# US 7,411,028 B2 · Process for preparing functionalized polyorganosiloxane resins by redistribution in the presence of triflic acid and/or of at least one derivative thereof and of a nonbasic filler > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 7,411,028 B2 - Document ID: US7411028B2 - Status: Granted - Kind: B2 - Application number: 10/509,060 - Filed: 2003-03-20 - Published: 2005-12-15 - Granted: 2008-08-12 - Earliest claimed: 2002-03-26 - Assignees: Bluestar Silicones France SAS - Inventors: Fernande Boisson; Lucile Gambut; Gérard Mignani - Web page: https://patentgrep.com/patent/US7411028B2 ## CPC - C08G 77/10: Equilibration processes - C08G 77/08: characterised by the catalysts used - C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS ## Abstract The invention provides a method for preparing functionalized polyorganosiloxane resins (POS) comprising units M: (R3SiO1/2), Q: (SiO4/2) and M′: (YaR3-aSiO1/2) and optionally D: (R2SiO2/2) and/or D′: (RYSiO2/2) and T: (RSiO3/2) and/or T′: (YSiO3/2), wherein in said units R is C1-C10, alkyl or C8-C12, aryl and Y is a functional group (such as Si—H), by redistributing POS resins, using POSf bearing functional groups M′ and/or D′ and/or in the presence of an acid catalyst such as triflic acid or one of its derivatives and a non-basic inert filler: carbon black, diatomaceous earth, zeolite or acid or neutral oxide (Al2O3, Na2O, TiO2, MgO, silica). The invention also provides said catalyst system. ## Claims ### Claim 1 A process for preparing functionalized polyorganosiloxane (POS) resins comprising units M: (R3SiO1/2), Q: (SiO4/2) and M′: (YaR3-aSiO1/2) and optionally D: (R2SiO2/2) and/or D′: (RYSiO2/2) and T: (RSiO3/2) and/or T′: (YSiO3/2), wherein: the radicals R, which are identical or different, represent C1-C10, alkyl or C8-C12 aryl; and the radicals Y, which are identical or different, represent a functional group Y selected from the group consisting of hydrogen, alkenyl, alkynyl, aryl, (alkyl)epoxy, ether, polyether, carboxylic acid, amide, amine, halide, alcohol, thiol and other sulfur derivative; said process comprising conducting a redistribution reaction between a POS resin and a POSf compound bearing functional units M′ and/or D′ and/or T′, as defined above, in the presence of an acid catalyst, wherein: at least one catalyst has formula (I) below: (CmF2m+1SO2)nA (I) wherein: m is an integer greater than or equal to 1; n is an integer equal to 1 or 2 and A represents OH, NH2 or NH with: (i) n=1 and A=OH; or (ii) n=1 and A=NH2 or NHR with R being a radical of SO2-Z type, with Z being a group other than CmF2m+1; or (iii) n=2 and A=NH; and wherein said catalyst is in the presence of a nonbasic inert filler; wherein the redistributed and functionalized resin obtained is subjected to at least one other redistribution/functionalization, using POSfs bearing functional units. ### Claim 2 (depends on 1) The process as claimed in claim 1, wherein the nonbasic inert filler is carbon black, a diatomaceous earth, or an acidic or neutral oxide, or a mixture thereof. ### Claim 3 (depends on 2) The process as claimed in claim 2, wherein the acidic or neutral oxide is Al2O3, Na2O, TiO2, MgO, silica or zeolite, or a mixture thereof. ### Claim 4 (depends on 1) The process as claimed in claim 1, wherein Y is phenyl. ### Claim 5 (depends on 1) The process as claimed in claim 1, wherein the catalyst is triflic acid (TFOH) of formula (I) (i) with m=1 and/or the trifluoromethanesulfonimide acid (TFSI) of formula (I) (iii) with m=1. ### Claim 6 (depends on 2) The process as claimed in claim 2, wherein the catalyst is triflic acid (TFOH) of formula (I) (i) with m=1 and/or the trifluoromethanesulfonimide acid (TFSI) of formula (I) (iii) with m=1. ### Claim 7 (depends on 1) The process as claimed in claim 1, wherein the catalyst is supported on the nonbasic inert filler, the concentration of acid catalyst (I) is between 1 ppm and 2% by weight relative to the starting resin and wherein the catalyst (I)/inert filler support mass ratio is between 0.1 and 10. ### Claim 8 (depends on 7) The process as claimed in claim 7, wherein the inert filler support is carbon black. ### Claim 9 (depends on 7) The process as claimed in claim 7, wherein the catalyst (I)/inert filler support mass ratio is of the order of 1. ### Claim 10 (depends on 9) The process as claimed in claim 9, wherein the inert filler support is carbon black. ### Claim 11 (depends on 7) The process as claimed in claim 7, wherein the catalyst is triflic acid (TFOH) of formula (I) (i) with m=1 and/or the trifluoromethanesulfonimide acid (TFSI) of formula (I) (iii) with m=1. ### Claim 12 (depends on 11) The process as claimed in claim 11, wherein the inert filler support is carbon black. ### Claim 13 The process for preparing functionalized polyorganosiloxane (POS) resins comprising units M: (R3SiO1/2), Q: (SiO4/2) and M′: (YaR3-aSiO1/2) and optionally D: (R2SiO2/2) and/or D′: (RYSiO2/2) and T: (RSiO3/2) and/or T′: (YSiO3/2), wherein: the radicals R, which are identical or different, represent C1-C10 alkyl or C8-C12 aryl; and the radicals Y, which are identical or different, represent a functional group Y selected from the group consisting of hydrogen, alkenyl, alkynyl, aryl, (alkyl)epoxy, ether, polyether, carboxylic acid, amide, amine, halide, alcohol, thiol and other sulfur derivative; said process comprising conducting a redistribution reaction between a POS resin and a POSf compound bearing functional units M′ and/or D′ and/or T′, as defined above, in the presence of an acid catalyst, wherein: at least one catalyst has formula (I) below: (CmF2m+1SO2)nA (I) wherein: m is an integer greater than or equal to 1; n is an integer equal to 1 or 2 and A represents OH, NH2 or NH with: (i) n=1 and A=OH; or (ii) n=1 and A=NH2 or NHR with R being a radical of SO2-Z type, with Z being a group other than CmF2m+1; or (iii) n=2 and A=NH; and wherein said catalyst is in the presence of a nonbasic inert filler; said process comprising the following essential steps: (1) combining the starting POS resin, the POSf bearing functional units, the acid catalyst (I) and the nonbasic inert filler in an organic solvent; (2) reacting at a temperature θr greater than or equal to room temperature and less than or equal to the boiling point of the solvent; (3) optionally quenching the reaction by adding an agent for neutralizing the acid catalyst (I); and (4) removing the inert filler from the reaction medium; wherein the redistributed and functionalized resin obtained is subjected to at least one other redistribution/functionalization, using POSfs bearing functional units. ### Claim 14 (depends on 13) The process as claimed in claim 13, wherein the inert filler comprises carbon black, and/or wherein the reaction temperature is between 50° C. and 100° C., and/or wherein the inert filler is removed from the reaction medium by filtration. ### Claim 15 (depends on 13) The process as claimed in claim 13, wherein the acid catalyst is triflic acid (TFOH) of formula (I) (i) with m=1 and/or the trifluoromethanesulfonimide acid (TFSI) of formula (I) (iii) with m=1. ### Claim 16 (depends on 15) The process as claimed in claim 15, wherein the inert filler comprises carbon black, and/or wherein the reaction temperature is between 50° C. and 100° C., and/or wherein the inert filler is removed from the reaction medium by filtration. ### Claim 17 (depends on 13) The process as claimed in claim 13, wherein the organic solvent is provided in the reaction medium by means of a solution of starting POS resin in said solvent, and wherein the nonbasic inert filler is in the form of powder dispersed in the POSf bearing functional units. ### Claim 18 (depends on 13) The process as claimed in claim 13, wherein the organic solvent is xylene or toluene, and/or wherein the nonbasic inert filler is carbon black. ### Claim 19 A process for preparing functionalized polyorganosiloxane (POS) resins comprising units M: (R3SiO1/2), Q: (SiO4/2) and M′: (YaR3-aSiO1/2) and optionally D: (R2SiO2/2) and/or D′: (RYSiO2/2) and T: (RSiO3/2) and/or T′: (YSiO3/2), wherein: the radicals R, which are identical or different, represent C1-C10 alkyl or C8-C12 aryl; and the radicals Y, which are identical or different, represent a functional group Y selected from the group consisting of hydrogen, alkenyl, alkynyl, aryl, (alkyl)epoxy, ether, polyether, carboxylic acid, amide, amine, halide, alcohol, thiol and other sulfur derivative; said process comprising conducting a redistribution reaction between a POS resin and a POSf compound bearing functional units M′ and/or D′ and/or T′, as defined above, in the presence of an acid catalyst, wherein: at least one catalyst has formula (I) below: (CmF2m+1SO2)nA (I) wherein: m is an integer greater than or equal to 1; n is an integer equal to 1 or 2 and A represents OH, NH2 or NH with: (i) n=1 and A=OH; or (ii) n=1 and A=NH2 or NHR with R being a radical of SO2-Z type, with Z being a group other than CmF2m+1; or (iii) n=2 and A=NH; and wherein said catalyst is in the presence of a nonbasic inert filler; wherein Y═H or alkenyl in the functional units M′ and/or D′ and/or T′ of the POSf, and wherein, after the redistribution, other functionalization radicals Y1 bearing at least one unsaturation or at least one Si—H unit are grafted by hydrosilylation onto the ≡Si—H or ≡Si-alkenyl units, respectively, of the redistributed resin; wherein the redistributed and functionalized resin obtained is subjected to at least one other redistribution/functionalization, using POSfs bearing functional units. ### Claim 20 (depends on 19) The process as claimed in claim 19, wherein other functionalization radicals Y1 bearing at least one ethylenic unsaturation are grafted by hydrosilylation onto the ≡Si—H or ≡Si-alkenyl units, respectively, of the redistributed resin. ### Claim 21 A process for preparing functionalized polyorganosiloxane (POS) resins comprising units M: (R3SiO1/2), Q: (SiO4/2) and M′: (YaR3-aSiO1/2) and optionally D: (R2SiO2/2) and/or D′: (RYSiO2/2) and T: (RSiO3/2) and/or T′: (YSiO3/2), wherein: the radicals R, which are identical or different, represent C1-C10 alkyl or C8-C12 aryl; and the radicals Y, which are identical or different, represent a functional group Y selected from the group consisting of hydrogen, alkenyl, alkynyl, aryl, (alkyl)epoxy, ether, polyether, carboxylic acid, amide, amine, halide, alcohol, thiol and other sulfur derivative; said process comprising conducting a redistribution reaction between a POS resin and a POSf compound bearing functional units M′ and/or D′ and/or T′, as defined above, in the presence of an acid catalyst, wherein: at least one catalyst has formula (I) below: (CmF2m+1SO2)nA (I) wherein: m is an integer greater than or equal to 1; n is an integer equal to 1 or 2 and A represents OH, NH2 or NH with: (i) n=1 and A=OH; or (ii) n=1 and A=NH2 or NHR with R being a radical of SO2-Z type, with Z being a group other than CmF2m+1; or (iii) n=2 and A=NH; and wherein said catalyst is in the presence of a nonbasic inert filler; said process comprising the following essential steps: (1) combining the starting POS resin, the POSf bearing functional units, the acid catalyst (I) and the nonbasic inert filler in an organic solvent; (2) reacting at a temperature θr greater than or equal to room temperature and less than or equal to the boiling point of the solvent; (3) optionally quenching the reaction by adding an agent for neutralizing the acid catalyst (I); and (4) removing the inert filler from the reaction medium; wherein Y═H or alkenyl in the functional units M′ and/or D′ and/or T′ of the POSf, and wherein, after the redistribution, other functionalization radicals Y1 bearing at least one unsaturation or at least one Si—H unit are grafted by hydrosilylation onto the ≡Si—H or ≡Si-alkenyl units, respectively, of the redistributed resin; wherein the redistributed and functionalized resin obtained is subjected to at least one other redistribution/functionalization, using POSfs bearing functional units.