Coupling agent

Abstract

Disclosed is a thermosetting composition comprising a dispersion of particulate solids in a thermosetting resin in the presence of a coupling agent according to formula I described herein. Also disclosed are various methods of making and / or using the coupling agent and / or the thermosetting composition. The disclosed technology relates to polymers that can be used as coupling agents in thermosetting compositions containing particulate solids and the like. The incorporation of particulate solids (e.g., fillers and / or fibers) into polymer materials (such as thermosetting polymers, thermoplastic polymers, elastomers, and / or rubbers) is known, and combinations of these materials represent a subset of composite materials.

Description

Technical Field

[0001] The disclosed technology relates to polymers that can be used as coupling agents in thermosetting compositions containing particulate solids and the like.

Background Art

[0002] The incorporation of particulate solids (e.g., fillers and / or fibers) into polymer materials (such as thermosetting polymers, thermoplastic polymers, elastomers, and / or rubbers) is known, and combinations of these materials represent a subset of composite materials. Molded articles made from these types of composite materials can exhibit improved rigidity, hardness, and / or creep resistance compared to the corresponding unfilled polymer materials. However, these types of composite materials may exhibit a significant decrease in toughness and / or ductility compared to the corresponding unfilled polymer materials. In the case of thermoplastic and thermosetting polymers, composite molded articles may be too brittle or have too low impact resistance and elongation for more practical use.

[0003] To improve such drawbacks, various approaches have been attempted to improve the compatibility between particulate solids and polymer materials. For example, incorporating a surface modifier or sizing agent by coating the particulate solid, etc., can improve compatibility. Surface modifiers / sizing agents can generally be classified into two categories: coupling agents and non-coupling modifiers. Non-coupling modifiers interact with the surface of the particulate solid but do not interact with the polymer matrix.

[0004] Coupling agents interact with both the surface of the particulate solid and the polymer matrix. In many cases, coupling agents covalently bond to both the particulate solid and the polymer matrix. In other cases, ion pair interactions between the coupling agent and the particulate solid may be appropriate, while entanglement and / or co-crystallization of the chains can provide sufficient interaction between the coupling agent and the polymer matrix.

[0005] For example, acid-functional modifiers can be represented in both categories. Certain fatty acids can typically be considered non-coupling modifiers where the carboxyl group binds to the surface of the particulate solid and the fatty group intercalates into the polymer matrix. Certain polymeric acids can generally be regarded as coupling agents where the carboxy groups interact with the surface of the particulate solid and the polymer chains interact with the polymer matrix. The degree of interaction between the polymer chains and the polymer matrix depends on the functionality of the polymer chains and the type of polymer material. Acrylic acid, for example, has been used as a coupling agent for calcium carbonate fillers in a polypropylene matrix, but the volatility of acrylic acid during processing represents an obvious drawback.

[0006] Currently, organosilanes are being used as coupling agents. Organosilanes contain alkoxysilane groups that can react with suitable hydroxyl groups on the surface of particulate solids (for example, in the case of metal hydroxide fillers, a [metal]-O-Si covalent bond is formed). Organosilane coupling agents also have another functional group that can react with the polymer matrix. A wide range of commercially available organosilane coupling agents are available to address the various reactive surface hydroxyl groups and different reactions with polymer chains in the matrix. Organosilanes can be very effective but have certain limitations. For example, they can be relatively expensive due to the high level of chemical processing required, they can be ineffective for fillers that do not have surface hydroxyl groups, they can have limited compatibility with the bulk polymer materials used (therefore, can be applied as a surface treatment on particulate solids, require additional process steps, and / or limit processing conditions), and they can release large amounts of alcohol when reacting with the surface of certain particulate solids.

[0007] Accordingly, the disclosed technology provides a polymer useful as a coupling agent that can overcome the above specific drawbacks. SUMMARY OF THE INVENTION MEANS FOR SOLVING THE PROBLEM

[0008] The subject matter disclosed in this specification provides a polymer having monomer units a, b, c, d, e, and f according to Formula I,

[0009]

Chemical formula

[0010] In certain embodiments, the polymer can be used as a coupling agent in a thermosetting composition. For example, the thermosetting composition can include a dispersion of particulate solids in a thermosetting resin in the presence of a coupling agent.

[0011] Various methods of making and / or using polymers, coupling agents, and / or thermosetting compositions are also provided.

DETAILED DESCRIPTION OF THE INVENTION

[0012] The following embodiments of the subject matter are contemplated. 1. A thermosetting composition comprising a dispersion of particulate solids in a thermosetting resin in the presence of a coupling agent comprising monomer units a, b, c, d, e, and f according to formula I, wherein, independently for each molecule of the polymer,

[0013]

CHEMICAL

[0014] The various features and embodiments of the present subject matter are described below by way of non-limiting illustration.

[0015] As used herein, the indefinite article "a" / "an" is intended to mean one or more than one. As used herein, the phrase "at least one" means one or more than one of the following terms. Accordingly, "a" / "an" and "at least one" may be used interchangeably. For example, "at least one of A, B or C" means that in alternative embodiments, only one of A, B or C may be included, or any mixture of two or more of A, B and C may be included.

[0016] As used herein, the term "substantially" means that a given quantity value is within ±10% of the recited value. In other embodiments, the value is within ±5% of the recited value. In other embodiments, the value is within ±2.5% of the recited value. In other embodiments, the value is within ±1% of the recited value.

[0017] As used herein, the transitional term "comprising", which is synonymous with "including", "containing", or "characterized by", is inclusive or open-ended and does not exclude additional, unrecited elements or method steps. However, in each instance of the use of "comprising" herein, this term is also intended to include, as alternative embodiments, the phrases "consisting essentially of" and "consisting of", where "consisting of" excludes any unrecited element or step, and "consisting essentially of" permits the inclusion of additional, unrecited elements or steps that do not substantially affect the essential or novel characteristics of the composition or method under consideration.

[0018] There is provided a thermosetting composition comprising a dispersion of particulate solids in a thermosetting resin in the presence of a coupling agent comprising monomer units a, b, c, d, e, and f according to formula I,

[0019]

Chemical formula

[0020] The phrase "comprising monomer units a, b, c, d, e, and f according to formula I" is to be understood simply as meaning that the monomer units are present (or, in the case of monomer units c, d, e, and f, optionally not present) as described in the variable definitions provided for formula I, and that it is possible for other monomer units different from monomer units a, b, c, d, e, and / or f to be included. This phrase is not intended to mean that all monomer units must be present or that other monomer units are excluded. Further, it is to be understood that the monomer units are not present in the order shown in formula I, but can be included in any order, such as a random order (and most likely will be included), although theoretically it is possible for the monomer units to be present in a block copolymer type structure in either the order shown in formula I or any other order. In practice, it may be difficult to control the placement of each monomer unit relative to any other monomer units, which generally results in a random structure. However, as will be understood by those skilled in the art, it is possible to control the number of units of each monomer unit present.

[0021] The "theoretical number average molecular weight" means the average molecular weight of the target group of bonded atoms determined by summing the molecular weights of each atom of the group based on its chemical formula.

[0022] Variable X 1 , X 2 , X 3 , X 4 , and X 5 With respect to the case where any of X 1 , X 2 , X 3 , X 4 , and X 5Each of them can be derived from (but not limited to) maleic anhydride or itaconic anhydride. When derived from maleic anhydride, each X 1 、X 2 、X 3 、X 4 、or X 5 The variable represents two carbon atoms, and the relevant part of the polymer is as follows.

[0023]

Chemical formula

[0024] When derived from itaconic anhydride, each X 1 、X 2 、X 3 、X 4 、or X 5 The variable represents three carbon atoms, and the relevant part of the polymer is as follows.

[0025]

Chemical formula

[0026] In certain embodiments, the particulate solid is present in an amount of 20 to 80 (e.g., 25 to 80, 30 to 80, 35 to 80, 40 to 80, 45 to 80, 50 to 80, 55 to 80, 60 to 80, 65 to 80, 70 to 80, 75 to 80, 20 to 75, 25 to 75, 30 to 75, 35 to 75, 40 to 75, 45 to 75, 50 to 75, 55 to 75, 60 to 75, 65 to 75, 70 to 75, 20 to 70, 25 to 70, 30 to 70, 35 to 70, 40 to 70, 45 to 70, 50 to 70, 55 to 70, 60 to 70, 65 to 70, 20 to 65, 25 to 65, 30 to 65, 35 to 65, 40 to 65, 45 to 65, 50 to 65, 55 to 65, 60 to 65, 20 to 60, 25 to 60, 30 to 60, 35 to 60, 40 to 60, 45 to 60, 50 to 60, 55 to 60, 20 to 55, 25 to 55, 30 to 55, 35 to 55, 40 to 55, 45 to 55, 50 to 55, 20 to 50, 25 to 50, 30 to 50, 35 to 50, 40 to 50, 45 to 50, 20 to 45, 25 to 45, 30 to 45, 35 to 45, 40 to 45, 20 to 40, 25 to 40, 30 to 40, 35 to 40, 20 to 35, 25 to 35, 30 to 35, 20 to 30, 25 to 30, or 20 to 25) weight percent, based on the total weight of the thermosetting composition. The particulate solid can be any solid material suitable for incorporation into a thermosetting resin, such as for producing a composite material. Depending on the intended use of the resulting composition and / or the desired properties of the resulting composition, particulate solids of various densities can be included in the thermosetting resin. Thus, the weight percent of particulate solid present in the composition can vary widely based on both the density and amount of particulate solid present.

[0027] In certain embodiments, the particulate solid is present in an amount of 20 to 80 (e.g., 25 to 80, 30 to 80, 35 to 80, 40 to 80, 45 to 80, 50 to 80, 55 to 80, 60 to 80, 65 to 80, 70 to 80, 75 to 80, 20 to 75, 25 to 75, 30 to 75, 35 to 75, 40 to 75, 45 to 75, 50 to 75, 55 to 75, 60 to 75, 65 to 75, 70 to 75, 20 to 70, 25 to 70, 30 to 70, 35 to 70, 40 to 70, 45 to 70, 50 to 70, 55 to 70, 60 to 70, 65 to 70, 20 to 65, 25 to 65, 30 to 65, 35 to 65, 40 to 65, 45 to 65, 50 to 65, 55 to 65, 60 to 65, 20 to 60, 25 to 60, 30 to 60, 35 to 60, 40 to 60, 45 to 60, 50 to 60, 55 to 60, 20 to 55, 25 to 55, 30 to 55, 35 to 55, 40 to 55, 45 to 55, 50 to 55, 20 to 50, 25 to 50, 30 to 50, 35 to 50, 40 to 50, 45 to 50, 20 to 45, 25 to 45, 30 to 45, 35 to 45, 40 to 45, 20 to 40, 25 to 40, 30 to 40, 35 to 40, 20 to 35, 25 to 35, 30 to 35, 20 to 30, 25 to 30, or 20 to 25) weight percent, based on the total weight of the thermosetting composition.

[0028] In certain embodiments, the particulate solid comprises at least one of a bulking agent, a reinforcing material, or a functional filler. Bulking agents (sometimes referred to as fillers) are generally materials included primarily to reduce the cost of the composition without generally adversely affecting the properties of the composition, as they are generally less expensive than other components of the composition. In certain embodiments, the bulking agent comprises at least one of calcium carbonate, talc, barium sulfate, alumina, or quartz. Suitable bulking agents include, but are not limited to, wollastonite (including surface-treated wollastonite); calcium sulfate (as its anhydride, dihydrate or trihydrate); calcium carbonate (including chalk); limestone, marble and synthetic precipitated calcium carbonate, generally containing 98+% CaCO3 and the balance being other inorganics such as magnesium carbonate, iron oxide and aluminosilicate in the form of ground particles; surface-treated calcium carbonate; talc including fibrous, modular, acicular and platy talc; both hollow and solid glass spheres; and kaolin including hard, soft, calcined kaolin, including various coatings known in the art to promote dispersion in and compatibility with thermosetting resins, kaolin; mica; feldspar and nepheline syenite; silicate spheres; fume; cenospheres; fly ash; aluminosilicate (spheroids); natural silica sand; quartz; siliceous rock; perlite; tripoli; diatomaceous earth; synthetic silica, etc.

[0029] Functional fillers are generally materials included primarily to provide and / or improve certain properties of the composition, such as fire retardant / flame retardant materials and / or pigments. In certain embodiments, the functional filler comprises at least one of a flame retardant material or a pigment. Suitable functional fillers include, but are not limited to, boron nitride powder and boron silicate powder for obtaining cured products having low dielectric constant and low dielectric loss tangent; or silica powder (e.g., fused silica and / or crystalline silica), alumina, and / or magnesium oxide (or magnesia) for high temperature conductivity.

[0030] In certain embodiments, the bulking agent and / or the functional filler can include particles having an average aspect ratio of less than about 5:1.

[0031] Reinforcing materials are generally known to be materials included to primarily increase certain physical properties of a composition, such as tensile strength. In certain embodiments, the reinforcing material includes at least one type of fibrous material. As used herein, the term “fibrous material” means any material in which each particle generally has a length (presumably an average of the longest dimension of each particle of the material) that is substantially longer than its width (presumably an average of the shortest dimension of each particle of the material), for example, a length-to-width ratio of greater than about 5:1, presumably on average. Suitable fibers can include, but are not limited to, fibers having a high tensile strength (e.g., greater than 500 kpsi (or 3447 MPa)), carbon or graphite fibers, glass fibers, and fibers formed from silicon carbide, alumina, boron, quartz, etc., and organic polymers such as fibers formed from polyolefins, poly(benzothiazole), poly(benzimidazole), polyarylate, poly(benzoxazole), aromatic polyamides, polyaryl ethers, etc., and mixtures having two or more such fibers can be included. The fibers can be used in the form of discontinuous or continuous tows composed of a plurality of filaments, as continuous unidirectional or multi-directional tapes, as chopped individual fibers, or as woven, non-crimped, or non-woven fabrics. The woven form can be selected from plain weave, twill weave, or satin weave styles. The non-crimped fabric can have multiple plies and fiber orientations.

[0032] In certain embodiments, the thermosetting resin is present in an amount of 80 to 20 (e.g., 75 to 20, 70 to 20, 65 to 20, 60 to 20, 55 to 20, 50 to 20, 45 to 20, 40 to 20, 35 to 20, 30 to 20, 25 to 20, 80 to 25, 75 to 25, 70 to 25, 65 to 25, 60 to 25, 55 to 25, 50 to 25, 45 to 25, 40 to 25, 35 to 25, 30 to 25, 80 to 30, 75 to 30, 70 to 30, 65 to 30, 60 to 30, 55 to 30, 50 to 30, 45 to 30, 40 to 30, 35 to 30, 80 to 35, 75 to 35, 70 to 35, 65 to 35, 60 to 35, 55 to 35, 50 to 35, 45 to 35, 40 to 35, 80 to 40, 75 to 40, 70 to 40, 65 to 40, 60 to 40, 55 to 40, 50 to 40, 45 to 40, 80 to 45, 75 to 45, 70 to 45, 65 to 45, 60 to 45, 55 to 45, 50 to 45, 80 to 50, 75 to 50, 70 to 50, 65 to 50, 60 to 50, 55 to 50, 80 to 50, 75 to 50, 70 to 50, 65 to 50, 60 to 50, 80 to 55, 75 to 55, 70 to 55, 65 to 55, 60 to 55, 80 to 60, 75 to 60, 70 to 60, 65 to 60, 80 to 65, 75 to 65, 70 to 65, 80 to 70, 75 to 70, or 80 to 75) weight percent, based on the total weight of the thermosetting composition.

[0033] In certain embodiments, the thermosetting resin includes an epoxide resin, an unsaturated polyester resin, a vinyl ester resin, a polyurethane resin, or a phenolic resin. Suitable thermosetting resins include resins that undergo a chemical reaction and become relatively insoluble when subjected to heating, catalysis, or irradiation with ultraviolet light, laser light, infrared light, cations, an electron beam, or microwaves. Exemplary reactions of thermosetting resins include oxidation of unsaturated double bonds, reactions involving epoxy / amine, epoxy / carbonyl, epoxy / hydroxyl, reactions of epoxy with a Lewis acid or a Lewis base, polyisocyanate / hydroxy, amino resin / hydroxy moieties, free radical reactions or reactions with polyacrylates, cationic polymerization of an epoxy resin and a vinyl ether, and condensation of silanols. Examples of unsaturated resins include polyester resins made by the reaction of one or more diacids or anhydrides with one or more diols. Such resins are typically supplied as a mixture with a reactive monomer such as styrene or vinyltoluene and are often referred to as orthophthalic resins and isophthalic resins. Further examples include resins that use dicyclopentadiene (DCPD) as a co-reactant in the polyester chain. Further examples also include the reaction product of bisphenol A diglycidyl ether and an unsaturated carboxylic acid such as methacrylic acid, which is subsequently supplied as a styrene solution, typically referred to as a vinyl ester resin. Polymers having a hydroxy functional group (such as a polyol) are widely used in thermosetting systems to crosslink with amino resins or polyisocyanates. Polyols include acrylic polyols, alkyd polyols, polyester polyols, polyether polyols, and polyurethane polyols. Exemplary amino resins include melamine formaldehyde resins, benzoguanamine formaldehyde resins, urea formaldehyde resins, and glycoluril formaldehyde resins. Polyisocyanates are resins having two or more isocyanate groups, including monomeric aliphatic diisocyanates, monomeric aromatic diisocyanates, and their polymers.Exemplary aliphatic diisocyanates include hexamethylene diisocyanate, isophorone diisocyanate, and hydrogenated diphenylmethane diisocyanate. Exemplary aromatic isocyanates include toluene diisocyanate and diphenylmethane diisocyanate.

[0034] In certain embodiments, the coupling agent is present in an amount of 0.5 to 5 (e.g., 1 to 5, 1.5 to 5, 2 to 5, 2.5 to 5, 3 to 5, 3.5 to 5, 4 to 5, 4.5 to 5, 0.5 to 4.5, 1 to 4.5, 1.5 to 4.5, 2 to 4.5, 2.5 to 4.5, 3 to 4.5, 3.5 to 4.5, 4 to 4.5, 0.5 to 4, 1 to 4, 1.5 to 4, 2 to 4, 2.5 to 4, 3 to 4, 3.5 to 4, 0.5 to 3.5, 1 to 3.5, 1.5 to 3.5, 2 to 3.5, 2.5 to 3.5, 3 to 3.5, 0.5 to 3, 1 to 3, 1.5 to 3, 2 to 3, 2.5 to 3, 0.5 to 2.5, 1 to 2.5, 1.5 to 2.5, 2 to 2.5, 0.5 to 2, 1 to 2, 1.5 to 2, 0.5 to 1.5, 1 to 1.5, or 0.5 to 1) weight percent based on the total weight of the thermosetting composition.

[0035] In certain embodiments, the monomer unit a according to formula I can be derived from the radical polymerization of aromatic vinyls such as styrene and / or substituted styrenes such as 4-acetoxystyrene, 4-benzhydrylstyrene, 4-benzyloxy-3-methoxystyrene, 2-bromostyrene, 3-bromostyrene, 4-bromostyrene, 4-tert-butoxystyrene, 4-tert-butylstyrene, 2-chlorostyrene, 3-chlorostyrene, 4-chlorostyrene, 2,6-dichlorostyrene, 2,6-difluorostyrene, 3,4-dimethoxystyrene, 2,4-dimethylstyrene, 2,5-dimethylstyrene, N,N-dimethylvinylbenzylamine, 4-ethoxystyrene, 2-fluorostyrene, 3-fluorostyrene, 4-fluorostyrene, 3-methylstyrene, 4-methylstyrene, 3-nitrostyrene, 2,3,4,5,6-pentafluorostyrene, 3-(trifluoromethyl)styrene, 4-(trifluoromethyl)styrene, 2,4,6-trimethylstyrene, 4-vinylanisole, 3-vinylbenzoic acid, 4-vinylbenzoic acid, 4-vinylbenzyl chloride, 4-vinylbiphenyl, 2-vinylnaphthalene and other aromatic or aliphatic vinyl monomers. In certain embodiments, R 2 can be a C1-C 20 alkyl group. In certain embodiments, R 2 can be a C6-C 10 aryl group.

[0036] In certain embodiments, the monomer unit b according to formula I can be derived from the radical polymerization of vinyl anhydride monomers such as maleic anhydride or itaconic anhydride.

[0037] In certain embodiments, the monomer unit c according to formula I can be derived from the radical polymerization of a vinyl anhydride monomer (such as maleic anhydride or itaconic anhydride) reacted with an amino-functional vinyl monomer such as vinyl ether or (meth)acrylate (such as 2-(2-propen-1-yloxy)-ethanamine or 2-aminoethyl methacrylate hydrochloride).

[0038] In certain embodiments, the monomer unit d according to formula I can be derived from the radical polymerization of a vinyl anhydride monomer (e.g., maleic anhydride or itaconic anhydride) reacted with a hydroxy-functional vinyl ether or (meth)acrylate (2-aryloxyethanol, allyl alcohol, 1,4-butanediol vinyl ether, di(ethylene glycol) vinyl ether, poly(ethylene glycol) vinyl ether, diethylene glycol monoallyl ether, 3-allyloxy-1,2-propanediol, 2-hydroxylethyl acrylate, 2-hydroxylethyl methacrylate, 4-hydroxylbutyl acrylate, 6-hydroxylhexyl methacrylate, poly(ethylene glycol) methacrylate, poly(ethylene glycol) acrylate, poly(propylene glycol) methacrylate, poly(propylene glycol) acrylate or 2,3-dihydroxypropyl methacrylate).

[0039] In certain embodiments, the monomer unit e according to formula I can be derived from the radical polymerization of a vinyl anhydride monomer (such as maleic anhydride or itaconic anhydride) reacted with POL via an amine bond 1 In certain embodiments, POL 1 can be a hydroxy-functional polyether chain, such as polyethylene glycol methyl ether or polypropylene glycol methyl ether. In certain embodiments, POL 1 can be an amino-functional polyether, such as a polyetheramine available from Huntsman under the trade names Surfonamine® L100, L207, L300, B100, and / or B200.

[0040] In certain embodiments, the monomer unit f according to formula I can be derived from the radical polymerization of a vinyl anhydride monomer (such as maleic anhydride or itaconic anhydride) reacted with POL via an amine or hydroxyl bond 2 In certain embodiments, POL 2can be a hydroxy-functional polyether chain, such as polyethylene glycol methyl ether or polypropylene glycol methyl ether. In certain embodiments, POL 2 can be an amino-functional polyether, such as a polyetheramine available from Huntsman under the trade names Surfonamine® L100, L207, L300, B100, and / or B200.

[0041] In certain embodiments, Z 1 and / or Z 2Each of them is, independently, oxygen, and the monohydroxyl-functional polyester is reacting on the anhydride monomer. This monohydroxy-functional polyester can be synthesized by polymerizing lactone and / or lactide and / or hydroxycarboxylic acid, optionally, in the presence of a monoalcohol for initiating polyester chain extension, by any method known to those skilled in the art.Useful alcohols include, but are not limited to, methanol, ethanol, n-propanol, n-butanol, neopentyl alcohol, n-hexanol, n-heptanol, n-octanol, n-decanol, n-dodecanol, n-tetradecanol, n-hexadecanol, oleyl alcohol, n-octadecanol, isopropanol, isobutanol, tert-butanol, 2-ethylbutanol, 2-ethylhexanol, 3-heptanol, 3,5,5-trimethylhexanol, 3,7-dimethyloctanol, cyclohexanol, cyclopentanol, cyclopentanemethanol, cyclohexylmethanol, 4-cyclohexyl-1-butanol, 4-ethylcyclohexanol, cycloheptanol, phenol, ortho-cresol, 2-ethylphenol, 2-propylphenol, 4-ethylphenol, octylphenol, nonylphenol, dodecylphenol, di- and tri-styrylphenol, benzyl alcohol, 2-phenylethanol, 1-naphthol, 2-naphthol, 2-phenylphenol, 4-phenylphenol, polyisobutylene phenol, sec-phenethyl alcohol, 4-ethylbenzyl alcohol, 4-butylbenzyl alcohol, 2-naphthalenemethanol, 3-phenyl-1-propanol, 4-phenyl-1-butanol, cinnamyl alcohol and 4-propoxyphenol, 2-dimethylaminoethanol, 2-diethylaminoethanol, 2-dibutylaminoethanol, 2-propen-1-ol, allyl alcohol, 4-penten-1-ol, 2-hexen-1-ol, 3-nonen-1-ol, 7-dodecen-1-ol, saturated straight-chain alcohols commercially available under the trade name Unilin™ (available from Baker Hughes), and saturated branched alcohols such as “Guerbet” alcohols commercially available under the trade name Isofol® (available from Sasol GmbH) (including mixtures thereof). Specific examples of commercially available Guerbet alcohols are Isofol 12, 14T, 16, 18T, 18E, 20, 24, 28, 32, 32T and 36.

[0042] In certain embodiments, the coupling agent comprises at least 90 (e.g., at least 91, at least 92, at least 93, at least 94, at least 95, at least 96, at least 97, at least 98, or at least 99) weight percent of monomer units a, b, c, d, e, and f according to Formula I, based on the total weight of the coupling agent. In certain embodiments, the coupling agent comprises 90 to 100 (e.g., 91 to 100, 92 to 100, 93 to 100, 94 to 100, 95 to 100, 96 to 100, 97 to 100, 98 to 100, 99 to 100, 90 to 99, 91 to 99, 92 to 99, 93 to 99, 94 to 99, 95 to 99, 96 to 99, 97 to 99, 98 to 99, 90 to 98, 91 to 98, 92 to 98, 93 to 98, 94 to 98, 95 to 98, 96 to 98, 97 to 98, 90 to 97, 91 to 97, 92 to 97, 93 to 97, 94 to 97, 95 to 97, 96 to 97, 90 to 96, 91 to 96, 92 to 96, 93 to 96, 94 to 96, 95 to 96, 90 to 95, 91 to 95, 92 to 95, 93 to 95, 94 to 95, 90 to 94, 91 to 94, 92 to 94, 93 to 94, 90 to 93, 91 to 93, 92 to 93, 90 to 92, 91 to 92, or 90 to 91) weight percent of monomer units a, b, c, d, e, and f according to Formula I, based on the total weight of the coupling agent.

[0043] In certain embodiments, the coupling agent comprises at least 70 (e.g., at least 75, at least 80, at least 85, at least 90, or at least 95) weight percent of monomer units a and b according to Formula I, based on the total weight of the coupling agent. In certain embodiments, the coupling agent comprises 70 to 95 (e.g., 75 to 95, 80 to 95, 85 to 95, 90 to 95, 70 to 90, 75 to 90, 80 to 90, 85 to 90, 70 to 85, 75 to 85, 80 to 85, 70 to 80, 75 to 80, or 70 to 75) weight percent of monomer units a and b according to Formula I, based on the total weight of the coupling agent.

[0044] In certain embodiments, the coupling agent comprises, based on the total weight of the coupling agent, 30 weight percent or less (e.g., 25 weight percent or less, 20 weight percent or less, 15 weight percent or less, 10 weight percent or less, or 5 weight percent or less) of monomer units c, d, e, and f according to Formula I. In certain embodiments, the coupling agent comprises, based on the total weight of the coupling agent, 5 to 30 (e.g., 10 to 30, 15 to 30, 20 to 30, 25 to 30, 5 to 25, 10 to 25, 15 to 25, 20 to 25, 5 to 20, 10 to 20, 15 to 20, 5 to 15, 10 to 15, or 5 to 10) weight percent of monomer units c, d, e, and f according to Formula I.

[0045] In certain embodiments, the coupling agent comprises, based on the total weight of the coupling agent, at least 50 (e.g., at least 55, at least 60, at least 65, at least 70, at least 75, or at least 80) weight percent of monomer unit a according to Formula I. In certain embodiments, the coupling agent comprises, based on the total weight of the coupling agent, 50 to 80 (e.g., 55 to 80, 60 to 80, 65 to 80, 70 to 80, 75 to 80, 50 to 75, 55 to 75, 60 to 75, 65 to 75, 70 to 75, 50 to 70, 55 to 70, 60 to 70, 65 to 70, 50 to 65, 55 to 65, 60 to 65, 50 to 60, 55 to 60, or 50 to 55) weight percent of monomer unit a according to Formula I.

[0046] In certain embodiments, the coupling agent comprises monomer unit b of formula I that is 40 weight percent or less (e.g., 35 weight percent or less, 30 weight percent or less, 25 weight percent or less, 20 weight percent or less, 15 weight percent or less, 10 weight percent or less, or 5 weight percent or less) based on the total weight of the coupling agent. In certain embodiments, the coupling agent comprises 5 to 40 (e.g., 10 to 40, 15 to 40, 20 to 40, 25 to 40, 30 to 40, 35 to 40, 5 to 35, 10 to 35, 15 to 35, 20 to 35, 25 to 35, 30 to 35, 5 to 30, 10 to 30, 15 to 30, 20 to 30, 25 to 30, 5 to 25, 10 to 25, 15 to 25, 20 to 25, 5 to 20, 10 to 20, 15 to 20, 5 to 15, 10 to 15, or 5 to 10) weight percent of monomer unit b of formula I based on the total weight of the coupling agent.

[0047] In certain embodiments, a is an integer from 5 to 500, such as 10 to 500, 15 to 500, 20 to 500, 25 to 500, 50 to 500, 75 to 500, 100 to 500, 150 to 500, 200 to 500, 250 to 500, 300 to 500, 350 to 500, 400 to 500, 450 to 500, 1 to 450, 5 to 450, 10 to 450, 15 to 450, 20 to 450, 25 to 450, 50 to 450, 75 to 450, 100 to 450, 150 to 450, 200 to 450, 250 to 450, 300 to 450, 350 to 450, 400 to 450, 1 to 400, 5 to 400, 10 to 400, 15 to 400, 20 to 400, 25 to 400, 50 to 400, 75 to 400, 100 to 400, 150 to 400, 200 to 400, 250 to 400, 300 to 400, 350 to 400, 1 to 250, 5 to 350, 10 to 350, 15 to 350, 20 to 350, 25 to 350, 50 to 350, 75 to 350, 100 to 350, 150 to 350, 200 to 350, 250 to 350, 300 to 350, 1 to 300, 5 to 300, 10 to 300, 15 to 300, 20 to 300, 25 to 300, 50 to 300, 75 to 300, 100 to 300, 150 to 300, 200 to 300, 250 to 300, 1 to 250, 5 to 250, 10 to 250, 15 to 250, 20 to 250, 25 to 250, 50 to 250, 75 to 250, 100 to 250, 150 to 250, 200 to 250, 1 to 200, 5 to 200, 10 to 200, 15 to 200, 20 to 200, 25 to 200, 50 to 200, 75 to 200, 100 to 200, 150 to 200, 1 to 150, 5 to 150, 10 to 150, 15 to 150, 20 to 150, 25 to 150, 50 to 150, 75 to 150, 100 to 150, 1 to 100, 5 to 100, 10 to 100, 15 to 100, 20 to 100, 25 to 100, 50 to 100, 75 to 100, 1 to 75, 5 to 75, 10 to 75, 15 to 75, 20 to 75, 25 to 75, 50 to 75, 1 to 50, 5 to 50, 10 to 50, 15 to 50, 20 to 50, 25 to 50, 1 to 25, 5 to 25, 10 to 25, 15 to 25, 20 to 25, 1 to 20, 5 to 20, 10 to 20, 15 to 20, 1 to 15, 5 to 15, 10 to 15, 1 to 10, 5 to 10, or 1 to 5.

[0048] In certain embodiments, b is an integer from 5 to 500, such as 10 to 500, 15 to 500, 20 to 500, 25 to 500, 50 to 500, 75 to 500, 100 to 500, 150 to 500, 200 to 500, 250 to 500, 300 to 500, 350 to 500, 400 to 500, 450 to 500, 1 to 450, 5 to 450, 10 to 450, 15 to 450, 20 to 450, 25 to 450, 50 to 450, 75 to 450, 100 to 450, 150 to 450, 200 to 450, 250 to 450, 300 to 450, 350 to 450, 400 to 450, 1 to 400, 5 to 400, 10 to 400, 15 to 400, 20 to 400, 25 to 400, 50 to 400, 75 to 400, 100 to 400, 150 to 400, 200 to 400, 250 to 400, 300 to 400, 350 to 400, 1 to 250, 5 to 350, 10 to 350, 15 to 350, 20 to 350, 25 to 350, 50 to 350, 75 to 350, 100 to 350, 150 to 350, 200 to 350, 250 to 350, 300 to 350, 1 to 300, 5 to 300, 10 to 300, 15 to 300, 20 to 300, 25 to 300, 50 to 300, 75 to 300, 100 to 300, 150 to 300, 200 to 300, 250 to 300, 1 to 250, 5 to 250, 10 to 250, 15 to 250, 20 to 250, 25 to 250, 50 to 250, 75 to 250, 100 to 250, 150 to 250, 200 to 250, 1 to 200, 5 to 200, 10 to 200, 15 to 200, 20 to 200, 25 to 200, 50 to 200, 75 to 200, 100 to 200, 150 to 200, 1 to 150, 5 to 150, 10 to 150, 15 to 150, 20 to 150, 25 to 150, 50 to 150, 75 to 150, 100 to 150, 1 to 100, 5 to 100, 10 to 100, 15 to 100, 20 to 100, 25 to 100, 50 to 100, 75 to 100, 1 to 75, 5 to 75, 10 to 75, 15 to 75, 20 to 75, 25 to 75, 50 to 75, 1 to 50, 5 to 50, 10 to 50, 15 to 50, 20 to 50, 25 to 50, 1 to 25, 5 to 25, 10 to 25, 15 to 25, 20 to 25, 1 to 20, 5 to 20, 10 to 20, 15 to 20, 1 to 15, 5 to 15, 10 to 15, 1 to 10, 5 to 10, or 1 to 5.

[0049] In certain embodiments, the ratio of a to b is from 1:1 to 10:1, 1:1 to 9:1, 1:1 to 8:1, 1:1 to 7:1, 1:1 to 6:1, 1:1 to 5:1, 1:1 to 4:1, 1:1 to 3:1, 1:1 to 2:1, 2:1 to 10:1, 2:1 to 9:1, 2:1 to 8:1, 2:1 to 7:1, 2:1 to 6:1, 2:1 to 5:1, 2:1 to 4:1, 2:1 to 3:1, 3:1 to 10:1, 3:1 to 9:1, 3:1 to 8:1, 3:1 to 7:1, 3:1 to 6:1, 3:1 to 5:1, 3:1 to 4:1, 4:1 to 10:1, 4:1 to 9:1, 4:1 to 8:1, 4:1 to 7:1, 4:1 to 6:1, 4:1 to 5:1, 5:1 to 10:1, 5:1 to 9:1, 5:1 to 8:1, 5:1 to 7:1, 5:1 to 6:1, 6:1 to 10:1, 6:1 to 9:1, 6:1 to 8:1, 6:1 to 7:1, 7:1 to 10:1, 7:1 to 9:1, 7:1 to 8:1, 8:1 to 10:1, 8:1 to 9:1, or 9:1 to 10:1.

[0050] In certain embodiments, c is an integer from 1 to 100, 5 to 100, 10 to 100, 15 to 100, 20 to 100, 30 to 100, 40 to 100, 50 to 100, 60 to 100, 70 to 100, 80 to 100, 90 to 100, 1 to 90, 5 to 90, 10 to 90, 15 to 90, 20 to 90, 30 to 90, 40 to 90, 50 to 90, 60 to 90, 70 to 90, 80 to 90, 1 to 80, 5 to 80, 10 to 80, 15 to 80, 20 to 80, 30 to 80, 40 to 80, 50 to 80, 60 to 80, 70 to 80, 1 to 70, 5 to 70, 10 to 70, 15 to 70, 20 to 70, 30 to 70, 40 to 70, 50 to 70, 60 to 70, 1 to 60, 5 to 60, 10 to 60, 15 to 60, 20 to 60, 30 to 60, 40 to 60, 50 to 60, 1 to 50, 5 to 50, 10 to 50, 15 to 50, 20 to 50, 30 to 50, 40 to 50, 1 to 40, 5 to 40, 10 to 40, 15 to 40, 20 to 40, 30 to 40, 1 to 30, 5 to 30, 10 to 30, 15 to 30, 20 to 30, 1 to 20, 5 to 20, 10 to 20, 15 to 20, 1 to 15, 5 to 15, 10 to 15, 1 to 10, 5 to 10, or 1 to 5.

[0051] In certain embodiments, d is an integer from 1 to 100, 5 to 100, 10 to 100, 15 to 100, 20 to 100, 30 to 100, 40 to 100, 50 to 100, 60 to 100, 70 to 100, 80 to 100, 90 to 100, 1 to 90, 5 to 90, 10 to 90, 15 to 90, 20 to 90, 30 to 90, 40 to 90, 50 to 90, 60 to 90, 70 to 90, 80 to 90, 1 to 80, 5 to 80, 10 to 80, 15 to 80, 20 to 80, 30 to 80, 40 to 80, 50 to 80, 60 to 80, 70 to 80, 1 to 70, 5 to 70, 10 to 70, 15 to 70, 20 to 70, 30 to 70, 40 to 70, 50 to 70, 60 to 70, 1 to 60, 5 to 60, 10 to 60, 15 to 60, 20 to 60, 30 to 60, 40 to 60, 50 to 60, 1 to 50, 5 to 50, 10 to 50, 15 to 50, 20 to 50, 30 to 50, 40 to 50, 1 to 40, 5 to 40, 10 to 40, 15 to 40, 20 to 40, 30 to 40, 1 to 30, 5 to 30, 10 to 30, 15 to 30, 20 to 30, 1 to 20, 5 to 20, 10 to 20, 15 to 20, 1 to 15, 5 to 15, 10 to 15, 1 to 10, 5 to 10, or 1 to 5.

[0052] In certain embodiments, e is an integer from 1 to 100, 5 to 100, 10 to 100, 15 to 100, 20 to 100, 30 to 100, 40 to 100, 50 to 100, 60 to 100, 70 to 100, 80 to 100, 90 to 100, 1 to 90, 5 to 90, 10 to 90, 15 to 90, 20 to 90, 30 to 90, 40 to 90, 50 to 90, 60 to 90, 70 to 90, 80 to 90, 1 to 80, 5 to 80, 10 to 80, 15 to 80, 20 to 80, 30 to 80, 40 to 80, 50 to 80, 60 to 80, 70 to 80, 1 to 70, 5 to 70, 10 to 70, 15 to 70, 20 to 70, 30 to 70, 40 to 70, 50 to 70, 60 to 70, 1 to 60, 5 to 60, 10 to 60, 15 to 60, 20 to 60, 30 to 60, 40 to 60, 50 to 60, 1 to 50, 5 to 50, 10 to 50, 15 to 50, 20 to 50, 30 to 50, 40 to 50, 1 to 40, 5 to 40, 10 to 40, 15 to 40, 20 to 40, 30 to 40, 1 to 30, 5 to 30, 10 to 30, 15 to 30, 20 to 30, 1 to 20, 5 to 20, 10 to 20, 15 to 20, 1 to 15, 5 to 15, 10 to 15, 1 to 10, 5 to 10, or 1 to 5.

[0053] In certain embodiments, f is an integer from 1 to 100, 5 to 100, 10 to 100, 15 to 100, 20 to 100, 30 to 100, 40 to 100, 50 to 100, 60 to 100, 70 to 100, 80 to 100, 90 to 100, 1 to 90, 5 to 90, 10 to 90, 15 to 90, 20 to 90, 30 to 90, 40 to 90, 50 to 90, 60 to 90, 70 to 90, 80 to 90, 1 to 80, 5 to 80, 10 to 80, 15 to 80, 20 to 80, 30 to 80, 40 to 80, 50 to 80, 60 to 80, 70 to 80, 1 to 70, 5 to 70, 10 to 70, 15 to 70, 20 to 70, 30 to 70, 40 to 70, 50 to 70, 60 to 70, 1 to 60, 5 to 60, 10 to 60, 15 to 60, 20 to 60, 30 to 60, 40 to 60, 50 to 60, 1 to 50, 5 to 50, 10 to 50, 15 to 50, 20 to 50, 30 to 50, 40 to 50, 1 to 40, 5 to 40, 10 to 40, 15 to 40, 20 to 40, 30 to 40, 1 to 30, 5 to 30, 10 to 30, 15 to 30, 20 to 30, 1 to 20, 5 to 20, 10 to 20, 15 to 20, 1 to 15, 5 to 15, 10 to 15, 1 to 10, 5 to 10, or 1 to 5.

[0054] In certain embodiments, the coupling agent comprises up to 10 (e.g., up to 9, up to 8, up to 7, up to 6, up to 5, up to 4, up to 3, up to 2, or up to 1) weight percent of other monomer units that are different from monomer units a, b, c, d, e, and f of formula I. In certain embodiments, the coupling agent comprises from greater than 0 to 10 (e.g., greater than 0 to 9, greater than 0 to 7, greater than 0 to 6, greater than 0 to 5, greater than 0 to 4, greater than 0 to 3, greater than 0 to 2, greater than 0 to 1, 1 to 10, 1 to 9, 1 to 8, 1 to 7, 1 to 6, 1 to 5, 1 to 4, 1 to 3, 1 to 2, 2 to 10, 2 to 9, 2 to 8, 2 to 7, 2 to 6, 2 to 5, 2 to 4, 2 to 3, 3 to 10, 3 to 9, 3 to 8, 3 to 7, 3 to 6, 3 to 5, 3 to 4, 4 to 10, 4 to 9, 4 to 8, 4 to 7, 4 to 6, 4 to 5, 5 to 10, 5 to 9, 5 to 8, 5 to 7, 5 to 6, 6 to 10, 6 to 9, 6 to 8, 6 to 7, 7 to 10, 7 to 9, 7 to 8, 8 to 10, 8 to 9, or 9 to 10) weight percent of other monomer units that are different from monomer units a, b, c, d, e, and f of formula I. In certain embodiments, the coupling agent substantially does not contain or does not contain other monomer units that are different from monomer units a, b, c, d, e, and f of formula I. In this context, "substantially does not contain" means that other monomer units are not intentionally added or generated, but they may be present due to the inclusion of impurities in the reactants and / or the formation of unintended reaction products. In certain embodiments, the other monomer units are vinyl-functional monomer units.

[0055] Also provided is a method of making a thermosetting composition described herein, the method comprising dissolving a coupling agent in a thermosetting resin with or without using a solvent, and then adding particulate solids and other additives. The other additives can include at least one of a dispersant, an antifoaming agent, an internal release agent, an accelerator, and the like.

[0056] Also provided is a method for producing a thermosetting composition described herein, which includes dispersing a coupling agent as a dry solid in a thermosetting resin and then adding particulate solids and other additives. The other additives may include at least one of a dispersant, an antifoaming agent, an internal mold release agent, an accelerator, and the like.

[0057] Also provided is a method for imparting high / improved tensile strength to a thermosetting composition described herein, which includes dispersing particulate solids in a thermosetting resin in the presence of a coupling agent.

[0058] Also provided is a method for imparting flame retardancy to a thermosetting composition described herein, which includes dispersing particulate solids (for imparting flame retardancy) in a thermosetting resin in the presence of a coupling agent.

[0059] Also provided is a method for lightening a thermosetting composition described herein, which includes dispersing hollow particles (glass spheres) and a filler (as particulate solids) in a thermosetting resin in the presence of a coupling agent.

[0060] Also provided is a method for producing a thermosetting composition described herein, which includes treating particulate solids with a coupling agent to produce treated particulate solids and then adding the treated particulate solids to a thermosetting resin. For example, a fiber material can be pretreated with a sizing agent that also acts as a coupling agent.

[0061] The subject matter disclosed herein can be better understood with reference to the following examples, which are described only to further illustrate the subject matter disclosed herein. The exemplary examples should not be construed as limiting the subject matter in any way.

Examples

[0062] Example 1: Polystyrene-co-poly(maleic anhydride) copolymer (20 parts of styrene:maleic anhydride in a 2:1 molar ratio) was dissolved in ethyl acetate (79.69 parts) at 70 °C under nitrogen. Polyetheramine (56.90 parts) was added and the reaction mixture was stirred for 2 hours until amine consumption was confirmed by titration. The temperature was then increased to 100 °C for 3 hours to remove the solvent. The nitrogen blanket was removed, 2-hydroxyethyl methacrylate (2.55 parts) and 2,6-di-tert-butyl-4-methylphenol (0.24 part) were added, and the reaction mixture was heated at 120 °C in air for 5 hours. An amber liquid was obtained.

[0063] Example 1 was incorporated into a dispersion containing calcium carbonate and recycled carbon fibers in an unsaturated polyester resin (Palapreg® P17-02 from AOC AG). The formulation contained a peroxide curing catalyst (tert-butyl peroxybenzoate from Sigma Aldrich). Examples 2 and 3 contained the number of parts of each component shown in Table 1 below. The tensile strength of each of Examples 2 and 3 was measured using an Instron tensile strength tester and reported in Table 1.

[0064]

Table 1

[0065] Example 4: Poly(isobutylene-alt-maleic anhydride) (average M W= 6000, 15.34 parts) was suspended in water (93 parts) at 70 °C under nitrogen. Polyetheramine (surfonamine® L207 from Huntsman, 69.07 parts) was added and the reaction mixture was stirred for 1 hour. The temperature was increased to > 100 °C and water was removed over 4 hours. The nitrogen blanket was removed and 2-hydroxyethyl methacrylate (4.45 parts) and 2,6-di-tert-butyl-4-methylphenol (0.29 part) were added and the reaction mixture was heated at 95 °C for 8 hours. A amber liquid with a molecular weight of Mn = 2623 and Mw = 11212 as determined by GPC in tetrahydrofuran with 1% acetic acid added relative to polystyrene standards was obtained.

[0066] The following tests were conducted to determine the suitability of the examples described herein for various applications where fiber and / or filler reinforced thermosetting plastics may be used. These formulations are not intended to be limiting, together with the exemplary, typical applications described, but rather are intended to highlight the multiple potential composite resin - filler / fiber interfaces present within composites where reactive coupling agents of the type described herein may be beneficial. "Bonding" of the filler / fiber surface to the bulk resin at the molecular level during cure is known to result in improved mechanical properties beneficial in the formed macroscopic composite parts or articles containing these interfaces.

[0067] The advantages observed in the measurement of such mechanical properties, and the modes selected to investigate such improvements, depend greatly on the anisotropy of the composite material, which is a result of the alignment of fillers and fibers within the resin matrix with respect to the applied forces. Therefore, the stresses and strains generated during different mechanical test modes are transmitted to different degrees at the existing resin-filler / fiber interfaces, depending on the relative orientation of these interfaces with respect to the forces applied in a particular test mode. Thus, depending on the formulation; the alignment and positioning of the fillers / fibers; and the molding and manufacturing techniques employed to produce the composite article being tested, the advantages of the coupling agents of the present subject matter may or may not be observed within the scope of standardized mechanical tests. There are a number of suitable tests (or modifications thereof) for evaluating mechanical improvements in composite articles, non-exhaustively summarized in ASTM D4762-18, and it is contemplated that any of these tests may be used to confirm the effectiveness of the present subject matter in a particular material and / or for a particular use of the resulting material. Therefore, any such test listed may be useful for demonstrating the benefits exemplified herein when appropriately used by one of ordinary skill in the art. Therefore, the advantages observed herein may be translated into advantages in more highly-ordered static or dynamic mechanical tests, appropriately selected, in more basic and dynamic tests that are used and described.

[0068] The tests of Examples 5 and 6 were conducted using milled fibers instead of other fiber forms, reducing the anisotropy in the composite materials formed during the exemplified tests and limiting the measurement complexities that can arise from the anisotropy due to other fiber forms. The mechanical advantages of the "bonding" at the resin-filler / fiber interfaces are more clearly interpreted from this basic test type and other strengthening and stiffening effects in the comparison of the measured elastic moduli. Therefore, the benefits observed are translated into benefits observable in more standardized mode-specific tests suitable for more anisotropic materials obtained from more highly-ordered fiber / filler forms and arrangements, and the test modes are appropriately selected to examine the bonding at the interfaces in question, as non-exhaustively listed in ASTM D4762-18.

[0069] Other basic test techniques that are likely to show convertible observations similar to other mechanical modes may focus on observing the advantages at a single isolated interface of interest, orienting this interface in a desired plane with respect to the stresses and strains of the mechanical modes being used, and measuring the modulus or stress at the time of failure of this separated interface. This type of test method for measuring interfacial shear strength (IFSS) can also be useful for demonstrating the benefits of the coupling agents of the present subject matter and can be applied to the study of thermosetting resins. Examples of such tests are described in Interface strength in glass fibre - polypropylene measured using the fibre pull - out and microbond methods. L.Yang & J.L.Thomason, 2010, Composites Part A: Applied Science and Manufacturing, Vol 41, issue 9 p 1077 - 1083.

[0070] The formation and curing of composite articles may need to be carried out within a range of conditions that depend on the manufacturing techniques used and the chemical composition of the resin formulation. Typically, other chemical additives such as promoters, accelerators or inhibitors, as well as curing agents, initiators or catalysts, are used within the formulation and can be selected to be compatible with the resin chemistry, enabling the curing of the thermosetting resin under the desired conditions of handling, forming and manufacturing of the composite article. It is important to determine whether additional additives such as the coupling agents of the present subject matter affect the curing rate of the entire composite formulation in order to understand the suitability of these agents for the intended application and formulation. Therefore, the "through cure" test used in the following examples enables a comparison of the curing times in the presence and absence of the exemplified additives of the present subject matter. Ideally, it is desirable that there is little or no change in the curing rate.

[0071] Generally, the described formulations were tested in "through cure" experiments of single - frequency oscillations of the type described by Tianhong T. Chen et al. (Characterising thermoset curing using rheology; SAMPE Conference proceedings 2019, Society for the advancement of Material and Process Engineering). Additional guidance from ASTM D4065 20 Standard Practice for Plastics: Dynamic Mechanical Properties: Determination and report Procedures is used.

[0072] A DHR - 1 rheometer (TA Instruments) fitted with 25 mm disposable aluminum parallel plates was used in conjunction with an ETC accessory. All tests involved subjecting a sample of the uncured formulation of set volume, determined by the initial shape gap, to torsional oscillations at a frequency of 1 Hz through a temperature profile that would cure the formulation of interest and be applicable to the intended use. While remaining within the linear viscoelastic limit of the material, active control was used in both strain and axial force during the test to enable monitoring of the curing process. Axial force adjustment was used through attempts to actively control the axial force to 0.0 ± 0.1 N in compression mode, and automatic strain adjustment was used as described in the referenced procedure. However, certain parameters were adjusted in tests for different formulations to better match the manufacturing conditions that might be used for each set of examples, and these are detailed for each case as follows, after the description of the formulations for the examples being elaborated.

[0073] Measurements obtained from individual experiments were calculated from the analysis performed in the instrument - assisted Trios software. The onset "gel" temperature of curing was calculated from the storage modulus cure with respect to temperature (d(Log(G’)) / dT). The storage modulus in the plateau region after isothermal curing was in this region (b ) It is calculated by correcting the gap difference between experiments for different samples through regression correlation as defined in ASTM D4065 20 and is faithful to the principle of equivalent sample dimensions applied in this experimental situation of torsion between parallel plates. The measured values obtained from the through-cure experiments were used to screen the exemplified coupling agents for their compatibility in the exemplified formulations and the speculated uses.

[0074] Example 8 was incorporated into a dispersion of aluminum trihydroxide (Martinal™ OL104 from Huber) and ground glass fiber (1320K from Owens Corning) in a liquid epoxy resin (Epikote™ 827 from Hexion) by mixing with a planetary stirrer at 2,000 rpm for a total of 6 - 10 minutes and cooling the sample to room temperature every 2 minutes. The formulation contains a dicyandiamide curing agent (Amicure® CG1400F from Evonik) and an imidazole curing accelerator (Curezol® 2MZ-Azine from Evonik). Table 2 details the weight % of each component in the formulations tested for Examples 5 and 6.

[0075]

Table 2

[0076] Examples 9 and 10 are representative examples of flame-retardant formulations typically used in GFRP compression molding electrical fittings.

[0077] For Examples 5 and 6, a temperature gradient of 25 to 135 °C was used at 5 °C / min. It was held at 135 °C for 10 minutes to continue the measurement after the sample hardened. The initial gap size was 1000 μm, the trim offset was 50 μm, and the minimum sample volume at the start of the test was 0.49087 mL. The gap temperature compensation - expansion coefficient was 2.7398 μm / °C, the compliance was 2.02 mrad / N·m, the stress constant was 325949 Pa / N·m, the strain constant was 12.5 1 / rad, and the vertical stress constant was 4074.37 Pa / N. However, the geometric inertia and friction were calibrated for each experiment. The variable trial parameters for Examples 5 and 6 are summarized in Table 3 below.

[0078]

Table 3

[0079] The measurements for Examples 5 and 6 are detailed in Table 4.

[0080]

Table 4

[0081] Except as otherwise indicated or required by context in the Examples or otherwise explicitly stated, all quantities in this specification that specify amounts of materials, reaction conditions, molecular weights, numbers of carbon atoms, etc. are to be understood as being modified by the term "about". As used herein, the term "about" means that the value of a given quantity is within ±20% of the stated value. In other embodiments, the value is within ±15% of the stated value. In other embodiments, the value is within ±10% of the stated value. In other embodiments, the value is within ±5% of the stated value. In other embodiments, the value is within ±2.5% of the stated value. In other embodiments, the value is within ±1% of the stated value. In other embodiments, the value is within the range of the explicitly stated value such that one of ordinary skill in the art would understand that it functions substantially the same as the composition containing the literal amount described herein based on the disclosure provided herein.

[0082] The upper and lower limits of the amounts, ranges, and ratios described in this specification can be combined independently, and any amount within the disclosed range is intended to provide the minimum or maximum value of a narrower range in alternative embodiments (provided, of course, that the minimum amount of the range must be lower than the maximum amount of the same range). Similarly, the ranges and amounts for each element of the subject matter disclosed in this specification can be used in conjunction with the ranges or amounts for any of the other elements.

[0083] For purposes of illustrating the subject matter disclosed in this specification, specific representative embodiments and details have been shown, but it will be apparent to those skilled in the art that various changes and improvements can be made without departing from the scope of the subject matter. In this regard, the scope of the invention should be limited only by the following claims.

Claims

1. A thermosetting composition comprising a dispersion of particulate solids in a thermosetting resin in the presence of a coupling agent containing monomer units a, b, c, d, e, and f according to formula I, wherein 【Chemical Formula 6】 for each molecule of the polymer, independently, R １ is H or CH ３ and R ２ is H, C １ ~C ２０ alkyl group, C ６ ~C １０ aryl group, C ７ ~C １４ alkaryl group, or C ４ ~C ６ cycloalkyl group, and X １ is 2 or 3 carbon atoms, where when X １ is 3 carbon atoms, one of the carbon atoms is not included in the polymer backbone X ２ is 2 or 3 carbon atoms, where when X ２ is 3 carbon atoms, one of said carbon atoms is not included in the polymer backbone R ３ is H or CH ３ and R ４ is C １ to C ２０ alkyl group, -C-O-R ７ -, or -(C=O)-O-C-R ７ where R ７ is C １ to C ２０ alkyl group, X ３ is 2 or 3 carbon atoms, where when X ３ is 3 carbon atoms, one of the carbon atoms is not included in the polymer backbone R ５ is H or CH ３ and R ６ is C １ to C ２０ alkyl group, -C-O-R ８ -, or -(C=O)-O-C-R ８ -, where R ８ is C １ to C ２０ alkyl group, Z １ is NH or O, X ４ is 2 or 3 carbon atoms, where when X ４ is 3 carbon atoms, one of said carbon atoms is not included in the polymer backbone POL １ is a polymer containing at least one of polyether or polyester, wherein the polymer has a theoretical number average molecular weight of 200 to 3,000, X ５ is 2 or 3 carbon atoms, where, when X ５ is 3 carbon atoms, one of the carbon atoms is not included in the polymer backbone POL ２ is a polymer containing at least one of polyether or polyester, wherein the polymer has a theoretical number average molecular weight of 200 to 3,000, Z ２ is NH or O, a is an integer from 1 to 500, b is an integer from 1 to 500, c is 0, or an integer from 1 to 100, d is 0, or an integer from 1 to 100, e is 0, or an integer from 1 to 100, f is 0, or an integer from 1 to 100, wherein when c is 0, d is at least 1, when d is 0, c is at least 1, when e is 0, f is at least 1, and when f is 0, e is at least 1, a thermosetting composition.

2. The thermosetting composition according to claim 1, wherein the particulate solids are present in an amount of 20 to 80 weight percent based on the total weight of the thermosetting composition.

3. The thermosetting composition according to claim 1 or 2, wherein the particulate solids comprise at least one of a filler, a reinforcing material, or a functional filler.

4. The thermosetting composition according to claim 3, wherein the filler comprises at least one of calcium carbonate, talc, barium sulfate, alumina, or quartz.

5. The thermosetting composition according to claim 3 or 4, wherein the reinforcing material comprises at least one type of fiber material.

6. The thermosetting composition according to any one of claims 3 to 5, wherein the functional filler comprises at least one of a flame retardant material or a pigment.

7. The thermosetting composition according to any one of claims 1 to 6, wherein the thermosetting resin is present in an amount of 80 to 20 weight percent based on the total weight of the thermosetting composition.

8. The thermosetting composition according to any one of claims 1 to 7, wherein the thermosetting resin comprises an epoxy resin, an unsaturated polyester resin, a vinyl ester resin, a polyurethane resin, or a phenolic resin.

9. The thermosetting composition according to any one of claims 1 to 8, wherein the coupling agent is present in an amount of 0.5 to 5 weight percent based on the total weight of the thermosetting composition.

10. The thermosetting composition according to any one of claims 1 to 9, wherein the coupling agent comprises at least 90 weight percent of monomer units a, b, c, d, e, and f according to formula I based on the total weight of the coupling agent.

11. The thermosetting composition according to any one of claims 1 to 10, wherein the coupling agent contains at least 70% by weight of monomer units a and b according to formula I, based on the total weight of the coupling agent.

12. The thermosetting composition according to any one of claims 1 to 11, wherein the coupling agent contains 30% by weight or less of monomer units c, d, e, and f according to formula I, based on the total weight of the coupling agent.

13. The thermosetting composition according to any one of claims 1 to 12, wherein the coupling agent contains at least 50% by weight of monomer unit a according to formula I, based on the total weight of the coupling agent.

14. The thermosetting composition according to any one of claims 1 to 13, wherein the coupling agent contains 40% by weight or less of monomer unit b according to formula I, based on the total weight of the coupling agent.

15. The thermosetting composition according to any one of claims 1 to 14, wherein a is an integer from 5 to 500.

16. The thermosetting composition according to any one of claims 1 to 15, wherein a is an integer from 20 to 50.

17. The thermosetting composition according to any one of claims 1 to 16, wherein b is an integer from 2 to 100.

18. The thermosetting composition according to any one of claims 1 to 17, wherein b is an integer from 3 to 12.

19. The thermosetting composition according to any one of claims 1 to 18, wherein the ratio of a to b is from 1:1 to 10:

1.

20. The thermosetting composition according to any one of claims 1 to 19, wherein c is an integer from 3 to 12.

21. The thermosetting composition according to any one of claims 1 to 20, wherein d is an integer from 3 to 12.

22. The thermosetting composition according to any one of claims 1 to 21, wherein e is an integer from 4 to 16.

23. The thermosetting composition according to any one of claims 1 to 22, wherein f is an integer from 4 to 16.

24. The thermosetting composition according to any one of claims 1 to 23, wherein the coupling agent contains up to 10% by weight of other monomer units different from monomer units a, b, c, d, e, and f according to formula I.

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