Polyfunctional poly(arylene ether) and method for the manufacture thereof

Abstract

A 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) and a polyol. The composition is substantially free of a volatile organic solvent or the composition includes 0-5,000 ppm of a poly(arylene ether) comprising a linking group comprising a carbonate functional group, an ester functional group, or a combination thereof. A method for the manufacture of a polyfunctional poly(arylene ether) is also disclosed.

Description

23SHPP0041-WO-PCT (SS370037PCT) POLYFUNCTIONAL POLY(ARYLENE ETHER) AND METHOD FOR THE MANUFACTURE THEREOF CROSS REFERENCE TO RELATED APPLICATION This application claims priority to and the benefit of European Patent Application No. 24171646.3 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 poly(arylene ethers) including 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. It is therefore desirable to incorporate poly(arylene ether)s into curable compositions to improve the dielectric performance, and moisture absorption of copolymers. However, conventional poly(arylene ethers) with functionalized phenolic terminal functional groups have glass transition temperatures that are too high for the fabrications where solvents are not used. Additionally, the reaction of conventional poly(arylene ethers) having phenolic terminal functional groups to introduce crosslinking groups is much slower than similar functionalization reactions for reactive resin systems such as epoxy, urethane, anhydride, and other derivatization reactions.

[0003] Accordingly, there remains a continuing need in the art for polyfunctional poly(arylene ethers) with lower glass transition temperatures with improved reactivity for further functionalization. It would be particularly desirable to provide improved methods for the manufacture of such polyfunctional poly(arylene ethers). SUMMARY

[0004] An aspect is a 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; and a polyol; wherein the composition is substantially free of a volatile organic solvent; or the wherein the composition comprises 0-23SHPP0041-WO-PCT (SS370037PCT) 5,000 ppm of a poly(arylene ether) comprising a linking group comprising a carbonate functional group, an ester functional group, or a combination thereof; or the composition is substantially free of a volatile organic solvent and the composition comprises 0-5,000 ppm of a poly(arylene ether) comprising a linking group comprising a carbonate functional group, an ester functional group, or a combination thereof.

[0005] A method for the manufacture of a polyfunctional 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 a salt thereof, or a combination thereof, and the linking group comprises a substituted or unsubstituted saturated hydrocarbylene group, or a substituted or unsubstituted saturated poly(hydrocarbylene ether), the method comprising: combining a polyfunctional hydroxy-terminated poly(arylene ether); and a polyol; to provide a reaction mixture; combining the reaction mixture with a base to provide a basic reaction mixture; removing water from the basic reaction mixture; and combining the basic reaction mixture with an agent comprising an alkylene oxide; to provide a product mixture comprising the polyfunctional poly(arylene ether) comprising the end group, wherein the polyfunctional poly(arylene ether) comprises an average of at least 1.8 terminal substituted or unsubstituted saturated hydrocarbylene alcohol terminal functional groups salts thereof, or a combination thereof, preferably wherein the product mixture comprises 0-5,000 ppm of a poly(arylene ether) comprising a linking group comprising a carbonate functional group, an ester functional group, or a combination thereof.

[0006] The above described and other features are exemplified by the following detailed description. DETAILED DESCRIPTION

[0007] The present inventors have advantageously discovered that polyfunctional ((e.g., bifunctional) poly(arylene ethers) having 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) can be provided by the method described herein. In some aspects, the composition comprises 0-5,000 parts per million by weight (ppm,) or 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, an ester functional group, or a combination thereof, each as determined by1H NMR. In some23SHPP0041-WO-PCT (SS370037PCT) aspects, the composition is substantially free of a volatile organic solvent as determined by1H NMR or by mass spectrometry. In some aspects, both conditions are present. The method according to the present disclosure can advantageously preclude the need for volatile organic solvents and can prevent or preclude the formation of carbonate linkages, ester linkages, or both at the end groups of the poly(arylene ether). A significant improvement is therefore provided by the present disclosure.

[0008] Accordingly, an aspect is a method for the manufacture of 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). For simplicity, this polyfunctional 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).”

[0009] Exemplary linking groups shown below include an ethyl group (structure on left) and an unsubstituted, saturated poly(hydrocarbylene ether) (e.g., diethyl ether; structure onright). The terminal functional group in both structures shown below is OH, and “ ”indicates a link to the remaining portion of the polyfunctional poly(arylene ether).

[0010] 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 hydrocarbylene linking group includes a substituted or unsubstituted C2-30hydrocarbylene group. The C2-30hydrocarbylene 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 alkyl, or C2-4 alkyl, or C2-3 alkyl.

[0011] The substituted or unsubstituted saturated poly(hydrocarbylene ether) linking group can include a substituted or unsubstituted a C4-100 poly(hydrocarbylene ether). The C4-10023SHPP0041-WO-PCT (SS370037PCT) 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 carbons and up to 90, up to 80, up to 70, up to 60, up to 50, up to 40, up to 30, or up to 20 carbons. A range of carbon atoms in the poly(hydrocarbylene ether) can include any of the foregoing limits.

[0012] The C4-100 poly(hydrocarbylene ether) can include a substituted or unsubstituted C4-100 poly(C2-4 alkylene ether). The number of carbons in the C4-100 poly(C2-4 alkylene ether) can include any of the above foregoing limits. In some aspects, the C4-100 poly(hydrocarbylene ether) includes a C4-100 poly(C2-3 alkylene ether). In certain aspects, the C4-100 poly(hydrocarbylene ether) includes a C4-100poly(C2alkylene ether).

[0013] A method comprises combining a polyfunctional hydroxy-terminated poly(arylene ether) and a polyol to provide a reaction mixture.

[0014] The polyfunctional hydroxy-terminated poly(arylene ether) can include two or more repeating units derived from a monohydric phenol, the repeating units having the formulawherein each occurrence of Q1is substituted or unsubstituted C1-12 primary or secondary alkyl or cycloalkyl, preferably substituted or unsubstituted C1-12 primary alkyl, more preferably substituted or unsubstituted C1-6 primary alkyl, even more preferably substituted or unsubstituted methyl; each occurrence of Q2is halogen, C1-12hydrocarbyl provided that the hydrocarbyl group is not tertiary hydrocarbyl, C1-12hydrocarbylthio, C1-12hydrocarbyloxy, or C2-12halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms, preferably C1-12alkyl or C3-12cycloalkyl, more preferably C1-6alkyl, even more preferably methyl. Each occurrence of Q3and Q4is independently hydrogen, halogen, unsubstituted or substituted C1-12hydrocarbyl provided that the hydrocarbyl group is not tertiary hydrocarbyl, C1-12hydrocarbylthio, C1-12hydrocarbyloxy, or C2-12halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms, preferably hydrogen; and e is 1-200, preferably 2-100, provided that when e is 1, at least one additional repeat unit is present in the polymer.

[0015] 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 each23SHPP0041-WO-PCT (SS370037PCT) 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(C1-6 alkyl)amino group or a morpholinyl group, and each Q2is methyl.

[0016] 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.

[0017] In addition to repeating units derived from a monohydric phenol, the polyfunctional poly(arylene ether) having the end groups 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 C1-15primary or secondary hydrocarbyl, C1-12hydrocarbylthio, C1-12hydrocarbyloxy, or C2-12halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms; each occurrence of Q3and Q4independently comprises hydrogen, halogen, unsubstituted or substituted C1-15primary or secondary hydrocarbyl, C1-12hydrocarbylthio, C1-12hydrocarbyloxy, or C2-12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms; x and y have an average value, and are each independently 0-100, or 0-50, or 0-20, preferably 0-15, still more preferably 0-10, even more preferably 0-8, provided that the sum of x and y is at least 2, preferably at least 3, more preferably at least 4, up to 20, or up to 40, up to 50, up to 100, or up to 200. In some aspects, each occurrence of Q1is independently methyl or cyclohexyl optionally substituted with an amine group having 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(C1-6 alkyl)amino group, and each Q2is methyl.

[0018] In formula (2), L can be of formula (3)23SHPP0041-WO-PCT (SS370037PCT)wherein each occurrence of R3, R4, R5, and R6is independently hydrogen, halogen, unsubstituted or substituted C1-12 primary or secondary hydrocarbyl, C1-12 hydrocarbylthio, C1-12 hydrocarbyloxy, or C2-12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms; and Y is a single bond, a trivalent linking group, or a divalent linking group of the formulawherein each occurrence of Ra, Rb, Rc, Rd, and Reis independently hydrogen, C1-12hydrocarbyl, or C1-6hydrocarbylene, optionally wherein Raand Rbor Rcand Rdtogether are a C4-8alkylene group; each occurrence of R1is independently hydrogen, a C1-14hydrocarbyl, a C1-14halohydrocarbyl, or a C1-14heterohydrocarbyl, preferably C1-13alkyl, C1-13alkoxy, C2-13alkenyl, C2-13alkenyloxy, C3-6cycloalkyl, C3-6cycloalkoxy, C6-14aryl, C6-10aryloxy, C7-13arylalkyl, C7-13arylalkoxy, C7-13alkylaryl, or C7-13alkylaryloxy, each of which can independently be substituted or unsubstituted, each R2is a C1-6 hydrocarbylene group, preferably a divalent C2-8 aliphatic group, 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.

[0019] In some aspects in formula (3), each occurrence of R3, R4, R5, and R6is independently hydrogen, halogen, unsubstituted or substituted C1-6 primary or secondary hydrocarbyl; and w is 0 or 1. In an aspect of formula (3), R3, R4, R5, and R6independently comprise hydrogen, halogen, or C1-12 alkyl, more preferably hydrogen or C1-6 alkyl.

[0020] Examples of dihydric phenols that can be used include 3,3',5,5'-tetramethy1-4,4'- biphenol, 2,2-bis(3-methyl-4-hydroxyphenyl)propane, 2,2-bis(3,5-dimethy-4-23SHPP0041-WO-PCT (SS370037PCT) hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)methane, 1, 1-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-hydroxypheny1)-n-butane, bi s(4-hydroxyphenyl)phenylmethane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 1,1-bis(4- hydroxy-3-methylphenyl)cyclohexane, 1,1-bis(4-hydroxy-3,5-dimethylphenyl)cyclopentane, 1,1-bis(4-hydroxy-3,5-dimethylphenyl)cyclohexane, 1,1-bis(4-hydroxy-3- methylphenyl)cycloheptane, 1,1-bis(4-hydroxy-3,5-dimethylphenyl)cycloheptane, 1,1 -bis(4- hydroxy-3-methylphenyl)cyclooctane, 1,1-bis(4-hydroxy-3,5-dimethylphenyl)cyclooctane, 1,1 - bis(4-hydroxy-3-methylphenyl)cyclononane, 1,1-bis(4-hydroxy-3,5- dimethylphenyl)cyclononane, 1,1-bis(4-hydroxy-3-methylphenyl)cyclodecane, 1,1-bis(4- hydroxy-3,5-dimethylphenyl)cyclodecane, 1,1-bis(4-hydroxy-3-methylphenyl)cycloundecane, 1,1-bis(4-hydroxy-3,5-dimethylphenyl)cycloundecane, 1,1-bis(4-hydroxy-3- methylphenyl)cyclododecane, 1,1-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 andwherein 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).

[0021] The polyfunctional poly(arylene ether) can have a structure of formula (5)wherein each occurrence of Q1, Q2, Q3, and Q4are as defined above; each occurrence of R3, R4, R5, and R6are as defined above; Y is as defined above; x and y are as defined above; and each “23SHPP0041-WO-PCT (SS370037PCT) ” indicates an attachment to an end group as described herein. 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(C1-6 alkyl)amino group or a morpholinyl group.

[0022] In some aspects, the polyfunctional poly(ether arylene) 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.

[0023] In some aspects, the end groups of the polyfunctional poly(arylene ether) can be of formula (6)wherein R10and R12are each independently hydrogen, halogen, or C1-18alkyl, preferably hydrogen or C1-6alkyl, more preferably hydrogen or C1-3alkyl; and m is 1 or more, for example 1-18, or 1-12, or 1-6, preferably 1-3; and n is 1 or more, for example 1-12, or 1-6, preferably 1- 3. In some aspects, each occurrence of n is independently 0-40, provided that at least one occurrence of n is 1 or more. 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 C1-6 alkyl. In some aspects n is 1; or m is 1; or both m and n are 1.

[0024] In some aspects, the polyfunctional poly(arylene ether) can be of formula (7)wherein each occurrence of Q1, Q2, Q3, and Q4, L, x, and y re as defined in formula (2); and each occurrence of R10, R12, m and n are as defined in formula (6).

[0025] In some aspects, the polyfunctional poly(arylene ether) can be of formula (7a)23SHPP0041-WO-PCT (SS370037PCT)wherein each occurrence of Q1, Q2, Q3, and Q4, L, x, and y are as defined in formula (2); and each occurrence of R12and n are as defined in formula (6). In some aspects, R12is independently at each occurrence hydrogen or methyl; and n is independently at each occurrence 0-15, provided that at least one occurrence of n is 1. In some aspects, Q1and Q2are each methyl, di-n- butylaminomethyl, or morpholinomethyl, Q3and Q4are each hydrogen, R12is hydrogen, and n is independently at each occurrence 0-5, provided that at least one occurrence of n is at least 1, and preferably each occurrence of n is 1.

[0026] The polyfunctional poly(arylene ether) can have a number average molecular weight (Mn) of 600-10,000, or 400-2,500 grams per mole (g / mol) as determined by gel permeation chromatography (GPC). In some aspects, the polyfunctional hydroxy-terminated poly(arylene ether) can have a weight average molecular weight (Mw) of 500-6,000 g / mol, each as determined by GPC. For example, the polyfunctional hydroxy-terminated poly(arylene ether)can have an Mn of 400-2,200 g / mol or 800-1,600 g / mol and an Mw of 600-5,000 g / mol or 800-4,500 g / mol, each as determined by GPC using polystyrene standards.

[0027] The polyfunctional 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 can be 0.06-0.1 dL / g, or 0.075-0.090 dL / g, or 0.05-0.1 dL / g, or 0.1-0.15 dL / g.

[0028] The polyfunctional poly(arylene ether) can be a bifunctional poly(arylene ether). The bifunctional poly(arylene ether) can have an average of 1.8-2 hydroxy groups per molecule. The polyfunctional poly(arylene ether) can be a trifunctional poly(arylene ether) or a poly(arylene ether) having a functionality greater than three. For example, the polyfunctional poly(arylene ether) can have an average of 2-6 functional groups, or 2-5, or 2-4, or 2-3 functional groups.

[0029] The polyfunctional poly(arylene ether) is the product of oxidative copolymerization of monomers comprising a monohydric phenol, a dihydric phenol, a trihydric phenol or higher, or a combination thereof, to form the polyfunctional hydroxy-terminated poly(arylene ether) having phenolic terminal groups.

[0030] The polyfunctional poly(arylene ether) can be derived from a poly(arylene ether) having phenolic terminal groups, which can be referred to hereinafter as “phenolic polyarylene23SHPP0041-WO-PCT (SS370037PCT) ether)”. These phenolic poly(arylene ether)s can be formed by polymerization of monomers, for example a monohydric phenol, a dihydric phenol, or a combination thereof, for example 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. In some aspects the phenolic poly(arylene ether) can be manufactured by continuous addition of oxygen to a reaction mixture including the monomers, optionally a solvent, and a polymerization catalyst. The molecular oxygen (O2) can be provided as air or pure oxygen. The polymerization catalyst can be a metal complex, i.e. a metal catalyst, including a transition metal cation, including cations from Group VIB, VIIB, VIIIB, or IB of the periodic table, or a combination thereof. The catalyst can include a metal cation such as chromium, manganese, cobalt, copper, or combination thereof and an anion such as chloride, bromide, iodide, sulfate, acetate, propionate, butyrate, laurate, palmitate, benzoate, or a combination of one or more of these anions, and optionally one or more charge-neutral ligands such as water, amines, phosphines, CO, or the like. Alternatively, a metal or metal oxide and an inorganic acid, organic acid, or an aqueous solution of such an acid can be combined to form a corresponding metal salt or hydrate in situ. For example, cuprous oxide and hydrobromic acid can be combined to generate cuprous bromide in situ.

[0031] 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, tert- butylethylamine, dimethylamine, di-n-propylamine, di-sec-butyl amine, dipentylamine, dihexylamine, dioctylamine, didecylamine , dibenzylamine, methylethylamine, methylbutylamine, dicyclohexylamine, N-ethylaniline, N-butyl aniline, N-methyl-2- methylaniline, N-methyl-2,6-dimethylaniline, diphenylamine, or a combination thereof. Exemplary diamines include a N,N'-di-tert-butylethylenediamine, or the like, and combinations thereof. Exemplary trialkylmonoamines include trimethylamine, triethylamine, tripropylamine, tributylamine, butyldimethylamine, phenyldiethylamine, or the like, and combinations thereof.

[0032] 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:23SHPP0041-WO-PCT (SS370037PCT)

[0033] The amount of covalently bound monoamine groups can be determined by1H- NMR spectroscopy. Covalently bound monoamine groups can adversely affect the oxidative stability of capped poly(arylene ether) and can result in yellowing of the capped poly(arylene ether) upon heat aging.

[0034] Phenolic poly(arylene ethers), 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 poly(arylene ethers) can be, or can be formed from, renewable, sustainable, bio-circular, circular, lower carbon footprint feedstocks, upcycled, and / or post-consumer / post-industrial recycled materials, including pyrolysis oil (“py- oil”) .

[0035] Phenolic poly(arylene ethers) made from renewable sources can include, for example, a bio-content or PCR content of up to about 99.9%, about 1-99%, 5-95%, 55-99%, or 80-99%, 1-50%, 1-25%, 1-15%, 1-10%, or 1-5%, based, e.g., on the monomer source. The poly(arylene ether) can be, e.g., an oligomer with as few as two repeating units to ultra-high molecular weight poly(arylene ethers). The weight average molecular weight (Mw) of the poly(arylene ethers) in some aspects can be 600-200,000 g / mol, as determined by gel permeation chromatography. In another non-limiting aspect, the poly(arylene ethers) can have an intrinsic viscosity of up to 1.5 deciliters per gram (dl / g) as measured at 25°C in chloroform. Poly(arylene ethers) 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.

[0036] 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 any combinations thereof. In some aspects, reaction components used in the polymerization of poly(arylene ethers) can be from sources as listed in the EU Renewable Energy Directive Annex IX.23SHPP0041-WO-PCT (SS370037PCT)

[0037] Poly(arylene ethers) can be further processed, such as by redistribution, or any chemical derivatization, such as post-polymerization coupling, or end-group addition as described herein, to make other materials that can transfer the 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 post-consumer / post-industrial recycled materials, including pyrolysis oil (“py-oil”), to produce a poly(arylene ether).

[0038] Biosourced and sustainable materials can be derived from biomass sources or industrial sources such as waste (e.g., municipal waste). Biomass is a renewable organic material that comes from organic matter. Lignocellulosic biomass 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.

[0039] Poly(arylene ether), such as a recycled poly(arylene ether) comprising an open- or closed-loop post-consumer recycled (“PCR”) poly(arylene ether), an open- or closed-loop post-industrial recycled (“PIR”) poly(arylene ether), or upcycled polyphenylene ether or a combination thereof can be used, provided that the desired property or combination of properties can be achieved. As used herein, the term “PCR poly(arylene ether)” refers to a poly(arylene ether) that has reached the intended user or consumer and which has been collected or reclaimed after utilization by the end-user or consumer. Thus, for example, it is understood that that the term refers to a poly(arylene ether) material in whole or in part that would have otherwise been disposed of as waste, but has instead been collected and recovered (reclaimed) as a material input, in lieu of a virgin material, for a recycling or manufacturing process. PCR-poly(arylene ether) is inclusive of material that has been reprocessed from collected or reclaimed material by means of a manufacturing process, (including e.g., purification, sorting, and pretreating) and made into a product or into a component for incorporation into a product. Such recycled poly(arylene ether)s can be further processed, for example, into the form of powders, ground materials, flakes, pellets, or other form. As used herein, the term “PIR poly(arylene ether)” refers to a poly(arylene ether) that has never reached the end user and that is production waste arising during polymerization reactions, during further processing, or during manufacturing the resin or an article and includes materials such as, but not limited to, sprues from injection molding, start-up material from injection molding or extrusion, extrusion scrap, molding scrap,23SHPP0041-WO-PCT (SS370037PCT) edge trims from extruded sheets or films, and the like, including materials diverted from the waste stream during a manufacturing process for an article.

[0040] In some aspects, to manufacture the polyfunctional poly(arylene ether) having the hydroxyl end groups, the poly(arylene ether) having phenolic terminal groups is combined with a polyol effective to dissolve the poly(arylene ether) having phenolic terminal groups, to provide a reaction mixture. The polyol can generally be any polyol, provided that the polyfunctional hydroxy-terminated poly(arylene ether) is soluble in the polyol. In an aspect, no non-polyol co- solvent (e.g., methyl butyl ketone) is present.

[0041] Polyols can include polyether polyols prepared by reacting an initiator having 2-8 hydroxyl groups per molecule, or 3-8 hydroxyl groups per molecule, with an alkoxylating agent such as ethylene oxide, propylene oxide, or butylene oxide. Exemplary polyols include an ethoxylated saccharide, a propoxylated saccharide, a butoxylated saccharide, an ethoxylated glycerin, a propoxylated glycerin, a butoxylated glycerin, an ethoxylated diethanolamine, a propoxylated diethanolamine, a butoxylated diethanolamine, an ethoxylated triethanolamine, a propoxylated triethanolamine, a butoxylated triethanolamine, an ethoxylated trimethylolpropane, a propoxylated trimethylolpropane, a butoxylated trimethylolpropane, an ethoxylated erythritol, a propoxylated erythritol, a butoxylated erythritol, an ethoxylated pentaerythritol, a propoxylated pentaerythritol, a butoxylated pentaerythritol, an aliphatic polyester diol, an aromatic polyester polyol, polyethylene glycol, polypropylene glycol, poly(tetramethylene glycol), butanediol, hexanediol, other C2-8 glycols, or a combination thereof.

[0042] In a specific aspect, the polyol is a polyether polyol comprising poly(tetramethylene glycol). The poly(tetramethylene glycol) can generally be of any molecular weight. For example, the poly(tetramethylene glycol) can have a number average molecular weight of 500-5000 g / mole, as determined by gel permeation chromatography with polystyrene standards. Within this range, the poly(tetramethylene glycol) can have a number average molecular weight of 500-4000 g / mol, or 500-3000 g / mole, or 500-2500 g / mole, or 650-1250 g / mole.

[0043] The phenolic poly(arylene ether) and the polyol are combined to provide a reaction mixture, preferably wherein the phenol poly(arylene ether) is fully dissolved in the polyol, with no cosolvents being present. The phenolic poly(arylene ether) can be present in the reaction mixture in an amount of 20-60 weight percent (wt%), or 30-50 wt%, or 35-45 wt%, each based on the total weight of the reaction mixture.

[0044] The reaction mixture in turn combined with a base to provide a basic reaction mixture. Suitable bases can include, for example alkali metal hydroxides (e.g., lithium23SHPP0041-WO-PCT (SS370037PCT) hydroxide, sodium hydroxide, and potassium hydroxide), alkaline earth hydroxides (e.g., magnesium hydroxide and calcium hydroxide), non-nucleophilic bases (e.g., amines such as triethyl amine), alkali metal hydrides (e.g., lithium hydride, sodium hydride, and potassium hydride), and alkali metal carbonates (e.g., sodium carbonate or sodium bicarbonate). In a preferred aspect, the base includes sodium hydroxide or potassium hydroxide, more preferably potassium hydroxide. Preferably, both phenolic OH groups are converted to a phenoxide salt when combined with the base.

[0045] The base can be added in an amount of 1-10 mole percent (mol%), based on the total moles of the poly(arylene ether) phenol groups. Within this range, the base can be added in an amount of 2-7 mol%, or 4-6 mol%, each based on the total moles of the poly(arylene ether) phenol groups.

[0046] 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, e.g., distillation, evaporation, vacuum concentration, addition of a desiccant, or the like. The water removal is preferably to a concentration of 100 parts per million (ppm) or less. In an aspect, 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.

[0047] Following reduction in water content to, e.g., a level of 100 ppm or less, the dried basic reaction mixture is combined with a compound to provide the end group (the linking groups and the terminal functional group) of the polyfunctional oligomer, preferably an alkylene oxide. The alkylene oxide can be of the formuladescribed in formula (6).

[0048] In some aspects, the alkylene oxide is of the formulawherein p is 1-3, preferably 1-2, and R12is hydrogen or C1-18 primary alkyl, preferably hydrogen or C1-6 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.23SHPP0041-WO-PCT (SS370037PCT)

[0049] In a specific aspect, the alkylene oxide comprises an epoxide according to the formulawherein R12is hydrogen or a substituted or unsubstituted C1-18 alkyl group. In an aspect, the alkylene oxide can comprise ethylene oxide, propylene oxide, or a combination thereof. In a specific aspect, the alkylene oxide is can comprise ethylene oxide.

[0050] 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.

[0051] After contacting with the alkylene oxide, a product mixture is provided, wherein the product mixture comprises the polyfunctional 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, a salt thereof, or a combination thereof, and the linking group comprises a substituted or unsubstituted saturated hydrocarbylene group, or a substituted or unsubstituted saturated poly(hydrocarbylene ether) and the polyol.

[0052] The synthesis of the polyfunctional poly(arylene ether) having the end group comprising a linking group and a terminal functional group can be performed with or without a solvent. The solvent can preferably be an aromatic hydrocarbon solvent, for example a C6-18aromatic hydrocarbon solvent. Suitable aromatic hydrocarbon solvents include, for example, benzene, toluene, xylenes, and the like, or a combination thereof. In an aspect, the aromatic hydrocarbon solvent comprises toluene. In addition to the aromatic hydrocarbon solvent, the solvent can, optionally, further comprise a C3-8 aliphatic alcohol that is a poor solvent for the poly(arylene ether), such as, for example, n-propanol, isopropanol, n-butanol, t-butanol, n- pentanol, and the like, or a combination thereof. A preferred C3-8 aliphatic alcohol is n-butanol. The solvent can further comprise, in addition to a C6-18 aromatic hydrocarbon and a C3-8 aliphatic alcohol, methanol or ethanol, which act as an anti-solvent for the poly(arylene ether). The C6-18 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% of the C6-18 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.23SHPP0041-WO-PCT (SS370037PCT)

[0053] A catalyst can be employed in the reaction of the phenolic poly(arylene ether) salt and the alkylene oxide. Examples of such catalysts are known to the art. For example, the catalyst can be a hydroxide salt such as sodium hydroxide, potassium hydroxide, tetraalkylammonium hydroxides, or the like; tertiary alkylamines such as tributyl amine, triethylamine, dimethylbenzylamine, dimethylbutylamine, or the like; tertiary mixed alkyl- arylamines 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-(1-pyrrolino)pyridine, 4-(1-piperidino)pyridine, 2-vinylpyridine, 3-vinylpyridine, 4-vinylpyridine, or the like.

[0054] Alternatively, the catalyst can be a transesterification catalyst that is capable of catalyzing transesterification of phenols with the agents described above can be used. For example, the 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, NaHCO3, and Na2CO3, or the like, non-volatile inorganic acid such as NaH2PO3, NaH2PO4, 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.

[0055] The process can further include isolating the polyfunctional 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 poly(arylene ether) having saturated hydrocarbylene alcohol terminal functional 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 copolymer containing solution is preferably done by reducing the pressure in a solvent flash vessel while preferably increasing the temperature of the copolymer containing solution. The isolated copolymer can be dried at a temperature that is below the softening temperature or Tgof the capped poly(phenylene ether) copolymer.23SHPP0041-WO-PCT (SS370037PCT)

[0056] In some aspects, polyfunctional poly(arylene ether) comprising an end group is combined with an isocyanate compound to provide a curable composition. Reaction of the isocyanate compound with the polyfunctional poly(arylene ether) comprising an end group can provide a polyurethane composition. Articles can be made from the cured polyurethane composition.

[0057] It will be understood that when the polyfunctional poly(arylene ether) (7) or (7a) 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 polyfunctional poly(arylene ether) comprising the end group comprises an average of at least 1.8 terminal substituted or unsubstituted saturated hydrocarbylene alcohol terminal functional groups, a salt thereof, or a combination thereof.

[0058] The method of preparing the polyfunctional poly(arylene ether) comprising the end group according to the present disclosure can have several advantages compared to conventional methods.

[0059] For example, the synthesis of the polyfunctional poly(arylene ether) having the end group can be performed with or without a solvent. Exemplary solvents include aromatic hydrocarbons such as toluene or xylene, or chlorinated aromatic hydrocarbons such as chlorobenzene, o-dichlorobenzene, or 1,2,4-trichlorobenzene, or ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, and the like or a combination thereof. For example, the solvent includes toluene. 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. Thus, in an aspect, solvents such as aromatic hydrocarbon solvents (e.g., chlorobenzene, ortho- dichlorobenzene, 1,2,4-trichlorobenzene, toluene, xylene, benzene, and the like) or ketone solvents (e.g., as methyl ethyl ketone, methyl isobutyl ketone, and the like or a combination thereof) can be excluded from the present method. As such, the resulting product mixture obtained by the present method is substantially free of a volatile organic solvent. As used herein, the term “substantially free” means that the mixture includes less than 5 wt%, or less than 1 wt%, or less than 0.5 wt%, or less than 0.1 wt%, or excludes the recited component.

[0060] Additionally, conventional methods use the following reagents to incorporate a saturated hydrocarbylene group. These methods include several disadvantages, including side reactions.23SHPP0041-WO-PCT (SS370037PCT)wherein R9to R18, R20to R23are each independently hydrogen, C1-12 primary alkyl, C2-12 alkenyl, C7-12arylalkyl, C2-12alkoxyalkyl, C7-12aryloxyalkyl, or C1-12hydroxyalkyl, preferably hydrogen or C1-6alkyl. Thus, another advantage of the poly(arylene ethers) and methods or preparations described herein is that reagents such as those of Formulas (9)-(11) 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.

[0061] An example of the end group comprising a carbonate-containing linking group side-product resulting from use of ethylene carbonate (e.g. formula (9)) is depicted below for illustrative purposes only.

[0062] An example of the end group comprising an ester-containing linking group side- product is depicted below for illustrative purposes only.

[0063] In some aspects, a composition including the polyfunctional poly(arylene ether) minimizes or eliminates the presence of products other than the polyfunctional poly(arylene ether) with end groups defined herein. Accordingly, in some aspects the polyfunctional poly(arylene ether) prepared as described herein does not comprise a linking group comprising a carbonate functional group, an ester functional group, or a combination thereof in an end group of the polyfunctional poly(arylene ether). Stated another way, in some aspects, the product mixture provided by the methods described herein comprises 0-5,000 ppm or less of a23SHPP0041-WO-PCT (SS370037PCT) poly(arylene ether) comprising a linking group comprising a carbonate functional group, an ester functional group, or a combination thereof. Preferably, the composition is free of carbonate- containing polyfunctional poly(arylene ethers) and ester-containing polyfunctional poly(arylene ethers). A concentration of these end groups can be determined by analytical methods known in the art, for example nuclear magnetic resonance (NMR), for example1H NMR. Without wishing to be bound by theory, the elimination of carbonate and ester linking groups in the polyfunctional poly(arylene ethers) is advantageous because the final products that are derived from the polyfunctional poly(arylene ethers) can have improved hydrolytic and thermal stability.

[0064] In another advantageous feature, the polyfunctional poly(arylene ether) comprising the end group need not be isolated from the product mixture. In an aspect, the product mixture comprising the polyfunctional poly(arylene ether) comprising the end group and the polyol can be directly used in further processing.

[0065] A composition represents another aspect. The composition can be made by the method according to the present disclosure. The composition comprises a polyfunctional 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) and a polyol. All possible permutations and combinations for each of the polyfunctional poly(arylene ether) and the polyol discussed above in the context of the method apply to the composition as well. In an aspect, the composition is substantially free of a volatile organic solvent. In an aspect, the composition comprises 0-5,000 ppm of a poly(arylene ether) comprising a linking group comprising a carbonate functional group, an ester functional group, or a combination thereof. In an aspect, the composition is substantially free of a volatile organic solvent and the composition comprises 0-5,000 ppm of a poly(arylene ether) comprising a linking group comprising a carbonate functional group, an ester functional group, or a combination thereof.

[0066] In an aspect, the composition can comprise 20-60 wt%, or 30-50 wt%, or 35-45 wt% of the polyfunctional poly(arylene ether), and 40-80 wt%, or 50-70 wt%, or 55-65 wt% of the polyol, each based on the total weight of the composition. In an aspect, the amounts of the polyfunctional poly(arylene ether) and the polyol total at least 90 wt%, or at least 95 wt%, or at least 99 wt%, each based on the total weight of the composition.

[0067] Another aspect is a composition, e.g., a curable thermosetting composition comprising any of the compositions disclosed herein, and optionally further comprising a23SHPP0041-WO-PCT (SS370037PCT) crosslinking agent, a curing agent, a curing catalyst, a curing initiator, or a combination thereof; one or more of a flame retardant, a filler, a coupling agent, or a combination thereof.

[0068] In some aspects, the composition can be a reactive composition including a multifunctional isocyanate for the formation of a polyurethane. Polyurethanes generally can be prepared from compounds with at least two hydroxyl groups and compounds with at least two isocyanate groups. The isocyanate groups of the isocyanate compound react with the hydroxyl groups of the hydroxyl compound to form urethane linkages. The isocyanate compound can be aliphatic or aromatic, and in the preparation of linear polyurethanes is typically difunctional (i.e., it is a diisocyanate). However, isocyanate compounds with greater functionality can be used in preparing thermoset polyurethanes. The family of polyurethane resins is very complex because of the enormous variation in the compositional features of the hydroxyl compounds and isocyanate compounds. This variety results in a large numbers of polymer structures and performance profiles. Indeed, polyurethanes can be rigid solids, soft and elastomeric, or a have a foam (cellular) structure. Flexible polyurethane foams are used in applications including bedding, furniture, transportation interiors, carpet underlay, and packaging.

[0069] Another aspect is an article including any of the compositions described herein. Shaped, formed, or molded articles can include compositions described herein. The compositions can be molded into useful shaped articles by a variety of methods, such as injection molding, extrusion, rotational molding, blow molding and thermoforming. EXAMPLE

[0070] Example 1: Preparation of a bifunctional poly(arylene ether) with aliphatic alcohol end groups

[0071] 1 Kg of a bifunctional poly(phenylene ether) oligomer was slowly charged in 10 portions over 90 minutes to a 3-neck 5-L reactor containing 1.5 kg of poly(tetramethylene glycol) 1000 stirring at 100 °C. The reactor was equipped with a mechanical stirrer, reflux condenser bearing a N2 inlet and a stopper. Upon completion of dissolution, 2.05 mol (56 g) equivalents of potassium hydroxide (as a 45 wt % solution in water) was added and the flask was evacuated to 0.1 torr for 2 hours to remove water. The contents were then sucked into a 5 L autoclave preheated to 135 °C. After degassing the solution again by applying vacuum and then repressurizing with N2, 47 g of ethylene oxide gas was added from a weighed cylinder over time and flushed into the reactor with N2maintaining the system pressure at <65 psi with each addition. After the last addition was made the pressure stabilized at a point just above the initial pressure and the autoclave was vented and flushed with N2before removing a sample for end23SHPP0041-WO-PCT (SS370037PCT) group analysis.1H- and31P-NMR showed the reaction to be 100%, that is, the phenolic end groups were completely converted to aliphatic alcohols.

[0072] This disclosure further encompasses the following aspects.

[0073] Aspect 1: A composition comprising: a polyfunctional 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; and a polyol; wherein the composition is substantially free of a volatile organic solvent; or the composition comprises 0-5,000 ppm, or 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 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; or the composition is substantially free of a volatile organic solvent as determined byNMR and the composition comprises 0-5,000 ppm, or 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, as determined by1H NMR, of a poly(arylene ether) comprising a linking group comprising a carbonate functional group, an ester functional group, or a combination thereof. Aspect 2: The composition of aspect 1, comprising 20-60 wt%, or 30-50 wt%, or 35-45 wt% of the polyfunctional poly(arylene ether); and 40-80 wt%, or 50-70 wt%, or 55-65 wt% of the polyol; wherein wt% is based on the total weight of the composition.

[0074] Aspect 3: The composition of aspect 1 or 2, wherein the polyol comprises poly(tetramethylene glycol), preferably having a number-average molecular weight of 500-5000 g / mole, as determined by gel permeation chromatography with polystyrene standards, preferably 650-1250 g / mole.

[0075] Aspect 4: The composition of any of aspects 1 to 3, wherein the polyfunctional poly(arylene ether) comprising the end group is a bifunctional poly(arylene ether) of the structurewherein Q1and Q2are each independently halogen, unsubstituted or substituted C1-12primary or secondary hydrocarbyl, C1-12hydrocarbylthio, C1-12hydrocarbyloxy, and C2-1223SHPP0041-WO-PCT (SS370037PCT) halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms; Q3and Q4are independently at each occurrence hydrogen, halogen, unsubstituted or substituted C1-12 primary or secondary hydrocarbyl, C1-12 hydrocarbylthio, C1-12 hydrocarbyloxy, and C2-12 halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms; R12is hydrogen or a substituted or unsubstituted C1-18 alkyl group, preferably hydrogen or methyl; n is independently at each occurrence 0 or 1;x and y are each independently 0-30, or 0- 20, or 0-15, or 0-10, or 0-8, provided that the sum of x and y is at least 2, or at least 3, or at least 4; L represents one or more units having the structurewherein * indicates a bond to another repeat unit or an end group R3-R6are independently at each occurrence hydrogen, halogen, unsubstituted or substituted C1-12primary or secondary hydrocarbyl, C1-12hydrocarbylthio, C1-12hydrocarbyloxy, and C2-12halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms; 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 C1-6 hydrocarbylene, optionally wherein Raand Rbor Rcand Rdtogether are a C4-8 alkylene group; each occurrence of R1is independently hydrogen, a C1-14hydrocarbyl, a C1-14halohydrocarbyl, or a C1-14heterohydrocarbyl, preferably C1-13alkyl, C1-13alkoxy, C2-13alkenyl, C2-13alkenyloxy, C3-6cycloalkyl, C3-6cycloalkoxy, C6-14aryl, C6-10aryloxy, C7-13arylalkyl, C7-13arylalkoxy, C7-13alkylaryl, or C7-13alkylaryloxy; each occurrence of R2is independently a C1-6hydrocarbylene group, preferably a divalent C2-8aliphatic group, more preferably dimethylene, trimethylene, or tetramethylene; and E is 2-200.

[0076] Aspect 5: The composition of any of aspects 1 to 4, comprising the bifunctional poly(arylene ether) of the structure23SHPP0041-WO-PCT (SS370037PCT)wherein Q5and Q6are independently at each occurrence methyl, di-n-butylaminomethyl, or morpholinomethyl; and each occurrence of x and y is independently 0-20, with the proviso that the sum of x and y is at least 2; R12is hydrogen or a substituted or unsubstituted C1-18 alkyl group, preferably hydrogen or methyl; n is independently at each occurrence 0 or 1; the polyol comprises poly(tetramethylene glycol), preferably having a number-average molecular weight of 500-5000 g / mole, as determined by gel permeation chromatography with polystyrene standards, preferably 650-1250 g / mole; and the composition comprises 0-5,000 ppm of a poly(arylene ether) comprising a linking group comprising a carbonate functional group, an ester functional group, or a combination thereof.

[0077] Aspect 6: A composition comprising the composition of any one of aspects 1 to 5, a multifunctional isocyanate, and optionally a crosslinking agent, a curing agent, a curing catalyst, a curing initiator, or a combination thereof; and a flame retardant, a filler, a coupling agent, or a combination thereof.

[0078] Aspect 7: A polyurethane composition formed by reaction of the composition of any one of aspects 1 to 5 with a multifunctional isocyanate to form a plurality of urethane linkages.

[0079] Aspect 8: An article including the composition of any of aspects 1 to 7.

[0080] Aspect 9: A method for the manufacture of a polyfunctional 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), the method comprising: combining a polyfunctional hydroxy-terminated poly(arylene ether); and a polyol; to provide a reaction mixture; combining the reaction mixture with a base to provide a basic reaction mixture; removing water from the basic reaction mixture; and combining the basic reaction mixture with an agent comprising an alkylene oxide; to provide a product mixture comprising the polyfunctional poly(arylene ether) comprising substituted or unsubstituted saturated hydrocarbylene alcohol terminal functional groups or a salt thereof and the polyol, wherein the polyfunctional poly(arylene ether) comprises an average of at least 1.8 terminal23SHPP0041-WO-PCT (SS370037PCT) substituted or unsubstituted saturated hydrocarbylene alcohol terminal functional groups or a salt thereof, preferably wherein the product mixture comprises 0-5,000 ppm of a poly(arylene ether) comprising a linking group comprising a carbonate functional group, an ester functional group, or a combination thereof.

[0081] Aspect 10: The method of aspect 9, wherein the method is in the absence of a solvent, preferably in the absence of an aromatic hydrocarbon solvent, more preferably in the absence of chlorobenzene, ortho-dichlorobenzene, 1,2,4-trichlorobenzene, toluene, xylene, benzene, or preferably in the absence of a ketone solvent, more preferably methyl ethyl ketone, methyl isobutyl ketone, or a combination thereof.

[0082] Aspect 11: The method of aspect 9 or 10, wherein the polyfunctional hydroxy- terminated poly(arylene ether) is of the structurewherein Q1and Q2are each independently halogen, unsubstituted or substituted C1-12 primary or secondary hydrocarbyl, C1-12hydrocarbylthio, C1-12hydrocarbyloxy, and C2-12halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms; Q3and Q4are independently at each occurrence hydrogen, halogen, unsubstituted or substituted C1-12primary or secondary hydrocarbyl, C1-12hydrocarbylthio, C1-12hydrocarbyloxy, and C2-12halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms; x and y are each independently 0-30, or 0-20, or 0-15, or 0-10, or 0-8, provided that the sum of x and y is at least 2, or at least 3, or at least 4; and L has the structurewherein R3-R6are independently at each occurrence hydrogen, halogen, unsubstituted or substituted C1-12 primary or secondary hydrocarbyl, C1-12 hydrocarbylthio, C1-12 hydrocarbyloxy, and 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 formula23SHPP0041-WO-PCT (SS370037PCT)wherein each occurrence of Ra, Rb, Rc, Rd, and Reis independently hydrogen, C1-12hydrocarbyl, 6 hydrocarbylene, optionally wherein Raand Rbor Rcand Rdtogether are a C4-8alkylene group; each occurrence of R1is independently hydrogen, a C1-14 hydrocarbyl, a C1-14 halohydrocarbyl, or a C1-14 heterohydrocarbyl, preferably C1-13 alkyl, C1-13 alkoxy, C2-13 alkenyl, C2-13 alkenyloxy, C3-6 cycloalkyl, C3-6 cycloalkoxy, C6-14 aryl, C6-10 aryloxy, C7-13 arylalkyl, C7-13 arylalkoxy, C7-13 alkylaryl, or C7-13 alkylaryloxy; each occurrence of R2is independently a C1-6 hydrocarbylene group, preferably a divalent C2-8 aliphatic group, more preferably dimethylene, trimethylene, or tetramethylene; and E is 2-200 ; and * is a linkage to the end group.

[0083] Aspect 12: The method of any of aspects 9 to 11, wherein the polyfunctional hydroxy-terminated poly(arylene ether) is of the structurewherein Q5and Q6are independently at each occurrence methyl, di-n-butylaminomethyl, or morpholinomethyl; and each occurrence of x and y is independently 0-20, with the proviso that the sum of x and y is at least 2.

[0084] Aspect 13: The method of any of aspects 9 to 12, wherein the polyfunctional hydroxy-terminated poly(arylene ether) is a bifunctional hydroxy-terminated poly(phenylene ether) oligomer, preferably having an intrinsic viscosity of 0.03-0.16 deciliter per gram, or 0.05- 0.1 deciliter per gram, or 0.1-0.15 deciliter per gram, measured at 25ºC in chloroform using an Ubbelohde viscometer.23SHPP0041-WO-PCT (SS370037PCT)

[0085] Aspect 14: The method of any of aspects 9 to 13, wherein the polyfunctional hydroxy-terminated poly(arylene ether) is soluble in the polyol.

[0086] Aspect 15: The method of any of aspects 9 to 14, wherein the polyol comprises poly(tetramethylene glycol), preferably having a number-average molecular weight of 500-5000 g / mole, as determined by gel permeation chromatography with polystyrene standards, preferably 650-1250 g / mole.

[0087] Aspect 16: The method of any of aspects 9 to 15, wherein the base is an alkali metal hydroxide, preferably potassium hydroxide; or a non-nucleophilic organic base, preferably an amine; or an alkali metal hydride, preferably sodium hydride or lithium aluminum hydride; or an alkali metal carbonate, preferably sodium carbonate or sodium bicarbonate.

[0088] Aspect 17: The method of any of aspects 9 to 16, wherein the agent is an epoxide of the formulawherein R12is hydrogen or a substituted or unsubstituted C1-18 alkyl group.

[0089] Aspect 18: The method of any of aspects 9 to 17, wherein the agent comprises ethylene oxide, propylene oxide, or a combination thereof.

[0090] Aspect 19: The method of any of aspects 9 to 18, wherein the polyfunctional poly(arylene ether) comprising the end group is of the structurewherein L, Q1-Q4, x and y are as defined in aspect 3; R12is hydrogen or a substituted or unsubstituted C1-18alkyl group, preferably hydrogen or methyl; and n is independently at each occurrence 0 or 1, provided that at least one occurrence of n is 1.

[0091] Aspect 20: The method of aspect 9, comprising combining a bifunctional hydroxy-terminated poly(arylene ether) having the structure23SHPP0041-WO-PCT (SS370037PCT) poly(tetramethylene glycol); to provide a reaction mixture; combining the reaction mixture with a base preferably comprising an alkali metal hydroxide to provide a basic reaction mixture; removing water from the basic reaction mixture; combining the basic reaction mixture with an agent comprising ethylene oxide, propylene oxide, or a combination thereof to provide a product mixture comprising the bifunctional poly(arylene ether) comprising the end group having the structureand the poly(tetramethylene glycol).

[0092] Aspect 21: The method of any of aspects 9 to 20, wherein the product mixture is substantially free of a volatile organic solvent; or the polyfunctional poly(arylene ether) does not comprise a carbonate linkage; or the product mixture is substantially free of a volatile organic solvent and the alkoxylated poly(phenylene ether) does not comprise a carbonate linkage.

[0093] Aspect 22: The method of any of aspects 9 to 21, wherein the product mixture comprises 0-5,000 ppm of a poly(arylene ether) comprising a linking group comprising a carbonate functional group, an ester functional group, or a combination thereof.

[0094] Aspect 23: The method of any of aspects 9 to 22, wherein the polyfunctional poly(arylene ether) comprising the end group is not isolated from the product mixture.

[0095] Aspect 24: A composition made by the method of any of aspects 9 to 23.

[0096] 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, which are otherwise not necessary to the achievement of the function or objectives of the compositions, methods, and articles.

[0097] 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 denote any order, quantity, or importance, but rather are used to distinguish one element from another. The terms “a” and “an” and “the” do not denote a limitation of quantity, and are to be construed23SHPP0041-WO-PCT (SS370037PCT) 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 “an aspect” 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. In addition, it is to be understood that the described elements can be combined in any suitable manner in the various aspects.

[0098] 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.

[0099] 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.

[0100] 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.

[0101] 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 hydrocarbylene residue is described as substituted, it may, optionally, contain heteroatoms over and above the carbon and hydrogen members of the substituent residue. Thus, when specifically described as substituted, the hydrocarbylene 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 hydrocarbylene 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,23SHPP0041-WO-PCT (SS370037PCT) monovalent hydrocarbon group having at least one carbon-carbon double bond (e.g., ethenyl (- HC=CH2)). “Alkoxy” means an alkyl group that is linked via an oxygen (i.e., alkyl-O-), for example methoxy, ethoxy, and sec-butyloxy groups. "Alkylene" means a straight or branched chain, saturated, divalent aliphatic hydrocarbon group (e.g., methylene (-CH2-) or, propylene (- (CH2)3-)). “Cycloalkylene” means a divalent cyclic alkylene group, -CnH2n-x, wherein x is the number of hydrogens replaced by cyclization(s). “Cycloalkenyl” means a monovalent group having one or more rings and one or more carbon-carbon double bonds in the ring, wherein all ring 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.

[0102] While particular embodiments have been described, alternatives, modifications, variations, improvements, and substantial equivalents 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, improvements, and substantial equivalents.

Claims

23SHPP0041-WO-PCT (SS370037PCT) CLAIMS 1. A composition comprising: a polyfunctional poly(arylene ether) comprising an end group, wherein the end group comprises a linking group and a terminal functional group, wherein the linking group comprises a substituted or unsubstituted saturated hydrocarbylene group or a substituted or unsubstituted saturated poly(hydrocarbylene ether), and the terminal functional group comprises a hydroxyl group, a salt thereof, or a combination thereof; and a polyol; wherein the composition is substantially free of a volatile organic solvent; or the composition comprises 0-5,000 ppm, or 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 as determined by1H NMR of a poly(arylene ether) comprising a linking group comprising a carbonate functional group, an ester functional group, or a combination thereof; or the composition is substantially free of a volatile organic solvent as determined by1H NMR and the composition comprises 0-5,000 ppm, or 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, as determined by1H NMR, of a poly(arylene ether) comprising a linking group comprising a carbonate functional group, an ester functional group, or a combination thereof. The composition of claim 1, comprising 20-60 wt%, or 30-50 wt%, or 35-45 wt% of the polyfunctional poly(arylene ether); and 40-80 wt%, or 50-70 wt%, or 55-65 wt% of the polyol; wherein weight percent is based on the total weight of the composition.

3. The composition of claim 1 or 2, wherein the polyol comprises poly(tetramethylene glycol), preferably having a number-average molecular weight of 500-5000 g / mole, as determined by gel permeation chromatography with polystyrene standards, or 650-1250 g / mole.

4. The composition of any of claims 1 to 3, wherein the polyfunctional poly(arylene ether) comprising the end group is a bifunctional poly(arylene ether) of the structure23SHPP0041-WO-PCT (SS370037PCT)wherein Q1and Q2are each independently each occurrence halogen, unsubstituted or substituted C1-12 primary or secondary hydrocarbyl, C1-12 hydrocarbylthio, C1-12 hydrocarbyloxy, and 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 C1-12 primary or secondary hydrocarbyl, C1-12 hydrocarbylthio, C1-12 hydrocarbyloxy, and C2-12halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms; x and y are each independently 0-30, or 0-20, or 0-15, or 0-10, or 0-8, provided that the sum of x and y is at least 2, preferably at least 3, more preferably at least 4; each R12is independently hydrogen, halogen, or substituted or unsubstituted C1-18alkyl, preferably hydrogen or substituted or unsubstituted C1-6alkyl, more preferably hydrogen or substituted or unsubstituted C1-3alkyl; each n is independently 1 or more, preferably 1-3; L represents one or more units having the structurewherein * indicates a bond to another repeat unit or an end group R3-R6are independently at each occurrence hydrogen, halogen, unsubstituted or substituted C1-12 primary or secondary hydrocarbyl, C1-12 hydrocarbylthio, C1-12 hydrocarbyloxy, and 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 formula23SHPP0041-WO-PCT (SS370037PCT)wherein each occurrence of Ra, Rb, Rc, Rd, and Reis independently hydrogen, C1-12hydrocarbyl, or C1-6hydrocarbylene, optionally wherein Raand Rbor Rcand Rdtogether are a C4-8alkylene group; each occurrence of R1is independently hydrogen, a C1-14 hydrocarbyl, a C1-14 halohydrocarbyl, or a C1-14 heterohydrocarbyl, preferably C1-13 alkyl, C1-13 alkoxy, C2-13 alkenyl, C2-13 alkenyloxy, C3-6 cycloalkyl, C3-6 cycloalkoxy, C6-14 aryl, C6-10 aryloxy, C7-13 arylalkyl, C7-13 arylalkoxy, C7-13 alkylaryl, or C7-13 alkylaryloxy; each occurrence of R2is independently a single bond, C1-6 hydrocarbylene group, preferably a divalent C2-8 aliphatic group, more preferably dimethylene, trimethylene, or tetramethylene; and E is 2-200.

5. The composition of any of claims 1 to 4, wherein the polyfunctional poly(arylene ether) comprising the end group is a bifunctional poly(arylene ether) of the structurewherein Q5and Q6are independently at each occurrence methyl, di-n-butylaminomethyl, or morpholinomethyl; and each occurrence of x and y is independently 0-20, with the proviso that the sum of x and y is at least 2; R12is hydrogen or a substituted or unsubstituted C1-18alkyl group, preferably hydrogen or methyl; n is independently at each occurrence 0 or 1;23SHPP0041-WO-PCT (SS370037PCT) the polyol comprises poly(tetramethylene glycol), preferably having a number-average molecular weight of 500-5000 g / mole, as determined by gel permeation chromatography with polystyrene standards, preferably 650-1250 g / mole; and the composition comprises 0-5,000 ppm of a poly(arylene ether) comprising a linking group comprising a carbonate functional group, an ester functional group, or a combination thereof.

6. A composition comprising the composition of any one of claims 1 to 5, a multifunctional isocyanate, and optionally a crosslinking agent, a curing agent, a curing catalyst, a curing initiator, or a combination thereof; and a flame retardant, a filler, a coupling agent, or a combination thereof.

7. A polyurethane composition formed by reaction of the composition of any one of claims 1 to 5 with a multifunctional isocyanate to form a plurality of urethane linkages.

8. An article including the composition of any of claims 1 to 7.

9. A method for the manufacture of a polyfunctional poly(arylene ether) of any one of claims 1 to 5, the method comprising: combining a polyfunctional hydroxy-terminated poly(arylene ether); and a polyol; to provide a reaction mixture; combining the reaction mixture with a base to provide a basic reaction mixture; removing water from the basic reaction mixture; and combining the basic reaction mixture with an agent comprising an alkylene oxide; to provide a product mixture comprising the polyfunctional poly(arylene ether).

10. The method of claim 9, wherein the method is in the absence of a solvent, preferably in the absence of an aromatic hydrocarbon solvent, more preferably in the absence of chlorobenzene, ortho-dichlorobenzene, 1,2,4-trichlorobenzene, toluene, xylene, benzene, or preferably in the absence of a ketone solvent, more preferably methyl ethyl ketone, methyl isobutyl ketone, or a combination thereof.

11. The method of claim 9 or claim 10, wherein the polyfunctional hydroxy-terminated poly(arylene ether) is a bifunctional hydroxy-terminated poly(arylene ether) of the structure23SHPP0041-WO-PCT (SS370037PCT)wherein Q5and Q6are independently at each occurrence methyl, di-n-butylaminomethyl, or morpholinomethyl; and each occurrence of x and y is independently 0-20, with the proviso that the sum of x and y is at least 2.

12. The method of any of claims 9 to 11, wherein the polyol comprises poly(tetramethylene glycol), preferably having a number-average molecular weight of 500-5000 g / mole, as determined by gel permeation chromatography with polystyrene standards, preferably 650-1250 g / mole, preferably wherein the polyfunctional hydroxy-terminated poly(arylene ether) is soluble in the polyol.

13. The method of any of claims 9 to 12, wherein the agent is an epoxide of the formulawherein R12is hydrogen or a substituted or unsubstituted C1-18alkyl group; preferably wherein the agent comprises ethylene oxide, propylene oxide, or a combination thereof.

14. The method of any of claims 9 to 13, wherein the polyfunctional poly(arylene ether) comprising the end group is a bifunctional poly(arylene ether) of the structurewherein L, Q1-Q4, x and y are as defined in claim 10;23SHPP0041-WO-PCT (SS370037PCT) R12is hydrogen or a substituted or unsubstituted C1-18 alkyl group, preferably hydrogen or methyl; and n is independently at each occurrence 0 or 1, provided that at least one occurrence of n is 15. The method of claim 9, comprising combining a bifunctional hydroxy-terminated poly(arylene ether) having the structurepoly(tetramethylene glycol); to provide a reaction mixture; combining the reaction mixture with a base, preferably comprising an alkali metal hydroxide, to provide a basic reaction mixture; removing water from the basic reaction mixture; combining the basic reaction mixture with an agent comprising ethylene oxide, propylene oxide, or a combination thereof to provide a product mixture comprising the bifunctional poly(arylene ether) comprising the end group having the structureand the poly(tetramethylene glycol).

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