Copolymers derived from dicyclopentadiene.

Abstract

The copolymer includes a polyphenylene ether component and a dicyclopentadiene copolymer component including those having structures represented by Structural Formula D1, D2, D3-1, D3-2, or D3-3: Structural Formula D1, Structural Formula D2, Structural Formula D3-1, Structural Formula D3-2, and Structural Formula D3-3. [Formula 1] JPEG2024544483000061.jpg40170Structural formula D1, [Case 2] JPEG2024544483000062.jpg27170 Structural formula D2, [C3] JPEG2024544483000063.jpg59170Structural formula D3-1, [C4] JPEG2024544483000064.jpg62170 Structural formula D3-2, [C5] JPEG2024544483000065.jpg62170 Structural formula D3-3

Description

[Technical field]

[0001] The present 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). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Publication No. 7-109338 Summary of the Invention [Problem to be solved by the invention]

[0004] 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, particularly electronic applications. Dicyclopentadiene is known to provide excellent moisture resistance and dramatically reduce the dielectric constant without adversely affecting thermal performance. It would therefore be beneficial to present 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] A copolymer comprising a polyphenylene ether component and a dicyclopentadiene copolymer component including those having structures represented by structural formulas D1, D2, D3-1, D3-2, or D3-3, [ka] Structural formula D1, [ka] Structural formula D2, [ka] Structural formula D3-1, [ka] Structural formula D3-2, [ka] Structural formula D3-3, In the formula, Z1 and Z3 are each independently a halogen, an unsubstituted or substituted C1-C 12 Hydrocarbyl (provided that the hydrocarbyl group is not a tertiary hydrocarbyl), C1-C 12 Hydrocarbylthio, C1-C 12 Hydrocarbyloxy, or C2-C 12 halohydrocarbyloxy (wherein the halogen and oxygen atoms are separated by at least two carbon atoms); Z2 and Z4 are each independently hydrogen, halogen, unsubstituted or substituted C1-C 12 Hydrocarbyl (provided that the hydrocarbyl group is not a tertiary hydrocarbyl), C1-C 12 Hydrocarbylthio, C1-C 12 Hydrocarbyloxy, or C2-C 12 halohydrocarbyloxy (wherein the halogen and oxygen atoms are separated by at least two carbon atoms); R1 to R4 are each independently hydrogen, C1 to C 12 Hydrocarbyl, or C1-C 12hydrocarbyloxy, x is 1 to 50, y is 1 to 50, n is 1 to 100, and Q1 comprises a single bond, hydrogen, or a terminal functional group.

[0006] A curable composition comprising the copolymer.

[0007] A cured thermoset composition comprising the cured product of the curable thermosetting composition.

[0008] An article comprising the cured thermoset composition.

[0009] An article made from a varnish composition comprising the curable thermosetting composition and a solvent.

[0010] These and other features are illustrated by way of example in the figures and detailed description that follow. [Brief description of the drawings]

[0011] The following figures are exemplary embodiments in which like elements are designated with like numbers.

[0012] [Figure 1] FIG. 1 is a side-by-side proton NMR spectrum of the copolymer prepared according to Example 1, dicyclopentadiene, and 1,4-dimethoxybenzene. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0013] The present inventors have discovered that copolymers can be prepared from phenylene ether oligomers and dicyclopentadiene copolymers that advantageously produce a favorable combination of dielectric properties, flame resistance, and thermal performance while maintaining compatibility between the phenylene ether component and the dicyclopentadiene copolymer component represented by structure D1, D2, D3-1, D3-2, or D3-3.

[0014] The present copolymers are believed to be particularly useful in curable thermosetting compositions.

[0015] The copolymer comprises a polyphenylene ether block and a dicyclopentadiene copolymer component having a structure represented by structural formula D1, D2, D3-1, D3-2, or D3-3; [ka] Structural formula D1, [ka] Structural formula D2, [ka] Structural formula D3-1, [ka] Structural formula D3-2, [ka] Structural formula D3-3, In the formula, Z1 and Z3 are independently halogen, unsubstituted or substituted C1-C 12 Hydrocarbyl (provided that the hydrocarbyl group is not a tertiary hydrocarbyl), C1-C 12 Hydrocarbylthio, C1-C 12 Hydrocarbyloxy, or C2-C 12halohydrocarbyloxy (wherein the halogen and oxygen atoms are separated by at least two carbon atoms); Z2 and Z4 are independently hydrogen, halogen, unsubstituted or substituted C1-C 12 Hydrocarbyl (provided that the hydrocarbyl group is not a tertiary hydrocarbyl), C1-C 12 Hydrocarbylthio, C1-C 12 Hydrocarbyloxy, or C2-C 12 halohydrocarbyloxy (wherein the halogen and oxygen atoms are separated by at least two carbon atoms); R1 to R4 are independently hydrogen, C1 to C 12 Hydrocarbyl, or C1-C 12 hydrocarbyloxy, x is 1 to 50, y is 1 to 50, n is 1 to 100, and Q1 comprises a single bond, hydrogen, or a terminal functional group.

[0016] In some embodiments, Z1 and Z3 independently comprise a halogen, an unsubstituted or substituted alkyl, a phenyl, a cycloalkyl, a bicycloalkyl, or an alkoxy, where the halogen and the oxygen atom are separated by at least two carbon atoms; Z2 and Z4 independently comprise a hydrogen, a halogen, an unsubstituted or substituted alkyl, a phenyl, a cycloalkyl, a bicycloalkyl, or an alkoxy, where the halogen and the oxygen atom are separated by at least two carbon atoms; R1 through R4 independently comprise a hydrogen, an alkyl, an alkenyl, or an alkoxy; x is 1 to 50, y is 1 to 50, n is 1 to 100; and Q1 comprises a single bond, hydrogen, or a terminal functional group.

[0017] In some embodiments, Z1 and Z3 each independently comprise a halogen, unsubstituted or substituted alkyl, phenyl, cycloalkyl, bicycloalkyl, or alkoxy (wherein the halogen and oxygen atoms are separated by at least two carbon atoms); Z2 and Z4 each independently comprise a hydrogen; R1 through R4 each independently comprise a hydrogen, an alkyl, an alkenyl, or an alkoxy; x is 1 to 50, y is 1 to 50, n is 1 to 100, and Q1 comprises a single bond, hydrogen, or a terminal functional group.

[0018] In any of the above embodiments, R2 and R3 are each hydrogen. In some embodiments, R1 and R4 are each independently methoxy, isopropyl, t-butyl, vinyl, or allyl, and R2 and R3 are each hydrogen.

[0019] In some embodiments, Z1 and Z3 independently comprise methyl, Z2 and Z4 independently comprise hydrogen, R1 to R4 independently comprise hydrogen, methyl, isopropyl, vinyl, allyl, or methoxy, x is 1 to 50, y is 1 to 50, n is 1 to 100, and Q1 comprises a single bond, hydrogen, or a terminal functional group. In some embodiments, Z1 and Z3 independently comprise methyl, Z2 and Z4 independently comprise hydrogen, R1 and R4 are each methoxy, and R2 and R3 are each hydrogen. In some embodiments, Z1 and Z3 independently comprise methyl, Z2 and Z4 independently comprise hydrogen, R1 is methyl, R4 is isopropyl, and R2 and R3 are each hydrogen. In some embodiments, Z1 and Z3 independently comprise methyl, Z2 and Z4 independently comprise hydrogen, and R1 to R4 are methyl.

[0020] Dicyclopentadiene copolymers represented by structural formulas D1, D2, D3-1, D3-2, and D3-3 can be derived from those represented by structural formulas P1, P2, P3-1, P3-2, and P3-3, respectively, where n is 1 to 100. [ka] Structural formula P1, [ka] Structural formula P2, [ka] Structural formula P3-1, [ka] Structural formula P3-2, [ka] Structural formula P3-3,

[0021] The carbon-carbon bond of the terminal dicyclopentadiene group can be alkylated (eg, Friedel-Crafts alkylation) with a monohydric phenol in the presence of an acid catalyst (eg, a Lewis acid catalyst) as shown below.

[0022] In addition to the dicyclopentadiene copolymer component, the copolymer includes a polyphenylene ether component. The polyphenylene ether includes repeat units derived from a substituted or unsubstituted monohydric phenol. The substituted or unsubstituted monohydric phenol can have the structure: [ka] In the formula, Z1 and Z2 are each independently a halogen, an unsubstituted or substituted C 1~12 Primary or secondary hydrocarbyl, C 1~12 Hydrocarbylthio, C 1~12 Hydrocarbyloxy, or C 2~12 halohydrocarbyloxy (wherein the halogen and oxygen atoms are separated by at least two carbon atoms); Z and Z at each occurrence are independently hydrogen, halogen, unsubstituted or substituted C 1~12 Primary or secondary hydrocarbyl, C 1~12 Hydrocarbylthio, C 1~12Hydrocarbyloxy, or C 2~12 In some embodiments, the substituted or unsubstituted monohydric phenol is a 2,6-(di-C 1~6 In some embodiments, Z and Z are each methyl, Z and Z are each hydrogen, and the monohydric phenol is 2,6-xylenol (also known as 2,6-dimethylphenol or "DMP").

[0023] Thus, the polyphenylene ether blocks comprise repeat units having the following structural formula: [ka] wherein Z1 through Z4 are as previously described. In some embodiments, the polyphenylene ether component includes repeat units derived from 2,6-dimethylphenol.

[0024] The phenylene ether oligomers corresponding to the polyphenylene ether component can have a number average molecular weight of less than 5,000 g / mol, preferably between 600 and 4,500 g / mol. The molecular weight can be determined by gel permeation chromatography (GPC) in comparison with polystyrene standards. Those skilled in the art are aware that when copolymers are prepared from dicyclopentadiene copolymer components in a process involving oxidative polymerization of polyphenylene ethers, molecular weight analysis of the phenylene ether oligomers using GPC may not be possible. In such cases, the number average molecular weight can be calculated from the degree of polymerization determined using nuclear magnetic resonance (NMR) spectroscopy.

[0025] The phenylene ether block oligomer corresponding to the polyphenylene ether component can have an intrinsic viscosity of 0.15 dL / g or less, preferably 0.02 to 0.15 dL / g, more preferably 0.12 to 0.13 dL / g. The intrinsic viscosity can be measured at 25°C in chloroform using an Ubbelohde viscometer. The intrinsic viscosity refers to the intrinsic viscosity of the phenylene ether oligomer before coupling with the dicyclopentadiene copolymer represented by structural formula D1, D2, D3-1, D3-2, or D3-3. As with molecular weight measurements, those skilled in the art know that intrinsic viscosity analysis of polyphenylene ether oligomers may not be possible when the copolymer is prepared from the dicyclopentadiene copolymer component by a process that includes oxidative polymerization of polyphenylene ether.

[0026] In some embodiments, the copolymer is a block copolymer including at least one block A including a polyphenylene ether component including repeat units derived from 2,6-dimethylphenol, and at least one block B including a dicyclopentadiene copolymer having the structure D1 or D2. In some embodiments, the copolymer is a graft copolymer including a dicyclopentadiene copolymer having the structure D3-1, D3-2, or D3-3. In some embodiments, the copolymer is a graft copolymer, and the polyphenylene ether component includes repeat units derived from 2,6-dimethylphenol.

[0027] In some embodiments, the copolymer comprises at least two blocks A comprising a polyphenylene ether component and one block B comprising a dicyclopentadiene copolymer component represented by structural formula D1 or D2. In some embodiments, the copolymer comprises at least two blocks B comprising a dicyclopentadiene copolymer component represented by structural formula D1, D2, or a combination thereof, and one block B comprising a polyphenylene ether component. In some embodiments, the copolymer is an ABA triblock copolymer. In some embodiments, the copolymer is a BAB triblock copolymer.

[0028] The copolymer may include at least one terminal functional group, which may include a vinylbenzene ether terminal functional group, a methacrylate terminal functional group, an acrylate terminal functional group, an epoxy 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 styrenic terminal functional group, an activated ester terminal functional group, or an anhydride terminal functional group.

[0029] When the polyphenylene ether component is in a terminal position, at least one terminal functional group can be covalently bonded to the polyphenylene ether component. When the dicyclopentadiene copolymer component represented by structural formula D1 or D2 is in a terminal position, at least one terminal functional group can be covalently bonded to the dicyclopentadiene copolymer component represented by structural formula D1 or D2. The graft copolymers containing the dicyclopentadiene copolymer component represented by structural formula D3-1, D3-2, or D3-3 can include terminal functional groups. In some embodiments, at least one terminal functional group of the copolymer can include a methacrylate group.

[0030] In one embodiment, the present copolymers can be prepared from dicyclopentadiene copolymer components represented by structural formulas D1, D2, D3-1, D3-2, or D3-3 by a process comprising the step of oxidatively polymerizing a substituted or unsubstituted monohydric phenol.

[0031] 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 they do not interfere with or interfere with 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 allows 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.

[0032] The amount of monohydric phenol present in the oxidative polymerization reaction mixture can be 5 to 90 weight percent (wt%), 10 to 85 wt%, or 40 to 60 wt%, based on the total weight of the monohydric phenol, the dicyclopentadiene copolymer having structural formula D1, D2, D3-1, D3-2, or D3-3, and the solvent. The amount of dicyclopentadiene copolymer having structural formula D1, D2, D3-1, D3-2, or D3-3 present in the oxidative polymerization reaction mixture can be 15 to 90 wt%, based on the total weight of the monohydric phenol, the dicyclopentadiene copolymer having structural formula D1, D2, D3-1, D3-2, or D3-3, and the solvent. The molar ratio of the monohydric phenol to the dicyclopentadiene copolymer having structural formula D1, D2, D3-1, D3-2, or D3-3 can be determined depending on the molecular weight desired for the phenylene ether oligomer. For example, the molar ratio of monohydric phenol to dicyclopentadiene copolymers represented by structural formula D1, D2, D3-1, D3-2, or D3-3 can be from 1:1 to 50:1.

[0033] 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.

[0034] Preferred copper-amine catalysts contain a secondary alkylenediamine ligand. Suitable secondary alkylenediamine ligands are described in U.S. Patent No. 4,028,341 to Hay and have the following structure: [ka] 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.

[0035] The preferred copper-amine catalysts containing a secondary alkylenediamine ligand can 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: [ka] 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.

[0036] Preferred copper-amine catalysts containing secondary alkylenediamine ligands can 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.

[0037] 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.

[0038] 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.

[0039] In certain embodiments, each of the above components of the copper-amine catalyst are added simultaneously to the oxidative polymerization reaction.

[0040] 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, or a phase transfer agent. Usually, it is not necessary to remove water, which is a by-product of the reaction, during the reaction.

[0041] 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 )4Q + 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 Examples of phase transfer catalysts include (CH3(CH2)3)4NX, (CH3(CH2)3)4PX, (CH3(CH2)5)4NX, (CH3(CH2)6)4NX, (CH3(CH2)4)4NX, CH3(CH3(CH2)3)3NX, and CH3(CH3(CH2)2)3NX (wherein X is Cl). - , Br - , C 1~8 Alkoxy, 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.

[0042] 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.

[0043] 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.

[0044] 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 limiting the 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.

[0045] In an embodiment, the copolymer can be prepared by a process that includes covalently bonding a dicyclopentadiene precursor having a structure of P1, P2, P3-1, P3-2, or P3-3 with a phenylene ether oligomer, where the dicyclopentadiene precursor having a structure of P1, P2, P3-1, P3-2, or P3-3 and the phenylene ether oligomer contain complementary reactive groups. For example, the dicyclopentadiene precursor having a structure of P1, P2, P3-1, P3-2, or P3-3 contains at least one reactive group (e.g., a carbon-carbon double bond). In the presence of a catalyst (e.g., an acid catalyst such as a Lewis acid catalyst), the carbon-carbon double bond of the dicyclopentadiene precursor having a structure of P1, P2, P3-1, P3-2, or P3-3 can react with a polyphenylene oligomer to produce the copolymer. In some embodiments, one carbon-carbon double bond of the dicyclopentadiene precursor represented by structural formula P1 or P2 can be reacted with a polyphenylene oligomer to produce a diblock copolymer. In some embodiments, both terminal carbon-carbon double bonds of the dicyclopentadiene precursor represented by structural formula P1 or P2 can be reacted with a polyphenylene oligomer to produce a triblock copolymer. In some embodiments, one carbon-carbon double bond of the dicyclopentadiene precursor represented by structural formula P3-1, P3-2, or P3-3 can be reacted with a polyphenylene oligomer to produce a graft copolymer.

[0046] The copolymer can be isolated, for example, by precipitation in a suitable non-solvent for the copolymer, such as methanol.

[0047] The method of making the copolymer may further include reacting the copolymer having at least one A block (e.g., a hydroxyl-terminated phenylene ether oligomer) occupying a terminal position of the copolymer with a compound selected to provide a desired functional group (e.g., a methacrylate group) at the chain end of the copolymer. Suitable compounds containing the desired functional group and a group reactive with the hydroxyl-terminated phenylene ether oligomer can be readily determined by one of ordinary skill in the art. The reaction may be carried out in a solvent. In some embodiments, the copolymer may be obtained as a powder and then combined with a compound containing the desired functional group and a solvent. In some embodiments, the solvent may not be removed and the copolymer may be obtained from the polymerization or coupling reaction as a solution, eliminating the need to isolate the copolymer prior to carrying out the reaction. Exemplary synthetic methods are further described in the Examples below.

[0048] Various methods for preparing the present copolymers are further described in the Examples below.

[0049] 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.

[0050] 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.

[0051] 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.

[0052] The thermosetting resin is not particularly limited, and the thermosetting resin may 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.

[0053] 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 resins (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 the epoxy resin 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.)). The term "epoxy resin" also includes 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).

[0054] 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.

[0055] Bismaleimide resins can be prepared by reaction of a monomeric bismaleimide with a nucleophile, such as a diamine, aminophenol, or aminobenzhydrazide, 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). 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.

[0056] 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.

[0057] 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 the like. 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.

[0058] 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.

[0059] The amines for producing the benzoxazines contain from 1 to 40 carbon atoms, except when they contain an aromatic ring, in which case they can contain from 6 to 40 carbon atoms. Difunctional or polyfunctional amines can be branch points linking one polybenzoxazine with another.

[0060] 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.

[0061] Vinylbenzyl ether resins can be prepared by the 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 chloride and resorcinol, catechol, hydroquinone, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2-(diphenylphosphorylhydroquinone, 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- 2,2'6,6'-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'-sulfo nyldiphenol, 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, dihydroxybenzophenone, tris(4-hydroxyphenyl)isobenzofuran-1(3H)-one Examples of vinyl benzyl ethers include those produced by reaction with tetrakis(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.

[0062] 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, and 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.

[0063] 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 allows the production of 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 ',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.

[0064] 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.

[0065] 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.

[0066] 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 groups 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).;

[0067] 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.

[0068] 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.

[0069] 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.

[0070] 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.

[0071] 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.

[0072] Examples of cure accelerators include heterocyclic accelerators (substituted or unsubstituted C 3~6Heterocycles, etc., where each heteroatom is independently the same or different and is nitrogen, oxygen, phosphorus, silicon, or sulfur. Heterocycle 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-propyl ... 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.

[0073] 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, diamide diphenylmethane, and diamide diphenylsulfonyl. 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-diaminocyclohexane, 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 diethyltoluenediamines; or tertiary amine accelerators (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 of these.

[0074] 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 including C 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] + SbF6 - (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.

[0075] The 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 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.

[0076] 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.

[0077] 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.

[0078] 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.

[0079] 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.

[0080] 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 salts 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.

[0081] 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.

[0082] 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.

[0083] Inorganic flame retardants, e.g., C 1~16 Salts of alkylsulfonic acids (potassium perfluorobutanesulfonate (Rimar salt), potassium perfluorooctanesulfonate, tetraethylammonium perfluorohexanesulfonate, potassium diphenylsulfonesulfonate, etc.), salts (Na2CO3, K2CO3, MgCO3, CaCO3, BaCO3, etc.), or fluorine anion complexes (Li3AlF6, BaSiF6, KBF4, K3AlF6, KAlF4, K2SiF6, Na3AlF6, etc.) can also be used.

[0084] When the curable thermosetting composition includes a flame retardant, the content of the flame retardant can be greater than 1 wt. %, alternatively from 1 to 20 wt. %, alternatively from 5 to 20 wt. %, based on the total weight of the curable thermosetting composition.

[0085] 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.

[0086] Examples of 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 (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.

[0087] 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.

[0088] 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.

[0089] Fillers can be selected based on the coefficient of thermal expansion (CTE) and thermal conductivity requirements. For example, for electronic modules with high thermal conductivity, Al2O3, BN, AlN, or combinations of these can be used. For example, for high thermal conductivity and high CTE, MgO can be used. For example, for lightweight modules with low CTE and low dielectric constant, SiO2 (e.g., amorphous SiO2) can be used.

[0090] 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.

[0091] 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.

[0092] 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.

[0093] 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-dimethylthio carbamoyl tetrasulfide, 2-triethoxysilylethyl-N,N-dimethylthiocarbamoyl tetrasulfide, 3-trimethoxysilylpropyl benzothiazolyl tetrasulfide, 3-triethoxysilylpropyl benzoyl tetrasulfide, 3-triethoxysilylpropyl methacrylate monosulfide, 3-trimethoxysilylpropyl methacrylate monosulfide, bis(3-diethoxymethylsilylpropyl) tetrasulfide, 3-mercaptopropyl dimethoxymethyl silane, 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.

[0094] 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.

[0095] 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. 4~8 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 ...

[0096] 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.

[0097] The curable thermosetting composition can further include a curable unsaturated monomer composition, such as, for example, 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), N-vinylcaprolactam, N-vinylpyrrolidone, (meth)acrylonitrile, and the like, or combinations thereof.

[0098] 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.

[0099] Curable thermoset compositions can be prepared by combining the copolymers and other optional ingredients disclosed herein using any suitable method.

[0100] 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.

[0101] 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, preferably 170° C. or more, more preferably 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, preferably less than 2.75, and more preferably 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, the thermoset composition including the copolymers disclosed herein can be particularly well suited for use in electronics applications.

[0102] 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 deposited on the surface of a variety of underlying substrates. For example, the compositions can be deposited on the surface 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 coating industry for packaging and containment). The curable thermosetting compositions and cured thermosetting compositions derived therefrom may also be particularly well suited for use in the manufacture of electronic and computer components.

[0103] 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.

[0104] 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 needed; and then further cured.

[0105] 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 tacky. However, if a laminate is to be made, the curing process is stopped before completion to allow for additional curing. The web is then wound onto a take-up roll.

[0106] 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.

[0107] 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.

[0108] 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.

[0109] 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.

[0110] The conductive metal layer and the supporting metal matrix layer may be pretreated to increase the surface roughness to enhance adhesion to the dielectric layer. Examples of treatments include cleaning, flame treatment, plasma discharge, corona discharge, etc. to enhance adhesion of the metal layer. The dielectric layer may be firmly adhered to the conductive metal layer or heat dissipating layer without the use of an adhesive, or an adhesive may be used to enhance adhesion of the dielectric layer to the conductive metal layer or heat dissipating layer. Examples of adhesives used to attach the composite sheet to the metal include polyimide adhesives, acrylic adhesives, epoxy resins, etc., or combinations thereof.

[0111] 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 bar.

[0112] Alternatively, the curable thermosetting composition can be cast directly onto a conductive metal layer using a solvent casting process and then 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 and then laminated to a conductive metal layer.

[0113] 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 fewer layer combinations). 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.

[0114] 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.

[0115] The curable thermosetting composition can be used as a coating, for example, to make a multi-layer article. A method for making a coating can include mixing the curable thermosetting composition and, optionally, a fluoropolymer, and forming the coating on a substrate. For example, a multi-layer article can be made by forming a layer comprising a curable thermosetting composition, removing solvent from the layer and, optionally, curing to produce a primer layer, forming a second layer over the primer layer comprising a ceramic (e.g., Al2O3, TiO2, ZrO2, Cr2O3, SiO2, MgO, BeO, YO3, Al2O3-SiO2, MgO-ZrO2, SiC, WC, B4C, TiC, Si3N4, TiN, BN, AlN, TiB, ZrB2, etc.), a thermoplastic polymer, a fluoropolymer (e.g., polytetrafluoroethylene, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, polychlorotrifluoroethylene, tetrafluoroethylene-ethylene copolymer, polyvinylidene fluoride, etc.), or combinations thereof to produce the multi-layer article, and, optionally, heat treating the multi-layer article to cure the curable thermosetting composition. In some embodiments, the second layer can further comprise a curable thermosetting composition.

[0116] 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. Tempering materials;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;Travel luggage;Outdoor vehicles;Pressure tanks;Optical waveguides;Radar domes;Fences;Railway 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.

[0117] 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 combination; and filament winding (such as cylindrical filament winding). For example, an article can be manufactured by resin transfer molding.

[0118] 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 molded article. In some embodiments, the article is a layer and can be molded 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 a coating disposed 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.

[0119] The present disclosure is further illustrated in the following non-limiting examples. EXAMPLES

[0120] Example 1: Preparation of alternating cooligomers According to Scheme 1, alternating dicyclopentadiene-dimethoxybenzene co-oligomers were prepared. Scheme 1 [ka]

[0121] Synthesis of dicyclopentadiene (DCPD)-dimethoxybenzene copolymer (I): A 100 mL three-neck round bottom flask equipped with a stirrer, condenser, and nitrogen inlet was purged with nitrogen. 6.28 grams (g) (0.045 moles) of 1,4-dimethoxybenzene, 20 mL of o-dichlorobenzene (ODCB), and 1.33 g (0.01 moles) of aluminum chloride were added to the reaction flask. The reaction mixture contents were heated to 100°C. Once the contents of the reaction flask reached equilibrium, 6.6 g (0.05 moles) of dicyclopentadiene (DCPD) dissolved in 10 mL of ODCB was added dropwise to the flask through the addition funnel. The rate of DCPD addition was maintained such that all of the DCPD solution was added in 2-3 hours. The contents were allowed to react for 16 hours, after which a sample was removed and the molecular weight was measured using GPC. AlCl3 catalyst was added periodically to increase the molecular weight of the reactants. The contents of the flask were added with 100 mL of 5 wt% NaOH solution to quench the cations 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 gray powder. 1 The H NMR is shown in Figure 1. The properties of the alternating copolymer are shown in Table 1.

[0122] [Table 1]

[0123] Prophetic Example 2: Preparation of dicyclopentadiene alternating cooligomers. Dicyclopentadiene-tetramethylbenzene co-oligomers may be prepared using the methods described in Example 1 and as shown in Scheme 2. Scheme 2 [ka]

[0124] [Example 3: Preparation of polyphenylene ether-dicyclopentadiene block copolymer] Synthesis of 2,6-dimethylphenol-capped DCPD-DMB cooligomer (II): Oligomers of DCPD and 1,4-dimethoxybenzene were synthesized using the method of Example 1 above, except that after 18 hours of reaction at 100°C, 1.83 g of 2,6-xylenol was added to the reaction flask. The end-capping reaction was completed after an additional 16 hours of reaction. The reaction mixture was added to methanol to form a slurry, which was stirred for 1 hour and filtered. The filtered solid was washed twice with methanol. The filtered solid was dried in a vacuum oven.

[0125] Synthesis of end-capped 2,6-dimethylphenol capped DCPD-DMB co-oligomer (x and y=1 in functionalized PPE-DCPD-co-DMB-PPE triblock copolymer (IV)): 25 g of 2,6-dimethylphenol-capped dicyclopentadiene-dimethoxybenzene co-oligomer (II) and 64 g of toluene were placed in a reactor and heated, and 40 mL was removed by azeotropic distillation. The reactor was cooled to 85°C and 0.25 g (0.002 mol) of 4-dimethylaminopyridine was added to the reactor. 0.2 g (0.0017 mol) of methacrylic anhydride (MAA) was added dropwise through the addition funnel. The reaction was heated to reflux until all of the MAA was consumed. The reaction was monitored for consumption of phenolic end groups and the chemical structure was confirmed by NMR analysis. The reaction mixture was diluted with 20 mL of toluene and slurried in methanol to a volume ratio of methanol / reaction mixture of approximately 5:1. The slurry was stirred for 1 hour. The precipitate was filtered off and washed twice with 1 L of methanol. The product was dried in an oven at ambient temperature under a N2 stream. Scheme 3 [ka]

[0126] Prophetic Example 4: Example 3 is repeated using dicyclopentadiene-tetramethylbenzene co-oligomer. Scheme 4 [ka]

[0127] [Example 5: Synthesis of polycyclopentadiene-dimethylphenol diadduct (PCPD-DMP diadduct)] Polycyclopentadiene oligomers were synthesized by Diels-Alder addition polymerization to give the following structure: The unsaturated double bonds were then alkylated with 2,6-dimethylphenol, followed by oxidative coupling polymerization and functionalization. Scheme 5a: Synthesis of polycyclopentadiene by cycloaddition polymerization [ka]

[0128] Procedure: Synthesis of polycyclopentadiene-dimethylphenol diadduct (PCPD-DMP diadduct) An open Parr reactor was charged with 250 g (2.02 mol) DCPD and 250 g (2.71 mol) toluene. All open valves to the atmosphere were closed and the reactor was sealed. The reactor was heated at 270° C. for 4 h. After the reaction, the reactor was cooled to room temperature (RT) and the product in 50 wt % toluene was removed from the reactor, stored and tested. NMR analysis confirmed the structure. Molecular weight was determined by GPC measurement (Mw=2542, Mn=827, PD=3.1).

[0129] Scheme 5b: Synthesis of polycyclopentadiene-dimethylphenol diadduct (PCPD-DMP diadduct) [ka]

[0130] Procedure: The assembled reactor was charged with 250 g of 2,6-dimethylphenol (2.04 moles, melt) and 11.5 g (0.067 moles) of p-toluenesulfonic acid (p-TSA). The reactor was heated to 170° C. While the reactor was heating, 217 g of 50 wt % PCPD / toluene (crude product from previous step) was placed in the addition funnel and added dropwise at 80° C. 1 The reaction was monitored by H NMR to observe the decrease in the intensity of the alkene protons. If the reaction was slow, the solvent (about 50 g) was removed to increase the reaction rate. When the alkene proton consumption rate (calculated by dividing the intensity of the alkene peak by the intensity of the starting alkene peak) reached about 99%, 6.65 g (0.067 mol) of KHCO3 was added to the reactor while stirring to stop the reaction. The reaction mixture was added to 2 L of methanol (MeOH) to precipitate the reaction product, and the resulting slurry was filtered. The removed precipitate was dissolved in 50 wt% CHCl3 and then precipitated in MeOH in a 1:1 ratio. The filter cake was washed with deionized water and then with MeOH, and then dried in a vacuum oven at 60 °C. 1 H NMR analysis confirmed the structure (i.e., the disappearance of peaks corresponding to the vinyl groups on the PCPD and to the bonds between 2,6-dimethylphenol and the terminal cyclopentane and norbornane rings).

[0131] Scheme 5c: Synthesis of end-capped polycyclopentadiene-dimethylphenol diadducts [ka]

[0132] Procedure: 40 g of PCPD-DMP diadduct and 79 g (0.85 mol) of toluene were placed in a reactor and heated, and 40 mL was removed by azeotropic distillation. The reactor was cooled to 85° C. and 0.41 g (0.0033 mol) of 4-dimethylaminopyridine was added to the reactor. 12.75 g (0.08 mol) of methacrylic anhydride (MAA) was added dropwise through the addition funnel. The reaction was heated to reflux until all of the MAA was consumed. The reaction was monitored by consumption of phenolic end groups and the chemical structure was confirmed by NMR analysis. The product was precipitated by adding 40 mL of toluene to dilute the reactor and adding the reaction mixture to methanol in a volume ratio of about 5:1 between methanol and reaction mixture. The resulting slurry was stirred for 1 hour. The precipitate was filtered and the filtered solid was washed with methanol twice (1 L each time). The product was dried in an oven at ambient temperature under a N2 sweep.

[0133] Scheme 5d: Synthesis of poly(phenylene ether)-polycyclopentadiene-poly(phenylene ether) triblock copolymer (PPE-PCPD-PPE). [ka]

[0134] Procedure: 40 g of PCPD-DMP diadduct in 160 g of toluene was added to the reactor. Once the PCPD-DMP diadduct was completely dissolved, the temperature was set to 30° C. and 0.9275 g of DBA, 2.1642 g of DMBA, and 0.3937 g of DBEDA were added to the reactor. 0.0817 g of Cu2O and 1.0591 g of HBr were added to the reactor and oxygen was started. 105.5 g of 50 wt. % 2,6-dimethylphenol (DMP) / toluene was added dropwise over 45 minutes. At the end of the reaction, 1.4686 g of NTA in 23.0126 g of water was added and the temperature was increased to 60° C. and stirred for 2 hours. After chelation, the toluene phase was separated and the toluene was removed to obtain the product. This material was further dried in vacuum at 110° C. overnight. The bond between polycyclopentadiene and poly(phenylene ether) blocks was confirmed by NMR. The molecular weight was determined by GPC (Mw=21083, Mn=4644, PDI=4.5). The Tg was determined by DSC (Tg=202℃).

[0135] Scheme 5e: Synthesis of end-capped polyphenylene ether-polycyclopentadiene-polyphenylene ether triblock copolymers [ka]

[0136] Procedure: 109g toluene was added to the reactor, the temperature was raised to 50°C and 70g PPE-PCPD-PPE was added to the reactor. Once completely dissolved, the solution was heated to 120°C for azeotropic distillation. Once the reaction mixture had a solution concentration of 50 / 50 (toluene / PPE-PCPD-PPE), the temperature was lowered to 85°C. 0.3282g (0.002686 moles) 4-dimethylaminopyridine was added to the solution. Once completely dissolved, MAA was added slowly and the temperature was set to 120°C. The reaction was monitored for consumption of phenolic end groups. The reaction mixture was cooled to 90°C and 40ml toluene was added and the reaction mixture was added to methanol (ratio of reaction mixture to methanol is about 5:1). Once a precipitate formed, the mixture was filtered using a Buchner funnel and rinsed twice with methanol. The solid was removed and placed in a vacuum oven to dry overnight. The molecular weight was determined by GPC (Mw=14187, Mn=3181, PDI=4.5), and the Tg was determined by DSC (Tg=204°C).

[0137] [Example 6] DCPD homo-oligomers (Scheme 6) can be obtained via three different synthetic routes and used to prepare 2,6-dimethylphenol (DMP)-functionalized DCPD homo-oligomers, block copolymers, and crosslinking group-functionalized block copolymers according to Scheme 7. Scheme 6 [ka] Scheme 7 [ka]

[0138] Scheme 6a: Synthesis of polydicyclopentadiene [ka]

[0139] Procedure: The reaction flask was cooled to -14.5°C and purged with N2 (g). DCPD monomer was mixed with 30% toluene and the mixture was transferred to the reactor. The reactor was purged with N2 and stirred for 30 minutes until the temperature reached -14.5°C. Once the target temperature was reached, 3 to 4.5 wt% AlCl3 was added to the reaction mixture and stirred for 15 minutes before quenching the reaction by adding 100 mL of methanol. The crude product was a yellow viscous mass in methanol. Additional methanol was added to precipitate the product. Chemical structure was confirmed by NMR analysis. Molecular weight was determined by GPC (Mw=3937, Mn=1584, PDI=2.5). Tg was determined by DSC (Tg=170°C).

[0140] Scheme 6b: Synthesis of polydicyclopentadiene-dimethylphenol adduct (PDCPD-DMP adduct) [ka]

[0141] Procedure: The reactor was purged with N2 (gas). 2.49 moles of 2,6-DMP monomer and 0.498 moles of polyDCPD (product of cationic polymerization) in toluene were transferred to the reactor, purged with N2, and stirred for 30 minutes until 60°C was reached. Once the target temperature was reached, 0.011 moles of p-toluenesulfonic acid were added to the reaction mixture and stirred for 60 minutes. 0.011 moles of NaHCO3 (5% by weight in deionized water) were added and stirred for an additional 30 minutes. The reaction was monitored by NMR for the loss of vinyl groups. The reaction mixture was washed with water three times or until the pH was the same as that of deionized water, after which the reaction mixture was added to methanol and precipitated in methanol. The mixture was filtered to obtain a brown powder.

[0142] Scheme 6c: Synthesis of end-capped polydicyclopentadiene-dimethylphenol adduct (predicted) [ka]

[0143] Procedure: PDCPD-DMP adduct and toluene are placed in a reactor and heated, and 40 mL of the toluene / water azeotrope is removed by azeotropic distillation. The reactor is cooled to 85°C and 4-dimethylaminopyridine (DMAP) is added to the reactor. Methacrylic anhydride (MAA) is added dropwise through the addition funnel. The reaction is heated to reflux until all of the MAA is consumed. The reaction mixture is added to methanol and the product is precipitated in methanol. The precipitate is filtered and dried.

[0144] Scheme 6d: Synthesis of polyphenylene ether-polycyclopentadiene graft copolymer (PDCPD-graft-PPE) (predicted) [ka]

[0145] Procedure: Add the PDCPD-DMP adduct in toluene to the reactor. Once the PDCPD-DMP adduct is completely dissolved, set the temperature to 30°C. Add DBA, DMBA, and DBEDA to the reactor. Add Cu2O and HBr to the reactor and start the oxygen flow. Add DMP in toluene dropwise over 45 minutes. Once the reaction is complete, add NTA in water and increase the temperature to 60°C and stir for 2 hours. Separate the toluene phase and remove the product by removing the toluene. This material is further dried in vacuum.

[0146] Scheme 6e: Synthesis of end-capped polyphenylene ether-polycyclopentadiene graft copolymer (predicted) [ka]

[0147] Procedure: PDCPD-graft-PPE and toluene are added to a reactor and heated, and 40 mL is removed by azeotropic distillation. The reactor is cooled to 85°C and 4-dimethylaminopyradine (DMAP) is added to the reactor. Methacrylic anhydride (MAA) is added dropwise through the addition funnel. The reaction is heated to reflux until all the MAA is consumed. The product is precipitated in methanol. The particles are filtered and dried.

[0148] The disclosure of the present application further includes the following aspects.

[0149] Aspect 1: A copolymer comprising a polyphenylene ether component and a dicyclopentadiene copolymer component comprising a structure represented by structural formula D1, D2, D3-1, D3-2, or D3-3, [ka] Structural formula D1, [ka] Structural formula D2, [ka] Structural formula D3-1, [ka] Structural formula D3-2, [ka] Structural formula D3-3, wherein each occurrence of Z1 and Z3 is independently a halogen, an unsubstituted or substituted C1-C 12 Hydrocarbyl (provided that the hydrocarbyl group is not a tertiary hydrocarbyl), C1-C 12 Hydrocarbylthio, C1-C 12 Hydrocarbyloxy, or C2-C 12halohydrocarbyloxy (wherein the halogen and oxygen atoms are separated by at least two carbon atoms); Z and Z at each occurrence are independently hydrogen, halogen, unsubstituted or substituted C1-C 12 Hydrocarbyl (provided that the hydrocarbyl group is not a tertiary hydrocarbyl), C1-C 12 Hydrocarbylthio, C1-C 12 Hydrocarbyloxy, or C2-C 12 including halohydrocarbyloxy (wherein the halogen and oxygen atoms are separated by at least two carbon atoms); R1 through R4 at each occurrence are independently selected from hydrogen, C1-C 12 Hydrocarbyl, or C1-C 12 hydrocarbyloxy, x is at least one 1 to 50, y is at least one 1 to 50, n is at least one 1 to 100, and Q1 comprises a single bond, hydrogen, or a terminal functional group.

[0150] Embodiment 1a: The copolymer composition of embodiment 1, wherein Z1 and Z3 each independently comprise a halogen, unsubstituted or substituted alkyl, phenyl, cycloalkyl, bicycloalkyl, or alkoxy (wherein the halogen and oxygen atoms are separated by at least two carbon atoms); Z2 and Z4 each independently comprise a hydrogen, halogen, unsubstituted or substituted alkyl, phenyl, cycloalkyl, bicycloalkyl, or alkoxy (wherein the halogen and oxygen atoms are separated by at least two carbon atoms); and R1 through R4 each independently comprise a hydrogen, alkyl, alkenyl, or alkoxy.

[0151] Embodiment 1b: The copolymer composition of embodiment 1, wherein Z1 and Z3 each independently comprise a halogen, an unsubstituted or substituted alkyl, phenyl, cycloalkyl, bicycloalkyl, or alkoxy (wherein the halogen and the oxygen atom are separated by at least two carbon atoms); Z2 and Z4 each independently comprise a hydrogen; and R1 through R4 each independently comprise a hydrogen, an alkyl, an alkenyl, or an alkoxy.

[0152] Embodiment 1c: The copolymer composition of embodiment 1, wherein Z1 and Z3 each independently comprise methyl, Z2 and Z4 each independently comprise hydrogen, and R1 through R4 each independently comprise hydrogen, methyl, isopropyl, vinyl, allyl, or methoxy.

[0153] Aspect 2: The copolymer composition of any of the preceding aspects, wherein the dicyclopentadiene copolymer component represented by structural formula D1 is derived from that represented by structural formula P1, the dicyclopentadiene copolymer component represented by structural formula D2 is derived from that represented by structural formula P2, the dicyclopentadiene copolymer component represented by structural formula D3-1 is derived from that represented by structural formula P3-1, the dicyclopentadiene copolymer component represented by structural formula D3-2 is derived from that represented by structural formula P3-2, and the dicyclopentadiene copolymer component represented by structural formula D3-3 is derived from that represented by structural formula P3-3, wherein n is 1 to 100. [ka] Structural formula P1, [ka] Structural formula P2, [ka] Structural formula P3-1, [ka] Structural formula P3-2, [ka] Structural formula P3-3,

[0154] Aspect 3: The copolymer composition of any of the preceding aspects, wherein the polyphenylene ether component has a structure as shown below: [ka] In the formula, Z1 and Z3 are each independently a halogen, an unsubstituted or substituted C1-C 12 Hydrocarbyl (provided that the hydrocarbyl group is not a tertiary hydrocarbyl), C1-C 12 Hydrocarbylthio, C1-C 12 Hydrocarbyloxy, or C2-C 12 halohydrocarbyloxy (wherein the halogen and oxygen atoms are separated by at least two carbon atoms); Z2 and Z4 are each independently hydrogen, halogen, unsubstituted or substituted C1-C 12 Hydrocarbyl (provided that the hydrocarbyl group is not a tertiary hydrocarbyl), C1-C 12 Hydrocarbylthio, C1-C 12 Hydrocarbyloxy, or C2-C 12 Includes halohydrocarbyloxy where the halogen and oxygen atoms are separated by at least two carbon atoms.

[0155] Aspect 4: The copolymer composition of any of the previous aspects, wherein the copolymer is a block copolymer derived from a dicyclopentadiene copolymer component represented by structural formula D1 or D2.

[0156]

[0023] Aspect 5: The copolymer composition of any of the previous aspects, comprising at least two A blocks comprising a dicyclopentadiene copolymer component, desirably the copolymer is an ABA triblock copolymer.

[0157]

[0023] Aspect 6: The copolymer composition of any of the previous aspects, comprising at least two B blocks comprising polyphenylene ether moieties, desirably the copolymer is a BAB triblock copolymer.

[0158] Example 7: The copolymer of any of the previous examples, comprising a graft copolymer derived from a dicyclopentadiene moiety represented by structural formula D3-1, D3-2, or D3-3.

[0159]

[0023] Embodiment 8: The copolymer composition of any of the preceding embodiments, wherein the dicyclopentadiene copolymer component comprises at least one terminal functional group comprising a vinylbenzene ether end functional group, a methacrylate end functional group, an acrylate end functional group, an epoxy end functional group, a hydroxyl end functional group, a cyanate ester end functional group, an amine end functional group, a maleimide end functional group, an allyl end functional group, a styrene end functional group, an activated ester end functional group, or an anhydride end functional group.

[0160] Aspect 9: A method of making a dicyclopentadiene copolymer of any of the previous aspects, the method comprising covalently bonding a dicyclopentadiene precursor represented by structural formula P1, P2, P3-1, P3-2, or P3-3 with a substituted or unsubstituted monohydric phenol, wherein the dicyclopentadiene precursor and the monohydric phenol contain complementary reactive groups.

[0161] Aspect 10: A method of making the copolymer of any of the preceding aspects, comprising oxidatively polymerizing a substituted or unsubstituted monohydric phenol to produce a copolymer from a dicyclopentadiene copolymer component, or covalently bonding a dicyclopentadiene precursor having structural formula P1, P2, P3-1, P3-2, or P3-3 to a polyphenylene ether oligomer, wherein the dicyclopentadiene precursor and the polyphenylene ether oligomer contain complementary reactive groups.

[0162] Example 11: A curable thermosetting composition comprising the copolymer of any of Examples 1 to 8, the thermosetting composition optionally further comprising 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.

[0163] Example 12: A cured thermoset composition comprising the cured product of the curable thermoset composition of Example 11.

[0164] Example 13: An article comprising the cured thermoset composition of Example 12, wherein the article is a composite, a foam, a fiber, a layer, a coating, an encapsulant, 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.

[0165] Embodiment 14: A varnish composition comprising the curable thermosetting composition of embodiment 11 and a solvent.

[0166] Embodiment 15: An article made from the varnish composition of embodiment 14, desirably said article is a fiber, a layer, a coating, a casting, a prepreg, a composite, or a laminate, or said article is a metal clad laminate.

[0167] 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.

[0168] 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% by weight, or, more specifically, 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 an 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.

[0169] 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.

[0170] 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.

[0171] 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.

[0172] 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 being substituted, it can contain heteroatoms in addition to carbon and hydrogen.

[0173] 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=CH2). "Alkoxy" refers to an alkyl group attached through an oxygen (i.e., alkyl-O-), such as methoxy, ethoxy, and sec-butyloxy groups. "Alkylene" refers to a branched or straight-chain, saturated divalent aliphatic hydrocarbon group, such as methylene (-CH2-), propylene (-(CH2)3-). "Cycloalkylene" refers to a 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 1~9Haloalkoxy, nitro (-NO2), cyano (-CN), C 1~6 Alkylsulfonyl (-S(=O)2-alkyl), C 6~12 Arylsulfonyl (-S(=O)2-aryl), thiol (-SH), thiocyano (-SCN), tosyl (CH3C6H4SO2-), 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, -CH2CH2CN is a C2 alkyl group substituted with nitrile.

[0174] 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 a polyphenylene ether component and a dicyclopentadiene copolymer component comprising a structure represented by structural formula D1, D2, D3-1, D3-2, or D3-3; 【Chemistry 1】 Structural formula D1, 【Chemistry 2】 Structural formula D2, 【Transformation 3】 Structural formula D3-1, 【Chemistry 4】 Structural formula D3-2, 【Transformation 5】 Structural formula D3-3, During the ceremony, Z for each appearance １ and Z ３ 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); Z for each appearance ２ and Z ４ 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 １２ including halohydrocarbyloxy (where the halogen and oxygen atoms are separated by at least two carbon atoms); R per occurrence １ From R ４ are independently hydrogen, C １ ~C １２ Hydrocarbyl, or C １ ~C １２ Contains hydrocarbyloxy, x is at least one 1 to 50; y is at least one 1 to 50; n is at least one 1 to 100; Q １ contains a single bond, hydrogen, or terminal functional group A copolymer characterized by:

2. The copolymer composition according to claim 1, wherein the dicyclopentadiene copolymer component represented by structural formula D1 is derived from that represented by structural formula P1, the dicyclopentadiene copolymer component represented by structural formula D2 is derived from that represented by structural formula P2, the dicyclopentadiene copolymer component represented by structural formula D3-1 is derived from that represented by structural formula P3-1, the dicyclopentadiene copolymer component represented by structural formula D3-2 is derived from that represented by structural formula P3-2, and the dicyclopentadiene copolymer component represented by structural formula D3-3 is derived from that represented by structural formula P3-3; 【Transformation 6】 Structural formula P1, 【Transformation 7】 Structural formula P2, 【Transformation 8】 Structural formula P3-1, 【Chemistry 9】 Structural formula P3-2, 【Chemistry 10】 Structural formula P3-3 A copolymer composition characterized in that n is 1 to 100.

3. 10. The copolymer composition of claim 1, wherein the polyphenylene ether component has the structure: 【Chemistry 11】 During the ceremony, Z １ and Z ３ are each independently a halogen, an 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); Z ２ and Z ４ are each 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 １２ including halohydrocarbyloxy (where the halogen and oxygen atoms are separated by at least two carbon atoms) A copolymer composition comprising:

4. The copolymer composition according to claim 1, characterized in that the copolymer is a block copolymer derived from a dicyclopentadiene copolymer component represented by structural formula D1 or D2.

5. 5. The copolymer composition of claim 4, wherein the copolymer composition comprises at least two A blocks comprising a dicyclopentadiene copolymer component, and preferably the copolymer is an A-B-A triblock copolymer.

6. 5. The copolymer composition of claim 4, wherein the copolymer composition comprises at least two B blocks comprising a polyphenylene ether component, and preferably the copolymer is a B-A-B triblock copolymer.

7. 2. The copolymer of claim 1, comprising a graft copolymer derived from a dicyclopentadiene copolymer component represented by structural formula D3-1, D3-2, or D3-3.

8. The copolymer composition of claim 1, wherein the dicyclopentadiene copolymer component comprises at least one terminal functional group comprising 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 styrenic terminal functional group, an activated ester terminal functional group, or an anhydride terminal functional group.

9. 10. A method for producing the dicyclopentadiene copolymer of claim 1, comprising the step of covalently bonding a dicyclopentadiene precursor having structural formula P1, P2, P3-1, P3-2, or P3-3 with a substituted or unsubstituted monohydric phenol, wherein the dicyclopentadiene precursor and the monohydric phenol contain complementary reactive groups.

10. 10. A method for producing the copolymer of claim 1, comprising: The manufacturing method comprises: oxidatively polymerizing a substituted or unsubstituted monohydric phenol to form said copolymer from a dicyclopentadiene copolymer component; or covalently bonding a dicyclopentadiene precursor having the structural formula P1, P2, P3-1, P3-2, or P3-3 to a polyphenylene ether oligomer; Including, The process wherein said dicyclopentadiene precursor and said polyphenylene ether oligomer contain complementary reactive groups.

11. A curable thermosetting composition comprising the copolymer of claim 1, said thermosetting composition optionally further comprising: one or more of a crosslinker, 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:

12. A cured thermoset composition comprising the cured product of the curable thermoset composition of claim 11.

13. 13. An article comprising the cured thermoset composition of claim 12, the article is a composite, a foam, a fiber, a layer, a coating, an encapsulant, an adhesive, a sealant, a cast component, a prepreg, a casing, a cast article, 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:

14. A varnish composition comprising the curable thermosetting composition of claim 11 and a solvent.

15. 15. An article made from the varnish composition of claim 14, preferably wherein the article is a fiber, a layer, a coating, a casting, a prepreg, a composite, or a laminate, or wherein the article is a metal clad laminate.

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