Rapid composition-controlled photo-copolymerization of styrene and methacrylate derivatives and uses thereof

Abstract

A composition of matter includes a mixture of styrene derivative monomers and methacrylate and/or acrylate derivative monomers, which have one or more urethane, carbamate, amide, and/or amine functional groups, and initiators, and the compositions are used to achieve composition control of the forming polymer, with the mole fraction of acrylate/methacrylate and styrene moieties in the forming polymer determined by the chemistry and composition of the feeding monomers.

I claim: 
     
         1 . A method for controlling a composition of a polymer, comprising:
 disposing in a monomer mixture, an equal molar quantity of urethane dimethacrylate (UDMA) and triethyleneglycol-divinylbenzyl ether (TEG-DVBE); and   polymerizing the monomer mixture by light irradiation to form a composition-controlled cross-linked resin.   
     
     
         2 . The method of  claim 1 , further comprising disposing in the monomer mixture one or more initiators selected from the group consisting of camphorquinone or derivatives, a combination of camphorquinone and amine(s) derivatives, phenylpropanedione or derivatives, bisacylphosphine oxide or derivatives, and 1-hydroxycyclohexyl phenyl ketone. 
     
     
         3 . The method of  claim 1 , further comprising;
 disposing in the monomer mixture one or more porous objects selected from the group consisting of metal oxide particles, ceramic particles, chitosan, and polysaccharide particles, wherein the particles are selected from the group consisting of nano-scale particles and micro-scale particles; and   polymerizing the monomer mixture following infiltration of the monomer mixture into pores of the porous objects.   
     
     
         4 . The method of  claim 1 , further comprising, disposing in the monomer mixture one or more solvents. 
     
     
         5 . The method of  claim 1 , further comprising adding heat during the polymerizing. 
     
     
         6 . The method of  claim 1 , wherein the light is visible light. 
     
     
         7 . The method of  claim 1 , further comprising:
 selectively exposing the monomer mixture to light irradiation to create exposed and reacted regions and unexposed and unreacted regions; and   removing unreacted monomer mixture from the unexposed and unreacted regions.   
     
     
         8 . The method of  claim 7 , comprising polymerizing the monomer mixture to form three-dimensional (3D) dental polymer products comprising dental restorative materials, laminate veneers, inlays, onlays, fixed bridges, and implants. 
     
     
         9 . The method of  claim 1 , controlling a degree of vinyl conversion (DC) of the monomer mixture by one or more of varying an intensity of the light irradiation and varying a length of time of the light irradiation. 
     
     
         10 . A method for rapid, azeotropic three-dimensional (3D) composition-controlled printing of dental polymer products, comprising:
 determining a desired polymerization shrinkage, hydrophilicity, hydrophobicity, and hydrogen bonding for a 3D printed dental polymer product;   disposing in a monomer mixture, a first molar quantity of acrylate or acrylate derivatives and a second molar quantity of triethyleneglycol-divinylbenzyl ether (TEG-DVBE);   disposing in the monomer mixture, a photo-initiator; and   polymerizing the monomer mixture by light irradiation to form a composition-controlled cross-linked resin having the desired polymerization shrinkage, hydrophilicity, hydrophobicity, and hydrogen bonding.   
     
     
         11 . The method of  claim 10 , wherein the first molar quantity and the second molar quantity are equal. 
     
     
         12 . The method of  claim 10 , wherein the acrylate derivatives have functional components selected from the group consisting of one or more carbamates and/or derivatives, one or more urethanes and/or derivatives, one or more amines and/or derivatives, and combinations thereof. 
     
     
         13 . The method of  claim 10 , wherein the acrylate derivative consists of urethane dimethacrylate (UDMA), and wherein the UDMA is the photo-initiator. 
     
     
         14 . The method of  claim 13 , wherein an additional photo-initiator is selected from the group consisting of camphorquinone (CQ) or derivatives, a combination of camphorquinone and amine(s) derivatives, phenylpropanedione or derivatives, bisacylphosphine oxide or derivatives, and 1-hydroxycyclohexyl phenyl ketone. 
     
     
         15 . The method of  claim 14 , comprising controlling a degree of vinyl conversion (DC) by selecting CQ/amine as the additional photo-initiator. 
     
     
         16 . The method of  claim 14 , comprising increasing a polymerization rate and increasing a degree of polymer conversion (DC) by increasing a molar ratio of UDMA to TEG-DVBE in the monomer mixture. 
     
     
         17 . The method of  claim 10 , comprising increasing a degree of vinyl conversion (DC) by adding heat during the polymerization. 
     
     
         18 . The method of  claim 10 , comprising varying a degree of vinyl conversion (DC) by one or more of varying an intensity of the light irradiation and varying a length of time of the light irradiation during the polymerization. 
     
     
         19 . A method for rapid, composition-controlled printing of relief polymeric objects, comprising:
 preparing one or more monomer mixtures, each monomer mixture having a desired and different molar ratio of an acrylate or acrylate derivative and TEG-DVBE;   adding to each of the monomer mixtures, one or more initiators; and   polymerizing the monomer mixtures using light irradiation, comprising:
 disposing a first layer of a first monomer mixture on substrate and polymerizing the first layer, 
 disposing a second layer of a second monomer mixture on the substrate and polymerizing the second layer, and 
 repeating the disposing and polymerizing, layer by layer, to achieve a desired 3D object. 
   
     
     
         20 . The method of  claim 19 , further comprising during polymerizing, varying a degree of vinyl conversion (DC) of one or more layers by:
 varying light intensity and duration; and   adding heat during the polymerizing.