Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – At least one aryl ring which is part of a fused or bridged...
Reexamination Certificate
1999-03-19
2001-07-17
Cain, Edward J. (Department: 1714)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
At least one aryl ring which is part of a fused or bridged...
C524S447000, C524S448000, C501S148000, C428S333000, C428S338000, C428S339000
Reexamination Certificate
active
06262162
ABSTRACT:
FIELD OF THE INVENTION
The present invention is directed to intercalated layered materials and, optionally, exfoliates thereof, prepared by contacting, and thereby intercalating, a layered silicate material, e.g., a phyllosilicate, such as a smectite clay, with a spacing/coupling agent that is multi-positively charged (hereinafter “multi-charged”), preferably dual-charged, and co-intercalation of the layered material with a co-intercalant (as co-intercalant polymerizable reactants, or as the oligomer co-intercalant or polymer co-intercalant) to form nanocomposite materials. The co-intercalant monomer, oligomer or polymer can be intercalated after or together with intercalation of the multi-charged spacing/coupling agent, such as by direct compounding, e.g., by combining a multi-charged onium ion-intercalated layered material and a co-intercalant monomer, polymer or oligomer in a mixing or extruding device to produce the co-intercalated layered material and the nanocomposite. The interlaminar spacing of adjacent layers (platelets) of the layered material (d-spacing minus one platelet thickness of the layered material) is expanded at least 3 Å, preferably at least 5 Å, to at least about 10 Å, preferably to at least about 15 Å, and usually to about 18 Å by contacting the layered material with the multi-charged spacing/coupling agent for simultaneous or subsequent intercalation with co-intercalant polymer reactants, an oligomer co-intercalant or a polymer co-intercalant. The multi-charged spacing/coupling agents have at least two charged, ion-exchange atoms capable of ion-exchanging with Li
+
, Na
+
, K
+
, Ca
+2
, Mg
+2
, or other inorganic cations that occur within the interlayer spaces between adjacent silicate layers or platelets of the layered silicate materials being intercalated. The association of the layered material inorganic cations with the at least two charged sites of the multi-charged spacing/coupling agent enables the conversion of the hydrophilic interior clay platelet surfaces to hydrophobic platelet surfaces, by substantially complete ion-exchange of the interlayer exchangeable cations on the platelet surfaces with the onium ions, while intercalating and ion-exchanging substantially less onium ions into the space between adjacent platelets, leaving more space for co-intercalation of an oligomer or polymer when compared with single-charged onium ion analogues. Therefore, polymerizable monomers capable of reacting to form a polymer co-intercalant, or polymerizable oligomer co-intercalant molecules, or a co-intercalant polymer can be easily and more fully intercalated between adjacent platelets of the layered silicate material, e.g., smectite clay platelets.
In accordance with the preferred embodiment of the present invention, a fully polymerized co-intercalant polymer, having a weight average molecular weight between about 100 and about 5 million, preferably about 1,000 to about 500,000, can be co-intercalated between adjacent platelets of the multi-charged spacing/coupling agent-intercalated layered material, preferably simultaneously with dispersing the multi-charged onium ion-intercalated layered material into a matrix polymer, i.e., by direct compounding of the multi-charged spacing/coupling agent-intercalated layered material with the co-intercalant oligomer or polymer, by adding excess co-intercalant oligomer or polymer, and without separation of the resulting intercalate, the excess co-intercalant polymer becomes the matrix polymer—the same as the co-intercalant polymer. The intercalation of the multi-charged spacing/coupling agent and a co-intercalant oligomer or polymer, or its monomeric reactants (co-intercalant polymerizable monomer reactants, co-intercalant oligomer, and co-intercalant polymer being referred to collectively as “intercalant polymer” or “co-intercalant polymer” hereinafter for simplicity), results in a completely homogeneous dispersion of co-intercalated layered material in a matrix polymer, or a nanocomposite composition. Optionally, the nanocomposite material can be sheared, at or above the melt temperature of the matrix polymer, to exfoliate up to 100% of the tactoids or platelet clusters into individual platelets such that more than 50% by weight of the platelets are in the form of single platelets, e.g., more than 60%; more than 70%; more than 80%; or more than 90% by weight of the layered material can be completely exfoliated into single platelet layers.
The intercalates of the present invention can be used as organoclays for sorption of organic materials, or can be dispersed uniformly into solvents to increase the viscosity of organic liquids; or the intercalates can be dispersed into matrix polymer materials to form polymer/clay intercalate nanocomposites, e.g., by direct compounding of the multi-charged spacing/coupling agent-intercalated clay with sufficient co-intercalant oligomer or polymer to achieve sufficient intercalation of the clay to form a concentrate, that can later be mixed with a matrix polymer and/or additional intercalant polymer, or different polymeric materials to form a nanocomposite. Alternatively, the multi-charged spacing/coupling agent-intercalated clay can be co-intercalated with monomer reactants that are polymerizable to form the polymer co-intercalant.
In another embodiment of the present invention, the multi-charged spacing/coupling agent-intercalated layered material can be dispersed in a matrix monomer followed by polymerization of the matrix monomer, in-situ, e.g., by adding a curing agent, to form the nanocomposite material. Also, curing agents can be directly incorporated into monomeric reactants that are co-intercalated between platelets of the multi-charged spacing/coupling agent-intercalated clay followed by polymerization of the reactant intercalant monomers that have been intercalated into the clay interlayer galleries.
In accordance with an important feature of the present invention, if an intercalant polymer is co-intercalated into the multi-charged spacing/coupling agent-intercalated clay galleries to form a co-intercalate and additional polymer is added to form a nanocomposite, the co-intercalant polymer can be directly compounded with the matrix polymer to form a nanocomposite easily, and the co-intercalate can be more fully loaded with co-intercalant polymer than if a single-charged onium ion spacing/coupling agent were used to space the platelets. If the polymerizable co-intercalant monomers, or a polymerizable oligomer intercalant is co-intercalated into the clay galleries, the co-intercalant(s) can be polymerized together with a desired monomer, oligomer or polymer matrix material, and the matrix material then can be polymerized or further polymerized together with the co-intercalant and compounded to form the nanocomposite.
BACKGROUND OF THE INVENTION AND PRIOR ART
It is well known that phyilosilicates, such as smectite clays, e.g., sodium montmorillonite and calcium montmorillonite, can be treated with organic molecules, such as organic ammonium ions, phosphonium ions, or sulfonium ions (onium ions), to intercalate the organic molecules between adjacent, planar silicate layers, for ion-exchange of the organic onium ion molecules with the interlayer exchangeable cations to space the adjacent layers or platelets of the layered silicate material (interlaminar spacing) sufficiently for intercalation of a polymer between the spaced layers, see, for example, U.S. Pat. Nos. 4,739,007; 4,810,734 and 5,164,460. The thus-treated, intercalated phyllosilicates, having interlayer spacings increased by at least 3 Å, preferably at least 5 Å, to an interlayer (interlaminer) spacing of at least about 10-25 Angstroms (Å) and up to about 100 Å then can be exfoliated, e.g., the silicate layers are separated, e.g., mechanically, by high shear mixing. The individual silicate layers, when admixed with a matrix polymer, before, after or during the polymerization of the matrix polymer, e.g., a polyamide—see 4,739,007; 4,810,73
Lan Tie
Liang Ying
Psihogios Vasiliki
Westphal Erin K.
Amcol International Corporation
Cain Edward J.
Marshall O'Toole Gerstein Murray & Borun
Wyrozebski-Lee K.
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