PROCESS FOR PREPARING A POLYMER

• US 20160340463A1
• Filed: 01/30/2015
• Published: 11/24/2016
• Est. Priority Date: 01/31/2014
• Status: Abandoned Application

• Current Assignee: NewSouth Innovations Pty Limited (University Of New South Wales)
• Original Assignee: NewSouth Innovations Pty Limited (University Of New South Wales)
• Inventors: Xu, Jiangtao, Boyer, Cyrille Andre Jean-Marie
• Application Number:
  US15/114,827
• Publication Number:
  US 20160340463A1
• Time in Patent Office: Days
• US Class Current: 1/1
• CPC Class Codes: C08F 18/04 Vinyl esters
• CPC Class Codes: C08F 18/08 Vinyl acetate
• CPC Class Codes: C08F 2/38 Polymerisation using regulators, e.g. chain terminating agents , e.g. telomerisation
• CPC Class Codes: C08F 2/46 Polymerisation initiated by wave energy or particle radiation
• CPC Class Codes: C08F 2/50 with sensitising agents
• CPC Class Codes: C08F 20/14 Methyl esters , e.g. methyl (meth)acrylate
• CPC Class Codes: C08F 20/56 Acrylamide; Methacrylamide
• CPC Class Codes: C08F 220/286 and containing polyethylene oxide in the alcohol moiety, e.g. methoxy polyethylene glycol (meth)acrylate
• CPC Class Codes: C08F 220/54 Amides , e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
• CPC Class Codes: C08F 2438/03 Use of a di- or tri-thiocarbonylthio compound, e.g. di- or tri-thioester, di- or tri-thiocarbamate, or a xanthate as chain transfer agent, e.g . Reversible Addition Fragmentation chain Transfer [RAFT] or Macromolecular Design via Interchange of Xanthates [MADIX]
• CPC Class Codes: C08F 2500/03 Narrow molecular weight distribution, i.e. Mw/Mn < 3
• CPC Class Codes: C08F 26/10 N-Vinyl-pyrrolidone
• CPC Class Codes: C08F 2800/10 as molar percentages
• CPC Class Codes: C08F 293/005 using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
• CPC Class Codes: C08F 30/02 containing phosphorus
• CPC Class Codes: C08F 4/40 Redox systems

Abstract

This application relates to a process of radical polymerization of a monomer, wherein the radical polymerization is carried out in the presence of a photoredox catalyst and a chain transfer agent. This application also relates to a process for preparing a polymer, comprising exposing a mixture comprising a monomer, an initiator, a chain transfer agent and a photoredox catalyst, to light, wherein exposing the mixture to light initiates radical polymerization of the monomer. The application also relates to polymers produced by these processes and polymerization systems suitable for carrying out these processes.

Claims

1. A process for preparing a polymer, comprising exposing a mixture comprising a monomer, an initiator, a chain transfer agent and a photoredox catalyst, to light, wherein exposing the mixture to light initiates radical polymerization of the monomer.

2. The process of claim 1, wherein the chain transfer agent and the initiator are present in the form of a PET-RAFT agent.

3. The process of claim 2, wherein the PET-RAFT agent is a compound of formula (I′

);

4. The process of claim 3, wherein X and A are both S.

5. The process of claim 2, wherein the PET-RAFT agent is selected from:

9. The process of claim 1, wherein the molecular weight distribution of the polymer has a M_w/M_n of less than about 1.5.

10. The process of claim 1, wherein the photoredox catalyst is a metal photoredox catalyst, an organo photocatalyst or a photo-biocatalyst.

11. The process of claim 1, wherein the photoredox catalyst is selected from fac-Ir(ppy)₃, Ru(bpy)₃Cl₂ and chlorophyll a.

12. The process of claim 1, wherein the mixture comprises the photoredox catalyst in an amount of less than about 5 ppm relative to the monomer.

13. The process of claim 1, wherein the monomer is selected from methyl methacrylate, ethyl methacrylate, propyl methacrylate (all isomers), butyl methacrylate (all isomers), 2-ethylhexyl methacrylate, isobornyl methacrylate, methacrylic acid, benzyl methacrylate, phenyl methacrylate, methacrylonitrile, alpha-methystyrene, methyl acrylate, ethyl acrylate, propyl acrylate (all isomers), butyl acrylate (all isomers), 2-ethylhexyl acrylate, isobornyl acrylate, acrylic acid, benzyl acrylate. phenyl acrylate, acrylonitrile, styrene, functional methacrylates, acrylates and styrenes selected from glycidyl methacrylate, 2-hydroxyethyl methacrylate, hydroxypropyl methacrylate (all isomers), hydroxybutyl methacrylate (all isomers), N,N-dimethylaniinoethyl methacrylate, N,N-diethylaminoethyl methacrylate, triethyleneglycol methacrylate, di(ethylene glycol) ethyl ether acrylate (DEGA), oligo(ethyleneglycol) methyl ether methacrylate (OEGMA), oligo(ethyleneglycol) methyl ether acrylate (OEGA), itaconic anhydride, itaconic acid, glycidyl acrylate, 2-hydroxyethyl acrylate, hydroxypropyl acrylate (all isomers), hydroxybutyl acrylate (all isomers), N,N-dimethylaminoethyl acrylate, N,N′

-diethylaminoethyl acrylate, triethyleneglycol acrylate, methacrylamide, N-methylacrylamide, N,N-dimethylacrylamide (DMA), N-ethylacrylamide, N,N-diethylacrylamide (DEA), N-tert-butylmethacrylamide, N-n-butylmethacrylamide, N-methylolmethacrylamide, N-ethylolmethacrylamide, N-isopropylacrylamide (NIPAAm), N-tert-butylacrylamide, N-n-butylacrylamide, N-methylolacrylamide, N-ethylolacrylamide, vinyl benzoic acid (all isomers), diethylaminostyrene (all isomers), alpha-methylvinyl benzoic acid (all isomers), diethylamino alpha-methylstyrene (all isomers). p-vinylbenzene sulfonic acid, p-vinylbenzene sulfonic sodium salt, trimethoxysilylpropyl methacrylate, triethoxysilylpropyl methacrylate, tributoxysilylpropyl methacrylate, dimethoxymethylsilylpropyl methacrylate, diethoxymethylsilyipropylmethacrylate, dibutoxymethylsilylpropyl methacrylate, diisopropoxymethylsilylpropyl methacrylate, dimethoxysilylpropyl methacrylate, diethoxysilylpropyl methacrylate, dibutoxysilylpropyl methacrylate, diisopropoxysilylpropyl methacrylate, trimethoxysilylpropyl acrylate, triethoxysilylpropyl acrylate, tributoxysilylpropyl acrylate, dimethoxymethylsilylpropyl acrylate, diethoxymethylsilylpropyl acrylate, dibutoxymethylsilylpropyl acrylate, diisopropoxymethylsilylpropyl acrylate, dimethoxysilylpropyl acrylate, diethoxysilyipropyl acrylate, dibutoxysilylpropyl acrylate, diisopropoxysilylpropyl acrylate, vinyl acetate, vinyl butyrate, vinyl benzoate, vinyl chloride, vinyl fluoride, vinyl bromide, maleic anhydride, N-phenylmaleimide, N-butylmaleimide, N-vinylpyrrolidone, N-vinylcarbazole, vinyl pivalate, dimethyl vinylphosphonate, butadiene, isoprene, chloroprene, vinyl difluoride, tetrafluoroethylene, vinyl chloride, vinyl dichloride, and combinations thereof.

14. The process of claim 1, wherein the mixture further comprises an aqueous solvent.

18. The process of claim 1, wherein the mixture is not degassed.

27. The process of claim 1, wherein the chain transfer agent is a biomolecule comprising, or bound to, a moiety capable of acting as a chain transfer agent, and wherein exposure of the mixture to light results in conjugation of the polymerized monomer to the biomolecule.

28. The process of claim 27, wherein the initiator and the biomolecule comprising, or bound to, a moiety capable of acting as a chain transfer agent are provided by the same compound.

32. A polymer produced by the process of claim 1.

33. A polymer produced by the process of claim 27, wherein the polymer is a polymer bioconjugate.

6-8. -8. (canceled)

15-17. -17. (canceled)

19-26. -26. (canceled)

29-31. -31. (canceled)

34. A composition comprising a monomer, an initiator, a chain transfer agent and a photoredox catalyst, wherein exposing the composition to light initiates radical polymerization of the monomer.

35. The composition of claim 34, wherein the initiation is reversibly controlled by the light.