composite material, and method of forming a composite material

专利摘要:
COMPOSITE MATERIAL, METHOD OF FORMING A COMPOSITE MATERIAL, AND, SYSTEM FOR FORMING AN ELASTOMERIC COMPOSITION THAT CONNECTS THE AGGREGATE A composite material, which comprises aggregate and an elastomeric composition. The elastomeric composition comprises the reaction product of an isocyanate component and an isocyanate reactive component. The isocyanate component comprises a polymeric isocyanate, and, optionally, a prepolymer-isocyanate. The isocyanate-reactive component comprises a hydrophobic polyol and a chain extender having at least two hydroxyl groups and a molecular weight from about 62 to about 220. The chain extender is present in the isocyanate reactive component in an amount from about 1 to about 20 parts, by weight, based on 100 parts, by weight, of the isocyanate reactive component. The aggregate can be rock, fragmented rubber, and / or glass. The composite material has excellent physical properties and can be formed under water, used in various places, and used in various applications, such as for paving, coatings, etc. The methods of forming and using the composite material and systems for forming the elastomeric composition are also exposed.
公开号:BR112012015224B1
申请号:R112012015224-6
申请日:2010-12-21
公开日:2021-03-09
发明作者:David K. Bower；Steven Hicks；Melissa Terry；Calvin T. Peeler
申请人:Basf Se；
IPC主号:

专利说明:

CROSS REFERENCE TO RELATED REQUESTS
[1] This application claims the benefit of Provisional Patent Application U.S Serial No. 61 / 288,637, filed on December 21, 2009, which is incorporated by reference, in its entirety, by reference. FIELD OF THE INVENTION
[2] The present invention relates to a composite material, which comprises an aggregate and an elastomeric composition, and more specifically to a composite material, which comprises aggregate and an elastomeric composition, which comprises an isocyanate component comprising an isocyanate polymeric and, optionally, a prepolymer-isocyanate, and the elastomeric composition further comprising an isocyanate-reactive component, comprising a hydrophobic polyol and a chain extender, and methods and systems, which employ the same. DESCRIPTION OF RELATED TECHNIQUE
[3] The use of composite materials to form articles, such as paving, is generally known in the construction technique. In general, the composite material is produced by mixing at least one aggregate and at least one binder composition together. For example, in the case of concrete, the aggregate comprises sand and gravel, and the binder composition comprises cement and water.
[4] Recently, there have been advances in the use of polymeric materials as binder compositions. In general, once the aggregate and binder composition are mixed together, the composite material remains foldable or "workable" for a short period of time, for example, 45 minutes, before the composite material is cured and is no longer foldable. In this way, such composite materials are typically produced on-site, as opposed to off-site, in order to increase the period of time in which they can be worked. Off-site production requires the composite material to be transported to a construction site, thereby further reducing the period of time that the composite material can be worked, once on site.
[5] Conventional methods of producing composite materials on site require the aggregate to be placed on the ground (or already present on the ground), before it is brought into contact with the binder composition. Subsequently, the aggregate is sprayed (or laminated) with the binder composition. A significant disadvantage of such a method is an inconsistent coating of the aggregate, which creates inconsistencies in the composite material. Inconsistencies in the composite material can result in an early failure of the composite material, thus requiring the composite material to be replaced, at an additional cost. In addition, such methods are time-consuming. A common form of failure of the composite material is the formation of chips, in which the aggregate is detached from the composite material, eventually being completely dislodged from the composite material.
[6] Alternatively, the aggregate and the coating composition are treated in a drum, in a batch mixer, for several minutes, until the aggregate is uniformly coated with the coating composition, before it is placed in the such that by pouring the composite material in place. A significant disadvantage of this process, commonly referred to as a batch process, is again the reduced working time, since the binder composition immediately begins to cure, once present in the batch mixer.
[7] In addition to paving, other forms of articles, formed from composite materials, include coatings. Coatings are an option for minimizing the threats faced by coastal areas, such as erosion threats. Conventional coatings typically comprise rock, wood, cement, sandbags, and / or masonry. The aforementioned coverings are disposed on the ground, thereby separating the soil mass from a coastal area. The coverings are used in a way to absorb energy from the waves and to prevent erosion of the soil mass. Erosion can come from natural wave cycles, tropic storms, tsunamis, tides, floods, rising sea levels, etc.
[8] A conventional coating form is produced by crushing rocks, mixing the crushed rocks with an isocyanate and a polyol to form a reaction mixture, and subsequently arranging the reaction mixture over a coastal area. The mixing stage covers the crushed rocks with isocyanate and polyol. A reaction then takes place between the isocyanate and the polyol, in order to form a polyurethane reaction product with the crushed rock dispersed in it. After a sufficient period of time for curing, a composite material is formed, which is suitable for use as a coating.
[9] Unfortunately, there are significant disadvantages with respect to the aforementioned method and the coating formed on it. A significant disadvantage is that a competitive reaction between water and the isocyanate weakens the cohesion between the polyurethane reaction product and the crushed rock in the composite material. In this way, it is necessary to cure the composite material in the absence of water, in order to give the composite material sufficient strength and durability so that it can function as the coating. This limitation prevents the composite material from being cured at high tide, or in an alternative way, measures must be taken so that the water is removed from the coastal area, before the composite material is disposed over it. Such measures are expensive, time consuming, and bulky. A common problem concerns the formation of bubbles or foam in or on the polyurethane reaction product, which leads to premature failure of the composite material. Foaming weakens the polyurethane reaction product, thereby increasing the chance of splintering of the aggregate from the composite material.
[10] In this way, there remains an opportunity to provide an improved system for the formation of an elastomeric composition, which can be applied to the aggregate. There is also an opportunity for improved methods of forming elastomeric compositions and composite materials formed from them. SUMMARY OF THE INVENTION AND ADVANTAGES
[11] The present invention provides a composite material. The composite material comprises aggregate and an elastomeric composition. The elastomeric composition comprises the reaction product of an isocyanate component and an isocyanate reactive component. The isocyanate component comprises a polymeric isocyanate and, optionally, a prepolymer-isocyanate. The isocyanate-reactive component comprises a hydrophobic polyol and a chain extender having at least two hydroxyl groups and a molecular weight from about 62 to 220. The chain extender is present in the isocyanate reactive component in an amount of a from about 1 to about 20 parts, by weight, based on 100 parts, by weight, of the isocyanate reactive component.
[12] The present invention further provides a method of forming the composite material. The method comprises the stages of providing the aggregate and forming the elastomeric composition. The method further comprises the stage of application of the elastomeric composition to the aggregate, in order to form the composite material.
[13] The present invention additionally provides a system for forming the elastomeric composition, which binds the aggregate. The system comprises the isocyanate component and the isocyanate reactive component. The isocyanate component of the system typically comprises the prepolymer-isocyanate and the polymeric isocyanate. The prepolymer-isocyanate is present in the isocyanate component in an amount of from about 25 to about 75 parts, by weight, based on 100 parts, by weight, of the isocyanate component.
[14] The present invention additionally provides a method of repairing a pavement. The paving has an external surface with a repairable vacuum. The method comprises the stages of disposing a quantity of composite material inside the repairable vacuum, and, optionally, on the pavement next to the repairable vacuum, in order to form a mound. The method may optionally include the stage of removing any residues from the repairable vacuum. The method further comprises the stage of compacting the mound, in order to form a repair structure for the repairable vacuum. The repair structure has a repair surface substantially parallel to the outer surface of the pavement.
[15] The elastomeric composition has excellent physical properties, which are imparted to the composite material, such that the improved bond strength between the elastomeric composition and the aggregate, improved compressive strength, improved shear strength, and improved flexural strength, which reduces splintering of the aggregate from the composite material. The elastomeric composition has excellent curing properties, which allows it to be used in various places and for various applications, such as for the formation of coatings and for the paving of the composite material. The composite material can be formed in the presence of water, such that it is formed while partially or completely submerged under water. As such, the composite material can be used for minimizing and / or preventing erosion of various areas, such as coastal areas. Other forms of the composite material, such as paving, can be either porous or non-porous, thereby reducing water runoff and other problems associated with conventional paving and similar structures. BRIEF DESCRIPTION OF THE DRAWINGS
[16] Other advantages of the present invention will be readily appreciated, as it becomes better understood by reference to the following detailed description, when considered in connection with the accompanying drawings, in which:
[17] Figure 1 is a partial cross-sectional view of a paving structure, which illustrates the migration of water through the paving structure, the paving structure including an upper layer, formed of composite material.
[18] Figure 2 is an enlarged view, which illustrates a porous modality of the composite material;
[19] Figure 3 is an enlarged view, which illustrates a non-porous modality of the composite material;
[20] Figure 4 is a bar graph, which illustrates the results of crushing resistance between the treated and untreated aggregates; and
[21] Figure 5 is a graphical representation, which illustrates the results of Dynamic Mechanical Analysis (DMA) of a composite material. DETAILED DESCRIPTION OF THE INVENTION
[22] The present invention provides a system for forming an elastomeric composition, which binds the aggregate. The system comprises an isocyanate component and an isocyanate reactive component. In certain embodiments, the isocyanate component comprises a polymeric isocyanate and, optionally, a prepolymer-isocyanate. In still other embodiments, the isocyanate component comprises the polymeric isocyanate and the prepolymer-isocyanate. The isocyanate-reactive component comprises a hydrophobic polyol and a chain extender. Typically, the system is provided with two or more distinct components, such as the isocyanate component and the isocyanate reactive component (or resin), that is, as a two component system (or 2C), which is additionally Described below.
[23] It should be appreciated that the reference to the resin and isocinate components, as used herein, refers only to the purpose of establishing a reference point for the placement of the individual components of the system, and to establish a part, in a weight basis. As such, it should not be construed as limiting the present invention to a 2C system only. For example, the individual components of the system can be kept separate from each other. The terminology component "reactive to isocyanate" and "resin component" is interchangeable in the description of the present invention.
[24] The system may also comprise additional components, which may be included with one or both of the resin and isocyanate components, or completely separate, such as a third component, as further described below. The system is used to form the elastomeric composition. In certain embodiments, the elastomeric composition is the product of the ratio of isocyanate and isocyanate-reactive components. The elastomeric composition is further described below.
[25] If used, the prepolymer-isocyanate is generally the product of the reaction of an isocyanate and a polyol and / or a polyamine, typically the product of the reaction of an isocyanate and a polyol. The prepolymer-isocyanate can be formed by various methods understood by those skilled in the art, or it can be obtained commercially from a manufacturer, a supplier, etc.
[26] With respect to the isocyanate used to form the prepolymer-isocyanate, the isocyanate includes one or more isocyanate functional groups (NCO), typically at least two NCO functional groups. Suitable isocyanates, for the purposes of the present invention, include, but are not limited to, conventional aliphatic, cycloaliphatic, aryl and aromatic isocyanates. In certain embodiments, the isocyanate is selected from the group of diphenyl methane diisocyanates (MDIs), polymeric diphenyl methane diisocyanates (PMDIs), and combinations thereof. Polymeric diphenyl methane diisocyanates are also referred to in the art as polymethylene polyphenylene polyisocyanates. Examples of other suitable isocyanates, for the purposes of the present invention, include, but are not limited to, toluene diisocyanates (TDIs), hexamethylene diisocyanates (HDIs), isophorone diisocyanates (IPDIs), naphthalene diisocyanates (NDIs), and combinations thereof. Typically, the isocyanate used to form the prepolymer-isocyanate comprises diphenyl methane diisocyanate (MDI).
[27] If used to form the prepolymer-isocyanate, the polyol includes one or more hydroxyl (OH) functional groups, typically at least two OH functional groups. The polyol can be any type of polyol known in the art. The polyol is typically selected from the group of ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butane diol, glycerol, trimethylol propane, triethanol amine, pentaerythritol, sorbitol and combinations thereof. Other suitable polyols, for the purposes of the present invention, are described below with the description of an optional, additional component, a supplementary polyol.
[28] The polyol can be used in various amounts related to the isocyanate, as long as an excess of NCO functional groups relative to the OH functional groups are present before the reaction, in such a way that the prepolymer-isocyanate, after formation , include NCO functional groups, for the subsequent reaction. The prepolymer-isocyanate typically has an NCO content of from about 18 to about 28, even more typically from about 20 to about 25, and even more typically about 22.9% by weight.
[29] If used to form the prepolymer-isocyanate, the polyamine includes one or more amine functional groups, typically at least two functional amine groups. The polyamine can be any type of polyamine, known in the art. Polyamine is typically selected from the group of ethylene diamine, toluene diamine, diamine diphenyl methane and polymethylene polyphenylene polyamines, amino alcohols, and combinations thereof. Examples of suitable amino alcohols include ethanol amine, diethanol amine, triethanol amine, and combinations thereof.
[30] The polyamine can be used in various amounts related to the isocyanate, as long as an excess of NCO functional groups relative to the amine functional groups, are present before the reaction, in such a way that the prepolymer-isocyanate, after formation , include NCO functional groups, for the subsequent reaction. The NCO content of the prepolymer-isocyanate is as described and exemplified above.
[31] It should be appreciated that the prepolymer-isocyanate can be formed from a combination of two or more of the aforementioned polyols and / or two or more of the aforementioned polyamines. Typically, the prepolymer-isocyanate is a product of the reaction of the isocyanate and at least one polyol, in such a way that the prepolymer-isocyanate includes urethane bonds and NCO functional groups after formation. In a specific embodiment of the present invention, the prepolymer-isocyanate comprises a mixture of polymeric methyl diphenyl diisocyanate and 4,4'-methyl diphenyl diisocyanate quasi prepolymers. Specific examples of suitable isocyanate prepolymers, for the purposes of the present invention, are commercially available from BASF Corporation of Florham Park, NJ, under the trademark LUPRANATE®, such as LUPRANATE® MP102. It should be appreciated that the system can include a combination of two or more of the aforementioned prepolymer-isocyanates.
[32] With respect to the polymeric isocyanate, the polymeric isocyanate includes two or more NCO functional groups. The polymeric isocyanate typically has an average functionality from about 1.5 to about 3.0, more typically from about 2.0 to about 2.8, and even more typically about 2.7. The polymeric isocyanate typically has an NCO content of from about 30 to about 33, more typically from about 30.5 to about 32.5, and even more typically about 31.5% by weight.
[33] Suitable polymeric isocyanates, for the purposes of the present invention, include, but are not limited to, the isocyanates described and exemplified above, for the description of the prepolymer-isocyanate. Typically, the polymeric isocyanate comprises polymeric diphenyl methane diisocyanate (PMDI).
[34] Specific examples of suitable polymeric isocyanates, for the purposes of the present invention, are those commercially available from BASF Corporation, under the trademark LUPRANATE®, such as the LUPRANATE® M20 Isocyanate. It should be appreciated that the system may include a combination of two or more of the aforementioned polymeric isocyanates.
[35] The prepolymer-isocyanate is typically present in the isocyanate component in an amount from about 25 to about 75, more typically from about 50 to about from 75, and even more typically from about 55 to about 65, and even more typically from about 60, parts by weight, each based on 100 parts, by weight, of the isocyanate component. In certain embodiments, the prepolymer-isocyanate is typically present in the system in an amount from about 50 to about 250, even more typically from about 100 to about 200, and even more typically from about 125 to about 175, and even more typically about 150, parts by weight, each per 100 parts, by weight, of the polymeric isocyanate in the system . In said other mode, the prepolymer-isocyanate and the polymeric isocyanate are present in the system, in a typical manner, for example, in the isocyanate component, in a ratio, by weight, from about 1: 2 to about 2.5: 1, more typically from about 1: 1 to about 2: 1, and even more typically from about 1.25: 1 to 1.75: 1, and even more so most typical of about 1.5: 1.
[36] Without being bound or limited by any particular theory, it is believed that the combination and reasons of the prepolymer-isocyanate and the polymeric isocyanate, as described and exemplified immediately above, give the elastomeric composition with increased tensile strength , elongation, hardness, and glass transition temperature, as well as improved resistance to rupture, in relation to conventional elastomeric compositions.
[37] With respect to the hydrophobic polyol, the hydrophobic polyol includes one or more OH functional groups, typically at least two OH functional groups. The hydrophobicity of the hydrophobic polyol can be determined by several methods, such as through visual inspection of the product of the reaction of the hydrophobic polyol with the isocyanate, in which the reaction product was immediately degassed after mixing the two components and then introduced into water , where the reaction product is allowed to cure. If there is no evidence of damage or wrinkling at the interface (or surface) between the reaction product and water, or if there is no evidence of bubble or foam formation, the hydrophobicity of the hydrophobic polyol is considered to be excellent.
[38] The hydrophobic polyol typically comprises a natural oil polyol (NOP). In other words, the hydrophobic polyol is not typically a petroleum-based polyol, that is, a polyol derived from petroleum products and / or petroleum by-products. Generally speaking, there are only a few naturally occurring vegetable oils, which contain unreacted OH functional groups, and castor oil is typically the only commercially available NOP produced directly from a source of plant, which has sufficient OH functional group content to produce castor oil for direct use as a polyol in urethane chemistry. Most, if not all, other NOPs require chemical modification of oils directly available from plants. NOP is typically derived from any natural oil known in the art, typically derived from vegetable or chestnut oil. Examples of suitable natural oils, for the purposes of the present invention, include castor oil, and NOPs derived from soybean oil, rapeseed oil, coconut oil, peanut oil, canola oil, etc. The use of natural oils can be useful for reducing environmental footprints.
[39] Typically, as alluded to above, the hydrophobic polyol comprises castor oil. Those skilled in the art will appreciate that castor oil inherently includes OH functional groups, while other NOPs may require one or more additional processing stages to obtain OH functional groups. Such processing stages, if necessary, are understood by those skilled in the art. Suitable grades of castor oil, for the purposes of the present invention, are available from a variety of suppliers. For example, T31® Castor Oil, from Eagle Specialty Products (ESP) Inc, from St. Louis, MO, can be used as the hydrophobic polyol. Specific examples of other suitable hydrophobic polyols, for the purposes of the present invention, are commercially available from Cognis Corporation of Cincinnati, OH, under the trademark SOVERMOL®, such as SOVERMOL® 750, SOVERMOL® 805, SOVERMOL® 1005, SOVERMOL® 1080 , and SOVERMOL® 1102.
[40] The hydrophobic polyol is typically present in the system in an amount of from about 80 to about 99, more typically from about 85 to about 95, still most typical of about 90 to about 95, and even more typically of about 92.5 parts by weight, each based on 100 parts by weight of the resin component of the system. It should be appreciated that the system may include a combination of two or more of the hydrophobic polyols mentioned above.
[41] With respect to the chain extender, the chain extender has at least two OH functional groups. The chain extender typically has a molecular weight of from about 62 to about 220, more typically of about 62 to about 150, and even more typically of about 132. As such, the chain extender can be referred to in the art as a "short" chain extender. The chain extender typically comprises an alkylene glycol. Examples of suitable chain extenders for the purposes of the present invention include dipropylene glycol (DPG), diethylene glycol (DEG), NIAX® DP-1022, 1,3-propanediol, 1,4-butane diol, 1,5- pentane diol, 1,5-hexane diol, and 2-butene-1,4-diol. In a specific embodiment, the chain extender is dipropylene glycol.
[42] The chain extender is typically present in the system in an amount from about 1.0 to about 20, more typically from about 5.0 to about 10, and even more typically about 7, parts by weight, each based on 100 parts, by weight, of the resin component. It should be appreciated that the system can include any combination of two or more of the aforementioned chain extenders.
[43] Without being bound by, or limited by, any particular theory, it is believed that the chain extender provides increased resistance to the elastomeric composition, as well as increased strength, resistance to breakage and hardness to the elastomeric composition.
[44] In still other embodiments of the present invention, a supplementary polyol, such as a petroleum-based polyol, can be used in addition to the hydrophobic polyol. If used, the supplementary polyol is typically selected from the group of conventional polyols, such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butane diol, glycerol, trimethylol propane, triethanol amine, pentaerythritol, sorbitol and combinations thereof. Typically, the supplementary polyol is selected from the group of polyether polyols, polyester polyols, polyether / ester polyols, and combinations thereof; however, other supplemental polyols can be employed, as further described below.
[45] Polyether polyols suitable for the purposes of the present invention include, but are not limited to, products obtained through the polymerization of a cyclic oxide, for example ethylene oxide (EO), propylene oxide (PO), oxide of oxide butylene (BO) or tetrahydrofuran, in the presence of polyfunctional initiators. Suitable initiator compounds contain a plurality of active hydrogen atoms, and include water, butane diol, ethylene glycol, propylene glycol (PG), diethylene glycol, triethylene glycol, dipropylene glycol, ethanol amine, diethanol amine, triethanol amine, toluene diamine, diethyl toluene diamine, phenyl diamine, diphenyl methane diamine, ethylene diamine, cyclohexane diamine, cyclohexane dimethanol, resorcinol, bisphenol A, glycerol, trimethylol propane, 1,2,6-hexanotriol, pentaerythritol, and combinations thereof.
[46] Other suitable polyether polyols include polyether diols and triols, such as polyoxypropylene diols and triols and poly (oxyethylene-oxypropylene) diols and triols, obtained by the simultaneous or sequential addition of ethylene and propylene oxides to di- or trifunctional. Copolymers having oxyethylene content from about 5 to about 90% by weight, based on the weight of the polyol component, of which the polyols can be block copolymers, random / block copolymers or random copolymers, can also be used. Still other suitable polyether polyols include polytetramethylene glycols, obtained through the polymerization of tetrahydrofuran.
[47] Suitable polyester polyols, for the purposes of the present invention, include, but are not limited to, hydroxyl-terminated reaction products of polyhydric alcohols, such as ethylene glycol, propylene glycol, diethylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, cyclohexane dimethanol, glycerol, trimethylol propane, pentaerythritol or polyether polyols or mixtures of such polyhydric alcohols, and polycarboxylic acids, in particular dicarboxylic acids or their ester-forming derivatives, for example, succinic, glutaric and adipic acids and their dimethyl esters, sebacic acid, phthalic anhydride, tetrachlorophthalic anhydride or dimethyl terephthalate, or mixtures thereof. Polyester polyols, obtained through the polymerization of lactones, for example, caprolactone, in conjunction with a polyol, or hydroxy carboxylic acids, for example, hydroxy hydroxy acid, can also be used.
[48] Suitable polystyrene polyols, for the purposes of the present invention, can be obtained through the inclusion of amino alcohols, such as ethanol amine in polyesterification mixtures. Polythioether polyols suitable for the purposes of the present invention include products obtained by condensing thiodiglycol, either alone, or with other glycols, alkylene oxides, dicarboxylic acids, formaldehyde, amino alcohols, or amino carboxylic acids. Polycarbonate polyols suitable for the purposes of the present invention include products obtained by reacting diols, such as 1,3-propane diol, 1,4-butane diol, 1,6-hexane diol, diethylene glycol or tetraethylene glycol with diaryl carbonates, for example, diphenyl carbonate, or with phosgene. Suitable polyacetal polyols, for the purposes of the present invention, include those prepared by reacting glycols, such as diethylene glycol, triethylene glycol or hexanediol with formaldehyde. Other suitable polyacetal polyols can also be prepared by polymerizing cyclic ketals. Suitable polyolefin polyols, for the purposes of the present invention, include hydroxy-terminated butadiene, homo- and copolymers and suitable polysiloxane polyols include polydimethyl siloxane diols and triols.
[49] Specific examples of suitable supplemental polyols for the purposes of the present invention are commercially available from BASF Corporation under the PLURACOL® trademark, such as the PLURACOL® GP series polyols. A specific example of a suitable supplement polyol, for the purposes of the present invention, is PLURACOL® GP 430.
[50] If used, the supplementary polyol is typically present in the system in an amount from about 1 to about 75, more typically from about 10 to about 50, and even more typically about 40, parts by weight, each based on 100 parts, by weight, of the resin component of the system. It should be appreciated that the system can include any combination of two or more of the aforementioned supplemental polyols.
[51] The system may also include one or more additional components, such as an additive component, in addition to or in an alternative way to the supplementary polyol. The additive component can comprise any conventional additive known in the art. Suitable additives, for the purposes of the present invention, include, but are not limited to, chain extenders, crosslinkers, chain terminators, processing additives, adhesion promoters, flame retardants, antioxidants, foam suppressants, antifreeze agents. foaming, water sweepers, molecular sieves, silica pyrogens, ultraviolet light stabilizers, filters, thixotropic agents, silicones, surfactants, catalysts, colorants, inert diluents and combinations thereof. If used, the additive component can be included in the system in any amount, such that from about 0.05 to 10 parts by weight, based on 100 parts by weight of the resin component of the system.
[52] In certain embodiments, the additive component comprises a foaming agent. In one embodiment, the anti-foaming agent comprises a silicone fluid, which includes a pulverized silica dispersed therein. The silicone fluid can be used to reduce and / or eliminate foaming of the elastomeric composition. It should be appreciated that the silicone fluid can be predisposed in a solvent. Examples of anti-foaming agents include Antifoam MSA and Antifoam A, commercially available from Dow Corning of Midland, MI.
[53] If used, the foaming agent is typically present in the system in an amount from about 0.01 to about 0.10, more typically than from about 0.025 to about 0.075, and even more typically about 0.05, parts by weight, each based on 100 parts, by weight, of the resin component of the system. It should be appreciated that the system can include any combination of two or more of the aforementioned foaming agents.
[54] In certain embodiments, the additive component comprises a molecular sieve. The molecular sieve is a hygroscopic agent, which can be used to maintain or to increase desiccation, that is, a state of dryness. The molecular sieve typically comprises molecules having a plethora of small pores. The small pores allow the molecules to be smaller in size than the pores, such as the water molecules, to be adsorbed, while the larger molecules, such as those present in the isocyanate and resin component, cannot be adsorbed. Typically, the molecular sieve can adsorb water up to, and in excess of, 20%, by weight, of the molecular sieve. The molecular sieve, therefore, can act in a synergistic way and in accordance with the hydrophobic polyol, in a way to minimize the effect of water on the elastomeric composition, through the adsorption of water, before the water has a chance to react with the isocyanate component of the system.
[55] If used, it should be appreciated that the molecular sieve known in the art can be used, such as aluminosilicate minerals, clays, porous glasses, microporous coals, zeolites, active coals, or synthetic compounds, which have open structures, through of which small molecules, for example water, can be diffused. Examples of suitable molecular sieves include Baylith Paste and Molecular Sieve 3A, which are available and from a variety of suppliers, such as Zeochem, from Louisville, KY.
[56] If used, the molecular sieve is typically present in the system in an amount from about 0.01 to about 5.0, more typically from 0, 10 to about 2.0, and even more typically about 0.50, parts by weight, each based on 100 parts, by weight, of the resin component of the system. It should be appreciated that the system can include any combination of two or more of the molecular sieves mentioned above.
[57] In certain embodiments, the additive component comprises Pyrogenic Silica, which is available from a variety of suppliers. An example of a suitable Pyrogenic Silica is AEROSIL® R-972, commercially available from Evonic Industries Inc. of Essen, Germany. Pyrogenic Silica acts, in general, as a rheology control agent, and, if Pyrogenic Silica is hydrophobic, it imparts additional hydrophobicity to the elastomeric composition.
[58] If used, Silica Pyrogen is typically present in the system in an amount from about 0.10 to about 10.0, more typically from about 1.0 to about 7.0, and even more typically about 5.0 parts by weight, each based on 100 parts, by weight, of the resin component of the system. It is appreciated that the system may further include any combination of two or more silica pyrogens.
[59] In certain embodiments, the additive component comprises a colorant. The colorant can be selected from the group of pigments, dyes, and combinations thereof. The dye can be either in liquid or powder form. If used, the dye is typically a pigment or a pigment combination of two or more pigments. The pigment, or combination of pigments, is used in order to impart a desired color to the elastomeric composition and, if the pigment is inorganic, the pigment can also provide UV protection to the elastomeric composition.
[60] Different types of pigments can be used for the purposes of the present invention. For example, titanium dioxide can be used to impart a white color and carbon black can be used to impart a black color to the elastomeric composition, respectively, while various mixtures of titanium dioxide and black Smoke can be used to impart various shades of gray to the elastomeric composition.
[61] Examples of suitable grades of carbon black and titanium dioxide for the purposes of the present invention are commercially available from Columbian Chemicals Company of Marietta, GA, and DuPont® Titanium Technologies of Wilmington, DE, respectively. Other pigments include, but are not limited to, red, green, blue, yellow, green and brown and mixtures of pigments thereof can also be used to impart color to the elastomeric composition, in addition to, or as an alternative to, black. smoke and / or titanium dioxide.
[62] More specific examples of colors, based on one or more colorants, include sapphire blue, jade green, Sedona red, amber brown, and topaz brown. Examples of suitable classes of pigments for the purposes of the present invention are commercially available from several companies, such as BASF Corporation and Penn Color, Inc. of Hatfield, PA. It should also be appreciated that various mixtures of the aforementioned colorants, for example, pigments, can be used to impart various colors, concentrations and hues to the elastomeric composition.
[63] If used, the colorant is typically present in the system in an amount from about 0.10 to about 5.0, more typically from about 1 0.0 to about 3.0, and even more typically about 2.0 parts by weight, each based on 100 parts by weight of the resin component of the system. It should be appreciated that the system can include any combination of two or more of the aforementioned colors.
[64] In certain embodiments, the additive component comprises a catalyst component. In one embodiment, the catalyst component comprises a tin catalyst. Suitable tin components, for the purposes of the present invention, include the tin (II) salts of organic carboxylic acids, for example, tin (II) acetate, tin (II) octoate, tin (II) ethyl hexanoate and tin (II) laurate. In one embodiment, the metal organo catalyst comprises dibutyl tin dilaurate, which is a dialkyl tin (IV) salt of an organic carboxylic acid. Specific examples of a suitable organo-metallic catalyst, for example, dibutyl tin dilaurates, for the purposes of the present invention, are commercially available from Air Products and Chemicals, Inc. of Allentown, PA, under the trademark DABCO®. The organo-metallic catalyst may also comprise other dialkyl tin (IV) salts of organic carboxylic acids, such as dibutyl tin diacetate, dibutyl tin maleate and dioctylt tin diacetate.
[65] Examples of other suitable catalysts, for the purposes of the present invention, include amine-based catalysts, bismuth-based catalysts, nickel-based catalysts, zirconium-based catalysts, zinc-based catalysts, catalysts based on aluminum based, lithium based catalysts, iron (II) chloride, zinc chloride; lead octoate; tris (dialkylaminoalkyl) -s-hexahydrotriazines, which include tris (N, N-dimethylaminopropyl) -s-hexahydrotriazine; tetraalkyl ammonium hydroxides including tetramethyl ammonium hydroxide; alkali metal hydroxides including sodium hydroxide and potassium hydroxide; alkali metal alkoxides including sodium methoxide and potassium isopropoxide; and alkali metal salts of long-chain fatty acids having 10 to 20 carbon atoms and / or OH side groups.
[66] Other examples of suitable catalysts, specifically trimerization catalysts, for the purposes of the present invention, include N, N, N-dimethylaminopropyl hexahydrotriazine, potassium, potassium acetate, N, N, N-trimethyl isopropyl amine / formate, and combinations thereof. A specific example of a suitable trimerization catalyst is commercially available from Air Products and Chemicals, Inc., under the trademark POLYCAT®.
[67] Still other examples of other suitable catalysts, specifically tertiary amine catalysts, for the purposes of the present invention, include 1-methyl imidazole, DABCO 33-LV dimethylaminoethanol, dimethylaminooxyethanol, triethylamine, N, N, N ', N'- tetramethylethylene diamine, N, N-dimethylaminopropylamine, N, N, N ', N', N ”- pentamethyldipropylenetriamine, tris (dimethylaminopropyl) amine, N, N-dimethylpiperazine, tetramethylimino-bis (propylamine), dimethylamine triethanolamine, N, N-diethyl ethanolamine, N-methyl pyrrolidone, N-methylmorpholine, N-ethylmorpholine, bis (2-dimethylamino-ethyl) ether, N, N-dimethylcyclohexylamine (DMCHA), N, N, N ', N' , N ”- pentamethyldiethylenetriamine, 1,2-dimethylimidazole, 3- (dimethylamino) propyl imidazole, and combinations thereof. Specific examples of suitable tertiary amine catalysts are commercially available from Air Products and Chemcials, Inc., under the trademark POLYCAT®, for example POLYCAT® 41.
[68] If used, the catalyst component can be used in various quantities. Typically, the catalyst component is used in an amount, which can ensure an adequate working / open time period. It should be appreciated that the catalyst component can include any combination of the aforementioned catalysts.
[69] The system can be supplied to consumers for use through various means, such as in rail cars, tanks, large drums and smaller containers or drums, kits and packaging. For example, one kit can contain the isocyanate component and another kit can contain the resin component. Providing the system components to consumers separately provides increased formulation flexibility for the elastomeric compositions formed from them. For example, a consumer may select a specific isocyanate component and a specific resin component, and / or amounts thereof, so that an elastomeric composition is prepared.
[70] The isocyanate and resin components typically have excellent storage stability or “free” stability. As such, the isocyanate and resin components can be stored separately (like the system) for extended periods of time, before they are combined, in order to form the elastomeric composition. It should be appreciated that the system can comprise two or more different isocyanate components and / or two or more different resin components, which can be employed in order to prepare the elastomeric composition. It should also be appreciated that other components (for example, the supplementary polyol, the additive component, etc.), if used, can be supplied in the aforementioned isocyanate and / or resin components, or supplied as separate components.
[71] The present invention further provides a composite material. The composite material comprises the aggregate and the elastomeric composition. The elastomeric composition is generally formed from isocyanate and resin components, as described and exemplified above. As introduced above, in certain embodiments, the isocyanate component comprises the polymeric isocyanate and, optionally, the prepolymer-isocyanate. In still other embodiments, the isocyanate component comprises the polymeric isocyanate and the prepolymer-isocyanate. The isocyanate-reactive component comprises the hydrophobic polyol and the chain extender.
[72] The amount of elastomeric composition, present in the composite material, depends, in general, on the particle size of the aggregate. Typically, the larger the particle size of the aggregate, the less elastomeric composition is required to form the composite material, and the smaller the size of the aggregate, the more elastomeric composition will be required for the composite material to be formed. The smaller aggregate generally requires more elastomeric composition, because there is a larger surface area to be coated, compared to the larger aggregate. For example, in the case of a 0.25 inch (0.635 cm) aggregate, the elastomeric composition is typically present in the composite material, in an amount from about 1.0 to about 10, 0, even more typically from about 2.5 to about 5.0, and even more typically, from 4.2 parts by weight, each based on 100 parts by weight, of the wax. composite material.
[73] As used here, the term aggregate should be interpreted as referring to an aggregate or aggregates, in general, and not to a single aggregate, nor should it be constructed in a way that requires more than one aggregate. In addition, the term aggregate, as used herein, is intended to cover a wide category of materials, which serves as reinforcement for the composite material, such as rock, glass, fragmented rubber, architectural stone, etc. The term rock, as used herein, is intended to cover all forms of rocks, including, but not limited to, gravel, sand, etc. In addition, the term rock, as used here, is intended to cover all types of rock, such as granite, limestone, marble, etc.
[74] In certain embodiments, the aggregate comprises rock. It must be appreciated that any type of rock can be used. The rock is selected, in a typical way, from the group of granite, limestone, marble, beach stone, river rock, and combinations thereof. In a specific modality, the rock is granite.
[75] The rock is typically present in the aggregate in an amount from about 1 to about 100, more typically from about 50 to about 100, even more more typical of about 90 to about 100, and even more typically of about 100, parts by weight, each based on 100 parts, by weight, of the aggregate in the composite material. The rest of the aggregate, if any, can be another different aggregate, such as sand, gravel, etc.
[76] The average diameter of the rock is typically about 0.001 in. (0.00254 cm) at about 7.0 in. (17.78 cm), more typically about 0.10 in. (0.254 cm) at about 5.0 in. (12.7 cm), and even more typically about 0.25 in. (0.635 cm) at about 5.0 in. (12.7 cm), and even more typically about 0.5 in. (1.27 cm) at about 3.0 in. (7.62 cm). In still other modalities, the rock may be larger or smaller.
[77] In certain embodiments, the aggregate comprises fragmented rubber. It should be appreciated that any type of fragmented rubber can be used. Although not required, fragmented rubber can be post-consumer rubber and / or recycled rubber. The fragmented rubber can be of several classifications, such as N ° 1, 2, 3, 4 and / or 5.
[78] Fragmented rubber is typically present in the aggregate in an amount from about 1 to about 100, more typically about 50 to about 100, even more typically about from 90 to about 100, and even more typically about 100, parts by weight, each based on 100 parts, by weight, of the aggregate in the composite material. The rest of the aggregate, if any, can be another different aggregate, such as sand, gravel, etc.
[79] The average diameter of the fragmented rubber is typically around 0.10 in. (0.254 cm) at about 3.0 in. (7.72 cm), more typically about 0.10 in. (0.254 cm) at about 2.0 in. (5.08 cm), and even more typically about 0.10 in. (0.254 cm) at about 0.25 in. (0.635 cm). Suitable grades of fragmented rubber, for the purposes of the present invention, are commercially available from Entech Inc. of White Pigeon, MI.
[80] In certain embodiments, the aggregate comprises glass. It should be appreciated that any type of glass can be used for the purposes of the invention. The glass can be transparent, tinted and / or colored. Although not required, the glass can be post-consumer glass and / or recycled glass. The use of such glass can reduce the total cost of the composite material and reduce the environmental footprint.
[81] Glass is typically present in the aggregate in an amount from about 1 to about 100, and more typically from about 50 to about 100, and even more typically from about 80 to about 100, and even more typically about 100, parts by weight, each based on 100 parts, by weight, of the aggregate present in the composite material. The rest of the aggregate, if any, can be another different aggregate, such as sand, gravel, etc. It is believed that the increase in the amount of glass present in the aggregate improves the flexural modulus and the compressive strength of the composite material.
[82] The average glass diameter is typically about 0.001 in. (0.00254 cm) at about 1.0 in. (2.54 cm), more typically about 0.10 in. (0.254 cm) at about 0.50 in. (1.27 cm), and even more typically about 0.125 in. (0.3175 cm) at about 0.25 in. (0.635 cm). It is believed that reducing the average diameter of the glass reduces the formation of splinters of the aggregate from the composite material (that is, loose or loose pieces of glass) and improves the resistance to flexural stresses, such as the stresses found from the moment when a tire is rotated on the composite material. When used, the glass is, in a typical way, crushed, in such a way that the bands of medium diameter, as described above, are satisfied. For safety reasons, the glass is typically processed in a drum or vibrated over sieves, so that the sharp edges of the glass are rounded. Glass grades suitable for the purposes of the present invention are commercially available from Glass Plus Inc. of Tomawhawk, WI.
[83] In certain embodiments, the glass includes a surface treatment, which comprises (or provides) at least one functional group, reactive with the isocyanate group of the elastomeric composition. Examples of suitable functional groups, for the purposes of the present invention, include hydroxyl, thiol, epoxy, and / or primary and secondary amine groups. Typically, the surface treatment comprises at least one amine and / or an amino functional group. It should be appreciated that the surface treatment may include a combination of different functional groups.
[84] The surface treatment can be imparted to the glass through several methods, such as through the use of an aminosilane, more specifically an organofunctional alkoxysilane, for example, SILQUEST® a-1100, SILQUEST® A-1120, and / or SILQUEST® A-1170, which are commercially available from Momentive Performance Materials of Albany, NY. For example, the glass can be washed and treated with aminosilane, in order to impart the surface treatment to the glass. In said other mode, the glass now includes one or more functional groups, conferred by the aminosilane, when reacting with the glass. The glass can be referred to as "base treated" or "silylated". The functional groups, for example, amine / amino groups, are reactive with the isocyanate functional groups of the elastomeric composition. The isocyanate functional groups can be free of isocyanate functional groups after the reaction to form the elastomeric composition, such as in cases of excess indexing, or the isocyanate functional groups conferred by one or more components of the elastomeric composition itself, for example, the prepolymer-isocyanate, such that the functional groups of the glass, are made part of the reaction to form the elastomeric composition.
[85] It is believed that surface treatment of glass improves durability, reduces chip formation of the aggregate, and increases the strength of the composite material. This is especially true if a chemical bond is formed between the elastomeric composition and the surface of the glass. For example, one or more -Si-O- bonds may be present between the glass surface and the elastomeric composition. It is also believed that the surface treatment makes the composite material much more stable to environmental forces, such as heat and humidity, which could potentially reduce its concentration during application. In certain embodiments, the glass used as the aggregate of the present invention comprises the glass aggregate described in co-pending application PCT / US10 / 58582, incorporated by reference, in its entirety, to an extent where the exposure does not conflicts with the general scope of the present invention described herein. PCT / US10 / 58582 describes several methods for the surface treatment of the glass aggregate, as well as the benefits of the surface treatment, which is conferred on the composite material of the present invention.
[86] It should be appreciated that the aggregate may include a combination of two or more of the aggregates mentioned above. For example, the composite material aggregate may comprise glass and rock. In these embodiments, the glass is typically present in the aggregate, in an amount from about 1.0 to about 99, more typically from about 25 to about 99, and even a typical method from about 75 to about 99 parts by weight, each based on 100 parts by weight of the aggregate present in the composite material. In addition, the rock is typically present in the aggregate in an amount from about 99 to about 1.0, more typically from about 75 to about 1.0 , and even more typically from about 25 to 1.0 parts by weight, each based on 100 parts by weight of the aggregate present in the composite material.
[87] The aggregate can be supplied to consumers for use through various modes, such as in rail cars, tanks, overpacks with large and small dimensions, large drums and containers or drums of smaller dimensions, kits and packaging. As described and exemplified above for the description of the system, the provision of the composite material components to consumers separately provides an increased formulation flexibility of the composite materials formed therefrom. For example, a consumer may select a specific aggregate, a specific isocyanate component, and a specific resin component, and / or quantities thereof, in order to prepare the composite material.
[88] Typically, the aggregate is dry (but also possible in ambient humidity, if present), in order to prevent a premature reaction with the system's isocyanate component. In addition, it is believed that the curing and bond strength of the elastomeric composition can be improved when the aggregate is dry. The aggregate can be kept dry using several methods. Such that through the use of water-resistant or waterproof packaging. However, in certain embodiments, the aggregate can be at least partially or completely submerged under water, as further described below. It should also be appreciated that the aggregate may already be present at the desired location, in order to include the composite material, for example, a track bed or along a coastline. As such, the aggregate may not need to be provided separately.
[89] Other examples of suitable components, for the purposes of the present invention, are generally described in U.S. Patent Publication No. s. 2009/0067924 and 2009/0067295, both by Kaul, whose exhibitions, as well as the patent and publication exposures referred to herein, are incorporated by reference, in their entirety, to the extent that the exhibitions do not conflict with the general scope of the present invention described herein.
[90] In certain embodiments, the material has a crush strength (or compressive strength) from about 100 psi (690 kPa) to about 2500 psi (17250 kPa), more typically from about 500 psi (3450 kPa) to about 1800 psi (12420 kPa), and even more typically from about 1300 psi (8970 kPa) to about 1600 psi (11040 kPa), and a even more typical about 1500 psi (10350 kPa) m in accordance with ASTM D 1621. In certain embodiments, the composite material typically has a flexural strength of from about 50 psi * 345 kPa ) at about 1000 psi (6900 kPa), and even more typically at about 700 psi (4830 kPa), according to ASTM D 790. In certain embodiments, the composite material typically has a flexural module from about 20,000 psi (138,000 kPa) to about 150,000 psi (1,035,000 kPa), and even more typically from about 50,000 psi (345,000 kPa), and even more typically from about 100,000 psi (690,000 kPa) to about 150,000 psi (1,035,000 kPa), and even more typically about 100,000 psi (690,000 kPa), according to ASTM D 790.
[91] In certain embodiments, the composite material has a porosity (or vacuum volume) of from about 30 to about 50, more typically from about 34 to about 45, and yet, more typically, from about 35 to about 42, and even more typically from about 37 to about 38%. The porosity of the composite material can be determined using various methods understood in the art, such as: Montes, F., Valvala, S., and Haselbach, L. “A New Test Method for Porosity Measurements of Portland Cement Pervious Concrete”, J ASTM Int. 2 (1), 2005 and Crouch, L., K., Cates, M. Dotson, V. James, Jr., Honeycutt, Keith B., and Badoe, DA “Measuring the Effective Air Void Content of Portland Cement Pervious Pavements, ”ASTM Journal of Cement, Concrete, and Agregates, 25 (1), 2003.
[92] Increasing the porosity of the composite material is useful for reducing runoff, such as a runoff from rain. In certain embodiments, vacuum fractions can also reduce hydrocarbons. For example, hydrocarbons, such that dripping motor oil from an automobile, can flow downward through the porous composite material and be adsorbed onto aggregate particles, for example glass, where hydrocarbons can be digested by bacteria over time, thereby preventing hydrocarbons from contaminating soil and / or soil water.
[93] It is believed that the porosity of the composite material allows the composite material to accept very large volumes of water in a short period of time. In certain embodiments, testing of a paving structure, formed from the composite material, indicated that the paving structure can accept about 1600 inches (40.64 cm) of water per hour. In addition, it is believed that porosity makes the maintenance of paving structures, formed from the composite material, easier, because the sediment deposited in the pores can be removed with little effort. The flow of air through the composite material also allows it to release heat, through convection, much faster than conventional pavements, so that the paving structure is cooled over a very long period of time. shorter, after a heat source has been removed, compared to conventional pavements.
[94] In certain embodiments, the composite material has a permeability of from about 500 inches / hour (1270 cm / hour) to about 4000 inches / hour (10160 cm / hour), and in a more typical way from about 1000 inches / hour (254000 cm / hour) to about 3000 inches / hour (7620 cm / hour), and even more typically from about 1500 inches / hour (3810 cm / hour) to about 2000 in. / hour (5080 in / hour), and even more typically 1650 in / hour (4191 cm / hour). The permeability of the composite material can be determined through various methods understood in the art, such as: Montes, F. Haselbach, L. “Measuring Hydraulic Conductivity in Pervious Concrete”, Env. Eng. Sci. 2396), 2006 and Schaefer, V Wang, K. Suleimman, M. And Kevern, J. “Mix Design Development for Pervious Concrete in Cold Weather Climates”, Final Report, Civil Engineering, Iowa State University, 2006. Increasing the permeability of the composite material is useful to reduce oozing. In yet other embodiments, such as those further described below, the composite material is non-porous.
[95] In certain embodiments, the elastomeric composition, upon approaching or reaching a final curing state, typically has a tensile strength of from about 1000 psi (6900 kPa) to about 3000 psi (20,700 kPa), more typically from about 1500 psi (10,350 kPa) to about 3000 psi (20,700 kPa), and even more typically from about 2000 psi (13,800 kPa) to about 3000 psi (20,700 kPa), and even more typically about 2300 psi (15,870 kPa) according to ASTM D 412 and / or ASTM D 638. In certain embodiments, the elastomeric composition, by approaching or reaching a final curing state, typically has an elongation from about 20 to about 150, more typically from about 60 to about 150, and even more typically from about 90 to about 150 about 150, and even more typically about 100%, according to ASTM D412 and / or ASTM D638.
[96] In certain embodiments, the elastomeric composition, upon approaching or reaching a final curing state, typically has a (Grave) breaking strength of from about 50 to about 400 , more typically from about 200 to about 400, and even more typically, from about 325 to about 400, and even more typically from about 365 ppi, according with ASTM F 624. In certain embodiments, the elastomeric composition, upon approaching or reaching a final curing state, typically has a Shore D hardness of from about 20 to about 60, more typically from about 40 to about 60, and even more typically from about 50 to about 60, and even more typically, from about 54, according to ASTM D 2240. In certain modalities, the elastomeric composition, by approaching or reaching a final curing state, typically, a resistance to detachment from about 30 to about 80, even more typically from about 50 to about 80, and even more typically from about 65 to about 80, and even more typically about 75 ppi, according to ASTM D 6862.
[97] As described above, in certain embodiments, the elastomeric composition comprises the reaction product of the prepolymer-isocyanate, the polymeric isocyanate, the hydrophobic polyol, and the chain extender. In still other embodiments, the elastomeric composition comprises the reaction product of a prepolymer-intermediate, the hydrophobic polyol, and the chain extender.
[98] In the modalities, which use the intermediate prepolymer, the intermediate prepolymer is equivalent to the isocyanate component. In said other mode, if used, the prepolymer-intermediate takes the place of the isocyanate component and, therefore, serves as the isocyanate component in such embodiments and descriptions thereof.
[99] The prepolymer-intermediate typically comprises the reaction product of the prepolymer-isocyanate, the polymeric isocyanate, and the hydrophobic polyol. Optionally, the intermediate prepolymer can comprise the additional reaction product of the chain extender. Alternatively, the intermediate prepolymer comprises the reaction product of the prepolymer isocyanate, the polymeric isocyanate and the chain extender. Alternatively, the intermediate prepolymer comprises the reaction product of the prepolymer-isocyanate, the polymeric isocyanate, and the chain extender. Optionally, the intermediate prepolymer can comprise the additional reaction product of the hydrophobic polyol.
[100] Typically, the total amount of the prepolymer-isocyanate and the polymeric isocyanate, used to form the polymeric composition, is used to form the prepolymer-intermediate. In contrast, only a portion of the hydrophobic polyol and / or the chain extender is used to form the prepolymer-intermediate, while the rest of the hydrophobic polyol and / or the chain extender is left for use as the composition of resin.
[101] If used, the prepolymer-intermediate is useful in achieving a desired NCO content of the isocyanate component, changing the curing properties of the elastomeric composition, and changing the viscosity of the elastomeric composition. The intermediate prepolymer is especially useful for use in wet or wetting conditions, as alluded to above and as further described below. Other advantages can also be appreciated with reference to the Example section below.
[102] The present invention further provides a method of forming the elastomeric composition. The method comprises the stages of providing the prepolymer-isocyanate, the polymeric isocyanate, the hydrophobic polyol, and the chain extender. In certain embodiments, the method further comprises the stage of reacting the isocyanate prepolymer and the polymeric isocyanate with the hydrophobic polyol, in order to form the intermediate prepolymer. In this embodiment, the method further comprises the stage of reacting the prepolymer-intermediate with the resin component to form the elastomeric composition. Typically, the intermediate prepolymer is formed separately from the resin component. Alternatively, as described above, the prepolymer-intermediate comprises the reaction product of the prepolymer-isocyanate, the polymeric isocyanate, and the chain extender.
[103] In one embodiment, the stage of formation of the elastomeric composition is further defined as the separate stages of first reacting the isocyanate prepolymer and the polymeric isocyanate with a quantity of the hydrophobic polyol, and, optionally, a quantity of the chain extender in order to form the intermediate prepolymer. Next, the intermediate prepolymer is reacted with the remainder of at least one of the chain extender and the hydrophobic polyol (i.e., the resin component), in order to form the elastomeric composition.
[104] The present invention further provides a method of forming the composite material. The method comprises the stages of providing the aggregate and forming the elastomeric composition. The method further comprises the stage of applying the elastomeric composition to the aggregate, in order to form the composite material.
[105] The elastomeric composition can be formed using various methods, such as those described above. In one embodiment, the method comprises the stages of providing the prepolymer-isocyanate, providing the polymeric isocyanate, providing the hydrophobic polyol, and providing the chain extender. The method comprises the additional stage of reacting the prepolymer-isocyanate and the polymeric isocyanate with the hydrophobic polyol, in order to form a prepolymer-intermediate. Typically, the prepolymer-isocinate and the polymeric isocinate are mixed before the reaction stage of the prepolymer-isocyanate and the polymeric isocyanate with the hydrophobic polyol. The method comprises the additional stage of reacting the intermediate prepolymer with the resin composition, in order to form the elastomeric composition. Typically, the reaction stages occur independently of one another.
[106] When formed from isocyanate and resin components, the isocyanate index of the elastomeric composition is typically from 70 to about 200, more typically from about 90 to about 175, and even more typically from about 100 to about 175, and even more typically from about 105 to about 168, and even more typically from about of 121.
[107] The elastomeric composition can be referred to in the art as an elastomeric 2C polyurethane composition. The isocyanate and the resin components are mixed to form the reaction product of the elastomeric composition. The term reaction product, as used herein, is intended to cover all stages of interaction and / or reaction between the isocyanate and the resin components, including the reaction products of the isocyanate and the resin components, even when the reaction product contacts the aggregate in order to form the composite material. In general, the reaction product begins to form when the isocyanate and resin components come into contact with each other.
[108] Typically, the application stage is further defined as the coating of the aggregate with the elastomeric composition. A suitable method of coating includes drum coating the aggregate with the elastomeric composition in an apparatus. Suitable devices include, but are not limited to, those described below. Typically, the training and application stages are contemporary.
[109] In certain embodiments, the composite material is at least partially submerged under water after the stage of application of the elastomeric composition to the aggregate. As such, the elastomeric composition is cured to a final curing state, while submerged in water in a partial or complete way. Typically, a surface of the elastomeric composition, i.e., an interface between the surface of the elastomeric composition and water, is substantially free of bubbles during curing of the elastomeric composition, while the composite material is submerged under water. The aforementioned lack of bubble formation is especially true when the prepolymer intermediate is employed, as alluded to above. These modalities can be found along shorelines, as introduced above.
[110] Typically, the surface of the elastomeric composition is substantially free of bubbles during the application stage of the elastomeric composition. Specifically, the hydrophobic nature of the elastomeric composition leads to little or no formation of bubbles on the surface of the elastomeric composition during formation, even in the presence of water, such that when the composite material is forming (ie curing) under the water. In said other method, little or no foaming occurs during the formation of the composite material. For example, if the isocyanate and resin components are mixed, degassed, placed in water while still liquid and allowed to cure in the form of a hard elastomer, the surface of the elastomer at the interface between the elastomer and the water does not in general, any signs of bubble formation, turbidity, wrinkling and / or any other type of deformation.
[111] Generally speaking, when the isocyanate and the resin components are brought into contact with each other, such that by mixing the isocinate and the resin components together, the isocyanate and the resin components they start to react, in a way to form the product of the reaction. The reaction product of the elastomeric composition, during formation, joins the aggregate, in order to form the composite material. It should be appreciated that the reaction product can begin to form over a period of time, before being introduced into the aggregate. This is especially true if the composite article is to be formed partially or completely under water. For example, the reaction product can be allowed to react for about 1 to about 25 minutes, before the introduction of the aggregate. Typically, the aggregate is introduced before the reaction product reaches a final curing state. It should also be appreciated that the reaction between the isocyanate and the resin components can be delayed for some period of time, after the isocyanate and the resin components are brought into contact with each other.
[112] The reaction between the isocyanate and the resin components is commonly referred to in the art as a crosslinking or crosslinking reaction, which generally results in an accumulation of molecular chains, that is, the molecular weight, in the reaction product in order to produce the cross-linked structure. The reaction of the isocyanate and resin components can occur at various temperatures, such as at room or natural temperature, although heating can be applied to one or more of the components, in order to trigger and / or accelerate the reaction between the isocyanate and resin components. In certain embodiments, although depending, in part, on the specific components employed, the application of heat accelerates the reaction between the isocyanate and the resin components. Typically, at least one of the reaction stages occurs in at least one reaction vessel, such that when the prepolymer-intermediate is formed.
[113] The composite material can be used in various applications and in various locations. For example, the composite material can be shaped, stretched, compacted or flattened to form the pavement. Examples of applications, which employ composite material, include, but are not limited to, formation liners, railroad track beds, pavements, sidewalks, patios, trails, playground surfaces, rails, landscape features, mooring areas boats, etc. Such applications of the composite material can be used to prevent erosion and / or to reduce sound transmission. For example, the composite material can be used as a coating along and / or in other ways, such as along rivers, lakes, or shorelines. The composite material can be used for coastal defense. As an example, the elastomeric composition can be used to coat stone, for example, through a tipping process, and the coated stone can be placed along the coastline. Alternatively, the elastomeric composition can be sprayed on the stones already in place, but tipping provides, in general, a better coating and bond strength. Geosynthetic materials, such as geotextiles, can also be used around and / or under the coated stone, in order to avoid undercutting. Once coated, the stone is cured to form the coating, the coating helps to prevent erosion of the coastline. Before the elastomeric composition is fully cured, sand, or other fine particles can be sprayed on the coated stones, in order to present an aesthetic appearance and slip resistance.
[114] The voids within the liner provide additional habitat for animals and plants and the liner is easily mixed with the surrounding environment, especially when the local aggregate is used, and the elastomeric composition is non-pigmented, in such a way that it is substantially transparent. As another example, the composite material can be used as a track ballast. As an example, the elastomeric composition can be used to coat rocks, for example, through a tipping process, and the coated rock can be placed in a way to form a track bed. Alternatively, the elastomeric composition can be sprayed on the rocks, already in place. Once the coated rocks are cured to form the ballast, the ballast helps to support the trail and distribute the load, reduces fly ash and dust and helps to prevent spraying of the rocks. The hollow spaces inside the ballast also provide drainage. The aforementioned applications can be formed using methods known to those skilled in the art, such as in civil engineering and road construction techniques. For example, a conventional paving process can be used only to replace concrete with the composite material of the present invention. Other applications of composite material, such as paving applications, are exposed in PCT / US2010 / 061574 deposited concurrently with the order in question (Power of Attorney No. 065333.00205), PCT / US2010 / 061587, deposited concurrently with the order in question (Power of Attorney Document No. 065333.00209), the exposures of which are incorporated into it, by reference, in their entirety.
[115] As yet another example, certain types of paving can be formed and finished, in a manner similar to low collapse concrete. The composite material can be mixed in a batch process, on a small scale, using a concrete or mortar mixer. The elastomeric composition is mixed and added to the aggregate in the mixer, mixed for a few minutes, and then put into forms. A vibrating belt can be used in order to provide light compaction / sedimentation of the composite material in the forms. A smooth finish can be achieved by working the surface with a Bull float (Fresno blade) or with a powder trowel, and the blades around the shapes can be finished with an end trowel.
[116] Depending on the weather conditions, the composite material can be free of stickiness within about 4 to 6 hours, can be stepped on in about 24 hours and, typically, should reach about 95% of its hardness final within 72 hours. If the surface has to withstand traffic, it will typically be able to withstand the force of vehicle traffic after about 4 days. Optionally, a surface coating of aliphatic polyurethane can be sprayed or laminated thereon, after the composite material is free of stickiness, in order to ensure a wear surface, which is quite stable to torsional forces, such that of tires rotating on it. In addition, sand or a small aggregate or fine particles can be spread over the top of the curing, in order to provide a non-slip surface on slopes or on areas with high pedestrian traffic.
[117] Typically, the composite material, once cured, is self-supporting. In said other mode, a support structure is not required for the support, or to be embedded within the composite material. An example of a conventional support structure used for paving applications is GEOBLOCK®, commercially available from PRESTOGEO SYSTEMS® from Apppleton, WI. An advantage regarding the use of such a support structure is that the support structure has a thermal expansion coefficient significantly greater than a thermal expansion coefficient of the composite material aggregate, for example, glass. Specifically, the coefficient of thermal expansion of the aggregate is typically less than the coefficient of thermal expansion of the support structure. The difference between the coefficient of thermal expansion between the aggregate and the support structure can result in a failure of the composite material.
[118] As such, in certain embodiments of the present invention, the composite material of the present invention, once cured, is completely free of an additional support structure, for example, GEOBLOCK®. For example, the composite material can be used for paving applications, which do not rest on the support structure. Surprisingly, the elastomeric composition of the present invention allows the exclusion of such support structures, which could negatively impact the cured composite articles that include them, such as through deformation or warping of the pavement, due to the differences in thermal expansion and contraction between the support material and the built-in or underlying support structure.
[119] The composite material, either before or after a final curing state, can be shaped into various shapes of varying dimensions. For example, the composite material can be essentially planar (for example, when the composite material is used as the flooring) having a thickness of from about 0.5 inches. (1.27 cm) at about 6.0 in. (15.24 cm), more typically about 1.0 in. (2.54 cm) at about 4.0 in. (10.16 cm), and even more typically about 2.0 inches. (5.08 cm) to 3.0 in. (7.62 cm). It should be appreciated that the thickness of the composite material, depending on its application, may be uniform or may vary.
[120] Once the elastomeric composition of the composite material begins to cure, the composite material only remains foldable or workable for a limited period of time, until the composite material reaches a curing state, in such a way that the material has a working time period of from about 1 to about 40, more typically from about 1 to about 30, and even more typically from about 1 to about 20 minutes. In one embodiment, the composite material has a working time of from about 30 to about 45 minutes. Once the elastomeric composition is fully cured, the composite material is fully formed. The composite material, even when fully cured, can be further processed, such that by cutting or sandblasting the composite material during various applications. The curing time of the composite material can be affected by many variables. Typically, the composite material reaches a final curing state, after about 30 days, at an average temperature of about 72 ° F (22 ° C) and an average relative humidity of about 50%.
[121] In the above methods, the coating stage of the aggregate with the elastomeric composition can be performed by many different methods and can be a batch, a semi-batch, or a continuous process. In one embodiment, the aggregate and the elastomeric composition are mixed over a period of time. It should be appreciated that the elastomeric composition can be formed before or during the introduction of the aggregate. Alternatively, the aggregate, the isocyanate component, and the resin component, can be introduced simultaneously and mixed. The order of addition of the components to form the composite material can be any order. The aforementioned period of time is the period of time for which the elastomeric composition is mixed with the aggregate. The period of time is sufficient to coat the aggregate with the elastomeric composition and is typically from about 10 seconds to about 10 minutes, and more typically from about 10 seconds about 5 minutes. The aggregate coated with the elastomeric composition is typically removed from the mixer or any other apparatus before final curing of the elastomeric composition to form the composite material.
[122] The elastomeric composition and the aggregate can be mixed using any method known in the art, including rotating drums, tippers, single axis batch mixers, double axis batch mixers, spiral blades drums. In yet another embodiment of the present invention, the stage of coating the aggregate with the elastomeric composition is spray-coated. In this embodiment, the elastomeric composition can be, at least partially, formed before or during the spraying stage. Spraying can be carried out by any method known in the art, through mixing by interfering with components in the elastomeric composition, mechanical mixing and spraying, etc. A specific example of an apparatus suitable for forming the composite material is shown in PCT / EP 2010/058989, which is incorporated into it, by reference, in its entirety. It should be appreciated that the aggregate can be stationary or, alternatively, the aggregate can be arranged on a tipper or another movable drum, in order to increase the surface area of the aggregate exposed to the pulverized elastomeric composition, as that the aggregate is in motion on the tipper or another movable drum. The aggregate must be sprayed while the rock is laid out over an area, for example, a coastal area, on which the composite material must be formed. As described above, when the aggregate is sprayed while the aggregate is in the tipper, the aggregate coated with the elastomeric composition should typically be removed from the tipper before the elastomeric bond composition is fully cured, a way to form the composite material.
[123] When the elastomeric composition is sprayed, it should be appreciated that the isocyanate component and the resin component can be mixed before or after the exit of a spray nozzle. In one embodiment, the resin and isocyanate components are separate streams when they exit the spray nozzle and are mixed before coating the aggregate. In still other embodiments, the resin and isocyanate components are pre-mixed before leaving the spray nozzle. For example, in one embodiment, the prepolymer-intermediate is formed prior to the formation of the elastomeric composition.
[124] After the aggregate has been coated with the elastomeric composition, and after optional mixing of the same, the elastomeric composition is cured in order to form the composite material. In embodiments, where the aggregate, for example, the rock, and the elastomeric composition are mixed in the mixer, the elastomeric composition is typically cured outside the mixer. For example, the composite material can be placed along a coastal area, which is reinforced before the elastomeric composition is fully cured.
[125] It should be appreciated that at least one layer, such as a compensating layer, can be placed on the coastal area before placing the aggregate coated with the elastomeric composition on it, in order to further increase the durability and adhesion of the composite material. In one embodiment, the compensation layer is placed over the coastal area and the aggregate, coated with the elastomeric composition, is placed over it, before the elastomeric composition is fully cured. The curing of the elastomeric composition is typically passive, that is, there is no need for an affirmative stage, such as heating, etc., in order to cure the bonding composition, and curing occurs naturally. .
[126] Typically, there is a need for a composite material, in which water is posing a threat of erosion current to a coastal area, and therefore water removal can be time-consuming, difficult and bulky. The elastomeric composition, especially when the prepolymer-intermediate is employed, can be cured in the presence of water, while maintaining an excellent cohesive resistance between the elastomeric composition and the aggregate, for example, the rock. The ability to cure in the presence of water is attributable to the components of the system, such as the hydrophobic polyol. The presence of water can exist from several sources, such as rain, high tide, waves from a body of water adjacent to the coastal area, etc. In addition, as described above, it should be appreciated that the elastomeric compositions can be cured while under water, that is, while partially or completely submerged, while maintaining an excellent cohesion between the elastomeric composition and the aggregate, excellent durability, and excellent compressibility of the composite material formed from it. The ability to cure under water greatly increases the versatility of the elastomeric composition and the composite material formed from it.
[127] The composite material can also be, at least partially, cured in a mold, which can be a closed type mold or an open type mold. The mold can define a cavity, which substantially encapsulates the aggregate coated with the elastomeric composition or, alternatively, it can define an open cavity, which does not substantially encapsulate the aggregate coated with the composition elastomeric. In addition, the mold can be a reaction injection mold (RIM), in which the isocyanate and resin components are separately injected into the mold, with the aggregate disposed within it. Molds can be useful for forming various shapes of the composite material, such as bricks.
[128] To reiterate, depending on the part in the environment, in which the system is used, the hydrophobic polyol is useful in preventing and / or minimizing a competitive reaction between the prepolymer-isocyanate, the polymeric isocyanate, and the molecules of water. In addition, the hydrophobic polyol reacts with the prepolymer-isocyanate and / or with the polymeric isocyanate in order to form the elastomeric composition. The water and the NCO functional group, containing the components, that is, the prepolymer-isocyanate and the polymeric isocyanate, react readily in the presence of each other. When a conventional composition is exposed to water before curing is completed, the competitive reaction between water and isocyanate components can have undesirable effects on the resulting conventional composite material, such as reduced durability, reduced cohesive strength, toughness reduced traction, etc. However, in the present invention, the resin component has a strong aversion to water, thereby reducing the interaction and competitive reaction between the isocyanate component and water. When the composite material of the present invention is used for coatings, the elastomeric composition is often exposed to water before complete curing, as described above.
[129] The composite material can also be used for repair purposes, such as for repairing a hole or other vacuum in a concrete or asphalt surface. As such, the present invention also provides a method of repairing a floor, having an outer surface with a repairable vacuum on the outer surface. The method may first comprise the stage of removing any waste from the repairable vacuum, such as removing trash or broken paving pieces from the repairable vacuum. The method further comprises the stage of placing a quantity of the composite material inside the repairable vacuum, and, optionally, on the floor next to the repairable vacuum, in order to form a mound. The method further comprises the compaction stage of the mound to form a repair structure for the repairable vacuum. The repair structure has a repair surface substantially parallel to the outer surface of the pavement. It should be appreciated that portions of the amount of the composite material can be arranged and compacted in a plurality of stages, in order to completely fill the repairable vacuum.
[130] The method may further comprise the stage of applying the elastomeric composition of the composite material to the interior of the repairable vacuum, prior to the disposal stage. This stage can be useful to ensure an airtight connection between the composite material and the surrounding asphalt or concrete. The hermetic bond may also be present without this stage, based merely on the presence of the elastomeric composition in the composite material itself. The hermetic connection is useful in order to prevent water, or another liquid, from being introduced in a vacuum, thus further degrading the pavement. Typically, the composite material is non-porous for such repair applications. The method may also include the stage of enlarging the orifice, such that by sawing around the repairable vacuum, in order to define a repairable vacuum with cleaner ends for the repair.
[131] In certain embodiments, the composite material is porous, in order to allow water or other liquids to pass through the pavement. For example, in certain embodiments, the paving has an internal surface, opposite to the external surface, and the method further comprises the stage of extending the repairable vacuum away from the external surface and through the internal surface, in order to form a channel through the pavement, before the disposal stage. If the composite material is porous, the liquid can flow from the outer surface to the inner surface of the paving, through the repair surface, arranged inside the paving channel. It should be appreciated that such stages, or similar stages, must also be performed, in a way to emulate grids, manhole covers, in a way to allow liquid to pass through the pavement.
[132] Referring now to the Figures, Figure 1 consists of a cross-sectional view of a paving structure 20, which illustrates the migration of water 22 through paving structure 20. Paving structure 20 includes an upper layer T1 , of composite material 24. Composite material 24 is typically porous; however, there are modalities, in which the composite material 24 is non-porous. In order to place such a paving structure 20, native soil 26 is typically excavated to a depth appropriate to regional weather conditions and how native soil 26 is drained. In some northern climates, this could be as much as 24 inches, if not more. The area is then typically covered with a geosynthetic material 28 and a T3 storage layer, including a 0.38 in. Open grid shaped aggregate. (0.965 cm) at about 0.75 in. (19.05 cm) is installed and compacted. The storage layer T3 can also be referred to as a base course layer T3. Next, about 2 inches (5.08 cm) of an open grid muffling stroke having an aggregate of about 0.25 to about 0.5 inches (0.635 cm) to (1.27 cm) in diameter , is installed and compacted to form a layer of muffling stroke T2. Next, the top layer T1 (or the wear stroke layer T1) of the composite material 24 is installed to a thickness of about 2.5 inches. (6.35 cm) at about 3.5 inches. (8, 89 cm), depending on the final application, such that for walking or driving pavements, that is, the paving for steering must be thicker, due to the increased load. It should be appreciated that each of the layers T1, T2 and T3 are not illustrated in scale and may have greater or lesser thicknesses, and such thicknesses may be uniform or may vary. It will also be appreciated that any of the layers of muffling course T2, storage layer T3, and / or layer of geosynthetic material 28 can be excluded from the paving structure 20, depending on the need or the application. In certain modalities, at least one of the layers T1, T2 and T3 does not have or has few fines. The fines are believed to prevent the flow of liquid through the paving structure 20. As such, in certain embodiments, the paving structure 20 does not include more than about 5% fines, based on the sweeping of the respective aggregates. The paving structure 20 may further include the additional storage base or the underground storage, below the T3 storage layer. In certain embodiments, the paving structure 20 includes a cover arranged on a surface of the upper layer T1. The cover can be formed in various thicknesses, such as 5,000 (122.7 microns) or greater, and can comprise the elastomeric composition 30. If the cover is not formed from the elastomeric composition 30, it should be formed from of a UV-stable composition, such that from a UV-stable polyurethane elastomer composition. UV stability can be achieved through the use of one or more additives known in the art, and / or from the use of an aliphatic isocyanate. The cover (not shown) is useful to prevent splintering of the aggregate 32. The cover can also be used to reduce the porosity of the paving structure 20. Sand, or other fines, can be sprayed on the top layer T1, before that the elastomeric composition 30 reaches a final curing state, in order to provide slip resistance. The cover can be dyed with a dye in order to provide an aesthetic appearance, or it can be left naturally colored.
[133] Geosynthetic material 28 can also be located on several levels, such that between the muffling layer T2 and the storage layer T3. Although not shown, the geosynthetic material 28 can also extend upwards, towards the upper layer T1, such that upwards and around the outer ends of the storage layer T3. Examples of suitable geosynthetic materials 28, for the purposes of the present invention, include geotextiles, geogrids, georedes, geomembranes, geosynthetic clay liners, geo-foam, drainage / infiltration cells, geocomposites, etc. In certain embodiments, the geosynthetic material 28 is a geotextile, such as a non-woven geotextile. In certain embodiments, the paving structure 20 is free of a grid, such as that set out in U.S. Patent Publication No. 2009/0067924 and 2009/0067295.
[134] Figure 2 is an enlarged view, illustrating a porous embodiment of composite material 24, for example, composite material 24 of Figure 1. Composite material 24 includes elastomeric composition 30 in a cured state and aggregate 32. Typically, the cured elastomeric composition 30 is substantially or completely free of bubbles and / or voids in itself. Composite material 24 defines a plurality of voids 34. It should be appreciated that aggregate 32 can either be completely or partially encapsulated by the elastomeric composition 30. Typically, when composite material 24 is in a porous configuration, there are no or there are few fines within the composite material 24 or the voids 34 thereof.
[135] Figure 3 is an enlarged view, which illustrates a non-porous embodiment of composite material 24. As illustrated, the voids 34 are smaller in number and in size. Such a transition of the composite material 24 from a non-porous state can run from an increased amount of the elastomeric composition 30, relative to the amount of aggregate 32, from an increased compaction during installation, and / or to from a different size distribution of the aggregate 32, where the smaller aggregate 32 or even the fines particles (not shown) are filled in many, if not all, of the empty spaces 34. Typically, the composite material 24 it is configured, in a way that it is non-porous, simply by increasing the amount of elastomeric composition 30, in relation to the amount of aggregate 32.
[136] The following examples, which illustrate the system, elastomeric compositions and composite materials of the present invention, are intended to illustrate, not to limit the invention. EXAMPLES
[137] Examples of the resin and isocyanate components of the system are prepared. Examples of the elastomeric composition are also prepared. The resin and isocyanate components are also formed by mixing their respective components in a vessel. The vessel consists of a vessel, capable of withstanding agitation and having resistance to chemical reactivity. The components of the resin and isocyanate components were mixed using a mixer, for 1 to 3 minutes, at 1000 to 3500 rpm. The resin and isocyanate components were mixed in a similar way to form the elastomeric compositions.
[138] The quantity and type of each component used to form the Resin and Isocyanate components are shown in TABLES I and II below, with all values in parts by weight (w / w) based on 100 parts in weight of the respective Resin or Isocyanate Component, unless otherwise indicated. The '-' symbol indicates that the component is missing from the respective Resin or Isocyanate Component. TABLE I
TABLE II


[139] Hydrophobic Polyol 1 is a branched polyether / polyester polyol, having a hydroxyl value of from 160-185 mg KOH / g and a functionality of about 3.5, commercially available from Cognis Corporation.
[140] Hydrophobic Polyol 2 is a slightly branched polyether / polyester polyol, having a hydroxyl value of from 210-245 mg KOH / g, and a functionality of about 2.1, commercially available from Cognis Corporation.
[141] Hydrophobic Polyol 3 is a branched polyether / polyester polyol, having a hydroxyl value of from 160-185 mg KOH / g and a functionality of about 3.5, commercially available from Cognis Corporation.
[142] Hydrophobic Polyol 4 is a slightly branched aliphatic diol, having a hydroxyl value of from 117-130 mg KOH / g and a functionality of about 2.2, commercially available from Cognis Corporation.
[143] Hydrophobic Polyol 5 is a branched polyether / polyester polyol, having a hydroxyl value of from 300-330 mg KOH / g, and a functionality of about 3.0, commercially available from Cognis Corporation.
[144] Hydrophobic Polyol 6 is a castor oil, commercially available from Eagle Specialty Products, Inc.
[145] Supplemental Polyol is a trifunctional polyol, formed by adding propylene oxide to a glycerin initiator, having a hydroxyl number from 388-408 mg KOH / g, commercially available from BASF Corporation.
[146] The Chain Extender is the DPG.
[147] The Molecular Sieve is Baylith Paste, commercially available from JACAAB L.L.C., of St Louis, MO.
[148] Molecular Sieve 2 is Molecular Sieve 3A.
[149] Aminosilane is SILQUEST® A-1100, commercially available from Momentive Performance Products.
[150] Antifoam Agent 1 is Antifoam MSA, commercially available from Dow Corning.
[151] Antifoam Agent 2 is Antifoam A, commercially available from Dow Corning.
[152] Pyrogenic Silica is AEROSIL® R-972, commercially available from Evonik Degussa.
[153] Prepolymer-Isocyanate is a modified, short chain prepolymer, liquid, based on pure 4,4'-MDI, and having an NCO content of 22.9%, by weight, commercially available from BASF Corporation.
[154] Polymeric Isocyanate is a PMDI with a functionality of about 2.7 and an NCO content of 31.5%, commercially available from BASF Corporation.
[155] Examples 1-4 are comparative examples and Examples 5 and 6 are inventive examples. Example 2 shows poor reproducibility. Example 3 is susceptible to water, causing composite materials formed from it to fail. Examples 4, 5 and 6 have excellent hydrophobicity and resistance properties.
[156] In order to assess the physical properties of composite materials, several tests have been conducted. Crush resistance (or compressive strength) is determined according to ASTM D 1621. Flexural strength is determined according to ASTM D 790. The flexural modulus is determined according to ASTM D 790. Porosity (or the vacuum volume) is determined using any of the methods described above in: Montes, F., Valaval, S., and Haselbach, L. “A New Test Method for Porosity Measurements of Portland Cement Pervious Concrete”, J. ASTM Int 2 (1), 2005 and Crouch, LK, Cates, M., Dotson, V. James, Jr. Honeycutt, Keith B., and Badoe, DA “Measuring the Effective Air Void Content of Portland Cement Pervious Pavements“, ASTM Journal of Cement, Concrete, and Aggregates, 25 (1), 2003. Permeability is determined using any of the methods described in: Montes, F., Haselbach, L. “Measuring Hydraulic Conductivity in Pervious Concrete”, Env. Eng Sci. 23 (6), 2006 and Schaefer, V., Wang, K., Suleimman, M. And Kevern J. “Mix Design Development for Pervious Conc rete in Cold Weather Climates, ”, Final Report, Civil Engineering, Iowa State University, 2006.
[157] The results of the physical tests of the elastomeric compositions of Examples 1-5 are shown in TABLE III below. The '---' symbol indicates that the result has not been tested or obtained. TABLE III

[158] The results of the physical tests of the elastomeric composition of Example 6, as well as the composite material, which includes it and the aggregate, are shown in TABLE IV below. In order to form the composite material, 4.2% by weight of the elastomeric composition are mixed with 95.8% by weight of the aggregate, which in Example 6 below consists of 100% glass having an average diameter of about ^ inch (0.635 cm). Glass is commercially available from Glass Plus Inc. of Tomahawk, WI. The glass is silylated. In order to produce silylated glass, the glass is subjected to drum treatment with an aqueous solution comprising 0.3%, by weight, of SILQUEST® A-1120, which is commercially available from Momentive Performance Products. In order to superficially treat the glass, 5 parts of the aqueous solution are subjected to drum treatment with 100 parts of the glass, for about 5 minutes. The aqueous solution is then drained and the glass is allowed to dry. The glass, now superficially treated (or "silylated") is used to form the composite material. In said other mode, the glass now includes one or more functional groups, conferred by the organofunctional alkoxy silane, i.e. SILQUEST® A-1120, reacting with the glass. The functional groups, for example, amine groups, are reactive with the isocyanate functional groups of the elastomeric composition. The isocyanate functional groups can be free functional groups after the reaction to form the elastomeric composition, such that in cases of excessive indexing, or the isocyanate functional groups, conferred by one or more components of the elastomeric composition itself, for example, the pre -polymer-isocyanate, such that the functional groups of the glass, become part of the reaction to form the elastomeric composition. The results for Example 6 * below, Composite Material, are with the surface treated glass, like the aggregate. TABLE IV


[159] Composite materials using both surface treated and untreated glass were prepared and tested. In TABLE V below, the Composite Material of Example 6 comprises the untreated glass and the Composite Material of Example 6 * uses the surface treated glass, as described and illustrated above. The crushing resistance of the two examples was also tested after boiling the Composite Materials in water for 140 minutes. The results of the physical test are shown in TABLE V below. The '---' symbol indicates that the result has not been tested or obtained. TABLE V

[160] With reference to TABLE V above, it can be appreciated that the surface treatment of glass, used to form the inventive composite materials of the present invention, can have dramatic effects on physical properties, with large increases in crushing strength (and resilience) increased with exposure to extended temperature), and large increases in flexural strength. Additional tests are performed to confirm the findings. Figure 6 shows a dramatic improvement in compressive strength (approximately 40%) achieved by pretreating the glass with an aminosilane solution. Thermal cycles in conditions of high humidity do not have, or have little compressive strength after 75 cycles between -10 ° C and 25 ° C.
[161] The additional preparations and tests of Example 6 * are performed in order to better establish their physical properties. These physical properties and the respective test methods are shown in TABLE VI below. TABLE VI

[162] The elastomeric composition of Examples 6 and 6 * provides consistent physical properties for the composite material over a wide temperature range, as shown through dynamic mechanical analysis (DMA) of the cured elastomeric composition, as illustrated in Figure 5.
[163] It is believed that the composite material can also be used to reduce the effects of urban thermal insulation. As such, an additional formulation and tests on the composite materials, similar to Examples 6 and 6 *, are performed, using different types of dye, as illustrated below in TABLE VII with examples E1-E6. TABLE VII

[164] As shown in TABLE VII above, all five color variants of the composite material, when formed as paving (E1-E5), have a Solar Reflective Index (SRI) substantially greater than 29, just as it does the non-pigmented example (E6). TABLE VII also includes the SRI data for conventional pavements, formed from asphalt and concrete. As shown, the pigmented and non-pigmented modalities of the composite material all have excellent SRI values. The SRI assessment is performed according to ASTM E 1980.
[165] Another example according to the invention is created, Example 7, which is chemically the same as Example 6. However, Example 7 is formed, gradually, including a stage of formation of a prepolymer-intermediate, whereas Example 6 is formed in a batch mode, excluding the formation of prepolymer-intermediate. To form Example 7, first, a quasi prepolymer is prepared by reacting a portion of the Resin Composition (or the whole or a portion of the Hydrophobic Polyol 6; or the whole or a portion of the Hydrophobic Polyol 6 and the Extender Chain) with the Isocyanate Component, in order to form a prepolymer-intermediate. Then, the intermediate prepolymer is reacted with the rest of the resin composition, in order to form the elastomeric composition. Example 7 has a number of advantages over Example 6. For example, prepolymer-intermediate 6 is more compatible with the rest of the Resin Composition (with respect to the Isocyanate and Resin Components of Example 6), than in such a way that mixing is improved.
[166] In addition, the prepolymer-intermediate has better low-temperature properties compared to the Isocyanate Component, which makes it more robust for use in various locations. For example, as the reaction between the intermediate prepolymer and the resin composition generally has a lower exotherm compared to the reaction of the resin and isocyanate components (that is, an immediate reaction), it is believed that the elastomeric compositions, formed from the prepolymer-intermediate will, in general, show less thermal shrinkage compared to the elastomeric compositions, which do not use the prepolymer-intermediate. Furthermore, as the mixing properties are improved through the use of the intermediate prepolymer, it is believed that the use of it would allow an improved reaction at lower temperatures, compared to elastomeric compositions that do not use the prepolymer. -intermediary.
[167] Additional examples according to the invention are prepared in order to further illustrate the properties of the prepolymer-intermediates of the present invention. One example, Example 8, includes a Resin Component, comprising 53, 99 parts by weight of Hydrophobic Polyol 6, 4.09 parts by weight of the Chain Extender, 0.029 parts by weight of Molecular Sieve 2, and 0 , 03 parts, by weight, of the Anti-foam Agent 2. Example 8 also includes an Isocyanate Component, which comprises 24.96 parts, by weight, of the prepolymer-isocyanate, and 16.64 parts, by weight, of the Isocyanate Polymeric. Each of the values, in parts by weight, is based on 100 parts by weight of the total elastomeric composition, on a pre-reaction basis, before the Resin and Isocyanate Components are mixed to form Example 8. in order to form an elastomeric composition, i.e., Example 8, the Resin and Isocyanate Components are mixed, in order to form a reaction mixture. The reaction mixture is allowed to react for 20 minutes. After this period of 20 minutes, the aggregate, for example, the glass, is coated with the reaction mixture, in order to form a composite material. The composite material comprises about 4.2%, by weight, of the elastomeric composition and about 95.8%, by weight, of the aggregate. When coating the aggregate, the composite material is immediately introduced into water, for example, by flushing, in such a way that the composite material is submerged, at the same time that it is cured to a final curing state. The material is composite cured to a final curing state very well and does not have, or has little evidence of reaction with water (based on visual inspection). The reaction mixture has a free NCO content of about 22.7%, over a period of 20 minutes, as described above. Based on the content of NCO, the point of the reaction, at which little or no reaction with water occurs, can be determined. In this way, a prepolymer-intermediate having the same content of free NCO is prepared. The reaction point can vary, based on which materials are employed, however, the method of determining the appropriate free NCO content, based on the allocation of certain time intervals, before the introduction of water, operates in the same way.
[168] Inventive Examples 9 and 10 are prepared, both of which are prepolymer-intermediates. Example 9 is prepared as follows: 362.48 g of Polymeric Isocyanate and 543.72 g of prepolymer-isocyanate are loaded into a 2 L flask, with stirring, in order to form the Isocyanate Component. The Isocyanate Component is heated to 60 ° C and 93.8 g of Hydrophobic Polyol 6 is added gradually, while the temperature is kept below 80 ° C. After the addition of the Hydrophobic Polyol 6 has been completed, the reaction mixture is heated to 80 ° C for one hour. The reaction mixture, that is, the prepolymer-intermediate, is thereafter cooled to room temperature.
[169] Example 10 is prepared as follows: 365.70 g of Polymeric Isocyanate and 548.55 g of prepolymer-isocyanate are loaded into a 2 L flask, with stirring, to form a Component of Isocyanate. The Isocyanate Component is heated to 60 ° C and 79.71 g of Hydrophobic Polyol 6 and 6.04 g of the Chain Extender are added gradually, while the temperature is kept below 80 ° C. After the addition of the Hydrophobic Polyol 6 and the Chain Extender has been completed, the reaction mixture is heated to 80 ° C for one hour. After the addition of the Hydrophobic Polyol 6 and the Chain Extender has been completed, the reaction mixture is heated to 80 ° C for one hour. The reaction mixture, that is, the prepolymer-intermediate, is thereafter cooled to room temperature.
[170] In order to evaluate the physical properties of elastomeric compositions (without the aggregate), when approaching or reaching a final curing state, several tests are conducted. The tensile strength and elongation are determined according to ASTM D 412 or according to ASTM D 638. Grave breaking strength is determined according to ASTM D 624. The Shore D hardness of the durometer is determined according to according to ASTM D 2240. The resistance to detachment is determined according to ASTM D 6862.
[171] It should be understood that the appended claims are not limited to expressing the particular compounds, compositions, or methods described in the detailed description, which may vary between the particular modalities, which fall within the scope of the appended claims. With respect to any Markush groups, which are based on them for the description of particular characteristics or aspects of various modalities, it should be appreciated that different, special, and / or unexpected results can be obtained for each member of the respective Markush group, regardless of all Markush members. Each member of a Markush group can be based, either individually or in combination, and provides adequate support for specific modalities within the scope of the attached claims.
[172] It should be understood that any bands and sub-bands, which are based on the description of various modalities of the present invention, fall, independently and collectively, within the scope of the appended claims, and must be understood as capable of describing and contemplate all ranges, which include the integer and / or fractional values in this, even if such values are not expressly written here. One of skill in the art will readily recognize that the enumerated bands and sub-bands sufficiently describe and enable various embodiments of the present invention, and such bands and sub-bands can be further delineated in the form of relevant halves, thirds, quarters, fifths, and so on. . Just as an example, a “from 0.1 to 0.9” range can be additionally outlined in a lower third, that is, from 0.1 to 0.3, an intermediate third, ie the from 0.4 to 0.6, and an upper third, that is, from 0.7 to 0.9, which, individually and collectively, are within the scope of the attached claims, and can be based, individually and / or collectively, and can provide adequate support for specific modalities within the scope of the attached claims. In addition, with respect to the language, which defines or modifies a range, such that “at least”, “greater than”, “less than”, “hand more than”, and similar ones, must be understood in a such a language includes sub-bands and / or an upper or lower limit. As another example, a “at least 10” range inherently includes a sub-range from at least 10 to 35, a sub-range from at least 0 to 25, a sub-range from 25 to 35, and so on, and each sub-range can be based, individually and collectively, and provide adequate support for specific modalities within the scope of the claims only. Finally, an individual number within an exposed range can be based and provide adequate support for specific modalities within the scope of the attached claims. For example, a “from 1 to 9” range includes several individual integers, such that 3, as well as the individual numbers include a decimal point (or fraction), such that 4.1, which can be taken as a basis and which can provide adequate support for the specific modalities within the scope of the attached claims.
[173] The present invention has been described herein by way of illustration, and it should be understood that the terminology, which was used, is intended to be in the nature of the words of the description, rather than in a limiting way. Many modifications and variations of the present invention are possible in light of the above teachings. The invention can be practiced in a manner other than that specifically described within the scope of the appended claims.

权利要求:
Claims (21)
[0001]
1. Composite material, characterized by the fact that it comprises: aggregate; and an elastomeric composition, which comprises the product of the reaction of; an isocyanate component, comprising: a polymeric isocyanate, and a prepolymer-isocyanate, and an isocyanate-reactive component, comprising: a hydrophobic polyol that is a natural oil polyol, and a chain extender having at least two hydroxyl groups and a molecular weight of 62 to 220, wherein said chain extender is present in said isocyanate-reactive component in an amount of 1 to 20 parts, by weight, based on 100 parts, by weight, of said component reactive to isocyanate; and wherein said elastomeric composition is present in said composite material in an amount of 1 to 10 parts, by weight, based on 100 parts, by weight, of said composite material in which said aggregate comprises 30-100% glass and 0-70% rock; and wherein said glass includes a surface treatment comprising at least one functional group, reactive with the isocyanate group of said elastomeric composition, wherein said surface treatment comprises at least one amine and / or an amino functional group, wherein said the isocyanate component comprises said polymeric isocyanate and said prepolymer-isocyanate and said prepolymer-isocyanate is present in said isocyanate component in an amount of 25 to 75 parts, by weight, based on 100 parts, in weight of said isocyanate component.
[0002]
2. Composite material according to claim 1, characterized by the fact that said chain extender is present in said isocyanate-reactive component in an amount of 5 to 10 parts, by weight, based on 100 parts, by weight, of said isocyanate-reactive component.
[0003]
3. Composite material according to claim 1, characterized by the fact that said rock is: i) selected from the group of marble, beach stone, river rock, and combinations thereof; or ii) granite.
[0004]
4. Composite material according to claim 1, characterized by the fact that said rock has an average diameter of 0.635 cm to 12.7 cm.
[0005]
Composite material according to claim 1, characterized by the fact that said aggregate comprises fragmented rubber.
[0006]
Composite material according to claim 1, characterized in that said hydrophobic polyol comprises a natural oil polyol and wherein said natural oil polyol is castor oil.
[0007]
7. Composite material according to claim 1, characterized in that said chair extender comprises an alkylene glycol and wherein said alkylene glycol is dipropylene glycol.
[0008]
8. Composite material according to claim 1, characterized by the fact that: i) said prepolymer-isocyanate comprises the reaction product of a diphenyl methane diisocyanate and a polyol, has an NCO content of 22.9% , by weight, and an average NCO functionality of 2 to 3; and / or ii) said polymeric isocyanate comprises polymeric diphenyl methane diisocyanate, has an NCO content of 31.5%, by weight, and an average NCO functionality of 2 to 3.
[0009]
9. Composite material according to claim 1, characterized by the fact that said hydrophobic polyol is present in said isocyanate reactive component in an amount of 80 to 99 parts, by weight, based on 100 parts, by weight, of the said isocyanate-reactive component.
[0010]
10. Composite material according to claim 1, characterized by the fact that said aggregate is selected from the group of glass, rock, fragmented rubber and combinations thereof, said isocyanate component comprises said polymeric isocyanate and said pre- polymer-isocyanate, said prepolymer-isocyanate comprises the reaction product of a diphenyl methane diisocyanate and a polyol, said polymeric isocyanate comprises polymeric diphenyl methane diisocyanate, said hydrophobic polyol comprises a natural oil polyol, said chain extender comprises an alkylene glycol.
[0011]
Composite material according to claim 10, characterized in that said prepolymer-isocyanate is present in said isocyanate component in an amount of 25 to 75 parts, by weight, based on 100 parts, by weight , of said isocyanate component, said hydrophobic polyol is present in said isocyanate-reactive component in an amount of 80 to 99 parts by weight, and said chain extender is present in said isocyanate-reactive component in an amount of 10 to 5 parts by weight, each based on 100 parts by weight, of said isocyanate reactive component.
[0012]
Composite material according to claim 10, characterized in that said natural oil polyol is castor oil, said alkylene glycol is dipropylene glycol, and said elastomeric composition is present in said composite material in an amount of 2 , 5 to 5.0 parts, by weight, based on 100 parts, by weight, of said composite material.
[0013]
13. Composite material according to claim 1, characterized in that it is used as a coating or as rail ballast.
[0014]
14. Method of forming a composite material as defined in claim 1, characterized by the fact that it comprises the stages of: providing an aggregate; forming an elastomeric composition, comprising the reaction product of; an isocyanate component comprising a polymeric isocyanate, and a prepolymer-isocyanate, and an isocyanate-reactive component, comprising: a hydrophobic polyol, which is a natural oil polyol, and a chain extender having at least two hydroxyl groups and a molecular weight of 62 to 220, wherein said chain extender is present in said isocyanate-reactive component in an amount of 1 to 20 parts, by weight, based on 100 parts, by weight of said isocyanate-reactive component ; and applying said elastomeric composition to the aggregate to form the composite material; wherein said elastomeric composition is present in the composite material in an amount of from 1 to 10 parts, by weight, based on 100 parts, by weight, of said composite material in which said aggregate comprises 30-100% of glass and 070% rock; and wherein said glass includes a surface treatment comprising at least one functional group, reactive with the isocyanate group of said elastomeric composition, wherein said surface treatment comprises at least one amine and / or an amino functional group, wherein said the isocyanate component comprises said polymeric isocyanate and said prepolymer-isocyanate and said prepolymer-isocyanate is present in said isocyanate component in an amount of 25 to 75 parts, by weight, based on 100 parts, in weight of said isocyanate component.
[0015]
15. Method according to claim 14, characterized by the fact that: i) the application stage is additionally defined as coating the aggregate with the elastomeric composition; and / or ii) the application stage is additionally defined as drum coating of the aggregate with the elastomeric composition in an apparatus; and / or iii) the training stage and the application stage are contemporary.
[0016]
16. Method according to claim 14, characterized in that: i) the isocyanate component comprises the polymeric isocyanate and the prepolymer-isocyanate and the prepolymer-isocyanate is present in the isocyanate component in an amount of 25 to 75 parts by weight based on 100 parts by weight of the isocyanate component; and / or ii) the chain extender is present in the isocyanate-reactive component in an amount of 5 to 10 parts, by weight, based on 100 parts, by weight, of said isocyanate-reactive component.
[0017]
17. Method according to claim 14, characterized by the fact that the aggregate comprises glass, rock, fragmented rubber or combinations thereof.
[0018]
18. Method according to claim 14, characterized by the fact that the aggregate comprises rock and in which the rock is: i) selected from the group of marble, beach stone, river rock, and combinations thereof; or ii) granite.
[0019]
19. Method according to claim 14, characterized in that: i) the hydrophobic polyol comprises a natural oil polyol and in which the natural oil polyol is castor oil; and ii) the chain extender comprises an alkylene glycol and where the alkylene glycol is dipropylene glycol.
[0020]
20. Method according to claim 14, characterized by the fact that: i) the prepolymer-isocyanate comprises the reaction product of a diphenyl methane diisocyanate and a polyol, has a NOC content of 22.9%, in weight, and an average NCO functionality of 2 to 3; and / or ii) the polymeric isocyanate comprises polymeric diphenyl methane diisocyanate, has an NCO content of 31.5% by weight, and an average NCO functionality of 2 to 3.
[0021]
21. Method according to claim 14, characterized in that the hydrophobic polyol is present in the isocyanate-reactive component in an amount of 80 to 99 parts, by weight, based on 100 parts, by weight, of the reactive component to isocyanate.

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法律状态:
2018-04-10| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2019-05-28| B06T| Formal requirements before examination [chapter 6.20 patent gazette]|

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2019-08-27| B07A| Application suspended after technical examination (opinion) [chapter 7.1 patent gazette]|

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2020-03-10| B07A| Application suspended after technical examination (opinion) [chapter 7.1 patent gazette]|

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2020-08-18| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|

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2020-12-29| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2021-03-09| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 10 (DEZ) ANOS CONTADOS A PARTIR DE 09/03/2021, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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US28863709P| true| 2009-12-21|2009-12-21|

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US61/288637|2009-12-21|

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PCT/US2010/061558|WO2011084793A1|2009-12-21|2010-12-21|Composite materials comprising aggregate and an elastomeric composition|

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