# US 10,501,562 B2 · Co-initiator and co-monomer for use in preparing polymer related compositions, methods of manufacture, and methods of use > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 10,501,562 B2 - Document ID: US10501562B2 - Status: Granted - Kind: B2 - Application number: 15/548,053 - Filed: 2016-03-17 - Published: 2018-01-18 - Granted: 2019-12-10 - Earliest claimed: 2015-03-18 - Assignees: University of Kansas - Applicants: University of Kansas - Inventors: Xueping Ge; Qiang Ye; Paulette Spencer; Jennifer Ann Chadwick; Linyong Song - Web page: https://patentgrep.com/patent/US10501562B2 ## CPC - C08F 2/50: with sensitising agents - A61K 6/62: Photochemical radical initiators - A61K 6/887: Compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds - C07C 271/16: to carbon atoms of hydrocarbon radicals substituted by singly-bound oxygen atoms - C07C 271/20: to carbon atoms of hydrocarbon radicals substituted by nitrogen atoms not being part of nitro or nitroso groups - C08F 4/00: Polymerisation catalysts - C08F 222/225: {the ester chains containing seven or more carbon atoms} - C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS - 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) - C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS ## Abstract The present disclosure relates to tertiary amine co-initiators that demonstrate reduced leaching and which may be utilized in dental restoration and other biomedical applications. Embodiments of the present disclosure provide compounds and compositions for use in preparing polymers and light curable dental resin composites, as well as methods for preparing photocurable polymer-based dental restorative materials. In one or more disclosed embodiments, a co-initiator for use in preparing a polymer comprises a tertiary amine core and two or more pendant, terminal methacrylate groups. In some embodiments, the co-initiator may also act as a co-monomer in a co-polymerization reaction. ## Claims ### Claim 1 A co-initiator for use in preparing a polymer, said co-initiator comprising: a tertiary amine core; and two or more pendant, terminal methacrylate groups. ### Claim 2 (depends on 1) A co-initiator as in claim 1, wherein the co-initiator also acts as a co-monomer in a co-polymerization reaction. ### Claim 3 (depends on 1) A co-initiator as in claim 1, the co-initiator consisting of the molecular structure of Formula 1, or a derivative thereof, wherein R1 is selected from the group consisting of: hydrogen, an alkyl, a hydroxyl, and an amino; and wherein R2 is selected from the group consisting of: an ether, an amido, an amino, an alkyl-ether, an alkyl-amido, an alkyl-amino, an ether-alkyl, an amido-alkyl, an amino-alkyl, an alkyl-ether-alkyl, an alkyl-amido-alkyl, and an alkyl-amino-alkyl. ### Claim 4 (depends on 1) A co-initiator as in claim 1, the co-initiator consisting of the molecular structure of Formula 2, or a derivative thereof, wherein R1 is selected from the group consisting of: hydrogen, an alkyl, a hydroxyl, and an amino; and wherein R2 is selected from the group consisting of: an ether and an amino. ### Claim 5 (depends on 1) A co-initiator as in claim 1, the co-initiator consisting of the molecular structure of Formula 3, or a derivative thereof. ### Claim 6 A composition for use in preparing a light curable dental resin composite, comprising: a co-initiator, the co-initiator comprising: a tertiary amine core; and two or more pendant, terminal methacrylate groups. ### Claim 7 (depends on 6) The composition as in claim 6, further comprising a photosensitizer and a diaryliodonium or a sulfonium salt. ### Claim 8 (depends on 6) The composition as in claim 6, wherein the composition further includes monomers or oligomers selected from monomers or oligomers having one or more ethylenically unsaturated groups, di-acrylates and methacrylates, tri-acrylates and methacrylates, poly-acrylates and methacrylates, 2-hydroxyethyl methacrylate (HEMA), methyl acrylate, methyl methacrylate, ethyl acrylate, isopropyl methacrylate, n-hexyl acrylate, stearyl acrylate, allyl acrylate, glycerol diacrylate, glycerol triacrylate, ethyl eneglycol diacrylate, diethyleneglycol diacrylate, triethyleneglycol dimethacrylate, diurethane dimethacrylate, 1,3-propanediol diacrylate, 1,3-propanediol dimethacrylate, trimethylolpropane triacrylate, 1,2,4-butanetriol trimethacrylate, 1,4-cyclohexanediol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, sorbitol hexacrylate, the diglycidyl methacrylate of bis-phenol (“BisGMA”), triethylene glycol dimethacrylate (TEGDMA), 1,6-bis-[2-methacryloyloxyethoxycarbonylamino]-2,4,4-trimethylhexane (UDMA), bis[1-(2-acryloxy)]-p-ethoxyphenyldimethylmethane, bis[1-(3-acryloxy-2-hydroxy)]-p-propoxyphenyldimethylmethane, trishydroxyethyl-isocyanurate trimethacrylate, the bis-acrylates and bis-methacrylates of polyethylene glycols of molecular weight 200-500, copolymerizable mixtures of acrylated monomers, copolymerizable acrylated oligomers, phosphoric acid derivatives and carboxylic acid derivatives of ethylenically unsaturated monomers, vinyl compounds, styrene, diallyl phthalate, divinyl succinate, divinyl adipate and divinylphthalate, and combinations thereof. ### Claim 9 (depends on 8) The composition as in claim 8, wherein the monomers or oligomers comprise at least one of 2-hydroxyethyl methacrylate (HEMA) and diglycidyl methacrylate of bis-phenol (BisGMA). ### Claim 10 (depends on 6, 8) The composition as in claim 8, wherein the monomers or oligomers comprise monomers or oligomers of the co-initiator of claim 6. ### Claim 11 (depends on 10) The composition as in claim 10, wherein the monomers or oligomers further comprise at least one of 2-hydroxyethyl methacrylate (HEMA) or diglycidyl methacrylate of bis-phenol (BisGMA). ### Claim 12 (depends on 11) The composition as in claim 11, further comprising a photosensitizer and a diaryliodonium or a sulfonium salt. ### Claim 13 A method of preparing a light cured polymer-based dental restorative material, comprising: combining a set of one or more monomers or oligomers with a photoinitiator system, the photoinitiator system comprising: a co-initiator comprising a tertiary amine core and two or more pendant, terminal methacrylate groups; exposing the combined set of one or more monomers or oligomers and photoinitiator system to light so as to polymerize the set of one or more monomers or oligomers to yield a polymer. ### Claim 14 (depends on 13) The method as in claim 13, wherein the polymer is prepared in a mouth of a subject. ### Claim 15 (depends on 13) The method as in claim 13, wherein the one or more monomers or oligomers are selected from monomers or oligomers having one or more ethylenically unsaturated groups, di-acrylates and methacrylates, tri-acrylates and methacrylates, poly-acrylates and methacrylates, 2-hydroxyethyl methacrylate (HEMA), methyl acrylate, methyl methacrylate, ethyl acrylate, isopropyl methacrylate, n-hexyl acrylate, stearyl acrylate, allyl acrylate, glycerol diacrylate, glycerol triacrylate, ethyleneglycol diacrylate, diethyleneglycol diacrylate, triethyleneglycol dimethacrylate, diurethane dimethacrylate, 1,3-propanediol diacrylate, 1,3-propanediol dimethacrylate, trimethylolpropane triacrylate, 1,2,4-butanetriol trimethacrylate, 1,4-cyclohexanediol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, sorbitol hexacrylate, the diglycidyl methacrylate of bis-phenol (“BisGMA”), triethylene glycol dimethacrylate (TEGDMA), 1,6-bis-[2-methacryloyloxyethoxycarbonylamino]-2,4,4-trimethylhexane (UDMA), bis[1-(2-acryloxy)]-p-ethoxyphenyldimethylmethane, bis[1-(3-acryloxy-2-hydroxy)]-p-propoxyphenyldimethylmethane, trishydroxyethyl-isocyanurate trimethacrylate, the bis-acrylates and bis-methacrylates of polyethylene glycols of molecular weight 200-500, copolymerizable mixtures of acrylated monomers, copolymerizable acrylated oligomers, phosphoric acid derivatives and carboxylic acid derivatives of ethylenically unsaturated monomers, vinyl compounds, styrene, diallyl phthalate, divinyl succinate, divinyl adipate and divinylphthalate, and combinations thereof. ### Claim 16 (depends on 15) The method as in claim 15, wherein the one or more monomers or oligomers are 2-hydroxyethyl methacrylate (HEMA), diglycidyl methacrylate of bis-phenol (BisGMA), or combinations thereof. ### Claim 17 (depends on 13) The method as in claim 13, wherein the photoinitiator system further comprises a photosensitizer. ### Claim 18 (depends on 17) The method as in claim 17, wherein the photoinitiator system further comprises a diaryliodonium or a sulfonium salt. ### Claim 19 (depends on 13) The method as in claim 13, wherein the set of monomers or oligomers comprises the co-initiator. ### Claim 20 (depends on 13) The method as in claim 13, wherein the polymer leaches substantially no co-initiator following polymerization.