# US 2013/0158151 A1 · Gels from polystyrene-based photoinitiators

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- Number: US 2013/0158151 A1
- Document ID: US20130158151A1
- Status: Published application
- Kind: A1
- Application number: 13/701,716
- Filed: 2011-06-01
- Published: 2013-06-20
- Earliest claimed: 2010-06-01
- Assignees: Coloplast A/S
- Inventors: Christian B. Nielsen; Niels Jørgen Madsen; Bo Rud Nielsen
- Web page: https://patentgrep.com/patent/US20130158151A1

## CPC

- C09D 125/18: Homopolymers or copolymers of aromatic monomers containing elements other than carbon and hydrogen
- A61K 9/06: Ointments; Bases therefor; {Other semi-solid forms, e.g. creams, sticks, gels (composition of ointments, creams or gels A61K47/00)}
- C08F 2/50: with sensitising agents
- C08F 8/10: Acylation
- C08F 12/22: Oxygen
- C08F 12/32: containing two or more rings
- C08F 212/08: Styrene
- C08J 3/075: Macromolecular gels
- C08J 3/246: {Intercrosslinking of at least two polymers}
- C08L 71/02: Polyalkylene oxides
- C09D 171/02: Polyalkylene oxides
- C08F 212/32: containing two or more rings
- C08J 2371/02: Polyalkylene oxides
- C08J 2425/04: Homopolymers or copolymers of styrene
- C09D: COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR (cosmetics A61K; processes for applying liquids or other fluent materials to surfaces, in general, B05D; staining wood B27K5/02; glazes or vitreous enamels C03C; natural resins, French polish, drying-oils, driers, turpentine, per se, C09F; polishing compositions other than French polish, ski waxes C09G; adhesives or use of materials as adhesives C09J; materials for sealing or packing joints or covers C09K3/10; materials for stopping leaks C09K3/12; processes for the electrolytic or electrophoretic production of coatings C25D)
- A61K: PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES (devices or methods specially adapted for bringing pharmaceutical products into particular physical or administering forms A61J3/00; chemical aspects of, or use of materials for deodorisation of air, for disinfection or sterilisation, or for bandages, dressings, absorbent pads or surgical articles A61L; soap compositions C11D)
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08J: WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H (working, e.g. shaping, of plastics B29)
- C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06)

## Abstract

The invention provides a method for the manufacture of a gel precursor. The method comprising the steps of combining a polymeric photoinitiator of the general formula (I): with one or more gel-forming polymers and/or gel-forming monomers to form a matrix composition, and curing the matrix composition obtained in the first step by exposing it to UV radiation. The invention also relates to the gel precursor itself, a method for the manufacture of a hydrophilic gel, the hydrophilic gel itself and a medical device comprising or coated with said gel.

## Claims

### Claim 1

A method for the manufacture of a hydrophilic gel precursor, said method comprising the steps of:
a. combining a polymeric photoinitiator of the general formula I:
R
1

(
A
1
)
q
-
{
—CH
2

CH
(
Ph
(
A
2
1
)
n
1

(
A
2
2
)
n
2

(
A
2
3
)
n
3

(
A
2
4
)
n
4

(
A
2
5
)
n
5
)
-
}
p
-
R
4

(
A
3
)
r
(
I
)
wherein:
R1 and R4 are each independently selected from C1-C25 linear alkyl, C3-C25 branched alkyl, C3-C25 cycloalkyl, aryl, heteroaryl, hydrogen, —OH, —CN, halogens, amines, amides, alcohols, ethers, thioethers, sulfones and derivatives thereof, sulfonic acid and derivatives thereof, sulfoxides and derivatives thereof, carbonates, isocyanates, nitrates, acrylates, polyethylenes, polyethylene oxides, polyvinyl pyrrolidones, polypropylenes, polyesters, polyamides, polyacrylates, polystyrenes, and polyurethanes; and when R1 and R4 are alkyl and aryl groups, they may be substituted with one or more substituents selected from CN; OH; azides; esters; ethers; amides; halogen atoms; sulfones; sulfonic derivatives; NH2 or Nalk2, where alk is any C1-C8 straight chain alkyl group, C3-C8 branched or cyclic alkyl group; n1, n2, n3, n4, and n5 are real numbers from 0 to 5, whereby the sum n1+n2+n3+n4+n5 is a real number greater than 0;
p is an integer from 1-10,000;
q and r are each an integer from 0-10,000;
A1 and A3 are identical or different photoinitiator moieties;
Ph is an optionally-substituted phenyl group; and
A21, A22, A23, A24 and A25—together with Ph—independently form optionally-substituted alkylphenone moieties or optionally-substituted benzophenone moieties;
with one or more gel-forming polymers and/or gel-forming monomers to form a matrix composition, and
b. curing the matrix composition obtained in step a. by exposing it to UV radiation.

### Claim 2 (depends on 1)

The method according to claim 1, wherein A1 and A3 are identical or different photoinitiator moieties selected from the group consisting of benzoin ethers, phenyl hydroxyalkyl ketones, phenyl aminoalkyl 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, maleimides and derivatives thereof.

### Claim 3 (depends on 1)

The method according to claim 1, wherein the molecular weight of the polymeric photoinitiator is between 0.2 kDa and 100 kDa, suitably between 0.2 kDa and 75 kDa and preferably between 0.5 and 50 kDa.

### Claim 4 (depends on 1)

The method according to claim 1, wherein R1 and R4 are each independently selected from C1-C25 linear alkyl, C3-C25 branched alkyl and C3-C25 cycloalkyl.

### Claim 5 (depends on 1)

The method according to claim 1, wherein A21, A22, A23, A24 and A25—together with Ph—independently form benzophenone moieties.

### Claim 6

(canceled)

### Claim 7 (depends on 1)

The method according to claim 1, wherein A21, A22, A23, A24 and A25—together with Ph—independently form substituted benzophenone moieties.

### Claim 8 (depends on 7)

The method according to claim 7, wherein at least one electron-withdrawing group is present on A21, A22, A23, A24 or A25.

### Claim 9 (depends on 7)

The method according to claim 7, wherein at least one electron-withdrawing group is present on Ph.

### Claim 10 (depends on 9)

The method according to claim 9, wherein the at least one electron-withdrawing group is selected from the group consisting of halogens, nitriles, carbonyls, nitro groups, sulfones, sulfonamides, sulfonates, trihalides, quarternary amines, amides, sulphonamides, thiocarboxylic acids and thioaldehydes.

### Claim 11 (depends on 1)

The method according to claim 1, wherein A21, A22, A23, A24 and A25—together with Ph—independently form optionally-substituted alkylphenone moieties in which A21, A22, A23, A24 and A25 each independently have the structure
wherein R10 is selected from the group consisting of optionally-substituted C1-C25 linear, branched or cyclic alkyl.

### Claim 12 (depends on 11)

The method according to claim 11, wherein R10 is selected from the group consisting of optionally-substituted C1-C10 linear, branched or cyclic alkyl, preferably optionally-substituted C1-C5 linear or branched alkyl.

### Claim 13 (depends on 11)

The method according to claim 11, wherein R10 is substituted with one or more substituents independently selected from the group consisting of C1-C25 linear, branched or cyclic alkyl, aryl, —OH, —CN, halogens, amines, amides, alcohols, ethers, thioethers, sulfones and derivatives thereof, sulfonic acid and derivatives thereof, sulfoxides and derivatives thereof, carbonates, isocyanates, nitrates, acrylates.

### Claim 14 (depends on 13)

The method according to claim 13, wherein the substituent on R10 is selected from the group consisting of —OH, —CN, halogens, amines, amides, alcohols, ethers, thioethers, sulfones and derivatives thereof, sulfonic acid and derivatives thereof, and sulfoxides and derivatives thereof.

### Claim 15 (depends on 1)

The method according to claim 1, wherein p is an integer from 1-5000, preferably 1-2000.

### Claim 16 (depends on 1)

The method according to claim 1, wherein q and r are each an integer from 0-5000, preferably 0-2000.

### Claim 17 (depends on 1)

The method according to claim 1, wherein the sum n1+n2+n3+n4+n5 is 1.

### Claim 18 (depends on 1)

The method according to claim 1, wherein the gel-forming polymer is selected from the group consisting of polyacrylates, polyalkylethers, polyurethanes, polyethylene vinyl acetates, polyvinylpyrrolidone and co-polymers and blends thereof.

### Claim 19 (depends on 1)

The method according to claim 1, wherein the gel-forming monomer is selected from the group consisting of acrylate monomers, N-vinylpyrrolidone, and epoxide monomers.

### Claim 20 (depends on 1)

The method according to claim 1, wherein the polymer is a polystyrene and the Mw of the polystyrene is 0.20-30 kDa and the loading is greater than 0% and below 50%.

### Claim 21

(canceled)

### Claim 22 (depends on 1)

A method for the manufacture of a hydrophilic gel, said method comprising steps a. and b. as defined in claim 1, said method comprising the further step of:
c. exposing the matrix composition to a swelling medium wherein step c. may take place before or after step b.

### Claim 23

A method for the manufacture of a hydrophilic gel, said method comprising the steps of:
a. providing a polymeric photoinitiator of the general formula I:
R
1

(
A
1
)
q
-
{
—CH
2

CH
(
Ph
(
A
2
1
)
n
1

(
A
2
2
)
n
2

(
A
2
3
)
n
3

(
A
2
4
)
n
4

(
A
2
5
)
n
5
)
-
}
p
-
R
4

(
A
3
)
r
(
I
)
wherein:
R1 and R4 are each independently selected from C1-C25 linear alkyl, C3-C25 branched alkyl, C3-C25 cycloalkyl, aryl, heteroaryl, hydrogen, —OH, —CN, halogens, amines, amides, alcohols, ethers, thioethers, sulfones and derivatives thereof, sulfonic acid and derivatives thereof, sulfoxides and derivatives thereof, carbonates, isocyanates, nitrates, acrylates, polyethylenes, polyethylene oxides, polyvinyl pyrrolidones, polypropylenes, polyesters, polyamides, polyacrylates, polystyrenes, and polyurethanes; and when R1 and R4 are alkyl and aryl groups, they may be substituted with one or more substituents selected from CN; OH; azides; esters; ethers; amides; halogen atoms; sulfones; sulfonic derivatives; NH2 or Nalk2, where alk is any C1-C8 straight chain alkyl group, C3-C8 branched or cyclic alkyl group; n1, n2, n3, n4, and n5 are real numbers from 0 to 5, whereby the sum n1+n2+n2+n4+n5 is a real number greater than 0;
p is an integer from 1-10,000;
q and r are each an integer from 0-10,000;
A1 and A3 are identical or different photoinitiator moieties;
Ph is an optionally-substituted phenyl group; and
A21, A22, A23, A24 and A25—together with Ph—independently form optionally-substituted alkylphenone moieties or optionally-substituted benzophenone moieties;
b. exposing the polymeric photoinitiator from step a. to UV radiation, and
c. exposing the polymeric photoinitiator to a swelling medium,
wherein steps b. and c. may take place in any order.

### Claim 24 (depends on 1, 23)

The method according to claim 23, wherein the polymeric photoinitiator has the structure defined in claim 1.

### Claim 25 (depends on 23)

The method according to claim 23, wherein R1 and R4 are selected from the group consisting of polyacrylates, polyethylene oxides, polyvinyl pyrrolidones, polyesters, polyamides and polyurethanes.

### Claim 26 (depends on 22)

The method according to claim 22, where the swelling medium is selected from the group consisting of water, C1-C5 alcohols, glycerol and polyethylene glycol (PEG), preferably PEG-2000.

### Claim 27 (depends on 22)

The method according to claim 22, where the swelling medium comprises water, and the hydrophilic gel thus produced is a hydrogel.

### Claim 28 (depends on 22)

The method according to claim 22, wherein the matrix composition or polymeric photoinitiator is cured after exposure to the swelling medium.

### Claim 29 (depends on 22)

The method according to claim 22, consisting of steps a. b. and c.

### Claim 30

(canceled)

### Claim 31

A matrix composition comprising a polymeric photoinitiator and one or more gel-forming polymers and/or gel-forming monomers; where the polymeric photoinitiator is of the general formula I:
R
1

(
A
1
)
q
-
{
—CH
2

CH
(
Ph
(
A
2
1
)
n
1

(
A
2
2
)
n
2

(
A
2
3
)
n
3

(
A
2
4
)
n
4

(
A
2
5
)
n
5
)
-
}
p
-
R
4

(
A
3
)
r
(
I
)
wherein:
R1 and R4 are each independently selected from C1-C25 linear alkyl, C3-C25 branched alkyl, C3-C25 cycloalkyl, aryl, heteroaryl, hydrogen, —OH, —CN, halogens, amines, amides, alcohols, ethers, thioethers, sulfones and derivatives thereof, sulfonic acid and derivatives thereof, sulfoxides and derivatives thereof, carbonates, isocyanates, nitrates, acrylates, polyethylenes, polyethylene oxides, polyvinyl pyrrolidones, polypropylenes, polyesters, polyamides, polyacrylates, polystyrenes, and polyurethanes; and when R1 and R4 are alkyl and aryl groups, they may be substituted with one or more substituents selected from CN; OH; azides; esters; ethers; amides; halogen atoms; sulfones; sulfonic derivatives; NH2 or Nalk2, where alk is any C1-C8 straight chain alkyl group, C3-C8 branched or cyclic alkyl group;
n1, n2, n3, n4, and n5 are real numbers from 0 to 5, whereby the sum n1+n2+n3+n4+n5 is a real number greater than 0;
p is an integer from 1-10,000;
q and r are each an integer from 0-10,000;
A1 and A3 are identical or different photoinitiator moieties;
Ph is an optionally-substituted phenyl group; and
A22, A22, A23, A24 and A25—together with Ph—independently form optionally-substituted alkylphenone moieties or optionally-substituted benzophenone moieties.

### Claim 32 (depends on 31)

The matrix composition according to claim 31, wherein the gel-forming polymer is selected from the group consisting of polyacrylates, polyalkylethers, polyurethanes, polyethylene vinyl acetates, polyvinylpyrrolidone and co-polymers and blends thereof.

### Claim 33 (depends on 31)

The matrix composition according to claim 31, wherein the gel-forming monomer is selected from the group consisting of acrylate monomers, N-vinylpyrrolidone, and epoxide monomers.

### Claim 34

(canceled)

### Claim 35 (depends on 34)

The medical device according to claim 34, coated on at least a surface portion thereof with the gel.

### Claim 36

(canceled)

### Claim 37 (depends on 23)

The method according to claim 23, where the swelling medium is selected from the group consisting of water, C1-C5 alcohols, glycerol and polyethylene glycol (PEG), preferably PEG-2000.

### Claim 38 (depends on 23)

The method according to claim 23, where the swelling medium comprises water, and the hydrophilic gel thus produced is a hydrogel.

### Claim 39 (depends on 23)

The method according to claim 23, wherein the matrix composition or polymeric photoinitiator is cured after exposure to the swelling medium.

### Claim 40 (depends on 23)

The method according to claim 23, consisting of steps a. b. and c.