Tri-block prepolymers and their use in silicone hydrogels

Patent metadata

Field	Value
Publication number	US-10676575-B2
Application number	US-201715691829-A
Country	US
Kind code	B2
Filing date	Aug 31, 2017
Priority date	Oct 6, 2016
Publication date	Jun 9, 2020
Grant date	Jun 9, 2020

Abstract

Described is a tri-block prepolymer having a chemical structure of [A]-[B]-[C], comprising at least one monovalent reactive group, wherein segment [A] and [C] independently comprise polymeric segments based on a first hydrophilic monomer comprising functionality selected from the group consisting of hydroxyalkyl, alkylamine, and mixtures thereof and optionally a second hydrophilic monomer, and [B] comprises a polymeric segment of at least one silicone-containing macromer and optionally a third hydrophilic monomer comprising functionality selected from the group consisting of hydroxyalkyl, alkylamine, and mixtures thereof and optionally a silicone-containing monomer. These prepolymers may be used alone or in combination with other components in reactive monomer mixtures for making silicone hydrogels and ophthalmic devices made therefrom, including contact lenses.

First claim

What is claimed is:

1. A tri-block prepolymer for making biomedical devices comprising formula
[A]-[B]-[C], wherein
[A] and [C] are independently polymeric segments formed from a first hydrophilic monomer comprising functionality selected from the group consisting of hydroxyalkyl, aminoalkyl, and mixtures thereof and optionally one or more second hydrophilic monomers; and
[B] is a polymeric segment formed from a silicone-containing macromer; optionally a third hydrophilic monomer comprising functionality selected from the group consisting of hydroxyalkyl, aminoalkyl, and mixtures thereof; and optionally a silicone-containing monomer; and
wherein said tri-block prepolymer comprises at least one monovalent reactive group,

and wherein the tri-block prepolymer is formed using an organotellurium mediated living radical polymerization (TERP) mediator.

2. The tri-block prepolymer of claim 1 , wherein the at least one monovalent reactive group is an end group.

3. The tri-block prepolymer of claim 1 comprising a plurality of monovalent reactive groups comprising a monovalent reactive end group and one or more monovalent reactive pendant groups.

4. The tri-block prepolymer of claim 3 , wherein the monovalent reactive group content is in the range of about 1 to about 25 mole percent of pre-acylated hydroxyalkyl or aminoalkyl content.

5. The tri-block prepolymer of claim 4 , wherein the monovalent reactive pendant group content is in the range of about 1 to about 10 mole percent.

6. The tri-block prepolymer of claim 1 having a weight average molecular in the range of about 10 to about 100 kDa.

7. The tri-block prepolymer of claim 6 having a weight average molecular in the range of about 20 to about 80 kDa.

8. The tri-block prepolymer of claim 7 having a weight average molecular in the range of about 20 to about 60 kDa.

9. The tri-block prepolymer of claim 8 having a weight average molecular in the range of about 20 to about 50 kDa.

10. The tri-block prepolymer of claim 1 , wherein the first hydrophilic monomer is the same as the third hydrophilic monomer.

11. The tri-block prepolymer of claim 1 , wherein the monovalent reactive group is selected from the group consisting of (meth)acrylate, (meth)acrylamide, styryl, vinyl, N-vinyl lactam, N-vinylamide, O-vinylether, O-vinylcarbonate, O-vinylcarbamate, and mixtures thereof.

12. The tri-block prepolymer of claim 1 , wherein the first hydrophilic monomer comprises a C 2 -C 8 linear or branched hydroxyalkyl (meth)acrylate, a C 2 -C 8 linear or branched dihydroxyalkyl (meth)acrylate, a C 2 -C 8 linear or branched trihydroxyalkyl (meth)acrylate, a N— C 2 -C 6 linear or branched hydroxyalkyl (meth)acrylamide, a N,N-bis C 2 -C 6 linear or branched hydroxyalkyl (meth)acrylamide, a N—C 2 -C 8 linear or branched dihydroxyalkyl (meth)acrylamide, a N,N-bis C 2 -C 8 linear or branched dihydroxyalkyl (meth)acrylamide, a N— C 2 -C 8 linear or branched trihydroxyalkyl (meth)acrylamide, a N,N-bis C 2 -C 8 linear or branched trihydroxyalkyl (meth)acrylamide, or mixtures thereof.

13. The tri-block prepolymer of claim 12 , wherein the first hydrophilic monomer comprises 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2,3-dihydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, N-(2-hydroxyethyl) (meth)acrylamide, N,N-bis(2-hydroxyethyl) (meth)acrylamide, N-(2-hydroxypropyl) (meth)acrylamide, N,N-bis(2-hydroxypropyl) (meth)acrylamide, N-(3-hydroxypropyl) (meth)acrylamide, N-(2-hydroxybutyl) (meth)acrylamide, N-(3-hydroxybutyl) (meth)acrylamide, N-(4-hydroxybutyl) (meth)acrylamide, or mixtures thereof.

14. The tri-block prepolymer of claim 1 , wherein the first hydrophilic monomer of both segments [A] and [C] is 2-hydroxyethyl (meth)acrylate.

15. The tri-block prepolymer of claim 1 , wherein [A] and [C] independently further comprise the second hydrophilic monomer that comprises acrylamide, N,N-dimethylacrylamide, N-vinylpyrrolidone, N-vinyl acetamide, N-vinyl N-methyl acetamide, N-isopropyl acrylamide, polyethylene glycol monoacrylate, polyethylene glycol monomethacrylate, acrylic acid, methacrylic acid, N-[(ethenyloxy)carbonyl]-β-alanine, 3-acrylamidopropanoic acid, 5-acrylamidopropanoic acid, 2-(methacryloyloxy)ethyl trimethylammonium chloride, 2-acrylamido-2-methylpropane sulfonic acid, 1-propanaminium, N-(2-carboxyethyl)-N,N-dimethyl-3-[(1-oxo-2-propen-1-yl)amino]-, inner salt; carboxybetaine, 1-propanaminium, N,N-dimethyl-N-[3-[(1-oxo-2-propen-1-yl)amino]propyl]-3-sulfo-, inner salt; 3,5-dioxa-8-aza-4-phosphaundec-10-en-1-aminium, 4-hydroxy-N,N,N-trimethyl-9-oxo-, inner salt, 4-oxide (9CI), or mixtures thereof.

16. The tri-block prepolymer of claim 15 , wherein the repeating units of the second hydrophilic monomer are present independently in segments [A] and [C] in the range of about 1 to about 50 mole percent.

17. The tri-block prepolymer of claim 16 , wherein the repeating units of the second hydrophilic monomer are present independently in segments [A] and [C] in the range of about 1 to about 25 mole percent.

18. The tri-block prepolymer of claim 17 , wherein the repeating units of the second hydrophilic monomer are present independently in segments [A] and [C] in the range of about 1 to about 15 mole percent.

19. The tri-block prepolymer of claim 18 , wherein the repeating units of the second hydrophilic monomer are present independently in segments [A] and [C] in the range of about 1 to about 10 mole percent.

20. The tri-block prepolymer of claim 1 , wherein [B] further comprises the third hydrophilic monomer that comprises a C 2 -C 8 linear or branched hydroxyalkyl (meth)acrylate, a C 2 -C 8 linear or branched dihydroxyalkyl (meth)acrylate, a C 2 -C 8 linear or branched trihydroxyalkyl (meth)acrylate, a N— C 2 -C 6 linear or branched hydroxyalkyl (meth)acrylamide, a N,N-bis C 2 -C 6 linear or branched hydroxyalkyl (meth)acrylamide, a N— C 2 -C 8 linear or branched dihydroxyalkyl (meth)acrylamide, a N,N-bis C 2 -C 8 linear or branched dihydroxyalkyl (meth)acrylamide, a N— C 2 -C 8 linear or branched trihydroxyalkyl (meth)acrylamide, a N,N-bis C 2 -C 8 linear or branched trihydroxyalkyl (meth)acrylamide, or mixtures thereof.

21. The tri-block prepolymer of claim 20 , wherein the third hydrophilic monomer comprises 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2,3-dihydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, N-(2-hydroxyethyl) (meth)acrylamide, N,N-bis(2-hydroxyethyl) (meth)acrylamide, N-(2-hydroxypropyl) (meth)acrylamide, N,N-bis(2-hydroxypropyl) (meth)acrylamide, N-(3-hydroxypropyl) (meth)acrylamide, N-(2-hydroxybutyl) (meth)acrylamide, N-(3-hydroxybutyl) (meth)acrylamide, N-(4-hydroxybutyl) (meth)acrylamide, or mixtures thereof.

22. The tri-block prepolymer of claim 21 , wherein the first hydrophilic monomer and the third hydrophilic monomer both comprise 2-hydroxyethyl (meth)acrylate.

23. The tri-block prepolymer of claim 20 , wherein the repeating units of the third hydrophilic monomer are present in segment [B] in the range of about 1 to about 70 mole percent.

24. The tri-block prepolymer of claim 23 , wherein the repeating units of the third hydrophilic monomer are present in segment [B] in the range of about 10 to about 60 mole percent.

Assignees

• Johnson & Johnson Vision Care

Inventors

• Zhang Yong
• Joslin Scott L
• Mahadevan Shivkumar
• Ford James D

Classifications

• C08G81/024

  Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G · CPC title

• G02B1/043

  Contact lenses · CPC title

• C08J3/075 Primary

  Macromolecular gels · CPC title

• C08G2210/00

  Compositions for preparing hydrogels · CPC title

• C08J2383/10

  Block- or graft-copolymers containing polysiloxane sequences · CPC title