Thermoset particles with enhanced crosslinking, processing for their production, and their use in oil and natural gas driliing applications

Abstract

Thermoset polymer particles are used in many applications requiring lightweight particles possessing high stiffness, strength, temperature resistance, and/or resistance to aggressive environments. The present invention relates to the use of methods to enhance the stiffness, strength, maximum possible use temperature, and environmental resistance of such particles. One method of particular interest is the application of post-polymerization process step(s) (and especially heat treatment) to advance the curing reaction and to thus obtain a more densely crosslinked polymer network. The most common benefits of said heat treatment are the enhancement of the maximum possible use temperature and the environmental resistance. The present invention also relates to the development of thermoset polymer particles. It also relates to the further improvement of the key properties (in particular, heat resistance and environmental resistance) of said particles via post-polymerization heat treatment. Furthermore, it also relates to processes for the manufacture of said particles. Finally, it also relates to the use of said particles in the construction, drilling, completion and/or fracture stimulation of oil and natural gas wells; for example, as a proppant partial monolayer, a proppant pack, an integral component of a gravel pack completion, a ball bearing, a solid lubricant, a drilling mud constituent, and/or a cement additive.

1 . A polymeric particle having a substantially cured polymer network; wherein a packing of said particles manifests a static conductivity of at least 100 mDft after 200 hours at temperatures greater than 80° F.; made by a method comprising: forming a polymer by polymerizing a reactive mixture containing at least one of a monomer, an oligomer, or combinations thereof; said at least one of a monomer, an oligomer, or combinations thereof having three or more reactive functionalities capable of creating crosslinks between polymer chains; and subjecting said particle to at least one post-polymerizing process that advances curing of a polymer network.  
     
     
         2 . The particle of  claim 1 , wherein said reactive mixture contains a crosslinking component comprising at least one of a first monomer, a first oligomer or a first combination thereof; and wherein said reactive mixture further contains a non-crosslinking component comprising at least one of a second monomer, a second oligomer or a second combination thereof.  
     
     
         3 . The particle of  claim 1 , wherein an amount of crosslinking component ranges from 1% to 100% by weight of the reactive mixture.  
     
     
         4 . The particle of  claim 1 , wherein said reactive mixture comprises at least one of monomer, oligomer or combinations thereof; said at least one of monomer, oligomer or combinations thereof being used to synthesize thermoset epoxies, epoxy vinyl esters, polyesters, phenolics, melamine-based resins, polyurethanes, polyureas, polyimides, or mixtures thereof.  
     
     
         5 . The particle of  claim 1 , wherein said reactive mixture comprises a crosslinking monomer selected from the group consisting of: Divinylbenzene, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, trimethylolpropane dimethacrylate, trimethylolpropane diacrylate, pentaerythritol tetramethacrylate, pentaerythritol trimethacrylate, pentaerythritol dimethacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, pentaerythritol diacrylate, bisphenol-A diglycidyl methacrylate, ethyleneglycol dimethacrylate, ethyleneglycol diacrylate, diethyleneglycol dimethacrylate, diethyleneglycol diacrylate, triethyleneglycol dimethacrylate, and triethyleneglycol diacrylate, a bis(methacrylamide) having the formula:  
       
         
           
           
               
               
           
         
         a bis(acrylamide) having the formula:  
         
           
             
             
                 
                 
             
           
         
         a polyolefin having the formula CH 2 ═CH—(CH 2 ) x —CH═CH 2  (wherein x ranges from 0 to 100, inclusive), a polyethyleneglycol dimethylacrylate having the formula:  
         
           
             
             
                 
                 
             
           
         
         a polyethyleneglycol diacrylate having the formula:  
         
           
             
             
                 
                 
             
           
         
         a molecule or a macromolecule containing at least three isocyanate (—N═C═O) groups, a molecule or a macromolecule containing at least three alcohol (—OH) groups, a molecule or a macromolecule containing at least three reactive amine functionalities where a primary amine (—NH 2 ) contributes two to the total number of reactive functionalities while a secondary amine (—NHR—, where R can be any aliphatic or aromatic organic fragment) contributes one to the total number of reactive functionalities; and a molecule or a macromolecule where the total number of reactive functionalities arising from any combination of isocyanate (—N═C═O), alcohol (—OH), primary amine (—NH 2 ) and secondary amine (—NHR—, where R can be any aliphatic or aromatic organic fragment) adds up to at least three, 1,4-divinyloxybutane, divinylsulfone, diallyl phthalate, diallyl acrylamide, triallyl cyanurate, triallyl isocyanurate, triallyl trimellitate or mixtures thereof.  
       
     
     
         6 . The particle of  claim 5 , wherein said reactive mixture comprises a non-crosslinking monomer selected from the group consisting of: Styrenic monomers, styrene, methylstyrene, ethylstyrene (ethylvinylbenzene), chlorostyrene, chloromethylstyrene, styrenesulfonic acid, t-butoxystyrene, t-butylstyrene, pentylstyrene, alpha-methylstyrene, alpha-methyl-p-pentylstyrene; acrylic and methacrylic monomers, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, lauryl acrylate, lauryl methacrylate, glycidyl acrylate, glycidyl methacrylate, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, diethylene glycol acrylate, diethylene glycol methacrylate, glycerol monoacrylate, glycerol monomethacrylate, polythylene glycol monoacrylate, polyethylene glycol monomethacrylate, butanediol monoacrylate, butanediol monomethacrylate; unsaturated carboxylic acid monomers, acrylic acid, methacrylic acid; alkyl vinyl ether monomers, methyl vinyl ether, ethyl vinyl ether; vinyl ester monomers, vinyl acetate, vinyl propionate, vinyl butyrate; N-alkyl substituted acrylamides and methacrylamides, N-methylacrylamide, N-methylmethacrylamide, N-ethyl acrylamide, N-ethyl methacrylamide; nitrile monomers, acrylonitrile, methacrylonitrile; olefinic monomers, ethylene (H 2 C═CH 2 ) and the alpha-olefins (H 2 C═CHR) where R is any saturated hydrocarbon fragment; vinylic alcohols, vinyl alcohol; vinyl halides, vinyl chloride; vinylidene halides, vinylidene chloride, or mixtures thereof.  
     
     
         7 . The particle of  claim 1 , said method further comprising using a formulation including at least one of said reactive mixture, and additional formulation ingredients wherein said additional formulation ingredients are selected from the group of ingredients consisting of initiators, catalysts, inhibitors, dispersants, stabilizers, rheology modifiers, buffers, antioxidants, defoamers, impact modifiers, or mixtures thereof.  
     
     
         8 . The particle of  claim 1 , said post-polymerizing process being performed as a manufacturing process step, as an “in situ” process step in a hydrocarbon reservoir, or combinations thereof.  
     
     
         9 . The particle of  claim 8 , wherein said post-polymerizing process further comprises at least one of heat treatment, stirring, flow, sonication, irradiation, or combinations thereof.  
     
     
         10 . The particle of  claim 9 , wherein said heat treatment is performed in a medium including a vacuum, a non-oxidizing gas, a mixture of non-oxidizing gases, a liquid, or a mixture of liquids; or in a downhole environment of a hydrocarbon reservoir.  
     
     
         11 . The particle of  claim 1 , wherein said particle has a shape selected from the group of shapes consisting of a powder, a pellet, a grain, a seed, a short fiber, a rod, a cylinder, a platelet, a bead, a spheroid, or mixtures thereof.  
     
     
         12 . The particle of  claim 1 , wherein a largest principal axis dimension of said particle does not exceed 10 millimeters.  
     
     
         13 . The particle of  claim 2 , wherein the crosslinking component comprises divinylbenzene, wherein the non-crosslinking component comprises styrene, said divinylbenzene in an amount ranging from 3% to 35% by weight of the reactive mixture.  
     
     
         14 . The particle of  claim 13 , wherein said non-crosslinking monomer further comprises ethylvinylbenzene.  
     
     
         15 . The particle of  claim 13 , wherein said polymerizing comprises suspension polymerizing.  
     
     
         16 . The particle of  claim 15 , wherein said suspension polymerizing comprises rapid rate polymerizing.  
     
     
         17 . The particle of  claim 15 , wherein said suspension polymerizing comprises isothermal polymerizing.  
     
     
         18 . The particle of  claim 13 , said method further comprising using a formulation including at least one of said reactive mixture and additional formulation ingredients wherein said additional formulation ingredients comprise at least one of initiators, catalysts, inhibitors, dispersants, stabilizers, rheology modifiers, buffers, antioxidants, defoamers, impact modifiers, or mixtures thereof.  
     
     
         19 . The particle of  claim 13 , said method further comprising subjecting said particle to at least one post-polymerizing process.  
     
     
         20 . The particle of  claim 19 , wherein said post-polymerizing process further comprises at least one of heat treatment, stirring, flow, sonication, irradiation, or combinations thereof.  
     
     
         21 . The particle of  claim 19 , wherein an unreactive gaseous environment with nitrogen as the preferred unreactive gas is used as the heat transfer medium during said post-polymerizing process.  
     
     
         22 . The particle of  claim 13 , wherein said particle is a spherical bead having a diameter does not exceed 10 millimeters.  
     
     
         23 . The particle of  claim 22 , wherein said diameter ranges from 0.1 mm to 4 mm.  
     
     
         24 . A polymeric particle exhibiting a static conductivity of at least 100 mDft after 200 hours at temperatures greater than 80 OF; and comprising a rigid thermoset polymer.  
     
     
         25 . The particle of  claim 24 , wherein said thermoset polymer comprises a terpolymer.  
     
     
         26 . The particle of  claim 24 , wherein said thermoset polymer comprises a styrene-ethylvinylbenzene-divinylbenzene terpolymer.  
     
     
         27 . The particle of  claim 24 , wherein said particle has a shape selected from the group of shapes consisting of a powder, a pellet, a grain, a seed, a short fiber, a rod, a cylinder, a platelet, a bead, a spheroid, or mixtures thereof.  
     
     
         28 . The particle of  claim 24 , wherein a largest principal axis dimension of said particle does not exceed 10 millimeters.  
     
     
         29 . The particle of  claim 24 , wherein said particle is a spherical bead having a diameter that does not exceed 10 millimeters.  
     
     
         30 . The particle of  claim 29 , wherein said diameter ranges from 0.1 mm to 4 mm.  
     
     
         31 . An assembly of particles comprising a rigid thermoset polymer; said polymer having a substantially cured polymer network, and wherein a packing of said particles manifests a static conductivity of at least 100 mDft after 200 hours at temperatures greater than 80° F., wherein the particles in said assembly have sizes that do not exceed 10 millimeters in any principal axis direction.  
     
     
         32 . The assembly of particles of  claim 31 , wherein said thermoset polymer comprises a terpolymer.  
     
     
         33 . The assembly of particles of  claim 31 , wherein said thermoset polymer comprises a styrene-ethylvinylbenzene-divinylbenzene terpolymer.  
     
     
         34 . The assembly of particles of  claim 31 , wherein said particle is a spherical bead having a diameter that does not exceed 10 millimeters.  
     
     
         35 . The assembly of particles of  claim 34 , wherein said diameter ranges from 0.1 mm to 4 mm.  
     
     
         36 . A method for producing substantially cured polymeric particles, comprising: 
 (a) forming polymeric particles by polymerizing a reactive mixture, dispersed within a liquid medium, containing at least one of an initiator; and at least one of a monomer, an oligomer or combinations thereof, said at least one of a monomer, an oligomer, or combinations thereof having three or more reactive functionalities capable of creating crosslinks between polymer chains; wherein a packing of particles resulting from step (a) manifests a first static conductivity when measured after 200 hours under a given compressive stress and at a given temperature greater than 80° F.; and    (b) subjecting the particles polymerized in step (a) to at least one post-polymerizing process, wherein said post-polymerizing process advances curing of a polymer network of the polymeric particles forming the substantially cured polymeric particles, wherein a packing of the substantially cured polymeric particles manifests a second static conductivity when measured after 200 hours under the given compressive stress and at the given temperature; wherein the second static conductivity is greater than the first static conductivity.    
     
     
         37 . The method of  claim 36 , wherein said reactive mixture contains a crosslinking component comprising at least one of a first monomer, a first oligomer or a first combination thereof; and wherein said reactive mixture further contains a non-crosslinking component comprising at least one of a second monomer, a second oligomer or a second combination thereof.  
     
     
         38 . The method of  claim 37 , wherein an amount of crosslinking component ranges from 1% to 100% by weight of the reactive mixture.  
     
     
         39 . The method of  claim 36 , wherein said reactive mixture comprises at least one of monomer, oligomer or combinations thereof, said at least one of monomer, oligomer or combinations thereof being used to synthesize thermoset epoxies, epoxy vinyl esters, polyesters, phenolics, melamine-based resins, polyurethanes, polyureas, polyimides, or mixtures thereof.  
     
     
         40 . The method of  claim 36 , wherein said reactive mixture comprises a crosslinking monomer selected from the following list, or mixtures thereof: Divinylbenzene, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, trimethylolpropane dimethacrylate, trimethylolpropane diacrylate, pentaerythritol tetramethacrylate, pentaerythritol trimethacrylate, pentaerythritol dimethacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, pentaerythritol diacrylate, bisphenol-A diglycidyl methacrylate, ethyleneglycol dimethacrylate, ethyleneglycol diacrylate, diethyleneglycol dimethacrylate, diethyleneglycol diacrylate, triethyleneglycol dimethacrylate, and triethyleneglycol diacrylate, a bis(methacrylamide) having the formula:  
       
         
           
           
               
               
           
         
         a bis(acrylamide) having the formula:  
         
           
             
             
                 
                 
             
           
         
         a polyolefin having the formula CH 2 ═CH—(CH 2 ) x —CH═CH 2  (wherein x ranges from 0 to 100, inclusive), a polyethyleneglycol dimethylacrylate having the formula:  
         
           
             
             
                 
                 
             
           
         
         a polyethyleneglycol diacrylate having the formula:  
         
           
             
             
                 
                 
             
           
         
         a molecule or a macromolecule containing at least three isocyanate (—N═C═O) groups, a molecule or a macromolecule containing at least three alcohol (—OH) groups, a molecule or a macromolecule containing at least three reactive amine functionalities where a primary amine (—NH 2 ) contributes two to the total number of reactive functionalities while a secondary amine (—NHR—, where R can be any aliphatic or aromatic organic fragment) contributes one to the total number of reactive functionalities; and a molecule or a macromolecule where the total number of reactive functionalities arising from any combination of isocyanate (—N═C═O), alcohol (—OH), primary amine (—NH 2 ) and secondary amine (—NHR—, where R can be any aliphatic or aromatic organic fragment) adds up to at least three, 1,4-divinyloxybutane, divinylsulfone, diallyl phthalate, diallyl acrylamide, triallyl cyanurate, triallyl isocyanurate, triallyl trimellitate.  
       
     
     
         41 . The method of  claim 36 , wherein said reactive mixture comprises a non-crosslinking monomer selected from the following list, or mixtures thereof: Styrenic monomers, styrene, methylstyrene, ethylstyrene (ethylvinylbenzene), chlorostyrene, chloromethylstyrene, styrenesulfonic acid, t-butoxystyrene, t-butylstyrene, pentylstyrene, alpha-methylstyrene, alpha-methyl-p-pentylstyrene; acrylic and methacrylic monomers, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, lauryl acrylate, lauryl methacrylate, glycidyl acrylate, glycidyl methacrylate, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, diethylene glycol acrylate, diethylene glycol methacrylate, glycerol monoacrylate, glycerol monomethacrylate, polythylene glycol monoacrylate, polyethylene glycol monomethacrylate, butanediol monoacrylate, butanediol monomethacrylate; unsaturated carboxylic acid monomers, acrylic acid, methacrylic acid; alkyl vinyl ether monomers, methyl vinyl ether, ethyl vinyl ether; vinyl ester monomers, vinyl acetate, vinyl propionate, vinyl butyrate; N-alkyl substituted acrylamides and methacrylamides, N-methylacrylamide, N-methylmethacrylamide, N-ethyl acrylamide, N-ethyl methacrylamide; nitrile monomers, acrylonitrile, methacrylonitrile; olefinic monomers, ethylene (H 2 C═CH 2 ) and the alpha-olefins (H 2 C═CHR) where R is any saturated hydrocarbon fragment; vinylic alcohols, vinyl alcohol; vinyl halides, vinyl chloride; vinylidene halides, vinylidene chloride or mixtures thereof.  
     
     
         42 . The method of  claim 36 , said method further comprising using a formulation including at least one of said reactive mixture, and additional formulation ingredients wherein said additional formulation ingredients are selected from the group of ingredients consisting of initiators, catalysts, inhibitors, dispersants, stabilizers, rheology modifiers, buffers, antioxidants, defoamers, impact modifiers, or mixtures thereof.  
     
     
         43 . The method of  claim 36 , said post-polymerizing process being performed as a manufacturing process step, as an “in situ” process step in a hydrocarbon reservoir, or combinations thereof.  
     
     
         44 . The method of  claim 43 , wherein said post-polymerizing process further comprises at least one of heat treatment, stirring, flow, sonication, irradiation, or combinations thereof.  
     
     
         45 . The method of  claim 44 , wherein said heat treatment is performed in a medium including a vacuum, a non-oxidizing gas, a mixture of non-oxidizing gases, a liquid, or a mixture of liquids; or in a downhole environment of a hydrocarbon reservoir.  
     
     
         46 . The method of  claim 36 , wherein said particle has a shape; selected from the group of shapes consisting of a powder, a pellet, a grain, a seed, a short fiber, a rod, a cylinder, a platelet, a bead, a spheroid, or mixtures thereof.  
     
     
         47 . The method of  claim 36 , wherein a largest principal axis dimension of said particle does not exceed 10 millimeters.  
     
     
         48 . The method of  claim 36 , wherein the crosslinking component comprises divinylbenzene, wherein the non-crosslinking component comprises styrene, said divinylbenzene in an amount ranging from 3% to 35% by weight of the reactive mixture.  
     
     
         49 . The method of  claim 48 , wherein said non-crosslinking monomer further comprises ethylvinylbenzene.  
     
     
         50 . The method of  claim 36 , said polymerizing comprises suspension polymerizing.  
     
     
         51 . The method of  claim 50 , wherein said suspension polymerizing comprises rapid rate polymerizing.  
     
     
         52 . The method of  claim 50 , wherein said suspension polymerizing comprises isothermal polymerizing.  
     
     
         53 . The method of  claim 48 , said method further comprising subjecting said particle to at least one post-polymerizing process.  
     
     
         54 . The method of  claim 53 , wherein said post-polymerizing process further comprises at least one of heat treatment, stirring, flow, sonication, irradiation, or combinations thereof.  
     
     
         55 . The method of  claim 53 , wherein said post polymerizing process occurs in an unreactive gaseous environment with nitrogen as the preferred unreactive gas.  
     
     
         56 . The method of  claim 48 , said method further comprising using a formulation including at least one of said reactive mixture and additional formulation ingredients wherein said additional formulation ingredients comprise at least one of initiators, catalysts, inhibitors, dispersants, stabilizers, rheology modifiers, buffers, antioxidants, defoamers, impact modifiers, or mixtures thereof.  
     
     
         57 . The method of  claim 48 , wherein said particle is a spherical bead having a diameter that does not exceed 10 millimeters.  
     
     
         58 . The method of  claim 57 , wherein said diameter ranges from 0.1 mm to 4 mm.  
     
     
         59 . A method of producing an assembly of particles comprising: 
 (a) forming polymeric particles by polymerizing a reactive mixture, dispersed within a liquid medium, containing at least one of an initiator; and at least one of a monomer, an oligomer or combinations thereof, said at least one of a monomer, an oligomer, or combinations thereof having three or more reactive functionalities capable of creating crosslinks between polymer chains; wherein a packing of particles resulting from step (a) manifests a first static conductivity when measured after 200 hours under a given compressive stress and at a given temperature greater than 80° F.; and    (b) subjecting the particles polymerized in step (a) to at least one post-polymerizing process, wherein said post-polymerizing process advances curing of a polymer network of the polymeric particles forming the substantially cured polymeric particles, wherein a packing of the substantially cured polymeric particles manifests a second static conductivity when measured after 200 hours under the given compressive stress and at the given temperature; wherein the second static conductivity is greater than the first static conductivity.    (c) separating the particles by shape and size range, wherein the particles in said assembly have sizes that do not exceed 10 millimeters in any principal axis direction.    
     
     
         60 . The method of  claim 59 , wherein the crosslinking component comprises divinylbenzene, wherein the non-crosslinking component comprises styrene, said divinylbenzene in an amount ranging from 3% to 35% by weight of the reactive mixture.  
     
     
         61 . The method of  claim 59 , wherein said non-crosslinking monomer further comprises ethylvinylbenzene.  
     
     
         62 . The method of  claim 60 , said method further comprising subjecting said particle to at least one post-polymerizing process.  
     
     
         63 . The method of  claim 62 , wherein said post-polymerizing process further comprises at least one of heat treatment, stirring, flow, sonication, irradiation, or combinations thereof.  
     
     
         64 . The method of  claim 59 , wherein said particle is a spherical bead having a diameter that does not exceed 10 millimeters.  
     
     
         65 . The method of  claim 64 , wherein said diameter ranges from 0.1 mm to 4 mm.  
     
     
         66 . A method for fracture stimulation of a subterranean formation having a wellbore, comprising: 
 injecting into the wellbore a slurry at sufficiently high rates and pressures such that said formation fails and fractures to accept said slurry;    said slurry comprising a fluid and a proppant, wherein said proppant comprises a particle comprising a rigid thermoset polymer; and    emplacing said proppant within the fracture network in a packed mass or a partial monolayer of particles within the fracture, which packed mass or partial monolayer props open the fracture; thereby allowing produced gases, fluids, or mixtures thereof, to flow towards the wellbore.    
     
     
         67 . A method for lightening a load of cement comprising: 
 mixing an uncured cement composition with an effective amount of a particle comprising a rigid thermoset polymer; and    placing the mixture in a selected location.    
     
     
         68 . A method for treating a well penetrating a subterranean formation comprising: 
 providing an effective amount of a particle comprising a rigid thermoset polymer; and    introducing said polymeric particle into said well.    
     
     
         69 . A method for treating a well penetrating a subterranean formation comprising: 
 mixing into a drilling mud formulation an effective amount of a particle comprising a rigid thermoset polymer; and    introducing said drilling mud formulation with said effective amount of the polymeric particle into said well.    
     
     
         70 . A method for reducing friction in a well penetrating a subterranean formation comprising: 
 mixing into a drilling fluid formulation as a solid lubricant an effective amount of a particle comprising a rigid thermoset polymer; and    introducing said drilling fluid formulation with said effective amount of the polymeric particle into said well.    
     
     
         71 . A method for reducing friction in a well penetrating a subterranean formation comprising: 
 mixing into a drilling fluid formulation as a ball bearing an effective amount of a particle comprising a rigid thermoset polymer; and    introducing said drilling fluid formulation with said effective amount of the polymeric particle into said well.    
     
     
         72 . A method for forming a gravel pack within a wellbore comprising: 
 blending into the gravel pack formulation an effective amount of a particle comprising a rigid thermoset polymer; and    introducing the gravel pack formulation with said effective amount of the polymeric particle into the wellbore.    
     
     
         73 . The method of claims  66 ,  67 ,  68 ,  69 ,  70 ,  71  or  72 , wherein said thermoset polymer has a substantially cured polymer network, wherein a packing of said particles manifests a static conductivity of at least 100 mDft after 200 hours at temperatures greater than 80° F.  
     
     
         74 . The method of claims  66 ,  67 ,  68 ,  69 ,  70 ,  71 ,  72  or  73  wherein said thermoset polymer comprises at least one of a thermoset epoxy, a thermoset epoxy vinyl ester, a thermoset polyester, a thermoset phenolic, a thermoset melamine-based resin, a thermoset polyurethane, a thermoset polyurea, a thermoset polyimide, or mixtures thereof.  
     
     
         75 . The method of claims  66 ,  67 ,  68 ,  69 ,  70 ,  71 ,  72  or  73  wherein said thermoset polymer comprises a terpolymer.  
     
     
         76 . The method of claims  66 ,  67 ,  68 ,  69 ,  70 ,  71 ,  72  or  73  wherein said thermoset polymer matirx comprises a styrene-ethylvinylbenzene-divinylbenzene terpolymer.  
     
     
         77 . The method of claims  66 ,  67 ,  68 ,  69 ,  70 ,  71 ,  72  or  73  wherein said particle has a shape; selected from the group of shapes consisting of a powder, a pellet, a grain, a seed, a short fiber, a rod, a cylinder, a platelet, a bead, a spheroid, or mixtures thereof.  
     
     
         78 . The method of claims  66 ,  67 ,  68 ,  69 ,  70 ,  71 ,  72  or  73 , wherein a largest principal axis dimension of said particle does not exceed 10 millimeters.  
     
     
         79 . The method of  claim 66 ,  67 ,  68 ,  69 ,  70 ,  71 ,  72  or  73  wherein said particle is a spherical bead having a diameter that does not exceed 10 millimeters.  
     
     
         80 . The method of  claim 66 ,  67 ,  68 ,  69 ,  70 ,  71 ,  72  or  73  wherein said diameter ranges from 0.1 mm to 4 mm.  
     
     
         81 . The method of  claim 66 ,  67 ,  68 ,  69 ,  70 ,  71 ,  72  or  73  wherein said polymeric particle is blended with other solid particles including at least one of sand, resin-coated sand, ceramic and resin-coated ceramic.