Cross-linked polymeric materials, methods of their preparation and uses thereof

Patent metadata

Field	Value
Publication number	US-2023096635-A1
Application number	US-202117759985-A
Country	US
Kind code	A1
Filing date	Feb 2, 2021
Priority date	Feb 3, 2020
Publication date	Mar 30, 2023
Grant date	—

Abstract

The present disclosure relates to methods for preparing cross-linked polymeric materials, cross-linked polymeric materials which can be prepared by such methods and uses of such cross-linked polymeric materials, for example, as antibacterial surfaces or coatings. The present disclosure also relates to polymers such as the polymer of the general Formula (III) which can be used, for example, to prepare such cross-linked polymeric materials:

First claim

1 . A method for preparing a cross-linked polymeric material, the method comprising:
irradiating a polymer comprising a plurality of aliphatic primary amine moieties or precursors thereto in the presence of oxygen and a sensitizer to form imine cross-links via the oxidative coupling of at least a portion of the aliphatic primary amine moieties and obtain the cross-linked polymeric material.

2 . The method of claim 1 , wherein the polymer comprises a polysiloxane comprising the aliphatic primary amine moieties, a polysaccharide comprising the aliphatic primary amine moieties, a polyamide comprising the aliphatic primary amine moieties, a polyester comprising the aliphatic primary amine moieties or a polymethacrylate comprising the aliphatic primary amine moieties.

3 . The method of claim 1 or 2 , wherein the polymer is of the general Formula (I):

wherein
R 1a , R 1b , R 1c , R 1d , R 1e , R 1f , R 1g , R 1h and R 1i are each independently C 1-10 alkyl, C 3-10 cycloalkyl, C 1-6 alkyleneC 3-10 cycloalkyl, aryl or C 1-6 alkylene-aryl;
each X is independently C 1-10 alkylene or C 3-10 cycloalkylene;
a is an integer of at least 2; and
b is an integer of at least 1.

4 . The method of claim 3 , wherein R 1a , R 1b , R 1c , R 1d , R 1e , R 1f , R 1g , R 1h and R 1i are each independently C 1-6 alkyl and each X is independently C 2-6 alkylene.

5 . The method of claim 4 , wherein R 1a , R 1b , R 1c , R 1d , R 1e , R 1f , R 1g , R 1h and R 1i are all methyl.

6 . The method of claim 4 or 5 , wherein each X is —(CH 2 ) 3 —.

7 . The method of any one of claims 3 to 6 , wherein a/(a+b) is about 0.001 to about 0.4.

8 . The method of any one of claims 3 to 6 , wherein a/(a+b) is about 0.04 to about 0.08.

9 . The method of any one of claims 1 to 8 , wherein the molecular mass of the polymer is from about 500 g/mol to about 100,000 g/mol.

10 . The method of any one of claims 1 to 9 , wherein the polymer is a (6-7% aminopropylmethylsiloxane)-dimethylsiloxane copolymer having a molecular mass of about 50,000 g/mol and/or a kinematic viscosity of about 1,800 cSt to about 2,200 cSt.

11 . The method of any one of claims 1 to 10 , wherein the polymer is a random copolymer.

12 . The method of any one of claims 1 to 11 , wherein the polymer comprises a combination of a polymer comprising the aliphatic primary amine moieties as side-chains and a polymer comprising end-terminated aliphatic primary amine moieties.

13 . The method of claim 12 , wherein the polymer comprising end-terminated aliphatic primary amine moieties is of the general Formula (II):

wherein
R 2a , R 2b , R 2c , R 2d , R 2e and R 2f are each independently C 1-10 alkyl, C 3-10 cycloalkyl, C 1-6 alkyleneC 3-10 cycloalkyl, aryl or C 1-6 alkylene-aryl;
each A is independently C 1-10 alkylene or C 3-10 cycloalkylene; and
n is an integer of at least 1.

14 . The method of claim 13 , wherein R 2a , R 2b , R 2c , R 2d , R 2e and R 2f are each independently C 1-6 alkyl and each A is independently C 2-6 alkylene.

15 . The method of claim 14 , wherein R 2a , R 2b , R 2c , R 2d , R 2e and R 2f are all methyl.

16 . The method of claim 14 or 15 , wherein each A is —(CH 2 ) 3 —.

17 . The method of any one of claims 12 to 16 , wherein the molecular mass of the polymer comprising end-terminated aliphatic primary amine moieties is from about 500 g/mol to about 50,000 g/mol.

18 . The method of any one of claims 12 to 17 , wherein the polymer comprising end-terminated aliphatic primary amine moieties is an aminopropyl-terminated polydimethylsiloxane having a molecular mass of about 850 g/mol to about 900 g/mol and/or a kinematic viscosity of about 10 to about 15 cSt.

19 . The method of any one of claims 1 to 18 , wherein the sensitizer is selected from an acridine, a porphyrin, a metalloporphyrin, a xanthene, a methylene blue, a metal oxide and combinations thereof.

20 . The method of any one of claims 1 to 19 , wherein prior to irradiation, the method comprises depositing the polymer and the sensitizer on a surface.

21 . The method of claim 20 , wherein the irradiating comprises exposure of the polymer and the sensitizer deposited on the surface through a mask defining a pattern.

22 . The method of claim 21 , further comprising removing the unexposed polymer and sensitizer thereby leaving the cross-linked polymeric material on the surface.

23 . The method of claim 20 , wherein the surface comprises a mold.

24 . The method of claim 20 , wherein the depositing comprises cryo-deposition, direct-write printing or vat stereolithography.

25 . The method of any one of claims 20 to 24 , further comprising removing the cross-linked polymeric material from the surface.

26 . The method of claim 20 , wherein the surface comprises a textile.

27 . The method of any one of claims 1 to 26 , wherein the irradiation comprises irradiating a solution comprising the polymer and the sensitizer.

28 . The method of any one of claims 1 to 26 , wherein the sensitizer is coupled to at least a portion of the polymer chains of the polymer.

29 . The method of claim 28 , wherein prior to irradiation and optionally deposition, the sensitizer is coupled to the polymer chains via a method comprising reacting a sensitizer comprising an amine-reactive group with the polymer comprising the plurality of aliphatic primary amine moieties.

30 . The method of claim 28 or 29 , wherein the irradiation comprises solvent-free conditions.

31 . The method of claim 28 or 29 , wherein the irradiation comprises irradiation of a solution comprising the sensitizer coupled to the at least a portion of the polymer chains.

32 . The method of any one of claims 28 to 31 , wherein the sensitizer is a xanthene.

33 . The method of claim 32 , wherein the sensitizer is rose bengal.

34 . The method of any one of claims 31 to 33 , wherein the sensitizer coupled to the at least a portion of the polymer chains absorbs light in a first region, the solution further comprises a second sensitizer that absorbs light in a second region, and the irradiation comprises irradiation of the solution at a wavelength in the second region.

35 . The method of claim 34 , wherein the second sensitizer is a porphyrin.

36 . The method of claim 35 , wherein the porphyrin is tetraphenylporphyrin.

37 . A cross-linked polymeric material prepared by a method as defined in any one of claims 1 to 36 .

38 . A polymer comprising:
a polymer chain comprising a plurality of aliphatic primary amine moieties or precursors thereto as side-chains; and a sensitizer coupled to the polymer chain via a moiety obtained from reaction of an aliphatic primary amine moiety with an amine-reactive group on the sensitizer.

39 . The polymer of claim 38 , wherein the polymer chain comprises a polysiloxane, a polysaccharide, a polyamide, a polyester or a polymethacrylate.

Assignees

• Univ British Columbia

Inventors

• Wolf Michael
• Wright Taylor

Classifications

• C08G77/388

  containing nitrogen · CPC title

• C08G77/32 Primary

  Post-polymerisation treatment · CPC title

• C08K5/1545

  Six-membered rings · CPC title

• D06M10/10

  Macromolecular compounds · CPC title

• D06M11/34

  with oxygen, ozone or ozonides · CPC title