WO2026010693A1 - Improved aqueous binders - Google Patents

Abstract

The invention provides a binder composition comprising a) at least one polyol and b) at least one polycarboxylic acid polymer, wherein molar equivalent of hydroxyl groups in the at least one polyol is present in excess to molar equivalent of carboxylic acid groups in the at least one polycarboxylic acid polymer. The binder composition of the invention are useful for making products with superior tensile strength.

Description

IMPROVED AQUEOUS BINDERS

CROSS-REFERENCE TO RELATED APPLICATIONS

[001] This application claims the benefit of priority from U.S. Provisional Patent Application No. 63/666,883, filed July 2, 2024, the disclosure of which is incorporated herein by reference.

FIELD OF THE INVENTION

[002] The present invention is in the field of polycarboxylic acid polymer binder compositions. Particularly, the present invention relates to thermosetting and acrylic acid-based binder resins that cure by crosslinking with a polyol. The binder compositions and resins are useful for manufactured products having non-woven fibers.

BACKGROUND OF THE INVENTION

[003] Binder resins are used in many different kinds of applications where stiffening and structural rigidity is desired. The applications include fabrication of products with woven and non-woven fibers. The cured binder resins produce a stiffer product. One particular application is insulation products where fibers are bonded together by a cured polymeric material.

[004] Binder resins and compositions generally require a low viscosity in the uncured state to facilitate handling, but cure to form a rigid polymeric matrix to support the fibers. For example, in insulation products, low viscosity of the uncured binder allows an insulation batting to be properly sized and assembled into uniform density. As the binder cures, a rigid matrix is formed that is also structurally flexible to allow for recovery of shape for efficient thermal insulation. [005] Binder resins of polyacid and a polyol, such as glycerol, are known. U.S. Pat. No.

7,241 ,487 discloses that the ratio of the number of equivalents of hydroxyl groups from a polyol to the number of equivalents of carboxy, anhydride, or salts thereof of a polyacid must be narrowly defined from about 0.4/1 to about 1 .0/1 . Preferably, the range is from about 0.6/1 to about 0.8/1. An excess of equivalents of carboxy, anhydride, or salts thereof of the poly acid is required so that the polyol is not more than 60-80% of the equivalents of carboxy units. Accordingly, the state of the art teaches that having excess hydroxyl groups from a polyol produces structurally inferior products.

SUMMARY OF THE INVENTION

[006] Binder compositions are needed that bind fibers for manufacturing products having high tensile strength and are formaldehyde free. The inventors have unexpectedly found that high levels of polyol in binder compositions produce products with superior tensile strength. In particular, the unexpected results comprises binder compositions wherein a molar equivalent of hydroxyl groups in excess to a molar equivalent of carboxylic acid groups produce at least 10% increase in tensile strength.

[007] In one aspect, the present invention provides a binder composition comprising a) at least one polyol and b) at least one polycarboxylic acid polymer, wherein molar equivalent of hydroxyl groups in the at least one polyol is present in excess to molar equivalent of carboxylic acid groups in the at least one polycarboxylic acid polymer.

[008] In another aspect, the present invention provides a fiberglass binder composition comprising a) at least one fiberglass b) at least one polyol, c) triethanolamine, and d) at least one polycarboxylic acid polymer, wherein molar equivalent of hydroxyl groups in the triethanolamine and the at least one polyol is 1.01 to 7.5 times the molar equivalent of carboxylic acid groups in the at least one polycarboxylic acid polymer.

[009] In one other aspect, the present invention provides a process for making a fiberglass mat or batting comprising preparing a binder solution comprising an aqueous solution comprising a) at least one polyol, and b) at least one polycarboxylic acid polymer, wherein molar equivalent of hydroxyl groups in the at least one polyol is present in excess to molar equivalent of carboxylic acid groups in the at least one polycarboxylic acid polymer, and c) optionally a catalyst; mixing the binder solution with fiberglass to form a fiberglass-binder mixture; and curing the fiberglass-binder mixture to produce the fiberglass mat or batting.

BRIEF DESCRIPTION OF THE DRAWINGS

[0010] Aspects, features, benefits, and advantages of the embodiments of the present invention will be apparent from the following detailed description and the claims with the accompanying drawings wherein: [0011] FIG. 1 shows the effect of molar excess of hydroxyl groups to carboxylic acid on the solidification time and tensile strength, and

[0012] Fig. 2 shows the improvement of dry tensile strength and hot/wet tensile strength for polyacrylic acid (Acrodur DS 3515) with increasing amounts of glycerin as prepared in Table 9.

DETAILED DESCRIPTION OF THE INVENTION

[0013] The present invention provides binder compositions useful in many different kinds of applications where stiffening and structural rigidity is desired after curing binder compositions. The applications include, but not limited to, fabrication of products having woven and non-woven fibers. Other applications for the binder compositions of the present invention include applications where binding of glass, synthetic and natural fibers are needed, roofing glass mat used to produce substrates such as asphalt shingles and built-up roofing, insulation, filtration, flooring substrates, acoustic wall and ceiling panels, abrasives, automotive light-weighting products, and furniture.

[0014] One particular application is glass batting applications, for example, insulation products that comprise randomly laid glass fibers. The binder compositions are useful for other types of batting fibers bonded together by a cured polymeric material.

[0015] The binder compositions of the present invention allows for compositions and applications that are formaldehyde-free, very low VOC, water-based, excellent in wet and dry strength, excellent in adhesive and strengthening properties, environmentally friendly and sustainable.

[0016] As disclosed herein, the molecular weight can be obtained using gel permeation chromatography (GPC). In certain embodiments, the molecular weight can be determined from the molecular formula, for examples, by determining the number of monomers in a polymer. The molecular weight determination can be employed for all components of the binder compositions according to the present invention.

[0017] As used herein, the singular forms “a,” “an,” and “the” include plural references unless the context clearly dictates otherwise. Unless defined otherwise, all technical and scientific terms used herein have the same meanings as commonly understood by one of ordinary skill in the art. As used herein this document, the term “comprising” means “including, but not limited to.”

[0018] As used herein, the term “about” means plus or minus 10% of the numerical value of the number with which it is being used. For example, “about 50%” means in the range of 45-55%. [0019] In the above detailed description, reference is made to the accompanying drawings, which form a part hereof. In the drawings, similar symbols typically identify similar components, unless context dictates otherwise. The illustrative embodiments described in the detailed description, drawings, and claims are not meant to be limiting. Other embodiments may be used, and other changes may be made, without departing from the spirit or scope of the subject matter presented herein.

[0020] The present disclosure is not to be limited in terms of the particular embodiments described in this application, which are intended as illustrations of various aspects. Many modifications and variations can be made without departing from its spirit and scope, as will be apparent to those skilled in the art. Functionally equivalent compounds, components, methods and apparatuses within the scope of the disclosure, in addition to those enumerated herein, will be apparent to those skilled in the art from the foregoing descriptions. Such modifications and variations are intended to fall within the scope of the appended claims. The present disclosure is to be limited only by the terms of the appended claims, along with the full scope of equivalents to which such claims are entitled. It is to be understood that this disclosure is not limited to particular processes, reagents, compounds, or compositions, which can, of course, vary. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments and is not intended to be limiting.

[0021] It will be understood by those within the art that, in general, terms used herein, and especially in the appended claims (for example, bodies of the appended claims) are generally intended as “open” terms (for example, the term “including” should be interpreted as “including but not limited to,” the term “having” should be interpreted as “having at least,” the term “includes” should be interpreted as “includes but is not limited to,” et cetera). While various compositions and processes are described in terms of “comprising” various components or steps (interpreted as meaning “including, but not limited to”), the compositions, methods, and devices can also “consist essentially of’ or “consist of” the various components and steps, and such terminology should be interpreted as defining essentially closed-member groups. It will be further understood by those within the art that if a specific number of an introduced claim recitation is intended, such an intent will be explicitly recited in the claim, and in the absence of such recitation no such intent is present.

[0022] For example, as an aid to understanding, the following appended claims may contain usage of the introductory phrases "at least one" and "one or more" to introduce claim recitations. However, the use of such phrases should not be construed to imply that the introduction of a claim recitation by the indefinite articles "a" or "an" limits any particular claim containing such introduced claim recitation to embodiments containing only one such recitation, even when the same claim includes the introductory phrases "one or more" or "at least one" and indefinite articles such as "a" or "an" (for example, “a” and/or “an” should be interpreted to mean “at least one” or “one or more”); the same holds true for the use of definite articles used to introduce claim recitations.

[0023] In addition, even if a specific number of an introduced claim recitation is explicitly recited, those skilled in the art will recognize that such recitation should be interpreted to mean at least the recited number (for example, the bare recitation of "two recitations," without other modifiers, means at least two recitations, or two or more recitations). Furthermore, in those instances where a convention analogous to “at least one of A, B, and C, et cetera” is used, in general such a construction is intended in the sense one having skill in the art would understand the convention (for example, “a system having at least one of A, B, and C” would include but not be limited to systems that have A alone, B alone, C alone, A and B together, A and C together, B and C together, and/or A, B, and C together, et cetera). In those instances where a convention analogous to “at least one of A, B, or C, et cetera” is used, in general such a construction is intended in the sense one having skill in the art would understand the convention (for example, “a system having at least one of A, B, or C” would include but not be limited to systems that have A alone, B alone, C alone, A and B together, A and C together, B and C together, and/or A, B, and C together, et cetera). It will be further understood by those within the art that virtually any disjunctive word and/or phrase presenting two or more alternative terms, whether in the description, claims, or drawings, should be understood to contemplate the possibilities of including one of the terms, either of the terms, or both terms. For example, the phrase “A or B” will be understood to include the possibilities of “A” or “B” or “A and B.”

[0024] In addition, where features or aspects of the disclosure are described in terms of Markush groups, those skilled in the art will recognize that the disclosure is also thereby described in terms of any individual member or subgroup of members of the Markush group. [0025] As will be understood by one skilled in the art, for any and all purposes, such as in terms of providing a written description, all ranges disclosed herein also encompass any and all possible subranges and combinations of subranges thereof. Any listed range can be easily recognized as sufficiently describing and enabling the same range broken down into at least equal halves, thirds, quarters, fifths, tenths, et cetera. As a non-limiting example, each range discussed herein can be readily broken down into a lower third, middle third and upper third, et cetera. As will also be understood by one skilled in the art all language such as “up to,” “at least,” and the like include the number recited and refer to ranges that can be subsequently broken down into subranges as discussed above. Finally, as will be understood by one skilled in the art, a range includes each individual member. Thus, for example, a group having 1-3 compounds refers to groups having 1 , 2, or 3 compounds. Similarly, a group having 1-5 compounds refers to groups having 1 , 2, 3, 4, or 5 compounds, and so forth.

[0026] Various of the above-disclosed and other features and functions, or alternatives thereof, may be combined into many other different systems or applications. Various presently unforeseen or unanticipated alternatives, modifications, variations, or improvements therein may be subsequently made by those skilled in the art, each of which is also intended to be encompassed by the disclosed embodiments.

[0027] In one aspect, the present invention provides a binder composition comprising a) at least one polyol and b) at least one polycarboxylic acid polymer, wherein molar equivalent of hydroxyl groups in the at least one polyol is present in excess to molar equivalent of carboxylic acid groups in the at least one polycarboxylic acid polymer.

[0028] The polycarboxylic acid polymer in the binder compositions of the present invention comprises an organic polymer, prepolymer or oligomer containing more than one pendant carboxy group. The polycarboxylic acid polymer may be a homopolymer or copolymer prepared from unsaturated carboxylic acids. The polycarboxylic acid polymer may be prepared from acrylic acid, methacrylic acid, crotonic acid, isocrotonic acid, maleic acid, cinnamic acid, 2- methylmaleic acid, itaconic acid, 2-methylitaeonic acid, [alpha], [beta]-methyleneglutaric acid, or mixtures thereof. The polycarboxylic acid polymer may also be prepared from unsaturated anhydrides including, but not limited to, maleic anhydride, methacrylic anhydride, as well as mixtures thereof. Methods for polymerizing acids and anhydrides are well-known in the art.

[0029] The polycarboxylic acid polymer of the present invention may comprise a copolymer of one or more unsaturated carboxylic acids or anhydrides, and one or more vinyl compounds including, but not limited to, styrene, [alpha]-methylstyrene, acrylonitrile, methacrylonitrile, methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, methyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, glycidyl methacrylate, vinyl methyl ether, vinyl acetate, or mixtures thereof. Methods for preparing copolymers are well-known in the art.

[0030] The binder compositions of the present invention allows for the polycarboxylic acid polymer to be of a wide range in molecular weight. That is, the polycarboxylic acid polymer is not limited to only low molecular weight polymers, for example, less than 10,000 g/mol. In one embodiment, the polycarboxylic acid polymer of the present invention comprise homopolymers and copolymers of polyacrylic acid. The polyacrylic acid polymer may have a molecular weight less than 10,000 g/mol, or from 500 g/mol to 10,000 g/mol, or from 1 ,000 g/mol to 9,000 g/mol, or from 2,000 g/mol to 8,000 g/mol, or from 4,000 g/mol to 6,000 g/mol.

[0031] In another embodiment, the polyacrylic acid polymer may have a molecular weight of 10,000 g/mol or greater, or from 10,000 g/mol to 100,000 g/mol, or from 15,000 g/mol to 80,000 g/mol, or from 20,000 g/mol to 60,000 g/mol, or from 40,000 g/mol to 50,000 g/mol.

[0032] The polyol of the present invention comprises at least two hydroxyl groups. For example, the polyol may be a diol, a triol, a tetraol, or a pentaol. The polyol have low vapor pressure such that the polyol can react with the polycarboxylic acid polymer in the composition during heating and curing. The polyol may be a monomeric or polymeric compound. The polyol may have a molecular weight less than about 1000 g/mol having at least two hydroxyl groups. Examples of the polyol of the present invention include, but is not limited to, triethanolamine, glycerol, diglycerol, triglycerol, polyglycerol, pentaerythritol, 2-methyl-1 ,3-propanediol, 1 ,3- propanediol, polyvinyl alcohol, xylitol, neopentyl glycol, ethylene glycol, propylene glycol, glucose, trimethylolpropane, sorbitol, N,N,N',N'-Tetrakis (2-hydroxypropyl) ethylene-diamine, diisopranolamine, methyldiethanolamine, butyldiethanolamine, sorbitol, sucrose, resorcinol, catechol, pyrogallol, glycollated ureas, 1 ,4-cyclohexane diol, diethanolamine, [beta]- hydroxyalkylamides, bis[N,N-di([beta]-hydroxyethyl)]adipamide, partially hydrolyzed polyvinyl acetate, polyallyl alcohol, homopolymers or copolymers of hydroxyethyl (meth) acrylate, hydroxypropyl(meth) acrylate, Pluracol SG360, Pluracol GP430, Pluracol GP730, Pluracol 1578, or mixtures thereof.

[0033] In some embodiments of the present invention, the polyol may be a bio-based or bioderived polyol. For example, the polyol may be derived or synthesized from natural resources, including but not limited to lignocellulose, lipids, or carbohydrates. Thus, an advantage of the binder compositions of the present invention is the use of renewable resources.

[0034] The binder compositions of the present invention comprise a molar equivalent of hydroxyl groups in the polyol in excess to a molar equivalent of carboxylic acid groups in the polycarboxylic acid polymer. In one embodiment, the molar equivalent of hydroxyl groups is 1.01 to 13.0 times the molar equivalent of carboxylic acid groups. In another embodiment, the molar equivalent of hydroxyl groups is 1 .01 to 12.0 times the molar equivalent of carboxylic acid groups. In another embodiment, the molar equivalent of hydroxyl groups is 1.01 to 10.0 times the molar equivalent of carboxylic acid groups. In another embodiment, the molar equivalent of hydroxyl groups is 1 .01 to 8.0 times the molar equivalent of carboxylic acid groups. In another embodiment, the molar equivalent of hydroxyl groups is 1.01 to 6 times the molar equivalent of carboxylic acid groups. In another embodiment, the molar equivalent of hydroxyl groups is 1 .01 to 4 times the molar equivalent of carboxylic acid groups. In another embodiment, the molar equivalent of hydroxyl groups is 1.01 to 2 times the molar equivalent of carboxylic acid groups. [0035] In one embodiment, the molar equivalent of hydroxyl groups is 1.01 to 7.5 times the molar equivalent of carboxylic acid groups. In another embodiment, the molar equivalent of hydroxyl groups is 1 .5 to 6.0 times the molar equivalent of carboxylic acid groups. In another embodiment, the molar equivalent of hydroxyl groups is 2 to 5 times the molar equivalent of carboxylic acid groups.

[0036] In one embodiment, the molar equivalent of hydroxyl groups is 2.2 to 13 times, 2.5 to 13 times, 2.7 to 13 times, 3 to 13 times, 3.2 to 13 times, 3.5 to 13 times, 3.7 to 13 times, 4 to 13 times, 4.2 to 13 times, 4.5 to 13 times, 4.7 to 13 times, 5 to 13 times, 2.2 to 11 times, 2.2 to 9 times, 2.2 to 7 times, 2.5 to 7 times, 2.7 to 7 times, 3 to 7 times, 3.2 to 7 times, or 3.5 to 7 times the molar equivalent of carboxylic acid groups.

[0037] In one embodiment, the polyol having hydroxyl groups is not an epoxidized plant oil or derived from an epoxidized plant oil, and the molar equivalent of hydroxyl groups is 2.2 to 13 times, 2.5 to 13 times, 2.7 to 13 times, 3 to 13 times, 2.2 to 7 times, 2.5 to 7 times, 2.7 to 7 times, 3 to 7 times, 3.2 to 7 times, or 3.5 to 7 times the molar equivalent of carboxylic acid groups.

[0038] Binder compositions wherein the molar equivalent of hydroxyl groups in the polyol is in excess to the molar equivalent of carboxylic acid groups cure to produce products with superior structural properties. For example, products made using the binder compositions of the present invention have increase tensile strength compared to products made with binder compositions where the molar equivalent of hydroxyl groups in the polyol is not in excess to the molar equivalent of carboxylic acid groups in the polycarboxylic acid polymer.

[0039] In some embodiments, the polycarboxylic acid polymer is a thermoset polymer or a thermoplastic polymer.

[0040] The binder compositions of the present invention may comprise a catalyst. The catalyst is a phosphorous-containing accelerator which may be a compound with a molecular weight less than about 1000 g/mol. For example, catalyst may be an alkali metal polyphosphate, an alkali metal dihydrogen phosphate, a polyphosphoric acid, an alkyl phosphinic acid, an oligomer or polymer bearing phosphorous-containing groups such as addition polymers of acrylic and/or maleic acids formed in the presence of sodium hypophosphite, addition polymers prepared from ethylenically unsaturated monomers in the presence of phosphorous salts, addition polymers containing acid-functional monomer residues such as copolymerized phosphoethyl methacrylate, phosphonic acid esters, or copolymerized vinyl sulfonic acid monomers. In some embodiments, the catalyst may comprise sodium hypophosphite, sodium phosphite, sodium bisulfite, or mixtures thereof. In other embodiments the catalyst comprises very low pH or acid form of certain surfactants.

[0041] The catalyst may be used at a level of from about 0.01% to about 40%, by weight based on the combined weight of the polycarboxylic acid polymer and the polyol. In some embodiments, catalyst is used at 2.5% to about 10%, by weight based on the combined weight of the polycarboxylic acid polymer and the polyol.

[0042] The binder compositions of the present invention may further contain emulsifiers, pigments, filler, anti-migration aids, curing agents, coalescing agents, wetting agents, biocides, plasticizers, organosilanes, anti-foaming agents, colorants, waxes, antioxidants, or mixtures thereof.

[0043] The excess molar equivalent of hydroxyl groups provides for the binder compositions of the present invention to exhibit a solidification time. During the solidification time the binder composition undergoes molecular mobility and rearrangement so that subsequent curing takes place efficiently and complete. In one embodiment, the solidification time is at 105°C is greater than 2.5 hours.

[0044] In one embodiment, the binder comprising of the present invention further comprises a fiber. The fiber may be selected from fiberglass, mineral fiber, polyester, cellulosic fiber, and mixtures thereof. In one embodiment, the fiber is fiberglass. In another embodiment, the fiber is a cellulosic fiber such as wood pulp, cotton, rayon, lyocell, bast fibers, kenaf fiber, jute fiber, or hemp fiber.

[0045] The binder composition of the present invention may be prepared by admixing the polycarboxylic acid polymer and the polyol. In one embodiment, a phosphorous-containing catalyst in added to the mixture of polycarboxylic acid polymer and the polyol. The mixture is allowed to remain for a solidification time, after which curing occurs. The duration and temperature of the solidification time generally is above 100°C, for example 105°C for at least 2.5 hours. Curing is at a temperature of from about 160°C to about 320°C for about 1 to about 10 minutes. In one embodiment, the curing temperature is 190°C for about 3 minutes.

[0046] In another aspect, the present invention provides a fiberglass binder composition comprising a) at least one fiberglass, b) at least one polyol, c) triethanolamine, and d) a least one polycarboxylic acid polymer, wherein molar equivalent of hydroxyl groups in the triethanolamine and the at least one polyol is 1 .01 to 7 times the molar equivalent of carboxylic acid groups in the at least one polycarboxylic acid polymer. [0047] The fiberglass binder composition may be used for making products, such as fiberglass battings. For example, a mat of fibrous glass can be produced by fiberizing molten glass and immediately forming a fibrous glass mat on a moving conveyor. In one embodiment, the fiberglass binder compositions are used for making a fiberglass article, such as insulation. [0048] According, in another aspect, the present invention provides a process for making a fiberglass mat comprising preparing a binder solution comprising an aqueous solution comprising a) at least one polyol, and b) a least one polycarboxylic acid polymer, wherein molar equivalent of hydroxyl groups in the at least one polyol is present in excess to molar equivalent of carboxylic acid groups in the at least one polycarboxylic acid polymer, and c) optionally a catalyst; mixing the binder solution with fiberglass to form a fiberglass-binder mixture; and curing the fiberglass-binder mixture to produce the fiberglass mat.

[0049] The curing process may be carried out in a curing oven wherein heated air is passed through the mat to cure the resin. The mat may be compressed during the curing to provide for a finished product having predetermined thickness and surface finish. The curing oven may be operated at a temperature from about 160°C to about 320°C for about 30 seconds to about 10 minutes. In one embodiment, the curing temperature is 190°C for about 3 minutes.

[0050] The following embodiments further illustrate the present invention. While the invention has been described with certain embodiments, it is to be understood that variations and modifications may be apparent to those skilled in the art. Such variations and modifications are to be considered within the scope of the present invention.

[0051] Embodiment 1. A binder composition comprising a) at least one polyol and b) at least one polycarboxylic acid polymer, wherein molar equivalent of hydroxyl groups in the at least one polyol is present in excess to molar equivalent of carboxylic acid groups in the at least one polycarboxylic acid polymer.

[0052] Embodiment 2. The composition of embodiment 1 , wherein the molar equivalent of hydroxyl groups is 1 .01 to 7.5 times the molar equivalent of carboxylic acid groups.

[0053] Embodiment 3. The composition of embodiment 2, wherein the molar equivalent of hydroxyl groups is 1 .5 to 6.0 times the molar equivalent of carboxylic acid groups.

[0054] Embodiment 4. The composition of embodiment 2 or 3, wherein the molar equivalent of hydroxyl groups is 2 to 5 times the molar equivalent of carboxylic acid groups.

[0055] Embodiment 5. The composition of any one of the preceding embodiments, wherein the polycarboxylic acid polymer comprises a homopolymer or copolymer of polyacrylic acid. [0056] Embodiment 6. The composition of any one of the preceding embodiments, wherein the polyol is selected from triethanolamine, glycerol, pentaerythritol, 2-methyl-1 ,3-propanediol, 1 ,3- propanediol, polyvinyl alcohol, neopentyl glycol, ethylene glycol, glucose, trimethylolpropane, sorbitol, N,N,N',N'-Tetrakis (2-hydroxypropyl) ethylene-diamine, diisopranolamine, methyldiethanolamine, butyldiethanolamine, diethanolamine, and mixtures thereof.

[0057] Embodiment 7. The composition of any one of the preceding embodiments, wherein the composition exhibits a solidification time at 105°C of greater than 2.5 hours

[0058] Embodiment 8. The composition of any one of the preceding embodiments, further comprising a fiber, wherein the fiber is selected from fiberglass, polyester, cellulosic fiber, and mixtures thereof.

[0059] Embodiment 9. A fiber reenforced article comprising the composition of embodiment 8. [0060] Embodiment 10. A fiberglass binder composition comprising a) at least one fiberglass b) at least one polyol, c) triethanolamine, and d) at least one polycarboxylic acid polymer, wherein molar equivalent of hydroxyl groups in the triethanolamine and the at least one polyol is 1 .01 to 7.5 times the molar equivalent of carboxylic acid groups in the at least one polycarboxylic acid polymer.

[0061] Embodiment 11. The composition of embodiment 10, wherein the molar equivalent of hydroxyl groups is 2 to 5 times the molar equivalent of carboxylic acid groups.

[0062] Embodiment 12. The composition of embodiment 10 or 11 , wherein the polycarboxylic acid polymer comprises a homopolymer or copolymer of polyacrylic acid.

[0063] Embodiment 13. The composition of any one of embodiments 10 to 12, wherein the polyol is selected from glycerol, pentaerythritol, 2-methyl-1 ,3-propanediol, 1 ,3-propanediol, polyvinyl alcohol, neopentyl glycol, ethylene glycol, glucose, trimethylolpropane, sorbitol, N,N,N',N'-tetrakis (2-hydroxypropyl) ethylene-diamine, diisopranolamine, methyldiethanolamine, butyldiethanolamine, diethanolamine, and mixtures thereof.

[0064] Embodiment 14. The composition of any one of embodiments 10 to 13, wherein the composition exhibits a solidification time at 105°C of greater than 2 hours.

[0065] Embodiment 15. A fiberglass article comprising the composition of any one of embodiments 10 to 14.

[0066] Embodiment 16. The article of embodiment 15, wherein the article is insulation.

[0067] Embodiment 17. A process for making a fiberglass mat comprising preparing a binder solution comprising an aqueous solution comprising a) at least one polyol, and b) a least one polycarboxylic acid polymer, wherein molar equivalent of hydroxyl groups in the at least one polyol is present in excess to molar equivalent of carboxylic acid groups in the at least one polycarboxylic acid polymer, and c) optionally a catalyst; mixing the binder solution with fiberglass to form a fiberglass-binder mixture; and curing the fiberglass-binder mixture to produce the fiberglass mat.

[0068] Embodiment 18. The process of embodiment 17, wherein the molar equivalent of hydroxyl groups is 1 .01 to 7.5 times the molar equivalent of carboxylic acid groups.

[0069] Embodiment 19. The process of embodiment 17 or 18, wherein the molar equivalent of hydroxyl groups is 1 .5 to 6.0 times the molar equivalent of carboxylic acid groups.

[0070] Embodiment 20. The process of any one of embodiments 17 to 19, wherein the molar equivalent of hydroxyl groups is 2 to 5 times the molar equivalent of carboxylic acid groups. [0071] Embodiment 21. The process of any one of embodiments 17 to 10, wherein the polycarboxylic acid polymer comprises a homopolymer or copolymer of polyacrylic acid.

[0072] Embodiment 22. The process of any one of embodiments 17 to214, wherein the polyol is selected from triethanolamine, glycerol, pentaerythritol, 2-methyl-1 ,3-propanediol, 1 ,3- propanediol, polyvinyl alcohol, neopentyl glycol, ethylene glycol, glucose, trimethylolpropane, sorbitol, N,N,N',N'-Tetrakis (2-hydroxypropyl) ethylene-diamine, diisopranolamine, methyldiethanolamine, butyldiethanolamine, diethanolamine, and mixtures thereof.

[0073] Embodiment 23. The composition of any one of embodiments 1-8, 10-14, or the article of any one of embodiments 9, 15-16, or the process of any one of embodiments 17-22, wherein the molar equivalent of hydroxyl groups is 2.2 to 13 times, 2.5 to 13 times, 2.7 to 13 times, 3 to 13 times, 3.2 to 13 times, 3.5 to 13 times, 3.7 to 13 times, 4 to 13 times, 4.2 to 13 times, 4.5 to 13 times, 4.7 to 13 times, 5 to 13 times, 2.2 to 11 times, 2.2 to 9 times, 2.2 to 7 times, 2.5 to 7 times, 2.7 to 7 times, 3 to 7 times, 3.2 to 7 times, or 3.5 to 7 times the molar equivalent of carboxylic acid groups.

[0074] Embodiment 24. The composition of any one of embodiments 1-8 and 10-14, or the article of any one of embodiments 9 and 15-16, or the process of any one of embodiments 17- 22, wherein the polyol having hydroxyl groups is not an epoxidized plant oil or derived from an epoxidized plant oil, and the molar equivalent of hydroxyl groups is 2.2 to 13 times, 2.5 to 13 times, 2.7 to 13 times, 3 to 13 times, 2.2 to 7 times, 2.5 to 7 times, 2.7 to 7 times, 3 to 7 times, 3.2 to 7 times, or 3.5 to 7 times the molar equivalent of carboxylic acid groups.

EXAMPLES [0075] Materials: Acrodur 950L, glycerol, Acrodur PLUS 2580, triethanolamine (TEA), 2-methyl- 1 ,3-propanediol (2-Me-1 ,3-PDO), sodium hypophosphite, Acrodur DS 3515, and 1 ,3- propanediol (1 ,3-PDO) were used as received.

Example 1 Preparation of Polyacrylic acid (PAA) homopolymer.

[0076] Polyacrylic acid (PAA) homopolymer, molecular weight of about 6000 g/mol, was prepared as outlined in US2012/0157596A1 , which is incorporated by reference. The process for polymerization was a semi-batch synthesis, wherein the monomer was simultaneously added with an initiator and a chain transfer agent. To a steel polymerization vessel were added 450 grams of deionized water and 23 grams of 59% sodium hypophosphite. The contents of the vessel were kept under agitation and inert atmosphere by nitrogen injection. A first separate vessel was filled with 400 grams of a 7.5% sodium persulfate aqueous solution. A second separate vessel was filled with 130 grams of a 59% sodium hypophosphite aqueous solution. A third vessel was filled with 1293.5 grams of acrylic acid. The polymerization vessel was heated to 85°C, then the contents of each of the three separate vessels were added simultaneously and/or linearly to the contents of the polymerization vessel over 225 minutes, maintaining the temperature at 95°C. After the addition step, the temperature of the contents of the polymerization vessel was reduced to 40°C, then a redox treatment was performed by adding 3 grams of hydrogen peroxide and 1 gram of sodium metabisulfite to the contents of the polymerization vessel. The final product was a 49-51% acid solution of polyacrylic acid homopolymer having a molecular weight of 6200 g/mol, a polydispersity (PD) of 1.8, and a pH of about 2.0.

Example 2 Preparation of Binder Composition [0077] For the evaluations of high polyol content systems, 24.39g of the polymer produced in Example 1 is diluted with 2.44g of triethanolamine to bring the pH to ~3.3, then 14.63g of glycerol is added. This gives a molar ratio of -OH I -COOH (alcohol to acid) of 3.51 , and then 101 ,0g of deionized water. This gave an average loading on the Whatman glass fiber of 20.6%. This fabric had a dry tensile strength of 8.81 Ibf and a hot/wet tensile strength of 7.87lbf.

Example 3 Preparation of Comparable Binder Composition [0078] For the evaluations of a low polyol content systems, 24.39g of the polymer produced in Example 1 is diluted with 2.44g of triethanolamine to bring the pH to ~3.3. This gives a molar ratio of -OH / -COOH (alcohol to acid) of 0.39, and then 38.6g of deionized water. This gave an average loading on the Whatman glass fiber of 21 .3%. This fabric had a dry tensile strength of 7.13lbf and a hot/wet tensile strength of 5.38lbf.

[0079] Fig. 1 shows the effect of adding excess amounts of polyol to polyacrylic acid. Fig. 1 shows that by going to higher amounts of moles of alcohol as compared to moles of acid the solidification time, determined as described in Example 6, increases the observed tensile strength. In Fig. 1 , Acrodur PLUS 2580 is a commercial reference, low amounts of polyol is a comparative formulation of Example 3, and inventive composition having 3.51 moles of alcohol to 1 mole acid is Example 2.

Example 4 Procedure to make Whatman Glass Mat samples

[0080] Formulation. Whatman Glass Mat preparation involved saturating a Whatman glass to achieve a 20% binder load. The binder load is determined by the weight of the final fabric (Wf) less the weight of the untreated fabric (Wi) divided by the weight of the final fabric. Binder load = 100 x (Wf - Wi) I Wf. Achieving the targeted binder loading is a matter of trial and error that involves adjusting the non-water content of the binder solution until the targeted binder load is reached.

[0081] Saturation and Drying. The desired pressure and speed was set on a Werner Mathis 2 Roll Padder, and the bath solution was poured into the trough. Before saturating, a sample of Whatman glass mat (7” x 10”) was weighed to record the dry weight value. The Whatman glass mat was then fed into the bath solution via the padder. The sample was allowed to dry in a Werner Mathis oven, typically at 190°C for 3 minutes. Once the sample was dried, the sample was then conditioned in a Controlled Temperature and Humidity (CTH) room overnight.

Example 5 Procedure for Sample Testing (Preparation and Testing)

[0082] Sample Preparation. Specimens prepared as in Example 4 were tested under two conditions: room temperature and hot/wet. Room temperature samples did not need further conditioning after being left in the CTH room. For hot/wet testing, a water bath was heated to 180°F and samples were conditioned in the water bath for 10 minutes. Prior to testing, samples were cut down to 1” x 8” specimens for tensile and elongation testing on a an Instron 3382. Three specimens are needed for each testing condition and the final tensile strength is an average of the three repeats.

[0083] Testing. A 500N Load Cell was used to the measure the amount of force needed to pull specimens. An upper and lower clamp was installed on the Instron, where specimens were loaded and pulled until rupturing. Additional parameters for Instron testing are listed in Table 1 below.

[0084] Results. Maximum Load (Ibf) and maximum % elongation were recorded, with averages and standard deviation.

Table 1

Example 6 Drying Time Testing: Solidification time

[0085] The drying time test assesses the time needed for a given sample to solidify at 105°C. Samples are checked at 30 minute intervals to determine solidification. In these studies, the following polyols are tested at varying amounts with either polyacrylic acid (Mw~6000) or Acrodur 950L: 1 ,3-propanediolb, 2-methyl-1 ,3-propanediolc, glycerol. For this test, a control is always used (Acrodur 2580 or Acrodur 950L). For each drying time study, the following amounts of polyol are used: 0.5 grams, 1 .0 grams, 1.2 grams, 2.5 grams, 3.0 grams. For evaluations of polyacrylic acid (Mw~6000), enough TEA is added to bring the pH ~ 3.3. Acrodur 950L is already at the desired pH and is ready to be used with the polyols. Samples are tested in an aluminum weigh boat. All samples are mixed using a tongue depressor and placed in the oven.

[0086] Results. The tables below illustrate that adding the large amounts of polyol to raise the alcohol to acid ratio (-OH I -COOH) to greater than 1 increases the time to solidify. It is speculated that the longer solidification time gives the polyacids time to react with the polyols and create an improved crosslink density. Note that the longer liquid I gel states are present after the water is evaporated which is important as the condensation reaction to form the crosslinks occurs primarily after the water is gone.

Table 2. Drying times for blends of polyacrylic acid (PAA), TEA, and glycerol.

Table 3. Drying times for blends of polyacrylic acid (PAA), TEA, and 1 ,3-propanediol.

Table 4. Drying times for blends of polyacrylic acid (PAA), TEA, and 2-methyl-1 ,3-propanediol.

Table 5. Drying times for blends of Acrodur 950L, TEA, and glycerol.

[0087] Tensile testing results show an improvement in performance at these higher alcohol to acid ratios (-OH I -COOH). However, if the excess of alcohol is too great the performance starts to diminish. For glycerol with polyacrylic acid (Mw~6000) the optimal ratio excess of alcohol is 5.88 (Table 6), while for 1 ,3-propanediol the optimal ratio excess of alcohol is 1 .32 (Table 7). For the Acrodur 950L polymer the optimal ratio excess of alcohol is 1.56 (Table 8). Table 6. Tensile performance for blends of polyacrylic acid (PAA), TEA, and glycerol.

Table 7. Tensile performance for blends of polyacrylic acid (PAA), TEA, and 1 ,3-propanediol.

Table 8. Tensile performance for blends of Acrodur 950L, TEA, and glycerol.

Table 9. Tensile performance for blends of Acrodur DS 3515, TEA, and glycerol.

Claims

CLAIMS What is claimed is:

1 . A binder composition comprising a) at least one polyol and b) at least one polycarboxylic acid polymer, wherein molar equivalent of hydroxyl groups in the at least one polyol is present in excess to molar equivalent of carboxylic acid groups in the at least one polycarboxylic acid polymer.

2. The composition of claim 1 , wherein the molar equivalent of hydroxyl groups is 1.01 to 7.5 times the molar equivalent of carboxylic acid groups.

3. The composition of claim 2, wherein the molar equivalent of hydroxyl groups is 1.5 to 6.0 times the molar equivalent of carboxylic acid groups.

4. The composition of claim 2, wherein the molar equivalent of hydroxyl groups is 2 to 5 times the molar equivalent of carboxylic acid groups.

5. The composition of claim 1 , wherein the polycarboxylic acid polymer comprises a homopolymer or copolymer of polyacrylic acid.

6. The composition of claim 1 , wherein the polyol is selected from triethanolamine, glycerol, pentaerythritol, 2-methyl-1 ,3-propanediol, 1 ,3-propanediol, polyvinyl alcohol, neopentyl glycol, ethylene glycol, glucose, trimethylolpropane, sorbitol, N,N,N',N'-Tetrakis (2-hydroxypropyl) ethylene-diamine, diisopranolamine, methyldiethanolamine, butyldiethanolamine, diethanolamine, and mixtures thereof.

7. The composition of claim 1 , wherein the composition exhibits a solidification time at 105°C of greater than 2.5 hours.

8. The composition of claim 1 , further comprising a fiber, wherein the fiber is selected from fiberglass, polyester, cellulosic fiber, and mixtures thereof.

9. A fiber reenforced article comprising the composition of claim 8.

10. A fiberglass binder composition comprising a) at least one fiberglass b) at least one polyol, c) triethanolamine, and d) at least one polycarboxylic acid polymer, wherein molar equivalent of hydroxyl groups in the triethanolamine and the at least one polyol is 1.01 to 7.5 times the molar equivalent of carboxylic acid groups in the at least one polycarboxylic acid polymer.

11. The composition of claim 10, wherein the molar equivalent of hydroxyl groups is 1.5 to 6.0 times the molar equivalent of carboxylic acid groups.

12. The composition of claim 10, wherein the polycarboxylic acid polymer comprises a homopolymer or copolymer of polyacrylic acid.

13. The composition of claim 10, wherein the polyol is selected from glycerol, pentaerythritol, 2-methyl-1 ,3-propanediol, 1 ,3-propanediol, polyvinyl alcohol, neopentyl glycol, ethylene glycol, glucose, trimethylolpropane, sorbitol, N,N,N',N'-Tetrakis (2-hydroxypropyl) ethylene-diamine, diisopranolamine, methyldiethanolamine, butyldiethanolamine, diethanolamine, and mixtures thereof.

14. The composition of claim 10, wherein the composition exhibits a solidification time at 105°C of greater than 2 hours.

15. A fiberglass article comprising the composition of any one of claims 10-14.

16. The article of claim 15, wherein the article is insulation.

17. A process for making a fiberglass mat comprising preparing a binder solution comprising an aqueous solution comprising a) at least one polyol, and b) a least one polycarboxylic acid polymer, wherein molar equivalent of hydroxyl groups in the at least one polyol is present in excess to molar equivalent of carboxylic acid groups in the at least one polycarboxylic acid polymer, and c) optionally a catalyst; mixing the binder solution with fiberglass to form a fiberglass-binder mixture; and curing the fiberglass-binder mixture to produce the fiberglass mat.

18 The process of claim 17, wherein the molar equivalent of hydroxyl groups is 1.01 to 7.5 times the molar equivalent of carboxylic acid groups.

19. The process of claim 18, wherein the molar equivalent of hydroxyl groups is 1 .5 to 6.0 times the molar equivalent of carboxylic acid groups.

20. The process of claim 19, wherein the molar equivalent of hydroxyl groups is 2 to 5 times the molar equivalent of carboxylic acid groups.

21. The process of claim 17, wherein the polycarboxylic acid polymer comprises a homopolymer or copolymer of polyacrylic acid.

22. The process of claim 17, wherein the polyol is selected from triethanolamine, glycerol, pentaerythritol, 2-methyl-1 ,3-propanediol, 1 ,3-propanediol, polyvinyl alcohol, neopentyl glycol, ethylene glycol, glucose, trimethylolpropane, sorbitol, N,N,N',N'-Tetrakis (2-hydroxypropyl) ethylene-diamine, diisopranolamine, methyldiethanolamine, butyldiethanolamine, diethanolamine, and mixtures thereof.