Hydrophilic gels derived from grafted photoinitiators

Patent metadata

Field	Value
Publication number	US-10011688-B2
Application number	US-201615049157-A
Country	US
Kind code	B2
Filing date	Feb 22, 2016
Priority date	Jun 22, 2010
Publication date	Jul 3, 2018
Grant date	Jul 3, 2018

Abstract

The invention provides a method for the manufacture of a gel, said method comprising the steps of: providing a matrix composition comprising a polymeric photoinitiator of the general formula (I): Polymer-[CR 2 —CHR-Spacer(PI) n ] m (I) curing the matrix composition by exposing it to UV radiation and exposing the matrix composition to a swelling medium. The invention also relates to gels obtainable via the above method. The invention provides a hydrophilic gel precursor manufactured from the polymeric photoinitiator of Formula (I). Medical devices comprising the gels and hydrophilic gel precursors of the invention are provided. The invention also provides the use of a polymeric photoinitiator in the manufacture of a gel.

First claim

The invention claimed is:

1. A method for the manufacture of a hydrophilic gel, said method comprising the steps of:
a. providing a matrix composition comprising a polymeric photoinitiator of the general formula I:
Polymer —[CR 2 —CHR-Ph-Spacer-(PI) n ] m   (I)

wherein m is an integer from 1-5000;
Ph is an optionally substituted phenyl group;
n is a real number above 0 and below 5; and
PI is a photoinitiator moiety;
Spacer is selected from the group consisting of a single bond, a C1-C25 linear alkylene, a C3-C25 branched alkylene, a C3-C25 cycloalkylene, an arylene, a heteroarylene, an amine, an amide, an alcohol, an ether, an ester, a thioether, a sulfone, a sulfonic ester, a sulfoxide, a carbonate and a ketone,
independently selected from hydrogen, C1-C25 linear alkyl, C3-C25 branched alkyl, C3-C25 cycloalkyl, aryl, heteroaryl, —OH, —CN, halogens, —NR′R″, —CONR′R″, and R′CONR″—, where R′ and R″ are alkyl groups,

b. curing the matrix composition obtained in step a) by exposing it to UV radiation,
c. exposing the matrix composition to a swelling medium, thus providing a hydrophilic gel further comprising a hydrophilic gel-forming polymer or a hydrophilic gel-forming monomer, wherein the hydrophilic gel-forming polymer is selected from the group consisting of polyacrylates, polyalkylethers, polyurethanes, polyethylene vinyl acetates, polyvinylpyrrolidone and co-polymers and blends thereof, or the hydrophilic gel-forming monomer is selected from the group consisting of acrylate monomers, N-vinylpyrrolidone, and epoxide monomers,
wherein step c) may take place before or after step b).

2. The method according to claim 1 , wherein the polymer in formula I is selected from the group consisting of polyolefines, polyacrylates, polyesters, polyurethanes, polyamides, polyalkyloxides, polydialkylsiloxanes or various copolymers comprising blocks or repeatable units of these polymers.

3. The method according to claim 2 , wherein the polymer in formula I is selected from the group consisting of polyolefines, polyacrylates, polyesters, polyurethanes, polyamides, polyalkyloxides and polydialkylsiloxanes.

4. The method according to claim 3 , wherein the polymer in formula I is a polyolefin or a polyalkyloxide.

5. The method according to claim 1 , wherein the polymer in formula I has a molecular weight in the range of 50-500,000 Da.

6. The method according to claim 1 , wherein X is selected from the group consisting of C1-C25 linear alkylene, C3-C25 branched alkylene, C3-C25 cycloalkylene, and esters.

7. The method according to claim 1 , wherein the spacer is selected from the group consisting of polyolefines, polyacrylates, polyurethanes, polyesters, polyamides, polydialkylsiloxanes, polyalkyloxides or various copolymers comprising blocks or repeatable units of the mentioned polymers.

8. The method according to claim 1 , wherein the spacer has a molecular weight in the range of 50-500,000 Da.

9. The method according to claim 1 , wherein the photoinitiator moiety is independently selected from the group consisting of benzoin ethers, phenyl hydroxyalkyl ketones, phenyl amino alkyl ketones, benzophenones, thioxanthones, xanthones, acridones, anthraquinones, fluorenones, dibenzosuberones, benzils, benzil ketals, α-dialkoxy-acetophenones, α-hydroxy-alkyl-phenones, α-amino-alkyl-phenones, acyl-phosphine oxides, phenyl ketocoumarins, silanes, and maleimides.

10. The method according to claim 9 , wherein the photoinitiator moiety is optionally-substituted benzophenone or thioxanthone.

11. The method according to claim 1 , wherein m is an integer from 1-3000.

12. The method according to claim 1 , wherein the polymeric photoinitiator of Formula I is synthesised by grafting photoinitiator moieties (PI) onto the polymer in the presence of a radical initiator.

13. The method according to claim 12 , wherein the grafting of the photoinitiator moieties (PI) onto the polymer takes place in an extruder.

14. The method according to claim 1 , wherein the photoinitiator units are pendant on the polymer.

15. The method according to claim 1 , wherein the matrix composition additionally comprises an anti-oxidant.

16. The method according to claim 1 , wherein the Ph group is substituted with one or more substituents independently selected from C1-C25 linear alkyl, C3-C25 branched alkyl, C3-C25 cycloalkyl, aryl, heteroaryl, —OH, —CN, halogens, —NR′R″, where R′ and R″ are alkyl groups, —CONR′R″, and R′CONR″—, where R′ and R″ are alkyl groups.

17. The method according to claim 1 , wherein R is independently selected from hydrogen, C1-C25 linear alkyl, C3-C25 branched alkyl, and C3-C25 cycloalkyl.

18. The method according to claim 1 , where the swelling medium is selected from the group consisting of water, C1-05 alcohols, glycerol, and polyethylene glycol (PEG).

19. The method according to claim 18 , where the swelling medium comprises water, and the gel thus produced is a hydrogel.

20. The method according to claim 1 , wherein step c) takes place before step b).

21. The method according to claim 1 , wherein m is an integer from 1-1000.

Assignees

• Coloplast As

Inventors

• Nielsen Christian B
• Madsen Niels Joergen
• Hoej Carsten

Classifications

• C08J2400/10

  Polymers characterised by the presence of specified groups, e.g. terminal or pendant functional groups · CPC title

• C08L71/02

  Polyalkylene oxides · CPC title

• C08F2/50

  with sensitising agents · CPC title

• C08J2300/14

  Water soluble or water swellable polymers, e.g. aqueous gels · CPC title

• C08L2312/06

  by radiation · CPC title