Monofunctional branched polysiloxanes, compositions and processes of preparing the same
View Patent ↗Branched monofunctional polysiloxanes are disclosed having the general formula: X-(D a )-(D b T c ), wherein X-(D a ) is a linear moiety and (D b T c ) is a branched moiety; X a substituted or unsubstituted, monovalent or divalent hydrocarbon having a functional group; R 5 and R 6 are independently halogenated or unhalogenated monovalent hydrocarbon or substituted or unsubstituted divalent hydrocarbon; T is (R 7 ) d SiO (4-d)/2 R 7 is a substituted or unsubstituted monovalent hydrocarbon; wherein the branched polysiloxane is end-capped by R 8 is a substituted or unsubstituted monovalent hydrocarbon; a is 1 to 300, b is 25 to 5000, c is 1 to 100, d is 0 or 1; and T c is randomly distributed in the branched polysiloxane. Additionally, processes for preparing such polysiloxanes, and coating compositions comprising the same is provided. A fuser member and substrate comprising a branched monofunctional polysiloxane of the above formula are also disclosed.
1. A branched polysiloxane having the general formula:
X-(D a )-(D b T c ),
wherein X-(D a ) is a linear moiety and (D b T C ) is a branched moiety
where X is a substituted or unsubstituted, monovalent or divalent C 1 to C 10 hydrocarbon having a functional group where the functional group comprises amino, mercapto, or carboxylic acid;
where D is
where R 5 and R 6 are independently halogenated or unhalogenated C 1 to C 10 monovalent hydrocarbon or substituted or unsubstituted C 1 to C 10 monovalent hydrocarbon;
where T is
(R 7 ) d SiO (4-d)/2
where R 7 is a substituted or unsubstituted monovalent C 1 to C 10 hydrocarbon;
wherein the branched polysiloxane is end-capped by
where R 8 is a monovalent C 1 to C 10 haloalkyl or an unsubstituted monovalent C 1 to C 10 hydrocarbon; and
wherein a is 1 to 300, b is 25 to 5000, c is 1 to 100, d is 0 or 1; and
T c is randomly distributed in the branched polysiloxane.
2. The branched polysiloxane of claim 1 , wherein X comprises amino.
3. The branched polysiloxane of claim 2 , wherein X is
(R 1 ) 2 N—R 2 —(NR 3 R 4 ) n —
where R 1 is hydrogen or monovalent C 1 to C 10 hydrocarbon; R 2 is a substituted or unsubstituted divalent C 1 to C 10 hydrocarbon; R 3 is hydrogen or monovalent C 1 to C 8 hydrocarbon; R 4 is a divalent substituted or unsubstituted C 1 to C 10 hydrocarbon; and n is 0 to 5.
4. The branched polysiloxane of claim 1 , wherein the branched polysiloxane has a mole ratio of functional group:Si atom range from about 1:5400 to 1:28.
5. The branched polysiloxane of claim 4 , wherein the branched polysiloxane has a mole ratio of functional group:Si atom range from about 1:2000 to 1:60.
6. The branched polysiloxane of claim 4 , wherein the branched polysiloxane has a viscosity from about 10 to about 200,000 cSt at 25° C.
7. The branched polysiloxane of claim 6 , wherein the branched polysiloxane has a viscosity from about 200 to about 60,000 cSt at 25° C.
8. The branched polysiloxane of claim 6 , wherein the branched polysiloxane has a weight average molecular weight range from about 800,000 to about 2,100 Daltons.
9. The branched polysiloxane of claim 8 , wherein the branched polysiloxane has a weight average molecular weight range from about 150,000 to about 9,000 Daltons.
10. The branched polysiloxane of claim 8 , wherein the branched polysiloxane comprises a branched dimethylsiloxane, diphenylsiloxane, methyl-3,3,3-trifluoropropylsiloxane, diphenyl(dimethyl)siloxane, methylphenylsiloxane, or copolymers thereof.
11. The branched polysiloxane of claim 10 , wherein the branched polysiloxane comprises a branched dimethylsiloxane.
12. A branched polysiloxane having the formula:
wherein p is 25 to 5000; q is 1 to 100; p+q is at least 27; R 1 is hydrogen or monovalent C 1 to C 10 hydrocarbon; R 2 is a substituted or unsubstituted divalent C 1 to C 10 hydrocarbon; R 3 is hydrogen or monovalent C 1 to C 8 hydrocarbon; R 4 is a substituted or unsubstituted divalent C 1 to C 8 hydrocarbon; R 5 , R 6 , R 7 and R 8 are independently monovalent C 1 to C 10 hydrocarbon; n is 0 to 5; m is 1 to 100; d is 0 or 1; and y is sufficient to endcap the polysiloxane chain.
13. The branched polysiloxane of claim 12 , wherein the branched polysiloxane has the formula:
wherein p is 25 to 5000; q is 1 to 100; p+q+r is at least 27; R 1 is hydrogen or monovalent C 1 to C 10 hydrocarbon; R 2 is a substituted or unsubstituted divalent C 1 to C 10 hydrocarbon; R 3 is hydrogen or monovalent C 1 to C 8 hydrocarbon; R 4 is a substituted or unsubstituted divalent C 1 to C 8 hydrocarbon; R 5 , R 6 , R 7 and R 8 are independently monovalent C 1 to C 10 hydrocarbon; n is 0 to 5; m is 1 to 100; and r is 0 to 100.
14. The branched polysiloxane of claim 13 , wherein the branched polysiloxane has the formula:
wherein p is 50 to 2000; q is 1 to 20; p +q is at least 52; R 1 is hydrogen or monovalent C 1 to C 10 hydrocarbon; R 2 is a substituted or unsubstituted divalent C 1 to C 10 hydrocarbon; R 3 is hydrogen or monovalent C 1 to C 8 hydrocarbon; R 4 is a substituted or unsubstituted divalent C 1 to C 8 hydrocarbon; R 5 , R 6 , R 7 and R 8 are independently monovalent C 1 to C 10 hydrocarbon; n is 0 to 1; and m is 1 to 100.
15. The branched polysiloxane of claim 14 , wherein the branched polysiloxane has the formula:
wherein p is 50 to 300; q is 2 to 20; p+q is at least 52; R 1 is hydrogen or monovalent C 1 to C 10 hydrocarbon; R 2 is a substituted or unsubstituted divalent C 1 to C 10 hydrocarbon; R 3 is hydrogen or monovalent C 1 to C 8 hydrocarbon; R 4 is a substituted or unsubstituted divalent C 1 to C 8 hydrocarbon; R 5 , R 6 , R 7 and R 8 are independently monovalent C 1 to C 10 hydrocarbon; n is 0; and m is 1 to 50.
16. A branched polysiloxane having the formula:
wherein R 3 is hydrogen or monovalent C 1 to C 8 hydrocarbon;
wherein R 5 , R 6 , and R 8 are independently monovalent C 1 to C 10 hydrocarbon; and
wherein n is 0 to 5; m is 1 to 100; p is 25 to 2000; r is 1.1 to 1.001; and q is 2 to 100 or sufficient to endcap the polysiloxane chain.
17. The branched polysiloxane of claim 16 , wherein the branched polysiloxane has the formula:
wherein R 3 is hydrogen or monovalent C 1 to C 8 hydrocarbon;
wherein R 5 , R 6 , and R 7 are independently monovalent C 1 to C 10 hydrocarbon; and
wherein n is 0 to 1; m is 1 to 50; p is 50 to 3000; r is 1.1 to 1.001; and q is 2 to 20.
18. A branched polysiloxane which is a copolymer having the formula:
wherein R 3 is hydrogen or monovalent C 1 to C 8 hydrocarbon;
wherein R 5 , R 6 , R 7 , R 8 are independently monovalent C 1 to C 10 hydrocarbon; and
wherein n is 0 to 5; m is 1 to 100; p is 25 to 2000; and q is 1 to 100.
19. The branched polysiloxane of claim 18 , wherein the branched polysiloxane is a copolymer having the formula:
wherein R 3 is hydrogen or monovalent C 1 to C 8 hydrocarbon;
wherein R 5 , R 6 , R 7 , R 8 are independently monovalent C 1 to C 10 hydrocarbon; and
wherein n is 0 to 1; m is 1 to 50; p is 50 to 300; and q is 2 to 20.
20. A branched polysiloxane which is a copolymer having the formula:
wherein m is 1 to 100, p is 50 to 2000, q is 1 to 50, and p+q is at least 51.
21. The branched polysiloxane of claim 20 , wherein the branched polysiloxane is a copolymer having the formula:
wherein m is 1 to 50, p is 50 to 300, q is 2 to 20, and p+q is at least 52.
22. A branched polysiloxane having the general formula:
X(D a )-(D b T c ),
wherein X-(D a ) is a linear moiety and (D b T C ) is a branched moiety
where X is a substituted or unsubstituted, monovalent or divalent C 1 to C 10 hydrocarbon having a functional group where the functional group comprises amino, mercapto, or carboxylic acid;
where D is
where R 5 and R 6 are independently halogenated or unhalogenated C 1 to C 10 monovalent hydrocarbon or substituted or unsubstituted C 1 to C 10 monovalent hydrocarbon;
where T is
(R 7 ) d SiO (4-d)/2
where R 7 is a substituted or unsubstituted monovalent C 1 to C 10 hydrocarbon;
wherein the branched polysiloxane is end-capped by
where R 8 is a substituted or unsubstituted monovalent C 1 to C 10 hydrocarbon; and
wherein a is 1 to 300, b is 25 to 5000, c is 1 to 100, d is 0 or 1; and
T c is randomly distributed in the branched polysiloxane; and
wherein the branched polysiloxane has a mole ratio of functional group:Si atom range from about 1:5400 to 1:28, a viscosity from about 10 to about 200,000 cSt at 25° C., a weight average molecular weight range from about 800,000 to about 2,100 Daltons, and a thermal stability of at least about 120° C.
23. The branched polysiloxane of claim 22 , wherein the branched polysiloxane has a thermal stability of at least about 150° C.
24. The branched polysiloxane of claim 1 , wherein the branched polysiloxane has a viscosity from about 200 to about 60,000 cSt, a weight average molecular weight range from about 150,000 to about 9,000 Daltons, a mole ratio of functional group:Si atom range from about 1:2000 to 1:60;
wherein the branched polysiloxane is dimethylsiloxane; and
wherein the functional group is amino.
25. A fuser member comprising a (a) substrate; (b) fluoropolymer; and (c) polymeric release agent wherein the polymeric release agent comprises at least one branched polysiloxane having the formula:
X-(D a )-(D b T c ),
wherein X-(D a ) is a linear moiety and (D b T c ) is a branched moiety
where X is a substituted or unsubstituted, monovalent or divalent C 1 to C 10 hydrocarbon having a functional group where the functional group comprises amino, hydroxyl, mercapto, carboxylic acid or anhydride, carboxyl, phenol or silane;
where D is
where R 5 and R 6 are independently halogenated or unhalogenated C 1 to C 10 monovalent hydrocarbon or substituted or unsubstituted C 1 to C 10 monovalent hydrocarbon;
where T is
(R 7 ) d SiO (4-d)/2
where R 7 is a substituted or unsubstituted monovalent C 1 to C 10 hydrocarbon;
wherein the branched polysiloxane is end-capped by
where R 8 is a monovalent C 1 to C 10 haloalkyl or an unsubstituted monovalent C 1 to C 10 hydrocarbon;
wherein a is 1 to 300, b is 25 to 5000, c is 2 to 100, d is 0 or 1; and
wherein T c is randomly distributed in the branched polysiloxane.
26. The fuser member of claim 25 , wherein X comprises mercapto, amino or carboxylic acid.
27. The fuser member of claim 26 , wherein X comprises amino.
28. The fuser member of claim 25 , wherein the fluoropolymer comprises a fluoroelastomer or a fluorocarbon resin.
29. The fuser member of claim 28 , wherein the fluoroelastomer comprises a copolymer of vinylidene fluoride with hexafluoropropylene, copolymer of vinylidene fluoride with tetrafluoroethylene and hexafluoropropylene, copolymer of perfluoroalkylvinylether with tetrafluoroethylene, copolymer of ethylene perfluoroalkylvinylether with tetrafluoroethylene, or mixtures thereof.
30. The fuser member of claim 29 , wherein the vinylidene fluoride is present in the fluoroelastomer at a concentration from about 30 to about 90 mole percent.
31. The fuser member of claim 29 , wherein the hexafluoropropylene is present in the fluoroelastomer at a concentration from about 10 to about 60 mole percent.
32. The fuser member of claim 29 , wherein the tetrafluoroethylene is present in the fluoroelastomer at a concentration from about 0 to about 50 mole percent.
33. The fuser member of claim 28 , wherein the fluoroelastomer further comprises a filler.
34. The fuser member of claim 33 , wherein the filler is a metal, metal alloy, metal oxide, metal salt, silicon carbide, boron nitride, graphite or silicon dioxide.
35. The fuser member of claim 34 , wherein the metal oxide comprises aluminum oxide, iron oxide, tin oxide, copper oxide, zinc oxide or silicon oxide.
36. The fuser member of claim 35 , wherein the filler is present in a concentration range from about 0% by volume to about 40% by volume based on the weight of the fluoroelastomer.
37. The fuser member of claim 36 , wherein the filler is present in a concentration range from about 1% by volume to about 35% by volume based on the weight of the fluoroelastomer.
38. A fuser member comprising (a) a substrate; (b) fluoropolymer; and (c) polymeric release agent wherein the polymeric release agent comprises at least one branched polysiloxane having the formula:
X-(D a )-(D b T c ),
wherein X-(D a ) is a linear moiety and (D b T c ) is a branched moiety
where X is
(R 1 ) 2 N—R 2 —(NR 3 R 4 ) n —
where R 1 is hydrogen or monovalent C 1 to C 10 hydrocarbon; R 2 is a substituted or unsubstituted divalent C 1 to C 10 hydrocarbon; R 3 is hydrogen or monovalent C 1 to C 8 hydrocarbon; R 4 is a substituted or unsubstituted divalent C 1 to C 10 hydrocarbon; and n is 0 to 5;
where D is
where R 5 and R 6 are independently halogenated or unhalogenated C 1 to C 10 monovalent hydrocarbon or substituted or unsubstituted C 1 to C 10 monovalent hydrocarbon;
where T is
(R 7 ) d SiO (4-d)/2
where R 7 is a substituted or unsubstituted monovalent C 1 to C 10 hydrocarbon;
wherein the branched polysiloxane is end-capped by
where R 8 is a substituted or unsubstituted monovalent C 1 to C 10 hydrocarbon;
wherein a is 1 to 300, b is 25 to 5000, c is 2 to 100, d is 0 or 1; and
wherein T c is randomly distributed in the branched polysiloxane.