Siloxane polyether copolymers
View Patent ↗The present invention is related to the preparation and use of moderately cross-linked (chin-extended), reverse (or “inverted”) surfactants, wherein the reverse surfactants comprise a polyether backbone with oligomeric or polymeric silicon-containing substitutions along the backbone. The present invention further describes crosslinked versions of the inverted surfactants, reaction products of alkenyl (allyl, vinyl, methallyl) functional copolymers (polyethers), silicone hydrides and cross-linking agents, which may be optionally reacted with water to react the remaining alkoxy groups. The crosslinking agent contains either SiH or Si-alkoxy groups or both. The compounds of the present invention exhibit only moderate cross-linking in order to be soluble or dispersible in appropriate solvents.
1. A soluble or dispersible copolymer composition, comprising the reaction products of
(a) a copolymer having the formula
where R A is a monovalent group containing at least one terminal alkenyl group, such as an allyl (—CH 2 —CH═CH 2 ), vinyl (—CH═CH 2 ) or methallyl (—C(CH 3 )═CH 2 ) group, optionally containing heteroatoms and hydroxyl groups;
R 1 is selected from —OH, —OC(O)CH 3 or a monovalent hydrocarbon radical, optionally containing heteroatoms and hydroxyl groups, having from about 1 to about 40 carbon atoms;
R 2 is a trivalent hydrocarbon radical optionally containing heteroatoms and hydroxyl groups, having from about 3 to about 40 carbon atoms;
R 3 is selected from hydrogen, a —C(O)CH 3 group or a monovalent hydrocarbon radical optionally containing heteroatoms and hydroxyl groups, having from about 1 to about 40 carbon atoms;
and subscripts a, b, c, d and e are subject to the limitation 3<a+b+c+d+e<about 1000 and subscripts d+e≧2;
(b) a silicone hydride having the formula
M f M H g D h D H i T j T H k Q l
wherein
M=R 4 R 5 R 6 SiO 1/2 ;
M H =R 7 R 8 HSiO 1/2 ;
D=R 9 R 10 SiO 2/2 ;
D H =R 11 HSiO 2/2 ;
T=R 12 SiO 3/2 ;
T H =HSiO 3/2 ;
Q=SiO 4/2 ;
R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 and R 12 are each independently selected from the groups of OR 13 or monovalent hydrocarbon radicals, optionally containing heteroatoms and hydroxyl groups, having from about 1 to about 20 carbon atoms;
R 13 is selected from the group of H or monovalent hydrocarbon radicals optionally containing heteroatoms and hydroxyl groups, having from about 1 to about 20 carbon atoms;
subscripts f, g, h, i, j, k and l are subject to the limitation 2<f+g+h+i+j+k+l<about 300, and g+i+k≧1;
and
(c) a cross-linking agent.
2. The copolymer composition of claim 1 where
R 1 is selected from —OH, —OC(O)CH 3 or a monovalent hydrocarbon radical, optionally containing heteroatoms and hydroxyl groups, having from about 1 to about 30 carbon atoms;
R 2 is a trivalent hydrocarbon radical optionally containing heteroatoms and hydroxyl groups, having from about 3 to about 30 carbon atoms;
R 3 is selected from hydrogen, a —C(O)CH 3 group or a monovalent hydrocarbon radical optionally containing heteroatoms and hydroxyl groups, having from about 1 to about 30 carbon atoms;
R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 and R 12 are each independently selected from the group of OR 13 or monovalent hydrocarbon radicals, optionally containing heteroatoms and hydroxyl groups, having from about 1 to about 15 carbon atoms;
R 13 is selected from the group of H or monovalent hydrocarbon radicals optionally containing heteroatoms and hydroxyl groups, having from about 1 to about 15 carbon atoms.
3. A method for separating emulsions comprising
(i) combining a demulsifying composition comprising a blend of an emulsion and the copolymer composition of claim 2 to produce a blended composition;
(ii) allowing the blended composition to separate into at least two phases, and
(iii) separating said phases.
4. The copolymer composition of claim 1 where
R 1 is selected from —OH, —OC(O)CH 3 or a monovalent hydrocarbon radical, optionally containing heteroatoms and hydroxyl groups, having from about 1 to about 20 carbon atoms;
R 2 is a trivalent hydrocarbon radical optionally containing heteroatoms and hydroxyl groups, having from about 3 to about 20 carbon atoms;
R 3 is selected from hydrogen, a —C(O)CH 3 group or a monovalent hydrocarbon radical optionally containing heteroatoms and hydroxyl groups, having from about 1 to about 20 carbon atoms;
R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 and R 12 are each independently selected from the groups of OR 13 or monovalent hydrocarbon radicals, optionally containing heteroatoms and hydroxyl groups, having from about 1 to about 10 carbon atoms;
R 13 is selected from the group of H or monovalent hydrocarbon radicals optionally containing heteroatoms and hydroxyl groups, having from about 1 to about 10 carbon atoms.
5. A method for separating emulsions comprising
(i) combining a demulsifying composition comprising a blend of an emulsion and a copolymer composition of claim 4 to produce a blended composition;
(ii) allowing the blended composition to separate into at least two phases, and
(iii) separating said phases.
6. The copolymer composition of claim 1 where said cross-linking agent (c) is a silicone hydride, having the formula
M m M H n D o D H p T q T H r Q s
wherein
M=R 14 R 15 R 16 SiO 1/2 ;
M H =R 17 R 18 HSiO 1/2 ;
D=R 19 R 20 SiO 2/2 ;
D H =R 21 HSiO 2/2 ;
T=R 22 SiO 3/2 ;
T H =HSiO 3/2 ;
Q=SiO 4/2 ;
R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 and R 22 are each independently selected from the groups of OR 23 or monovalent hydrocarbon radicals, optionally containing heteroatoms and hydroxyl groups, having from about 1 to about 20 carbon atoms;
R 23 is independently selected from the group of H or monovalent hydrocarbon radicals, optionally containing heteroatoms and hydroxyl groups, having from about 1 to about 20 carbon atoms;
subscripts m, n, o, p, q, r and s are subject to the limitation 1≦m+n+o+p+q+r+s<about 300.
7. A method for separating emulsions comprising
(i) combining a demulsifying composition comprising a blend of an emulsion and a copolymer composition of claim 6 to produce a blended composition;
(ii) allowing the blended composition to separate into at least two phases, and
(iii) separating said phases.
8. The copolymer composition of claim 1 where said cross-linking agent (c) is an organosilane, having the formula
R 24 R 25 R 26 SiH
Wherein R 24 , R 25 and R 26 each independently selected from the group of H or monovalent hydrocarbons having from about 1 to about 15 carbon atoms, preferably from about 1 to about 12 carbon atoms and more preferably from about 1 to about 10 carbon atoms, optionally containing nitrogen or oxygen or OR 27 , subject to the limitation that the sum of the SiH and OR 27 groups in cross-linking agent (c) is more than one;
R 27 is independently selected from H or monovalent hydrocarbons having from about 1 to about 15 carbon atoms, preferably from about 1 to about 12 carbon atoms and more preferably from about 1 to about 10 carbon atoms, optionally containing nitrogen or oxygen.
9. A method for separating emulsions comprising:
(i) combining a demulsifying composition comprising a blend of an emulsion and a copolymer composition of claim 8 to produce a blended composition;
(ii) allowing the blended composition to separate into at least two phases, and
(iii) separating said phases.
10. The copolymer composition of claim 1 where said silicon hydride (b) has the formula
MD t D H u M
wherein
M=R 28 R 29 R 30 SiO 1/2 ,
D=R 31 R 32 SiO 2/2 ,
D H =R 33 HSiO 2/2 ;
R 28 , R 29 , R 30 , R 31 , R 32 and R 33 are each independently selected from the group of OR 34 or monovalent hydrocarbon radicals, optionally containing heteroatoms and hydroxyl groups, having from about 1 to about 20 carbon atoms;
R 34 is independently selected from the group of H or monovalent hydrocarbon radicals, optionally containing heteroatoms and hydroxyl groups, having from about 1 to about 20 carbon atoms;
subscripts t and u are subject to the limitations 1≦t+u<about 300 and 1≦u.
11. A method for separating emulsions comprising
(i) combining a demulsifying composition comprising a blend of an emulsion and a copolymer composition of claim 10 to produce a blended composition;
(ii) allowing the blended composition to separate into at least two phases, and
(iii) separating said phases.
12. The copolymer composition of claim 1 where said cross-linking agent (c) is a silicone hydride having the formula
MD v D H w M
wherein
M=R 35 R 36 R 37 SiO 1/2 ;
D=R 38 R 39 SiO 2/2 ;
D H =R 40 HSiO 2/2 ;
R 35 , R 36 , R 37 , R 38 , R 39 and R 40 are each independently selected from the group of OR 41 or monovalent hydrocarbon radicals, optionally containing heteroatoms and hydroxyl groups, having from about 1 to about 20 carbon atoms, subject to the limitation that the sum of the SiH and OR 41 groups in cross-linking agent (c) is more than one;
R 41 is independently selected from the group of H or monovalent hydrocarbon radicals optionally containing heteroatoms and hydroxyl groups, having from about 1 to about 20 carbon atoms;
subscripts v and w are subject to the limitation 1≦v+w<about 300.
13. A method for separating emulsions comprising
(i) combining a demulsifying composition comprising a blend of an emulsion and a copolymer composition of claim 12 to produce a blended composition;
(ii) allowing the blended composition to separate into at least two phases, and
(iii) separating said phases.
14. The copolymer composition of claim 1 where said reaction products are further reacted with water.
15. A composition comprising a blend of
(i) an emulsion, and
(ii) a demulsifying-effective amount of said copolymer composition of claim 1 .
16. The demulsifying composition in claim 15 where said emulsion is an emulsion comprising crude oil.
17. The demulsifying composition of claim 15 where said composition further comprises an additional demulsifier selected from the group consisting of organic or silicone demulsifiers or mixtures thereof wherein the weight ratio of the reaction products of claim 1 to the total amount of organic and silicone demulsifiers is in the range of about 100:1 to about 1:1000.
18. A method for separating emulsions comprising
(i) combining a demulsifying composition comprising a blend of an emulsion and a copolymer composition of claim 1 to produce a new composition;
(ii) allowing the new composition to separate into at least two phases, and
(iii) separating said phases.
19. The method for separating emulsions of claim 18 wherein blend further comprises an additional demulsifier selected from the group consisting of organic or silicone demulsifiers or mixtures thereof wherein the weight ratio of the reaction products of claim 1 to the total amount of organic and silicone demulsifiers is in the range of about 100:1 to about 1:1000.
20. The method for separating emulsions of claim 18 wherein the concentration of said demulsifying-effective amount of the reaction products is from about 0.1 ppm to about 10,000 ppm.
21. The reaction products of claim 1 wherein said composition further comprises an additional demulsifier selected from the group consisting of organic or silicone demulsifiers or mixtures thereof wherein the weight ratio of the reaction products of claim 1 to the total amount of organic and silicone demulsifiers is in the range of about 100:1 to about 1:1000.
22. The method of reacting copolymer (a) and cross-linking agent (c) in claim 1 , followed by reaction with silicone hydride (b) in claim 1 .