Olefin metathesis photopolymers

Abstract

Described herein are compositions and methods for processing photopolymers based on olefin metathesis. The compositions and methods comprise latent ruthenium complexes and photoacids and/or photoacid generators.

1 .- 74 . (canceled) 
     
     
         75 . A composition for generating a polymer, comprising (i) a latent ruthenium (Ru) complex;
 (ii) an initiator that is configured to undergo activation upon exposure of said initiator to electromagnetic radiation to yield an activated initiator that reacts with said latent Ru complex to yield an activated Ru complex; (iii) a sensitizer that is configured to sensitize said initiator; (iv) at least one polymer precursor that is configured to react with said activated Ru complex to yield at least a portion of said polymer.   
     
     
         76 . The composition of  claim 75 , wherein said initiator is an iodonium salt, a sulfonium salt, a dicarboximide, a thioxanthone, or an oxime. 
     
     
         77 . The composition of  claim 76 , wherein said initiator is an iodonium salt, a sulfonium salt, or a dicarboximide. 
     
     
         78 . The composition of  claim 75 , wherein said sensitizer is a conjugated aromatic molecule, a phenothiazine, a thioxanthone, a coumarin, an indoline, a porphyrin, a rhodamine, a pyrylium, a phenazine, a phenoxazine, an alpha hydroxy ketone, or a phosphine oxide. 
     
     
         79 . The composition of  claim 78 , wherein said sensitizer is a compound selected from the group consisting of: 
       
         
           
           
               
               
           
         
       
     
     
         80 . The composition of  claim 75 , wherein said at least one polymer precursor is selected from the group consisting of a dicyclopentadiene, a branched, a crosslinked poly(dicyclopentadiene), an oligomeric poly(dicyclopentadiene), or a polymeric poly(dicyclopentadiene)), norbornene, aliphatic olefin, cyclooctene, cyclooctadiene, tricyclopentadiene, polybutadiene, an ethylene propylene diene monomer (EPDM) rubber, a polypropylene, a polyethylene, a cyclic olefin polymer, and a diimide. 
     
     
         81 . The composition of  claim 75 , wherein said latent Ru complex is a compound selected from the group consisting of. 
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
       
     
     
         82 . The composition of  claim 75 , further comprising an additive. 
     
     
         83 . The composition of  claim 82 , wherein said additive is selected from the group consisting of an antioxidant, a filler, an optical brightener, an ultraviolet (UV) absorber, a pigment, a dye, a photoredox agent, an oxygen scavenger, a flame retardant, an impact modifier, a particle, a filler, a fiber, a nanoparticle, a plasticizer, a solvent, an oil, a wax, a vulcanizing agent, a crosslinker, hindered amine light stabilizer (HALS), a polymerization inhibitor, a shelf-life stabilizer, a chain-transfer agent, and a sizing agent. 
     
     
         84 . The composition of  claim 82 , wherein said additive is a compound selected from the group consisting of 
       
         
           
           
               
               
           
         
       
     
     
         85 . A mixture for use in a system for making a three-dimensional (3D) object, said mixture comprising:
 (i) a polymerizable component including one or more monomers that comprise at least one olefin;   (ii) a ruthenium (Ru) complex; and   (iii) an initiator that is activatable upon exposure to electromagnetic radiation, wherein said initiator is a photoacid or a photoacid generator.   
     
     
         86 . The mixture of  claim 85 , wherein said one or more monomers that comprise at least one olefin is selected from the group consisting of dicyclopentadiene, norbornene, aliphatic olefin, cyclooctene, cyclooctadiene, tricyclopentadiene, polybutadiene, an ethylene propylene diene monomer (EPDM) rubber, a polypropylene, a polyethylene, and a cyclic olefin polymer (e.g., a cyclic olefin copolymer). 
     
     
         87 . The mixture of  claim 85 , wherein said photoacid or photoacid generator comprises an iodonium salt or a sulfonium salt. 
     
     
         88 . The mixture of  claim 85 , further comprising a sensitizer that is configured to sensitize said initiator. 
     
     
         89 . The mixture of  claim 88 , wherein said sensitizer is a conjugated aromatic molecule, a phenothiazine, a thioxanthone, a coumarin, an indoline, a porphyrin, a rhodamine, a pyrylium, a phenazine, a phenoxazine, an alpha hydroxy ketone, or a phosphine oxide. 
     
     
         90 . The mixture of  claim 89 , wherein said sensitizer is a compound selected from the group consisting of: 
       
         
           
           
               
               
           
         
       
     
     
         91 . The mixture of  claim 85 , wherein said Ru complex is a compound selected from the group consisting of: 
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
       
     
     
         92 . The mixture of  claim 85 , further comprising an additive. 
     
     
         93 . The mixture of  claim 92 , wherein said additive is selected from the group consisting of an antioxidant, a filler, an optical brightener, an ultraviolet (UV) absorber, a pigment, a dye, a photoredox agent, an oxygen scavenger, a flame retardant, an impact modifier, a particle, a filler, a fiber, a nanoparticle, a plasticizer, a solvent, an oil, a wax, a vulcanizing agent, a crosslinker, hindered amine light stabilizer (HALS), a polymerization inhibitor, a shelf-life stabilizer, a chain-transfer agent, and a sizing agent. 
     
     
         94 . The mixture of  claim 92 , wherein said additive is a compound selected from the group consisting of