Methods For Extensive Dark Curing Based on Visible-Light Initiated, Controlled Radical Polymerization

• US 20110166306A1
• Filed: 07/01/2009
• Published: 07/07/2011
• Est. Priority Date: 07/01/2008
• Status: Active Grant

• Current Assignee: The Board of Regents of the University of Colorado (University of Colorado System)
• Original Assignee: The Board of Regents of the University of Colorado (University of Colorado System)
• Inventors: Kim, Dongkwan, Stansbury, Jeffrey W.
• Granted Patent: US 8,883,948 B2
• Time in Patent Office: Days
• US Class Current: 526/205
• CPC Class Codes: A61C 13/0003 Making bridge-work, inlays, implants or the like
• CPC Class Codes: A61C 13/08 Artificial teeth; Making same kilns for artificial teeth F27B
• CPC Class Codes: A61C 5/50 Implements for filling root canals; Methods or instruments for medication of tooth nerve channels
• CPC Class Codes: A61K 6/20 Protective coatings for natural or artificial teeth, e.g. sealings, dye coatings or varnish
• CPC Class Codes: A61K 6/30 Compositions for temporarily or permanently fixing teeth or palates, e.g. primers for dental adhesives
• CPC Class Codes: A61K 6/887 Compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
• CPC Class Codes: C08L 25/04 Homopolymers or copolymers of styrene
• CPC Class Codes: C08L 33/00 Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers

Abstract

Optimized methods to achieve extensive dark curing from a three-component visible light-initiated system though controlled radical polymerization and compositions useful in these optimized methods are provided. These compositions and methods are particularly suited for use in certain dental applications.

Claims

1. A dark curing polymerizable composition comprising:

a. a monomer with at least one abstractable hydrogen; and

b. a three-component initiator system, soluble in said monomer, comprising;

i. a photo-oxidizable photosensitizing agent;

ii. an electron donor; and

iii. an electron acceptor.

2. The composition of claim 1, wherein the monomer is selected from the group consisting of 2-hydroxyethyl acrylate (HEA), 2-hydroxyethyl methacrylate (HEMA), acrylamide, methacrylamide, bisGMA {2,2-bis[4-(2-hydroxy-3-methacryloxyprop-1-oxy)phenyl]propane}, urethane dimethacrylate, glycerol monomethacrylate, 1,3, glycerol dimethacrylate, tetrahydrofurfuryl methacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate (HDDA), methacrylic acid, triethylene glycol dimethacrylate, styrene, and neodecyl vinyl ester.

3. The composition of claim 1, wherein the photosensitizing agent is selected from the group consisting of safranin O, eosin Y disodium salt, fluorescein sodium salt, erythrosin B sodium salt, acriflavine, camphorquinone, methylene blue, 1-Phenyl-1,2-propanedione, acridine orange, resorufin, resazurin, phenosafranin, rose bengal, rhodamine B, or thioxanthen-9-one.

4. The composition of claim 1, wherein the electron donor is selected from the group consisting of triethanolamine, 4-dimethylaminophenethyl alcohol, ethyl 4-dimethylaminobenzoate, quinuclidine, N,N-diisopropyl-3-pentylamine, N-Phenylglycine, N-ethyldiisopropylamine, N-methyldiethanolamine, triethylamine (TEA), N,N-dimethylacetamide, 1,4-diazabicyclo[2.2.2]octane, 4-dimethylaminobenzaldehyde, N,N-dimethylbenzylamine, 4-tert-butyl-N,N-dimethylaniline, 9,10-dimethylanthracene, N,N-dimethylbenzylamine, or 1,2,2,6,6-pentamethylpiperidine.

5. The composition of claim 1, wherein the electron acceptor is selected from the group consisting of ferrocenium hexafluorophosphate, diphenyliodonium hexafluoroarsenate, [4[(2-hydroxytetradecyl)oxyl]phenyl]phenyliodonium hexafluoroantimonate, diphenyliodonium hexafluorophosphate, 2,4,6-tris(trifluoromethyl)-1,3,5-triazine, diphenyl iodonium chloride and diphenyl iodonium tetrafluoroborate.

6-9. -9. (canceled)

10. A method for dark curing polymerization, comprising

dissolving a photosensitizing agent, electron donor, and electron acceptor in monomer solution;

initiating polymerization using a visible-light source;

allowing polymerization to cure under dark conditions.

11-13. -13. (canceled)

14. A dark curing polymerizable composition comprising 4.122×

10<sup>−

2</sup> mol. (neat) of an acrylate selected from the group consisting of 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate, and a three-component initiator system comprising methylene blue, N-ethyldiisopropylamine; and

diphenyliodonium chloride.

15. The dark curing polymerizable composition of claim 14, wherein the acrylate is 2-hydroxyethyl methacrylate and the three-component initiator system comprises 0.075 mol % methylene blue;

2.5 mol % N-ethyldiisopropylamine; and

0.5 mol % diphenyliodonium chloride, dissolved in said 2-hydroxyethyl methacrylate.

16. The dark curing polymerizable composition of claim 14, wherein the acrylate is 2-hydroxyethyl acrylate and the three-component initiator system comprises 0.015 mol % methylene blue;

3.0 mol % N-ethyldiisopropylamine; and

0.25 mol % diphenyliodonium chloride, dissolved in said 2-hydroxyethyl acrylate.