Granted Patent B2

US 9,296,764 · App. 14/102,025 · Granted Mar 29, 2016

Abstract

Claims (105)

1. A composition comprising an alpha, beta-unsaturated organosilicon compound having the structure of Formula (1):

wherein:

X 1 is independently selected from linear or branched alkyl group containing 1-16 carbon atoms, trimethoxy silyl, trimethylsilyloxy, —O[Si(CH 3 ) 2 O—] n wherein n is an integer chosen from 1 to 9, (CH 3 ) 3 Si(CH 2 ) o CH 2 — wherein o is an integer from 0-3, (CH 3 ) 3 SiCH 2 CH 2 Si(CH 3 ) 2 O—, or (CH 3 ) 3 Si(CH 2 CH 2 Si(CH 3 ) 2 O) q wherein q is an integer chosen from 0-200; and, if X 1 is a monovalent radical, p is 0;

X 2 is independently selected from linear or branched alkyl group containing 1-16 carbon atoms, trimethoxy silyl, trimethylsilyloxy, —O[Si(CH 3 ) 2 O—] n wherein n is an integer chosen from 1 to 9, (CH 3 ) 3 Si(CH 2 ) o CH 2 — wherein o is an integer from 0-3, (CH 3 ) 3 SiCH 2 CH 2 Si(CH 3 ) 2 O—, or (CH 3 ) 3 Si(CH 2 CH 2 Si(CH 3 ) 2 O) q — wherein q is an integer chosen from 0-200, or —[OSi(CH 3 ) 2 ] m G 1 , wherein G 1 is (CH 3 ) 3 SiO—, or a reactive or non reactive silicone group with the general Formula (2a) or (2b):

where l is an integer chosen from 0-200; and p in Formula 1 is 0 when X 2 is of the Formula (2a), Formula (2b), or a monovalent radical;

X 6 , X 7 , and X 8 are independently chosen from a linear or branched alkyl group containing 1-16 carbon atoms, alkoxy, trimethylsilyloxy, or —O[Si(CH 3 ) 2 O—] n , wherein n is an integer chosen from 1 to 9, and wherein X 6 and X 7 , X 7 and X 8 , or X 6 and X 8 may form a ring;

X 3 and X 5 are independently chosen from methyl, butyl, trimethylsiloxy, (CH 3 ) 3 SiCH 2 CH 2 —, (CH 3 ) 3 SiCH 2 CH 2 Si(CH 3 ) 2 O— or —OSi(CH 3 ) 2 —, with the provisos that (i) when X 1 or X 6 is —O[Si(CH 3 ) 2 O—] n , then at least one of X 3 or X 5 is —OSi(CH 3 ) 2 — and X 1 forms a chemical bond with the X 3 and/or X 5 forms a chemical bond with X 6 to correspondingly form a divalent —X 1 -X 3 — or X 5 —X 6 — group, which is bonded to the silicon atom to form a cyclic polysiloxane ring, and (ii) when X 3 and/or X 5 is —O[Si(CH 3 ) 2 O—] n then X 1 and/or X 6 is —OSi(CH 3 ) 2 — and the corresponding X 1 forms a chemical bond with the X 3 and/or X 5 forms a chemical bond with X 6 to form a divalent —X 1 -X 3 — or X 5 -X 6 — group, which is bonded to the silicon atom to form a cyclic polysiloxane ring; or

X 1 , X 2 , and X 3 optionally are each —O[Si(R 16 )O 3/2 —] n and interconnected to form a polysilsequioxane ring as described in formula (2c)

wherein R 16 is independently chosen from a linear or branched alkyl or aralkyl group;

X 4 is an optional connecting group selected independently from dimethylsiloxy, —O[Si(CH 3 ) 2 O—], or —CH 2 CH 2 (CH 3 ) 2 SiO—,

p is an integer chosen from 0-5;

R 1 is chosen from a chemical bond or an alkylene group containing from 1 to 16 carbon atoms and optionally containing a heteroatom of oxygen, sulfur and/or nitrogen;

G is a bridging unit between the siloxane moiety and reactive moiety independently selected from a linear or branched alkyl group or a carbocyclic group, the G unit optionally containing one or more heteroatoms;

A is a heteroatom;

I is a hydrophilic moiety with 0-100 carbon atoms which may contain heteroatoms;

Z is a polymerizable group of Formula (3):

wherein R 6 , R 7 , and R 8 are independently selected from hydrogen or monovalent hydrocarbon radical with 1-5 carbon atoms; and

F is an optional linker group chosen from aliphatic, cycloaliphatic, or aromatic hydrocarbon radical of 1 to about 16 carbons and optionally contains heteroatoms, with the proviso that if F is not utilized, then A is directly linked to the carbonyl group in Formula (3).

2. The composition of claim 1 , wherein G is a branched alkyl moiety with the general formula (4a)

wherein a is 0-16 and b is 1.

3. The composition of claim 1 , wherein G comprises a saturated carbocyclic unit comprising 5 to 10 carbon atoms, having the general formula:

wherein c=0-5.

4. The composition of claim 3 , wherein G is chosen from a positional isomer of the formula:

or a combination of two or more thereof.

5. The composition of claim 3 , wherein G is chosen from:

or a combination of two or more thereof.

6. The composition of claim 1 , wherein R 1 is a divalent radical having a structure of Formula (5):

wherein R 3 , R 4 , and R 5 are independently selected from hydrogen, a linear, branched and/or cyclic hydrocarbon radical with 1 to 10 carbon atoms, and one or more of optionally contains heteroatoms; a R 2 is a hydrocarbon radical with 1 to 5 carbon atoms; and q is an integer chosen from 0 to 10.

7. The composition of claim 1 , wherein I is a hydrophilic moiety having a structure of Formula (6):

—K-L-M  (6)

wherein:

K is a divalent heteroatom or an oxygen;

L is chosen from a divalent hydrocarbon radical chosen from a substituted or unsubstituted, linear or branched, aliphatic or aromatic hydrocarbon comprising 50 or fewer carbon atoms, which optionally contain heteroatoms and has a functionality chosen from an alcohol, an ether, an ester, an amide, an amine, a urea, a urethane, a cyano, a carbonate, a carbamate, a thiol, a thioether, thiol ester, or a combination of two or more thereof; and

M is an ionic group chosen from —COOR, —NR 2 , —PO(OR) 2 , —OPO(OR) 2 , —OSO 3 H, —OH, where R is hydrogen or an alkyl group of from 1 to 3 carbon atoms, with the proviso that when L is a functionality that does not contain any carbon atoms then M cannot comprise any —NR 2 , —OPO(OR) 2 , —OSO 3 H, or —OH groups.

8. The composition of claim 1 , wherein F on the polymerizable group Z has a structure of the Formula (7):

wherein:

r is an integer selected from 0 to about 15;

S is a divalent heteroatom independently selected from O, CH 2 , NR 11 , and sulfur;

J is independently selected from a functional group chosen from —C(O)—, —NR 12 C(O)—, —OC(O)—, —OS(O)—, and —P(O)OR 13 —;

R 9 and R 10 are independently chosen from a hydrocarbon radical with 1 to 5 carbon atoms; and

R 11 , R 12 , and R 13 are independently selected from hydrogen or a monovalent hydrocarbon radical with 1-5 carbon atoms.

9. The composition of claim 1 , wherein the alpha, beta-unsaturated compound has a structure of the formula:

wherein:

x and y are each integers chosen from 0-100;

X is independently chosen from linear or branched alkyl group containing 1-16 carbon atoms, alkoxy, trimethoxysilyl, trimethylsilyloxy, (CH3)3Si[OSi(CH3)2] q O— wherein q is an integer chosen from 0-100;

R 1 , R 6 , R 7 , R 8 , R 16 are independently chosen from a linear or branched alkyl or aralkyl;

G is chosen from a structure of the formula:

wherein a is 0-16 and b is 1

I is independently chosen from the following structures:

R 14 and R 15 are independently chosen from a hydrogen, linear or branched alkyl, aralkyl, or aromatic units with 1-20 carbon atoms, an alkali or alkaline earth metal anions, or a transition metal complex;

X— is independently selected from a halide, a carboxylate, a tosylate, a sulfonate, a phosphate, a phthalate, a phenolate, or an alkoxide, and;

t is an integer chosen from 1-16; and

A is an oxygen atom.

10. The composition of claim 1 , wherein the alpha, beta-unsaturated compound has a structure of the formula:

wherein:

m is an integer chosen from 0-200;

R 1 , R 6 , R 7 , R 8 are independently chosen from a linear or branched alkyl or aralkyl;

G is chosen from the following structures:

wherein a is 0-16 and b is 1

I is independently chosen from the following structures:

R 14 and R 15 are independently selected from hydrogen; a linear or branched alkyl, aralkyl, or aromatic linear or branched units with 1-20 carbon atoms, an alkali or alkaline earth metal anion or a transition metal complex;

X— is independently selected from a halide, a carboxylate, a tosylate, a sulfonate, a phosphate, a phthalate, a phenolate, and an alkoxide;

t is an integer chosen from 1-16;

A is an oxygen atom.

11. The composition of claim 1 , wherein the alpha, beta-unsaturated compound has a structure of the formula:

wherein:

n is an integer chosen from 0-200;

R 1 , R 6 , R 7 , R 8 are independently selected from a linear or branched alkyl or aralkyl;

G is chosen from the following structures:

wherein a is 0-16 and b is 1

I is independently chosen from the following structures:

R 14 and R 15 are independently chosen from hydrogen; a linear alkyl, aralkyl, or aromatic linear or branched units with 1-20 carbon atoms, an alkali or alkaline earth metal anion and/or a transition metal complex;

X— is independently selected from a halide, a carboxylate, a tosylate, a sulfonate, a phosphate, a phthalate, a phenolate, and an alkoxide;

t is an integer chosen from 1-16; and

A is an oxygen atom.

12. The composition of claim 1 , wherein the alpha, beta-unsaturated compound has a structure of the formula:

wherein:

R 1 , R 6 , R 7 , R 8 , R 16 are independently chosen from a linear or branched alkyl or aralkyl;

G is chosen from the following structures:

wherein a is 0-16 and b is 1

I is independently chosen from the following structures:

R 14 and R 15 are independently chosen from hydrogen; a linear or branched alkyl, aralkyl, or aromatic unit with 1-20 carbon atoms, an alkali or alkaline earth metal anion or a transition metal complex;

X— is independently selected from a halide, a carboxylate, a tosylate, a sulfonate, a phosphate, a phthalate, a phenolate, or an alkoxide;

t is an integer chosen from 1-16; and

A is an oxygen atom.

13. The composition of claim 1 , wherein the composition is a copolymer comprising the organosilicon compound.

14. The composition of claim 13 , wherein the copolymer is reactive or non-reactive.

15. The composition of claim 14 , wherein the copolymer is a prepolymer.

16. The composition of claim 15 , wherein the prepolymer is monofunctional or multifunctional.

17. The composition of claim 16 , wherein the prepolymer is a (meth)acrylated reaction product of (1) the organosilicon compound, (2) a chain transfer agent, (3) one or more organic monomers, and (4) a radical initiator.

18. The composition of claim 17 , wherein the chain transfer agent is chosen from 2-mercapto ethanol, 2-aminoethyl mercaptans, alkane thiols, thioglycolic acid and esters, bromotricloromethane, 3-mercaptopropionic acid and esters, isooctyl 3-mercaptopropionate, Pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate), trimethylolpropane tris(3-mercaptopropionate), 4,4′-thiobisbenzenethiol, iodonitriles, etc.

19. The composition of claim 1 , wherein the composition is a hydrogel.

20. The composition of claim 19 , further comprising a free-radical polymerizable organic monomer, an initiator, and optionally a crosslinker.

21. The composition of claim 20 , wherein the free-radical polymerizable organic monomer is chosen from a vinylic monomer, an acrylide monomer, an acrylic monomer, or a combination of two or more thereof.

22. The composition of claim 21 , wherein the vinylic monomer is chosen from N-vinyl-pyrrolidone, N-vinyl-caprolactam, N-vinyl-acetamide, N-vinyl-formamide, N-vinyl-isopropylamide, vinyl benzene, vinyl naphthalene, vinyl pyridine, vinyl alcohol, vinyl containing silicone, or a combination of two or more thereof.

23. The composition of claim 21 , wherein the acrylic monomer is chosen from 2-hydroxy-ethyl-methacrylate (HEMA), 2-hydroxy-ethyl-acrylate (HEA), hydroxyl propyl methacrylate, trimethylammonium 2-hydroxy propyl methacrylate hydrochloride, dimethylaminoethyl methacrylate, glycerol methacrylate, N,N-dimethylacrylamide, N-isopropylacrylamide, acrylamide, methacrylamide, acrylic acid, methacrylic acid, acrylated hydrophilic or hydrophobic organo-silicone, or a combination of two or more thereof.

24. The composition of claim 19 , wherein a hydrophilic silicone macromer is present in an amount of from about 5 weight percent to about 50 weight percent of the hydrogel composition.

25. The composition of claim 24 , wherein the ratio of a hydrophilic silicone macromer to a free-radical polymerizable organic monomer is from about 1:100 to about 100:1.

26. The composition of claim 24 , wherein the ratio of a hydrophilic silicone macromer to a free-radical polymerizable organic monomer is from about 1:50 to about 50:1.

27. The l composition of claim 24 , wherein the ratio of a hydrophilic silicone macromer to a free-radical polymerizable organic monomer is from about 1:10 to about 10:1.

28. The composition of claim 24 , wherein the ratio of a hydrophilic silicone macromer to a free-radical polymerizable organic monomer is about 1:1.

29. The composition of claim 19 , optionally comprising a cross-linker chosen from ethylene glycol dimethacrylate, trimethyloylpropane trimethacrylate, diethyleneglycol dimethacrylate, bisphenol A dimethacrylate, diglycidyl bisphenol A dimethacrylate, dimethacrylate-terminated polyethylene glycol, a reactive linear or pendant polyether modified silicone, or a combination of two or more thereof.

30. The composition of claim 19 , wherein the composition comprises a thermal or a photo initiator chosen from 2,2′-azobis(2,4-dimethylpentanenitrile), 2,2′-azobis(2-methylpropanenitrile), 2,2′-azobis(2-methylbutanenitrile), peroxides such as benzoyl peroxide, benzoin methyl ether, diethoxyacetophenone, a benzoylphosphine oxide, 2-hydroxy-2-methyl propiophenone (HMPP), 1-hydroxycyclohexyl phenyl ketone, a Darocur type, an Irgacure type, or a combination of two or more thereof.

31. A contact lens comprising a hydrogel film formed from the composition of claim 19 .

32. The composition according to claim 19 , wherein the composition is a film forming additive in a textile, paper, leather, personal care, health care, home care, coating, painting or seed treatment formulations.

Assignments (24)