Methods for extensive dark curing based on visible-light initiated, controlled radical polymerization
View Patent ↗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.
1. A dark curing polymerizable composition comprising:
a. a monomer with at least one abstractable hydrogen 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; and
b. a three-component initiator system, soluble in said monomer, comprising:
i. methylene blue;
ii. an electron donor selected from the group consisting of N,N-diisopropyl-3-pentylamine, N-ethyldiisopropylamine, and 1,2,2,6,6-pentamethylpiperidine; and
iii. an electron acceptor 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.
2. A method for dark curing polymerization, comprising initiating polymerization in a dark curing polymerizable composition of claim 1 , using a visible-light source;
removing the visible light source to allow polymerization to cure under dark conditions.
3. A dark curing polymerizable composition comprising 4.122×10 −2 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.
4. The dark curing polymerizable composition of claim 3 , 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.
5. The dark curing polymerizable composition of claim 3 , 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.
6. The dark curing polymerizable composition of claim 1 , wherein the electron donor is selected from the group consisting of N-ethyldiisopropylamine, and N,N-diisopropyl-3-pentylamine.
7. The dark curing polymerizable composition of claim 1 , wherein the monomer is selected from the group consisting of 2-hydroxyethyl acrylate (HEA), 2-hydroxyethyl methacrylate (HEMA), and glycerol monomethacrylate.