Infusion of cyclic olefin resins into porous materials

Abstract

The present invention relates to novel compositions comprising porous materials infused with polymers obtained from metathesis reactions, for example ROMP derived polymers and ADMET derived polymers. The invention further relates to cyclic olefin monomer formulations, including ruthenium or osmium carbene metathesis catalysts, useful for the infusion of porous materials. Also disclosed are methods for preparing the porous materials infused with cyclic olefin resin formulations.

What is claimed is:  
     
         1 . A composition comprising a porous material infused with a metathesis-derived polyolefin.  
     
     
         2 . The composition of  claim 1 , further comprising a coupling agent.  
     
     
         3 . The composition of  claim 2 , wherein the coupling agent is selected from the group consisting of organotitanates, organozirconates, and silanes.  
     
     
         4 . The composition of  claim 1  wherein the porous material is selected from the group consisting of a non-organic material and an organic material.  
     
     
         5 . The composition of  claim 1 , wherein the porous material is selected from the group consisting of wood, cement, concrete, open-cell and reticulated foams and sponges, papers, cardboards, felts, ropes and braids of natural or synthetic fibers, sintered materials, unglazed porous ceramics, compacted free standing metal powder objects, porous concrete aggregates, wood, wood products, and cellulosic materials.  
     
     
         6 . The composition of  claim 1 , wherein the metathesis-derived polyolefin is selected from the group consisting of a ROMP polymer and an ADMET polymer.  
     
     
         7 . The composition of  claim 1 , wherein the metathesis-derived polyolefin is prepared from one or more olefin monomers selected from the group consisting of norbornenes, cyclopropenes, cyclobutenes, benzocyclobutenes, cyclopentenes, cyclopentadiene oligomers, cyclohexenes, cycloheptenes, cyclooctenes, cyclooctadienes, norbornadienes, [2.2.1]bicycloheptenes, and [2.2.2]bicyclooctene, cyclohexenylnorbornenes, and norbornene dicarboxylic anhydrides.  
     
     
         8 . The composition of  claim 1 , wherein the metathesis-derived polyolefin is polydicyclopentadiene.  
     
     
         9 . The composition of  claim 1 , wherein the metathesis-derived polyolefin is polymerized using a ruthenium or osmium metal carbene catalyst.  
     
     
         10 . The composition of  claim 1 , wherein the metathesis-derived polyolefin is polymerized using a catalyst selected from the group consisting of a catalyst of the formula:  
       
         
           
           
               
               
           
         
         wherein: 
 M is ruthenium or osmium;  
 n is an integer between 0-5;  
 L, L 1  and L 2  are each independently any neutral electron donor ligand;  
 R and R 1  are each independently hydrogen or any hydrocarbyl or silyl moiety;  
 X and X 1  are each independently any anionic ligand;  
 Y is any noncoordinating anion; and  
 Z and Z 1  are each independently any linker selected from the group consisting of —O—, —S—, —NR 2 —, —PR 2 —, —P(═O)R 2 —, —P(OR 2 )—, —P(═O)(OR 2 )—, —C(═O)—, —C(═O)O—, —OC(═O)—, —OC(═O)O—, —S(═O)—, or —S(═O) 2 —.  
 
       
     
     
         11 . A method for preparing a polyolefin-infused porous material comprising: 
 mixing an olefin monomer resin formulation with a metathesis catalyst to form a catalyzed resin formulation, infusing the mixture into the porous material, and curing the catalyzed resin formulation within said porous material.    
     
     
         12 . The method of  claim 11  wherein the porous material is selected from the group consisting of wood, cement, concrete, open-cell and reticulated foams and sponges, papers, cardboards, felts, ropes or braids of natural or synthetic fibers, and sintered materials.  
     
     
         13 . The method of  claim 11 , wherein the olefin monomer resin formulation comprises an olefin monomer selected from the group consisting of norbornenes, cyclopropenes, cyclobutenes, benzocyclobutenes, cyclopentenes, cyclopentadiene oligomers, cyclohexenes, cycloheptenes, cyclooctenes, cyclooctadienes, norbornadienes, [2.2.1]bicycloheptenes, and [2.2.2]bicyclooctene, cyclohexenylnorbornenes, and norbornene dicarboxylic anhydrides.  
     
     
         14 . The method of  claim 11 , wherein the olefin monomer resin formulation comprises dicyclopentadiene.  
     
     
         15 . The method of  claim 11 , wherein the olefin monomer resin formulation includes a coupling agent.  
     
     
         16 . The method of  claim 11 , wherein the coupling agent is selected from the group consisting of organotitanates, organozirconates, and silanes.  
     
     
         17 . The method of  claim 11 , wherein the metathesis catalyst is a ruthenium or osmium metal carbene complex.  
     
     
         18 . The method of  claim 11 , wherein the wherein the metathesis catalyst is selected from the group consisting of a catalyst of the formula:  
       
         
           
           
               
               
           
         
         wherein: 
 M is ruthenium or osmium;  
 n is an integer between 0-5;  
 L, L 1  and L 2  are each independently any neutral electron donor ligand;  
 R and R 1  are each independently hydrogen or any hydrocarbyl or silyl moiety;  
 X and X 1  are each independently any anionic ligand;  
 Y is any noncoordinating anion; and  
 Z and Z 1  are each independently any linker selected from the group consisting of —O—, —S—, —NR 2 —, —PR 2 —, —P(═O)R 2 —, —P(OR 2 )—, —P(═O)(OR 2 )—, —C(═O)—, —C(═O)O—, —OC(═O)—, —OC(═O)O—, —S(═O)—, or —S(═O) 2 —.  
 
       
     
     
         19 . A method for preparing a polyolefin-infused wood object comprising: 
 spraying the wood object with a cleaning and wetting high-pressure water spray;    drying the object, wherein the drying is performed by heat and vacuum;    infusing the object with a mixture of an olefin monomer resin formulation and a metathesis catalyst under pressure;    curing the catalyzed resin formulation within the wood object;    and post-curing the polyolefin-infused wood object.    
     
     
         20 . An article of manufacture comprising a porous material infused with a metathesis-derived polyolefin.  
     
     
         21 . The article of manufacture of  claim 20 , wherein the article is selected from the group consisting of golf tees, golf clubs, weighted golf club heads, golf club shafts, golf club gradient shafts, basketball backboards, tennis rackets, squash rackets, racquetball rackets, badminton rackets, snow boards, surfboards, boogie board, skis, backboards, sleds, toboggans, baseball bats, cricket bats, hockey sticks, pool cues, archery bows, archery arrows, rifle butts, polo mallets, croquet mallets, tent stakes, piers, docks, posts, decking, hulls, oars, propellers, rudders, keels, masts, boat fascia, kayaks, canoes, ferro-cement boats, hand-tool handles, knife handles, ladders, wood flooring panels, deck lumber, treated concrete or cinder blocks, door and window frames, office furniture, concrete bridge decks, parking structure ramps, post-tensional beams and slabs, treated concrete pipes and channel liners for aggressive and acidic fluids, sewer pipes, containment structures, pavers, stone consolidation, plaster or concrete ornamental objects, and pre-cast concrete objects.  
     
     
         22 . The article of manufacture of  claim 20 , wherein the article is a baseball bat.