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 incorporation of particulate solids (e.g., fillers and / or fibers) into polymeric 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 can 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 can 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 can 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 treatment 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 specific drawbacks described above. SUMMARY OF THE INVENTION MEANS FOR SOLVING THE PROBLEM 【0008】 The subject matter disclosed herein provides a polymer having monomer units a, b, c, d, and e according to Formula I, 【0009】 【Chemical formula】 wherein, for each molecule of the polymer, independently, R 1 is H or CH3, R 2 is H, a C1-C 20 alkyl group, a C6-C 10 aryl group, a C7-C 14 alkaryl group, or a C4-C6 cycloalkyl group, R 3 is H or CH3, R 4 is a C1-C 20 alkyl group, -C-O-R 12 -, or -(C=O)-O-C-R 12 -, where R 12 is a C1-C 20 alkyl group, R 5 is H or CH3, R 6 is -C-O- or -(C=O)-O-C-, R 7 is a C1-C 20 alkyl group, R 8 is H or CH3, R 9 is a C1-C 20 alkyl group, -C-O-R 14 -, or -(C=O)-O-C-R 14 -, where R 14 is a C1-C 20 alkyl group, R 10 is H or CH3, R 11 is a C1-C 20 alkyl group, -C-O-R15 - or -(C=O)-O-C-R 15 - wherein R 15 is a C1-C 20 alkyl group, POL 1 is a polymer containing at least one of a polyether or a polyester, wherein the polymer has a theoretical number average molecular weight of 200 to 3,000, POL 2 is a polymer containing at least one of a polyether or a polyester, wherein the polymer has a theoretical number average molecular weight of 200 to 3,000, X is S, O, NH, or -O-(C=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. 【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】 Also provided are various methods of making and / or using the polymer, coupling agent, and / or thermosetting composition. 【DETAILED DESCRIPTION OF THE INVENTION】 【0012】 The following embodiments of the subject matter are contemplated. 【0013】 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, and e according to Formula I, 【0014】 【Chemical formula】 In the formula, for each molecule of the coupling agent independently, R 1 is H or CH3, R 2 is H, a C1-C 20 alkyl group, a C6-C 10 aryl group, a C7-C 14 alkaryl group, or a C4-C6 cycloalkyl group, R 3 is H or CH3, R 4 is a C1-C 20 alkyl group, -C-O-R 12 -, or -(C=O)-O-C-R 12 -, where R 12 is a C1-C 20 alkyl group, R 5 is H or CH3, R 6 is -C-O- or -(C=O)-O-C-, R 7 is a C1-C 20 alkyl group, R 8 is H or CH3, R 9 is a C1-C 20 alkyl group, -C-O-R 14 -, or -(C=O)-O-C-R 14 -, where R 14 is a C1-C 20 alkyl group, R 10 is H or CH3, R 11 is a C1-C 20 alkyl group, -C-O-R 15 -, or -(C=O)-O-C-R 15 -, where R 15 is a C1-C 20 alkyl group, POL 1 is a polymer containing at least one of polyether or polyester, where the polymer has a theoretical number average molecular weight of 200-3,000, POL 2 is a polymer containing at least one of polyether or polyester, where the polymer has a theoretical number average molecular weight of 200 to 3,000, X is S, O, NH, or -O-(C=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, However, when d is greater than 0, e is 0, and when e is greater than 0, d is 0, a thermosetting composition. 【0015】 2. The thermosetting composition according to Embodiment 1, wherein the particulate solid is present in an amount of 20 to 80 weight percent based on the total weight of the thermosetting composition. 【0016】 3. The thermosetting composition according to either Embodiment 1 or Embodiment 2, wherein the particulate solid comprises at least one of a filler, a reinforcing material, or a functional filler. 【0017】 4. The thermosetting composition according to Embodiment 3, wherein the filler comprises at least one of calcium carbonate, talc, barium sulfate, alumina, or quartz. 【0018】 5. The thermosetting composition according to either Embodiment 3 or Embodiment 4, wherein the reinforcing material comprises at least one type of fiber material. 【0019】 6. The thermosetting composition according to any one of Embodiments 3 to 5, wherein the functional filler comprises at least one of a flame retardant material or a pigment. 【0020】 7. The thermosetting composition according to any one of Embodiments 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. 【0021】 8. The thermosetting resin-containing thermosetting composition according to any one of Embodiments 1 to 7, wherein the thermosetting resin contains an epoxy resin, an unsaturated polyester resin, a vinyl ester resin, a polyurethane resin, or a phenol resin. 【0022】 9. The thermosetting composition according to any one of Embodiments 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. 【0023】 10. The thermosetting composition according to any one of Embodiments 1 to 9, wherein the coupling agent contains at least 90 weight percent of monomer units a, b, c, d, and e according to Formula I based on the total weight of the coupling agent. 【0024】 11. The thermosetting composition according to any one of Embodiments 1 to 10, wherein the coupling agent contains at least 70 weight percent of monomer units a and b according to Formula I based on the total weight of the coupling agent. 【0025】 12. The thermosetting composition according to any one of Embodiments 1 to 11, wherein the coupling agent contains 30 weight percent or less of monomer units c, d, and e according to Formula I based on the total weight of the coupling agent. 【0026】 13. The thermosetting composition according to any one of Embodiments 1 to 12, wherein the coupling agent contains at least 50 weight percent of monomer unit a according to Formula I based on the total weight of the coupling agent. 【0027】 14. The thermosetting composition according to any one of Embodiments 1 to 13, wherein the coupling agent contains 40 weight percent or less of monomer unit b according to Formula I based on the total weight of the coupling agent. 【0028】 15. The thermosetting composition according to any one of Embodiments 1 to 14, wherein a is an integer from 5 to 500. 【0029】 16. The thermosetting composition according to any one of Embodiments 1 to 15, wherein a is an integer from 10 to 300. 【0030】 17. The thermosetting composition according to any one of Embodiments 1 to 16, wherein b is an integer from 2 to 100. 【0031】 18. The thermosetting composition according to any one of Embodiments 1 to 17, wherein b is an integer from 5 to 80. 【0032】 19. The thermosetting composition according to any one of Embodiments 1 to 18, wherein the ratio of a to b is from 1:1 to 10:1. 【0033】 20. The thermosetting composition according to any one of Embodiments 1 to 19, wherein c is an integer from 1 to 20. 【0034】 21. (i) The thermosetting composition according to any one of Embodiments 1 to 20, wherein d is 0 or an integer from 1 to 20, and (ii) e is 0 or an integer from 1 to 20, provided that when d is greater than 0, e is 0, and when e is greater than 0, d is 0. 【0035】 22. The thermosetting composition according to any one of Embodiments 1 to 21, wherein the coupling agent contains up to 10 weight percent of other monomer units different from the monomer units a, b, c, d, and e of Formula I. 【0036】 23. The thermosetting composition according to Embodiment 22, wherein the other monomer units are vinyl-functional monomer units. 【0037】 Various features and embodiments of the present subject matter are described below by way of non-limiting illustration. 【0038】 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. Thus, "a" / "an" and "at least one" may be used interchangeably. For example, "at least one of A, B or C" means that in an alternative embodiment, 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. 【0039】 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. 【0040】 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. 【0041】 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, and e according to formula I, 【0042】 【Chemical formula】 In the formula, for each molecule of the coupling agent, independently, R 1 is H or CH3, R 2 is H, a C1-C 20 alkyl group, a C6-C 10 aryl group, a C7-C 14 alkaryl group, or a C4-C6 cycloalkyl group, R 3 is H or CH3, R 4 is a C1-C 20 alkyl group, -C-O-R 12 -, or -(C=O)-O-C-R 12 -, where R 12 is a C1-C 20 alkyl group, R 5 is H or CH3, R 6 is -C-O- or -(C=O)-O-C-, R 7 is a C1-C 20 alkyl group, R 8 is H or CH3, R 9 is a C1-C 20 alkyl group, -C-O-R 14 -, or -(C=O)-O-C-R 14 -, where R 14 is a C1-C 20 alkyl group, R 10 is H or CH3, R 11 is a C1-C 20 alkyl group, -C-O-R 15 -, or -(C=O)-O-C-R 15 -, where R 15 is a C1-C 20 alkyl group, POL 1is a polymer containing at least one of polyether or polyester, where the polymer has a theoretical number average molecular weight of 200 to 3,000 (e.g., 250 to 3,000, 300 to 3,000, 350 to 3,000, 400 to 3,000, 450 to 3,000, 500 to 3,000, 600 to 3,000, 700 to 3,000, 800 to 3,000, 900 to 3,000, 1,000 to 3,000, 1,200 to 3,000, 1,400 to 3,000, 1,600 to 3,000, 1,800 to 3,000, 2,000 to 3,000, 2,500 to 3,000, 200 to 2,500, 250 to 2,500, 300 to 2,500, 350 to 2,500, 400 to 2,500, 450 to 2,500, 500 to 2,500, 600 to 2,500, 700 to 2,500, 800 to 2,500, 900 to 2,500, 1,000 to 2,500, 1,200 to 2,500, 1,400 to 2,500, 1,600 to 2,500, 1,800 to 2,500, 2,000 to 2,500, 200 to 2,000, 250 to 2,000, 300 to 2,000, 350 to 2,000, 400 to 2,000, 450 to 2,000, 500 to 2,000, 600 to 2,000, 700 to 2,000, 800 to 2,000, 900 to 2,000, 1,000 to 2,000, 1,200 to 2,000, 1,400 to 2,000, 1,600 to 2,000, 1,800 to 2,000, 200 to 1,800, 250 to 1,800, 300 to 1,800, 350 to 1,800, 400 to 1,800, 450 to 1,800, 500 to 1,800, 600 to 1,800, 700 to 1,800, 800 to 1,800, 900 to 1,800, 1,000 to 1,800, 1,200 to 1,800, 1,400 to 1,800, 1,600 to 1,800, 200 to 1,600, 250 to 1,600, 300 to 1,600, 350 to 1,600, 400 to 1,600, 450 to 1,600, 500 to 1,600, 600 to 1,600, 700 to 1,600, 800 to 1,600, 900 to 1,600, 1,000 to 1,600, 1,200 to 1,600, 1,400 to 1,600, 200 to 1,400, 250 to 1,400, 300 to 1,400, 350 to 1,400, 400 to 1,400, 450 to 1,400, 500 to 1,400, 600 to 1,400, 700 to 1,400, 800 - 1,400, 900 - 1,400, 1,000 - 1,400, 1,200 - 1,400, 200 - 1,200, 250 - 1,200, 300 - 1,200, 350 - 1,200, 400 - 1,200, 450 - 1,200, 500 - 1,200, 600 - 1,200, 700 - 1,200, 800 - 1,200, 900 - 1,200, 1,000 - 1,200, 200 - 1,000, 250 - 1,000, 300 - 1,000, 350 - 1,000, 400 - 1,000, 450 - 1,000, 500 - 1,000, 600 - 1,000, 700 - 1,000, 800 - 1,000, 900 - 1,000, 200 - 900, 250 - 900, 300 - 900, 350 - 900, 400 - 900, 450 - 900, 500 - 900, 600 - 900, 700 - 900, 800 - 900, 200 - 800, 250 - 800, 300 - 800, 350 - 800, 400 - 800, 450 - 800, 500 - 800, 600 - 800, 700 - 800, 200 - 700, 250 - 700, 300 - 700, 350 - 700, 400 - 700, 450 - 700, 500 - 700, 600 - 700, 200 - 600, 250 - 600, 300 - 600, 350 - 600, 400 - 600, 450 - 600, 500 - 600, 200 - 500, 250 - 500, 300 - 500, 350 - 500, 400 - 500, or 450 - 500),, POL 2is a polymer containing at least one of polyether or polyester, where the polymer has a number average molecular weight of 200 to 3,000 (e.g., 250 to 3,000, 300 to 3,000, 350 to 3,000, 400 to 3,000, 450 to 3,000, 500 to 3,000, 600 to 3,000, 700 to 3,000, 800 to 3,000, 900 to 3,000, 1,000 to 3,000, 1,200 to 3,000, 1,400 to 3,000, 1,600 to 3,000, 1,800 to 3,000, 2,000 to 3,000, 2,500 to 3,000, 200 to 2,500, 250 to 2,500, 300 to 2,500, 350 to 2,500, 400 to 2,500, 450 to 2,500, 500 to 2,500, 600 to 2,500, 700 to 2,500, 800 to 2,500, 900 to 2,500, 1,000 to 2,500, 1,200 to 2,500, 1,400 to 2,500, 1,600 to 2,500, 1,800 to 2,500, 2,000 to 2,500, 200 to 2,000, 250 to 2,000, 300 to 2,000, 350 to 2,000, 400 to 2,000, 450 to 2,000, 500 to 2,000, 600 to 2,000, 700 to 2,000, 800 to 2,000, 900 to 2,000, 1,000 to 2,000, 1,200 to 2,000, 1,400 to 2,000, 1,600 to 2,000, 1,800 to 2,000, 200 to 1,800, 250 to 1,800, 300 to 1,800, 350 to 1,800, 400 to 1,800, 450 to 1,800, 500 to 1,800, 600 to 1,800, 700 to 1,800, 800 to 1,800, 900 to 1,800, 1,000 to 1,800, 1,200 to 1,800, 1,400 to 1,800, 1,600 to 1,800, 200 to 1,600, 250 to 1,600, 300 to 1,600, 350 to 1,600, 400 to 1,600, 450 to 1,600, 500 to 1,600, 600 to 1,600, 700 to 1,600, 800 to 1,600, 900 to 1,600, 1,000 to 1,600, 1,200 to 1,600, 1,400 to 1,600, 200 to 1,400, 250 to 1,400, 300 to 1,400, 350 to 1,400, 400 to 1,400, 450 to 1,400, 500 to 1,400, 600 to 1,400, 700 to 1,400, 800 - 1,400, 900 - 1,400, 1,000 - 1,400, 1,200 - 1,400, 200 - 1,200, 250 - 1,200, 300 - 1,200, 350 - 1,200, 400 - 1,200, 450 - 1,200, 500 - 1,200, 600 - 1,200, 700 - 1,200, 800 - 1,200, 900 - 1,200, 1,000 - 1,200, 200 - 1,000, 250 - 1,000, 300 - 1,000, 350 - 1,000, 400 - 1,000, 450 - 1,000, 500 - 1,000, 600 - 1,000, 700 - 1,000, 800 - 1,000, 900 - 1,000, 200 - 900, 250 - 900, 300 - 900, 350 - 900, 400 - 900, 450 - 900, 500 - 900, 600 - 900, 700 - 900, 800 - 900, 200 - 800, 250 - 800, 300 - 800, 350 - 800, 400 - 800, 450 - 800, 500 - 800, 600 - 800, 700 - 800, 200 - 700, 250 - 700, 300 - 700, 350 - 700, 400 - 700, 450 - 700, 500 - 700, 600 - 700, 200 - 600, 250 - 600, 300 - 600, 350 - 600, 400 - 600, 450 - 600, 500 - 600, 200 - 500, 250 - 500, 300 - 500, 350 - 500, 400 - 500, or 450 - 500),, X is S, O, NH, or -O-(C=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. 【0043】 The phrase "comprising monomer units a, b, c, d, and e according to formula I" is merely to be understood as meaning that the monomer units are present (or, optionally, not present as in the case of monomer units c, d, and e), and that it is possible that other monomer units different from monomer units a, b, c, d, and / or e may be included, as described in the variable definitions provided for formula I, and 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 may be included in any order, such as a random order (presumably most likely), although it is theoretically 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 with respect 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. 【0044】 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. 【0045】 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 the 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. 【0046】 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. 【0047】 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, since 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 remainder being other inorganic materials such as magnesium carbonate, iron oxide and aluminosilicate in the form of ground particles; surface-treated calcium carbonate; talc including fibrous, modular, acicular and lamellar talc; both hollow and solid glass spheres; and kaolin including hard, soft, calcined kaolin, including various coatings known in the art to promote dispersion into the thermosetting resin and compatibility with the thermosetting resin; mica; feldspar and nepheline syenite; silicate spheres; soot; cenospheres; fly ash; aluminosilicate (spheroids); natural silica sand; quartz; siliceous rock; perlite; tripoli; diatomaceous earth; synthetic silica and the like. 【0048】 Functional fillers are generally materials included primarily to provide and / or improve certain properties of the composition, such as fireproof / 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 borosilicate powder for obtaining cured products having a low dielectric constant and a 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. 【0049】 In certain embodiments, the bulking agent and / or functional filler can include particles having an average aspect ratio of less than about 5:1. 【0050】 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), e.g., 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 fibers formed from organic polymers such as 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. 【0051】 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. 【0052】 In certain embodiments, the thermosetting resin includes an epoxy 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 upon heating, catalysis, or exposure to ultraviolet light, laser light, infrared light, cations, electron beam, or microwave irradiation. Exemplary reactions of thermosetting resins include reactions involving oxidation of unsaturated double bonds, epoxy / amine, epoxy / carbonyl, epoxy / hydroxyl, reaction of epoxy with a Lewis acid or Lewis base, polyisocyanate / hydroxyl, amino resin / hydroxyl moieties, free radical reactions or reactions with polyacrylates, cationic polymerization of epoxy resin and vinyl ether, and condensation of silanol. 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 commonly referred to as a vinyl ester resin. Polymers having a hydroxy functional group (such as polyols) 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. 【0053】 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. 【0054】 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. 【0055】 In certain embodiments, monomer unit b according to formula I can be derived from the radical polymerization of (meth)acrylates, such as epoxy-functional vinyl or (meth)acrylate monomers like glycidyl methacrylate. In certain embodiments, monomer unit b according to formula I is glycidyl methacrylate or other unsaturated epoxy-functional monomers, such as glycidyl methacrylate, glycidyl acrylate, glycidyl oxyalkyl (meth)acrylate, 2-[(allyloxy)methyl]oxirane, 2-(3-buten-1-yl)oxirane, 2-(2-propen-1-yl)oxirane, 2-methyl-3-(2-propen-1-yl)oxirane, 2-(2-methyl-2-propen-1-yl)oxirane, 2-(1-methyl-2-propen-1-yl)oxirane, 4,5-anhydro-1,2-dideoxy-penta-1-enitol, 2-(1,1-dimethyl-2-propen-1-yl)oxirane, 2-ethyl-3-(2-propen-1-yl)oxirane, 2-(4-penten-1-yl)oxirane, α-2-propen-1-yl-2-oxiranemethanol, 2-(5-hexen-1-yl)oxirane, 2-(2-methyl)epoxyalkene (e.g., butene, pentene, hexene), and / or 1,2-epoxyalkene (e.g., butene, pentene, hexene) by radical polymerization. 【0056】 In certain embodiments, monomer unit c according to formula I can be derived from the radical polymerization of an alkyl methacrylate, such as a (meth)acrylate monomer like methyl methacrylate. In certain embodiments, monomer unit c according to formula I can be derived from the radical polymerization of methyl (meth)acrylate or other unsaturated alkyl monomers, such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, isodecyl (meth)acrylate, and / or isobornyl (meth)acrylate. 【0057】 In certain embodiments, monomer unit d according to formula I can be derived from the radical polymerization of a (meth)acrylate monomer having a polyether chain, such as poly(ethylene) glycol methyl ether (meth)acrylate, poly(propylene) glycol methacrylate, poly(ethylene) glycol vinyl ether, and / or poly(propylene) glycol vinyl ether. In certain embodiments, POL 1 is a polymer comprising at least one of a polyether or a polyester, where the polymer has a theoretical number average molecular weight of 200 to 3,000. The polyester can be made from the polymerization of a lactone and a hydroxy-functional (meth)acrylate, such as 2-hydroxyethyl (meth)acrylate, or a hydroxy-functional vinyl monomer, such as allyl alcohol, 2-allyloxyethanol, 2-allylphenol, 2-vinyloxyethanol, 2-hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, and / or cinnamyl alcohol. Examples of lactones that can be used include, but are not limited to, lactides such as L-lactide, caprolactone, valerolactone, and alkyl-substituted caprolactones such as 7-methylcaprolactone. 【0058】 In certain embodiments, monomer unit e according to formula I can be derived from further functionalizing monomer unit b according to formula I, wherein X is a heteroatom linking POL 2 to the epoxy group. In certain embodiments, the hydroxy-functional polyether chain can react with an epoxy group, for example, polyethylene glycol methyl ether or polypropylene glycol methyl ether. In certain embodiments, an amino-functional polyether, for example, a polyetheramine available from Huntsman under the trade names Surfonamine® L100, L207, L300, B100, and / or B200, can react with the epoxy group. 【0059】 In certain embodiments, X is oxygen and the monohydroxyl functional polyester is reacting on the epoxy 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. 【0060】 In certain embodiments, X is -O-(C=O)-, where the monoacid-functional polyester is reacting on the epoxy monomer. This monoacid-functional polyester can be synthesized by the polymerization of lactones and / or lactides and / or hydroxycarboxylic acids, optionally in the presence of a monocarboxylic acid to initiate polyester chain extension, by any method known to those skilled in the art. Non-limiting specific examples of suitable hydroxycarboxylic acids are ricinoleic acid, 12-hydroxystearic acid, 6-hydroxycaproic acid, 5-hydroxyvaleric acid, 12-hydroxydodecanoic acid, 5-hydroxydodecanoic acid, 5-hydroxydecanoic acid, 4-hydroxydecanoic acid, 10-hydroxyundecanoic acid, lactide, glycolide, glycolic acid and / or lactic acid. Non-limiting examples of lactones include C 1~4 alkyl-substituted ε-caprolactone, optionally substituted C 1~4 alkyl δ-valerolactone, and β-propiolactone. Hydroxycarboxylic acids and lactones can also include dihydroxy compounds of the same carbon number range and substitution, such as 2,2-bis(hydroxymethyl)butyric acid; 2,2-bis(hydroxymethyl)propionic acid, and similar dihydroxycarboxylic acids of a specified carbon number range. These form branched polyesters that still have one carboxylic acid end group per polyester, and as taught in the present disclosure, the carboxylic acid groups can be converted to anhydrides. 【0061】 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, and e 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, and e according to Formula I, based on the total weight of the coupling agent. 【0062】 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. 【0063】 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, and e of Formula I. In certain embodiments, the coupling agent comprises, based on the total weight of the coupling agent, 5 - 30 (e.g., 10 - 30, 15 - 30, 20 - 30, 25 - 30, 5 - 25, 10 - 25, 15 - 25, 20 - 25, 5 - 20, 10 - 20, 15 - 20, 5 - 15, 10 - 15, or 5 - 10) weight percent of monomer units c, d, and e of Formula I. 【0064】 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 of Formula I. In certain embodiments, the coupling agent comprises, based on the total weight of the coupling agent, 50 - 80 (e.g., 55 - 80, 60 - 80, 65 - 80, 70 - 80, 75 - 80, 50 - 75, 55 - 75, 60 - 75, 65 - 75, 70 - 75, 50 - 70, 55 - 70, 60 - 70, 65 - 70, 50 - 65, 55 - 65, 60 - 65, 50 - 60, 55 - 60, or 50 - 55) weight percent of monomer unit a of Formula I. 【0065】 In certain embodiments, the coupling agent comprises monomer unit b of formula I in an amount of 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 monomer unit b of formula I in an amount of 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 based on the total weight of the coupling agent. 【0066】 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. 【0067】 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. 【0068】 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. 【0069】 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. 【0070】 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. 【0071】 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. 【0072】 In certain embodiments, when d is greater than 0, e is 0, and when e is greater than 0, d is 0. In certain embodiments, (i) d is an integer of 0, or 1 to 100 (e.g., 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), and (ii) e is an integer of 0, or 1 to 100 (e.g., 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,an integer of 5 to 10, or 1 to 5), provided that when d is greater than 0, e is 0, and when e is greater than 0, d is 0., 【0073】 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 different from the monomer units a, b, c, d, and e 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 different from the monomer units a, b, c, d, and e of formula I. In certain embodiments, the coupling agent substantially does not contain or does not contain other monomer units different from the monomer units a, b, c, d, and e 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. 【0074】 Also provided is a method of making a thermosetting composition described herein, 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 mold release agent, an accelerator, and the like. 【0075】 Also provided is a method for producing a thermosetting composition described herein, the method including dispersing a coupling agent as a dry solid in a thermosetting resin and then adding a particulate solid and other additives. The other additives may include at least one of a dispersant, an antifoaming agent, an internal release agent, an accelerator, and the like. 【0076】 Also provided is a method for imparting high / improved tensile strength to a thermosetting composition described herein, the method including dispersing a particulate solid in a thermosetting resin in the presence of a coupling agent. 【0077】 Also provided is a method for imparting flame retardancy to a thermosetting composition described herein, the method including dispersing a particulate solid (for imparting flame retardancy) in a thermosetting resin in the presence of a coupling agent. 【0078】 Also provided is a method for lightening the weight of a thermosetting composition described herein, the method including dispersing hollow particles (glass spheres) and a filler (as a particulate solid) in a thermosetting resin in the presence of a coupling agent. 【0079】 Also provided is a method for producing a thermosetting composition described herein, the method including treating a particulate solid with a coupling agent to produce a treated particulate solid and then adding the treated particulate solid to a thermosetting resin. For example, a fiber material may be pretreated with a sizing agent that also acts as a coupling agent. 【Examples】 【0080】 The subject matter disclosed herein may 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. 【0081】 All monomers and solvents were sparged with nitrogen for 30 minutes prior to polymerization. 【0082】 Example 1: Styrene (46.6 parts), glycidyl methacrylate (15.9 parts), and butyl 3-mercaptopropionate (0.14 part) were dissolved in butyl acetate (45.7 parts) and heated to 65°C under nitrogen. Then, 2,2'-azobis(2,4-dimethylvaleronitrile) (V65 ex Fujifilm (registered trademark), 1.35 parts) was added to the reaction mixture over 81 hours. During the first 3 hours, an additional 17 parts of butyl acetate were added. A viscous colorless liquid having an Mn of 17,670 and an Mw of 52,550 was obtained when determined by GPC in THF using a polystyrene standard, and the solid content was 65.6%. 【0083】 Example 2: Styrene (46.6 parts) and glycidyl methacrylate (15.9 parts) were dissolved in butyl acetate (44.5 parts) and heated to 80°C under nitrogen. Then, 2,2'-azobis(isobutyronitrile) (AIBN, 2 parts) was added to the reaction mixture over 50 hours. During the first 3 hours, an additional 20 parts of butyl acetate were added. A viscous colorless liquid having an Mn of 11,000 and an Mw of 37,540 was obtained when determined by GPC in THF using a polystyrene standard, and the solid content was 60.3%. 【0084】 Example 3: Styrene (46.6 parts), glycidyl methacrylate (15.9 parts), and bis[(difluoroboryl)dimethylglyoximato]cobalt(II) (CoBF, 0.046 part) were dissolved in butyl acetate (54.02 parts) and heated to 80°C under nitrogen. Then, 2,2'-azobis(isobutyronitrile) (AIBN, 1.47 parts) was added to the reaction mixture over 50 hours. During the first 2 hours, an additional 10 parts of butyl acetate were added. An amber liquid having an Mn of 570 and an Mw of 1570 was obtained when determined by GPC in THF using a polystyrene standard, and the solid content was 55.4%. 【0085】 Example 4 was a styrene and glycidyl methacrylate random copolymer having a number average molecular weight of 50,000 g / mol and containing 20 mol% glycidyl methacrylate and 80 mol% styrene. 【0086】 Example 5 was a styrene, glycidyl methacrylate, and methyl methacrylate random copolymer having a number average molecular weight of 80,000 g / mol and containing 15 mol% glycidyl methacrylate and 85 mol% styrene / methyl methacrylate. 【0087】 Examples 4 and 5 were mixed in a planetary stirrer at 2,000 rpm for a total of 10 minutes, and the samples were cooled to room temperature every 2 minutes and incorporated into a dispersion of calcium carbonate (Imercarb™ 2L from Imerys) in a liquid epoxy resin (Epikote™ 827 from Hexion). The formulations included a dicyandiamide curing agent (Amicure® CG1400F from Evonik), a polyetheramine (Jeffamine® D-230 from Huntsman), and an imidazole curing accelerator (Curezol® 2MZ-Azine from Evonik). The resulting compounds were compressed onto a PTFE mold at 130 °C for 30 minutes using a hot press and then conditioned in an oven at 60 °C for 2 days. Examples 6 - 8 contained the parts by number of each component shown in Table 1 below. The tensile strength of each of Examples 6 - 8 of the cured composition was measured using an Instron® 3367 tensile tester (5 kN load cell at 1 mm / min) and reported in MPa. 【0088】 【Table 1】 【0089】 Example 9: Styrene (24.55 parts), glycidyl methacrylate (11.17 parts), polyethylene glycol methyl ether methacrylate (MW = 500, 39.28 parts), and butyl 3-mercaptopropionate (0.19 part) were dissolved in butyl acetate (55.83 parts). The mixture was heated to 90 °C under nitrogen, and benzoyl peroxide (Luperox® A75, 0.63 part) and butyl acetate (20 parts) were added over 4 hours. The reaction mixture was stirred at 90 °C for 18 hours. Benzoyl peroxide (Luperox® A75, 0.25 part) was added, and the reaction mixture was stirred at 90 °C for 5.5 hours. Benzoyl peroxide (Luperox® A75, 0.25 part) was added, and the reaction mixture was stirred at 90 °C for 18.5 hours. A viscous colorless liquid having Mn = 37665 and Mw = 180802 was obtained when determined by GPC in THF using a polystyrene standard. 【0090】 Intermediate A: Lauric acid (50.99 parts), ε-caprolactone (399.51 parts), δ-valerolactone (71.34 parts), and zirconium IV butoxide (80% in 1-butanol, 2.28 parts) were heated under nitrogen to 160 °C for 15 minutes and then to 172 °C for 5 hours. An amber liquid was obtained, which solidified upon cooling, and had an acid value = 24.0 mg KOH g -1 and was. 【0091】 Example 10: Example 2 (40 parts), Intermediate A (17.27 parts), and tetrabutylammonium iodide (0.17 part) were stirred under nitrogen for 24 hours. A very viscous liquid having Mn = 13583 and Mw = 99612 was obtained when determined by GPC in THF using a polystyrene standard. 【0092】 Example 11: Styrene (24.29 parts), glycidyl methacrylate (24.87 parts), methyl methacrylate (5.84 parts) and butyl 3-mercaptopropionate (0.38 part) were dissolved in toluene (36.02 parts). The mixture was heated to 80 °C under nitrogen, and azobisisobutyronitrile (AIBN, 0.64 part) and toluene (20 parts) were added over 4 hours. The reaction mixture was stirred at 80 °C for 18 hours. Azobisisobutyronitrile (AIBN, 0.32 part) was added and the reaction mixture was stirred at 80 °C for 17 hours. Azobisisobutyronitrile (AIBN, 0.32 part) and toluene (2.5 parts) were added and the reaction mixture was stirred at 85 °C for 4 hours. A viscous colorless liquid having Mn = 9881 and Mw = 20888 was obtained when determined by GPC in THF using a polystyrene standard. 【0093】 Example 12: Styrene (18.94 parts), glycidyl methacrylate (12.93 parts), lauryl methacrylate (23.13 parts) and butyl 3-mercaptopropionate (0.18 part) were dissolved in toluene (45.12 parts). The mixture was heated to 90 °C under nitrogen, and benzoyl peroxide (Luperox® A75, 0.59 part) and toluene (10 parts) were added over 4 hours. The reaction mixture was stirred at 90 °C for 18 hours. Benzoyl peroxide (Luperox® A75, 0.6 part) and toluene (5 parts) were added and the reaction mixture was stirred at 90 °C for 6.5 hours. Benzoyl peroxide (Luperox® A75, 0.3 part) and toluene (5 parts) were added and the reaction mixture was stirred at 85 °C for 6 hours. A viscous colorless liquid having Mn = 20280 and Mw = 55755 was obtained when determined by GPC in THF using a polystyrene standard. 【0094】 Example 13: Styrene (46.60 parts), glycidyl methacrylate (15.90 parts), and butyl 3-mercaptopropionate (0.27 part) were dissolved in butyl acetate (52.84 parts). The mixture was heated to 80 °C under nitrogen, and azobisisobutyronitrile (AIBN, 0.07 part) and butyl acetate (10 parts) were added over 2 hours. The reaction mixture was stirred at 80 °C for 21 hours. Azobisisobutyronitrile (AIBN, 0.21 part) was added over 7 hours, and the reaction mixture was stirred at 80 °C for 18.5 hours. Azobisisobutyronitrile (AIBN, 0.07 part) was added, and the reaction mixture was stirred at 80 °C for 6.5 hours. Azobisisobutyronitrile (AIBN, 0.07 part) was added, and the reaction mixture was stirred at 80 °C for 5 hours. A viscous colorless liquid having Mn = 23059 and Mw = 62994 was obtained as determined by GPC in THF using polystyrene standards. 【0095】 The following tests were conducted to determine the suitability of the above-described examples for various applications in which fiber and / or filler reinforced thermosetting plastics may be used. There are numerous suitable tests (or modifications thereof) for evaluating the mechanical properties in composite articles, non-exhaustively summarized in ASTM D4762-18, and any of these tests may be used to confirm the effectiveness of the subject matter in a particular material and / or for a particular use of the resulting material. One exemplary test applicable to the study of thermosetting materials is 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. Any such test, when appropriately used by one of ordinary skill in the art, may be useful in demonstrating the benefits of the subject matter described herein (through the above examples). Therefore, the advantages observed herein may indicate that there may be other advantages that can be demonstrated in appropriately selected higher-order static or dynamic mechanical tests. 【0096】 Examples 1, 2, 3, 4, 5, 9, 11 and 13 were incorporated by mixing in a dispersion of calcium carbonate (“calcium carbonate, CC”, Carbital™ 110s from Imerys) or aluminium trihydroxide (“aluminium trihydroxide, AT”, Martinal™ OL104 from Huber) and milled carbon fibre (“milled carbon fibre, MCF”, Carbiso™ MF from ELG Carbon Fibre) or milled glass fibre (“milled glass fibre, MGF”, 1320K from Owens Corning) or cut carbon fibre (“cut carbon fibre, CCF”, Carbiso™ C IMP56P-03-10 from ELG Carbon Fibre) in a liquid epoxy resin (“epoxy resin, ER”, Epikote™ 827 from Hexion) with a planetary stirrer at 2,000 rpm for a total of 6 - 10 minutes, cooling the sample to room temperature every 2 minutes. The formulations included a dicyandiamide curing agent (“dicyandiamide curing agent, DCA”, Amicure® CG1400F from Evonik) and an imidazole curing accelerator (“imidazole curing accelerator, ICA”, Curezol® 2MZ-Azine from Evonik). Table 2 details the weight % of each component in the formulations tested for Examples 14, 15, 16, 17, 18, 19, 20 and 21, 22, 23. 【0097】 【Table 2】 【0098】 Examples 14, 15, 16, 17, 21, 22 and 23 are representative examples of typical formulations suitable for compression moulding of CFRP parts. On the other hand, Examples 18, 19 and 20 are representative examples of flame-retardant formulations typically used in GFRP compression moulded electrical fittings. 【0099】 The tests of Examples 14, 15, 16, 17, 18, 19, 20, 24, 25, 26, 27, 28 and 29 were conducted using milled fibers. Generally, the described formulations were tested in a single frequency vibration “through cure” experiment 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. 【0100】 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 vibration at a frequency of 1 Hz through a temperature profile that would cure the formulation of interest and was applicable to the intended use. Active control was used in both strain and axial force during the test to stay within the linear viscoelastic limit of the material while maintaining a good signal-to-noise ratio to enable monitoring of the cure 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. 【0101】 Measurements obtained from individual experiments were calculated from the analysis performed in the instrument-assisted Trios software. The onset “gel” temperature of cure was calculated from the storage modulus curve versus temperature (T vs Log(G’)), and the end-set time of cure was calculated from the storage modulus versus time (T vs Log(G’)). The storage modulus in the isothermal cure post-plateau region of the experiment was the selected time range data points (a ) by averaging over, or correcting to account for the difference in gaps between experiments for different samples through regression correlation in this region ( b ), can be obtained directly, 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. Measurements obtained from the through-cure experiments were used to screen the exemplified coupling agents for their compatibility in the exemplified formulations and the hypothesized uses. 【0102】 In the full cure experiments conducted in Examples 14, 15, 16, 17, 18, 19, 20, 21, 22, and 23, the temperature was raised from 25 to 135 °C at 5 °C / min. It was held at 135 °C for 10 minutes to continue the measurements after sample curing. 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 (「geometry inertia, GI」, μN·m·s 2 ) and friction (「friction, FR」, μN·m / (rad / sec)) were calibrated for each trial. The variable trial parameters for Examples 14, 15, 16, 17, 18, 19, 20, 21, 22, and 23 are summarized in Table 3 below. 【0103】 【Table 3】 【0104】 The measurements for Examples 14, 15, 16, 17, 18, 19, 20, 21, 22, and 23 are detailed in Table 4. 【0105】 【Table 4】 * The temperature of the gel occurred during the isothermal region of temperature maintenance in the experiment. 【0106】 In Table 4, Examples 14, 15, 16, 17, 18, 19, and 20 show that the variation at the starting gel temperature is very small, indicating that the coupling agent present does not affect the curing rate of the resin. Examples 15, 16, and 17 are the same but show an increase in the modulus of elasticity measured in the plateau region after curing compared to Example 14, which is a formulation without a coupling agent. Examples 18, 19, and 20 also show an increase in the modulus of elasticity measured against Comparative Example 14, but in this case, the formulations are not the same (the fillers and fibers are changed in these examples). Examples 21, 22, and 23 have different levels of promoter / accelerator from Examples 14 to 20 and cut the fibers instead of grinding. Small changes in the promoter / accelerator loading are accompanied by changes in the gelation time to the temperature maintenance region for the experiment. However, in this set, Examples 22 and 23, which are coupling agent-containing formulations, show little change at the comparative starting temperature and also show a higher modulus of elasticity than Example 21, which is the comparative formulation. 【0107】 Examples 24 and 25: Example 12 was incorporated into a dispersion containing calcium carbonate (Carbital™ 110s from Imerys), glass bubbles (S32HS from 3M), and chopped glass fibers (1320K from Owens Corning) in an unsaturated polyester resin (Palapreg® P17-02 from AOC) and a polystyrene low-profile additive (Norpol® LP 9887-A from Reichold). Additionally, a thickener (Luvatol® MK25 from Luvatol) and zinc stearate (Sigma Aldrich) were added to the mixture. The formulation contained a peroxide curing catalyst (tert-butyl peroxybenzoate from Sigma Aldrich). The formulation was mixed with a planetary mixer at 2,000 rpm for a total of 16 minutes, and the sample was cooled to room temperature every 2 minutes for preparation. Table 5 details the weight percentages of each component in Examples 24 and 25. Example 25 represents a typical formulation that can be used for the compression molding of lightweight GFRP body panels for vehicles and other transportation purposes. 【0108】 【Table 5】 【0109】 For Examples 24 and 25, the temperature gradient was 25 - 135 °C at 5 °C / min. It was held at 135 °C for 3 minutes to continue the measurement after sample curing. 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, for Example 24, the geometric inertia was 2.36008 μN.m.s 2 and the friction was 0.27782 μN.m / (rad / sec), for Example 25, the geometric inertia was 2.36547 μN.m.s 2and a friction of 0.276771 μN·m / (rad / second), and for both examples, the stress constant was 325949 Pa / N·m, the strain constant was 12.5 1 / rad, and the perpendicular stress constant was 4074.37 Pa / N. The measurements of Examples 24 and 25 are detailed in Table 6. 【0110】 【Table 6】 【0111】 A direct comparison between Example 25 and 24 shows only a slight change in the onset gelation time and an increase in the storage modulus in the plateau region after curing. 【0112】 Example 10 was incorporated into a dispersion containing talc (TL-3 from International) and chopped glass fibers (1320K from Owens Corning) in a vinyl ester resin (Crystic® VE 676 from Scott Bader) containing dimethylaniline (Sigma Aldrich) and cobalt ethylhexanoate solution (Sigma Aldrich). The formulation was mixed with a planetary mixer at 2,000 rpm for a total of 8 minutes, and the sample was cooled to room temperature every 2 minutes for preparation. Exactly 5 minutes before conducting the experiments described below for each example, a peroxide curing catalyst (tert-butyl peroxybenzoate from Sigma Aldrich) was mixed into the formulation with a planetary mixer at 2,000 rpm for 30 seconds. Table 7 details the weight % of each component in the formulations tested for Examples 26 and 27. Examples 26 and 27 represent typical formulations that can be used for GFRP repair in marine or industrial applications. 【0113】 【Table 7】 【0114】 For Examples 26 and 27, temperature holding at 40°C and holding at 40°C for 1 hour at the temperature during measurement were used. The initial gap size was 1500 μm, the trim offset was 50 μm, and the minimum sample volume at the start of the test was 0.736311 mL. Gap temperature compensation - expansion coefficient 2.7398 μm / °C, compliance 2.02 mrad / N.m, for Example 26, geometric inertia 2.40223 μN.m.s 2 , friction 0.275298 μN.m / (rad / second), for Example 27, geometric inertia 2.32433 μN.m.s 2 , friction 0.280915 μN.m / (rad / second), and for both examples, stress constant 325949 Pa / N.m, strain constant 12.5 1 / rad, and vertical stress constant 4074.37 Pa / N. The measurements for Examples 26 and 27 are detailed in Table 8. 【0115】 【Table 8】 【0116】 A comparison between Example 27 and 26 shows a slight increase in the elastic modulus in the plateau region after curing, in which case some waiting time is observed in the cure kinetics. In some applications, a controlled waiting time in curing can be advantageous for processing. 【0117】 Example 11 was incorporated into a homogeneous mixture of metakaolin (Metaever® O from NewChem) and standardized silica sand (ASTM C778 20-30 from Howie&Howie Ltd) in Part A of a polyurethane casting resin (Xencast® P6 Toughned PU Part A from Xencast polymers). The formulation was mixed with a dual-arm mixer at 2,000 rpm for a total of 6 minutes, and the sample was cooled to room temperature every 2 minutes. It was then mixed with Part B of a polyurethane casting resin (Xencast® P6 Toughned PU Part B from Xencast polymers), and the mixing process was started with a dual-arm mixer at 2,000 rpm for 30 seconds, 10 minutes before starting the full cure experiment (described for Examples 28 and 29). Table 9 details the weight % of each component in the test formulations for Examples 28 and 29. Examples 28 and 29 represent formulations that can be used for polymer marble or polymer casting applications. 【0118】 【Table 9】 【0119】 For Examples 28 and 29, temperature holding at 50 °C was used and held at 50 °C for 1 hour at the temperature during measurement. The initial gap size was 1500 μm, the trim offset was 50 μm, and the minimum sample volume at the start of the test was 0.736311 mL. Gap temperature compensation - expansion coefficient 2.7398 μm / °C, compliance 2.02 mrad / N.m, for Example 28, geometric inertia 2.40905 μN.m.s 2 friction 0.274824 μN.m / (rad / sec), for Example 29, geometric inertia 2.35425 μN.m.s 2 friction 0.278082 μN.m / (rad / sec), for both examples, stress constant 325949 Pa / N.m, strain constant 12.5 1 / rad, and vertical stress constant 4074.37 Pa / N. The measurements for Examples 26 and 27 are detailed in Table 10. 【0120】 【Table 10】 【0121】 The comparison between Example 29 and Example 28 shows an increase in the storage modulus plateau after curing. This is accompanied by a minimal change in the end-set curing time. 【0122】 For all examples related to each comparative example, an increase in the storage modulus was observed. This indicates that the formulations containing the coupling agent are more rigid, which implies a greater density of cross-linking within the cured compound matrix and to the fillers and fibers therein. 【0123】 Except where otherwise indicated, or unless otherwise explicitly stated, or unless required by context, all numerical 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 recited value. In other embodiments, the value is within ±15% of the recited value. In other embodiments, the 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. In other embodiments, the value is within the range of the explicitly recited value, such that it would be understood by one of ordinary skill in the art, based on the disclosure provided herein, to function substantially the same as a composition containing the exact amount described herein. 【0124】 The upper and lower limits of the amounts, ranges, and ratios described herein can be combined independently, and any amount within the disclosed ranges is contemplated to provide the minimum or maximum value of a narrower range in alternative embodiments (provided, of course, that the minimum amount of a 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 herein can be used in conjunction with the ranges or amounts for any of the other elements. 【0125】 For purposes of illustrating the subject matter disclosed herein, specific representative embodiments and details have been shown, but it will be apparent to those skilled in the art that various changes and modifications 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

[Claim 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, and e according to formula I, 【Chemistry 4】 In the formula, each molecule of the coupling agent is considered independently, R １ However, 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 R ３ However, H or CH ３ And, R ４ However, C １ ~C ２０ Alkyl alkyl group, -C-O-R １２ -, or -(C=O)-O-C-R １２ - and here, R １２ C １ ~C ２０ It is an alkyl group, R ５ However, H or CH ３ And, R ６ However, it is -C-O- or -(C=O)-O-C-, R ７ However, C １ ~C ２０ It is an alkyl group, R ８ However, H or CH ３ And, R ９ However, C １ ~C ２０ Alkyl alkyl group, -C-O-R １４ -, or -(C=O)-O-C-R １４ - and here, R １４ C １ ~C ２０ It is an alkyl group, R １０ However, H or CH ３ And, R １１ However, C １ ~C ２０ Alkyl alkyl group, -C-O-R １５ -, or -(C=O)-O-C-R １５ - and here, R １５ C １ ~C ２０ It is an alkyl group, POL １ However, the polymer comprises at least one of polyether or polyester, wherein the polymer has a theoretical number average molecular weight of 200 to 3,000. POL ２ However, the polymer comprises at least one of polyether or polyester, wherein the polymer has a theoretical number average molecular weight of 200 to 3,000. X is S, O, NH, or -O-(C=O)-, a is an integer between 1 and 500. b is an integer between 1 and 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. A thermosetting composition in which, if d is greater than 0, e is 0, and if e is greater than 0, d is 0. [Claim 2] The thermosetting composition according to claim 1, wherein the particulate solid is present in an amount of 20 to 80 weight percent based on the total weight of the thermosetting composition. [Claim 3] The thermosetting composition according to claim 1, wherein the functional filler comprises at least one of a flame-retardant material or a pigment. [Claim 4] The thermosetting composition according to claim 1, wherein the thermosetting resin is present in an amount of 80 to 20 percent by weight based on the total weight of the thermosetting composition. [Claim 5] The thermosetting composition according to claim 1, wherein the thermosetting resin comprises an epoxide resin, an unsaturated polyester resin, a vinyl ester resin, a polyurethane resin, or a phenolic resin. [Claim 6] The thermosetting composition according to claim 1, 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. [Claim 7] The thermosetting composition according to claim 1, wherein the coupling agent comprises at least 90 weight percent of monomer units a, b, c, d, and e according to formula I, based on the total weight of the coupling agent. [Claim 8] The thermosetting composition according to claim 1, wherein the coupling agent comprises at least 70 weight percent of monomer units a and b according to formula I, based on the total weight of the coupling agent. [Claim 9] The thermosetting composition according to claim 1, wherein the coupling agent comprises 30% by weight or less of monomer units c, d, and e according to formula I, based on the total weight of the coupling agent. [Claim 10] The thermosetting composition according to claim 1, wherein the coupling agent comprises at least 50 weight percent of monomer units a according to formula I, based on the total weight of the coupling agent. [Claim 11] The thermosetting composition according to claim 1, wherein the coupling agent comprises 40% by weight or less of monomer units b according to formula I, based on the total weight of the coupling agent. [Claim 12] The thermosetting composition according to claim 1, wherein a is an integer from 5 to 500. [Claim 13] The thermosetting composition according to claim 1, wherein a is an integer from 10 to 300. [Claim 14] The thermosetting composition according to claim 1, wherein b is an integer from 2 to 100. [Claim 15] The thermosetting composition according to claim 1, wherein b is an integer from 5 to 80. [Claim 16] The thermosetting composition according to claim 1, wherein the ratio of a to b is 1:1 to 10:

1. [Claim 17] The thermosetting composition according to claim 1, wherein c is an integer from 1 to 20. [Claim 18] (i) d is 0 or an integer from 1 to 20, and (ii) e is 0 or an integer from 1 to 20, provided that if d is greater than 0, e is 0, and if e is greater than 0, d is 0. The thermosetting composition according to claim 1. [Claim 19] The thermosetting composition according to claim 1, wherein the coupling agent comprises up to 10 weight percent of other monomer units different from monomer units a, b, c, d, and e according to formula I. [Claim 20] The thermosetting composition according to claim 19, wherein the other monomer unit is a vinyl functional monomer unit.

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