Poly(arylene ethers) and thermosetting and cured compositions thereof

Abstract

A poly(arylene ether) is derived from monomers comprising a first monohydric phenol, and optionally a second monohydric phenol and / or a multi-functional phenol comprising at least two phenolic groups, wherein at least one of the first monohydric phenol, second monohydric phenol, or multifunctional phenol comprises a substituted or unsubstituted C10-30 hydrocarbyl substituent and the poly(arylene ether) comprises at least one end group that is not a phenolic hydroxyl group. A thermosetting composition is composed of the poly(arylene ether), a thermoset, a monomer, oligomer, or polymer with ethylenic unsaturation, optionally a hydrocarbon resin, and optionally a curing catalyst or initiator. A cured composition is formed by heating the thermosetting composition made from the poly(arylene ether) for a time and temperature sufficient to effect curing.

Description

24SHPP0025-WO-PCT(SS370041PCT)POLY(ARYLENE ETHERS) AND THERMOSETTINGAND CURED COMPOSITIONS THEREOFCROSS REFERENCE TO RELATED APPLICATIONThis application claims priority to and the benefit of European Patent Application No.24219559.2 filed December 12, 2024, the contents of which are hereby incorporated by reference in their entirety.BACKGROUND

[0001] This disclosure relates to poly(arylene ethers) that are compatible with non-polar resins, such as hydrocarbon resins. The disclosure also relates to curable compositions, cured compositions, and articles thereof.

[0002] Poly(arylene ethers) are a class of thermoplastics known for excellent water resistance, dimensional stability, and inherent flame retardancy. They also have outstanding dielectric properties over wide frequency and temperature ranges, which makes them well suited for electronics applications. It is therefore desirable to incorporate poly (arylene ethers) into thermosetting compositions used in electronics applications to impart dielectric performance and moisture resistance. Poly(arylene ethers) can be functionalized with reactive groups such as, e.g. (meth)acrylate, vinyl, for use in thermosetting compositions. However, poly(arylene ethers) have properties such as high glass transition temperatures (Tg) that make them difficult to process when solvents are not used. Hydrocarbon resins, e.g. liquid polybutadiene resins, butadiene-styrene copolymer resins, and butadiene-styrene-divinyl benzene terpolymer resins, can be used to lower Tg and improve processability. However, poly(arylene ethers) can be incompatible with hydrocarbon resins, resulting in phase separation into poly(arylene ether) and hydrocarbon resins. Phase separation adversely affects mechanical properties of resins due to interfaces between the phases. Phase separation also adversely affects curing kinetics and efficiency. There remains a need in the art for poly(arylene ethers), including reactive poly(arylene ethers), that are compatible with hydrocarbon resins and form homogeneous blends to overcome these deficiencies.BRIEF DESCRIPTION

[0003] The above-described and other deficiencies of the art are addressed with a poly(arylene ether) derived from monomers comprising a first monohydric phenol, and optionally a second monohydric phenol and / or a multi-functional phenol comprising at least two24SHPP0025-WO-PCT(SS370041PCT)phenolic groups, wherein at least one of the first monohydric phenol, second monohydric phenol, or multifunctional phenol comprises a substituted or unsubstituted C10-30 hydrocarbyl substituent and the poly(arylene ether) comprises at least one end group that is not a phenolic hydroxyl group.

[0004] In some embodiments, the poly (arylene ether) is derived from first and second monohydric phenols having the structural formula:wherein: Qi, Q2, Q3, and Q4 are each independently, hydrogen, substituted or unsubstituted C1-30 hydrocarbyl or di(Ci-6-alkyl)aminomethyl, wherein at least one of Qi, Q2, Q3, or Q4 is a substituted or unsubstituted C10-30 hydrocarbyl; Ri, R2, R3, and R4 are each independently hydrogen, halogen, substituted or unsubstituted C1-30 primary or secondary hydrocarbyl, C1-30 hydrocarbylthio, C1-30 hydrocarbyloxy, C2-30 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms, or di(Ci-6-alkyl)aminomethyl; X is H or a residue derived from a polyhydric phenol; Y is H or a monovalent end group derived from a capping agent reactive with phenols; m is 1 to 50; n is 0 to 50; x is 1 to 6; and the poly(arylene ether) is a random copolymer or block copolymer of the first and second monohydric phenols.

[0005] In another embodiment, a thermosetting composition is composed of the poly(arylene ether), a thermoset, a monomer, oligomer, or polymer with ethylenic unsaturation, optionally a hydrocarbon resin, and optionally at least one of a curing catalyst or initiator.

[0006] In another embodiment, a cured composition is formed by heating the thermosetting composition made from the poly( arylene ether) for a time and temperature sufficient to effect curing.

[0007] In another embodiment, the cured composition made from the poly(arylene ether) is in the form of 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, a metal clad laminate, a composite, an electronic composite, a structural composite, or a printed circuit board.

[0008] The above-described and other features are exemplified by the following drawings and detailed description.24SHPP0025-WO-PCT(SS370041PCT)BRIEF DESCRIPTION OF THE DRAWINGS

[0009] The following figures are exemplary embodiments.

[0010] Fig. 1A is optical microscopy image of the casting of bifunctional methacrylate - capped PPE (PPE-MA) oligomer blended with liquid polybutadiene resin in a 50:50 weight ratio of Comparative Example 1.

[0011] Fig. IB is an optical microscopy image of a casting of bifunctional methacrylate- capped PPE (PPE-MA) oligomer blended with liquid butadiene- v -styrcnc copolymer resin in a 50:50 weight ratio of Comparative Example 2.

[0012] Fig. 1C is an optical microscopy image of a casting of bifunctional methacrylate- capped PPE (PPE-LCAP-l-MA) oligomer blended with liquid polybutadiene resin in a 50:50 weight ratio of Example 1.

[0013] Fig. ID an optical microscopy image of a casting of bifunctional methacrylate - capped PPE (PPE-LCAP-l-MA) oligomer blended with liquid butadiene-stat-styrene copolymer resin in a 50:50 weight ratio. (The fibers are contaminants.)

[0014] Fig. 2A depicts photographic images of the casting of bifunctional methacrylate - capped PPE (PPE-MA) oligomer blended with liquid polybutadiene resin in a 50:50 weight ratio of Comparative Example 1 (“PPE”) and the casting of bifunctional methacrylate-capped PPE ((PPE-LCAP-l-MA) oligomer blended with liquid polybutadiene resin in a 50:50 weight ratio of Example 1. (“MPPE”)

[0015] Fig. 2B depicts photographic images of the casting of bifunctional methacrylate- capped PPE (PPE-MA) oligomer blended with liquid butadiene- v -styrcnc copolymer resin of Comparative Example 2 (“PPE”) and the casting of bifunctional methacrylate-capped PPE (PPE-LCAP-l-MA) oligomer blended with liquid butadiene-stat-styrene copolymer resin of Example 2. (“MPPE”)DETAILED DESCRIPTION

[0016] The present inventors have synthesized poly(arylene ethers) that advantageously exhibit resistance to phase separation when mixed with hydrocarbon resins, such as polybutadiene resins, butadiene-styrene copolymer resins, and butadiene-styrene-divinyl benzene terpolymer resins. Curable compositions comprising the poly (arylene ethers) are expected to exhibit increased curing rates and efficiency due to the homogeneity of the compositions. Moreover, other properties associated with poly(arylene ethers), such as favorable dielectric properties, water resistance, dimensional stability, and inherent flame retardancy are retained in the present poly (arylene ethers). Advantageously, the present24SHPP0025-WO-PCT(SS370041PCT)poly(arylene ethers) allow for the use of hydrocarbon resins to enhance the processability of curable compositions comprising the poly (arylene ethers).

[0017] Accordingly, a poly(arylene ether) is derived from monomers comprising a first monohydric phenol, and optionally a second monohydric phenol and / or a multi-functional phenol comprising at least two phenolic groups, wherein at least one of the first monohydric phenol, second monohydric phenol, or multifunctional phenol comprises a substituted or unsubstituted Cio-30 hydrocarbyl substituent and the poly(arylene ether) comprises at least one end group that is not a phenolic hydroxyl group. The substituted or unsubstituted Cio-30 hydrocarbyl can be, a C12-30, C20-30, or C24-28 hydrocarbyl. In some embodiments, the C10-30 hydrocarbyl is a branched or unbranched C12-30 C20-30, or C24-28 alkyl, or a branched or unbranched C24-28 secondary alkyl. For example, the C10-30 hydrocarbyl can be a mixture of secondary C24-28 hydrocarbyl groups, e.g. a mixture of tetracosan-2-yl, pentacosan-2-yl, hexcosan-2-yl, heptacosan-2-yl, and octacosan-2-yl groups.

[0018] In some embodiments, the poly (arylene ether) is derived from first and second monohydric phenols and has the structural formula (I):wherein: Qi, Q2, Q3, and Q4 are each independently, hydrogen or a substituted or unsubstituted Cio-30 hydrocarbyl or di(Ci-6-alkyl)aminomethyl, wherein at least one of Qi, Q2, Q3, or Q4 is a substituted or unsubstituted Cio-30 hydrocarbyl; Ri, R2, R3, and R4 are each independently hydrogen, halogen, substituted or unsubstituted C1-30 primary or secondary hydrocarbyl, C1-30 hydrocarbylthio, C1-30 hydrocarbyloxy, or C2-30 halohydrocarbyloxy, wherein at least two carbon atoms separate the halogen and oxygen atoms, or di(Ci-6-alkyl)aminomethyl; X is H or a residue derived from a polyhydric phenol; Y is H or a monovalent end group derived from a capping agent reactive with phenols; m is 1 to 50; n is 0 to 50; x is 1 to 6; and the poly(arylene ether) is a random copolymer or block copolymer of the first and second monohydric phenols.

[0019] The structural formula of the poly(arylene ether) is an idealized structure, which indicates that the poly(arylene ether) contains a total of m first repeat units of the structural formula (II):24SHPP0025-WO-PCT(SS370041PCT)derived from a first monohydric phenol. The poly(arylene ether) also contains n second repeat units of the structural formula (III):hderived from a second monohydric phenol. The poly(arylene ether) can be without further limitation a random copolymer or block copolymer of the first and second monohydric phenols, i.e. any pattern of first repeat units and second repeat units can be present, so long as m is 1 to 50; n is 0 to 50. Idealized structural formula (I) has group Y bonded to the repeat unit of formula (II) and the group X bonded to the repeat unit of formula (III). However, both groups X and Y can be bonded to either of repeat units of formula (II) or (III) in individual polymer molecules.

[0020] In some embodiments of the second repeat units of structural formula (III), R2 and R4 are methyl, and Ri and R3 are hydrogen, i.e. the second repeat unit is derived from copolymerization of 2,6-dimethylphenol. In these embodiments, the ratio of n to m can be greater than or equal to 0: 1 and less than or equal to 50: 1. Within this range the ratio of n to m can be greater than or equal to 1: 1, 10: 1, or 15: 1 and less than or equal to 45: 1 or 30: 1.

[0021] The first monohydric phenol has the structural formula:> —Q39wherein Qi, Q2, Q3, or Q4 are each independently, hydrogen, halogen, or a substituted or unsubstituted C1-30 hydrocarbyl, wherein at least one of Qi, Q2, Q3, or Q4 is a substituted or unsubstituted C10-30 hydrocarbyl. At least one of Qi, Q2, Q3, or Q4 can also be a substituted or24SHPP0025-WO-PCT(SS370041PCT)unsubstituted Cio-30, C12-30, C20-30, or C24-28 hydrocarbyl. In some embodiments, at least one of Qi, Q2, Q3 or Q4 is a branched or unbranched C12-30 alkyl. In some embodiments, at least one of Qi, Q2, Q3 or Q4 is a branched or unbranched C24-28 secondary alkyl. For example, at least one of Q2 or Q4 can be a mixture of secondary C24-28 hydrocarbyls groups, e.g. a mixture of tetracosan-2-yl, pentacosan-2-yl, hexcosan-2-yl, heptacosan-2-yl, and octacosan-2-yl groups. Thus in some embodiments, the first monohydric phenol can be a mixture of 2-(tetracosan-2- yl)phenol, 2-(pentacosan-2-yl)phenol, 2-(hexcosan-2-yl)phenol, 2-(heptacosan-2-yl)phenol, and 2-(octacosan-2-yl)phenol. In related embodiments of the first monohydric phenol, one of Q2 or Q4 and one of Qi and Q3 are each independently, tetracosane-2-yl, pentacosan-2-yl, hexcosan-2- yl, heptacosan-2-yl, and octacosan-2-yl. Thus in some embodiments, the first monohydric phenol is a mixture of 2-(tetracosan-2-yl)phenol, 4-(tetracosan-2-yl)phenol, 2-(pentacosan-2- yl)phenol, 4-(pentacosan-2-yl)phenol, 2-(hexcosan-2-yl)phenol, 4-(hexcosan-2-yl)phenol, 2-(heptacosan-2-yl)phenol, 4-(heptacosan-2-yl)phenol, 2-(octacosan-2-yl)phenol, and4-(octacosan-2-yl)phenol.

[0022] In some embodiments, the first monohydric phenol is a phenol of Formula IV or a mixture of phenols of Formulae (IV) and (V).Q3 Q4 Q3 H(IV) (V),wherein Qi, Q2, Q3 and Q4 are as defined above. In some embodiments of Formulae (IV) and (V), Qi, Q3 and Q2 are H, and Q4 is a substituted or unsubstituted Cio-30, C12-30, C20-30, or C24-28 hydrocarbyl. In some embodiments, Formula (IV) can be ort / zo-Cio-so-i'ec-alkylphenol and Formula (V) can be para-Cio-30-.sec-alkylphenol. For example, Formula (IV) can be ortho-C.5 sec- alkylphenol, a mixture of sec-alkylphenols having an average.scc-alkyl chain length of 12.5 (corresponding to LCAP-2 in Table 1). The first monohydric phenol can also be a mixture of Formulae (IV) and (V). For example, the first monohydric phenol can be a mixture of ortho- and para-C24-28 sec-alkylphenol (CAS No. 1333248-54-6). Average.st' -al ky I chain length = 27.7 for both ortho- and para-isomers, the mixture of which is LCAP-1 in Table 1.Polymerization is known to occur via the para-hydrogen atom in phenols of Formula (IV). Polymerization can theoretically also occur via the ort / zo-hydrogen in phenols of Formula (V).24SHPP0025-WO-PCT(SS370041PCT)

[0023] The second monohydric phenol has the structural formula:wherein Ri, R2, R3, and R4 are each independently hydrogen, halogen, substituted or unsubstituted C1-30 primary or secondary hydrocarbyl, C1-30 hydrocarbylthio, C1-30 hydrocarbyloxy, or C2-30 halohydrocarbyloxy, wherein at least two carbon atoms separate the halogen and oxygen atoms. For example, Ri, R2, R3, and R4 can each independently be methyl, phenyl, cyclohexyl, or allyl. In some embodiments, R2 and R4 are methyl, and Ri and R3 are hydrogen, i.e. the second monohydric phenol is 2,6-dimethylphenol.

[0024] Exemplary second monohydric phenols 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 be 2,6-dimethylphenol.

[0025] In some embodiments, the poly(arylene ether) has a number average molecular weight (Mn) of less than 5,000 g / mol, calculated based on the molar ratios of the monomers. In some embodiments, the poly(arylene ether) has a number average molecular weight (Mn) of less than 5,000 g / mol, as determined by gel permeation chromatography (GPC) using a cross-linked styrene-divinylbenzene column. In some embodiments, the Mnis determined against monodisperse polystyrene standards at a sample concentration of 1 milligram per milliliter. Within these ranges, the calculated or measured Mncan be greater or equal to 500 or 1,000 g / mol and less than or equal to 5,000, 4,500, 4,000, or 3,000 g / mol.

[0026] In some embodiments, the poly(arylene ether) is monofunctional, i.e. x = 1 and X is hydrogen as depicted in structural formula:

[0027] In some embodiments, the poly(arylene ether) is bifunctional, i.e. x = 2 and X has the structural formula:24SHPP0025-WO-PCT(SS370041PCT)which is derived from a dihydric phenol of formula:R; R' R / R5HO — ( Y-OHR^ RsRbR*In both X and the corresponding dihydric phenol, each occurrence of R5, R6, R7, and R8independently comprises hydrogen, halogen, unsubstituted or substituted C1-30 primary or secondary hydrocarbyl, C1-30 hydrocarbylthio, C1-30 hydrocarbyloxy, or C2-30 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms; y is 0 or 1; and Y is a divalent linking group of formulawherein each occurrence of Ra, Rb, Rc, Rd, and Reis independently hydrogen, C1-30 hydrocarbyl, or C1-6 hydrocarbylene, or wherein Raand Rbtogether or Rcand Rdtogether are a C4-11— C — RcRL <?hydrocarbylene group, e.g. forms a C5-12 cycloaliphatic group or _ forms a Ce-13 cycloalkene group; each occurrence of Rfis independently hydrogen, a C1-14 hydrocarbyl, a C1-14 halohydrocarbyl, or a C1-14 heterohydrocarbyl, preferably 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 occurrence24SHPP0025-WO-PCT(SS370041PCT)of Rgis independently a Ci-6 hydrocarbylene group, preferably a divalent C2-8 aliphatic group, e.g. dimethylene, trimethylene, or tetramethylene; and E is 2 to 200.

[0028] In some embodiments of the bifunctional poly (arylene ether), Y is the divalent linking group:R3— 0 —9wherein at least one of Raand Rbis a C10-30 hydrocarbyl group. At least one of Raand Rbcan also be a C12-30, C20-30, or C24-28, hydrocarbyl group. In other embodiments of the bifunctional poly(arylene ether), Y in the structural formula (V) is the divalent linking group:— C —Rb9wherein each occurrence of Raand Rbis independently hydrogen, C1-30 hydrocarbyl, or C1-6 hydrocarbyl, or wherein Raand Rbtogether are a C4-11 hydrocarbylene group. For example, P?— C — RcR';ican be a divalent C5-12 cycloaliphatic group andcan be a Ce-io cycloalkene group.

[0029] In some embodiments of the bifunctional poly(arylene ether), X is derived from a dihydric phenol. Examples of suitable dihydric phenols include 3,3',5,5’-tetramethyl-4,4’- biphenol, 2,2-bis(3-methyl-4-hydroxyphenyl)propane, 2,2-bis(3,5-dimethy-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, bis(4-hydroxyphenyl)phenylmethane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 1, 1 -bis(4-hydroxy-3 -methylphenyl)cyclohexane, 1, 1 -bis(4-hydroxy-3,5 - dimethylphenyl)cyclopentane, 1, 1 -bis(4-hydroxy-3,5-dimethylphenyl)cyclohexane, 1, 1 -bis(4- hydroxy-3-methylphenyl)cycloheptane, 1, l-bis(4-hydroxy-3,5-dimethylphenyl)cycloheptane, 1, 1 -bis(4-hydroxy-3 -methylphenyl)cyclooctane, 1, 1 -bis(4-hydroxy-3,5- dimethylphenyl)cyclooctane, 1,1 -bis(4-hydroxy-3-methylphenyl)cyclononane, l,l-bis(4- hydroxy-3,5-dimethylphenyl)cyclononane, l,l-bis(4-hydroxy-3-methylphenyl)cyclodecane,24SHPP0025-WO-PCT(SS370041PCT)1.1-bis(4-hydroxy-3,5-dimethylphenyl)cyclodecane, l,l-bis(4-hydroxy-3- methylphenyl)cycloundecane, 1, 1 -bis(4-hydroxy-3,5-dimethylphenyl)cycloundecane, 1, 1 -bis(4- hydroxy-3-methylphenyl)cyclododecane, l,l-bis(4-hydroxy-3,5-dimethylphenyl)cyclododecane, 1.1-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, or a combination thereof. For example, the dihydric phenol includes 2,2-bis(3,5-dimethyl-4-hydroxyphenol)propane. In some embodiments of the poly (arylene ether), X has the structural formula:Hsq CH?\ — CH? / —o— ^y —c— —0—CHjY\HsC CH?which is derived from the dihydric phenol 4,4 / -(propane-2,2-diyl)bis(2,6-dimethylphenol) (TMBPA)

[0030] In some embodiments of the polyarylene ether, X is derived from any one of more of the following dihydric phenols:24SHPP0025-WO-PCT(SS370041PCT)wherein Raand Rbare each independently a C1-12 alkyl, C1-12 alkoxy, or C1-12 alkylaryl; each R14is independently a C1-12 alkyl, C1-12 alkoxy, or C1-12 alkylaryl; R15is hydrogen, C1-6 alkyl, or a substituted or unsubstituted phenyl; j, p, and q are each independently an integer of 0, 1, 2, 3, or 4; k is an integer of 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 (or 1, 2, 3, 4, or 5; or 2, 3, or 4; or 3); R20and R21are each independently C1-3 alkyl or phenyl; and each Rfis hydrogen or both Rf together are a carbonyl group.

[0031] In some embodiments of the poly(arylene ether), X has the structural formula:wherein: E is 6-100, 11-80, or 11-60; each occurrence of R is independently an unsubstituted or substituted C1-30 alkyl, C1-13 alkoxy, C3-6 cycloalkyl, Ce-i4 aryl, Ce-io aryl C7-13 arylalkylene, or C7-13 alkylarylene; each p and q is independently 0 or 1; R1is a divalent unsubstituted or substituted C2-8 aliphatic group, and each occurrence of U independently comprises halogen, hydrogen, cyano, nitro, an unsubstituted or substituted C1-8 alkylthio, C1-30 alkyl, C1-8 alkoxy, C2- s alkenyl, C2-8 alkenyloxy, C3-8 cycloalkyl, C3-8 cycloalkoxy, Ce-io aryl, Ce-io aryloxy, C7-12 aralkyl, C7-12 aralkoxy, C7-12 alkylaryl, or C7-12 alkylaryloxy, and each r is independently 0, 1, 2, 3, or 4. In some embodiments of the poly(arylene ether), each R is methyl, each Rlr> is -CH2- CH2-CH2- and E is 5 to 100, or 10 to 60.

[0032] In some embodiments of the poly(arylene ether), x = 3 and X has the structural formula:i" S> (S'X- TT owherein T is a C1-30 alkyl, C1-20 alkoxy, C7-12 arylalkyl, or C7-12 alkylaryl; each S is independently halogen, C1-3 alkyl, C1-3 alkoxy, C7-12 arylalkyl, C7-12 alkylaryl, or nitro; and each z is independently an integer of 0 to 4. X is derived from a trihydric phenol of structural formula:24SHPP0025-WO-PCT(SS370041PCT)

[0033] The trihydric phenol can be, for example, tris-p-hydroxy phenyl ethane (THPE), in which each z is zero and T is methyl, or 4,4'-(l-(4-hydroxyphenyl)ethane-l,l-diyl)bis(2,6- dimethylphenol) of structural formula:OHIn some embodiments, X is derived from the trihydric phenol 4,4'-(l - { 4-[2-(4- hydroxyphenyl)propan-2-yl]phenyl}ethane-l,l-diyl)diphenol (Trisphenol PA, C. A. S. No. 110726-28-8) of structural formula:QHor l,3,5-tris((p-hydroxyphenyl)isopropyl)benzene) (Trisphenol TC) of structural formula:24SHPP0025-WO-PCT(SS370041PCT)

[0034] Advantageously, the poly(arylene ether) of structural formula (I) can comprise at least one reactive end group Y so that it serves as a reactive component in a curable composition. The poly(arylene ether) can be present in a curable composition in an amount of 1 to 95 wt%, 5 to 95 wt%, 10 to 85 wt%, 20 to 80 wt%, 30 to 70 wt%, 5 to 30 wt%, or 5 to 15 wt%, based on the total weight of the curable composition.

[0035] The reactive end groups Y are not particularly limited, and can comprise, for example, 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, and the like. In some embodiments, each Y independently comprises a reactive group of the structural formulae:wherein Y2is a divalent linking group having one of structural formulae:O S Q Oit it S 8 Si—C. C. C. S. s —t, IV,. or 59wherein each occurrence of Rhand R1independently is hydrogen or C1-12 alkyl; R9is an epoxide-containing group, a cyanate-containing group, or a C1-12 hydrocarbyl substituted with one or two carboxylic acid groups; each occurrence of R10, R11, and R12independently is hydrogen, Ci-is hydrocarbyl, C2-18 hydrocarbyloxycarbonyl, nitrile, formyl, carboxylic acid, imidate, or thiocarboxylic acid; and each occurrence of R13, R14, R15, R16, and R17independently is hydrogen, halogen, C1-12 alkyl, C2-12 alkenyl, hydroxy, amino, maleimide, carboxylic acid, or a C2-20 alkyl ester. In some embodiments, each Y independently comprises vinyl, allyl, styryl (–(C6H5)-CH=CH2), -CH2-(CeH4)-CH=CH2, (meth)acryloyl, cyanate ester, glycidyl ether, anhydride, maleimide, amino, phenylamino, or activated ester.

[0036] In some embodiments, the poly(arylene ether) is monofunctional, i.e. in structural formula (I), x is 1 and X is H, wherein at least one of Qi, Q2, Q3 or Q4 is a branched or unbranched C12-30 alkyl; R2 and R4 are methyl, and Ri and R3 are hydrogen; and Y is -C(=O)-C(CH3)=CH2.24SHPP0025-WO-PCT(SS370041PCT)

[0037] In some embodiments, the poly(arylene ether) is bifunctional, i.e. in structural formula (I), x is 2, and X has the structural formula:wherein at least one of Qi, Q2, Q3 or Q4 is a branched or unbranched C12-30 alkyl; R2 and R4 are methyl, and Ri and R3 are hydrogen; and Y is -C(=O)-C(CH3)=CH2.

[0038] In some embodiments, the poly(arylene ether) the poly(arylene ether) is trifunctional, i.e. in structural formula (III), X is derived from a trihydric phenol of structural formula:OHof structural formula:CHwherein at least one of Qi, Q2, Q3 or Q4 is a branched or unbranched C12-30 alkyl; R2 and R4 are methyl, and Ri and R3 are hydrogen; and Y is -C(=O)-C(CH3)=CH2.

[0039] Poly(arylene ethers), for example, poly(phenylene ether), which optionally may 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) may be, or may be formed from, renewable,24SHPP0025-WO-PCT(SS370041PCT)sustainable, bio-circular, circular, lower carbon footprint feedstocks, upcycled, and / or postconsumer / post-industrial recycled materials, including pyrolysis oil (“py-oil”).

[0040] Poly(arylene ethers) made from renewable sources may include, for example, a bio-content or PCR content of up to about 99.9%, about 1-99%, 5- 95%, 55-99%, or 80-99%, 1-50%, 1-25%, 1-15%, 1-10%, or 1-5%, based, e.g., on the monomer source. The 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 one non-limiting embodiment may range from 600 to 200,000 grams per mole, as determined by gel permeation chromatography. In another non-limiting embodiment, the poly(arylene ethers) may have an intrinsic viscosity of up to 1.5 deciliters per gram (dl / g) as measured at 25 °C in chloroform. Poly(arylene ethers) made from renewable sources may include material made by a mass balance approach and certified by regulatory bodies such as, for example, the ISCC Plus.

[0041] Poly (arylene ethers) in one embodiment may be prepared by oxidative polymerization of monomers in the presence of a polymerization catalyst in the presence of oxygen. Any of the components used in the polymerization reaction or their synthetic precursors, or the solvents used in the process, may 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) may be from sources as listed in the EU Renewable Energy Directive Annex IX.

[0042] Poly(arylene ethers) can be further processed, such as by redistribution, or any chemical derivitization, such as post-polymerization end-group capping or coupling, to make other materials that can transfer the sustainability characteristic to the new material. Such reagents and / or their synthetic precursors may be sustainable, bio-sourced, bio-circular, or renewable raw materials, upcycled, and / or post-consumer / post-industrial recycled materials, including pyrolysis oil (“py-oil”), to produce a poly(arylene ether).

[0043] Poly (arylene ethers) tend to have high glass transition temperatures (Tg), which make them difficult to process when solvents are not used. Hydrocarbons resins can be used to lower the Tg of poly(arylene ethers) and thereby improve their processability in the absence of solvents. Thus, in some embodiments, a poly (arylene ether) composition comprises the poly(arylene ethers) disclosed herein and a hydrocarbon resin. Useful hydrocarbon resins include polybutadiene resins, butadiene-styrene copolymer resins and butadiene-styrene-divinyl24SHPP0025-WO-PCT(SS370041PCT)benzene terpolymer resins. Butadiene can polymerize via 1,2- or 1,4-addition mechanisms. 1,2- Addition provides pendant vinyl groups along the polymer chain, while 1,4-addition provides linear polymers. Polybutadiene resins containing elevated levels of 1,2 addition are desirable for thermosetting matrices due to the reactivity of the pendant vinyl groups. Examples include the functionalized polybutadienes and poly(butadiene-styrene) random copolymers sold by Cray Valley 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 MA17, 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 included are powder dispersions of functional polybutadiene derivatives including, for example, RICON 150D, 152D, 153D, 154D, P30D, RICOBOND 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 to 50,000 g / mol and polybutadiene homopolymers having molecular weights from 3,000 to 50,000 g / mol. Also included are polybutadiene, polyisoprene, and polybutadiene-isoprene copolymers functionalized with maleic anhydride, 2-hydroxyethylmaleic (HEMA / MA), or hydroxyl groups.

[0044] The poly(arylene ether) can be a reactive component in a curable composition, i.e. a thermosetting resin. The poly( arylene ether) can be present in the curable thermosetting composition in an amount of 1 to 95 wt%, 5 to 95 wt%, 10 to 85 wt%, 20 to 80 wt%, 30 to 70 wt%, 5 to 30 wt%, or 5 to 15 wt%, based on the total weight of the curable composition. The curable composition can comprise a hydrocarbon resin as described above. In some embodiments, a curable composition comprises the poly (arylene ether) described herein, a hydrocarbon resin, a thermoset, a monomer, oligomer, or polymer with ethylenic unsaturation, and optionally at least one of a curing catalyst or initiator. In some embodiments, the curable composition can further comprise an additive, for example a flame retardant, a filler, a coupling24SHPP0025-WO-PCT(SS370041PCT)agent, or a combination thereof. In some embodiments, the thermoset is at least one of an epoxy resin, a cyanate ester resin, a bismaleimide resin, a benzoxazine resin, a vinyl benzyl ether resin, an arylcyclobutene resin, a perfluorovinyl ether resin, an unsaturated polyester resin, an alkyd resin, or a phenolic resin. There can be some overlap among components of the curable composition. For example, the hydrocarbon resin can be an oligomer or polymer with ethylenic unsaturation. The thermoset can also be an oligomer or polymer with ethylenic unsaturation. For example, the thermoset can be an alkyd resin or other unsaturated polyester resin. In these embodiments, an additional monomer, oligomer, or polymer with ethylenic unsaturation is also present in the curable composition.

[0045] In some embodiments, the thermoset is an epoxy resin. The epoxy resin can be any epoxy resin that is suitable for use in thermosets. The term “epoxy resin” in this context refers to a curable composition of oxirane ring-containing 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 thoseobtained 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-epoxycyclohexane carboxylate; dicyclopentadiene - containing poly epoxides; 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, 1,3-bis(3-aminophenoxy)benzene, 2,2-bis(4-amino-phenoxyphenyl)propane, p-phenylenediamine, m-phenylenediamine, 2,4-toluenediamine, 2,6-toluenediamine, -xylylene-diamine, m-xylylenediamine, l,4-cyclohexane-bis(methylamine), 5-amino-l-(4'-aminophenyl)-24SHPP0025-WO-PCT(SS370041PCT)1,3, 3 -trimethy lindane, 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.

[0046] 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 dicyclopentadienephenol copolymers, and prepolymers prepared from these monomers. An example of a prepolymer is PRIMASET BA-230S (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 U. S. Pat. Nos. 7,393,904, 7,388,057, 7,276,563, and 7,192,651.

[0047] 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 include1,2-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,24SHPP0025-WO-PCT(SS370041PCT)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-methaxylene- bismaleimide, N, N'-4,4'-diphenylcyclohexanebismaleimide, and N, N'-methylene-bis(3-chloro- p-phenylene)bismaleimide, as well as those disclosed in U. S. Patent Nos. 3,562,223, 4,211,860, and 4,211,861, or as prepared by methods as described, for example, in U. S. Pat. No. 3,018,290.

[0048] Benzoxazine comprise the benzoxazine ring system. 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 groups reactive 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 poly (benzoxazine).

[0049] 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.24SHPP0025-WO-PCT(SS370041PCT)

[0050] The aldehydes used to form the benzoxazine can be any aldehyde, such as an aldehyde having 1 to 10 carbon atoms. For example, the aldehyde can be formaldehyde. The amine used to form the benzoxazine can be an aromatic amine, an aliphatic amine, an alkyl substituted aromatic, or an aromatic substituted alkyl amine. The amine can be a polyamine, for example to prepare polyfunctional benzoxazine monomers for crosslinking. The amines for forming benzoxazines have 1 to 40 carbon atoms unless they include aromatic rings, and then they can have 6 to 40 carbon atoms. The amine of di- or polyfunctional can be a branch point to connect one poly(benzoxazine) to another.

[0051] In some examples, thermal polymerization at 150 to 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.

[0052] 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 crosslinked thermosetting 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’ -(1,4-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'-24SHPP0025-WO-PCT(SS370041PCT)tetramethyl-2,2',3,3'-tetrahydro-l,r-spirobi[indene]-5,6'-diol, dihydroxybenzo-phenone, 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.

[0053] Arylcyclobutenes include those derived from compounds of the structureL z Jnwherein 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 C6-20 phenolic compounds); each occurrence of X is independently hydroxy or C1-24 hydrocarbyl (including linear and branched alkyl and cycloalkyl); and each occurrence of Z is independently hydrogen, halogen, or C1-12 hydrocarbyl; and n is 1 to 1000,or 1 to 8, or n is 2, 3, or 4. Other exemplary arylcyclobutenes and methods of arylcyclobutene synthesis can be found in U. S. Patent Nos. 4,743,399, 4,540,763, 4,642,329, 4,661,193, 4,724,260, and 5,391,650.

[0054] 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'-( 1,3-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)-24SHPP0025-WO-PCT(SS370041PCT)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)diphenol4,4'-(bicyclo[2.2. l]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 (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.

[0055] Phenol-formaldehyde resins, (phenolic resins), are the reaction products of a phenolic compound and formaldehyde. The phenolic resin can be, for example, novolac phenolic resins, resole phenolic resins, cresol novolac resins, aralkyl phenolic resins, phenol aralkyl resins, cresol aralkyl resins, naphthol aralkyl resins, dicyclopentadiene phenolic resins, terpene modified phenolic resins, biphenyl type phenolic resins, biphenyl-modified phenol aralkyl resins, bisphenols, triphenylmethane phenolic resins, tetraphenylol ethane resins, naphthol novolac resins, naphthol-phenol co-condensed novolac resins, naphthol-cresol cocondensed novolac resins, amino triazine modified phenolic resins, or a combination thereof. Examples of carboxylic anhydrides 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.

[0056] The thermoset can further comprise an epoxy curing agent, also known as a hardener. Exemplary hardeners include phenolic resins, polyamines, carboxylic acids, carboxylic anhydrides, and the like. In some embodiments of the curable composition, the thermoset further comprises at least one of a polyamine, a dicyandiamide, a polyamide, an amidoamine, a Mannich base, a carboxylic acid, a carboxylic anhydride, a phenol-formaldehyde resin, a carboxylic acid- functional polyester, a polysulfide, a polymercaptan, an alkoxysilane, a carbodiimide, or an isocyanate.

[0057] The hardener can be a polymercaptan, an alkoxysilane, or a carbodiimide. The polymercaptan can be, for example, trimethylolpropane tris(mercaptopropionate), pentaerythritol24SHPP0025-WO-PCT(SS370041PCT)tetrakis(3-mercaptopropionate), or the like. The alkoxysilane can be, for example, tetramethoxysilane, tetraethoxysilane, tetrapropoxy silane, tetra-n-butoxysilane, vinyltris(methylethyloximino)silane, vinyl tris-(acetoxime)silane, methyltris(methylethyloximino)silane, methyl tris(acetoxime)silane, vinyl trimethoxysilane, methyl trimethoxysilane, vinyl tris(isopropenoxy)silane, tetraacetoxy-silane, methyl triacetoxysilane, ethyl triacetoxysilane, vinyl triacetoxysilane, di-t-butoxy-diacetoxysilane, methyl tris(ethyl lactate)silane, vinyl tris(ethyl lactate)silane, or the like. The carbodiimide can be, for example, N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide hydrochloride, dicyclohexylcarbodiimide, or the like.

[0058] As discussed above, the curable composition comprises a monomer, oligomer, or polymer with ethylenic unsaturation. The ethylenic unsaturation can be in the form of, for example, vinyl, allyl, styryl, vinyl benzyl, meth(acryloyl), maleimide, maleic anhydride, or - CH=CH- groups. Oligomers and polymers with ethylenic unsaturation 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, diethylene glycol bisallyl carbonate resin, and polyethylene polythiol resins. The monomer can be polyfunctional such as a (meth) acrylate monomer having two or more (meth)acrylate groups. 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, l-chloro-2,3-epoxypropyl (meth)acrylate,24SHPP0025-WO-PCT(SS370041PCT)2-bromo-3,4-epoxybutyl (meth)acrylate, 2-(epoxyethyloxy)-ethyl (meth)acrylate,2-(3,4-epoxybutyloxy)-ethyl (meth)acrylate, or the like.

[0059] The monomer, oligomer, or polymer with ethylenic unsaturation can be an alkene-containing monomer or an alkyne-containing monomer. Exemplary alkene- and alkyne - containing monomers includes those described in U. S. Pat. No. 6,627,704, and include (meth)acrylates, (meth)acrylamides, N- vinylpyrrolidone, and vinyl azalactones as disclosed in U. S. Pat. No. 4,304,705. 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-vinyl caprolactam, N-vinylpyrrolidone, (meth)acrylonitrile, or the like, or a combination thereof.

[0060] The monomer, oligomer, or polymer with ethylenic unsaturation can also be an unsaturated hydrocarbon resin. Examples of unsaturated hydrocarbon resins include styrenebutadiene rubber (SBR), butadiene rubber (BR), and nitrile-butadiene rubber (NBR) having ethylenic unsaturation derived from butadiene, natural rubber (NR), isoprene rubber (IR), chloroprene rubber (CR), butyl rubber (IIR), and halogenated butyl rubber having ethylenic unsaturation derived from isoprene; ethylene-a-olefin copolymer elastomers having ethylenic unsaturation based on dicyclopentadiene (DCPD), ethylidene norbornene (ENB), or1,4-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)). 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-addition prepared by anionic living polymerization. It is also possible to use liquid styrene-butadiene rubber, liquid nitrile butadiene rubber (CTBN, VTBN, ATBN, etc. available from Ube Industries, Ltd.), liquid chloroprene rubber, liquid polyisoprene, dicyclopentadiene-type hydrocarbon polymer, and polynorbornene (for example, as available from Elf Atochem). Polybutadienes and related polymers are further described supra.

[0061] The curable composition can include other synthetic rubbers, such as hydrogenated nitrile rubber, fluorocarbon rubbers such as vinylidene fluoride -hexafluoropropene copolymer and vinylidene fluoride-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), urethane24SHPP0025-WO-PCT(SS370041PCT)rubber (U), silicone rubber (Q), chlorosulfonated polyethylene rubber (CSM), polysulfide rubber (T) and ethylene acrylic rubber.

[0062] The at least one monomer, oligomer, or polymer can be monofunctional or polyfunctional, i.e. it can contain one ethylenically unsaturated group (monofunctional) or at least two ethylenically unsaturated groups (polyfunctional). In some embodiments, the monomer, oligomer, or polymer with ethylenic unsaturation comprises at least one of a monofunctional styrenic compound, a monofunctional (meth)acryloyl compound, a polyfunctional allylic compound, a polyfunctional (meth)acrylate, a polyfunctional (meth)acrylamide, a polyfunctional styrenic compound, tri(meth)allyl cyanurate, tri(meth) allyl isocyanurate, or an unsaturated polyester. When the curable composition includes a monomer, oligomer, or polymer with ethylenic unsaturation, it can be present in an amount of 1 to 60 wt%, or 5 to 50 wt%, or 10 to 40 wt%, based on total weight of the curable composition.

[0063] The curable composition can optionally include a curing catalyst. As used herein, the term “curing catalyst” includes compounds that are variously described as catalysts, co-catalysts, accelerators, and promoters. The curing catalyst can be, for example, a heterocyclic compound, such as a substituted or unsubstituted C3-6 heterocycle having 1 to 4 ring heteroatoms, wherein each heteroatom is independently the same or different, and is nitrogen, oxygen, phosphorus, silicon, or sulfur. Heterocyclic catalysts 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- 1 H-imidazole, 2-heptadecyl- 1 H-imidazole,1,2-dimethylimidazole, 1,3-dimethylimidazole, 2,4-dimethylimidazole, 2-ethyl-4- methylimidazole, 1 -phenylimidazole, 2-phenyl-l H-imidazole, 4-methyl-2-phenyl-l H-imidazole, 2 -phenyl-4- methylimidazole, 1 -benzyl-2-methylimidazole, 1 -benzyl-2-phenylimidazole, 1 -cyanoethyl-2-methylimidazole, 1 -cyanoethyl-2-ethyl-4-methylimidazole, 1 -cyanoethyl-2- undecylimidazole, 1 -cyanoethyl-2-phenylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, l-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.24SHPP0025-WO-PCT(SS370041PCT)

[0064] The curing catalyst can also be an amine catalyst. The amine catalyst can be, for example, isophorone diamine, triethylenetetraamine, diethylenetriamine, 1,2- and1,3-diaminopropane, 2,2-dimethylpropylenediamine, 1,4-diaminobutane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,12-diaminododecane,4-azaheptamethylenediamine, N, N’ -bis(3-aminopropyl)butane- 1,4-diamine, dicyanamide, diamide diphenylmethane, diamide diphenylsulfonic acid (amine adduct),4,4’ -methylenedianiline, diethyltoluenediamine, m-phenylenediamine, p-phenylenediamine, melamine formaldehyde 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, 1,2-diamino-4-ethylcyclohexane, 1,4-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- and1.4-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-dimethyl amino pyridine, / V, / V-dimcthylaminocthanol, / V, / V-dimcthylaminocrcsol,tri(A, A-dimethylaminomethyl)phenol; or a combination thereof.

[0065] The curing catalyst can be a latent cationic catalyst. The cationic catalyst can be, for example, a diaryliodonium salts, a phosphonic acid ester, a sulfonic acid ester, a carboxylic acid ester, a phosphonic ylide, a triarylsulfonium salt, a benzylsulfonium salt, an aryldiazonium salt, a benzylpyridinium salt, a benzylammonium salt, an isoxazolium salt, 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-14 monovalent aromatic hydrocarbon radical, optionally substituted with from 1 to 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 [(R10)(R11)I]+SbF6-, wherein R10and R11are each independently a Ce -14 monovalent aromatic hydrocarbon, optionally substituted with from 1 to 4 C1-20 alkyl, C1-20 alkoxy, nitro, or chloro; for example, 4-octyloxyphenyl phenyl iodonium hexafluoroantimonate.

[0066] The curing catalyst can be a metal salt complex. The metal salt complex can be, for example, a copper (II), aluminum (III), zinc, cobalt, or tin salt of an aliphatic or aromatic carboxylic acid selected from copper (II), tin (II), and aluminum (III) salts of acetate, stearate,24SHPP0025-WO-PCT(SS370041PCT)gluconate, citrate, benzoate, and mixtures thereof. For example, the metal salt complex can be a copper (II) or aluminum (III) salt of a [3-diketonate; copper (II), iron (II), iron (III), cobalt (II), cobalt (III), or aluminum (III) salts of an acetylacetonate; zinc (II), chromium (II), or manganese (II) salts of an octoate; or a combination thereof. When the curable composition includes a curing catalyst, the curing catalyst can be present in an amount of 0.1 to 5 wt%, or 0.5 to 5 wt%, or 1 to 5 wt%, based on total weight of the curable composition.

[0067] The curable composition can optionally include an initiator, especially when a thermoset with ethylenic unsaturation is present. The initiator can be a radical initiator, for example, a peroxide. Exemplary peroxide free radical initiators include benzoyl peroxide, dicumyl peroxide, methyl ethyl ketone peroxide, lauryl peroxide, cyclohexanone peroxide, t-butyl hydroperoxide, t-butyl benzene hydroperoxide, t-butyl peroctoate,t-butylperoxybenzoate, t-butylperoxy 2-ethylhexyl carbonate, 2,4-dichlorobenzoyl peroxide, 2.5-dimethylhexane-2,5-dihydroperoxide, butyl-4,4-bis(tert-butyldioxy)valerate, 2,5-dimethyl- 2.5-di(t-butylperoxy)-hex-3-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. When the curable composition includes an initiator, it can be present in an amount of 0.1 to 5 wt%, or 0.5 to 5 wt%, or 1 to 5 wt%, based on total weight of the curable composition.

[0068] The curable thermosetting compositions may 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. Examples of phosphorous flame retardants include phosphates, phosphazenes, phosphite esters, phosphines, phosphinates, polyphosphates, and phosphonium salts.

[0069] 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.

[0070] Inorganic flame retardants can also be used, for example salts of C1-16 alkyl24SHPP0025-WO-PCT(SS370041PCT)sulfonate salts such as potassium perfluorobutane sulfonate (Rimar salt), potassium perfluoroctane sulfonate, tetraethylammonium perfluorohexane sulfonate, and potassium diphenylsulfone sulfonate; salts such as Na2CO3, K2CO3, MgCO3, CaCO3, and BaCO3, or fluoro-anion complexes such as Li3AlF6, BaSiF6, KBF4, K3AlF6, KAlF4, K2SiF6, or Na3AlF6.

[0071] 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.

[0072] 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.

[0073] 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 to 30 micrometers (pm), or 5 to 25 [tm, or 5 to 15 pm. The length of the glass fibers before compounding are not limited and can be 2 to 7 millimeters (mm), or 1.5 to 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.

[0074] 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.

[0075] 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. 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.

[0076] When the curable composition includes a filler, the filler can be included in an24SHPP0025-WO-PCT(SS370041PCT)amount of greater than 1 wt%, or 1 to 50 wt%, or 1 to 30 wt%, or 10 to 30 wt%, based on total weight of the curable composition.

[0077] The curable thermosetting compositions may include a coupling agent. 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. When the curable composition includes a coupling agent, the coupling agent can be included in an amount of 0.01 to 5 wt%, or 0.05 to 5 wt%, or 0.1 to 5 wt%, based on total weight of the curable composition.

[0078] The curable composition can optionally include a solvent. The solvent can be, for example, a C3-8 ketone, a C3-8 N,N-dialkylamide, 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, N-methyl-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 non-halogenated. 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, 1,3-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, ethyl24SHPP0025-WO-PCT(SS370041PCT)cellosolve acetate, ethyl carbitol acetate, propylene carbonate, sulfolane, an ionic liquid, or a combination thereof.

[0079] When a solvent is utilized, the curable composition can include 2 to 99 wt% of the solvent, based on total weight of the curable thermosetting composition. For example, the solvent amount can be 5 to 80 wt%, or 10 to 70 wt%, or 20 to 60 wt%, based on weight total of the curable 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.

[0080] The curable 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, anti-blocking 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, additional additives can be included in any effective amount, for example in an amount of 0.01 to 20 wt%, 0.01 to 10 wt%, 0.01 to 5 wt%, or 0.01 to 1 wt%, based on the total weight of the curable composition.

[0081] The curable composition described herein can be prepared by combining and mixing the poly(arylene ether), the hydrocarbon resin, the monomer, oligomer, or polymer with ethylenic unsaturation and the other optional components disclosed herein using any suitable method.

[0082] Also provided is a cured composition comprising the cured product of the curable composition. There is no limitation on the method by which the curable 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. In some embodiments, a cured composition is obtained by heating the curable composition described herein for a time and temperature sufficient to effect curing. For example, a cured product can be obtained by heating the curable thermosetting composition defined herein for a time and temperature24SHPP0025-WO-PCT(SS370041PCT)sufficient to evaporate the solvent and effect curing. When heat curing is used, the temperature can be, for example, 30 to 400 °C, 50 to 250 °C, or 100 to 250 °C. The heating can be for 1 minute to 24 hours, 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. The cured composition can exhibit 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.

[0083] The curable compositions and the cured compositions disclosed herein can be used in a variety of applications, including any applications where conventional thermosets are used. For example, the cured composition can be in the form of 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, a metal clad laminate, a composite, an electronic composite, or a structural composite.

[0084] Articles can be manufactured by, for example, casting, molding, extruding, or the like, and removing the solvent from the formed article. In some embodiments, 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.

[0085] 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 curable 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 curable compositions can be used as a coating on a surface of a metal24SHPP0025-WO-PCT(SS370041PCT)container (e.g., aluminum or steel), such as those commonly used for packaging and containment in the paint and surface covering industries.

[0086] Methods of forming a composite can include impregnating a reinforcing structure with the curable composition; partially curing the curable 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 suitable for the components of the curable composition.

[0087] The method of manufacturing the articles from the curable composition can include partially curing the curable 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 an aspect, the article is formed, and the solvent is removed; the article is partially cured (B -staged); optionally shaped; and then further cured.24SHPP0025-WO-PCT(SS370041PCT)

[0088] 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 to 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.

[0089] The curable composition and the cured composition derived therefrom can also be particularly well suited for use in electrical and electronic components. For example, a printed circuit board can comprise the electronic composite formed by curing the curable composition disclosed herein. Electrical and electronic articles include printed circuits boards. Still other articles include antennae and like articles. 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, and 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 include copper clad laminates (CCL), for example, metal core copper clad laminates (MCCCL), composite articles, and coated articles, for example multilayer articles.

[0090] Dielectric layers 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.

[0091] 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,24SHPP0025-WO-PCT(SS370041PCT)silver, platinum, titanium, or the like, or a combination thereof. Other metals include a coppermolybdenum 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 to 200 pm, 5 to 50 pm, or 5 to 40 pm.

[0092] 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 to 20 mm, 0.5 to 10 mm, or 0.8 to 2 mm.

[0093] 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.

[0094] 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 from the 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.24SHPP0025-WO-PCT(SS370041PCT)

[0095] 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.

[0096] 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 an aspect, 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.

[0097] Printed circuit boards prepared from the curable thermosetting composition can have an overall thickness of 0.1 to 20 mm, and specifically 0.5 to 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 to 2 mm, and specifically 0.5 to 1.5 mm. There is no limitation on the thickness of the dielectric layer, which and can be 5 to 1500 pm, 5 to 750 pm, 10 to 150 pm, or 10 to 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.

[0098] The curable composition can be used as a coating, for example in the preparation of a multilayer article. A method of manufacturing the coating can include combining the curable 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 composition, removing the solvent from the layer and optionally curing to provide a primer layer, forming a second layer including a ceramic (e.g., Al2O3, TiO2, ZrO2, Cr2O3, SiO2, MgO, BeO, Y2O3, Al2O3-SiO2, MgO-ZrO2, SiC, WC, B4C, TiC, Si3N4, TiN, BN, AlN, TiB, ZrB2, or the like), a thermoplastic polymer, a fluoropolymer (e.g., polytetrafluoroethylene, tetrafluoroethylene-perfluoroalkylvinylether copolymers, tetr afluoroethylene- hexafluoropropylene copolymers, polychlorotrifluoroethylene, tetrafluoroethylene-ethylene24SHPP0025-WO-PCT(SS370041PCT)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 composition. In some embodiments, the second layer can further include the curable composition.

[0099] Additional applications for the curable compositions disclosed herein 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 for 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; vacuum24SHPP0025-WO-PCT(SS370041PCT)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; 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.

[0100] 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;24SHPP0025-WO-PCT(SS370041PCT)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.

[0101] 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, Inc.; Johan Bjorksten (President) Henry Tovey (Chief, Literature Division), Betty Harker (Administrative Assistant), James Henning (Administrative Assistant), 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; contact molding, including cylindrical contact molding; compression molding; 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.

[0102] This disclosure is further illustrated by the following examples, which are nonlimiting.EXAMPLES

[0103] The materials used in the Examples are described in Table 1.Table 1. MaterialsComponent Chemical Description Source DMP 2,6-Dimethylphenol Sigma Aldrich LCAP-1 Mixture of ortho-, para-C^-n seoalkylphenol (CAS No. 1333248- SI Group54-6). Average.sw-alkyl chain length = 27.7.24SHPP0025-WO-PCT(SS370041PCT)Component Chemical Description Source LCAP-2 Ortho-C11-15sec-alkylphenol. Average sec-alkyl chain length = SI Group 12.5.TMBPA 4,4'-(Propane-2,2-diyl)bis(2,6-dimethylphenol) Deepak Novochem THPE 4,4',4"-(Ethane- 1,1,1 -triyl)triphenol Deepak Novochem DBA Di-n-butylamine, CAS Reg. No. 111-92-2 Oxea DMBA N,N-Dimethylbutylamine, CAS Reg. No. 927-62-8 Oxea DBEDA Di-tert-butylethylenediamine, CAS Reg. No. 4062-60-6 Achiewell DMAP N,N-Dimethylaminopyridine, CAS No. 1122-58-3 Sigma Aldrich MAQUAT N,N,N',N'-Didecyldimethyl ammonium chloride, CAS Reg. Mason No. 7173-51-5, obtained as MAQUAT™ 4450T Chemical NTA Nitrilotriacetic acid trisodium salt, CAS Reg. No. 5064-31-3 Akzo Nobel Functional Chemicals MAA Methacrylic anhydride, CAS No. 760-93-0 Alfa Aeser PPE-MA Bifunctional methacrylate-capped copolymer of DMP and TMBPA SABIC PPE-LCAP-1 -MA Methacrylate-capped copolymer of DMP and LCAP-1; SABIC Mn = 3360, Mw = 5986PPE-LCAP-2-MA Bifunctional methacrylate-capped copolymer of DMP, LCAP-2, SABIC and TMBPA; Mn = 3074, Mw = 5595PB-1 Liquid butadiene resin Cray ValleyPB-2 Liquid butadiene-stat-styrene copolymer resin Cray ValleyPreparative Example 1

[0104] This example describes the synthesis of a monofunctional PPE-LCAP-1 oligomer. Toluene (157 grams), 5 grams DMP, 30 grams LCAP-1, 2.22 grams DMBA, 0.95 grams DBA, 0.16 grams DBEDA, 0.07 grams, MAQUAT, and 0.37 grams toluene were charged to a 500 mL bubbling polymerization vessel and stirred under nitrogen. A premixed 0.11 g CU2O and 1.47 g HBr (48% aqueous) solution was added to the above reaction mixture. After the addition of catalyst solution, oxygen flow was started and 120 g DMP solution in toluene (50 wt%) was added over 60 minutes. The temperature was maintained at 40 °C. Oxygen flow was maintained for 120 minutes, at which point the flow was stopped, and 2.00 grams NTA and 22.00 grams DI water were added to the reaction mixture. The resulting mixture was stirred at 60 °C for 2 hours. The layers were separated by centrifugation and the light phase was isolated by removal of toluene. The product (PPE-LCAP-1, schematically depicted below, wherein o = 24 to 28, and the ratio of n: m is about 16:1) was further dried under vacuum at 110 °C for 12 hours.24SHPP0025-WO-PCT(SS370041PCT)Preparative Example 2

[0105] This example describes the synthesis of monofunctional methacrylate-capped PPE-LCAP oligomer (PPE-LCAP-l-MA). 50 g of the PPE-LCAP-1 oligomer powder from Preparative Example 1 was dissolved in toluene (40% wt / wt) and transferred into a 500 mL 3-neck round bottom flask equipped with a heating mantle, dean-stark condenser, agitator, and thermocouple. The solution was then subjected to azeotropic distillation at 120 °C to remove water. After the removal of water, the reaction mixture was cooled to 85 °C and 0.50 g of DMAP was added thereto. After complete dissolution of the added DMAP, 5.60 g of MAA was added slowly over 15 minutes using an addition funnel. The reaction temperature was raised to 110 °C to obtain a gentle reflux. The reaction was maintained at this temperature under stirring for 4 hours. The PPE-LCAP-l-MA oligomer product was isolated by cooling of the reaction mixture and precipitating the product into methanol. The product (PPE-LCAP-l-MA, schematically depicted below, wherein o = 24 to 28, and the ratio of n: m is about 16:1) was further dried under vacuum at 110 °C for 12 hours.Preparative Example 3

[0106] This example describes the synthesis of bifunctional methacrylate-capped PPE-LCAP-2 oligomers. Toluene (237 grams), 55 grams DMP, 12 grams LCAP-2, 12 grams TMBPA, 2.37 grams DMBA, 0.79 grams DBA, 0.14 grams DBEDA, 0.07 grams, MAQUAT, and 0.25 grams toluene are charged to a 500 ml bubbling polymerization vessel and stirred under nitrogen. A premixed 0.10 g CU2O and 1.28 g HBr (48% aqueous) solution is added to the above reaction mixture. After the addition of catalyst solution, oxygen flow is started, addition of 110 g DMP solution in toluene (50 wt%) for 60 minutes. The temperature is maintained at 40 °C. Oxygen flow is maintained for 120 minutes, at which point the flow is stopped, and 1.78 grams NTA and 22.00 grams DI water are added to the reaction mixture. The resulting mixture is stirred at 60 °C for 2 hours. The layers are separated by centrifugation and the light phase is24SHPP0025-WO-PCT(SS370041PCT)isolated by removal of toluene. PPE-LCAP-2 oligomer is obtained after drying in a vacuum oven at 110 °C under nitrogen overnight. A capping reaction with methacrylic anhydride is conducted by the procedure of Preparative Example 2 to provide the bifunctional PPE-LCAP- 2-MA schematically depicted below, wherein o is 12 to 15, and the ratio of n to m is about 45:1.Preparative Example 4

[0107] This example describes the synthesis of trifunctional methacrylate-capped PPE-LCAP oligomers. Toluene (230 grams), 55 grams DMP, 11.76 grams LCAP-2, 9.76 grams THPE, 2.29 grams DMBA, 0.76 grams DBA, 0.14 grams DBEDA, 0.07 grams, MAQUAT, and 0.25 grams toluene are charged to a 500 ml bubbling polymerization vessel and stirred under nitrogen. A premixed 0.10 g CU2O and 1.28 g HBr (48% aqueous) solution is added to the above reaction mixture. After the addition of catalyst solution, oxygen flow is started, addition of 110 g DMP solution in toluene (50 wt%) for 60 minutes. The temperature is maintained at 40 °C. Oxygen flow is maintained for 120 minutes, at which point the flow is stopped, and 1.71 grams NTA and 21.58 grams DI water are added to the reaction mixture. The resulting mixture is stirred at 60 °C for 2 hours. The layers are separated by centrifugation and the light phase is isolated by removal of toluene. Trifunctional PPE-LCAP-2-MA oligomer is obtained after drying in a vacuum oven at 110 °C under nitrogen overnight. Capping reaction is conducted by the procedure of Preparative Example 2 to provide the bifunctional PPE-LCAP-2-MA schematically depicted below, wherein o is 24 to 26, and the ratio of n to m is about 45:1.24SHPP0025-WO-PCT(SS370041PCT)24SHPP0025-WO-PCT(SS370041PCT)Comparative Example 1

[0108] Bifunctional methacrylate-capped PPE (PPE-MA) oligomer was blended with liquid polybutadiene resin in a 50:50 weight ratio. A casting was prepared from the blend and an optical microscopy image of the casting is reproduced in Fig. 1A.Comparative Example 2

[0109] Bifunctional methacrylate-capped PPE (PPE-MA) oligomer was blended with liquid butadiene-stat-styrene copolymer resin in a 50:50 weight ratio. A casting was prepared from the blend, and an optical microscopy image of the casting is reproduced in Fig. 1B.Example 1

[0110] Methacrylate-capped (PPE-LCAP-l-MA) was blended with liquid polybutadiene resin in a 50:50 weight ratio. A casting was prepared from the blend, and an optical microscopy image of the casting is reproduced in Fig. 1C.Example 2

[0111] Methacrylate-capped (PPE-LCAP-l-MA) was blended with liquid butadiene-stat-styrene copolymer resin in a 50:50 weight ratio. A casting was prepared from the blend, and an optical microscopy image of the casting is reproduced in Fig. 1D. The fibers visible in the image are contaminants.

[0112] Visual inspection, as well as optical microscopy images (not shown) demonstrated that the presence of the PPE-LCAP-l-MA in the mixture resulted in a compatibilized blend. In particular, Comparative Examples 1-2 had visible phase separation, whereas Examples 1-2 did not have visible phase separation.Example 3

[0113] This example provides visual side-by-side comparisons of castings of the blend of Comparative Example 1 (“PPE”) with the blend of Example 1 (“MPPE”) (Fig. 2A), and of castings of the blend of Comparative Example 2 (“PPE”) with the blend of Example 2 (“MPPE”) (Fig. 2B). As can be seen from Fig. 2A and 2B, the blends of Comparative Examples 1 and 2 both had visible phase separation, while the blends of Examples 1 and 2 did not have visible phase separation.

[0114] This disclosure further encompasses the following aspects.

[0115] Aspect 1. A poly (arylene ether) derived from monomers comprising a first monohydric phenol, and optionally a second monohydric phenol and / or a multi-functional phenol comprising at least two phenolic groups, wherein at least one of the first monohydric24SHPP0025-WO-PCT(SS370041PCT)phenol, second monohydric phenol, or multifunctional phenol comprises a substituted or unsubstituted C10-30 hydrocarbyl substituent and the poly(arylene ether) comprises at least one end group that is not a phenolic hydroxyl group.

[0116] Aspect 2. The poly( arylene ether) of aspect 1, derived from first and second monohydric phenols and having the structural formula:R21 [Q1Q2] 1xU~4 Y""" OH411 11 V / I ILL^3 ^4 JplPs ^4 JtfiJxwherein: Qi, Q2, Q3, and Q4 are each independently, hydrogen, substituted or unsubstituted C1-30 hydrocarbyl or di(Ci-6-alkyl)aminomethyl, wherein at least one of Qi, Q2, Q3, or Q4 is a substituted or unsubstituted C10-30 hydrocarbyl; Ri, R2, R3, and R4 are each independently hydrogen, halogen, substituted or unsubstituted C1-30 primary or secondary hydrocarbyl, C1-30 hydrocarbylthio, C1-30 hydrocarbyloxy, C2-30 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms, or di(Ci-6-alkyl)aminomethyl; X is H or a residue derived from a polyhydric phenol; Y is H or a monovalent end group derived from a capping agent reactive with phenols; m is 1 to 50; n is 0 to 50; x is 1 to 6; and the poly(arylene ether) is a random copolymer or block copolymer of the first and second monohydric phenols.

[0117] Aspect 3. The poly( arylene ether) of any of aspect 2, wherein at least one of Qi, Q2, Q3 or Q4 is a branched or unbranched C12-30 alkyl.

[0118] Aspect 4. The poly( arylene ether) of any of aspects 1-3, wherein the number average molecular weight (Mn) is less than 5,000 g / mol, calculated based on the molar ratios of the monomers.

[0119] Aspect 5. The poly( arylene ether) of any of aspects 1-3, wherein the number average molecular weight (Mn) is less than 5,000 g / mol, as determined by gel permeation chromatography (GPC) using a crosslinked styrene-divinyl benzene column.

[0120] Aspect 6. The poly( arylene ether) of any of aspects 2-5, wherein Ri, R3, Qi, and Q3 are hydrogen; R2, R4 and one of Q2 or Q4 is methyl, and the other one of Q2 or Q4 is a substituted or unsubstituted C10-30 secondary alkyl.

[0121] Aspect 7. The poly( arylene ether) of any of aspects 2-5, wherein Ri, R3, Qi, and Q3 are hydrogen, one of Q2 or Q4 is hydrogen and the other one of Q2 or Q4 is a C12-30 secondary hydrocarbyl.24SHPP0025-WO-PCT(SS370041PCT)

[0122] Aspect 8. The poly( arylene ether) of aspect 7, wherein the other one of Q2 or Q4 is a C22-24 secondary alkyl.

[0123] Aspect 9. The poly( arylene ether) of any of aspects 2-8, wherein R2 and R4 are methyl, and Ri and R3 are hydrogen, and n: m is greater than or equal to 0: 1 and less than or equal to 50: 1.

[0124] Aspect 10. The poly(arylene ether) of any of aspects 2-9, wherein x = 1 and X is hydrogen.

[0125] Aspect 11. The poly(arylene ether) of any of aspects 2-9, wherein x = 2 and X has the structural formula:R' R?FT Rs / \>; / ' -r\ / R^ V RsVWherein each occurrence of R5, R6, R7, and R8independently comprises hydrogen, halogen, unsubstituted or substituted C1-30 primary or secondary hydrocarbyl, C1-30 hydrocarbylthio, C1-30 hydrocarbyloxy, or C2-30 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms; y is 0 or 1; and Y is a divalent linking groupI $ 3 II II I II II — C — ’ — C=C — ’ — C —. — C —. — N —, — O —, - S -, - S - ’ - S - I IIRb 0orwherein each occurrence of Ra, Rb, Rc, Rd, and Reis independently hydrogen, C1-30 hydrocarbyl, or wherein Raand Rbtogether or Rcand Rdtogether are a C4-11 hydrocarbylene group; each occurrence of Rfis independently hydrogen, a C1-14 hydrocarbyl, a C1-14 halohydrocarbyl, or a Ci-14 heterohydrocarbyl, preferably 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 C1-6 hydrocarbylene group, preferably a divalent C2-8 aliphatic group; and E is 2 to 200.24SHPP0025-WO-PCT(SS370041PCT)

[0126] Aspect 12. The poly(arylene ether) of aspect 11, wherein Y is the divalent linking group:R*— £ —wherein at least one of Raand Rbis a C10-30 hydrocarbyl group.

[0127] Aspect 13. The poly(arylene ether) of aspect 11, wherein Y is the divalent linking group:Ra— —RSiwherein each occurrence of Raand Rbis independently hydrogen, C1-30 hydrocarbyl or wherein Raand Rbtogether are a C4-11 hydrocarbylene group.

[0128] Aspect 14. The poly(arylene ether) of aspect 11, wherein X has the structural formula:wherein: E is 6-100; each occurrence of R is independently an unsubstituted or substituted C1-30 alkyl, Ci-13 alkoxy, C3-6 cycloalkyl, Ce-i4 aryl, C7-13 arylalkylene, or C7-13 alkylarylene; each p and q is independently 0 or 1; R1is a divalent unsubstituted or substituted C2-8 aliphatic group, and each occurrence of U is independently halogen, hydrogen, cyano, nitro, an unsubstituted or substituted C1-8 alkylthio, C1-30 alkyl, C1-8 alkoxy, C2-8 alkenyl, C2-8 alkenyloxy, C3-8 cycloalkyl, C3-8 cycloalkoxy, Ce-io aryl, Ce-io aryloxy, C7-12 aralkyl, C7-12 aralkoxy, C7-12 alkylaryl, or C7-12 alkylaryloxy, and each r is independently 0, 1, 2, 3, or 4.

[0129] Aspect 15. The poly(arylene ether) of aspect 14, wherein each R is methyl, each R1pis -CH2-CH2-CH2- and E is 5 to 100.

[0130] Aspect 16. The poly(arylene ether) of any of aspects 2-9, wherein x = 3 and X has the structural formula:24SHPP0025-WO-PCT(SS370041PCT)wherein T is a C1-30 alkyl, C1-20 alkoxy, C7-12 arylalkyl, or C7-12 alkylaryl; each S is independently halogen, C1-3 alkyl, C1-3 alkoxy, C7-12 arylalkyl, C7-12 alkylaryl, or nitro; and each z is independently an integer of 0 to 4.

[0131] Aspect 17. The poly(arylene ether) of any of aspects 2-16, wherein each Y independently comprises a reactive group of the structural formulawherein Y2is a divalent linking group having one of structural formula:O S RhO 0C ''' "’ 3 s, 6wherein each occurrence of Rhand R1independently is hydrogen or C1-12 alkyl; R9is an epoxide- containing group, a cyanate-containing group, or a C1-12 hydrocarbyl substituted with one or two carboxylic acid groups; each occurrence of R10, R11, and R12independently is hydrogen, Ci-is hydrocarbyl, C2-18 hydrocarbyloxycarbonyl, nitrile, formyl, carboxylic acid, imidate, or thiocarboxylic acid; and each occurrence of R13, R14, R15, R16, and R17independently is hydrogen, halogen, C1-12 alkyl, C2-12 alkenyl, hydroxy, amino, maleimide, carboxylic acid, or a C2-20 alkyl ester.

[0132] Aspect 18. The poly(arylene ether) of any of aspects 2-16, wherein each Y independently comprises vinyl, allyl, styryl (–(C6H5)-CH=CH2), -CH2-(CeH4)-CH=CH2, (meth)acryloyl, cyanate ester, glycidyl ether, anhydride, maleimide, amino, phenylamino, or activated ester.24SHPP0025-WO-PCT(SS370041PCT)

[0133] Aspect 19. The poly(arylene ether) of aspect 18, wherein Y is-C(=O)-C(CH3)=CH2.

[0134] Aspect 20. The poly(arylene ether) of aspect 13, wherein:X has the structural formulaHjC CH;;\.. / 5. i. ( ).CH3. \H;. C CM;at least one of Qi, Q2, Q3or Q4 is a branched or unbranched Ci2.3o alkyl; R2and R4 are methyl, and Ri and R3are hydrogen; and Y is -C(=O)-C(CH3)=CH2.

[0135] Aspect 21. The poly(arylene ether) of aspect 16, wherein:X is derived from a trihydric phenol of structural formula:OHof structural formula:OHat least one of Qi, Q2, Q3or Q4 is a branched or unbranched Ci2.3o alkyl; R2and R4 are methyl, and Ri and R3are hydrogen; and Y is -C(=O)-C(CH3)=CH2.

[0136] Aspect 22. The poly(arylene ether) of any of aspects 1-5, 7-10 and 17-19 having the chemical structure:24SHPP0025-WO-PCT(SS370041PCT)wherein m is 1 to 50, n is 0 to 50, and o is 7 to 30.

[0137] Aspect 23. The poly(arylene ether) of any of aspects 1-5, 7-10 and 17-18 having the chemical structure:wherein m is 1 to 50, n is 0 to 50, and o is 7 to 30.

[0138] Aspect 24. The poly(arylene ether) of any of aspects 1-5, 7-9, 11, 13 and 17-20 having the chemical structure:wherein m is 1 to 50, n is 0 to 50, and o is 7 to 30.

[0139] Aspect 25. The poly(arylene ether) of any of aspects 1-5, 7-9, 11, 13 and 17-18 having the chemical structure:wherein m is 1 to 50, n is 0 to 50, and o is 7 to 30.

[0140] Aspect 25a. A poly(arylene ether) composition comprising the poly( arylene ether) of any of aspects 1 to 25 and a hydrocarbon resin.

[0141] Aspect 26. A thermosetting composition comprising: the poly(arylene ether) of any of aspects 1-25; a thermoset; a monomer, oligomer, or polymer with ethylenic unsaturation; optionally a hydrocarbon resin; and optionally at least one of a curing catalyst or initiator.

[0142] Aspect 27. The thermosetting composition of aspect 26, wherein the thermoset comprises, depending on at least one reactive functional group of the poly(arylene ether), at least one of an epoxy resin, a cyanate ester resin, a bismaleimide resin, a benzoxazine resin, a vinyl24SHPP0025-WO-PCT(SS370041PCT)benzyl ether resin, an arylcyclobutene resin, a perfluorovinyl ether resin, an unsaturated polyester resin, an alkyd resin, or a phenolic resin.

[0143] Aspect 27a. The thermosetting composition of aspect 27, wherein the thermoset further comprises at least one of a polyamine, a dicyandiamide, a polyamide, an amidoamine, a Mannich base, a carboxylic acid, a carboxylic anhydride, a phenol-formaldehyde resin, a carboxylic acid-functional polyester, a polysulfide, a polymercaptan, an alkoxysilane, a carbodiimide, or an isocyanate.

[0144] Aspect 27b. The thermosetting composition of aspect 27 or 27a, wherein the monomer, oligomer, or polymer with ethylenic unsaturation comprises at least one of a monofunctional styrenic compound, a monofunctional (meth)acryloyl compound, a polyfunctional allylic compound, a polyfunctional (meth)acrylate, a polyfunctional (meth)acrylamide, a polyfunctional styrenic compound, tri(meth)allyl cyanurate, tri(meth) allyl isocyanurate, or an unsaturated polyester.

[0145] Aspect 28. A cured composition obtained by heating the thermosetting composition of any of aspects 27, 27a, and 27b for a time and temperature sufficient to effect curing.

[0146] Aspect 29. The cured composition of aspect 28, in the form of 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, a metal clad laminate, a composite, an electronic composite, a structural composite, or printed circuit board.

[0147] Aspect 29a. A printed circuit board comprising the electronic composite of aspect 29.

[0148] The compositions, methods, and articles can alternatively comprise, 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.

[0149] 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 specifically, 5 wt.% to 20 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,” and the like, do not denote any order, quantity, or importance, but rather are used to distinguish one element from another. The terms24SHPP0025-WO-PCT(SS370041PCT)“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. Reference throughout the specification to “some embodiments”, “an embodiment”, and so forth, means that a particular element described in connection with the embodiment is included in at least one embodiment described herein, and may or may not be present in other embodiments. In addition, it is to be understood that the described elements may be combined in any suitable manner in the various embodiments. A “combination thereof’ is open and includes any combination comprising at least one of the listed components or properties optionally together with a like or equivalent component or property not listed

[0150] 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.

[0151] 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

[0152] As used herein, “polyfunctional” denotes having at least two functional (reactive) groups. For example, the at least two functional groups can be at least two ethylenically unsaturated groups.

[0153] Compounds are described using standard nomenclature. For example, any carbon atom in a hydrocarbon 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 indicates a substituent on the carbon of the carbonyl group.

[0154] The term “alkyl” means a branched or straight chain, saturated 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. The prefix “s” or “sec” indicates “secondary”. A secondary carbon atom is a carbon atom bonded to two other carbon atoms. A secondary alkyl group is an alkyl radical one carbon atom removed from the end of the carbon chain. A example of a secondary alkyl group - sec-butyl - is illustrated below.24SHPP0025-WO-PCT(SS370041PCT)se -butyl

[0155] “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 secbutyloxy 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, -CnFfcn-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 members are 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. The prefix “hetero” means that the compound or group includes at least one ring member that is a heteroatom (e.g., 1, 2, or 3 heteroatom(s)), wherein the heteroatom(s) is each independently N, O, S, Si, or P. “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.

[0156] Unless substituents are otherwise specifically indicated, each of the foregoing groups can be unsubstituted or substituted, provided that the substitution does not significantly adversely affect synthesis, stability, or use of the compound. “Substituted” means that the compound, group, or atom is substituted with at least one (e.g., 1, 2, 3, or 4) substituents instead of hydrogen, where each substituent is independently nitro (-NO2), cyano (-CN), hydroxy (-OH),24SHPP0025-WO-PCT(SS370041PCT)halogen, thiol (-SH), thiocyano (-SCN), Ci-6 alkyl, C2-6 alkenyl, C2-6 alkynyl, C1-6 haloalkyl, C1-9 alkoxy, C1-6 haloalkoxy, C3-12 cycloalkyl, C5-18 cycloalkenyl, C6-12 aryl, C7-13 arylalkylene (e.g., benzyl), C7-12 alkylarylene (e.g, toluyl), C4-12 heterocycloalkyl, C3-12 heteroaryl, C1-6 alkyl sulfonyl (-S(=O)2-alkyl), C6-12 arylsulfonyl (-S(=O)2-aryl), or tosyl (CH3C6H4SO2-), provided that the substituted atom’s normal valence is not exceeded, and that the substitution does not significantly adversely affect the manufacture, stability, or desired property of the compound. When a compound is substituted, the indicated number of carbon atoms is the total number of carbon atoms in the compound or group, including those of any substituents.

[0157] 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

1. 24SHPP0025-WO-PCT2.(SS370041PCT)3.CLAIMS4.What is claimed is:

1. A poly(arylene ether) derived from monomers comprising a first monohydric phenol, and optionally a second monohydric phenol and / or a multi-functional phenol comprising at least two phenolic groups, wherein at least one of the first monohydric phenol, second monohydric phenol, or multifunctional phenol comprises a substituted or unsubstituted C10-30 hydrocarbyl substituent and the poly(arylene ether) comprises at least one end group that is not a phenolic hydroxyl group.

2. The poly (arylene ether) of claim 1, derived from first and second monohydric phenols and having the structural formula:

8. 10.wherein:11.Qi, Q2, Q3, and Q4 are each independently, hydrogen, substituted or unsubstituted Ci-30 hydrocarbyl or di(Ci-6-alkyl)aminomethyl, wherein at least one of Qi, Q2, Q3, or Q4 is a substituted or unsubstituted C10-30 hydrocarbyl;12.Ri, R2, R3, and R4 are each independently hydrogen, halogen, substituted or unsubstituted C1-30 primary or secondary hydrocarbyl, C1-30 hydrocarbylthio, C1-30 hydrocarbyloxy, C2-30 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms, or di(Ci-6-alkyl)aminomethyl;13.X is H or a residue derived from a polyhydric phenol;14.Y is H or a monovalent end group derived from a capping agent reactive with phenols;15.m is 1 to 50;16.n is 0 to 50;17.x is 1 to 6; and18.the poly(arylene ether) is a random copolymer or block copolymer of the first and second monohydric phenols. 24SHPP0025-WO-PCT19.(SS370041PCT)3. The poly(arylene ether) of claim 2 wherein at least one of Qi, Q2, Q3 or Q4 is a branched or unbranched C12-30 alkyl.

4. The poly(arylene ether) of any of claims 1-3, wherein the number average molecular weight (Mn) is less than 5,000 g / mol, calculated based on the molar ratios of the monomers.

5. The poly(arylene ether) of any of claims 1-3, wherein the number average molecular weight (Mn) is less than 5,000 g / mol, as determined by gel permeation chromatography (GPC) using a crosslinked styrene-divinyl benzene column.

6. The poly(arylene ether) of any of claims 2-5, wherein Ri, R3, Qi, and Q3 are hydrogen; R2, R4 and one of Q2 or Q4 is methyl, and the other one of Q2 or Q4 is a substituted or unsubstituted C10-30 secondary alkyl.

7. The poly(arylene ether) of any of claims 2-5, wherein Ri, R3, Qi, and Q3 are hydrogen, one of Q2 or Q4 is hydrogen and the other one of Q2 or Q4 is a C12-30 secondary hydrocarbyl.

8. The poly (arylene ether) of claim 7, wherein the other one of Q2 or Q4 is a C22-24 secondary alkyl.

9. The poly(arylene ether) of any of claims 2-8, wherein R2 and R4 are methyl, and Ri and R3 are hydrogen, and n: m is greater than or equal to 0: 1 and less than or equal to 50: 1.

10. The poly(arylene ether) of any of claims 2-9, wherein x = 1 and X is hydrogen.

11. The poly(arylene ether) of any of claims 2-9, wherein x = 2 and X has the structural formula:

30. 32.wherein 24SHPP0025-WO-PCT33.(SS370041PCT)34.each occurrence of R5, R6, R7, and R8independently comprises hydrogen, halogen, unsubstituted or substituted C1-30 primary or secondary hydrocarbyl, C1-30 hydrocarbylthio, C1-30 hydrocarbyloxy, or C2-30 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms;35.y is 0 or 1; and36.Y is a divalent linking group37.RaR R O S Reo I 3 3 II II I II — C — ’ — C=C — ’ — C —. — C —. — N —, — O —, - S -. - S - I38.Rbor40.

41. wherein42.each occurrence of Ra, Rb, Rc, Rd, and Reis independently hydrogen, C1-30 hydrocarbyl, or wherein Raand Rbtogether or Rcand Rdtogether are a C4-11 hydrocarbylene group;43.each occurrence of Rfis independently hydrogen, a C1-14 hydrocarbyl, a C1-14 halohydrocarbyl, or a C1-14 heterohydrocarbyl, preferably 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;44.each occurrence of Rgis independently a C1-6 hydrocarbylene group, preferably a divalent C2-8 aliphatic group; and45.E is 2 to 200.

12. The poly(arylene ether) of claim 11, wherein Y is the divalent linking group:47.R*48.— C —50.

51. Rb52.wherein at least one of Raand Rbis a C10-30 hydrocarbyl group.

13. The poly(arylene ether) of claim 11, wherein Y is the divalent linking group:24SHPP0025-WO-PCT54.(SS370041PCT)55.— i—56.Rb57.wherein each occurrence of Raand Rbis independently hydrogen, C1-30 hydrocarbyl or wherein Raand Rbtogether are a C4-11 hydrocarbylene group.

14. The poly(arylene ether) of claim 11, wherein X has the structural formula:

60. 62.wherein:63.E is 6-100;64.each occurrence of R is independently an unsubstituted or substituted C1-30 alkyl, C1-13 alkoxy, C3-6 cycloalkyl, Ce-i4 aryl, C7-13 arylalkylene, or C7-13 alkylarylene;65.each p and q is independently 0 or 1;66.R1is a divalent unsubstituted or substituted C2-8 aliphatic group, and67.each occurrence of U is independently halogen, hydrogen, cyano, nitro, an unsubstituted or substituted Ci-s alkylthio, C1-30 alkyl, Ci-s alkoxy, C2-8 alkenyl, C2-8 alkenyloxy, C3-8 cycloalkyl, C3-8 cycloalkoxy, Ce-io aryl, Ce-io aryloxy, C7-12 aralkyl, C7-12 aralkoxy, C7-12 alkylaryl, or C7-12 alkylaryloxy, and68.each r is independently 0, 1, 2, 3, or 4.

15. The poly(arylene ether) of claim 14, wherein each R is methyl, each R1pis -CH2-CH2-CH2- and E is 5 to 100.

16. The poly(arylene ether) of any of claims 2-9, wherein x = 3 and X has the structural formula:24SHPP0025-WO-PCT71.(SS370041PCT)73. 75.wherein T is a C1-30 alkyl, C1-20 alkoxy, C7-12 arylalkyl, or C7-12 alkylaryl;76.each S is independently halogen, C1-3 alkyl, C1-3 alkoxy, C7-12 arylalkyl, C7-12 alkylaryl, or nitro; and77.each z is independently an integer of 0 to 4.

17. The poly(arylene ether) of any of claims 2-16, wherein each Y independently comprises a reactive group of the structural formula80.

81. wherein Y2is a divalent linking group having one of structural formula:82.O S 0 O83.8 8 8 |85.

86. , R4> O87.wherein each occurrence of Rhand R1independently is hydrogen or C1-12 alkyl;88.R9is an epoxide-containing group, a cyanate-containing group, or a C1-12 hydrocarbyl substituted with one or two carboxylic acid groups;89.each occurrence of R10, R11, and R12independently is hydrogen, Ci-is hydrocarbyl, C2-18 hydrocarbyloxycarbonyl, nitrile, formyl, carboxylic acid, imidate, or thiocarboxylic acid; and each occurrence of R13, R14, R15, R16, and R17independently is hydrogen, halogen, C1-12 alkyl, C2-12 alkenyl, hydroxy, amino, maleimide, carboxylic acid, or a C2-20 alkyl ester. 24SHPP0025-WO-PCT90.(SS370041PCT)18. The poly(arylene ether) of any of claims 2-16, wherein each Y independently comprises vinyl, allyl, styryl (–(C6H5)-CH=CH2), -CH2-(CeH4)-CH=CH2, (meth)acryloyl, cyanate ester, glycidyl ether, anhydride, maleimide, amino, phenylamino, or activated ester.

19. The poly(arylene ether) of claim 18, wherein Y is -C(=O)-C(CH3)=CH2.

20. The poly (arylene ether) of claim 13, wherein:94.X has the structural formula95.CH?96.CH;, / 97.C. A.98.CH5. •'<100.

101. CH?102.at least one of Qi, Q2, Q3 or Q4 is a branched or unbranched C12-30 alkyl; R2 and R4 are methyl, and Ri and R3 are hydrogen; and103.Y is -C(=O)-C(CH3)=CH2.

21. The poly (arylene ether) of claim 16, wherein:105.X is derived from a trihydric phenol of structural formula:106.OH108. 110.of structural formula: 24SHPP0025-WO-PCT111.(SS370041PCT)112.OH114. 116.5117.at least one of Qi, Q2, Q3 or Q4 is a branched or unbranched C12-30 alkyl;118.R2 and R4 are methyl, and Ri and R3 are hydrogen; and119.Y is -C(=O)-C(CH3)=CH2.

22. The poly(arylene ether) of any of claims 1-5, 7-10 and 17-19, having the chemical structure:

122. 124.wherein m is 1 to 50, n is 0 to 50, and o is 7 to 30.

23. The poly(arylene ether) of any of claims 1-5, 7-10 and 17-18126., having the chemical structure:

128. 130.wherein m is 1 to 50, n is 0 to 50, and o is 7 to 30.

24. The poly(arylene ether) of any of claims 1-5, 7-9, 11, 13 and 17-20, having the chemical structure:

133.

134. 24SHPP0025-WO-PCT135.(SS370041PCT)136.wherein m is 1 to 50, n is 0 to 50, and o is 7 to 30.

25. The poly(arylene ether) of any of claims 1-5, 7-9, 11, 13 and 17-18, having the chemical structure:

139.

140. wherein m is 1 to 50, n is 0 to 50, and o is 7 to 30.

26. A thermosetting composition comprising:142.the poly(arylene ether) any of claims 1-25;143.a thermoset;144.a monomer, oligomer, or polymer with ethylenic unsaturation;145.optionally a hydrocarbon resin; and146.optionally at least one of a curing catalyst or initiator.

27. The thermosetting composition of claim 26, wherein the thermoset is at least one of an epoxy resin, a cyanate ester resin, a bismaleimide resin, a benzoxazine resin, a vinyl benzyl ether resin, an arylcyclobutene resin, a perfluorovinyl ether resin, an unsaturated polyester resin, an alkyd resin, or a phenolic resin.

28. A cured composition obtained by heating the thermosetting composition of claim 27 for a time and temperature sufficient to effect curing.

29. The cured composition of claim 28, in the form of 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, a metal clad laminate, a composite, an electronic composite, a structural composite, or printed circuit board.

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