Copolymer derived from dicyclopentadiene

Abstract

A copolymer comprising a polyphenylene ether component and a dicyclopentadiene copolymer component having a structure of the chemical formula D1, D2, D3-1, D3-2 or D3-3:

Description

Technology Field

[0001] The present disclosure relates to a copolymer derived from dicyclopentadiene, a method for forming the same, a curable thermosetting composition comprising the same, and an article derived therefrom. Background Technology

[0002] Thermosetting resins are materials that harden to form extremely rigid plastics. These materials can be used in a wide variety of consumer and industrial products. For example, thermosetting resins can be used in protective coatings, adhesives, electronic laminates (e.g., those used in the manufacture of computer circuit boards), flooring, packaging applications, fiberglass-reinforced pipes, and automotive parts (including leaf springs, pumps, and electrical components).

[0003] Poly(phenylene ether) oligomers can improve the dielectric performance, heat resistance, flame retardancy, and hygroscopicity of thermosetting materials, making them highly suitable for various applications, particularly electronic applications. Dicyclopentadiene is known to contribute to excellent moisture resistance and a dramatic reduction in the dielectric constant without adverse effects on thermal performance. Therefore, it would be advantageous to provide a composition having a combination of poly(phenylene ether) oligomers with reduced dielectric performance and dicyclopentadiene for use in curable thermosetting compositions. means of solving the problem

[0004] The copolymer comprises a polyphenylene ether component and a dicyclopentadiene copolymer component having the structure of the following chemical formula D1, D2, D3-1, D3-2 or D3-3.

[0005]

[0006] In the above formula, Z1 and Z3 are each independently a halogen, a C1-C where the hydrocarbyl group is unsubstituted or substituted and not a tertiary hydrocarbyl. 12 Hydrocarbyl, C1-C 12 Hydrocarbilthio, C1-C12 Hydrocarbyloxy, or C2-C in which at least two carbon atoms separate a halogen and an oxygen atom. 12 Containing a halohydrocarbyloxy; Z2 and Z4 are each independently C1-C groups in which hydrogen, halogen, or hydrocarbyl groups are non-tertiary hydrocarbyls or are unsubstituted or substituted. 12 Hydrocarbyl, C1-C 12 Hydrocarbilthio, C1-C 12 Hydrocarbyloxy, or C2-C in which at least two carbon atoms separate a halogen and an oxygen atom. 12 Contains a halohydrocarbyloxy; R1 to R4 are each independently hydrogen, C1-C 12 Hydrocarbyl, or C1-C 12 It includes a hydrocarbyloxy; x is 1 to 50; y is 1 to 50; n is 1 to 100; and Q1 includes a single bond, a hydrogen, or a terminal functional group.

[0007] The curable composition includes the copolymer.

[0008] The cured thermosetting composition includes the cured product of the curable thermosetting composition.

[0009] The article includes a hardened thermosetting composition.

[0010] The article is manufactured from a varnish composition comprising a curable thermosetting composition and a solvent.

[0011] The aforementioned features and other features are exemplified by the following drawings and detailed descriptions. Brief explanation of the drawing

[0012] The following drawings are exemplary embodiments in which the same drawing numbers are assigned to the same components. Figure 1 shows the superposition of the proton NMR spectra of the copolymer, dicyclopentadiene, and 1,4-dimethoxybenzene prepared according to Example 1. Specific details for implementing the invention

[0013] The inventors have discovered that the copolymer can be prepared from a phenylene ether oligomer and a dicyclopentadiene copolymer. The copolymer can advantageously provide a desirable combination of dielectric properties, flame retardancy, and thermal performance while maintaining compatibility between the phenylene ether component and the dicyclopentadiene copolymer component of formula D1, D2, D3-1, D3-2, or D3-3.

[0014] The above copolymer may be particularly useful in curable thermosetting compositions.

[0015] The copolymer comprises a polyphenylene ether block and a dicyclopentadiene copolymer component having the structure of the following chemical formula D1, D2, D3-1, D3-2 or D3-3.

[0016]

[0017] In the above formula, Z1 and Z3 are independently halogens, C1-C hydrocarbyl groups that are unsubstituted or substituted and are not tertiary hydrocarbyls. 12 Hydrocarbyl, C1-C 12 Hydrocarbilthio, C1-C 12 Hydrocarbyloxy, or C2-C in which at least two carbon atoms separate a halogen and an oxygen atom. 12 Contains a halohydrocarbyloxy; Z2 and Z4 are independently C1-C groups in which hydrogen, halogen, or hydrocarbyl groups are non-tertiary hydrocarbyls or are unsubstituted or substituted. 12 Hydrocarbyl, C1-C 12 Hydrocarbilthio, C1-C 12 Hydrocarbyloxy, or C2-C in which at least two carbon atoms separate a halogen and an oxygen atom. 12 Contains a halohydrocarbyloxy; R1 to R4 are independently hydrogen, C1-C 12 Hydrocarbyl, or C1-C 12It includes a hydrocarbyloxy; x is 1 to 50; y is 1 to 50; n is 1 to 100; and Q1 includes a single bond, a hydrogen, or a terminal functional group.

[0018] In some embodiments, Z1 and Z3 independently comprise a halogen, an unsubstituted or substituted alkyl, phenyl, cycloalkyl, bicycloalkyl, or alkoxy, wherein at least two carbon atoms separate the halogen and oxygen atoms; Z2 and Z4 independently comprise a hydrogen, a halogen, an unsubstituted or substituted alkyl, phenyl, cycloalkyl, bicycloalkyl, or alkoxy, wherein at least two carbon atoms separate the halogen and oxygen atoms; R1 to R4 independently comprise a hydrogen, alkyl, alkenyl, or 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.

[0019] In some embodiments, Z1 and Z3 each independently comprise a halogen, an unsubstituted or substituted alkyl, phenyl, cycloalkyl, bicycloalkyl, or alkoxy, wherein at least two carbon atoms separate the halogen and oxygen atoms; Z2 and Z4 each independently comprise hydrogen; R1 to R4 each independently comprise 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.

[0020] In any of the aforementioned 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.

[0021] 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 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; R1 to R4 are methyl.

[0022] Dicyclopentadiene copolymers of formulas D1, D2, D3-1, D3-2, and D3-3 can be derived from the following formulas P1, P2, P3-1, P3-2, and P3-3, respectively, where n is 1 to 100:

[0023]

[0024] The carbon-carbon bonds of the terminal dicyclopentadiene groups can undergo alkylation with monovalent phenol (e.g., Friedel-Crafts alkylation) in the presence of an acid catalyst (e.g., Lewis acid catalyst) as described below.

[0025] In addition to the dicyclopentadiene copolymer component, the copolymer comprises a polyphenylene ether component. The polyphenylene ether comprises repeating units derived from substituted or unsubstituted monovalent phenols. The substituted or unsubstituted monovalent phenols may have the following structure:

[0026]

[0027] In the above formula, Z1 and Z2 are each independently halogen, unsubstituted, or substituted C1-C 12 Class 1 or 2 hydrocarbyl, C1-C 12 Hydrocarbilthio, C1-C 12 Hydrocarbiloxy, or C2-C 12 It is a halohydrocarbyloxy, wherein at least two carbon atoms separate a halogen and an oxygen atom; Z3 and Z4 are each independently hydrogen, a halogen, an unsubstituted or substituted C1-C 12 Class 1 or 2 hydrocarbyl, C1-C 12 Hydrocarbilthio, C1-C 12 Hydrocarbiloxy, or C2-C 12 It is a halohydrocarbyloxy, wherein at least two carbon atoms separate a halogen and an oxygen atom. In one embodiment, the substituted or unsubstituted monovalent phenol is 2,6-(di-C 1-6 It includes alkyl) phenols. In one embodiment, Z1 and Z2 are each methyl, Z3 and Z4 are each hydrogen, and the monovalent phenol is 2,6-xylenol (also called 2,6-dimethylphenol or "DMP").

[0028] Accordingly, the polyphenylene ether block comprises a repeating unit of the following chemical formula:

[0029]

[0030] In the above formula, Z1 to Z4 are as described above. In one embodiment, the polyphenylene ether component comprises a repeating unit derived from 2,6-dimethylphenol.

[0031] The phenylene ether oligomer corresponding to the polyphenylene ether component may have a number average molecular weight of less than 5,000 g / mol, preferably 600 to 4,500 g / mol. The molecular weight can be determined by gel permeation chromatography (GPC) in comparison to a polystyrene standard. Those skilled in the art will recognize that when a copolymer is prepared by a method involving the oxidative polymerization of polyphenylene ether from a dicyclopentadiene copolymer component, characterization of the molecular weight of the phenylene ether oligomer will not be possible using GPC. In such cases, the number average molecular weight can be calculated from the degree of polymerization determined using nuclear magnetic resonance (NMR) spectroscopy.

[0032] The phenylene ether block oligomer corresponding to the polyphenylene ether component may have an intrinsic viscosity of 0.15 deciliters per gram or less, preferably 0.02 to 0.15 deciliters per gram, and more preferably 0.12 to 0.13 deciliters per gram. The intrinsic viscosity can be measured using a Ubbelohde viscometer with chloroform at 25°C. The intrinsic viscosity refers to the intrinsic viscosity of the phenylene ether oligomer prior to coupling with the dicyclopentadiene copolymer of formulas D1, D2, D3-1, D3-2, or D3-3. As with the determination of molecular weight, a person skilled in the art will recognize that it may not be possible to characterize the intrinsic viscosity of the polyphenylene ether oligomer when the copolymer is prepared by a method involving the oxidative polymerization of polyphenylene ether from the dicyclopentadiene copolymer component.

[0033] In one embodiment, the copolymer is a block copolymer comprising at least one block A comprising a polyphenylene ether component comprising repeating units derived from 2,6-dimethylphenol and at least one block B comprising a dicyclopentadiene copolymer of formula D1 or D2. In one embodiment, the copolymer is a graft copolymer comprising a dicyclopentadiene copolymer component of formula D3-1, D3-2 or D3-3. In some embodiments, the copolymer is a graft copolymer, and the polyphenylene ether component comprises repeating units derived from 2,6-dimethylphenol.

[0034] In one embodiment, the copolymer comprises at least two blocks A comprising a polyphenylene ether component and a block B comprising a dicyclopentadiene copolymer component of formula D1 or D2. In one embodiment, the copolymer comprises at least two blocks B comprising a dicyclopentadiene copolymer component of formula D1, D2 or a combination thereof; and a 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.

[0035] The copolymer may include at least one terminal functional group. Examples of at least one terminal functional group of the copolymer include a vinyl benzene 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 styrene terminal functional group, an activated ester terminal functional group, or an anhydride terminal functional group.

[0036] If the polyphenylene ether component is at the terminal position, at least one terminal functional group may be covalently bonded to the polyphenylene ether component. If the dicyclopentadiene copolymer component of Formula D1 or D2 is at the terminal position, at least one terminal functional group may be covalently bonded to the dicyclopentadiene copolymer component of Formula D1 or D2. A graft copolymer comprising the dicyclopentadiene copolymer component of D3-1, D3-2, or D3-3 may include a terminal functional group. In one embodiment, at least one terminal functional group of the copolymer may include a methacrylate group.

[0037] In one embodiment, the copolymer may be prepared by a method comprising oxidative polymerization of a substituted or unsubstituted monovalent phenol from a dicyclopentadiene copolymer component of formula D1, D2, D3-1, D3-2, or D3-3.

[0038] Oxidative polymerization may 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, mixed ether-esters, sulfoxides, etc., provided that they do not interfere with or participate in the oxidation reaction. High molecular weight poly(phenylene ether) can significantly increase the viscosity of the reaction mixture. Therefore, it is sometimes desirable to use a solvent system that induces precipitation while allowing low molecular weight polymers to remain in solution until high molecular weight polymers are formed. Organic solvents may include, for example, toluene, benzene, chlorobenzene, ortho-dichlorobenzene, nitrobenzene, trichloroethylene, ethylene dichloride, dichloromethane, chloroform, or combinations thereof. Preferred solvents include aromatic hydrocarbons. In one embodiment, the organic solvent comprises toluene, benzene, xylene, chloroform, chlorobenzene, or a combination thereof, preferably toluene.

[0039] Monovalent phenol may be present in the oxidative polymerization reaction mixture in an amount of 5 to 90 weight%, 10 to 85 weight%, or 40 to 60 weight% based on the total weight of the monovalent phenol, the dicyclopentadiene copolymer of formula D1, D2, D3-1, D3-2, or D3-3, and the solvent. The dicyclopentadiene copolymer of formula D1, D2, D3-1, D3-2, or D3-3 may be present in the oxidative polymerization reaction mixture in an amount of 15 to 90 weight% based on the total weight of the monovalent phenol, the dicyclopentadiene copolymer of formula D1, D2, D3-1, D3-2, or D3-3, and the solvent. The molar ratio of monovalent phenol to dicyclopentadiene copolymer of formula D1, D2, D3-1, D3-2, or D3-3 can be determined based on the desired molecular weight of the phenylene ether oligomer. For example, the molar ratio of monovalent phenol to dicyclopentadiene copolymer of formula D1, D2, D3-1, D3-2, or D3-3 can be 1:1 to 50:1.

[0040] Oxidative polymerization is further carried out in the presence of a copper-amine catalyst. Copper sources for the copper-amine catalyst may include salts of copper or copper ions, including halides, oxides, and carbonates. Alternatively, copper may be provided in the form of pre-formed salts of alkylene diamine ligands. Preferred copper salts include cuprous halides, copper halides, and combinations thereof. Cuprous brominated, cuprous brominated, and combinations thereof are particularly preferred.

[0041] A preferred copper-amine catalyst comprises a secondary alkylene diamine ligand. A suitable secondary alkylene diamine ligand is described in Hay’s U.S. Patent No. 4,028,341 and is represented by the following formula.

[0042] R b ―NH―R a ―NH―R c

[0043] In the above equation, R a is a substituted or unsubstituted divalent residue, where two or three aliphatic carbon atoms form the closest link between two diamine nitrogen atoms; R b and R c Each is independently isopropyl or substituted or unsubstituted C 4-8 It is a tertiary alkyl group. R a Examples of include ethylene, 1,2-propylene, 1,3-propylene, 1,2-butylene, 1,3-butylene, 2,3-butylene, various pentylene isomers having 2 to 3 carbon atoms separating two free valences, phenylethylene, tolylethylene, 2-phenyl-1,2-propylene, cyclohexylethylene, 1,2-cyclohexylene, 1,3-cyclohexylene, 1,2-cyclopropylene, 1,2-cyclobutylene, 1,2-cyclopentylene, etc. Preferably, R a is ethylene. R b and R c Examples of include isopropyl, t-butyl, 2-methyl-but-2-yl, 2-methyl-pent-2-yl, 3-methyl-pent-3-yl, 2,3-dimethyl-but-2-yl, 2,3-dimethylpent-2-yl, 2,4-dimethyl-pent-2-yl, 1-methylcyclopentyl, 1-methylcyclohexyl, etc. R b and R c A very desirable example is t-butyl. An exemplary secondary alkylene diamine ligand is N,N'-di-t-butylethylenediamine (DBEDA). A suitable molar ratio of copper to secondary alkylene diamine is 1:1 to 1:5, preferably 1:1 to 1:3, more preferably 1:1.5 to 1:2.

[0044] A preferred copper-amine catalyst comprising a secondary alkylene diamine ligand may further comprise a secondary monoamine. Suitable secondary monoamine ligands are generally described in the assigned U.S. Patent No. 4,092,294 by Bennett et al. and are represented by the following formula:

[0045] R d ―NH―R e

[0046] In the above equation, R d and R e C, each independently substituted or unsubstituted 1-12 Alkyl group, preferably substituted or unsubstituted C 3-6 It is an alkyl group. Examples of secondary monoamines include di-n-propylamine, di-isopropylamine, 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 highly preferred secondary monoamine is di-n-butylamine (DBA). A 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.

[0047] A preferred copper-amine catalyst comprising a secondary alkylene diamine ligand may further comprise a tertiary monoamine. Suitable tertiary monoamine ligands are described in the aforementioned U.S. Patent No. 4,028,341 of Hay and U.S. Patent No. 4,092,294 of Bennett, and comprise heterocyclic amines and certain trialkyl amines characterized by amine nitrogen being attached to at least two groups having a small 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 It is preferable that the third substituent be an alkyl group. It is particularly preferable that the third substituent has four or fewer carbon atoms. A highly preferred tertiary amine is dimethylbutylamine (DMBA). A suitable molar ratio of copper to tertiary amine is less than 1:20, preferably less than 1:15, preferably between 1:1 and less than 1:15, and more preferably between 1:1 and 1:12.

[0048] A suitable molar ratio (measured in moles of metal) of copper-amine catalyst to poly(phenylene ether) oligomer starting material is 1:50 to 1:400, preferably 1:100 to 1:200, more preferably 1:100 to 1:180.

[0049] The reaction carried out in the presence of a copper-amine catalyst can optionally be carried out in the presence of bromide ions. It has already been mentioned that bromide ions can be supplied as copper(I) bromide or copper(II) bromide. Bromide ions may also be supplied by adding 4-bromophenols, such as 2,6-dimethyl-4-bromophenol. Additional bromide ions may be supplied in the form of hydrobromide, alkali metal bromides, or alkaline earth metal bromides. Sodium bromide and hydrobromide are highly desirable sources of bromide. A suitable ratio of bromide ions to copper ions is 2 to 20, preferably 3 to 20, and more preferably 4 to 7.

[0050] In one embodiment, each of the above-described components of the copper-amine catalyst is simultaneously applied to the oxidative polymerization reaction.

[0051] Oxidative polymerization may optionally be further carried out in the presence of one or more additional components including lower alkanols or glycols, a small amount of water, or a phase transition agent. Generally, it is not necessary to remove water, which is a reaction byproduct, during the reaction.

[0052] In one embodiment, a phase transition agent is present. Suitable phase transition agents include, for example, quaternary ammonium compounds, quaternary phosphonium compounds, tertiary sulfonium compounds, or combinations thereof. Preferably, the phase transition agent is of the formula (R 3 )4Q + It can be X, where each R 3 is identical or different and C 1-10 It is alkyl; Q is a nitrogen or phosphorus atom; X is a halogen atom, C 1-8 Alkoxy or C6-18 It is an aryloxy. Exemplary phase transition 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 (where X is Cl - , Br - , C 1-8 Alkoxy or C 6-18 Examples include aryloxyims. The effective amount of the phase transition agent may be 0.1 to 10 weight% or 0.5 to 2 weight% based on the weight of the reaction mixture. In one embodiment, a phase transition agent comprising N,N,N'N'-didecyldimethylammonium chloride is present.

[0053] Oxidative polymerization can be carried out at a temperature of 20 to 70°C, preferably 30 to 60°C, and more preferably 45 to 55°C. Depending on the selected precise reaction conditions, the total polymerization reaction time, i.e., the elapsed time between the start of oxidative polymerization and the end of oxidative polymerization, may vary, but is generally 100 to 250 minutes, specifically 145 to 210 minutes.

[0054] The present method further includes a step of terminating oxidative polymerization to form a reaction mixture after termination. The reaction is terminated when the flow of oxygen into the reaction vessel is stopped. Residual oxygen in the upper space of the reaction vessel is washed down and removed with an oxygen-free gas such as nitrogen.

[0055] After the polymerization reaction is terminated, copper ions of the polymerization catalyst are separated from the reaction mixture. This is achieved by combining a chelating agent with the reaction mixture after termination 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, ethylenediaminetetraacetic acid, or a combination thereof, 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 nitrilotriacetic acid. After stirring the chelated mixture, the mixture comprises an aqueous phase containing chelated copper ions and an organic phase containing dissolved poly(phenylene ether). The chelating mixture may exclude the divalent phenol required by U.S. Patent No. 4,110,311 of Cooper et al., the aromatic amine required by U.S. Patent No. 4,116,939 of Cooper et al., and the weak reducing agent required by U.S. Patent No. 4,110,311 of Cooper et al., such as sulfur dioxide, sulfite, sodium disulfite, sodium thionite, tin(II) chloride, iron(II) sulfate, chromium(II) sulfate, titanium(III) chloride, hydroxylamine and its salts, phosphates, glucose, and mixtures thereof. The chelating mixture is maintained at a temperature of 40 to 55°C, specifically 45 to 50°C, for 5 to 100 minutes, specifically 10 to 60 minutes, more specifically 15 to 30 minutes. This combination of temperature and time is effective for copper sequestration while minimizing the reduction in molecular weight of poly(phenylene ether). The chelation step involves separating the aqueous phase and the organic phase of the chelation mixture (and terminating with this separation).This separation step is performed at a temperature of 40–55°C, specifically 45–50°C. The time interval of 5–100 minutes for maintaining the chelation mixture at 40–55°C is measured from the time the reaction mixture first combines with the chelating agent after termination until the separation of the aqueous phase and the organic phase is completed.

[0056] In one embodiment, the copolymer may be prepared by a method comprising covalently coupling a dicyclopentadiene precursor of formula P1, P2, P3-1, P3-2, or P3-3 with a phenylene ether oligomer, wherein the dicyclopentadiene precursor of formula P1, P2, P3-1, P3-2, or P3-3 and the phenylene ether oligomer comprise complementary reactive groups. For example, the dicyclopentadiene precursor of formula P1, P2, P3-1, P3-2, or P3-3 comprises 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 of formula P1, P2, P3-1, P3-2, or P3-3 may react with the polyphenylene oligomer to provide the copolymer. In some embodiments, one carbon-carbon double bond of the dicyclopentadiene precursor of formula P1 or P2 may react with a polyphenylene oligomer to provide a diblock copolymer. In some embodiments, both carbon-carbon double bonds of the dicyclopentadiene precursor of formula P1 or P2 may react with a polyphenylene oligomer to provide a triblock copolymer. In some embodiments, one carbon-carbon double bond of the dicyclopentadiene precursor of formula P3-1, P3-2, or P3-3 may react with a polyphenylene oligomer to provide a graft copolymer.

[0057] The copolymer can be isolated, for example, by precipitating it in a non-solvent suitable for the copolymer, for example, methanol.

[0058] A method for preparing a copolymer may further comprise reacting a copolymer having at least one A block occupying a terminal position of the copolymer (e.g., a hydroxyl-terminated phenylene ether oligomer) with a compound selected to provide a desired functional group, e.g., a methacrylate group, at the chain ends of the copolymer. Suitable compounds comprising a group reactive to the desired functional group and the hydroxyl-terminated phenylene ether oligomer can be readily determined by those skilled in the art. The reaction may be carried out in a solvent. In one embodiment, the copolymer may be obtained as a powder that is subsequently combined with a solvent and a compound containing the desired functional group. In one embodiment, the copolymer may be obtained as a solution from a polymerization or coupling reaction without removing the solvent, and the copolymer is not isolated before carrying out the reaction. Exemplary synthesis is further described in the following examples.

[0059] Various methods for manufacturing copolymers are further described in the following examples.

[0060] Additionally, a curable thermosetting composition comprising the copolymer is provided. For example, the copolymer may be present in the curable thermosetting composition in an amount of 1 to 95 wt%, or 5 to 95 wt%, or 10 to 85 wt%, or 20 to 80 wt%, 30 to 70 wt%, or 5 to 30 wt%, or 5 to 15 wt%, based on the total weight of the curable thermosetting composition.

[0061] The curable thermosetting composition may further comprise one or more of a crosslinking agent, a curing agent, a curing catalyst, a curing initiator, or a combination thereof. In one embodiment, the curable thermosetting composition may further comprise one or more of a flame retardant, a filler, a coupling agent, or a combination thereof. For example, the curable thermosetting composition may comprise one or more of a crosslinking agent, a curing agent, a curing catalyst, a curing initiator, or a combination thereof; and may further comprise one or more of a flame retardant, a filler, a coupling agent, or a combination thereof.

[0062] There is significant overlap between thermosetting resins, crosslinkers, and coupling agents. As used herein, the term "crosslinker" includes compounds that can be used as thermosetting resins, crosslinkers, coupling agents, or combinations thereof. For example, in some cases, a compound that is a thermosetting resin may also be used as a crosslinker, a coupling agent, or both.

[0063] The thermosetting resin is not particularly limited and may be used alone or in combination of two or more thermosetting resins (e.g., including one or more auxiliary thermosetting resins). Exemplary thermosetting resins include epoxy resins, cyanate ester resins, (bis)maleimide resins, (poly)benzoxazine resins, vinyl resins (e.g., vinyl benzyl ether resins), phenol resins, alkyd resins, unsaturated polyester resins, arylcyclobutene resins, perfluorovinyl ether resins, monomers, oligomers, or polymers having curable unsaturation (e.g., vinyl functional), or combinations thereof.

[0064] The epoxy resin may generally be any epoxy resin suitable for use in thermosetting resins. In the context herein, the term "epoxy resin" refers to a curable composition of an oxirane ring-containing compound as described, for example, in the literature [CA May, Epoxy Resins, 2nd supplement Edition, (New York & Basle: Marcel Dekker Inc.), 1988]. Epoxy resins include bisphenol A type epoxy resins, such as a resin obtained from bisphenol A and a resin obtained by substituting at least one of the 2nd, 3rd, and 5th positions of bisphenol A with a halogen atom, an alkyl group having 6 or fewer carbon atoms, or a phenyl group; bisphenol F type epoxy resins, such as a resin obtained from bisphenol F and a resin obtained by substituting at least one of the 2nd, 3rd, and 5th positions of bisphenol F with a halogen atom, an alkyl group having 6 or fewer carbon atoms, or a phenyl group; Glycidyl ether compounds derived from phenols of divalent or trivalent or higher phenols, such as hydroquinone, resorcinol, tris-4-(hydroxyphenyl)methane, and 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane; novolak-type epoxy resins derived from novolak resins that are reaction products between formaldehyde and phenols such as phenol and o-cresol, including bisphenol A novolak-type epoxy resin and cresol novolak-type epoxy resin; cyclic aliphatic epoxy compounds such as 2,2-bis(3,4-epoxycyclohexyl)propane, 2,2-bis[4-(2,3-epoxypropyl)cyclohexyl]propane, vinylcyclohexedeoxide, and 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate; dicyclopentadiene-containing polyepoxides;Aniline, p-aminophenol, m-aminophenol, 4-amino-m-cresol, 6-amino-m-cresol, 4,4'-diaminodiphenyl-ethane, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 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-amino-phenoxyphenyl)propane, p-phenylenediamine, m-phenylenediamine, 2,4-toluenediamine, 2,6-toluenediamine, p-xylylene-diamine, m-xylylenediamine, Amine-type epoxy resins derived from 1,4-cyclohexane-bis(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, such as those derived from glycidyl esters of aromatic carboxylic acids like p-oxybenzoic acid, m-oxybenzoic acid, terephthalic acid, and isophthalic acid. The "epoxy resin" may also comprise a reaction product of an aromatic dihydroxy compound with a compound containing two or more epoxy groups, which may optionally be halogen-substituted and used alone or in combination of two or more.

[0065] Cyanate esters are not limited and any resin composed of cyanate ester monomers polymerized to form a polymer containing multiple cyanate ester (-OCN) functional groups may be used. Cyanate ester monomers, prepolymers (i.e., partially polymerized cyanate ester monomers or mixtures of cyanate ester monomers), homopolymers, copolymers prepared using cyanate ester precursors, and combinations of these compounds. For example, cyanate esters may be prepared according to the methods described in the literature ["Chemistry and Technology of Cyanate Ester Resins", by Ian Hamerton, Blackie Academic and Professional]; U.S. Patent No. 3,553,244; and JP-A-7-53497. Exemplary cyanate ester resins include cyanate ester resins 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 copolymer, and prepolymers prepared from these monomers. An example of a prepolymer is PRIMASET BA-230S (Lonza). The cyanate ester prepolymer may be a homopolymer or a copolymer incorporating other monomers. Examples of such copolymers include BT resins available from Mitsubishi Gas Chemical, such as BT 2160 and BT 2170, which are prepolymers prepared from cyanate ester monomers and bismaleimide monomers.Other cyanate ester polymers, monomers, prepolymers, and blends of cyanate ester monomers and other non-cyanate ester monomers are disclosed in US 7393904, US 7388057, US 7276563, and US 7192651.

[0066] Bismaleimide resin can be prepared by the reaction of monomeric bismaleimide with a nucleophile, such as a diamine, aminophenol, or aminobenzhydrazide, or by the reaction of bismaleimide with diallyl bisphenol A. Exemplary bis-maleimide resins include 1,2-bis-maleimidoethane, 1,6-bis-maleimidohexane, 1,3-bis-maleimidobenzene, 1,4-bis-maleimidobenzene, 2,4-bis-maleimidotoluene, 4,4'-bis-maleimidodiphenylmethane, 4,4'-bis-maleimidodiphenyl ether, 3,3'-bis-maleimidodiphenylsulfone, 4,4'-bis-maleimidodiphenylsulfone, 4,4'-bis-maleimidodicyclohexylmethane, 3,5-bis(4-maleimidophenyl)pyridine, 2,6-bis-maleimidopyridine, 1,3-bis(maleimidomethyl)cyclohexane, 1,3-bis(maleimidomethyl)benzene, 1,1-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, N,N-Bis(4-maleimidophenyl)toluene, 3,5-Bismaleimido-1,2,4-triazole, N,N'-ethylenebismaleimide, N,N'-hexamethylenebismaleimide, N,N'-m-phenylenebismaleimide, N,N'-p-phenylenebismaleimide, N,N'-4,4'-diphenylmethanebismaleimide, N,N'-4,4'-diphenyletherbismaleimide, Examples include N,N'-4,4'-diphenylsulfonebismaleimide, N,N'-4,4'-dicyclohexylmethanebismaleimide, N,N'-α,α'-4,4'-dimethylenecyclohexanebismaleimide, N,N'-m-methaxylenebismaleimide, N,N'-4,4'-diphenylcyclohexanebismaleimide, and N,N'-methylene-bis(3-chloro-p-phenylene)bismaleimide, as well as those described in US 3,562,223, US 4,211,860 and US 4,211,861, or those prepared by the method described, for example, in US 3,018,290.

[0067] Benzoxazine compounds have a benzoxazine ring within the molecule. Exemplary benzoxazine monomers can be prepared from the reaction of an aldehyde, a phenol, and a primary amine, with or without a solvent. Phenol compounds for forming benzoxazine include phenols and polyphenols. When using polyphenols having two or more hydroxyl groups reactive to the formation of benzoxazine, branched, cross-linked, or a combination of branched and cross-linked products may be produced. The group connecting the phenol group into the phenol may be a branching point or a linking group in polybenzoxazine.

[0068] Exemplary phenols for use in the preparation of benzoxazine monomers include phenol, cresol, resorcinol, catechol, hydroquinone, 2-allylphenol, 3-allylphenol, 4-allylphenol, 2,6-dihydroxynaphthalene, 2,7-dihydrooxynaphthalene, 2-(diphenyl-phosphoryl)hydroquinone, 2,2'-biphenol, 4,4-biphenol, 4,4'-isopropylidene diphenol, 4,4'-isopropylidene-bis(2-methyl-phenol), 4,4'-isopropylidene-bis(2-allylphenol), 4,4'-(1,3-phenylenediisopropylidene)bisphenol (Bisphenol M), 4,4'-isopropylidene-bis(3-phenylphenol), and 4,4'-(1,4-phenylenediisopropylidene)-bisphenol. 4,4'-Ethylidene Diphenol, 4,4'-Oxidiphenol, 4,4'-Thiodiphenol, 4,4'-Sulfonyl Diphenol, 4,4'-Sulfinyl Diphenol, 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, Isopropylidene-Bis(2-Allylphenol), 3,3-Bis(4-hydroxyphenyl)isobenzofuran-1(3H)-one, 1-(4-hydroxyphenyl)-3,3-dimethyl-2,3-dihydro-1H-indene-5-ol, 3,3,3',3'-tetramethyl-2,2',3,3'-tetrahydro-1,1'-spirobi-[indene]-5,6'-diol, dihydroxybenzophenone, 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, dicyclopentadienyl-bis(2,6-dimethylphenol), Examples include dicyclopentadienyl-bis(ortho-cresol), dicyclopentadienyl bisphenol, etc.

[0069] The aldehyde used to form benzoxazine may be any aldehyde, for example, an aldehyde having 1 to 10 carbon atoms. For example, the aldehyde may be formaldehyde. The amine used to form benzoxazine may be an aromatic amine, an aliphatic amine, an alkyl-substituted aromatic, or an aromatic-substituted alkyl amine. The amine may be, for example, a polyamine for preparing a multifunctional benzoxazine monomer for crosslinking.

[0070] The amine for forming benzoxazine has 1 to 40 carbon atoms, provided it does not contain an aromatic ring, and can subsequently have 6 to 40 carbon atoms. A difunctional or polyfunctional amine can serve as a branching point connecting one polybenzoxazine to another polybenzoxazine.

[0071] As some examples, thermal polymerization at 150 to 300°C may be used to polymerize benzoxazine monomers. Polymerization may be carried out in bulk, from solution, or in other ways. Catalysts such as carboxylic acids may be used to lower the polymerization temperature or accelerate the polymerization rate at the same temperature.

[0072] Vinyl benzyl ether resins can be prepared from the condensation of vinyl benzyl halides, such as vinyl benzyl chloride, and phenols. Bisphenol-A, trisphenol, and polyphenols are generally used to produce poly(vinylbenzyl ethers) that can be used to produce cross-linked thermosetting resins. Exemplary vinyl benzyl ethers include resorcinol, catechol, hydroquinone, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2-(diphenyl-phosphoryl)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, 4,4'-Isopropylidenebis(2,6-Dibromophenol), 4,4'-Isopropylidenebis(2,6-Dimethylphenol)(Therionic Bisphenol 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-PhenyleneDiisoprolylidene)Bisphenol, 4,4'-EthylideneDiphenol, 4,4'-Oxidiphenol, 4,4'-Thiodiphenol, 4,4'-Thiobis(2,6-Dimethylphenol), 4,4'-SulfonylDiphenol, 4,4'-SulfonylBis(2,6-Dimethylphenol), 4,4'-sulfinyldiphenol, 4,4'-hexafluoroisopropylidene)bisphenol, 4,4'-(1-phenylethylidene)bisphenol, bis(4-hydroxyphenyl)-2,2-dichloro-ethylene, bis(4-hydroxy-phenyl)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-indene-5-ol, 1-(4-hydroxy-3,5-dimethylphenyl)-1,3,3,4,6-pentamethyl-2,3-dihydro-1H-indene-5-ol, 3,3,3',3'-tetramethyl-2,2',3,3'-tetrahydro-1,1'-spirobi[indene]-5,6'-diol, dihydroxybenzophenone, tris(4-hydroxyphenyl)methane, tris(4-hydroxyphenyl)ethane, Examples include vinylbenzyl ethers produced from the reaction of vinylbenzyl halides with tris(4-hydroxyphenyl)-propane, tris(4-hydroxyphenyl)butane, tris(3-methyl-4-hydroxyphenyl)methane, tris(3,5-dimethyl-4-hydroxy-phenyl)methane, tetrakis(4-hydroxyphenyl)ethane, tetrakis(3,5-dimethyl-4-hydroxyphenyl)-ethane, bis(4-hydroxyphenyl)phenylphosphine oxide, dicyclopentadienyl-bis(2,6-dimethylphenol), dicyclopentadienyl bisphenol, etc.

[0073] Arylcyclobutenes include those derived from compounds of the following structures:

[0074]

[0075] In the above formula, B is an organic or inorganic radical with valence n (carbonyl, sulfonyl, sulfinyl, sulfide, oxy, alkylphosphonyl, arylphosphonyl, isoalkylidene, cycloalkylidene, arylalkylidene, diarylmethylidene, methylidene dialkylsilanyl, arylalkylsilanyl, diarylsilanyl and C 6-20 (including phenol compounds) and; X is each independently a hydroxy or C 1-24 Hydrocarbyl (including linear and branched alkyl and cycloalkyl); Z is each independently hydrogen, halogen, or C 1-12It is hydrocarbyl; n is 1 to 1000 or 1 to 8, or n is 2, 3, or 4. Other exemplary arylcyclobutene and methods for synthesizing arylcyclobutene can be found in US 4,743,399, US 4,540,763, US 4,642,329, US 4,661,193, US 4,724,260 and 5,391,650.

[0076] Perfluorovinyl ethers are typically synthesized from phenol and bromotetrafluoroethane, and then ZnFBr and the desired perfluorovinyl ether are produced by zinc-catalyzed reduction removal. Through this route, bis, tris, and other polyphenols can produce bis-, tris-, and poly(perfluorovinyl ethers). Phenols useful for these syntheses include resorcinol, catechol, hydroquinone, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2-(diphenyl-phosphoryl)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, and 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-Phenyphenol), 4,4'-(1,4-PhenyleneDiisopropylidene)-Bisphenol, 4,4'-EthylideneDiphenol, 4,4'-Oxidiphenol, 4,4'-Thiodiphenol, 4,4'-Thiobis(2,6-Dimethylphenol), 4,4'-SulfonylDiphenol, 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-indene-5-ol, 1-(4-hydroxy-3,5-dimethylphenyl)-1,3,3,4,6-pentamethyl-2,3-dihydro-1H-indene-5-ol, 3,3,3',3'-tetramethyl-2,2',3,3'-tetrahydro-1,1'-spirobi[indene]-5,6'-diol (spirobiindane), dihydroxybenzophenone, tris(4-hydroxyphenyl)methane, tris(4-hydroxyphenyl)ethane, Tris(4-hydroxyphenyl)propane, tris(4-hydroxyphenyl)butane, tris(3-methyl-4-hydroxyphenyl)methane, tris(3,5-dimethyl-4-hydroxyphenyl)methane, tetrakis(4-hydroxyphenyl)ethane, tetrakis(3,5-dimethyl-4-hydroxyphenyl)ethane, bis(4-hydroxyphenyl)-phenylphosphine oxide, dicyclopentadienylbis(2,6-dimethylphenol), dicyclopentadienylbis(2-methylphenol), dicyclopentadienylbisphenol, etc. are included.

[0077] Crosslinkers, including auxiliary crosslinkers, are not particularly limited. Crosslinkers may be used alone or in combination of two or more different crosslinkers. Exemplary crosslinkers and auxiliary crosslinkers include oligomers or polymers having curable vinyl functionality. These materials include oligomers and polymers having crosslinkable unsaturation. Examples of these include styrene butadiene rubber (SBR), butadiene rubber (BR), and nitrile butadiene rubber (NBR) having unsaturated bonds based on butadiene; natural rubber (NR), isoprene rubber (IR), chloroprene rubber (CR), butyl rubber (IIR), and butyl halogenated rubber having unsaturated bonds based on isoprene; Examples include ethylene-α-olefin copolymer elastomers having unsaturated bonds based on dicyclopentadiene (DCPD), ethylidene norbornene (ENB), or 1,4-dihexadiene (1,4-HD) (e.g., ethylene-α-olefin copolymers obtained by copolymerizing ethylene, α-olefin, and diene, such as ethylene-propylene-diene terpolymer (EPDM) and ethylene-butene-diene terpolymer (EBDM). In addition, examples of these include hydrogenated nitrile rubber, fluorocarbon rubbers such as vinylidene fluoride-hexafluoropropene copolymer and vinylidene fluoride-pentafluoropropene copolymer, epichlorohydrin homopolymer (CO), copolymer rubber made 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.Additional examples include various liquid rubbers, such as various types of liquid butadiene rubber, and liquid atactic butadiene rubber, which is a butadiene polymer having 1,2-vinyl links produced by anionic living polymerization. It is also possible to use liquid styrene butadiene rubber, liquid nitrile butadiene rubber (CTBN, VTBN, ATBN, etc. from Ube Industries, Ltd.), liquid chloroprene rubber, liquid polyisoprene, dicyclopentadiene-based hydrocarbon polymers, and polynorbornene (commercially available, e.g. from Elf Atochem).

[0078] Polybutadiene resins containing elevated levels of 1,2 addition are preferred for thermosetting matrices. Examples of these include functionalized polybutadiene and poly(butadiene-styrene) random copolymers sold by Ricon Resins, Inc. under the trade names RICON, RICACRYL, and RICOBOND resins. These include butadienes with low vinyl content, such as RICON 130, 131, 134, and 142; polybutadienes with high vinyl content, such as RICON 150, 152, 153, 154, 156, 157, and P30D; Examples include random copolymers of styrene and butadiene comprising RICON 100, 181, 184 and maleic anhydride-grafted polybutadiene, and alcohol condensates derived from said random copolymers such as RICON 130MA8, RICON MA13, RICON 130MA20, RICON 131MAS, RICON 131MA10, RICON MA17, RICON MA20, RICON 184MA6, and RICON 156MA17. Additionally, polybutadienes that can be used to improve adhesion, including RICOBOND 1031, RICOBOND 1731, RICOBOND 2031, RICACRYL 3500, RICOBOND 1756, and RICACRYL 3500; Examples include polybutadiene RICON 104 (25% polybutadiene in heptane), RICON 257 (35% polybutadiene in styrene), and RICON 257 (35% polybutadiene in styrene); (meth)acrylated polybutadienes such as polybutadiene diacrylate and polybutadiene dimethacrylate may also be included. These materials are sold under the trade names RICACRYL 3100, RIACRYL 3500, and RICACRYL 3801. Additionally, powder dispersions of functional polybutadiene derivatives are also included, for example, RICON 150D, 152D, 153D, 154D, P30D, RICOBOND 0 1731 HS, and RICOBOND 1756HS.Additional butadiene resins include poly(butadiene-isoprene) block and random copolymers, such as those with a molecular weight of 3,000 to 50,000 g / mol, and polybutadiene homopolymers with a molecular weight of 3,000 to 50,000 g / mol. Additionally, polybutadiene, polyisoprene, and polybutadiene-isoprene copolymers functionalized with maleic anhydride functional groups, 2-hydroxyethylmaleic acid functional groups, or hydroxylation functional groups are also included.

[0079] Further examples of oligomers and polymers having curable vinyl functional groups 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. Other exemplary crosslinking agents may further include polyfunctional crosslinking monomers, such as (meth)acrylate monomers having two or more (meth)acrylate residues per monomer molecule. Exemplary polyfunctional monomers include di(meth)acrylates such as 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 such as trimethylolpropane tri(meth)acrylate, 1,2,4-butanetriol tri(meth)acrylate, trimethylolpropane ethoxylate tri(meth)acrylate, etc.; tri(meth)allyls such as 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 such as pentaerythritol tetra(meth)acrylate; penta(meth)acrylates such as dipentaerythritol penta(meth)acrylate; hexa(meth)acrylates such as dipentaerythritol hexa(meth)acrylate, sorbitol hexa(meth)acrylate, etc.; glycidyl compounds such as glycidyl(meth)acrylate, (meth)allylglycidyl 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 such as trimethylolpropane tris(mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate), etc.; silanes such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetra-n-butoxysilane, vinyltris(methylethyloxymino)silane, vinyltris(acetoxymino)silane, methyltris(methylethyloxymino)silane, methyltris(acetoxymino)silane, vinyltrimethoxysilane, methyltrimethoxysilane, vinyltris(isopropenoxy)silane, tetraacetoxysilane, methyltriacetoxysilane, ethyltriacetoxysilane, vinyltriacetoxysilane, di-t-butoxy-diacetoxysilane, methyltris(ethyl lactate)silane, vinyltris(ethyl lactate)silane, etc.; Carbodiimides such as N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide hydrochloride, dicyclohexylcarbodiimide, etc.; or combinations thereof are included. The curable thermosetting composition may optionally include a crosslinking catalyst such as a carboxylic acid salt.;

[0080] When a curable thermosetting composition includes a crosslinking agent, the crosslinking agent may be included in an amount of 1 to 60 weight%, 5 to 45 weight%, or 10 to 30 weight% based on the total weight of the curable thermosetting composition.

[0081] A curable thermosetting composition may include one or more curing agents. The term "curing agent" as used herein includes compounds described as curing agents, hardeners, or both.

[0082] Exemplary curing agents and hardening agents include amines, alcohols, phenols, carboxylic acids, acid anhydrides, etc. For example, phenolic hardening agents include novolak-type phenol resin, resol-type phenol resin, cresol novolak resin, aralkyl-type phenol resin, phenol aralkyl resin, cresol aralkyl resin, naphthol aralkyl resin, dicyclopentadiene-type phenol resin, terpene-modified phenol resin, biphenyl-type phenol resin, biphenyl-modified phenol aralkyl resin, bisphenol, triphenylmethane-type phenol resin, tetraphenylol ethane resin, naphthol novolak resin, naphthol-phenol cocondensation novolak resin, naphthol-cresol cocondensation novolak resin, aminotriazine-modified phenol resin, or combinations thereof. Examples of anhydride curing agents include methylhexahydrophthalic anhydride (MHHPA), methyltetrahydrophthalic anhydride, styrene-maleic anhydride copolymer (SMA), and olefin-maleic anhydride copolymers (e.g., maleic anhydride grafted polyethylene, maleic anhydride grafted polypropylene), or combinations thereof. Other curing agents and curing agents include compounds such as dicyandiamide, polyamide, amidoamine, phenalkamine, Mannich base, anhydride, phenol-formaldehyde resin, amine-formaldehyde resin, phenol-formaldehyde resin, carboxylic acid functional polyester, polysulfide, polymercaptan, isocyanate, cyanate ester compounds, or combinations thereof. Other exemplary curing agents include tertiary amines, Lewis acids, unsaturated oligomers, or polymers.

[0083] When a curable thermosetting composition includes a curing agent, the curing agent may be included in an amount of 0.01 to 50 weight%, 0.1 to 30 weight%, or 0.1 to 20 weight% based on the total weight of the curable thermosetting composition.

[0084] Curable thermosetting compositions may include a curing catalyst. The term "curing catalyst" as used herein includes compounds described as variously curing accelerators, curing accelerators, curing catalysts, and curing co-catalysts.

[0085] An exemplary curing accelerator comprises a substituted or unsubstituted C containing 1 to 4 cyclic heteroatoms. 3-6Heterocyclic promoters such as heterocycles are included, wherein each heteroatom is independently identical or different and is nitrogen, oxygen, phosphorus, silicon, or sulfur. Heterocyclic promoters include benzotriazole; triazine; piperazines such as aminoethylpiperazine, N-(3-aminopropyl)piperazine; 1-Methylimidazole, 2-Methylimidazole, 3-Methylimidazole, 4-Methylimidazole, 5-Methylimidazole, 1-Ethylimidazole, 2-Ethylimidazole, 3-Ethylimidazole, 4-Ethylimidazole, 5-Ethylimidazole, 1-n-Propylimidazole, 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, such as 2,4-dimethylimidazole, 2-ethyl-4-methylimidazole, 1-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, and 1-cyanoethyl-2-phenyl-4,5-di(2-cyanoethoxy)methylimidazole Imidazole; cyclic amidines such as 4-diazabicyclo(2,2,2)octane, diazabicycloundecene, 2-phenylimidazoline; N,N-dimethylaminopyridine; sulfamidate; or combinations thereof are included.

[0086] 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, diamide diphenylsulfonic 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-Diiminocyclohexane, 4,4'-Diaminodicyclohexylmethane, 4,4'-Diaminodicyclohexylpropane, 2,2-Bis(4-aminocyclohexyl)propane, 3,3'-Dimethyl-4,4'-Diaminodicyclohexylmethane, Examples include 3-amino-1-cyclohexaneaminopropane, 1,3- and 1,4-bis(aminomethyl)cyclohexane, m- and p-xylylenediamine, or diethyl toluene diamine; or tertiary amine curing accelerators such as triethylamine, tributylamine, dimethylaniline, diethylaniline, benzyldimethylamine (BDMA), α-methylbenzyldimethylamine, N,N-dimethylaminopyridine, N,N-dimethylaminoethanol, N,N-dimethylaminocresol, or tri(N,N-dimethylaminomethyl)phenol; or combinations thereof.

[0087] The curing accelerator may be a potential cation curing catalyst comprising, for example, diaryl iodonium salts, phosphonic acid esters, sulfonic acid esters, carboxylic acid esters, phosphonylides, triaryl sulfonium salts, benzyl sulfonium salts, aryl diazonium salts, benzylpyridinium salts, benzylammonium salts, isoxazolium salts, etc., or a combination thereof. The diaryl iodonium salt [(R 10 )(R 11 )I] + X - It can have the structure of, where R 10 and R 11 C each independently 1-20 Alkyl, C 1-20 C optionally substituted with 1 to 4 monovalent radicals selected from alkoxy, nitro, and chloro. 6-14 It is a monovalent aromatic hydrocarbon radical; X - is an anion. Additional curing accelerators are [(R 10 )(R 11 )I] + SbF6 - It can have the structure of, where R 10 and R 11 C each independently 1-20 Alkyl, C 1-20 C optionally substituted with 1 to 4 monovalent radicals selected from alkoxy, nitro, and chloro. 6-14 It is a monovalent aromatic hydrocarbon radical; for example, 4-octyloxyphenyl phenyl iodonium hexafluoroantimonate.

[0088] The curing accelerator may be a metal salt complex such as copper (II), aluminum (III), zinc, cobalt, or tin salts of an aliphatic or aromatic carboxylic acid selected from copper (II), tin (II), and aluminum (III) salts of acetate, stearate, gluconate, citrate, benzoate, and mixtures thereof. For example, the curing accelerator may be a copper (II) or aluminum (III) salt of β-diketonate; a copper (II), iron (II), iron (III), cobalt (II), cobalt (III), or aluminum (III) salt of acetylacetonate; a zinc (II), chromium (II), or manganese (II) salt of octoate; or a combination thereof.

[0089] When a curable thermosetting composition includes a curing catalyst, the curing catalyst may be included in an amount of 0.01 to 5 weight%, 0.05 to 5 weight%, or 0.1 to 5 weight% based on the total weight of the curable thermosetting composition.

[0090] The curable thermosetting composition may optionally include a curing initiator such as a peroxide compound. Exemplary peroxide curing initiators include benzoyl peroxide, dicumyl peroxide, methyl ethyl ketone peroxide, lauryl peroxide, cyclohexanone peroxide, t-butyl hydroperoxide, t-butyl benzene hydroperoxide, t-butyl peroctoate, t-butylperoxybenzoate, 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-phosphorus, di-t-butylperoxide, t-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-butylperoxybenzoate, 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, trimethylsilylphenyltriphenylsilyl peroxide, etc., or combinations thereof.

[0091] When a curable thermosetting composition includes a curing initiator, the curing initiator may be included in an amount of 0.1 to 5 weight%, 0.5 to 5 weight%, or 1 to 5 weight% based on the total weight of the curable thermosetting composition.

[0092] Flame retardants include, for example, organic compounds containing phosphorus, bromine, or chlorine. Non-brominated and non-chlorinated phosphorus-containing flame retardants may be preferred for certain applications for regulatory reasons, for example, organic phosphates and organic compounds containing phosphorus-nitrogen bonds.

[0093] Examples of phosphorus-based flame retardants include phosphates, phosphazenes, phosphite esters, phosphines, phosphinates, polyphosphates, and phosphonium salts. As for phosphates, triphenyl phosphate, tricresyl phosphate, isopropyl 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, tri(nonylphenyl) phosphate, bis(dodecyl)p-tolyl phosphate, dibutylphenyl phosphate, 2-chloroethyl diphenyl phosphate, p-tolyl bis(2,5,5'-trimethylhexyl) phosphate, 2-ethylhexyl diphenyl phosphate, and xylenyl-diphenyl Examples include phosphates; cresyl-diphenyl phosphate; 1,3-phenylenebis(di-2,6-xylenyl phosphate); condensation phosphate compounds such as 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), tetraphenyl diphosphate (RDP), and aromatic condensation phosphate compounds; and cyclic phosphate compounds, bis(diphenyl)phosphate of hydroquinone, bis(diphenyl)phosphate of bisphenol A, etc., or their oligomeric or polymeric counterparts, or combinations thereof.

[0094] Examples of phosphazene compounds include cyclic and chain-type phosphazene compounds. Cyclic phosphazene compounds (cyclophosphazene) have a cyclic structure in which a phosphorus-nitrogen double bond exists within the molecule. Examples of phosphinate compounds include aluminum dialkylphosphinate, aluminum tris-(diethylphosphinate), aluminum tris-(methylethylphosphinate), aluminum tris-(diphenylphosphinate), zinc bis-(diethylphosphinate), zinc bis-(methylphosphinate), zinc bis-(diphenylphosphinate), titanyl bis-(diethylphosphinate), titanyl bis-(methylethylphosphinate), and titanyl bis-(diphenylphosphinate). Examples of polyphosphonate compounds include melamine polyphosphonate, melam polyphosphonate, and melem polyphosphonate. Examples of phosphonium salt compounds include tetraphenylphosphonium tetraphenylborate. Examples of phosphite ester compounds include trimethylphosphite and triethylphosphite. Flame-retardant compounds containing a phosphorus-nitrogen bond include phosphonitrile chloride, phosphorus esteramide, phosphate amide, phosphonic acid amide, phosphinic acid amide, and tris(aziridinyl)phosphine oxide.

[0095] In addition, halogenated substances can also be used as flame retardants, such as bisphenol, 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; Examples include 2,2-bis-(3,5-dichloro-4-hydroxyphenyl)-propane and 2,2-bis-(3-bromo-4-hydroxyphenyl)-propane. Other halogenated substances include 1,3-dichlorobenzene, 1,4-dibromobenzene, 1,3-dichloro-4-hydroxybenzene, and 2,2'-dichlorobiphenyl, polybrominated 1,4-diphenoxybenzene, 2,4'-dibromobiphenyl, and 2,4'-dichlorobiphenyl, as well as biphenyls such as decabromobiphenyl ether and decabromodiphenylethane, as well as oligomeric and polymerizable halogenated aromatic compounds such as styrene bromide, 4,4-dibromobiphenyl, ethylene-bis(tetrabromophthalimide) or copolycarbonates of bisphenol A, and tetrabromobisphenol A and carbonate precursors, e.g., phosgene. Metal synergists, e.g., antimony oxide, may also be used with flame retardants.

[0096] Inorganic flame retardants may also be used, such as potassium perfluorobutane sulfonate (Rimar salt), potassium perfluorooctane sulfonate, tetraethylammonium perfluorohexane sulfonate, and potassium diphenylsulfone sulfonate, etc. 1-16 Alkyl sulfonate salts; salts such as Na2CO3, K2CO3, MgCO3, CaCO3 and BaCO3, or salts of fluoroanion complexes such as Li3AlF6, BaSiF6, KBF4, K3AlF6, KAlF4, K2SiF6 or Na3AlF6 are included.

[0097] When a curable thermosetting composition includes a flame retardant, the flame retardant may be included in an amount of more than 1 weight%, 1 to 20 weight%, or 5 to 20 weight% based on the total weight of the curable thermosetting composition.

[0098] The curable thermosetting composition may further include inorganic or organic fillers, such as particulate fillers, fibrous fillers, or combinations thereof. Any inorganic or organic fillers, including those known in the art, may be used without limitation.

[0099] Exemplary fillers include, for example, clay, talc, kaolin, wollastonite, mica, calcium carbonate, magnesium carbonate; B-based or Sn-based fillers such as alumina, thiourea, glass powder, or zinc borate, zinc tartrate, and zinc hydroxide; metal oxides such as zinc oxide and tin oxide; alumina, silica (including fused silica, fumigated silica, spherical silica, and crystalline silica), boron nitride (including spherical boron nitride), aluminum nitride, silicon nitride, magnesia, magnesium silicate, antimony trioxide, glass fibers (shredded, ground, or cloth), glass mats, glass bubbles, hollow glass microspheres, aramid fibers, quartz, etc., or combinations thereof. Other exemplary inorganic fillers include powdered titanium ceramics such as any one of the titanates of barium, lead, strontium, calcium, bismuth, magnesium, etc. In addition, inorganic fillers also include hydrates such as aluminum hydroxide, magnesium hydroxide, zeolite, and hydrotalcite. In one embodiment, the filler may be treated with a coupling agent as disclosed herein.

[0100] Glass fibers include E, A, C, ECR, R, S, D, and NE glasses, as well as quartz-based fibers. Glass fibers can have any suitable diameter, such as 2 to 30 micrometers (μm), 5 to 25 μm, or 5 to 15 μm. The length of the glass fibers before compounding is not limited and can be 2 to 7 mm or 1.5 to 5 mm. Alternatively, longer glass fibers or continuous glass fibers may be used. Suitable glass fibers are commercially available from suppliers such as Owens Corning, Nippon Electric Glass, PPG, and Johns Manville.

[0101] Organic fillers may be, for example, polytetrafluoroethylene powder, polyphenylene sulfide powder and poly(ether sulfone) powder, poly(phenylene ether) powder, polystyrene, divinylbenzene resin, etc., or a combination thereof.

[0102] Fillers can be selected based on the coefficient of thermal expansion (CTE) and thermal conductivity requirements. For example, Al2O3, BN, AlN, or combinations thereof can be used in electronic modules with high thermal conductivity. For example, MgO can be used to increase thermal conductivity and CTE. For example, SiO2 (e.g., amorphous SiO2) can be used in lightweight modules with low CTE and small dielectric constant.

[0103] When a curable thermosetting composition includes a filler, the filler may be included in an amount of more than 1 weight%, 1 to 50 weight%, 1 to 30 weight%, or 10 to 30 weight% based on the total weight of the curable thermosetting composition.

[0104] Coupling agents, also referred to as adhesion promoters, include chromium complexes, silanes, titanates, zircon-aluminates, olefin-maleic anhydride copolymers, reactive cellulose esters, etc. Exemplary olefin-maleic anhydride copolymers include maleic anhydride-grafted polyethylene, maleic anhydride-grafted polypropylene, or combinations thereof. Exemplary silanes may include epoxysilane compounds, aminosilane compounds, methacryloxysilane compounds, vinylsilane compounds, or combinations thereof.

[0105] Examples of aminosilane coupling agents are γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-beta(aminoethyl)γ-aminopropylmethyl-dimethoxysilane, N-beta(aminoethyl)γ-aminopropyltrimethoxysilane, and N-beta(aminoethyl)γ-aminopropyltriethoxysilane. Exemplary epoxysilane coupling agents include γ-glycidoxypropylmethyldiethoxysilane, gamma-glycidoxypropyltrimethoxysilane, and γ-glycidoxypropyltriethoxysilane. Examples of methacryloxysilane coupling agents include γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyl-trimethoxysilane, γ-methacryloxypropyldiethoxysilane, and γ-methacryloxypropyltriethoxysilane.

[0106] Other exemplary 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-dimethylthiocarbamoyl tetrasulfide, 3-triethoxysilylpropyl-N,N-dimethylthiocarbamoyl tetrasulfide, Examples include 2-triethoxysilylethyl-N,N-dimethylthiocarbamoyl tetrasulfide, 3-trimethoxysilylpropylbenzothiazoyl tetrasulfide, 3-triethoxysilylpropylbenzoyl tetrasulfide, 3-triethoxysilylpropyl methacrylate monosulfide, 3-trimethoxysilylpropyl methacrylate monosulfide, bis(3-diethoxymethylsilylpropyl) tetrasulfide, 3-mercaptopropyldimethoxymethylsilane, dimethoxymethylsilylpropyl-N,N-dimethylthiocarbamoyl tetrasulfide, dimethoxymethylsilylpropylbenzothiazoyl tetrasulfide, etc., or combinations thereof. The silane coupling agent may be a polysulfide silane coupling agent having 2 to 4 sulfur atoms that form polysulfide crosslinks. For example, the coupling agent may be bis(3-triethoxysilylpropyl) di-, tri-, or tetra-sulfide.

[0107] When a curable thermosetting composition includes a coupling agent, the coupling agent may be included in an amount of 0.01 to 5 weight%, 0.05 to 5 weight%, or 0.1 to 5 weight% based on the total weight of the curable thermosetting composition.

[0108] The curable thermosetting composition may optionally include a solvent. The solvent is, for example, C 3-8 Ketone, C 3-8 N,N-dialkylamide, C 4-16 Dialkyl ether, C 6-12Aromatic hydrocarbons, C 1-3 Chlorinated hydrocarbon, C 3-6 Alkyl alkanoate, C 2-6 It may be alkyl cyanides or combinations thereof. Certain ketone solvents include, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, or combinations thereof. Certain C 4-8 N,N-dialkylamide solvents include, for example, dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, or combinations thereof. Certain dialkyl ether solvents include, for example, tetrahydrofuran, ethylene glycol monomethyl ether, dioxane, or combinations thereof. Certain aromatic hydrocarbon solvents include, for example, benzene, toluene, xylene, styrene, divinylbenzene, or combinations thereof. Aromatic hydrocarbon solvents may be non-halogenated. Certain C 3-6 Alkyl alkanoates include, for example, methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, or combinations thereof. Specific C 2-6 Alkyl cyanides include, for example, acetonitrile, propionitrile, butyronitrile, or combinations thereof. Certain C 2-6Alkyl cyanides include, for example, acetonitrile, propionitrile, butyronitrile, or combinations thereof. For example, the solvent is 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, dimethyl sulfoxide, benzophenone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diglaime, triglaime, tetraglaime, N,N-dimethylethyleneurea, N,N-dimethylpropyleneurea, tetramethylurea, propylene glycol phenyl ether, anisole, veratrol, o-dichlorobenzene, chlorobenzene, trichloroethane, methylene chloride, chloroform, pyridine, picolin, ethyl lactate, n-butyl acetate, butyl cellosolve acetate, butyl carbitol acetate, ethyl cellosolve acetate, ethyl carbitol acetate, propylene carbonate, sulfolane, ionic liquid, or a combination thereof.

[0109] When a solvent is used, the curable thermosetting composition may contain 2 to 99 weight percent of solvent based on the total weight of the curable thermosetting composition. For example, the amount of solvent may be 5 to 80 weight percent, 10 to 60 weight percent, or 20 to 50 weight percent based on the total weight of the curable thermosetting composition. The solvent may be selected to partially control the viscosity of the curable thermosetting composition. Accordingly, the amount of solvent may vary depending on variables including the type and amount of other components such as copolymers and curing additives, the type and amount of auxiliary thermosetting resin(s), and the processing temperature used in subsequent processing steps of the curable thermosetting composition, for example, the process of impregnating a reinforcing structure with the curable thermosetting composition for the manufacture of a composite. The solvent may be anhydrous. For example, the solvent may contain less than 100 ppm, less than 50 ppm, or less than 10 ppm of water based on its total weight.

[0110] The curable thermosetting composition may further comprise a curable unsaturated monomer composition that may include, for example, a monofunctional styrene-based compound (e.g., styrene), a monofunctional (meth)acrylic-based compound, or a combination thereof. For example, the curable unsaturated monomer composition may be an alkene-containing monomer or an alkyne-containing monomer. Exemplary alkene- and alkyne-containing monomers include those described in U.S. Patent No. 6,627,704 of Yeager et al., and (meth)acrylates, (meth)acrylamides, N-vinylpyrrolidone, and vinylazalactone as described in U.S. Patent No. 4,304,705 of Heilman et al. Exemplary monofunctional monomers include mono(meth)acrylates such as 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, etc., or combinations thereof.

[0111] The curable thermosetting composition may optionally further include one or more additional additives. Additional additives include, for example, dyes, pigments, colorants, antioxidants, heat stabilizers, light stabilizers, plasticizers, defoamers, lubricants, dispersants, flow control agents, drop retarders, anti-blocking agents, antistatic agents, flow promoters, processing aids, substrate adhesives, release agents, tougheners, low-profile additives, stress-relieving additives, etc., or combinations thereof. Where present, the additional additive may be included in any effective amount, for example, in an amount of 0.01 to 20 weight%, 0.01 to 10 weight%, 0.01 to 5 weight%, or 0.01 to 1 weight% based on the total weight of the curable thermosetting composition.

[0112] Curable thermosetting compositions can be prepared by combining the copolymer disclosed herein and any other components using any suitable method.

[0113] Additionally, a cured thermosetting composition comprising a cured product of a curable thermosetting composition is provided. There are no particular limitations on the method by which the curable thermosetting composition can be cured. The curable composition may be cured, for example, by thermal curing, or by using irradiation techniques including UV irradiation or electron beam irradiation. For example, a cured product may be obtained by heating the curable thermosetting composition defined herein for a time and temperature sufficient to evaporate the solvent and cure it. When using thermal curing, the temperature may be 30 to 400°C, 50 to 250°C, or 100 to 250°C. Heating may be 1 minute to 24 hours, 1 minute to 6 hours, or 3 hours to 5 hours. Curing may be stepwise to produce a partially cured and often non-tacky resin, which is then fully cured by heating for a longer period at a temperature within the aforementioned ranges. As used herein, the term "cured" includes a partially cured or fully cured product.

[0114] The cured thermosetting composition may have one or more desirable properties. For example, the thermosetting composition may have a glass transition temperature of 165°C or higher, preferably 170°C or higher, more preferably 165 to 180°C. The thermosetting composition may also advantageously exhibit a low dielectric constant (Dk), a low dissipation factor (Df), and reduced water absorption. For example, the thermosetting composition may have a dielectric constant of less than 3.0, preferably less than 2.75, more preferably less than 2.6 at a frequency of 10 GHz. The thermosetting composition may have a dissipation factor of less than 0.01 or less than 0.005 at a frequency of 10 GHz. Accordingly, the thermosetting composition comprising the copolymer of the present disclosure may be particularly suitable for use in the electronic field.

[0115] Curable thermosetting compositions and cured thermosetting compositions may be used in a variety of applications and uses, including any application where conventional thermosetting compositions are used. For example, useful articles comprising a curable thermosetting composition or a cured thermosetting composition may be in the form of composites, foams, fibers, layers, coatings, encapsulating agents, adhesives, sealants, molded parts, prepregs, casings, laminates, metal-clad laminates, electronic composites, structural composites, or combinations thereof. Exemplary uses and applications include coatings such as protective coatings, sealants, weather-resistant coatings, scratch-resistant coatings, and electrical insulation coatings; adhesives; binders; glues; and composite materials such as those using carbon fiber and glass fiber reinforcements. When utilized as a coating, the disclosed compounds and compositions may be deposited on the surface of various underlying substrates. For example, the compositions may be deposited on the surface of metal, plastic, glass, fiber sizing, ceramics, stone, wood, or any combination thereof. The disclosed composition can be used as a coating for the surface of metal containers (e.g., aluminum or steel), such as those commonly used for packaging and sealing in the paint and surface coating industries. The curable thermosetting composition and the cured thermosetting composition derived therefrom may also be particularly suitable for use in forming electrical components and computer components.

[0116] A method for forming a composite comprises the steps of: impregnating a reinforcing structure with a curable thermosetting composition; partially curing the curable thermosetting composition to form a prepreg; and laminating a plurality of prepregs. The reinforcing structure may be a porous base material such as a fibrous preform or a substrate, or other porous material comprising ceramics, polymers, glass, carbon, or a combination thereof. For example, the porous base material may be a woven or non-woven glass fabric, a glass fiber fabric, or carbon fiber. Where the article comprises a fibrous preform, a method for manufacturing the article may include the step of forming the article from the curable thermosetting composition by coating or impregnating the preform with the curable composition. The impregnated fibrous preform may optionally be formed before or after the removal of the solvent. In some embodiments, the layer of the curable thermosetting composition may further comprise a woven or non-woven glass fabric. For example, a curable layer can be prepared by impregnating a glass fabric with a curable composition and removing the solvent from the impregnated glass fabric. Exemplary reinforcing structures are described, for example, in the literature [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", CompositesWorld.com, September 2006]. The weight and thickness of the reinforcing structure are selected according to the intended use of the composite using standards widely known to experts in the manufacture of fiber-reinforced resin composites.The reinforced structure may contain various finishing materials suitable for the thermosetting component of the curable thermosetting composition.

[0117] A method for manufacturing an article from a curable thermosetting composition may include partially curing the curable thermosetting composition to form a prepreg, or fully curing the curable thermosetting composition to form a composite article. The characteristic of "cured composition" refers, by reference to this specification, to a composition that is substantially fully cured. For example, the resin in a laminate formed from a prepreg is generally substantially fully cured. A person skilled in the art of thermosetting can determine whether a sample is partially cured or substantially fully cured without excessive experimentation. Curing may take place before or after removing the solvent from the curable composition. Additionally, the article may be further shaped, for example by thermoforming, before the removal of the solvent, after the removal of the solvent, before curing, after partial curing, or after full curing. In one embodiment, the article is formed, the solvent is removed; the article is partially cured (Step B); optionally shaped; and then further cured.

[0118] Commercial-scale methods for forming composites are known in the art, and the curable thermosetting compositions described herein are readily applicable to existing processes and equipment. For example, prepregs are often produced in processors. The main components of a processor include feeder rollers, resin impregnation tanks, processing ovens, and receiver rollers. Reinforcement structures (e.g., E-glass) are typically wound onto a large spool. The spool is then placed over feeder rollers that rotate and slowly roll the reinforcement structure. The reinforcement structure then moves through a resin impregnation tank containing a curable thermosetting composition. The curable composition impregnates the reinforcement structure. After exiting the tank, the coated reinforcement structure moves upward through a vertical processing oven, typically at a temperature of 175–200°C, where the solvent evaporates. At this point, the resin begins to polymerize. When the composite exits the tower, it is sufficiently cured so that the web does not become wet or sticky. However, since the curing process is stopped before completion, additional curing may occur when making the laminate. Next, the web rolls the prepreg over the receiver roller.

[0119] Electrical and electronic articles comprising or derived from a curable thermosetting composition are also provided. Examples of articles include articles comprising printed circuits used in the medical or aerospace industries. Other examples include antennas and similar articles. Articles such as printed circuit boards are used, for example, in lighting, solar energy, displays, cameras, audio and video equipment, personal computers, mobile phones, electronic notepads and similar devices or office automation equipment. For example, electrical components may be mounted on printed circuit boards comprising laminates. Other exemplary articles manufactured from the curable composition for various applications include copper clad laminates (CCL), for example, metal core copper clad laminates (MCCCL), composite articles, and coated articles, for example, multilayer articles.

[0120] The dielectric layer can be manufactured from a curable thermosetting composition and may be useful in circuit assemblies, such as metal-clad laminates, such as copper-clad laminates. For example, the laminate may comprise a dielectric layer, a conductive metal circuit layer disposed on the dielectric layer, and optionally a heat-dissipating metal matrix layer disposed on the dielectric layer opposite to the conductive metal layer. The dielectric layer may optionally comprise a fibrous preform (e.g., a fabric layer). For example, the dielectric layer may further comprise a glass fabric layer.

[0121] The conductive metal layer may be in the form of a circuit and may be copper, zinc, tin, brass, chromium, molybdenum, nickel, cobalt, aluminum, stainless steel, iron, gold, silver, platinum, titanium, etc., or a combination 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 derived from two layers of copper and one layer of INVAR, and trimetals derived from two layers of copper and one layer of molybdenum. An exemplary metal layer comprises copper or a copper alloy. Alternatively, forged copper foil may be used. The thickness of the conductive metal layer may be 2 to 200 μm, 5 to 50 μm, or 5 to 40 μm.

[0122] The heat dissipation metal matrix layer may be a thermally conductive metal such as aluminum, boron nitride, aluminum nitride, copper, iron, steel, etc., or a combination thereof. Thermally conductive and electrically conductive metals may be used under the condition that the metal is electrically insulated from the metal circuit layer. A preferred supporting metal matrix layer may have a thickness of 0.1 to 20 mm, 0.5 to 10 mm, or 0.8 to 2 mm.

[0123] The conductive metal layer and the supporting metal matrix layer may be pretreated to have high surface roughness to enhance adhesion to the dielectric layer. Treatment methods include, for example, cleaning, flame treatment, plasma discharge, corona discharge, etc., to improve the adhesion of the metal layer. The dielectric layer may be firmly adhered to the conductive metal layer or the heat dissipation layer without the use of an adhesive, or the adhesion between the dielectric layer and the conductive metal layer or the heat dissipation layer may be enhanced by using an adhesive. Exemplary adhesives used to bond the composite sheet to the metal include polyimide adhesives, acrylic adhesives, epoxy, etc., or combinations thereof.

[0124] Copper clad laminates can be manufactured by thermal lamination of one or more dielectric layers, one or more conductive metal layers, and a supporting metal matrix layer under pressure without using a thermosetting adhesive. The dielectric layer can be manufactured from a curable thermosetting composition and can be manufactured prior to the thermal lamination step by a solvent casting process to form the layer. For example, the dielectric layer, the conductive metal layer, and the heat dissipation layer can be thermally laminated together under pressure by an adhesive-free process to form a laminate. The electrically conductive metal layer may optionally be in the form of a circuit before lamination, or the conductive metal layer may optionally be etched to form an electrical circuit after lamination. Lamination can be performed by a hot press or a roll calendering method, for example, a roll-to-roll method. The conductive metal layer within the copper clad laminate may be further patterned to provide a printed circuit board. Furthermore, the copper clad laminate may be shaped to provide a circuit board having the shape of a sheet, tube, or rod.

[0125] Alternatively, a laminate for a circuit assembly can be manufactured by a solution casting method in which a curable thermosetting composition is cast directly onto an electrically conductive metal layer and then laminated onto a heat-dissipating metal matrix layer. For example, the curable thermosetting composition can be cast directly onto a heat-dissipating metal matrix layer and then laminated onto an electrically conductive metal layer.

[0126] Multilayer laminates including additional layers may also be manufactured by thermal lamination in one step or in two or more consecutive steps by a process such as a hot press or roll calendering method. For example, the laminate may have seven or fewer layers, or sixteen or fewer layers. In one embodiment, the laminate may be formed in one step or in two or more consecutive steps using a continuous layer of fabric-thermosetting-metal-thermosetting-fabric-thermosetting-metal foil or a subcombination of said foil having a smaller number of layers, such that the laminate includes a thermosetting film layer between any metal foil layer and any fabric layer. In another embodiment, the first laminate may be formed in one step or in two or more consecutive steps using a fabric layer between two layers of thermosetting resin, such as a woven glass fabric layer between two layers of thermosetting resin. Next, a second laminate can be manufactured by laminating a metal foil onto the thermosetting side of the first laminate.

[0127] A printed circuit board manufactured from a curable thermosetting composition may have a total thickness of 0.1 to 20 mm, specifically 0.5 to 10 mm, wherein the total thickness refers to an assembly comprising layers of a dielectric layer, an electrically conductive metal layer, and a supporting metal matrix layer. The total thickness of the circuit assembly may be 0.5 to 2 mm, specifically 0.5 to 1.5 mm. There is no particular limitation on the thickness of the dielectric layer, and it may be 5 to 1500 μm, 5 to 750 μm, 10 to 150 μm, or 10 to 100 μm. For example, the printed circuit board may be a metal core printed circuit board (MCPCB) for use in light-emitting diode (LED) applications.

[0128] A curable thermosetting composition can be used as a coating, for example, when manufacturing a multilayer article. A method for manufacturing a coating may include combining a curable thermosetting composition with optionally a fluoropolymer and forming a coating on a substrate. For example, a multilayer article comprises forming a layer comprising a curable thermosetting composition, removing a solvent from the layer and optionally curing to provide a primer layer, and applying a second layer comprising a ceramic (e.g., Al2O3, TiO2, ZrO2, Cr2O3, SiO2, MgO, BeO, Y2O3, 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 a combination thereof onto the primer layer to provide a multilayer article, and optionally heat-treating the multilayer article to provide a curable thermosetting composition It can be manufactured by curing. In some embodiments, the second layer may further comprise a curable thermosetting composition.

[0129] Additional applications for curable thermosetting compositions include, for example, acid bath vessels; neutralization tanks; aircraft parts; bridge beams; bridge decks; electrolytic cells; exhaust stacks; scrubbers; sports equipment; stair cases; walkways; automotive exterior panels such as hoods and trunk lids; floor fans; air scoops; pipes and ducts including heater ducts; industrial fans, fan housings, and blowers; industrial mixers; boat hulls and decks; marine terminal fenders; tiles and coatings; construction panels; business machine housings; trays including cable trays; concrete modifiers; dishwasher and refrigerator parts; electro-sealing agents; electrical panels; tanks including electrolytic refining tanks, water softeners, fuel tanks, and various filament-winding tanks and tank linings; furniture; garage doors; gratings; protective body gear; luggage; outdoor motor vehicles; pressure tanks; optical waveguides; radomes; handrails; railway parts such as tank cars; Hopper car covers; car doors; truck bed liners; satellite dishes; signs; solar energy panels; telephone switchgear housings; tractor parts; transformer covers; truck parts such as fenders, hoods, car bodies, cabs, and beds; insulators for rotating machinery including ground insulation, turn insulation, and phase separation insulation; rectifiers; core insulators, cords, and lacing tapes; drive shaft couplings; propeller blades; missile parts; rocket motor cases; wing sections; sucker rods; fuselage sections; wing skin and flaring; engine nacelles; cargo doors; tennis rackets; golf club shafts; fishing rods; skis and ski poles; bicycle parts; transverse leaf springs; pumps such as automotive smog pumps;Electrical components, embeddings, and tooling such as electrical cable joints; wire windings and densely packed multi-element assemblies; sealing of electromechanical devices; battery cases; resistors; fuses and thermal breakers; coatings for printed circuit boards; casting items such as capacitors, transformers, and crankcase heaters; small molded electronic components including coils, capacitors, resistors, and semiconductors; steel substitutes in chemical processing, pulp and paper, power generation, and wastewater treatment; scrubbing towers; pultrusion parts in the structural field including structural members, gratings, and safety rails; swimming pools, pool slides, hot tubs, and saunas; drive shafts for hood applications; dry toner resins for photocopiers; marine tools and composites; thermal shields; submarine hulls; prototype generation; development of experimental models; laminated trims; drilling fixtures; bonding jigs; inspection fixtures; industrial metal forming dies; aircraft stretch blocks and hammer forms; vacuum forming tools; Flooring materials including production and assembly areas, clean rooms, machine plants, control rooms, laboratories, parking lots, freezers, coolers, and outdoor loading and unloading flooring; electrically conductive compositions for antistatic purposes; flooring for decorative purposes; expansion joints for bridges; injectable mortar for patching and repairing cracks in structural concrete; grouting for tiles; rails for machines; metal dowels; bolts and posts; repair of oil and fuel storage tanks; and various other applications.

[0130] Processes useful for manufacturing the present article and material include processes generally known in the field of processing thermosetting resins. These processes are, for example, [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 the literature [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 forming; bulk forming; pultrusion; injection molding including reaction injection molding (RIM); atmospheric pressure molding (APM); casting including centrifugal and static casting and open mold casting; lamination including wet or dry layup and spray layup; contact molding including cylindrical contact molding; compression molding; vacuum-assisted resin transfer molding and chemical-assisted resin transfer molding; alignment tool forming; autoclave curing; air heat curing; vacuum bagging; pultrusion; Seeman's composite resin injection manufacturing The process (SCRIMP); open molding, continuous combination of resin and glass; and filament winding including a cylindrical filament winding are included. For example, the article can be manufactured through a resin transfer molding process.

[0131] Additionally, articles derived from a curable thermosetting composition are provided, wherein the articles are composites, foams, fibers, layers, coatings, encapsulating agents, adhesives, sealants, molded parts, prepregs, casings, cast articles, laminates, or combinations thereof; or the articles are metal-clad laminates, electronic composites, structural composites, or combinations thereof. The articles may be manufactured as disclosed herein by, for example, by casting, molding, extrusion, etc., and by removing the solvent from the molded articles. In one embodiment, the articles may be layers and may be manufactured by casting the curable composition onto a substrate to form a cast layer. The solvent may be removed by any many means, including heating the cast layer, heating the cast layer under heating and pressure, for example, laminating the cast layer onto another substrate. In one embodiment, articles manufactured by the above-described method may include adhesives, packaging materials, capacitor films, or circuit board layers. In one embodiment, an article produced from the curable composition may be a dielectric layer or a coating disposed on a substrate, e.g., a wire or cable coating. For example, the article may be a circuit material, e.g., a dielectric layer within a printed circuit board used in lighting or communication applications. Another exemplary article produced from the curable composition may be one or more coated layers. The curable composition may be used to produce articles disclosed herein for other curable thermosetting compositions.

[0132] The present disclosure is further illustrated by the following non-limiting examples.

[0133] Example

[0134] Example 1: Preparation of Cross-Co-Oligomers

[0135] A dicyclopentadiene dimethoxybenzene cross-co-oligomer was prepared according to the following reaction scheme 1.

[0136] Reaction Equation 1.

[0137]

[0138] Synthesis of dicyclopentadiene (DCPD) and dimethoxybenzene copolymer (I): A 100 mL round-bottom flask equipped with a mechanical stirrer, condenser, and nitrogen inlet was purged with nitrogen. 6.28 g (0.045 mol) of 1,4-dimethoxybenzene, 20 mL of o-dichlorobenzene (ODCB), and 1.33 g (0.01 mol) of aluminum chloride were loaded into the reaction flask. The contents of the reaction mixture were heated to 100°C. When the contents of the reaction flask reached equilibrium, 6.6 g (0.05 mol) of dicyclopentadiene (DCPD) dissolved in 10 mL of ODCB was added dropwise to the flask through an addition funnel. The addition rate of DCPD was maintained so that all DCPD solution was added within 2 to 3 hours. After reacting the contents for 16 hours, the sample was removed, and the molecular weight was measured using GPC. AlCl3 catalyst was added periodically to increase the molecular weight of the reaction. 100 mL of a 5 wt% NaOH solution was added to the contents of the flask to quench the cations, and the mixture was stirred for 1 hour. Subsequently, the contents of the reaction were precipitated in methanol. The oligomer was washed for 30 minutes with a 50:50 volume mixture of methanol and water (shaken in a laboratory shaker) and filtered. Similarly, the polymer was washed three times with methanol to obtain a light gray powder upon drying. The copolymer 1 1H NMR is shown in Figure 1. Table 1 shows the physical properties of the cross-copolymer.

[0139] M w (g / mol) 3300 M n (g / mol) 1105 PDI 2.98 T g (°C) 153 T d,5 (°C) (N2) 342 T d,50 (°C) (N2) 427

[0140] Predictive Example 2: Preparation of Dicyclopentadiene Cross-Co-Oligomer

[0141] Dicyclopentadiene tetramethylbenzene co-oligomer will be prepared as shown in Reaction Scheme 2 below using the method described in Example 1.

[0142] Reaction Equation 2.

[0143]

[0144] Example 3: Preparation of Polyphenylene Ether Dicyclopentadiene Block Copolymer

[0145] Synthesis of 2,6-dimethylphenol-capped DCPD-DMB co-oligomer (II): Synthesis was performed using Example 1, except that an oligomer of DCPD and 1,4-dimethoxybenzene was reacted at 100°C for 18 hours, and then 1.83 g of 2,6-xylenol was added to the reaction flask. The reaction was continued for 16 more hours to confirm the completion of the terminal capping reaction. The reaction mixture was added to methanol to form a slurry, stirred for 1 hour, and filtered. The filtered solid was washed twice with methanol. The filtered solid was dried in a vacuum oven.

[0146] Synthesis of end-capped 2,6-dimethylphenol-capped DCPD-DMB co-oligomer (x and y = 1 in functionalized PPE-DCPDcoDMB-PPE triblock copolymer (IV)): 25 g of 2,6-dimethylphenol-capped dicyclopentadiene dimethoxybenzene co-oligomer (II) and 64 g of toluene were charged into a reactor and heated to remove 40 mL 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 an addition funnel. After all the MAA was consumed, the reaction mixture was heated and refluxed. The reaction was monitored for the consumption of the phenol end groups, and the chemical structure was confirmed by NMR analysis. The reaction mixture was diluted with 20 mL of toluene, and a slurry was prepared by adding the reaction mixture to methanol such that the volume ratio of methanol to reaction mixture was approximately 5:1. The slurry was stirred for 1 hour. The precipitate was filtered and washed twice with 1 L of methanol. The product was dried in an oven at ambient temperature with an N2 sweep.

[0147] Reaction Equation 3

[0148]

[0149] Predicted Example 4: Example 3 will be repeated using dicyclopentadiene tetramethylbenzene co-oligomer.

[0150] Reaction Equation 4

[0151]

[0152] Example 5: Synthesis of Polycyclopentadiene Dimethylphenol Di-adduct (PCPD-DMP Di-adduct)

[0153] Polycyclopentadiene oligomers were synthesized through Diels-Alder addition polymerization to form the following structure. Then, the unsaturated double bonds were alkylated with 2,6-dimethylphenol, followed by oxidative coupling polymerization and functionalization.

[0154] Reaction Scheme 5a. Synthesis of polycyclopentadiene by cycloaddition polymerization

[0155]

[0156] Procedure. Synthesis of Polycyclopentadiene Dimethylphenol Di-adduct (PCPD-DMP Di-adduct)

[0157] 250 g (2.02 mol) of DCPD and 250 g (2.71 mol) of toluene were charged into an open Parr reactor. The reactor was sealed so that none of the valves were open to the atmosphere. The reactor was heated to 270°C for 4 hours. After the reaction, the reactor was cooled to room temperature (RT), and the product was removed from the reactor in 50 wt% toluene for storage and testing. Its structure was confirmed by NMR analysis. The molecular weight was determined by GPC measurement (Mw = 2542, Mn = 827, PD = 3.1).

[0158] Reaction Scheme 5b. Synthesis of Polycyclopentadiene Dimethylphenol Di-adduct (PCPD-DMP Di-adduct)

[0159]

[0160] Procedure. 250 g of 2,6-dimethylphenol (2.04 mol, molten) and 11.5 g (0.067 mol) of p-toluenesulfonic acid (p-TSA) were loaded into a prefabricated reactor. The reactor was heated to 170°C. While the reactor was heating, 217 g of PCPD (crude product from the previous step) at 50 wt% in toluene was loaded into an addition funnel and added dropwise at 80°C. The reaction was determined by observing a decrease in the intensity of the alkene protons. 1The reaction was monitored using 1H NMR. If the reaction was slow, the reaction rate was increased by removing the solvent (approx. 50 g). When the alkene proton consumption rate (%), calculated by dividing the alkene peak intensity by the alkene peak intensity at 0 hours, exceeded 99%, 6.65 g (0.067 mol) of KHCO3 was charged into the reactor under stirring, and the reaction was quenched. The reaction mixture was added to 2 L of methanol (MeOH) to precipitate the reaction product, and the resulting slurry was filtered. The isolated precipitate was dissolved in 50 wt% CHCl3 and then precipitated in MeOH at a 1:1 ratio. The filter cake was washed with DI water, then washed with MeOH, and dried in an oven at 60°C under vacuum. Its structure 1 It was confirmed by H NMR analysis (i.e., the disappearance of the peak corresponding to the vinyl group on the PCPD and the connectivity between 2,6-dimethylphenol and the terminal cyclopentane and norbornan rings).

[0161] Reaction Scheme 5c. Synthesis of terminal-capped polycyclopentadiene dimethylphenol di-adduct

[0162]

[0163] Procedure. 40 g of PCPD-DMP diadduct and 79 g (0.85 mol) of toluene were charged into a reactor and heated to remove 40 mL 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 an addition funnel. After all the MAA was consumed, the reaction mixture was heated and refluxed. The consumption of the phenol terminal group of the reaction mixture was monitored, and its chemical structure was confirmed by NMR analysis. The reaction mixture was diluted with 40 mL of toluene, and the product was precipitated by adding the reaction mixture to methanol such that the volume ratio of methanol to reaction mixture was approximately 5:1. The resulting slurry was stirred for 1 hour. The precipitate was filtered, and the filtered solid was washed twice with methanol (1 L each time). The product was dried in an oven at ambient temperature with an N2 sweep.

[0164] Reaction Scheme 5d. Synthesis of Poly(phenylene ether)-Polycyclopentadiene-Poly(phenylene ether) Triblock Copolymer (PPE-PCPD-PPE)

[0165]

[0166] Procedure. 40 g of PCPD-DMP di-adduct was added to a reactor in 160 g of toluene. Once the PCPD-DMP di-adduct 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 charged into the reactor. 0.0817 g of Cu2O and 1.0591 g of HBr were added to the reactor, and an oxygen flow was started. 105.5 g of 2,6-dimethylphenol (DMP) at 50 wt% in toluene was added dropwise over 45 minutes. After the reaction was complete, 1.4686 g of NTA was added in 23.0126 g of water, and the temperature was raised to 60°C while stirring for 2 hours. After chelation, the toluene phase was separated, and the product was isolated by removing the toluene. The material was further dried overnight at 110°C under vacuum. The connectivity between polycyclopentadiene and poly(phenylene ether) blocks was confirmed using NMR. Molecular weight was measured by GPC (Mw=21083, Mn=4644, PDI=4.5). Tg was measured by DSC (Tg= 202°C).

[0167] Reaction Scheme 5e. Synthesis of terminal-capped polyphenylene ether-polycyclopentadiene-polyphenylene ether triblock copolymer

[0168]

[0169] Procedure. 109 g of toluene was added to the reactor, and the temperature was raised to 50°C. Then, 70 g of PPE-PCPD-PPE was added to the reactor. After complete dissolution, the solution was heated to 120°C for azeotropic distillation. When the solution concentration of the reaction mixture reached 50 / 50 (toluene / PPE-PCPD-PPE), the temperature was lowered to 85°C. 0.3282 g (0.002686 mol) of 4-dimethylaminopyridine was added to the solution. Once completely dissolved, MAA was slowly added, and the temperature was set to 120°C. The reaction was monitored for the consumption of phenol terminal groups. The reaction mixture was cooled to 90°C, 40 ml of toluene was added, and the reaction mixture was added to methanol, at which point the ratio of reaction mixture to methanol was approximately 5:1. After the precipitate formed, the mixture was filtered using a Buchner funnel and rinsed twice with methanol. The isolated solid was placed in a vacuum oven and dried overnight. The molecular weight was determined by GPC (Mw = 14187, Mn = 3181, PDI = 4.5). Tg was determined by DSC (Tg = 204°C).

[0170] Example 6.

[0171] DCPD homo-oligomers (Reaction Scheme 6) can be obtained from three different synthetic routes and can be used to prepare DCPD homo-oligomers functionalized with 2,6-dimethylphenol (DMP), which is a block copolymer, and the block copolymer functionalized with crosslinking groups will be prepared according to Reaction Scheme 7 below.

[0172] Reaction Equation 6.

[0173]

[0174] Reaction Equation 7.

[0175]

[0176] Reaction Scheme 6a. Synthesis of Polydicyclopentadiene.

[0177]

[0178] Procedure. The reaction flask was cooled to -14.5°C and purged with N2 (g). DCPD monomer was mixed with 30% toluene, the mixture was transferred to a reactor, the reactor was purged with N2, and the mixture was stirred for 30 minutes until the temperature reached -14.5°C. Once the target temperature was reached, 3–4.5 wt% AlCl3 was added to the reaction mixture and stirred for 15 minutes; subsequently, 100 ml of methanol was added to quench the reaction. The crude product was a yellow viscous substance in the methanol. Additional methanol was added to precipitate the product. Its chemical structure was confirmed by NMR analysis. Molecular weight was measured by GPC (Mw = 3937, Mn = 1584, PDI = 2.5). Tg was measured by DSC (Tg = 170°C).

[0179] Reaction Scheme 6b. Synthesis of polydicyclopentadiene dimethylphenol adduct (PDCPD-DMP adduct).

[0180]

[0181] Procedure. The reactor was purged with N2 (g). 2.49 moles of 2,6-DMP monomer containing 0.498 moles of poly-DCPD (cationic polymerization product) in toluene were transferred to the reactor, purged with N2, and stirred for 30 minutes to reach 60°C. Upon reaching the target temperature, 0.011 moles of p-toluenesulfonic acid were added to the reaction mixture and stirred for 60 minutes. 0.011 moles of NaHCO3 (5 wt% in DI water) were added and stirred for an additional 30 minutes. The reaction was monitored by NMR for the reduction of vinyl groups. After washing the reaction mixture with water three times or until the pH was equal to that of DI water, the reaction mixture was added to methanol and precipitated in methanol. The mixture was filtered to obtain a brown powder.

[0182] Reaction Scheme 6c. Synthesis of terminal-capped polydicyclopentadiene dimethylphenol adduct (predicted).

[0183]

[0184] Procedure. Charge the PDCPD-DMP adduct and toluene into a reactor and heat to remove 40 mL of the toluene / water azeotropic mixture by azeotropic distillation. Cool the reactor to 85°C and add 4-dimethylaminopyridine (DMAP) to the reactor. Add methacrylic anhydride (MAA) dropwise through an addition funnel. After all MAA is consumed, heat the reaction mixture and reflux. Add the reaction mixture to methanol to precipitate the product in the methanol. Filter and dry the precipitate.

[0185] Reaction Scheme 6d. Synthesis of polyphenylene ether-polycyclopentadiene graft copolymer (PDCPD-graft-PPE) (predicted).

[0186]

[0187] 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. Charge the reactor with DBA, DMBA, and DBEDA. 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 raise the temperature to 60°C while stirring for 2 hours. Separate the toluene phase and remove the toluene to isolate the product. The material is further dried under vacuum.

[0188] Reaction Scheme 6e. Synthesis of terminal-capped polyphenylene ether-polycyclopentadiene graft copolymer (predicted).

[0189]

[0190] Procedure. Charge PDCPD-graft-PPE and toluene into a reactor and heat to remove 40 mL by azeotropic distillation. Cool the reactor to 85°C and add 4-dimethylaminopyridine (DMAP) to the reactor. Add methacrylic anhydride (MAA) dropwise through an addition funnel. After all MAA is consumed, heat the reaction mixture to reflux. Precipitate the product in methanol. Filter and dry the particles.

[0191] The present disclosure further includes the following aspects.

[0192] Embodiment 1: A copolymer comprising a polyphenylene ether component and a dicyclopentadiene copolymer component having the structure of the following chemical formula D1, D2, D3-1, D3-2 or D3-3:

[0193]

[0194] In the above formula, Z1 and Z3 are each independently a halogen, a C1-C where the hydrocarbyl group is unsubstituted or substituted and not a tertiary hydrocarbyl. 12 Hydrocarbyl, C1-C 12 Hydrocarbilthio, C1-C 12 Hydrocarbyloxy, or C2-C in which at least two carbon atoms separate a halogen and an oxygen atom. 12 Containing a halohydrocarbyloxy; Z2 and Z4 are each independently C1-C groups in which hydrogen, halogen, or hydrocarbyl groups are non-tertiary hydrocarbyls or are unsubstituted or substituted. 12 Hydrocarbyl, C1-C 12 Hydrocarbilthio, C1-C 12 Hydrocarbiloxy, or C2-C 12 It comprises a halohydrocarbyloxy, wherein at least two carbon atoms separate a halogen and an oxygen atom; R1 to R4 are each independently hydrogen, C1-C 12 Hydrocarbyl, or C1-C 12It comprises a hydrocarbyloxy; x is at least 1 to 50; y is at least 1 to 50; n is at least 1 to 100; and Q1 comprises a single bond, hydrogen, or terminal functional group.

[0195] Embodiment 1a. The copolymer according to Embodiment 1, wherein Z1 and Z3 independently comprise a halogen, an unsubstituted or substituted alkyl, phenyl, cycloalkyl, bicycloalkyl, or alkoxy, wherein at least two carbon atoms separate the halogen and oxygen atoms; Z2 and Z4 independently comprise a hydrogen, a halogen, an unsubstituted or substituted alkyl, phenyl, cycloalkyl, bicycloalkyl, or alkoxy, wherein at least two carbon atoms separate the halogen and oxygen atoms; and R1 to R4 independently comprise a hydrogen, an alkyl, alkenyl, or alkoxy.

[0196] Embodiment 1b. The copolymer of Embodiment 1, wherein Z1 and Z3 each independently comprise a halogen, an unsubstituted or substituted alkyl, phenyl, cycloalkyl, bicycloalkyl, or alkoxy, wherein at least two carbon atoms separate the halogen and oxygen atoms; Z2 and Z4 each independently comprise hydrogen; and R1 to R4 each independently comprise hydrogen, an alkyl, alkenyl, or alkoxy.

[0197] Embodiment 1c. A copolymer composition according to Embodiment 1, wherein Z1 and Z3 independently comprise methyl; Z2 and Z4 independently comprise hydrogen; and R1 to R4 independently comprise hydrogen, methyl, isopropyl, vinyl, allyl, or methoxy.

[0198] Embodiment 2. In any one of the aforementioned embodiments, the dicyclopentadiene copolymer component of Formula D1 is derived from Formula P1 below, the dicyclopentadiene copolymer component of Formula D2 is derived from Formula P2 below, the dicyclopentadiene copolymer component of Formula D3-1 is derived from Formula P3-1 below, the dicyclopentadiene copolymer component of Formula D3-2 is derived from Formula P3-2 below, and the dicyclopentadiene copolymer component of Formula D3-3 is derived from Formula P3-3 below, wherein n is 1 to 100, a copolymer:

[0199]

[0200] Embodiment 3. In any one of the aforementioned embodiments, a copolymer in which the polyphenylene ether component has the following structure:

[0201]

[0202] In the above formula, Z1 and Z3 are each independently a halogen, a C1-C where the hydrocarbyl group is unsubstituted or substituted and not a tertiary hydrocarbyl. 12 Hydrocarbyl, C1-C 12 Hydrocarbilthio, C1-C 12 Hydrocarbyloxy, or at least two carbon atoms, C2-C that separates a halogen and an oxygen atom. 12 Includes halohydrocarbyloxy; and

[0203] Z2 and Z4 are each independently C1-C groups in which hydrogen, halogen, or hydrocarbyl groups are non-tertiary hydrocarbyls, either unsubstituted or substituted. 12 Hydrocarbyl, C1-C 12 Hydrocarbilthio, C1-C 12 Hydrocarbyloxy, or C2-C in which at least two carbon atoms separate halogen and oxygen atoms. 12 Contains halohydrocarbyloxy.

[0204] Aspect 4. In any one of the aforementioned aspects, the copolymer is a block copolymer derived from a dicyclopentadiene copolymer component of formula D1 or D2.

[0205] Aspect 5. In any one of the aforementioned aspects, the copolymer comprises at least two A blocks containing a dicyclopentadiene copolymer component, and preferably the copolymer is an ABA triblock copolymer.

[0206] Embodiment 6. In any one of the aforementioned embodiments, the copolymer comprises at least two B blocks containing a polyphenylene ether component, and preferably the copolymer is a BAB triblock copolymer.

[0207] Aspect 7. A copolymer of any one of the aforementioned aspects, comprising a graft copolymer derived from a dicyclopentadiene component of chemical formula D3-1, D3-2 or D3-3.

[0208] Embodiment 8. In any one of the aforementioned embodiments, the copolymer wherein the dicyclopentadiene copolymer component comprises at least one terminal functional group including a vinyl benzene ether terminal functional group, a methacrylate terminal functional group, an acrylate terminal functional group, an epoxy terminal functional group, a hydroxyl terminal functional group, a cyanate ester terminal functional group, an amine terminal functional group, a maleimide terminal functional group, an allyl terminal functional group, a styrene terminal functional group, an activated ester terminal functional group, or an anhydride terminal functional group.

[0209] Aspect 9. Covalently coupling a dicyclopentadiene precursor of formula P1, P2, P3-1, P3-2, or P3-3 with a substituted or unsubstituted monovalent phenol, comprising

[0210] A method for preparing a dicyclopentadiene copolymer of any one of the aforementioned embodiments, wherein the dicyclopentadiene precursor and the monovalent phenol comprise complementary reactive groups.

[0211] Embodiment 10. Providing a copolymer by oxidative polymerization of a substituted or unsubstituted monovalent phenol from a dicyclopentadiene copolymer component; or comprising covalently coupling a polyphenylene ether oligomer with a dicyclopentadiene precursor of formula P1, P2, P3-1, P3-2, or P3-3,

[0212] Herein, a method for preparing a copolymer of any one of the aforementioned embodiments, wherein the dicyclopentadiene precursor and the polyphenylene ether oligomer comprise complementary reactive groups.

[0213] Embodiment 11. A curable thermosetting composition comprising a copolymer of any one of Embodiments 1 to 8, optionally one or more of a crosslinking agent, a curing agent, a curing catalyst, a curing initiator, or a combination thereof; one or more of a flame retardant, a filler, a coupling agent, or a combination thereof; or further comprising a combination thereof.

[0214] Embodiment 12. A cured thermosetting composition comprising a cured product of the curable thermosetting composition of Embodiment 11.

[0215] Embodiment 13. An article comprising the cured thermosetting composition of Embodiment 12, wherein the article is a composite, foam, fiber, layer, coating, encapsulating agent, adhesive, sealant, molded part, prepreg, casing, casting, laminate, or a combination thereof; or the article is a metal-clad laminate, electronic composite, structural composite, or a combination thereof.

[0216] Embodiment 14. A varnish composition comprising the curable thermosetting composition of Embodiment 11 and a solvent.

[0217] Embodiment 15. An article manufactured from the varnish composition of Embodiment 14, wherein, preferably, the article is a fiber, layer, coating, casting article, prepreg, composite, or laminate; or the article is a metal-clad laminate.

[0218] The above compositions, methods, and articles may alternatively include, be composed of, or essentially consist of any suitable materials, steps, or components disclosed herein. The above compositions, methods, and articles may additionally or alternatively be formulated without or substantially without any materials (or species), steps, or components that are not necessary to achieve the function or purpose of the compositions, methods, and articles.

[0219] All ranges disclosed herein include endpoints, and endpoints may be combined independently of one another (e.g., a range of “up to 25 wt%, or more specifically 5 wt% to 20 wt%” includes endpoints and all intermediate values ​​of the “5 wt% to 25 wt%” range, etc.). “Combinations” include kneaded materials, mixtures, alloys, reaction products, etc. Terms such as “first,” “second,” etc. do not indicate order, quantity, or importance, but are used to distinguish one element from another. The terms “a,” “an,” and “the” do not imply a limitation of quantity and should be interpreted to include both singular and plural forms unless otherwise indicated in this specification or clearly contradicted by the context. “Or” means “and / or” unless otherwise specified. Throughout the entirety of the specification, the criteria for “some embodiments,” “embodiments,” etc., mean that a specific element described in relation to an embodiment is included in at least one embodiment described herein and may or may not be present in other embodiments. Furthermore, it should be understood that the described elements may be combined in any appropriate manner in various embodiments. “Combinations thereof” is open and includes all combinations in which at least one of the listed components or attributes is optionally included together with identical or equivalent components or attributes that are not listed.

[0220] Unless otherwise specified in this specification, all test standards are the most recent standards valid as of the filing date of this application or, where priority is claimed, as of the filing date of the first priority application in which the test standards appeared.

[0221] Unless otherwise defined, technical and scientific terms used herein have the same meaning as generally understood by those skilled 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, in the event that the terms of this application contradict or conflict with the terms of a cited reference, the terms of this application shall prevail over the conflicting terms of the cited reference.

[0222] Compounds are described using standard nomenclature. For example, any position not substituted by any indicated group is understood to have the indicated bond or a valence filled with hydrogen atoms. A dash ("-") between two letters or symbols is used to indicate the attachment point of a substituent. For example, -CHO is bonded through the carbon of the carbonyl group.

[0223] As used herein, the term “hydrocarbyl” means a residue containing only carbon and hydrogen, whether used as itself or as a prefix, suffix, or fragment of another term, unless specifically identified as “substituted hydrocarbyl.” Hydrocarbyl residues may be aliphatic or aromatic, straight-chain, cyclic, bicyclic, branched, saturated, or unsaturated. It may also include combinations of aliphatic, aromatic, straight-chain, cyclic, bicyclic, branched, saturated, or unsaturated hydrocarbon components. If a hydrocarbyl residue is described as substituted, it may contain heteroatoms in addition to carbon and hydrogen.

[0224] The term "alkyl" means a branched or straight-chain unsaturated aliphatic hydrocarbon group, e.g., methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, t-butyl, n-pentyl, s-pentyl, n-hexyl, and s-hexyl. "Alkenyl" means a straight-chain or branched-chain monovalent hydrocarbon group having at least one carbon-carbon double bond (e.g., ethenyl (-HC=CH2)). "Alkoxy" means an alkyl group connected via oxygen (i.e., alkyl-O-), e.g., methoxy, ethoxy, and sec-butyloxy groups. "Alkylene" means a straight-chain or branched saturated divalent aliphatic hydrocarbon group (e.g., methylene (-CH2-) or propylene (-(CH2) 3- It means )). "Cycloalkylene" refers to the divalent cyclic alkylene group -C n H 2n-x It means, where x is the number of hydrogens substituted by the cyclization(s). "Cycloalkenyl" means a monovalent group having one or more rings and one or more carbon-carbon double bonds within the rings, where all ring members are carbon (e.g., cyclopentyl and cyclohexyl). "Aryl" means an aromatic hydrocarbon group containing a specified number of carbon atoms, such as phenyl, tropone, indanyl, or naphthyl. "Aryllene" 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 of fluoro, chloro, bromo, or iodo substituents. A combination of other halogen groups (e.g., bromo and fluoro) may be present, or only chloro groups may be present. The prefix "hetero" indicates that the compound or group comprises at least one ring member that is a heteroatom (e.g., 1, 2, or 3 heteroatom(s)), wherein each heteroatom(s) is independently N, O, S, Si, or P. "Substituted" indicates that the compound or group is independently C instead of hydrogen. 1-9 Alkoxy, C1-9 Haloalkoxy, nitro(-NO2), cyano(-CN), C 1-6 Alkyl sulfonyl(-S(=O)2-alkyl), C 6-12 Aryl sulfonyl (-S(=O)2-aryl), thiol (-SH), thiocyano (-SCN), tosyl (CH3C6H4SO 2- ), C 3-12 Cycloalkyl, C 2-12 Alkenyl, C 5-12 Cycloalkenyl, C 6-12 Aril, C 7-13 Arylalkylene, C 4-12 Heterocycloalkyl and C 3-12 It means being substituted with at least one (e.g., 1, 2, 3, or 4) substituents that may be heteroaryl, provided that the normal valence of the substituted atoms is not exceeded. The number of carbon atoms indicated in the group excludes any substituents. For example, -CH2CH2CN is a C2 alkyl group substituted with a nitrile.

[0225] Although specific embodiments have been described, alternatives, modifications, changes, improvements, and substantial equivalents that are not currently foreseen or cannot be foreseen may occur to the applicant or those skilled in the art. Accordingly, the appended claims as filed and as they may be amended are intended to cover all alternatives, modifications, changes, improvements, and substantial equivalents.

Claims

Claim 1 A copolymer comprising a polyphenylene ether component and a dicyclopentadiene copolymer component having the structure of the following chemical formula D1, D3-1, D3-2 or D3-3: In the above formula, Z1 and Z3 are each independently halogen, C1-C 12 Hydrocarbyl is an unsubstituted or substituted C1-C that is not a tertiary hydrocarbyl 12 Hydrocarbyl, C1-C 12 Hydrocarbilthio, C1-C 12 Hydrocarbyloxy, or C2-C in which at least two carbon atoms separate a halogen and an oxygen atom. 12 Containing a halohydrocarbyloxy; Z2 and Z4 are each independently C1-C groups in which hydrogen, halogen, or hydrocarbyl groups are non-tertiary hydrocarbyls or are unsubstituted or substituted. 12 Hydrocarbyl, C1-C 12 Hydrocarbilthio, C1-C 12 Hydrocarbyloxy, or C1-C in which at least two carbon atoms separate a halogen and an oxygen atom. 12 Contains a halohydrocarbyloxy; R1 to R4 are each independently hydrogen, C1-C 12 Hydrocarbyl, or C1-C 12 It comprises a hydrocarbyloxy; x is at least 1 to 50; y is at least 1 to 50; n is at least 1 to 100; and Q1 comprises a single bond, hydrogen, or terminal functional group. Claim 2 A copolymer comprising a polyphenylene ether component and a dicyclopentadiene copolymer component having the structure of the following chemical formula D2: In the above formula, the copolymer comprises at least two A blocks comprising the formula D2, at least one Q1 is a single bond for each of the at least two A blocks, and Z1 and Z3 are each independently a halogen, a C1-C group in which the hydrocarbyl group is unsubstituted or substituted and not a tertiary hydrocarbyl. 12 Hydrocarbyl, C1-C 12 Hydrocarbilthio, C1-C 12 Hydrocarbyloxy, or C2-C in which at least two carbon atoms separate a halogen and an oxygen atom. 12 Containing a halohydrocarbyloxy; Z2 and Z4 are each independently C1-C groups in which hydrogen, halogen, or hydrocarbyl groups are non-tertiary hydrocarbyls or are unsubstituted or substituted. 12 Hydrocarbyl, C1-C 12 Hydrocarbilthio, C1-C 12 Hydrocarbyloxy, or C2-C in which at least two carbon atoms separate a halogen and an oxygen atom. 12 It comprises a halohydrocarbyloxy; x is at least 1 to 50; y is at least 1 to 50; n is at least 1 to 100; and Q1 comprises a single bond, hydrogen, or terminal functional group. Claim 3 A copolymer comprising a polyphenylene ether component and a dicyclopentadiene copolymer component having the structure of the following chemical formula D2: In the above formula, Z1 and Z3 are each independently halogen, C1-C 12 Hydrocarbilthio, C1-C 12 Hydrocarbyloxy, or C2-C in which at least two carbon atoms separate a halogen and an oxygen atom. 12 Containing a halohydrocarbyloxy; Z2 and Z4 are each independently C1-C groups in which hydrogen, halogen, or hydrocarbyl groups are non-tertiary hydrocarbyls or are unsubstituted or substituted. 12 Hydrocarbyl, C1-C 12 Hydrocarbilthio, C1-C 12 Hydrocarbyloxy, or C2-C in which at least two carbon atoms separate a halogen and an oxygen atom. 12 It comprises a halohydrocarbyloxy; x is at least 1 to 50; y is at least 1 to 50; n is at least 1 to 100; and Q1 comprises a single bond, hydrogen, or terminal functional group. Claim 4 A copolymer comprising a polyphenylene ether component and a dicyclopentadiene copolymer component having the structure of the following chemical formula D2: In the above formula, Z1 and Z3 each independently comprise a halogen, cycloalkyl, bicycloalkyl, or alkoxy; Z2 and Z4 each independently comprise a hydrogen, halogen, unsubstituted or substituted alkyl, phenyl, cycloalkyl, bicycloalkyl, or alkoxy in which at least two carbon atoms separate the halogen and oxygen atoms; x is at least 1 to 50; y is at least 1 to 50; n is at least 1 to 100; and Q1 comprises a single bond, hydrogen, or terminal functional group. Claim 5 In claim 1, the copolymer of formula D1 is derived from the following formula P1, the copolymer of formula D3-1 is derived from the following formula P3-1, the copolymer of formula D3-2 is derived from the following formula P3-2, and the copolymer of formula D3-3 is derived from the following formula P3-3, wherein n is 1 to 100, a copolymer: Claim 6 In any one of claims 2 to 4, the copolymer of formula D2 is derived from the following formula P2, and n is 1 to 100, a copolymer: Claim 7 A copolymer according to any one of claims 1 to 5, wherein at least one Q1 comprises a single bond, and the copolymer further comprises an additional polyphenylene ether component comprising a repeating unit having the following structure: In the above formula, Z1 and Z3 are each independently a halogen, a C1-C where the hydrocarbyl group is unsubstituted or substituted and not a tertiary hydrocarbyl. 12 Hydrocarbyl, C1-C 12 Hydrocarbilthio, C1-C 12 Hydrocarbyloxy, or at least two carbon atoms, C2-C that separates a halogen and an oxygen atom. 12 Containing a halohydrocarbyloxy; and Z2 and Z4 are each independently C1-C in which hydrogen, halogen, or hydrocarbyl groups are non-substituted or substituted hydrocarbyls. 12 Hydrocarbyl, C1-C 12 Hydrocarbilthio, C1-C 12 Hydrocarbyloxy, or C2-C in which at least two carbon atoms separate halogen and oxygen atoms. 12 Contains halohydrocarbyloxy. Claim 8 In claim 1, the copolymer is a copolymer having the chemical formula D1. Claim 9 A copolymer according to any one of claims 1 to 5 and 8, comprising at least two A blocks including the copolymer, wherein at least one Q1 of each A block is a single bond. Claim 10 In claim 9, the copolymer is an ABA triblock copolymer, and the repeating unit of the B block has the following structure: In the above formula, Z1 and Z3 are each independently a halogen, a C1-C where the hydrocarbyl group is unsubstituted or substituted and not a tertiary hydrocarbyl. 12 Hydrocarbyl, C1-C 12 Hydrocarbilthio, C1-C 12 Hydrocarbyloxy, or at least two carbon atoms, C2-C that separates a halogen and an oxygen atom. 12 Containing a halohydrocarbyloxy; and Z2 and Z4 are each independently C1-C in which hydrogen, halogen, or hydrocarbyl groups are non-substituted or substituted hydrocarbyls. 12 Hydrocarbyl, C1-C 12 Hydrocarbilthio, C1-C 12 Hydrocarbyloxy, or C2-C in which at least two carbon atoms separate halogen and oxygen atoms. 12 Contains halohydrocarbyloxy. Claim 11 In claim 7, the copolymer comprises at least two B blocks containing an additional polyphenylene ether component. Claim 12 In claim 1, the copolymer is a BAB triblock copolymer, and the repeating unit of the B block has the following structure: In the above formula, Z1 and Z3 are each independently a halogen, a C1-C where the hydrocarbyl group is unsubstituted or substituted and not a tertiary hydrocarbyl. 12 Hydrocarbyl, C1-C 12 Hydrocarbilthio, C1-C 12 Hydrocarbyloxy, or at least two carbon atoms, C2-C that separates a halogen and an oxygen atom. 12 Containing a halohydrocarbyloxy; and Z2 and Z4 are each independently C1-C in which hydrogen, halogen, or hydrocarbyl groups are non-substituted or substituted hydrocarbyls. 12 Hydrocarbyl, C1-C 12 Hydrocarbilthio, C1-C 12 Hydrocarbyloxy, or C2-C in which at least two carbon atoms separate halogen and oxygen atoms. 12 Contains halohydrocarbyloxy. Claim 13 In claim 1, the copolymer comprises a graft copolymer derived from a dicyclopentadiene component of formula D3-1, D3-2 or D3-3. Claim 14 A copolymer according to claim 1, wherein the dicyclopentadiene copolymer component comprises at least one terminal functional group including a vinyl benzene ether terminal functional group, a methacrylate terminal functional group, an acrylate terminal functional group, an epoxy terminal functional group, a hydroxyl terminal functional group, a cyanate ester terminal functional group, an amine terminal functional group, a maleimide terminal functional group, an allyl terminal functional group, a styrene terminal functional group, an activated ester terminal functional group, or an anhydride terminal functional group. Claim 15 A method for preparing the copolymer of claim 1, comprising covalently coupling a copolymer precursor of formula P1, P3-1, P3-2, or P3-3 with a substituted or unsubstituted monovalent phenol. Claim 16 A method for preparing the copolymer of claim 1, comprising: providing a copolymer by oxidative polymerization of a substituted or unsubstituted monovalent phenol from a dicyclopentadiene copolymer component; or covalently coupling a polyphenylene ether oligomer with a dicyclopentadiene precursor of formula P1, P3-1, P3-2, or P3-3. Claim 17 A curable thermosetting composition comprising the copolymer of claim 1 and optionally further comprising: one or more of a crosslinking agent, a curing agent, a curing catalyst, a curing initiator, or a combination thereof; one or more of a flame retardant, a filler, a coupling agent, or a combination thereof; or a combination thereof. Claim 18 A cured thermosetting composition comprising a cured product of the curable thermosetting composition of claim 17. Claim 19 Articles comprising a cured thermosetting composition of claim 18, wherein the article is a composite, foam, fiber, layer, coating, encapsulating agent, adhesive, sealant, molded part, prepreg, casing, casting, laminate, or combination thereof; or articles comprising a cured thermosetting composition, wherein the article is a metal-clad laminate, electronic composite, structural composite, or combination thereof. Claim 20 A varnish composition comprising the curable thermosetting composition of claim 17 and a solvent. Claim 21 Articles produced from the varnish composition of claim 20, wherein the articles are fibers, layers, coatings, cast articles, prepregs, composites, or laminates; or articles produced from the varnish composition, wherein the articles are metal-clad laminates.

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