Thiol-containing dual cure polymers and methods using same
The invention includes a composition comprising a vinyl sulfone monomer, a thiol monomer and an acrylate monomer. In one embodiment, the thiol monomer reacts with the vinyl sulfone monomer preferentially over the acrylate monomer, and this differential selectivity allows for the control of the architecture of crosslinking polymer network. The invention further includes a composition comprising an electrophilic monomer, a nucleophilic monomer, a nucleophilic catalyst and an acid, wherein the concentrations of the nucleophilic catalyst and acid are selected as to provide a specific induction time for the polymerization reaction of the composition.
1. A composition comprising a vinyl sulfone monomer, a thiol monomer, and an acrylate monomer, wherein the thiol equivalent concentration is substantially equal to one selected from the group consisting of: the vinyl sulfone equivalent concentration; and the sum of the vinyl sulfone equivalent concentration and the acrylate equivalent concentration.
2. The composition of claim 1 , further comprising at least one catalyst, wherein the catalyst comprises a base or nucleophile.
3. The composition of claim 2 , wherein the catalyst comprises a tertiary amine or phosphine, wherein each substituent on the tertiary amine or phosphine is independently alkyl, substituted alkyl, aryl or substituted aryl.
4. The composition of claim 1 , further comprising a polymerization photoinitiator, wherein the photoinitiator promotes photopolymerization of at least a portion of the acrylate monomer upon irradiation with UV radiation.
5. The composition of claim 4 , wherein the polymerization photoinitiator is selected from the group consisting of 2,2-dimethoxy-1,2-diphenylethan-1-one, bis(2,4,6-trimethylbenzoyl)-phenylphosphineoxide, 1-hydroxycyclohexyl benzophenone, trimethyl-benzoyl-diphenyl-phosphine-oxide, and any combinations thereof.
6. The composition of claim 4 , further comprising a polymerization accelerator or inhibitor.
7. The composition of claim 1 , wherein the acrylate monomer is selected from the group consisting of ethylene glycoldi(meth)acrylate, tetraethyleneglycol-di(meth)acrylate, poly(ethylene glycol)dimethacrylates, the condensation product of bisphenol A and glycidyl methacrylate, 2,2′-bis[4-(3-methacryloxy-2-hydroxypropoxy)-phenyl]propane, hexanediol di(meth)acrylate, tripropylene glycol di(meth)acrylate, butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, allyl(meth)acrylate trimethylolpropane triacrylate, tricyclodecane dimethanol diacrylate, and any combinations thereof.
8. The composition of claim 1 , wherein the thiol monomer is selected from the group consisting of 2,5-dimercaptomethyl-1,4-dithiane, 2,3-dimercapto-1-propanol, 2-mercapto-ethylsulfide, 2,3-(dimercaptoethylthio)-1-mercaptopropane, 1,2,3-trimercaptopropane, ethylene glycol bis(thioglycolate), ethylene glycol bis(3-mercaptopropionate), pentaerythritol tetra(3-mercaptopropionate), trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetra(2-mercaptoacetate), trimethylolpropane tris(2-mercaptoacetate), 1,6-hexanedithiol, 1,2-benzenedithiol, 1,3-benzenedithiol, isophorone diurethane thiol, and any combinations thereof.
9. The composition of claim 1 , wherein the vinyl sulfone monomer is selected from the group consisting of ethyl vinyl sulfone, divinyl sulfone, the compounds depicted in FIG. 45 , and any combinations thereof.
10. A method of generating a polymeric material, comprising the steps of:
providing a composition comprising a vinyl sulfone monomer, a thiol monomer, an acrylate monomer, and at least one catalyst, wherein the catalyst comprises a base or nucleophile, wherein the thiol equivalent concentration is substantially equal to one selected from the group consisting of: the vinyl sulfone equivalent concentration; and the sum of the vinyl sulfone equivalent concentration and the acrylate equivalent concentration;
submitting the composition to a first polymerization process, whereby the vinyl sulfone monomer is substantially polymerized and the acrylate monomer is substantially not polymerized; and,
submitting the composition to a second polymerization process, whereby the acrylate monomer is substantially polymerized;
thereby generating the polymeric material.
11. The method of claim 10 , wherein the second polymerization process comprises photopolymerization and the composition further comprises a polymerization photoinitiator.