Anaerobic composite matrix resins

Abstract

A matrix resin composition for fiber reinforced composite materials is described. The resin is thermosetting and achieves a glass transition temperature of at least 177° C. (Tg), obtained by curing under anaerobic conditions at room temperature. The matrix resin will streamline composite fabrication processes by eliminating the need for heating during the cure process. The implications of this development are significant in terms of the ease of use and elimination of procedural steps. While the resin system was developed specifically for vacuum bagging, it is expected to be viable for other composite fabrication methods including resin transfer molding (RTM) and vacuum-assisted resin transfer molding (VARTM). The resin system is viable for use with carbon fiber reinforcements to fabricate laminates at least 0.20 inches thick. The resulting laminintes have low porosity and mechanical properties equivalent to those prepared with common epoxy matrix resins.

What is claimed is: 
     
         1 . An anaerobically curing resin system, comprising:
 a matrix resin comprising acrylate based resin materials and curing agents, wherein the curing agents comprise peroxide initiators, aromatic amine accelerators, and benzoic sulfimide, and wherein the curing agents initiate curing in anaerobic conditions at ambient temperature; and   a primer, wherein the primer comprises a solvent, acrylate based resin materials, an elastomeric toughener, and a catalyst comprising a transition metal.   
     
     
         2 . The anaerobically curing resin system of  claim 1 , wherein the acrylate based resin materials comprise tricyclodecane dimethanol diacrylate, methacrylic acid, epoxy acrylate, tris(2-hydroxyethyl) isocyanurate triacrylate, polybutadiene acrylonitrile dimethacrylate, hydroxypropyl methacrylate, and combinations thereof. 
     
     
         3 . The anaerobically curing resin system of  claim 1 , wherein the peroxide initiators comprise cumene hydroperoxide, t-butylhydroperoxide, p-menthane hydroperoxide, diisopropylbenzene hydroperoxide, pinene hydroperoxide, methyl ethyl ketone peroxide, and combinations thereof. 
     
     
         4 . The anaerobically curing resin system of  claim 1 , wherein the aromatic amine accelerators comprise N,N-diethyl-p-toluidine, N,N-dimethyl-o-toluidine, acetyl phenylhydrazine, N,N-dimethylaniline, N,N-dimethyl-p-toluidine, N,N-dimethyl-p-anisidine, N,N-diethylaniline, N,N-bis-(2-hydroxyethyl)-p-toluidine, and combinations thereof. 
     
     
         5 . The anaerobically curing resin system of  claim 1 , wherein the elastomeric toughener comprises chlorosulfonated polyethylene. 
     
     
         6 . The anaerobically curing resin system of  claim 1 , wherein the catalyst is copper ethylhexanoate. 
     
     
         7 . The anaerobically curing resin system of  claim 1 , wherein the matrix resin consists of tricyclodecane dimethanol diacrylate, methacrylic acid, epoxy acrylate, tris(2-hydroxyethyl) isocyanurate triacrylate, polybutadiene acrylonitrile dimethacrylate, hydroxypropyl methacrylate, benzoic sulfimide, dimethylaniline, and cumene hydroperoxide. 
     
     
         8 . The anaerobically curing resin system of  claim 1 , wherein the primer consists of tertiary butyl acetate, hydroxypropyl methacrylate, chlorosulfonated polyethylene, isobornyl methacrylate, hexafunctional aromatic urethane acrylate, methacrylic acid, and copper ethylhexanoate. 
     
     
         9 . An anaerobically curing composite matrix resin system, comprising:
 a reinforcement matrix, wherein the reinforcement matrix comprises a residual coating of organometallic compounds formed by pre-treatment of the reinforcement matrix with an activator sizing agent; and   an anaerobically curing resin system, wherein the anaerobically curing resin system comprises a matrix resin comprising acrylate based resin materials and curing agents, and a primer formulation, wherein the curing agents comprise peroxide initiators, aromatic amine accelerators, and benzoic sulfimide, wherein the primer formulation comprises a solvent, acrylate based resin materials, an elastomeric toughener, and a catalyst comprising a transition metal, and wherein the curing agents initiate curing in anaerobic conditions at ambient temperature.   
     
     
         10 . The anaerobically curing composite matrix resin system of  claim 9 , wherein the reinforcement matrix is carbon fiber, fiberglass, or quartz. 
     
     
         11 . The anaerobically curing composite matrix resin system of  claim 9 , wherein the activator sizing agent is copper acetylacetonate and gamma-aminopropyltrimethoxy silane dissolved in methylene chloride. 
     
     
         12 . The anaerobically curing composite matrix resin system of  claim 9 , wherein the acrylate based resin materials comprise tricyclodecane dimethanol diacrylate, methacrylic acid, epoxy acrylate, tris(2-hydroxyethyl) isocyanurate triacrylate, polybutadiene acrylonitrile dimethacrylate, hydroxypropyl methacrylate, and combinations thereof. 
     
     
         13 . The anaerobically curing composite matrix resin system of  claim 9 , wherein the peroxide initiators comprise cumene hydroperoxide, t-butylhydroperoxide, p-menthane hydroperoxide, diisopropylbenzene hydroperoxide, pinene hydroperoxide, methyl ethyl ketone peroxide, and combinations thereof. 
     
     
         14 . The anaerobically curing composite matrix resin system of  claim 9 , wherein the aromatic amine accelerators comprise N,N-diethyl-p-toluidine, N,N-dimethyl-o-toluidine, acetyl phenylhydrazine, N,N-dimethylaniline, N,N-dimethyl-p-toluidine, N,N-dimethyl-p-anisidine, N,N-diethylaniline, N,N-bis-(2-hydroxyethyl)-p-toluidine, and combinations thereof. 
     
     
         15 . The anaerobically curing composite matrix resin system of  claim 9 , wherein the elastomeric toughener comprises chlorosulfonated polyethylene. 
     
     
         16 . The anaerobically curing composite matrix resin system of  claim 9 , wherein the catalyst is copper ethylhexanoate. 
     
     
         17 . The anaerobically curing composite matrix resin system of  claim 9 , wherein the matrix resin consists of tricyclodecane dimethanol diacrylate, methacrylic acid, epoxy acrylate, tris(2-hydroxyethyl) isocyanurate triacrylate, polybutadiene acrylonitrile dimethacrylate, hydroxypropyl methacrylate, benzoic sulfimide, dimethylaniline, and cumene hydroperoxide. 
     
     
         18 . The anaerobically curing composite matrix resin system of  claim 9 , wherein the primer consists of tertiary butyl acetate, hydroxypropyl methacrylate, chlorosulfonated polyethylene, isobornyl methacrylate, hexafunctional aromatic urethane acrylate, methacrylic acid, and copper ethylhexanoate. 
     
     
         19 . A method for repairing a composite material having a damaged region, comprising:
 treating at least a portion of the damaged region of the composite material with a primer to produce a primer-treated damaged region;   pre-treating a reinforcement matrix with an activator sizing agent by applying a solution of the activator sizing agent to the reinforcement matrix and allowing the reinforcement matrix to dry, whereby the reinforcement matrix is coated with a residual coating of organometallic compounds, to produce a pre-treated reinforcement matrix;   sizing the pre-treated reinforcement matrix to an appropriate size for application to the primer-treated damaged region;   placing the pre-treated reinforcement matrix on the primer-treated damaged region;   impregnating the pre-treated reinforcement matrix with an anaerobically curing matrix resin, wherein the anaerobically curing matrix resin contacts the primer in the primer-treated damaged region, wherein the anaerobically curing matrix resin comprises acrylate based resin materials and curing agents, and wherein the curing agents comprise peroxide initiators,   aromatic amine accelerators, and benzoic sulfimide, to form a pre-cured composite matrix resin at the primer-treated damaged region; and   exposing the pre-cured composite matrix resin to anaerobic conditions, to form an anaerobically cured composite matrix resin to repair the damaged region of the composite material.   
     
     
         20 . The method of  claim 19 , wherein the reinforcement matrix is carbon fiber, fiberglass, or quartz. 
     
     
         21 . The method of  claim 19 , wherein the activator sizing agent is copper acetylacetonate and gamma-aminopropyltrimethoxy silane dissolved in methylene chloride. 
     
     
         22 . The method of  claim 19 , wherein the acrylate based resin materials comprise tricyclodecane dimethanol diacrylate, methacrylic acid, epoxy acrylate, tris(2-hydroxyethyl) isocyanurate triacrylate, polybutadiene acrylonitrile dimethacrylate, hydroxypropyl methacrylate, and combinations thereof. 
     
     
         23 . The method of  claim 19 , wherein the peroxide initiators comprise cumene hydroperoxide, t-butylhydroperoxide, p-menthane hydroperoxide, diisopropylbenzene hydroperoxide, pinene hydroperoxide, methyl ethyl ketone peroxide, and combinations thereof. 
     
     
         24 . The method of  claim 19 , wherein the aromatic amine accelerators comprise N,N-diethyl-p-toluidine, N,N-dimethyl-o-toluidine, acetyl phenylhydrazine, N,N-dimethylaniline, N,N-dimethyl-p-toluidine, N,N-dimethyl-p-anisidine, N,N-diethylaniline, N,N-bis-(2-hydroxyethyl)-p-toluidine, and combinations thereof. 
     
     
         25 . The method of  claim 19 , wherein the elastomeric toughener comprises chlorosulfonated polyethylene. 
     
     
         26 . The method of  claim 19 , wherein the catalyst is copper ethylhexanoate. 
     
     
         27 . The method of  claim 19 , wherein the matrix resin consists of tricyclodecane dimethanol diacrylate, methacrylic acid, epoxy acrylate, tris(2-hydroxyethyl) isocyanurate triacrylate, polybutadiene acrylonitrile dimethacrylate, hydroxypropyl methacrylate, benzoic sulfimide, dimethylaniline, and cumene hydroperoxide. 
     
     
         28 . The method of  claim 19 , wherein the primer consists of tertiary butyl acetate, hydroxypropyl methacrylate, chlorosulfonated polyethylene, isobornyl methacrylate, hexafunctional aromatic urethane acrylate, methacrylic acid, and copper ethylhexanoate.