IPC분류정보
국가/구분 |
United States(US) Patent
공개
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국제특허분류(IPC7판) |
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출원번호 |
US-0343178
(2012-01-04)
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공개번호 |
US-0172510
(2013-07-04)
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발명자
/ 주소 |
- Saxena, Anubhav
- Sarkar, Alok
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출원인 / 주소 |
- Momentive Performance Materials Inc.
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인용정보 |
피인용 횟수 :
0 인용 특허 :
0 |
초록
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A process for the manufacture of polyorganosiloxanes having ionic groups and reactive functional groups includes (a) conversion of a low molecular weight aralkylene modified polysiloxane to a corresponding sulfonic acid functional material by treating the low molecular weight aralkylene modified pol
A process for the manufacture of polyorganosiloxanes having ionic groups and reactive functional groups includes (a) conversion of a low molecular weight aralkylene modified polysiloxane to a corresponding sulfonic acid functional material by treating the low molecular weight aralkylene modified polysiloxane with a sulfonating agent; (b) subjecting the reaction product obtained in step (a) to an equilibration reaction with an acid catalyzed ring opening polymerization-effective polyorganosiloxane; and (c) subjecting the reaction product obtained in step (b) to a hydrosilylation reaction with an unsaturated hydrocarbon containing at least one epoxy group, an unsaturated hydrocarbon containing at least two unsaturation moieties, an unsaturated hydrocarbon containing at least one sulfur heteroatom, an unsaturated hydrocarbon containing a monovalent organosilane group, an unsaturated hydrocarbon containing one hydroxyl containing group, an unsaturated hydrocarbon containing one or more of a halogen, carboxylate, imine, isocyanate, amide, nitrile or tertiary amine with other than alkyl groups moiety.
대표청구항
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1. A process for the manufacture of functional polyorganosiloxanes comprising ionic groups comprising: (a) conversion of a low molecular weight aralkylene modified polysiloxane to a corresponding sulfonic acid functional material by treating the low molecular weight aralkylene modified polysiloxane
1. A process for the manufacture of functional polyorganosiloxanes comprising ionic groups comprising: (a) conversion of a low molecular weight aralkylene modified polysiloxane to a corresponding sulfonic acid functional material by treating the low molecular weight aralkylene modified polysiloxane with a sulfonating agent;(b) subjecting the reaction product obtained in step (a) to an equilibration reaction with an acid catalyzed ring opening polymerization-effective polyorganosiloxane; and optionally(c) subjecting the reaction product obtained in step (b) to a hydrosilylation reaction with an unsaturated hydrocarbon containing at least one epoxy group, an unsaturated hydrocarbon containing at least two unsaturation moieties, an unsaturated hydrocarbon containing at least one sulfur heteroatom, an unsaturated hydrocarbon containing a monovalent organosilane group, an unsaturated hydrocarbon containing one hydroxyl containing group, an unsaturated hydrocarbon containing one or more of a halogen, carboxylate, imine, isocyanate, amide, nitrile or tertiary amine with other than alkyl groups moiety and optionally,(d) subjecting the epoxide-containing reaction product of (c) to a ring-opening reaction with a hydroxyl, amine, acid and thiol containing hydrocarbons. 2. The process of claim 1 wherein the low molecular weight aralkylene modified polysiloxane subjected to a sulfonation reaction in step (a) is of at least one of the formulae (Ia), (Ib) or (Ic): (Me)rR3sSiO-[MeR3SiO]n[Me2SiO]m—Si(Me)rR3s (Ia) wherein Me is CH3, R3 is —CH2—CH(R1)(CH2)kC6H5, or —CH2CH(R1)(CH2)lC6H4(CHR2)kCH3 where R1, R2 is hydrogen or an aliphatic, aromatic or fluoro containing monovalent hydrocarbon radical containing from 1 to about 60 carbon atoms, l has a value of about 0 to about 20 and k has a value of 0 to about 10, r is 2 or 3, s is 0 or 1, n is 1 to about 300, s+n is greater than 0, m is 0 to about 400, and the siloxy units may have a random or blockwise distribution; [MeR3SiO]p (Ib)wherein Me and R3 have the same meaning as above and p=3 to about 10; and R3sTsQ (Ic)wherein R3, T and Q have the same meaning as described above. 3. The process of claim 1 wherein the sulfonating agent is selected from the group consisting of chlorosulfonic acid, sulfuric acid, liquid SO3, gaseous SO3, SO3 containing gases, oleum, and SO3 complexes or mixtures thereof. 4. The process of claim 1 wherein the reaction of step (a) can be conducted at a temperature of from 0 degrees Celsius to about 180 degrees Celsius and at a pressure between 0.001 to about 100 bar. 5. The process of claim 1 wherein in the reaction of step (a) the amount of sulfonating agent is from about 0.01 to about 10.0 equivalents with respect to the arylalkylene groups present in the low molecular weight aralkylene modified polysiloxane. 6. The process of claim 1 further comprising wherein the reaction product obtained in step (a) is neutralized in the presence of a solvent at a temperature of from −25 degrees Celsius to about 180 degrees Celsius and at a pressure between 0.001 to about 100 bar. 7. The process of claim 6 wherein the solvent is a base selected from the group consisting of hydroxides, ammonia, carbonates, bicarbonates and organic amines. 8. The process of claim 7 wherein the hydroxide is selected from the group consisting of sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide, aluminum hydroxide and ammonium hydroxide. 9. The process of claim 7 wherein the carbonate is selected from the group consisting of sodium carbonate, potassium carbonate, lithium carbonate, and ammonium carbonate. 10. The process of claim 7 wherein the bicarbonate is selected from the group consisting of sodium bicarbonate, potassium bicarbonate, lithium bicarbonate and ammonium bicarbonate. 11. The process of claim 7 wherein the organic amine is selected from the group consisting of ethanolamine, diethanolamine, triethanolamine, diethyl amine, dimethyl amine, trimethyl amine, triethyl amine and tributyl amine. 12. The process of claim 1 wherein the reaction product of step (a) has one of the general formulae (IIa) to (IIc): (Me)rR45SiO-[MeR4SiO]n-[Me2SiO]m—Si(Me)rR4s (IIa) wherein Me is CH3, R4 is a monovalent radical bearing ionic group and having the formula -A-SO3M where A is a divalent aralkylene group selected from the group consisting of —(CHR′)kC6H4(CH2)l—, —CH2CH(R1)(CH2)kC6H4—, and —CH2CH(R′)(CH2)lC6H3R″—, where R′ is hydrogen or is an aliphatic, aromatic or fluoro containing monovalent hydrocarbon radical containing from 1 to about 60 carbon atoms, l has a value of 0 to 20, k has a value of 0 to 10, M is hydrogen or a cation independently selected from alkali metals, alkali earth metals, transition metals, metals, metal complexes and quaternary ammonium groups, organic cations, alkyl cations, hydrocarbon cations and cationic biopolymers, m is 0 to 400, n is 1 to 50, specifically from about 0 to about 10, r is 2 or 3, s is 0 or 1 and s+n is greater than 0; R″ is a monovalent radical specifically from about 1 to about 20 carbon atoms, sulfur atom(s), nitrogen atom(s), oxygen atom(s) or a radical containing combinations of the above atoms, and the siloxy units have a random or blockwise distribution; and, [MeR4SiO]p (IIb)wherein Me and R4 are as defined above, and p=3 to about 10; and, R4sTsQ (IIc)wherein R4, T and Q have the same meaning as described above. 13. The process of claim 12 wherein each M is a cation independently selected from but not limited to Li, Na, K, Cs, Mg, Ca, Ba, Zn, Cu, Fe, Ni, Ga, Al, Mn, Cr, Ag, Au, Pt, Pd, Pb, Sb, Sn, Ru, and Rh and their multivalent forms. 14. The process of claim 1 wherein the equilibration reaction of step (b) is conducted with an equilibration catalyst at a temperature of between −25 degrees Celsius to about 150 degrees Celsius and at a pressure of from about 0.001 to about 100 bar. 15. The process of claim 1 wherein the equilibration reaction of step (b) is optionally conducted with an equilibration catalyst selected from the group consisting of sulfuric acid, acid modified clay, triflic acid, potassium hydroxide, sodium hydroxide, tetramethylammonium siloxanolate and potassium siloxanolate. 16. The process of claim 1 wherein the equilibration reaction of step (b) is conducted with the reaction product of step (a) and one or more of a linear, branched or cyclic polyorganosiloxane. 17. The process of claim 1 wherein the equilibration reaction of step (b) is conducted with the reaction product of step (a) and at least one polyorganosiloxane of the general formulae (IIIa) and (IIIb): R5R6R7SiO(R8R9SiO)vSiR10R11R12 (IIIa) where R5, R6, R7, R8, R9, R10, R11, R12, R13, R14 are independently selected from hydride, methyl or a vinyl group and v=1 to about 4000; (R13R14SiO)w (IIIb) where R13 and R14 are as defined and w=3 to about 10. 18. The process of claim 17 wherein the cyclic polyorganosiloxanes of formula (IIIb) are selected from the group consisting of hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, tetramethylcyclotetrasiloxane, decamethylcyclopentasiloxane and mixtures thereof. 19. The process of claim 17 wherein the linear polyorganosiloxanes of formula (IIIa) are selected from the group consisting of trialkylsilyl endcapped polyorganosiloxanes or alkylhydride end-capped polyorganosiloxanes of the formula (IIIa), wherein the index “v” is 1 to about 2500. 20. The process of claim 12 wherein the equilibration reaction of step (b) is conducted with either formula (IIa) or formula (IIb) with a cyclic siloxane of the formula (IIIb): (R13R14SiO)w (IIb) where R13 and R14 are independently selected from hydride, methyl or a vinyl group and w=3-10. 21. The process of claim 12 wherein the equilibration reaction of step (b) is conducted with the cyclic siloxane of formula (IIb) and with a linear siloxane of formula (IIIa): R5R6R7SiO(R8R9SiO)vSiR10R11R12 (IIIa) where R5, R6, R7, R8, R9, R10, R11, R12, R13, R14 are independently selected from hydride, methyl or a vinyl group and v=1 to about 4000. 22. The process of claim 21 wherein the cyclic siloxane of formula (IIc) is in a mixture with at least one trialkylsilyl-endcapped linear polydimethylsiloxane. 23. The process of claim 1 wherein the reaction product of step (b) is a silicone of the formula (A): M1aM2bM3cD1dD2eD3fT1gT2hT3iQj (A)wherein: M1=R1R2R3SiO1/2 M2=R4R5R6SiO1/2 M3=R7R8R9SiO1/2 D1=R10R11SiO2/2 D2=R12R13SiO2/2 D3=R14R15SiO2/2 T1=R16SiO3/2 T2=R17SiO3/2 T3=R18SiO3/2 Q=SiO4/2 where R1, R2, R3, R5, R6, R8, R9, R10, R11, R13, R15, R16 are aliphatic, aromatic or fluoro containing monovalent hydrocarbon radicals containing from 1 to about 60 carbon atoms;where R4, R12, R17 are independently selected from a group consisting of monovalent radical bearing an ionic group and having the formula -A-SO3M wherewhere A is a divalent arylalkylene group selected from the group consisting of divalent aralkylene group selected from the group consisting of —(CHR′)kC6H4(CH2)l—, —CH2CH(R′)(CH2)kC6H4—, and —CH2CH(R′)(CH2)lC6H3R″— where R′ is hydrogen or an aliphatic, aromatic or fluoro containing monovalent hydrocarbon radical containing from 1 to about 60 carbon atoms, l has a value of 0 to 20, k has a value of 0 to 10, specifically from about 0 to about 5, M is hydrogen or a cation independently selected from alkali metals, alkali earth metals, transition metals, metals, metal complexes and quaternary ammonium groups, organic cations, alkyl cations, hydrocarbon cations and cationic biopolymers, m is 0 to 400, specifically from about 0 to about 10, n is 1 to 50, specifically from about 0 to about 10, r is 2 or 3, s is 0 or 1 and s+n>0; where R′ is a hydrogen or defined by R1, where R″ is a monovalent radical specifically from about 1 to about 20 carbon atoms, sulfur atom(s), nitrogen atom(s), oxygen atom(s) or a radical containing combinations of the above atoms, where M is hydrogen or a cation independently selected from alkali metals, alkali earth metals, transition metals, metals, metal complexes, quaternary ammonium and phosphonium groups, organic cations, alkyl cations, hydrocarbon cations and cationic biopolymers; R7, R14, R18 are independently selected from hydrogen or vinyl groups, and where the subscript a, b, c, d, e, f, g, h, i, j are zero or positive subject to the following limitations: the sum a+b+c+d+e+f+g+h+i+j is greater than or equal to 2 and less than or equal to 6000, b+e+h is greater than zero and c+f+i is greater than or equal to zero. 24. The process of claim 1 further comprising wherein following the equilibration reaction of step (b) the catalyst is deactivated. 25. (canceled) 26. The process of claim 1 wherein the hydrosilylation reaction of step (c) is conducted in the presence of a hydrosilylation catalyst selected from the group consisting of transition metals selected from platinum, rhodium, iridium, palladium, nickel, osmium, iron, cobalt, tin, zirconium, titanium, hafnium, and ruthenium, manganese, copper, silver, gold, chromium, rhenium, calcium, strontium, potassium, their various ligands, complexes, precatalysts, or mixtures thereof; Lewis acids such as TiCl4, EtAlCl2, AlCl3 and AlBr3 and mixtures thereof, or transition metal compounds or mixtures thereof. 27. The process of claim 26 wherein the metal of the catalyst is in the range of 1 to about 1000 ppm relative to the weight of the silylhydride containing siloxane which is present in the reaction product of step (b). 28. The process of claim 1 wherein the unsaturated hydrocarbons in step (c) have one of the general formulae (IV to XIII): where R20, R21, R26, R29, R30, R33, R34, R40, R46, R47, R52, R63 are independently selected from —H, —OH, —R66 and aliphatic/aromatic monovalent hydrocarbon having from 1 to about 60 carbon atoms,where R22, R23, R24, R25, R27, R28, R31, R32, R35, R36, R37, R38, R39, R41, R42, R43, R44, R45, R48, R51, R53, R56, R57, R59, R60, R61, R62 are independently selected from hydrogen, aliphatic/aromatic monovalent hydrocarbon having from 1 to 60 carbon atoms,where R58 is hydrogen or a monovalent alkyl radical with 2 to about 20 carbon atoms or or a heteroatomwhere R49, R50, R54, R55 are independently selected from —H, —CtH2tOH and aliphatic/aromatic monovalent hydrocarbon having from 1 to 60 carbon atoms wherein t is a positive integer,where L is a monovalent radical independently selected from halogen, OR64, —CO(O)R65, —N═CR662, —NCO, —NC(O)R67, —C≡N, —N≡N and —NR682 where R64, R65, R66, R67, R68 are independently selected from a group consisting of hydrogen, alkyl, alkenyl, cycloalkyl and aryl,where Z is a monovalent radical independently selected from halogen, OR64A, —CO(O)R65, —N═CR662, —NCO, —NC(O)R67, —C≡N, —N≡N and —NR68A2 where R65, R66, R67 are independently selected from a group consisting of hydrogen, alkyl, alkenyl, cycloalkyl and aryl, and where R64A is hydrogen or independently selected from a group consisting of alkyl, alkenyl, cycloalkyl and aryl containing from 2 to about 60 carbon atoms, and where R68A is independently selected from a group consisting of hydrogen, alkenyl, cycloalkyl and aryl containing from 2 to about 60 carbon atoms,where X is divalent radical selected from —CHR65—, —O —, —NR65— and —S— linkages,where B is a divalent radical selected from a linear, branched, cyclic hydrocarbon radical or aralkyl radical of from 1 to about 60 carbon atoms and may contain a heteroatom;where the subscript n is zero or positive integer and has a value in the range of 0 to 60,where subscript o is positive integer and has a value in the range of 1 to about 60, where subscripts p, q r u and v are zero or positive and independently selected from a value in the range of 0 to about 100, subject to the limitation of p+q+r+v being greater than or equal to 1 and s is zero or positive integers and has a value of 0 to 2. 29. The process of claim 1 wherein the epoxide-containing reaction product of step (c) to a ring-opening reaction preferentially in presence of a suitable catalyst with a hydroxyl, amine, carboxylic acid and thiol containing hydrocarbons, azide containing molecules or water. 30. The process of claim 1 wherein the epoxide-containing product used in the step (d) can have the general formula (A) Where R7, R14 and R18 are monovalent hydrocarbon radical selected from the group of formula XIII and XIV: where R25, R26, R27, R28, R29, R30 and R31 are defined above. 31. The process of claim 30 wherein the hydroxyl containing hydrocarbons used in step (d) can be selected from the group consisting of aliphatic or aromatic alcohol containing 1 to 60 carbon atoms. 32. The process of claim 30 wherein the amine containing hydrocarbons used in step (d) can be selected from the group consisting of aliphatic or aromatic amine containing 1 to 60 carbon atoms. 33. The process of claim 30 wherein the carboxylic acid containing hydrocarbons used in step (d) can be selected from the group consisting of aliphatic or aromatic carboxylic acid containing 1 to 60 carbon atoms. 34. The process of claim 30 wherein thiol containing hydrocarbons used in (d) can be selected from the group consisting of the aliphatic or aromatic alcohol containing 1 to 60 carbon atoms. 35. The process of claim 30 wherein the azide containing molecules used in step (d) can be a selected from a group consisting of sodium azide, calcium azide, potassium azide, lithium azide, trimethylsilyl azide. 36. The process of claim 30 wherein catalyst used in step (d) are selected from the group of a variety of organometallic compounds preferably organo tin, titanium, zinc, calcium compounds but one can also use Lewis acids or Broensted acids or basis, preferred acids and basis are such types with low vapour pressure, C1-C8 carbonacids or alkylamines. 37. The process of claim 1 wherein the reaction of step (d) can optionally be done in presence of suitable solvent selected from the group consisting of aliphatic alcohols, glycol ethers, cycloaliphatic alcohols, aliphatic esters, cycloaliphatic esters, aliphatic hydrocarbons, cycloaliphatic hydrocarbons, aromatic hydrocarbons, halogenated aliphatic compounds, halogenated cycloaliphatic compounds, halogenated aromatic compounds, aliphatic ethers, cycloaliphatic ethers, amide solvents, and sulfoxide solvents.
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