Nanocomposites formed by onium ion-intercalated clay and rigid anhydride-cured epoxy resins

A method of intercalating a phyllosilicate comprising:

• contacting the phyllosilicate with an intercalating composition comprising at least a 0.25:1 molar ratio of quaternary onium ion cations, having the structure
• wherein X=N, P, O or S and R1, R2, R3 and R4, same or different, are epoxy non-reactive organic radicals, to phyllosilicate interlayer exchangeable cations, to achieve intercalation of, and ion-exchange of said onium ion cations with said interlayer cations, between said adjacent phyllosilicate platelets in an amount sufficient to space said adjacent phyllosilicate platelets at least about 3 Å;
• and
• co-intercalating the onium ion-intercalated layered silicate material with an anhydride-curable epoxy resin that is not covalently bonded to the layered silicate material or to the onium ion cations.

A method of manufacturing a composite material containing about 0.05% to about 60% by weight of an intercalated phyllosilicate material, said phyllosilicate having intercalant quaternary onium ions, having the structure

• wherein X=N, P, O or S and R1, R2, R3 and R4, same or different, are epoxy non-reactive organic radicals, intercalated between and bonded, by ion-exchange, to an inner surface of the phyllosilicate platelets, and about 40% to about 99.95% by weight of a matrix polymer comprising an anhydride-curable epoxy resin that is not covalently bonded to the phyllosilicate material or to the onium ions, comprising:
• contacting the phyllosilicate with said intercalant onium ions to achieve intercalation of said intercalant onium ions between said adjacent phyllosilicate platelets in an amount sufficient to space said adjacent phyllosilicate platelets a distance of at least about 3 Å;
• and
• dispersing the intercalate throughout said matrix polymer to achieve intercalation of a portion of the matrix polymer between the phyllosilicate platelets, in an amount sufficient to further space said adjacent phyllosilicate platelets an additional at least 3 Å.

A method of manufacturing a composite material containing about 40% to about 99.95% by weight of a matrix thermoplastic or thermosetting polymer, and about 0.05% to about 60% by weight of an intercalated phyllosilicate material, said intercalated phyllosilicate having an intercalant quaternary onium ion spacing/coupling agent, having the structure

• wherein X=N, P, O or S and R1, R2, R3, and R4, same or different, are epoxy non-reactive organic radicals, intercalated between adjacent phyllosilicate platelets comprising:
• contacting the phyllosilicate with an intercalating composition including said intercalant onium ion spacing/coupling agent in a molar ratio of onium ions:phyllosilicate interlayer cations of at least 0.25:1 and an anhydride-curable epoxy resin that is not covalently bonded to the phyllosilicate or to the onium ion spacing/coupling agent, to achieve intercalation of said intercalant onium ion spacing/coupling agent and said anhydride-curable epoxy resin between said adjacent phyllosilicate platelets in an amount sufficient to space said adjacent phyllosilicate platelets at least an additional 3 Å;
• combining the intercalated phyllosilicate with said thermoplastic or thermosetting polymer, and heating the thermoplastic polymer sufficiently to provide for flow of said thermoplastic polymer;
• and
• dispersing said intercalated phyllosilicate throughout said matrix polymer.

A method of manufacturing a composite material containing about 40% to about 99.95% by weight of an oligomer or polymer of an anhydride-curable epoxy resin, and about 0.05% to about 60% by weight of an intercalated phyllosilicate material comprising intercalating the phyllosilicate material with a quaternary onium ion spacing agent, having the structure

• wherein X=N, P, O or S and R1, R2, R3 and R4, same or different, are epoxy non-reactive organic radicals, by contacting the phyllosilicate with onium ions in a molar ratio of onium ions:phyllosilicate interlayer exchangeable cations of at least 0.25:1;
• forming a mixture of the intercalated phyllosilicate material with an anhydride-curable epoxy resin;
• and
• subjecting the mixture to conditions sufficient to react and polymerize the anhydride-curable epoxy resin with an anhydride curing agent for the epoxy resin to cure the epoxy resin while in contact with the intercalated phyllosilicate and to co-intercalate the epoxy resin between adjacent platelets of the phyllosilicate material, wherein the anhydride-curable epoxy resin is combined in amounts such that the resulting composite material contains 40% to 99.95% oligomer or polymer and 0.05% to 60% intercalated phyllosilicate.

A method of manufacturing a composite material containing about 10% to about 99.95% by weight of a matrix polymer selected from the group consisting of a thermoplastic polymer, a thermosetting polymer, and mixtures thereof, and about 0.05% to about 60% by weight of an intercalated phyllosilicate material, said intercalated phyllosilicate having an intercalant quaternary onium ion spacing/coupling agent, having the structure

• wherein X=N, P, O or S and R1, R2, R3 and R4, same or different, are epoxy non-reactive organic radicals, intercalated between and bonded, by ion-exchange, to an inner surface of the phyllosilicate platelets, comprising:
• contacting the phyllosilicate with water and said intercalant onium ion spacing/coupling agent, to achieve intercalation of said intercalant onium ion spacing/coupling agent between said adjacent phyllosilicate platelets in an amount sufficient to space said adjacent phyllosilicate platelets a distance of at least about 3 Å;
• contacting the phyllosilicate with a second intercalant selected from the group consisting of polymerizable monomers, a polymerizable oligomer, a polymer, and a mixture thereof, said second intercalant being an anhydride-curable epoxy resin, or monomer reactants capable of polymerization to form an anhydride-curable epoxy resin;
• combining the intercalate with said matrix polymer;
• and
• dispersing said intercalate throughout said matrix polymer.

A method of manufacturing a composite material containing about 40% to about 99.95% by weight of a matrix thermoplastic or thermosetting polymer, and about 0.05% to about 60% by weight of exfoliated platelets of a phyllosilicate material, said platelets derived from an intercalated phyllosilicate having an intercalant quaternary onium ion spacing/coupling agent, having the structure

• wherein X=N, P, O or S and R1, R2, R3 and R4, same or different, are epoxy non-reactive organic radicals, intercalated between adjacent phyllosilicate platelets comprising:
• contacting the phyllosilicate with an intercalating composition including said intercalant quaternary onium ion spacing/coupling agent in a molar ratio of onium ions:phyllosilicate interlayer cations of at least about 0.25:1, and a second intercalant selected from the group consisting of polymerizable monomers, a polymerizable oligomer, a polymer, and a mixture thereof, said second intercalant being an anhydride-curable epoxy resin, or is monomer reactants capable of polymerization to form an anhydride-curable epoxy resin, wherein the concentration of second intercalant in said intercalating composition is at least about 5% by weight, based on the dry weight of the phyllosilicate, to achieve intercalation of said intercalant onium ion spacing/coupling agent and said second intercalant between said adjacent phyllosilicate platelets in an amount sufficient to space said adjacent phyllosilicate platelets a distance of at least about 3 Å;
• combining the intercalated phyllosilicate with said thermoplastic or thermosetting polymer, and heating the thermoplastic polymer sufficiently to provide for flow of said thermoplastic polymer;
• and
• dispersing said intercalated phyllosilicate throughout said matrix polymer.