Homopolymers of terpenoid alcohols and their uses

Abstract

The present disclosure relates to the homopolymerization of terpenoids containing an alcohol functional group by free radical polymerization.

1 . A terpenoid homopolymer having the general representative structure (II) 
       
         
           
           
               
               
           
         
         wherein the broken lines represent either a carbon-carbon single or double bond, with at least one carbon double bond being present in the structure, 
         n is an integer between 1 and 10,000; 
         R 1  to R 14  are independently or simultaneously H, halo, (C 1 -C 24 )-alkyl, (C 2 -C 24 )-alkenyl, (C 2 -C 24 )-alkynyl, (C 6 -C 14 )-aryl or (C 5 -C 14 )-heteroaryl, wherein the latter 5 groups are optionally substituted and wherein the optional substituents are chosen from one or more of halogen, —OH, (C 1 -C 6 )-alkyl, (C 1 -C 6 )-alkoxy, thionyl, nitro, amino (—NH2), (C 6 -C 14 )-aryl, (C 5 -C 14 )-heteroaryl, phosphate (—PO 4 ), and phosphoryl (—PO 3 ), 
         wherein at least one of R 1 -R 14  contains at least one —OH group; 
         and wherein R 1 -R 14  can also optionally comprise one or more isoprene subunits according to the general structure 
       
       
         
           
           
               
               
           
         
       
     
     
         2 . The terpenoid homopolymer of  claim 1 , wherein the homopolymer is comprised of covalently joined terpenoid monomers having the general structures 
       
         
           
           
               
               
           
         
       
       wherein R1-R14 and the dashed lines are as defined in  claim 1 . 
     
     
         3 . The terpenoid homopolymer of  claim 2 , wherein the terpenoid monomer is a cyclic terpenoid or a poly-cyclic terpenoid. 
     
     
         4 . The terpenoid homopolymer of  claim 3 , wherein the cyclic terpenoid is chosen from terpineol and its isomers. 
     
     
         5 . The terpenoid homopolymer of  claim 1 , wherein n is an integer between about 5 and about 1,000. 
     
     
         6 . The terpenoid homopolymer of  claim 1 , wherein n is an integer between about 5 and about 15. 
     
     
         7 . The terpenoid homopolymer of  claim 1 , wherein the terpenoid homopolymer is a functional polyol pre-polymer. 
     
     
         8 . The terpenoid homopolymer of  claim 1 , wherein the terpenoid homopolymer is a functional pre-polymer for urethane chemistry. 
     
     
         9 . The terpenoid homopolymer of  claim 1 , wherein the terpenoid homopolymer has therapeutic, antimicrobial, preservative or insecticidal properties. 
     
     
         10 . The terpenoid homopolymer of  claim 1 , wherein the terpenoid homopolymer is incorporated as an organoleptic agent in a cosmetic formulation 
     
     
         11 . The terpenoid homopolymer of  claim 1 , wherein the terpenoid homopolymer is incorporated into a finished consumer product or packaging materials to impart antimicrobial or organoleptic properties to the material. 
     
     
         12 . The terpenoid homopolymer of  claim 1 , the terpenoid homopolymer forms a liquid antimicrobial coating by non-covalently bonding to the desired surface or substrate. 
     
     
         13 . The terpenoid homopolymer of  claim 1 , wherein the antimicrobial terpenoid homopolymer is incorporated into bandages, shrink coatings, polymeric and other composite materials for medicinal, protective coatings and packaging applications. 
     
     
         14 . The terpenoid homopolymer of  claim 1 , wherein the terpenoid homopolymer is applied as a film or surface coating by chemical functionalization or reactions of the hydroxyl group with the surface. 
     
     
         15 . The terpenoid homopolymer of  claim 1 , wherein the terpenoid homopolymer is a feedstock for renewable plastic materials. 
     
     
         16 . A method of synthesizing a terpenoid homopolymer as defined in  claim 1 , comprising homopolymerizing a terpenoid monomer comprising at least one double bond, conjugated double bond or aromatic double bond and at least one hydroxyl functional group by free radical polymerization, the method comprising
 i. Reacting the monomer with a free radical initiator without deprotonation or without protecting groups;   ii. Optionally deprotonating or protecting the hydroxyl functionality of the monomer prior to polymerization.   
     
     
         17 . The method of  claim 16 , wherein the free radical initiator is selected from hydrogen peroxide, an azo initiator, a halogen initiator, an organic peroxide initiator, an inorganic peroxide initiator, a hydroxyperoxy initiator, a photosensitizer, a photo initiator and a transition metal catalyst capable of generating radicals for polymerization. 
     
     
         18 . The method of  claim 17 , wherein the polymerization is initiated thermally or photoinitiated.