Curable composition and cured compositions derived therefrom

Abstract

A curable composition includes a polyfunctional poly(arylene ether) having an end group including a linking group and a terminal functional group, wherein the terminal functional group comprises a hydroxyl group or a salt thereof, and the linking group comprises a substituted or unsubstituted saturated hydrocarbylene group, or a substituted or unsubstituted saturated poly(hydrocarbylene ether), a curable component, and optionally, one or more of a crosslinking agent, a curing agent, a curing catalyst, a curing initiator, or a combination thereof. The curable composition can be useful in providing cured compositions, such as thermoset compositions, for a variety of applications.

Description

CURABLE COMPOSITION AND CURED COMPOSITIONS DERIVED THEREFROMCROSS REFERENCE TO RELATED APPLICATIONThis application claims priority to and the benefit of European Patent Application No. 24171638.0, filed April 22, 2024, the contents of which are hereby incorporated by reference in their entirety.BACKGROUND

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

[0002] Poly(arylene ether) copolymers are a class of thermoplastics known for excellent water resistance, dimensional stability, and inherent flame retardancy, as well as outstanding dielectric properties over wide frequency and temperature ranges. Properties such as ductility, stiffness, chemical resistance, and heat resistance can be tailored by reacting thermosetting poly(arylene ether) copolymers with various crosslinking agents to meet requirements of a wide variety of end uses, for example, fluid engineering parts, electrical enclosures, automotive parts, and insulation for wire and cable. In particular, poly(arylene ether) copolymers have been used in thermoset compositions for electronics applications, where they provide improved toughness and dielectric properties, among other benefits. It has been shown that the incorporation of poly(arylene ether)s can decrease dielectric constants and loss tangents in epoxy- and vinylbased thermosets. However, these methods have the disadvantage that their uncured compositions have high viscosity, which make processing more difficult.

[0003] Accordingly, there remains a continuing need in the art for improved curable compositions. It would be particularly desirable to provide curable compositions based on poly(arylene ether)s having reduced viscosity, thereby facilitating subsequent processing.SUMMARY

[0004] Some aspects of the present disclosure is a curable composition comprising: a polyfunctional, e.g., bifunctional poly(arylene ether) comprising an end group, wherein the end group comprises a linking group and a terminal functional group, wherein the terminal functional group comprises a hydroxyl group or a salt thereof, and the linking group comprises a substituted or unsubstituted saturated hydrocarbylene group, or a substituted or unsubstituted saturated poly(hydrocarbylene ether), wherein the polyfunctional, e.g., bifunctional poly(arylene ether) comprises an average of at least 1.8 terminal hydroxyl groups per molecule; a curablecomponent; and optionally, one or more of a crosslinking agent, a curing agent, a curing catalyst, a curing initiator, or a combination thereof.

[0005] Another aspect is a composition comprising a cured product derived from the curable composition.

[0006] Another aspect is an article comprising the composition, for example an article in the form of a composite, a foam, a fiber, a layer, a coating, a film, an encapsulant, an adhesive, a sealant, a molded component, a prepreg, a casing, a laminate, a metal clad laminate, an electronic composite, a structural composite, or a combination thereof.

[0007] The above described and other features are exemplified by the following detailed description.DETAILED DESCRIPTION

[0008] The present inventors have advantageously discovered that curable compositions having reduced viscosity can be provided by inclusion of a particular polyfunctional, e.g., bifunctional poly (arylene ether), for example a bifunctional poly(arylene ether) having an end group, wherein the end group comprises a linking group and a terminal functional group. The terminal functional group comprises a hydroxyl group, a salt thereof, or a combination thereof. The linking group comprises a substituted or unsubstituted saturated hydrocarbylene group, or a substituted or unsubstituted saturated poly(hydrocarbylene ether). The bifunctional poly(arylene ether) can have an average of at least 1.8 terminal hydroxyl groups per molecule. In some aspects, the polyfunctional, e.g., bifunctional poly(arylene ether) has an average of at least at least 1.85, or at least 1.9, or at least 1.95, or at least 2.0 end groups. In some aspects, the composition comprises 0-5,000 ppm, or 0-2,500 ppm, or 0-1,000 ppm, as determined byNMR of a poly(arylene ether) comprising a linking group comprising a carbonate functional group, an ester functional group, or a combination thereof.

[0009] Advantageously, due to the reduced viscosity of the polyfunctional, e.g., bifunctional poly(arylene ether) as described herein, no reactive diluents or organic solvents are needed to process the curable compositions. A significant improvement is therefore provided using the polyfunctional, e.g., bifunctional poly(arylene ether).

[0010] Accordingly, some aspects of the present disclosure include a curable composition. The curable composition comprises the polyfunctional, e.g., bifunctional poly (arylene ether), a curable component, and optionally one or more of a crosslinking agent, a curing agent, a curing catalyst, a curing initiator, or a combination thereof.

[0011] The polyfunctional, e.g., bifunctional poly(arylene ether) includes an end group, wherein the end group includes a linking group and a terminal functional group. The linkinggroup includes a substituted or unsubstituted saturated hydrocarbylene group, or a substituted or unsubstituted saturated poly(hydrocarbylene ether). The terminal functional group includes a hydroxyl group, a salt thereof, or a combination thereof, and the polyfunctional, e.g., bifunctional poly(arylene ether) comprises an average of at least 1.8 terminal hydroxyl groups, salts thereof, or a combination thereof, per molecule. For simplicity, this polyfunctional, e.g., bifunctional poly (arylene ether) can be referred to herein as “the polyfunctional poly (arylene ether) having the end groups”, or simply “the polyfunctional poly(arylene ether)”.

[0012] For illustrative purposes only, shown below is a portion of two polyfunctional poly(arylene ether) having the end groups, one having an unsubstituted, saturated hydrocarbylene group (e.g., an ethyl group) as the linking group (structure on left) and another having an unsubstituted, saturated poly(hydrocarbylene ether) (e.g., diethyl ether) as the linking group (structure on right). The terminal functional group in both structures shown below is OH, and “> / vvv’ ” indicates a link to the remaining portion of the polyfunctional poly(arylene ether).

[0013] As will be discussed in further detail below, in addition to the illustrative end groups shown in the structures above, the substituted or unsubstituted saturated hydrocarbyl linking group includes a substituted or unsubstituted C2-30 hydrocarbylene group. The C2-30 hydrocarbylene group can include at least 2, at least 3, at least 4, or at least 6 carbons and up to 30, up to 20, up to 10, up to 8, up to 6, or up to 4 carbons. A range of carbon atoms in the hydrocarbylene group can include any of the foregoing limits. For example, the C2-30 hydrocarbylene group can include a substituted or unsubstituted C2-10 alkylene, or an unsubstituted C2-4 alkylene, or an unsubstituted C2-3 alkylene.

[0014] The substituted or unsubstituted, saturated poly(hydrocarbylene ether) linking group can be a substituted or unsubstituted, saturated C4-100 poly(hydrocarbylene ether). The C4- 100 poly(hydrocarbylene ether) can include at least 10, at least 15, at least 20, at least 25, at least 30, at least 35, at least 40, at least 45, at least 50, at least 55, or at least 60 carbon atoms; and up to 90, up to 80, up to 70, up to 60, up to 50, up to 40, up to 30, or up to 20 carbon atoms. A range of carbon atoms in the substituted or unsubstituted, saturated poly(hydrocarbylene ether) can include any of the foregoing limits. In some aspects the C4-100 poly(hydrocarbylene ether) is unsubstituted.

[0015] In some aspects, the substituted or unsubstituted, saturated C4-100 poly(hydrocarbylene ether) is a substituted or unsubstituted, saturated C4-100 poly(C2-4 alkylene ether), where the number of carbon atoms are any of the foregoing limits. In some aspects, the alkylene groups of the substituted or unsubstituted, saturated C4-ioopoly(C2-3 alkylene ether) have 2-3 carbon atoms, or a combination of 2 and 3 carbon atoms, or 2 carbon atoms. . In some aspects saturated C4-100 poly(C2 alkylene ether) is unsubstituted.

[0016] The polyfunctional, e.g., bifunctional poly(arylene ether) having the end groups includes repeating units derived from a monohydric phenol, the repeating units having the formula (1)wherein each occurrence of Q1is substituted or unsubstituted C1-12 primary or secondary alkyl or cycloalkyl, or substituted or unsubstituted C1-12 primary alkyl, or substituted or unsubstituted Ci- 6 primary alkyl, or substituted or unsubstituted methyl; each occurrence of Q2is halogen, C1-12 hydrocarbyl provided that the hydrocarbyl group is not tertiary hydrocarbyl, C1-12 hydrocarbylthio, C1-12 hydrocarbyloxy, or C2-12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms, or C1-12 alkyl or C3-12 cycloalkyl, or C1-6 alkyl, or methyl; each occurrence of Q3and Q4is independently hydrogen, halogen, unsubstituted or substituted C1-12 hydrocarbyl provided that the hydrocarbyl group is not tertiary hydrocarbyl, Ci- 12 hydrocarbylthio, C1-12 hydrocarbyloxy, or C1-12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms, or hydrogen; and e is 1-200, for example 2-100, or 5-100, or 2-50, provided that when e is 1, at least one additional repeat unit is present in the polymer.

[0017] In some aspects, each occurrence of Q1in the polymer is independently methyl or cyclohexyl, optionally substituted with a amine group having from 1-12 carbon atoms, and each occurrence of Q2is halogen, unsubstituted C1-12 alkyl provided that the alkyl group is not tertiary alkyl, or unsubstituted C1-12 aryl. In some aspects, each occurrence of Q1is independently methyl or methyl substituted with a di(Ci-6 alkyl)amino group or a morpholinyl group, and each Q2is methyl.

[0018] Exemplary monohydric phenols that can be used include 2,6-dimethylphenol, 2- methylphenol, 2, 5 -dimethylphenol, 2-allyl-6-methylphenol, 2,3,6-trimethylphenol, 2-methyl-6- phenyl phenol, 2-cyclohexyl-6-methylphenol, or a combination thereof. For example, the monohydric phenol can include 2,6-dimethylphenol.

[0019] In addition to repeating units derived from a monohydric phenol, the monomers can comprise repeating units derived from a dihydric phenol, the repeating units having the structure of formula (2)wherein each occurrence of Q1and Q2are independently halogen, unsubstituted or substituted Ci-i5 primary or secondary hydrocarbyl, unsubstituted or substituted C1-12 hydrocarbylthio, unsubstituted or substituted C1-12 hydrocarbyloxy, or unsubstituted or substituted C2-12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms; each occurrence of Q3and Q4are independently hydrogen, halogen, unsubstituted or substituted Ci-15 primary or secondary hydrocarbyl, unsubstituted or substituted C1-12 hydrocarbylthio, unsubstituted or substituted C1-12 hydrocarbyloxy, or unsubstituted or substituted C2-12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms, preferably hydrogen or unsubstituted or substituted Ci-s primary or secondary hydrocarbyl; x and y have an average value, and are each independently 2-100, or 2-50, or 2-30, 2-20, or 2-15, or 2-10, or 2-8, provided that the sum of x and y is at least 2, or at least 3, or at least 4, up to 20 or up to 40 up to 50, or up to 100, or up to 200. In some aspects, each occurrence of Q1is independently methyl or cyclohexyl optionally substituted with an amine group having from 1- 12 carbon atoms, and each occurrence of Q2is halogen, unsubstituted C1-12 alkyl provided that the alkyl group is not tertiary alkyl, or unsubstituted C1-12 aryl. In some aspects, each occurrence of Q1is independently methyl or methyl substituted with a di(Ci-6 alkyl)amino group, and each Q2is methyl.

[0020] In formula (2), L can be of formula (3)wherein each occurrence of R3, R4, R5, and R6is independently hydrogen, halogen, unsubstituted or substituted C1-12 primary or secondary hydrocarbyl, unsubstituted or substituted C1-12 hydrocarbylthio, unsubstituted or substituted C1-12 hydrocarbyloxy, or unsubstituted or substituted C2-12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms; and Y is a single bond or a divalent linking group of the formulawherein each occurrence of Ra, Rb, Rc, Rd, and Reis independently hydrogen, C1-12 hydrocarbyl, or Ci -6 hydrocarbylene, optionally wherein Raand Rbor Rcand Rdtogether are a C4-8 alkylene group, each occurrence of R1is independently hydrogen, 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 of which can independently be substituted or unsubstituted, and R2is independently at each occurrence is a single bond, a unsubstituted or substituted C1-12 hydrocarbylene, or a unsubstituted or substituted C6-12 arylene, preferably an unsubstituted C2-8 alkylene, more preferably dimethylene, trimethylene, or tetramethylene; and E is, on average, 2-200, 2-125, 5-125, 5-100, 5-50, 20-80, 10-60, or 5-20.

[0021] In some aspects in formula (3), Y is a single bond or 2,2-dimethylisopropylidene; each occurrence of R3, R4, R5, and R6is independently hydrogen, halogen, unsubstituted or substituted C1-6 primary or secondary hydrocarbyl. In some aspects of formula (3), each occurrence of R3, R4, R5, and R6is independently hydrogen, halogen, or C1-12 alkyl, more preferably hydrogen or unsubstituted C1-6 alkyl.

[0022] Examples of dihydric phenols that can be used include 3,3',5,5'-tetramethyl-4,4'- biphenol, 2,2-bis(3-methyl-4-hydroxyphenyl)propane, 2,2-bis(3,5-dimethyl-4- hydroxyphenyl)propane, l,l-bis(4-hydroxyphenyl)methane, 1, l-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4- hydroxyphenyl)octane, 1 , 1 -bis(4-hydroxyphenyl)propane, 1 , 1 -bis(4-hydroxypheny 1 )-n-butane, bi s(4-hydroxyphenyl)phenylmethane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 1 , l-bis(4- hydroxy-3-methylphenyl)cyclohexane, 1 , 1 -bis(4-hydroxy-3 ,5-dimethylphenyl)cyclopentane, l,l-bis(4-hydroxy-3,5-dimethylphenyl)cyclohexane, l,l-bi(4-hydroxy-3- methylphenyl)cycloheptane, l,l-bis(4-hydroxy-3,5-dimethylphenyl)cycloheptane, 1,1 -bis(4-hydroxy-3-methylphenyl)cyclooctane, l,l-bis(4-hydroxy-3,5-dimethylphenyl)cyclooctane, 1,1 - bis(4-hydroxy-3-methylphenyl)cyclononane, l,l-bis(4-hydroxy-3,5- dimethylphenyl)cyclononane, 1 , 1 -bis(4-hydroxy-3-methylphenyl)cyclodecane, 1 , 1 -bis(4- hydroxy-3,5-dimethylphenyl)cyclodecane, l,l-bis(4-hydroxy-3-methylphenyl)cycloundecane,1 , 1 -bis(4-hydroxy-3 ,5 -dimethylphenyl)cycloundecane, 1 , 1 -bis(4-hydroxy-3- methylphenyl)cyclododecane, 1 , 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, a dihydric phenol of the formulawherein E is as described in formula 3, or a combination of the foregoing diphenols. In some aspects, the dihydric phenol includes 2,2-bis(3,5-dimethyl-4-hydroxyphenol)propane (bisphenol A).

[0023] The bifunctional poly(arylene ether) can have a structure of formula (5)wherein each occurrence of Q1, Q2, Q3, and Q4are as defined in formula (2); “> / vvv' ” indicates a link to an end group; each occurrence of R3, R4, R5, and R6, Y, x, and y are as defined in formula (3). In some aspects, each occurrence of Q1in formula (5) is independently methyl or cyclohexyl, optionally substituted with an amine group having from 1-12 carbon atoms, and each occurrence of Q2is halogen, unsubstituted C1-12 alkyl provided that the alkyl group is not tertiary alkyl, or unsubstituted C1-12 aryl. In some aspects, each occurrence of Q1in formula (5) is independently methyl or methyl substituted with a di(Ci-6 alkyl)amino group or a morpholinyl group.

[0024] In some aspects, the polyfunctional, e.g., bifunctional poly(arylene ether) is derived from 2,6-dimethyl phenol, 2,3,6-trimethyl phenol, or a combination thereof, in combination with 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane.

[0025] In some aspects, the end groups of the polyfunctional, e.g., bifunctional poly(arylene ether) can be of formula (6)wherein R10and R12are each independently hydrogen, halogen, or Ci-is alkyl, preferably hydrogen or Ci-6 alkyl; “' / uuv' ” is a link to the poly(arylene ether), m is 1-3, preferably 1-2, and each occurrence of n is 1 or more, for example 1-18, or 1-12, or 1-6, or 1-3. In some aspects, each occurrence of R10and R12are hydrogen. In some aspects, each occurrence of R10is hydrogen, and one occurrence of R12is hydrogen and one occurrence of R12is Ci-6 alkyl. In some aspects each n is 1.

[0026] Accordingly, in some aspects, the bifunctional poly(arylene ether) can be of formula (7)wherein each occurrence of Q1, Q2, Q3, and Q4, L, x, and y are as defined in formula (2); and each occurrence of R10, R12, m and n are as defined in formula (6).

[0027] In some aspects, the bifunctional poly(arylene ether) can be of formula (7a)wherein each occurrence of Q1, Q2, Q3, and Q4, L, x, and y re as defined in formula (2); and each occurrence of R12and n are as defined in formula (6). In some aspects, R12independently at each occurrence is hydrogen or methyl; and n is independently at each occurrence 0-15, provided that at least one occurrence of n is 1, preferably wherein each occurrence of n is at least 1. In some aspects, Q1and Q2are each methyl groups, Q3and Q4are each hydrogen, R is hydrogen, and n isindependently at each occurrence 0-5, provided that at least one occurrence of n is at least 1, or the sum of each occurrence of n has an average value of at least 1.8,

[0028] The polyfunctional, e.g., the bifunctional poly(arylene ether) can have a number average molecular weight (Mn) of 600-10,000, or 400-2,500 grams per mole (g / mol) as determined by gel permeation chromatography (GPC) using polystyrene standards. In some aspects, the polyfunctional, e.g., bifunctional poly(arylene ether) can have a weight average molecular weight (Mw) of 500-6,000 g / mol, each as determined by GPC using polystyrene standards. For example, the bifunctional hydroxy-terminated poly(arylene ether) can have a number average molecular weight (Mn) of 400-2,200 g / mol or 800-1,600 g / mol and a weight average molecular weight (Mw) of 600-5,000 g / mol or 800-4,500 g / mol, each as determined by GPC using polystyrene standards.

[0029] The polyfunctional, e.g., bifunctional poly(arylene ether) can have an intrinsic viscosity of 0.03-0.16 deciliter per gram (dL / g) as measured at 25°C in chloroform. For example, the intrinsic viscosity is preferably 0.06-0.1 dL / g, more preferably 0.075-0.090 dL / g, or 0.05-0.1 deciliter per gram, or 0.1-0.15 deciliter per gram.

[0030] The polyfunctional, e.g., bifunctional poly(arylene ether) can have a glass transition temperature of not more than 100°C, preferably not more than 80°C as determined according to differential scanning calorimetry (DSC) as per ASTM D3418 with a 20°C / min heating rate.

[0031] The polyfunctional, e.g., bifunctional poly(arylene ether) having the end groups as described herein is the product of a poly(arylene ether) having phenolic terminal groups reacted with an alkylene oxide. The poly(arylene ether) having phenolic end groups can be obtained by the oxidative copolymerization of monomers comprising a monohydric phenol, a dihydric phenol, or a combination thereof. Use of a poly (arylene ether) having two phenolic end groups provides the bifunctional poly(arylene ether). A polyfunctional poly(arylene ether) can be obtained by the oxidative copolymerization of monomers comprising a monohydric phenol, a dihydric phenol, or a combination thereof, together with a trihydric phenol or a tetrahydric phenol, or other branching group, and can be used to provide the polyfunctional poly(arylene ether).

[0032] The poly(arylene ether) having phenolic terminal groups can be referred to hereinafter as the “phenolic poly( arylene ether)”. The phenolic poly(arylene ether) can be formed by polymerization of monomers, for example, including a monohydric phenol, a dihydric phenol, or a combination thereof. In some aspects, the phenolic (arylene ether) is derived from 2,6-dimethyl phenol, 2,3,6-trimethyl phenol, or a combination thereof, in combination with 2,2- bis(3,5-dimethyl-4-hydroxyphenyl)propane. The polymerization can be by continuous additionof oxygen to a reaction mixture including the monomers, optionally a solvent, and a polymerization catalyst. The molecular oxygen (O2) can be provided as air or pure oxygen. The polymerization catalyst can be a metal complex, i.e. a metal catalyst, including a transition metal cation, including cations from Group VIB, VIIB, VIIIB, or IB of the periodic table, or a combination thereof. The catalyst can include a metal cation such as chromium, manganese, cobalt, copper, or combination thereof and an anion such as chloride, bromide, iodide, sulfate, acetate, propionate, butyrate, laurate, palmitate, benzoate, or a combination of one or more of these anions, and optionally one or more charge-neutral ligands such as water, amines, phosphines, CO, or the like. Alternatively, a metal or metal oxide and an inorganic acid, organic acid, or aqueous solution of such an acid can be combined to form a corresponding metal salt or hydrate in situ. For example, cuprous oxide and hydrobromic acid can be combined to generate cuprous bromide in situ.

[0033] Exemplary amine ligands can be, for example, a monoamine, an alkylene diamine, or a combination thereof. Monoamines include dialkylmonoamines (such as di-n- butylamine) and trialkylmonoamines (such as N,N-dimethylbutylamine). Exemplary monoamines include di-n-butylamine, n-butylethylamine, di-tert-butylamine, tertbutylethylamine, dimethylamine, di-n-propylamine, di-sec-butyl amine, dipentylamine, dihexylamine, dioctylamine, didecylamine, dibenzylamine, methylethylamine, methylbutylamine, dicyclohexylamine, N-ethylaniline, N-butyl aniline, N-methyl-2- methylaniline, N-methyl-2,6-dimethylaniline, diphenylamine, or a combination thereof. Exemplary diamines include a N,N'-di-tert-butylethylenediamine, or the like, or a combination thereof. Exemplary trialkylmonoamines include trimethylamine, triethylamine, tripropylamine, tributylamine, butyldimethylamine, phenyldiethylamine, or the like, or a combination thereof.

[0034] When the amine ligand includes a secondary amine such as di-n-butylamine, some of the secondary amine can be chemically incorporated into the poly(arylene ether) having phenolic terminal groups at the benzylic position of terminal monohydric phenol units. The covalently bound monoamine groups can be present as aminomethyl groups ortho to the phenol oxygen in terminal units as shown below:

[0035] The amount of covalently bound monoamine groups can be determined by1H- NMR spectroscopy. Covalently bound monoamine groups can adversely affect the oxidativestability of capped poly(arylene ether) and can result in yellowing of the capped poly(arylene ether) upon heat aging.

[0036] The phenolic poly(arylene ether), for example, phenolic poly(phenylene ether), which optionally can be in the form of a copolymer of two or more monomers, for example a terpolymer, and the raw materials used to produce the phenolic poly(arylene ether) poly(arylene ether) can be, or can be formed from, renewable, sustainable, bio-circular, circular, lower carbon footprint feedstocks, upcycled, and / or post-consumer / post-industrial recycled materials, including pyrolysis oil (“py-oil”).

[0037] The phenolic poly(arylene ether) made from renewable sources can include, for example, a bio-content or PCR content of up to 99.9%, 1-99%, or 5-95%, or 55-99%, or 80- 99%, or 1-50%, or 1-25%, or 1-15%, or 1-10%, or 1-5%, each 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 an ultra-high molecular weight phenolic poly (arylene ether). The weight average molecular weight (Mw)of the phenolic poly(arylene ether) in some aspects can be 600-200,000 g / mol as determined by GPC using polystyrene standards. In some aspects, the phenolic poly (arylene ether) can have an intrinsic viscosity of up to 1.5 dl / g as measured at 25°C in chloroform. The phenolic poly( arylene ether) made from renewable sources can include material made by a mass balance approach and certified by regulatory bodies such as, for example, the ISCC Plus.

[0038] Any of the components used in the polymerization reaction as described above or their synthetic precursors, or the solvents used in the process, can be bio-sourced, bio-circular, or renewable raw materials. Such components and precursors include monomers (e.g., monohydric phenol, dihydric phenol and other comonomers), reagents, solvents, catalysts (e.g., a metal source, a secondary alkylene diamine ligand, a tertiary monoamine, and optionally a secondary monoamine or alternatively enzyme catalysts), gases (e.g., oxygen gas), or a combination thereof. In some aspects, reaction components used in the polymerization of phenolic poly(arylene ether) can be from sources as listed in the EU Renewable Energy Directive Annex IX.

[0039] The phenolic poly(arylene ether) can be further processed, such as by redistribution, or any chemical derivatization, such as post-polymerization coupling, or end- group capping as described herein, to make other materials that can transfer the sustainability characteristic to the new material. Such reagents and / or their synthetic precursors can be sustainable, bio-sourced, bio-circular, or renewable raw materials, upcycled, and / or postconsumer / post-industrial recycled materials, including pyrolysis oil (“py-oil”), to produce the poly (arylene ether).

[0040] Biosourced and sustainable materials can be derived from biomass sources (a renewable organic material that comes from organic matter) or industrial sources such as waste (e.g., municipal waste). Lignocellulosic biomass is the most abundant type of biomass, and includes a wide variety of different biomass types including grasses, wood, energy crops, and agricultural and municipal wastes, and is mostly composed of cellulose, hemicellulose, and lignin. Depolymerization of lignin, which is a phenolic polymer, can provide phenol. Solvents used in the production of monomers, such as methanol and acetone can be obtained from syngas, which is a product of the gasification of biomass.

[0041] Poly(arylene ether), such as a recycled poly(arylene ether) comprising an open- or closed-loop post-consumer recycled (“PCR”) poly(arylene ether), an open- or closed-loop postindustrial recycled (“PIR”) poly(arylene ether), or upcycled polyphenylene ether or a combination thereof can be used, provided that the desired property or combination of properties can be achieved. As used herein, the term “PCR poly(arylene ether)” refers to a poly(arylene ether) that has reached the intended user or consumer and which has been collected or reclaimed after utilization by the end-user or consumer. Thus, the term refers to a poly (arylene ether) material in whole or in part that would have otherwise been disposed of as waste, but has instead been collected and recovered (reclaimed) as a material input, in lieu of a virgin material, for a recycling or manufacturing process. PCR-poly(arylene ether) is inclusive of material that has been reprocessed from collected or reclaimed material by means of a manufacturing process, (including e.g., purification, sorting, and pretreating) and made into a product or into a component for incorporation into a product. Such recycled poly(arylene ether)s can be further processed, for example, into the form of powders, ground materials, flakes, pellets, or other form. As used herein, the term “PIR poly(arylene ether)” refers to a poly(arylene ether) that has never reached the end user and that is production waste arising during polymerization reactions, during further processing, or during manufacturing the resin or an article and includes materials such as, but not limited to, sprues from injection molding, start-up material from injection molding or extrusion, extrusion scrap, molding scrap, edge trims from extruded sheets or films, and the like, including materials diverted from the waste stream during a manufacturing process for an article.

[0042] In some aspects, manufacture of the polyfunctional, e.g., bifunctional poly(arylene ether) is by reacting the phenolic poly(arylene ether) with an alkylene oxide. The phenolic poly( arylene ether) can first be converted to the metal salt by treatment with a base to provide a basic reaction mixture. Bases include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide, as well as alkaline earth hydroxides such as magnesium hydroxide and calcium hydroxide. In a preferred aspect, the base includessodium hydroxide or potassium hydroxide, more preferably potassium hydroxide. Both phenolic OH groups are converted to a phenoxide salt in this reaction. The base can be added in an amount of 1-10 mole percent, based on the total moles of the polyfunctional, e.g., bifunctional poly(arylene ether) hydroxyl groups. Within this range, the base can be added in an amount of 2- 7 mole percent, or 4-6 mole percent, each based on the total moles of the polyfunctional, e.g., bifunctional poly (arylene ether) hydroxyl groups.

[0043] The method further comprises removing water from the basic reaction mixture. Removing water from the basic reaction mixture can generally be by any method effective to reduce the concentration of water in the basic reaction mixture, for example evaporation, distillation, preferably to a concentration of 100 parts per million (ppm) or less. In some aspects, removing the water can comprise passing dry nitrogen through the basic reaction mixture for a time sufficient to reduce the moisture content to 100 ppm or less.

[0044] The end groups (the linking and the terminal functional group) can be introduced by reacting the dried basic reaction mixture including the salt of the phenolic poly(arylene ether), and preferably with 100 ppm or less of water, with an alkylene oxide (epoxide) of formula (8)wherein each R10, R12, and m is as described in formula (6). In some aspects, the alkylene oxide is of formula (8a)wherein p is 1-3, preferably 1-2, and R12is hydrogen or Ci-is primary alkyl, preferably hydrogen or Ci-6 alkyl, more preferably hydrogen or C1-3 alkyl. In some aspects, p is 1-3, R12is hydrogen or methyl, preferably p is 1-2 and R12is hydrogen, more preferably p is 1 and R12is hydrogen.

[0045] In some aspects, the alkylene oxide is of formula (8b)wherein R12is hydrogen or a substituted or unsubstituted Ci-is alkyl group, or an unsubstituted C1-6 alkyl group. The agent can include ethylene oxide, propylene oxide, or a combination thereof, or the agent can be ethylene oxide.

[0046] The alkylene oxide is combined with the dried basic reaction mixture in an amount effective to provide a molar ratio of alkylene oxide:poly(arylene ether) hydroxyl groups of 0.01:1 to 1:1, or 0.01:1 to 0.1:1, or 0.02:1 to 0.07:1.

[0047] After contacting with the alkylene oxide, a product mixture is provided, wherein the product mixture comprises the polyfunctional, e.g., bifunctional poly(arylene ether) including an end group, wherein the end group includes a linking group including a substituted or unsubstituted saturated hydrocarbyl group or a substituted or unsubstituted saturated poly(hydrocarbylene ether), and a terminal functional group including a hydroxyl group, a salt thereof, or a combination thereof.

[0048] The synthesis of the polyfunctional, e.g., bifunctional poly(arylene ether) having the end groups can be performed with or without a solvent. The solvent can preferably be an aromatic hydrocarbon solvent, for example a Ce-is aromatic hydrocarbon solvent. Suitable aromatic hydrocarbon solvents include, for example, benzene, toluene, xylenes, and the like, or a combination thereof. In some aspects, the aromatic hydrocarbon solvent comprises toluene. In addition to the aromatic hydrocarbon solvent, the solvent can, optionally, further comprise a C3-8 aliphatic alcohol that is a poor solvent for the poly (arylene ether), for example n-propanol, isopropanol, n-butanol, t-butanol, n-pentanol, and the like, or a combination thereof. A preferred C3-8 aliphatic alcohol is n-butanol. The solvent can further comprise, in addition to a Ce-is aromatic hydrocarbon and a C3-8 aliphatic alcohol, methanol or ethanol, which act as an antisolvent for the poly(arylene ether). The Ce-is aromatic hydrocarbon, the C3-8 aliphatic alcohol, and the methanol or ethanol can be combined in a wide range of proportions, but it can be preferred that the solvent comprise at least 50 wt% (wt%) of the Ce-is aromatic hydrocarbon. In some aspects, no solvents other than the aromatic hydrocarbon solvent are present. In a preferred aspect, the metal salt of the poly(arylene ether) having phenolic terminal groups is reacted with the alkylene oxide in the absence of solvent.

[0049] A catalyst can be used in the reaction of the phenolic poly(phenylene ether) salt with the alkylene oxide. Examples of such catalysts include those known to the art. For example, the catalyst can be a hydroxide salt such as sodium hydroxide, potassium hydroxide, tetraalkylammonium hydroxides, or the like; tertiary alkylamines such as tributyl amine, triethylamine, dimethylbenzylamine, dimethylbutylamine, or the like; tertiary mixed alkylarylamines and substituted derivatives thereof such as N,N-dimethylaniline; heterocyclic amines such as imidazoles, pyridines, and substituted derivatives thereof such as 2-methylimidazole, 2- vinylimidazole, 4-(dimethylamino)pyridine, 4-(l-pyrrolino)pyridine, 4-(l-piperidino)pyridine, 2- vinylpyridine, 3-vinylpyridine, 4-vinylpyridine, or the like.

[0050] Alternatively, the catalyst can be a transesterification catalyst that is capable of catalyzing transesterification of phenols with the capping agents described above can be used. For example, the capping catalyst can be a catalyst that includes a source of alkali or alkaline earth ions. The sources of these ions include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide, as well as alkaline earth hydroxides such as magnesium hydroxide and calcium hydroxide. Other sources of alkali and alkaline earth metal ions include the corresponding salts of carboxylic acids (such as sodium acetate) and derivatives of ethylene diamine tetraacetic acid (EDTA) (such as EDTA tetrasodium salt, and EDTA magnesium disodium salt). Other transesterification catalysts include alkali or alkaline earth metal salts of carbonate, such as CS2CO3, NaHCO s. and Na^COi. or the like, non-volatile inorganic acid such as NaFEPCh, NaFEPCE, Na2HPO3, KH2PO4, CSH2PO4, CS2HPO4, or the like, or mixed salts of phosphoric acid, such as NaKHPO4, CsNaHPO4, CSKHPO4, or the like. Combinations of the foregoing catalysts can be used.

[0051] The process can further include isolating the polyfunctional, e.g., bifunctional poly(arylene ether) having the end group from the reaction mixture. Suitable methods include precipitation and total isolation methods. A total isolation process can be used for isolating the polyfunctional, e.g., bifunctional poly(arylene ether) having the end groups when the intrinsic viscosity (I.V.) is less than about 0.25 deciliters per gram (dL / g), as measured in chloroform at 25 °C. As part of the total isolation, a portion of the solvent is preferably removed to reduce the solvent load on the total isolation equipment. Concentration of the polyfunctional, e.g., bifunctional poly(arylene ether)-containing solution is preferably done by reducing the pressure in a solvent flash vessel while preferably increasing the temperature of the solution. The isolated polyfunctional, e.g., bifunctional poly(arylene ether) can be dried at a temperature that is below the softening temperature or Tgof the polyfunctional poly (arylene ether).

[0052] It will be understood that when the polyfunctional, e.g., bifunctional poly(arylene ether) (7) or (7a) obtained by this process is present in the salt form, the hydrogen of the terminal hydroxyl groups can be replaced in whole or in part with a cationic counterion (e.g., an alkali metal or an alkaline earth metal). The bifunctional poly(arylene ether) comprising the end group comprises an average of at least 1.8 terminal substituted or unsubstituted saturated hydrocarbyl alcohol terminal functional groups, a salt thereof, or a combination thereof.

[0053] The process described herein can have advantages over known methods of providing bifunctional poly (arylene ethers), which can use the following reagents to incorporate a saturated hydrocarbylene group.wherein R9to R12, R15to R16, and R20to R23are each independently hydrogen, C1-12 primary alkyl, C2-12 alkenyl, C7-12 arylalkyl, C2-12 alkoxyalkyl, C7-12 aryloxyalkyl, or C1-12 hydroxyalkyl, preferably hydrogen or C1-6 alkyl. Thus, another advantage of the poly(arylene ethers) and methods described herein is that reagents such as those of Formulas (9)-(l 1) are excluded, thus avoiding the formation of side-products. For example, reaction with a reagent of formula (9) results in the formation of a carbonate side product, formula (10) is not widely commercially available and can form elimination products, and reaction with formula (11) results in the formation of an ester side product.

[0054] An example of the end group including a carbonate-containing linking group side-product resulting from use of ethylene carbonate is depicted below for illustrative purposes only.

[0055] An example of the end group comprising an ester-containing linking group sideproduct is depicted below for illustrative purposes only.OO— (CH2)2-O-C - (CH2)2--OHLinking group

[0001] In some aspects, a composition including the polyfunctional, e.g., bifunctional poly(arylene ether) minimizes or eliminates the presence of products other than the polyfunctional, e.g., bifunctional poly(arylene ether). Accordingly, in some aspects, the curable composition does not include a carbonate functional group, an ester functional group, or a combination thereof in an end group of the polyfunctional, e.g., bifunctional poly( arylene ether). Stated another way, in some aspects, the linking group of the polyfunctional poly( arylene ether) made by the methods described herein includes 0-5,000 parts per million by weight (ppm), 0-2,500 ppm, or 0-1,000 ppm, or 0-500 ppm, or 50-5,000 ppm, or 50-2,500 ppm, or 50-1,000 ppm, or 50-500 ppm, or less than 50 ppm of a poly(arylene ether) comprising a linking group comprising a carbonate functional group; or 0-5,000 ppm, 0-2,500 ppm, or 0-1,000 ppm, or 0- 500 ppm, or 50-5,000 ppm, or 50-2,500 ppm, or 50-1,000 ppm, or 50-500 ppm, or less than 50 ppm of a poly(arylene ether) comprising a linking group comprising an ester functional group; or a combination thereof. The amount of the carbonate functional group and the ester functional group can be determined, for example by proton nuclear magnetic resonance (^H NMR) spectroscopy. In some aspects, the composition is free of carbonate-containing polyfunctional poly(arylene ethers) and ester-containing polyfunctional poly( arylene ethers).

[0056] The elimination of carbonate and ester linking groups in the polyfunctional, e.g., bifunctional poly(arylene ethers) is advantageous because the final products that are derived from the polyfunctional, e.g., bifunctional poly(arylene ethers) can have improved hydrolytic and thermal stability.

[0057] In some aspects, the method of providing the polyfunctional, e.g., bifunctional poly(phenylene ether) does not use a capping agent comprising a carbonate, for example according to Formula (9). When a carbonate-containing capping agent is not used to provide the polyfunctional, e.g., bifunctional poly(phenylene ether), the product can advantageously exclude carbonate linkages. Thus, the curable composition can comprise 0-5,000 ppm of a poly(arylene ether) comprising a linking group comprising a carbonate functional group.

[0058] The polyfunctional, e.g., bifunctional poly(arylene ether) can be present in the curable composition in an amount of 1-90 wt%, based on the total weight of the curable composition. Within this range, the polyfunctional, e.g., bifunctional poly(phenylene ether) can be present in the curable composition in an amount of at least 5 wt%, or at least 10 wt%, or at least 15 wt%, or at least 20 wt%, or at least 30 wt%, or at least 40 wt%, or at least 45 wt%, or at least 50 wt%, each based on the total weight of the curable composition. Also within this range, the polyfunctional, e.g., bifunctional poly(phenylene ether) can be present in the curable composition in an amount of less than or equal to 85 wt%, or less than or equal to 80 wt%, or less than or equal to 75 wt%, or less than or equal to 70 wt%, or less than or equal to 60 wt%, or less than or equal to 50 wt%, each based on the total weight of the curable composition.

[0059] In addition to the polyfunctional, e.g., bifunctional poly(phenylene ether), the curable composition comprises a curable component. The curable component is at least partially miscible with the polyfunctional, e.g., bifunctional poly(phenylene ether) at a temperature of 15- 100°C. The curable component can include, but is not limited to, an epoxy resin, cyanate ester resin, benzoxazine resin, vinyl resin, esterimide resin, silicone resin, a bismaleimide resin, or a combination of two or more of the foregoing curable components. The term “resin” as usedherein refers to oligomers and monomers that are reactive to form an at least partially cured material.

[0060] Examples of epoxy resins can include bisphenol A epoxy resins, glycidylamine epoxy resins, novolak epoxy resins, modified bisphenol A epoxy resins, alicyclic epoxy resins; and epoxy resins derived from Bisphenol F, resorcinol, tetramethyl biphenol, tetrahydroxyphenylethane, polyalcohols, polyglycols, and the like. The epoxy resins can comprise difunctional epoxy compounds, polyfunctional epoxy compounds or a combination thereof. As used herein, the term difunctional epoxy compound refers to a compound having two epoxy groups per molecule. The term polyfunctional epoxy compound refers to a compound having more than two epoxy groups per molecule.

[0061] Examples of vinyl resins include triallyl cyanurate, triallyl isocyanurate, styrene, butadiene, vinyl esters, or a combination thereof. In some aspects, the curable component comprises cyanate ester resin, vinyl resin, difunctional epoxy compounds, cresol novolac epoxy resin, or a combination thereof. In some aspects, the curable component is an epoxy resin, for example a bisphenol A epoxy resin, which is a reaction product of bisphenol A and epichlorohydrin.

[0062] The curable composition can comprise the curable component in an amount of 10-99 wt%, based on the total weight of the curable composition. Within this range, the curable component can be present in an amount of at least 15 wt%, or at least 20 wt%, or at least 25 wt%, or at least 30 wt%, or at least 40 wt%, or at least 50 wt%, each based on the total weight of the curable composition. Also within this range, the curable component can be present in an amount of less than or equal to 95 wt%, or less than or equal to 90 wt%, or less than or equal to 85 wt%, or less than or equal to 80 wt%, or less than or equal to 70 wt%, or less than or equal to 60 wt%, or less than or equal to 55 wt%, or less than or equal to 50 wt%, each based on the total weight of the curable composition.

[0063] In addition to the polyfunctional, e.g., bifunctional poly(phenylene ether) and the curable component, the curable composition can optionally further include one or more of a curing agent, a curing catalyst, a curing initiator, or a combination thereof.

[0064] As used herein, the term “curing agent” includes compounds that are variously described as curing agents, hardeners, or the like, or as both. Exemplary curing agents and hardeners include amines, alcohols, phenols, carboxylic acids, acid anhydrides, and the like. For example, phenolic hardeners include novolac type phenol resins, resole type phenol resins, cresol novolac resins, aralkyl type phenol resins, phenol aralkyl resins, cresol aralkyl resins, naphthol aralkyl resins, dicyclopentadiene type phenol resins, terpene modified phenol resins, biphenyl type phenol resins, biphenyl-modified phenol aralkyl resins, bisphenols,triphenylmethane type phenol resins, tetraphenylol ethane resins, naphthol novolac resins, naphthol-phenol co-condensed novolac resins, naphthol-cresol co-condensed novolac resins, amino triazine modified phenol resins, or a combination thereof. Examples of the anhydride hardeners include methylhexahydrophthalic anhydride (MHHPA), methyltetrahydrophthalic anhydride, styrene-maleic anhydride copolymers (SMA), and olefin-maleic anhydride copolymers such as maleic anhydride grafted polyethylene, maleic anhydride grafted polypropylene, or a combination thereof. Other curing agents and hardeners include compounds such as dicyandiamides, polyamides, amidoamines, phenalkamines, Mannich bases, anhydrides, phenol-formaldehyde resins, amine-formaldehyde resins, phenol-formaldehyde resins, carboxylic acid functional polyesters, polysulfides, polymercaptans, isocyanates, cyanate ester compounds, or any combination thereof. Other exemplary curing agents include tertiary amines, Lewis acids, and oligomers or polymers with unsaturation.

[0065] When the curable thermosetting composition includes a curing agent, the curing agent can be included in an amount of 0.01-50 wt%, or 0.1-30 wt%, or 0.1-20 wt%, based on total weight of the curable thermosetting composition.

[0066] The curable thermosetting composition can include a curing catalyst. As used herein, the term “curing catalyst” includes compounds that are variously described as curing accelerators, curing promoters, curing catalysts, and curing co-catalysts.

[0067] Exemplary curing accelerators include heterocyclic accelerators such as a substituted or unsubstituted C3-6 heterocycle comprising 1-4 ring heteroatoms, wherein each heteroatom is independently the same or different, and is nitrogen, oxygen, phosphorus, silicon, or sulfur. Heterocyclic accelerators include benzotriazoles; triazines; piperazines such as aminoethylpiperazine, N-(3-aminopropyl)piperazine, or the like; imidazoles such as 1- methylimidazole, 2-methylimidazole, 3-methyl imidazole, 4-methylimidazole, 5- methylimidazole, 1 -ethylimidazole, 2-ethylimidazole, 3-ethylimidazole, 4-ethylimidazole, 5- ethylimidazole, 1-n-propylimidazole, 2-n-propylimidazole, 1 -isopropylimidazole, 2- isopropylimidazole, 1-n-butylimidazole, 2-n-butylimidazole, 1 -isobutylimidazole, 2- isobutylimidazole, 2-undecyl-lH-imidazole, 2-heptadecyl-lH-imidazole, 1 ,2-dimethylimidazole, 1,3-dimethylimidazole, 2,4-dimethylimidazole, 2-ethyl-4-methylimidazole, 1 -phenylimidazole, 2-phenyl-lH-imidazole, 4-methyl-2-phenyl-lH-imidazole, 2-phenyl-4-methylimidazole, 1- benzyl-2-methylimidazole, l-benzyl-2-phenylimidazole, l-cyanoethyl-2-methylimidazole, 1- cyanoethyl-2-ethyl-4-methylimidazole, 1 -cyanoethyl-2-undecylimidazole, 1 -cyanoethyl-2- phenylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5- hydroxymethylimidazole, 1 -cyanoethyl-2-phenyl-4,5-di(2-cyanoethoxy)methylimidazole; cyclic amidine such as 4-diazabicyclo(2,2,2)octane, diazabicycloundecene, 2-phenyl imidazoline, orthe like; N,N-dimethylaminopyridine; a sulfamidate; or a combination thereof.

[0068] Amine curing accelerators include isophoronediamine, triethylenetetraamine, diethylenetriamine, 1,2- and 1,3 -diaminopropane, 2,2-dimethylpropylenediamine,1.4-diaminobutane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8 -diaminooctane, 1 ,9-diaminononane, 1 , 12-diaminododecane, 4-azaheptamethylenediamine, N,N’-bis(3-aminopropyl)butane-l,4-diamine, dicyanamide, diamide diphenylmethane, diamide diphenylsulfonic acid (amine adduct), 4,4’ -methylenedianiline, diethyltoluenediamine, m-phenylenediamine, p-phenylenediamine, melamine formaldehyde resins, urea formaldehyde resins, tetraethylenepentamine, 3-diethylaminopropylamine, 3,3’-iminobispropylamine, 2,4- bis(p-aminobenzyl)aniline, tetraethylenepentamine, 3-diethylaminopropylamine, 2,2,4- and2.4.4-trimethylhexamethylenediamine, 1,2- and 1,3-diaminocyclohexane, l,4-diamino-3,6- diethylcyclohexane, l,2-diamino-4-ethylcyclohexane, l,4-diamino-3,6-diethylcyclohexane, l-cyclohexyl-3,4-diminocyclohexane, 4,4’-diaminondicyclohexylmethane,4,4’ -diaminodicyclohexylpropane, 2,2-bis(4-aminocyclohexyl)propane, 3,3’-dimethyl-4,4’- diaminodicyclohexylmethane, 3-amino-l -cyclohexaneaminopropane, 1,3- and 1,4- bis(aminomethyl)cyclohexane, m- and p-xylylenediamine, or diethyl toluene diamines; or a tertiary amine hardening accelerator such as triethylamine, tributylamine, dimethylaniline, diethylaniline, benzyldimethylamine (BDMA), a-methylbenzyldimethylamine, N,N-dimethyl amino pyridine, A,A-dimethylaminoethanol, / V, / V-dimcthylaminocrcsol, or trif / V. / V- dimethylaminomethyl)phenol; or a combination thereof.

[0069] The curing accelerator can be a latent cationic cure catalyst including, for example, diaryliodonium salts, phosphonic acid esters, sulfonic acid esters, carboxylic acid esters, phosphonic ylides, triarylsulfonium salts, benzylsulfonium salts, aryldiazonium salts, benzylpyridinium salts, benzylammonium salts, isoxazolium salts, or the like, or a combination thereof. The diaryliodonium salt can have the structure [(R1O)(RU)I]+X" , wherein R10and R11are each independently a Ce-i4 monovalent aromatic hydrocarbon radical, optionally substituted with from 1-4 monovalent radicals selected from C1-20 alkyl, C1-20 alkoxy, nitro, and chloro; and wherein X- is an anion. The additional cure accelerator can have the structure [(R1O)(RU)I]+SbFe" , wherein R10and R11are each independently a Ce-14 monovalent aromatic hydrocarbon, optionally substituted with from 1-4 C1-20 alkyl, C1-20 alkoxy, nitro, or chloro; for example, 4- octyloxyphenyl phenyl iodonium hexafluoroantimonate.

[0070] The curing accelerator can be a metal salt complex, such as a copper (II) aluminum (III), zinc, cobalt, tin salt of an aliphatic or aromatic carboxylic acid selected from copper (II), tin (II), and aluminum (III) salts of acetate, stearate, gluconate, citrate, benzoate, and mixtures thereof. For example, the cure accelerator can be a copper (II) or aluminum (III) saltsof P-diketonates; copper (II), iron (II), iron (III), cobalt (II), cobalt (III), or aluminum (III) salts of acetylacetonates; zinc (II), chromium (II), or manganese (II) salts of octoates; or a combination thereof.

[0071] When the curable thermosetting composition includes a curing catalyst, the curing catalyst can be included in an amount of 0.01-5 wt%, or 0.05-5 wt%, or 0.1-5 wt%, based on total weight of the curable thermosetting composition.

[0072] The curable thermosetting composition can optionally include a curing initiator, such as a peroxide compound. Exemplary peroxide curing initiators can include benzoyl peroxide, dicumyl peroxide, methyl ethyl ketone peroxide, lauryl peroxide, cyclohexanone peroxide, t-butyl hydroperoxide, t-butyl benzene hydroperoxide, t-butyl peroctoate, t- butylperoxybenzoate, t-butylperoxy 2-ethylhexyl carbonate, 2,4-dichlorobenzoyl peroxide, 2,5- dimethylhexane-2,5-dihydroperoxide, butyl-4,4-bis(tert-butyldioxy)valerate, 2,5-dimethyl-2,5- di(t-butylperoxy)-hex-3-yne, di-t-butylperoxide, t-butylcumyl peroxide, a,a'-bis(t-butylperoxy- m-isopropyl)benzene, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, dicumylperoxide, di(t- butylperoxy isophthalate, t-butylperoxybenzoate, 2,2-bis(t-butylperoxy)butane, 2,2-bis(t- butylperoxy)octane, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, l,l-di-(tert-butylperoxy)-3,3,5- trimethylcyclohexane, di(trimethylsilyl)peroxide, trimethylsilylphenyltriphenylsilyl peroxide, or the like, or a combination thereof.

[0073] When the curable thermosetting composition includes a curing initiator, the curing initiator can be included in an amount of 0.1-5 wt%, or 0.5-5 wt%, or 1-5 wt%, based on total weight of the curable thermosetting composition.

[0074] The curable thermosetting composition can optionally include a solvent. The solvent can be, for example, a C3-8 ketone, a C3-8 / V, / V-dialkylamidc, a C4-16 dialkyl ether, a C6-12 aromatic hydrocarbon, a C1-3 chlorinated hydrocarbon, a C3-6 alkyl alkanoate, a C2-6 alkyl cyanide, or a combination thereof. Specific ketone solvents include, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, or a combination thereof. Specific C4-8 N,N- dialkylamide solvents include, for example, dimethylformamide, dimethylacetamide, / V-mcthyl- 2-pyrrolidone, or a combination thereof. Specific dialkyl ether solvents include, for example, tetrahydrofuran, ethylene glycol monomethylether, dioxane, or a combination thereof. Specific aromatic hydrocarbon solvents include, for example, benzene, toluene, xylenes, styrene, divinylbenzenes, or a combination thereof. The aromatic hydrocarbon solvent can be nonhalogenated. Specific C3-6 alkyl alkanoates include, for example, methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, or a combination thereof. Specific C2-6 alkyl cyanides include, for example, acetonitrile, propionitrile, butyronitrile, or a combination thereof. Specific C2-6 alkyl cyanides include, for example, acetonitrile, propionitrile, butyronitrile, or acombination thereof. For example, the solvent can be N,N-dimethylformamide, N,N- dimethylacetamide, N,N-diethylacetamide, N,N-dimethylmethoxyacetamide, N-methyl-2- pyrrolidone, N-cyclohexylpyrrolidinone, N-methylcaprolactam, l,3-dimethyl-2-imidazolidone, 1 ,2-dimethoxyethane, 1,3-dioxane, 1,4-dioxane, tetrahydrofuran, y-butyrolactone, y- caprolactone, dimethylsulfoxide, benzophenone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diglyme, triglyme, tetraglyme, N,N-dimethylethyleneurea, N,N- dimethylpropyleneurea, tetramethylurea, propylene glycol phenyl ether, anisole, veratrole, o- dichlorobenzene, chlorobenzene, trichloroethane, methylene chloride, chloroform, pyridine, picoline, ethyl lactate, n-butyl acetate, butyl cellosolve acetate, butyl carbitol acetate, ethyl cellosolve acetate, ethyl carbitol acetate, propylene carbonate, sulfolane, an ionic liquid, or a combination thereof.

[0075] When a solvent is utilized, the curable thermosetting composition can include 2- 99 wt% of the solvent, based on weight total of the curable thermosetting composition. For example, the solvent amount can be 5-80 wt%, or 10-60 wt%, or 20-50 wt%, based on weight total of the curable thermosetting composition. The solvent can be chosen, in part, to adjust the viscosity of the curable thermosetting composition. Thus, the solvent amount can depend on variables including the type and amount of capped poly(arylene ether) copolymer, the type and amount of other components such as curing additive, the type and amount of any auxiliary thermosetting resin(s), and the processing temperature used for any subsequent processing of the curable thermosetting composition, for example, impregnation of a reinforcing structure with the curable thermosetting composition for the preparation of a composite. The solvent can be anhydrous. For example, the solvent can include less than 100 parts per million (ppm), or less than 50 ppm, or less than 10 ppm of water based on total weight of the solvent.

[0076] The curable thermosetting composition can further include a curable unsaturated monomer composition, which can include, for example, a monofunctional styrenic compound (e.g., styrene), a monofunctional (meth)acrylic compound, or the like, or a combination thereof. For example, the curable unsaturated monomer composition can be an alkene-containing monomer or an alkyne-containing monomer. Exemplary alkene- and alkyne-containing monomers includes those described in U.S. Patent No. 6,627,704 to Yeager et al., and include (meth)acrylates, (meth)acrylamides, N- vinylpyrrolidone, and vinylazalactones as disclosed in U.S. Pat. No. 4,304,705 of Heilman et al. Exemplary monofunctional monomers include mono(meth)acrylates, such as methyl (meth)acrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate, isooctyl (meth)acrylate, isobornyl (meth)acrylate, (meth)acrylic acid, n-hexyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, N-vinylcaprolactam, N-vinylpyrrolidone, (meth)acrylonitrile, or the like, or a combination thereof.

[0077] Advantageously, the curable composition as described herein does not require the use of a solvent or a reactive diluent. For example, in some aspects, the curable composition can comprise less than 5 wt%, or less than 1 wt%, or less than 0.1 wt% of each of a solvent or a reactive diluent, wherein wt% is based on the total weight of the curable composition. In some aspects, the curable composition can be devoid of a solvent, a reactive diluent, or both.

[0078] The composition can, optionally, further include one or more additives selected from the group consisting of dyes, pigments, colorants, antioxidants, heat stabilizers, light stabilizers, plasticizers, lubricants, flow modifiers, drip retardants, flame retardants, antiblocking agents, antistatic agents, flow-promoting agents, processing aids, substrate adhesion agents, toughening agents, low-profile additives, stress-relief additives, air release additives, wetting and dispersing agents, surface and leveling agents, or a combination thereof. When present, additives are generally used in an amount of 0.1-10 wt%, based on the total weight of the curable composition, for example 0.5-5 wt%, or 0.5-2 wt%.

[0079] The curable composition can be prepared by combining the polyfunctional, e.g., bifunctional poly(phenylene ether), the curable component, and the other optional components disclosed herein, using any suitable method.

[0080] A cured thermoset composition includes a cured product of the curable composition. There is no particular 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. For example, a cured product can be obtained by heating the curable composition defined herein for a time and at a temperature sufficient effect curing, including evaporating solvent, when present.

[0081] When heat curing is used, the temperature can be 30-400°C, or 50-250°C, or 100- 250°C. The heating can be for 1 minute to 24 hours, or 1 minute to 6 hours, or 3-5 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.

[0082] The cured thermoset composition can have one or more desirable properties. For example, the thermoset composition can have higher thermal resistance, better dielectric properties, lower moisture absorption, or a combination thereof.

[0083] The curable thermosetting compositions and cured thermoset compositions can be used in a variety of applications, including any applications where conventional thermosetting compositions are used. For example, useful articles including the curable thermosetting composition or the cured thermoset composition can be in the form of a composite, a foam, a fiber, a layer, a coating, an encapsulant, an adhesive, a sealant, a molded component, a prepreg, acasing, a laminate, a metal clad laminate, an electronic composite, a structural composite, or a combination thereof. Exemplary uses and applications include coatings such as protective coatings, sealants, weather resistant coatings, scratch resistant coatings, and electrical insulative coatings; adhesives; binders; glues; composite materials such as those using carbon fiber and fiberglass reinforcements. When utilized as a coating, the disclosed compounds and compositions can be deposited on a surface of a variety of underlying substrates. For example, the compositions can be deposited on a surface of metals, plastics, glass, fiber sizings, ceramics, stone, wood, or any combination thereof. The disclosed compositions can be used as a coating on a surface of a metal container (e.g., aluminum or steel), such as those commonly used for packaging and containment in the paint and surface covering industries. The curable thermosetting composition and the cured thermoset composition derived therefrom can also be particularly well suited for use in forming electrical components and computer components.

[0084] Methods of forming a composite can include impregnating a reinforcing structure with a curable thermosetting composition; partially curing the curable thermosetting composition to form a prepreg; and laminating a plurality of prepregs. The reinforcing structure can be a porous base material such as a fibrous preform or substrate, or other porous material comprising 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 comprise 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 thermosetting components of the curable thermosetting composition.

[0085] The method of manufacturing the articles from the curable thermosetting composition can include partially curing the curable thermosetting composition to form aprepreg, or fully curing the curable thermosetting composition to form a composite article. References herein to properties of the “cured composition” refer to a composition that is substantially fully cured. For example, the resin in a laminate formed from prepregs is typically substantially fully cured. One skilled in the thermoset arts can determine whether a sample is partially cured or substantially fully cured without undue experimentation. The curing can be before or after removing the solvent from the curable composition. In addition, the article can be further shaped before removal of the solvent or after removal of the solvent, before curing, after partial curing, or after full curing, for example by thermoforming. In some aspects, the article is formed, and the solvent is removed; the article is partially cured (B -staged); optionally shaped; and then further cured.

[0086] Commercial-scale methods of forming composites are known in the art, and the curable thermosetting compositions described herein are readily adaptable to existing processes and equipment. For example, prepregs are often produced on treaters. The main components of a treater include feeder rollers, a resin impregnation tank, a treater oven, and receiver rollers. The reinforcing structure (E-glass, for example) is usually rolled into a large spool. The spool is then put on the feeder rollers that turn and slowly roll out the reinforcing structure. The reinforcing structure then moves through the resin impregnation tank, which contains the curable thermosetting composition. The curable composition impregnates the reinforcing structure. After emerging from the tank, the coated reinforcing structure moves upward through the vertical treater oven, which is typically at a temperature of 175-200°C, and the solvent is evaporated. The resin begins to polymerize at this time. When the composite comes out of the tower it is sufficiently cured so that the web is not wet or tacky. The cure process, however, is stopped short of completion so that additional curing can occur when laminate is made. The web then rolls the prepreg onto a receiver roll.

[0087] Electrical and electronic articles including or derived from the curable thermosetting composition are also provided. Articles include those comprising printed circuits as used in medical or aerospace industries. Still other articles include antennae and like articles. Articles such as printed circuit boards are used, for example, in lighting, solar energy, displays, cameras, audio and video equipment, personal computers, mobile telephones, electronic notepads, and similar devices, or office automation equipment. For example, electrical parts can be mounted on printed circuit boards comprising a laminate. Other exemplary articles prepared from the curable composition for various applications can include copper clad laminates (CCL), for example, metal core copper clad laminates (MCCCL), composite articles, and coated articles, for example multilayer articles.

[0088] A dielectric layer prepared from the curable thermosetting composition can beuseful in a circuit assembly, for example, in a metal-clad laminate such as a copper clad laminate. For example, a laminate can comprise a dielectric layer, a conductive metal circuit layer disposed on the dielectric layer, and optionally, a heat dissipating metal matrix layer disposed on the dielectric layer 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.

[0089] The conductive metal layer can be in the form of a circuit, and can be copper, zinc, tin, brass, chromium, molybdenum, nickel, cobalt, aluminum, stainless steel, iron, gold, silver, platinum, titanium, or the like, or a combination thereof. Other metals include a copper molybdenum alloy, a nickel-cobalt iron alloy such as KOVAR, available from Carpenter Technology Corporation, a nickel-iron alloy such as INVAR, available from National Electronic Alloys, Inc., a bimetal, a trimetal, a trimetal derived from two-layers of copper and one layer of INVAR, and a trimetal derived from two layers of copper and one layer of molybdenum. Exemplary metal layers comprise copper or a copper alloy. Alternatively, wrought copper foils can be used. Conductive metal layers can have a thickness of 2-200 micrometers (pm), or 5-50 pm, or 5-40 pm.

[0090] A heat-dissipating metal matrix layer can be a thermally conductive metal such as aluminum, boron nitride, aluminum nitride, copper, iron, steel, or the like, or a combination thereof. A thermally conductive, electrically conductive metal can be used provided that the metal is electrically isolated from the metal circuit layer. Preferred supporting metal matrix layers can have a thickness of 0.1-20 millimeters (mm), or 0.5-10 mm, or 0.8-2 mm.

[0091] 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.

[0092] 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 anadhesive-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.

[0093] 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.

[0094] Multilayer laminates including additional layers can also be made by thermal lamination in one step or in two or more consecutive steps by such processes as hot press or roll calendaring methods. For example, seven layers or fewer can be present in the laminate, or sixteen layers or fewer. In some aspects, a laminate can be formed in one step or in two or more consecutive steps with sequential layers of fabric-thermoset-metal-thermoset-fabric-thermoset- metal foil or a sub-combination thereof with fewer layers, such that the laminate comprises 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.

[0095] Printed circuit boards prepared from the curable thermosetting composition can have an overall thickness of 0.1-20 mm, or 0.5-10 mm, wherein overall thickness refers to an assembly comprising a layer each of the dielectric layer, the electrically conductive metal layer, and the supporting metal matrix layer. Circuit assemblies can have an overall thickness of 0.5-2 mm, or 0.5-1.5. There is no particular limitation on the thickness of the dielectric layer and can be 5-1500 m, or 5-750 pm, or 10-150 pm, or 10-100 pm. For example, the printed circuit board can be a metal core printed circuit board (MCPCB) for use in a light emitting diode (LED) application.

[0096] The curable thermosetting 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 thermosetting composition and optionally a fluoropolymer and forming a coating on a substrate. For example, a multilayer article can be manufactured by forming a layerincluding the curable thermosetting composition, removing the solvent from the layer and optionally curing to provide a primer layer, forming a second layer comprising a ceramic (e.g., AI2O3, TiCh, Z1O2. CnCh, SiCh, MgO, BeO, Y2O3, AhCh-SiCh, MgO-ZrCh, SiC, WC, B4C, TiC, Si3N4, TiN, BN, AIN, TiB, ZrB2, or the like), a thermoplastic polymer, a fluoropolymer (e.g., polytetrafluoroethylene, tetrafluoroethylene-perfluoroalkylvinylether copolymers, tetrafluoroethylene-hexafluoropropylene copolymers, polychlorotrifluoroethylene, tetrafluoroethylene-ethylene copolymers, polyvinylidene fluoride, or the like), or a combination thereof on the primer layer to provide the multilayer article, and optionally thermally treating the multilayer article to cure the curable thermosetting composition. In some aspects, the second layer can further include the curable thermosetting composition.

[0097] 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 structuralmembers, gratings, and safety rails; swimming pools, swimming pool slides, hot-tubs, and saunas; drive shafts for under the hood applications; dry toner resins for copying machines; marine tooling and composites; heat shields; submarine hulls; prototype generation; development of experimental models; laminated trim; drilling fixtures; bonding jigs; inspection fixtures; industrial metal forming dies; aircraft stretch block and hammer forms; vacuum molding tools; flooring, including flooring for production and assembly areas, clean rooms, machine shops, control rooms, laboratories, parking garages, freezers, coolers, and outdoor loading docks; electrically conductive compositions for antistatic applications; for decorative flooring; expansion joints for bridges; injectable mortars for patch and repair of cracks in structural concrete; grouting for tile; machinery rails; metal dowels; bolts and posts; repair of oil and fuel storage tanks, and numerous other applications.

[0098] Processes useful for preparing the articles and materials include those generally known to the art for the processing of thermosetting resins. Such processes have been described in the literature as in, for example, Engineered Materials Handbook, Volume 1, Composites, ASM International Metals Park, Ohio, copyright 1987 Cyril A. Dostal Senior Ed, pp. 105-168 and 497-533, and “Polyesters and Their Applications” by Bjorksten Research Laboratories, Johan Bjorksten (pres.) Henry Tovey (Ch. Lit. Ass.), Betty Harker (Ad. Ass.), James Henning (Ad. Ass.), Reinhold Publishing Corporation, New York, 1956. Processing techniques include resin transfer molding; sheet molding; bulk molding; pultrusion; injection molding, including reaction injection molding (RIM); atmospheric pressure molding (APM); casting, including centrifugal and static casting open mold casting; lamination including wet or dry lay up and spray lay up; also included are contact molding, including cylindrical contact molding; compression molding; including vacuum assisted resin transfer molding and chemically-assisted resin transfer molding; matched tool molding; autoclave curing; thermal curing in air; vacuum bagging; pultrusion; Seeman's composite resin infusion manufacturing processing (SCRIMP); open molding with continuous combination of resin and glass; and filament winding, including cylindrical filament winding. An article can be prepared by a resin transfer molding process.

[0099] Also provided is an article derived from the curable thermosetting composition, wherein the article is a composite, a foam, a fiber, a layer, a coating, an encapsulant, an adhesive, a sealant, a molded component, a prepreg, a casing, a cast article, a laminate, or a combination thereof; or, wherein the article is a metal clad laminate, an electronic composite, a structural composite, or a combination thereof. Articles can be manufactured as disclosed herein, for example by casting, molding, extruding, or the like, and removing the solvent from the formed article. In some aspects, the article can be a layer, and can be formed by casting the curable composition onto a substrate to form a cast layer. The solvent can be removed by anynumber 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 can be one or more painted layers. The curable compositions can be used to prepare articles as disclosed herein for other curable thermosetting compositions.

[0100] This disclosure is further illustrated by the following examples, which are nonlimiting.EXAMPLESPreparative Example 1

[0101] Synthesis of PPE-2EO. In a reaction vessel the desired amount of o-xylene was added. A 40 wt% solution of PPE was the target. The PPE used was S A90 available from SABIC. Heating the vessel to 100°C and stirring provided a solution. When the PPE was fully dissolved in o-xylene, the appropriate amount of potassium bicarbonate was added. Before adding ethylene carbonate, the vessel was heated to between 45 and 70°C. When all the reagents were added, the reaction vessel was heated to reflux (e.g., 143-145°C). Using a bubbler, the evolution of CO2 can be monitored during the reaction. When CO2 evolution ceased the reaction was held for an additional hour, then cooled to room temperature. Upon cooling, the mixture was poured onto five volumes of methanol to precipitate the PPE, which was collected by filtration, washed with a little methanol, and dried in a vacuum oven at 120°C.1H NMR spectroscopy did not indicate the presence of any carbonate-containing linking groups in the polymer product.Preparative Example 2

[0102] Synthesis of PPE-22EO. A 50 wt% solution of PPE (obtained as SA90 from SABIC) was prepared by dissolving 1 kilogram (kg) of PPE in 1.1 kg of methyl isobutyl ketone (MIBK) at 60°C with stirring. To this solution was added 2 mol% of KOH (39.2 g of a 50 wt% solution in water) and the solution dried by pulling a slight vacuum and distilling out 100 g of the solvent (i.e., until it ran clear.) This solution was then transferred under N2 into a 4-liter autoclave and ethylene oxide (4.5 g, gas) was transferred into it. The autoclave was heated to 135 °C and held until the pressure drop stopped and was stable. This process was repeated with aliquots of EO sequentially added. The reactor was cooled to 25 °C and the solution discharged.The resin was collected by precipitation with 5 equivalents of methanol, filtered and dried in a 100°C vacuum oven overnight.Comparative Example 1

[0103] A hydroxy 1-functionalized poly (phenylene ether) oligomer (obtained as S A90 from SABIC) (2 grams) was dissolved in bisphenol A diglycidyl ether (18 grams) at 80°C for 2 hours until the hydroxyl-functionalized poly(phenylene ether) oligomer was dissolved. The viscosity of the mixture was measured using a Brookfield DV3T rheometer using a cone and plate viscometer cell CP-41Z at 25°C, 50°C, and 70°C.Example 1

[0104] An hydroxyalkyl-functionalized poly(phenylene ether) oligomer obtained by the process of Preparative Example 1 (2 grams) was dissolved in bisphenol A diglycidyl ether (18 grams) at 80°C for 2 hours until the hydroxyl-functionalized poly(phenylene ether) oligomer was dissolved. The viscosity of the mixture was measured using a Brookfield DV3T rheometer using a cone and plate viscometer cell CP-41Z at 25°C, 50°C, and 70°C.Comparative Example 2

[0105] As a control, the viscosity of bisphenol A diglycidyl ether was measured using a Brookfield DV3T rheometer using a cone and plate viscometer cell CP-41Z at 25°C, 50°C, and 70°C.

[0106] Results of the viscosity measurements of Example 1 and Comparative Examples 1 and 2 are summarized in Table 1.Table 1

[0107] Advantageously, the polyfunctional, e.g., bifunctional poly(phenylene ether) provided a significant reduction in the measured viscosity, enabling easier processing. A significant improvement in curable compositions is therefore provided by the present disclosure.

[0108] This disclosure further encompasses the following aspects.

[0109] Aspect 1. A curable composition comprising: a polyfunctional, e.g., bifunctional poly(arylene ether) comprising an end group, wherein the end group comprises a linking group comprising a substituted or unsubstituted saturated hydrocarbylene group or a substituted or unsubstituted saturated poly(hydrocarbylene ether), and a terminal functional group comprisinga hydroxyl group, a salt thereof, or a combination thereof, a curable component co-curable with the polyfunctional, e.g., bifunctional poly(arylene ether); and optionally, one or more of a crosslinking agent, a curing agent, a curing catalyst, a curing initiator, or a combination thereof; wherein the bifunctional poly(arylene ether), comprises an average of at least 1.8 terminal hydroxyl groups per molecule.

[0110] Aspect 2: The curable composition of aspect 1, comprising 0-5,000 ppm, or 0- 2,500 ppm, or 0-1,000 ppm, as determined by proton nuclear magnetic resonance spectroscopy of a poly( arylene ether) comprising a linking group comprising a carbonate functional group, an ester functional group, or a combination thereof.

[0111] Aspect 3: The curable composition of aspect 1, wherein the polyfunctional poly(arylene ether) is a bifunctional poly(arylene ether) of the structure (7) as described herein.

[0112] Aspect 4: The curable composition of claim 3, wherein in the polyfunctional, e.g., bifunctional poly(arylene ether), Q1and Q2at each occurrence are independently methyl or cyclohexyl optionally substituted with an amine group having from 1-12 carbon atoms, Q3and Q4at each occurrence are independently halogen, unsubstituted C1-12 alkyl provided that the alkyl group is not tertiary alkyl, or unsubstituted C1-12 aryl the sum of x and y is 2-50; Y is a single bond or 2,2-dimethyl isopropylidene; R3, R4, R5, and R6are independently at each occurrence hydrogen, halogen, unsubstituted or substituted C1-6 primary or secondary hydrocarbyl; and R10and R12are each independently hydrogen or C1-6 alkyl; and n at each occurrence is independently 1-18.

[0113] Aspect 5: The curable composition of aspect 1, wherein the polyfunctional poly(arylene ether) is a bifunctional poly(arylene ether) of structure (7a) as described herein.

[0114] Aspect 6: The curable composition of aspect 5, wherein in the bifunctional poly(arylene ether), Q1and Q2at each occurrence are independently methyl or cyclohexyl optionally substituted with an amine group having from 1-12 carbon atoms, Q3and Q4at each occurrence are independently halogen, unsubstituted C1-12 alkyl provided that the alkyl group is not tertiary alkyl, or unsubstituted C1-12 aryl; the sum of x and y is 2-50; Y is a single bond or 2,2-dimethyl isopropylidene; R3, R4, R5, and R6are independently at each occurrence hydrogen, halogen, unsubstituted or substituted C1-6 primary or secondary hydrocarbyl; R10and R12are each independently hydrogen or C1-6 alkyl; and n at each occurrence is independently 1-18.

[0115] Aspect 6a: The curable composition of any one or more of the foregoing aspects, wherein the bifunctional poly (arylene ether) is of the structure (7 a), wherein rein Q5and Q6are independently at each occurrence methyl, di-n-butylaminomethyl, or morpholinomethyl; and each occurrence of a and b is independently 2-20, with the proviso that the sum of a and b is at least 2; and R12and n each independently 1-20; and the composition comprises 0-5,000 ppm of apoly(arylene ether) comprising a linking group comprising a carbonate functional group, an ester functional group, or a combination thereof.

[0116] Aspect 7: The curable composition any one or more of the foregoing aspects, wherein the polyfunctional, e.g., bifunctional poly(arylene ether) has a number average molecular weight of 600-10,000 g / mol a determined by gel permeation chromatography.

[0117] Aspect 8: The curable composition any one or more of the foregoing aspects, wherein the polyfunctional, e.g., bifunctional poly(arylene ether) has an average of at least 1.8 hydroxyl groups per molecule.

[0118] Aspect 9: The curable composition of any one or more of the foregoing aspects, wherein the curable component comprises an epoxy resin, cyanate ester resin, benzoxazine resin, bismaleimide, vinyl resin, esterimide resin, silicone resin, or a combination thereof.

[0119] Aspect 10: The curable composition of any one of the foregoing aspects, comprising 1-90 wt% of the polyfunctional, e.g., bifunctional poly(arylene ether); and 10-99 wt% of the curable component.

[0120] Aspect 11: The curable composition of aspect 10, wherein the curable component comprises an epoxy resin.

[0121] Aspect 12: The curable composition of any of any one of the foregoing aspects, comprising 1-90 wt% of the polyfunctional, e.g., bifunctional poly(arylene ether); and 10-99 wt% of the curable component.

[0122] Aspect 13: A composition comprising a cured product derived from the curable composition of any of any one of the foregoing aspects.

[0123] Aspect 14: An article comprising the composition of aspect 13.

[0124] Aspect 15: The article of aspect 14, wherein the article is in the form of a composite, a foam, a fiber, a layer, a coating, a film, an encapsulant, an adhesive, a sealant, a molded component, a prepreg, a casing, a laminate, a metal clad laminate, an electronic composite, a structural composite, or a combination thereof.

[0125] 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.

[0126] All ranges disclosed herein are inclusive of the endpoints, and the endpoints are independently combinable with each other. “Combinations” is inclusive of blends, mixtures, alloys, reaction products, and the like. The terms “first”, “second”, and the like, do not denoteany order, quantity, or importance, but rather are used to distinguish one element from another. The terms “a” and “an” and “the” do not denote a limitation of quantity, and are to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. “Or” means “and / or” unless clearly stated otherwise. Reference throughout the specification to “some aspects” means that a particular element described in connection with the aspect is included in at least one aspect described herein, and can or can not be present in other aspects. The term “combination thereof’ as used herein includes one or more of the listed elements, and is open, allowing the presence of one or more like elements not named. The described elements can be combined in any suitable manner in the various aspects.

[0127] 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.

[0128] 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.

[0129] Compounds are described using standard nomenclature. For example, any position not substituted by any indicated group is understood to have its valency filled by a bond as indicated, or a hydrogen atom. A dashthat is not between two letters or symbols is used to indicate a point of attachment for a substituent. For example, -CHO is attached through carbon of the carbonyl group.

[0130] As used herein, the term “hydrocarbyl”, whether used by itself, or as a prefix, suffix, or fragment of another term, refers to a residue that contains only carbon and hydrogen. The residue can be aliphatic or aromatic, straight-chain, cyclic, bicyclic, branched, saturated, or unsaturated. It can also contain combinations of aliphatic, aromatic, straight chain, cyclic, bicyclic, branched, saturated, and unsaturated hydrocarbon moieties. However, when the hydrocarbyl residue is described as substituted, it may, optionally, contain heteroatoms over and above the carbon and hydrogen members of the substituent residue. Thus, when described as substituted, the hydrocarbyl residue can also contain one or more carbonyl groups, amino groups, hydroxyl groups, or the like, or it can contain heteroatoms within the backbone of the hydrocarbyl residue. 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. “Alkenyl” means a straight or branched chain, monovalenthydrocarbon group having at least one carbon-carbon double bond (e.g., ethenyl (-HC=CH2)). “Alkoxy” means an alkyl group that is linked via an oxygen (i.e., alkyl-O-), for example methoxy, ethoxy, and sec-butyloxy groups. "Alkylene" means a straight or branched chain, saturated, divalent aliphatic hydrocarbon group (e.g., methylene (-CH2-) or, propylene (-(CH2)3- )). “Cycloalkylene” means a divalent cyclic alkylene group, -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 atoms (e.g., bromo and fluoro), or only chloro atoms 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.

[0131] While particular embodiments have been described, alternatives, modifications, variations, and improvements that are or can be presently unforeseen can arise to applicants or others skilled in the art. Accordingly, the appended claims as filed and as they can be amended are intended to embrace all such alternatives, modifications variations, and improvements.

Claims

CLAIMSWhat is claimed is:

1. A curable composition comprising: a polyfunctional poly(arylene ether) comprising an end group, wherein the end group comprises a linking group comprising a substituted or unsubstituted saturated hydrocarbylene group or a substituted or unsubstituted saturated poly(hydrocarbylene ether), and a terminal functional group comprising a hydroxyl group, a salt thereof, or a combination thereof, a curable component co-curable with the polyfunctional poly(arylene ether); and optionally, one or more of a crosslinking agent, a curing agent, a curing catalyst, a curing initiator, or a combination thereof; wherein the polyfunctional poly (arylene ether), comprises an average of at least 1.8 terminal hydroxyl groups per molecule, and2. The curable composition of claim 1, comprising 0-5,000 ppm, or 0-2,500 ppm, or 0- 1 ,000 ppm, as determined by proton nuclear magnetic resonance spectroscopy of a poly(arylene ether) comprising a linking group comprising a carbonate functional group, an ester functional group, or a combination thereof.

3. The curable composition of claim 1 or claim 2, wherein the polyfunctional poly(arylene ether) is a bifunctional poly(arylene ether) of the structurewhereinQ1and Q2are independently at each occurrence halogen, unsubstituted or substituted Ci- 15 primary or secondary hydrocarbyl, unsubstituted or substituted C1-12 hydrocarbylthio, unsubstituted or substituted C1-12 hydrocarbyloxy, or unsubstituted or substituted C2-12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms;Q3and Q4are independently at each occurrence hydrogen, halogen, unsubstituted or substituted C1-15 primary or secondary hydrocarbyl, unsubstituted or substituted C1-12 hydrocarbylthio, unsubstituted or substituted C1-12 hydrocarbyloxy, or unsubstituted or substituted C2-12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms; x and y are each independently 0-100, provided that the sum of x and y is at least 2;L represents one or more units having the structurewhereinR3, R4, R5, and R6are independently at each occurrence hydrogen, halogen, unsubstituted or substituted C1-12 primary or secondary hydrocarbyl, unsubstituted or substituted C1-12 hydrocarbylthio, unsubstituted or substituted C1-12 hydrocarbyloxy, or unsubstituted or substituted C2-12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms; andY is a single bond or a divalent linking group of the formulawhereinRa, Rb, Rc, Rd, and Reare independently at each occurrence hydrogen, C1-12 hydrocarbyl, or Ci -6 hydrocarbylene, optionally wherein Raand Rbor Rcand Rdtogether are a C4-8 alkylene group;R1is independently at each occurrence hydrogen, C1-12 hydrocarbyl, or C1-6 hydrocarbylene, optionally wherein Raand Rbor Rcand Rdtogether are a C4-8 alkylene group, each occurrence of R1is independently hydrogen, C1-13 alkyl, C1-13 alkoxy, C2-13 alkenyl, C2-13 alkenyloxy, C3-6 cycloalkyl, C3-6 cycloalkoxy, Ce-i4 aryl, Ce-io aryloxy, C7-13 arylalkyl, C7-13 arylalkoxy, C7-13 alkylaryl, or C7-13 alkylaryloxy, each of which can independently be substituted or unsubstituted;R2is independently at each occurrence a single bond, unsubstituted or substituted C1-12 hydrocarbylene, or unsubstituted or substituted C6-12 arylene, C6-12 arylene;E is 2-200;R10and R12are each independently hydrogen, halogen, or Ci-is alkyl, preferably hydrogen or C1-6 alkyl; and n at each occurrence is independently 1 or more.

4. The curable composition of claim 3, wherein in the bifunctional poly(arylene ether),Q1and Q2at each occurrence are independently methyl or cyclohexyl optionally substituted with an amine group having from 1-12 carbon atoms,Q3and Q4at each occurrence are independently halogen, unsubstituted C1-12 alkyl provided that the alkyl group is not tertiary alkyl, or unsubstituted C1-12 aryl; the sum of x and y is 2-50;Y is a single bond or 2,2-dimethyl isopropylidene;R3, R4, R5, and R6are independently at each occurrence hydrogen, halogen, unsubstituted or substituted C1-6 primary or secondary hydrocarbyl;R10and R12are each independently hydrogen or C1-6 alkyl; and n at each occurrence is independently 1-18.

5. The curable composition of claim 3, wherein the bifunctional poly(arylene ether) is of the structurewherein each occurrence of Q1, Q2, Q3, and Q4, L, x, y, re as defined in claim 2;6. The curable composition of claim 5, wherein in the bifunctional poly(arylene ether), Q1and Q2at each occurrence are independently methyl or cyclohexyl optionally substituted with an amine group having from 1-12 carbon atoms,Q3and Q4at each occurrence are independently halogen, unsubstituted C1-12 alkyl provided that the alkyl group is not tertiary alkyl, or unsubstituted C1-12 aryl; the sum of x and y is 2-50;Y is a single bond or 2,2-dimethyl isopropylidene;R3, R4, R5, and R6are independently at each occurrence hydrogen, halogen, unsubstituted or substituted Ci-6 primary or secondary hydrocarbyl; andR10and R12are each independently hydrogen or Ci-6 alkyl; and n at each occurrence is independently 1-18.

7. The curable composition of any one of the foregoing claims, wherein the polyfunctional poly(arylene ether) has a number average molecular weight of 600-10,000 grams per mole as determined by gel permeation chromatography, using polystyrene standards.

8. The curable composition of any one of the foregoing claims, wherein the polyfunctional poly(arylene ether) has an average of 1.8-3 hydroxyl groups per molecule.

9. The curable composition of any one of the foregoing claims, wherein the polyfunctional poly(arylene ether) has a number average molecular weight of 600-10,000 grams per mole as determined by gel permeation chromatography using polystyrene standards.

10. The curable composition of any one of the foregoing claims, comprising 1-90 wt% of the polyfunctional poly(arylene ether); and10-99 wt% of the curable component.

11. The curable composition of any one of the foregoing claims, wherein the curable component comprises an epoxy resin, cyanate ester resin, benzoxazine resin, bismaleimide, vinyl resin, esterimide resin, silicone resin, or a combination thereof.

12. The curable composition of claim 11, wherein the curable component comprises an epoxy resin.

13. A composition comprising a cured product derived from the curable composition of any one of the foregoing claims.

14. An article comprising the composition of claim 13.

15. The article of claim 14, wherein the article is in the form of a composite, a foam, a fiber, a layer, a coating, a film, an encapsulant, an adhesive, a sealant, a molded component, a prepreg, a casing, a laminate, a metal clad laminate, an electronic composite, a structural composite, or a combination thereof.

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