric or oligomeric phosphorus compounds, polyhedral oligomeric silsesquioxanes, other siloxanes, melamine isocyanate phosphates , Carbon nanotubes, fullerenes, montmorillonite or aluminum hydroxide can be added. It is also possible to add further additives, as described, for example, in Progress in Polymer Science 34 (2009) 1068-1133.
  • heterocycle-functional polyoxyalkylene polyols produced by the process according to the invention react more rapidly with isocyanates than unmodified polyols, so that the reaction to the polyurethane can also take place without external urethanization catalysts.
  • the heterocycle-functional polyoxyalkylenes according to the invention also form complexes with metals. This can also lead to better adhesion to metallic substrates and improved corrosion protection.
  • the heterocycle-functional polyoxyalkylene polyols can be crosslinked by adding di- or polyisocyanates in a further process step.
  • mixtures of polyoxyalkylene polyols and heterocycle-functional polyoxyalkylene polyols are reacted with one or more di- or polyisocyanates.
  • At least one heterocylcene-functional polyoxyalkylene polyol is preferably reacted with one or more di- or polyisocyanates.
  • the details of the reaction of polyols with di- or polyisocyanates are known to those skilled in polyurethane chemistry.
  • Crosslinked heterocylene-functional polyoxyalkylene polyol polymers can also be obtained according to the invention by the process according to the invention.
  • the crosslinked heterocycle-functional polyoxyalkylene polyol polymers are characterized by reproducible mechanical properties and a controllable reaction procedure, since the starting materials have a narrow and defined molecular weight distribution and the further crosslinking only afterwards he follows. In this way, side reactions in the context of crosslinking the polyoxyalkylene polyols can already be avoided as part of the functionalization with heterocycles.
  • the heterocycle-functional polyoxyalkylene polyols obtainable by the process according to the invention can be used as adhesion promoters, filler activators or additives. They can also improve the adhesion of polyurethanes to metal surfaces or the adhesion to metallic fillers.
  • the combination according to the invention of the different functional groups in the polymer because of the combination of hydrophilic and hydrophobic properties, can lead to particularly good suitability for connecting different polar interfaces to one another.
  • the heterocycle-functional polyoxyalkylene polyols which can be prepared according to the invention can be used particularly well in those cases in which adhesion between different polar interfaces is desired.
  • the use of phosphorus-functional polyoxyalkylene polyols also enables better dispersion of fillers. This can contribute to a faster reaction in the context of crosslinking reactions and consequently to a more uniform end product.
  • crosslinked heterocylene-functional polyoxyalkylene polyol polymers which can be obtained by the process according to the invention can be used as a coating, foam, sealing compound, thermoplastic material, thermosetting plastic, rubber.
  • heterocycle-functional polyoxyalkylene polyols according to the invention are also intended to be applicable to the process according to the invention and the crosslinked phosphorus-functional polyoxyalkylene polyol polymers according to the invention and to be disclosed and vice versa.
  • the invention also includes all combinations of at least two of the features disclosed in the description and / or the claims.
  • PET-l di functional poly (oxypropylene) polyol with an OH number of 112 mg KOH / g
  • the DMC catalyst was produced 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 inside diameter of 6.35 cm.
  • the reactor was equipped with an electric heating jacket (510 watt maximum heating power).
  • the counter-cooling consisted of a U-shaped immersion tube with an outer diameter of 6 mm, which protruded up to 5 mm above the bottom into the reactor and which was flowed through with cooling water of approx. 10 ° C. The water flow was switched on and off via a solenoid valve.
  • the reactor was equipped with an inlet pipe and a thermal sensor with a diameter of 1.6 mm, which protruded up to 3 mm above the bottom into the reactor.
  • the heating power of the electric heating jacket was approximately 20% of the maximum heating power during activation [first activation stage]. Due to the regulation, the heating output fluctuated by ⁇ 5% of the maximum heating output.
  • the occurrence of increased heat development in the reactor caused by the rapid conversion of propylene oxide during the activation of the catalyst [second activation stage], was observed via a reduced heat output of the heating jacket, switching on the countercooling and possibly a rise in temperature in the reactor.
  • the occurrence of heat development in the reactor caused by the continuous conversion of propylene oxide during the reaction [polymerization stage] led to a reduction in the output of the heating jacket to approximately 8% of the maximum heating output. Due to the regulation, the heating output fluctuated by ⁇ 5% of the maximum heating output.
  • the hollow-shaft stirrer used in the examples was a hollow-shaft stirrer in which the gas entered the reaction mixture via a hollow contraction of the stirrer was initiated.
  • the stirring body attached to the hollow shaft 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 that were 3 mm in diameter.
  • the rotation of the stirrer resulted in a suppression in such a way that the gas (CO2 and possibly alkylene oxide) above the reaction mixture was drawn off and was introduced into the reaction mixture via the hollow shaft of the stirrer.
  • the impeller stirrer used in some examples was an inclined-blade turbine, in which a total of two stirring stages with four stirring blades (45 °) each having a diameter of 35 mm and a height of 7 mm were attached to the stirring shaft 10 mm.
  • the polyether carbonate polyol which on the one hand contains polycarbonate units shown in formula (Xa),
  • the polymer chain When cyclic anhydrides are incorporated into the polymer chain, the polymer chain additionally contains ester groups.
  • the reaction mixture was characterized by I-NMR spectroscopy and gel permeation chromatography.
  • the ratio of the amount of cyclic propylene carbonate to polyether carbonate polyol (selectivity; ratio g / e) and the proportion of the unreacted monomers (propylene oxide RPO, allyl glycidyl ether RAGE in mol%) were determined by means of II-NMR spectroscopy.
  • a sample of the reaction mixture obtained after the reaction was dissolved in deuterated chloroform and measured on a spectrometer from Bruker (AV400, 400 MHz). The reaction mixture was then 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 tube 70 mm in diameter and 200 mm in length which was heated from the outside to 120 ° C., the reaction mixture being passed through three rollers rotating 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.
  • a pressure of 3 mbar was set inside the tube by means of a pump.
  • the reaction mixture cleaned of volatile constituents (unreacted epoxides, cyclic carbonate, solvent) was collected in a receiver at the lower end of the heated tube.
  • the molar ratio of carbonate groups to ether groups in the polyether carbonate polyol (ratio e / f) and the molar proportion of the comonomers incorporated into the polymer were determined by means of I-NMR spectroscopy.
  • a sample of the purified reaction mixture was dissolved in deuterated chloroform and measured on a spectrometer from Bruker (AV400, 400 MHz).
  • the molar ratio of the amount of cyclic propylene carbonate to carbonate units in the polyether carbonate polyol or polyether ester carbonate polyol (selectivity g / e) and the molar ratio of carbonate to ether groups in the polyether carbonate polyol or polyether ester carbonate polyol (e / f) and the proportions of the unreacted are given Propylene oxide (in mol%) and maleic anhydride (in mol%).
  • RPO in mol% The molar proportion of the unreacted propylene oxide (RPO in mol%) based on the sum of the amount of propylene oxide used in the activation and copolymerization is calculated using the formula:
  • RMSA molar proportion of the unreacted maleic anhydride
  • Acarbonate [(12/3) / ((11/3) + (12/3) + (16/2))] X 100% (XV) Percentage of the double bonds resulting from the incorporation of the maleic anhydride in the repeating units of the polyetherestercarbonate polyol:
  • Polyether carbonate polvol A Terpolymerization of propylene oxide, maleic anhydride (9.5 mol%) and CO2
  • polyoxyalkylene polyol 1.0 g
  • 4-methyl-triazole-3-thiol 175 mg
  • 1,1,3,3-tetramethylguanidine 360 mg
  • Example 3 Preparation of heterocycle-functional polyoxyalkylene polyol
  • polyoxyalkylene polyol 10.0 g
  • 4-methyl-4H-1,2,4-triazole-3-thiol 175 mg 0.06 mol
  • 1 , 1,3,3-tetramethylguanidine 360 mg
  • acetonitrile 50.0 mL
  • polyoxyalkylene polyol (10.0 g), 1,3-diaza-2,4-cyclopentadiene (1.05 g) and 1,1,3,3-tetramethylguanidine (360 mg) in acetonitrile (50, 0 mL) solved.
  • the reaction mixture was stirred at 70 ° C for 12 hours. The solvent was then removed under reduced pressure.
  • polyoxyalkylene polyol (10.0 g), 2,5-pyrrolidinedione (1.52 g) and 1,1,3,3-tetramethylguanidine (360 mg) were dissolved in acetonitrile (50.0 ml).
  • acetonitrile 50.0 ml
  • the reaction mixture was stirred at 70 ° C for 12 hours. The solvent was then removed under reduced pressure.
  • polyoxyalkylene polyol (10.0 g), 2-thiazoline-2-thiol (1.52 g) and 1,1,3,3-tetramethylguanidine (360 mg) were dissolved in acetonitrile (50.0 ml) , The reaction mixture was stirred at 70 ° C for 12 hours. The solvent was then removed under reduced pressure.

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Abstract

L'invention concerne un procédé de préparation d'un polyol de polyoxyalkylène à fonction hétérocycle, selon lequel un polyol de polyoxyalkylène possédant des groupes insaturés est mis en réaction avec un composé hétérocyclique.
EP19737776.5A 2018-07-19 2019-07-16 Polyéthers ou carbonates de polyéther à fonction hétérocycle et leur procédé de préparation Withdrawn EP3824013A1 (fr)

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