Polymer compositions containing grafted polymeric networks and processes for their preparation and use

Patent metadata

Field	Value
Publication number	US-2025263512-A1
Application number	US-202519186799-A
Country	US
Kind code	A1
Filing date	Apr 23, 2025
Priority date	Aug 5, 2016
Publication date	Aug 21, 2025
Grant date	—

Abstract

Provided are polymer compositions made by a process comprising: (a) providing a first reactive composition containing: (i) a polymerization initiator that is capable, upon a first activation, of forming two or more free radical groups, at least one of which is further activatable by subsequent activation; (ii) one or more ethylenically unsaturated compounds; and (iii) a crosslinker; (b) subjecting the first reactive composition to a first activation step such that the first reactive composition polymerizes therein to form a crosslinked substrate network containing a covalently bound activatable free radical initiator, (c) combining the crosslinked substrate network with a second reactive composition containing one or more ethylenically unsaturated compounds; and (d) activating the covalently bound activatable free radical initiator of the crosslinked substrate network such that the second reactive composition polymerizes therein with the crosslinked substrate network to form a grafted polymeric network and a byproduct polymer. Also provided are precursors to the polymer compositions, processes for preparation of the polymer compositions, and methods of using the polymer compositions, for instance in medical devices.

First claim

1 . A contact lens formed by a process comprising:
(a) providing a first reactive composition containing: (i) a polymerization initiator that is capable, upon a first activation, of forming two or more free radical groups, at least one of which is further activatable by subsequent activation; (ii) one or more ethylenically unsaturated compounds comprising a hydrophilic component and a silicone-containing component, the silicone-containing component having at least one reactive group and at least one siloxane group; and (iii) a crosslinker; (b) subjecting the first reactive composition to a first activation step such that the first reactive composition polymerizes therein to form a crosslinked substrate network containing a covalently bound activatable free radical initiator; (c) combining the crosslinked substrate network with a second reactive composition containing one or more ethylenically unsaturated compounds; and (d) activating the covalently bound activatable free radical initiator of the crosslinked substrate network such that the second reactive composition polymerizes therein with the crosslinked substrate network to form a grafted polymeric network and a byproduct polymer.

2 . The contact lens of claim 1 wherein step (d) is conducted in the presence of a crosslinker such that the byproduct polymer is covalently bound with the grafted polymeric network.

3 . The contact lens of claim 1 wherein step (d) is conducted in the substantial absence of a crosslinker such that at least a portion of the byproduct polymer is not covalently bound to the grafted polymeric network.

4 . The contact lens of claim 1 wherein the one or more ethylenically unsaturated compounds of step (a) comprise one or more reactive groups independently selected from: (meth)acrylate, (meth)acrylamide, styryl, vinyl, N-vinyl lactam, N-vinylamide, O-vinylether, O-vinylcarbonate, O-vinylcarbamate, C 2-12 alkenyl, C 2-12 alkenylphenyl, C 2-12 alkenylnaphthyl, and C 2-6 alkenylphenyl-C 1-6 alkyl.

5 . The contact lens of claim 1 wherein the one or more ethylenically unsaturated compounds of step (c) comprise one or more reactive groups independently selected from: (meth)acrylate, (meth)acrylamide, styryl, vinyl, N-vinyl lactam, N-vinylamide, O-vinylether, O-vinylcarbonate, O-vinylcarbamate, C 2-12 alkenyl, C 2-12 alkenylphenyl, C 2-12 alkenylnaphthyl, and C 2-6 alkenylphenyl-C 1-6 alkyl.

6 . The contact lens of claim 1 wherein the polymerization initiator is a bisacylphosphine oxide, a bisacylphosphane oxide, a di-azo compound, a di-peroxide compound, an azo-bis(monoacylphosphine oxide), an azo-bis(monoacylphosphane oxide), a peroxy-bis(monoacylphosphine oxide), a peroxy-bis(monoacylphosphane oxide), an azo-bis(alpha-hydroxy ketone), a peroxy-bis(alpha-hydroxy ketone), an azo-bis(1,2-diketone), a peroxy-bis(1,2-diketone), a germanium based compound, tert-butyl 7-methyl-7-(tert-butylazo) peroxyoctanoate, or combinations thereof.

7 . The contact lens of claim 1 wherein the polymerization initiator is a bisacylphosphine oxide or a bis(acyl)phosphane oxide.

8 - 9 . (canceled)

10 . The contact lens of claim 1 wherein the first reactive composition further comprises one or more of a polyamide, a UV-VIS absorber, a dye, a tint, a pigment, an antimicrobial, a pharmaceutical, and a nutraceutical.

11 . The contact lens of claim 1 wherein the second reactive composition further comprises one or more of a polyamide, a UV-VIS absorber, a dye, a tint, a pigment, an antimicrobial, a pharmaceutical, and a nutraceutical.

12 - 18 . (canceled)

19 . The contact lens of claim 1 wherein the first reactive composition contains an ethylenically unsaturated zwitterionic compound, N,N-dimethyl acrylamide (DMA), N-vinylpyrrolidone (NVP), 2-hydroxyethyl methacrylamide, polyethyleneglycol monomethacrylate, methacrylic acid, acrylic acid, 2-hydroxyethyl(meth)acrylate (HEMA), 3-hydroxypropyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2,3-dihydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 1-hydroxypropyl 2-(meth)acrylate, 2-hydroxy-2-methyl-propyl (meth)acrylate, 3-hydroxy-2,2-dimethyl-propyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxyethyl(meth)acrylamide, N-(2-hydroxypropyl) (meth)acrylamide, N,N-bis(2-hydroxyethyl) (meth)acrylamide, N,N-bis(2-hydroxypropyl) (meth)acrylamide, N-(3-hydroxypropyl) (meth)acrylamide, 2,3-dihydroxypropyl (meth)acrylamide, glycerol (meth)acrylate, polyethyleneglycol monomethacrylate, and mixtures thereof.

20 . The contact lens of claim 1 wherein the second reactive composition contains N,N-dimethylacrylamide (DMA), 2-hydroxyethyl(meth)acrylate, glycerol methacrylate, 2-hydroxyethyl methacrylamide, polyethyleneglycol monomethacrylate, methacrylic acid, acrylic acid, N-vinylpyrrolidone (NVP), N-vinyl methacrylamide, polyethylene glycol methyl ether methacrylate or an ethylenically unsaturated zwitterionic compound.

21 . The contact lens of claim 19 wherein the ethylenically unsaturated zwitterionic compound is 3-acrylamido-N-(2-carboxyethyl)-N,N-dimethylpropane-1-aminium; 3-((3-acrylamidopropyl)dimethylammonio)propane-1-sulfonate; 3-((3-methacrylamidopropyl) dimethylammonio)propane-1-sulfonate; 3,5-Dioxa-8-aza-4-phosphaundec-10-en-1-aminium, 4-hydroxy-N,N,N-trimethyl-9-oxo, inner salt, 4-oxide; 2-(acrylamidoethoxy)-(2-(trimethylammonio)ethyl) phosphate; 2-(methacrylamidoethoxy)-(2-(trimethylammonio)ethyl) phosphate; 2-(methacryloyloxy)ethyl(2-(trimethylammonio)ethyl) phosphate (MPC); or 2-(acryloyloxy)ethyl(2-(trimethylammonio)ethyl) phosphate.

22 . The contact lens of claim 20 wherein the ethylenically unsaturated zwitterionic compound is 3-acrylamido-N-(2-carboxyethyl)-N,N-dimethylpropane-1-aminium; 3-((3-acrylamidopropyl)dimethylammonio)propane-1-sulfonate; 3-((3-methacrylamidopropyl) dimethylammonio)propane-1-sulfonate; 3,5-Dioxa-8-aza-4-phosphaundec-10-en-1-aminium, 4-hydroxy-N,N,N-trimethyl-9-oxo, inner salt, 4-oxide; 2-(acrylamidoethoxy)-(2-(trimethylammonio)ethyl) phosphate; 2-(methacrylamidoethoxy)-(2-(trimethylammonio)ethyl) phosphate; 2-(methacryloyloxy)ethyl(2-(trimethylammonio)ethyl)phosphate (MPC); or 2-(acryloyloxy)ethyl(2-(trimethylammonio)ethyl) phosphate.

Assignees

• Johnson & Johnson Vision Care

Inventors

• Aitken Brian
• Scales Charles
• Joslin Scott
• Zhang Yong
• Sinha Dola
• Mahadevan Shivkumar
• Martin Patricia
• Lu Fang
• Duis Donnie
• Arnold Stephen C

Classifications

• G02B1/043

  Contact lenses · CPC title

• C09B69/109

  containing other specific dyes · CPC title

• C08L2203/02

  for biomedical use · CPC title

• C08L2201/50

  Aqueous dispersion, e.g. containing polymers with a glass transition temperature (Tg) above 20°C · CPC title

• C08L51/085

  on to polysiloxanes · CPC title