# US 10,766,913 B2 · Mixtures of cyclic branched siloxanes of the D/T type and conversion products thereof > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 10,766,913 B2 - Document ID: US10766913B2 - Status: Granted - Kind: B2 - Application number: 16/140,573 - Filed: 2018-09-25 - Published: 2019-04-11 - Granted: 2020-09-08 - Earliest claimed: 2017-10-09 - Assignees: Evonik Operations GmbH - Applicants: Evonik Degussa GmbH - Inventors: Wilfried Knott; Horst Dudzik - Web page: https://patentgrep.com/patent/US10766913B2 ## CPC - C07F 7/0838: {Compounds with one or more Si-O-Si sequences (compounds with a ring containing only alternating Si and O atoms, i.e. cyclosilanes C07F7/21)} - C07F 7/0878: {Si-C bond} - C08G 18/3893: {containing silicon} - C08G 77/06: Preparatory processes - C08G 77/10: Equilibration processes - C08G 77/12: containing silicon bound to hydrogen - C08L 83/04: Polysiloxanes - C08G 77/70: {Siloxanes defined by use of the MDTQ nomenclature} - C07F: ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM (metal-containing porphyrins C07D487/22) - C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS - C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06) ## Abstract Mixtures of cyclic branched siloxanes having exclusively D and T units, with the proviso that the cumulative proportion of the D and T units having Si-alkoxy and/or SiOH groups that are present in the siloxane matrix, determinable by 29Si NMR spectroscopy, is less than 2.0 and preferably less than 1.0 mole percent, are described, as are branched organomodified siloxanes obtainable therefrom. ## Claims ### Claim 1 A mixture of cyclic branched siloxanes having exclusively D and T units, wherein the cumulative proportion of the D and T units having Si-alkoxy and/or SiOH groups that are present in the siloxane matrix, determinable by 29Si NMR spectroscopy, is less than 2 mole percent based on the totality of silicon detected by spectroscopy, and further comprising at least 5% by weight of siloxane cycles selected from the group consisting of octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), dodecamethylcyclohexasiloxane (D6) and mixtures thereof. ### Claim 2 (depends on 1) The mixture according to claim 1, wherein the branching T unit derives from alkyltrialkoxysilanes and/or phenyltrialkoxysilanes. ### Claim 3 (depends on 1) The mixture according to claim 1, wherein the branching T unit derives from methyltriethoxysilane. ### Claim 4 (depends on 1) A process for preparing siloxane mixtures according to claim 1, the process comprising (a) an acid-catalysed equilibration of trialkoxysilanes with siloxane cycles and/or α,ω-dihydroxypolydimethylsiloxane in the presence of at least one acidic catalyst and then (b) a hydrolysis and condensation reaction initiated by addition of water, followed by the addition of a silicon-containing solvent, (c) with a subsequent distillative removal of the alcohol released and proportions of the water present in the system, (d) with subsequent addition of toluene and separation of residual water remaining in the system, (e) followed by a neutralization or removal of the acidic catalyst and, removal of any salts formed, (f) with final distillative removal of toluene still present in the system, wherein the silicon-containing solvent comprises the isomeric siloxane cycles octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5) and/or mixtures thereof, and mass ratios of silicon-containing solvent to the siloxane having D and T units of 1:1 to 5:1 are advantageously employed. ### Claim 5 (depends on 4) The process according to claim 4, wherein the acidic catalyst is selected from the group consisting of para-toluenesulfonic acid, trifluoromethanesulfonic acid, trichloroacetic acid, sulfuric acid, perchloric acid, phosphoric acid and hexafluorophosphoric acid, in amounts of 0.1 to 2.0 percent by weight based in each case on the silicon-containing component of the reaction matrix. ### Claim 6 (depends on 4) The process according to claim 4, wherein the acidic catalyst used is a macrocrosslinked sulfonic acid ion exchange resin, preferably in amounts of 1.0 to 10.0 percent by weight based in each case on the silicon-containing component of the reaction matrix. ### Claim 7 (depends on 4) The process according to claim 4, wherein the reaction is conducted at temperatures in the range from 20° C. to 120° C. ### Claim 8 (depends on 4) The process according to claim 4, wherein an at least 100% H2O excess is used, based on the groups to be condensed. ### Claim 9 (depends on 4) The process according to claim 4, wherein the reaction comprises a preliminary equilibration step at temperatures of T>40° C., followed by a condensation initiated by addition of water at temperatures of T>60° C., where the water is added in one portion, in several portions or continuously. ### Claim 10 (depends on 1) A process for preparing branched organomodified siloxanes, wherein in a first step mixtures of cyclic branched siloxanes are provided, according to claim 1, and in a second step the mixtures of cyclic branched siloxanes are acid-equilibrated with silanes and/or siloxanes. ### Claim 11 (depends on 10) A process according to claim 10, characterized in that the silanes and/or siloxanes used are acid-equilibratable silicon compounds, wherein the silanes used are diethoxydimethylsilane, trimethylalkoxysilanes and/or dimethyldichlorosilane, and/or wherein the siloxanes used are preferably tetramethyldisiloxane, α,ω-dihydropolydimethylsiloxanes, poly(methylhydro)siloxanes, α,ω-dialkoxypolydimethylsiloxanes and/or σ,ω-divinylpolydimethylsiloxanes. ### Claim 12 (depends on 10) A process according to claim 10, wherein, in the second step, the mixtures of cyclic branched siloxanes are equilibrated with silanes and/or siloxanes in the presence of an acidic catalyst, acid, in an amount of ≥0.1% by weight. ### Claim 13 (depends on 10) A process according to claim 10, wherein, in the second step in which the mixtures of cyclic branched siloxanes are acid-equilibrated with silanes and/or siloxanes, the equilibration is undertaken over a water-containing macroporous sulfonic acid polystyrene resin, which is used in amounts of 3% to 9% by weight and, which has been wetted with 8% to 12% by weight of water, and the specific surface area of which is ≥35 m2/g and the mean pore diameter of which is—preferably at least 65 nm. ### Claim 14 (depends on 4) The process according to claim 4, wherein the acidic catalyst is selected from the group consisting of para-toluenesulfonic acid, trifluoromethanesulfonic acid, trichloroacetic acid, sulfuric acid, perchloric acid, phosphoric acid and hexafluorophosphoric acid, in amounts of 0.15 to 1.0 percent by weigh based in each case on the silicon-containing component of the reaction matrix. ### Claim 15 (depends on 4) The process according to claim 4, wherein the acidic catalyst used is a macrocrosslinked sulfonic acid ion exchange resin, in amounts of 2.0 to 6.0 percent by weight based in each case on the silicon-containing component of the reaction matrix. ### Claim 16 (depends on 1) A process for preparing branched silicone oils, wherein in a first step cyclic branched siloxanes are provided, according to claim 1, and in a second step the cyclic branched siloxanes are reacted with polydimethylsiloxanes or hexamethyldisiloxane. ### Claim 17 A mixture of cyclic branched siloxanes having exclusively D and T units, wherein the cumulative proportion of the D and T units having Si-alkoxy and/or SiOH groups that are present in the siloxane matrix, determinable by 29Si NMR spectroscopy, is less than 2 mole percent, and further comprising at least 5% by weight of siloxane cycles selected from the group consisting of octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), dodecamethylcyclohexasiloxane (D6) and mixtures thereof wherein the ratio of D to T units is between 10:1 and 3:1. ### Claim 18 (depends on 17) The mixture according to claim 17, wherein the molar mass ratio of the mixture Mw/Mn is in the range of 2