Organo-modified silicone polymers
View Patent ↗A linear silicone polymer suitable for use in producing homopolymers, copolymers, polymerized emulsions, latex compositions, and hydrogel polymer films. In one aspect, a hydrophilic silicone monomer is of the Formula 1: W A m B n W (1) Where, A is a divalent block comprising a silicone-containing pendant group. In one embodiment, the silicone-containing pendant group comprises polyalkylene oxide groups. The structure of the polymer can be controlled and tuned to provide a material with excellent wettability and oxygen permeability. The polymers are suitable for use in a variety of applications including in providing a film for forming contact lenses.
1. A linear polymer of the formula:
W A m B n W
where m is a positive integer from 2-100, and n is a positive integer from 0-100; A is a divalent block having a general formula:
where, R 1 , R 2 , and R 3 are independently hydrogen and a monovalent radical with 1 to 50 carbon atoms optionally containing one or more heteroatoms; E is a mono-valent group having a general structure of F-L-G, where F is a divalent linkage which is an alkyl, an ester, an ether, an amine, an amide, a carbonate, and a carbamate; L is a divalent moiety which is a substituted, unsubstituted, linear, branched, cyclic aliphatic hydrocarbon or an aromatic hydrocarbon of 1-100 carbon atom optionally containing one or more heteroatoms; and G is a siloxane unit having the general structure M 1 a M 2 b D 1 c D 2 d T 1 e T 2 f Q g where M 1 =R 5 R 6 R 7 SiZ 1/2 , M 2 =R 8 R 9 R 10 SiZ 1/2 , D 1 =R 11 R 12 SiZ 2/2 , D 2 =R 13 R 14 SiZ 2/2 , T 1 =R 15 SiZ 3/2 , T 2 =R 16 SiZ 3/2 , Q=SiZ 4/2 ; R 5 , R 6 , R 7 , R 9 , R 10 , R 11 , R 12 , R 14 , and R 15 are independently a monovalent hydrocarbon radical having 1 to about 50 carbon atoms optionally containing one or more heteroatoms; R 8 , R 13 , and R 16 are independently a divalent residue of a non-isomerizable hydrosilylation effective terminal olefin with the general structure:
where R 18 , R 19 , and R 20 are independently hydrogen and a hydrocarbon radical with 1 to 10 carbon atoms optionally containing one or more heteroatoms, the integer q is 0 to 10 and R 17 is a hydrocarbon radical with 1 to 5 carbon atoms or a hydrogen atom such that R 17 is hydrogen when q=0 and L is a cyclic residue; a, c, e, and g are zero or a positive integer such that 0<a+b+c+d+e+f+g<500; subscripts b, d, and f have values of 0 or 1 such that b+d+f=1; and Z is O or a CH 2 group subject to the limitation that the molecule contains an even number of O 1/2 and an even number of (CH 2 ) 1/2 groups, and the O 1/2 and the (CH 2 ) 1/2 groups both are all paired in the molecule;
B is a divalent radical having general formula:
where R 25 , R 26 , R 27 , and R 28 are independently selected from the group consisting of hydrogen, a halogen, hydroxyl, a hydrocarbon radical comprising aromatic, aliphatic, and/or aralkyl moieties optionally having one or more heteroatoms; W is X or Y where X stands for reactive group and Y stands for chain stopper group, wherein:
X is a free radical polymerizable group having the general formula:
where R 21 , R 22 , and R 23 are hydrogen or a monovalent hydrocarbon radical with 1 to 5 carbon atoms, optionally containing one or more heteroatoms; H is O or NR 24 , where R 24 is hydrogen or a monovalent hydrocarbon radical with 1-5 carbons; J is a divalent moiety which is a substituted or unsubstituted aliphatic or aromatic hydrocarbon having of 1-10 carbon atoms optionally containing a heteroatom; and
Y can be independently selected from the group consisting of hydrogen, hydroxyl, thiol, amine, or a monovalent hydrocarbon radical having 1 to 10 carbon atoms, optionally containing one or more heteroatoms.
2. The polymer of claim 1 , wherein L is a polyalkyleneoxide residue.
3. The polymer of claim 1 , wherein L is a polyalkyleneoxide which is —CH 2 CH 2 O—, —CH 2 CH(CH 3 )O—, —CH 2 CH 2 CH 2 O—, or their analogues with up to 6 carbon atoms.
4. The polymer of claim 1 , wherein L is a cyclic hydrocarbon residue with the structure:
5. The polymer of claim 1 , wherein R 9 , R 10 , R 11 , R 13 , R 14 , R 15 , R 16 , R 18 , and R 20 in the unit G of group E are independently a hydrocarbon radical selected from the group consisting of methyl, ethyl, propyl, iso-propyl, butyl, isobutyl, phenyl, naphthyl, and aralkyl radical with 8 to 20 carbon atoms, trifluoromethylpropyl, and combinations of two or more thereof.
6. The polymer of claim 1 , wherein the mono-functional group E has a structure which is of the formula:
where, a is 0-50 and m is 0-50, K═O or NH
where, a+b is 0-50 and m is 0-50, K═O or NH
where, a+b+c is 0-100 and m is 0-50, K═O or NH
where, a is 1-50 and m is 0-50, K═O or NH
where m is 0-50, K═O or NH
where K is O or NH, R is —CH 3 or —(OSi(CH 3 ) 2 ) n , b is 0-100, and n+b is 0-100; or
where K is O or NH, and a is 0-100.
7. The polymer of claim 1 , where R 25 and R 26 are hydrogen, R 27 is hydrogen or a methyl radical, and R 28 is a part of an ethylenically-unsaturated hydrophilic monomer or a hydrophobic monomer.
8. The polymer of claim 1 having at least one W which is an X group to yield a pre-polymer.
9. The polymer of claim 1 , wherein both the W groups are a Y group as a chain stopper to yield a non-reactive polymer.
10. A homo or co-polymer comprising at least one pre-polymer of claim 8 .
11. The copolymer of claim 10 , wherein the polymer is a copolymer further comprising a free-radical polymerizable organic monomer chosen from the group consisting of a vinylic monomer, an acrylide monomer, an acrylic monomer, or a combination of two or more thereof.
12. The copolymer of claim 11 , wherein the vinylic monomer is selected from the group consisting of 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.
13. The copolymer of claim 11 , wherein the acrylic monomers are selected from the group consisting of 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-silicones, or combinations of two or more thereof.
14. The polymer according to claim 10 where the polymer is a hydrogel film.
15. A film forming additive comprising the polymer of claim 10 in the form of emulsion or latex.
16. The siloxane of claim 1 , wherein the polymer is a film forming additive in a textile, a paper, a leather, a personal care, a health care, a home care, a coating, a painting, or a seed treatment formulation.