WO2019117952A1

WO2019117952A1 - Fatty acid modified polyurethane composites with improved dimensional stability

Info

Publication number: WO2019117952A1
Application number: PCT/US2017/066742
Authority: WO
Inventors: Amitabha Kumar; Cassandra HILL; Li Ai; Russell Hill
Original assignee: Boral Ip Holdings (Australia) Pty Limited
Priority date: 2017-12-15
Filing date: 2017-12-15
Publication date: 2019-06-20

Abstract

Polyurethane composites having improved dimensional stability and methods of manufacturing are described herein. The composites can include (a) a polyurethane formed by the reaction of (i) one or more isocyanates selected from the group consisting of diisocyanates, polyisocyanates, and mixtures thereof, and (ii) one or more polyols in the presence of a fatty acid, a fatty acid salt, or a combination thereof; and (b) an inorganic filler. The one or more polyols and the fatty acid mixture are not pre-reacted prior to reacting with the one or more isocyanates. The filler can be present in an amount of from greater than 50% to 90% by weight, based on the total weight of the polyurethane composite. The fatty acid, the fatty acid salt, or the combination can be present in an amount of from 0.05% to 10% by weight, based on the total weight of the composite.

Description

FATTY ACID MODIFIED POLYURETHANE COMPOSITES WITH IMPROVED

DIMENSIONAL STABILITY

FIELD OF THE DISCLOSURE

This disclosure relates generally to polyurethane composites, more particularly, to the use of fatty acids in polyurethane composites.

BACKGROUND OF THE DISCLOSURE

Organic-inorganic composite materials provide for a class of materials with superior flexural properties compared to inorganic materials without organic matter. In general, the superior properties of organic-inorganic materials are achieved through use of the organic material as a matrix material that acts as a glue with enhanced flexural properties or as a fibrous component providing reinforcement and improved tensile properties. The inorganic material imparts various properties of rigidity, toughness, hardness, optical appearance and interaction with electromagnetic radiation, density, and many other physical and chemical attributes. A proper blend of the inorganic and organic materials provides for a composite with optimal properties at an optimal cost.

Organic-inorganic materials, with or without fillers and/or fiber reinforcement, have been shown to be very useful for preparing structural or non-structural products such as buildings, vehicles, and marine products. Specific uses of such materials include applications as interior and exterior cladding on buildings. However, one of the major challenges for organic-inorganic materials is that they may expand and shrink when absorbing and desorbing moisture. This is especially true if the materials are exposed to wetting and drying cyclic conditions. The dimensional instability in the organic-inorganic materials may cause potential structural and cosmetic problems. For example, products derived from organic-inorganic materials may increase in length when exposed to water for an extended period of time. When installed and dried, these products may shrink resulting in the appearance of a gap.

There is a need for materials with improved dimensionally stability, that is, materials that resist contraction and expansion during changes in humidity and/or temperature. Such materials must be chosen so that the properties of the resulting product and the processability of the materials are commercially viable. The compositions and methods described herein address these and other needs. SUMMARY OF THE DISCLOSURE

Polyurethane composites comprising a fatty acid, a fatty acid salt, or a combination thereof and methods of manufacturing are described herein. In addition to the fatty acid, the fatty acid salt, or the combination thereof, the polyurethane composites can include a) a polyurethane formed by the reaction of (i) one or more isocyanates selected from the group consisting of diisocyanates, polyisocyanates, and mixtures thereof, and (ii) one or more polyols; and (b) an inorganic filler. In making the polyurethane composites described herein, the fatty acid, the fatty acid salt, or the combination thereof are not pre-reacted with the one or more polyols prior to reacting with the one or more isocyanates. The amount of polyurethane in the polyurethane composites can be from 15% to 60% by weight, for example, from 15% to 45% by weight, based on the total weight of the polyurethane composite.

Suitable fatty acids for use in the polyurethane composites can be derived from a C6-C26 fatty acid. In some embodiments, the fatty acid can be derived from a C12-C24 fatty acid. Specific examples of fatty acids can include lauric acid, maleic acid, myristic acid, palmitic acid, stearic acid, palmitoleic acid, oleic acid, erucic acid, linoleic acid, linolenic acid, eleostearic acid, arachidonic acid or mixtures thereof. Suitable fatty acid salts can be derived from any one or more of the fatty acids described herein. In some embodiments, the fatty acid salts can include a Group I metal, a Group II metal, a Group III metal, zinc, or ammonium cation. In some examples of the polyurethane composites, the fatty acid salts comprise a stearate such as calcium stearate. The fatty acid, fatty acid salt, or combination thereof can be present in an amount of from 0.05% to 10% by weight, such as from 0.1% to 5% by weight, based on the total weight of the composite.

The fatty acid, the fatty acid salt, or the combination thereof can associate with the polyurethane through non-covalent interaction. In some embodiments, 50% or greater by weight (for example, greater than 50%, greater than 60%, greater than 70%, greater than 75%, greater than 80%, or greater than 85% by weight) of the fatty acid, the fatty acid salt, or the combination thereof associate with the polyurethane through non-covalent interaction.

As described herein, the polyurethane composites can include an inorganic filler. The inorganic filler can include a particulate filler. The inorganic filler in the polyurethane composites can include limestone, coal ash such as fly ash, or a mixture thereof. Specific examples of fly ash that can be used in the composites include Class C or Class F fly ash. The amount of inorganic filler in the polyurethane composites can be from 40 to 90% by weight, based on the total weight of the polyurethane composite. For example, the inorganic filler can be present in an amount from 50% to 90%, from 50% to 80% or from 60% to 80% by weight, based on the total weight of the polyurethane composite. In some embodiments, the fatty acid, the fatty acid salt, or the combination thereof can interact with the inorganic filler. For example, the fatty acid, the fatty acid salt, or the combination thereof can interact with the inorganic filler through covalent, non-covalent, and/or ionic interactions.

The composites can further comprise glass fibers. The glass fibers can be present in an amount from 0.2% to 20%, based on the total weight of the polyurethane composite.

The polyurethane composites described herein are dimensionally stable. In some embodiments, the polyurethane composites exhibit a higher dimensional stability compared to identical composites that do not include a fatty acid and/or fatty acid salt. For example, the polyurethane composites, after wetting in water for 8 days and drying at 46^°C for 48 hours, exhibit a dimensional change that is less than 50% of the dimensional change of an identical composite excluding the fatty acid and/or fatty acid salt. The dimensional change can be in length, width, weight, or a combination thereof. In certain embodiments, the polyurethane composites, after wetting in water for 8 days and drying at 46^°C for 48 hours, exhibit a water absorption or desorption of from 0% to less than 0.5% by weight, based on the weight of the initial composite. In certain embodiments, the polyurethane composites, after wetting in water for 8 days and drying at 46^°C for 48 hours, increase or decrease in length by 0% to less than 0.2% compared to the initial composite.

The density of the polyurethane composites can be from 10 lb/ft³ to 75 lb/ft³. In some embodiments, the density of the polyurethane composites can be from 10 lb/ft³ to 30 lb/ft³, from 35 lb/ft³ to 75 lb/ft³, or from 35 lb/ft³ to 50 lb/ft³. In some examples, the polyurethane composites are foamed. The polyurethane composites can have a flexural strength of 200 psi or greater, such as from 200 psi to 2,500 psi, as measured by ASTM Cl 185.

Articles comprising the polyurethane composites are also disclosed. In some

embodiments, the articles can be building products. The building products formed from the composites can be selected from sidings, building panels, sheets, architectural moldings, sound barriers, thermal barriers, insulations, wall boards, ceiling tiles, ceiling boards, soffits, trims, backers, or roofing materials. Methods of making the polyurethane composites are also described herein. The method can include mixing the (a) one or more isocyanates selected from the group consisting of diisocyanates, polyisocyanates, and mixtures thereof, one or more polyols, a fatty acid, a fatty acid salt, or a combination thereof, and an inorganic filler to produce a mixture. The method of making the polyurethane composites does not include pre-reacting the fatty acid, the fatty acid salt, or the combination thereof with the one or more polyols prior to mixing with the one or more isocyanates. In some embodiments, the method can include mixing the one or more isocyanates and the one or more polyols prior to mixing with the fatty acid, the fatty acid salt, or the combination thereof. In some embodiments, the method can include mixing the one or more isocyanates and the fatty acid, the fatty acid salt, or the combination thereof prior to mixing with the one or more polyols. In other embodiments, the method can include simultaneously mixing the one or more isocyanates, the one or more polyols, and the fatty acid, the fatty acid salt, or the combination thereof. The mixture may further comprise a catalyst. The mixture can include the catalyst at 0.05 to 0.5 part per hundred parts of polyol. The polyurethane mixture can be formed in a mold. In some embodiments, the method can include applying the mixture to a mold at the temperature of the mixture. The method of making the polyurethane composite can include allowing the mixture to react and expand to form the polyurethane composite. In some embodiments, the mixture can be allowed to rise freely during foaming in the mold.

DESCRIPTION OF THE DRAWINGS

Figure 1 is a line graph showing the changes in the weight of filled polyurethane composites during absorption and desorption at room temperature.

Figure 2 is a line graph showing the changes in the weight of filled polyurethane composites during absorption and desorption at 46°C.

Figure 3 is a line graph showing the changes in the length of filled polyurethane composites during absorption and desorption at room temperature.

Figure 4 is a line graph showing the changes in the width of filled polyurethane composites during absorption and desorption at room temperature.

Figure 5 is a line graph showing the changes in the length of filled polyurethane composites during absorption and desorption at 46°C.

Figure 6 is a line graph showing the changes in the width of filled polyurethane composites during absorption and desorption at 46°C. DETAILED DESCRIPTION

Polyurethane composites comprising a fatty acid, a fatty acid salt, or a combination thereof and methods of preparing the composites are described herein. The polyurethane composites can include a) a polyurethane formed by the reaction of (i) one or more isocyanates selected from the group consisting of diisocyanates, polyisocyanates, and mixtures thereof, and (ii) one or more polyols in the presence of the fatty acid, the fatty acid salt, or the combination thereof; and (b) an inorganic filler.

Without wishing to be bound by theory, it is believed that moisture can be incorporated into filled polyurethane composite materials attributable to one or more of the following reasons. First, it is believed that the urethane (-NH-) bond and ester (-COO-) bond in polyurethane are both hydrophilic and thus make it easy for the polyurethane resin to absorb moisture. Second, it is believed that water can penetrate into the composite structure by interacting with polyurethane through hydrogen bond and subsequently causing increased free volume and plasticizing of the polymer matrix. Third, it is believed that imperfect bonding between the polymer matrix and inorganic fillers/fibers as a result of the incompatible nature of the two materials may allow moisture to penetrate into the interfacial zone and cause swelling. By modifying the hydrophilic nature of the polyurethane composite, the tendency of water to be incorporated into the polyurethane can be reduced and in turn mitigate the movement of the composite.

The polyurethane composites described herein include a fatty acid salt, a fatty acid salt, or a combination thereof that associates with the polyurethane matrix. Fatty acids and their salts usually have non-polar alkyl chains and polar carboxylic functional groups. The fatty acid and/or the fatty acid salt can be dispersed within the polyurethane matrix. Specifically, when used in polyurethane composites comprising inorganic fillers, it is believed that the hydrocarbon chain of the fatty acids or fatty acid salts associates with the polyurethane matrix, and the carboxylic functional group associates with the inorganic filler surface. Because of this association, the polyurethane matrix and fillers can form stronger interactions, making it more difficult for water and moisture to penetrate into the interfacial zone of the composite and cause expansion and shrinkage. Further, the fatty acids or fatty acid salts can increase the hydrophobicity of the polyurethane matrix, thus reducing the potential for moisture to induce volume change by plasticizing the matrix. The fatty acids or fatty acid salts may also function as a lubricant to improve the flow of the raw material mixture of the filled polyurethane material. Accordingly, the composite structure may become denser and less likely for moisture to be incorporated.

The term“associate” as used herein refers to the interaction between two or more individual components (e.g. molecules) present in the polyurethane composites by non-covalent or covalent bonds. The association may depend on, for example, polarity, charge, and/or other characteristics of the individual components, and includes, without limitation, electrostatic (e.g., ionic) interactions, dipole-dipole interactions, van der Waal’s forces, covalent bonds, and combinations of two or more thereof. In some embodiments, a substantial amount of the fatty acids or fatty acid salts associate with the polyurethane composites through non-covalent interactions. For example, greater than 50% by weight, 60% by weight or more, 70% by weight or more, 75% by weight or more, 80% by weight or more, 85% by weight or more, 90% by weight or more, 95% by weight or more, 98% by weight or more, or 100% by weight of the fatty acids or fatty acid salts can associate with the polyurethane composite through non-covalent interactions. The strength of the association can be modulated by altering one or more of the above-mentioned intermolecular interactions. In some embodiments, the fatty acids or fatty acid salts do not associate with the polyurethane composite through covalent bonds. In specific embodiments, the fatty acids or fatty acid salts do not associate with the polyol or isocyanate present in the polyurethane composite through covalent bonds. In other specific embodiments, less than 50% by weight (for example, less than 40% by weight, less than 30% by weight, less than 20% by weight, less than 15% by weight, or less than 10% by weight) of the fatty acids or fatty acid salts associate with the polyol or isocyanate present in the polyurethane composite through covalent bonds.

To impart hydrophobicity to the polyurethane composites, the fatty acids or fatty acid salts should have relatively low solubility in water. For instance, the polyurethane composites can include fatty acids or fatty acid salts whose equivalent fatty acids have a water solubility of 1 g/lOO g water or less at 20°C. For example, the polyurethane composites can include fatty acids or fatty acid salts whose equivalent fatty acids have a water solubility in water, measured at 20°C, of 0.8 g/lOO g water or less, 0.6 g/lOO g water or less, 0.2 g/lOO g water or less, 0.1 g/lOO g water or less, 0.05 g/lOO g water or less, 0.03 g/lOO g water or less, or 0.01 g/lOO g water or less.

Suitable fatty acids or fatty acid salts for use in the composites can be derived from a Ce- or greater fatty acid. For example, the fatty acids or fatty acid salts can be derived from a CV or greater, a Cs- or greater, a Cs>- or greater, a Cio- or greater, a C12- or greater, or a C14- or greater fatty acid. In some embodiments, the fatty acids or fatty acid salts can be derived from a C26- or less, a C24- or less, a C20- or less, or a Cie- or less fatty acid. In some embodiments, the fatty acid salts can be derived from a C6-C26, a C6-C24, a C8-C24, a C10-C24, a C12-C24, a C6-C20, a C8-C20, a C10-C20, or a C12-C20 fatty acid. The fatty acids or fatty acid salts used in the composites can include saturated and/or unsaturated fatty acids as well as branched and/or unbranched carbon chain. In some embodiments, the“fatty acid” may additionally include hydroxyl groups or epoxy groups.

In some embodiments, at least 50% by weight of the fatty acids or fatty acid salts in the polyurethane composites can be saturated. For example, at least 55% by weight (e.g., at least 60%, at least 65%, at least 70%, at least 75%, 30 at least 80%, at least 85%, at 90%, at least 95%, from 50% to 99%, from 55% to 99%, from 60% to 98%, from 70% to 98%, from 80% to 98%, from 80% to 95%, or from 85% to 95%) of the fatty acids or fatty acid salts in the polyurethane composites can be saturated.

In some embodiments, at least 50% by weight of the fatty acids or fatty acid salts in the polyurethane composites comprise a C12- or greater hydrocarbon chain. For example, at least 55% by weight (e.g., at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at 90%, at least 95%, from 50% to 99%, from 55% to 99%, from 60% to 98%, from 70% to 98%, from 80% to 98%, from 80% to 95%, or from 85% to 95%) of the fatty acids or fatty acid salts in the polyurethane composites comprise a C12- or greater hydrocarbon chain.

Specific examples of fatty acids or fatty acid salts can include salts derived from lauric acid, maleic acid, myristic acid, palmitic acid, stearic acid, palmitoleic acid, oleic acid, erucic acid, linoleic acid, linolenic acid, eleostearic acid, arachidonic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, pentadecylic acid, hepatadecanoic acid, behenic acid, lignoceric acid, myristoleic acid, trans-9-octadecenoic acid, vaccenic acid, stearidonic acid, gadoleic acid, eicosapentaenoic acid (EPA), cis-l3-docosenoic acid, clupanodonic acid, docosahexaenoic acid (DHA), cis-l5-tetracosenoic acid, or mixtures thereof.

The fatty acid salts can include any suitable cationic group. For example, the fatty acid salts can include a cationic group derived from a Group I metal, a Group II metal, a Group III metal, zinc, or ammonium. For example, the fatty acid salts can include sodium, potassium, calcium, magnesium, aluminum, or a mixture thereof. In some examples of the polyurethane composites, the fatty acid salt can comprise calcium stearate. In some embodiments, the polyurethane compositions can include fatty acids or fatty acid salts derived from the hydrolysis of a natural fat or oil. Particularly suitable natural fats or oils include those which contain a comparatively high proportion of fatty acids with a C6-or greater chain length. For example, the fatty acids or fatty acid salts can be derived from coconut oil with a high proportion of lauric acid (from 45 to 51% by weight) and myristic acid (16.5 to 18.5% by weight). The natural fats or oils can be hydrolyzed, for example, by addition of metal hydroxides.

The fatty acids and/or fatty acid salts can be present in an amount of 0.05% or greater by weight, based on the total weight of the composite. For example, the fatty acids and/or fatty acid salts can be present in an amount of 0.1% or greater, 0.2% or greater, 0.3% or greater, 0.5% or greater, 1% or greater, 1.5% or greater, 2% or greater, 2.5% or greater, or 3% or greater by weight, based on the total weight of the composite. In some embodiments, the fatty acids and/or fatty acid salts can be present in an amount of 10% or less, 9% or less, 8% or less, 7% or less, 5% or less, 4% or less, 3% or less, 2.5% or less, 2% or less, 1.5% or less, or 1% or less by weight, based on the total weight of the composite. In some embodiments, the fatty acids and/or fatty acid salts can be present in an amount of from 0.05% to 10%, from 0.1% to 10%, from 0.1% to 8%, from 0.5% to 8%, from 0.1% to 5%, from 0.5% to 5% by weight, based on the total weight of the composite.

In addition to the fatty acid and/or fatty acid salt, the polyurethane composites can comprise a polyurethane formed using reactive systems such as reactive isocyanates and reactive polyols. In some embodiments, the composites can be formed using highly reactive systems including highly reactive polyols, highly reactive isocyanates, or both. Isocyanates suitable for use in the polyurethane composites can include one or more monomeric or oligomeric poly- or di-isocyanates. The monomeric or oligomeric poly- or di-isocyanate may include aromatic diisocyanates and polyisocyanates. The isocyanates can also be blocked isocyanates or pre polymer isocyanates. The particular isocyanate used in the composites can be selected based on the desired properties of the composites, such as the amount of foaming, strength of bonding to the filler, wetting of the inorganic particulates in the reaction mixture, strength of the resulting composite, stiffness (elastic modulus), reactivity, and viscosity of the mixture.

An example of a useful diisocyanate is methylene diphenyl diisocyanate (MDI). Suitable MDI’s include MDI monomers, MDI oligomers, and mixtures thereof. Further examples of useful isocyanates include those having NCO (i.e., the reactive group of an isocyanate) contents ranging from about 25% to about 35% by weight. Examples of useful isocyanates are found, for example, in Polyurethane Handbook: Chemistry, Raw Materials, Processing Application, Properties, 2^nd Edition, Ed: Gunter Oertel; Hanser/Gardner Publications, Inc., Cincinnati, OH, which is herein incorporated by reference. Suitable examples of aromatic polyisocyanates include 2,4- or 2,6-toluene diisocyanate, including mixtures thereof; p-phenylene diisocyanate; tetramethylene and hexamethylene diisocyanates; 4,4-dicyclohexylmethane diisocyanate;

isophorone diisocyanate; 4,4-phenylmethane diisocyanate; polymethylene

polyphenylisocyanate; and mixtures thereof. In addition, triisocyanates may be used, for example, 4, 4, 4-triphenylmethane triisocyanate; 1,2, 4-benzene triisocyanate; polymethylene polyphenyl polyisocyanate; methylene polyphenyl polyisocyanate; and mixtures thereof.

Suitable blocked isocyanates are formed by the treatment of the isocyanates described herein with a blocking agent (e.g., diethyl malonate, 3,5-dimethylpyrazole, methylethylketoxime, and caprolactam). Isocyanates are commercially available, for example, from Bayer Corporation (Pittsburgh, PA) under the trademarks MONDUR and DESMODUR. Other examples of suitable isocyanates include MONDUR MR Light (Bayer Corporation; Pittsburgh, PA), PAPI 27 (Dow Chemical Company; Midland, MI), Lupranate M20 (BASF Corporation; Florham Park, NJ), Lupranate M70L (BASF Corporation; Florham Park, NJ), Rubinate M (Huntsman

Polyurethanes; Geismar, LA), Econate 31 (Ecopur Industries), and derivatives thereof. In some embodiments, the isocyanate compositions used to form the composite can include those having viscosities ranging from 25 to 700 cPs at 25°C.

The average functionality of isocyanates useful with the polyurethane composites described herein can be from 1.5 to 5. Further, examples of useful isocyanates include isocyanates with an average functionality of from 2 to 4.5, from 2.2 to 4, from 2.4 to 3.7, from 2.6 to 3.4, or from 2.8 to 3.2.

As indicated herein, the polyurethane composites can include one or more polyols. The one or more polyols for use in the polyurethane composites can include polyester polyols, poly ether polyols, Mannich polyols, or combinations thereof. In some embodiments, the one or more polyols can include a first polyol and/or a second polyol as described herein.

The one or more polyols can include one or more less reactive (or first) polyols. The less reactive polyol can have lower numbers of primary hydroxyl groups, lower primary hydroxyl numbers, and higher numbers of secondary hydroxyl groups, than a highly reactive polyol. As used herein, the primary hydroxyl number is defined as the hydroxyl number multiplied by the percentage of primary hydroxyl groups based on the total number of hydroxyl groups in the polyol. The one or more less reactive polyols can have about 40% or less primary hydroxyl groups, about 35% or less primary hydroxyl groups, about 30% or less primary hydroxyl groups, about 25% or less primary hydroxyl groups, about 20% or less primary hydroxyl groups, about 15% or less primary hydroxyl groups, or even about 10% or less primary hydroxyl groups. The one or more less reactive polyols can have primary hydroxyl numbers (as measured in units of mg KOH/g) of less than about 220, less than about 200, less than about 180, less than about 160, less than about 140, less than about 120, less than about 100, less than about 80, less than about 60, less than about 40, or even less than about 20. The number of primary hydroxyl groups can be determined using fluorine NMR spectroscopy as described in ASTM D4273.

The one or more less reactive polyols can have hydroxyl numbers (as measured in units of mg KOH/g) of 700 or less, 650 or less, 600 or less, 550 or less, 500 or less, 450 or less, 400 or less, 350 or less, 300 or less, 250 or less, 200 or less, 150 or less, 125 or less, 100 or less, 80 or less, 60 or less, 40 or less, or even 20 or less. The one or more less reactive polyols can have hydroxyl numbers (as measured in units of mg KOH/g) of 50 or more, 100 or more, 150 or more, 200 or more, 250 or more, 300 or more, 350 or more, 400 or more, 450 or more, or 500 or more. In some embodiments, the average hydroxyl number can be 700 or less, 650 or less, 600 or less, 550 or less, 500 or less, 450 or less, 400 or less, 350 or less, 300 or less, or 250 or less, and/or is 100 or more, 150 or more, 200 or more, 250 or more, 300 or more, 350 or more, 400 or more,

450 or more, or 500 or more. For example, the average hydroxyl number can be from 100 to 700, from 100 to 500, from 150 to 450, or from 200 to 400. In some embodiments, the one or more less reactive polyols can include two or more polyols. For example, there can be a blend of 75% of a polyol having a hydroxyl number of 400 and 25% of a polyol having a hydroxyl number of 100 to produce an average hydroxyl number of 325.

The functionality of the one or more less reactive polyols useful with the polyurethane composites described herein can be 4 or less, 3.5 or less, 3.25 or less, 3 or less, 2.75 or less, 2.5 or less, or 2.25 or less. In some embodiments, the functionality of the one or more less reactive polyols can be 2 or greater, 2.25 or greater, 2.5 or greater, 2.75 or greater, 3 or greater, 3.25 or greater, 3.5 or greater, or 3.75 or greater. The average functionality of the one or more less reactive polyols useful with the composites described herein can be 4 or less, 3.5 or less, 3.25 or less, 3 or less, 2.75 or less, 2.5 or less, or 2.25 or less. In some embodiments, the average functionality of the one or more less reactive polyols can be 2 or greater, 2.25 or greater, 2.5 or greater, 2.75 or greater, 3 or greater, 3.25 or greater, 3.5 or greater, or 3.75 or greater. Further, examples of useful less reactive polyols include polyols with an average functionality of from 2 to 4, from 2.5 to 4, or from 2 to 3.5.

The one or more less reactive polyols can have an average molecular weight of 250 g/mol or greater (e.g., 300 g/mol or greater, 350 g/mol or greater, 400 g/mol or greater, 450 g/mol or greater, 500 g/mol or greater, 550 g/mol or greater, 600 g/mol or greater, 650 g/mol or greater, or 700 g/mol or greater). In some cases, the one or more less reactive polyols have an average molecular weight of 700 g/mol or less (e.g., 650 g/mol or less, 600 g/mol or less, 550 g/mol or less, 500 g/mol or less, 450 g/mol or less, 400 g/mol or less, 350 g/mol or less, or 300 g/mol or less). In some cases, the one or more less reactive polyols have an average molecular weight of from 250 g/mol to 750 g/mol, from 250 g/mol to 600 g/mol, or from 250 g/mol to 500 g/mol.

The one or more less reactive polyols can include an aromatic polyester polyol, an aromatic poly ether polyol, or a combination thereof. The aromatic polyol can have an aromaticity of 50% or less, such as 45% or less, or 40% or less. In some embodiments, the aromatic polyol can have an aromaticity of 35% or greater, such as 38% or greater, 40% or greater, or 45% or greater. In some examples, the one or more less reactive polyols include an aromatic polyester polyol such as those sold under the TEROL® trademark (e.g., TEROL® 198 and TEROL® 250). Other examples of less reactive polyols include a glycerin-based polyol and derivatives thereof commercially available from Carpenter Co. (e.g., Carpol® GP-240; Carpol® GP-725; Carpol® GP-700; Carpol® GP-1000; Carpol® GP-1500); polypropylene-based polyol and derivatives thereof commercially available from Huntsman International (e.g., Jeffol®

FX31-240; Jeffol® G30-650; Jeffol® FX31-167; Jeffol® A-630; Jeffol® AD-310); polyester polyols available from Huntsman International (e.g., XO 13001); castor oil; Stepanpol PS- 2052A (commercially available from the Stepan Company); Agrol 2.0, 3.6, 4.3, 5.6 and 7.0 (plant-based polyols commercially available from BioBased Technologies); Ecopol 123 and Ecopol 124, which are commercially available from Ecopur Industries; Honey Bee HB-150 and HB-230, soybean oil-based polyols commercially available from MCPU Polymer Engineering; Terol 1154, commercially available from Oxid (Houston, TX); Multranol 3900, Multranol 3901, Arcol 11-34, Arcol 24-32, Arcol 31-28, Arcol E-351, Arcol LHT-42, and Arcol LHT -112, commercially available from Bayer; and Voranol 220-028, 220-094, 220-110N, 222-056, 232- 027, 232-034, and 232-035, commercially available from Dow Chemical Company. The one or more less reactive polyols can be present in an amount of greater than 10%, greater than 20%, greater than 30%, greater than 40%, greater than 45%, greater than 50%, greater than 55%, greater than 60%, greater than 65%, greater than 70%, greater than 75%, greater than 80%, greater than 85%, greater than 90%, greater than 95%, or 100% by weight, based on the weight of the at one or more polyols. In some embodiments, the one or more less reactive polyols can be present in an amount of 95% or less, 90% or less, 85% or less, 80% or less, 75% or less, 70% or less, 65% or less, 60% or less, 55% or less, 50% or less, 45% or less, 35% or less, 25% or less, or 20% or less, based on the weight of the at one or more polyols.

The one or more polyols can include one or more highly reactive (or second) polyols.

The one or more highly reactive polyols can include polyols having a large number of primary hydroxyl groups (e.g. 75% or more) based on the total number of hydroxyl groups in the polyol. For example, the high primary hydroxyl group polyols can include 80% or more, 85% or more, 90% or more, 95% or more, or 100% of primary hydroxyl groups. In some embodiments, the one or more highly reactive polyols can include polyols having a primary hydroxyl number of greater than 250. For example, the primary hydroxyl number can be greater than 300, greater than 320, greater than 340, greater than 360, greater than 380, greater than 400, greater than 420, greater than 460, greater than 465, or greater than 470.

The one or more highly reactive polyols can include polyols having a hydroxyl number of greater than 250. For example, the hydroxyl number can be greater than 275, greater than 300, greater than 325, greater than 350, greater than 375, greater than 400, greater than 425, greater than 450, greater than 475, greater than 500, greater than 525, greater than 550, greater than 575, greater than 600, greater than 625, greater than 650, greater than 675, greater than 700, greater than 725, or greater than 750.

The average functionality of the one or more highly reactive polyols useful with the polyurethane composites described herein can be 3.5 or greater, (e.g., 3.5 or greater, 3.6 or greater, 3.7 or greater, 3.8 or greater, 3.9 or greater, 4.0 or greater, 4.1 or greater, 4.2 or greater,

4.5 or greater, 5 or greater, or 6 or greater). In some embodiments, the average functionality of the one or more highly reactive polyols useful with the polyurethane composites can be 8 or less, (e.g., 7 or less, 6 or less, 5.5 or less, 5 or less, or 4.5 or less). Further, examples of useful one or more highly reactive polyols include polyols with an average functionality of from 3.5 to 8, from

3.5 to 7, from 3.5 to 6, from 3.5 to 5, or from 4 to 5. In some cases, the one or more highly reactive polyols has a molecular weight of 350 g/mol or greater (e.g., 400 g/mol or greater, 450 g/mol or greater, 460 g/mol or greater, 470 g/mol or greater, 480 g/mol or greater, or 500 g/mol or greater). In some cases, the one or more highly reactive polyols has a molecular weight of 1000 g/mol or less (e.g., 900 g/mol or less, 800 g/mol or less, 700 g/mol or less, 600 g/mol or less, 550 g/mol or less, 540 g/mol or less, 530 g/mol or less, 520 g/mol or less, 500 g/mol or less, 480 g/mol or less, or 450 g/mol or less). In some cases, the one or more highly reactive polyols has a molecular weight of from 350 g/mol to 1000 g/mol or less, from 350 g/mol to 900 g/mol or less, from 400 g/mol to 800 g/mol or less, or from 400 g/mol to 700 g/mol or less.

In some embodiments, the one or more highly reactive polyols can include a Mannich polyol. Mannich polyols are the condensation product of a substituted or unsubstituted phenol, an alkanolamine, and formaldehyde. Mannich polyols can be prepared using methods known in the art. For example, Mannich polyols can be prepared by premixing the phenolic compound with a desired amount of the alkanolamine, and then slowly adding formaldehyde to the mixture at a temperature below the temperature of Novolak formation. At the end of the reaction, water is stripped from the reaction mixture to provide a Mannich base. See, for example, U.S. Patent No. 4,883,826, which is incorporated herein by reference in its entirety. The Mannich base can then be alkoxylated to provide a Mannich polyol.

The substituted or unsubstituted phenol can include one or more phenolic hydroxyl groups. In certain embodiments, the substituted or unsubstituted phenol includes a single hydroxyl group bound to a carbon in an aromatic ring. The phenol can be substituted with substituents which do not undesirably react under the conditions of the Mannich condensation reaction, a subsequent alkoxylation reaction (if performed), or the preparation of polyurethanes from the final product. Examples of suitable substituents include alkyl (e.g., a Ci-Cie alkyl, or a C1-C12 alkyl), aryl, alkoxy, phenoxy, halogen, and nitro groups.

Examples of suitable substituted or unsubstituted phenols that can be used to form Mannich polyols include phenol, 0-, p-, or m-cresols, ethylphenol, nonylphenol, dodecylphenol, p-phenylphenol, various bisphenols including 2,2-bis(4-hydroxyphenyl)propane (bisphenol A), b-naphthol, b-hydroxyanthracene, p-chlorophenol, o-bromophenol, 2,6-dichlorophenol, p- nitrophenol, 4- or 2-nitro-6-phenylphenol, 2-nitro-6- or 4-methylphenol, 3,5-dimethylphenol, p- isopropylphenol, 2-bromo-6-cyclohexylphenol, and combinations thereof. In some

embodiments, the Mannich polyol is derived from phenol or a monoalkyl phenols (e.g., a para- alkyl phenols). In some embodiments, the Mannich polyol is derived from a substituted or unsubstituted phenol selected from the group consisting of phenol, para-n-nonylphenol, and combinations thereof.

The alkanolamine used to produce the Mannich polyol can include a monoalkanolamine, a dialkanolamine, a trialkanolamine, a tetraalkanolamine, or combinations thereof. Examples of suitable monoalkanolamines include methylethanolamine, ethylethanolamine,

methylisopropanolamine, ethylisopropanolamine, methyl-2 -hydroxybutylamine,

phenylethanolamine, ethanolamine, isopropanolamine, and combinations thereof. Suitable dialkanolamines include dialkanolamines which include two hydroxy -substituted C1-C12 alkyl groups (e.g., two hydroxy-substituted C i-Cs alkyl groups, or two hydroxy-substituted C1-C6 alkyl groups). The two hydroxy-substituted alkyl groups can be branched or linear, and can be of identical or different chemical composition. Examples of suitable dialkanolamines include diethanolamine, diisopropanolamine, ethanolisopropanolamine, ethanol-2-hydroxybutylamine, isopropanol-2 -hydroxybutylamine, isopropanol-2-hydroxyhexylamine, ethanol-2- hydroxyhexylamine, and combinations thereof. Suitable trialkanolamines include

trialkanolamines which include three hydroxy-substituted C1-C12 alkyl groups (e.g., three hydroxy-substituted Ci-Ce alkyl groups, or three hydroxy-substituted C1-C6 alkyl groups). The three hydroxy-substituted alkyl groups can be branched or linear, and can be of identical or different chemical composition. Examples of suitable trialkanolamines include

triisopropanolamine (TIP A), triethanolamine, N,N-bis(2 -hydroxy ethyl)-N-(2- hydroxypropyl)amine (DEIPA), N,N-bis(2-hydroxypropyl)-N-(hydroxyethyl)amine (EDIPA), tris(2 -hydroxybutylamine, hydroxy ethyl di(hydroxypropyl)amine, hydroxypropyl

di(hydroxyethyl)amine, tri(hydroxypropyl)amine, hydroxyethyl di(hydroxy-n-butyl)amine, hydroxybutyl di(hydroxypropyl)amine, and combinations thereof. Exemplary

tetraalkanolamines include four hydroxy-substituted C1-C12 alkyl groups (e.g., four hydroxy- substituted Ci-Ce alkyl groups, or four hydroxy-substituted C1-C6 alkyl groups). In certain embodiments, the alkanolamine is selected from the group consisting of diethanolamine, diisopropanolamine, and combinations thereof.

Any suitable alkylene oxide or combination of alkylene oxides can be used to form the Mannich polyol. In some embodiments, the alkylene oxide is selected from the group consisting of ethylene oxide, propylene oxide, butylene oxide, and combinations thereof. In certain embodiments, the Mannich polyol is alkoxylated with from 100% to about 80% propylene oxide and from 0 to about 20 wt% ethylene oxide.

Mannich polyols are known in the art, and include, for example, ethylene and propylene oxide-capped Mannich polyols sold under the trade names CARPOL® MX-425 and CARPOL® MX-470 (Carpenter Co., Richmond, VA).

The one or more highly reactive polyols can be present in an amount of greater than 10%, greater than 20%, greater than 30%, greater than 40%, greater than 45%, greater than 50%, greater than 55%, greater than 60%, greater than 65%, greater than 70%, greater than 75%, greater than 80%, greater than 85%, greater than 90%, greater than 95%, or 100% by weight, based on the weight of the at one or more polyols. In some embodiments, the one or more highly reactive polyols can be present in an amount of 95% or less, 90% or less, 85% or less, 80% or less, 75% or less, 70% or less, 65% or less, 60% or less, 55% or less, 50% or less, 45% or less, 35% or less, 25% or less, or 20% or less, based on the weight of the at one or more polyols.

In some embodiments, the one or more polyols can include a sucrose and/or amine-based polyol. The sucrose and/or amine-based polyol can include, for example, a poly ether polyol (including for example ethylene oxide, propylene oxide, butylene oxide, and combinations thereof) which is initiated by a sucrose and/or amine group. Sucrose and/or amine-based polyols are known in the art, and include, for example, sucrose/amine initiated poly ether polyol sold under the trade name CARPOL® SPA-357 or CARPOL® SPA-530 (Carpenter Co., Richmond, VA) and triethanol amine initiated poly ether polyol sold under the trade name CARPOL® TEAP-265 (Carpenter Co., Richmond, VA). The sucrose and/or amine-based polyol can be present in an amount of greater than 10%, greater than 20%, greater than 30%, greater than 40%, greater than 45%, greater than 50%, greater than 55%, greater than 60%, greater than 65%, greater than 70%, greater than 75%, greater than 80%, greater than 85%, greater than 90%, greater than 95%, or 100% by weight, based on the weight of the at one or more polyols. In some embodiments, the sucrose and/or amine-based polyol can be present in an amount of 95% or less, 90% or less, 85% or less, 80% or less, 75% or less, 70% or less, 65% or less, 60% or less, 55% or less, 50% or less, 45% or less, 35% or less, 25% or less, or 20% or less, based on the weight of the at one or more polyols.

Other suitable isocyanate-reactive monomers that can be used in the polyurethane composites include one or more polyamines. Suitable polyamines can correspond to the polyols described herein (for example, a polyester polyol or a poly ether polyol), with the exception that the terminal hydroxy groups are converted to amino groups, for example by amination or by reacting the hydroxy groups with a diisocyanate and subsequently hydrolyzing the terminal isocyanate group to an amino group. By way of example, the polyamine can be polyether polyamine, such as polyoxyalkylene diamine or polyoxyalkylene triamine. Polyether polyamines are known in the art, and can be prepared by methods including those described in U.S. Patent 3,236,895 to Lee and Winfrey. Exemplary polyoxyalkylene diamines are commercially available, for example, from Huntsman Corporation under the trade names Jeffamine® D-230, Jeffamine® D-400 and Jeffamine® D-2000. Exemplary polyoxyalkylene triamines are commercially available, for example, from Huntsman Corporation under the trade names Jeffamine® T-403, Jeffamine® T-3000, and Jeffamine® T-5000.

In some embodiments, the one or more polyols can include an alkoxylated polyamine (i.e., alkylene oxide-capped polyamines) derived from a polyamine and an alkylene oxide. Alkoxylated polyamines can be formed by reacting a suitable polyamine with a desired number of moles of an alkylene oxide. Suitable polyamines include monomeric, oligomeric, and polymeric poly amines. In some cases, the poly amines has a molecular weight of less than 1000 g/mol (e.g., less than 800 g/mol, less than 750 g/mol, less than 500 g/mol, less than 250 g/mol, or less than 200 less than 200 g/mol). Examples of suitable poly amines that can be used to form alkoxylated poly amines include ethylenediamine, l,3-diaminopropane, putrescine, cadaverine, hexamethylenediamine, l,2-diaminopropane, o-phenylenediamine, m-phenylenediamine, p- phenylenediamine, spermidine, spermine, norspermidine, toluene diamine, 1, 2-propane-diamine, diethylenetriamine, triethylenetetramine, tetraethylene-pentamine (TEPA),

pentaethylenehexamine (PEHA), and combinations thereof. Any suitable alkylene oxide or combination of alkylene oxides can be used to cap the polyamine. In some embodiments, the alkylene oxide is selected from the group consisting of ethylene oxide, propylene oxide, butylene oxide, and combinations thereof. Alkylene oxide-capped polyamines are known in the art, and include, for example, propylene oxide-capped ethylene diamine sold under the trade name CARPOL® EDAP-770 (Carpenter Co., Richmond, VA) and ethylene and propylene oxide-capped ethylene diamine sold under the trade name CARPOL® EDAP-800 (Carpenter Co., Richmond, VA).

The polyamines or alkoxylated polyamines (when used) can be present in varying amounts relative the one or more polyols used to form the polyurethane composite. In some embodiments, the polyamines or alkoxylated polyamines can be present in an amount of 30% or less, 25% or less, 20% or less, 15% or less, 10% or less, or 5% or less by weight based on the weight of the one or more polyols.

In some embodiments, the one or more polyols can include one or more C3-C4 alkoxylated polyol. The one or more C3-C4 alkoxylated polyols can be present in an amount of 50% or greater by weight, based on the total weight of the one or more polyols present in the polyurethane composites. The one or more C3-C4 alkoxylated polyols can include a highly reactive polyol, a less reactive polyol, or a mixture thereof.

In certain cases, the polyurethane composite can include at least two polyols. For example, the polyurethane composite can be produced from one or more less reactive polyols and one or more highly reactive polyols. In some embodiments, the at least two polyols can include 50% or more of the first (less reactive) polyol and 30% or less of the second (highly reactive) polyol. In some embodiments, the at least two polyols can include 50% or less of the first (less reactive) polyol and 30% or more of the second (highly reactive) polyol. The one or more polyols for use in the polyurethane composite can have an average functionality of 1.5 to 6.0, 1.5 to 5.0, 1.8 to 4.0, or 1.8 to 3.5. The average hydroxyl number values (as measured in units of mg KOH/g) for the one or more polyols can be from 20 to 600 such as from 20 to 100, 100 to 600, from 150 to 550, from 200 to 500, from 250 to 440, from 300 to 415, from 340 to 400.

As indicated herein, in the polyurethane composite, one or more isocyanates are reacted with the one or more polyols (and any additional isocyanate-reactive monomers) to produce the polyurethane formulation. In general, the ratio of isocyanate groups to the total isocyanate reactive groups, such as hydroxyl groups, water and amine groups, is in the range of about 0.5: 1 to about 1.5:1, which when multiplied by 100 produces an isocyanate index between 50 and 150. Additionally, the isocyanate index can be from about 80 to about 120, from about 90 to about 120, from about 100 to about 115, or from about 105 to about 110. Polyisocyanurate composites can also be formed from the one or more isocyanates and the one or more polyols described herein. With regards to the polyisocyanurate formulation, the isocyanate index can be from 180 to 380, for example, from 180 to 350, from 200 to 350, or from 200 to 270. As used herein, an isocyanate may be selected to provide a reduced isocyanate index, which can be reduced without compromising the chemical or mechanical properties of the composite material.

One or more catalysts can be added to facilitate curing and can be used to control the curing time of the polyurethane matrix. Examples of useful catalysts include amine-containing catalysts (including tertiary amines such as DABCO and tetramethylbutanediamine, and diethanolamine) and tin-, mercury-, and bismuth-containing catalysts. In some embodiments, the catalyst includes a delayed-action tin catalyst. In some embodiments, 0.01 wt% to 2 wt% catalyst or catalyst system (e.g., 0.025 wt% to 1 wt%, 0.05 wt% to 0.5 wt %, or 0.1 wt% to about 0.25 wt%) can be used based on the weight of the polyurethane. In some embodiments, 0.05 to 0.5 parts catalyst or catalyst system per hundred parts of polyol can be used.

The polyurethane can be present in the polyurethane composite in amounts from 10% to 60% based on the weight of polyurethane composite. For example, the polyurethane can be included in an amount from 14% to 60% or 20% to 50% by weight, based on the weight of the polyurethane composite. In some embodiments, the polyurethane can be present in an amount of 10% or greater, 15% or greater, 20% or greater, 25% or greater, 30% or greater, 35% or greater, 40% or greater, 45% or greater, 50% or greater, or 55% or greater by weight, based on the weight of the polyurethane composite. In some embodiments, the polyurethane can be present in an amount of 60% or less, 55% or less, 50% or less, 45% or less, 40% or less, 35% or less, 30% or less, 25% or less, 20% or less, or 15% or less by weight, based on the weight of polyurethane composite.

The polyurethane composite can include an inorganic filler, particularly an inorganic particulate filler. Suitable examples of inorganic fillers can be an ash, ground/recycled glass (e.g., window or bottle glass); milled glass; glass spheres; glass flakes; calcium carbonate;

aluminum trihydrate (ATH); silica; sand; ground sand; silica fume; slate dust; crusher fines; red mud; amorphous carbon (e.g., carbon black); clays (e.g., kaolin); mica; talc; wollastonite;

alumina; feldspar; bentonite; quartz; garnet; saponite; beidellite; granite; slag; calcium oxide; calcium hydroxide; antimony trioxide; barium sulfate; magnesium oxide; titanium dioxide; zinc carbonate; zinc oxide; nepheline syenite; perlite; diatomite; pyrophillite; flue gas desulfurization (FGD) material; soda ash; trona; expanded clay; expanded shale; expanded perlite; vermiculite; volcanic tuff; pumice; hollow ceramic spheres; hollow plastic spheres; expanded plastic beads (e.g., polystyrene beads); ground tire rubber; and mixtures thereof.

The inorganic filler can have a median particle size diameter of from 0.2 micron to 100 microns. For example, the inorganic filler can have a median particle size diameter of 100 microns or less, 95 microns or less, 90 microns or less, 85 microns or less, 80 microns or less, 75 microns or less, 70 microns or less, 65 microns or less, 60 microns or less, 55 microns or less, 50 microns or less, 45 microns or less, 40 microns or less, 35 microns or less, 30 microns or less, 25 microns or less, or 20 microns or less. In some embodiments, the inorganic filler can have a median particle size diameter of 0.2 microns or more, 0.3 microns or more, 0.4 microns or more, 0.5 microns or more, 0.7 microns or more, 1 micron or more, 2 microns or more, 5 microns or more, 10 microns or more, 15 microns or more, 20 microns or more, 25 microns or more, 30 microns or more, 35 microns or more, 40 microns or more, or 45 microns or more. In some examples, the inorganic filler can have a median particle size diameter of from 0.2 microns to 100 microns, 0.2 microns to 90 microns, or 0.3 microns to 80 microns, 1 to 50 microns, 1 to 25 microns, or 5 to 15 microns.

In some embodiments, the inorganic filler includes an ash. The ash can be a coal ash or another type of ash such as those produced by firing fuels including industrial gases, petroleum coke, petroleum products, municipal solid waste, paper sludge, wood, sawdust, refuse derived fuels, switchgrass or other biomass material. The coal ash can be fly ash, bottom ash, or combinations thereof. In some examples, the inorganic filler includes fly ash. Fly ash is produced from the combustion of pulverized coal in electrical power generating plants. The fly ash useful with the composite materials described herein can be Class C fly ash, Class F fly ash, or a mixture thereof. Fly ash produced by coal-fueled power plants is suitable for incorporation in the composites described herein. In some embodiments, the inorganic filler consists of or consists essentially of fly ash.

The fly ash can have a particle size distribution with at least two modes. For example, the particle size distribution of the fly ash can be three, four, five, or more modes. Alternatively, the fly ash can be blended with another fly ash to modify the properties of the fly ash to produce a fly ash having a particle size distribution with at least three modes.

In some embodiments, the particle size distribution can include 11-35% of the particles by volume in the first mode, 65-89% of the particles by volume in the second mode. In some embodiments, the particle size distribution can include 11-17% of the particles by volume in the first mode, 56-74% of the particles by volume in the second mode, and 12-31% of the particles by volume in the third mode. The ratio of the volume of particles in the second mode to the volume of particles in the first mode can be from 4.5 to 7.5.

The inorganic filler can be present in the polyurethane composite described herein in amounts from 20% to 90% by weight. Examples of the amount of inorganic filler present in the polyurethane composite described herein include 20%, 25%, 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, 40%, 41%, 42%, 43%, 44%, 45%, 46%, 47%, 48%, 49%, 50%, 51%, 52%, 53%, 54%, 55%, 56%, 57%, 58%, 59%, 60%, 61%, 62%, 63%, 64%, 65%, 66%, 67%

68%, 69%, 70%, 71%, 72%, 73%, 74%, 75%, 76%, 77%, 78%, 79%, 80%, 81%, 82%, 83%,

84%, 85%, 86%, 87%, 88%, 89%, or 90% by weight. In some embodiments, the inorganic filler, for example fly ash, can be present in amounts from 35% to 80% by weight such as from 50% to 80% by weight or from 50% to 75% by weight. In some embodiments, the inorganic filler can include calcium carbonate and can be present from 20% to 70% by weight such as from 45% to 65% by weight. In some embodiments, the calcium carbonate can be limestone.

In some embodiments, the inorganic filler can include fly ash and calcium carbonate. When used with fly ash, the amount of calcium carbonate in the polyurethane composites can be 0.1% or greater, 0.5% or greater, 1% or greater, 2% or greater, 3% or greater, 5% or greater, 7% or greater, 10% or greater, 12% or greater, or 15% or greater by weight, based on the weight of the polyurethane composites. In some embodiments, the polyurethane composites can include 15% or less, 14% or less, 12% or less, 10% or less, 8% or less, 5% or less, or 3% or less by weight calcium carbonate. In some embodiments, when used with fly ash, the polyurethane composites can include 1% to 15%, 1% to 10%, or 1% to 8% by weight calcium carbonate.

In some embodiments, the fatty acid, the fatty acid salt, or the combination thereof can interact with the inorganic filler. For example, the fatty acid, the fatty acid salt, or the combination thereof can interact with the inorganic filler through covalent, non-covalent, and/or ionic interactions. In certain embodiments, the fatty acid, the fatty acid salt, or the combination thereof can react with fly ash filler present in the composites. In certain embodiments, the fatty acid, the fatty acid salt, or the combination thereof can adhere via non-covalent interactions to fly ash filler present in the composites.

In some embodiments, the polyurethane composites can include an organic filler, such as a recycled polymeric material. Suitable examples include pulverized polymeric foam or recycled rubber material.

The composites can include a plurality of inorganic fibers. The inorganic fibers can be any natural or synthetic fiber. Inorganic fibers suitable for use with the composites can include glass fibers, basalt fibers, alumina silica fibers, aluminum oxide fibers, silica fibers, carbon fibers, metal fibers, metal and metal-coated fibers, and mineral fibers (such as stone wool, slag wool, or ceramic fiber wool). In some embodiments, the inorganic fibers can include glass fibers. Glass fibers can include fibrous glass such as E-glass, C-glass, S-glass, and AR-glass fibers. In some examples, fire resistant or retardant glass fibers can be included to impart fire resistance or retarding properties to the polyurethane composites. In some embodiments, the composites can include a combination of fibers that break and fibers that do not break when the polyurethane composites is being formed using processing machinery and/or fractured by external stress.

In some embodiments, the glass fibers can be dispersed within the composite. The glass fibers in the polyurethane composites can be present in the form of individual fibers, chopped fibers, bundles, strings such as yams, fabrics, papers, rovings, mats, or tows. In some embodiments, the composite can include a plurality of glass fibers having an average length of 1 mm or greater, 1.5 mm or greater, 2 mm or greater, 3 mm or greater, 4 mm or greater, 5 mm or greater, or 6 mm or greater. In some embodiments, the average length of the glass fibers can be 50 mm or less, 40 mm or less, 30 mm or less, 20 mm or less, 15 mm or less, 12 mm or less, or 10 mm or less. In some examples, the glass fibers can be from 1 mm to 50 mm in average length. For example, the glass fibers can be from 1.5 mm to 30 mm, from 2 mm to 30 mm, from 3 mm to 30 mm, or from 3 mm to 15 mm in average length. The glass fibers in the composite can have any dimension of from 1 pm to 30 pm in average diameter. For example, the average diameter of the glass fibers can be 1.5 pm to 30 pm, 3 pm to 20 pm, 4 pm to 18 pm, or 5 pm to 15 pm. The glass fibers can be provided in the composite in a random orientation or can be axially oriented.

The glass fibers can be present in the polyurethane composite in amounts of 15% or less by weight, based on the weight of composite. For example, the glass fibers can be present in amounts from 0.25% to 15%, 0.5% to 15%, 1% to 15%, 0.25% to 10%, 0.5% to 10%, 1% to 10%, 0.25% to 8%, 0.25% to 6%, or 0.25% to 4% by weight, based on the weight of the polyurethane composite.

The polyurethane composite can include additional fiber materials. The additional fiber materials can include polyalkylene fibers, polyamide fibers, polyester fibers, phenol- formaldehyde fibers, polyvinyl chloride fibers, polyacrylic fibers, acrylic polyester fibers, polyurethane fibers, polyacrylonitrile fibers, rayon fibers, cellulose fibers, carbon fibers, or combinations thereof. In certain embodiments, the additional fiber materials can include hemp fibers, sisal fibers, coton fibers, straw, reeds, or other grasses, jute, bagasse fibers, bamboo fibers, abaca fibers, flax, southern pine fibers, wood fibers, cellulose, saw dust, wood shavings, lint, vicose, leather fibers, rayon, and mixtures thereof. Other suitable additional fiber materials include synthetic fibers such as, Kevlar, viscose fibers, Dralon® fibers, polyethylene fibers, polyethylene naphthalate fibers, polypropylene fibers, polyvinyl alcohol fibers, aramid fibers, or combinations thereof.

In some embodiments, the fibers and/or the inorganic filler such as fly ash can be coated with a composition to modify their reactivity. For example, the fibers and/or the inorganic filler can be coated with a sizing agent such as a coupling agent (compatibilizer). In some embodiments, the fibers and/or the inorganic filler can be coated with a composition for promoting adhesion. U.S. Patent No. 5,064,876 to Hamada et al. and U.S. Patent No. 5,082,738 to Swofford, for example, disclose compositions for promoting adhesion. U.S. Patent No.

4,062,999 to Kondo et al, and U.S. Patent No. 6,602,379 to Li et al. describe suitable aminosilane compounds for coating fibers. In some embodiments, the fibers and/or the inorganic filler are surface coated with a composition comprising a silane compound such as aminosilane. In some embodiments, the fibers and/or the inorganic filler are surface coated with a

composition comprising an oil, starch, or a combination thereof. In some embodiments, the fibers and/or the inorganic filler are surface coated with a composition comprising a fatty acid and/or fatty acid salt as described herein.

Additional components useful with the polyurethane composites can include foaming agents, blowing agents, surfactants, chain-extenders, crosslinkers, UV stabilizers, fire retardants, antimicrobials, anti-oxidants, and pigments. Though the use of such components is well known to those of skill in the art, some of these additional additives are further described herein.

Chemical foaming agents include azodicarbonamides (e.g., Celogen manufactured by Lion Copolymer Geismar); and other materials that react at the reaction temperature to form gases such as carbon dioxide. In the case of polyurethane foam, water is an exemplary foaming agent that reacts with isocyanate to yield carbon dioxide. The presence of water as an added component or in the filler also can result in the formation of poly urea bonds through the reaction of the water and isocyanate. In some embodiments, water may be present in the mixture used to produce the polyurethane composites in an amount of from greater than 0% to 5% by weight or less, based on the weight of the mixture. In some embodiments, water can be present in a range of 0.02% to 4%, 0.05% to 3%, 0.1% to 2%, or 0.2% to 1% by weight, based on the weight of the mixture. In some embodiments, the mixture used to produce the composite includes less than 0.5% by weight water. In some embodiments, no chemical foaming agents are used. In some embodiments, water is the only foaming agent used. Surfactants can be used as wetting agents and to assist in mixing and dispersing the materials in a composite. Surfactants can also stabilize and control the size of bubbles formed during the foaming event and the resultant cell structure. Surfactants can be used, for example, in amounts below about 0.5 wt % based on the total weight of the mixture. Examples of surfactants useful with the polyurethanes described herein include anionic, non-ionic and cationic surfactants. For example, silicone surfactants such as Tegostab B-8870, DC-197 and DC-193 (Air Products; Allentown, PA) can be used.

Low molecular weight reactants such as chain-extenders and/or crosslinkers can be included in the polyurethane composites described herein. These reactants help the polyurethane composites to distribute and contain the fiber material and/or inorganic filler within the composite. Chain-extenders are difunctional molecules, such as diols or diamines, that can polymerize to lengthen the urethane polymer chains. Examples of chain-extenders include ethylene glycol; l,4-butanediol; ethylene diamine, 4,4’-methylenebis(2-chloroaniline)

(MBOCA); diethyltoluene diamine (DETDA); and aromatic diamines such as Unilink 4200 (commercially available from UOP). Crosslinkers are tri- or greater functional molecules that can integrate into a polymer chain through two functionalities and provide one or more further functionalities (i.e., linkage sites) to crosslink to additional polymer chains. Examples of crosslinkers include glycerin, trimethylolpropane, sorbitol, diethanolamine, and triethanolamine. In some polyurethane composites, a crosslinker or chain-extender may be used to replace at least a portion of the one or more polyols in the polyurethane composites. For example, the polyurethane can be formed by the reaction of an isocyanate, a polyol, and a crosslinker.

Coupling agents and other surface treatments such as viscosity reducers, flow control agents, or dispersing agents can be added directly to the filler or fiber, or incorporated prior to, during, and/or after the mixing and reaction of the polyurethane composites. Coupling agents may also reduce the viscosity of the polyurethane composites mixture. Coupling agents can also allow higher filler loadings of the inorganic filler such as fly ash, and/or fiber material, and may be used in small quantities. For example, the polyurethane composites may comprise about 0.01 wt % to about 0.5 wt % of a coupling agent. Examples of coupling agents useful with the polyurethane composites described herein include Ken-React LICA 38 and KEN-React KR 55 (Kenrich Petrochemicals; Bayonne, NJ). Examples of dispersing agents useful with the polyurethane composites described herein include JEFFSPERSE X3202, JEFFSPERSE

X3202RF, and JEFFSPERSE X3204 (Huntsman Polyurethanes; Geismar, LA). Ultraviolet light stabilizers, such as UV absorbers, can be added to the polyurethane composites described herein. Examples of UV light stabilizers include hindered amine type stabilizers and opaque pigments like carbon black powder. Fire retardants can be included to increase the flame or fire resistance of the polyurethane composites. Antimicrobials can be used to limit the growth of mildew and other organisms on the surface of the composite. Antioxidants, such as phenolic antioxidants, can also be added. Antioxidants provide increased UV protection, as well as thermal oxidation protection.

Pigments or dyes can optionally be added to the polyurethane composites described herein. An example of a pigment is iron oxide, which can be added in amounts ranging from about 2 wt% to about 7 wt%, based on the total weight of the polyurethane composites.

As described herein, the polyurethane composites can include a fatty acid, a fatty acid salt, or a combination thereof. Incorporation of the fatty acid, fatty acid salt, or combination thereof salt in the polyurethane composites can improve the dimensional stability of the composites, compared to otherwise identical composites without the fatty acid and/or fatty acid salt.“Dimensional stability” as used herein refers to the ability of the composites to resist a change in its dimensions, particularly, in length, width, and/or weight. In some embodiments, the polyurethane composites described herein are dimensionally stable to moisture related movements such as shrinking, swelling, warping, cupping, bowing, or twisting.

The dimensional stability of the polyurethane composites can be determined by water absorption and desorption cycling experiments. Specifically, the dimensions of the composite are determined for a first time prior to the cycling experiment. The composite is then soaked in water at 46°C for eight (8) days and then dried at 46^°C for 48 hours. The dimensions of the composite are then determined for a second time after completion of the wet/dry cycle. The dimensional stability of the polyurethane composites can be expressed in terms of % change in length, width, weight, or a combination thereof. The % change in width can be calculated as 100% x (widtht - initial width)/initial width, where the initial width can be determined within 15 minutes of extrusion and widtht can be determined after the absorption/desorption cycle.

The polyurethane composites described herein are desirably dimensionally stable to the extent that the change in dimensions of the composites, after at least one (1)

absorption/desorption (wet/dry) cycle as described herein, is less than the change in dimensions of an otherwise identical composite excluding the fatty acid and/or fatty acid salt. In some embodiments, the composites described herein are at least 5% more dimensionally stable (in length, weight, and width) after at least one absorption/desorption cycle (i.e. when wetted in water for 8 days then dried at 46^°C for 48 hours) compared to an otherwise identical composite excluding the fatty acid and/or fatty acid salt. For example, the composites described herein are greater than 5%, greater than 10%, greater than 15%, greater than 20%, greater than 25%, greater than 30%, greater than 35%, greater than 40%, greater than 45%, or greater than 50% more dimensionally stable after at least one absorption/desorption cycle when compared to an otherwise identical composite excluding the fatty acid and/or fatty acid salt. In some

embodiments, the dimensional change of the composites described herein, when wetted in water for 8 days then dried at 46^°C for 48 hours, can be less than 50%, less than 40%, less than 30%, less than 25%, less than 20%, less than 15%, or less than 10% of the dimensional change of an otherwise identical composite excluding the fatty acid and/or fatty acid salt.

In certain embodiments, the polyurethane composites when wetted in water for 8 days then dried at 46^°C for 48 hours are dimensionally stable exhibiting less than 0.5% (e.g., less than 0.4%, less than 0.3%, less than 0.2%, or less than 0.1%) shrinkage in length and/or width. In certain embodiments, the polyurethane composites when wetted in water for 8 days then dried at 46^°C for 48 hours are dimensionally stable exhibiting less than 0.5% (e.g., less than 0.4%, less than 0.3%, less than 0.2%, or less than 0.1%) swelling (expansion) in length and/or width. In certain embodiments, the polyurethane composites when wetted in water for 8 days then dried at 46^°C for 48 hours are dimensionally stable exhibiting less than 0.5% by weight (e.g., less than 0.4% by weight, less than 0.3% by weight, or less than 0.2% by weight) water absorption. In certain embodiments, the polyurethane composites when wetted in water for 8 days then dried at 46^°C for 48 hours are dimensionally stable exhibiting less than 0.2% (e.g., less than 0.15%, less than 0.10%, or less than 0.05%) increase in length.

In certain embodiments, the polyurethane composites when wetted in water for 14 days at 46°C then dried at 46°C for 48 hours are dimensionally stable exhibiting less than 1% (e.g., less than 0.9%, less than 0.8%, less than 0.7%, or less than 0.6%) swelling (expansion) in length and/or width. As discussed herein, the fatty acids and/or fatty acid salts can provide additional lubrication to the composite’s raw material mixture and thus improve the flow of the mixture during manufacturing. As a result, the composite structure may become denser and less likely for moisture to be incorporated. The density of the polyurethane composites described herein can be 5 lb/ft³ or greater. For example, the density of the polyurethane composite can be from 10 lb/ft³ to 75 lb/ft³, from 40 lb/ft³ to 75 lb/ft³, from 45 lb/ft³ to 70 lb/ft³, from 5 lb/ft³ to 60 lb/ft³, from 10 lb/ft³ to 60 lb/ft³, from 35 lb/ft³ to 50 lb/ft³, from 35 lb/ft³ to 60 lb/ft³, from 5 lb/ft³ to 30 lb/ft³, from 10 lb/ft³ to 35 lb/ft³, from 15 lb/ft³ to 35 lb/ft³ or from 20 lb/ft³ to 40 lb/ft³. In some embodiments, the density of the polyurethane composite can be at least 10 lb/ft³.

Incorporation of the fatty acid and/or fatty acid salt may also lead to improvements in the flexural strength of the polyurethane composites. In some embodiments, the flexural strength of the polyurethane composites described herein can be 200 psi or greater. For example, the flexural strength of the composites can be 300 psi or greater, 500 psi or greater, 750 psi or greater, 900 psi or greater, 1,000 psi or greater, 1,100 psi or greater, or 1,200 psi or greater. In some embodiments, the flexural strength of the polyurethane composites can be from 900 to 2,000 psi or from 900 to 1,500 psi. The flexural strength can be determined by the load required to fracture a rectangular prism loaded in the three point bend test as described in ASTM Cl 185- OS (2012).

The polyurethane composites can exhibit a ratio of flexural strength (in psi) to density (in lb/ft³) of from 10: 1 to 200: 1. In some embodiments, the polyurethane composites can exhibit a ratio of flexural strength (in psi) to density (in lb/ft³) of from 10: 1 to 100: 1 or from 20: 1 to 100: 1.

In some embodiments, the modulus of elasticity (stiffness) of the polyurethane composites described herein can be 100 ksi or greater, 110 ksi or greater, 120 ksi or greater, 125 ksi or greater, 130 ksi or greater, 135 ksi or greater, 140 ksi or greater, or 145 ksi or greater. For example, the modulus of elasticity can be from 110 to 200 ksi or from 110 to 150 ksi. The modulus of elasticity can be determined as described in ASTM C947-03.

The polyurethane composites can exhibit a ratio of modulus of elasticity (in ksi) to density (in lb/ft³) of from 1: 1 to 10: 1. In some embodiments, the polyurethane composites can exhibit a ratio of modulus of elasticity (in ksi) to density (in lb/ft³) of 1.5: 1 to 10: 1 or from 1.5: 1 to 5:1.

In some embodiments, the handleability of the polyurethane composites can be 3 in lb/in or greater ( e.g from 3 in lb/in to 8 in lb/in or from 3.5 in lb/in to 6 in lb/in). The handleability can be determined by measuring the ability of the composite to be flexed during use and is calculated as 0.5 x breaking load x ultimate deflection/thickness of the test specimen. The handleability of the composites can be determined using ASTM Cl 185-08.

A reinforcement can be included on one or more surfaces of the polyurethane composites described herein. Fiber reinforcements are described in PCT/US2016/027863, the disclosure of which is herein incorporated by reference in its entirety. In some embodiments, the

polyurethane composite can include a first fiber reinforcement on a first surface of the composite. In some embodiments, the composite can include a first fiber reinforcement on a first surface of the polyurethane composite and a second fiber reinforcement on a second surface, opposite the first surface, of the polyurethane composite. The fiber reinforcement can include any of the fiber materials as described herein and can include a blend of different fibers (either type or size). In some embodiments, the fiber reinforcement can include glass fibers. The fiber reinforcement can be woven or non-woven. In some embodiments, the polyurethane composite can include a first fiber reinforcement on a first surface of the composite and a material, other than a fiber reinforcement, on a second surface of the composite. In some embodiments, the material can include a cementitious layer, a paper sheet, a metal sheet, a polymeric layer, or a combination thereof. Examples of such materials include an aluminum sheet, an aluminum- plated sheet, a zinc sheet, a zinc-plated sheet, an aluminum/zinc alloy sheet, an aluminum/zinc alloy-plated sheet, a stainless steel sheet, craft paper, a polymeric surfacing film, or a combination thereof. Further advantages of using a fiber reinforcement with the polyurethane composites described herein can also be realized. For example, in some cases, the fiber reinforcement can improve the dimensional stability of the composites.

Methods of preparing the polyurethane composites described herein are also disclosed. The composites can be produced using a batch, semi-batch, or continuous process. In some embodiments, the method can include forming a polyurethane mixture. The polyurethane mixture can be produced by mixing the one or more isocyanates, the one or more polyols, and the inorganic filler in a mixing apparatus. The materials can be added in any suitable order. For example, in some embodiments, the mixing stage of the method used to prepare the polyurethane composite can include: (1) mixing the polyol, fatty acid and/or fatty acid salt, and inorganic filler; (2) mixing the isocyanate with the polyol, fatty acid and/or fatty acid salt, and inorganic filler; and optionally (3) mixing the catalyst with the isocyanate, polyol, fatty acid and/or fatty acid salt, and inorganic filler. The optional fibers can be added at the same time as the inorganic filler, or can be added prior to, during, or after stage (2) or (3). In other embodiments, the mixing stage of the method used to prepare the polyurethane composite can include: (1) mixing the polyol and inorganic filler; (2) mixing the isocyanate with the polyol and inorganic filler; (3) mixing the fatty acid and/or fatty acid salt with the isocyanate, polyol, and inorganic filler; and optionally (4) mixing the catalyst with the isocyanate; polyol; inorganic filler, and fatty acid and/or fatty acid salt. In certain embodiments, the mixing stage of the method used to prepare the polyurethane composite can include simultaneously mixing the isocyanate; polyol; inorganic filler, fatty acid and/or fatty acid salt, and optional catalyst.

Polyols and fatty acids can react to form an ester. U.S. Patent No. 9,353,234 describes reacting a fatty acid, a polyol, and an alkylene oxide at l30°C for 4 hours to form a

polyetherester polyol. The method of making the polyurethane composites disclosed herein does not include pre-reacting the fatty acid, the fatty acid salt, or the combination thereof with the one or more polyols prior to mixing with the one or more isocyanates. In some embodiments, the one or more polyols and the one or more isocyanates are mixed prior to mixing with the fatty acid and/or fatty acid salt. In some embodiments, the one or more isocyanates and the fatty acid, the fatty acid salt, or the combination thereof are mixed prior to mixing with the one or more polyols. Accordingly, the method does not include reacting the one or more polyols with the fatty acid and/or fatty acid salt prior to reacting with the one or more isocyanates. Similarly, the method does not include reacting the one or more polyols with an alkylene oxide and the fatty acid and/or fatty acid salt prior to reacting with the one or more isocyanates. In some embodiments, the one or more polyols are mixed with the inorganic filler before the one or more polyols and the inorganic filler are mixed with the one or more isocyanates, the fatty acid, the fatty acid salt, or the combination thereof, and the optional catalyst.

It is desirable that the polyurethane mixture has a viscosity below a particular threshold at the desired loadings so it can be effectively processed. In some embodiments, the amount of fatty acid and/or fatty acid salt, filler, and/or fiber material can be present in the composite mixture in amounts to produce a workable viscosity (initial viscosity) of from 25 Pa*s to 400 Pa*s. For example, the fatty acid and/or fatty acid salt, filler, and/or fiber material in the polyurethane mixture can be in amounts to produce a workable viscosity from 30 Pa*s to 400 Pa^»s, 65 Pa^»s to 400 Pa^»s, or 80 Pa^»s to 400 Pa^»s. The viscosity of the composite mixture can be measured using a Brookfield Viscometer.

The polyurethane composite mixture can be blended in any suitable manner to obtain a homogeneous or heterogeneous blend of the one or more isocyanate, the one or more polyols, the inorganic filler, and the optional fiber material and catalyst. In some embodiments, mixing can be conducted in a high speed mixer or an extruder an extruder. An ultrasonic device can be used for enhanced mixing and/or wetting of the various components of the composite. The ultrasonic device produces an ultrasound of a certain frequency that can be varied during the mixing and/or extrusion process. The ultrasonic device useful in the preparation of composite panels described herein can be attached to or adjacent to the extruder and/or mixer. For example, the ultrasonic device can be attached to a die or nozzle or to the port of the extruder or mixer. An ultrasonic device may provide de-aeration of undesired gas bubbles and better mixing for the other components, such as blowing agents, surfactants, and catalysts.

The method of making the polyurethane composites can include allowing the one or more isocyanates and the one or more polyols to react in the presence of the inorganic filler to form a polyurethane composite. The composite has a first surface and a second surface opposite the first surface. The curing stage of the method used to prepare the polyurethane composite can be carried out in a mold cavity of a mold, the mold cavity formed by at least an interior mold surface. The mold can be a continuous forming system such as a belt molding system or can include individual batch molds. The belt molding system can include a mold cavity formed at least in part by opposing surfaces of two opposed belts. In some embodiments, a molded article can then be formed prior to the additional method steps in forming the composites.

In some embodiments, the polyurethane mixture can be foamed. The polyols and the isocyanate can be allowed to produce a foamed composite material after mixing the components according to the methods described herein. In some embodiments, polyurethane foams can be formed by allowing the mixture to expand via a gas phase to form the foam. The gas phase can be generated in situ from reaction of water with the one or more isocyanates. The gas can be introduced into the polyurethane mixture. Suitable gases are known in the art. In some embodiments, the gas can be captured after gelation (i.e., formation) of the foam. The polyurethane composite can be formed while they are actively foaming or after they have foamed. For example, the polyurethane composite can be placed under the pressure of a mold cavity prior to or during the foaming of the polyurethane composite. In some cases, the mixture can be allowed to rise freely during foaming in the mold.

As discussed herein, incorporation of the fatty acid and/or fatty acid salt into the polyurethane composites can improve their dimensional stability, compared to when the fatty acid and/or fatty acid salt are excluded from the polyurethane composite. The optimization of the dimensional stability of the composites allows their use in exterior building materials and other structural applications that is subject to typical fluctuations in the temperature and humidity of the outdoor environment that surrounds it. For example, the polyurethane composites can be formed into shaped articles and used in building materials. Suitable building materials include siding materials, building panels, sheets, architectural moldings, sound barriers, thermal barriers, insulation, wall boards, ceiling tiles, ceiling boards, soffits, roofing materials, and other shaped articles. Examples of shaped articles made using the composite panels described herein include roof tiles such as roof tile shingles, roof cover boards, slate panels, shake panels, cast molded products, moldings, sills, stone, masonry, brick products, posts, signs, guard rails, retaining walls, park benches, tables, slats, comer arches, columns, ceiling tiles, or railroad ties.

EXAMPLES

The following examples are put forth so as to provide those of ordinary skill in the art with a complete disclosure and description of how the compounds, compositions, articles, devices and/or methods claimed herein are made and evaluated, and are intended to be purely exemplary and are not intended to limit the scope of the disclosure. Unless indicated otherwise, parts and percentages are on a weight basis, temperature is in °C or is at ambient temperature, and pressure is at or near atmospheric.

Dimensional properties of filled polyurethane composites with fatty acid salt.

Preparation of polyurethane composite: The composites listed in Table 1 were prepared by mixing the polyol SPA357 with 2% by weight calcium stearate, 1% by weight of an amine catalyst (diethanolamine) and 2% by weight of a silicone surfactant in a mixer. Fly ash was added and wetted with the polyol mixture. Methylene diphenyl diisocyanate (MDI; 104 index; 51.5 g) was then added to the mixer with simultaneous stirring. The mixture was introduced into a confined mold and allowed to cure into a molded shape.

The dimensional stability of the composites, including changes in weight, length, and width as a function of temperature were determined on samples extracted from the molded product.

The composites listed in Table 2 were prepared by adding a fatty acid or fatty acid salt to a polyurethane matrix filled with fly ash and reinforced with glass fibers.

Determination of the dimensional stability: The samples were dried at 46°C for 48 hours. The weight, length, and width of the sample were determined. Absorption and desorption experiments were carried out at different temperatures to compare the weight absorption and dimensional change as compared to a control. Particularly, the samples listed in Table 1 were soaked in water at a predetermined temperature for 8 days. The samples were then removed and dried at 46°C for 48 hours. The weight, length, and width of the sample were measured again over time. The resultant dimensional size change as the sample was exposed to water at various temperatures was determined as a percent change from the initial measurement at the same temperature. From the data, a curve was generated showing the dimensional change (as %) over time. The samples listed in Table 2 were soaked in water for 14 days at 46°C. The length was measured and compared to the original length and the moisture content determined after submersion.

Table 1. Composition of filled polyurethane composites comprising various amounts of calcium stearate.

^L - samples were classified based on fly ash used.

Table 2: Effect of the addition of fatty acids or fatty acid salts to a filled polyurethane matrix.

* - determined after 14 days water submersion at 46°C

Summary: The results for the composites listed in Table 1 are shown in Figures 1 to 6. As can be seen, the change in length and width of the polyurethane composite samples with 2% calcium stearate was significantly less compared to the control (without any calcium stearate). For example, Figure 3 shows that, at room temperature, the sample with Class-C fly ash and 2% calcium stearate expanded only 0.27% in length at 96 hours, while the control sample expanded 0.73% in length. Another example, as illustrated in Figure 6, is that by the end of the desorption at 192 hours, at 46°C, the sample with Class-F fly ash and 2% calcium stearate has about 0.08% shrinkage in width, while the control sample still has 0.52% expansion in width. The total absorption rates are similar for samples with and without calcium stearate (with the exception of Class-F ash at room temperature).

The results for the composites listed in Table 2 are also summarized in table 2. There was a general increase in length for all the composites after submersion in water at 46°C for 14 days. However, the increase in length of the composites comprising a fatty acid or fatty acid salt is generally less than the increase in length for the control sample without the addition of fatty acids or fatty acid salts. It was also noted that the increase in length or expansion was reduced with additional amounts of the fatty acid or fatty acid salt.

As is commonly known, polyurethane resin and inorganic fillers/fibers may have compatibility problems because it can be difficult for the siliceous surface of fillers to form strong bonds with the polymer matrix. Fatty acids and their salts usually have long alkyl chains with carboxylic functional groups at the end. It is believed that when the fatty acid salts are used in the filled polyurethane composite, the hydrocarbon chain of fatty acid salts can react with polymer matrix, and the carboxylic functional groups can react with the filler surface. As a result, the polymer matrix and fillers/fillers can form a strong bond, making it more difficult for water and moisture to penetrate into the interfacial zone and cause expansion and shrinkage. Another benefit of the use of fatty acid salts is that they can increase the hydrophobicity of the polyurethane composite and consequently reduce the potential for moisture to induce volume change by plasticizing the matrix. In both polyurethane and polyurea, urethane functional group (-NH-) may interact with water through hydrogen bond and thus can facilitate the penetration of moisture into polymer structure. Overall, by modifying the hydrophilic nature of the

polyurethane resin, fatty acid salts can reduce the tendency of water to invade the polymer and in turn mitigate the movement of the composite. The compositions and methods of the appended claims are not limited in scope by the specific compositions and methods described herein, which are intended as illustrations of a few aspects of the claims and any compositions and methods that are functionally equivalent are intended to fall within the scope of the claims. Various modifications of the compositions and methods in addition to those shown and described herein are intended to fall within the scope of the appended claims. Further, while only certain representative materials and method steps disclosed herein are specifically described, other combinations of the materials and method steps also are intended to fall within the scope of the appended claims, even if not specifically recited. Thus, a combination of steps, elements, components, or constituents may be explicitly mentioned herein; however, other combinations of steps, elements, components, and constituents are included, even though not explicitly stated. The term“comprising” and variations thereof as used herein is used synonymously with the term“including” and variations thereof and are open, non-limiting terms. Although the terms“comprising” and“including” have been used herein to describe various embodiments, the terms“consisting essentially of’ and“consisting of’ can be used in place of“comprising” and“including” to provide for more specific embodiments and are also disclosed. As used in this disclosure and in the appended claims, the singular forms“a”, “an”,“the”, include plural referents unless the context clearly dictates otherwise.

Claims

What is claimed is:

1. A filled polyurethane composite, comprising:

(a) a polyurethane formed by the reaction of (i) one or more isocyanates selected from the group consisting of diisocyanates, polyisocyanates, and mixtures thereof, and (ii) one or more polyols in the presence of a fatty acid, a fatty acid salt, or a combination thereof, wherein the one or more polyols and the fatty acid, the fatty acid salt, or the combination thereof are not pre-reacted prior to reacting with the one or more isocyanates; and

(b) an inorganic filler ;

wherein the fatty acid, the fatty acid salt, or the combination thereof is present in the composite in an amount of from 0.05% to 10% by weight, based on the total weight of the composite.

2. The composite of claim 1, wherein the fatty acid, the fatty acid salt, or the combination thereof is derived from a Ce-Cie fatty acid.

3. The composite of claim 1 or 2, wherein the fatty acid, the fatty acid salt, or the combination thereofis derived from a C 12-C24 fatty acid.

4. The composite of any one of claims 1-3, wherein the fatty acid, the fatty acid salt, or the combination thereofis derived from lauric acid, maleic acid, myristic acid, palmitic acid, stearic acid, palmitoleic acid, oleic acid, erucic acid, linoleic acid, linolenic acid, eleostearic acid, arachidonic acid or mixtures thereof.

5. The composite of any one of claims 1-4, wherein the fatty acid salt comprises a Group I metal, a Group II metal, a Group III metal, zinc, or ammonium cation.

6. The composite of any one of claims 1-5, wherein the fatty acid salt comprises calcium stearate.

7. The composite of any one of claims 1-6, wherein the fatty acid, the fatty acid salt, or the combination thereofis present in an amount of from 0.1% to 5% by weight, based on the total weight of the composite.

8. The composite of any one of claims 1-7, wherein 50% or greater of the fatty acid, the fatty acid salt, or the combination thereof associates with the polyurethane through non-covalent interactions.

9. The composite of any one of claims 1-8, wherein the inorganic filler comprises fly ash, limestone, or a mixture thereof.

10. The composite of claim 9, wherein the inorganic filler comprises fly ash and the fly ash is a Class F fly ash.

11. The composite of any of claims 1-10, wherein the inorganic filler is present in an amount of from 40% to 90% by weight, based on the total weight of the composite.

12. The composite of claim 11, wherein the inorganic filler is present in an amount of from 50% to 80% by weight, based on the total weight of the composite.

13. The composite of any one of claims 1-12, wherein at least a portion of the fatty acid, the fatty acid salt, or the combination thereof interacts with the inorganic filler.

14. The composite of any one of claims 1-13, wherein the inorganic filler further comprises glass fibers.

15. The composite of claim 14, wherein the glass fibers are present in an amount of from 0.2% to 20% by weight, based on the total weight of the composite.

16. The composite of any one of claims 1-15, wherein the polyurethane is present in an amount of from 20% to 40% by weight, based on the total weight of the composite.

17. The composite of any one of claims 1-16, wherein the composite is foamed.

18. The composite of any one of claims 1-17, wherein the composite has a density of from 5 lb/ft³ to 75 lb/ft³.

19. The composite of any one of claims 1-18, wherein the flexural strength of the composite is from 200 psi to 2,500 psi, as measured by ASTM Cl 185.

20. The composite of any one of claims 1-19, wherein the composite, after wetting in water for 8 days and drying at 46°C for 48 hours, exhibits a water absorption or desorption of from 0% to less than 0.5% by weight, based on the weight of the composite.

21. The composite of any one of claims 1-20, wherein the composite, after wetting in water for 8 days and drying at 46°C for 48 hours, increases or decreases in length by 0% to less than 0.2%.

22. The composite of any one of claims 1-21, wherein the composite, after wetting in water for 8 days and drying at 46°C for 48 hours, exhibits a dimensional change that is less than 50% of the dimensional change of an otherwise identical composite excluding the fatty acid, the fatty acid salt, or the combination thereof.

23. The composite of claim 22, wherein the dimensional change is in length, width, weight, or a combination thereof.

24. A building material comprising the composite of any one of claims 1-23.

25. The building material of claim 24, wherein the building material is selected from sidings, building panels, sheets, architectural moldings, sound barriers, thermal barriers, insulations, wall boards, ceiling tiles, ceiling boards, soffits, trims, backers, or roofing materials.

26. A filled polyurethane composite, comprising:

(a) from 20% to 40% by weight, based on the total weight of the composite, of a polyurethane formed by the reaction of (i) one or more isocyanates selected from the group consisting of diisocyanates, polyisocyanates, and mixtures thereof, and (ii) one or more polyols in the presence of a Ci2-C24-fatty acid, Ci2-C24-fatty acid salt, or combination thereof, wherein 50% or greater of the one or more polyols are derived from a C3-C4 alkoxylated polyol, and wherein the one or more polyols and the fatty acid, the fatty acid salt, or the combination thereof are not pre-reacted prior to reacting with the one or more isocyanates;

(b) from greater than 40% to 90% by weight, based on the total weight of the composite, of a Class F fly ash;

wherein the Ci2-C24-fatty acid, the Ci2-C24-fatty acid salt, or the combination thereof is present in an amount of from 0.05% to 10% by weight, based on the total weight of the composite,

wherein the composite, after wetting in water for 8 days and drying at 46 C for 48 hours, increases or decreases in length by 0% to less than 0.2%.

27. The composite of claim 26, wherein the fatty acid, the fatty acid salt, or the combination thereof is derived from lauric acid, maleic acid, myristic acid, palmitic acid, stearic acid, palmitoleic acid, oleic acid, erucic acid, linoleic acid, linolenic acid, eleostearic acid, arachidonic acid or mixtures thereof.

28. The composite of claim 26 or 27, wherein the fatty acid salt includes calcium stearate.

29. The composite of any one of claims 26-25, wherein the fatty acid, the fatty acid salt, or the combination thereof is present in an amount of from 0.1% to 5% by weight, based on the total weight of the composite.

30. The composite of any one of claims 26-29, wherein the fly ash is present in an amount of from 50% to 80% by weight, based on the total weight of the composite.

31. The composite of any one of claims 26-30, wherein the composite is foamed.

32. The composite of any one of claims 26-31, wherein the composite has a density of from 5 lb/ft³ to 75 lb/ft³.

33. A building material comprising the composite of any one of claims 26-32.

34. The building material of claim 33, wherein the building material is selected from siding, building panels, sheets, architectural moldings, sound barriers, thermal barriers, insulations, wall boards, ceiling tiles, ceiling boards, soffits, or roofing materials.

35. A method of making a polyurethane composite, comprising:

(a) mixing one or more isocyanates selected from the group consisting of diisocyanates, polyisocyanates, and mixtures thereof, one or more polyols, a fatty acid, a fatty acid salt, or a combination thereof, and an inorganic filler to produce a mixture, wherein the one or more polyols and the fatty acid, the fatty acid salt, or the combination thereof are not pre-reacted prior to reacting with the one or more isocyanates, wherein the fatty acid, the fatty acid salt, or the combination thereof is present in an amount from 0.05% to 10% by weight, based on the total weight of the mixture,

(b) applying the mixture to a mold; and

(c) allowing the mixture to react and expand to form the polyurethane composite.

36. The method of claim 35, wherein the method includes mixing the one or more isocyanates and the one or more polyols prior to mixing with the fatty acid, the fatty acid salt, or the combination thereof.

37. The method of claim 35, wherein the method includes mixing the one or more isocyanates with the fatty acid, the fatty acid salt, or the combination thereof prior to mixing the one or more polyols with the one or more isocyanates.

38. The method of claim 35, wherein the method includes mixing the one or more isocyanates, the one or more polyols, and the fatty acid, the fatty acid salt, or the combination thereof simultaneously.

39. The method of any one of claims 35-38, wherein the mixture further comprises a catalyst.

40. The method of any one of claims 35-39, wherein the fatty acid, the fatty acid salt, or the combination thereof is present in an amount of from 0.1% to 5% by weight, based on the total weight of the composite.

41. The method of any one of claims 35-40, wherein the fatty acid, the fatty acid salt, or the combination thereof is derived from lauric acid, maleic acid, myristic acid, palmitic acid, stearic acid, palmitoleic acid, oleic acid, erucic acid, linoleic acid, linolenic acid, eleostearic acid, arachidonic acid or mixtures thereof.

42. The method of any one of claims 35-41, wherein the inorganic filler comprises fly ash.

43. The method of any one of claims 35-42, wherein the inorganic filler is present in an amount of from 40% to 90% by weight, based on the total weight of the composite.

44. The method of claim 43, wherein the inorganic filler is present in an amount of from 50% to 80% by weight, based on the total weight of the composite.

45. The method of any one of claims 35-44, further comprising allowing the composite to foam.