Copolymers derived from dicyclopentadiene.

Abstract

A copolymer containing repeating units and terminal units each derived from dicyclopentadiene.

Description

[Technical field]

[0001] FIELD OF THE DISCLOSURE This disclosure relates to dicyclopentadiene derived copolymers, methods for their preparation, curable thermoset compositions containing same, and articles derived therefrom. [Background technology]

[0002] Thermosets are materials that cure into extremely hard plastics. These materials can be used in a wide variety of consumer and industrial products. For example, thermosets are used in protective coatings, adhesives, electronic laminates (such as those used in making computer circuit boards), flooring and paving materials, fiberglass reinforced tubing, and automotive parts (such as leaf springs, pumps, and electrical components).

[0003] Poly(phenylene ether) oligomers can improve the dielectric performance, heat resistance, flame resistance, and moisture absorption of thermoset materials, making such materials particularly well suited for a variety of applications, especially electronic applications. Dicyclopentadiene is known to provide excellent moisture resistance and dramatically reduce the dielectric constant without adversely affecting thermal performance. Summary of the Invention [Problem to be solved by the invention]

[0004] It would therefore be advantageous to provide a composition comprising a combination of poly(phenylene ether) oligomers and dicyclopentadiene, which has poor dielectric performance, for use in curable thermoset compositions. [Means for solving the problem]

[0005] Copolymers containing repeating units and terminal units each derived from dicyclopentadiene address these and other shortcomings in the art.

[0006] One embodiment is a copolymer comprising repeat units and terminal units each derived from dicyclopentadiene, the terminal units optionally being fused with an epoxide or aziridine ring, and the terminal units optionally being substituted with at least one terminal functional group.

[0007] One embodiment is a copolymer comprising repeat units and terminal units each derived from dicyclopentadiene, the terminal units being represented by structural formula E-1, structural formula E-2, or a combination thereof: [ka] Structural formula E-1, [ka] Structural formula E-2 During the ceremony, [ka] indicates a bond that is a single or double bond and an occurrence of [ka] is a single bond, then q is 2, each occurrence of Q contains a single bond, hydrogen, or a terminal functional group, and if both occurrences of Q are each a single bond, then Q joins to form an epoxide ring or an aziridine ring.

[0008] One embodiment is a copolymer derived from a first monomer, a second monomer, and a terminal unit monomer, wherein the first monomer and the terminal unit monomer are each dicyclopentadiene.

[0009] One embodiment is a copolymer derived from a first monomer, a second monomer, and a terminal unit monomer, wherein the first monomer and the terminal unit monomer are each dicyclopentadiene, and the terminal unit is optionally fused with an epoxide ring or an aziridine ring, or is optionally substituted with at least one terminal functional group.

[0010] One embodiment is a copolymer comprising repeat units derived from a first monomer, a second monomer, and a terminal unit monomer, wherein the first monomer comprises dicyclopentadiene, the second monomer comprises benzene (optionally substituted with hydrocarbyl groups, hydrocarbyloxy groups, or combinations thereof), the terminal unit monomer is dicyclopentadiene, and the terminal unit is optionally fused with an epoxide ring or an aziridine ring or is optionally substituted with at least one terminal functional group.

[0011] A curable composition comprising the copolymer.

[0012] A cured thermoset composition comprising the cured product of the curable thermosetting composition.

[0013] An article comprising the cured thermoset composition.

[0014] An article made from a varnish composition comprising the curable thermosetting composition and a solvent.

[0015] These and other features are illustrated by way of example in the figures and detailed description that follow. [Brief description of the drawings]

[0016] The following figures are exemplary embodiments in which like elements are numbered alike.

[0017] [Figure 1] FIG. 1 shows side-by-side proton NMR spectra of the copolymer prepared according to Example 1, dicyclopentadiene, and 1,4-dimethoxybenzene. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0018] The present inventors have discovered that, for example, copolymer additives useful in curable thermoset compositions can be prepared from dicyclopentadiene copolymers which, when cross-linked with poly(phenylene ether) resins, advantageously produce a favorable combination of dielectric properties, flame resistance, and thermal performance while maintaining compatibility between the poly(phenylene ether) and the dicyclopentadiene copolymer.

[0019] The present copolymers are believed to be particularly useful in curable thermosetting compositions.

[0020] The copolymer contains repeating units and terminal units each derived from dicyclopentadiene.

[0021] The copolymer is derived from a first monomer, a second monomer, and a terminal unit monomer, where the first monomer and the terminal unit monomer are each dicyclopentadiene.

[0022] The terminal units of the copolymer are optionally fused with an epoxide or aziridine ring, or are optionally substituted with at least one terminal functional group.

[0023] In some embodiments, the terminal unit is represented by structural formula E-1, structural formula E-2, or a combination thereof: [ka] Structural formula E-1, [ka] Structural formula E-2 During the ceremony, [ka] indicates a bond that is either single or double, and [ka] is a single bond, then q is 2, and each occurrence of Q contains a single bond, hydrogen, or a terminal functional group, and if both occurrences of Q are each single bonds, then the Qs join to form an epoxide or aziridine ring.

[0024] The copolymer additive can include a structure shown in Formula A1. [ka] Structural formula A1

[0025] where R for each occurrence 1 From R 4 are independently hydrogen, C 1 ~C 12 Hydrocarbyl, or C 1 ~C 12 hydrocarbyloxy, n is at least one 1 to 100; [ka] indicates a bond that is single or double, and [ka] If is a single bond, then Q a and Q b or Q c and Q d exists, and each occurrence [ka] If is a single bond, then Q a From Q d exists and Qa From Q d each independently contains a single bond, hydrogen, or a terminal functional group; Q a and Q b If each is a single bond, then Q a and Q b are linked to form an epoxide or aziridine ring, and Q c and Q d If each is a single bond, then Q c and Q d are linked to form an epoxide ring or an aziridine ring.

[0026] The copolymer represented by structural formula A1 can include those represented by structural formulas A1-1 to A1-9, [ka] Structural formula A1-1, [ka] Structural formula A1-2, [ka] Structural formula A1-3, [ka] Structural formula A1-4, [ka] Structural formula A1-5, [ka] Structural formula A1-6, [ka] Structural formula A1-7, [ka] Structural formula A1-8, [ka] Structural formula A1-9 In the formula, R 1 From R 4 and Q a From Q d is as previously described, and J is N or O.

[0027] The copolymer of formula A1 may include at least one terminal functional group. As used herein, the term "terminal functional group" includes a group that reacts with a complementary functional group of a monomer, oligomer, or polymer, and also includes a synthetic precursor of a group that reacts with a complementary functional group of a monomer, oligomer, or polymer. For example, the terminal functional group may be a vinyl, acrylate, or styryl group that can be crosslinked with a vinyl, acrylate, or styryl group. In another example, the terminal functional group may be an epoxide, which may be a synthetic precursor of an alcohol or a synthetic precursor of another functional group (e.g., an ether terminal functional group via an ether-forming reaction, or an ester terminal functional group via an ester-forming reaction). In yet another example, the terminal functional group may be an aldehyde functional group, which may also be a synthetic precursor of an amine via a reductive amination reaction, for example. The ether, ester, and amine functional groups produced from these examples can react with complementary functional groups on monomers, oligomers, or polymers, or serve as synthetic precursors to other functional groups. The foregoing is for illustrative purposes only and is not intended to limit the present copolymers in any way.

[0028] The terminal functional group can include an aldehyde, an alcohol, an ether, an ester, a thiol, a thioether, a thioester, a primary amine, a secondary amine, an amide, or an alkene. The terminal functional group can include those of the following structure: [ka] wherein X is a halogen and each occurrence of Y independently includes the following structures: [ka]

[0029] Non-limiting examples of end functional groups include vinylbenzene ether end functional groups, methacrylate end functional groups, acrylate end functional groups, epoxy end functional groups, hydroxyl end functional groups, cyanate ester end functional groups, amine end functional groups, maleimide end functional groups, allyl end functional groups, styrenic end functional groups, activated ester end functional groups, or anhydride end functional groups.

[0030] Q a From Q d If at least one of Q is a terminal functional group, the copolymer represented by formula A1 can be crosslinked with another polymer having a complementary terminal functional group. a and Q b At least one of Q can be a terminal functional group. c and Q d At least one of Q can be a terminal functional group. a From Q d At least one of Q can be a terminal functional group. a and Q b At least one of and Q c and Q d At least one of the groups may be a terminal functional group.

[0031] In structural formula A1, each occurrence of R 1 From R 4 are independently hydrogen, C 1 ~C 12 Hydrocarbyl, or C 1 ~C 12 In some embodiments, R 1 From R 4 Each independently comprises hydrogen, alkyl, alkenyl, or alkoxy. 2 and R 3can both be hydrogen, and R 1 and R 4 is C 1 ~C 12 Hydrocarbyl or C 1 ~C 12 In some embodiments, R 1 and R 4 are each independently methoxy, isopropyl, t-butyl, vinyl, or allyl; R 2 and R 3 are hydrogen.

[0032] At least one of the copolymers represented by structural formula A1 [ka] Those in which the group is a single bond rather than a double bond (e.g., those represented by structural formulae A1-2 to A1-9) are represented by structural formula A1-1( [ka] The copolymer represented by the structural formula A1-1 can be derived from a copolymer of dicyclopentadiene and R 1 ~R 4 The copolymers can be prepared by a process comprising reacting a copolymer having structure A1-1 with a benzene monomer substituted with Q in the presence of a catalyst (e.g., a Lewis acid catalyst) to produce a copolymer having structure A1-1. Suitable reaction conditions (e.g., one or more synthetic steps may be required) for converting one terminal functional group to another terminal functional group can be readily determined by one of ordinary skill in the art. In some embodiments, the copolymer having structure A1-1 is subjected to an epoxidation reaction to produce one or more of the epoxy copolymers having structure A1-5 through A1-9, where J is O. The epoxy copolymer can then be reacted with a complementary functional group (e.g., an acid, anhydride, amine, thiol). In some embodiments, the copolymer having structure A1-1 is subjected to a hydroformylation reaction to produce one or more of the epoxy copolymers having structure A1-2 through A1-4, where Q is O. a From Q dwhere one or two of the aldehyde groups are aldehyde groups. The copolymers having one or two aldehyde groups can then be reduced to produce alcohol functionalities, reductively aminated to produce one or two amine terminal functionalities, or reacted with an azide in the presence of a catalyst to produce one or two amine terminal functionalities. The foregoing embodiments are illustrative, and the methods disclosed herein are not limited to the specific functional group transformations described. Exemplary syntheses are further described in the Examples below.

[0033] The copolymers can be combined with polymer compositions to form curable compositions. In some embodiments, the curable compositions include poly(phenylene ethers). Suitable poly(phenylene ethers) include those that include repeating structural units according to structural formula (1): [ka] (1) where Z for each occurrence 1 are independently halogen, unsubstituted or substituted C 1 ~C 12 hydrocarbyl (provided that the hydrocarbyl group is not a tertiary hydrocarbyl), C 1 ~C 12 Hydrocarbylthio, C 1 ~C 12 Hydrocarbyloxy, or C 2 ~C 12 including halohydrocarbyloxy (where the halogen and oxygen atoms are separated by at least two carbon atoms); 2 are independently hydrogen, halogen, unsubstituted or substituted C 1 ~C 12 hydrocarbyl (provided that the hydrocarbyl group is not a tertiary hydrocarbyl), C 1 ~C 12 Hydrocarbylthio, C 1 ~C 12 Hydrocarbyloxy, or C 2 ~C 12It includes halohydrocarbyloxy, where the halogen and oxygen atoms are separated by at least two carbon atoms. The term "hydrocarbyl" as used herein, whether used alone or as a prefix, suffix, or part of other terms, refers to a residue containing only carbon and hydrogen. The residue can be aliphatic or aromatic, straight-chain, cyclic, bicyclic, branched, saturated, or unsaturated. It can also include combinations of aliphatic, aromatic, straight-chain, cyclic, bicyclic, branched, saturated, and unsaturated hydrocarbon groups. However, when a hydrocarbyl residue is described as being substituted, it may contain heteroatoms, if desired, in addition to the carbon and hydrogen that make up the substituent residue. That is, when stated to be substituted, the hydrocarbyl residue can also contain one or more carbonyl groups, amino groups, hydroxyl groups, etc., or can contain heteroatoms within the backbone of the hydrocarbyl residue. As an example, Z 1 may be a di-n-butylaminomethyl group produced by reacting a terminal 3,5-dimethyl-1,4-phenyl group with the di-n-butylamine component of an oxidative polymerization catalyst.

[0034] As used herein, the term "poly(phenylene ether)" can also refer to low molecular weight phenylene ether oligomers. In some embodiments, the phenylene ether oligomers include 2,6-dimethyl-1,4-phenylene ether units, 2,3,6-trimethyl-1,4-phenylene ether units, or combinations thereof. In some embodiments, the phenylene ether oligomers can have an intrinsic viscosity of 0.03 to 0.13 deciliters per gram (dL / g), 0.05 to 0.1 dL / g, or 0.1 to 0.15 dL / g, as measured in chloroform at 25° C. using an Ubbelohde viscometer. The phenylene ether oligomers can have a number average molecular weight of 500 to 7,000 g / mole and a weight average molecular weight of 500 to 15,000 g / mole, as measured by gel permeation chromatography using polystyrene standards. In some embodiments, the number average molecular weight can be from 750 to 4,000 g / mole and the weight average molecular weight can be from 1,500 to 9,000 g / mole, as measured by gel permeation chromatography using polystyrene standards.

[0035] The phenylene ether oligomer can be monofunctional or difunctional. In some embodiments, the phenylene ether oligomer can be monofunctional. For example, it can have a functional group at one end of the polymer chain. The functional group can be, for example, a hydroxyl group or a (meth)acrylate group, desirably a (meth)acrylate group. In some embodiments, the phenylene ether oligomer comprises poly(2,6-dimethyl-1,4-phenylene ether).

[0036] In some embodiments, the phenylene ether oligomer can be difunctional. For example, it can have a functional group at both ends of the oligomer chain. The phenylene ether oligomer can have at least one terminal functional group complementary to a terminal functional group of the copolymer represented by Structure A1. In some aspects, the functional group can be, for example, a hydroxyl group or a (meth)acrylate group, desirably a (meth)acrylate group. A difunctional polymer having functional groups at both ends of the polymer chain is also referred to as a "telechelic" polymer. In some embodiments, the phenylene ether oligomer comprises a difunctional phenylene ether oligomer having a structure represented by Structure (2): [ka] (2) In the formula, Q 1 and Q 2 each independently represents a halogen, an unsubstituted or substituted C 1 ~C 12 Primary or secondary hydrocarbyl, C 1 ~C 12 Hydrocarbylthio, C 1 ~C 12 Hydrocarbyloxy, and C 2 ~C 12 including halohydrocarbyloxy (where the halogen and oxygen atoms are separated by at least two carbon atoms); 3 and Q 4 are independently hydrogen, halogen, unsubstituted or substituted C 1 ~C 12 Primary or secondary hydrocarbyl, C 1 ~C 12 Hydrocarbylthio, C 1 ~C 12 Hydrocarbyloxy, and C 2 ~C 12halohydrocarbyloxy (wherein the halogen and oxygen atoms are separated by at least two carbon atoms); Z is hydrogen or (meth)acrylate; x and y are independently 0 to 30, specifically 0 to 20, more specifically 0 to 15, even more specifically 0 to 10, and even more specifically 0 to 8 (provided that the sum of x and y is at least 2, specifically at least 3, and more specifically at least 4); and L has a structure according to formula (3); [ka] (3) where R for each occurrence 3 and R 4 and R 5 and R 6 are independently hydrogen, halogen, unsubstituted or substituted C 1 ~C 12 Primary or secondary hydrocarbyl, C 1 ~C 12 Hydrocarbylthio, C 1 ~C 12 Hydrocarbyloxy, and C 2 ~C 12 containing halohydrocarbyloxy (wherein the halogen and oxygen atoms are separated by at least two carbon atoms), z is 0 or 1, and Y has the structure: [ka] where R for each occurrence 7 are independently hydrogen and C 1 ~C 12 R for each occurrence, including hydrocarbyl 8 and R 9 are independently hydrogen, C 1 ~C 12 Hydrocarbyl, and C 1 ~C 6 Hydrocarbylene (where R 8 and R 9 And C 4 ~C 12 forming an alkylene group).

[0037] In another embodiment, L in structural formula (3) is represented by structural formula (4): [ka] (4) wherein E is 6 to 100, 11 to 80, or 11 to 60; and each occurrence of R is independently an unsubstituted or substituted C 1~13 Alkyl, C 1~13 Alkoxy, C 3~6 Cycloalkyl, C 3~6 Cycloalkoxy, C 6~14 Aryl, C 6~10 Aryloxy, C 7~13 Aryl alkylene, or C 7~13 The aforementioned groups may be fully or partially halogenated with fluorine, chlorine, bromine, or iodine, or combinations thereof. Further, in structure (4), each p and q is independently 0 or 1, and R 1 is a divalent C 2~8 an aliphatic group, each occurrence of M is independently halogen, cyano, nitro, C 1~8 Alkylthio, C 1~8 Alkyl, C 1~8 Alkoxy, C 2~8 Alkenyl, C 2~8 Alkenyloxy, C 3~8 Cycloalkyl, C 3~8 Cycloalkoxy, C 6~10 Aryl, C 6~10 Aryloxy, C 7~12 Aralkyl, C 7~12 Aralkoxi, C 7~12 Alkylaryl, or C 7~12 alkylaryloxy, where each n is independently 0, 1, 2, 3, or 4. Preferably, in formula 4, E is 5 to 60, and each occurrence of R is independently C 1~6 Alkyl, C 3~6 Cycloalkyl, or C 6~14 aryl, more preferably methyl; p and q are each 1; R 1 is a divalent C 2~8is an aliphatic group, M is a halogen, cyano, C 1~4 Alkyl, C 1~4 Alkoxy, C 6~10 Aryl, C 7~12 Aralkyl, or C 7~12 and alkylaryl, more preferably methyl or methoxy, and each n is independently 0, 1, or 2.

[0038] In some embodiments, L is represented by structure (4a): [ka] (4a) In the formula, the average value of n is 5 to 100, 10 to 80, or 10 to 60.

[0039] In some embodiments, the phenylene ether oligomer comprises a difunctional phenylene ether oligomer having the following structural formula: [ka] In the formula, Q 1 , Q 2 , Q 3 , Q 4 , L, x, and y are as defined above, and R 10 is methyl or hydrogen.

[0040] In the (meth)acrylate terminated phenylene ether structure above, there are limitations on the variables x and y, which correspond to the number of phenylene ether repeat units at two different positions in the bifunctional phenylene ether oligomer. In this structure, x and y are independently from 0 to 30, specifically from 0 to 20, more specifically from 0 to 15, even more specifically from 0 to 10, and even more specifically from 0 to 8. The sum of x and y is at least 2, specifically at least 3, and more specifically at least 4. The phenylene ether oligomers can be characterized by proton nuclear magnetic resonance spectroscopy: 1Analysis by 1 H NMR can determine whether the average falls within this range. 1 H NMR can distinguish between internal and terminal phenylene ether groups, internal and terminal residues of polyhydric phenols, as well as terminal residue protons, allowing one to determine the average number of phenylene ether repeat units per molecule and the relative abundance of internal and terminal residues derived from dihydric phenols.

[0041] In some embodiments, the phenylene ether oligomer comprises a difunctional phenylene ether oligomer having the structure: [ka] where Q for each occurrence 5 and Q 6 each occurrence of a and b is independently 0 to 20 (provided that the sum of a and b is at least 2); 10 is methyl or hydrogen. In some embodiments, the phenylene ether oligomer comprises a difunctional phenylene ether oligomer having the structure: [ka] where Q for each occurrence 5 and Q 6 independently includes methyl, di-n-butylaminomethyl, or morpholinomethyl; and each occurrence of a and b is independently 0 to 20 (with the proviso that the sum of a and b is at least 2).

[0042] The poly(polyphenylene ether) oligomer may further be a block copolymer comprising a poly(phenylene ether) block containing units represented by structural formula (1) above, and an aryloxy-terminated polysiloxane block containing end groups Z, represented by structural formula (2), and repeating siloxane units represented by structural formula (5): [ka] (5) where R for each occurrence 3 is independent, C 1~12 Hydrocarbyl or C 1~12 and the polysiloxane block further comprises a terminal unit represented by structural formula (6): [ka] (6) In the formula, Y is hydrogen, halogen, C 1~12 Hydrocarbyl, or C 1~12 R is hydrocarbyloxy at each occurrence 3 are independently hydrogen, C 1~12 Hydrocarbyl, or C 1~12 Preferably, Y is hydrogen, halogen, C 1~6 Hydrocarbyl, or C 1~6 R is hydrocarbyloxy at each occurrence 3 are independently hydrogen, C 1~6 Hydrocarbyl, or C 1~6 More preferably, Y is hydrogen, methyl, or methoxy, and each R 3 is methyl. In some embodiments, the polysiloxane block is represented by structure (7): [ka] (7) wherein the average value of n is 5 to 80 or 10 to 60. In some embodiments, the block copolymer comprises a poly(2,6-dimethyl-1,4-phenylene ether) block, a poly(2,6-dimethyl-1,4-phenylene ether-co-2,3,6-trimethyl-1,4-phenylene ether) block, or a combination thereof, a polysiloxane block having a structural formula containing an average of 10 to 100 siloxane repeat units of structural formula (7), and a terminal Z group, desirably a (meth)acrylate group, as shown in structural formula (2). Preparation of hydroxyl-terminated block copolymers is described, for example, in U.S. Pat. No. 8,722,837. One or both of the terminal hydroxyl groups can be derivatized to produce the Z group by methods known in the art.

[0043] In some embodiments, the poly(polyphenylene ether) oligomer is essentially free of diphenoquinone residues. In this context, "essentially free" means that less than 1% by weight of the poly(polyphenylene ether) oligomer molecules contain diphenoquinone residues. As described in U.S. Patent No. 3,306,874 to Hay, the synthesis of poly(polyphenylene ether) oligomers by oxidative polymerization of monohydric phenols produces not only the desired poly(polyphenylene ether) oligomers, but also diphenoquinone as a by-product. For example, when the monohydric phenol is 2,6-dimethylphenol, 3,3',5,5'-tetramethyldiphenoquinone is produced. Generally, when the polymerization reaction mixture is heated, the diphenoquinone "reequilibrated" into the poly(polyphenylene ether) oligomer (i.e., the diphenoquinone is incorporated into the poly(polyphenylene ether) oligomer structure), resulting in poly(polyphenylene ether) oligomers containing terminal or internal diphenoquinone residues. For example, when 2,6-dimethylphenol is oxidatively polymerized to prepare poly(polyphenylene ether) oligomers, poly(2,6-dimethyl-1,4-phenylene ether) and 3,3',5,5'-tetramethyldiphenoquinone are produced, and reequilibration of the reaction mixture can produce poly(polyphenylene ether) oligomers incorporating diphenoquinone as terminal and internal residues. However, such reequilibration reduces the molecular weight of the poly(polyphenylene ether) oligomer. Thus, if higher molecular weight poly(polyphenylene ether) oligomers are desired, it may be advantageous to separate the diphenoquinone from the poly(polyphenylene ether) oligomer rather than re-equilibrating the diphenoquinone into the poly(polyphenylene ether) oligomer chain, which may be accomplished, for example, by precipitating the poly(polyphenylene ether) oligomer in a solvent or mixture of solvents in which the poly(polyphenylene ether) oligomer is insoluble but the diphenoquinone is soluble.For example, when preparing poly(polyphenylene ether) oligomers by oxidative polymerization of 2,6-dimethylphenol in toluene to produce a toluene solution containing poly(2,6-dimethyl-1,4-phenylene ether) and 3,3',5,5'-tetramethyldiphenoquinone, one volume of the toluene solution can be combined with 1-4 volumes of methanol or a methanol / water mixture to obtain poly(2,6-dimethyl-1,4-phenylene ether) essentially free of diphenoquinone. Alternatively, the amount of diphenoquinone by-product produced during the oxidative polymerization can be reduced (e.g., by initiating the oxidative polymerization in the presence of less than 10% by weight of monohydric phenol and adding at least 95% by weight of monohydric phenol over a period of at least 50 minutes) and / or the re-equilibration of diphenoquinone into the poly(polyphenylene ether) oligomer chain can be reduced (e.g., by isolating the poly(polyphenylene ether) oligomer within 200 minutes after the oxidative polymerization is completed). These methods are described in WO 2009 / 104107 A1 by Delsman et al.. Another method exploits the temperature dependence of the solubility of diphenoquinone in toluene by adjusting the temperature of a toluene solution containing diphenoquinone and poly(polyphenylene ether) oligomer to 25°C (at which diphenoquinone is poorly soluble but poly(polyphenylene ether) oligomer is highly soluble) and performing a solid-liquid separation (e.g., filtration) to remove the insoluble diphenoquinone.

[0044] The poly(polyphenylene ether) oligomers useful herein are low molecular weight poly(polyphenylene ether) oligomers. The poly(polyphenylene ether) oligomers can have a number average molecular weight of 500-7,000 g / mole and a weight average molecular weight of 500-15,000 g / mole, as measured by gel permeation chromatography using polystyrene standards. In some embodiments, the number average molecular weight can be 750-4,000 g / mole and the weight average molecular weight can be 1,500-9,000 g / mole, as measured by gel permeation chromatography using polystyrene standards.

[0045] In some embodiments, the poly(polyphenylene ether) oligomer has an intrinsic viscosity of 0.03 to 1 dL / g. For example, the poly(polyphenylene ether) oligomer can have an intrinsic viscosity of 0.25 to 1 dL / g, 0.25 to 0.7 dL / g, 0.35 to 0.55 dL / g, or 0.35 to 0.50 dL / g, as measured in chloroform at 25° C. using an Ubbelohde viscometer. In other embodiments, the poly(polyphenylene ether) oligomer can have an intrinsic viscosity of 0.03 to 0.13 dL / g, 0.05 to 0.1 dL / g, or 0.1 to 0.15 dL / g, as measured in chloroform at 25° C. using an Ubbelohde viscometer. The poly(phenylene ether)-polysiloxane block copolymer can have an intrinsic viscosity of at least 0.1 dL / g as measured by Ubbelohde viscometer in chloroform at 25° C. In some embodiments, the intrinsic viscosity is 0.1-0.5 dL / g.

[0046] The oxidative polymerization can be carried out in the presence of an organic solvent. Suitable organic solvents include alcohols, ketones, aliphatic and aromatic hydrocarbons, chlorohydrocarbons, nitrohydrocarbons, ethers, esters, amides, ether-ester mixtures, sulfoxides, and the like, provided that they do not interfere with or participate in the oxidation reaction. High molecular weight poly(phenylene ethers) can significantly increase the viscosity of the reaction mixture. For this reason, it may be desirable to use a solvent system that will allow them to precipitate while allowing the lower molecular weight polymers to remain in solution until they become the higher molecular weight polymers. Organic solvents can include, for example, toluene, benzene, chlorobenzene, o-dichlorobenzene, nitrobenzene, trichloroethylene, dichloroethane, dichloromethane, chloroform, or combinations thereof. Preferred solvents include aromatic hydrocarbons. In some embodiments, the organic solvent includes toluene, benzene, xylene, chloroform, chlorobenzene, or combinations thereof, preferably toluene.

[0047] The oxidative polymerization is further carried out in the presence of a copper-amine catalyst. The copper source of the copper-amine catalyst can include a salt of copper(II) or copper(I) ions (halides, oxides, carbonates, etc.). Alternatively, the copper can be added in the form of a preformed salt of an alkylenediamine ligand. Preferred copper salts include copper(I) halides, copper(II) halides, and combinations thereof. Particularly preferred are copper(I) bromide, copper(II) bromide, and combinations thereof.

[0048] Preferred copper-amine catalysts contain a secondary alkylenediamine ligand. Suitable secondary alkylenediamine ligands are described in U.S. Pat. No. 4,028,341 to Hay and have the following structure: R b -NH-R a -NH-R c In the formula, R a is a substituted or unsubstituted divalent residue in which two or three aliphatic carbon atoms form the nearest bond between the two diamine nitrogen atoms; R b and R c each independently represents isopropyl, or a substituted or unsubstituted C 4~8 R is a tertiary alkyl group. a Examples of R include ethylene, 1,2-propylene, 1,3-propylene, 1,2-butylene, 1,3-butylene, 2,3-butylene, the various pentylene isomers (having from two to three carbon atoms separating the two free valances), phenylethylene, tolylethylene, 2-phenyl-1,2-propylene, cyclohexylethylene, 1,2-cyclohexylene, 1,3-cyclohexylene, 1,2-cyclopropylene, 1,2-cyclobutylene, 1,2-cyclopentylene, and the like. Preferably, R a is ethylene. b and R cExamples of R include isopropyl, t-butyl, 2-methylbutan-2-yl, 2-methylpentan-2-yl, 3-methylpentan-3-yl, 2,3-dimethylbutan-2-yl, 2,3-dimethylpentan-2-yl, 2,4-dimethylpentan-2-yl, 1-methylcyclopentyl, and 1-methylcyclohexyl. Particularly preferred R b and R c An example of a secondary alkylenediamine ligand is t-butyl. An example of a secondary alkylenediamine ligand is N,N'-di-t-butylethylenediamine (DBEDA). Suitable molar ratios of copper to secondary alkylenediamine are 1:1 to 1:5, preferably 1:1 to 1:3, more preferably 1:1.5 to 1:2.

[0049] Preferred copper-amine catalysts containing a secondary alkylenediamine ligand may further contain a secondary monoamine. Suitable secondary monoamine ligands are described in commonly assigned U.S. Patent No. 4,092,294 to Bennett et al. and have the following structure: R d -NH-R e In the formula, R d and R e each independently represents a substituted or unsubstituted C 1~12 Alkyl group, preferably substituted or unsubstituted C 3~6 The secondary monoamine is an alkyl group. Examples of the secondary monoamine include di-n-propylamine, diisopropylamine, di-n-butylamine, di-sec-butylamine, di-t-butylamine, N-isopropyl-t-butylamine, N-sec-butyl-t-butylamine, di-n-pentylamine, bis(1,1-dimethylpropyl)amine, etc. A particularly preferred secondary monoamine is di-n-butylamine (DBA). The suitable molar ratio of copper to secondary monoamine is 1:1 to 1:10, preferably 1:3 to 1:8, more preferably 1:4 to 1:7.

[0050] Preferred copper-amine catalysts containing secondary alkylenediamine ligands may further contain a tertiary monoamine. Suitable tertiary monoamine ligands are described in the aforementioned U.S. Pat. No. 4,028,341 to Hay and U.S. Pat. No. 4,092,294 to Bennett, and include heterocyclic amines and certain trialkylamines, characterized in that they have an amine nitrogen bound to at least two groups with low cross-sectional area. In the case of trialkylamines, at least two of the alkyl groups are methyl and the third is a primary C 1~8 Alkyl group or secondary C 3~8 Preferably, the third substituent is an alkyl group. Particularly preferred are those having 4 or fewer carbon atoms. A highly preferred tertiary amine is dimethylbutylamine (DMBA). Suitable molar ratios of copper to tertiary amine are less than 1:20, preferably less than 1:15, preferably from 1:1 to less than 1:15, more preferably from 1:1 to 1:12.

[0051] Suitable molar ratios of copper-amine catalyst (measured in moles of metal) to poly(phenylene ether) oligomer starting material are from 1:50 to 1:400, preferably from 1:100 to 1:200, and more preferably from 1:100 to 1:180.

[0052] The reaction carried out in the presence of a copper-amine catalyst can, if desired, be carried out in the presence of bromide ions. It has already been mentioned that bromide ions can be provided as copper(I) bromide or copper(II) bromide salts. Bromide ions can also be provided by the addition of 4-bromophenols (such as 2,6-dimethyl-4-bromophenol). Additional bromide ions can be provided in the form of hydrobromic acid, alkali metal bromides, or alkaline earth metal bromides. Sodium bromide and hydrobromic acid are highly preferred sources of bromide. A suitable ratio of bromide ions to copper ions is 2 to 20, preferably 3 to 20, more preferably 4 to 7.

[0053] In one embodiment, each of the above components of the copper-amine catalyst are added simultaneously to the oxidative polymerization reaction.

[0054] The oxidative polymerization can be carried out, if desired, in the presence of one or more additional components, such as a lower alkanol or glycol, a small amount of water, a phase transfer agent, etc. Usually, it is not necessary to remove water, which is a reaction by-product, during the reaction.

[0055] In some embodiments, a phase transfer agent is present. Suitable phase transfer agents can include, for example, quaternary ammonium compounds, quaternary phosphonium compounds, tertiary sulfonium compounds, or combinations thereof. Desirably, the phase transfer agent has the structural formula (R 3 ) 4 Q + X (wherein each R 3 are the same or different, C 1~10 alkyl, Q is a nitrogen or phosphorus atom, X is a halogen atom, C 1~8 Alkoxy, or C 6~18 An example of a phase transfer catalyst is (CH 3 (CH 2 ) 3 ) 4 NX, (CH 3 (CH 2 ) 3 ) 4 PX, (CH 3 (CH 2 ) 5 ) 4 NX, (CH 3 (CH 2 ) 6 ) 4 NX, (CH 3 (CH 2 ) 4 ) 4 NX, CH 3 (CH 3 (CH 2 ) 3 ) 3 NX, and CH 3 (CH 3 (CH 2 ) 2 ) 3 NX (wherein X is Cl - , Br - , C 1~8Alkoxy, or C 6~18 aryloxy). An effective amount of the phase transfer agent can be 0.1 to 10% by weight or 0.5 to 2% by weight based on the weight of the reaction mixture. In some embodiments, the phase transfer agent is present and comprises N,N,N',N'-didecyldimethylammonium chloride.

[0056] The oxidative polymerization can be carried out at a temperature of from 20 to 70° C., preferably from 30 to 60° C., more preferably from 45 to 55° C. Depending on the exact reaction conditions selected, the total polymerization reaction time, i.e., the time elapsed from the start of the oxidative polymerization to the end of the oxidative polymerization, may vary, but is generally from 100 to 250 minutes, more particularly from 145 to 210 minutes.

[0057] The method further includes terminating the oxidative polymerization to produce a post-termination reaction mixture. The reaction is terminated by stopping the flow of oxygen to the reactor. Residual oxygen in the headspace of the reactor is removed by flowing in an oxygen-free gas, such as nitrogen.

[0058] After the polymerization reaction is complete, the copper ions of the polymerization catalyst are separated from the reaction mixture. This is done by adding a chelating agent to the reaction mixture after the reaction is complete to form a chelated mixture. The chelating agent comprises an alkali metal salt of an aminopolycarboxylic acid, preferably an alkali metal salt of aminoacetic acid, more preferably an alkali metal salt of nitrilotriacetic acid, an alkali metal salt of ethylenediaminetetraacetic acid, or a combination thereof, and even more preferably a sodium salt of nitrilotriacetic acid, a sodium salt of ethylenediaminetetraacetic acid, or a combination thereof. In one embodiment, the chelating agent comprises an alkali metal salt of nitrilotriacetic acid. In one embodiment, the chelating agent is a sodium or potassium salt of nitrilotriacetic acid, specifically trisodium nitrilotriacetate. After stirring the chelated mixture, the mixture comprises an aqueous phase containing chelated copper ions and an organic phase containing dissolved poly(phenylene ether). Chelating mixtures containing sulfur dioxide, sulfurous acid, sodium bisulfite, sodium dithionite, tin(II) chloride, iron(II) sulfate, chromium(II) sulfate, titanium(III) chloride, hydroxylamine and its salts, phosphates, glucose, and mixtures thereof can be made excluding dihydric phenols (required by Cooper et al., U.S. Pat. No. 4,110,311), excluding aromatic amines (required by Cooper et al., U.S. Pat. No. 4,116,939), and excluding mild reducing agents (Cooper et al., U.S. Pat. No. 4,110,311). The chelation mixture is maintained at a temperature of 40 to 55° C., more particularly 45 to 50° C., for a period of 5 to 100 minutes, more particularly 10 to 60 minutes, and even more particularly 15 to 30 minutes. This temperature and time combination is effective for copper sequestering while also limiting degradation of the molecular weight of the poly(phenylene ether). The chelation step includes (and ends with) separation of the aqueous and organic phases of the chelation mixture. This separation step is carried out at a temperature of 40 to 55° C., more particularly 45 to 50° C. The time from the initial mixing of the chelating agent with the post-reaction mixture to complete separation of the aqueous and organic phases takes 5 to 100 minutes while the chelation mixture is maintained at 40-55° C.

[0059] Curable thermosetting compositions comprising the copolymers are also provided. For example, the copolymers can be present in the curable thermosetting compositions in an amount of 1 to 95 wt%, 5 to 95 wt%, 10 to 85 wt%, 20 to 80 wt%, 30 to 70 wt%, 5 to 30 wt%, or 5 to 15 wt%, based on the total weight of the curable thermosetting composition.

[0060] The curable thermosetting composition can further include one or more of a crosslinking agent, a curing agent, a curing catalyst, a curing initiator, or a combination thereof. In some embodiments, the curable thermosetting composition can further include one or more of a flame retardant, a filler, a coupling agent, or a combination thereof. For example, the curable thermosetting composition can include one or more of a crosslinking agent, a curing agent, a curing catalyst, a curing initiator, or a combination thereof, and can further include one or more of a flame retardant, a filler, a coupling agent, or a combination thereof.

[0061] There is considerable overlap between thermosetting resins, crosslinkers, and coupling agents. As used herein, the term "crosslinking agent" includes compounds that can be used as thermosetting resins, crosslinkers, coupling agents, or combinations thereof. For example, in some instances, compounds that are thermosetting resins could also be used as crosslinkers, coupling agents, or both.

[0062] The thermosetting resin is not particularly limited, and the thermosetting resin can be used alone or in combination of two or more thermosetting resins (e.g., including one or more auxiliary thermosetting resins). Examples of the thermosetting resin include epoxy resins, cyanate ester resins, (bis)maleimide resins, (poly)benzoxazine resins, vinyl resins (e.g., vinylbenzyl ether resins), phenolic resins, alkyd resins, unsaturated polyester resins, arylcyclobutene resins, perfluorovinyl ether resins, monomers, oligomers, or polymers having a curable unsaturated group (e.g., a vinyl functional group), or combinations thereof.

[0063] The epoxy resin may generally be any epoxy resin suitable for use in thermosetting resins. In this context, the term "epoxy resin" refers to a curable composition of compounds containing an oxirane ring, such as those described in CA May, Epoxy Resins, 2nd Edition, (New York & Basle: Marcel Dekker Inc.), 1988. Epoxy resins include bisphenol A type epoxy resins (those obtained from bisphenol A, and resins obtained by substituting at least one of the 2-, 3-, and 5-positions of bisphenol A with a halogen atom, an alkyl group containing 6 or less carbon atoms, or a phenyl group); bisphenol F type epoxy resins (those obtained from bisphenol F, and resins obtained by substituting at least one of the 2-, 3-, and 5-positions of bisphenol F with a halogen atom, an alkyl group containing 6 or less carbon atoms, or a phenyl group); glycidyl ether compounds (divalent, trivalent, or higher phenols (hydroquinone, resorcinol, tris(4-hydroxyphenyl)methane, etc.); , 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane, etc.); novolac epoxy resins (derived from novolac resins, which are reaction products of phenols (phenol, o-cresol, etc.) with formaldehyde) (bisphenol A novolac epoxy resins, cresol novolac epoxy resins, etc.); cyclic aliphatic epoxy compounds (2,2-bis(3,4-epoxycyclohexyl)propane, 2,2-bis[4-(2,3-epoxypropyl)cyclohexyl]propane, vinylcyclohexene dioxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, etc.); polyepoxides containing dicyclopentadiene;Amine type epoxy resin (aniline, p-aminophenol, m-aminophenol, 4-amino-m-cresol, 6-amino-m-cresol, 4,4'-diaminodiphenylethane, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylether, 3,4'-diaminodiphenylether, 1,4-bis(4-aminophenoxy)benzene, 1,4-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 2,2-bis(4-aminophenoxyphenyl)propane, p-phenylenediamine, m-phenylenediamine Examples of epoxy resins include those derived from diamine, 2,4-toluenediamine, 2,6-toluenediamine, p-xylylenediamine, m-xylylenediamine, 1,4-cyclohexanebis(methylamine), 5-amino-1-(4'-aminophenyl)-1,3,3-trimethylindane, 6-amino-1-(4'-aminophenyl)-1,3,3-trimethylindane, etc.; heterocyclic epoxy compounds, and glycidyl ester type epoxy compounds (e.g., those derived from glycidyl esters of aromatic carboxylic acids (p-oxybenzoic acid, m-oxybenzoic acid, terephthalic acid, isophthalic acid, etc.). "Epoxy resin" can also include reaction products of compounds containing two or more epoxy groups with aromatic dihydroxy compounds, which may be substituted with halogens as necessary, and may be used alone or in combination of two or more.;

[0064] The cyanate ester is not limited, and any resin consisting of a cyanate ester monomer that can be polymerized to produce a polymer containing multiple cyanate ester (-OCN) functional groups can be used. Cyanate ester monomers, prepolymers (i.e., partially polymerized cyanate ester monomers, or mixtures of cyanate ester monomers), homopolymers, copolymers made using cyanate ester precursors, and combinations of these compounds can be used. For example, cyanate esters can be prepared according to the methods disclosed in "Chemistry and Technology of Cyanate Ester Resins", by Ian Hamerton, Blackie Academic and Professional; U.S. Pat. No. 3,553,244; and JP-A-7-53497. Examples of cyanate ester resins include those prepared from 2,2-bis(4-cyanatophenyl)propane, bis(4-cyanatophenyl)ethane, bis(3,5-dimethyl-4-cyanatophenyl)methane, 2,2-bis(4-cyanatophenyl)-1,1,1,3,3,3-hexafluoropropane, α,α'-bis(4-cyanatophenyl)-m-diisopropylbenzene, dicyclopentadiene-phenol copolymers, and prepolymers prepared from these monomers. An example of a prepolymer is PRIMASET BA-230S (Lonza). The cyanate ester prepolymers may be homopolymers or may be copolymers incorporating other monomers. Examples of such copolymers include BT resins (BT 2160, BT 2170, etc.) available from Mitsubishi Gas Chemical Co., Ltd., which are prepolymers made from cyanate ester monomers and bismaleimide monomers. Other cyanate ester polymers, monomers, prepolymers, and mixtures of cyanate ester monomers with other monomers that are not cyanate esters are disclosed in U.S. Patent Nos. 7,393,904, 7,388,057, 7,276,563, and 7,192,651.

[0065] Bismaleimide resins can be prepared by reaction of a monomeric bismaleimide with a nucleophile (such as a diamine, aminophenol, aminobenzhydrazide, etc.) or by reaction of a bismaleimide with diallyl bisphenol A. Exemplary bismaleimide resins include 1,2-bismaleimidoethane, 1,6-bismaleimidohexane, 1,3-bismaleimidobenzene, 1,4-bismaleimidobenzene, 2,4-bismaleimidotoluene, 4,4'-bismaleimidodiphenylmethane, 4,4'-bismaleimidodiphenylether, 3,3'-bismaleimidodiphenylsulfone, 4,4'-bismaleimidodiphenylsulfone, 4,4'-bismaleimidodicyclohexylmethane, 3,5-bis(4-maleimidophenyl)benzene, 4,4'-bismaleimidodiphenylmethane ... N,N'-bis(4-maleimidophenyl)toluene, 3,4'-bis(4-maleimidophenyl)propane, 1,1-bis(4-maleimidophenyl)ethane, 1,3-bis(dichloromaleimido)benzene, 4,4'-bis(citraconimido)diphenylmethane, 2,2-bis(4-maleimidophenyl)propane, 1-phenyl-1,1-bis(4-maleimidophenyl)ethane, N,N'-bis(4-maleimidophenyl)toluene, 3,4'-bis(4-maleimidophenyl)cyclohexane, 1,3-bis(dichloromaleimido)benzene, 4,4'-bis(citraconimido)diphenylmethane, 2,2-bis(4-maleimidophenyl)propane, 1-phenyl-1,1-bis(4-maleimidophenyl)ethane, 3,4 ... ,5-Bismaleimide-1,2,4-triazole, N,N'-ethylene bismaleimide, N,N'-hexamethylene bismaleimide, N,N'-m-phenylene bismaleimide, N,N'-p-phenylene bismaleimide, N,N'-4,4'-diphenylmethane bismaleimide, N,N'-4,4'-diphenylether bismaleimide, N,N'-4,4'-diphenylsulfone bismaleimide, N,N'-4,4'-dicyclohexylmethane bismaleimide, N,N'-α,α'-4,4 Nos. 3,562,223, 4,211,860, and 4,211,861, or prepared by the method described, for example, in U.S. Pat. No. 3,018,290.

[0066] Benzoxazine compounds have a benzoxazine ring in the molecule. Representative benzoxazine monomers can be prepared from the reaction of aldehydes, phenols, and primary amines with or without solvent. Phenolic compounds for producing benzoxazines include phenols and polyphenols. The use of polyphenols with two or more hydroxyl groups reacting in the production of benzoxazines can result in branched products, crosslinked products, or combinations of branched and crosslinked products. The groups connecting the phenolic groups to the phenols can be branch points or linking groups in polybenzoxazines.

[0067] Examples of phenols used in the preparation of benzoxazine monomers include phenol, cresol, resorcinol, catechol, hydroquinone, 2-allylphenol, 3-allylphenol, 4-allylphenol, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2-(diphenylphosphoryl)hydroquinone, 2,2'-biphenol, 4,4'-biphenol, 4,4'-isopropylidenediphenol, 4,4'-isopropylidenebis(2-methylphenol), 4,4'-isopropylidenebis(2-allylphenol), 4,4'-(1,3-phenylenediisopropylidene)bisphenol (bisphenol M), 4,4'-isopropylidenebis(3-phenylenediisopropylidene)bisphenol, and 4,4'-isopropylidenebis(1,3-phenylenediisopropylidene)bisphenol (bisphenol M). phenylphenol), 4,4'-(1,4-phenylenediisopropylidene)bisphenol, 4,4'-ethylidene diphenol, 4,4'-oxydiphenol, 4,4'-thiodiphenol, 4,4'-sulfonyldiphenol, 4,4'-sulfinyldiphenol, 4,4'-(hexafluoroisopropylidene)bisphenol, 4,4'-(1-phenylethylidene)bisphenol, bis(4-hydroxyphenyl)-2,2-dichloroethylene, bis(4-hydroxyphenyl)methane, 4,4'-(cyclopentylidene)diphenol, 4,4'-(cyclohexylidene)diphenol, 4,4'-(cyclododecylidene)diphenol, 4,4'-(bicyclo[2.2.1]heptylidene)diphenol, 4,4'-(9H-fluorene-9,9-diyl)diphenol, isopropylidenebis(2-allylphenol), 3,3-bis(4-hydroxyphenyl)isobenzofuran-1(3H)-one, 1-(4-hydroxyphenyl)-3,3-dimethyl-2,3-dihydro-1H-inden-5-ol, 3,3,3',3'-tetramethyl-2,2',3,3'-tetrahydro-1,1'-spirobi[indene]-5,6'-diol, dihydro Examples of benzophenone include tris(4-hydroxyphenyl)methane, tris(4-hydroxyphenyl)ethane, tris(4-hydroxyphenyl)propane, tris(4-hydroxyphenyl)butane, tris(3-methyl-4-hydroxyphenyl)methane, tetrakis(4-hydroxyphenyl)ethane, dicyclopentadienylbis(2,6-dimethylphenol), dicyclopentadienylbis(o-cresol), and dicyclopentadienylbisphenol.

[0068] The aldehyde used to form the benzoxazine can be any aldehyde, including aldehydes containing 1 to 10 carbon atoms. For example, the aldehyde can be formaldehyde. The amine used to form the benzoxazine can be an aromatic amine, an aliphatic amine, an alkyl-substituted aromatic amine, or an aromatic-substituted alkyl amine. The amine can be a polyamine, for example, to prepare a multifunctional benzoxazine monomer for crosslinking.

[0069] The amines for producing the benzoxazines contain from 1 to 40 carbon atoms, except when they contain an aromatic ring, which can then contain from 6 to 40 carbon atoms. Difunctional or polyfunctional amines can be branch points linking one polybenzoxazine with another.

[0070] In some embodiments, thermal polymerization at 150 to 300° C. can be used to polymerize the benzoxazine monomers. Polymerization can be carried out in bulk, in solution, or by other methods. Catalysts (such as carboxylic acids) can be used to lower the polymerization temperature or to increase the rate of polymerization at the same temperature.

[0071] Vinylbenzyl ether resins can be prepared by condensation of phenol with vinylbenzyl halides, such as vinylbenzyl chloride. Bisphenol A, trisphenols, and polyphenols are commonly used to produce poly(vinylbenzyl ethers), which can be used to make crosslinked thermosets. Examples of vinylbenzyl ethers include vinylbenzyl halides and resorcinol, catechol, hydroquinone, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2-(diphenylphosphoryl)hydroquinone, bis(2,6-dimethylphenol), 2,2'-biphenol, 4,4'-biphenol, 2,2',6,6'-tetramethylbiphenol, 2,2',3,3',6,6'-hexamethylbiphenol, 3,3',5,5'-tetramethylbiphenol, 4,4'-diphenyldiphenylphosphine, 5,5'-tetramethylbiphenol, 5,5 ... bromo-2,2',6,6'-tetramethylbiphenol, 3,3'-dibromo-2,2',6,6'-tetramethylbiphenol, 2,2',6,6'-tetramethyl-3,3',5-dibromobiphenol, 4,4'-isopropylidenediphenol, 4,4'-isopropylidenebis(2,6-dibromophenol), 4,4'-isopropylidenebis(2,6-dimethylphenol) (tetra(tera)methylbisphenol A), 4,4'-isopropylidenebis( 2-Methylphenol), 4,4'-isopropylidenebis(2-allylphenol), 4,4'-(1,3-phenylenediisopropylidene)bisphenol, 4,4'-isopropylidenebis(3-phenylphenol), 4,4'-(1,4-phenylenediisopropylidene)bisphenol, 4,4'-ethylidene diphenol, 4,4'-oxydiphenol, 4,4'-thiodiphenol, 4,4'-thiobis(2,6-dimethylphenol), 4,4'-sulfur phenyldiphenol, 4,4'-sulfonylbis(2,6-dimethylphenol), 4,4'-sulfinyldiphenol, 4,4'-(hexafluoroisopropylidene)bisphenol, 4,4'-(1-phenylethylidene)bisphenol, bis(4-hydroxyphenyl)-2,2-dichloroethylene, bis(4-hydroxyphenyl)methane, bis(2,6-dimethyl-4-hydroxyphenyl)methane, 4,4'-(cyclopentylidene)diphenol, 4,4'-(cyclohexylidene)diphenol, 4,4'-(cyclododecylidene)diphenol, 4,4'-(bicyclo[2.2.1]heptylidene)diphenol, 4,4'-(9H-fluorene-9,9-diyl)diphenol, 3,3-bis(4-hydroxyphenyl)isobenzofuran-1(3H)-one, 1-(4-hydroxyphenyl)-3,3-dimethyl-2,3-dihydro-1H-inden-5-ol, 1-(4-hydroxy-3,5-dimethylphenyl)-1,3,3,4,6-pentamethyl-2,3-dihydro-1H-inden-5-ol, 3,3,3',3'-tetramethyl-2,2',3,3'-tetrahydro-1,1'-spirobi[indene]-5,6'-diol, Examples of vinyl benzyl ethers include those produced by reaction with dihydroxybenzophenone, tris(4-hydroxyphenyl)methane, tris(4-hydroxyphenyl)ethane, tris(4-hydroxyphenyl)propane, tris(4-hydroxyphenyl)butane, tris(3-methyl-4-hydroxyphenyl)methane, tris(3,5-dimethyl-4-hydroxyphenyl)methane, tetrakis(4-hydroxyphenyl)ethane, tetrakis(3,5-dimethyl-4-hydroxyphenyl)ethane, bis(4-hydroxyphenyl)phenylphosphine oxide, dicyclopentadienylbis(2,6-dimethylphenol), dicyclopentadienylbisphenol, and the like.

[0072] Arylcyclobutenes include those derived from compounds represented by the following structural formula: [ka] In the formula, B is an organic or inorganic radical of valence n (carbonyl, sulfonyl, sulfinyl, sulfide, oxy, alkyl phosphonyl, aryl phosphonyl, isoalkylidene, cycloalkylidene, aryl alkylidene, diaryl methylidene, methylidene, dialkyl silanyl, aryl alkyl silanyl, diaryl silanyl, C 6~20phenolic compounds), and X at each occurrence is independently hydroxy or C 1~24 Hydrocarbyl (linear and branched alkyl, cycloalkyl, etc.), where Z at each occurrence is independently hydrogen, halogen, or C 1~12 hydrocarbyl, where n is 1 to 1000, or 1 to 8, or n is 2, 3, or 4. Other examples of arylcyclobutenes and methods of synthesizing arylcyclobutenes can be found in U.S. Pat. No. 4,743,399, U.S. Pat. No. 4,540,763, U.S. Pat. No. 4,642,329, U.S. Pat. No. 4,661,193, U.S. Pat. No. 4,724,260, and U.S. Pat. No. 5,391,650.

[0073] Perfluorovinyl ethers are typically synthesized from phenols and bromotetrafluoroethane by zinc-catalyzed reductive elimination to produce ZnFBr and the desired perfluorovinyl ether. This reaction pathway can produce bis-, tris-, and poly(perfluorovinyl ethers) from bis-, tris-, and other polyphenols. Phenols useful in these syntheses include resorcinol, catechol, hydroquinone, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2-(diphenylphosphoryl)hydroquinone, bis(2,6-dimethylphenol), 2,2'-biphenol, 4,4'-biphenol, 2,2',6,6'-tetramethylbiphenol, 2,2',3,3',6,6'-hexamethylbiphenol, 3,3',5,5'-tetrabromo-2,2',4,5'-tetramethyl-2,2',5,5'-tetramethyl-2,2',6,6'-tetramethyl-2,2',3,3',6,6'-hexamethyl-2,2',5,5'-tetramethyl-2,2',6 ... ',6,6'-Tetramethylbiphenol, 3,3'-dibromo-2,2',6,6'-tetramethylbiphenol, 2,2',6,6'-tetramethyl-3,3',5-dibromobiphenol, 4,4'-isopropylidenediphenol (bisphenol A), 4,4'-isopropylidenebis(2,6-dibromophenol), 4,4'-isopropylidenebis(2,6-dimethylphenol), 4,4'-isopropylidenebis(2-methylphenol) , 4,4'-isopropylidenebis(2-allylphenol), 4,4'-(1,3-phenylenediisopropylidene)bisphenol, 4,4'-isopropylidenebis(3-phenylphenol), 4,4'-(1,4-phenylenediisopropylidene)bisphenol, 4,4'-ethylidene diphenol, 4,4'-oxydiphenol, 4,4'-thiodiphenol, 4,4'-thiobis(2,6-dimethylphenol), 4,4'-sulfonyldiphenol phenol, 4,4'-sulfonylbis(2,6-dimethylphenol), 4,4'-sulfinyldiphenol, 4,4'-(hexafluoroisopropylidene)bisphenol, 4,4'-(1-phenylethylidene)bisphenol, bis(4-hydroxyphenyl)-2,2-dichloroethylene, bis(4-hydroxyphenyl)methane, bis(2,6-dimethyl-4-hydroxyphenyl)methane, 4,4'-(cyclopentylidene)diphenol, 4,4'-(Cyclohexylidene)diphenol, 4,4'-(Cyclododecylidene)diphenol, 4,4'-(Bicyclo[2.2.1]heptylidene)diphenol, 4,4'-(9H-fluorene-9,9-diyl)diphenol, 3,3-bis(4-hydroxyphenyl)isobenzofuran-1(3H)-one, 1-(4-hydroxyphenyl)-3,3-dimethyl-2,3-dihydro-1H-inden-5-ol, 1-(4-hydroxy-3,5-dimethylphenyl)-1,3,3,4,6-pentamethyl-2,3-dihydro-1H-inden-5-ol, 3,3,3',3'-tetramethyl-2,2',3,3'-tetrahydro-1,1'-spirobi[indene]-5,6'-diol (spirobi indane), dihydroxybenzophenone, tris(4-hydroxyphenyl)methane, tris(4-hydroxyphenyl)ethane, tris(4-hydroxyphenyl)propane, tris(4-hydroxyphenyl)butane, tris(3-methyl-4-hydroxyphenyl)methane, tris(3,5-dimethyl-4-hydroxyphenyl)methane, tetrakis(4-hydroxyphenyl)ethane, tetrakis(3,5-dimethyl-4-hydroxyphenyl)ethane, bis(4-hydroxyphenyl)phenylphosphine oxide, dicyclopentadienyl bis(2,6-dimethylphenol), dicyclopentadienyl bis(2-methylphenol), dicyclopentadienyl bisphenol, etc.

[0074] The crosslinking agent (including the auxiliary crosslinking agent) is not particularly limited. A single crosslinking agent may be used, or two or more different crosslinking agents may be used in combination. Examples of crosslinking agents and auxiliary crosslinking agents include oligomers or polymers with curable vinyl functional groups. Such materials include oligomers and polymers with crosslinkable unsaturated moieties. Examples of such elastomers include styrene butadiene rubber (SBR), butadiene rubber (BR), and nitrile-butadiene rubber (NBR), which have unsaturated bonds derived from butadiene; natural rubber (NR), isoprene rubber (IR), chloroprene rubber (CR), butyl rubber (IIR), and halogenated butyl rubber, which have unsaturated bonds derived from isoprene; and ethylene-α-olefin copolymer elastomers having unsaturated bonds derived from dicyclopentadiene (DCPD), ethylidene norbornene (ENB), or 1,4-dihexadiene (1,4-HD) (e.g., ethylene-α-olefin copolymers obtained by copolymerization of ethylene, α-olefins, and dienes, such as ethylene-propylene-diene terpolymer (EPDM), ethylene-butene-diene terpolymer (EBDM), etc.). Examples also include hydrogenated nitrile rubber, fluorocarbon rubber (vinylidene fluoride-hexafluoropropene copolymer, vinylidene fluoride-pentafluoropropene copolymer, etc.), epichlorohydrin homopolymer (CO), copolymer rubber prepared from epichlorohydrin and ethylene oxide (ECO), epichlorohydrin-allyl glycidyl copolymer, propylene oxide-allyl glycidyl ether copolymer, propylene oxide-epichlorohydrin-allyl glycidyl ether terpolymer, acrylic rubber (ACM), urethane rubber (U), silicone rubber (Q), chlorosulfonated polyethylene rubber (CSM), polysulfide rubber (T), and ethylene-acrylic rubber. Further examples include various liquid rubbers, such as some types of liquid butadiene rubber, liquid atactic butadiene rubber (i.e., butadiene polymers with 1,2-vinyl bonds prepared by anionic living polymerization).Liquid styrene butadiene rubber, liquid nitrile-butadiene rubber (such as CTBN, VTBN, and ATBN available from Ube Industries, Ltd.), liquid chloroprene rubber, liquid polyisoprene, dicyclopentadiene-type hydrocarbon polymers, and polynorbornene (such as those available from Elf Atochem) may also be used.

[0075] Polybutadiene resins with a high percentage of 1,2-addition are desirable for the thermosetting matrix, examples of which include functionalized polybutadiene and poly(butadiene-styrene) random copolymers (available from Ricon Resins, Inc. under the trade names RICON, RICACRYL, and RICOBOND resins). These include low vinyl content polybutadienes (RICON 130, 131, 134, 142, etc.), high vinyl content polybutadienes (RICON 150, 152, 153, 154, 156, 157, P30D, etc.), random copolymers of styrene and butadiene (RICON 100, 181, 184, etc.), and maleic anhydride grafted polybutadienes and alcohol condensates derived therefrom (RICON 130MA8, RICON MA13, RICON 130MA20, RICON 131MAS, RICON 131MA10, RICON MA17, RICON MA20, RICON 184MA6, RICON 156MA17, etc.). Further included are polybutadienes used to improve adhesion (RICOBOND 1031, RICOBOND 1731, RICOBOND 2031, RICACRYL 3500, RICOBOND 1756, RICACRYL 3500); polybutadienes RICON 104 (25% polybutadiene / heptane), RICON 257 (35% polybutadiene / styrene), and RICON 257 (35% polybutadiene / styrene); (meth)acrylic-functionalized polybutadienes (polybutadiene diacrylate, polybutadiene dimethacrylate, etc.). These materials are commercially available under the trade names RICACRYL 3100, RICACRYL 3500, and RICACRYL 3801. Also included are powder dispersions of functionalized polybutadiene derivatives, such as RICON 150D, 152D, 153D, 154D, P30D, RICOBOND 0 1731 HS, and RICOBOND 1756HS.Still other butadiene resins include poly(butadiene-isoprene) block and random copolymers, such as those having a molecular weight of 3,000 to 50,000 g / mol, polybutadiene homopolymers, such as those having a molecular weight of 3,000 to 50,000 g / mol, and polybutadiene, polyisoprene, and polybutadiene-isoprene copolymers functionalized with maleic anhydride, 2-hydroxyethyl maleic acid, or hydroxylated functional groups.

[0076] Further examples of curable vinyl-functional oligomers and polymers include unsaturated polyester resins based on maleic anhydride, fumaric acid, itaconic acid, and citraconic acid, unsaturated epoxy (meth)acrylate resins containing acryloyl or methacryloyl groups, unsaturated epoxy resins containing vinyl or allyl groups, urethane (meth)acrylate resins, polyether (meth)acrylate resins, polyalcohol (meth)acrylate resins, alkyd acrylate resins, polyester acrylate resins, spiroacetal acrylate resins, diallyl phthalate resins, diallyl tetrabromophthalate resins, diethylene glycol bisallyl carbonate resins, and polyethylene polythiol resins. For example, crosslinking agents. Further examples of crosslinking agents include multifunctional crosslinking monomers, such as (meth)acrylate monomers having two or more (meth)acrylate moieties per monomer molecule. Examples of polyfunctional monomers include di(meth)acrylates (1,6-hexanediol di(meth)acrylate, 1,4-cyclohexanediol di(meth)acrylate, tripropylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, neopentyl glycol propoxylate di(meth)acrylate, neopentyl glycol ethoxylate di(meth)acrylate, neopentyl glycol propoxylate di(meth)acrylate, neopentyl glycol ethoxylate di(meth)acrylate, polyethylene glycol di(meth)acrylate, glycerol di(meth)acrylate) etc.); tri(meth)acrylates (trimethylolpropane tri(meth)acrylate, 1,2,4-butanetriol tri(meth)acrylate, trimethylolpropane ethoxylate tri(meth)acrylate, etc.); tri(meth)allyls (tri(meth)allyl cyanurate, tri(meth)allyl isocyanurate, tri(meth)allyl ester of citric acid, tri(meth)allyl ester of phosphoric acid, pentaerythritol tri(meth)acrylate, tris(hydroxyethyl)isocyanurate tri(meth)acrylate, etc.); tetra(meth)acrylates (pentaerythritol tetra(meth)acrylate, etc.);Penta(meth)acrylates (dipentaerythritol penta(meth)acrylate, etc.); hexa(meth)acrylates (dipentaerythritol hexa(meth)acrylate, sorbitol hexa(meth)acrylate, etc.); glycidyl compounds (glycidyl (meth)acrylate, (meth)allyl glycidyl ether, 1-chloro-2,3-epoxypropyl (meth)acrylate, 2-bromo-3,4-epoxybutyl (meth)acrylate, 2-(epoxyethyloxy)ethyl (meth)acrylate, 2-(3,4-epoxybutyloxy)ethyl (meth)acrylate, etc.); polythiol compounds (trimethylolpropane tris(mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate), etc.); silanes (tetramethoxysilane, tetraethoxy Silane, tetrapropoxysilane, tetra-n-butoxysilane, vinyltris(methylethyloxyimino)silane, vinyltris(acetoxime)silane, methyltris(methylethyloxyimino)silane, methyltris(acetoxime)silane, vinyltrimethoxysilane, methyltrimethoxysilane, vinyltris(isopropenoxy)silane, tetraacetoxysilane, methyltriacetoxysilane, ethyltriacetoxysilane, vinyltriacetoxysilane, di-t-butoxydiacetoxysilane, methyltris(ethyllacto)silane, vinyltris(ethyllacto)silane, etc.; carbodiimides (N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide hydrochloride, dicyclohexylcarbodiimide, etc.); or combinations thereof. The curable thermosetting composition may optionally include a crosslinking catalyst (such as a carboxylate).;

[0077] When the curable thermosetting composition includes a crosslinking agent, the content of the crosslinking agent can be from 1 to 60% by weight, from 5 to 45% by weight, or from 10 to 30% by weight, based on the total weight of the curable thermosetting composition.

[0078] Curable thermosetting compositions can include one or more curing agents. As used herein, the term "curing agent" includes compounds variously referred to as curing agents, hardeners, or both.

[0079] Examples of the curing agent include amines, alcohols, phenols, carboxylic acids, acid anhydrides, etc. For example, phenol-based curing agents include novolac-type phenolic resins, cresol-type phenolic resins, cresol novolac resins, aralkyl-type phenolic resins, phenol aralkyl resins, cresol aralkyl resins, naphthol aralkyl resins, dicyclopentadiene-type phenolic resins, terpene-modified phenolic resins, biphenyl-type phenolic resins, biphenyl-modified phenol aralkyl resins, bisphenols, triphenylmethane-type phenolic resins, tetraphenylolethane resins, naphthol novolac resins, naphthol-phenol co-condensed novolac resins, naphthol-cresol co-condensed novolac resins, aminotriazine-modified phenolic resins, or combinations thereof. Examples of anhydride curing agents include methylhexahydrophthalic anhydride (MHHPA), methyltetrahydrophthalic anhydride, styrene-maleic anhydride copolymers (SMA), and olefin-maleic anhydride copolymers (such as maleic anhydride grafted polyethylene, maleic anhydride grafted polypropylene, or combinations thereof). Other curing agents include compounds such as dicyandiamide, polyamides, amidoamines, phenalkamines, Mannich bases, anhydrides, phenol-formaldehyde resins, amine-formaldehyde resins, phenol-formaldehyde resins, carboxylic acid functional polyesters, polysulfides, polymercaptans, isocyanates, cyanate ester compounds, or any combinations thereof. Other curing agents include tertiary amines, Lewis acids, and oligomers or polymers with unsaturated groups.

[0080] When the curable thermosetting composition includes a curing agent, the content of the curing agent can be 0.01 to 50% by weight, 0.1 to 30% by weight, or 0.1 to 20% by weight, based on the total weight of the curable thermosetting composition.

[0081] Curable thermosetting compositions can include a curing catalyst. As used herein, the term "curing catalyst" includes compounds variously referred to as curing accelerators, curing promoters, curing catalysts, and curing cocatalysts.

[0082] Examples of cure accelerators include heterocyclic accelerators (substituted or unsubstituted C aryl groups containing 1 to 4 ring heteroatoms, each heteroatom being independently the same or different and being nitrogen, oxygen, phosphorus, silicon, or sulfur). 3~6Examples of heterocyclic promoters include benzotriazoles, triazines, piperazines (aminoethylpiperazine, N-(3-aminopropyl)piperazine, etc.), imidazoles (1-methylimidazole, 2-methylimidazole, 3-methylimidazole, 4-methylimidazole, 5-methylimidazole, 1-ethylimidazole, 2-ethylimidazole, 3-ethylimidazole, 4-ethylimidazole, 5-ethylimidazole, 1-n-propylimidazole, etc.), 2-n-propylimidazole, 1-isopropylimidazole, 2-isopropylimidazole, 1-n-butylimidazole, 2-n-butylimidazole, 1-isobutylimidazole, 2-isobutylimidazole, 2-undecyl-1H-imidazole, 2-heptadecyl-1H-imidazole, 1,2-dimethylimidazole, 1,3-dimethylimidazole, 2,4-dimethylimidazole, 2-ethyl-4-methylimidazole, 1-furan phenylimidazole, 2-phenyl-1H-imidazole, 4-methyl-2-phenyl-1H-imidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 2-phenyl- 4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 1-cyanoethyl-2-phenyl-4,5-di(2-cyanoethoxy)methylimidazole, etc.), cyclic amidines (4-diazabicyclo[2,2,2]octane, diazabicycloundecene, 2-phenylimidazoline, etc.), N,N-dimethylaminopyridine, sulfamidate, or combinations thereof.

[0083] Amine curing accelerators include isophoronediamine, triethylenetetraamine, diethylenetriamine, 1,2- and 1,3-diaminopropane, 2,2-dimethylpropylenediamine, 1,4-diaminobutane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,12-diaminododecane, 4-azaheptamethylenediamine, N,N'-bis(3-aminopropyl)butane-1,4-diamine, dicyanamide, diaminodiphenylmethane ... Phenylsulfonic acid (amine adduct), 4,4'-methylenedianiline, diethyltoluenediamine, m-phenylenediamine, p-phenylenediamine, melamine-formaldehyde resin, urea-formaldehyde resin, tetraethylenepentamine, 3-diethylaminopropylamine, 3,3'-iminobispropylamine, 2,4-bis(p-aminobenzyl)aniline, tetraethylenepentamine, 3-diethylaminopropylamine, 2,2,4- and 2,4,4-trimethylhexamethylenediamine, 1,2- and 1,3-diaminocyclohexyl cyclohexane, 1,4-diamino-3,6-diethylcyclohexane, 1,2-diamino-4-ethylcyclohexane, 1,4-diamino-3,6-diethylcyclohexane, 1-cyclohexyl-3,4-diamino(dimino)cyclohexane, 4,4'-diamino(diaminon)dicyclohexylmethane, 4,4'-diaminodicyclohexylpropane, 2,2-bis(4-aminocyclohexyl)propane, 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane, 3-amino-1-cyclohexaneaminopropane, 1,3- and 1,4-bis(aminomethyl)cyclohexane, m- and p-xylylenediamine, or diethyltoluenediamine; or a tertiary amine cure accelerator, such as triethylamine, tributylamine, dimethylaniline, diethylaniline, benzyldimethylamine (BDMA), α-methylbenzyldimethylamine, N,N-dimethylaminopyridine, N,N-dimethylaminoethanol, N,N-dimethylaminocresol, or tris(N,N-dimethylaminomethyl)phenol; or a combination thereof.

[0084] The cure accelerator may be a latent cationic cure catalyst, such as diaryliodonium salts, phosphonate esters, sulfonate esters, carboxylate esters, phosphonic ylides, triarylsulfonium salts, benzylsulfonium salts, aryldiazonium salts, benzylpyridinium salts, benzylammonium salts, isoxazolium salts, or the like, or combinations thereof. Diaryliodonium salts are represented by the formula [(R 10 )(R 11 )I] + X - (In the formula, R 10 and R 11 are each independently C 6~14 Monovalent aromatic hydrocarbon radicals, optionally 1~20 Alkyl, C 1~20 substituted with one to four monovalent radicals selected from alkoxy, nitro, and chloro; X - The additional accelerator can be represented by the formula [(R 10 )(R 11 )I] + SbF 6 - (In the formula, R 10 and R 11 are each independently C 6~14 Monovalent aromatic hydrocarbons, optionally having 1 to 4 C 1~20 Alkyl, C 1~20 substituted with alkoxy, nitro, or chloro), for example, 4-octyloxyphenylphenyliodonium hexafluoroantimonate.

[0085] The hardening accelerator may be a metal salt complex (such as copper(II), aluminum(III), zinc, cobalt, or tin salts of aliphatic or aromatic carboxylic acids) and may be selected from copper(II), tin(II), and aluminum(III) acetates, stearates, gluconates, citrates, benzoates, and mixtures thereof. For example, the hardening accelerator may be copper(II) or aluminum(III) salts of β-diketonates; copper(II), iron(II), iron(III), cobalt(II), cobalt(III), or aluminum(III) salts of acetylacetonates; zinc(II), chromium(II), or manganese(II) salts of octoates; or combinations thereof.

[0086] When the curable thermosetting composition includes a curing catalyst, the content of the curing catalyst can be 0.01 to 5 wt%, 0.05 to 5 wt%, or 0.1 to 5 wt%, based on the total weight of the curable thermosetting composition.

[0087] The curable thermosetting composition may optionally contain a curing initiator such as a peroxide compound. Examples of peroxide curing initiators include benzoyl peroxide, dicumyl peroxide, methyl ethyl ketone peroxide, lauryl peroxide, cyclohexanone peroxide, t-butyl hydroperoxide, t-butylbenzene hydroperoxide, t-butyl peroctoate, t-butyl peroxybenzoate, t-butylperoxy-2-ethylhexyl carbonate, 2,4-dichlorobenzoyl peroxide, 2,5-dimethylhexane-2,5-dihydroperoxide, butyl-4,4-bis(tert-butyldioxy)valerate, 2,5-dimethyl-2,5-di(t-butylperoxy)hex-3-yne, di-t-butyl peroxide, ... butylcumyl peroxide, α,α'-bis(t-butylperoxy-m-isopropyl)benzene, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, dicumyl peroxide, di(t-butylperoxy)isophthalate, t-butyl peroxybenzoate, 2,2-bis(t-butylperoxy)butane, 2,2-bis(t-butylperoxy)octane, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, 1,1-di(tert-butylperoxy)-3,3,5-trimethylcyclohexane, di(trimethylsilyl)peroxide, trimethylsilylphenyltriphenylsilylperoxide, and the like, or combinations thereof.

[0088] When the curable thermosetting composition includes a curing initiator, the content of the curing initiator can be 0.1 to 5 wt%, 0.5 to 5 wt%, or 1 to 5 wt%, based on the total weight of the curable thermosetting composition.

[0089] Flame retardants include, for example, organic compounds containing phosphorus, bromine, or chlorine. In certain applications, regulations may recommend non-brominated and non-chlorinated phosphorus-containing flame retardants, such as organic phosphates and organic compounds containing phosphorus-nitrogen bonds.

[0090] Examples of phosphorus-containing flame retardants include phosphate esters, phosphazenes, phosphites, phosphines, phosphinates, polyphosphates, and phosphonium salts. Phosphates include triphenyl phosphate, tricresyl phosphate, isopropylated triphenyl phosphate, phenyl bis(dodecyl) phosphate, phenyl bis(neopentyl) phosphate, phenyl bis(3,5,5'-trimethylhexyl) phosphate, ethyl diphenyl phosphate, 2-ethylhexyl di(p-tolyl) phosphate, bis(2-ethylhexyl)-p-tolyl phosphate, tritolyl phosphate, bis(2-ethylhexyl)phenyl phosphate, tris(nonylphenyl) phosphate, bis(dodecyl)-p-tolyl phosphate, dibutylphenyl phosphate, 2-chloroethyl diphenyl phosphate, p-tolyl bis(2,5,5'-trimethylhexyl) phosphate, and bis(2-ethylhexyl)phenyl phosphate. Examples of the phosphate compounds include 2-ethylhexyl diphenyl phosphate, 2-ethylhexyl diphenyl phosphate, xylenyl diphenyl phosphate, cresyl diphenyl phosphate, 1,3-phenylene bis(di-2,6-xylenyl phosphate), 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), tetraphenyl diphosphate (RDP), condensed phosphate compounds (such as aromatic condensed phosphate compounds), cyclic phosphate compounds, bis(diphenyl) phosphate ester of hydroquinone, bis(diphenyl) phosphate ester of bisphenol A, and the like, or oligomeric or polymeric substances thereof, or combinations thereof.

[0091] Examples of phosphazene compounds include cyclic and chain phosphazene compounds. Cyclic phosphazene compounds (cyclophosphazenes) have a ring structure in which a phosphorus-nitrogen double bond exists in the molecule. Examples of phosphinic acid compounds include aluminum dialkylphosphinate, aluminum tris(diethylphosphinate), aluminum tris(methylethylphosphinate), aluminum tris(diphenylphosphinate), zinc bis(diethylphosphinate), zinc bis(methylphosphinate), zinc bis(diphenylphosphinate), titanium bis(diethylphosphinate), titanium bis(methylethylphosphinate), and titanium bis(diphenylphosphinate). Examples of polyphosphate compounds include melamine polyphosphate, melam polyphosphate, and melem polyphosphate. Examples of phosphonium salt compounds include tetraphenylphosphonium tetraphenylborate. Examples of phosphite ester compounds include trimethyl phosphite and triethyl phosphite. Flame retardant compounds containing phosphorus-nitrogen bonds include phosphonitrilic chlorides, phosphorus ester amides, phosphoric acid amides, phosphonic acid amides, phosphinic acid amides, and tris(aziridinyl)phosphine oxide.

[0092] Halogenated materials can also be used as flame retardants, such as bisphenols, such as 2,2-bis(3,5-dichlorophenyl)propane, bis(2-chlorophenyl)methane, bis(2,6-dibromophenyl)methane, 1,1-bis(4-iodophenyl)ethane, 1,2-bis(2,6-dichlorophenyl)ethane, 1,1-bis(2-chloro-4-iodophenyl)ethane, 1,1-bis(2-chloro-4-methylphenyl)ethane, 1,1-bis(3,5-dichlorophenyl)ethane, 2,2-bis(3-phenyl-4-bromophenyl)ethane, 2,6-bis(4,6-dichloronaphthyl)propane, 2,2-bis(3,5-dichloro-4-hydroxyphenyl)propane, and 2,2-bis(3-bromo-4-hydroxyphenyl)propane. Other halogenated materials include 1,3-dichlorobenzene, 1,4-dibromobenzene, 1,3-dichloro-4-hydroxybenzene, and biphenyls such as 2,2'-dichlorobiphenyl, polybrominated 1,4-diphenoxybenzene, 2,4'-dibromobiphenyl, 2,4'-dichlorobiphenyl, as well as decabromodiphenyl ether, decabromodiphenylethane, and oligomeric and polymeric halogenated aromatic compounds such as brominated styrene, 4,4-dibromobiphenyl, ethylene bis(tetrabromophthalimide), or copolycarbonates of bisphenol A and tetrabromobisphenol A with carbonate precursors such as phosgene. Metal synergists, such as antimony oxide, may also be used with the flame retardants.

[0093] Inorganic flame retardants, e.g., C 1~16 Salts of alkylsulfonic acid (potassium perfluorobutanesulfonate (Rimar salt), potassium perfluorooctanesulfonate, tetraethylammonium perfluorohexanesulfonate, potassium diphenylsulfonesulfonate, etc.), salts (Na 2 CO 3 , K 2 CO 3 , MgCO 3 , CaCO 3 , BaCO 3 etc.), or fluorine anion complexes (Li3 AlF 6 , BaSiF 6 , K.B.F. 4 , K 3 AlF 6 , KAlF 4 , K 2 SiF 6 , Na 3 AlF 6 etc.) can also be used.

[0094] When the curable thermosetting composition includes a flame retardant, the content of the flame retardant can be greater than 1 wt%, or from 1 to 20 wt%, or from 5 to 20 wt%, based on the total weight of the curable thermosetting composition.

[0095] The curable thermosetting composition may further include inorganic or organic fillers (particulate fillers, fibrous fillers, etc., or combinations thereof). Any inorganic and organic fillers may be used, including those known to those skilled in the art, without limitation.

[0096] Representative fillers include, for example, clay, talc, kaolin, wollastonite, mica, calcium carbonate, magnesium carbonate, alumina, thiourea, glass powder, B or Sn-containing fillers (such as zinc borate, zinc stannate, zinc hydroxystannate, etc.), metal oxides (such as zinc oxide, tin oxide, etc.), alumina, silica (such as fused silica, fumed silica, spherical silica, crystalline silica, etc.), boron nitride (such as spherical boron nitride), aluminum nitride, silicon nitride, magnesia, magnesium silicate, antimony trioxide, glass fibers (chopped, milled, or woven), glass mat, foam glass, hollow glass microspheres, aramid fiber, quartz, etc., or combinations thereof. Other examples of inorganic fillers include powdered titanium ceramics (such as any of the titanates of barium, lead, strontium, calcium, bismuth, magnesium, etc.). Inorganic fillers also include hydrates (such as aluminum hydroxide, magnesium hydroxide, zeolites, hydrotalcites, etc.). In some embodiments, the filler can be treated with a coupling agent as disclosed herein.

[0097] Glass fibers include those made from E, A, C, ECR, R, S, D, and NE glass, and quartz. The glass fibers may be of any suitable diameter, such as 2 to 30 micrometers (μm), 5 to 25 μm, 5 to 15 μm, etc. The length of the glass fibers before compounding is not limited and may be 2 to 7 millimeters (mm) or 1.5 to 5 mm. Alternatively, longer or continuous glass fibers may be used. Suitable glass fibers are commercially available from suppliers such as Owens Corning, Nippon Electric Glass Co., Ltd., PPG, Johns Manville, etc.

[0098] The organic filler can be, for example, polytetrafluoroethylene powder, polyphenylene sulfide powder, poly(ether sulfone) powder, poly(phenylene ether) powder, polystyrene, divinylbenzene resin, and the like, or combinations thereof.

[0099] Fillers can be selected based on the coefficient of thermal expansion (CTE) and thermal conductivity requirements. For example, Al is used for electronic modules with high thermal conductivity. 2 O 3 , BN, AlN, or a combination of these can be used. For example, MgO can be used for high thermal conductivity and high CTE. For example, SiO for a lightweight module with low CTE and low dielectric constant. 2 (e.g., amorphous SiO 2 ) can be used.

[0100] When the curable thermosetting composition includes a filler, the filler content can be greater than 1 wt.%, or from 1 to 50 wt.%, or from 1 to 30 wt.%, or from 10 to 30 wt.%, based on the total weight of the curable thermosetting composition.

[0101] Coupling agents (also called adhesion promoters) include chromium complexes, silanes, titanates, zirconium aluminates, olefin-maleic anhydride copolymers, reactive cellulose esters, etc. Examples of olefin-maleic anhydride copolymers include maleic anhydride grafted polyethylene, maleic anhydride grafted polypropylene, or combinations thereof. Examples of silanes include epoxy silane compounds, amino silane compounds, methacryloxy silane compounds, vinyl silane compounds, or combinations thereof.

[0102] Examples of aminosilane coupling agents are γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β-(aminoethyl)-γ-aminopropylmethyldimethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, and N-β-(aminoethyl)-γ-aminopropyltriethoxysilane. Representative epoxysilane coupling agents include γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-glycidoxypropyltriethoxysilane. Examples of methacryloxysilane coupling agents include γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyldiethoxysilane, and γ-methacryloxypropyltriethoxysilane.

[0103] Examples of other silane coupling agents include bis(3-triethoxysilylpropyl)tetrasulfide, bis(3-triethoxysilylpropyl)trisulfide, bis(3-triethoxysilylpropyl)disulfide, bis(2-triethoxysilylethyl)tetrasulfide, bis(3-trimethoxysilylpropyl)tetrasulfide, bis(2-trimethoxysilylethyl)tetrasulfide, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyltriethoxysilane, 3-trimethoxysilylpropyl-N,N-dimethylthiocarbamoyltetrasulfide, 3-triethoxysilylpropyl-N,N-di Examples of suitable silane coupling agents include methylthiocarbamoyl tetrasulfide, 2-triethoxysilylethyl-N,N-dimethylthiocarbamoyl tetrasulfide, 3-trimethoxysilylpropyl benzothiazolyl tetrasulfide, 3-triethoxysilylpropyl benzolyl tetrasulfide, 3-triethoxysilylpropyl methacrylate monosulfide, 3-trimethoxysilylpropyl methacrylate monosulfide, bis(3-diethoxymethylsilylpropyl)tetrasulfide, 3-mercaptopropyldimethoxymethylsilane, dimethoxymethylsilylpropyl-N,N-dimethylthiocarbamoyl tetrasulfide, dimethoxymethylsilylpropyl benzothiazolyl tetrasulfide, and the like, or combinations thereof. The silane coupling agent may be a polysulfide silane coupling agent, which contains 2 to 4 sulfur atoms forming a polysulfide bridge. For example, the coupling agent may be bis(3-triethoxysilylpropyl) di, tri, or tetrasulfide.

[0104] When the curable thermosetting composition includes a coupling agent, the content of the coupling agent can be 0.01 to 5 wt%, 0.05 to 5 wt%, or 0.1 to 5 wt%, based on the total weight of the curable thermosetting composition.

[0105] The curable thermosetting composition may optionally contain a solvent. The solvent may be, for example, C 3~8 Ketone, C 3~8 N,N-Dialkylamides, C 4~16 Dialkyl ether, C 6~12 Aromatic Hydrocarbons, C 1~3 Chlorinated hydrocarbons, C 3~6 Alkyl alkanoates, C 2~6 Specific ketone solvents include, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, or combinations thereof. 3~8 Examples of N,N-dialkylamide solvents include dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, or combinations thereof. Examples of dialkyl ether solvents include tetrahydrofuran, ethylene glycol monomethyl ether, dioxane, or combinations thereof. Examples of aromatic hydrocarbon solvents include benzene, toluene, xylene, styrene, divinylbenzene, or combinations thereof. The aromatic hydrocarbon solvents may be non-halogenated. Examples of C 3~6 Examples of alkyl alkanoates include methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, or combinations thereof. 2~6 The alkyl cyanide may be, for example, acetonitrile, propionitrile, butyronitrile, or a combination thereof. 2~6Examples of the alkyl cyanide include acetonitrile, propionitrile, butyronitrile, or a combination thereof. For example, the solvent may be N,N-dimethylformamide, N,N-dimethylacetamide, N,N-diethylacetamide, N,N-dimethylmethoxyacetamide, N-methyl-2-pyrrolidone, N-cyclohexylpyrrolidinone, N-methylcaprolactam, 1,3-dimethyl-2-imidazolidone, 1,2-dimethoxyethane, 1,3-dioxane, 1,4-dioxane, tetrahydrofuran, γ-butyrolactone, γ-caprolactone, dimethylsulfoxide, benzophenone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanoic acid, methyl ethyl ketone ... The solvent may be selected from the group consisting of dimethyl ether, dimethyl ether, dimethyl ether, dichloromethane ...

[0106] When a solvent is used, the curable thermosetting composition can include 2 to 99 wt. % of the solvent, based on the total weight of the curable thermosetting composition. For example, the amount of solvent can be 5 to 80 wt. %, 10 to 60 wt. %, or 20 to 50 wt. %, based on the total weight of the curable thermosetting composition. The solvent can be selected, in part, to adjust the viscosity of the curable thermosetting composition. That is, the amount of solvent can vary depending on variables such as the type of copolymer, the type and amount of other ingredients (such as curing additives), the type and amount of any supplemental thermosetting resins, and the processing temperature used in any subsequent processing of the curable thermosetting composition (e.g., impregnation of a reinforcing structure with the curable thermosetting composition to prepare a composite material). The solvent can be anhydrous. For example, the solvent can include less than 100 parts per million (ppm), less than 50 ppm, or less than 10 ppm of water, based on the total weight of the solvent.

[0107] The curable thermosetting composition can further include a curable unsaturated monomer composition, such as a monofunctional styrenic compound (e.g., styrene), a monofunctional (meth)acrylic compound, or the like, or a combination thereof. For example, the curable unsaturated monomer composition can be an alkene-containing monomer or an alkyne-containing monomer. Examples of alkene- and alkyne-containing monomers include those described in U.S. Patent No. 6,627,704 to Yeager et al., and (meth)acrylates, (meth)acrylamides, N-vinylpyrrolidones, and vinylazalactones, as disclosed in U.S. Patent No. 4,304,705 to Heilman et al. Examples of monofunctional monomers include mono(meth)acrylates (methyl (meth)acrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate, isooctyl (meth)acrylate, isobornyl (meth)acrylate, (meth)acrylic acid, n-hexyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, etc.), N-vinylcaprolactam, N-vinylpyrrolidone, (meth)acrylonitrile, etc., or combinations thereof.

[0108] The curable thermosetting composition may further include one or more additional additives, if necessary. The additional additives may include, for example, dyes, pigments, colorants, antioxidants, heat stabilizers, light stabilizers, plasticizers, defoamers, lubricants, dispersants, flow control agents, drip retardants, antiblocking agents, antistatic agents, flow promoters, processing aids, substrate adhesives, mold release agents, toughening agents, low-profile additives, stress-relief additives, and the like, or combinations thereof. When the additional additives are present, they may be present in any effective amount, for example, 0.01 to 20% by weight, 0.01 to 10% by weight, 0.01 to 5% by weight, or 0.01 to 1% by weight, based on the total weight of the curable thermosetting composition.

[0109] Curable thermoset compositions can be prepared by combining the copolymers and other optional ingredients disclosed herein using any suitable method.

[0110] Also provided is a cured thermosetting composition, including the cured product of the curable thermosetting composition. There is no particular limit to the method of curing the curable thermosetting composition. The curable composition can be cured, for example, by heat or using radiation techniques, including UV radiation or electron beam radiation. For example, the curable thermosetting composition as defined herein can be heated for a time and temperature sufficient to evaporate the solvent and cure to obtain a cured product. When using heat curing, the temperature can be 30 to 400°C, 50 to 250°C, or 100 to 250°C. Heating can be performed for 1 minute to 24 hours, 1 minute to 6 hours, or 3 hours to 5 hours. Curing can be performed in stages to produce a partially cured, often tack-free resin that is then heated for a longer time or temperature within the aforementioned ranges to fully cure. The term "cured" as used herein includes partially cured or fully cured products.

[0111] The cured thermoset composition can have one or more desirable properties. For example, the thermoset composition can have a glass transition temperature of 165° C. or more, desirably 170° C. or more, and more desirably 165 to 180° C. The thermoset composition can also advantageously exhibit a low dielectric constant (Dk), a low dissipation factor (Df), and less moisture absorption. For example, the thermoset composition can have a dielectric constant of less than 3.0, desirably less than 2.75, and more desirably less than 2.6 at a frequency of 10 GHz. The thermoset composition can have a dissipation factor of less than 0.01, or less than 0.005 at a frequency of 10 GHz. Thus, it is believed that the thermoset composition including the copolymers disclosed herein is particularly well suited for use in electronics applications.

[0112] The curable thermosetting compositions and cured thermosetting compositions can be used in a variety of applications and uses, including all applications where conventional thermosetting compositions are used. For example, useful articles comprising the curable thermosetting compositions or the cured thermosetting compositions can be in the form of composites, foams, fibers, layers, coatings, encapsulants, adhesives, sealants, molded components, prepregs, casings, laminates, metal clad laminates, electronic composites, structural composites, or combinations thereof. Examples of applications and uses include coatings (such as protective coatings, sealants, weatherable coatings, scratch resistant coatings, electrically insulating coatings, etc.), adhesives, binders, glues, composites (such as those using carbon fiber and glass fiber reinforcements). When used as coatings, the disclosed compounds and compositions can be coated onto the surfaces of various underlying substrates. For example, the compositions can be coated onto the surfaces of metals, plastics, glass, fiber sizings, ceramics, masonry, wood, or any combination thereof. The disclosed compositions can be used as coatings on the surfaces of metal containers (e.g., aluminum or steel, such as those commonly used in the paint and surface coating industries for packaging and containment). The curable thermoset compositions and cured thermoset compositions derived therefrom are also believed to be particularly well suited for use in the manufacture of electronic and computer components.

[0113] A method for making a composite material can include impregnating a reinforcing structure with a curable thermosetting composition, partially curing the curable thermosetting composition to make a prepreg, and stacking a plurality of prepregs. The reinforcing structure can be a porous substrate (such as a fiber preform or substrate) or other porous material (including ceramic, polymer, glass, carbon, or combinations thereof). For example, the porous substrate can be a woven or nonwoven glass fabric, woven glass fiber fabric, or carbon fiber. If the article includes a fiber preform, a method for making the article can include coating or impregnating the preform with the curable composition to form the article from the curable thermosetting composition. The impregnated fiber preform can be shaped before or after removing the solvent, as needed. In some embodiments, the layer of the curable thermosetting composition can further include a woven or nonwoven glass fabric. For example, a curable layer can be prepared from impregnating a glass fabric with the curable composition and removing the solvent from the impregnated glass fabric. Examples of reinforcing structures are described, for example, in Anonymous (Hexcel Corporation), "Prepreg Technology", March 2005, Publication No. FGU 017b; Anonymous (Hexcel Corporation), "Advanced Fibre Reinforced Matrix Products for Direct Processes", June 2005, Publication No. ITA 272; and Bob Griffiths, "Farnborough Airshow Report 2006", Composites World.com, September 2006. The mass and thickness of the reinforcing structure are selected according to the intended use of the composite material, using criteria familiar to those skilled in the art of fiber reinforced resin composite manufacturing. The reinforced structure can include a variety of finishes suitable for the thermosetting component of the curable thermosetting composition.

[0114] A method of making an article from a curable thermosetting composition can include partially curing the curable thermosetting composition to make a prepreg or fully curing the curable thermosetting composition to make a composite article. References in the text to the property of a "cured composition" refer to a composition that is nearly fully cured. For example, the resin in a laminate made from a prepreg is usually nearly fully cured. Those familiar with thermosetting techniques can determine whether a sample is partially cured or nearly fully cured without undue experimentation. Curing can occur before or after removal of the solvent from the curable composition. Additionally, the article can be further shaped, for example by thermoforming, before or after removal of the solvent, before curing, after partial curing, or after full curing. In some embodiments, the article is produced and the solvent is removed; the article is partially cured (B-staged); shaped as necessary; and then further cured.

[0115] Commercial scale manufacturing of composites is known in the art, and the curable thermosetting compositions described herein are easily adaptable to existing manufacturing processes and equipment. For example, prepregs are often manufactured in treaters. The main components of a treater include a feed roller, a resin impregnation tank, a treater oven, and a take-up roller. The reinforcing structure (e.g., E-glass) is typically wound on a large spool. The spool is then placed on a feed roller, which rotates to slowly unwind the reinforcing structure. The reinforcing structure is then passed through a resin impregnation tank containing a curable thermosetting composition. The curable composition permeates the reinforcing structure. After removal from the tank, the coated reinforcing structure is passed upward through a vertical treater oven, typically at a temperature of 175 to 200° C., to evaporate the solvent. At this point the resin begins to polymerize. Upon emerging from the tower, the composite is sufficiently cured so that the web is not wet or sticky. However, the curing process is stopped before full curing to allow additional curing to occur in making the laminate. The web is then wound onto a take-up roll.

[0116] Also provided are electrical and electronic articles comprising or derived from the curable thermosetting composition. Articles include those comprising printed circuits, such as those used in the medical or aerospace industries. Other articles include antennas and similar articles. Articles such as printed circuit boards are used, for example, in devices such as lighting, solar energy, displays, cameras, audio and video equipment, personal computers, mobile phones, electronic organizers, or office automation equipment. For example, electrical components can be placed on printed circuit boards comprising laminates. Other examples of articles prepared from the curable composition for various applications include copper clad laminates (CCL), such as metal core copper clad laminates (MCCCL), composite articles, and coated articles, such as multi-layer articles.

[0117] The dielectric layer that can be prepared from the curable thermosetting composition may be useful in circuit assemblies, for example, metal clad laminates, such as copper clad laminates. For example, the laminate may include a dielectric layer, a conductive metal circuit layer disposed on the dielectric layer, and, optionally, a heat dissipating metal matrix layer disposed on the opposite side of the dielectric layer from the conductive metal layer. The dielectric layer may optionally include a fiber preform (e.g., a woven layer). For example, the dielectric layer may further include a woven glass layer.

[0118] The conductive metal layer can be in the form of a circuit and can be copper, zinc, tin, brass, chromium, molybdenum, nickel, cobalt, aluminum, stainless steel, iron, gold, silver, platinum, titanium, and the like, or combinations thereof. Other metals include copper-molybdenum alloys, nickel-cobalt-iron alloys (such as KOVAR available from Carpenter Technology Corporation), nickel-iron alloys (such as INVAR available from National Electronic Alloys, Inc.), bimetals, trimetals, trimetals made from two layers of copper and one layer of INVAR, and trimetals made from two layers of copper and one layer of molybdenum. Exemplary metal layers include copper or copper alloys. Alternatively, wrought copper foil may be used. The conductive metal layer can be 2 to 200 μm, 5 to 50 μm, or 5 to 40 μm thick.

[0119] The heat dissipating metal matrix layer can be a thermally conductive metal such as aluminum, boron nitride, aluminum nitride, copper, iron, steel, or the like, or a combination thereof. Any thermally or electrically conductive metal can be used, provided that the metal is electrically insulated from the metal circuit layer. The preferred thickness of the supporting metal matrix layer can be 0.1 to 20 mm, 0.5 to 10 mm, or 0.8 to 2 mm.

[0120] The conductive metal layer and the supporting metal matrix layer may be pretreated to increase the surface roughness to improve adhesion with the dielectric layer. Examples of treatments include cleaning, flame treatment, plasma discharge, corona discharge, etc. to improve adhesion of the metal layer. The dielectric layer may be firmly attached to the conductive metal layer or heat dissipating layer without the use of adhesives, or adhesives may be used to improve adhesion between the conductive metal layer or heat dissipating layer and the dielectric layer. Examples of adhesives used to bond the composite sheet to the metal include polyimide adhesives, acrylic adhesives, epoxy resins, etc., or combinations thereof.

[0121] Copper clad laminates can be produced by thermally laminating one or more dielectric layers, one or more conductive metal layers, and a supporting metal matrix layer under pressure without the use of a thermosetting adhesive. The dielectric layers can be prepared from a curable thermosetting composition, or can be prepared by forming the layers by solvent casting prior to the thermal lamination step. For example, the dielectric layers, conductive metal layers, and heat dissipating layers can be thermally laminated together under pressure in an adhesive-free manner to form a laminate. The conductive metal layers can be optionally shaped into a circuit prior to lamination, or the conductive metal layers can be optionally etched into an electrical circuit prior to lamination. Lamination can be performed by hot pressing or roll calendaring, e.g., roll-to-roll. The conductive metal layers of the copper clad laminate can be further patterned to form a printed circuit board. The copper clad laminate can further be shaped to form a circuit board in the form of a sheet, tube, or rod.

[0122] Alternatively, the curable thermosetting composition can be cast directly onto a conductive metal layer using a solvent casting process, which can then be laminated to a heat dissipating metal matrix layer to produce a laminate for circuit assembly. For example, the curable thermosetting composition can be cast directly onto a heat dissipating metal matrix layer, which can then be laminated to a conductive metal layer.

[0123] Multi-layer laminates containing additional layers can also be produced in one step or in two or more successive steps by thermal lamination methods such as hot pressing or roll calendering. For example, there can be up to 7 layers or up to 16 layers in a laminate. In one embodiment, the laminate can be produced in one step or in two or more successive steps, such as a laminate containing a layer of thermoset film between any layer of metal foil and any layer of fabric (successive layers of fabric-thermoset-metal-thermoset-fabric-thermoset-metal foil or a combination of fewer layers). In another embodiment, a first laminate can be produced in one step or in two or more successive steps, such as a layer of fabric between two layers of thermoset (such as a layer of glass fabric between two layers of thermoset). A second laminate can then be produced by applying a metal foil to the thermoset side of the first laminate.

[0124] The overall thickness of the printed circuit board made from the curable thermosetting composition can be 0.1 to 20 mm, more specifically 0.5 to 10 mm, where the overall thickness refers to the assembly including the dielectric layer, the conductive metal layer, and the supporting metal matrix layer. The overall thickness of the circuit assembly can be 0.5 to 2 mm, more specifically 0.5 to 1.5 mm. There is no particular limit to the thickness of the dielectric layer, and it can be 5 to 1500 μm, 5 to 750 μm, 10 to 150 μm, or 10 to 100 μm. For example, the printed circuit board can be a metal core printed circuit board (MCPCB) used in light emitting diode (LED) applications.

[0125] The curable thermosetting composition can be used as a coating, for example, in the manufacture of a multi-layer article. A method for making a coating can include mixing the curable thermosetting composition with, optionally, a fluoropolymer, and forming a coating on a substrate. For example, a multi-layer article can be made by forming a layer comprising the curable thermosetting composition, removing solvent from the layer and optionally curing to produce a primer layer, and then applying a ceramic (e.g., Al 2 O 3 , TiO 2 , ZrO 2 , Cr 2 O 3 , SiO 2 , MgO, BeO, Y 2 O 3 , Al 2 O 3 -SiO 2 , MgO-ZrO 2 , SiC, WC, B 4 C, TiC, Si 3 N 4 , TiN, BN, AlN, TiB, ZrB 2 and the like), a thermoplastic polymer, a fluoropolymer (e.g., polytetrafluoroethylene, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, polychlorotrifluoroethylene, tetrafluoroethylene-ethylene copolymer, polyvinylidene fluoride, and the like), or a combination thereof, over the primer layer to produce a multilayer article, and optionally heat treating the multilayer article to cure the curable thermosetting composition. In some embodiments, the second layer can further comprise a curable thermosetting composition.

[0126] Other uses for the curable thermosetting compositions include, for example, acid baths; neutralization tanks; aircraft components; bridge girders; bridge decks; electrolytic cells; exhaust stacks; scrubbers; sporting goods; stairwells; walkways; automotive exterior panels (hoods, trunk lids, etc.); floor pans; air scoops; pipes and ducts (heater ducts, etc.); industrial blowers, fan housings, and blowers; industrial mixers; boat hulls and decks; marine terminal fenders; tiles and coatings; architectural panels; office equipment housings; trays (such as cable trays); concrete conditioners; dishwasher and refrigerator parts; electrical seals. agents;electrical panels;tanks (electrical smelting tanks, water softening tanks, fuel tanks, various filament wound tanks and tank linings, etc.);furniture;garage doors;gratings;protective gear;luggage;outdoor vehicles;pressure tanks;optical waveguides;radar domes;fences;railroad parts (tank cars, etc.);hopper car covers;car doors;truck bed liners;satellite dishes;signs;solar energy panels;telephone switchgear housings;tractor parts;transformer covers;truck parts (fenders, hoods, bodies, cabs, beds, etc.);insulation for rotating machinery (ground insulation, turn insulation, phase isolation insulation) separation insulation, etc.);commutators;core insulation and cord and ligating tape;drive shaft couplings;propeller blades;missile components;rocket motor cases;wing sections;suction tubes;fuselage sections;wing skins and flares;engine nacelles;cargo doors;tennis racquets;golf club shafts;fishing rods;skis and ski poles;bicycle parts;lateral leaf springs;pumps (such as automobile exhaust pumps);electrical components, embeds, and tools (such as electrical cable joints);windings and densely packed multi-element assemblies;sealing of electromechanical devices;battery cases;resistors;fuses and thermal cutoff devices;coatings for printed wiring boards;casting items (such as capacitors, transformers, crankcase heaters);small molded electronic components (such as coils, capacitors, resistors, semiconductors);steel replacement in chemical processing, pulp and paper, power generation, and wastewater treatment;scrub towers;structural pultrusions (such as structural members, gratings, safety fences);swimming pools, swimming pool slides, hot tubs, and saunas;drive shafts used under the hood;dry toner resins for photocopiers;tooling and composites for marine use;heat shields;submarine hulls;prototype generation;laboratory modeling;laminate trim;drilling fixtures;bonding jigs;inspection fixtures;industrial metal forming dies;aircraft stretch blocks and hammer forms;vacuum forming tools;flooring (flooring for manufacturing and assembly areas, clean rooms, machine shops, control rooms, laboratories, parking lots, freezers, coolers, outside loading docks, etc.);conductive compositions for static prevention;decorative flooring;bridge expansion joints;injectable mortars for sealing and repairing cracks in structural concrete;tile grout;machine rails;metal dowels;bolts and posts;repair of oil and fuel storage tanks, and many other applications.

[0127] Methods useful for making these articles and materials include those generally known in the art for processing thermosets, as described, for example, in Engineered Materials Handbook, Volume 1, Composites, ASM International Metals Park, Ohio, copyright 1987 Cyril A. Dostal Senior Ed, pp. 105-168 and 497-533, and in "Polyesters and Their Applications" by Bjorksten Research Laboratories, Johan Bjorksten (pres.) Henry Tovey (Ch. Lit. Ass.), Betty Harker (Ad. Ass.), James Henning (Ad. Ass.), Reinhold Publishing Corporation, New York, 1956. Processing techniques include resin transfer molding; sheet molding; bulk molding; pultrusion; injection molding (such as reaction injection molding (RIM)); atmospheric pressure molding (APM); casting (such as centrifugal and static casting, open mold casting); lamination processes (such as wet or dry lamination and spray lamination); contact molding (such as cylindrical contact molding); compression molding (such as vacuum assisted resin transfer molding and chemically assisted resin transfer molding); matched tool molding; autoclave curing; heat curing in air; vacuum bagging; pultrusion; Seeman's Composite Resin Infusion Manufacturing Processing (SCRIMP); open mold molding with continuous resin and glass combinations; and filament winding (such as cylindrical filament winding). For example, an article can be made by resin transfer molding.

[0128] Also provided are articles derived from the curable thermosetting compositions, the articles being composites, foams, fibers, layers, coatings, encapsulants, adhesives, sealants, cast components, prepregs, casings, cast articles, laminates, or combinations thereof, or the articles being metal clad laminates, electronic composites, structural composites, or combinations thereof. The articles can be made, for example, by casting, molding, extrusion, or the like, as disclosed herein, and removing the solvent from the formed article. In some embodiments, the article is a layer and can be formed by casting the curable composition onto a substrate to form a cast layer. The solvent can be removed by any method, including heating the cast layer and heating the cast layer under heat and pressure, for example, by coating the cast layer onto another substrate. In some embodiments, the articles made by the above methods can include adhesives, packaging materials, capacitor films, or circuit board layers. In some embodiments, the article prepared from the curable composition may be a dielectric layer or coating on a substrate, such as a wire or cable coating. For example, the article may be a dielectric layer in a circuit material, such as a printed circuit board, for example, used in lighting or communication applications. Another example of an article prepared from the curable composition may be one or more paint layers. The curable composition may be used to manufacture articles as disclosed herein for other curable thermosetting compositions. EXAMPLES

[0129] The present disclosure is further illustrated in the following non-limiting examples.

[0130] [Example 1: Synthesis of dicyclopentadiene-dimethoxybenzene copolymer] A 100 mL three-neck round bottom flask equipped with a stirrer, condenser, and nitrogen inlet was purged with nitrogen. 6.28 g (0.045 mol) of 1,4-dimethoxybenzene, 20 mL of o-dichlorobenzene (ODCB), and 1.33 g (0.01 mol) of aluminum chloride were added to the reaction flask. The reaction mixture was heated to 100 °C. Once the contents of the reaction flask reached equilibrium, 6.6 g (0.05 mol) of dicyclopentadiene (DCPD) dissolved in 10 mL of ODCB was added dropwise to the flask through an addition funnel. The rate of DCPD addition was maintained such that all of the DCPD solution was added in 2-3 hours. After the contents were allowed to react for 16 hours, a sample was removed and the molecular weight was measured using GPC. AlCl was added to increase the molecular weight of the reactants. 3 The catalyst was added in portions. The cations were quenched by adding 100 mL of 5 wt. % NaOH solution to the contents of the flask and stirred for 1 h. The reaction contents were then precipitated in methanol. The oligomer was washed with 50:50 (v / v) methanol / water for 30 min (shaking in a laboratory shaker) and filtered. Similarly, the polymer was washed three times with methanol and dried to yield a light grey powder. The oligomer was characterized by NMR (see Figure 1). [ka] Scheme 1: Synthesis of alternating copolymers

[0131] [Table 1]

[0132] Prophetic Example 2 Using the procedure described in Example 1, additional copolymers derived from DCPD and substituted benzene monomers can be prepared as shown in Scheme 2. [ka] Scheme 2: Synthesis of dicyclopentadiene-substituted benzene copolymers

[0133] Prophetic Example 3: Epoxidation of terminal DCPD groups. The epoxidation reaction is shown in Scheme 3. The copolymer derived from DCPD and substituted benzene monomers is dissolved in chloroform. To this solution, m-chloroperoxybenzoic acid is added. The reaction mixture is stirred for several hours. The by-product m-chlorobenzoic acid is removed by filtration or neutralization. Precipitation in methanol gives the epoxidized alternating copolymer. The product is further dried in a vacuum oven under a nitrogen stream at ambient temperature. [ka] Scheme 3: Synthesis of epoxy-capped copolymers

[0134] Prophetic Example 4: Ring-opening and derivatization of epoxy-capped copolymers. The epoxy groups can be further reacted with acids, anhydrides, amines, thiols to further functionalize the end groups. The synthesis of a tetraacrylate-functionalized copolymer from an epoxy-capped alternating copolymer and acrylic anhydride is shown below in Scheme 4. [ka] Scheme 4: Synthesis of acrylate-functionalized oligomers

[0135] Prophetic Example 5: Introduction of Hydroxyl End Groups Copolymers derived from DCPD and substituted benzene monomers can undergo hydroformylation as described in US Patent Application Publication No. 2013 / 0108761 A1 and as shown in Scheme 5 below. [ka] Scheme 5: Synthesis of alcohol-capped copolymers

[0136] Alternatively, the DCPD end groups of copolymers derived from DCPD and substituted benzene monomers can be brominated and then converted to alcohol functionalities according to standard synthetic methods known to those skilled in the art.

[0137] Prophetic Example 6 The synthesis of ether-, ester-, or amine-functionalized copolymers from hydroxyl-capped alternating copolymers is shown below in Scheme 6. [ka] Scheme 6: Synthesis of ether-capped copolymers

[0138] Prophetic Example 7 Hydroxyl-capped alternating copolymers can be prepared using NaN as described in Synthetic Communications 30(12), 2233-2237 (2000) and shown in Scheme 7 below. 3 Alternatively, OH can be converted to NH using ammonia. 2 can be converted to [ka] Scheme 7: Synthesis of amine-, amide-, and maleimide-capped copolymers

[0139] Prophetic Example 8 The hydroxyl-capped alternating copolymers can be converted to esters as shown in Scheme 8 below. [ka] Scheme 8: Synthesis of (meth)acrylate-capped copolymers

[0140] Alternatively, the DCPD-terminated alternating copolymer can be converted to an ester-capped copolymer in a one-pot reaction as shown in Scheme 9, described in EP 2,492,258 A1. The DCPD-terminated alternating copolymer and methyl formate were reacted at room temperature in a catalytic system (Ru(CO) as the ruthenium compound in a stainless steel high-pressure reactor with an internal volume of 50 mL) to form a copolymer. 3 Cl 2 ] 2 , Co as a cobalt compound2 (CO) 8 , and butylmethylpyrrolidinium chloride as a halide salt were mixed. Next, the reactor was purged with nitrogen gas at 0.5 MPa and kept at 120°C for 8 hours. After that, the inside of the reactor was cooled to room temperature and depressurized. [ka] Scheme 9: Synthesis of ester-capped copolymers

[0141] The disclosure of the present application further includes the following aspects.

[0142] Embodiment 1a: A copolymer comprising repeat units and terminal units each derived from dicyclopentadiene.

[0143] Embodiment 1b: A copolymer derived from a first monomer, a second monomer, and a terminal unit monomer, wherein the first monomer and the terminal unit monomer are each dicyclopentadiene.

[0144] Embodiment 1c: The copolymer of embodiment 1a or 1b, wherein the terminal units are represented by structural formula E-1, structural formula E-2, or a combination thereof; [ka] Structural formula E-1, [ka] Structural formula E-2 During the ceremony, [ka] indicates a bond that is either single or double, and [ka] is a single bond, then q is 2, and each occurrence of Q contains a single bond, hydrogen, or a terminal functional group, and if both occurrences of Q are each single bonds, then the Qs join to form an epoxide or aziridine ring.

[0145] Embodiment 1d: A copolymer of embodiment 1a, 1b, or 1c derived from a first monomer, a second monomer, and a terminal unit monomer, wherein the first monomer comprises dicyclopentadiene, the second monomer comprises benzene (optionally substituted with a hydrocarbyl group, a hydrocarbyloxy group, or a combination thereof), and the terminal unit monomer is dicyclopentadiene, and the terminal unit is optionally fused with an epoxide ring or an aziridine ring or is optionally substituted with at least one terminal functional group.

[0146] Embodiment 1e: The copolymer of embodiment 1a, 1b, or 1c, wherein the terminal unit is optionally fused with an epoxide or aziridine ring, or is optionally substituted with at least one terminal functional group.

[0147] Aspect 2: The copolymer of any of Aspects 1a to 1e, including a structure represented by Formula A1, [ka] Structural formula A1 where R for each occurrence 1 From R 4 are independently hydrogen, C 1 ~C 12 Hydrocarbyl, or C 1 ~C 12 hydrocarbyloxy, n is at least 1 to 100; [ka] indicates a bond that is either single or double, and [ka] If is a single bond, then Qa and Q b or Q c and Q d exists, and each occurrence [ka] If is a single bond, then Q a From Q d exists and Q a From Q d each independently contains a single bond, hydrogen, or a terminal functional group; Q a and Q b If each is a single bond, then Q a and Q b are linked to form an epoxide or aziridine ring, and Q c and Q d If each is a single bond, then Q c and Q d are linked to form an epoxide ring or an aziridine ring.

[0148] Aspect 3: The copolymer of aspect 2, wherein the copolymer represented by structural formula A1 includes those represented by structural formulas A1-1 to A1-9; [ka] Structural formula A1-1, [ka] Structural formula A1-2, [ka] Structural formula A1-3, [ka] Structural formula A1-4, [ka] Structural formula A1-5, [ka] Structural formula A1-6, [ka] Structural formula A1-7, [ka] Structural formula A1-8, [ka] Structural formula A1-9 In the formula, J is O or N.

[0149] Aspect 4: The copolymer of Aspect 3, wherein the copolymers represented by structural formulas A1-2 to A1-9 are each derived from the one represented by structural formula A1-1.

[0150] Embodiment 5: The copolymer of any of the preceding embodiments, wherein the terminal functional groups comprise vinylbenzene ether terminal functional groups, methacrylate terminal functional groups, acrylate terminal functional groups, epoxy terminal functional groups, hydroxyl terminal functional groups, cyanate ester terminal functional groups, amine terminal functional groups, maleimide terminal functional groups, allyl terminal functional groups, styrene terminal functional groups, activated ester terminal functional groups, or anhydride terminal functional groups.

[0151] Aspect 6: The copolymer of any of the preceding aspects, wherein the terminal functional group comprises the structure: [ka] wherein X is a halogen and each occurrence of Y independently includes the following structures: [ka]

[0152] Aspect 7. The copolymer of any of the preceding aspects, wherein each occurrence of R 1 From R 4 independently includes the following structures: [ka]

[0153] Aspect 8: A method for producing the copolymer of any of Aspects 2-7, comprising reacting a double bond of dicyclopentadiene of structural formula A1 with a reagent to produce a synthetic precursor to at least one copolymer of structural formula A1-2 through A1-9, or at least one copolymer of structural formula A1-2 through A1-9.

[0154] Aspect 9: A method of making the copolymer of aspect 8, the method further comprising preparing a copolymer of formula A1 (dicyclopentadiene), the method comprising reacting dicyclopentadiene with R 1 From R 4 with a substituted benzene monomer.

[0155] Embodiment 10: A curable thermosetting composition comprising the copolymer of any of embodiments 1a through 1d and 2 through 7.

[0156] Example 11: The curable thermosetting composition of example 10, the composition comprising: a poly(phenylene ether); one or more of a crosslinker, a curing agent, a curing catalyst, a curing initiator, or combinations thereof; one or more of a flame retardant, a filler, a coupling agent, or combinations thereof; or combinations thereof.

[0157]

[0033] Example 12: A cured thermoset composition comprising the cured product of the curable thermoset composition of Example 10 or 11.

[0158] Example 13: An article comprising the cured thermoset composition of Example 12, the article being a composite, a foam, a fiber, a layer, a coating, an encapsulant, an adhesive, a sealant, a cast component, or the article being a metal clad laminate, an electronic composite, a structural composite, or combinations thereof.

[0159] Embodiment 14: A varnish composition comprising the curable thermosetting composition of embodiment 10 or 11 and a solvent.

[0160] Embodiment 15: An article made from the varnish composition of embodiment 14, desirably the article is a fiber, a layer, a coating, a casting, a prepreg, a composite, or a laminate, or the article is a metal clad laminate.

[0161] The compositions, methods, and articles may, in the alternative, comprise, consist of, or consist essentially of any suitable material, step, or component disclosed herein. The compositions, methods, and articles may additionally, or in the alternative, be configured to exclude, or be substantially free of, any material (or species), step, or component that is not necessary to the function or accomplishment of the purpose of the compositions, methods, and articles.

[0162] All ranges disclosed herein are inclusive of the endpoints, and the endpoints are independently combinable with each other (for example, the range "up to 25%, or, more specifically, from 5% to 20% by weight" includes the endpoints and all values ​​within that range, such as "5% to 25% by weight"). "Combinations" include blends, mixtures, alloys, reaction products, and the like. The terms "first", "second", and the like do not denote any order, quantity, or importance but rather are used to distinguish one element from another. The terms "a", "an", and "the" do not denote a limitation of quantity and should be construed to include both the singular and the plural unless otherwise indicated or clearly contradicted by context. "Or" means "and / or" unless expressly stated otherwise. References in the specification to "some embodiments," "an embodiment," etc., mean that a particular element described in connection with that embodiment is included in at least one of the embodiments described in the text, but may or may not be present in other embodiments. Moreover, it is understood that the described elements can be combined in any suitable manner in the various embodiments. "Combinations thereof" are open and include any combination that includes at least one of the recited components or features, together with, where appropriate, similar or equivalent components or features that are not recited.

[0163] Unless otherwise specified in the text, all test standards are the most current standards in effect as of the filing date of this application or, if priority is claimed, the filing date of the earliest priority application in which the test standard is listed.

[0164] Unless otherwise defined, technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application pertains. All cited patents, patent applications, and other references are incorporated herein by reference in their entirety. However, if a term in this application conflicts or is inconsistent with a term in an incorporated reference, the term in this application shall take precedence over the conflicting term from the incorporated reference.

[0165] Compounds are described using standard nomenclature. For example, any position not substituted with any indicated group shall have its valence filled at the indicated bond or with a hydrogen atom. A dash ("-") that is not between two letters or symbols is used to indicate the position at which a substituent is attached. For example, -CHO is attached at the carbon of a carbonyl group.

[0166] As used herein, the term "hydrocarbyl", whether used alone or as a prefix, suffix, or part of other terms, refers to a residue that contains only carbon and hydrogen, unless specifically stated to be "substituted hydrocarbyl". The hydrocarbyl residue can be aliphatic or aromatic, straight-chain, cyclic, bicyclic, branched, saturated, or unsaturated. It can also include combinations of aliphatic, aromatic, straight-chain, cyclic, bicyclic, branched, saturated, and unsaturated hydrocarbon groups. When the hydrocarbyl residue is described as substituted, it can contain heteroatoms in addition to carbon and hydrogen.

[0167] The term "alkyl" refers to a branched or straight-chain, saturated, aliphatic hydrocarbon group, such as methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, t-butyl, n-pentyl, s-pentyl, n- and s-hexyl. "Alkenyl" refers to a branched or straight-chain, monovalent hydrocarbon group containing at least one carbon-carbon double bond, such as ethenyl (-HC=CH 2)). "Alkoxy" means an alkyl group attached through an oxygen (i.e., alkyl-O-), e.g., methoxy, ethoxy, sec-butyloxy groups. "Alkylene" means a branched or straight-chain, saturated divalent aliphatic hydrocarbon group, e.g., methylene (-CH 2 -), propylene (-(CH 2 ) 3 "Cycloalkylene" means the divalent cyclic alkylene group -C n H 2n-x where x is the number of hydrogens replaced by the cyclization. "Cycloalkenyl" means a monovalent group containing one or more rings and one or more carbon-carbon double bonds within the ring, all of the ring members being carbon (e.g., cyclopentyl, cyclohexyl). "Aryl" means an aromatic hydrocarbon group containing the specified number of carbon atoms (e.g., phenyl, tropone, indanyl, naphthyl, etc.). "Arylene" means a divalent aryl group. "Alkylarylene" means an arylene group substituted with an alkyl group. "Arylalkylene" means an alkylene group substituted with an aryl group (e.g., benzyl). The prefix "halo" means a group or compound containing one or more fluoro, chloro, bromo, or iodo substituents. Combinations of different halo groups (e.g., bromo and fluoro) or only chloro groups may be present. The prefix "hetero" means a compound or group that contains at least one ring member that is a heteroatom (e.g., 1, 2, or 3 heteroatoms), where each heteroatom is, independently, N, O, S, Si, or P. "Substituted" means that the compound or group contains at least one (e.g., 1, 2, 3, or 4) substituents (each independently, C ... 1~9 Alkoxy, C 1~9 Haloalkoxy, Nitro(-NO 2 ), cyano (-CN), C 1~6 Alkylsulfonyl (-S(=O) 2 -alkyl), C 6~12 Arylsulfonyl (-S(=O) 2-aryl), thiol (-SH), thiocyano (-SCN), tosyl (CH 3 C 6 H 4 SO 2 -), C 3~12 Cycloalkyl, C 2~12 Alkenyl, C 5~12 Cycloalkenyl, C 6~12 Aryl, C 7~13 Aryl alkylene, C 4~12 Heterocycloalkyl, and C 3~12 The number of carbon atoms shown for a group does not include the substituents. For example, -CH 2 CH 2 CN is a nitrile-substituted C 2 It is an alkyl group.

[0168] While particular embodiments have been described, alternatives, modifications, variations, improvements, and substantial equivalents that are not presently foreseen or contemplated may be conceived by applicant or other persons skilled in the art, and it is therefore intended that the appended claims, as filed and as they may be amended, cover all such alternatives, modifications, variations, improvements, and substantial equivalents.

Claims

1. A copolymer comprising repeat units and terminal units each derived from dicyclopentadiene.

2. A copolymer derived from a first monomer, a second monomer, and a terminal unit monomer, wherein said first monomer and said terminal unit monomer are each dicyclopentadiene.

3. 3. The copolymer of claim 1 or claim 2, wherein the terminal units include those represented by structural formula E-1, structural formula E-2, or a combination thereof, 【Chemistry 1】 Structural formula E-1, 【Chemistry 2】 Structural formula E-2 During the ceremony, 【Chemistry 3】 indicates a bond that is a single or double bond, One that appeared 【Chemistry 4】 is a single bond, then q is 2; Q at each occurrence comprises a single bond, hydrogen, or a terminal functional group; If both occurrences of Q are each a single bond, then the Qs join to form an epoxide ring or an aziridine ring. A copolymer characterized in that

4. 3. The copolymer of claim 1 or claim 2, wherein the terminal unit is optionally condensed with an epoxide or aziridine ring or is optionally substituted with at least one terminal functional group.

5. The copolymer according to any one of claims 1 to 4, wherein the copolymer comprises a structure represented by structural formula A1, 【Chemistry 5】 Structural formula A1 During the ceremony, R per occurrence １ From R ４ are independently hydrogen, C １ ~C １２ Hydrocarbyl, or C １ ~C １２ Contains hydrocarbyloxy, n is at least 1 to 100; 【Chemistry 6】 indicates a bond that is a single or double bond, One that appeared 【Chemistry 7】 If is a single bond, then Q ａ and Q. ｂ Or Q ｃ and Q. ｄ exists, Per occurrence 【Chemistry 8】 If is a single bond, then Q ａ From Q ｄ exists, Q ａ From Q ｄ each independently comprises a single bond, hydrogen, or a terminal functional group; Q ａ and Q. ｂ If each is a single bond, then Q ａ and Q ｂ are linked to form an epoxide ring or an aziridine ring, Q ｃ and Q. ｄ If each is a single bond, then Q ｃ and Q ｄ are linked to form an epoxide ring or an aziridine ring A copolymer characterized in that

6. 6. The copolymer according to claim 5, wherein the copolymer represented by structural formula A1 includes those represented by structural formulas A1-1 to A1-9, 【Chemistry 9】 Structural formula A1-1, 【Chemistry 10】 Structural formula A1-2, 【Chemistry 11】 Structural formula A1-3, 【Chemistry 12】 Structural formula A1-4, 【Chemistry 13】 Structural formula A1-5, 【Chemistry 14】 Structural formula A1-6, 【Chemistry 15】 Structural formula A1-7, 【Chemistry 16】 Structural formula A1-8, 【Chemistry 17】 Structural formula A1-9, A copolymer characterized in that J is O or N.

7. 7. The copolymer according to claim 6, wherein the copolymers represented by structural formulas A1-2 to A1-9 are each derived from the copolymer represented by structural formula A1-1.

8. 8. The copolymer according to claim 1, wherein the terminal functional group comprises a vinylbenzene ether terminal functional group, a methacrylate terminal functional group, an acrylate terminal functional group, an epoxy terminal functional group, a hydroxyl terminal functional group, a cyanate ester terminal functional group, an amine terminal functional group, a maleimide terminal functional group, an allyl terminal functional group, a styrene terminal functional group, an activated ester terminal functional group, or an anhydride terminal functional group.

9. The copolymer according to any one of claims 1 to 8, The terminal functional group comprises the structure: 【Chemistry 18】 wherein X is a halogen and each occurrence of Y independently includes the structure 【Chemistry 19】 A copolymer characterized in that

10. A copolymer according to any one of claims 1 to 9, wherein each occurrence of R １ From R ４ independently includes the following structure: 【Chemistry 20】 A copolymer characterized in that

11. A method for producing the copolymer of any one of claims 5 to 7, comprising reacting the double bond of dicyclopentadiene of formula A1 with a reagent to produce a synthetic precursor to at least one copolymer of formulas A1-2 to A1-9 or at least one copolymer of formulas A1-2 to A1-9.

12. 12. The method of claim 11 for producing a copolymer, the method further comprising the step of preparing a copolymer represented by structural formula A1, the method comprising reacting dicyclopentadiene with R １ From R ４ with a benzene monomer substituted with .

13. A curable thermosetting composition comprising the copolymer according to any one of claims 1 to 12.

14. 14. The curable thermosetting composition of claim 13, The curable thermosetting composition comprises: poly(phenylene ether), one or more of a crosslinking agent, a curing agent, a curing catalyst, a curing initiator, or a combination thereof; one or more of a flame retardant, a filler, a coupling agent, or a combination thereof; Or a combination of these A curable thermosetting composition comprising:

15. 15. A cured thermoset composition comprising the cured product of the curable thermoset composition of claim 13 or claim 14.

16. 16. An article comprising the cured thermoset composition of claim 15, the article is a composite, a foam, a fiber, a layer, a coating, a sealant, an adhesive, a sealant, a cast component, a prepreg, a casing, a casting, a laminate, or a combination thereof; or The article is a metal clad laminate, an electronic composite, a structural composite, or a combination thereof. An article characterized by:

17. A varnish composition comprising the curable thermosetting composition according to claim 13 or 14 and a solvent.

18. 18. An article made from a varnish composition according to claim 17, preferably characterized in that the article is a fiber, a layer, a coating, a casting, a prepreg, a composite or a laminate, or the article is a metal clad laminate.

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