MXPA05009617A - Structural and other composite materials and methods for making same. - Google Patents
Structural and other composite materials and methods for making same.Info
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- MXPA05009617A MXPA05009617A MXPA05009617A MXPA05009617A MXPA05009617A MX PA05009617 A MXPA05009617 A MX PA05009617A MX PA05009617 A MXPA05009617 A MX PA05009617A MX PA05009617 A MXPA05009617 A MX PA05009617A MX PA05009617 A MXPA05009617 A MX PA05009617A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
- B29C44/34—Auxiliary operations
- B29C44/56—After-treatment of articles, e.g. for altering the shape
- B29C44/5618—Impregnating foam articles
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C67/00—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00
- B29C67/24—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00 characterised by the choice of material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
- B29C70/58—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising fillers only, e.g. particles, powder, beads, flakes, spheres
- B29C70/66—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising fillers only, e.g. particles, powder, beads, flakes, spheres the filler comprising hollow constituents, e.g. syntactic foam
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/02—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by the reacting monomers or modifying agents during the preparation or modification of macromolecules
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/35—Composite foams, i.e. continuous macromolecular foams containing discontinuous cellular particles or fragments
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2425/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
- C08J2425/02—Homopolymers or copolymers of hydrocarbons
- C08J2425/04—Homopolymers or copolymers of styrene
- C08J2425/06—Polystyrene
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Composite Materials (AREA)
- Mechanical Engineering (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Laminated Bodies (AREA)
- Paper (AREA)
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
MATE RIALES COM PU THESE AND STRUCTURES AND M ETHODS FOR S U FAB RICACIO N
FIELD OF THE INVENTION The present invention relates to composite and structural materials and to methods for making such materials. In a particular aspect, the present invention relates to construction materials. In another aspect, the present invention relates to composite and structural materials that have a variety of shapes, sizes and physical properties. In still another aspect, the present invention relates to various applications of composite and structural materials of the invention. In still another aspect, the present invention relates to light weight, high strength articles, prepared from the composite and structural materials of the invention.
ANTEC EDENTS OF THE INVENTION Polymeric materials have been used for a long time in the art, for the manufacture of structural elements. In one application, a structural element can be formed simply as a solid sheet of the polymeric material, for example, by extrusion. However, the structural elements prepared in this way tend to be quite 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 the polymeric material is required to form such structures. An alternative method employed in the art for the preparation of structural elements is the use of formed polymeric materials such as, for example, polyethylene, polypylene, polystyrene or polyurethane. Although the resulting structures are much less dense than an equivalent solid structural element, and have improved insulating properties, these are generally rather expensive structures to produce. In addition, specifically in the case of polystyrene, the resin structures have relatively poor structural integrity. To form a structural element from the 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 foam production reaction takes place inside the mold, and the volume of the polymer material within the mold increases. Once the volume of the foamed material becomes equal to the volume of the mold, the foam is pressed against the mold, increasing the strength of the resulting element. To obtain a structural element of high strength, it is necessary to allow a substantial amount of compression to occur, which requires the use of a large amount of polyurethane, thereby increasing the expense of the structural element. In addition, since the foam is compressed to provide increased strength, the density of the foam is increased so that the thermal insulation properties of the resulting article are quite poor. In addition, the method described above must be carried out quickly to ensure that the reaction components are all introduced into the mold before the foam production reaction begins. 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 pearls, which can then be combined to form a structural element. Although the resulting structural element is relatively light, it is not particularly strong. In addition, the final foam product is of an open cellular structure, and thus permeable to liquids and gases. Also, since the volume of the structural element is reduced when the pearls are fused, this method also requires the use of large quantities of starting materials. Yet another method for the preparation of building materials employing expanded polystyrene beads is described in British Patent Application No. GB 2,298,424, which discloses a thermally insulating lightweight filler disposed within a rigid foamed plastic matrix. The main thermally insulating filler described in the application '424, is referred to as "expanded polystyrene" without details given as the chemical and / or physical properties of the material used in the preparation of the claimed product. Similarly, the single rigid foamed plastic matrix described in the '424 application is a rigid, specific, simple polyurethane, defined only in terms of one of several components used for the preparation thereof, ie the polyurethane used in The application '424 is prepared from the "resin" (described only as "a mixture of pot I") and isocyanate (described only as a mixture of diphenylmethane diisocyanate and "polymeric components"). The current composition of the polyurethane employed in the '424 application is obtainable only by reference to a material allegedly commercially available by reference to its trade name only. Additional methods for preparing structural materials are described in U.S. Patent No. 4,714,715 (directed to a method for forming a flame retardant insulation material from rigid plastic foam slag); US Patent No. 5,055,339 (directed to a shaped element comprising a panel of a soft foamed material having a cellular network comprised of networks defining open cells and granules of a soft foamed material having a cellular network comprised of networks defining cells and at least one additional filler material); U.S. Patent No. 5,791,085 (directed to a method for preparing a porous solid material for the propagation of plants consisting of a single step to react a polyisocyanate and a polyethylene oxide derivative in the presence of granules of a porous expanded mineral and in the presence of 0.5% by weight of water or less to produce a porous, solid, open cell foamed hydrophilic retentive polyurethane hydrogel material matrix that is substantially rigid in the dry condition and which is capable of absorb water and become flexible 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 for producing a part of three-dimensional shaped plastic foam); U.S. Patent No. 6,045,345 (directed to an installation for producing a part of three-dimensional formed plastic foam from plastic foam granules bonded together to produce foam from a primary liquid material); U.S. Patent No. 6,265,457 (directed to an isocyanate-based polymeric foam); US Patent No. 6,583,189 (directed to an extruded article comprising a closed cellular foam of a first thermoplastic, containing between about 1% and 40% diatomaceous earth powder by weight, the extruded article is formed with diatomaceous earth containing no more than about 2% by weight of moisture); and US Patent No. 6,605,650 (directed to a process for generating a polyurethane foam by forming a mixture comprising an isocyanate and polyol reagents, a catalyst and a blowing agent, the mixture of which reacts exothermically to produce a rigid polyurethane foam). There is, however, a need in the art for structural materials, which may be strong and light in weight, which are also preferably relatively resistant to moisture, and yet do not require large amounts of starting materials for the preparation of the materials. same. The present invention addresses this and related claims in the field, as detailed by the specification and claims that follow.
BRIEF SUMMARY OF THE INVENTION In accordance with the present invention, composite and structural materials have been developed, which have superior performance properties, including high compressive strength, high tensile strength, high flexural strength, high shear strength, and / or a high weight resistance ratio. The materials of the invention can also exhibit a high, flexural and shear stress modulus. In addition, the materials of the invention can be substantially resistant to moisture. The materials of the invention may have agribused benefits for ease of manufacture, and may also be relatively inexpensive to manufacture. In addition, the materials of the invention can be prepared at relatively low temperatures, which often require little heating or cooling during preparation. The superior performance properties of the materials of the invention present such materials suitable for a variety of end uses. For example, numerous adhesives may be applied to the materials of the invention without melting, dissolving or de-radaring the basic structure of the materials of the invention. This facilitates the materials of the invention binding to virtually any surface or substrate, including the joining of two or more pieces of the materials of the invention to another as an alternative way to generate a desired profile. In addition, the bond between the materials of the invention and a variety of substrates (including the joining between two or more pieces of the materials of the invention) is exceptionally strong, providing the resulting cohesive article suitable for use in a variety of applications. plaintiffs Certainly, the adhesion between the materials of the invention and a substrate can be further improved by eroding the surface of the substrate (eg, mechanically or by chemical attack) prior to contact with the materials of the invention. Similarly, the materials of the invention can be modified by the application of liquid polyester resin coatings, liquid styrene or other liquid polymers thereto. Such coatings may be sprayed or otherwise applied directly to the materials of the invention without dissolving or otherwise compromising the core structure provided by the material of the invention. The materials of the invention can be manufactured in a wide variety of sizes, shapes, densities, in multiple layers and the like.
BRIEF DESCRIPTION OF THE FIGURES Figure 1 is a scanning electron microscope image of a cross section of an expanded polyester bead. Figure 2 is a scanning electron microscope image of an expanded polystyrene bead. Figure 3 is a schematic depiction of a cross section of a polymer matrix containing porous beads, illustrating polymeric filaments or other projections extending within the porous bead. Figure 4 is a cross-sectional view of an exemplary article of the invention, wherein large beads of a porous material (10) are incorporated within a polymer matrix (1). The composite and structural materials of the invention are also sometimes referred to herein as PetriFoam ™ brand and structural materials. Figure 5 is a cross-sectional view of another article of the exemplary invention, wherein small beads of a porous material (11) are incorporated into a polymeric matrix (1). Figure 6 is a cross-sectional view of yet another exemplary invention article, wherein a mixture of large and small beads of porous material (10 and 11) are incorporated into a polymeric matrix (1). Figure 7 is a cross-sectional view of an article of the invention further comprising a structural material according to the invention (20) and a material (30) for coatings adhered thereto. Figure 8 is a cross-sectional view of an article of the invention comprising a structural material according to the invention (20) and a material (30), which also comprises a coating (31) thereof. Figure 9 is a cross-sectional view of an article of the invention in the form of an interleaved structure, comprising a material or structural materials (20) marked PetriFoam u nes a, or that are incorporated into the reinforcement material (32) . FIG. 10 presents a graph of the results of the flexural module tests with representative materials of the invention. Figure 1 1 presents a graph of results of compression tests with representative materials of the invention.
DETAILED DESCRIPTION OF THE INVENTION In accordance with one aspect of the present invention, composite and structural materials are provided comprising: a porous material, wherein the porous material has a diameter in the range of about 0.05 mm to about 60 mm, and a bead density in the range of about 0.1 kg / m3 to about 1000 kg / m3, usually in the range of about 1 kg / m3 to about 1000 kg / m3, and a polymer, wherein the polymer is repaired. from a polymerizable component capable of curing at a temperature below the melting point of the porous material, where the polymer encapsulates the porous material, and wherein the filaments or other projections comprising the polymer extend into the porous material . As is readily recognized by those of skill in the art, the polymeric material can be extended within the porous material to varying degrees, depending on such factors as the viscosity of the polymer system, the pore size in the porous material, the pressure at the which the system is subjected to, and the like. In certain embodiments of the invention, the polymer is prepared from a polymerizable component that generates gas such as polyurethane, and the polymer comprises a substantially solid matrix. As used herein, "substantially solid" refers to a material with sufficient structural integrity to retain a given shape absent from any extraordinary external forces. Without wishing to be bound by theory, it is believed that the preparation of the polymerizable component that generates gas in close proximity to the porous materials can produce a polymer matrix that is significantly stronger than the matrix prepared in the absence of such porous materials. because the porous materials can serve as a nearby reservoir or collector that contains some portion of the generated gas which could otherwise form macroscopic and / or microscopic bursts within the matrix, so its structural integrity. As contemplated in the present, pressure and / or other means can be used to further improve these processes. Such methods for generating composite and structural materials may have the added advantage to reduce the amounts of the volatile organic compounds that are released during the preparation. By virtue of such technical characteristics, the composite and structural materials according to the present invention can be generated where the matrix is 5-20, 20-40, 40-80, 80-120 percent or even more solid ( that is, dense when compared to the 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 by being relatively light in weight, but strong. The partial physical inputs and / or bonding of the matrix to the porous material can be used to improve the structural integrity of the composite by providing a means of "blocking" the matrix mechanically and / or chemically to the porous material. As described below, the materials of the present invention can be easily prepared for exh ibing 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 may be employed. easily together with the p ractics of the present invention. Substantially solid materials according to the present invention may vary from substantially rigid (i.e., substantially not deformed to substantially flexible (ie, deformable, but generally with sufficient memory to return to the original shape once the distorting disturbance is removed). The composite and structural 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 more detail herein, the continuous phase can be based on any of a variety of homopolymer systems, as well as co-and polyetheric systems, including block copolymers, graft copolymers and the like. Similarly, the discontinuous material can be selected from a variety of porous materials. According to another aspect of the present invention, composite and structural materials comprising: a porous material are provided, wherein the porous material has a diameter in the range of approximately 0.05 mm to approximately 60 mm, and a density of pearl in the range of about 0.1 kg / m3 to about 1000 kg / m3, usually in the range of about 1 kg / m3 to about 100 kg / m3, and a polymer, wherein the polymer is prepared from a first polymerizable component that is capable of polymerizing within the pores of the porous material, and from a second polymerizable component that is capable of binding polymers of the first polymerizable component, either directly or through a linker, wherein the polymerizable components, in curing, they produce a substantially solid matrix that encapsulates and partially penetrates the porous material. According to another aspect of the present invention, articles having a defined shape, strength and excellent compression modulus, and an elevated flexional module are provided, the articles comprise a polymer matrix containing a porous material substantially uniformly distributed therethrough, where the filaments or other projections comprising the polymer extend at least partially within the porous material. The degree of penetration of the porous material by the polymer can be easily modified as desired for a particular application. For example, the relative strength can generally be improved by increasing the degree of penetration, and can be increased however, if desired, by causing filaments of the penetrating polymer to join 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 combination of porous material and polymer that favors interaction and penetration (for example, by selecting combinations that have particularly compatible surface energies). , having or applying additional pressure during the polymerization to drive the penetration, increasing the viscosity of the polymer, raising the temperature or by other kinetic or thermodynamic means that facilitate the interaction and the potential for penetration. It is also possible to include an agent which promotes or facilitates the interaction (such as a surfactant) which may be included during the polymerization or may for example be used to pre-treat the porous material to make it particularly receptive for penetration by the polymer. The use of a graft copolymer system as described herein may be employed to achieve desired levels of penetration, while at the same time allowing the outer portion of the polymer matrix to be independently selected for other advantageous characteristics such as the resistance or other desirable characteristics. By applying such techniques to the compounds of the present invention, filaments or other polymer projections can easily be caused to spread to variable gums within a given porous material. The relatively high strength compositions of the present invention can thus be prepared where the polymer matrix can be extended 1 -10, 1 0-20, 20-30, 30-40, 40-50, 50-60, 60-70, 70-80, 80-90 or 90-1 00 percent within the diameter (or linear dimension) of the material porous, as desired. Structural materials and other compounds 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. In certain embodiments, the articles of the present invention may have compressive strengths in excess of 20 pounds per square inch (psi), preferably exceeding 40, 100, 150, 210, 300 or 400 psi; the compression module exceeding 2000 psi, preferably exceeding 4000, 8000, 10,000, 20,000, 40,000 or 100,000 psi; the flexural strength exceeding 50 psi, preferably exceeding 100, 200, 350-375 or 500 psi; the flexural modulus exceeding 2000 psi, preferably exceeding 4000, 8000, 10,000, 20,000, 40,000 or 100,000 psi; the shear strength exceeding 20 psi, preferably exceeding 40, 100, 150, 210, 300 or 400 psi; and the 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 the voltage module exceeding 1000 psi, preferably exceeding 2000, 3000, 4000, 5000, 6000, 8000 or 10,000 psi. As used herein, "high compressive strength", as determined for example, by ASTM 1621, refers to the ability of the materials of the invention to withstand exposure to compressive forces without undergoing significant structural breakdown. basic of it. The materials of the invention deploy compression strengths substantially in excess of what might be expected when compared to the performance properties of the individual components from which the materials of the invention are prepared. Descriptions of ASTM standards and proof can be found in ASTM International publications as well as their web sites (see for example, www.astm.org). As used herein, "high tensile strength" as determined for example by ASTM 1623, refers to the ability of the materials of the invention to withstand longitudinal tension, i.e., can withstand maximum force of the material without separating. The materials of the invention deploy tensile strengths substantially in excess of what would be expected when compared to the performance properties of the individual components from which the materials of the invention are prepared. As used herein, the "high shear strength" as determined, for example by ASTM 273, refers to the strength of the materials of the invention for deformation when subjected to a defined stress. The materials of the invention release shear strengths substantially in excess of what would be expected when compared to the performance properties of the individual components from which the materials of the invention are repaired. As used herein, "high flexural strength" as determined for example by ASTM 790, refers to the strength of the materials of the invention for deformation when subjected to a bending stress. The materials of the invention deploy flexural strengths substantially in excess of what would be expected when compared to the performance properties of the individual components from which the materials of the invention are prepared. As used herein, the "high weight strength ratio" refers to the surprisingly high strength of the materials of the invention, despite their relatively low weight. For example, an article of the invention weighing a fraction of the weight of the materials of the prior art is capable of providing the same or better performance properties than materials of substantially greater weight, such as, for example, wood. or concrete. The materials of the invention can also be prepared having weight strength ratios in excess of what would be expected when compared to the ratios of materials prepared from the individual materials from which the materials of the invention are prepared, such as as for example, from materials made of a polymer such as polyurethane. The materials of the invention can also be characterized in terms of their superior impact strength, hardness or surface stiffness (such as by the Rockwell hardness test of a material's ability to resist surface indentation) as well as other properties, including the resulting product density, thermal conductivity and thermal expansion of the resulting product, as well as such as the thermal conductivity and thermal expansion of each component material, the coefficient of expansion, the absorption coefficient (ie conductivity), the resistance and the dielectric volume and the resistance to the arc, the flammability (as per the index of oxygen or UL flammability indexes), shrinkage, permeability and absorption of water and aqueous vapor, specific gravity and other physical-chemical, mechanical, thermal or electrical properties. The materials of the invention can easily be made resistant to moisture, since the particulate material can be substantially encapsulated in a polymeric matrix and the polymer can be selected to be relatively resistant to incorporation and moisture absorption (for example, by selecting a relatively hydrophobic polymer). or 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. When using ASTM D570, for example, the materials of the invention can be easily prepared by having a range of water absorptions different in percent by weight after 24 hours, usually 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 the materials of the invention having relatively high rates of aqueous absorption for applications in which it may be desirable (such as applications where it is desired for a material to absorb and maintain a large volume of liquid and it is potentially released over time). In the latter aspect, agents that promote aqueous absorption can be employed (such as sodium polyacrylates and the like) as well as, for example, agents that control or effect the release of fluids over time. According to yet another aspect of the present invention, methods for making composite and structural materials are provided, the method comprising: combining the porous material and a polymerizable component, and subjecting the resulting combination, in a mold or other container ( can be opened or closed), under suitable conditions for curing the polymerizable component in the optional presence of the blowing agent (s), whereby the blowing agents and any gases generated during the curing and / or compression of the materials The porous materials are substantially absorbed by the porous material to produce a composite structural material. When increased strength is desired, a portion of the polymerizable component can be forced into the porous material, whereby the structural material comprising the porous material encapsulated in a solid polymer matrix is produced, and wherein the filaments or other projections comprising the polymer extend within the porous material. According to yet 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 improvers, plasticizers, curing retardants, accelerators, curing, strength enhancers, UV protectants, dyes, pigments and fillers, wherein the porous material has a diameter in the range of about 0.05 mm 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 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, until curing, produces a substantially solid matrix, which encapsulates the porous material, and wherein the filaments and other projections that comprise the polymer extend into the porous material. Also contemplated are the composite and structural materials prepared from the formulations described above. According to an additional aspect of the present invention, forms are provided which comprise: a porous material, and a polymerizable component, wherein the porous material is not expanded polystyrene, and has a diameter in the range of approximately 0.05. mm to about 60 mm, and a bead density in the range of about 0.1 kg / m3 to about 1000 kg / m3, preferably in the range of about 1 kg / m3 to about 1000 kg / m3, and wherein the The polymer component is capable of curing at a temperature below the melting point of the porous material, wherein the polymerizable component, up to the cure, produces a substantially solid matrix that encapsulates the porous material, and where the filaments or other projections comprising the polymer extend into the porous material. Also contemplated are composite and structural materials prepared from the formulations described above.
According to a still further aspect of the present invention, forms are provided which comprise: a porous material, and a polymerizable component, wherein the porous material has a diameter in the range of about 0.05 mm to about 60 mm. , and a bead density in the range of about 0.1 kg / m3 to about 1000 kg / m3, preferably in the range of about 1 kg / m3 to about 100 kg / m3, and wherein the polymerizable component is not a It is able to be cured at a temperature below the melting point of the porous material, where the polymerizable component, until curing, produces a substantially solid matrix, which encapsulates the porous material, and where the filaments or other projections comprising the polymer extend within the porous material. Also contemplated are the composite and structural materials prepared from the formulations described above. According to another still further aspect of the present invention, formulations are provided which comprise: a porous material, a first polymerizable component which is capable of polymerizing within the pores of the porous material, a second polymerizing component which It is capable of going 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 to about 60 mm, and a bead density in the range of about 0.1 kg / m3 to about 1000 kg / m3, preferably in the range of about 1 kg / m3 to about 100 kg / m3, and where the polymerizable components until curing, have a substantially solid matrix which is encapsulated and at least partially penetrates the porous material. Also contemplated are the composite and structural materials prepared from the formulations described above. Optionally, the formulations of the invention may contain one or more additional additives selected from the group consisting of flame retardants, light stabilizers, antioxidants, antimicrobial agents, plasticizers, metal soap stabilizers, UV absorbers, pigments, dyes, antistatic agents, blowing agents, anti-foaming agents, foaming agents, lubricity agents, reinforcing agents, thermal stabilizers, particulate fillers, process aids, flow improvers, fiber fillings, slip additives , curing agents and co-agents, curing retardants, curing accelerators, strength improvers, impact modifiers, catalysts and the like. The materials may be waterproof or waterproof, UV-stable, resistant to insects, microbes, fungi, atmospheric conditions, moisture, dry rot, and the like. The materials may also generally not emit significant amounts of volatile organic compounds (VOCs) such as regulated VOCs. The porous materials contemplated for use in the practice of the present invention may be rigid, semi-rigid, flexible or compressible, and may have any of a variety of shapes, for example, beads, granules, rods, cords, irregularly shaped particles , and similar. As is readily recognized by those skilled in the art, porous materials formed in other shapes can also be employed, for example, sheets, lattices, tubes, open cellular three-dimensional structures, woven fabrics, non-woven fabrics, felts, sponges, and the like. . See also U.S. Patent No. 4,458,963 for additional forms contemplated for use herein. Applications where the materials of the invention are employed play a role in the selection of a suitable porous or shaped particulate material. For example, if the material blocks are to be formed, and the final cut to classify, then a particulate porous material may be desirable. In contrast, if the material is to be used for the preparation of a fixed sized object, then a sheet or monolith of a porous material may be desirable. For example, porous sheets can be used in the preparation of an elastic tile, or a monolithic lattice of a porous material can be used in the preparation of a load-bearing shape. Porous material in the form of spherical beads is especially preferred in certain embodiments of the invention. The porous materials contemplated for use in the practice of the present invention typically have a particle size (ie, the cross-sectional diameter in a larger dimension of the particle) in the range of about 0.05 mm 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 from about 1 mm to about 5 mm are preferred, and more preferably from about 1.0, 1.25, 1.5, 1.75, 2.0, 2.25 or 2.5 mm at approximately 2.75, 3.0, 3.25, 3.5, 3.75, 4.0, 4.25, 4.5 or 5.0 mm). 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 to about 1000 kg / m3, typically in the range of about 1 kg / m3 to about 100 kg / m3, with pearl densities that vary as a function of the purpose of the contemplated use. Normally, the pearl 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 at 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 more 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. The preferred porous materials currently contemplated for use herein may be further characterized as having sufficient porosity to absorb at least 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95% or substantially all of the gases generated in the curing of 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 conduction flow, and / or capillary or other flow). kinetic and / or thermodynamic processes), resulting in potentially macroscopic tendrils, fingers, filaments or other p rojections of the polymer that penetrate into the body of the porous material. In addition, the ability of the porous material that does serve as a reservoir for at least a portion of the gas generated may allow the reduction in the number and / or size of the gas bubbles that become trapped within the gas. polymer matrix, which increases the strength and density of the polymer matrix. In contrast, the non-porous materials would not have such a capacity, and would not allow the escape of substantial quantities of the gas or gases generated in the curing of the polymeric system generating gas used in the practice of the present invention. The average pore size of the porous materials contemplated for use in the practice of the present invention is usually in the range of about 0.05 m or less to about 1000 m or more, preferably from about 0. 1 microns to about 500 microns, and more preferably from about 1, 5, 10, 15, 20, 25, 30, 35 or 40 microns to about 50, 60, 70, 80, 90, 100 , 150, 200, 250, 300, 350, 400 or 450 microns. Although average pore sizes are generally preferred, larger or smaller pore sizes may be preferred in certain embodiments. Likewise, although a used pore size distribution is generally preferred, wider pore distributions may be acceptable or desirable in certain embodiments. For example, where it is desired to increase the relative strength of composite and structural materials by causing more of the polymer matrix to penetrate the porous material, the number and depth of the pores may increase or decrease when necessary to improve or discourage capillary flow within the pores. Alternatively, it is also possible to increase the polymeric entry into the porous material by applying the pressure and / or temperature to the material during the preparation, decreasing the viscosity of the polymer, selecting a combination of the polymeric and porous material (or modifying a porous material). selected) to provide compatible or similar surface energies for the interaction, as well as other kinetic and / or thermodynamic processes that favor the entry of the polymeric matrix into the porous material. It is also possible to employ a graft copolymer system in which a first polymeric component can be preferably polymerized within the pores of the porous material, and can also project outside the porous material, whose first polymeric component can be attached (either directly or through one or more linker molecules) to a second polymer component which can form a relatively continuous matrix outside the porous material. As a result of employing such a system, the first polymeric component can be selected to facilitate the desired level of penetration of the porous material, while the second polymeric component can be selected to promote desired properties of the matrix, such as a strength and other properties. physical-chemical, thermal, electrical and other. The resulting composite and structural materials may exhibit superior properties by virtue of them comprising a potentially light porous material of weight that is substantially encapsulated and penetrates by a potentially strong matrix material. The chemical and / or mechanical interlocking matrix and porous material may provide substantially improved properties of the resulting structure materials, including, for example, the strength and the compression modulus, the resistance and the shear modulus. , the resistance and the flexural modulus, the resistance and the voltage module. Using two polymer components has an advantage in allowing each of them to be relatively optimized independently to maximize their respective functional properties. In the case of a graft copolymer system, the preparation can be through a one or several stage polymerization process. For example, in a multi-stage process, the first polymeric component can be allowed to polymerize within the pores of the porous material, after which the porous material with the first polymer can be subjected to further steps wherein a second component Polymeric is attached directly or through linkers to the former, to form a matrix that encapsulates and penetrates the porous material. In a process of an exemplary step, the first polymer is selected or introduced in a manner resulting in the first polymer, preferably divided within the pores of the porous material, and the second polymer is selected or introduced. in a way that results in the sec undo polymer, it is preferably divided outside the pores of the porous material and the polymerization (with or without linker molecules) is allowed to carry out the grafting of the first and second polymeric components together. Porous materials contemplated for use in the present may also be characterized by the surface area thereof. Normally, surface areas in the range of about 0.5 to about 500 m / g2 are contemplated, with surface areas in the range of about 2 to about 1 00 m / g2 currently preferred. As is readily recognized by those of skill in the art, the shape and density of the porous material employed in the practice of the present invention can be varied so that a finished product having different physical properties (e.g. , different resistances and densities). In general, the smallest particles used, the higher the compressive strength, the shear strength, and the weight of the resulting product. Conversely, the larger the particles used, generally more flexible, less rigid and lighter are the products obtained. With respect to particle density, in general, the higher the density of the particles used, the higher the compressive strength, the shear strength and the weight of the resulting product. The porous material such as polystyrene, polyethylene, polypropylene, other polyolefin, and other beads can be manufactured in various densities 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, for example, by adjusting the amount or type of blowing agent employed in the preparation of the pearl precursor. In accordance with the present invention, the porous material (particulate or non-particulate) is usually in the range of about 50 to more than 99 volume percent of the volume of the finished article. Preferably, the 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 percent by volume of the formulation described above, with the preferred volume percent depending on the end use contemplated. For example, higher particulate contents are preferred where the product's floatability is desired (eg, materials for use in boats, sliders, flotation devices, spring buoys, and the like), while the particulate contents inferiors are preferred where high structural integrity is required. Generally, a material having at least about 90 volume% of the porous material is preferred, with at least about 95, 96, 97, 98 or 99% by volume being especially preferred. It should be noted that since the material can be subjected to compression during the preparation, as described herein, the volume of the porous input material can be substantially ter than 1 00% of the volume of the finished material, with such volumes which easily exceed 10, 120, 130, 140, 150, 160, 170, 180, 190, 200, 220, 240, 260, 280, 300, 400, 500 to about 800 percent of the volume of the finished material. Furthermore, in this regard, the articles of the invention may be described in terms of the percentage of compression to which they may be subjected during the preparation. The compression can be measured by physical-chemical expansion of the formulation within a confined space (such as a mold) or exogenously applied to a system that generates gas or other polymeric content within a mold or other confined space. During the preparation, the materials of the invention can be subjected to compressions of as little as 5-10 volume percent., with compressions up to and exceeding 80 or 90 percent in volume contemplated herein. Compressions in the range of about 5, 10, 15, 20, 25 or 30 volume percent to about 35, 40, 45, 50, 55, 60, 65, 70 or 75 volume percent are currently preferred for applications where an increased resistance range is desirable. In terms of the relative weight of the components used for the preparation of formulations of the invention, the porous material is usually in the range of about 5% by weight to about 90% by weight of the formulation, with the range by weight of the material variable porous particulate based on the end use contemplated. Preferably, the contemplated porous material comprises about 10, 12, 15, 18, 20, 25, 30, 35, 40, or 45% by weight at about 50, 55, 60, 65, 70, 75, 80, or 85% by weight. weight of the formulation. In certain embodiments, those skilled in the art recognize that higher or lower volume percentages, and / or higher or lower weight percentages may also be acceptable or desirable. For example, when used for the isolation and strengthening of acrylic tubs of a spa, thermal insulation and compressive strength are desirable characteristics of the material. Satisfactory compressive strength can reduce the likelihood of fracture of the acrylic due to the weight load caused by the contained water and spa occupants. By way of illustration of such embodiment, the porous material may be in the range of about 40-80% by weight, preferably in the range of about 50-70% by weight or more preferably to about 60% by weight (using a mixture of 5 mm or smaller polyolefin beads (eg expanded polystyrene and polyethylene beads) with a final density of approximately 2 pounds per cubic foot). Alternatively, when used for the production of sliders, it is desired that the resulting product be of light weight and have a strength exceeding that of a homogeneous polyurethane foam of toluene diisocyanate (TD I). By way of illustration of such embodiment, the porous material may be in the range of about 30-70% by weight, preferably in the range of about 40-60% by weight, or more preferably at about 50% by weight ( using 1.2 mm beads with a final density of approximately 3 pounds per cubic foot). As another alternative; When used for the production of building materials, materials that have high strength and lightweight characteristics are desired. By way of illustration of such embodiment, the porous material is in the range of about 10-40% by weight, preferably in the range of about 15-30% by weight, with about 18% by weight, which is preferred currently (using, for example, 1.2 mm beads with a final density of approximately 10.5 pounds per cubic foot). 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 materials based on silica, glass beads, ceramics, vermiculite, perlite, lytag, loose pulverized ash, unburned carbon, activated carbon, and the like, as well as mixtures of any of two or more thereof. In view of many porous materials contemplated for use herein, in certain embodiments of the invention, the use of porous materials other than polystyrene is contemplated herein. Exemplary porous materials contemplated for use in the practice of the present invention include expanded polystyrene (and other polyolefins) having a particle size widely in the range of 0.4-25 mm, and a density in the range of about 0.75-60 lbs. / foot3; with the 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 pounds / feet3; with currently preferred 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 pounds / ft3. Exemplary expanded polystyrenes include those having 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 pounds / ft3, the expanded polystyrene has a particle size in the range of about 0.4-0.7 mm, and a density in the range of approximately 1.5-3.0 lb / ft3, expanded polystyrene has a size in the range of approximately 0.7-1.1 mm, and a density in the range of approximately 1.0-1.5 lb / ft3 , the expanded polystyrene has 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 pounds / ft3, and a density in the range of about 1.1-1.6 mm, and a density in the range of approximately 1.0-1.2 lb / ft3, expanded polystyrene has 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 / ft3, polystyrene The expanded polystyrene has 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 pounds / ft3, the expanded polystyrene has a particle size in the range of about 0.6-0.85 mm, and a density in the range of approximately 1.25-4.0 lb / ft3, expanded polystyrene has a particle size in the range of approximately 0.75-1.2 mm, and a density in the range of approximately 1.25-4.0 lb / ft3, expanded polystyrene has 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 pounds / ft3, the expanded polystyrene has a particle size in the range of about 0.65-2.0 mm, and a density in the range of approximately 1.15-2.0 lb / ft3, expanded polystyrene has a particle size in the range of approximately 0.4-0.8 mm, and a density in the range of approximately 1.35-1.8 lb / ft3, expanded polystyrene has a particle size in the range of approximately 0.8-1.3 mm, and a density in the range of approximately 0.9-1.35 lb / ft3, expanded polystyrene has 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 pounds / ft3, and the like. An exemplary polyolefin, expanded polystyrene is usually made by heating the crystalline polystyrene, referred to in the trademark as "sugar" due to its similar appearance, with a blowing agent, such as cyclopentane, which has been entrained in the crystalline polystyrene during the fabrication process. The size of the crystal is controlled to produce a final bead size distribution of the desired modal diameter. Under conditions of controlled heat and pressure, the crystal softens and the blowing agent gasifies, forming microscopic gas bubbles within the body of the crystal. After sufficient softening, the crystal is eventually transformed by capillary forces into a spherical shape, with an internal structure comprising a semi-hexagonally closed packed cell structure, similar to a honeycomb of slightly irregularly shaped and sorted cells, as described in Figure 1. After expansion, the bead is removed from the reaction vessel for storage for curing. The bead is radically cooled to prevent implosion of the pearl surface within the interior and the cells collapse while the entrained blowing agent continues to draw gas at atmospheric pressure. When cooled sufficiently, the pearl retains its spherical shape without merging with its adjacent beads. The external appearance of the bead is rough and irregular, with craters and grooves, as described in Figure 2. The percentage of air in the expanded polystyrene beads is usually from about 90 to 97%. The technical characteristics of a number of different materials that can be used as porous materials in conjunction with the present invention are known in the art, see for example, the references provided following the Examples below. When porous materials, such as, for example, expanded polystyrene, polypropylene, other polyolefin or other porous materials as described in the present and in the art are completely mixed with the polymeric precursors that generate gas under controlled conditions of In such a way that each individual bead can be wetted with the polymeric mixture, and the polymerization reaction begins to occur, the liquid polymer can be forced into the interior structure of the bead in a branched or filiform filamentary form, through surface imperfections. and empty by the gases produced by the polymeric reaction of polymerization when the mass shrinks in a closed mold. Optionally, the additional pressure could be applied to additional amounts of polymer strength within the porous material, resulting in a stronger material, but a little more dense. When they are cooled and cured, the microscopic filaments or other hardened projections become rigid, while the remaining polymer on the outside of each pearl acts to maintain the molded structure in a more or less uniform matrix. Depending on the choice of the porous material and the polymer, some filaments or other projections may co-go inside the spherical expanded polystyrene bead although with others not. A cross section of a polymeric matrix containing porous beads is described schematically in Figure 3. The beads include portions into which the filaments or other projections of the polimeric material have penetrated, as well as porous areas which have gasses. absorbed generated in the process. Although it is not desired to join by any particular theory, it is believed that the filaments or other projections formed (for example, by controlled hydraulic pressure caused by the degassing of the polymerization reaction or applied exogenously, and / or capillary pressures or other forces) contribute to the superior strength and other properties of the materials of the invention when compared to conventional materials. By varying the proportion of the expanded polyolefin (eg polystyrene, polyethylene, and the like) to the total polymer can thus be used to prepare a range of materials that are strong and very light at one end of the spectrum to materials that are significantly heavier and extremely stronger than the conventional foamed polymer of the same density. An exemplary material according to the invention incorporating large beads (10) in a polymer matrix (1) is schematically described in Figure 4. An exemplary material according to the invention incorporating small beads (11) into a matrix (1) ) polymer is described schematically in Figure 5. An exemplary material according to the invention incorporating a mixture of large beads (10) and small beads (11) in a polymeric matrix (1) is schematically described in Figure 6. The polymerizable components contemplated for use in the practice of the present invention, include polymeric systems that generate gas in the polymerization thereof, or that can be treated with one or more blowing agents during curing, 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 to about 50,000 centipoise, with viscosities in the range of about 400 to about 20,000 centipoise which are currently preferred, with especially preferred viscosities that fall in the range of about 800 to about 10,000 centipoise. As is readily recognized by those of skill in the art, there are many polymer systems known in the art that are suitable for use in the practice of the present invention. For example, homopolymers, copolymers, block copolymers, graft copolymers, and the like can be used. Exemplary polymers contemplated for use herein include polyethylenes, polyvinyl resins, polypropylenes (high and low density), butadiene-acrylonitrile (ABS) copolymers, polyurethanes, and the like, as well as combinations of any two or more of them, each with specific pre-cured and post-curing physical properties. In one embodiment of the present invention, a combination of polymer components can be used to coat the porous material and form the polymer matrix. Thus, in one aspect, a first polymer can be used to coat the porous material (often a low viscous material having good wettability for the porous material, whereby the coating of the porous material is facilitated and enters into the pores thereof), and thereafter, the coated particles can also be contacted with a second polymer, which in the form substantially forms the matrix of the finished article. If the first and second polymeric materials are selected ap riately in the curing of each polymer system, the two polymer systems will also react with each other to further improve the properties of the resulting article. In another aspect, the functional properties of the two different polymer systems referred to above may be combined in a single-graft copolymer, so that a portion of the graft copolymer will have significant affinity for the porous material, and the rest of the graft copolymer will form a strong matrix in the cure. Some cures are exothermic and some are endothermic. Presently preferred polymeric systems contemplated for use in the practice of the present invention are mildly or moderately exothermic., so that only minimum heating and cooling is required in the preparation of the materials of the invention. Moderately exothermic systems offer particular convenience in the manufacture of materials according to the present invention where they do not require heat to be applied to conduct the reaction, and yet do not generate as much heat as to melt many of the materials contemplated for use herein as the porous component of the composite and structural materials of the invention, or potential additives. The currently referenced aspects of the present invention, the high strength, lightweight materials can be easily produced and be cost effective without the need for heating or cooling exogenously applied during manufacture. However, for certain applications and where the fastest cycle is desired, it is possible to apply exogenous heat and / or cooling to facilitate processing, as is known in the art. Some polymer systems generate gas as part of the curing process, while some polymeric systems require the addition of external blowing agents, in which there is a wide variety with different physical characteristics (for example, pentane, cyclopentane, d). carbon dioxide, nitrogen, and similar). As recognized by a person skilled in the art, a blowing agent may be introduced externally, or it may be generated in situ during the repair of the materials of the invention (for example, by compression of the porous material, which may contain gas caught in the present). Polymerization of the systems described above can occur in a variety of temperatures, sometimes exceeding 1000 ° C.; such processes are sometimes carried out at high pressures also, for example, up to several bars. As discussed herein, increasing the pressure during the preparation of the composite and structural materials of the invention can be used to compact the components thereof, and to drive the additional polymer matrix within the interior of the porous material, each of which tends to strengthen the resulting product. The amount of pressure applied is preferably sufficient to force some polymer ingress into the porous material, without being so large as to cause collapse of a substantial portion of the porous material. In view of the many polymeric gas generating systems contemplated for use herein, in certain embodiments of the present invention, the use of polymeric systems that generate gas, different from polyurethane, are contemplated herein. Alternatively, the graft copolymer systems may be employed so that one portion of the graft copolymer is preferably located within the porous material and another portion of the graft copolymer is located outside the porous material, and the The two copolymer components (either directly or through molecules in laminators) result in a core of the porous material that is substantially encapsulated inside and is penetrated by a polymeric matrix, resulting in composite and structural materials. They are of relatively low weight and still high strength and structural integrity. Preferably, the polymerizable components used in the practice of the present invention are stable at temperatures of at least about 50 ° C. This facilitates the handling of these materials, and minimizes the appearance of premature curing. Furthermore, it is also frequently desired that the polymerizable components used in the practice of the present invention be stable to such exposures as light, atmosphere, oxygen, water and the like, which may impact stability and / or reactivity of the same. As is readily recognized by one skilled in the art, numerous combinations of porous material plus the polymerizable system (s) may be employed in the practice of the present invention. When selecting the appropriate combinations, the compatibility of the two components must be taken into account, with reference to such considerations as the contact angle between the two components, the surface tension of the polymerizable system in relation to the porous material, the or pore sizes of the porous material, the capillary radius of the pores of the porous material, the pressure applied in the processing of the selected combination, and similar. As will be appreciated by those of skill in the art, various such aspects can be used to alter the "wettability" of the porous material as well as to alter the relative penetration of the polymer into the porous material (and thereby potentially increasing the strength of the resulting compound) as described herein. The ability to easily produce a variety of different materials that have properties optimized by several particular applications, provides a significant advantage of this method.
The presently preferred processes according to the invention employ a polymeric system that generates gas, based for example on diisocyanates, for the preparation of a polyurethane matrix. The curing of the diisocyanate has the benefit of being simple, that it occurs at or above room temperature and that it generates its own gas (ie, carbon dioxide) and only moderates heat during the polymerization of the reactants, the isocyanate and the polyol. As discussed above, the gas generated during curing can be substantially absorbed by the porous material. Among the advantages of the formulations of the invention based on the currently preferred urethane matrices is the fact that these formulations emit substantially non-volatile organic compounds (VOCs) in the cure, different from many conventional gas-generating formulations. The presently preferred polymerizable gas generating 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 known in the art, polyurethanes can be prepared in a variety of forms, including rigid foams, flexible foams, solids, adhesives, and the like. As is 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 may be employed, such as, for example, m-phenylene isocyanate, p-phenylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 3-diisocyanate, 3'-dimethyl-4,4'-biphenylene, durene diisocyanate, 4,4'-diphenylisopropylene diisocyanate, 4,4'-diphenylsulfone diisocyanate, 4,4'-diphenylether diisocyanate, biphenylene diisocyanate, diisocyanate of 1, 5-naphthalene, and the like. 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, 1,4-butantriol, trimethylolpropane, polyvinyl alcohol, partially hydrolyzed cellulose acetate, and the like. The flame retardants can be added to the porous material (for example before mixing with resin) or they can be incorporated during or after the polymerization according to the present invention. Flame retardants contemplated for use in certain embodiments of the present invention include any compound that retards the propagation of the flame, such as, for example, butylated triphenyl phosphate, and the like. Flow improvers contemplated for use in certain embodiments of the present invention include any compounds that reduce viscosity and / or improve the flow properties of the formulation, such as, for example, 2,2-dimethyl bis (2-methylpropanoate). -1- (methylethyl) -l, 3- clothingndiyl, and the like. The plasticizers (also referred to as flexibilizers) contemplated for use in certain embodiments of the present invention include compounds that reduce the fragility of the formulation, such as, for example, polyamines or branched polysiloxanes which decrease the temperature of the vitreous transition (Tg) of the formulation. Such plasticizers include, for example, polyethers, polyesters, polythiols, polysulphurs, and the like. The plasticizers, when employed, typically present in the range of about 0.5% by weight to about 30% by weight of the formulation. Treatment retardants (also known as cell dimming regulators or quenching agents) contemplated for use in certain embodiments of the present invention include compounds that form low reactivity radicals, such as, for example, silicone surfactants (generally), and the like. Accelerators of curing contemplated for use in certain embodiments of the present invention include compounds that improve the rate of cure of the base polymer system, such as, for example, catalytically active materials, water, and the like. Contemplated resistance enhancers for use in certain embodiments of the present invention include compounds that increase the performance properties of the polymeric material to which they are added, such as, for example, crosslinking agents, and the like. The UV protectants contemplated for use in certain embodiments of the present invention include compounds that absorb incident radiation or UV radiation, thereby reducing the negative effects of such exposure on the resin or polymer system to which the shield is applied. has added. Exemplary UV protectants include bis (1, 2,2, 6,6-pentamethyl-4-piperidinyl) sebacate, silicon, puZed metal compounds, and the like. The dyes contemplated for use in certain embodiments of the present invention include n igrosin, Ozulfol, O, phthalocyanines, and the like. When organic dyes are used in relatively low amounts (i.e., amounts less than about 0.2% by weight) they provide a contrast. The pigments contemplated for use in certain embodiments of the present invention include any particulate material added solely for the purpose of imparting color to the formulation, for example, carbon black, metal oxides (e.g., Fe203, titanium oxide), and similar.
When presented, the pigments normally present in the range of about 0.5% by weight to about 5% by weight relative to the base formulation. Fillers are also contemplated for use in certain embodiments of the invention. The fillers may be introduced into the formulations of the invention to improve one or more of the following properties: compressive strength, shear strength, flexibility, internal strength (useful, for example, for maintaining nails, screws, and the like) , wear durability, impact resistance, fire resistance, corrosion resistance, increased density, decreased 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 may optionally be conductive (electrically and / or thermally). The 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, copper alloys, such metals, and the like, as well as non-metals such as graphite, conducting polymers and the like, and mixtures of any of two or more thereof. Both forms of flakes and filler powder can be used in the compositions of the present invention. Preferably, the leaflet has a thickness of about 2 microns or less, with flat dimensions of about 20 to about 25 microns. The flake employed herein preferably has a surface area of about 0.15 to 5.0 m2 / g and a vibrated density of about 0.4 to about 5.5 g / cc. In certain embodiments, flakes of different sizes, surface areas and vibrated densities may be used in a desirable manner. It is currently preferred that the powders used in the practice of the invention have a diameter of about 0.5 to 15 microns. If present, the filler is normally in the range of about 5% by volume to about 95% by volume of the formulation, preferably 10, 15, 20 or 25% by volume to about 90% by volume of the formulation, more preferably about 30, 35, 40, 45, 50, 55% by volume to about 60, 65, 70, 75, 80 or 85% by volume of the formulation. The 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 from about 0.1 to about 100 microns, preferably from about 0.5 to about 10 microns, and most preferably from about 1 micron. However, larger or smaller particle sizes can be used in certain modalities. If the aluminum nitride is used as a filler, it is preferred that it be less active by a conformal, adherent coating (eg, silica or the like). Optionally, a filler that is not an electrical or thermal conductor can be used. Such fillers may be desirable to impart some other property to the formulations of the invention such as, for example, the reduced thermal expansion of the cured material, reduced dielectric constant, improved hardness, improved hydrophobic properties, and the like. Examples of such fillers include synthetic materials, such as, for example, perfluorinated hydrocarbon polymers, thermoplastic polymers (eg, polypropylene), thermoplastic elastomers, poly-paraphenylene terephthalimide, glass fiber, graphite sheets, graphite fibers, nylon, rayon , recycled polymers, recycled solid materials, solid cutouts, solid polymeric material, cut metal, bits turned into powder, flake pieces, dust, paper, crumbs, rubber, glass, hollow polymer beads, solid polymer beads, hollow glass beads, glass beads solid, waste glass, recycled composition slats, recycled asphalt, recycled roofing materials, recycled concrete, recycled tires, coal, as well as a variety of other post-industrial or post-consumer plastics and other materials, and the like. The fillers may also include materials of natural origin, such as, for example, mica, fumed silica, combined silica, sand, sawdust, gravel, stone conglomerates, cotton, hemp, rice hulls, coconut sheath fibers, shrimp shells , bamboo fiber, paper, popcorn, popcorn conglomerates, bones, seeds, shredded straw fibers (eg, rice, wheat or barley) and the like, as well as mixtures of any two or more of the same. The fillers can be either porous or relatively non-porous. In the case of porous fillers, the polymeric matrix of the materials of the invention can be spread within, as well as around such fillers, thereby potentially contributing further resistance to the materials of the invention. The composite and structural materials of the invention, sometimes referred to herein as "PetriFoam ™" composite and structural materials, can be made to have a superior compression modulus (as desired), which can fall in the range of about 8,000. psi up to approximately 10,000 psi or higher. Depending on the desired application, the materials of the present invention can be prepared by having the compression module exceeding 2000, 4000, 8000, 10,000, 20,000, 40,000, 100,000 or higher. In addition to the superior compressive strength of the materials of the invention, these materials are capable of withstanding compressive pressures exceeding 400, 1000, 4000, 8000, 12,000 or even a higher anterior fracture.
Certainly, the exposure of the articles of the invention, after curing the materials of the invention to raise the compression pressures (but lack of fracture), can produce an article with improved strength. The composite and structural materials of the invention may also have higher elasticity, as measured for example by the flexural moduli of a sample. Such materials are useful in a variety of specific applications, as set forth in detail below. Normally the materials of the invention have a flexural modulus that falls in the range of about 10,000 psi to about 14,000 psi or higher. Even the materials of the highest bending module can be obtained by the use of suitable fillers. For example, flexibility can be improved if desired for certain applications by incorporating flexible materials such as flexible plastics or rubber, which can be made of recycled materials, as well as other flexible materials. Additional desirable properties that may be provided by the materials of the invention include superior insulation properties, water resistance properties, energy absorption properties (optionally including excellent memory effects, wherein the materials of the invention substantially return to its original shape after impact), mildew resistance, radar absorption, and the like.
In the embodiments of the invention, where the superior strength is a desired characteristic of the resulting structural material, it is preferred that the polymer matrix comprises smaller and smaller cavities formed during the production of foam. For such a modulus, a majority and preferably at least 20, 30, 40, 50, 60, 70, 80, 90, 95, 98% or more preferably substantially all the gas generated during the polymer curing it 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 the filaments and other projections of the polymer spread within 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 within the body of the porous material contributes to the exceptional properties of the particles. materials of the invention, including strength, flexural modulus, and compression. Although a relatively solid polymer matrix is generally preferred, in certain embodiments where resistance can be resolved, a matrix having cavities may be acceptable, or even desirable since it may be used to generate lighter materials and at a lower cost.
To produce composite and structural materials that have even greater structural integrity suitable for use in an even wider range of potential applications, one or more reinforcing structures can be incorporated within the materials of the invention. Exemplary reinforcing materials include natural fibers, synthetic fibers, silica-based materials, or other structures, as well as combinations of any two or more thereof. Such reinforcing materials may be of any size, shape, length, etc. One skilled in the art can easily determine the appropriate dimensions of any aggregate reinforcing materials, depending on the end use contemplated for the material. As an alternative or including one or more reinforcements in the materials of the invention, or in addition to such inclusion, or no or more coating materials may be applied to the materials of the invention, optionally emplg a suitable adhesive material, an adhesive promoter or a binding coat, as necessary. A wide variety of coating materials are suitable for such purposes, such as, for example, metals comprising coatings, polymers, cloth, plant fiber or other natural fibers, synthetic fibers, glass, ceramics, expanded metals and grids, and the like, as well as combinations of any two or more of the same. Additional coating materials contemplated for use herein include materials of natural origin (such as, for example, wood), synthetic sheet materials (such as, for example, acrylic sheet material), natural or synthetic woven materials (such as example, a Kevlar fabric), and the like. Although only illustrated in Figure 7 as being attached to any face of the material of the invention, coating materials may be attached to a plurality of faces of the materials of the invention (e.g., the top and bottom of the materials of the invention). invention may have a coating material applied thereto, all faces of the materials of the invention may have a coating material applied thereto, as well as other variations that will be apparent to those skilled in the art). Such coating materials can be in the form of a solid surface, a porous surface, a surface that can be chemically attacked, a chemically attacked surface, a physically erodible surface, a physically eroded surface, and the like, as well as combinations of any of two or more of them. In a particularly preferred embodiment, a length of bamboo is filled with the material of the invention, producing a strong structural member suitable for use in, for example, 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. Among the advantages of composite and structural materials is the fact that these materials do not emit substantially the discharge of gases, differing from many conventional composite and structural materials, specifically those prepared using gas-generating formulations. According to yet another embodiment of the present invention, methods are provided for making composite and structural materials having a compression modulus of at least about 8000 psi, and a flexural modulus in the range of approximately 10,000 psi to about 14,000, the method comprises: combining the porous material with a polymerizable component that generates gas, and subjecting the resulting combustion to suitable conditions to allow the polymerizable component to polymerize. During the polymerization process using a substantially closed or pressurized system, substantially all of the gas generated or absorbed by the porous material and some of the polymeric material can be forced into the body of the porous material. The combination contemplated by the method of the invention can be carried out in a variety of ways. For example, the polymerizable component that generates gas and the porous material (and any additional components contemplated for a specific use) can be mixed, then the polymerizable component that generates gas is allowed to cure. In one embodiment of the present invention, the mixture is introduced into a mold, the mold is closed, and the polymerizable component generating gas is allowed to set. In another embodiment of the present invention, the mixture is introduced into a confined space and compressed to a smaller volume of the original volume of the starting components. The mixture can, as another alternative to prepare in an open system, or it can be sprayed or otherwise applied onto a surface. If additional strength is desired, this may occur under compression so that the gases generated are substantially absorbed by the porous material and so that some of the polymer is forced into the body of the porous material. When the formulations of the invention are subjected to pressure to reduce the volume of the same, a wide range of pressures may be employed, usually in the range of about 1 to about 10 psi, but the higher pressures may Also, if desired, to produce relatively higher strength compounds. Alternatively, regardless of the pressure that may be involved, the formulations of the invention may be cured in a confined space such that the cured article is of a network volume with respect to the volume of the starting materials. Reductions in volume in the range of about 5-1 0 percent, to 20-40, 40-60, 60-80, 80-90 percent or higher, are contemplated in the practice of the present invention. In yet another embodiment of the invention, instead of preparing the articles of the invention in a mold to achieve a specific shape, standardized "block building" structures can be prepared and later combined into a desired shaped article. This is possible because the materials of the invention can easily adhere to each other using standard adhesive materials such as, for example, brooms, epoxies, and the like. Preferably, when the limiting component (such as a foamable polymerizable component) is prepared from a multi-component system (for example two components), the porous material is first mixed with only one of the polymerizable components, before the introduction of the second component into the reaction vessel. It is generally preferred that the porous material be mixed with the most 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 may be only partially coated with a p-recursor of the polymerizable component. Alternatively, the articles of the invention can be prepared from a one-component monomer (eg, poly-urethane), wherein all of the polymer components are combined with the porous material, and the polymerization is started by the polymer. water to it. The copolymers can also be em plexed, such as block copolymers, wherein the matrix can be designed to incorporate two or more different functional polymer groups, and / or graft copolymers such as the copolymer system shown. to facilitate the penetration of the porous material as described above. The coatings or coatings can be applied to the articles of the invention by introducing coatings and / or coatings into the mold before the reaction mixture is introduced. Alternatively, the coatings and / or moldings can be applied after molding. It is also within the scope of the present invention to irrigate reinforcing materials (such as metal mists, ceramic or silica based materials, fabrics or other fabrics, rubbers, and the like) to the mold to produce an integral reinforcement material. A structural description of an article of the invention according to the present invention having a coating material attached thereto is presented in Figure 7. The coating materials contemplated for application to the materials of the invention include materials of natural origin (such as, for example, wood, bamboo or other fiber derived from plants), 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 is readily recognized by those of skill in the art, the coating materials may be attached to a plurality of faces of the materials of the invention (eg, the upper and lower faces of the materials of the invention may have coating materials applied thereto, all faces of the materials of the invention may have coating materials applied thereto, as well as other variations as are apparent to those of skill in the art). As is readily recognized by those skilled in the art, a wide variety of coatings can be applied to the materials of the invention. Coating materials contemplated for application to materials of the invention include Portland cement (usually applied as a slurry in water, or with a silica-based material, which imparts flame retardant properties to the treated article), gypsum, gel cover, transparent cover, color coats, non-fixed coatings, slip-resistant coatings, adhesive, tear-resistant coatings, metallized coatings, and the like. Figure 8 provides a structural description of the invention material having a coating material applied thereto. For some coating materials, it is beneficial to improve the ability of the coatings to adhere to the articles of the invention. This can be achieved in a variety of ways, such as, for example, physically and / or chemically attacking the surface of such articles. Thus, as illustrated herein, the surface area of the article to which a coating is to be applied may be increased, whereby the ability of the coating material to adhere to the article being treated is improved. When the coating and / or coating materials are to be applied to the materials of the invention, the surface of the material of the invention to which the coating and / or coating is to be applied may be subject to physical abrasion and / or chemical to increase the porosity of the substrate and improve the adhesion of the coating materials and / or coating thereto. For example, the materials of the invention can be subjected to sand blasting and / or chemical etching or abrasion to erode the surface skin thereof, providing the surface of the material of the invention more receptive to the application of the materials of the invention. coating and / or coatings therein. In certain embodiments of the present invention, the coating and / or coating material may be applied to either side of a support. Such a configuration is schematically described in Figure 9. Those skilled in the art can easily determine the suitable conditions for polymerizing the gas generating or other polymerizable component employed herein. Typically, such conditions comprise irrigating the polymerizing agent to the combination of the porous material and the precursor of the gas generating or other polymerizable component, generally at or above the ambient temperature. In this way, the heating or cooling requirements of the processes of the invention are minimal, so that the process can be easily achieved, for example, by vibrating the container containing the porous material, the precursor of the component that generates gas or other polymerizable component and the polymerizing agent immediately after the introduction of the polymerizing agent thereto. In accordance with certain modalities of the present invention, up to about 25, 30, 35, 40, 45, 50% by weight or more of the porous material employed may comprise a recycled (ground) structural material as described herein. As is easily recognized by those skilled in the art, higher amounts of the recycled material of the invention can be employed, depending on the material being recycled and the end use contemplated by the same.
According to another aspect of the present invention, articles prepared according to the methods described above are provided. According to yet another aspect of the present invention, articles manufactured from the materials of the invention are provided. Such articles may have a defined shape, a resistance and a higher modulus of compression, and if desired, a high flexure modulus. Such articles may comprise a flexible or rigid polymeric matrix, which contains the porous material substantially uniformly distributed therethrough. The articles of the invention have superior performance properties that make them suitable for a wide variety of applications. A particularly useful application of the materials of the invention is in applications where a structure prepared therefrom is at risk of exposure to seismic activity. Because the materials of the invention can have such high strength and other desirable properties (including elasticity and superior structural memory), and relatively low weight, the very low moving force is generated if a structure prepared from the m isma is subjected to seismic forces. Thus, the materials of the invention have particularly desirable properties for use in a variety of construction applications. A non-exhaustive list of examples of the wide variety of applications for which the articles of the invention may be employed herein is provided. The articles of the invention may be shaped as is appropriate to facilitate any of the following uses: Aircraft / aerospace / defense / force generation (eg, components of airplanes, components of remotely piloted vehicles, powerful missiles, energy-powered aircraft solar, thermal shields, wrapping of the choke engine, accessories, military drone aircraft, game airplanes, ultralight airplanes, aircraft security / reserve components, lightweight / reinforced doors, aircraft furniture, panels, security structural protection systems solar, propellers and blades that generate wind energy, wheels or blades that generate hydraulic energy, turbines, support structures for solar power generation, manual works of wing effect on the ground, radar absorption materials, aircraft engine covers, aircraft propeller harps, aircraft fins, aircraft rudders, fus aircraft airplanes, aircraft wings, seaplane floats, hang gliders, insulation for projectile fuel tanks, and the like). Agricultural (for example, protectors and sowers of plants, feeders of cattle, pillars for electrical fencing, corrals for cattle, and similar). Patio / meadow / garden / pet / horticulture / greenhouse (eg kennels, food and irrigation dishes, shelters and canopies, kennels, sleeping rugs, animal boarding cages, dog and cat beds, cat scratches, furniture plastic (for example, for grass, porch, garden, patio and similar), panels and screens of decorative arts, prints and decorative ornaments, fencing for snow, vases, pots, tubes, vases, fountains for lawn and garden, ornaments for garden, urns, and the like). Electronics (for example, telecommunications antennas, cable reels, cable trays, battery boxes, battery storage shelves, photovoltaic, cellular antennas, electrical wiring channels, and the like). Appliances (for example, home appliances such as refrigerators, dishwashers, stoves, microwave ovens, washing machines, dryers, and the like, as well as containers for various household appliances, such as, for example, mounting for televisions, computers, CRTs, commercial machines, microwave ovens, dishwashers, clothes washers and dryers, compressors, refrigerators, refrigerators, air conditioners, dehumidifiers, portable heaters, and the like). Refrigeration (for example, conservation building in refrigerators, champagne buckets, ice buckets, beverage chillers, condenser drip pans, freezer cabinets, refrigerated rail transport wagons, ice shelves, refrigerated trailers, refrigeration insulation , and the like), Business and electronic equipment (eg, copiers, computers, computer components, calculators, television components, telephone, moldings and wrappings for electrical appliances, power tools, electronic cases and shelves, and the like), Construction and building - any application that can benefit from impenetrable materials to the mold, termite infestation, and the like, such as, for example, swimming pools, pool covers, hot tubs, hot tub covers, cooling towers, tubs and showers units , bridge decks, bridges, structures Products, seismic reinforcement structures, road signs, energy absorbing barriers on highways and acoustic absorbent side walls, insulated structural panels, building construction for homes, panels for commercial building construction, details and architectural facades, sound attenuation barriers , insulation, waterproof materials, forms and molds of concrete, forms and molds for manufacturing, structural framing systems, stacking, interleaved components, road delineators, prefabricated homes, pre-fabricated offices, road impact absorption barriers, impact absorption barriers in race tracks, ceilings, floors, walls, door laminates, carpentry laminates, tables and dimensional panels, shelters for military temporary housing, buildings and tanks for sanitary waste processing, hospitals and operating rooms, cleaning rooms and laboratories, edifici decontamination, spas, refrigerated storage buildings, kitchens, lobbies, offices, warehouses, workshops and vehicle maintenance buildings, computer control rooms, furniture, tables, doors, aircraft hangars, stretchers, coffins, beds, boats for garbage, insulated containers for drinking water, containers for perishable food isolated, network of insulated ducts for heating and air conditioning units, manufacture and construction of houses, accommodation, offices, temporary quarters, blocks and bricks for construction- building, arctic structures, internal structural fillings for houses formed with expanded polystyrene foam, replacement for green boards for landing surfaces under tiles, countertops, desktops, desktop computers, work table surfaces, decorative boards, strips, blinds, moldings architectural and ornamental moldings, doors, portals, sea window frames, insulated and structural sliding panels, retaining walls, light weight portable walkways and personal bridges, platforms, handrails, fences, entrances, pens, car sheds, awnings, mud carpets for heavy equipment, carpet rugs of cranes, barricades for cars and pedestrians, closed of traffic, parapets and poles, signs of caution and security, shelters of cabins of taxis and buses, awnings for storage and farm buildings, portable buildings, pre-fabricated structures, buildings and structures pre-designed, cabins, canopies, drywall, portable classrooms, cleaning rooms, cofferdams, construction forms for laying cement and concrete, contractor mixing pans, composite dimensional wood, various types of laminate, boards and beams designed, laminated and shaped extruded, cast iron mantels, roof and floor reinforcement, insulated doors, insulated roof systems, laminated varnish sheets, interleaved honeycomb panels, noise barriers, pedestrian bridges, garage doors, sheets for ceilings, roof tiles, streets, scaffolding systems, scaffolding plates, saunas and bathrooms, bark for doors, temporary sidewalk plates, subfloors, cabinets, and the like. Industrial (for example, warehouses, fences and systems resistant to bullets and traps, hoods, canteens, load carriers, ramps, slides, spouts, gaskets, pipes, light installations, ceiling fan blades, air diffusers, baskets for washing machines, fan housings, wheels, weather vanes, gates and covers, cabinets for fire hoses, safety covers, pallet wrappers, mailboxes, pallets (reusable and / or recyclable), pallet box, raised doors, parking barricades , edges for parking, room dividers, seats and benches, shelving, ballistic armoring, shower enclosures and bathrooms, reels and stools, trays, and the like), Industrial coatings (eg coatings and bulk container systems, coatings for railway wagons, cabinet liners, all types of coatings, cylinder liners, shells, trench lining s for irrigation, fences for noise control, and the like), Furniture (eg, upholstery frames, benches, seats, bleachers, chairs, stools, folding tables for playing cards, tables, office divisions, and the like), Products for packaged consumer and industrial
(for example, waste and carry boxes, food storage containers, ultra-light air transport containers, reusable boxes and shipping containers, wooden boxes, burial vaults, mausoleums, recyclable packaging, containers for packaging and boarding, crypts for cemeteries, cartons, jars, cannons, carton boxes and ammunition boxes, barrels and barrels, folding boxes and wooden shipping boxes, ocean shipping containers, containers and packaging of corrugated plastic, boxes plastic molded custom and lodges, drums, cardboard boxes and egg cases, instrument cases, folding cartons, cardboard boxes, garbage cans, grain containers, retail accessories, shelving, boxes and molded cases, counters , furniture, and the like). Demonstration of signs and products (for example, poster for advertisements, erasable posters, changeable letter posters, clipboards, demonstration posters, boxes, cabinets, cases, accessories, panels, shelves and platforms, tables, trays, light boxes, boxes of painting, military objectives (land, sea, air), warning signs in the open, landscapes and stadium stands, exhibition booths and demonstrations, and the like), Recreational items (eg, sports equipment, golf clubs, camping, exercise equipment, snow boards, surf boards, boogie boards, golf carts, bowling equipment, carts and boxes, motorcycle helmets, bicycle helmets, helmets for other sports, elbow and knee protectors, gloves, footwear athletic and non-athletic including shoes and boots, skis, skates, camping trailers, rifles, shotguns, revolvers, forearm weapons, lures, snowshoes, chairs for m ontar, snow sleds, and the like), Children's toys / toys for farmyard (for example, castles, dollhouses, swings, slides, snow sleds, sand boxes, trunks and boxes for games, building blocks, games alphabet, seats and brakes for passenger safety, furniture such as baby seats, chairs, cribs, desks, beds, litter boxes, tables, vehicles and rides in cars, wagons, swings, animals to mount with springs, horses toy, hammock horse, and the like), Corrosion-resistant equipment (eg, pollution prevention equipment, wastewater treatment products, pipe fitting, underground and external storage tanks, pumps, containers, and various equipment used in chemical processing, pulp / paper processing and oil / gas industries, oil and gas recovery equipment, wheels for generating power, and the like), Eq electrical / electronic equipment (for example, circuit breaker and housing boxes, polar line hardware, electrical connections and insulation, plugs and ducts, substation equipment, electronic microwave components, electric fences and lighting fences, 3D boards , polyester panel boards, and the like). Marina (for example, yachts, boats, jet skis, canoes, marine docks, commercial boats and moorings, naval boats, boats, racing boats, commercial boats and component parts, including marine equipment and engine covers, marine vehicles that operate in effect due to the ground, marker buoys, mooring buoys, channel, instrumented, scientific buoys, clima buoys, fishing net buoys, life rafts, fenders, rigid hulls for inflatable boats, dock storage boxes , water and fogging supplies, oars and buoyancy blades, water sports games, trap markers for cang and lobster traps, hatch covers, boat anchors composition, dock passages, swimming platform floats, ladders for the embarkation, float boats, steering consoles, galleys for construction of galleys, refrigerators, tables and galley cabinets, stations for cleaning fish, tables for cabins, preservers of life, buoys of bell, rigid candles for sailboats, artificial fish hooks and baits, fish ladders, collapsible boats, floats and decks, dagger boards and rudders for sailboats, houseboats, boat hulls and boats, lifeboats, sailboats, and the like), Muelles ( for example, boards and quays composed of floating, folding, portable, ramp, canopies, decks, shelters, handrails, diving floats, floating storage docks for dry storage of personal watercraft, and similar), Transportation (for example, automotive components, cabins for trucks, cabins for automobiles, recreational vehicle components (RV), equipment for cultivation, reinforce buffer zone, side impact reinforcement, structural improvements, safety equipment, boxes, shipping containers, train components, subway components, rail cars, composite rail moorings, motorcycles, skateboards, automotive panels, appearance accessories, reinforcements police vehicles, pre-fabricated impact units for fire protection and rear impacts, front and rear bumpers, new production vehicles and against existing fleet adjustment, reinforcing the monocoque body design, reinforcing the design of cages and improving the designs of squeezing zones, making the unified body more rigid, allowing the vehicles to withstand higher impacts without losing the structural integrity, tire wheels, with reinforcements according to the invention inside the rim, between the rim surface and rolling in contact (allowing a vehicle to recover a safe stop after is from tire failure or explosion, diverting the vehicle, turning the path, and refinancing, and eliminating the need for a reserve wheel), sun visors, steering wheels, collapsible armrests, wheel covers, marching boards, acoustic and thermal automotive insulation for firebreaks, roof, cape, doors, floorboard, impact absorbers from the occupant's interior cabin, columns, door panels, roof, instrument panel, front and rear seats, armrests , interior rear fender panels lined with the materials of the invention, deck and trunk floor, rear seat anchoring panel, gas tank to help stop penetration breaks of stopping frame anchor point and fires and absorb the energy caused from the rear end collisions to the vehicle, lateral impacts, lateral intrusions, for hits of trucks and vehicles, automotive, commercial and industrial equipment, cab bodies, mats, rail cars, car and wedge brakes, armored cars and trucks, custom trailers, vans, vehicles, instrument panel, airplanes, boats, boats, covers for thick holes of the ship, cases for boat batteries, cable car, van, and similar), Environmental treatment / wastewater (for example, portable and temporary secondary spill containment systems for accidents involving hazardous materials and containment systems) decontamination material, upper parts of floating tanks, floating sewerage lagoon covers, modular tanks, channels, dams, dams, detention trunks, floating decanters, oil spill supports, bowls and spill pans, cesspools, cisterns and decks, ramps, cooling tanks, condenser tanks, air tunnels, soul tanks built in the field, fish farming tanksfish hatcheries, floats for oil spill recovery systems, lagoon coatings, garbage dumps, oil spill recovery systems, solar collector panels, and the like), Medical / health care (by example, molds, adjustments, linings for medical equipment, orthopedic devices, prosthetics, disposable tablets, furniture, and the like), and so on. Presently preferred applications of the methods and articles of the invention produced therefore include the preparation of building panels, structural reinforcements, sound reinforcement, insulation, waterproofing, counter surfaces, swimming pools, pool covers, surfboards, hot tubs, covers for hot tubs, cooling towers, bathtubs, shower units, storage tanks, automotive components, components for personal watercraft, and the like. According to the additional embodiments of the present invention, the articles described above can be further modified in a variety of ways, depending on the end use. For example, fire-proof coating, non-slip coating, a wood coating, an acrylic layer, a woven fabric covering, or the like, can be applied thereto (see, for example, Figures 7, 8 and 9) . The article may be formed in a predetermined form, or the article may be subjected to sufficient compression energy to reduce the thickness thereof. Desirable shapes can be cut and / or drilled within the article, the article can be ground to full recycling, sanded, flattened, shaped, drilled, compressed, demolished, or the like. According to yet another embodiment of the present invention, articles produced by any of the methods described above are provided. According to a still further embodiment of the present invention, methods are provided for making composite and structural materials that have improved properties, including a compression modulus of at least
,000 psi, and a flexural modulus in the range of approximately 10,000 psi to approximately 14,000 psi, the method comprises: combining the porous material with a polymerizable component that generates gas to produce a pre-polymerization mixture, subjecting the polymerization at suitable conditions to allow the polymerizable component generating gas to polymerize, whereby a cured article is produced, 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 sufficient time for the article to achieve the desired physical properties. Those of skill in the art can easily determine the proper conditions to allow to polymerize the polymerizable component that generates gas. The selected conditions depend on the type of polymerizable component used. Polyurethanes, for example, once various components of a polyurethane resin are combined, will usually initiate cure at relatively mild temperatures (i.e., in the range from about room temperature (about 25 ° C) to about 70 ° C. ). According to yet another embodiment of the present invention, methods for making composite and structural materials having a compression modulus of at least 20,000 psi, and a flexural modulus in the range of approximately 10,000 psi to approximately 14,000 psi, are provided. The method comprises: subjecting a prepolymerization mixture comprising the particulate material, at least a portion which is porous, and a polymerizable component foamable at suitable conditions to allow polymerizing the foamable polymerizable component, whereby a cured article is produced, and later submitting the compression cured article 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 sufficient time for the article to achieve the desired physical properties. According to yet another embodiment of the present invention, methods for making composite and structural materials having a compression modulus of at least 20,000 psi, and a flexural modulus in the range of approximately 10,000 psi to approximately 14,000 psi, are provided. method comprises: subjecting the pressure cured article by compression 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 sufficient time for the article to achieve the desired physical properties, wherein the cured article is prepared by subjecting a pre-polymerization mixture comprising the particulate material, at least a portion which is porous, and a polymerizable component foamable at suitable conditions that allow to polymerize the foamable polymerizable component, whereby the cured article is produced. The invention will now be described in greater detail with reference to the following non-limiting examples.
EXAMPLE 1 Various polyurethane formulations were prepared by mixing with porous material according to the present invention. For each formulation, all the ingredients (of each component) were introduced into a closed system mixing vessel, then mixed under constant agitation for 1 to 2 hours, depending on the size of the batch. No heating was required to carry out the curing processes.
Formulation 1 (BLACK / Flame Retardant) Weight% Range Component A - Isocyanate: Diphenylmethane Diisocyanate (Polymeric DI) 88.5-94.5
Trichloropropylphosphate (Flame Retardant) 5.5-11.5 Component B - Polio !: Polyether Polyol (Sucrose / Glycol Mix) Hydroxyl # 375 to 400 73.1-93.4
Polyol Polyether Diol, Hydroxyl # 265 8.4-12.5
Tertiary Amina (Catalyst) 0.1-2.50
Dimethylethanol Amine (DMEA) (Catalyst) 0.35-1.2 Water (Blowing Agent) 0.4-1.5 Silicone Surfactant 0.08-2.2 Black Pigment (in Polyether Polyol dispersion) 0.3-1.5 Formulation 2 (WHITE) Weight% Range Component A - Isocyanate: Modified Monomeric MDI 100.00
Component - Polyol: Polyether Polyol (Sucrose / Glycol Mix) PO Tip, Hydroxyl # 375 to 400 82.5-91.5
Poliol Polyether Test, 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 Amina (Catalyst) 0.25-1.2
Surfactant Body (9 to 10 Moles) 0.35-0.7
Formulation 3 (NATURAL COLOR) Weight% Range Component A - Isocyanate: Diphenylmethane Diisocyanate (Polymeric MDI) 100.00
Component B - Polyol: Sucrose Amina, Hydroxyl # 350 30.5-42.0
Sucrose Amina, Hydroxyl # 530 45.0-60.0
Amina polyol, Hydroxyl # 600 2.8-9.0 Water 0.20-1.3 Silicone Surfactant 0.35-0.7 Formulation 4% Weight 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 Mix) 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 (Formulation of a Component): Range of% in Weight
Poliol 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 Several polymeric systems useful in the practice of the present invention were prepared and the performance properties of the same were evaluated, as summarized herein. Formulation 1 described in Example 1 was used to produce a two-component, rigid, aqueous, aqueous blown-textured structural material. This material provides superior performance for applications that require a hard and rough surface, and is a cost-effective wood replacement, which is why it is in use in a variety of industries such as the furniture industry (for example, the manufacture of furniture, cabinets, and the like) and in the paint shop business. The parts can easily be molded out of the urethane materials that might otherwise require machining or heavy-duty turning. The normal physical properties of the cured material are presented in Table 1.
Table 1 TYPICAL PHYSICAL PROPERTIES
(For Components) TEST METHOD Component A Component E
Viscosity, cps ASTM D-2393 100-200 1000-1400 Brookfield LVF, Axis # 2, @ 12 rpm Specific Gravity ASTM D-1638 1.2 1.04 Weight / gal. Lb 10.0 8.68 Mixing ratio by weight 52 48 Mixing ratio by volume 50 50 (For Material 10 (other Curing) densities also Density, available) lb / ft3 The cremation time of the formulation was approximately 30 to approximately 60 seconds, and can be modified by adjusting the conditions of the process or through the use of ad itives. The lifting time was approximately 2 to approximately 4 minutes, and can be modified by adjusting the conditions of the process or through the use of additives. The storage or shelf life of Component A (isocyanate) and Component B (resin) can be maximized by keeping the materials at a temperature from about 1 0.33 ° C to about 29.44 ° C (65 ° F to about 85 ° F). Protection against moisture and foreign material is produced by keeping the storage containers tightly closed. Formulation 2 described in Example 1 (I PS 3001 -10LV) is a rigid, two component, aqueous blown polyurethane structural material. This material also provides superior performance for applications that require a hard or rough surface and can be used as a cost-effective replacement for wood. The parts can easily be molded away from urethane-based materials that would otherwise require intensive laboring or turning. The standard physical properties of the same are summarized in Table 2.
Table 2 TYPICAL PHYSICAL PROPERTIES (For Components) METHOD of Component A Component E
Viscosity, cps TEST 200-300 2400-2600 ASTM D-2393 Brookfield LVF, Specific Gravity Axis # 2, @ 12 1.2 1.04 Weight / gal. (Lbs) rpm 10.0 8.68 Mixing ratio ASTM D-1638 52 48 (For Cured Weight Material) Density, lb / ft3 Shore Hardness D 35 - 40 10
The mix can be mixed by hand with an instant mixer (3"diameter) at 1,200 rpm.The skimming time of the formulation was approximately 180 seconds, and can be modified by adjusting the process conditions or through the use of additives. The shelf life was about 60 to about 70 minutes, and can be modified by adjusting the process conditions or through the use of additives.The shelf life or storage of Component A (isocyanate) and Component B (resin) can be maximized by keeping materials at a temperature from approximately 18.33 ° C to approximately 29.44 ° C (65 ° F to approximately 85 ° F) Protection from moisture and foreign material is produced by keeping the storage containers tightly closed.
Formulation 3 described in Example 1 is a rigid, two-component, aqueous blown poly-urethane structural material. This material also provides superior performance for applications that require a hard or rough surface, and can also be used as a cost-effective replacement for wood. The parts can easily be molded out of the retaining materials that would otherwise require intensive laboring or turning. The typical physical properties of these are summarized in Table 3. Table 3 TYPICAL PHYSICAL PROPERTIES
(For METHOD of Component A Component E
Components) PROOF 1 00-200 1000-1400
Viscosity, cps ASTM D-2393 B Rookfield LVF, Axis # 2, @ 12 rpm 1 .2 1 .04 Gravity ASTM D- 638 10.0 8.68 specific 52 48 Weight / gal. Lb in weight 50 50 Ratio of in volume mix Ratio of 1 0 (other mix densities also (For Material available) Cured) Density, lbs / ft3
The skimming time of the formulation was approximately 4 seconds, and can be modified by adjusting the process conditions, or through the use of additives. The lifting time was approximately 14 minutes, and can be modified by adjusting the process conditions or through the use of additives. The shelf life or storage of Component A (isocyanate) and Component B (resin) can be maximized by keeping the materials at a temperature from about 18.33 ° C to about 29.4 ° C (65 ° F to about 85 ° F). Protection from moisture and foreign material is produced by keeping the storage containers tightly closed. The flame retardant can be added to the formulation.
EXAMPLE 3 Making an Exemplary PetriFoam ™ As discussed above, the proportion of ingredients in the reaction mixture depends on the desired physical characteristics of the final product and therefore can not be specified in detail without identifying the final application of the material. The process of the invention can be carried out in both batch and continuous mode. The batch mode can be carried out as follows. An amount of porous particulate material (eg, expanded polystyrene beads or polyethylene beads, or polypropylene beads, or mixtures of any two or more thereof) sufficient to overload the mold volume by ten to twelve percent is Place in a mixing tub. A resin (eg, isocyanate reagent) is mixed into the beads with agitation until each individual bead has been substantially coated with the resin. The macroglycol reagent (cure) is then added to the resin / bead mixture and the mixture is continued until the glycol has been distributed evenly throughout the mixture. The polymerization reaction begins with the first addition of the glycol. Preferably, the material moves to the waiting mold, which has been coated with a suitable release agent, in an expeditious manner to ensure sufficient working time to fill all parts of the mold one-fold. After the mold is filled, it is closed to ensure compression of the mixture when the polyurethane mixture generates gas. The mold can be opened after about 10 to about 30 minutes, depending on the nature of the mixture and the article or material prepared. The process can then be repeated to prepare additional articles or materials. A product is usually cured generally in final physical characteristics in approximately twenty-four hours. The curing process can be accelerated by adding additional heat to the liquid forms and / or components. When the formulation of the component is used, the process is substantially the same until the point where the resin has been mixed with the porous particulate material. At that point, a stoichiometric amount of water (to effect curing) was sprayed into the agitated mixture, the final mixture is added to the mold as previously described, and the mold is closed with compression. The preparation of the materials of the invention in continuous mode can be carried out as follows. One or more storage tanks are provided containing a porous particulate material, one or more tanks are provided containing the components of the polymerizable component that generates gas and one or more tanks are provided containing any other components that are incorporated into the finished article. Each of these components is measured and fed to a mixing extruder, either in a single mixing step or in stages (for example, the isocyanate precursor of a polyurethane resin can be mixed with suitable porous particulate material, then added subsequently the polyol at the same). The combined mixture of the components is then supplied to the site where the formation of the material of the invention is desired.
EXAMPLE 4 Performance Properties of the Structural Materials of the Invention The 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 blend (50% by weight / 50% by weight) with carbon black and the added flame retardant. The beads were added to the mold to an excess (115% of the mold volume). These tests were conducted in accordance with American Society for Testing and Materials (ASTM) standards to determine the strength and performance of PetriFoam ™ brand structural materials in terms of compression, bending, tension and shear stress. Additionally, PetriFoam ™ brand structural materials were evaluated for performance characteristics in relation to thermal conductivity, water resistance, exfoliation resistance, fatigue resistance, impact resistance and sound attenuation.
Table 4
* Estimated based on another test
The test results presented in Table 4, and the flexure modulus and the compression test results presented in Fig. 1 0 and 1 1 demonstrate that PetriFoam ™ brand structural materials possess performance characteristics and properties. superiors The primary tests conducted include ASTM 1621, "Compression Test of Plastics Cells Rigid"; and AST 790, "Standard Test Methods for Flexural Properties of Non-Reinforced Plastics and Electrical Insulation". These tests show that PetriFoam ™ brand structural materials often have the compressive strength and flexural strength of most polyurethane foams and styrofoam. Normal polyurethane foams have a compressive strength in the range of 40 psi to 1 00 psi, while typical styrofoam 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 exude conclusively superior materials that can provide exponentially greater strength characteristics than conventional materials.
EJ EM PLO 5 Preparation of Structural Panels Structural panels were prepared that were configured for use with standard parts, rails, channel and other steel parts that provide the rigid reading frame for transporting a cloth or other panel. of office covered in decorative form. Conventional panels are constructed from wood or particulate agglomerates and both surfaces are covered with ASON ITE®, which is completed with the filling and the fabric or other decorative material, depending on the model and decoration of the office. Assembly in all parts is labor intensive and very expensive. Also, boarding is expensive since the finished panels are quite heavy. Any immersion of water from the panel, such as by scrubbing the normal floor, causes the agglomeration of particles to be incrusted and deg radioed. The panels prepared from the materials according to the preferred embodiments exhibit superior water resistance, less weight and can be inserted into conventional structures using conventional fasteners. A mold with adequate interior dimensions was fabricated using a Doug laminated wood the one-inch Fir as the base, two-inch angular steel welded on the sides for the sides and four 1 'x 2' pieces of articulated steel plate in a long dimension of the angular iron to make the upper side of the mold. The free sides of the upper sections were configured to be screwed down against the opposing angular iron to keep the mixture of material placed inside shrunk when polled, expand and cure. The shape of the upper part was expanded with expanded polystyrene beads, and then a small amount of additional beads was added. The beads were then transferred to a vessel and mixed with the Part A urethane using a substantial mixer (a mixer similar to that used to mix mud for interior finishing walls) until the beads were thoroughly wetted with the resin. Part B of the buret was then added, and the resulting mixture mixed for two minutes. The formula used was 48%, Part A with 52% of Part B for the weight of the mixture (corresponding to pearls of 37 ounces, 100 ounces A and 1 15 ounces B). Three panels were prepared.
EXAMPLE 6 Use of Plating Materials A mold with interior dimensions of 12"x 12" x 2"was manufactured.The top and bottom were one-inch-thick Douglas Fir laminated wood of approximately 1 8" squared, with sides comprising 2"x 2" of the substance prepared from the cut substance of 2"x 4". Twelve 3/8"bolts with washers, top and bottom, through the bottom, sides and top of the four corners and the midpoints of the sides, were used to secure the upper part and limit the expansion mixture The spacers were cut from the thin laminated wood of 12"squares, which were placed in the mold to vary the thickness of the final product: 2", 1"and ½ "SC Johnson® Paste Wax was used as the form release agent.Several surface materials were placed in the mold before the mixture was added.The superior adhesion of the coating material to the body of the material was observed for the tested coverings, including acrylic, wood varnish, KEVLAR ™, and wire mesh The half-inch material coated with impregnated KEVLAR ™ was extremely strong and resistant to torsion.The materials can easily accept the gel cover of the type fiber of glass to produce a beautiful surface with a minimum number of covers, especially in a completely dehusked sample.
EXAMPLE 7 Effects of Pearl Size and Incorporation of Surface Materials Different bead sizes and varying amounts of resin were tested to affect different final weights of the sample board. The proportions of components A and B were kept relatively constant in their optimized proportions. Quantitative studies indicate that the smaller the size of the pearl, the stronger the board. Also, increasing the proportion of the total resin regardless of the size of the pearl strengthens the board. The curing times for opening the mold were relatively constant and in thickness of two inches or less, and the heat generated by the exothermic polymerization reaction heated the outside of the wood mold sparingly.
EJ EM PLO 8 Effects of Perl Size and I ncoporation of Surface Materials An 8"x 9" x 9"mold was prepared The mold included a one inch thick spacer inside From the top to allow for easy placement of 1 1 0% by volume or more of the fill in the mold, the optimum amount depends on the size of the bead and the subsequent compression of the mix.The superior insulation characteristic of the material and the heat generated by the exothermic polymerization reaction it caused the "cure until the opening time" to exceed one hour or more.If it opens prematurely, the material was hot, spongy and not imensively stable.Therefore, the greater the thickness of the shorter dimension of the material required for an application, slower the production of the material preferably .To prepare a block of 9"x 9" x 7"material, 1 1 0% of the volume of the beads is added to the mold, together with 21 ounces of u Part A retaining and 20 ounces of Part B urethane. The resulting locker is completely flaked, resulting in increased compression and torsional strength. As those of skill in the art will appreciate based on the detailed descriptions and illustrative examples provided herein, there is a number of known alternatives to the components described and / or illustrated herein, which they may be employed to practice aspects of the present invention, and these are supplemented regularly by the 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 describe various plastic polymers, additives, compounds, 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 Warren 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: Fundamentáis Colorants, Preparations, by Albrecht Muller, 2003; Plastics Flammability Handbook: Principies, 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 Pierre J. Carreau 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 Principies, 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 Ed ard W. Orr, 1998; Plastics and Coatings, by Rose Ryntz, 2001; Advanced Protective Coatings for Manufacturing and Engineering, by Wit Grzesik, 2003; and similar. As those of skill in the art will appreciate based on the detailed descriptions and illustrative examples provided herein, the references cited in the previous section are considered particularly pertinent to the extent that they relate to the components and / or processes as is described or illustrated herein as well as alternatives of such components or processes. The above description describes various methods and materials of the present invention. This invention is susceptible to modifications in methods and materials, as well as alterations in manufacturing methods and equipment. Such modifications will be apparent to those skilled in the art from a consideration of this description or practice of the invention described herein. Accordingly, it is not intended that this invention be limited to the specific embodiments described herein, but this covers all modifications and alternatives that originate within the scope and spirit of the invention as set forth in the claims. Attached All patents, applications and other references cited herein are incorporated herein by reference in their entirety.
Claims (63)
- CLAIMS 1. A structural material, characterized in that it comprises: a porous material, wherein the porous material has a diameter in the range of approximately 0.05 mm to approximately 60 mm, and a pearl density in the range of approximately 0.1 kg / m3 to about 1000 kg / m3, and a polymer, wherein the polymer is repaired 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 that it encapsulates the porous material, and wherein the filaments and other projections that compose the polymer extend into the porous material.
- 2. The structural material according to claim 1, characterized in that the polymerization component comprises a first polymerizable component that is capable of polymerizing within the pores of the porous material, and a second polymerizable component that is capable of binding to the Polymers of the first polymerizable component, either directly or through a linker, wherein the polymerizable components, up to curing, produce a substantially solid matrix which encapsulates and partially penetrates the porous material.
- 3. The structural material according to claim 1, characterized in that 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 two or more thereof.
- 4. The structural material according to claim 1, characterized in that the porous material comprises polystyrene.
- 5. The structural material according to claim 1, characterized in that the porous material comprises expanded polystyrene beads.
- The structural material according to claim 1, characterized in that 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 according to claim 1, characterized in that the polymerizable component is a polyurethane.
- The structural material according to claim 7, characterized in that the polyurethane is prepared from at least one aromatic diisocyanate selected from the group consisting of / n-phenylene diisocyanate, p-phenylene diisocyanate, 4.4-diisocyanate. '-diphenylmethane, 2,4-tolylene diisocyanate, 3,3'-dimethyl-4,4'-biphenylene diisocyanate, diurethane diurenate, diisocyanate of 4,4, -diphenylpropylidene, diisocyanate of 4,4'- diphenylsulfone, 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-butanediol, trimethylolpropane, polyvinyl alcohol, and partially hydrolyzed cellulose acetate.
- 9. The structural material according to claim 1, further characterized in that it comprises at least one additive selected from the group consisting of flow improvers, plasticizers, curing retardants, curing accelerators, strength enhancers, UV protectants, dyes, pigments , fillers and flame retardants.
- 10. The structural material according to claim 1, characterized in that the diameter of the porous material falls in the range of about 0.4 mm to about 5 mm.
- The structural material according to claim 1, characterized in that the porous material is in the range of about 80 to about 99 volume percent of the structural material.
- 12. The structural material according to claim 1, characterized in that the porous material is in the range of about 15% by weight, up to about 40% by weight of the structural material.
- The structural material according to claim 1, characterized in that the compression module of the structural material is at least about 8000 psi.
- The structural material according to claim 1, characterized in that the compression module of the structural material falls in the range of about 8000 psi to about 10,000 psi.
- 15. The structural material according to claim 1, characterized in that the flexural modulus of the structural material is at least about 10,000 psi.
- 16. The structural material according to claim 1, characterized in that the flexural modulus of the structural material falls in the range from about 10,000 psi to about 14,000 psi.
- 17. The structural material according to claim 1, characterized in that the material has a thickness of R value per inch of at least 3.
- The structural material according to claim 1, further characterized in that it comprises one or more structures of reinforcement contained inside.
- 19. The structural material according to claim 18, characterized in that the reinforcing material is selected from the group consisting of natural fibers, synthetic fibers, and combinations of any two or more thereof.
- 20. The structural material according to claim 1, further characterized in that it comprises at least one coating material applied thereto.
- The structural material according to claim 20, characterized in that the coating material is selected from the group consisting of metal, polymer, cloth, glass, ceramic, natural fiber, synthetic fiber, and combinations of any two or more of them.
- 22. The structural material according to claim 20, characterized in that the coating material is selected from the group consisting of a solid surface, a porous surface, a surface that can be chemically attacked, a chemically etched surface, a surface that can be eroded physically, a physically eroded surface, and combinations of any two or more thereof.
- 23. The structural material according to claim 1, characterized in that the structural material does not substantially emit the gas discharge.
- 24. The structural material according to claim 1, characterized in that the matrix is flexible.
- 25. The structural material according to claim 1, characterized in that the matrix is rigid.
- 26. The structural material in accordance with claim 1, characterized in that the structural material is essentially impermeable to water, UV-stable, and substantially resistant to degradation caused by exposure to insects, fungi, moisture and conditions. atmospheric
- 27. A structural material, characterized in that it comprises: a porous material, wherein the porous material has a diameter in the range of about 0.05 mm to about 60 mm, and a bead density in the range of about 0.1 kg / m3 up to approximately 1 000 kg / m3, and a flexible polymer matrix, wherein the polymer matrix is prepared from a polymerizable component that generates gas capable of curing at a temperature below the melting point of the porous material, wherein the matrix The polymer comprises a substantially impenetrable, elastic matrix, providing a dimensionally stable structure, which encapsulates the porous material, and wherein the filaments or other projections comprising the polymer extend into the porous material.
- 28. A material, characterized in that it comprises: a porous material, and a polymer, wherein the polymer comprises a matrix that substantially encapsulates the porous material, wherein the matrix is substantially solid, and wherein the filaments or other projections comprising the polymer extend into the porous material.
- 29. An article having a defined shape, excellent compressive strength and a high flexural modulus, the article is characterized in that it comprises a polymeric matrix containing a porous material evenly distributed substantially through it, wherein the filaments or other projections comprising the polymer extend within the porous material.
- 30. The article according to claim 29, characterized in that the compression module is at least about 8000 psi.
- 31. The article according to claim 29, characterized in that the compression module of the structural material falls in the range of about 8000 psi to about 10,000 psi.
- 32. The article according to claim 29, characterized in that the flexural modulus is at least about 10,000 psi.
- 33. The article according to claim 29, characterized in that the matrix is rigid.
- 34. The article according to claim 33, characterized in that the article is selected from the group consisting of a construction panel, a structural reinforcement, a soundproofing, an insulation, a waterproofing, a counter, a swimming pool, a cover for swimming pool, a slider, a tub with hot water, a tub cover with hot water, a cooling tower, a bathtub, a shower unit, a storage tank, an automotive component, and a personal boat component.
- 35. The article according to claim 29, characterized in that the matrix is flexible.
- 36. The article according to claim 35, characterized in that the article is selected from the group consisting of soundproofing, insulation, waterproofing, an automotive component, furniture filler, and impact absorption barriers.
- 37. A method for making a structural material, the method is characterized in that it comprises: combining the porous material and a polymerizable component, and subjecting the resulting combination in a mold, to conditions suitable for curing the polymerizable component, whereby any gases generated during curing they are substantially absorbed by the porous material, and wherein a portion of the polymerizable component is forced into the porous material, whereby the structural material is produced, wherein the structural material comprises the porous material encapsulated in a polymer matrix substantially solid, and wherein the filaments or other projections comprising the polymer extend at least partially within the porous material.
- 38. The method according to claim 37, characterized in that 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 substantially polymerizes outside the porous material, and wherein the first and second polymerizable components come to bond with each other either directly or through a linker.
- 39. The method according to claim 37, characterized in that the cure is conducted under conditions whereby substantially no foam is generated in the solid polymer matrix.
- 40. The method according to claim 37, characterized in that the combination comprises substantially completely covering a surface of the porous material with a precursor of the polymerizable component.
- 41 The method according to claim 37, characterized in that suitable conditions for allowing the polymerizable component to polymerize comprises adding a polymerizing agent to the combustion of the porous material and the precursor of the polymerizable component.
- 42. The method according to claim 41, characterized in that the combination comprises the porous material, the precursor of the polymerizable component and the polymerizing agent is vibrated after the introduction of the polymerizing agent thereto.
- 43. The method according to claim 37, characterized in that the polymerizable component has a viscosity in the range of about 200 to about 50,000 centipoise.
- 44. The method according to claim 37, characterized in that the polymerizable component is stable at temperatures of at least about 50 ° C.
- 45. The method according to claim 37, characterized in that the gas discharge is not substantially generated until curing.
- 46. The method according to claim 37, further characterized in that it comprises applying a coating to the structural material, wherein the coating is selected from the group consisting of a fire-proof coating, a flame retardant coating, a non-slip coating, a wood coating, an acrylic coating and a woven fabric covering.
- 47. The method according to claim 37, further characterized in that it comprises forming the structural material within a predetermined shape.
- 48. The method according to claim 37, further characterized in that it comprises subjecting the structural material to energy by compression sufficient to reduce a thickness of the structural material.
- 49. The method according to claim 37, further characterized in that it comprises cutting the structural material in a defined manner.
- 50. The method according to claim 37, further characterized in that it comprises piercing a defined shape within the structural material.
- 51. The method according to claim 37, characterized in that at least a portion of the porous material is a recycled (ground) structural material.
- 52. The method according to claim 37, further characterized by comprising grinding and recycling the structural material.
- 53. The method according to claim 37, further characterized in that it comprises subjecting the structural material to at least one chemical attack and one physical attack.
- 54. The method according to claim 37, further characterized by comprising subjecting the structural material to a compression pressure for a sufficient time to increase the compression modulus of the structural material to at least 20,000 psi, and to increase the flexural modulus from the structural material to at least about 1,000,000 psi to approximately 14,000 psi.
- 55. A method for making a structural material, the method is characterized in that it comprises subjecting the combination of a porous material and a polymerizable component that generates gas, in a closed mold, to conditions suitable for removing the polymerizable component that generates gas, whereby the 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, whereby the structural material is produced, wherein the structural material comprises the porous material encapsulated in a solid polymeric matrix, and wherein the filaments or other projections comprising the polymer extend at least partially within the porous material.
- 56. The product produced characterized by the method of any of claims 37 to 55.
- 57. A formulation, characterized in that it comprises: a porous material, a component that generates gas or another unfeasible polymer, and at least one additive selected from the group consisting of flow improvers, plasticizers, curing retardants, cure accelerators, strength improvers, UV protectants, dyes, pigments and fillers, wherein the porous material has a diameter in the range of about 0.05 mm to approximately 60 mm, and a pearl density in the range of approximately 0.1 kg / m3 to approximately 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 material When the component that generates gas or another polymerizable material, in the curing, produces a substantially impenetrable solid matrix, which encapsulates the porous material, and wherein the filaments or other projections comprising the polymer extend at least partially inside the porous material.
- 58. A formulation, characterized in that it comprises: a porous material, and a gas generating component, or another polymerization, wherein the porous material is not expanded polystyrene, and has a diameter in the range of about 0.05 mm to about 60 mm, and a bead density in the range of about 0.1 kg / m3 to about 1000 kg / m3, and wherein the component generating gas and another polymerizable is capable of curing at a temperature below the melting point of the porous material, wherein the component generating gas or other polymerizable material, until curing, produces a substantially impenetrable solid matrix, which encapsulates the porous material, and wherein the filaments or other projections comprising the polymer extend at least partially inside the porous material.
- 59. A formulation, characterized in that it comprises: a porous material, and a gas generating component, or another polymerizable component, wherein the porous material has a diameter in the range of about 0.05 mm to about 60 mm, and a density of pearl in the range of about 0.1 kg / m3 to about 1000 kg / m3, and wherein the component that generates gas or other polymerizable is not a polyurethane, and is capable of curing at a temperature below the melting point of the material porous, wherein the component that generates gas or other polymerizable material, until curing, produces a substantially impenetrable solid matrix which encapsulates the porous material and wherein the fi laments or other projections comprising the polymer extend at least partially inside the porous material.
- 60. A method for modifying an article, characterized in that it comprises a flexible or rigid polymer matrix containing the porous material, substantially distributed uniformly therethrough, wherein the filaments or other projections comprising the polymer are At least partially extending within the porous material, the method comprises applying a fireproof coating thereon, a non-slip coating, a wood coating thereon, an acrylic coating thereon, or a coating of fabric woven in the same.
- 61 A method for modifying an article, characterized in that it comprises a flexible or rigid polymer matrix, containing the porous material, substantially uniformly distributed through the, wherein the filaments or other projections comprising the polymer extend to the less partially within the porous material, the method comprises forming the article in a predetermined manner.
- 62. A method for modifying an article, characterized in that it comprises a rigid polymer matrix containing the porous material substantially evenly distributed therethrough, where the filaments or other projections comprising the polymer extend. at least partially within the porous material, the method comprises subjecting the article to sufficient compressive energy to reduce the thickness of the same.
- 63. A method for modifying an article, characterized in that it comprises a rigid or flexible polymer matrix containing the porous material substantially distributed in an asymmetric manner through the, wherein the filaments or other projections comprising the polymer extend at least partially within the porous material, the method comprises cutting and / or perforating desirable shapes within the article. RES UME N In accordance with the present invention, composite and structural materials have been developed which have superior performance properties, including high compressive strength, high tensile strength, high shear strength, and high weight resistance ratio, and methods to prepare them. The materials of the invention have the added benefits of ease of manufacture, and are short for manufacturing. The superior performance properties of the materials of the invention produce such materials suitable for a wide variety of end uses. For example, a variety of substances can be applied to the materials of the invention without melting, dissolving or de-radaring the basic structure of the same. This facilitates the joining of the materials of the invention to virtually any surface or substrate. In addition, the bond between the materials of the invention and a variety of substrates is exceptionally strong, providing the resulting bonded article suitable for use in a variety of demanding applications. The materials of the invention can be manufactured in a wide variety of sizes, shapes, densities, in multiple and similar layers.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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US38829503A | 2003-03-12 | 2003-03-12 | |
PCT/US2004/007800 WO2004081311A2 (en) | 2003-03-12 | 2004-03-12 | Structural and other composite materials and methods for making same |
Publications (1)
Publication Number | Publication Date |
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MXPA05009617A true MXPA05009617A (en) | 2006-03-21 |
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Family Applications (1)
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MXPA05009617A MXPA05009617A (en) | 2003-03-12 | 2004-03-12 | Structural and other composite materials and methods for making same. |
Country Status (12)
Country | Link |
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EP (1) | EP1611194A2 (en) |
JP (1) | JP2006519908A (en) |
KR (1) | KR20060009234A (en) |
CN (1) | CN1759139A (en) |
AR (1) | AR043604A1 (en) |
AU (1) | AU2004219602A1 (en) |
BR (1) | BRPI0408487A (en) |
CA (1) | CA2518873A1 (en) |
EA (1) | EA200501400A1 (en) |
MX (1) | MXPA05009617A (en) |
TW (1) | TW200500402A (en) |
WO (1) | WO2004081311A2 (en) |
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-
2004
- 2004-03-12 EA EA200501400A patent/EA200501400A1/en unknown
- 2004-03-12 MX MXPA05009617A patent/MXPA05009617A/en unknown
- 2004-03-12 TW TW093106735A patent/TW200500402A/en unknown
- 2004-03-12 WO PCT/US2004/007800 patent/WO2004081311A2/en not_active Application Discontinuation
- 2004-03-12 AU AU2004219602A patent/AU2004219602A1/en not_active Abandoned
- 2004-03-12 CA CA002518873A patent/CA2518873A1/en not_active Abandoned
- 2004-03-12 BR BRPI0408487-0A patent/BRPI0408487A/en not_active Application Discontinuation
- 2004-03-12 JP JP2006507182A patent/JP2006519908A/en active Pending
- 2004-03-12 CN CNA2004800064084A patent/CN1759139A/en active Pending
- 2004-03-12 EP EP04720493A patent/EP1611194A2/en not_active Withdrawn
- 2004-03-12 KR KR1020057016813A patent/KR20060009234A/en not_active Application Discontinuation
- 2004-03-15 AR ARP040100844A patent/AR043604A1/en unknown
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CA2518873A1 (en) | 2004-09-23 |
JP2006519908A (en) | 2006-08-31 |
CN1759139A (en) | 2006-04-12 |
EP1611194A2 (en) | 2006-01-04 |
AU2004219602A1 (en) | 2004-09-23 |
EA200501400A1 (en) | 2006-04-28 |
AR043604A1 (en) | 2005-08-03 |
KR20060009234A (en) | 2006-01-31 |
TW200500402A (en) | 2005-01-01 |
WO2004081311A2 (en) | 2004-09-23 |
BRPI0408487A (en) | 2006-05-02 |
WO2004081311A3 (en) | 2005-04-07 |
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