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

Patent metadata

Field	Value
Publication number	US-11820850-B2
Application number	US-202117242948-A
Country	US
Kind code	B2
Filing date	Apr 28, 2021
Priority date	Aug 5, 2016
Publication date	Nov 21, 2023
Grant date	Nov 21, 2023

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

We claim:

1. A polymer composition 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; and (iii) a crosslinker;
(b) subjecting the first reactive composition to a first activation step using visible light consisting essentially of wavelengths above 420 nm 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 using light having a wavelength of 420 nm or below 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 polymer composition 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 polymer composition 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 polymer composition 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 polymer composition 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 polymer composition 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 polymer composition of claim 1 wherein the polymerization initiator is a bisacylphosphine oxide or a bis(acyl)phosphane oxide.

8. The polymer composition of claim 1 that is in the form of a hydrogel and wherein the first reactive composition contains silicone reactive components and the second reactive composition contains hydrophilic reactive components.

9. The polymer composition of claim 1 that is in the form of a hydrogel and wherein the first reactive composition contains hydrophilic reactive components and the second reactive composition contains silicone reactive components.

10. The polymer composition 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 polymer composition 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. A medical device comprising the polymer composition of claim 1 .

13. An ophthalmic device comprising the polymer composition of claim 1 .

14. The ophthalmic device of claim 13 selected from the group consisting of a contact lens, an intraocular lens, a punctal plug and an ocular insert.

15. A contact lens comprising a polymer composition, wherein the polymer composition is formed by the process of claim 1 .

16. The contact lens of claim 15 wherein the first reactive composition, the second reactive composition, or both the first reactive composition and the second reactive composition contain one or more additives selected from UV absorbers, photochromic compounds, pharmaceutical compounds, nutraceutical compounds, antimicrobial compounds, reactive tints, pigments, copolymerizable dyes, non-polymerizable dyes, release agents, wetting agents, and release agents.

17. A crosslinked substrate network containing a covalently bound activatable free radical initiator, wherein the crosslinked substrate network is 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; and (iii) a crosslinker; and
(b) subjecting the first reactive composition to a first activation step using visible light consisting essentially of wavelengths above 420 nm such that the first reactive composition polymerizes therein to form the crosslinked substrate network containing a covalently bound activatable free radical initiator.

18. A process for making a polymer composition, the 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 using visible light consisting essentially of wavelengths above 420 nm 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 using light having a wavelength of 420 nm or below such that the second reactive composition polymerizes therein with the crosslinked substrate network to form a grafted polymeric network and a byproduct polymer.

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

• C08F283/124 Primary

  on to polysiloxanes having carbon-to-carbon double bonds · CPC title

• C08F290/068

  Polysiloxanes · CPC title

• C08J7/16

  with polymerisable compounds · CPC title

• C08L51/085

  on to polysiloxanes · CPC title

• C09B69/109

  containing other specific dyes · CPC title