WO2004081311A2

WO2004081311A2 - Structural and other composite materials and methods for making same

Info

Publication number: WO2004081311A2
Application number: PCT/US2004/007800
Authority: WO
Inventors: Ray F. HOFMANN; Bruce Ackert; Craig K. Collins; Randy E. Meirowitz; Tyler M. Dylan
Original assignee: Petritech, Inc.
Priority date: 2003-03-12
Filing date: 2004-03-12
Publication date: 2004-09-23
Also published as: MXPA05009617A; AR043604A1; CA2518873A1; KR20060009234A; BRPI0408487A; CN1759139A; AU2004219602A1; EA200501400A1; WO2004081311A3; JP2006519908A; TW200500402A; EP1611194A2

Abstract

In accordance with the present invention, we have developed structural and other composite materials having superior performance properties, including high compressive strength, high tensile strength, high shear strength, and high strength-to-weight ratio, and methods for preparing same. Invention materials have the added benefits of ease of manufacture, and are inexpensive to manufacture. The superior performance properties of invention materials render such materials suitable for a wide variety of end uses. For example, a variety of substances can be applied to invention materials without melting, dissolving or degrading the basic structure thereof. This facilitates bonding invention materials to virtually any surface or substrate. Moreover, the bond between invention materials and a variety of substrates is exceptionally strong, rendering the resulting bonded article suitable for use in a variety of demanding applications. Invention materials can be manufactured in a wide variety of sizes, shapes, densities, in multiple layers, and the like.

Description

STRUCTURAL AND OTHER COMPOSITE MATERIALS AND METHODS FOR MAKING SAME

RELATED APPLICATIONS

[0001] This application is a continuation-in-part of Application No. 10/388,295, filed March 12, 2003, now pending, the entire contents of which are hereby incorporated by reference herein.

FIELD OF THE INVENTION

[0002] The present invention relates to structural and other composite materials and methods for making such materials, hi a particular aspect, the present invention relates to building materials. In another aspect, the present invention relates to structural and other composite materials having a variety of shapes, sizes and physical properties. In yet another aspect, the present invention relates to various applications of invention structural and other composite materials. In still another aspect, the present invention relates to lightweight, high- strength articles prepared from invention structural and other composite materials.

BACKGROUND OF THE INVENTION

[0003] Polymeric materials have long been used in the art for the manufacture of structural elements. In one application, a structural element can be simply formed as a solid sheet of polymeric material, for example, by extrusion. However, structural elements prepared in this way tend to be fairly heavy (due to the density of the polymeric material), and have poor thermal insulating properties. In addition, such structures also tend to be quite expensive since a considerable amount of polymeric material is required to form such structures. [0004] An alternate method employed in the art for preparation of structural elements is the use of foamed polymeric materials, such as, for example, polyethylene, polypropylene, polystyrene or polyurethane. While the resulting structures are much less dense than an equivalent solid structural element, and have enhanced insulating properties,, they are generally rather expensive structures to produce. Moreover, specifically in the case of polystyrene, the resulting foam structures have relatively poor structural integrity.

[0005] To form a structural element from foamed polyurethane using a typical two- component system, a resin is mixed with an isocyanate, and the mixture is then introduced into a mold, which is then closed. The foaming reaction takes place inside the mold, and the volume of the polymeric material inside the mold increases. Once the volume of the foamed material becomes equal to the volume of the mold, the foam is compressed against the mold, increasing the strength of the resulting element. In order to obtain a high-strength structural element, it is necessary to allow for a substantial amount of compression to occur, which requires the use of a large amount of polyurethane, thus increasing the expense of the structural element. Furthermore, as the foam is compressed to provide increased strength, the density of the foam is increased such that the thermal insulation properties of the resulting article are quite poor. Moreover, the above-described method must be carried out quickly to ensure that the reaction components are all introduced into the mold before the foaming reaction commences.

[0006] Yet another method known in the art for the preparation of structural elements from foamed polymeric materials involves the use of expanded polystyrene or polypropylene beads, which are placed in a mold and subjected to steam heating, which softens the beads, which can then be coalesced to form a structural element. While the resulting structural element is relatively light, it is not particularly strong. In addition, the final foam product is of an open cell structure, and thus permeable to liquids and gases. Moreover, since the volume of the structural element is reduced as the beads coalesce, this method also requires the use of large quantities of starting materials. [0007] Still another method for the preparation of building materials employing expanded polystyrene beads is described in UK Patent Application No. GB 2,298,424, which discloses a lightweight thermally insulating filler disposed within a rigid foamed plastics matrix. The principal thermally insulating filler disclosed in the '424 application is referred to as "expanded polystyrene" with no details given as to the chemical and/or physical properties of the material employed in the preparation of the claimed product. Similarly, the only rigid foamed plastics matrix disclosed in the '424 application is a single, specific rigid polyurethane, defined only in terms of one of several components used for the preparation thereof, i.e., the polyurethane employed in the '424 application is prepared from "resin" (described only as "a polyol blend") and isocyanate (described only as a mixture of diphenylmethane diisocyanate and "polymeric components"). The actual makeup of the polyurethane employed in the '424 application is obtainable only by reference to an allegedly commercially available material by reference to its trade name only.

[0008] Additional methods for preparing structural materials are described in U.S. Patent No. 4,714,715 (directed to a method of forming fire retardant insulation material from rigid plastic foam scrap); U.S. Patent No. 5,055,339 (directed to a shaped element comprising a panel of a soft foamed material having a cellular lattice comprised of webs defining open cells and granules of a soft foamed material having a cellular lattice comprised of webs defining cells and of at least one additional filler material); U.S. Patent No. 5,791,085 (directed to a method of preparing a porous solid material for the propagation of plants consisting of a single step of reacting a polyisocyanate and a polyethylene oxide derivative in the presence of granules of a porous expanded mineral and in the presence of 0.5 weight % water or less to produce a substantially dry, solid porous open-cell foamed hydrophilic water- retentive polyurethane hydrogel material matrix, which is substantially rigid in the dry condition and which is capable of absorbing water and becoming pliant when wet); U.S. Patent No. 5,885,693 (directed to a three-dimensional shaped part having a predetermined volume); U.S. Patent No. 6,042,764 (directed to a method of producing a three-dimensional shaped plastic foam part); U.S. Patent No. 6,045,345 (directed to an installation for producing a three-dimensional shaped plastic foam part from plastic foam granules bonded together by foaming a liquid primary material); U.S. Patent No. 6,265,457 (directed to an isocyanate- based polymer foam); U.S. Patent No. 6,583,189 (directed to an extruded article comprising a closed cell foam of a first thermoplastic, containing between about 1% and 40% of powdered diatomaceous earth by weight, the extruded article being formed with diatomaceous earth containing no more than about 2% by weight of moisture); and U.S. Patent No. 6,605,650 (directed to a process of generating a polyurethane foam by forming a mixture comprising isocyanate and polyol reactants, catalyst, and blowing agent, which mixture reacts exothermically to yield a rigid polyurethane foam).

[0009] There remains, however, a need in the art for structural materials which can be strong and lightweight, which are preferably also relatively moisture resistant, and yet which do not require large amounts of starting materials for the preparation thereof. The present invention addresses this and related needs in the field, as detailed by the specification and claims which follow.

SUMMARY OF THE INVENTION

[0010] In accordance with the present invention, structural and other composite materials have been developed which have superior performance properties, including high compression strength, high tensile strength, high flexural strength, high shear strength, and/or high strength-to-weight ratio. Invention materials can likewise exhibit high compression, tensile, flexural and shear moduli. In addition, invention materials can also be substantially moisture resistant. Invention materials can have the added benefits of ease of manufacture, and can also be relatively inexpensive to manufacture. In addition, invention materials can be prepared at relatively low temperatures, frequently requiring little heating or cooling during preparation. The superior performance properties of invention materials render such materials suitable for a wide variety of end uses.

[0011] For example, numerous adhesives can be applied to invention materials without melting, dissolving or degrading the basic structure of invention materials. This facilitates bonding invention materials to virtually any surface or substrate, including bonding of two or more pieces of invention materials to one another as an alternate way to generate a desired shape. Moreover, the bond between invention materials and a variety of substrates (including the bond between two or more pieces of invention materials) is exceptionally strong, rendering the resulting bonded article suitable for use in a variety of demanding applications. Indeed, the adhesion between invention materials and a substrate can be further enhanced by abrading the surface of the substrate (for example, mechanically or by chemical etching) prior to contact with invention materials.

[0012] Similarly, invention materials can be modified by application of liquid polyester resin coatings, liquid styrene or other liquid polymers thereto. Such coatings can be sprayed or otherwise directly applied to invention materials without dissolving or otherwise compromising the core structure provided by invention material.

[0013] Invention materials can be manufactured in a wide variety of sizes, shapes, densities, in multiple layers, and the like.

BRIEF DESCRIPTION OF THE FIGURES

[0014] Figure 1 is a scanning electron microscope image of a cross section of an expanded polystyrene bead.

[0015] Figure 2 is a scanning electron microscope image of an expanded polystyrene bead.

[0016] Figure 3 is a schematic depiction of a cross section of a polymer matrix containing porous beads, illustrating the polymer filaments or other projections extending into the porous bead.

[0017] Figure 4 is a cross-sectional view of an exemplary invention article, wherein large beads of a porous material (10) are incorporated into a polymer matrix (1). Invention structural and other composite materials are also sometimes referred to herein as PetriFoam™ brand structural and other composite materials. [0018] Figure 5 is a cross-sectional view of another exemplary invention article, wherein small beads of a porous material (11) are incorporated into a polymer matrix (1).

[001 ] Figure 6 is a cross-sectional view of yet another exemplary invention article, wherein a mixture of large and small beads of a porous material (10 and 11) are incorporated into a polymer matrix (1).

[0020] Figure 7 is a cross-sectional view of an invention article further comprising structural material according to the invention (20) and a facing material (30) adhered thereto.

[0021] Figure 8 is a cross-sectional view of an invention article comprising structural material according to the invention (20), further comprising a coating (31) thereon.

[0022] Figure 9 is a cross-sectional view of an invention article in the form of a sandwich structure, comprising PetriFoam™ brand structural material(s) (20) bound to, or incorporating, a reinforcement material (32).

[0023] Figure 10 presents a graph of results of flexural modulus tests with representative invention materials.

[0024] Figure 11 presents a graph of results of compression tests with representative invention materials.

DETAILED DESCRIPTION OF THE INVENTION

[0025] In accordance with one aspect of the present invention, there are provided structural and other composite materials comprising: a porous material, wherein the porous material has a diameter in the range of about 0.05 mm up to about 60 mm, and a bead density in the range of about 0.1 kg/m up to about 1000 kg/m³, typically in the range of about 1 kg/m³ up to about 100 kg/m³, and a polymer, wherein the polymer is prepared from a polymerizable component capable of curing at a temperature below the melting point of the porous material, wherein the polymer encapsulates the porous material, and wherein filaments or other projections comprising the polymer extend into the porous material. As readily recognized by those of skill in the art, polymer material can extend into the porous material to varying degrees, depending on such factors as the viscosity of the polymer system, the dimension of the pores in the porous material, the pressure to which the system is subjected, and the like.

[0026] In certain embodiments of the invention, the polymer is prepared from a gas- generating polymerizable component such as polyurethane, and the polymer comprises a substantially solid matrix. As used herein, "substantially solid" refers to a material with sufficient structural integrity so as to retain a given shape absent any extraordinary outside forces. Without wishing to be bound by theory, it is believed that the preparation of gas- generating polymerizable component in close proximity with porous materials can yield a polymer matrix that is significantly more solid than matrix prepared in the absence of such porous materials because the porous materials can serve as a proximal reservoir or sink to contain some portion of the generated gas which might otherwise form macroscopic and/or microscopic bubbles within the matrix, thereby weakening its structural integrity. As contemplated herein, pressure and/or other means can be used to further enhance these processes. Such methods of generating structural and other composite materials can have the added advantage of reducing the amounts of volatile organic compounds that are released during preparation. By virtue of such technical features, structural and other composite materials according to the present invention can be generated in which the matrix is 5-20, 20- 40, 40-80, 80-120 percent or even more solid (i.e. dense) as compared to matrix prepared in the absence of such porous materials). Since at the same time, the porous material can provide a lightweight structure that can be encapsulated and/or penetrated by the matrix as described herein, the resulting products can exhibit highly desirable properties of being relatively lightweight yet strong. Partial physical ingress and/or bonding of the matrix to the porous material can also be used to enhance structural integrity of the composite by providing a means of mechanically and/or chemically "locking" the matrix to the porous material. As described below, materials of the present invention can readily be prepared to exhibit superior properties in terms of a number of strength as well as other mechanical and/or other physicochemical or electrical characteristics. Illustrative examples of such materials are provided herein and as will be apparent to those of skill in the art, based on the detailed teachings and descriptions provided herein, various additions and/or alternatives known in the art can be readily employed in connection with the practice of the present invention. Substantially solid materials according to the present invention can range from substantially rigid (i.e., substantially non-deformable) to substantially flexible (i.e., deformable, yet generally with sufficient memory so as to return to the original shape once the deforming perturbation is removed).

[0027] Structural and other composite materials according to the present invention typically comprise a continuous phase (comprising the polymer) and a discontinuous phase (comprising the porous material). As discussed in greater detail herein, the continuous phase can be based on any of a variety of homopolymeric systems, as well as co- and multi- polymeric systems, including block copolymers, graft copolymers, and the like. Similarly, the discontinuous material can be selected from a variety of porous materials.

[0028] In accordance with another aspect of the present invention, there are provided structural and other composite materials comprising: a porous material, wherein the porous material has a diameter in the range of about 0.05 mm up to about 60 mm, and a bead density in the range of about 0.1 kg/m³ up to about 1000 kg/m³, typically in the range of about 1 kg/m³ up to about 100 kg/m³, and a polymer, wherein the polymer is prepared from a first polymerizable component which is capable of polymerizing within pores of the porous material, and from a second polymerizable component which is capable of binding to polymers of the first polymerizable component, either directly or through a linker, wherein the polymerizable components, upon curing, produce a substantially solid matrix which encapsulates and partially penetrates the porous material.

[0029] In accordance with another aspect of the present invention, there are provided articles having a defined shape, excellent compression strength and modulus, and a high flexural modulus, the articles comprising a polymer matrix containing a porous material substantially uniformly distributed therethrough, wherein filaments or other projections comprising the polymer extend at least partially into the porous material. The extent of penetration of the porous material by polymer can be readily modified as desired for a particular application. For example, relative strength can generally be enhanced by increasing the extent of penetration, and can be increased still further if desired by causing filaments of penetrating polymer to bind to each other and/or to surfaces within the porous material. Such increased penetration can be achieved by a variety of means, including for example, selecting a polymer and porous material combination that favors interaction and penetration (e.g., by selecting combinations having particularly compatible surface energies), by having or applying additional pressure during polymerization to drive penetration, by increasing the viscosity of the polymer, by raising the temperature or by other kinetic or thermodynamic means that facilitate the interaction and potential for penetration. It is also possible to include an agent that promotes or facilitates the interaction (such as a surfactant) which may be included during polymerization or may for example be used to pre-treat the porous material to make it particularly receptive to penetration by the polymer. Use of a graft copolymer system as described herein can be employed to achieve desired levels of penetration while at the same time allowing the external portion of the polymer matrix to be relatively independently selected for other advantageous characteristics such as strength or other desirable features. By applying such techniques to composites of the present invention, filaments or other projections of the polymer can readily be caused to extend to varying degrees into a given porous material. Relatively high-strength composites of the present invention can thus be prepared in which the polymer matrix can extend 1-10, 10-20, 20-30, 30-40, 40-50, 50-60, 60-70, 70-80, 80-90, or 90-100 percent into the diameter (or linear dimension) of the porous material, as desired. Structural materials and other composites having a range of strengths and weights as described and illustrated herein can thus be prepared, for use in various applications such as those described below.

[0030] In certain embodiments, articles of the present invention can have compression strengths exceeding 20 pounds per square inch (psi), preferably exceeding 40, 100, 150, 210, 300 or 400 psi; compression modulus exceeding 2000 psi, preferably exceeding 4000, 8000, 10,000, 20,000, 40,000 or 100,000 psi; flexural strength exceeding 50 psi, preferably exceeding 100, 200, 350-375 or 500 psi; flexural modulus exceeding 2000 psi, preferably exceeding 4000, 8000, 10,000, 20,000, 40,000 or 100,000 psi; shear strength exceeding 20 psi, preferably exceeding 40, 100, 150, 210, 300 or 400 psi; and shear modulus exceeding 1000 psi, preferably exceeding 2000, 3000, 4000, 5000, 6000, 8000 or 10,000 psi; tensile strength exceeding 40 psi, preferably exceeding 80, 100, 150, 210, 300 or 400 psi; and tensile modulus exceeding 1000 psi, preferably exceeding 2000, 3000, 4000, 5000, 6000, 8000 or 10,000 psi.

[0031] As employed herein, "high compression strength," as determined, for example, by ASTM 1621, refers to the capacity of invention materials to withstand exposure to compressive forces without suffering significant breakdown of the basic structure thereof. Invention materials display compression strengths substantially in excess of what one would expect when comparing to the performance properties of the individual components from which invention materials are prepared. Descriptions of ASTM standards and testing can be found in the publications of ASTM International as well as their web sites (see, e.g., www.astm.org).

[0032] As employed herein, "high tensile strength," as determined, for example, by ASTM 1623, refers to the capacity of invention materials to withstand longitudinal strain, i.e., the maximum force the material can endure without separating. Invention materials display tensile strengths substantially in excess of what one would expect when comparing to the performance properties of the individual components from which invention materials are prepared.

[0033] As employed herein, "high shear strength," as determined, for example, by ASTM 273, refers to the resistance of invention materials to deformation when subjected to a defined stress. Invention materials display shear strengths substantially in excess of what one would expect when comparing to the performance properties of the individual components from which invention materials are prepared. [0034] As employed herein, "high flexural strength," as determined, for example, by ASTM 790, refers to the resistance of invention materials to deformation when subjected to a bending stress. Invention materials display flexural strengths substantially in excess of what one would expect when comparing to the performance properties of the individual components from which invention materials are prepared.

[0035] As employed herein, "high strength-to- eight ratio" refers to the surprisingly high strength of invention materials, in spite of their relatively low weight. For example, an invention article weighing a fraction of the weight of prior art materials is capable of providing the same or better performance properties than materials of substantially greater weight, such as, for example, wood or concrete. Invention materials can also be prepared having strength-to-weight ratios in excess of what one would expect when comparing to the ratios of materials prepared from the individual materials from which invention materials are prepared, such as for example, from materials made from a polymer such as polyurethane.

[0036] Invention materials can also be characterized in terms of their superior impact strength, hardness or surface stiffness (such by the Rockwell hardness test of a material's ability to resist surface indentation), as well as by other properties including the density of the resulting product, thermal conductivity and thermal expansion of the resulting product, as well as the thermal conductivity and thermal expansion of each component material, coefficient of expansion, coefficient of absorption (i.e., conductivity), dielectric strength and volume and arc resistance, flammability (such as by oxygen index or UL flammability ratings), shrinkage, water and water vapor permeability and absorption, specific gravity and other such physicochemical, mechanical, thermal or electric properties. Invention materials can be readily made resistant to moisture, since the particulate material can be substantially encapsulated in a polymer matrix and the polymer can be selected to be relatively resistant to moisture uptake and absorption (for example by selecting a relatively hydrophobic polymer or by coating the polymer or article with a relatively hydrophobic agent). Standard tests for moisture include, for example, ASTM D570-98, ASTM 2842-01, BS4370: Method 8, DIN 53434, and others known in the art. Using ASTM D570, for example, invention materials can readily be prepared having a range of different water absorptions in weight percent after 24 hours, typically less than 5, 4, 3, 2, 1, 0.5, 0.2, 0.1, 0.05, 0.01 or even lower as desired for a particular application. Conversely, it is also possible to prepare invention materials having relative^ high rates of water absoφtion for applications in which that may be desirable (such as applications in which it is desired that a material absorb and hold a large volume of liquid, and potentially release it over time). In the latter regard, agents that promote water absorption can be employed (such as sodium polyacrylates and the like) as well as, for example, agents that control or effect release of fluid over time.

[0037] In accordance with yet another aspect of the present invention, there are provided methods of making structural and other composite materials, the method comprising: combining porous material and a polymerizable component, and subjecting the resulting combination, in a mold or other container (which may be open or closed), to conditions suitable to cure the polymerizable component in the optional presence of blowing agent(s), whereby said blowing agent(s) and any gases generated during curing and/or compression of the porous materials are substantially absorbed by the porous material to produce a composite structural material. Where increased strength is desired, a portion of the polymerizable component can be forced into the porous material, thereby producing structural material comprising the porous material encapsulated in a solid polymer matrix, and wherein filaments or other projections comprising the polymer extend into the porous material.

[0038] In accordance with still another aspect of the present invention, there are provided formulations comprising: a porous material, a polymerizable component, and at least one additive selected from the group consisting of flow enhancers, plasticizers, cure retardants, cure accelerators, strength enhancers, UV protectors, dyes, pigments and fillers, wherein the porous material has a diameter in the range of about 0.05 mm up to about 60 mm, and a bead density in the range of about 0.1 kg/m up to about 1000 kg/m , preferably in the range of about 1 kg/m³ up to about 100 kg/m³, and wherein the polymerizable component is capable of curing at a temperature below the melting point of the porous material, wherein the polymerizable component, upon curing, produces a substantially solid matrix which encapsulates the porous material, and wherein filaments or other projections comprising the polymer extend into the porous material. Also contemplated are structural and other composite materials prepared from the above-described formulations.

[0039] In accordance with a further aspect of the present invention, there are provided formulations comprising: a porous material, and a polymerizable component, wherein the porous material is not expanded polystyrene, and has a diameter in the range of about 0.05 mm up to about 60 mm, and a bead density in the range of about 0.1 kg/m³ up to about 1000 kg/m³, preferably in the range of about 1 kg/m³ up to about 100 kg/m , and wherein the polymerizable component is capable of curing at a temperature below the melting point of the porous material, wherein the polymerizable component, upon curing, produces a substantially solid matrix which encapsulates the porous material, and wherein filaments or other projections comprising the polymer extend into the porous material. Also contemplated are structural and other composite materials prepared from the above-described formulations.

[0040] In accordance with a still further aspect of the present invention, there are provided formulations comprising: a porous material, and a polymerizable component, wherein the porous material has a diameter in the range of about 0.05 mm up to about 60 mm, and a bead density in the range of about 0.1 kg/m up to about 1000 kg/m , preferably in the range of about 1 kg/m³ up to about 100 kg/m³, and wherein the polymerizable component is not a polyurethane, and is capable of curing at a temperature below the melting point of the porous material, wherein the polymerizable component, upon curing, produces a substantially solid matrix which encapsulates the porous material, and wherein filaments or other projections comprising the polymer extend into the porous material. Also contemplated are structural and other composite materials prepared from the above-described formulations.

[0041] In accordance with a still further aspect of the present invention, there are provided formulations comprising: a porous material, a first polymerizable component which is capable of polymerizing within pores of the porous material, a second polymerizable component which is capable of binding to polymers of the first polymerizable component, either directly or through a linker, wherein the porous material has a diameter in the range of about 0.05 mm up to about 60 mm, and a bead density in the range of about 0.1 kg/m up to about 1000 kg/m , preferably in the range of about 1 kg/m up to about 100 kg/m , and wherein the polymerizable components, upon curing, produce a substantially solid matrix which encapsulates and at least partially penetrates the porous material. Also contemplated are structural and other composite materials prepared from the above-described formulations.

[0042] Optionally, invention formulations may also contain one or more additional additives selected from the group consisting of fire retardants, light stabilizers, antioxidants, antimicrobial agents, plasticizers, metal soap stabilizers, UV absorbers, pigments, dyes, antistatic agents, blowing agents, antifoam agents, foaming agents, lubricity agents, reinforcing agents, thermal stabilizers, particulate fillers, process aids, flow enhancers, fibrous fillers, slip additives, crosslinking agents and co-agents, cure retardants, cure accelerators, strength enhancers, impact modifiers, catalysts, and the like. The materials can be wateφroof or water resistant, ultraviolet (UV) stable, resistant to insects, microbes, fungi, atmospheric conditions, moisture, dry rot, and the like. The materials also generally do not emit significant quantities of volatile organic compounds (VOCs), such as regulated VOCs. [0043] Porous materials contemplated for use in the practice of the present invention can be rigid, semi-rigid, flexible, or compressible, and can have any of a variety of shapes, e.g., beads, granules, rods, ribbons, irregularly shaped particles, and the like. As readily recognized by those of skill in the art, shaped porous materials in other forms can also be employed, for example, sheets, lattices, tubes, open celled three dimensional structures, woven fabrics, non-woven fabrics, felts, sponges, and the like. See also, U.S. Patent No. 5,458,963 for additional shapes which are contemplated for use herein. The applications in which invention materials are employed play a role in the selection of a suitable particulate or shaped porous material. For example, if blocks of the material are to be formed, and later cut to size, then a particulate porous material can be desirable. In contrast, if the material is to be used for preparation of a fixed sized object, then a sheet or monolith of a porous material can be desirable. For example, porous sheets can preferably be employed in the preparation of a resilient floor tile, or a monolithic lattice of porous material can be employed in the preparation of a load-bearing form. Porous material in the form of spherical beads is especially preferred in certain embodiments of the invention.

[0044] Porous materials contemplated for use in the practice of the present invention typically have a particle size (i.e., the cross-sectional diameter at the largest dimension of the particle) in the range of about 0.05 mm up to about 60 mm, with particle sizes in the range of about 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9 or 1.0 mm to about 5.5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 20, 25, 30, 35, 40, 45, 50, or 55 mm (with particle sizes of from about 1 mm to about 5 mm prefeπed, and more preferably from about 1.0, 1.25, 1.5, 1.75, 2.0, 2.25, or 2.5 mm to about 2.75, 3.0, 3.25, 3.5, 3.75, 4.0, 4.25, 4.5, or 5.0 mm).

[0045] Porous materials contemplated for use in the practice of the present invention typically have a bead density in the range of about 0.1 kg/m³ up to about 1000 kg/m³, typically in the range of about 1 kg/m³ up to about 100 kg/m³, with bead densities varying as a function of the end use contemplated. Typically, bead densities fall in the range of about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15 kg/m³ to about 75, 100, 150, 200, 250, 300, 350, 400, 450, 500, 550, 600, 650, 700, 750, 800, 850, 900 or 950 kg/m³, more preferably from about 16, 17, 18, or 19 kg/m³ to about 51, 52, 53, 54, 55, 60, 65, 70, 80, 90, 100, 110, 120, 130, 140, 150 160, 170, 180 190 or 200 kg/m³, and most preferably from about 20, 21, 22,

23, 24, 25, 26, 27, 28, 29, or 30 kg/m³ to about 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 60, 70, 80, 90 or 100 kg/m³.

[0046] Presently preferred porous materials contemplated for use herein can be further characterized as having a porosity sufficient to absorb at least 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95% or substantially all of the gas(es) generated upon curing the polymer system employed in the practice of the present invention. In certain preferred embodiments, the porosity of the porous material is also such that at least a portion of the polymeric material can be forced into the porous material (e.g., by passive flow, pressure- driven flow, and/or capillary flow or by other kinetic and/or thermodynamic processes), resulting in microscopic and potentially macroscopic tendrils, fingers, filaments or other projections of the polymer penetrating into the body of the porous material. In addition, the ability of the porous material to serve as a reservoir for at least a portion of the generated gas can allow reduction in the number and/or size of gas bubbles that become trapped within the polymer matrix, thereby increasing the strength and density of the polymer matrix. In contrast, non-porous materials would not have such ability, and would allow escape of substantial amounts of the gas(es) generated upon curing the gas-generating polymer system employed in the practice of the present invention.

[0047] The average pore size of porous materials contemplated for use in the practice of the present invention is typically in the range of about 0.05 microns or less up to about 1,000 microns or more, preferably from about 0.1 microns up to about 500 microns, and more preferably from about 1, 5, 10, 15, 20, 25, 30, 35, or 40 microns up to about 50, 60, 70, 80, 90, 100, 150, 200, 250, 300, 350, 400, or 450 microns. While these average pore sizes are generally prefeπed, smaller or larger pore sizes can be prefeπed in certain embodiments. Likewise, while a tight pore size distribution is generally prefeπed, broader pore size distributions can be acceptable or desirable in certain embodiments. For example, where it is desired to increase the relative strength of the invention structural and other composite materials by causing more of the polymer matrix to enter the porous material, the number and depth of the pores can be increased or decreased as needed to enhance or discourage capillary flow into the pores. Alternatively, it is also possible to increase polymer ingress into the porous material by applying increased pressure and/or temperature to the material during preparation, by lowering the viscosity of the polymer, by selecting a polymer and porous material combination (or modifying a selected porous material) to provide similar or compatible surface energies for interaction, as well as other kinetic and/or thermodynamic processes that favor ingress of the polymer matrix into the porous material.

[0048] It is also possible to employ a graft copolymer system in which a first polymer component may be preferentially polymerized within pores of the porous material, and may also project outside of the porous material, which first polymer component may be joined (either directly or through one or more linker molecules) to a second polymer component which can form a relatively continuous matrix outside of the porous material. As a result of employing such a system, the first polymer component can be selected to facilitate the desired level of penetration of the porous material, while the second polymer component can be selected to promote desired properties of the matrix, such as strength and other physicochemical, thermal, electrical or other properties. The resulting structural and other composite materials can exhibit superior properties by virtue of their comprising a potentially lightweight porous material that is substantially encapsulated and penetrated by a potentially strong matrix material. The resulting mechanical and/or chemical interlocking of matrix and porous material can contribute to substantially improved properties of the resulting structure materials, including for example in compression strength and modulus, shear strength and modulus, flexural strength and modulus, and tensile strength and modulus. Using two polymer components has an advantage in allowing each of them to be relatively independently optimized to maximize their respective functional properties.

[0049] In the case of a graft copolymer system, preparation can be via a multi- or one- step polymerization process. For example, in a multi-step process, the first polymer component can be allowed to polymerize within pores of the porous material, after which porous material with first polymer may be subjected to additional steps in which a second polymer component is joined directly or via linkers to the first, to form a matrix that both encapsulates and penetrates the porous material. In an exemplary one-step process, the first polymer is selected or introduced in a manner that results in the first polymer being preferentially partitioned within the pores of the porous material and the second polymer is selected or introduced in a manner that results in the second polymer being preferentially partitioned outside of the pores of the porous material, and polymerization (with or without linker molecules) is allowed to proceed to graft the first and second polymer components to each other.

[0050] Porous materials contemplated for use herein can be further characterized by the surface area thereof. Typically, surface areas in the range of about 0.5 up to about 500 m/g² are contemplated, with surface areas in the range of about 2 up to about 100 m/g² presently prefeπed.

[0051] As readily recognized by those of skill in the art, the shape and dimension of porous material employed in the practice of the present invention can be varied so as to provide a finished product having different physical properties (e.g., different strengths and densities). In general, the smaller the particles employed, the higher the compression strength, shear strength, and weight of the resulting product. Conversely, the larger the particles employed, generally the more flexible, less rigid and lighter are the products obtained. With respect to particle density, in general, the higher the density of the particles employed, the higher the compression strength, shear strength and weight of the resulting product. Porous material such as polystyrene, polyethylene, polypropylene, other polyolefin, or other beads can be manufactured in various densities in order to meet the requirements of a specific end-use application. For example, various densities of expanded polystyrene or other beads can be obtained in a variety of ways, e.g., by adjustment of the quantity or type of blowing agent employed in the preparation of the bead precursor.

[0052] In accordance with the present invention, porous (particulate or non-particulate) material typically comprises in the range of about 50 up to greater than 99 volume percent of the volume of the finished article. Preferably, volumes fall in the range of 50, 60, 70, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, or 99 volume percent of the above-described formulation, with the prefeπed volume percent depending on the end use contemplated. For example, higher particulate contents are prefeπed where product buoyancy is desired (e.g., materials for use in boats, surfboards, flotation devices, dock buoys, and the like), whereas lower particulate contents are prefeπed where high structural integrity is required. Generally, a material having at least about 90% by volume porous material is prefeπed, with at least about 95, 96, 97, 98 or 99% by volume being especially prefeπed. It should be noted that since the material may be subject to compression during preparation, as described herein, the volume of input porous material may be substantially greater than 100% of the volume of the finished material, with such volumes readily exceeding 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 220, 240, 260, 280, 300, 400, 500 up to about 800 percent of the volume of the finished material.

[0053] Further in that regard, invention articles can be described in terms of the percent compression to which they can be subjected during preparation. Compression can be mediated by physicochemical expansion of the formulation within a confined space (such as a mold) or exogenously applied to a gas-generating or other polymer system contained within a mold or other confined space. During preparation, invention materials may be subjected to compressions of as little as 5-10 volume percent, with compressions up to and exceeding 80 or 90 volume percent contemplated herein. Compressions in the range of about 5, 10 15, 20, 25 or 30 volume percent up to about 35, 40, 45, 50, 55, 60, 65, 70, or 75 volume percent are presently prefeπed for applications in which a range of increased strengths is desirable.

[0054] In terms of the relative weight of the components employed for the preparation of invention formulations, porous material typically comprises in the range of about 5 wt % up to about 90 wt % of the formulation, with the weight range of the porous particulate material varying based on the contemplated end use. Preferably the porous material comprises about 10, 12, 15, 18, 20, 25, 30, 35, 40, or 45 wt. % to about 50, 55, 60, 65, 70, 75, 80, or 85 wt. % of the formulation. In certain embodiments, those of skill in the art recognize that higher or lower volume percents, and/or higher or lower weight percents can also be acceptable or desirable. [0055] For example, when used for insulation and strengthening the acrylic tub of a spa, thermal insulation and compressive strength are both desirable features of the material. Satisfactory compressive strength can reduce the likelihood of fracture of the acrylic due to weight loading caused by the contained water and occupants of the spa. By way of illustration of such an embodiment, the porous material can be present in the range of about 40-80 wt. %, preferably in the range of about 50-70 wt. %, or more preferably at about 60 wt. % (using a mixture of 5 mm or smaller polyolefin beads (e.g., expanded polystyrene and polyethylene beads) with a final density of about 2 pounds per cubic foot). Alternatively, when used for production of surfboards, it is desired that the resulting product be lightweight and have a strength exceeding that of a toluene diisocyanate (TDI) homogeneous polyurethane foam. By way of illustration of such an embodiment, the porous material can be present in the range of about 30-70 wt. %, preferably in the range of about 40-60 wt. %, or more preferably at about 50 wt. % (using 1.2 mm beads with a final density of about 3 pounds per cubic foot). As another alternative; when used for production of construction materials, materials having lightweight and high strength characteristics are desired. By way of illustration of such an embodiment, the porous material is present in the range of about 10- 40 wt. %, preferably in the range of about 15-30 wt. %, with about 18 wt. % being presently prefeπed (using, for example, 1.2 mm beads with a final density of about 10.5 pounds per cubic foot).

[0056] Exemplary porous materials contemplated for use in the practice of the present invention include polyolefins (e.g., beads comprising polyethylene, polypropylene, polystyrene, and the like, as well as mixtures and/or copolymers thereof), gravel and other silica-based materials, glass beads, ceramics, vermiculite, perlite, lytag, pulverized fly ash, unburned carbon, activated carbon, and the like, as well as mixtures of any two or more thereof. In view of the many porous materials contemplated for use herein, in certain embodiments of the invention, the use of porous materials other than polystyrene is contemplated herein.

[0057] Illustrative porous materials contemplated for use in the practice of the present invention include expanded polystyrene (and other polyolefins) having a particle size broadly in the range of about 0.4-25 mm, and a density in the range of about 0.75-60 lb/ft³; with expanded polystyrene preferably having a particle size in the range of about 0.75-15 mm, and a density in the range of about 0.75-30 lb/ft³; with presently prefeπed expanded polystyrenes having a particle size in the range of about 0.75-10 mm, and a density in the range of about 0.75-10 lb/ft³. Exemplary expanded polystyrenes include those have a particle size in the range of about 0.4-0.7 mm, and a density in the range of about 1.25-2.0 lb/ft³, expanded polystyrene having a particle size in the range of about 0.4-0.7 mm, and a density in the range of about 1.5-3.0 lb/ft³, expanded polystyrene having a particle size in the range of about 0.7- 1.1 mm, and a density in the range of about 1.0-1.5 lb/ft , expanded polystyrene having a particle size in the range of about 0.7-1.1 mm, and a density in the range of about 1.5-3.0 lb/ft , expanded polystyrene having a particle size in the range of about 1.1-1.6 mm, and a density in the range of about 1.0-1.2 lb/ft³, expanded polystyrene having a particle size in the range of about 1.1-1.6 mm, and a density in the range of about 1.5-3.0 lb/ft , expanded polystyrene having a particle size in the range of about 0.4-0.65 mm, and a density in the range of about 1.25-4.0 lb/ft³, expanded polystyrene having a particle size in the range of about 0.6-0.85 mm, and a density in the range of about 1.25-4.0 lb/ft³, expanded polystyrene having a particle size in the range of about 0.75-1.2 mm, and a density in the range of about 1.25-4.0 lb/ft³, expanded polystyrene having a particle size in the range of about 0.375-0.75 mm, and a density in the range of about 1.35-2.0 lb/ft³, expanded polystyrene having a particle size in the range of about 0.65-2.0 mm, and a density in the range of about 1.15-2.0 lb/ft³, expanded polystyrene having a particle size in the range of about 0.4-0.8 mm, and a density in the range of about 1.35-1.8 lb/ft³, expanded polystyrene having a particle size in the range of about 0.8-1.3 mm, and a density in the range of about 0.9-1.35 lb/ft , expanded polystyrene having a particle size in the range of about 1.3-1.6 mm, and a density in the range of about 0.75-1.15 lb/ft³, and the like.

[0058] An exemplary polyolefin, expanded polystyrene is typically made by heating crystalline polystyrene, refeπed to in the trade as "sugar" because of its similar appearance, with a blowing agent, such as cyclopentane, which has been entrained in the crystalline polystyrene during the manufacturing process. Crystal size is controlled to yield a final bead size distribution of the desired modal diameter. Under controlled heat and pressure conditions, the crystal softens and the blowing agent gasifies, forming microscopic gaseous bubbles within the crystal body. After sufficient softening, the crystal is eventually transformed by capillary forces into a spherical shape, with an internal structure comprising a honeycomb like, semi-hexagonally close packed cellular structure of somewhat iπegularly shaped and sized cells, as depicted in Figure 1. After expansion, the bead is removed from the reaction vessel to storage for curing. The bead is cooled gradually to prevent implosion of the bead surface into the interior and collapse of the cells while the entrained blowing agent continues to off-gas at atmospheric pressure. When sufficiently cooled, the bead retains its spherical shape without coalescing with its neighboring beads. The external appearance of the bead is rough and iπegular, with craters and ridges, as depicted in Figure 2. The percentage of air in expanded polystyrene beads is typically about 90 to 97%. Technical features of numerous other materials that can be employed as porous materials in connection with the present invention are known in the art, see, e.g., the references provided following the Examples below.

[0059] When porous materials, such as, for example, expanded polystyrene, polypropylene, other polyolefin or other porous materials as described herein and in the art, are thoroughly mixed with gas-generating polymer precursors under controlled conditions such that each individual bead can be wetted with the polymer mix, and the polymerization reaction begins to occur, the liquid polymer can be forced into the interior structure of the bead in a threadlike or branched filamentous fashion, through surface imperfections and voids by the gases produced by the polymerization chemical reaction when the mass is constrained in a closed mold. Optionally, additional pressure could be applied to force additional amounts of polymer into the porous material, thereby resulting in a stronger, but somewhat more dense material. When cooled and cured, the microscopic filaments or other projections harden, becoming rigid, while the polymer remaining on the exterior of each bead acts to hold the molded structure together in a more or less uniform matrix. Depending on the choice of porous material and polymer, some filaments or other projections may conjoin within the spherical expanded polystyrene bead while others do not. A cross section of a polymer matrix containing porous beads is depicted schematically in Figure 3. The beads include portions into which filaments or other projections of polymer material have penetrated, as well as porous areas that have absorbed gases generated upon curing. While not wishing to be bound to any particular theory, it is believed that the filaments or other projections formed (e.g., by controlled hydraulic pressure caused by the off gassing of the polymerization reaction or exogenously applied, and/or by capillary pressures or other forces) contribute to the superior strength and other properties of invention materials when compared to conventional materials. Varying the proportion of expanded polyolefin (e.g., polystyrene, polyethylene, or the like) to total polymer can thus be used to prepare a range of materials that are strong and very light on one end of the spectrum to materials that are significantly heavier and exceedingly stronger than conventional foamed polymer of the same density.

[0060] An exemplary material according to the invention incoφorating large beads (10) in a polymer matrix (1) is depicted schematically in Figure 4. An exemplary material according to the invention incoφorating small beads (11) in a polymer matrix (1) is depicted schematically in Figure 5. An exemplary material according to the invention incoφorating a mixture of large beads (10) and small beads (11) in a polymer matrix (1) is depicted schematically in Figure 6.

[0061] Polymerizable components contemplated for use in the practice of the present invention include polymer systems which generate gas upon polymerization thereof, or which can be treated with one or more blowing agents during cure, as well as other systems. Such systems can be further characterized in a variety of ways, for example, in terms of their viscosity. Suitable polymerizable components contemplated for use herein typically have a viscosity at 25°C in the range of about 200 up to about 50,000 centipoise, with viscosities in the range of about 400 up to about 20,000 centipoise being presently prefeπed, with especially prefeπed viscosities falling in the range of about 800 up to about 10,000 centipoise.

[0062] As readily recognized by those of skill in the art, there are many polymer systems known in the art which are suitable for use in the practice of the present invention. For example, homopolymers, copolymers, block copolymers, graft copolymers, and the like can be employed. Exemplary polymers contemplated for use herein include polyethylenes, polyvinyl resins, polypropylenes (high and low density), acrylonitrile-butadiene-styrene (ABS) copolymers, polyurethanes, and the like, as well as combinations of any two or more thereof, each with specific pre-cure and post-cure physical properties.

[0063] In one embodiment of the present invention, a combination of polymeric components can be employed to coat the porous material and form the polymer matrix. Thus, in one aspect, a first polymer can be employed to coat the porous material (frequently a low viscosity material having good wettability for the porous material, thereby facilitating coating of the porous material and ingress into the pores thereof), and thereafter, the coated particles can be further contacted with a second polymer, which, upon cure, substantially forms the matrix of the finished article. If the first and second polymeric materials are selected properly, upon cure of each polymer system, the two polymer systems will also react with one another to further enhance the properties of resulting article. In another aspect, the functional properties of the two different polymer systems refeπed to above can be combined in a single, graft copolymer, such that a portion of the graft copolymer will have significant affinity for the porous material, and the remainder of the graft copolymer will form a strong matrix upon cure.

[0064] Some curing processes are exothermic and some are endothermic. Presently prefeπed polymer systems contemplated for use in the practice of the present invention are mildly or moderately exothermic, so that only minimal heating and cooling are required in the preparation of invention materials. Moderately exothermic systems offer particular convenience in the manufacture of materials according to the present invention in that they do not require that heat be applied to drive the reaction, and yet do not generate so much heat as to melt many of the materials contemplated for use herein as the porous component of invention structural and other composite materials, or potential additives thereto. In presently prefeπed aspects of the present invention, lightweight, high-strength materials can be readily and cost-effectively produced without the need for exogenously applied heating or cooling during manufacture. However, for certain applications and where more rapid cycling is desired, it is possible to apply exogenous heat and/or cooling to facilitate processing, as is known in the art.

[0065] Some polymer systems generate gas as part of the curing process, while some polymer systems require the addition of external blowing agents, of which there are a wide variety with different physical characteristics (e.g., pentane, cyclopentane, carbon dioxide, nitrogen, and the like). As recognized by one of skill in the art, blowing agents can be introduced externally, or they can be generated in situ during preparation of invention materials (e.g., by compression of the porous material,, which may contain gas entrapped therein). Polymerization of the above-described systems can occur at a variety of temperatures, sometimes exceeding 100°C; such processes sometimes are carried out at elevated pressures as well, e.g., up to several bars. As discussed herein, increasing the pressure during preparation of invention structural and other composite materials can be used to both compact the components thereof, and to drive additional polymer matrix into the interior of the porous material, each of which tends to strengthen the resulting product. The amount of pressure to be applied is preferably sufficient to force some ingress of polymer into the porous material, without being so great as to cause collapse of a substantial portion of the porous material. In view of the many gas-generating polymer systems contemplated for use herein, in certain embodiments of the present invention, the use of gas-generating polymer systems other than polyurethane is contemplated herein. Alternatively, graft copolymer systems can be employed such that one portion of the graft copolymer is preferentially localized within the porous material and another portion of the graft copolymer is preferentially localized outside of the porous material, and joining of the two copolymer components (either directly or through linker molecules) results in a porous material core that is substantially encapsulated within and penetrated by a polymer matrix, resulting in structural and other composite materials that are of relatively low weight and yet high strength and structural integrity.

Preferably, polymerizable components employed in the practice of the present invention are stable to temperatures of at least about 50°C. This facilitates handling of these materials, and minimizes the occuπence of premature curing. In addition, it is also frequently desirable that polymerizable components employed in the practice of the present invention be stable to such exposures as light, atmosphere, oxygen, water, and the like, which can impact the stability and/or reactivity thereof.

[0067] As readily recognized by one of skill in the art, numerous combinations of porous material plus polymerizable system(s) can be employed in the practice of the present invention. In selecting suitable combinations, one should take into account the compatibility of the two components, with reference to such considerations as the contact angle between the two components, the surface tension of the polymerizable system relative to the porous material, the pore size(s) of the porous material, the capillary radius of the pores of the porous material, the pressure to be applied upon processing of the selected combination, and the like. As will be appreciated by those of skill in the art, varying such aspects can be used to alter the "wettability" of the porous material as well as altering the relative penetration of the polymer into the porous material (and thereby potentially increasing strength of the resulting composite) as described herein. The ability to easily produce a variety of different materials having properties optimized for various particular applications, provides a significant advantage of this approach.

[0068] The presently prefeπed processes according to the invention employ a gas- generating polymer system, based, for example, on diisocyanates, for the preparation of a polyurethane matrix. The curing of diisocyanate has the benefit of being simple, occurring at or about room temperature and generating its own gas (i.e., carbon dioxide) and only moderate heat during the polymerization of the reactants, isocyanate and polyol. As discussed above, the gas generated during curing can be substantially absorbed by the porous material.

[0069] Among the advantages of invention formulations based on presently prefeπed urethane matrices is the fact that these formulations emit substantially no volatile organic compounds (VOCs) upon cure, unlike many conventional gas-generating formulations.

[0070] Presently prefeπed gas-generating polymerizable components contemplated for use in the practice of the present invention include polyurethanes, substituted polyurethanes, and the like, as well as mixtures of any two or more thereof. As is well known in the art, polyurethanes can be prepared in a variety of forms, including rigid foams, flexible foams, solids, adhesives, and the like.

[0071] As readily recognized by those of skill in the art, a wide variety of diisocyanate and polyol starting materials can be employed for the preparation of polyurethanes useful in the practice of the present invention. For example, a wide variety of aromatic diisocyanates can be employed, such as, for example, m-phenylene diisocyanate, -phenylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 3,3'-dimethyl-4,4'- biphenylene diisocyanate, durene diisocyanate, 4,4'-diphenylisopropylidene diisocyanate, 4,4'-diphenyl sulfone diisocyanate, 4,4'-diphenyl ether diisocyanate, biphenylene diisocyanate, 1,5-naphthalene diisocyanate, and the like.

[0072] Similarly, a wide variety of polyol starting materials are suitable for use in the preparation of polyurethanes according to the present invention, including ethylene glycol, 1,2-propanediol, 1,4-butanediol, 1,4-cyclohexanediol, glycerol, 1,2,4-butanetriol, trimethylol propane, poly( vinyl alcohol), partially hydrolyzed cellulose acetate, and the like. Fire retardants can be added to the porous material (e.g. prior to mixing with resin) or they can be incoφorated during or after polymerization according to the present invention.

[0073] Fire retardants contemplated for use in certain embodiments of the present invention include any compound which retards the propagation of fire, such as, for example, butylated triphenyl phosphate, and the like.

[0074] Flow enhancers contemplated for use in certain embodiments of the present invention include any compounds which reduce the viscosity and/or improve the flow properties of the formulation, such as, for example, 2,2-dimethyl-l(methylethyl)-l,3- propanediyl bis(2-methylpropanoate), and the like.

[0075] Plasticizers (also called flexibilizers) contemplated for use in certain embodiments of the present invention include compounds that reduce the brittleness of the formulation, such as, for example, branched polyalkanes or polysiloxanes that lower the glass transition temperature (Tg) of the formulation. Such plasticizers include, for example, polyethers, polyesters, polythiols, polysulfides, and the like. Plasticizers, when employed, are typically present in the range of about 0.5 wt. % up to about 30 wt. % of the formulation.

[0076] Cure retardants (also known as cell size regulators or quenching agents) contemplated for use in certain embodiments of the present invention include compounds which form radicals of low reactivity, such as, for example, silicone surfactants (generally), and the like.

[0077] Cure accelerators contemplated for use in certain embodiments of the present invention include compounds which enhance the rate of cure of the base polymer system, such as, for example, catalytically active materials, water, and the like.

[0078] Strength enhancers contemplated for use in certain embodiments of the present invention include compounds which increase the performance properties of the polymeric material to which they are added, such as, for example, crosslinking agents, and the like.

[0079] UV protectors contemplated for use in certain embodiments of the present invention include compounds which absorb incident ultraviolet (UV) radiation, thereby reducing the negative effects of such exposure on the resin or polymer system to which the protector has been added. Exemplary UV protectors include bis(l,2,2,6,6-pentamethyl-4- piperidinyl) sebacate, silicon, powdered metallic compounds, and the like.

[0080] Dyes contemplated for use in certain embodiments of the present invention include nigrosine, Orasol blue GN, phthalocyanines, and the like. When used, organic dyes in relatively low amounts (i.e., amounts less than about 0.2 % by weight) provide contrast.

[0081] Pigments contemplated for use in certain embodiments of the present invention include any particulate material added solely for the puφose of imparting color to the formulation, e.g., carbon black, metal oxides (e.g., Fe₂O₃, titanium oxide), and the like. When present, pigments are typically present in the range of about 0.5 wt. % up to about 5 wt. %, relative to the base formulation.

)82] Fillers are also contemplated for use in certain embodiments of the invention. Fillers can be introduced into invention formulations to enhance one or more of the following properties: compression strength, shear strength, pliability, internal resistance (useful, for example, for holding nails, screws, and the like), wear durability, impact strength, fire resistance, coπosion resistance, increased density, decreases density, and the like. Fillers contemplated for use in certain embodiments of the present invention include metals, minerals, natural fibers, synthetic fibers, and the like. Such fillers can optionally be conductive (electrically and/or thermally). Electrically conductive fillers contemplated for use in certain embodiments of the present invention include, for example, transition metals (such as silver, nickel, gold, cobalt, copper), aluminum, silver-coated graphite, nickel-coated graphite, alloys of such metals, and the like, as well as non-metals such as graphite, conducting polymers, and the like, and mixtures of any two or more thereof. Both powder and flake forms of filler may be used in the compositions of the present invention. Preferably, the flake has a thickness of about 2 microns or less, with planar dimensions of about 20 to about 25 microns. Flake employed herein preferably has a surface area of about 0.15 to 5.0 m /g and a tap density of about 0.4 up to about 5.5 g/cc. In certain embodiments, flakes of different sizes, surface areas, and tap densities may desirably be employed. It is presently prefeπed that powders employed in the practice of the invention have a diameter of about 0.5 to 15 microns. If present, the filler typically comprises in the range of about 5 vol. % up to about 95 vol. % of the formulation, preferably 10, 15, 20, or 25 vol. % to about 90 vol. % of the formulation, more preferably about 30, 35, 40, 45, 50, 55 vol. % to about 60, 65, 70, 75, 80, or 85 vol. % of the formulation.

[0083] Thermally conductive fillers contemplated for use in certain embodiments of the present invention include, for example, aluminum nitride, boron nitride, silicon carbide, diamond, graphite, beryllium oxide, magnesia, silica, alumina, and the like. Preferably, the particle size of these fillers will fall in the range of about 0.1 up to about 100 microns, preferably about 0.5 to about 10 microns, and most preferably about 1 micron. However, larger or smaller particle sizes can be employed in certain embodiments. If aluminum nitride is used as a filler, it is prefeπed that it is passivated by an adherent, conformal coating (e.g., silica, or the like).

[0084] Optionally, a filler can be used that is neither an electrical nor thermal conductor. Such fillers can be desirable to impart some other property to invention foπuulations such as, for example, reduced thermal expansion of the cured material, reduced dielectric constant, improved toughness, increased hydrophobicity, and the like. Examples of such fillers include synthetic materials, such as, for example, perfluorinated hydrocarbon polymers, thermoplastic polymers (e.g., polypropylene), thermoplastic elastomers, poly-paraphenylene terephthalimide, fiberglass, graphite plies, graphite fibers, nylon, rayon, recycled polymers, recycled solid materials, solid scrap, solid polymeric material, scrap metal, re-ground chips, flaked chips, powder, paper, crumb, rubber, glass, hollow polymer beads, solid polymer beads, hollow glass beads, solid glass beads, scrap glass, recycled composition shingles, recycled asphalt, recycled roofing materials, recycled concrete, recycled tires, carbon, as well as a variety of other post-industrial or post-consumer plastics and other materials, and the like. Fillers can also include naturally occurring materials, such as, for example, mica, fumed silica, fused silica, sand, sawdust, gravel, stone aggregate, cotton, hemp, rice hulls, coconut husk fibers, shrimp carcasses, bamboo fiber, paper, popcorn, popcorn aggregate, bone, seeds, shredded straw fibers (e.g., from rice, wheat or barley), and the like, as well as mixtures of any two or more thereof. Fillers may be either porous or relatively non-porous. In the case of porous fillers, the polymeric matrix of invention materials may extend into, as well as, around such fillers, thereby potentially contributing further strength to invention materials.

[0085] Invention structural and other composite materials, sometimes refeπed to herein as PetriFoam™ brand structural and other composite materials, can be made to have superior compression moduli (as desired), which can fall in the range of about 8000 psi up to about 10,000 psi or higher. Depending on the desired application, materials of the present invention can be prepared having compression moduli exceeding 2000, 4000, 8000, 10,000, 20,000, 40,000, 100,000 or higher. In addition to the superior compression strength of invention materials, these materials are capable of withstanding compressive pressures exceeding 400, 1000, 4000, 8000, 12,000, or even higher before fracture. Indeed, exposure of invention articles, after curing of invention materials, to elevated compression pressures (but short of fracture) can produce an article with enhanced strength.

)86] Invention structural and other composite materials may also have superior resilience, as measured, for example, by the flexural modulus of a sample. Such materials are useful in a variety of specific applications, as set forth in detail below. Typically invention materials have a flexural modulus which falls in the range of about 10,000 psi up to about 14,000 psi or higher. Even higher flexural modulus materials can be obtained by the use of suitable fillers. For example, flexibility can be enhanced if desired for certain applications by incoφorating flexible materials such as flexible plastics or rubber, which can be from recycled materials, as well as other flexible materials.

[0087] Additional desirable properties which can be provided by invention materials include superior insulating properties, water resistance properties, energy absoφtion properties (optionally including excellent memory effects, wherein invention materials return substantially to their original shape after impact), mold resistance, radar absoφtion, and the like.

[0088] In embodiments of the invention where superior strength is a desired feature of the resulting structural material, it is prefeπed that the polymer matrix comprises fewer and smaller cavities formed during foaming. For such an embodiment, a majority and preferably at least 20, 30, 40, 50, 60, 70, 80, 90, 95, 98% or more preferably substantially all of the gas generated during curing of the polymer is absorbed by the porous material, and a quantity of the polymeric material is preferably forced into the body of the porous material. The resulting polymer matrix is preferably relatively solid, except for those portions occupied by the porous material, and filaments or other projections of polymer extend into the body of the porous material. While not wishing to be bound by any particular theory, it is believed that the combination of a relatively solid polymer matrix with polymer filaments or other projections extending into the body of the porous material contributes to the exceptional properties of invention materials, including strength, flexural modulus, and compression. While a relatively solid polymer matrix is generally prefeπed, in certain embodiments where strength can be reduced, a matrix having cavities can be acceptable, or even desirable since it can be used to generate lighter materials and at a lower cost.

[0089] In order to produce structural and other composite materials having even greater structural integrity suitable for use in an even wider range of potential applications, one or more reinforcement structures can be incoφorated within invention materials. Exemplary reinforcement materials include natural fibers, synthetic fibers, silica-based materials, or other structures, as well as combinations of any two or more thereof. Such reinforcement materials can be of any size, shape, length, etc. One of skill in the art can readily determine suitable dimensions of any added reinforcement materials, depending on the end use contemplated for the material.

[0090] As an alternative to including one or more reinforcement(s) in invention materials, or in addition to such inclusion, one or more facing materials can be applied to invention materials, optionally employing a suitable adhesive material, adhesive promoter, or tie coat, as needed. A wide variety of facing materials are suitable for such puφose, such as, for example, facings comprising metal, polymers, cloth, plant fiber or other natural fibers, synthetic fibers, glass, ceramic, expanded metals and screens, and the like, as well as combinations of any two or more thereof. Additional facing materials contemplated for use herein include naturally occurring materials (such as, for example, wood), synthetic sheet materials (such as, for example, acrylic sheet material), natural or synthetic woven materials (such as for example, a Kevlar weave), and the like. While only illustrated in Figure 7 as being bonded to one face of the invention material, facing materials can be bonded to a plurality of faces of invention materials (e.g., top and bottom of invention materials may have a facing material applied thereto, all faces of invention materials may have a facing material applied thereto, as well as other variations which will be apparent to those of skill in the art). Such facing materials can be in the form of a solid surface, a porous surface, a surface that can be chemically etched, a chemically etched surface, a surface that can be physically abraded, a physically abraded surface, and the like, as well as combinations of any two or more thereof. In a particularly prefeπed embodiment, a length of bamboo is filled with invention material, yielding a strong structural member suitable for use in, e.g., construction materials, or scaffolding. Suitable adhesive materials contemplated for use in this aspect of the present invention include epoxies, polyesters, acrylics, urethanes, rubbers, cyanoacrylates, and the like, as well as combinations of any two or more thereof.

[0091] Among the advantages of invention structural and other composite materials is the fact that these materials emit substantially no off-gases, unlike many conventional structural and other composite materials, especially those prepared employing gas-generating formulations.

[0092] In accordance with yet another embodiment of the present invention, there are provided methods of making structural and other composite materials having a compression modulus of at least about 8000 psi, and a flexural modulus in the range of about 10,000 psi up to about 14,000, the method comprising: combining porous material with a gas-generating polymerizable component, and subjecting the resulting combination to conditions suitable to allow the polymerizable component to polymerize. During the polymerization process using a substantially closed or pressurized system, substantially all of the gas generated is absorbed by the porous material and some of the polymeric material can be forced into the body of the porous material.

[0093] The combining contemplated by the invention method can be carried out in a variety of ways. For example, the gas-generating polymerizable component and the porous material (and any additional components contemplated for a specific use) can be mixed, then the gas-generating polymerizable component allowed to cure. In one embodiment of the present invention, the mixture is introduced into a mold, the mold closed, and the gas- generating polymerizable component is allowed to set. In another embodiment of the present invention, the mixture is introduced into a confined space and compressed to a volume less than the original volume of the starting components. The mixture may, as another alternative, be prepared in an open system, or may be sprayed or otherwise applied onto a surface. If additional strength is desired, it may be cured under compression such that the generated gases are substantially absorbed by the porous material and such that some of the polymer is forced into the body of the porous material.

[0094] When invention formulations are subjected to pressure to reduce the volume thereof, a wide range of pressures can be employed, typically in the range of about 1 up to about 10 psi, but higher pressures can also be applied if desired to produce relatively higher strength composites. Alternatively, without regard to the pressure that may be involved, invention formulations can be cured in a confined space so that the cured article is of reduced volume relative to the volume of the starting materials. Volume reductions in the range of about 5-10 percent, up to 20-40, 40-60, 60-80, 80-90 percent, or higher, are contemplated in the practice of the present invention.

[0095] In still another embodiment of the invention, rather than prepare invention articles in a mold to achieve a specific shape, standardized "building block" structures can be prepared and thereafter combined into a desired shaped article. This is possible because invention materials can be readily adhered to one another using standard adhesive materials such as, for example, urethanes, epoxies, and the like.

[0096] Preferably, when the polymerizable component (such as a foamable polymerizable component) is prepared from a multi-component (e.g., a two-component) system, the porous material is first mixed with only one of the polymerizable components, before introduction of the second component into the reaction vessel. It is generally prefeπed that the porous material first be mixed with the more viscous of the components of the two-component system. For example, the surface of the porous material can be substantially completely coated with a precursor of the polymerizable component. Alternatively, the surface of the porous material can be only partially coated with a precursor of the polymerizable component.

[0097] Alternatively, invention articles can be prepared from a one-component monomer (e.g., polyurethane), wherein all components of the polymer are combined with the porous material, and cure of the polymer is commenced by addition of water thereto. Copolymers can also be employed, such as block-copolymers, in which the matrix can be designed to incoφorate two or more different functional polymer groups, and/or graft copolymers such as the copolymer system designed to facilitate porous material penetration as described above.

[0098] Facings or coatings can be applied to invention articles by introducing facings and/or coatings into the mold before the reaction mixture is introduced. Alternatively, facings and/or moldings can be applied after molding. It is also within the scope of the present invention to add reinforcement materials (such as metallic meshes, ceramic or silica- based materials, textiles or other fabrics, rubber, and the like) to the mold so as to produce an integral reinforced material. A schematic depiction of an example article according to the present invention having a facing material attached thereto is presented in Figure 7.

[0099] Facing materials contemplated for application to invention materials include naturally-occurring materials (such as, for example, wood, bamboo or other plant-derived fiber), synthetic sheet materials (such as, for example, acrylic sheet material), natural woven materials (such as for example, cotton or hemp), synthetic woven materials (such as for example, KEVLAR weave, weaves of various synthetic fibers such as carbon, graphite, glass fibers, and the like), and the like. As readily recognized by those of skill in the art, facing materials can be bonded to one or a plurality of faces of invention materials (e.g., the top and bottom faces of invention materials may have facing materials applied thereto, all faces of invention materials may have facing materials applied thereto, as well as other variations as are apparent to those of skill in the art).

[0100] As readily recognized by those of skill in the art, a wide variety of coatings can be applied to invention materials. Coating materials contemplated for application to invention materials include Portland cement (typically applied as a sluπy in water, or with a silica-based material, imparting fire retardant properties to the treated article), gypsum, gel coat, clear coat, color layers, non-stick coatings, slip resistant coatings, adhesives, scratch resistant coatings, metallized coatings, and the like. Figure 8 provides a schematic depiction of invention material having a coating material applied thereto. For some coating materials, it is beneficial to enhance the ability of coatings to adhere to invention articles. This can be accomplished in a variety of ways, such as, for example, by physically and/or chemically etching the surface of such articles. Thus, as illustrated herein, the surface area of the article to which a coating is to be applied can be increased, thereby improving ability of the coating material to adhere to the article being treated.

[0101] When facing materials and/or coatings are to be applied to invention materials, the surface of the invention material to which the facing and/or coating is to be applied can be subjected to physical and/or chemical abrasion to increase the porosity of the substrate and enhance the adhesion of facing materials and/or coatings thereto. For example, the invention materials can be subjected to sandblasting and/or chemical etching or abrasion to abrade the surface skin thereof, rendering the surface of the invention material more receptive to application of facing materials and/or coatings thereon. In certain embodiments of the present invention, one can apply facing material and/or coating to either side of a support. Such a configuration is depicted schematically in Figure 9.

[0102] Those of skill in the art can readily determine conditions suitable to allow the gas-generating or other polymerizable component employed herein to polymerize. Typically, such conditions comprise adding polymerizing agent to the combination of porous material and precursor of the gas-generating or other polymerizable component, generally at or about room temperature. Thus, the heating and cooling requirements of the invention process are minimal, such that the process can readily be accomplished, for example, by vibrating the vessel containing porous material, precursor of the gas-generating or other polymerizable component and the polymerizing agent immediately after introduction of polymerizing agent thereto.

[0103] In accordance with certain embodiments of the present invention, up to about 25, 30, 35, 40, 45, 50 wt. % or more of the porous material employed can comprise recycled (ground) structural material as described herein. As readily recognized by those of skill in the art, even higher amounts of recycled invention material can be employed, depending on the material being recycled and the end use contemplated therefor. [0104] In accordance with another aspect of the present invention, there are provided articles prepared according to the above-described methods.

[0105] In accordance with yet another aspect of the present invention, there are provided articles fabricated from invention materials. Such articles can have a defined shape, superior compression strength and modulus, and if desired, a high flexural modulus. Such articles can comprise a flexible or rigid polymer matrix containing porous material substantially uniformly distributed therethrough. Invention articles have superior performance properties that render them suitable for a wide variety of applications. An especially useful application of invention materials is in applications where a structure prepared therefrom is at risk of exposure to seismic activity. Because invention materials can have such high strength and other desirable properties (including superior structural elasticity and memory), and relatively low weight, very low momentum is generated if a structure prepared therefrom is subjected to seismic forces. Thus, invention materials have particularly desirable properties for use in a variety of construction applications.

[0106] A non-exhaustive list of examples of the wide variety of applications for which invention articles can be employed is provided herein. Invention articles can be shaped as appropriate to facilitate any of the following uses:

aircraft/aerospace/defense/power generation (e.g., aiφlane components, remotely piloted vehicle components, cruise missiles, solar powered aircraft, heat shields, rocket motor casings, accessories, military drones, kit planes, ultralight planes, aircraft security/stealth components, lightweight/strengthened doors, aircraft furniture, panels, homeland security structural protection systems, wind-power-generation propellers and blades, water power generating wheels or blades, turbines, supporting structures for solar power generation, wings-in-ground-effect craft, radar absoφtion materials, aircraft engine cowlings, aircraft propeller blades, aircraft flaps, aircraft rudders, aircraft fuselage, aircraft ailerons, seaplane floats, hang gliders, insulation for rocket motor fuel tanks, and the like), agricultural (e.g., plant protectors and planters, livestock feeders, electric fencing posts, livestock pens, and the like), yard/lawn/garden pet/horticultural/greenliouses (e.g., doghouses, feeding and watering dishes, shelters and canopies, kennels, sleeping mats, animal shipping cages, dog and cat beds, cat scratchier, plastic furniture (e.g., for lawn, porch, garden, patio, and the like), decorative art panels and screens, decorative stampings and trims, snow fencing, flower boxes, pots, tubes, vases, lawn and garden fountains, garden ornamentals, urns, and the like), electronics (e.g., telecommunications antennas, cable reels, cable trays, battery boxes, battery storage racks, photovoltaic, cellular antennas, electric wiring raceways, and the like), appliances (e.g., household appliances, such as refrigerators, dishwashers, ranges, microwave ovens, washers, dryers, and the like, as well as housing for various appliances, such as, for example, housing for televisions, computers, CRTs, business machines, microwave ovens, dishwashers, laundry washers and dryers, compactors, freezers, refrigerators, air conditioners, dehumidifiers, portable heaters, and the like), refrigeration (e.g., cold storage buildings, champagne buckets, ice buckets, beverage coolers, condenser drip pans, walk in freezers, refrigerated railroad freight cars, ice bunkers, reefer trailers, refrigeration insulation, and the like), business equipment and electronics (e.g., copiers, computers, computer components, computers, television components, telephones, appliance moldings and casings, electrical tools, electronic cases and racks, and the like), building and construction — any application which can benefit from materials impervious to mold, termite infestation, and the like, such as, for example, swimming pools, swimming pool covers, hot tubs, hot tub covers, cooling towers, tub and shower units, bridge decks, bridges, oveφass structures, seismic reinforcement structures, highway signs, freeway energy absorbing barriers and acoustic absorbent side walls, insulated structural panels, home building construction, panels for commercial building construction, architectural details and facades, sound attenuation barriers, insulation, wateφroofing materials, concrete forms and molds, manufacturing forms and molds, structural framing systems, pilings, sandwich components, highway delineators, pre-manufactured homes, pre-manufactured offices, highway impact-absoφtion barriers, racetrack impact absoφtion barriers, roofing, flooring, siding, door laminates, woodwork laminates, dimensional lumber and panels, disaster and military-temporary living shelters, sanitary waste processing buildings and tanks, hospitals and operating rooms, clean rooms and laboratories, decontamination buildings, bathhouses, refrigerated storage buildings, kitchens, mess hall's, offices, warehouses, workshops and vehicle maintenance buildings, computer control rooms, furniture, tables, doors, aiφlane hangers, stretchers, coffins, beds, garbage cans, insulated drinking water cans, insulated perishable food containers, insulated ductwork for heating and air-conditioning units, on-site fabrication and construction of homes, housing, offices, temporary quarters, construction building blocks and bricks, arctic structures, internal structural fill for expanded polystyrene foam formed houses, replacement for green board for under tiled landing surfaces, countertops, tabletop, desktops, workbench surfaces, trim boards, sash, shutters, siding, sheeting, architectural moldings and ornamental moldings, doors, doorframes, window frames, insulated and structural sliding panels, retaining walls, lightweight portable walkways and personnel bridges, decking, railing, fences, gates, coπals, caφorts, awnings, mud mats for heavy equipment, crane rigging mats, automobile and pedestrian barricades, traffic cones, guardrails and posts, caution and safety signs, cab and bus stand shelters, farm buildings and storage sheds, portable buildings, prefab structures, pre-engineered buildings and structures, cabanas, canopies, wallboard, portable classrooms, clean rooms, cofferdams, construction forms for placement of cement and concrete, contractor mixing pans, composite dimensional lumber, various types of sheeting, engineered lumber and beams, extruded sheeting and shapes, cast fireplace mantels, roof and floor trusses, insulated doors, insulated roofing systems, laminated veneer sheets, sandwich honeycomb panels, noise barriers, pedestrian bridges, garage doors, roofing sheets, roofing shingles, roads, scaffolding systems, scaffold planks, sauna buildings and baths, door skins, temporary sidewalk plates, sub floors, cabinets, and the like, industrial (e.g., storage buildings, bullet resistant enclosures and systems and traps, hoods, canteens, loading booms, chutes, spouts, gaskets, tubes, light fixtures, ceiling fan blades, air diffusers, laundry hampers, fan housings, wheels, vanes, manhole and covers, fire hose cabinets, safety guard covers, palette wrapping, mailboxes, palettes (reusable and/or recyclable), palette box, overhead doors, parking barricades, parking curbs, room dividers, seats and benches, shelving, ballistic shields, shower and bathroom stalls, reels and stools, trays, and the like), industrial liners (e.g., bulk container liners and systems, railroad car liners, closet liners, all types of coatings, drum liners, hoods, irrigation ditch lining, noise control enclosures, and the like), furniture (e.g., upholstered furniture frames, benches, bleacher seats, chairs, stools, folding card tables, tables, office partitions, and the like), consumer and industrial packaging products (e.g., refuse containers and tote boxes, food preservation containers, ultra-light airfreight containers, reusable boxes and shipping containers, crates, burial vaults, mausoleums, recyclable packaging, packing and shipping containers, cemetery vaults, cartons, canisters, cannons, cartridge boxes and ammunition boxes, casks and baπels, collapsible boxes and shipping crates, oceangoing shipping containers, corrugated plastic containers and packing, custom molded plastic boxes and housings, drums, egg cartons and cases, instrument cases, folding boxes, cartons, garbage cans, grain bins, retail store fixtures, shelving, molded cases and boxes, countertops, furniture, and the like), signs and product displays (e.g., bulletin boards, erasable boards, changeable letter boards, clipboards, display boards, boxes, cab nets, cases, fixtures, panels, racks and stands, tables, trays, light boxes, picture frames, military targets (land, sea, air), outdoor advertising signs, stage scenery and props, tradeshow booths and displays, and the like), recreational goods (e.g., sports equipment, golf clubs, campers, exercise equipment, snowboards, surfboards, boogie boards, golf carts, bowling equipment, totes and boxes, motorcycle helmets, bicycle helmets, other sports helmets, elbow and knee protectors, gloves, athletic and non-athletic footwear including shoes and boots, skis, skateboards, camping trailers, rifles, shotguns, revolver stocks, forearms, decoys, snowshoes, riding saddles, snow sleds, and the like), children's toys/yard toys (e.g., castles, playhouses, swing seats, slides, sandboxes, toy chests and boxes, building blocks, alphabet toys, passenger safety seats and restraints, furniture such as high chairs, chairs, cribs, desk, beds, sandboxes, tables, toy vehicles and ride in vehicles, wagons, swing seats, spring-loaded riding animals, hobby horses, rocking horse, and the like), coπosion-resistant equipment (e.g., pollution-prevention equipment, wastewater treatment products, pipe fittings, aboveground and underground storage tanks, pumps, containers, and various equipment used in the chemical processing, pulp/paper processing and oil/gas industries, oil and gas recovery equipment, wheels that generate power, and the like), electrical/electronic equipment (e.g., housing and circuit breaker boxes, pole line hardware, electronic connections and insulation, rods and tubes, substation equipment, electronic microwave components, electrical enclosures and lighting enclosures, 3D boards, polyester panel boards, and the like), marine (e.g., yachts, boats, jet skis, canoes, marine docks, personal watercraft and moorings, naval boats, ships, racing craft, commercial ships and component parts, including marine equipment and motor covers, marine vehicles that operate in ground effect, marker buoys, mooring buoys, channel, instrumented, scientific buoys, weather buoys, fishnet buoys, life rafts, boat fenders, rigid hulls for inflatable boats, dock storage boxes, dingy and water tenders, floatable paddles and oars, water sport toys, diveyaks, crab and lobster trap markers, hatch covers, composition boat anchors, dock steps, swimming platform floats, boarding ladders, pontoon boats, steering consoles, portable and built-in galley ice chests, refrigerators, galley tables and cabinets, fish cleaning stations, cockpit tables, life preservers, life ring buoys, rigid sails for sailboats, artificial fishing bait and lures, fish ladders, collapsible boats, pontoon and decks, dagger boards and rudders for sailboats, houseboats, boat and ship hulls, lifeboats, sailboards, and the like), docks (e.g., floating, folding, portable, ramps, composite dock boards and timbers, canopies, covers, shelters, handrail, diving floats, floating storage docks for dry storage of personal watercraft, and the like), transportation (e.g., automobile components, truck cabs, auto cabs and interiors, recreational vehicle (RV) components, farming equipment, bumper reinforcement, side-impact reinforcement, structural enhancements, safety equipment, boxes, shipping containers, train components, subway components, boxcars, composite railroad ties, motorcycles, scooters, automotive panels, appearance accessories, police vehicle reinforcements, prefab impact units for protection from rear-end impacts and fires, front and rear bumpers, new production vehicles and back-fitting of existing fleets, reinforcing monocouqe body designs, reinforcing cages design and enhancing crumpled zones designs, making the unitized body more rigid, enabling vehicles to withstand higher impacts without losing structural integrity, tire doughnuts, with reinforcements according to the invention inside the tire, between the rim and contact tread surface (enabling a vehicle to come to a safe stop after tire failure or blowout, averting vehicle swerving, lane crossover, and rollover, and eliminating the need for a spare tire), sun visors, steering wheels, collapsible armrests, wheel covers, running boards, thermal and acoustical automotive insulation for firewall, roof, hoods, doors, floorboards, occupant interior cab impact absorbers, pillars, door panels, roof, dashboard, backside of front seats, seat frames, lined rear fender inside panels with invention materials, trunk lid and floor, backseat anchor panel, around gas tank to help stop frame point anchor penetration ruptures and fires and absorb the energy caused from rear end collisions to the vehicle, side impacts, side intrusions, truck and vehicle bumpers, automotive and commercial, industrial equipment, cab bodies, floor mats, railroad cars, car stops and chocks, armored cars and trucks, custom trailers, vans, vehicles, dashboards, aircraft, boats, ships, ship hole dick covers, auto and boat battery cases, cable gondola cars, moving vans, and the like), environmental/wastewater treatment (e.g., temporary and portable secondary spill containment systems for hazardous material accidents and decontamination material containment systems, floating tank tops, floating sewage lagoon covers, modular tanks, flumes, sluice gates, weir gates, stop logs, floating decanters, oil spill booms, spill basins and pans, cesspools, cisterns and covers, chutes, cooling vats, digester tanks, wind tunnels, field erected storage tanks, fish farming tanks, fishponds, floats for oil spill recovery systems, lagoon liners, landfill liners, oil spill recovery systems, solar collector panels, and the like), medical/healthcare (e.g., casts, fittings, casings for medical equipment, orthopedic devices, prosthetics, disposable splints, furniture, and the like), and so on.

[0107] Presently prefeπed applications of invention methods and articles produced thereby include preparation of building panels, structural reinforcements, soundproofing, insulation, wateφroofing, countertops, swimming pools, swimming pool covers, surfboards, hot tubs, hot tub covers, cooling towers, bathtubs, shower units, storage tanks, automotive components, personal watercraft components, and the like.

[0108] In accordance with additional embodiments of the present invention, the above- described articles can be further modified in a variety of ways, depending upon the end use. For example, a fireproof coating, a non-slip coating, a wood facing, an acrylic layer, a woven fabric facing, or the like, can be applied thereto (see, for example, Figures 7, 8 and 9). The article can be formed into a predetermined shape, or the article can be subjected to sufficient compression energy to reduce the thickness thereof. Desirable shapes can be cut and/or drilled into the article, the article can be ground up for total recycling, sanded, planed, shaped, drilled, compressed, routed, or the like.

[0109] In accordance with still another embodiment of the present invention, there are provided articles produced by any of the above-described methods. [0110] In accordance with a still further embodiment of the present invention, there are provided methods of making structural and other composite materials having enhanced properties, including a compression modulus of at least 20,000 psi, and a flexural modulus in the range of about 10,000 psi up to about 14,000 psi, the method comprising: combining porous material with a gas-generating polymerizable component to produce a pre-polymerization mix, subjecting the pre-polymerization mix to conditions suitable to allow the gas- generating polymerizable component to polymerize, thereby producing a cured article, and thereafter subjecting the cured article to compression pressure in the range of about 5-10, 10-40, 40-80, 80-100, 100-400, 400-800, 800-1600, 1600-3000, 3000-5000 or 5000-10,000 psi or higher for a time sufficient for the article to achieve the desired physical properties.

[0111] Those of skill in the art can readily determine conditions suitable to allow the gas-generating polymerizable component to polymerize. The conditions selected depend upon the type of polymerizable component employed. Polyurethanes, for example, once the various components of a polyurethane resin are combined, will typically initiate cure at relatively mild temperatures (i.e., in the range of about room temperature (about 25°C) up to about 70°C).

[0112] In accordance with yet another embodiment of the present invention, there are provided methods of making structural and other composite materials having a compression modulus of at least 20,000 psi, and a flexural modulus in the range of about 10,000 psi up to about 14,000 psi, the method comprising: subjecting a pre-polymerization mix comprising particulate material, at least a portion of which is porous, and a foamable polymerizable component to conditions suitable to allow the foamable polymerizable component to polymerize, thereby producing a cured article, and thereafter subjecting the cured article to compression pressure in the range of about 5-10, 10-40, 40-80, 80-100, 100-400, 400-800, 800-1600, 1600-3000, 3000-5000 or 5000-10,000 psi or higher for a time sufficient for the article to achieve the desired physical properties.

[0113] In accordance with still another embodiment of the present invention, there are provided methods of making structural and other composite materials having a compression modulus of at least 20,000 psi, and a flexural modulus in the range of about 10,000 psi up to about 14,000 psi, the method comprising: subjecting thecured article to compression pressure in the range of about 5-10, 10-40, 40-80, 80-100, 100-400, 400-800, 800-1600, 1600-3000, 3000-5000 or 5000-10,000 psi or higher for a time sufficient for the article to achieve the desired physical properties, wherein the cured article is prepared by subjecting a pre-polymerization mix comprising particulate material, at least a portion of which is porous, and a foamable polymerizable component tp conditions suitable to allow the foamable polymerizable component to polymerize, thereby producing the cured article.

[0114] The invention will now be described in greater detail with reference to the following non-limiting examples.

EXAMPLE 1

[0115] Several polyurethane formulations were prepared for blending with porous material in accordance with the present invention. For each formulation, all ingredients (of each component) were introduced into a closed system mixing pot, then blended under constant agitation for 1 to 2 hours, depending on the batch size. No heating was required to carry out the curing process.

Formulation 1 (BLACK/Fire Retardant)

Wt. % Range

Component A - Isocyanate:

Diphenylmethane Diisocyanate (Polymeric MDI) 88.5-94.5

Trichloropropylphosphate (Fire Retardant) 5.5-11.5 Component B - Polyol:

Polyether Polyol (Sucrose/Glycol Blend), Hydroxyl # 375 to 400 73.1-93.4

Polyol Polyether Diol, Hydroxyl # 265 8.4-12.5

Tertiary Amine (Catalyst) 1-2.50

Dimethylethanol Amine (DMEA) (Catalyst) 35-1.2

Water (Blowing Agent) 4-1.5

Silicone Surfactant 08-2.2

Black Pigment (in Polyether Polyol dispersion) 3-1.5

Formulation 2 (WHITE)

Wt. % Ranee

Component A - Isocyanate:

Modified Monomeric MDI 100.00

Component B - Polyol:

Polyether Polyol (Sucrose/Glycol Blend) PO Tip,

Hydroxyl # 375 to 400 82.5-91.5 Polyol Polyether Trial, Hydroxyl #250 5.5-13.5 Silicone Surfactant 0.08-1.5

Dimethylethanol Amine (DMEA) (Catalyst) 0.35-1.0 Water 0.20-1.3

Tertiary Amine (Catalyst) 0.25-1.2 Organo Surfactant (9 to 10 Mol) 0.35-0.7

Formulation 3 (NATURAL COLOR)

Wt. % Range

Component A - Isocyanate:

Diphenylmethane Diisocyanate (Polymeric MDI) 100.00

Component B - Polyol:

Sucrose Amine, Hydroxyl # 350 30.5-42.0

Sucrose Amine, Hydroxyl # 530 45.0-60.0

Amine Polyol, Hydroxyl # 600 2.8-9.0

Water 0.20-1.3

Silicone Surfactant 0.35-0.7 Formulation 4

Wt. % Range

Component A — Isocyanate:

Diphenylmethane Diisocyanate (Polymeric MDI) 100.00

Component B - Polyol:

Aromatic Polyol, Hydroxyl # 350 37.0-60.0

Polyether Polyol (Sucrose/Glycol Blend), Hydroxyl # 370 60.0-35.0

DEG (Diethylene Glycol) 1.5-4.0

Silicone Surfactant 0.08-1.5

Dimethylethanol Amine (DMEA) (Catalyst) 0.35-1.0

245(a) HCFC (Blowing Agent) 0.4-1.5

Water 0.4-1.5

Formulation 5 (One Component Formulation):

Wt. % Range

Polyol Polyether Triol, Hydroxyl #34 42.0-50.0

Diphenylmethane Diisocyanate (Polymeric MDI) 42.0-50.0

Plasticizer 10.0-20.0

Diamine Catalyst 0.01-0.2

EXAMPLE 2 Performance Properties

[0116] Several polymer systems useful in the practice of the present invention were prepared and the performance properties thereof evaluated, as summarized herein.

[0117] Formulation 1 described in Example 1 was used to produce a two component, rigid, water blown polyurethane structural material. This material provides superior performance for applications requiring a hard or tough surface, and is a cost-effective replacement for wood, thereby finding use in a variety of industries such as the furniture industry (e.g., for manufacture of furniture, cabinetry, and the like) and the picture frame business. Parts can be easily molded out of urethane materials that would otherwise require labor intensive carving or lathing. Typical physical properties of the cured material are presented in Table 1.

Table 1

TYPICAL PHYSICAL PROPERTIES

(For Components) TEST METHOD Component A Component B

Viscosity, cps ASTM D-2393 100 - 200 1000 - 1400 Brookfield LVF,

Spindle #2 @ 12 φm

Specific gravity ASTM D-1638 1.2 1.04

Weight/ gal. lb 10.0 8.68

Mix ratio by weight 52 48

Mix ratio by volume 50 50

(For Cured Material)

Density, lbs./ft.³ 10 (other densities also available)

[0118] The cream time of the formulation was about 30 to about 60 seconds, and can be modified by adjusting process conditions or through the use of additives. The rise time was about 2 to about 4 minutes, and can be modified by adjusting process conditions or through the use of additives. The shelf or storage life of Component A (isocyanate) and Component B (resin) can be maximized by maintaining the materials at a temperature of from about 65 °F to about 85°F. Protection from moisture and foreign material is afforded by keeping storage containers tightly closed.

[0119] Formulation 2 described in Example 1 (IPS 3001-10LV) is a two-component rigid, water blown polyurethane structural material. This material also provides superior performance for applications requiring a hard or tough surface and can be used as a cost- effective replacement for wood. Parts can be easily molded out of urethane-based materials that otherwise would require labor intensive carving or lathing. Typical physical properties thereof are summarized in Table 2. Table 2

TYPICAL PHYSICAL PROPERTIES

(For Components) TEST METHOD Component A Component B

Viscosity, cps ASTM D-2393 200 - 300 2400 - 2600

Brookfield LVF,

Spindle #2 @ 12 φm

Specific gravity ASTM D-1638 1.2 1.04

Weight/gal. (Lbs.) 10.0 8.68

Mix ratio by weight 52 48

(For Cured Material)

Density, Lbs./ft³. 35 - 40

Shore D hardness 10

[0120] The mixture can be hand mixed with a jiffy mixer (3" diameter) at 1,200 φm. The cream time of the formulation was about 180 seconds, and can be modified by adjusting process conditions or through the use of additives. The rise time was about 60 to about 70 minutes, and can be modified by adjusting process conditions or through the use of additives. The shelf or storage life of Component A (isocyanate) and Component B (resin) can be maximized by maintaining the materials at a temperature of from about 65 °F to about 85°F. Protection from moisture and foreign material is afforded by keeping storage containers tightly closed.

[0121] Formulation 3 described in Example 1 is a two component, rigid, water blown polyurethane structural material. This material also provides superior performance for applications requiring a hard or tough surface, and can also be used as a cost-effective replacement for wood. Parts can be easily molded out of urethane materials that would otherwise require labor intensive carving or lathing. Typical physical properties thereof are summarized in Table 3. Table 3

TYPICAL PHYSICAL PROPERTIES

(For Components) TEST METHOD Component A Component B

Viscosity, cps ASTM D-2393 100 - 200 1000 - 1400

Brookfield LVF,

Spindle #2 @ 12 φm

Specific gravity ASTM D-1638 1.2 1.04

Weight/ gal. lb 10.0 8.68

Mix ratio by weight 52 48

Mix ratio by volume 50 50

(for cured material)

Density, lbs./ft.³ 10 (other densities also available)

[0122] The cream time of the formulation was about 4 seconds, and can be modified by adjusting process conditions or through the use of additives. The rise time was about 14 minutes, and can be modified by adjusting process conditions or through the use of additives. The shelf or storage life of Component A (isocyanate) and Component B (resin) can be maximized by maintaining the materials at a temperature of from about 65°F to about 85°F. Protection from moisture and foreign material is afforded by keeping storage containers tightly closed. Fire retardant can be added to the formulation.

EXAMPLE 3 Making an Exemplary PetriFoam™ Material

[0123] As discussed above, the proportion of ingredients in the reaction mixture depends upon the desired physical characteristics of the end product and hence can not be specified in detail without identifying the final application of the material.

[0124] Invention process can be carried out in both batch and continuous mode. Batch mode can be carried out as follows. An amount of porous particulate material (e.g., expanded polystyrene beads, or polyethylene beads, or polypropylene beads, or mixtures of any two or more thereof) sufficient to overcharge the mold volume by ten to twenty percent is placed in a mixing vat. A resin (e.g., isocyanate reagent) is mixed into the beads with agitation until each individual bead has been substantially coated with the resin. The macroglycol (curing) reagent is then added to the resin/bead mixture and mixing is continued until the glycol has been evenly distributed throughout the mixture. The polymerization reaction commences with the first addition of the glycol. Preferably, the material is moved to the awaiting mold, which has been coated with a suitable release agent, in an expeditious fashion to assure sufficient working time for filling all parts of the mold uniformly. After the mold is filled, it is closed to assure compression of the mixture as the polyurethane mixture generates gas. The mold can be opened after about 10 up to about 30 minutes, depending upon nature of the mixture and the article or material prepared. The process can then be repeated to prepare additional articles or material. An article is generally fully cured to final physical characteristics after about twenty-four hours. The curing process can be accelerated by adding supplemental heat to the forms and/or the liquid components.

[0125] When using the one component formulation, the procedure is substantially the same up to the point where the resin has been mixed with the porous particulate material. At that point, a stoichiometric amount of water (to effect cure) is sprayed into the agitated mix, the final mixture is added to the mold as described previously, and the mold is closed with compression.

[0126] Preparation of invention materials in continuous mode can be carried out as follows. One or more storage tanks are provided containing porous particulate material, one or more tanks are provided containing the components of the gas-generating polymerizable component, and one or more tanks are provided containing any other components to be incoφorated into the finished article. Each of these components are metered and fed to a mixer extruder, either in a single mixing step or in stages (e.g., the isocyanate precursor of a polyurethane resin can be blended with suitable porous particulate material, then polyol subsequently added thereto). The mixed blend of components is then delivered to the site where formation of invention material is desired. EXAMPLE 4 Perfoπnance Properties of Invention Structural Materials

[0127] Structural materials prepared according to the invention were subjected to a variety of tests to determine the physical properties thereof, as summarized in Table 4. The material was prepared using expanded polystyrene beads having a diameter of 1.5 mm and an IPS urethane mixture (50 wt.% / 50 wt. %) with carbon black and fire retardant added. The beads were added to the mold at an excess (115% of the volume of the mold). These tests were conducted in accordance with American Society for Testing and Materials (ASTM) standards to determine the sfrength and performance of PetriFoam™ brand structural materials in terms of compression, flex, strain and shear. Additionally, PetriFoam™ brand structural materials were evaluated for performance characteristics relating to thermal conductivity, water resistance, peel strength, fatigue resistance, impact resistance and sound attenuation.

Table 4

* Estimate based upon other testing

[0128] The test results presented in Table 4, and the flexural modulus and compression test results presented in Figures 10 and 11 demonstrate that PetriFoam™ brand structural materials possess superior performance characteristics and properties. The primary tests conducted included ASTM 1621, "Compression Testing of Rigid Cellular Plastics"; and ASTM 790, "Standard Test Methods for Flexural Properties of Unreinforced Plastics and Electrical Insulation." These tests show that PetriFoam™ brand structural materials have many times the compressive strength and flexural strength of most polyurethane foams and styrofoams. Typical polyurethane foams have a compressive strength in the range of 40 psi to 100 psi, while typical styrofoams have a compressive strength in the range of 5 psi to 30 psi. As demonstrated by the data provided herein, PetriFoam™ brand structural materials can be made to exhibit conclusively superior materials that can deliver exponentially greater strength characteristics than conventional materials. EXAMPLE 5 Preparation of Structural Panels

[0129] Structural panels were prepared that were configured to be employed with standards, rails, channel, and other steel parts that provide the rigid framework to carry a fabric or other decoratively covered office panel. Conventional panels are constructed out of wood or particleboard and both surfaces are covered with MASONITE®, which is finished with padding and fabric or other decorative material, depending upon model and office decor. Assembling all the parts is labor intensive and very expensive. Also, shipping is expensive since the finished panels are quite heavy. Any water immersion of the panel, such as by normal floor mopping, causes the particleboard to swell and degrade. Panels prepared from materials according to the prefeπed embodiments exhibit superior water resistance, weigh less, and can be inserted into conventional frames using conventional fasteners.

[0130] A mold was fabricated with suitable inside dimensions using one inch Douglas Fir plywood as the base, two inch angle iron welded in the corners for the sides and four pieces of l'x2' steel plate hinged on the one long dimension of the angle iron to make the top side of the mold. The free sides of the top sections were configured to be bolted down against the opposing angle iron to keep the material mixture placed within constrained as it polymerized, expanded, and cured. The form was filled to the top with expanded polystyrene beads, and then a small quantity of additional beads was added. The beads were then transfeπed to a container and mixed with Part A of a urethane using a substantial mixer (a mixer similar to that used to mix mud for finishing interior walls) until the beads were thoroughly wetted with the resin. Part B of the urethane was then added, and the resulting mixture was mixed for two minutes. The formula used was 48% Part A with 52% Part B by weight of the mixture (coπesponding to 37 oz beads, 100 oz A and 115 oz B). Three panels were prepared. EXAMPLE 6 Use of Surfacing Materials

[0131] A mold was fabricated with inside dimensions of 12"xl2"x2." The top and bottom were one inch thick Douglas Fir plywood approximately 18" square, with sides comprising 2"χ2" stock prepared from cut down 2"x4" stock. Twelve 3/8" inch bolts with washers, top and bottom, through the bottom, sides, and top at the four corners and midpoints of the sides, were used to secure the top and constrain the expanding mixture. Spacers were cut from thin plywood 12" square, which were placed in the mold to vary the thickness of the final product: 2", 1", and V". SC Johnson® Paste Wax was employed as the form release agent.

[0132] Various surface materials were placed in the mold before adding the mixture. Superior adhesion of the covering material to the body of the material was observed for all coverings tested, including acrylic, wood veneer, KEVLAR™, and metal mesh. Half-inch material covered with impregnated KEVLAR™ was exceedingly strong and resistant to torsion. The materials also readily accept fiberglass-type gel coat to yield a beautiful surface with a minimum number of coats, especially on a fully skinned sample.

EXAMPLE 7 Effects of Bead Size and icoφoration of Surface Materials

[0133] Different bead sizes and varying amounts of resin were tested to affect different final weights of the sample board. The proportions of the A and B components were maintained relatively constant at their optimized proportions. Quantitative studies indicate that the smaller the bead size, the stronger the board. Also, increasing the proportion of the total resin regardless of bead size strengthens the board.

[0134] Cure times to opening the mold were relatively constant and at two-inch thickness or less, and the heat generated by the exotheπnic polymerization reaction hardly warmed the exterior of the wooden mold. EXAMPLE 8 Effects of Bead Size and Incoφoration of Surface Materials

[0135] A 8"x9"x9" mold was prepared. The mold included a one inch thick spacer on the inside of the top to allow for ease in placing 110 vol. % or more of the fill in the mold, the optimum amount depending upon bead size and subsequent compression of the mixture. The superior insulation characteristic of the material and the heat generated by the exothermic polymerization reaction caused the "cure until opening time" to exceed an hour or more. If opened prematurely, the material was hot, spongy, and not dimensionally stable. Therefore, the greater the thickness of the shortest dimension of the material required for an application, the preferably slower the production of the material.

[0136] To prepare a 9"x9"x7" block of material, 110% by volume of beads is added to the mold, along with 21 oz of urethane Part A and 20 oz of urethane Part B. The resulting block is fully skinned, which results in increased torsional and compression strength.

[0137] As those of skill in the art will appreciate based on the detailed descriptions and illustrative examples provided herein, there are a number of known alternatives of components described and/or illustrated herein which can be employed to practice aspects of the present invention, and these are regularly being supplemented by additional components. Numerous technical references describing such alternatives, and methods applicable to the preparation and/or testing of such alternatives are available. For example, references describing various plastic polymers, additives, composites and related systems and processes include the following: Plastics Encyclopedia, by Dominick Rosato, 1993; Physics Of Plastics: Processing, Properties and Materials Engineering, by Jim Batchelor et al. 1992; Reaction of Polymers, by Wilson Gum et al., 1992; Plastics for Engineers: Materials, Properties and Applications, by Hans Dominghaus, 1993; Reactive Polymer Blending, by Waπen E. Baker et al., 2001; Plastics Additives Handbook, by Hans Zweifel, 2001; Guide to Short Fiber Reinforced Plastics, by Roger F. Jones, 1998; Coloring of Plastics: Fundamentals, Colorants, Preparations, by Albrecht Muller, 2003; Plastics Flammability Handbook: Principles, Testing, Regulation and Approval, by Jurgen H. Troitzsch, 2004; Discovering Polyurethanes, Konrad Uhlig, 1999; Polyurethane Handbook: Chemistry, Raw Materials, Processing, Application, Properties, by Gunter Oertel, 1994; Introduction to Industrial Polymers, by Henri Ulrich, 1993; Performance of Plastics, by Witold Brostow, 2000; Rheology of Polymeric Systems, by Pieπe J. Caπeau et al., 1997; Plastics: How Structure Determines Properties, by Geza Gruenwald, 1993; Polymeric Material and Processing: Plastics, Elastomers and Composites, by Jean-Michel Charrier et al., 1990; Composite Materials Technology: Processes and Properties, by P.K. Mallick, 1990; Compression Molding, by Bruce Davis et al, 2003; Plastics Failure Guide: Cause and Prevention, by Meyer Ezrin, 1996; Failure of Plastics, by Witold Brostow, 1986; Wear in Plastics Processing: How to Understand, Protect, and Avoid, by Gunter Menning, 1995; Polymer Interfaces: Structure and Strength, by Richard P. Wool, 1995; Polymer Engineering Principles, by Richard C, Progelhof et al., 1993; Polymer Mixing, by Chris Rauendaal, 1998; Polymeric Compatibilizers: Uses and Benefits in Polymer Blends, by Sudhin Datta et al., 1996; Materials Science of Polymers for Engineers, by Georg Menges, 2003; Reaction Injection Molding, by Christopher W. Makosko, 1988; Successful Injection Molding, by John Beaumont et al, 2002; Injection Molding Handbook, by Paul Gramann, 2001; Mold Engineering, by Herbert Rees, 2002; Mold Making Handbook for the Plastics Engineer, by Gunter Menning, 1998; Total Quality Process Control for Injection Molding, by Joseph M. Gordon, Jr., 1992; Adhesion and Adhesives Technology, by Alphonsus V. Pocius, 2002; Performance Enhancement in Coatings, by Edward W. On, 1998; Plastics and Coatings, by Rose Ryntz, 2001; Advanced Protective Coatings for Manufacturing and Engineering, by Wit Grzesik, 2003; and the like.

[0138] As those of skill in the art will appreciate based on the detailed descriptions and illustrative examples provided herein, the references cited in the preceding section are considered particularly pertinent to the extent that they relate to components and/or processes as described or illustrated herein as well as to alternatives of such components or processes.

[0139] The above description discloses several methods and materials of the present invention. This invention is susceptible to modifications in the methods and materials, as well as alterations in the fabrication methods and equipment. Such modifications will be apparent to those skilled in the art from a consideration of this disclosure or practice of the invention disclosed herein. Consequently, it is not intended that this invention be limited to the specific embodiments disclosed herein, but that it cover all modifications and alternatives coming within the true scope and spirit of the invention as embodied in the attached claims. All patents, applications, and other references cited herein are hereby incoφorated by reference in their entirety.

Claims

That which is claimed is:

1. A structural material comprising: a porous material, wherein the porous material has a diameter in the range of about 0.05 mm up to about 60 mm, and a bead density in the range of about 0.1 kg/m up to about 1000 kg/m³, and a polymer, wherein the polymer is prepared from a polymerizable component capable of curing at a temperature below the melting point of the porous material, wherein the polymer comprises a substantially solid matrix which encapsulates the porous material, and wherein filaments or other projections comprising the polymer extend into the porous material.

2. The structural material of claim 1, wherein the polymerizable component comprises a first polymerizable component which is capable of polymerizing within pores of the porous material, and a second polymerizable component which is capable of binding to polymers of the first polymerizable component, either directly or through a linker, wherein the polymerizable components, upon curing, produce a substantially solid matrix which encapsulates and partially penetrates the porous material.

3. The structural material of claim 1 wherein the porous material is selected from the group consisting of polyolefins, gravel, glass beads, ceramics, vermiculite, perlite, lytag, pulverized fuel ash, unburned carbon, activated carbon, and mixtures of any two or more thereof.

4. The structural material of claim 1 wherein the porous material comprises polystyrene.

5. The structural material of claim 1 wherein the porous material comprises expanded polystyrene beads.

6. The structural material of claim 1 wherein the polymerizable component is selected from the group consisting of polyethylenes, polypropylenes, polyvinyl resins, acrylonitrile-butadiene-styrenes, polyurethanes, and mixtures of any two or more thereof.

7. The structural material of claim 1 wherein the polymerizable component is a polyurethane.

8. The structural material of claim 7 wherein the polyurethane is prepared from at least one aromatic diisocyanate selected from the group consisting of rø-phenylene diisocyanate, j-phenylene diisocyanate, 4,4 '-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 3,3'-dimethyl-4,4'-biphenylene diisocyanate, durene diisocyanate, 4,4'-diphenylisopropylidene diisocyanate, 4,4'-diphenyl sulfone diisocyanate, 4,4'-diphenyl ether diisocyanate, biphenylene diisocyanate, and 1,5-naphthalene diisocyanate, and at least one polyol selected from the group consisting of ethylene glycol, 1,2-propanediol, 1,4- butanediol, 1,4-cyclohexanediol, glycerol, 1,2,4-butanetriol, trimethylol propane, poly( vinyl alcohol), and partially hydrolyzed cellulose acetate.

9. The structural material of claim 1 further comprising at least one additive selected from the group consisting of flow enhancers, plasticizers, cure retardants, cure accelerators, strength enhancers, UV protectors, dyes, pigments, fillers, and fire retardants.

10. The structural material of claim 1 wherein the diameter of the porous material falls in the range of about 0.4 mm up to about 5 mm.

11. The structural material of claim 1 wherein the porous material comprises in the range of about 80 up to about 99 volume percent of the structural material.

12. The structural material of claim 1 wherein the porous material comprises in the range of about 15 wt. % up to about 40 wt. % of the structural material.

13. The structural material of claim 1 wherein the compression modulus of the structural material is at least about 8000 psi.

14. The structural material of claim 1 wherein the compression modulus of the structural material falls in the range of about 8000 psi up to about 10,000 psi.

15. The structural material of claim 1 wherein the flexural modulus of the structural material is at least about 10,000 psi.

16. The structural material of claim 1 wherein the flexural modulus of the structural material falls in the range of about 10,000 psi up to about 14,000 psi.

17. The structural material of claim 1 wherein the material has an R-value per inch thickness of at least 3.

18. The structural material of claim 1 further comprising one or more reinforcement structures contained within.

19. The structural material of claim 18 wherein the reinforcement material is selected from the group consisting of natural fibers, synthetic fibers, and combinations of any two or more thereof.

20. The structural material of claim 1 further comprising at least one facing material applied thereto.

21. The structural material of claim 20 wherein the facing material is selected from the group consisting of metal, polymer, cloth, glass, ceramic, natural fiber, synthetic fiber, and combinations of any two or more thereof.

22. The structural material of claim 20 wherein the facing material is selected from the group consisting of a solid surface, a porous surface, a surface that can be chemically etched, a chemically etched surface, a surface that can be physically abraded, a physically abraded surface, and combinations of any two or more thereof.

23. The structural material of claim 1 wherein the structural material emits substantially no off-gases.

24. The structural material of claim 1 wherein the matrix is flexible.

25. The structural material of claim 1 wherein the matrix is rigid

26. The structural material of claim 1 wherein the structural material is essentially water proof, UV stable, and substantially resistant to degradation caused by exposure to insects, fungi, moisture, and atmospheric conditions.

27. A structural material comprising: a porous material, wherein the porous material has a diameter in the range of about 0.05 mm up to about 60 mm, and a bead density in the range of about 0.1 kg/m³ up to about 1000 kg/m³, and a flexible polymeric matrix, wherein the polymeric matrix is prepared from a gas-generating polymerizable component capable of curing at a temperature below the melting point of the porous material, wherein the polymeric matrix comprises a resilient, substantially impervious matrix providing a dimensionally stable structure which encapsulates the porous material, and wherein filaments or other projections comprising the polymer extend into the porous material.

28. A material comprising: a porous material, and a polymer, wherein the polymer comprises a matrix which substantially encapsulates the porous material, wherein the matrix is substantially solid, and wherein filaments or other projections comprising the polymer extend into the porous material.

29. An article having a defined shape, excellent compression strength and a high flexural modulus, the article comprising a polymer matrix containing a porous material substantially uniformly distributed therethrough, wherein filaments or other projections comprising the polymer extend into the porous material.

30. The article of claim 29 wherein the compression modulus is at least about 8000 psi.

31. The article of claim 29 wherein the compression modulus of the structural material falls in the range of about 8000 psi up to about 10,000 psi.

32. The article of claim 29 wherein the flexural modulus is at least about 10,000 psi.

33. The article of claim 29 wherein the matrix is rigid.

34. The article of claim 33 wherein the article is selected from the group consisting of a building panel, a structural reinforcement, soundproofing, insulation, wateφroofing, a countertop, a swimming pool, a swimming pool cover, a surfboard, a hot tub, a hot tub cover, a cooling tower, a bathtub, a shower unit, a storage tank, an automotive component, and a personal watercraft component.

35. The article of claim 29 wherein the matrix is flexible.

36. The article of claim 35 wherein the article is selected from the group consisting of soundproofing, insulation, wateφroofing, an automotive component, furniture padding, and impact absoφtion barriers.

37. A method of making a structural material, the method comprising: combining porous material and a polymerizable component, and subjecting the resulting combination, in a mold, to conditions suitable to cure the polymerizable component, whereby any gases generated during curing are substantially absorbed by the porous material, and wherein a portion of the polymerizable component is forced into the porous material, thereby producing the structural material, wherein the structural material comprises the porous material encapsulated in a substantially solid polymer matrix, and wherein filaments or other projections comprising the polymer extend at least partially into the porous material.

38. The method of claim 37 wherein the resulting combination is further contacted with a second polymerizable component, wherein the first polymerizable component polymerizes substantially within the porous material and the second polymerizable component polymerizes substantially outside of the porous material, and wherein the first and second polymerizable components become joined to each other either directly or through a linker.

39. The method of claim 37 wherein curing is conducted under conditions whereby substantially no foam is generated in the solid polymer matrix

40. The method of claim 37 wherein combining comprises substantially completely coating a surface of the porous material with a precursor of the polymerizable component.

41. The method of claim 37 wherein conditions suitable to allow the polymerizable component to polymerize comprise adding a polymerizing agent to the combination of porous material and precursor of the polymerizable component.

42. The method of claim 41 wherein the combination comprising the porous material, the precursor of the polymerizable component, and the polymerizing agent is vibrated after introduction of polymerizing agent thereto.

43. The method of claim 37 wherein the polymerizable component has a viscosity in the range of about 200 up to about 50,000 centipoise.

44. The method of claim 37 wherein the polymerizable component is stable to temperatures of at least about 50°C.

45. The method of claim 37 wherein substantially no off-gases are generated upon cure.

46. The method of claim 37, further comprising applying a coating to the structural material, wherein the coating is selected from the group consisting of a fireproof coating, a fire retardant coating, a non-slip coating, a wood facing, an acrylic facing, and a woven fabric facing.

47. The method of claim 37, further comprising forming the structural material into a predetermined shape.

48. The method of claim 37, further comprising subjecting the structural material to compression energy sufficient to reduce a thickness of the structural material.

49. The method of claim 37, further comprising cutting the structural material into a defined shape.

50. The method of claim 37, further comprising drilling a defined shape into the structural material.

51. The method of claim 37 wherein at least a portion of the porous material is recycled (ground) structural material.

52. The method of claim 37, further comprising grinding and recycling the structural material.

53. The method of claim 37, further comprising subjecting the structural material to at least one of chemical etching and physical etching.

54. The method of claim 37, further comprising subjecting the structural material to a compression pressure for a time sufficient to increase the compression modulus of the structural material to at least 20,000 psi, and to increase the flexural modulus of the structural material to at least about 10,000 psi up to about 14,000 psi.

55. A method of making a structural material, the method comprising subj ecting the combination of a porous material and a gas-generating polymerizable component, in a closed mold, to conditions suitable to cure the gas-generating polymerizable component, whereby gases generated during curing are substantially absorbed by the porous material, and wherein a portion of the polymerizable component is forced into the porous material, thereby producing the structural material, wherein the structural material comprises the porous material encapsulated in a solid polymer matrix, and wherein filaments or other projections comprising the polymer extend at least partially into the porous material.

56. A product produced by the method of any one of claims 37 to 55.

57. A formulation comprising: a porous material, a gas-generating or other polymerizable component, and at least one additive selected from the group consisting of flow enhancers, plasticizers, cure retardants, cure accelerators, strength enhancers, UV protectors, dyes, pigments and fillers, wherein the porous material has a diameter in the range of about 0.05 mm up to about 60 mm, and a bead density in the range of about 0.1 kg/m³ up to about 1000 kg/m³, and wherein the gas- generating or other polymerizable component is capable of curing at a temperature below the melting point of the porous material, wherein the gas-generating or other polymerizable component, upon curing, produces a substantially impervious solid matrix which encapsulates the porous material, and wherein filaments or other projections comprising the polymer extend at least partially into the porous material.

58. A formulation comprising: a porous material, and a gas-generating or other polymerizable component, wherein the porous material is not expanded polystyrene, and has a diameter in the range of about 0.05 mm up to about 60 mm, and a bead density in the range of about 0.1 kg/m up to about 1000 kg/m , and wherein the gas-generating or other polymerizable component is capable of curing at a temperature below the melting point of the porous material, wherein the gas-generating or other polymerizable component, upon curing, produces a substantially impervious solid matrix which encapsulates the porous material, and wherein filaments or other projections comprising the polymer extend at least partially into the porous material.

59. A formulation comprising: a porous material, and a gas-generating or other polymerizable component, wherein the porous material has a diameter in the range of about 0.05 mm up to about 60 mm, and a bead density in the range of about 0.1 kg/m³ up to about 1000 kg/m³, and wherein the gas-generating or other polymerizable component is not a polyurethane, and is capable of curing at a temperature below the melting point of the porous material, wherein the gas-generating or other polymerizable component, upon curing, produces a substantially impervious solid matrix which encapsulates the porous material, and wherein filaments or other projections comprising the polymer extend at least partially into the porous material.

60. A method of modifying an article comprising a flexible or rigid polymeric matrix containing porous material, substantially uniformly distributed therethrough, wherein filaments or other projections comprising the polymer extend at least partially into the porous material, the method comprising applying a fireproof coating thereon, a non-slip coating, a wood facing thereon, an acrylic facing thereon, or a woven fabric facing thereon.

61. A method of modifying an article comprising a flexible or rigid polymeric matrix containing porous material, substantially uniformly distributed therethrough, wherein filaments or other projections comprising the polymer extend at least partially into the porous material, the method comprising forming the article into a predetermined shape.

62. A method of modifying an article comprising a rigid polymeric matrix containing porous material substantially uniformly distributed therethrough, wherein filaments or other projections comprising the polymer extend at least partially into the porous material, the method comprising subjecting the article to sufficient compression energy to reduce the thickness thereof.

63. A method of modifying an article comprising a flexible or rigid polymeric matrix containing porous material substantially uniformly distributed therethrough, wherein filaments or other projections comprising the polymer extend at least partially into the porous material, the method comprising cutting and/or drilling desirable shapes into the article.