# US 2010/0168367 A1 · NOVEL POLYETHER SILOXANE-CONTAINING ALKOXYLATION PRODUCTS BY DIRECT ALKOXYLATION OF ORGANOMODIFIED a,w-DIHYDROXYSILOXANES OVER DOUBLE METAL CYANIDE (DMC) CATALYSTS, AND ALSO PROCESS FOR PRODUCING THEM > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 2010/0168367 A1 - Document ID: US20100168367A1 - Status: Published application - Kind: A1 - Application number: 12/492,586 - Filed: 2009-06-26 - Published: 2010-07-01 - Earliest claimed: 2008-06-27 - Assignees: Evonik Goldschmidt GmbH - Inventors: Frank SCHUBERT; Wilfried Knott - Web page: https://patentgrep.com/patent/US20100168367A1 ## CPC - C08G 77/46: containing polyether sequences - C08G 65/2606: {containing hydroxyl groups} - C08G 65/2639: {the other compounds containing elements other than oxygen, nitrogen or sulfur} - C08G 65/2663: {Metal cyanide catalysts, i.e. DMC's} - C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS ## Abstract Novel silicone polyethers by alkoxylating polymerization of epoxide monomers with (poly)organosiloxanes starting from an α,ω-dihydroxysiloxane as starter by means of DMC catalysis and process for preparing them. ## Claims ### Claim 1 Process for the alkoxylation of organosiloxanes bearing SiOH groups by means of one or more alkylene oxides or epoxide monomers, characterized in that the alkoxylation takes place in the presence of double metal cyanide catalysts. ### Claim 2 (depends on 1) Process for preparing silicone polyethers according to claim 1 by alkoxylating polymerization of epoxide monomers with (poly)organosiloxanes starting from at least one SiOH-functional starter by means of DMC catalysis. ### Claim 3 Process for the DMC-catalysed alkoxylation reaction, in which, in a first step, a starter mixture comprising at least one α,ω-dihydroxysiloxane starter and the double metal cyanide catalyst, which may, if appropriate, have previously been slurried in a suspension medium, is placed in a reactor, in a second step, only part of the total amount of the epoxide monomer to be introduced is added to this initially charged mixture in order to activate the DMC catalyst and, after this initialization phase, further epoxide monomer and if appropriate further α,ω-dihydroxysiloxane are introduced, characterized in that α,ω-dihydroxysiloxanes are used for the alkoxylation. ### Claim 4 (depends on 3) Process according to claim 3, characterized in that one or more organomodified α,ω-dihydroxysiloxanes of the general formula (I), where the radicals R are identical or different linear or branched, saturated, monounsaturated or polyunsaturated alkyl radicals having from 1 to 20 carbon atoms, and a is an integer from 0 to 5000, are used as SiOH-functional starter. ### Claim 5 (depends on 4) Process according to claim 4, characterized in that the radical R in formula (I) is methyl. ### Claim 6 (depends on 5) Process according to claim 5, characterized in that one or more polydimethylsiloxanes having two terminal hydroxyl groups and an average molar mass of from 100 to 400 000 g/mol are used as SiOH-functional starter compounds (I). ### Claim 7 (depends on 1) Process according to at claims 1, characterized in that the epoxide monomers are incorporated terminally, in isolated positions, cumulated in blocks or randomly distributed into the alkylene oxide chain of the silicone polyether. ### Claim 8 (depends on 7) Process according to claim 7, characterized in that one or more polydimethylsiloxanes of the formula (I) are reacted with epoxides of the formula (II) or (III) or with a mixture of these epoxides, where R2 or R3 and R5 or R6 are identical or different and are each, independently of one another, H or a saturated or monounsaturated or polyunsaturated, monovalent or polyvalent hydrocarbon radical which may be further substituted, where the radicals R5 or R6 are each a monovalent hydrocarbon radical and the hydrocarbon radical can be cycloaliphatically bridged via the fragment Y; Y can be absent or be a methylene bridge having 1 or 2 methylene units, when Y is 0 then R2 and R3 are each, independently of one another, a linear or branched radical having from 1 to 20 carbon atoms, the hydrocarbon radicals R2 and R3 in the formula (II) can in turn be further substituted and bear functional groups such as halogens, hydroxyl groups or glycidyloxypropyl groups; or where at least one glycidyloxypropyl group is bound via an ether or ester function R4 to a linear or branched alkyl radical having from 1 to 24 carbon atoms, an aromatic or cycloaliphatic radical, added in blocks or randomly as desired onto a chain starter of the formula (I). ### Claim 9 (depends on 8) Process according to claim 8, characterized in that lactones, saturated, unsaturated or aromatic cyclic dicarboxylic anhydrides or carbon dioxide are used either alone or in any mixtures with one another as monomers. ### Claim 10 (depends on 9) Process according to claim 9, characterized in that the reaction is carried out in an inert solvent or a mixture of a plurality of inert solvents. ### Claim 11 (depends on 10) Process according to claim 10, characterized in that the starter of the formula (I) and/or a previously prepared silicone polyether of the formula (VII) is used as solvent or suspension medium for the DMC catalyst. ### Claim 12 (depends on 11) Process according to claim 11, characterized in that the molar ratio of epoxide to the reactive groups of the starter of the formula (I), in particular the OH groups in the starter mixture, is 0.1-100:1 in the start phase. ### Claim 13 (depends on 12) Process according to claim 12, characterized in that the reaction is carried out batchwise or continuously. ### Claim 14 (depends on 13) Process according to claim 13, characterized in that the DMC catalyst concentration is from >0 to 5000 wppm based on the total mass of the alkoxylation products formed. ### Claim 15 (depends on 14) Process according to claim 14, characterized in that the catalyst is introduced as solid or in the form of a catalyst suspension. ### Claim 16 Silicone polyether of the formula (VII), where the radicals R are identical or different linear or branched, saturated, monounsaturated or polyunsaturated alkyl radicals having from 1 to 20 carbon atoms, and a is an integer from 0 to 5000, and A is a polyether fragment represented by the formula (VIII) in which R2 or R3 and R5 or R6 are identical or different and are each, independently of one another, H or a saturated or monounsaturated or polyunsaturated, monovalent or polyvalent hydrocarbon radical which may be further substituted, where the radicals R5 and R6 are each a monovalent hydrocarbon radical and the hydrocarbon radical can be cycloaliphatically bridged via the fragment Y; Y can be absent or be a methylene bridge having 1 or 2 methylene units, when Y is 0 then R2 and R3 are each, independently of one another, a linear or branched hydrocarbon radical having 1 to 20 carbon atoms, R4 is an ether or ester function on a linear or branched alkyl radical having from 1 to 24 carbon atoms or an aromatic or cycloaliphatic radical, n is an integer from 2 to 8 and R7, R6, R9, R10, R11 and R12 are each, independently of one another, hydrogen or an alkyl, alkoxy, aryl or aralkyl group, a is an integer from 0 to 5000, b is an integer from 0 to 1000, c is an integer from 0 to 500, d is an integer from 0 to 500, e, f and g are integers from 0 to 500, with the proviso that a) the fragments having the indices b to g can be freely permutated among one another, i.e. can be exchanged with one another in the sequence within the polyether chain, and b) the fragments having the indices b, c and e can be present in blocks or randomly distributed as desired and c) the sumb+c+d+e+f+g>zero and d) the indices c to g are different from zero when the index b is from 1 to 200 and at the same time the fragment having the index b is EO (ethylenoxy group) or PO (propylenoxy group) or e) when the sum of the indices c to g is zero and the index b is from 1 to 200 and the fragments are EO or PO units, these are not present in a random sequence. ### Claim 17 (depends on 3) Polyether siloxanes of the formula (VII) prepared by a process according to claim 3, with the proviso that compounds of the formula where R′ is a methyl group and A′ is —(CH2—CH2—O)h—(CH2—CH(CH3)O)i—(CH2—CH2—O)j—H and h, i and j can, independently of one another, be from 0 to 200 and the polyether units h, i and j are randomly distributed, are not present. ### Claim 18 (depends on 17) Polyether siloxanes according to claim 17, with the proviso that compounds of the formula (IX) in which the sum h+i+j>0 and a″ is an integer from 1 to 2000 are not encompassed.