Polyfunctional poly(arylene ethers) and curable compositions thereof

Abstract

A polyfunctional poly(arylene ether) includes an end group including a linking group and a terminal functional group, wherein the linking group includes a substituted or unsubstituted saturated hydrocarbylene group, or a substituted or unsubstituted saturated poly(hydrocarbylene ether), and wherein the terminal functional group includes the formula -X- T, wherein each occurrence of X is independently an oxygen or substituted or unsubstituted nitrogen, and each occurrence of T is independently a reactive end group and optionally hydrogen, and wherein the polyfunctional poly(arylene ether) includes at least one reactive end group.

Description

POLYFUNCTIONAL POLYfARYLENE ETHERS) AND CURABLE COMPOSITIONSTHEREOFCROSS REFERENCE TO RELATED APPLICATIONThis application claims priority to and the benefit of European Patent Application No. 24171640.6 filed April 22, 2024, the contents of which are hereby incorporated by reference in their entirety.BACKGROUND

[0001] This disclosure relates to poly(arylene ethers), copolymers thereof, and in particular polyfunctional poly(arylene ethers), curable and cured compositions thereof, methods of manufacture, and uses thereof.

[0002] Poly(arylene ethers) are a class of thermoplastics known for excellent water resistance, as well as outstanding dielectric properties over wide frequency and temperature ranges. It is therefore desirable to incorporate poly(arylene ethers) in thermosetting compositions to impart dielectric performance and moisture resistance. However, conventional poly(arylene ethers) with functionalized phenolic terminal functional groups have properties such as high glass transition temperatures that make them difficult to process in fabrications where solvents are not used. Additionally, the reaction of conventional poly(arylene ethers) having phenolic terminal functional groups to introduce crosslinking groups is much slower than similar functionalization reactions for reactive resin systems such as epoxy, urethane, anhydride, and other derivatization reactions.

[0003] There accordingly remains a continuing need in the art for poly functional poly(arylene ethers) with improved reactivity and processability.BRIEF DESCRIPTION

[0004] The above-described and other deficiencies of the art are met with a polyfunctional poly(arylene ether) including an end group including a linking group and a terminal functional group, wherein the linking group includes a substituted or unsubstituted saturated hydrocarbylene group or a substituted or unsubstituted saturated poly(hydrocarbylene ether), and wherein the terminal functional group is of the formula -X-T, wherein each occurrence of X is independently an oxygen or substituted or unsubstituted nitrogen, and each occurrence of T is independently a reactive end group and optionally hydrogen.

[0005] In another aspect, a method for preparing the above-described polyfunctional poly(arylene ether) includes reacting a polyfunctional poly(arylene ether) precursor with an endcapping agent to provide the polyfunctional poly (arylene ether), wherein the polyfunctional poly(arylene ether) precursor includes an end group including a linking group and a terminalfunctional group of the formula -XH, wherein each occurrence of X is independently an oxygen or substituted or unsubstituted nitrogen.

[0006] A curable composition includes the above-described polyfunctional poly(arylene ether) and optionally, a curing agent reactive with the polyfunctional poly(arylene ether).

[0007] An aspect is the cured product of the curable composition.

[0008] In another aspect, an article includes the above-described cured product.

[0009] A method for manufacturing the above-described article includes molding, casting, extruding, spinning, printing, spraying, coating or foaming the curable composition, and curing the compositions to provide the article.

[0010] The above-described and other features are exemplified by the following drawing, detailed description, examples, and claims.BRIEF DESCRIPTION OF THE DRAWING

[0011] The FIGURE is a graph showing the glass transition temperature (Tg) of each material produced versus the number of equivalents of ethylene oxide added of an exemplary aspect.DETAILED DESCRIPTION

[0012] Poly(arylene ethers) can improve dielectric performance, heat resistance, flame resistance and moisture absorption of materials, making them particularly well suited for a variety of applications, particularly electronic applications. It is therefore desirable to incorporate poly(arylene ether) oligomers into thermosetting compositions to improve properties, such as one or more of dielectric performance, heat resistance, flame resistance and moisture absorption of the resulting compositions.

[0013] In some applications, lower processing temperatures are used. To that end, the presence of a linking group including a substituted or unsubstituted saturated hydrocarbylene group, or a substituted or unsubstituted saturated poly(hydrocarbylene ether) can decrease the glass transition temperature (Tg) of the polyfunctional poly(arylene ether). For example, polyurethanes are typically processed at temperatures of not more than 80°C. The present methods allow for control over the length of linking group, thus providing control over the Tg of the material. The polyfunctional poly(arylene ethers) are therefore customizable for use in various applications.

[0014] In curable thermosetting compositions, the reactivity of conventional poly(arylene ethers) having reactive end groups (attached to phenolic oxygens) is less than other reactive resins. By functionalizing poly(arylene ethers) with end groups including linking groups, the reactivity of the reactive end groups can be improved, simplifying the curing process. The processability of the polyfunctional poly( arylene ether)s can also be improvedcompared to conventional poly (arylene ethers) without the linking groups. In some aspects, the Tg of the polyfunctional poly (arylene ether) is lower compared to those conventional poly (arylene ethers) without the linking groups.

[0015] The polyfunctional poly(arylene ether) includes one or more end groups, for example, 2, 3, 4, 5, or more end groups. The end group includes a linking group and a terminal functional group. The linking group includes a substituted or unsubstituted saturated hydrocarbylene group, or a substituted or unsubstituted saturated poly(hydrocarbylene ether) group.

[0016] As used herein, the term “hydrocarbyl”, whether used by itself, or as a prefix, suffix, or fragment of another term, e.g., hydrocarbylene, refers to a residue that contains only carbon and hydrogen unless it is specifically identified as “substituted hydrocarbyl”. The hydrocarbylene residue can be aliphatic or aromatic, straight-chain, cyclic, bicyclic, branched, saturated, or unsaturated. It can also contain combinations of aliphatic, aromatic, straight chain, cyclic, bicyclic, branched, saturated, and unsaturated hydrocarbon moieties. When the hydrocarbylene residue is described as substituted, it can contain heteroatoms in addition to carbon and hydrogen.

[0017] As used herein, the term “saturated hydrocarbyl,” “saturated hydrocarbylene,” and the like refers to a residue that contains only carbon and hydrogen unless it is specifically identified as “substituted saturated hydrocarbyl” or “substituted saturated hydrocarbylene.” Saturated hydrocarbylene and saturated hydrocarbylene groups include straight-chain, cyclic, bicyclic, and branched groups and excludes unsaturated groups, such as aromatic groups, partially aromatic groups, and groups having double bonds and triple bonds. The saturated hydrocarbylene and saturated hydrocarbylene can also include combinations of straight-chain, cyclic, bicyclic, and branched groups. Examples of saturated hydrocarbyl and hydrocarbylene groups include alkyl groups, alkylene groups, cycloalkyl groups, and cycloalkylene groups, wherein each of the foregoing can be substituted by alkyl groups or cycloalkyl groups.

[0018] As used herein, the term “saturated poly(hydrocarbylene ether)” refers to an ether-containing or polyether group wherein the hydrocarbylene moiety of the polyether group contains only carbon and hydrogen unless it is specifically identified as “substituted poly(hydrocarbylene ether).” The ether-containing groups have at least two hydrocarbylene groups, and the polyether groups are repeating groups of the formula -hydrocarbylene-O-.

[0019] Exemplary linking groups shown below include an unsubstituted saturated hydrocarbylene group, (e.g., an ethylene; structure on left) and an unsubstituted, saturated poly(hydrocarbylene ether) (e.g., diethyl ether; structure on right). The terminal functional group in both structures shown below is XT, and ” indicates a link to the remaining portion ofthe bifunctional poly(arylene ether).

[0020] The linking group can include a substituted or unsubstituted saturated hydrocarbylene linking group, which includes a substituted or unsubstituted C2-30 hydrocarbylene group. The C2-30 hydrocarbylene group can include at least 2, at least 3, at least4, or at least 6 carbon atoms and up to 30, up to 20, up to 10, up to 8, up to 6, or up to 4 carbon atoms. A range of carbon atoms in the hydrocarbylene group can include any of the foregoing limits. For example, the C2-30 hydrocarbylene group can include a substituted or unsubstituted C2-10 alkyl, or C2-4 alkyl, or C2-3 alkyl.

[0021] The linking group can include a substituted or unsubstituted C4-100 poly(hydrocarbylene ether). The C4-100 hydrocarbylene ether can include at least 10, at least 15, at least 20, at least 25, at least 30, at least 35, at least 40, at least 45, at least 50, at least 55, or at least 60 carbons and up to 90, up to 80, up to 70, up to 60, up to 50, up to 40, up to 30, or up to 20 carbons. A range of carbon atoms in the poly(hydrocarbylene ether) can include any of the foregoing limits.

[0022] The linking group can include a substituted or unsubstituted C4-100 poly(C2-4 alkylene ether). The number of carbons in the C4-100 poly(C2-4 alkylene ether) can include any of the foregoing limits for the C4-100 poly(hydrocarbylene ether). In certain aspects, the C4-100 poly(hydrocarbylene ether) includes a C4-100 poly(C2-3 alkylene ether). In certain aspects, the C4- 100 poly (hydrocarbylene ether) includes a C4-100 poly(C2 alkylene ether).

[0023] The linking group can include a substituted or unsubstituted C4-100 poly(C2-4 alkylene ether). The number of carbons in the C4-100 poly(C2-4 alkylene ether) can include any of the foregoing limits for the C4-100 poly(hydrocarbylene ether). In certain aspects, the C4-100 poly(hydrocarbylene ether) includes a C4-100 poly(C2-3 alkylene ether). In certain aspects, the C4- 100 poly (hydrocarbylene ether) includes a C4-100 poly(C2 alkylene ether).

[0024] The linking groups can include units derived from a multifunctional polyol. As used herein, a multifunctional polyol includes at least two hydroxyl groups, for example 2-6, 2-5, 2-4, or 2-3 hydroxyl groups. The multifunctional polyol can be any multifunctional polyol known in the art. Exemplary multifunctional polyols include glycerol, trimethylolpropane, triethanolamine, pentaerythritol, xylitol, sorbitol, and sucrose. In some aspects, multifunctional polyols include polyether polyols such as ethoxylated, propoxylated, and butoxylated polyols, wherein two or more hydroxyl groups are not alkoxylated.

[0025] The linking groups of the polyfunctional poly (arylene ether) can include the following formulas -C(RI)(R2)-, or -[(C(Ri)(R2))mi-O]ni-(C(Ri)(R2))-, wherein: Ri and R2 are each independently hydrogen, halogen, or Ci-6 alkyl, ml is 2 or more, or 2-4, and nl is 1 or more, or 1-25. In some aspects, Ri and R2 are each independently hydrogen, halogen, or C1-3 alkyl, ml is 2 or more, or 2-4, and nl is 1 or more, or 1-25. In some aspects, Ri and R2 are each independently hydrogen, halogen, or methyl, ml is 2 or more, or 2-4, and nl is 1 or more, or 1- 25. In some aspects, Ri and R2 are each independently hydrogen, ml is 2-3, and nl is 1-25. In the foregoing aspects, nl can be 5-25, or 15-25. The present inventors discovered that as the poly(hydrocarbylene) or the poly(hydrocarbylene ether) chain grows longer, the Tg of the material decreases. This is an advantage when lower processing temperatures are needed. For example, polyurethanes are typically processed at temperatures of not more than 80°C. When the value of nl is 5-25, the Tg can be about 20°C less, or 40°C less, or 60°C less than the Tg of the corresponding conventional poly(arylene ether) with phenolic end groups. In some aspects, the Tg of the polyfunctional poly(arylene ether) is not more than 100°C, or not more than 80°C, as measured using differential scanning calorimetry (DSC) per ASTM D3418 at a heating rate of 20°C per minute. In the foregoing aspects, units derived from a multifunctional polyol can be present in the end groups.

[0026] In addition to the linking groups, the polyfunctional poly( arylene ether) includes one or more terminal functional groups, for example 2-6, 2-5, 2-4, or 2-3 functional groups . The terminal functional group are of the formula X-T, wherein each occurrence of X is independently an oxygen or substituted or unsubstituted nitrogen, and each occurrence of T is independently a reactive end group and optionally hydrogen. In some aspects, X can be oxygen or a substituted or unsubstituted nitrogen, preferably oxygen or an unsubstituted nitrogen, more preferably, oxygen.

[0027] The reactive end groups are not particularly limited, and can be derived from a compound including unsaturation, an epoxy, a benzoxazine, an isocyanate, a cyanate ester, a melamine, a cyanophenyl, a maleimide, a phthalonitrile, a cycloalkylphenyl, an ethoxylate, a urethane, an anhydride, an allylhydroxypropyl, a methacrylate, an acrylate, an allyl, or a vinylbenzyl. In some aspects, the reactive end group comprises an unsaturated moiety. In some aspects, the reactive end group comprises an epoxy. In some aspects, the reactive end group comprises a benzoxazine. In some aspects, the reactive end group comprises an isocyanate. In some aspects, the reactive end group comprises a cyanate ester. In some aspects, the reactive end group comprises a melamine. In some aspects, the reactive end group comprises a cyanophenyl. In some aspects, the reactive end group comprises a maleimide. In some aspects, the reactive end group comprises a phthalonitrile. In some aspects, the reactive end group comprises acycloalkylphenyl. In some aspects, the reactive end group comprises an ethoxylate. In some aspects, the reactive end group comprises a urethane. In some aspects, the reactive end group comprises an anhydride. In some aspects, the reactive end group comprises an allylhydroxypropyl. In some aspects, the reactive end group comprises a methacrylate. In some aspects, the reactive end group comprises an acrylate. In some aspects, the reactive end group comprises an allyl. In some aspects, the reactive end group comprises a vinylbenzyl. In some aspects, the reactive end group excludes terephthalic acid. In some aspects, the reactive end group excludes moieties derived from terephthalic acid. In some aspects, the reactive end group excludes phthalic acid. In some aspects, the reactive end group excludes moieties derived from phthalic acid.

[0028] In some aspects, the reactive end groups can each independently be of the following formulas of Scheme B:Scheme B wherein Y2is a divalent linking group having one of formulas of Scheme CScheme C wherein each occurrence of Rcand Rdindependently is hydrogen or C1-12 alkyl, R5ais an epoxide-containing group, a cyanate-containing group, or a C1-12 hydrocarbylene optionally substituted with one or two carboxylic acid groups, each occurrence of R6, R7, and R8independently is hydrogen, Ci-is hydrocarbyl, C2-18 hydrocarbyloxycarbonyl, nitrile, formyl, carboxylic acid, imidate, or thiocarboxylic acid, and each occurrence of R9, R10, R11, R12, and R13independently is hydrogen, halogen, C1-12 alkyl, C2-12 alkenyl, hydroxy, amino, maleimide, carboxylic acid, or a C2-20 alkyl ester; provided that at least one of Rxand Ryis not a hydrogen atom; m is an integer of 0-3, or 0-2, or 0-1; and n is an integer of 2-20, or 3 to 16.

[0029] In some aspects, the polyfunctional poly( arylene ether) includes repeating units derived from a monohydric phenol, the repeating units having the formula (1)wherein each occurrence of Q1is independently substituted or unsubstituted C1-C12 primary orsecondary alkyl or cycloalkyl, or substituted or unsubstituted C1-C12 primary alkyl, or substituted or unsubstituted Ci-Ce primary alkyl, or substituted or unsubstituted methyl; each occurrence of Q2is independently halogen, C1-C12 hydrocarbylene provided that the hydrocarbylene group is not tertiary hydrocarbyl, C1-C12 hydrocarbylthio, C1-C12 hydrocarbyloxy, or C2-C12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms, or C1-C12 alkyl or C3-C12 cycloalkyl, or Ci-Ce alkyl, or methyl; each occurrence of Q3and Q4is independently hydrogen, halogen, unsubstituted or substituted C1-C12 hydrocarbylene provided that the hydrocarbylene group is not tertiary hydrocarbyl, C1-C12 hydrocarbylthio, C1-C12 hydrocarbyloxy, or C2-C12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms, preferably hydrogen; and e is 1-200, or 1-100, provided that when e is 1, at least one additional repeat unit is present in the polymer. In some aspects, each occurrence of Q1is independently methyl or cyclohexyl, optionally substituted with a amine group having from 1-12 carbon atoms, and each occurrence of Q2is independently halogen, unsubstituted C1-12 alkyl provided that the alkyl group is not tertiary alkyl, or unsubstituted C1-12 aryl. In some aspects, each occurrence of Q1is independently methyl, methyl substituted with a di(Ci-6 alkyl)amino group, or a morpholinylmethyl group, and each Q2is methyl.

[0030] Exemplary monohydric phenols that can be used include 2,6-dimethylphenol, 2- methylphenol, 2, 5 -dimethylphenol, 2-allyl-6-methylphenol, 2,3,6-trimethylphenol, 2-methyl-6- phenyl phenol, 2-cyclohexyl-6-methylphenol, or a combination thereof. For example, the monohydric phenol can include 2,6-dimethylphenol.

[0031] In addition to repeating units derived from a monohydric phenol, the polyfunctional poly(arylene ether) having the end groups may comprise repeating units derived from a dihydric phenol, the repeating units having the structure of formula (2)wherein each occurrence of Q1and Q2is independently halogen, unsubstituted or substituted Ci- 15 primary or secondary hydrocarbyl, C1-12 hydrocarbylthio, C1-12 hydrocarbyloxy, or C2-12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms; each occurrence of Q3and Q4is independently hydrogen, halogen, unsubstituted or substituted C1-C15 primary or secondary hydrocarbyl, C1-C12 hydrocarbylthio, C1-12 hydrocarbyloxy, or C2-12halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms; x and y have an average value, and are each independently 0-100, 0-50, or 0-20, or 0-15, or 0- 10, or 0-8, provided that the sum of x and y is at least 2, or at least 3, or at least 4, up to 20, up to 40, up to 50, up to 100, or up to 200. In some aspects, each occurrence of Q1is independently methyl or cyclohexyl optionally substituted with an amine group having from 1-12 carbon atoms, and each occurrence of Q2is halogen, unsubstituted C1-12 alkyl provided that the alkyl group is not tertiary alkyl, or unsubstituted C1-12 aryl. In some aspects, each occurrence of Q1is independently methyl or methyl substituted with a di(Ci-6 alkyl)amino group, and each Q2is methyl.

[0032] In Formula (2), L can be of formula (3)wherein each occurrence of P1, P2, P3, and P4is independently hydrogen, halogen, unsubstituted or substituted C1-12 primary or secondary hydrocarbyl, C1-12 hydrocarbylthio, C1-12 hydrocarbyloxy, or C2-12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms; and Y is a single bond or a divalent linking group of Scheme Ame A wherein each occurrence of Ra, Rb, Rc, Rd, and Reis independently hydrogen, C1-12 hydrocarbyl, or Ci -6 hydrocarbylene, optionally wherein Raand Rbor Rcand Rdtogether are a C4-8 alkylene group; each occurrence of Rfis independently hydrogen, a C1-14 hydrocarbyl, a C1-14 halohydrocarbyl, or a C1-14 heterohydrocarbyl, or C1-13 alkyl, C1-13 alkoxy, C2-13 alkenyl, C2-13 alkenyloxy, C3-6 cycloalkyl, C3-6 cycloalkoxy, Ce-14 aryl, Ce-io aryloxy, C7-13 arylalkyl, C7-13 arylalkoxy, C7-13 alkylaryl, or C7-13 alkylaryloxy; wherein each occurrence of Rgis independently a substituted or unsubstituted C1-12 hydrocarbylene group, a C6-12 arylene group, or a combination thereof, or wherein each occurrence of Rgis the same and is a divalent C2-8 aliphatic group, or wherein each occurrence of Rgis the same and is dimethylene, trimethylene, or tetramethylene; and E is 2-200, or 6-100.

[0033] Examples of dihydric phenols that can be used include 3,3',5,5'-tetramethyl-4,4'- biphenol, 2,2-bis(3-methyl-4-hydroxyphenyl)propane, 2,2-bis(3,5-dimethyl-4- hydroxyphenyl)propane, l,l-bis(4-hydroxyphenyl)methane, 1, l-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4- hydroxyphenyl)octane, 1 , 1 -bis(4-hydroxyphenyl)propane, 1 , 1 -bis(4-hydroxypheny 1 )-n-butane, bi s(4-hydroxyphenyl)phenylmethane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 1 , l-bis(4- hydroxy-3-methylphenyl)cyclohexane, 1 , 1 -bis(4-hydroxy-3 ,5-dimethylphenyl)cyclopentane, l,l-bis(4-hydroxy-3,5-dimethylphenyl)cyclohexane, l,l-bis(4-hydroxy-3- methylphenyl)cycloheptane, l,l-bis(4-hydroxy-3,5-dimethylphenyl)cycloheptane, 1,1 -bis(4- hydroxy-3-methylphenyl)cyclooctane, l,l-bis(4-hydroxy-3,5-dimethylphenyl)cyclooctane, 1,1 - bis(4-hydroxy-3-methylphenyl)cyclononane, l,l-bis(4-hydroxy-3,5- dimethylphenyl)cyclononane, 1 , 1 -bis(4-hydroxy-3-methylphenyl)cyclodecane, 1 , 1 -bis(4- hydroxy-3,5-dimethylphenyl)cyclodecane, l,l-bis(4-hydroxy-3-methylphenyl)cycloundecane, 1 , l-bis(4-hydroxy-3,5-dimethylphenyl)cycloundecane, 1, l-bis(4-hydroxy-3- methylphenyl)cyclododecane, 1 , l-bis(4-hydroxy-3,5-dimethylphenyl)cyclododecane, 1 , l-bis(4- hydroxy-3-t-butylphenyl)propane, 2,2-bis(4-hydroxy-2,6-dimethylphenyl)propane, 2,2-bis(4- hydroxy-3-bromophenyl)propane, 1 , 1 -bis(4-hydroxyphenyl)cyclopentane, 1 , 1 -bis(4- hydroxyphenyl)cyclohexane, 2,2',6,6'-tetramethyl-3,3',5,5'-tetrabromo-4,4'-biphenol, 2, 2', 5,5'- tetramethyl-4,4'-biphenol, and a dihydric phenol of formula (4)wherein n is, on average, 5-100, or 10-60.

[0034] The polyfunctional poly(arylene ether) can further include repeating units derived from a multifunctional monomer. The multifunctional monomer includes at least 3 functional groups, 3-8 functional groups, 3-6 functional groups, or 3-4 functional groups, wherein at least 2 functional groups are hydroxyl groups. The multifunctional monomer can be any multifunctional monomer known in the art. Exemplary multifunctional monomers include glycerol, trimethylolpropane, triethanolamine, pentaerythritol, xylitol, sorbitol, and sucrose. In some aspects, multifunctional polyols include polyether polyols such as, for example, ethoxylated, propoxylated, and butoxylated polyols, wherein two or more hydroxyl groups are not alkoxylated.

[0035] The polyfunctional poly(arylene ether) can have a structure of formula (5)wherein each occurrence of Q1, Q2, Q3Q4of P1, P2, P3, P4, and Y are independently as defined above with regard to formula 2 and formula 3. Each occurrence of P5is independently Q1or a (Ci-C6-hydrocarbyl)(Ci-C6-hydrocarbyl)aminomethylene group; x' and y' represent the number of repeat units, and hence the relative mole ratios, of the arylene ether units wherein x' and y' are each independently 0-50, provided that the sum of x' and y' is at least 2; or e is the number of repeating units of the arylene ether unit and e is 1-200, or 1-100; z is 0 or 1. For example, x' and y' can be independently 0-30. The asterisks (“*”) indicate where the end groups are attached.

[0036] For example, the polyfunctional poly(arylene ether) is of the formula (6a)wherein Q1, Q2, Q3, Q4, P1, P2, P3, P4, and P5x', and y' are as defined above. The asterisks (“*”) indicate where the end groups are attached. In some aspects, the polyfunctional poly (arylene ether) is derived from 2,6-dimethyl phenol, 2,3,6-trimethyl phenol, or a combination thereof, in combination with 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane.

[0037] The polyfunctional poly(arylene ether) can be the product of a polyfunctional phenolic poly( arylene ether), and subsequent reaction with an alkylene oxide and optionally, a multifunctional polyol to form the polyfunctional poly(arylene ether)

[0038] The poly(arylene ether) having phenolic terminal groups (sometimes referred to hereinafter as the phenolic poly(arylene ether)) can be formed by polymerization of the abovedescribed monomers, for example a monohydric phenol, a dihydric phenol, or a combination thereof, by continuous addition of oxygen to a reaction mixture including the monomers, optionally a solvent, and a polymerization catalyst. The molecular oxygen (O2) can be provided as air or pure oxygen. The polymerization catalyst can be a metal complex, i.e. a metal catalyst, including a transition metal cation, including cations from Group VIB, VIIB, VIIIB, or IB of the periodic table, or a combination thereof. The catalyst can include a metal cation such as chromium, manganese, cobalt, copper, or combination thereof and an anion such as chloride, bromide, iodide, sulfate, acetate, propionate, butyrate, laurate, palmitate, benzoate, or a combination of one or more of these anions, and optionally one or more charge-neutral ligands such as water, amines, phosphines, CO, or the like. Alternatively, a metal or metal oxide and aninorganic acid, organic acid, or an aqueous solution of such an acid can be combined to form a corresponding metal salt or hydrate in situ. For example, cuprous oxide and hydrobromic acid can be combined to generate cuprous bromide in situ.

[0039] Exemplary amine ligands can be a monoamine, an alkylene diamine, or a combination thereof. Monoamines include dialkylmonoamines (such as di-n-butylamine) and trialkylmonoamines (such as N,N-dimethylbutylamine). Exemplary monoamines include di-n- butylamine, n-butylethylamine, di-tert-butylamine, tert-butylethylamine, dimethylamine, di-n- propylamine, di-sec-butyl amine, dipentylamine, dihexylamine, dioctylamine, didecylamine , dibenzylamine, methylethylamine, methylbutylamine, dicyclohexylamine, N-ethylaniline, N- butyl aniline, N-methyl-2-methylaniline, N-methyl-2,6-dimethylaniline, diphenylamine, or a combination thereof. Exemplary diamines include a N,N'-di-tert-butylethylenediamine, or the like, and combinations thereof. Exemplary trialkylmonoamines include trimethylamine, triethylamine, tripropylamine, tributylamine, butyldimethylamine, phenyldiethylamine, or the like, or a combination thereof.

[0040] When the amine ligand includes a secondary amine such as di-n-butylamine, some of the secondary amine can be chemically incorporated into the phenolic poly(arylene ether) at the benzylic position of terminal monohydric phenol units. The covalently bound monoamine groups can be present as aminomethyl groups ortho to the phenol oxygen in terminal units as shown below:

[0041] The amount of covalently bound monoamine groups can be determined by1H- NMR spectroscopy. Covalently bound monoamine groups can adversely affect the oxidative stability of capped poly(arylene ether) and can result in yellowing of the capped poly(arylene ether) upon heat aging.

[0042] The poly(arylene ether) having phenolic terminal groups can be isolated using any method known in the art. Isolation can be by, for example, precipitation of the poly(arylene ether) which can be induced by appropriate selection of reaction solvent described above, or by the addition of an anti-solvent to the reaction mixture. Suitable anti-solvents include lower alkanols having one to about ten carbon atoms, acetone and hexane. A preferred anti-solvent is methanol. The anti-solvent can be used at a range of concentrations relative to the organic solvent, with the optimum concentration depending on the identities of the organic solvent and anti-solvent, as well as the concentration and intrinsic viscosity of the poly(arylene ether)product. When the organic solvent is toluene and the anti-solvent is methanol, a toluene: methanol weight ratio of 50:50 to 80:20 is suitable, with ratios of 60:40 to 70:30 being preferred, and 63:37 to 67:33 being more preferred. Alternatively, the poly(arylene ether) solution and the aqueous sequestrant solution can be separated with a liquid-liquid centrifuge. Once this separation has been effected, the polyfunctional poly(arylene ether) can be isolated from the poly(arylene ether) solution using a total isolation method. Suitable total isolation methods include, for example, devolatilizing extrusion, spray drying, wiped film evaporation, flake evaporation, and combinations of the foregoing methods.

[0043] Phenolic poly(arylene ether), for example, phenolic poly(phenylene ether) optionally can be in the form of a copolymer of two or more monomers, for example a terpolymer, and the raw materials used to produce the poly (arylene ethers) can be, or can be formed from, renewable, sustainable, bio-circular, circular, lower carbon footprint feedstocks, upcycled, and / or post-consumer / post-industrial recycled materials, including pyrolysis oil (“py- oil”) . Phenolic poly( arylene ethers) made from renewable sources can include, for example, a bio-content or PCR content of up to 99.9%, 1-99%, 5-95%, 55-99%, 80-99%, 1-50%, 1-25%, 1- 15%, 1-10%, or 1-5%, based, e.g., on the monomer source. The phenolic poly(arylene ether) can be, e.g., an oligomer with as few as two repeating units to ultra-high molecular weight poly(arylene ethers). The weight average molecular weight of the poly(arylene ethers) in some aspects can be 600-200,000 grams per mole, as determined by gel permeation chromatography (GPC) using polystyrene standards. In some aspects, the phenolic poly(arylene ethers) can have an intrinsic viscosity of up to 1.5 deciliters per gram (dl / g) as measured at 25 °C in chloroform. Phenolic poly(arylene ethers) made from renewable sources can include material made by a mass balance approach and certified by regulatory bodies such as the ISCC Plus.

[0044] Any of the components used in the polymerization reaction to prepare the phenolic poly( arylene ethers) as described above or their synthetic precursors, or the solvents used in the process, can be bio-sourced, bio-circular, or renewable raw materials. Such components and precursors include monomers (e.g., monohydric phenol, dihydric phenol and other comonomers), reagents, solvents, catalysts (e.g., a metal source, a secondary alkylene diamine ligand, a tertiary monoamine, and optionally a secondary monoamine or alternatively enzyme catalysts), gases (e.g., oxygen gas), or any combinations thereof. In some aspects, reaction components used in the polymerization of poly(arylene ethers) can be from sources as listed in the EU Renewable Energy Directive Annex IX.

[0045] The phenolic poly(arylene ethers) can be further processed, such as by redistribution, or any chemical derivatization, such as post-polymerization coupling or end- group addition as described herein, to make other materials that can transfer the sustainabilitycharacteristic to the new material. Such reagents or their synthetic precursors can be sustainable, bio-sourced, bio-circular, or renewable raw materials, upcycled, and / or post-consumer / postindustrial recycled materials, including pyrolysis oil (“py-oil”), to produce a poly( arylene ether).

[0046] Biosourced and sustainable materials can be derived from biomass sources or industrial sources such as waste (e.g., municipal waste). Biomass is a renewable organic material that comes from organic matter. Lignocellulosic biomass, the most abundant type of biomass and includes a wide variety of different biomass types including grasses, wood, energy crops, and agricultural and municipal wastes, is mostly composed of cellulose, hemicellulose, and lignin. Depolymerization of lignin, which is a phenolic polymer, can provide phenol. Solvents used in the production of monomers, such as methanol and acetone can be obtained from syngas, which is a product of the gasification of biomass.

[0047] The phenolic poly(arylene ether), such as a recycled poly(arylene ether) comprising an open- or closed-loop post-consumer recycled (“PCR”) poly(arylene ether), an open- or closed-loop post-industrial recycled (“PIR”) poly(arylene ether), or upcycled polyphenylene ether or a combination thereof can be used, provided that the desired property or combination of properties can be achieved. As used herein, the term “PCR poly(arylene ether)” refers to a poly(arylene ether) that has reached the intended user or consumer and which has been collected or reclaimed after utilization by the end-user or consumer. Thus, for example, it is understood that that the term refers to a poly(arylene ether) material in whole or in part that would have otherwise been disposed of as waste, but has instead been collected and recovered (reclaimed) as a material input, in lieu of a virgin material, for a recycling or manufacturing process. PCR-poly(arylene ether) is inclusive of material that has been reprocessed from collected or reclaimed material by means of a manufacturing process, (including e.g., purification, sorting, and pretreating) and made into a product or into a component for incorporation into a product. Such recycled poly(arylene ether)s can be further processed, for example, into the form of powders, ground materials, flakes, pellets or other form. As used herein, the term “PIR poly(arylene ether)” refers to a poly(arylene ether) that has never reached the end user and that is production waste arising during polymerization reactions, during further processing, or during manufacturing the resin or an article and includes materials such as sprues from injection molding, start-up material from injection molding or extrusion, extrusion scrap, molding scrap, edge trims from extruded sheets or films, and the like, including materials diverted from the waste stream during a manufacturing process for an article.

[0048] In some aspects, the linking groups are introduced by reacting the phenolic poly(arylene ether) with an alkylene oxide. The phenolic poly(arylene ether) can be converted to the metal salt by treatment with a base prior to reaction with an alkylene oxide and optionally, amultifunctional polyol.

[0049] Bases include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide, as well as alkaline earth hydroxides such as magnesium hydroxide and calcium hydroxide. In a preferred aspect, the base includes sodium hydroxide or potassium hydroxide, or potassium hydroxide. Both phenolic OH groups are converted to a phenoxide salt in this reaction.

[0050] In some aspects, the linking groups are introduced by reacting the phenolic poly(arylene ether) with an alkylene oxide of formula (8) to form a polyfunctional poly(arylene ether) precursor,wherein each occurrence of R16and R17is independently hydrogen, halogen, or Cl-18 alkyl, or hydrogen or Ci-6 alkyl, or hydrogen or C1-3 alkyl; each occurrence of n is 1 or more, or 1-3; each occurrence of m is 1 or more, or 1-3.

[0051] In some aspects, the linking groups are introduced by reacting the phenolic poly(arylene ether) with an alkylene oxide of formula (8a) form the polyfunctional poly(arylene ether) precursorwherein p is 1-3, or 1-2 and R17is hydrogen or Ci-Cis primary alkyl, or hydrogen or C1-6 alkyl, or hydrogen or C1-3 alkyl. In some aspects, m is 1-3, R17is hydrogen or methyl, or p is 1-2 and R17is hydrogen, or m is 1 and R17is hydrogen. In some aspects, the alkylene oxide can comprise ethylene oxide, propylene oxide, or a combination thereof. In a specific aspect, the alkylene oxide is can comprise ethylene oxide.

[0052] The synthesis of the polyfunctional poly(arylene ether) precursor or the polyfunctional poly(arylene ether) in subsequent steps can be performed with or without a solvent. The solvent can be an aromatic hydrocarbon solvent, for example a Ce-is aromatic hydrocarbon solvent. Suitable aromatic hydrocarbon solvents include, for example, benzene, toluene, xylenes, and the like, or a combination thereof. In some aspects, the aromatic hydrocarbon solvent comprises toluene. In addition to the aromatic hydrocarbon solvent, the solvent can, optionally, further comprise a C3-8 aliphatic alcohol that is a poor solvent for the poly(arylene ether), such as, for example, n-propanol, isopropanol, n-butanol, t-butanol, n- pentanol, and the like, and combinations thereof. A preferred C3-8 aliphatic alcohol is n-butanol.The solvent can further comprise, in addition to a Ce-is aromatic hydrocarbon and a C3-8 aliphatic alcohol, methanol or ethanol, which act as an anti-solvent for the poly(arylene ether). The Ce -is aromatic hydrocarbon, the C3-8 aliphatic alcohol, and the methanol or ethanol can be combined in a wide range of proportions, but it can be preferred that the solvent comprise at least 50 weight percent (wt%) of the Ce-is aromatic hydrocarbon. In some aspects, no solvents other than the aromatic hydrocarbon solvent are present.

[0053] Conventional methods for introducing a linking group to form the polyfunctional poly(arylene ether) precursor use the following reagents which include several disadvantages:wherein R9to R13, R9to R14to R19, and R20to R23are each independently hydrogen, C1-C12 primary alkyl, C2-12 alkenyl, C7-C12 arylalkyl, C2-C12 alkoxyalkyl, C7-C12 aryloxyalkyl, or Ci- C12 hydroxyalkyl, or hydrogen or C1-6 alkyl. Another advantage of the poly(arylene ethers) and methods or preparation of the present disclosure is that reagents such as those of Formulas (9)- (11), thus avoiding the formation of side-products. For example, reaction with a reagent of formula (9) results in the formation of a carbonate side product, formula (10) is not widely commercially available and can form elimination products, and reaction with formula (11) results in the formation of an ester side product.

[0054] An example of the carbonate side -product resulting from use of ethylene carbonate is depicted below for illustrative purposes only.

[0055] An example of an ester side-product is depicted below for illustrative purposes only.

[0056] In contrast, in some aspects, the linking group of the polyfunctional poly(arylene ether) made by the methods described herein includes 0-5,000 parts per million by weight(ppm), 00-2,500 ppm, or 0-1,000 ppm, or 0-500 ppm, or 50-5,000 ppm, or 50-2,500 ppm, or 50- 1 ,000 ppm, or 50-500 ppm, or less than 50 ppm of a poly(arylene ether) comprising a linking group comprising a carbonate functional group; or 0-5,000 ppm, 0-2,500 ppm, or 0-1,000 ppm, or 0-500 ppm, or 50-5,000 ppm, or 50-2,500 ppm, or 50-1,000 ppm, or 50-500 ppm, or less than 50 ppm of a poly(arylene ether) comprising a linking group comprising an ester functional group, or a combination thereof. The amount of the carbonate functional group and the ester functional group can be determined, for example by proton nuclear magnetic resonanceNMR spectroscopy.

[0057] In some aspects, a composition including the polyfunctional poly(arylene ether) minimizes or eliminates the presence of products other than the polyfunctional poly(arylene ether). For example, the compositions include 0-5,000 ppm, 0-2,500 ppm, or 0-1,000 ppm, or 0- 500 ppm, or 50-5,000 ppm, or 50-2,500 ppm, or 50-1,000 ppm, or 50-500 ppm, or less than 50 ppm of a poly(arylene ether) of a carbonate-containing polyfunctional poly( arylene ether) including a linking group, wherein the linking group of the carbonate-containing polyfunctional poly(arylene ether) includes a carbonate group; 0-5,000 ppm, 0-2,500 ppm, or 0-1,000 ppm, or 0-500 ppm, or 50-5,000 ppm, or 50-2,500 ppm, or 50-1,000 ppm, or 50-500 ppm, or less than 50 ppm of a poly(arylene ether) of an ester-containing polyfunctional poly(arylene ether) wherein the linking group of the ester-containing polyfunctional poly(arylene ether) includes an ester group; or a combination thereof. In some aspects, the composition is free of carbonate- containing polyfunctional poly(arylene ethers) and ester-containing polyfunctional poly(arylene ethers).

[0058] Minimizing or eliminating carbonate and ester linking groups from the polyfunctional poly(arylene ethers) and compositions including polyfunctional poly(arylene ethers) is advantageous because the final products that are derived from the polyfunctional poly(arylene ethers) can have improved hydrolytic and thermal stability.

[0059] The present methods allow for excellent control over product structure. As the length of the linking group increases, in addition to modifying the solubility of the polyfunctional poly (arylene ether), the Tg of the polyfunctional poly (arylene ether) can decrease. This is an advantage when lower processing temperatures are needed for materials derived from poly(arylene ethers). The Tg of the polyfunctional poly(arylene ether) can be about 20°C less, or 40°C less, or 60°C less than the Tg of the corresponding poly(arylene ether) with phenolic end groups and no linking groups. In some aspects, the Tg of the polyfunctional poly(arylene ether) is not more than 100°C, or not more than 80°C, as measured using DSC per ASTM D3418, at a heating rate of 20°C per minute.

[0060] A catalyst can be used in the reaction of an polyfunctional poly(arylene ether)precursor salt and the alkylene oxide. Examples of such catalysts are known to the art. For example, the catalyst can be a hydroxide salt such as sodium hydroxide, potassium hydroxide, tetraalkylammonium hydroxides, or the like; tertiary alkylamines such as tributyl amine, triethylamine, dimethylbenzylamine, dimethylbutylamine, or the like; tertiary mixed alkylarylamines and substituted derivatives thereof such as N,N-dimethylaniline; heterocyclic amines such as imidazoles, pyridines, and substituted derivatives thereof such as 2-methylimidazole, 2- vinylimidazole, 4-(dimethylamino)pyridine, 4-(l-pyrrolino)pyridine, 4-(l-piperidino)pyridine, 2-vinylpyridine, 3-vinylpyridine, 4-vinylpyridine, or the like.

[0061] In some aspects, the catalyst is an organic amine catalyst. Preferred organic amine catalysts include, for example, tertiary alkylamines, tertiary mixed alkyl-aryl amines, heterocyclic amines, and the like. It will be understood that the organic amine catalyst includes ammonium ions formed by protonation of the organic amine. In one aspect, the catalyst includes a 4-dialkylaminopyridine, for example 4-dimethylaminopyridine (DMAP).

[0062] Alternatively, the catalyst can be a transesterification catalyst that is capable of catalyzing transesterification of phenols with the alkylene oxide . For example, the catalyst can be a catalyst that include a source of alkali or alkaline earth ions, such as alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide, as well as alkaline earth hydroxides such as magnesium hydroxide and calcium hydroxide. Other sources of alkali and alkaline earth metal ions include the corresponding salts of carboxylic acids (such as sodium acetate) and derivatives of ethylene diamine tetraacetic acid (EDTA) (such as EDTA tetrasodium salt, and EDTA magnesium disodium salt). Other alpha transesterification catalysts include alkali or alkaline earth metal salts of carbonate, such as CS2CO3, NaHCO s. and Na^COi. or the like, non-volatile inorganic acid such as NatEPCh. NaH2PO4, Na2HPO3, KH2PO4, CSH2PO4, CS2HPO4, or the like, or mixed salts of phosphoric acid, such as NaKHPO4, CsNaHPO4, CSKHPO4, or the like. Combinations including at least one of any of the foregoing catalysts can be used.

[0063] The catalyst can alternatively be a beta transesterification catalyst that includes a quaternary ammonium compound, a quaternary phosphonium compound, or a combination including at least one of the foregoing. The quaternary ammonium compound can be a compound of the structure (R14)4N+X", wherein each R14is the same or different, and is a C1-20 alkyl, a C4-20 cycloalkyl, or a C4-20 aryl; and X" is an organic or inorganic anion, for example a hydroxide, halide, carboxylate, sulfonate, sulfate, formate, carbonate, or bicarbonate. Examples of organic quaternary ammonium compounds include tetramethyl ammonium hydroxide, tetrabutyl ammonium hydroxide, tetramethyl ammonium acetate, tetramethyl ammonium formate, tetrabutyl ammonium acetate, and combinations including at least one of the foregoing.Tetramethyl ammonium hydroxide is often used. The quaternary phosphonium compound can be a compound of the structure (R15)4P+X", wherein each R15is the same or different, and is a C1-C20 alkyl, a C4-C20 cycloalkyl, or a C4-C20 aryl; and X" is an organic or inorganic anion, for example a hydroxide, phenoxide, halide, carboxylate such as acetate or formate, sulfonate, sulfate, formate, carbonate, or bicarbonate. Where X" is a polyvalent anion such as carbonate or sulfate it is understood that the positive and negative charges in the quaternary ammonium and phosphonium structures are properly balanced. For example, where R14or R15are each methyl and X" is carbonate, it is understood that X" represents 1 / 2(CO32). Examples of organic quaternary phosphonium compounds include tetramethyl phosphonium hydroxide, tetramethyl phosphonium acetate, tetramethyl phosphonium formate, tetrabutyl phosphonium hydroxide, tetrabutyl phosphonium acetate (TBPA), tetraphenyl phosphonium acetate, tetraphenyl phosphonium phenoxide, and combinations including at least one of the foregoing. TBPA is often used.

[0064] The process can further include isolating the polyfunctional poly(arylene ether) from the reaction mixture. Suitable methods include the methods described above for the phenolic poly( arylene ether). The isolated capped polyfunctional poly(arylene ether) can further be dried at elevated temperatures.

[0065] The polyfunctional poly(arylene ether) can also be a part of a composition that can include a blend of at least two polyfunctional poly (arylene ethers). Such blends can be prepared from individually prepared and isolated polyfunctional poly(arylene ethers). Alternatively, such blends can be prepared by reacting a single uncapped polyfunctional poly(arylene ether) with at least two different capping agents.

[0066] In some aspects, the poly(arylene ether) is of the formula (12)wherein Q1, Q2, Q3, Q4, P1, P2, P3, P4, and P5x, and y are as defined above with regard to formula 2 and formula 3; each occurrence of R16and R17is independently hydrogen, halogen, or C1-18 alkyl, or hydrogen or C1-6 alkyl, or hydrogen or C1-3 alkyl; each occurrence of n is 1 or more, or 1-3; and each occurrence of m is 1 or more, or 1-3.

[0067] The polyfunctional poly(arylene ether) can have a number average molecular weight (Mn) of 600-10,000, or 400-2,500 grams per mole (g / mol) as determined by GPC using polystyrene standards. In some aspects, the polyfunctional poly(arylene ether) can have a weightaverage molecular weight (Mw) of 500-6,000 g / mol, each as determined by GPC using polystyrene standards. For example, the polyfunctional poly(arylene ether) can have an Mnof 400-2,200 g / mol or 800-1,600 g / mol and an Mwof 600-5,000 g / mol or 800-4,500 g / mol, each as determined by GPC using polystyrene standards.

[0068] The polyfunctional poly(arylene ether) can have an intrinsic viscosity of 0.04 to 0.16 deciliter per gram (dL / g) as measured at 25 °C in chloroform. For example, the intrinsic viscosity is or 0.06-0.1 dL / g, or 0.075-0.095 dL / g.

[0069] The polyfunctional poly(arylene ether) can have a Tg (Tg) of not more than 100°C, or not more than 80°C as determined using DSC per ASTM D3418 with a 20°C / min heating rate.

[0070] The polyfunctional poly(arylene ether) can be included as a reactive component in a curable composition including, for example, a thermosetting resin. Also provided is a curable thermosetting composition including the polyfunctional poly (arylene ether). For example, the polyfunctional poly(arylene ether) can be present in the curable thermosetting composition in an amount of 1-95 wt%, or 5-95 wt%, or 10-85 wt%, or 20-80 wt%, 30-70 wt%, or 5-30 wt%, or 5-15 wt%, based on the total weight of the curable thermosetting composition.

[0071] The curable thermosetting composition can further include one or more of a crosslinking agent, a curing agent, a curing catalyst, a curing initiator, or a combination thereof. In some aspects, the curable thermosetting composition can further include an additive composition. For example, the curable thermosetting composition can include one or more of a crosslinking agent, a curing agent, a curing catalyst, a curing initiator, or a combination thereof; and can further include one or more of a flame retardant, a filler, a coupling agent, or a combination thereof.

[0072] There is considerable overlap among thermosetting resins, crosslinking agents, and coupling agents. As used herein, the term “crosslinking agent” includes compounds that can be used as thermosetting resins, crosslinkers, coupling agents, or a combination thereof. For example, in some instances a compound that is a thermosetting resin could also be used as a crosslinking agent, a coupling agent, or both.

[0073] The thermosetting resins are not particularly limited, and thermosetting resins can be used alone or in combinations 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., a vinyl benzyl ether resin), phenolic resins, alkyd resins, unsaturated polyester resins, arylcyclobutene resins, perfluorovinyl ether resins, monomers, oligomers, or polymers with curable unsaturation (e.g., a vinyl functionality), or the like, or a combination thereof.

[0074] The epoxy resin can be any epoxy resin that is suitable for use in thermosetting resins. The term “epoxy resin” in this context refers to a curable composition of oxirane ringcontaining compounds as described in, for example, C. A. May, Epoxy Resins, 2nd Edition, (New York & Basle: Marcel Dekker Inc.), 1988. The epoxy resins can include bisphenol A type epoxy resins such as those obtained from bisphenol A and resins obtained by substituting at least one position of the 2-position, the 3-position and the 5-position of bisphenol A with a halogen atom, an alkyl group having 6 or less carbon atoms or a phenyl group; bisphenol F type epoxy resins such as those obtained from bisphenol F and a resin obtained by substituting at least one position of the 2-position, the 3-position and the 5-position of bisphenol F with a halogen atom, an alkyl group having 6 or less carbon atoms or a phenyl group; glycidyl ether compounds derived from bivalent or tri- or more-valent phenols such as hydroquinone, resorcinol, tris-4-(hydroxyphenyl)methane and l,l,2,2-tetrakis(4-hydroxyphenyl)ethane; a novolak type epoxy resin derived from a novolak resin which is a reaction product between phenols such as phenol and o-cresol and formaldehyde, including bisphenol A novolak type epoxy resins and cresol novolak type epoxy resins; cyclic aliphatic epoxy compounds such as 2,2-bis(3,4-epoxycyclohexyl)propane, 2,2-bis[4-(2,3-epoxypropyl)cyclohexyl]propane, vinylcyclohexene dioxide, 3, 4-epoxycyclohexylmethyl-3,4-epoxy cyclohexane carboxylate; dicyclopentadiene-containing polyepoxides; amine type epoxy resins derived from 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'-diaminodiphenylether, 1 ,4-bis(4-aminophenoxy)benzene, l,4-bis(3-aminophenoxy)-benzene, l,3-bis(4-aminophenoxy)- benzene, l,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, l,4-cyclohexane-bis(methylamine), 5-amino-l-(4'-aminophenyl)- 1,3, 3 -trimethylindane, 6-amino-l-(4'-aminophenyl)-l,3,3-trimethyl-indane or the like; heterocyclic epoxy compounds, and glycidyl ester type epoxy compounds, for example, those derived from glycidyl ester of aromatic carboxylic acids such as p-oxybenzoic acid, m-oxybenzoic acid, terephthalic acid, and isophthalic acid. An “epoxy resin” can also include reaction products of compounds containing two or more epoxy groups and aromatic dihydroxy compounds, which can be optionally halogen-substituted and can be used alone or in a combination of two or more.

[0075] Cyanate esters are not limited, and any resin composed of cyanate ester monomers, which polymerize to form a polymer containing a plurality of cyanate ester (-OCN) functional groups can be used. Cyanate ester monomers, prepolymers (i.e., partially polymerized cyanate ester monomers or blends of cyanate ester monomers), homopolymers, and copolymers made using cyanate ester precursors, and combinations of these compounds. For example,cyanate esters can be prepared according to methods as disclosed in “Chemistry and Technology of Cyanate Ester Resins,” by Ian Hamerton, Blackie Academic and Professional; U.S. Pat. No. 3,553,244, and JP-A-7-53497. Exemplary cyanate ester resins include 2,2-bis(4-cyanatophenyl)- propane, bis(4-cyanatophenyl)ethane, bis(3,5-dimethyl-4-cyanatophenyl)methane, 2,2-bis(4- cyanatophenyl)-l,l,l,3,3,3-hexafluoropropane, a,a'-bis(4-cyanatophenyl)-m-diisopropyl- benzene, cyanate ester resins prepared from dicyclopentadiene-phenol copolymers, and prepolymers prepared from these monomers. An example of a prepolymer is PRIMASET BA- 2308 (Lonza). The cyanate ester prepolymers can be homopolymers or can be copolymers that incorporate other monomers. Examples of such copolymers include BT resins available from Mitsubishi Gas Chemical, such as, BT 2160 and BT2170, which are prepolymers made with cyanate ester monomers and bismaleimide monomers. Other cyanate esters polymers, monomers, prepolymers, and blends of cyanate ester monomers with other non-cyanate ester monomers are disclosed in US 7393904, US 7388057, US 7276563, and US 7192651.

[0076] Bismaleimide resins can be produced by reaction of a monomeric bismaleimide with a nucleophile such as a diamine, aminophenol, or amino benzhydrazide, or by reaction of a bismaleimide with diallyl bisphenol A. Exemplary bismaleimide resins include 1 ,2- bismaleimidoethane, 1,6-bismaleimidohexane, 1,3-bismaleimidobenzene, 1 ,4-bismaleimido- benzene, 2,4-bismaleimidotoluene, 4,4’-bismaleimidodiphenylmethane, 4,4’-bismaleimido- diphenylether, 3,3’-bismaleimidodiphenylsulfone, 4,4’-bismaleimido-diphenylsulfone, 4,4'- bismaleimidodicyclohexylmethane, 3,5-bis(4-maleimidophenyl)pyridine, 2,6-bismaleimido- pyridine, 1 ,3-bis(maleimidomethyl)cyclohexane, 1 ,3-bis(maleimidomethyl)benzene, 1 , l-bis(4-maleimidophenyl)cyclohexane, 1 ,3-bis(dichloromaleimido)benzene, 4,4’-bis(citracon- imido)diphenylmethane, 2,2-bis(4-maleimidophenyl)propane, 1 -phenyl- 1 , 1 -bis(4-maleimido- phenyl)ethane, N,N-bis(4-maleimidophenyl)toluene, 3,5-bismaleimido-l,2,4-triazole N,N’- ethylenebismaleimide, N,N’-hexamethylenebismaleimide, N,N’-m-phenylene-bismaleimide, N,N’-p-phenylenebismaleimide, N,N'-4,4’-diphenylmethanebismaleimide, N,N'-4,4'-diphenyl- etherbismaleimide, N,N'-4,4'-diphenylsufonebismaleimide, N,N'-4,4'-dicyclohexylmethane- bismaleimide, N,N'-a,a'-4,4'-dimethylenecyclohexanebismaleimide, N,N'-m-meta-xylene- bismaleimide, N,N'-4,4'-diphenylcyclohexanebismaleimide, and N,N'-methylene-bis(3-chloro- p-phenylene)bismaleimide, as well as those disclosed in US 3,562,223; US 4,211,860; and US 4,211,861, or as prepared by methods as described, for example, in US 3,018,290.

[0077] The benzoxazine compounds have a benzoxazine ring in the molecule. Exemplary benzoxazine monomers can be prepared from the reaction of aldehydes, phenols, and primary amines with or without solvent. The phenolic compounds for forming benzoxazines include phenols and polyphenols. The use of polyphenols with two or more hydroxyl groupsreactive in forming benzoxazines can result in branched, crosslinked, or a combination of branched and crosslinked products. The groups connecting the phenolic groups into a phenol can be branch points or connecting groups in the polybenzoxazine.

[0078] 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-dihydrooxynapthalene, 2-(diphenyl-phosphoryl)hydroquinone, 2,2’ -biphenol, 4,4-biphenol, 4,4’-isopropylidenediphenol, 4,4’-isopropylidenebis(2-methyl- phenol), 4,4’-isopropylidenebis(2-allylphenol), 4,4’(l,3-phenylenediisopropylidene)bisphenol (bisphenol M), 4,4’-isopropylidenebis(3-phenylphenol) 4,4’-(l,4-phenylenediisoproylidene)- bisphenol, 4,4’-ethylidenediphenol, 4,4’ -oxydiphenol, 4,4’ -thiodiphenol, 4,4’-sufonyldiphenol, 4,4’ -sulfinyldiphenol, 4,4’ -hexafluoroisopropylidene)bisphenol, 4,4’ (1 -phenylethylidene)- bisphenol, bis(4-hydroxyphenyl)-2,2-dichloroethylene, bis(4-hydroxyphenyl)methane, 4,4'- (cyclopentylidene)diphenol, 4,4'-(cyclohexylidene)diphenol, 4,4'-(cyclododecylidene)diphenol 4,4'-(bicyclo[2.2. l]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-lH-inden-5-ol, 3,3,3',3'-tetramethyl-2,2',3,3'-tetrahydro-l,T-spirobi- [indene] 5,6'-diol, dihydroxybenzophenone, tris(4-hydroxyphenyl)methane, tris(4-hydroxy- phenyl)ethane, tris(4-hydroxyphenyl)propane, tris(4-hydroxyphenyl)butane, tris(3-methyl-4- hydroxyphenyl)methane, tetrakis(4-hydroxyphenyl)ethane dicyclopentadienylbis(2,6-dimethyl phenol), dicyclopentadienyl bis(ortho-cresol), dicyclopentadienyl bisphenol, or the like.

[0079] The aldehydes used to form the benzoxazine can be any aldehyde, such as an aldehyde having 1-10 carbon atoms. For example, the aldehyde can be formaldehyde. The amine used to form the benzoxazine can be an aromatic amine, an aliphatic amine, an alkyl substituted aromatic, or an aromatic substituted alkyl amine. The amine can be a polyamine, for example to prepare polyfunctional benzoxazine monomers for crosslinking.

[0080] The amines for forming benzoxazines have 1-40 carbon atoms unless they include aromatic rings, and then they can have 6-40 carbon atoms. The amine of di- or polyfunctional can be a branch point to connect one polybenzoxazine to another.

[0081] In some examples, thermal polymerization at 150-300° C can be used for polymerizing benzoxazine monomers. The polymerization can be done in bulk, from solution, or otherwise. Catalysts, such as carboxylic acids, can be used to reduce the polymerization temperature or accelerate the polymerization rate at the same temperature.

[0082] Vinyl benzyl ether resins can be prepared from condensation of a phenol with a vinyl benzyl halide, such as vinyl benzyl chloride. Bisphenol- A and trisphenols and polyphenols are generally used to produce poly(vinylbenzyl ethers) which can be used to produce crosslinkedthermosetting resins. Exemplary vinyl benzyl ethers can include those vinylbenzyl ethers produced from reaction of a vinylbenzyl halide with 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’-iso- propylidenediphenol, 4,4’ -isopropylidenebis(2,6-dibromophenol), 4,4’ -isopropylidenebis(2,6- dimethylphenol) (teramethylbisphenol A), 4,4’-isopropylidenebis(2-methylphenol), 4,4’- ispropylidenebis(2-allylphenol), 4,4’(l,3-phenylenediisopropylidene)bisphenol, 4,4’-isopropyli- denebis(3-phenylphenol) 4,4’-(l,4-phenylenediisoproylidene)bisphenol, 4,4’-ethylidenedi- phenol, 4,4’ -oxydiphenol, 4,4’ -thiodiphenol, 4,4’-thiobis(2,6-dimethylphenol), 4,4’-sufonyldi- phenol, 4,4’-sulfonylbis(2,6-dimethylphenol) 4,4’-sulfinyl-diphenol, 4,4’-hexafluoroisopropyli- dene)bisphenol, 4,4’(l-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-l(3H)-one, l-(4-hydroxyphenyl)-3,3-dimethyl-2,3-dihydro-lH- inden-5-ol, l-(4-hydroxy-3, 5-dimethylphenyl)-l, 3,3,4, 6-pentamethyl-2,3-dihydro-lH-inden-5- ol, 3,3,3',3'-tetramethyl-2,2',3,3'-tetrahydro-l,r-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, 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-dimethyl phenol), dicyclopentadienyl bisphenol, or the like.

[0083] Arylcyclobutenes include those derived from compounds of the structurewherein B is an organic or inorganic radical of valence n (including carbonyl, sulfonyl, sulfinyl, sulfide, oxy, alkylphosphonyl, arylphosphonyl, isoalkylidene, cycloalkylidene, arylalkylidene, diarylmethylidene, methylidene dialkylsilanyl, arylalkylsilanyl, diarylsilanyl and Ce-20 phenolic compounds); each occurrence of X is independently hydroxy or Ci-24 hydrocarbylene (including linear and branched alkyl and cycloalkyl); and each occurrence of Z is independently hydrogen, halogen, or C1-12 hydrocarbyl; and n is 1-1000 ,or 1-8, or n is 2, 3, or 4. Other exemplary arylcyclobutenes and methods of arylcyclobutene synthesis can be found in US 4,743,399, US4,540,763, US 4,642,329, US 4,661,193, US 4,724,260, and 5391,650.

[0084] Perfluorovinyl ethers are typically synthesized from phenols and bromotetrafluoroethane followed by zinc catalyzed reductive elimination producing ZnFBr and the desired perfluorovinylether. By this route bis, tris, and other polyphenols can produce bis-, tris- and poly(perfluorovinylether)s. Phenols useful in their synthesis include resorcinol, catechol, hydroquinone, 2,6-dihydroxy naphthalene, 2,7-dihydroxynapthalene, 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’-tetra- methylbiphenol, 3,3’-dibromo-2,2’,6,6’-tetramethylbiphenol, 2,2’,6,6’-tetramethyl-3,3’5- dibromobiphenol, 4,4’-isopropylidenediphenol (bisphenol A), 4,4’-isopropylidenebis(2,6- dibromophenol), 4,4’-isopropylidenebis(2,6-dimethylphenol), 4,4’-isopropylidenebis(2- methylphenol), 4,4’-isopropylidenebis(2-allylphenol), 4,4’(l,3-phenylenediisopropylidene)- bisphenol, 4,4’-isopropylidenebis(3-phenylphenol) 4,4’-(l,4-phenylenediisoproylidene)- bisphenol, 4,4’-ethylidenediphenol, 4,4’ oxydiphenol, 4,4’thiodiphenol, 4,4’thiobis(2,6- dimethylphenol), 4,4’-sufonyldiphenol, 4,4’-sulfonylbis(2,6-dimethylphenol) 4,4’- sulfinyldiphenol, 4,4 ’ -hexafluoroisoproylidene)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-l(3H)-one, l-(4-hydroxyphenyl)-3,3- dimethyl-2,3-dihydro-lH-inden-5-ol, l-(4-hydroxy-3, 5-dimethylphenyl)-l, 3,3,4, 6-pentamethyl- 2,3-dihydro-lH-inden-5-ol, 3,3,3',3'-tetramethyl-2,2',3,3'-tetrahydro-l,T-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-dimethyl phenol), dicyclopentadienyl bis(2- methylphenol), dicyclopentadienyl bisphenol, or the like.

[0085] The crosslinking agents, which also include auxiliary crosslinking agents, are not particularly limited. The crosslinking agents can be used alone or in combinations of two or more different crosslinking agents. Exemplary crosslinking agents and auxiliary crosslinking agents include oligomers or polymers with curable vinyl functionality. Such materials include oligomers and polymers having crosslinkable unsaturation. Examples include styrene butadiene rubber (SBR), butadiene rubber (BR), and nitrile butadiene rubber (NBR) having unsaturated bonding based on butadiene; natural rubber (NR), isoprene rubber (IR), chloroprene rubber(CR), butyl rubber (IIR), and halogenated butyl rubber having unsaturated bonding based on isoprene; ethylene-a-olefin copolymer elastomers having unsaturated bonding based on dicyclopentadiene (DCPD), ethylidene norbornene (ENB), or 1,4-dihexadiene (1,4-HD) (e.g., ethylene-a-olefin copolymers obtained by copolymerizing ethylene, an a-olefin, and a diene, such as ethylene -propylene-diene terpolymer (EPDM) and ethylene-butene-diene terpolymer (EBDM)). Examples also include hydrogenated nitrile rubber, fluorocarbon rubbers such as vinylidenefluoride-hexafluoropropene copolymer and vinylidenefluoride-pentafluoropropene copolymer, epichlorohydrin homopolymer (CO), copolymer rubber (ECO) prepared from epichlorohydrin and ethylene oxide, epichlorohydrin allyl glycidyl copolymer, propylene oxide allyl glycidyl ether copolymer, propylene oxide epichlorohydrin allyl glycidyl ether terpolymer, acrylic rubber (ACM), urethane rubber (U), silicone rubber (Q), chlorosulfonated polyethylene rubber (CSM), polysulfide rubber (T) and ethylene acrylic rubber. Further examples include various liquid rubbers, for example several types of liquid butadiene rubbers, and the liquid atactic butadiene rubber that is butadiene polymer with 1 ,2-vinyl connection prepared by anionic living polymerization. It is also possible to use liquid styrene butadiene rubber, liquid nitrile butadiene rubber (CTBN, VTBN, ATBN, etc. by Ube Industries, Ltd.), liquid chloroprene rubber, liquid polyisoprene, dicyclopentadiene type hydrocarbon polymer, and polynorbornene (for example, as sold by Elf Atochem).

[0086] Polybutadiene resins containing elevated levels of 1,2 addition are desirable for thermosetting matrices. Examples include the functionalized polybutadienes and poly(butadiene- styrene) random copolymers sold by Ricon Resins, Inc. under the trade names RICON, RICACRYL, and RICOBOND resins. These include butadienes containing both low vinyl content such as RICON 130, 131, 134, 142; polybutadienes containing high vinyl content such as RICON 150, 152, 153, 154, 156, 157, and P30D; random copolymers of styrene and butadiene including RICON 100, 181, 184, and maleic anhydride grafted polybutadienes and the alcohol condensates derived therefrom such as RICON 130MA8, RICON MA13, RICON 130MA20, RICON 131MAS, RICON 131MA10, RICON MA 17, RICON MA20, RICON 184MA6 and RICON 156MA17. Also included are polybutadienes that can be used to improve adhesion including RICOBOND 1031, RICOBOND 1731, RICOBOND 2031, RICACRYL 3500, RICOBOND 1756, RICACRYL 3500; the polybutadienes RICON 104 (25% polybutadiene in heptane), RICON 257 (35% polybutadiene in styrene), and RICON 257 (35% polybutadiene in styrene); (meth)acrylic functionalized polybutadienes such as polybutadiene diacrylates and polybutadiene dimethacrylates. These materials are sold under the tradenames RICACRYL 3100, RICACRYL 3500, and RICACRYL 3801. Also are included are powder dispersions of functional polybutadiene derivatives including, for example, RICON 150D,152D, 153D, 154D, P30D, RICOBOND 0 1731 HS, and RICOBOND 1756HS. Further butadiene resins include poly(butadiene-isoprene) block and random copolymers, such as those with molecular weights from 3,000-50,000 g / mol and polybutadiene homopolymers having molecular weights from 3,000-50,000 g / mol. Also included are polybutadiene, polyisoprene, and polybutadiene-isoprene copolymers functionalized with maleic anhydride functions, 2- hydroxyethylmaleic functions, or hydroxylated functionality.

[0087] Further examples of oligomers and polymers with curable vinyl functionality include unsaturated polyester resins based on maleic anhydride, fumaric acid, itaconic acid and citraconic acid; unsaturated epoxy (meth)acrylate resins containing acryloyl groups, or methacryloyl group; unsaturated epoxy resins containing vinyl or allyl groups, urethane (meth)acrylate resin, polyether (meth)acrylate resin, polyalcohol (meth)acrylate resins, alkyd acrylate resin, polyester acrylate resin, spiroacetal acrylate resin, diallyl phthalate resin, diallyl tetrabromophthalate resin, diethyleneglycol bisallylcarbonate resin, and polyethylene polythiol resins. For example, the crosslinking agent. Other exemplary crosslinking agents further include polyfunctional crosslinking monomers such as (meth)acrylate monomers having two or more (meth)acrylate moieties 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, or the like; tri(meth)acrylates such as trimethylolpropane tri(meth)acrylate, 1,2,4-butanetriol tri(meth)acrylate, trimethylolpropane ethoxylate tri(meth)acrylate, or the like; tri(meth)allyls such as tri(meth)allyl cyanurate, tri(meth)allyl isocyanurate, tri(meth)allyl esters of citric acid, tri(meth)allyl esters of phosphoric acid, pentaerythritol tri(meth)acrylate, tris(hydroxyethyl)isocyanurate tri(meth)acrylate, or the like; tetra(meth)acrylates such as pentaerythritol tetra(meth)acrylate or the like; penta(meth)acrylates such as dipentaerythritol penta(meth)acrylate, or the like; hexa(meth)acrylates such as dipentaerythritol hexa(meth)acrylate, sorbitol hexa(meth)acrylate, or the like; glycidyl compounds such as glycidyl (meth)acrylate, (meth)allyl glycidyl ether, 1- chloro-2,3-epoxypropyl (meth)acrylate, 2-bromo-3,4-epoxybutyl (meth)acrylate, 2- (epoxyethyloxy)-ethyl (meth)acrylate, 2-(3,4-epoxybutyloxy)-ethyl (meth)acrylate, or the like; polythiol compounds such as trimethylolpropane tris(mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate), or the like; silanes such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetra-n-butoxysilane, vinyltris(methylethyloximino)silane, vinyltris-(acetoxime)silane, methyltris(methylethyloximino)silane, methyltris(acetoxime)silane,vinyltrimethoxysilane, methyltrimethoxysilane, vinyltris(isopropenoxy)silane, tetraacetoxysilane, methyltriacetoxysilane, ethyltriacetoxy silane, vinyltriacetoxysilane, di-t-butoxy- diacetoxysilane, methyltris(ethyl lactate)silane, vinyltris(ethyl lactate)silane, or the like; carbodiimides such as N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide hydrochloride, dicyclohexylcarbodiimide, or the like; or a combination thereof. The curable thermosetting composition can optionally include a crosslinking catalyst, such as a carboxylic acid salt. When the curable thermosetting composition includes a crosslinking agent, the crosslinking agent can be included in an amount of 1-60 wt%, or 5-50 wt%, or 10-40 wt%, based on total weight of the curable thermosetting composition.

[0088] The curable thermosetting composition can include one or more curing agents. As used herein, the term “curing agent” includes compounds that are variously described as curing agents, hardeners, or the like, or as both.

[0089] Exemplary curing agents and hardeners include amines, alcohols, phenols, carboxylic acids, acid anhydrides, and the like. For example, phenolic hardeners include novolac type phenol resins, resole type phenol resins, cresol novolac resins, aralkyl type phenol resins, phenol aralkyl resins, cresol aralkyl resins, naphthol aralkyl resins, dicyclopentadiene type phenol resins, terpene modified phenol resins, biphenyl type phenol resins, biphenyl-modified phenol aralkyl resins, bisphenols, triphenylmethane type phenol resins, tetraphenylol ethane resins, naphthol novolac resins, naphthol-phenol co-condensed novolac resins, naphthol-cresol co-condensed novolac resins, amino triazine modified phenol resins, or a combination thereof. Examples of the anhydride hardeners include methylhexahydrophthalic anhydride (MHHPA), methyltetrahydrophthalic anhydride, styrene-maleic anhydride copolymers (SMA), and olefinmaleic anhydride copolymers such as maleic anhydride grafted polyethylene, maleic anhydride grafted polypropylene, or a combination thereof. Other curing agents and hardeners include compounds such as dicyandiamides, polyamides, amidoamines, phenalkamines, Mannich bases, anhydrides, phenol-formaldehyde resins, amine-formaldehyde resins, phenol-formaldehyde resins, carboxylic acid functional polyesters, polysulfides, polymercaptans, isocyanates, cyanate ester compounds, or any combination thereof. Other exemplary curing agents include tertiary amines, Lewis acids, and oligomers or polymers with unsaturation.

[0090] When the curable thermosetting composition includes a curing agent, the curing agent can be included in an amount of 0.01-50 wt%, or 0.1-30 wt%, or 0.1-20 wt%, based on total weight of the curable thermosetting composition.

[0091] The curable thermosetting composition can include a curing catalyst. As used herein, the term “curing catalyst” includes compounds that are variously described as curing accelerators, curing promoters, curing catalysts, and curing co-catalysts.

[0092] Exemplary curing accelerators include heterocyclic accelerators such as a substituted or unsubstituted C3-6 heterocycle including 1-4 ring heteroatoms, wherein each heteroatom is independently the same or different, and is nitrogen, oxygen, phosphorus, silicon, or sulfur. Heterocyclic accelerators include benzotriazoles; triazines; piperazines such as aminoethylpiperazine, N-(3-aminopropyl)piperazine, or the like; imidazoles such as 1- methylimidazole, 2-methylimidazole, 3-methyl imidazole, 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-lH-imidazole, 2-heptadecyl-lH-imidazole, 1,2- dimethylimidazole, 1,3-dimethylimidazole, 2,4-dimethylimidazole, 2-ethyl-4-methylimidazole, 1 -phenylimidazole, 2-phenyl-lH-imidazole, 4-methyl-2-phenyl-lH-imidazole, 2-phenyl-4- methylimidazole, l-benzyl-2-methylimidazole, l-benzyl-2-phenylimidazole, l-cyanoethyl-2- methylimidazole, l-cyanoethyl-2-ethyl-4-methylimidazole, l-cyanoethyl-2-undecylimidazole, 1- cyanoethyl-2-phenylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5- hydroxymethylimidazole, 1 -cyanoethyl-2-phenyl-4,5-di(2-cyanoethoxy)methylimidazole; cyclic amidine such as 4-diazabicyclo(2,2,2)octane, diazabicycloundecene, 2-phenyl imidazoline, or the like; N,N-dimethylaminopyridine; a sulfamidate; or a combination thereof.

[0093] 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-l,4-diamine, dicyanamide, diamide diphenylmethane, diamide diphenylsulfonic acid (amine adduct), 4,4’ -methylenedianiline, diethyltoluenediamine, m-phenylenediamine, p-phenylenediamine, melamine formaldehyde resins, urea formaldehyde resins, tetraethylenepentamine, 3-diethylaminopropylamine, 3,3’-iminobispropylamine, 2,4- bis(p-aminobenzyl)aniline, tetraethylenepentamine, 3-diethylaminopropylamine, 2,2,4- and2.4.4-trimethylhexamethylenediamine, 1,2- and 1,3-diaminocyclohexane, l,4-diamino-3,6- diethylcyclohexane, l,2-diamino-4-ethylcyclohexane, l,4-diamino-3,6-diethylcyclohexane, l-cyclohexyl-3,4-diminocyclohexane, 4,4’-diaminondicyclohexylmethane,4,4’ -diaminodicyclohexylpropane, 2,2-bis(4-aminocyclohexyl)propane, 3,3’-dimethyl-4,4’- diaminodicyclohexylmethane, 3-amino-l -cyclohexaneaminopropane, 1,3- and 1,4- bis(aminomethyl)cyclohexane, m- and p-xylylenediamine, or diethyl toluene diamines; or a tertiary amine hardening accelerator such as triethylamine, tributylamine, dimethylaniline, diethylaniline, benzyldimethylamine (BDMA), a-methylbenzyldimethylamine, N,N-dimethylamino pyridine, / V, / V-dimcthylaminocthanol, / V, / V-dimcthylaminocrcsol, or trif / V. / V- dimethylaminomethyl)phenol; or a combination thereof.

[0094] The curing accelerator can be a latent cationic cure catalyst including, for example, diaryliodonium salts, phosphonic acid esters, sulfonic acid esters, carboxylic acid esters, phosphonic ylides, triarylsulfonium salts, benzylsulfonium salts, aryldiazonium salts, benzylpyridinium salts, benzylammonium salts, isoxazolium salts, or the like, or a combination thereof. The diaryliodonium salt can have the structure [(R10)(R11)I]+X" , wherein R10and R11are each independently a Ce-i4 monovalent aromatic hydrocarbon radical, optionally substituted with from 1-4 monovalent radicals selected from C1-20 alkyl, C1-20 alkoxy, nitro, and chloro; and wherein X- is an anion. The additional cure accelerator can have the structure [(R1O)(RU)I]+SbFe" , wherein R10and R11are each independently a Ce-i4 monovalent aromatic hydrocarbon, optionally substituted with from 1-4 C1-20 alkyl, C1-20 alkoxy, nitro, or chloro; for example, 4- octyloxyphenyl phenyl iodonium hexafluoroantimonate.

[0095] The curing accelerator can be a metal salt complex, such as a copper (II) aluminum (III), zinc, cobalt, tin salt 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 cure accelerator can be a copper (II) or aluminum (III) salts of [3-diketonates; copper (II), iron (II), iron (III), cobalt (II), cobalt (III), or aluminum (III) salts of acetylacetonates; zinc (II), chromium (II), or manganese (II) salts of octoates; or a combination thereof.

[0096] When the curable thermosetting composition includes a curing catalyst, the curing catalyst can be included in an amount of 0.01-5 wt%, or 0.05-5 wt%, or 0.1-5 wt%, based on total weight of the curable thermosetting composition.

[0097] The curable thermosetting composition can optionally include a curing initiator, such as a peroxide compound. Exemplary peroxide curing initiators can 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-yne, di-t-butylperoxide, t-butylcumyl peroxide, a,a'-bis(t-butylperoxy- m-isopropyl)benzene, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, dicumylperoxide, 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, l,l-di-(tert-butylperoxy)-3,3,5- trimethylcyclohexane, di(trimethylsilyl)peroxide, trimethylsilylphenyltriphenylsilyl peroxide, or the like, or a combination thereof.

[0098] When the curable thermosetting composition includes a curing initiator, the curing initiator can be included in an amount of 0.1-5 wt%, or 0.5-5 wt%, or 1-5 wt%, based on total weight of the curable thermosetting composition.

[0099] The curable thermosetting compositions can include a flame retardant. Flame retardants include, for example, organic compounds that include phosphorus, bromine, or chlorine. Non-brominated and non-chlorinated phosphorus-containing flame retardants can be preferred in certain applications for regulatory reasons, for example organic phosphates and organic compounds containing phosphorus-nitrogen bonds.

[0100] Examples of phosphorous flame retardants include phosphates, phosphazenes, phosphite esters, phosphines, phosphinates, polyphosphates, and phosphonium salts.

[0101] Halogenated materials can also be used as flame retardants, for example halogenated bisphenols, halogenated aromatics, oligomeric and polymeric halogenated aromatic compounds, or a copolycarbonate of bisphenol A and tetrabromobisphenol A and a carbonate precursor, e.g., phosgene. Metal synergists, e.g., antimony oxide, can also be used with the flame retardant.

[0102] Inorganic flame retardants can also be used, for example salts of Ci-16 alkyl sulfonate salts such as potassium perfluorobutane sulfonate (Rimar salt), potassium perfluoroctane sulfonate, tetraethylammonium perfluorohexane sulfonate, and potassium diphenylsulfone sulfonate; salts such as Na2CC>3, K2CO3, MgCCh. CaCCh. and BaCCh. or fluoro-anion complexes such as LhAIFe. BaSiFe, KBF4, K3AIF6, KAIF4, K^SiFe, or NasAIFe.

[0103] The curable thermosetting composition can further include inorganic or organic fillers, such as a particulate filler, a fibrous filler, or the like, or a combination thereof. Any inorganic and organic fillers, including those known in the art, can be used without limitation.

[0104] Exemplary fillers include, for example, clay, talc, kaolin, wollastonite, mica, calcium carbonate, magnesium carbonate; alumina, thiourea, glass powder, B- or Sn-based fillers such as zinc borate, zinc stannate and zinc hydroxystannate; metal oxides such as zinc oxide and tin oxide, alumina, silica (including fused silica, fumed silica, spherical silica, and crystalline silica), boron nitride (including spherical boron nitride), aluminum nitride, silicon nitride, magnesia, magnesium silicate, antimony trioxide, glass fibers (chopped, milled, or cloth), glass mat, glass bubbles, hollow glass microspheres, aramid fibers, quartz, or the like, or a combination thereof. Other exemplary inorganic fillers include powdered titanium ceramics such as any one of the titanates of barium, lead, strontium, calcium, bismuth, magnesium, or the like. Inorganic fillers also include hydrates such as aluminum hydroxide, magnesium hydroxide, zeolite, and hydrotalcite. In some aspects, the filler can be treated with a coupling agent as disclosed herein.

[0105] Glass fibers include those based on E, A, C, ECR, R, S, D, and NE glasses, as well as quartz. The glass fiber can have any suitable diameter, such as from 2-30 micrometers (pm), or 5-25 pm, or 5-15 pm. The length of the glass fibers before compounding are not limited and can be 2-7 millimeters (mm), or 1.5-5 mm. Alternatively, longer glass fibers or continuous glass fibers can be used. Suitable glass fiber is commercially available from suppliers such as Owens Corning, Nippon Electric Glass, PPG, and Johns Manville.

[0106] The organic filler can be, for example, polytetrafluoroethylene powder, polyphenylene sulfide powder, and poly(ether sulfones) powder, poly(phenylene ether) powder, polystyrene, divinylbenzene resin, or the like, or a combination thereof.

[0107] The filler can be selected based on the thermal expansion coefficient (CTE) and thermal conductivity requirements. For example, AI2O3, BN, AIN, or a combination thereof, can be used for an electronics module with high thermal conductivity. For example, MgO can be used for increased thermal conductivity and increased CTE. For example, SiO2 (e.g., amorphous SiO2) can be used for a lightweight module having a low CTE and a small dielectric constant.

[0108] When the curable thermosetting composition includes a filler, the filler can be included in an amount of greater than 1 wt%, or 1-50 wt%, or 1-30 wt%, or 10-30 wt%, based on total weight of the curable thermosetting composition.

[0109] Coupling agents, also referred to as adhesion promoters, include chromium complexes, silanes, titanates, zircon-aluminates, olefin-maleic anhydride copolymers, reactive cellulose esters, and the like. Exemplary olefin-maleic anhydride copolymers can include maleic anhydride grafted polyethylene, maleic anhydride grafted polypropylene, or a combination thereof. Exemplary silanes can include epoxysilane compound, aminosilane compounds methacryloxysilane compounds, vinylsilane compounds, or a combination thereof.

[0110] When the curable thermosetting composition includes a coupling agent, the coupling agent can be included in an amount of 0.01-5 wt%, or 0.05-5 wt%, or 0.1-5 wt%, based on total weight of the curable thermosetting composition.

[0111] The curable thermosetting composition can optionally include a solvent. The solvent can be, for example, a C3-8 ketone, a C3-8 / V, / V-dialkylamidc, a C4-16 dialkyl ether, a C6-12 aromatic hydrocarbon, a C1-3 chlorinated hydrocarbon, a C3-6 alkyl alkanoate, a C2-6 alkyl cyanide, or a combination thereof. Specific ketone solvents include, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, or a combination thereof. Specific C4-8 N, N- dialkylamide solvents include, for example, dimethylformamide, dimethylacetamide, / V-mcthyl- 2-pyrrolidone, or a combination thereof. Specific dialkyl ether solvents include, for example, tetrahydrofuran, ethylene glycol monomethylether, dioxane, or a combination thereof. Specific aromatic hydrocarbon solvents include, for example, benzene, toluene, xylenes, styrene,divinylbenzenes, or a combination thereof. The aromatic hydrocarbon solvent can be nonhalogenated. Specific C3-6 alkyl alkanoates include, for example, methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, or a combination thereof. Specific C2-6 alkyl cyanides include, for example, acetonitrile, propionitrile, butyronitrile, or a combination thereof. Specific C2-6 alkyl cyanides include, for example, acetonitrile, propionitrile, butyronitrile, or a combination thereof. For example, the solvent can be N,N-dimethylformamide, N,N- dimethylacetamide, N,N-diethylacetamide, N,N-dimethylmethoxyacetamide, N-methyl-2- pyrrolidone, N-cyclohexylpyrrolidinone, N-methylcaprolactam, l,3-dimethyl-2-imidazolidone, 1 ,2-dimethoxyethane, 1,3-dioxane, 1,4-dioxane, tetrahydrofuran, y-butyrolactone, y- caprolactone, dimethylsulfoxide, benzophenone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diglyme, triglyme, tetraglyme, N,N-dimethylethyleneurea, N,N- dimethylpropyleneurea, tetramethylurea, propylene glycol phenyl ether, anisole, veratrole, o- dichlorobenzene, chlorobenzene, trichloroethane, methylene chloride, chloroform, pyridine, picoline, ethyl lactate, n-butyl acetate, butyl cellosolve acetate, butyl carbitol acetate, ethyl cellosolve acetate, ethyl carbitol acetate, propylene carbonate, sulfolane, an ionic liquid, or a combination thereof.

[0112] When a solvent is utilized, the curable thermosetting composition can include 2- 99 wt% of the solvent, based on weight total of the curable thermosetting composition. For example, the solvent amount can be 5-80 wt%, or 10-70 wt%, or 20-60 wt%, based on weight total of the curable thermosetting composition. The solvent can be chosen, in part, to adjust the viscosity of the curable thermosetting composition. Thus, the solvent amount can depend on variables including the type and amount of capped poly(arylene ether) copolymer, the type and amount of other components such as curing additive, the type and amount of any auxiliary thermosetting resin(s), and the processing temperature used for any subsequent processing of the curable thermosetting composition, for example, impregnation of a reinforcing structure with the curable thermosetting composition for the preparation of a composite. The solvent can be anhydrous. For example, the solvent can include less than 100 parts per million (ppm), or less than 50 ppm, or less than 10 ppm of water based on total weight of the solvent.

[0113] The curable thermosetting composition can further include a curable unsaturated monomer composition, which can include, for example, a monofunctional styrenic compound (e.g., styrene), a monofunctional (meth)acrylic compound, or the like, or a combination thereof. For example, the curable unsaturated monomer composition can be an alkene-containing monomer or an alkyne-containing monomer. Exemplary alkene- and alkyne-containing monomers includes those described in U.S. Patent No. 6,627,704 to Yeager et al., and include (meth)acrylates, (meth)acrylamides, N- vinylpyrrolidone, and vinylazalactones as disclosed inU.S. Pat. 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, or the like, or a combination thereof.

[0114] The curable thermosetting composition can, optionally, further include one or more additional additives (“additive composition”). Additional additives include, for example, dyes, pigments, colorants, antioxidants, heat stabilizers, light stabilizers, plasticizers, defoaming agents, lubricants, dispersants, flow modifiers, drip retardants, antiblocking agents, antistatic agents, flow-promoting agents, processing aids, substrate adhesion agents, mold release agents, toughening agents, low-profile additives, stress-relief additives, or the like, or a combination thereof. When present, the additional additives can be included in any effective amount, for example in an amount of 0.01-20 wt%, or 0.01-10 wt%, or 0.01-5 wt%, or 0.01-1 wt%, based on the total weight of the curable thermosetting composition.

[0115] The curable thermosetting composition can be prepared by combining the polyfunctional poly(arylene ether) and the other optional components disclosed herein using any suitable method.

[0116] Also provided is a cured thermoset composition including a cured product of the curable thermosetting composition. There is no limitation on the method by which the curable thermosetting composition can be cured. The curable composition can, for example, be cured thermally or by using irradiation techniques, including UV irradiation or electron beam irradiation. For example, a cured product can be obtained by heating the curable thermosetting composition defined herein for a time and temperature sufficient to evaporate the solvent and effect curing. When heat curing is used, the temperature can be 30-400°C, or 50-250°C, or 100- 250°C. The heating can be for 1 minute to 24 hours, or 1 minute to 6 hours, or 3 hours to 5 hours. The curing can be staged to produce a partially cured and often tack-free resin, which then is fully cured by heating for longer periods or temperatures within the aforementioned ranges. As used herein, the term “cured” encompasses products that are partially cured or fully cured.

[0117] The cured thermoset composition can achieve one or more desirable properties such as improved viscosity, gel time, glass transition temperature (Tg), coefficient of thermal expansion (CTE), dielectric constant (Dk), dissipation factor (Df), equilibrium water absorption, or the like, or a combination thereof.

[0118] The curable thermosetting compositions and cured compositions can be used in a variety of applications, including any applications where conventional thermosettingcompositions are used. For example, useful articles including the curable thermosetting composition or the cured thermoset composition can be in the form of a composite, a foam, a fiber, a layer, a coating, an encapsulant, an adhesive, a sealant, a molded component, a prepreg, a casing, a laminate, a metal clad laminate, an electronic composite, a structural composite, or a combination thereof. Exemplary uses and applications include coatings such as protective coatings, sealants, weather resistant coatings, scratch resistant coatings, and electrical insulative coatings; adhesives; binders; glues; composite materials such as those using carbon fiber and fiberglass reinforcements. When utilized as a coating, the disclosed compounds and compositions can be deposited on a surface of a variety of underlying substrates. For example, the compositions can be deposited on a surface of metals, plastics, glass, fiber sizings, ceramics, stone, wood, or any combination thereof. The disclosed compositions can be used as a coating on a surface of a metal container (e.g., aluminum or steel), such as those commonly used for packaging and containment in the paint and surface covering industries. The curable thermosetting composition and the cured thermoset composition derived therefrom can also be particularly well suited for use in forming electrical components and computer components.

[0119] Methods of forming a composite can include 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 can be a porous base material such as a fibrous preform or substrate, or other porous material including a ceramic, a polymer, a glass, carbon, or a combination thereof. For example, the porous base material can be woven or non-woven glass fabric, a fiberglass fabric, or carbon fiber. When the article includes a fibrous preform, the method of manufacturing the article can include forming the article from the curable thermosetting composition by coating or impregnating the preform with the curable composition. The impregnated fibrous preform can optionally be shaped before or after removing the solvent. In some aspects, the curable thermosetting composition layer can further include a woven or nonwoven glass fabric. For example, the curable layer can be prepared by impregnating the glass fabric with a curable composition and removing the solvent from the impregnated glass fabric. Exemplary reinforcing structures are described, for example, in Anonymous (Hexcel Corporation), “Prepreg Technology”, March 2005, Publication No. FGU 017b; Anonymous (Hexcel Corporation), “Advanced Fibre Reinforced Matrix Products for Direct Processes”, June 2005, Publication No. ITA 272; and Bob Griffiths, “Farnborough Airshow Report 2006”, CompositesWorld.com, September 2006. The weight and thickness of the reinforcing structure are chosen according to the intended use of the composite using criteria well known to those skilled in the production of fiber reinforced resin composites. The reinforced structure can contain various finishes suitablefor the thermosetting components of the curable thermosetting composition.

[0120] The method of manufacturing the articles from the curable thermosetting composition can include partially curing the curable thermosetting composition to form a prepreg, or fully curing the curable thermosetting composition to form a composite article. References herein to properties of the “cured composition” refer to a composition that is substantially fully cured. For example, the resin in a laminate formed from prepregs is typically substantially fully cured. One skilled in the thermoset arts can determine whether a sample is partially cured or substantially fully cured without undue experimentation. The curing can be before or after removing the solvent from the curable composition. In addition, the article can be further shaped before removal of the solvent or after removal of the solvent, before curing, after partial curing, or after full curing, for example by thermoforming. In some aspects, the article is formed, and the solvent is removed; the article is partially cured (B -staged); optionally shaped; and then further cured.

[0121] Commercial-scale methods of forming composites are known in the art, and the curable thermosetting compositions described herein are readily adaptable to existing processes and equipment. For example, prepregs are often produced on treaters. The main components of a treater include feeder rollers, a resin impregnation tank, a treater oven, and receiver rollers. The reinforcing structure (E-glass, for example) is usually rolled into a large spool. The spool is then put on the feeder rollers that turn and slowly roll out the reinforcing structure. The reinforcing structure then moves through the resin impregnation tank, which contains the curable thermosetting composition. The curable composition impregnates the reinforcing structure. After emerging from the tank, the coated reinforcing structure moves upward through the vertical treater oven, which is typically at a temperature of 175-200°C, and the solvent is evaporated. The resin begins to polymerize at this time. When the composite comes out of the tower it is sufficiently cured so that the web is not wet or tacky. The cure process, however, is stopped short of completion so that additional curing can occur when laminate is made. The web then rolls the prepreg onto a receiver roll.

[0122] Electrical and electronic articles including or derived from the curable thermosetting composition are also provided. Articles include those including printed circuits as used in medical or aerospace industries. Still other articles include antennae and like articles. Articles such as printed circuit boards are used, for example, in lighting, solar energy, displays, cameras, audio and video equipment, personal computers, mobile telephones, electronic notepads, and similar devices, or office automation equipment. For example, electrical parts can be mounted on printed circuit boards including a laminate. Other exemplary articles prepared from the curable composition for various applications can include copper clad laminates (CCL),for example, metal core copper clad laminates (MCCCL), composite articles, and coated articles, for example multilayer articles.

[0123] Dielectric layer can be prepared from the curable thermosetting composition can be useful in a circuit assembly, for example, in a metal-clad laminate such as a copper clad laminate. For example, a laminate can include a dielectric layer, a conductive metal circuit layer disposed on the dielectric layer, and optionally, a heat dissipating metal matrix layer disposed on the dielectric layer on a side opposite the conductive metal layer. The dielectric layer can optionally include a fibrous preform (e.g., a fabric layer). For example, the dielectric layer can further include a glass fabric layer.

[0124] The conductive metal layer can be in the form of a circuit, and can be copper, zinc, tin, brass, chromium, molybdenum, nickel, cobalt, aluminum, stainless steel, iron, gold, silver, platinum, titanium, or the like, or a combination thereof. Other metals include a copper molybdenum alloy, a nickel-cobalt iron alloy such as KOVAR, available from Carpenter Technology Corporation, a nickel-iron alloy such as INVAR, available from National Electronic Alloys, Inc., a bimetal, a trimetal, a trimetal derived from two-layers of copper and one layer of INVAR, and a trimetal derived from two layers of copper and one layer of molybdenum. Exemplary metal layers include copper or a copper alloy. Alternatively, wrought copper foils can be used. Conductive metal layers can have a thickness of 2-200 pm, or 5-50 pm, or 5-40 pm.

[0125] A heat dissipating metal matrix layer can be a thermally conductive metal such as aluminum, boron nitride, aluminum nitride, copper, iron, steel, or the like, or a combination thereof. A thermally conductive, electrically conductive metal can be used provided that the metal is electrically isolated from the metal circuit layer. Preferred supporting metal matrix layers can have a thickness of 0.1-20 mm, or 0.5-10 mm, or 0.8 to 2 mm.

[0126] The conductive metal layer and the supporting metal matrix layers can be pretreated to have high surface roughness for enhanced adhesion to the dielectric layer. Treatment methods include washing, flame treatment, plasma discharge, corona discharge, or the like, for example to enhance adhesion of the metal layer. The dielectric layer can adhere firmly to the conductive metal layer or the heat dissipation layer without using an adhesive, or an adhesive can be used to improve adhesion of the dielectric layer to the conductive metal layer or the heat dissipation layer. Exemplary adhesives used to bond the composite sheet to a metal include polyimide adhesives, acrylic adhesives, epoxies, or the like, or a combination thereof.

[0127] The copper clad laminates can be made 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 thermosetting adhesives. The dielectric layer can be prepared fromthe curable thermosetting composition and can be prepared prior to the thermal lamination step by a solvent casting process to form a layer. For example, the dielectric layer, the conductive metal layer, and the thermal dissipation layer can be thermally laminated together by an adhesive-free process under pressure to form a laminate. The electrically conductive metal layer can optionally be in the form of a circuit before laminating, or the conductive metal layer can optionally be etched to form the electrical circuit following lamination. The laminating can be by hot press or roll calendaring methods, for example, a roll-to-roll method. The conductive metal layer in a copper clad laminate can further be patterned to provide a printed circuit board. Furthermore, the copper clad laminates can be shaped to provide a circuit board having the shape of a sheet, a tube, or a rod.

[0128] Alternatively, laminates for a circuit assembly can be made by a solution casting method in which the curable thermosetting composition is cast directly onto the electrically conductive metal layer, followed by lamination to the heat dissipating metal matrix layer. For example, the curable thermosetting composition can be cast directly onto the heat dissipating metal matrix layer, followed by lamination to the electrically conductive metal layer.

[0129] Multilayer laminates including additional layers can also be made by thermal lamination in one step or in two or more consecutive steps by such processes as hot press or roll calendaring methods. For example, seven layers or fewer can be present in the laminate, or sixteen layers or fewer. In some aspects, a laminate can be formed in one step or in two or more consecutive steps with sequential layers of fabric-thermoset-metal-thermoset-fabric-thermoset- metal foil or a sub-combination thereof with fewer layers, such that the laminate includes a layer of thermoset film between any layer of metal foil and any layer of fabric. In another aspect, a first laminate can be formed in one step or in two or more consecutive steps with a layer of fabric between two layers of the thermoset, such as a layer of woven glass fabric between two layers of the thermoset. A second laminate can then be prepared by laminating a metal foil to a thermoset side of the first laminate.

[0130] Printed circuit boards prepared from the curable thermosetting composition can have an overall thickness of 0.1-20 mm, or 0.5-10 mm, wherein overall thickness refers to an assembly including a layer each of the dielectric layer, the electrically conductive metal layer, and the supporting metal matrix layer. Circuit assemblies can have an overall thickness of 0.5-2 mm, or 0.5-1.5 mm. There is no limitation on the thickness of the dielectric layer and can be 5- 1500 pm, or 5-750 pm, or 10-150 pm, or 10-100 pm. For example, the printed circuit board can be a metal core printed circuit board (MCPCB) for use in a light emitting diode (LED) application.

[0131] The curable thermosetting composition can be used as a coating, for example inthe preparation of a multilayer article. A method of manufacturing the coating can include combining the curable thermosetting composition and optionally a fluoropolymer and forming a coating on a substrate. For example, a multilayer article can be manufactured by forming a layer including the curable thermosetting composition, removing the solvent from the layer and optionally curing to provide a primer layer, forming a second layer including a ceramic (e.g., AI2O3, TiCh, Z1O2. Cr2C>3, SiC>2, MgO, BeO, Y2O3, AhCh-SiCh, MgO-ZrCh, SiC, WC, B4C, TiC, Si3N4, TiN, BN, AIN, TiB, ZrB2, or the like), a thermoplastic polymer, a fluoropolymer (e.g., polytetrafluoroethylene, tetrafluoroethylene-perfluoroalkylvinylether copolymers, tetrafluoroethylene-hexafluoropropylene copolymers, polychlorotrifluoroethylene, tetrafluoroethylene-ethylene copolymers, polyvinylidene fluoride, or the like), or a combination thereof on the primer layer to provide the multilayer article, and optionally thermally treating the multilayer article to cure the curable thermosetting composition. In some aspects, the second layer can further include the curable thermosetting composition.

[0132] Additional applications for the curable thermosetting compositions include, for example, acid bath containers; neutralization tanks; aircraft components; bridge beams; bridge deckings; electrolytic cells; exhaust stacks; scrubbers; sporting equipment; stair cases; walkways; automobile exterior panels such as hoods and trunk lids; floor pans; 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; building panels; business machine housings; trays, including cable trays; concrete modifiers; dishwasher and refrigerator parts; electrical encapsulants; electrical panels; tanks, including electrorefining tanks, water softener tanks, fuel tanks, and various filament-wound tanks and tank linings; furniture; garage doors; gratings; protective body gear; luggage; outdoor motor vehicles; pressure tanks; optical waveguides; radomes; railings; railroad 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, bodies, cabs, and beds; insulation for rotating machines including ground insulation, turn insulation, and phase separation insulation; commutators; core insulation and cords and lacing tape; drive shaft couplings; propeller blades; missile components; rocket motor cases; wing sections; sucker rods; fuselage sections; wing skins and flarings; engine narcelles; cargo doors; tennis racquets; golf club shafts; fishing rods; skis and ski poles; bicycle parts; transverse leaf springs; pumps, such as automotive smog pumps; electrical components, embedding, 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 cut-off devices; coatings for printed wiring boards; casting items such as capacitors, transformers, crankcase heaters;small molded electronic parts including coils, capacitors, resistors, and semiconductors; as a replacement for steel in chemical processing, pulp and paper, power generation, and wastewater treatment; scrubbing towers; pultruded parts for structural applications, including structural members, gratings, and safety rails; swimming pools, swimming pool slides, hot-tubs, and saunas; drive shafts for under the hood applications; dry toner resins for copying machines; marine tooling and composites; heat shields; submarine hulls; prototype generation; development of experimental models; laminated trim; drilling fixtures; bonding jigs; inspection fixtures; industrial metal forming dies; aircraft stretch block and hammer forms; vacuum molding tools; flooring, including flooring for production and assembly areas, clean rooms, machine shops, control rooms, laboratories, parking garages, freezers, coolers, and outdoor loading docks; electrically conductive compositions for antistatic applications; for decorative flooring; expansion joints for bridges; injectable mortars for patch and repair of cracks in structural concrete; grouting for tile; machinery rails; metal dowels; bolts and posts; repair of oil and fuel storage tanks, and numerous other applications.

[0133] Processes useful for preparing the articles and materials include those generally known to the art for the processing of thermosetting resins. Such processes have been described in the literature as in, 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 “Polyesters and Their Applications” by Bjorksten Research Laboratories, Johan Bjorksten (pres.) Henry Tovey (Ch. Lit. Ass.), Betty Harker (Ad. Ass.), James Henning (Ad. Ass.), Reinhold Publishing Corporation, New York, 1956. Processing techniques include resin transfer molding; sheet molding; bulk molding; pultrusion; injection molding, including reaction injection molding (RIM); atmospheric pressure molding (APM); casting, including centrifugal and static casting open mold casting; lamination including wet or dry lay-up and spray lay up; also included are contact molding, including cylindrical contact molding; compression molding; including vacuum assisted resin transfer molding and chemically assisted resin transfer molding; matched tool molding; autoclave curing; thermal curing in air; vacuum bagging; pultrusion; Seeman's Composite Resin Infusion Manufacturing Processing (SCRIMP); open molding, continuous combination of resin and glass; and filament winding, including cylindrical filament winding. For example, an article can be prepared by a resin transfer molding process.

[0134] Also provided is an article derived from the curable thermosetting composition, wherein the article is a composite, a foam, a fiber, a layer, a coating, an encapsulant, an adhesive, a sealant, a molded component, a prepreg, a casing, a cast article, a laminate, or a combination thereof; or, wherein the article is a metal clad laminate, an electronic composite, astructural composite, or a combination thereof. Articles can be manufactured as disclosed herein, for example by casting, molding, extruding, or the like, and removing the solvent from the formed article. In some aspects, the article can be a layer, and can be formed by casting the curable composition onto a substrate to form a cast layer. The solvent can be removed by any number of means, including by heating the cast layer, heating the cast layer under heat and pressure, for example by laminating the cast layer to another substrate. In some aspects, articles prepared by the above-described methods can include adhesives, packaging material, capacitor films, or circuit board layers. In some aspects, articles prepared from the curable composition can be a dielectric layer, or a coating disposed on a substrate, for example a wire or cable coating. For example, the article can be a dielectric layer in a circuit material, for example in a printed circuit board, used, for example, in lighting or communications applications. Other exemplary articles prepared from the curable composition can be one or more painted layers. The curable compositions can be used to prepare articles as disclosed herein for other curable thermosetting compositions.

[0135] This disclosure is further illustrated by the following examples, which are nonlimiting.EXAMPLES

[0136] Ethoxylation of poly(phenylene ether) oligomer: A 50 wt% solution of poly(phenylene ether) oligomer was prepared by dissolving 1 kg of a phenolic poly(phenylene ether) oligomer in 1.1 kg of MIBK (methyl isobutyl ketone) at 60°C with stirring. To this solution was added 2 mol% of KOH (39.2 g of a 50 wt% solution in water) and the solution dried by pulling a slight vacuum and distilling out 100 g of the solvent (until it ran clear.) This solution was then transferred under N2 into a 4-L autoclave and ethylene oxide (4.5 g, gas) was transferred into it. The autoclave was heated to 135 °C and held until the pressure drop stopped and was stable. The reactor was cooled to 25 °C and the solution discharged. The resin was collected by precipitation with 5 equivalents of methanol, filtered and dried in a 100°C vacuum oven overnight.

[0137] This process was repeated with samples being removed after aliquots of ethylene oxide were sequentially added. The results are shown in the FIGURE, which is a plot of the Tg of each material produced vs. the number of equivalents of ethylene oxide added.1H-NMR was used to determine the equivalents of ethylene oxide from the ratio of peaks in the PPE backbone to the ethylene oxide groups.31P-NMR was used to check for remaining phenolic end-groups from the original oligomer. In all cases, the phenolic end groups if present, were less than the detection limit (10 ppm). As demonstrated by the data in the FIGURE, there was excellent linearity in the response of Tg to equivalents of ethylene oxide. Further, since the target Tg forcustomers was 80°C, this process can readily produce oligomers that satisfy the requirement.

[0138] Preparation of a methacrylate-capped alkoxylated PPE oligomer: 100.08 g of ethoxylated PPE oligomer from the first example was dissolved in 144.4 g of toluene in a round bottom flask attached to a dean-stark condenser. Under nitrogen atmosphere, the reaction mixture was heated to 111 °C and dried through azeotropic distillation. Once dry, the reaction was cooled to 85°C. 0.2272 g of 4-dimethylaminopyridine was added to the reactor flask and 21.55 g of methacrylic anhydride was added dropwise over 30 minutes. After addition, the reaction was allowed to mix and monitored using NMR Which confirmed completion of the reaction. Once reaction completion was confirmed, the oligomer solution was precipitated into 1300 mL of methanol, and the resulting powder was isolated via vacuum filtration, yielding a methacrylate capped PPE oligomer. The Mnwas 2935 g / mol as determined by GPC (polystyrene standards), and the Tg was 121°C as determined by DSC.

[0139] Preparation of an acrylate-capped alkoxylated PPE oligomer was accomplished in the same manner as the methacrylate-capped example, except acrylic anhydride was utilized in place of methacrylic anhydride to produce an acrylate-capped PPE oligomer. The number average molecular weight was 3040 g / mol as determined by GPC (polystyrene standards), and the Tg was 130°C as determined by differential scanning calorimetry.

[0140] Preparation of an allyl-capped PPE oligomer: 100.00 g of ethoxylated PPE oligomer from the first example, 30.3302 g of allyl bromide, and 0.8134 of Adogen 464 were dissolved in 100.0 g of toluene in a round bottom flask with a reflux condenser attached. The reaction mixture was heated to 75°C then 35.1303 g of 50 wt. % sodium hydroxide solution in deionized water was added dropwise to reaction via addition funnel over the course of 30 minutes and the reaction was continued for 4 hours. Once the reaction was complete, the oligomer solution was neutralized with 83 g of 0.1 N Hydrochloric acid. The mixture was centrifuged to separate the organic and aqueous layers. The aqueous layer was removed and discarded. The organic layer was precipitated into 1500 mL of methanol, and isolated using vacuum filtration. The course powder was dried overnight under vacuum at ambient temperature to yield an allyl functionalized PPE oligomer. The number average molecular weight was 2754 g / mol as determined by GPC (polystyrene standards), the Tg was 122 °C as determined by DSC.

[0141] The vinylbenzyl-capped PPE oligomer was prepared in the same manner as the allyl-capped, except 4-vinyl benzyl chloride was utilized in place of allyl bromide to produce a vinylbenzyl-capped PPE oligomer. The number average molecular weight was 2748 g / mol as determined by GPC (polystyrene standards), and the Tg was 90°C as determined by DSC.

[0142] This disclosure further encompasses the following aspects.

[0143] Aspect 1. A polyfunctional poly(arylene ether) including an end group includinga linking group and a terminal functional group, wherein the linking group includes a substituted or unsubstituted saturated hydrocarbylene group, or a substituted or unsubstituted saturated poly(hydrocarbylene ether), and wherein the terminal functional group includes the formula -X- T, wherein each occurrence of X is independently an oxygen or substituted or unsubstituted nitrogen, and each occurrence of T is independently a reactive end group comprising an unsaturated moiety, a melamine, a cyanophenyl, a maleimide, a phthalonitrile, a cycloalkylphenyl, an ethoxylate, a urethane, an anhydride, an allylhydroxypropyl, a methacrylate, an acrylate, an allyl moiety, a vinylbenzyl moiety, or a combination thereof, and optionally end groups of the formula X-H.

[0144] Aspect 2. The polyfunctional poly (arylene ether) of aspect 1, wherein the linking group independently includes the following formulas -C(RI)(R2)-, or -[(C(Ri)(R2))mi-0]ni- (C(RI)(R2))-, wherein Ri and R2 are each independently hydrogen, halogen, hydroxyl, or Ci-Ce alkyl, ml is 2 or more, or 2-4, and nl is 1 or more, or 1-25.

[0145] Aspect 3. The polyfunctional poly(arylene ether) of aspect 1 or 2, wherein the linking group further includes a unit derived from a multifunctional polyol, and wherein the multifunctional polyol includes two or more hydroxyl groups.

[0146] Aspect 4. The polyfunctional poly(arylene ether) of any one of the preceding aspects, wherein the end group excludes terephthalic acid, units derived from terephthalic acid, phthalic acid, units derived from phthalic acid, or a combination thereof.Aspect 5. The polyfunctional poly (arylene ether) of any one of the preceding aspects, wherein the poly(arylene ether) is derived from a monohydric phenol and optionally, a dihydric phenol, a multifunctional monomer including at least two hydroxyl groups, or wherein the polyfunctional poly(arylene ether) includes the formula (12) as described herein, wherein each occurrence of Q1and Q2independently include halogen, unsubstituted or substituted C1-12 primary or secondary hydrocarbyl, C1-12 hydrocarbylthio, C1-12 hydrocarbyloxy, Ci-6alkyl(C6-3ocycloalkenyl), or C2-12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms; each occurrence of Q3and Q4independently include hydrogen, halogen, unsubstituted or substituted C1-C12 primary or secondary hydrocarbyl, C1-C12 hydrocarbylthio, C1-12 hydrocarbyloxy, Ci-6alkyl(C6-30cycloalkenyl), or C2-12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms; x and y are each independently 0-30; each occurrence of Pl, P2, P3, and P4 is independently hydrogen, halogen, unsubstituted or substituted Cl-12 primary or secondary hydrocarbyl, Cl-12 hydrocarbylthio, Cl-12 hydrocarbyloxy, or C2-12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms; each occurrence of R16and R17is independently hydrogen, halogen, or C1-18 alkyl, or hydrogen or C1-6 alkyl, or hydrogen or C1-3 alkyl; each occurrence of n is 1 ormore, or 1-3; each occurrence of m is 1 or more, or 1-3; Y is a single bond or a divalent linking group of the formulas of Scheme A as described herein wherein each occurrence of Ra, Rb, Rc, Rd, and Reis independently hydrogen, C1-12 hydrocarbyl, or Ci -6 hydrocarbylene, optionally wherein Raand Rbor Rcand Rdtogether are a C4-8 alkylene group; each occurrence of Rfis independently hydrogen, a C1-14 hydrocarbyl, a C1-14 halohydrocarbyl, or a C1-14 heterohydrocarbyl, or C1-13 alkyl, C1-13 alkoxy, C2-13 alkenyl, C2-13 alkenyloxy, C3-6 cycloalkyl, C3-6 cycloalkoxy, Ce-14 aryl, Ce-io aryloxy, C7-13 arylalkyl, C7-13 arylalkoxy, C7-13 alkylaryl, or C7-13 alkylaryloxy; each occurrence of Rgis independently a substituted or unsubstituted C1-12 hydrocarbylene group, a C6-12 arylene group, or a combination thereof, or wherein each occurrence of Rgis the same and is a divalent C2-8 aliphatic group, or wherein each occurrence of Rgis the same and is dimethylene, trimethylene, or tetramethylene; and E is 2-200, or 6-100.

[0147] Aspect 6. The polyfunctional poly(arylene ether) of any one of aspects 2-5, wherein the end group includes the formula -C(RI)(R2)-X-T.

[0148] Aspect 7. The polyfunctional poly(arylene ether) of any one of aspects 2-5, wherein the end group includes the formula -[(C(Ri)(R2))mi-O]ni-(C(Ri)(R2))-XT, and nl is 5- 25, or 15-25.

[0149] Aspect 8. The polyfunctional poly (arylene ether) of any one of the preceding aspects, wherein the linking group includes 0-5,000 ppm of a carbonate functional group, 0- 5,000 ppm of an ester functional group, or a combination thereof, each as determined bydH NMR.

[0150] Aspect 9. The polyfunctional poly(arylene ether) of any one of the preceding aspects, wherein the reactive end group T comprises a group of the formulas of Scheme B, wherein Y2is a divalent linking group having one of formulas of Scheme C, wherein each occurrence of Rdand Reindependently is hydrogen or C1-12 alkyl; R5ais an epoxide-containing group, a cyanate-containing group, or a C1-12 hydrocarbylene substituted with one or two carboxylic acid groups; each occurrence of R6, R7, and R8independently is hydrogen, C1-18 hydrocarbyl, C2-18 hydrocarbyloxycarbonyl, nitrile, formyl, carboxylic acid, imidate, or thiocarboxylic acid; and each occurrence of R9, R10, R11, R12, and R13independently is hydrogen, halogen, C1-12 alkyl, C2-12 alkenyl, hydroxy, amino, maleimide, carboxylic acid, or a C2-20 alkyl ester.

[0151] Aspect 10. A method for preparing the polyfunctional poly(arylene ether) of any one of aspects 1-9, the method including reacting a polyfunctional poly (arylene ether) precursor with an end-capping agent to provide the polyfunctional poly (arylene ether), wherein the polyfunctional poly(arylene ether) precursor includes an end group including a linking groupand a terminal functional group of the formula -X-H, wherein each occurrence of X is independently an oxygen or substituted or unsubstituted nitrogen.

[0152] Aspect 11. A composition including the polyfunctional poly(arylene ether) of any one of aspects 1-9, wherein the composition includes 0-5,000 ppm of a carbonate-containing polyfunctional poly(arylene ether) including an end group, wherein the end group includes a linking group and a terminal functional group, wherein the terminal functional group includes the formula -X-T, wherein each occurrence of X is independently an oxygen or substituted or unsubstituted nitrogen, and each occurrence of T is independently hydrogen or a reactive end group, and wherein the linking group of the carbonate-containing polyfunctional poly(arylene ether) includes a carbonate group, 0-5,000 ppm of an ester-containing polyfunctional poly(arylene ether) including an end group, wherein the end group includes a linking group and a terminal functional group, wherein the terminal functional group includes the formula -X-T, wherein each occurrence of X is independently an oxygen or substituted or unsubstituted nitrogen, and each occurrence of T is independently hydrogen or a reactive end group, and wherein the linking group of the ester-containing polyfunctional poly(arylene ether) includes an ester group, or a combination thereof.

[0153] Aspect 12. A curable composition including the polyfunctional poly(arylene ether) of any one of aspects 1-9 or the composition of aspect 10, and optionally, a curing promoter.

[0001] Aspect 13. An article derived from the cured product of the curable composition of aspect 12.

[0002] Aspect 14. The article of aspect 13, wherein the article is a composite, a foam, a fiber, a layer, a coating, an encapsulant, an adhesive, a sealant, a molded component, a prepreg, a casing, a cast article, or a laminate.

[0003] Aspect 15. A method for manufacturing the article of aspect 14 including molding, casting, extruding, foaming, spinning, or printing the curable composition to provide the article.

[0154] The compositions, methods, and articles can alternatively include, consist of, or consist essentially of, any appropriate materials, steps, or components herein disclosed. The compositions, methods, and articles can additionally, or alternatively, be formulated so as to be devoid, or substantially free, of any materials (or species), steps, or components that are otherwise not necessary to the achievement of the function or objectives of the compositions, methods, and articles.

[0155] All ranges disclosed herein are inclusive of the endpoints, and the endpoints are independently combinable with each other (e.g., ranges of “up to 25 wt%, or, more or, 5 wt% to20 wt%”, is inclusive of the endpoints and all intermediate values of the ranges of “5 wt% to 25 wt%,” etc.). “Combinations” is inclusive of blends, mixtures, alloys, reaction products, and the like. The terms “first,” “second,” etc., do not denote any order, quantity, or importance, but rather are used to distinguish one element from another. The terms “a” and “an” and “the” do not denote a limitation of quantity and are to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. “Or” means “and / or” unless clearly stated otherwise or by context. Reference to “some aspects”, “an aspect”, and so forth, means that a particular element described in connection with the aspect is included in at least one aspect described herein, and may or may not be present in other aspects. The described elements can be combined in any suitable manner in the various aspects. A “combination thereof’ is open and includes any combination including at least one of the listed components or properties optionally together with a like or equivalent component or property not listed

[0156] Unless specified to the contrary herein, all test standards are the most recent standard in effect as of the filing date of this application, or, if priority is claimed, the filing date of the earliest priority application in which the test standard appears.

[0157] Unless defined otherwise, technical and scientific terms used herein have the same meaning as is commonly understood by one of skill in the art to which this application belongs. All cited patents, patent applications, and other references are incorporated herein by reference in their entirety. However, if a term in the present application contradicts or conflicts with a term in the incorporated reference, the term from the present application takes precedence over the conflicting term from the incorporated reference.

[0158] Compounds are described using standard nomenclature. For example, any position not substituted by any indicated group is understood to have its valency filled by a bond as indicated, or a hydrogen atom. A dashthat is not between two letters or symbols is used to indicate a point of attachment for a substituent. For example, -CHO is attached through carbon of the carbonyl group. 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, and n- and s-hexyl. “Alkenyl” means a straight or branched chain, monovalent hydrocarbon group having at least one carbon-carbon double bond (e.g., ethenyl (-HC=CH2)). “Alkoxy” means an alkyl group that is linked via an oxygen (i.e., alkyl-O-), for example methoxy, ethoxy, and sec-butyloxy groups. "Alkylene" means a straight or branched chain, saturated, divalent aliphatic hydrocarbon group (e.g., methylene (-CH2-) or, propylene (-(CH2)3- )). “Cycloalkylene” means a divalent cyclic alkylene group, -CnH2n-x, wherein x is the number of hydrogens replaced by cyclization(s). “Cycloalkenyl” means a monovalent group having one or more rings and one or more carbon-carbon double bonds in the ring, wherein all ring membersare carbon (e.g., cyclopentyl and cyclohexyl). "Aryl" means an aromatic hydrocarbon group containing the specified number of carbon atoms, such as phenyl, tropone, indanyl, or naphthyl. “Arylene” means a divalent aryl group. “Alkylarylene” means an arylene group substituted with an alkyl group. “Arylalkylene” means an alkylene group substituted with an aryl group (e.g., benzyl). The prefix "halo" means a group or compound including one more of a fluoro, chloro, bromo, or iodo substituent. A combination of different halo groups (e.g., bromo and fluoro), or only chloro groups can be present. “Substituted” means that the compound or group is substituted with at least one (e.g., 1, 2, 3, or 4) substituents that can each independently be a C1-9 alkoxy, a C1-9 haloalkoxy, a nitro (-NO2), a cyano (-CN), a C1-6 alkyl sulfonyl (-S(=O)2-alkyl), a C6-12 aryl sulfonyl (-S(=O)2-aryl)a thiol (-SH), a thiocyano (-SCN), a tosyl (CH3C6H4SO2-), a C3- 12 cycloalkyl, a C2-12 alkenyl, a C5-12 cycloalkenyl, a C6-12 aryl, a C7-13 arylalkylene, a C4-12 heterocycloalkyl, and a C3-12 heteroaryl instead of hydrogen, provided that the substituted atom’s normal valence is not exceeded. The number of carbon atoms indicated in a group is exclusive of any substituents. For example -CH2CH2CN is a C2 alkyl group substituted with a nitrile.

[0159] While particular embodiments have been described, alternatives, modifications, variations, improvements, and substantial equivalents that are or may be presently unforeseen may arise to applicants or others skilled in the art. Accordingly, the appended claims as filed and as they may be amended are intended to embrace all such alternatives, modifications variations, improvements, and substantial equivalents.

Claims

CLAIMSWhat is claimed is:

1. A polyfunctional poly(arylene ether) including an end group including a linking group and a terminal functional group, wherein the linking group includes a substituted or unsubstituted saturated hydrocarbylene or a substituted or unsubstituted saturated poly(hydrocarbylene ether), the terminal functional group is of the formula -X-T, wherein each occurrence of X is independently an oxygen or substituted or unsubstituted nitrogen, and each occurrence of T is independently reactive end group comprising an unsaturated moiety, a melamine, a cyanophenyl, a maleimide, a phthalonitrile, a cycloalkylphenyl, an ethoxylate, a urethane, an anhydride, an allylhydroxypropyl, a methacrylate, an acrylate, an allyl moiety, a vinylbenzyl moiety, or a combination thereof, and optionally end groups of the formula X-H.

2. The polyfunctional poly(arylene ether) of claim 1, wherein each occurrence of the linking group is independently of the formulawhereinR1and R2are each independently hydrogen, halogen, hydroxyl, or Ci-Ce alkyl, ml is 2 or more, or 2-4, and nl is 1 or more, or 1-25.

3. The polyfunctional poly(arylene ether) of claim 1 or 2, wherein the linking group further includes a unit derived from a multifunctional polyol, wherein the multifunctional polyol comprises two or more hydroxyl groups.

4. The polyfunctional poly(arylene ether) of any one of the preceding claims, wherein the end group excludes terephthalic acid, units derived from terephthalic acid, phthalic acid, units derived from phthalic acid, or a combination thereof.

5. The polyfunctional poly(arylene ether) of any one of the preceding claims, wherein the poly(arylene ether) is derived from a monohydric phenol and optionally, a dihydric phenol, a multifunctional monomer including at least two hydroxyl groups, or wherein the polyfunctional poly(arylene ether) is of the formulawherein each occurrence of Q1and Q2is independently halogen, unsubstituted or substituted C1-12 primary or secondary hydrocarbyl, C1-12 hydrocarbylthio, C1-12 hydrocarbyloxy, Ci- 6alkyl(C6-3ocycloalkenyl), or C2-12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms; each occurrence of Q3and Q4is independently hydrogen, halogen, unsubstituted or substituted C1-C12 primary or secondary hydrocarbyl, C1-C12 hydrocarbylthio, C1-12 hydrocarbyloxy, Ci-6alkyl(C6-3ocycloalkenyl), or C2-12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms; x and y are each independently 0-30; each occurrence of P1, P2, P3, and P4is independently hydrogen, halogen, unsubstituted or substituted C1-12 primary or secondary hydrocarbyl, C1-12 hydrocarbylthio, C1-12 hydrocarbyloxy, or C2-12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms; each occurrence of R16and R17is independently hydrogen, halogen, or Ci-is alkyl, or hydrogen or C1-6 alkyl, or hydrogen or C1-3 alkyl; each occurrence of n is 1 or more, or 1-3; each occurrence of m is 1 or more, or 1-3;Y is a single bond or a divalent linking group of the formulawherein each occurrence of Ra, Rb, Rc, Rd, and Reis independently hydrogen, C1-12 hydrocarbyl, or Ci -6 hydrocarbylene, optionally wherein Raand Rbor Rcand Rdtogether are a C4-8 alkylene group; each occurrence of Rfis independently hydrogen, a C1-14 hydrocarbyl, a C1-14 halohydrocarbyl, or a C1-14 heterohydrocarbyl, or C1-13 alkyl, C1-13 alkoxy, C2-13 alkenyl, C2-13 alkenyloxy, C3-6 cycloalkyl, C3-6 cycloalkoxy, Ce-i4 aryl, Ce-io aryloxy, C7-13 arylalkyl, C7-13 arylalkoxy, C7-13 alkylaryl, or C7-13 alkylaryloxy; each occurrence of Rgis independently a substituted or unsubstituted C1-12 hydrocarbylene group, a C6-12 arylene group, or a combination thereof, or wherein eachoccurrence of Rgis the same and is a divalent C2-8 aliphatic group, or wherein each occurrence of Rgis the same and is dimethylene, trimethylene, or tetramethylene; andE is 2-200, or 6-100.

6. The polyfunctional poly(arylene ether) of any one of claims 2-5, wherein the end group is of the formula -C(R1)(R2)-X-T.

7. The polyfunctional poly(arylene ether) of any one of claims 2-5, wherein the end group is of the formula -[(C(R1)(R2))mi-O]ni-(C(R1)(R2))-XT, and nl is 5-25, or 15-25.

8. The polyfunctional poly(arylene ether) of any one of the preceding claims, wherein the linking group includes 0-5,000 ppm of a carbonate functional group, 0-5,000 ppm of an ester functional group, or a combination thereof, each as determined byNMR.

9. The polyfunctional poly(arylene ether) of any one of the preceding claims, wherein each reactive end group T is independently a group of the formulaor a combination thereof, wherein each occurrence of Y2is independently a divalent linking group of theformula ’ ’ Re’ ’or° , wherein each occurrence of Rdand Reindependently is hydrogen or C1-12 alkyl;R5ais an epoxide-containing group, a cyanate-containing group, or a C1-12 hydrocarbylene substituted with one or two carboxylic acid groups; each occurrence of R6, R7, and R8is independently hydrogen, Ci-is hydrocarbyl, C2-18 hydrocarbyloxycarbonyl, nitrile, formyl, carboxylic acid, imidate, or thiocarboxylic acid; and each occurrence of R9, R10, R11, R12, and R13independently is hydrogen, halogen, C1-12 alkyl, C2-12 alkenyl, hydroxy, amino, maleimide, carboxylic acid, or a C2-20 alkyl ester.

10. A method for preparing the polyfunctional poly (arylene ether) of any one of claims 1-9, the method comprising: reacting a polyfunctional poly(arylene ether) precursor with an end-capping agent to provide the polyfunctional poly(arylene ether), wherein the polyfunctional poly(arylene ether) precursor includes an end group including a linking group and a terminal group of the formula -X-H, wherein each occurrence of X isindependently an oxygen or substituted or unsubstituted nitrogen.

11. A composition including the polyfunctional poly(arylene ether) of any one of claims 1-9, wherein the composition includes0-5,000 ppm, as determined byNMR, of a carbonate-containing polyfunctional poly(arylene ether) including an end group, wherein the end group includes a linking group and a terminal functional group, wherein the end group includes the formula -X-T, wherein each occurrence of X is independently an oxygen or substituted or unsubstituted nitrogen, and each occurrence of T is independently hydrogen or a reactive end group, and wherein the linking group of the carbonate-containing polyfunctional poly(arylene ether) includes a carbonate group,0-5,000 ppm, as determined byNMR, of an ester-containing polyfunctional poly(arylene ether), including an end group, wherein the end group includes a linking group and a terminal functional group, wherein the terminal functional group includes the formula -X-T, wherein each occurrence of X is independently an oxygen or substituted or unsubstituted nitrogen, and each occurrence of T is independently hydrogen or a reactive end group, and wherein the linking group of the ester-containing polyfunctional poly(arylene ether) includes an ester group, or a combination thereof.

12. A curable composition including the polyfunctional poly( arylene ether) of any one of claims 1-9 or the composition of claim 10, and optionally, a curing promoter.

13. An article comprising the cured product of the curable composition of claim 12.

14. The article of claim 13, wherein the article is a composite, a foam, a fiber, a layer, a coating, an encapsulant, an adhesive, a sealant, a molded component, a prepreg, a casing, a cast article, or a laminate.

15. A method for manufacturing the article of claim 14 including molding, casting, extruding, foaming, spinning spraying, coating or printing the curable composition, and curing the composition, to provide the article.

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