Polyfunctional poly(arylene ethers) and copolymers thereof

Abstract

A polyfunctional poly(arylene ether) includes an end group including an end group, wherein the end group includes a linking group including a substituted or unsubstituted saturated hydrocarbylene 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, wherein the linking group includes 0 to 5,000 ppm of a carbonate functional group, 0 to 5,000 ppm of an ester functional group, or a combination thereof.

Description

POLYFUNCTIONAL POLY(ARYLENE ETHERS) AND COPOLYMERS THEREOFCROSS REFERENCE TO RELATED APPLICATIONThis application claims priority to and the benefit of European Patent Application No. 24171645.5 filed April 22, 2024, the contents of which are hereby incorporated by reference in their entirety.BACKGROUND

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

[0002] Poly(arylene ethers) are a class of thermoplastic polymers 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) oligomers into copolymers to impart dielectric performance and moisture resistance. However, poly(arylene ethers) have glass transition temperatures that are too high for the processing equipment of some copolymers such as polyurethanes.

[0003] There accordingly remains a need in the art for polyfunctional poly (arylene ethers) with lower glass transition temperatures.BRIEF DESCRIPTION

[0004] The above-described and other deficiencies of the art are met by a polyfunctional poly(arylene ether) including an end group, wherein the end group includes a linking group including a substituted or unsubstituted saturated hydrocarbylene 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, and wherein the linking group includes 0 to 5,000 ppm of a carbonate functional group, 0 to 5,000 ppm of an ester functional group, or a combination thereof.

[0005] In another aspect, a composition includes the above-described polyfunctional poly(arylene ether), wherein the composition includes 0 to 5,000 ppm of a carbonate-containing polyfunctional poly(arylene ether) including an end group, wherein the end group includes a terminal functional group including a hydroxyl group, salt thereof, or a combination thereof, and a linking group wherein the linking group of the carbonate-containing polyfunctional poly(arylene ether) includes a carbonate group, 0 to 5,000 ppm of an ester-containingpolyfunctional poly(arylene ether), including an end group, wherein the end group includes a linking group and a terminal functional group, wherein the terminal functional group includes a hydroxyl group, salt thereof, or a combination thereof, and wherein the linking group of the ester-containing polyfunctional poly(arylene ether) includes an ester group, or a combination thereof.

[0006] In another aspect, a method for preparing the above-described polyfunctional poly(arylene ether) includes reacting a substituted or unsubstituted alkylene oxide and optionally, a multifunctional polyol with a poly(arylene ether) including phenolic terminal functional groups under conditions effective to provide a reaction mixture including the polyfunctional poly (arylene ether).

[0007] In another aspect, a method for decreasing the glass transition temperature of a polymer that is different from the above-described polyfunctional poly(arylene ether) includes reacting the above-described polyfunctional poly(arylene ether) with the polymer that is different from the polyfunctional poly(arylene ether) under conditions effective to provide a reaction mixture including a copolymer derived from a polymer that is different from the abovedescribed polyfunctional poly(arylene ether) and the above-described polyfunctional poly (arylene ether).

[0008] In another aspect, a copolymer is derived from the above-described polyfunctional poly (arylene ether).

[0009] In another aspect, a copolymer composition includes the above-described copolymer, and an additive composition.

[0010] In another aspect, an article includes the above-described copolymer, or the above-described copolymer composition.

[0011] In another aspect, a method for manufacturing the above-described article includes molding, casting, fiber spinning, extruding, or foaming the above-described copolymer or above-described copolymer composition to provide the article.

[0012] The above-described and other features are exemplified by the following drawing, detailed description, examples, and claims.BRIEF DESCRIPTION OF THE DRAWINGS

[0013] The following is a brief description of the drawings wherein like elements are numbered alike and which are exemplary of the various aspects described herein.

[0014] The FIGURE is a graph showing the glass transition temperature (Tg) of each material produced versus the number of equivalents of ethylene oxide added.DETAILED DESCRIPTION

[0015] Poly (arylene ethers) can improve one or more of the dielectric performance, heat resistance, flame resistance or moisture absorption of materials, making them particularly well suited for a variety of applications, particularly electronic applications. It is therefore desirable to incorporate poly(arylene ethers) into other materials, such as other copolymers, to improve one or more of the dielectric performance, heat resistance, flame resistance, or moisture absorption of the resulting copolymers. For example, polyurethane is a versatile material that has a variety of applications. It can be used for insulation, furniture, car parts, paints, and adhesives. Polyurethanes have high electrical resistance and are useful for electrical insulation and dielectrics in electronic devices. However, polyurethanes can be hydrolytically unstable over time. The inventors hereof have determined that the hydrolytic stability of polyurethanes can be improved by incorporating poly (arylene ethers).

[0016] In addition, lower processing temperatures are used for some materials and applications. For example, polyurethanes are typically processed at temperatures of 80°C or less. To that end, the presence of a linking group in the material including a substituted or unsubstituted saturated hydrocarbylene, or a substituted or unsubstituted saturated poly(hydrocarbylene ether) can decrease the glass transition temperature of the polyfunctional poly(arylene ether). The present methods allow control over the length of linking group, thus providing control over the glass transition temperature of the material incorporating poly(arylene ethers). The polyfunctional poly (arylene ethers) are therefore customizable for use in various applications.

[0017] 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 unless it is specifically identified as “substituted hydrocarbyl”. The hydrocarbyl residue can be aliphatic or aromatic, straight-chain, cyclic, bicyclic, branched, saturated, or unsaturated. It can also contain combinations of aliphatic, aromatic, straight chain, cyclic, bicyclic, branched, saturated, and unsaturated hydrocarbon moieties. When the hydrocarbyl residue is described as substituted, it can contain heteroatoms in addition to carbon and hydrogen.

[0018] As used herein, the term “saturated hydrocarbyl” refers to a residue that contains only carbon and hydrogen unless it is specifically identified as “substituted saturated hydrocarbyl.” “Saturated hydrocarbyl” includes straight-chain, cyclic, bicyclic, and branched groups and excludes unsaturated groups, such as aromatic groups, partially aromatic groups, and groups having double bonds and triple bonds. The saturated hydrocarbyl can also includecombinations of straight-chain, cyclic, bicyclic, and branched groups. Non-limiting examples of saturated hydrocarbylenes include alkyl groups (branched and straight-chain), cycloalkyl groups, alkylene groups substituted by cycloalkyl groups, and cycloalkyl groups substituted with alkyl groups.

[0019] As used herein, the term “saturated poly(hydrocarbylene ether)” refers to a polyether group wherein the hydrocarbylene moiety of the polyether group contains only carbon and hydrogen unless it is specifically identified as “substituted poly(hydrocarbylene ether).” “Saturated hydrocarbylene” includes straight-chain, cyclic, polycyclic (e.g., bicyclic), and branched groups and excludes unsaturated groups, such as aromatic groups, partially aromatic groups, and groups having double bonds and triple bonds. The saturated hydrocarbylene can also include combinations of straight-chain, cyclic, polycyclic, and branched groups. Examples of saturated hydrocarbylene groups include alkyl groups, cycloalkyl groups, alkylene groups substituted by cycloalkyl groups, and cycloalkyl groups substituted with alkyl groups.

[0020] The polyfunctional poly(arylene ether) includes one or more end groups. The end group includes a linking group and a terminal functional group. The linking group includes a substituted or unsubstituted saturated hydrocarbylene, or a substituted or unsubstituted saturated poly(hydrocarbylene ether). For illustrative purposes only, shown below are a portion of a polyfunctional poly(arylene ether) having a hydrocarbylene (e.g., an ethyl group) as the linking group (structure on left) and a portion of a polyfunctional poly(arylene ether) having a 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.

[0021] 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.

[0022] 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.

[0023] 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.

[0024] The linking groups can include unit(s) derived from multifunctional polyols. As used herein, a multifunctional polyol includes at least two hydroxyl groups, for example up to six hydroxyl groups. The multifunctional polyols can be any multifunctional polyol known in the art. Exemplary multifunctional polyols include glycerol, trimethylolpropane, triethanolamine, pentaerythritol, xylitol, sorbitol, and sucrose. In some aspects, multifunctional polyols include polyether polyols such as, for example, ethoxylated, propoxylated, and butoxylated polyols, wherein two or more hydroxyl groups are not alkoxy lated.

[0025] The polyfunctional poly(arylene ether) can include linkers of the formulas -C(Rx)(Ry)--[(C(Rx)(Ry))m-O]o-(C(Rx)(Ry))- or a combination thereof, wherein Rxand Ryare each independently hydrogen, halogen, or C1-6 alkyl, m is 2 or more, preferably 2-4, and o is 1 or more, preferably 1-25. In some aspects, Rxand Ryare each independently hydrogen, halogen, or C1-3 alkyl, m is 2 or more, preferably 2-4, and o is 1 or more, preferably 1-25. In some aspects, Rxand Ryare each independently hydrogen, halogen, or methyl, m is 2 or more, preferably 2-4, and o is 1 or more, preferably 1- 25. In some aspects, Rxand Ryare each independently hydrogen, m is 2-3, and o is 1-25. In the foregoing aspects, o can be 5-25, or 15-25. The present inventors have discovered that as the linking group grows longer (includes more carbon atoms in the backbone), the glass transition temperature of the material decreases. This is an advantage when lower processing temperatures are preferred. For example, polyurethanes are typically processed at temperatures of not morethan 80°C. When the value of o is 5-25, the glass transition temperature can be about 20°C less, preferably 40°C less, more preferably 60°C less than the glass transition temperature of the corresponding poly( arylene ether) with phenolic end groups and no end groups that include a linking group and a terminal functional group (as defined for the polyfunctional poly(arylene ether)). In some aspects, the glass transition temperature of the polyfunctional poly(arylene ether) is not more than 100°C, or not more than 80°C, as measured using differential scanning calorimetry per ASTM D3418 at a heating rate of 20°C per minute.

[0026] 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.

[0027] 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 Q1isindependently methyl or methyl substituted with a di(Ci-6 alkyl)amino group or a morpholinyl group, and each Q2is methyl.

[0028] 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.

[0029] 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.

[0030] 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 formulaor wherein each occurrence of Ra, Rb, Rc, Rd, and Reis independently hydrogen, C1-12 hydrocarbyl, or Ci -6 hydrocarbylene, optionally wherein Raand Rbor Rcand Rdtogether are a C4-8 alkylene group, each occurrence of 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.

[0031] 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.

[0032] 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 I )- / z-bu tanc, 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, 1 , 1 -bis(4-hydroxy-3 ,5 -dimethylphenyl)cyclohexane, 1 , 1 -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).

[0033] 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 nottertiary 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.

[0034] 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.

[0035] The polyfunctional poly(arylene ether) can be derived from a poly(arylene ether) having phenolic terminal groups, by reaction with an alkylene oxide and optionally, a multifunctional polyol to form the polyfunctional poly (arylene ether). Use of a poly (arylene ether) having two phenolic end groups and an alkylene oxide and optional diol provides the bifunctional poly (arylene ether). A polyfunctional poly (arylene ether) having more than two end groups 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).

[0036] The poly(arylene ether) having phenolic terminal groups can be formed by polymerization of monomers, for example, including a monohydric phenol, a dihydric phenol, or a combination thereof, by continuous addition of oxygen to a reaction mixture including the monomers, optionally a solvent, and a polymerization catalyst. The molecular oxygen (O2) can be provided as air or pure oxygen. The polymerization catalyst can be a metal complex, i.e. a metal catalyst, including a transition metal cation, including cations from Group VIB, VIIB, VIIIB, or IB of the periodic table, or a combination thereof. The catalyst can include a metal cation such as chromium, manganese, cobalt, copper, or combination thereof and an anion such as chloride, bromide, iodide, sulfate, acetate, propionate, butyrate, laurate, palmitate, benzoate, or a combination of one or more of these anions, and optionally one or more charge-neutral ligands such as water, amines, phosphines, CO, or the like. Alternatively, a metal or metal oxide and 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.

[0037] 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, and combinations thereof. Exemplary trialkylmonoamines include trimethylamine, triethylamine, tripropylamine, tributylamine, butyldimethylamine, phenyldiethylamine, or the like, and combinations thereof.

[0038] 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 wherein * indicates a bond to the polymer chain.

[0039] 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.

[0040] The poly(arylene ether) can be isolated using any method known in the art. Isolation can be by, for example, precipitation of the poly(arylene ether) which can be induced by appropriate selection of reaction solvent described above, or by the addition of an antisolvent to the reaction mixture. Suitable anti-solvents include lower alkanols having one to about ten carbon atoms, acetone, and hexane. The preferred anti-solvent is methanol. The antisolvent can be employed at a range of concentrations relative to the organic solvent, with the optimum concentration depending on the identities of the organic solvent and anti-solvent, as well as the concentration and intrinsic viscosity of the poly(arylene ether) product. When the organic solvent is toluene and the anti-solvent is methanol, a toluene: methanol weight ratio of 50:50 to 80:20 is suitable, with ratios of 60:40 to 70:30 being preferred, and 63:37 to 67:33 being more preferred. These preferred and more preferred ratios are useful for producing a desirable powder morphology for the isolated poly(phenylene ether) resin, without generating either stringy powder or excessive powder fines.

[0041] Alternatively, the poly(arylene ether) solution and the aqueous sequestrant solution can be separated with a liquid-liquid centrifuge. Once this separation has been effected,the polyfunctional poly(arylene ether) can be isolated from the poly(arylene ether) solution using a total isolation method. Suitable total isolation methods include, for example, devolatilizing extrusion, spray drying, wiped film evaporation, flake evaporation, and combinations of the foregoing methods.

[0042] The poly(arylene ethers), for example, 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) 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”).

[0043] 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 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.

[0044] 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.

[0045] 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 post-consumer / post-industrial recycled materials, including pyrolysis oil (“py-oil”), to produce the poly (arylene ether).

[0046] 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.

[0047] 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, 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.

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

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

[0050] 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.

[0051] The method can further comprise 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.

[0052] The end groups (the linking group and the terminal functional group) can be introduced by reacting the basic reaction mixture or dried basic reaction mixture including the salt of the phenolic poly( arylene ether), and preferably with 100 ppm or less of water, with a polyol if used, followed be 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.

[0053] 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 Ci-6 alkyl group. The agent can include ethylene oxide, propylene oxide, or a combination thereof, or the agent can be ethylene oxide.

[0054] 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.

[0055] After contacting with the optional polyol and 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 hydrocarbylene 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.

[0056] The synthesis of the polyfunctional poly(arylene ether) 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, and combinations thereof. In an aspect, the aromatic hydrocarbon solvent includes toluene. In addition to the aromatic hydrocarbon solvent, the solvent can, optionally, further include a C3-8 aliphatic alcohol that is a poor solvent for the poly(arylene ether), such as, for example, n-propanol, isopropanol, n-butanol, t-butanol, n- pentanol, and the like, and combinations thereof. A preferred C3-8 aliphatic alcohol is n-butanol. The solvent can further include, in addition to a Ce-is aromatic hydrocarbon and a C3-8 aliphatic alcohol, methanol or ethanol, which act as an anti-solvent for the poly(arylene ether). The Ce-Cis aromatic hydrocarbon, the C3-C8 aliphatic alcohol, and the methanol or ethanol can be combined in a wide range of proportions, but it can be preferred that the solvent include at least 50 weight percent of the Ce-Cis aromatic hydrocarbon. In some aspects, no solvents other than the aromatic hydrocarbon solvent are present.

[0057] 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 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-(l-pyrrolino)pyridine, 4-(l-piperidino)pyridine, 2-vinylpyridine, 3-vinylpyridine, 4-vinylpyridine, or the like.

[0058] 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 Na2CC>3, 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.

[0059] 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, e.g., bifunctional poly(arylene ether) having saturated hydrocarbyl 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.

[0060] Conventional methods for introducing an end group to poly(arylene ether)s have used the following reagents, which include several disadvantages, including side reactions.In formndently 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. Another advantage of the phenolic poly( arylene ether) and methods or preparation described herein is that reagents such as those of Formulas (9)-(l 1) are not used, 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 carbonate side -product resulting from use of ethylene carbonate (e.g., formula (9))is shown below for illustrative purposes only.

[0062] An example of an ester side-product arising from use of a compound of formula (11) is shown below for illustrative purposes only.

[0001] 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 as defined herein. 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 comprisinga 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).

[0063] 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] The present methods allow for excellent control over product structure. As the length of the linking group backbone increases, in addition to modifying the solubility of the polyfunctional poly(arylene ether), the glass transition temperature of the polyfunctional poly(arylene ether) can decrease. This is an advantage when lower processing temperatures are needed for materials derived from poly(arylene ethers). The glass transition temperature of the polyfunctional poly(arylene ether) can be about 20°C less, preferably 40°C less, more preferably 60°C less than the glass transition temperature of the corresponding poly(arylene ether) with phenolic end groups and no linking groups. In some aspects, the glass transition temperature of the polyfunctional poly(arylene ether) is not more than 100°C, or not more than 80°C, as measured using differential scanning calorimetry per ASTM D3418 at a heating rate of 20°C per minute.

[0065] The polyfunctional poly(arylene ether) can have a number average molecular weight (Mn) of 600 to 10,000, or 400 to 2,500 grams per mole (g / mol) as determined by gel permeation chromatography (GPC) using polystyrene standards. In some aspects, the polyfunctional poly(arylene ether) can have a weight average molecular weight (Mw) of 500 to 6,000 g / mol, each as determined by GPC. For example, the polyfunctional poly(arylene ether) can have a number average molecular weight (Mn) of 400 to 2,200 g / mol or 800 to 1,600 g / mol and a weight average molecular weight (Mw) of 600 to 5,000 g / mol or 800 to 4,500 g / mol, each as determined by GPC.

[0066] The polyfunctional poly(arylene ether) can have an intrinsic viscosity of 0.04 to 0.16 deciliter per gram (dL / g) as measured at 25 °C in chloroform. For example, the intrinsic viscosity is preferably 0.06 to 0.1 dL / g, more preferably 0.075 to 0.090 dL / g.

[0067] The polyfunctional poly(arylene ether) includes an average of at least 1.8 end groups. In some aspects, the polyfunctional poly(arylene ether) includes an average of at least atleast 1.85, or at least 1.9, or at least 1.95, or at least 2.0 end groups. In some aspects, the polyfunctional poly(arylene ether) includes an average of 1.8-2.0 or 1.8-3.0 end groups.

[0068] The polyfunctional 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.

[0069] Based on the excellent dielectric performance and moisture resistance of poly(arylene ethers) and the ability to modulate the glass transition temperature of materials, a method is disclosed for decreasing the glass transition temperature of a different polymer, i.e., a polymer differs from the polyfunctional poly( arylene ethers), i.e., is not itself a poly(arylene ether) (which can be referred to herein as a “different polymer”). The different polymer is coreactive with the polyfunctional poly(arylene ethers). The method includes preparing a copolymer from the polyfunctional poly(arylene ethers) with the different polymer. In particular, the method includes reacting the polyfunctional poly( arylene ether) with the polymer that differs from the polyfunctional poly (arylene ether), under conditions effective to provide a reaction mixture including the copolymer, wherein the copolymer includes the reaction product of the polyfunctional poly(arylene ether) and the different polymer.

[0070] The polymer that is different from the polyfunctional poly(arylene ether) can be any polymer capable of copolymerization with the polyfunctional poly(arylene ether), or capable of being derivatized to be reactive with the polyfunctional poly (arylene ether). Exemplary polymers of this type include polycarbonates, polyurethanes, polyureas, polyesters, poly(ester carbonate)s, poly(carbonate-siloxane)s, and the like. The copolymers thus produced can be a poly(arylene-ether)-polycarbonate, poly poly(arylene-ether)-polyurethane, poly(arylene-ether)- polyurea, poly(arylene-ether)-polyester, poly(arylene-ether)-polyester, poly(arylene-ether)- poly(ester-carbonate), poly(arylene-ether)-poly(carbonate-siloxane).

[0071] A copolymer composition can include a copolymer derived from the polyfunctional poly(arylene ethers) and the different polymer, and optionally, an additive composition. Additives can include catalysts, surfactants, flame retardants, smoke suppressants, fillers and / or reinforcements, antioxidants, UV stabilizers, antistatic agents, infrared radiation absorbers, viscosity reducing agents, pigments, dyes, mold release agents, antifungal agents, biocides, blowing agents, and combinations thereof. The additive composition can be present in an amount up to 10 wt%, for example from 0.01-10 wt%, from 0.1-5 wt%, from 0.1-2 wt%, or 0.01-1 wt%, based on the total weight of the polymer composition.

[0072] Articles can be prepared from the copolymers derived from the polyfunctional poly(arylene ether) or from the copolymer compositions. Shaped, formed, or molded articlesincluding the copolymer compositions. The copolymer compositions can be molded into useful shaped articles by a variety of methods, such as injection molding, extrusion, rotational molding, blow molding and thermoforming.

[0073] In some aspects, the copolymer derived from the polyfunctional poly (arylene ether) includes polyurethane groups, termed herein a “poly(arylene ether-urethane)”. These copolymers can be distinguished from the poly(arylene ether)-poly(urethane) copolymers described above, which are formed from the reaction of the polyfunctional poly(arylene ether) and co-reactive polyurethane polymers. 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 are 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.

[0074] The poly(arylene ether-urethane)is derived from a isocyanate compound having an average of at least 2 isocyanate groups per molecule. In some aspects, the number of isocyanate groups per molecule is 2 to 4, or 2 to 3, or 2 to 2.5. Exemplary isocyanates include1.4-tetramethylene diisocyanate, 1 ,6-hexamethylene diisocyanate, 2,2,4-trimethyl-l,6- hexamethylene diisocyanate, 1,12-dodecamethylene diisocyanate, cyclohexane- 1,3-diisocyanate, and cyclohexane- 1 ,4-diisocyanate, l-isocyanato-2-isocyanatomethyl cyclopentane, 1- isocyanato-3-isocyanatomethyl-3,5,5-trimethyl-cyclohexane, bis(4- isocyanatocyclohexyljme thane, 2,4'-dicyclohexyl-methane diisocyanate, 1,3- bis(isocyanatomethyl)-cyclohexane, 1 ,4-bis-(isocyanatomethyl)-cyclohexane, bis(4-isocyanato- 3-methyl-cyclohexyl)methane, alpha, alpha, alpha', alpha'-tetramethyl- 1 ,3-xylylene diisocyanate, alpha, alpha, alpha', alpha'-tetramethyl- 1 ,4-xylylene diisocyanate, 1 -isocyanato- 1 -methyl-4(3)- isocyanatomethyl cyclohexane, 2, 4-hexahydro toluene diisocyanate, 2,6-hexahydrotoluene diisocyanate, 1,3-phenylene diisocyanate, 1 ,4-phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 2,4-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate,1.5-diisocyanato naphthalene, an oligomeric diphenylmethane diisocyanate having an average ofgreater than 2 and less than or equal to 4 isocyanate groups per molecule, or a combination thereof.

[0075] The poly(arylene ether-urethane) can further include repeating urethane units derived from a polyol that is different from the polyfunctional poly (arylene ether). As used herein, the term “polyol” refers to an organic compound with at least two hydroxyl groups, for example up to eight hydroxyl groups. In some aspects, the polyol includes an ethylene oxide capped polyether triol, a propylene oxide capped polyether triol, an ethylene oxide capped polyether polyol, or a combination thereof. Additional examples of polyols include diethylene glycol, diethanolamine, dipropylene glycol, ethoxylated glycerins, and combinations thereof. Polyols include polyether polyols prepared by reacting an initiator having 2 to 8 hydroxyl groups per molecule, specifically 3 to 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, butanediol, hexanediol, other C2-C8 glycols, or a combination thereof.

[0076] The poly(arylene ether-urethane) composition or the poly(arylene ether)- poly(urethane)copolymer compositions can include the poly(arylene ether-urethane) and an additive composition. Exemplary additives can include catalysts, surfactants, flame retardants, smoke suppressants, fillers including reinforcing fillers, antioxidants, UV stabilizers, antistatic agents, infrared radiation absorbers, viscosity reducing agents, pigments, dyes, mold release agents, antifungal agents, biocides, blowing agents, or a combination thereof.

[0077] Additives can include a blowing agent. The blowing agent can include a physical blowing agent such as 1,1-difluoroethane, 1,1,1,2-tetrafluoroethane, pentafluoroethane, 1,1,1,3,3-pentafluoropropane, 1,1,1,3,3-pentafluorobutane, 2-bromopentafluoropropene, 1- bromopentafluoropropene, 3-bromopentafluoropropene, 3,4,4,5,5,5-heptafluoro-l-pentene, 3- bromo-l,l,3,3-tetrafluoropropene, 2-bromo-l,3,3,3-tetrafluoropropene, 1 -bromo-2, 3,3,3- tetrafluoropropene, 1,1,2,3,3,4,4-heptafluorobut-l-ene, 2-bromo-3,3,3-trifluoropropene, E-l- bromo-3,3,3-trifluoropropene-l, (Z)-l,l,l,4,4,4-hexafluoro-2-butene, 3,3,3-trifluoro-2-(trifluoromethyl)propene, l-chloro-3,3,3-trifluoropropene, 2-chloro-3,3,3-trifluoropropene, l,l,l-trifluoro-2-butene, or a combination thereof. The physical blowing agent, when used, can be present at 2 to 20 wt%, based on the total weight of the reaction mixture. Within this range, the physical blowing agent amount can be 2.5 to 15 wt%.

[0078] Chemical blowing agents include water and carboxylic acids that react with isocyanate groups to liberate carbon dioxide. When present, chemical blowing agents, and specifically water, can be used in an amount of 0.2 to 5 wt%, based on the total weight of the reaction mixture. Within this range, the chemical blowing agent amount can be 0.2 to 3 wt%.

[0079] Catalysts include urethane catalysts, isocyanurate catalysts, and combinations thereof. Suitable catalysts include tertiary amine catalysts such as dimethylcyclohexylamine, benzyldimethylamine, N,N,N',N'',N"-pentamethyldiethylenetriamine, 2,4,6-tris- (dimethylaminomethyl)-phenol, triethylenediamine, N,N-dimethyl ethanolamine, and combinations thereof; organometallic compounds such as potassium octoate (2-ethyl hexanoate), potassium acetate, dibutyltin dilaurate, dibutlytin diacetate, and combinations thereof quaternary ammonium salts such as 2-hydroxpropyl trimethylammonium formate; N-substituted triazines such as N,N',N"-dimethylaminopropylhexahydrotriazine; and combinations thereof. The additive composition can include a surfactant such as polyorganosiloxanes, polyorganosiloxane polyether copolymers, phenol alkoxylates (such as ethoxylated phenol), alkylphenol alkoxylates (such as ethoxylated nonylphenol), and combinations thereof. The surfactants can function as emulsifiers and / or foam stabilizers.

[0080] The additive composition can include flame retardants such as, for example, organophosphorous compounds such as organic phosphates (including trialkyl phosphates such as triethyl phosphate and tris(2-chloropropyl)phosphate, and triaryl phosphates such as triphenyl phosphate and diphenyl cresyl phosphate), phosphites (including trialkyl phosphites, triaryl phosphites, and mixed alkyl-aryl phosphites), phosphonates (including diethyl ethyl phosphonate, dimethyl methyl phosphonate), polyphosphates (including melamine polyphosphate, ammonium polyphosphates), polyphosphites, polyphosphonates, phosphinates (including aluminum tris(diethyl phosphinate); halogenated fire retardants such as tetrabromophthalate esters and chlorinated paraffins; metal hydroxides such as magnesium hydroxide, aluminum hydroxide, cobalt hydroxide, and hydrates of the foregoing metal hydroxide; and combinations thereof. The flame retardant can be a reactive type flame-retardant (including polyols which contain phosphorus groups, 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10- phospha-phenanthrene-10-oxide, phosphorus-containing lactone-modified polyesters, ethylene glycol bis(diphenyl phosphate), neopentylglycol bis(diphenyl phosphate), amine- and hydroxyl-functionalized siloxane oligomers). These flame retardants can be used alone or in conjunction with other flame retardants.

[0081] The additive composition can include flame retardant synergists such as antimony pentoxide; antioxidants, surfactants, thermal and ultraviolet stabilizers, lubricants, anti-static agents, dyes, pigments, particulates, reinforcing materials and other constituents, or the like.

[0082] Those skilled in the art understand that there is a continuum between polyurethane and polyisocyanurate. Either or both can be prepared from the polyfunctional poly (arylene ether), the optional polyol, and the isocyanate compound. Reaction mixtures used to prepare polyurethanes and polyisocyanurates are characterized by an isocyanate index, which is calculated according to the equationIsocyanate MOICSNCO> x 100 Index -MOICSOH + MOICSHOH + MOICSNH wherein MOICSNCO is the moles of isocyanate groups in the reaction mixture, MOICSOH is the moles of OH groups in the reaction mixture from sources other than water (including OH groups from alcohols and carboxylic acids), MOICSHOH is the moles of OH groups in the reaction mixture from water, and MOICSNH is the moles of NH groups in the reaction mixture. In general, the reaction mixture is characterized by an isocyanate index of 105 to 350. When the reaction mixture molar ratio of isocyanate groups to hydroxyl groups is 1 : 1 and no water or NH groups are present in the reaction mixture, the isocyanate index is 100, and a “pure” polyurethane is formed. The products of reaction mixtures having an isocyanate index of 100 to 125, specifically 105 to 125, are typically characterized as polyurethanes, while the products of reaction mixtures having an isocyanate index of 180 to 350 are typically characterized as polyisocyanurates.Formation of isocyanurate groups is favored not only by high isocyanate indices, but also by use of catalysts for isocyanurate formation, such as N-hydroxy alkyl quaternary ammonium carboxylates.

[0083] When the poly(arylene ether-urethane) composition or the poly(arylene ether)- poly(urethane)copolymer composition further includes a blowing agent, a polyurethane or polyisocyanurate foam can be prepared by thoroughly mixing the components together. The reaction starts after a brief period and progresses with heat development. The reaction mixture is continually expanded by the blowing gases released, until the reaction product reaches the solid state because of progressive cross-linkage, the foam structure being retained.

[0084] In a specific aspect, a polyurethane or a polyisocyanurate product is preparedfrom a composition including an isocyanate compound, a diol, and the polyfunctional poly (arylene ether), wherein the polyfunctional poly (arylene ether) is prepared from the reaction of 2,6-dimethylphenol and 2,2-bis(3,5-dimethyl-4- hydroxyphenyl)propane to form the poly(arylene ether) having phenolic terminal groups, and subsequently reacted with ethylene oxide or propylene oxide under conditions effective to provide the polyfunctional poly(arylene ether).

[0085] Also provided is a polyurethane product prepared from the composition, preferably wherein the product is a thermoplastic polyurethane, polyurethane foam, polyisocyanurate foam, or a combination thereof. To prepare the polyurethane or polyisocyanurate product, the polyfunctional poly(arylene ether), the optional polyol, and the isocyanate compound, which have been optionally temperature controlled and provided with additives, are thoroughly mixed together until the reaction product reaches the solid state because of progressive cross-linkage. When a blowing agent is included, the reaction mixture is continually expanded by the blowing gases released and a foam structure is obtained.

[0086] The product can have an isocyanate index of 105 to 350, preferably 105 to 125 or 180 to 350.

[0087] A particular product, preferably a poly(arylene ether-urethane) or a poly( arylene ether)-poly(urethane)copolymer foam product, can be prepared from the composition disclosed herein, wherein the product can have one or more of the following properties: a Shore D hardness of 45 to 90, or 50 to 80 according to ASTM D2240; a tensile stress at 100% elongation of 15 to 40 MPa, or 20 to 40 MPa according to ISO 527-1 and 527-2 (2012); a tensile stress at 300% elongation of 18 to 30 MPa, or 20 to 25 MPa according ISO 527-1 and 527-2 (2012); a tear strength of 1500 to 2500 Newtons per centimeter (N / cm), or 1600 to 2500 N / cm according to ASTM D 624-00; and a compressive strength of 5 to 15 MPa, or 6 to 10 MPa according to ASTM D 1621-00.

[0088] Specific examples of articles that can utilize the polyurethane product, and in particular a polyurethane or polyisocyanurate foam as described herein, include thermal insulation materials such as domestic appliances (such as domestic and commercial refrigerators and freezers, and hot water tanks); building materials (such as wall and roofing panels, cut-to- size pieces from slab stock, and spray-in-place foam for insulation and sealing); thermally insulated tanks and containers, pipelines, heating pipes, cooling pipes, and cold stores; and thermally insulated refrigerated vehicles for road and rail including containers.

[0089] Specific articles including the polyurethane foam as described herein include bedding, furniture, automotive interiors, mass transportation interiors (such as seating, padding,instrument panels, door panels, steering wheels, armrests, and headrests), flooring underlay, packaging, textiles, lining and gasketing applications, acoustic dampening materials, and weather stripping.

[0090] In some aspects, the article is prepared by a slabstock foam process. In this process, the raw materials are mixed, poured onto a moving conveyor, and allowed to react and expand. The resulting foam rises to form a “slab” that is typically from two to four feet high. The continuous slab is then cut into “buns”, stored, and allowed to cure for up to 24 hours. The cured foam is subsequently fabricated into useful shapes. The slabstock process can be used for foams employed in furniture, bedding and carpet cushion. The slabstock process is an example of free rise foaming.

[0091] In other aspects, the article is prepared by a molded foam process. In the molded foam process, the raw materials are mixed and poured into specially shaped molds where the foam reaction takes place. Hence, molded foam is a cellular foam product having the shape of the mold cavity in which it was produced. The molded foam process can be used for automotive cushioning, contract furniture cushioning, and cushioning for residential upholstered designs.

[0092] Articles can be manufactured using any method known in the art. In some aspects, the articles are manufactured by molding, casting, fiber spinning, extruding, or foaming the composition to provide the article.

[0093] This disclosure is further illustrated by the following examples, which are nonlimiting.EXAMPLESEthoxylation of poly(phenylene ether) oligomer:

[0094] A 50 wt% solution of poly(phenylene ether) oligomer was prepared by dissolving 1 kg of poly (phenylene ether) oligomer in 1.1 kg of MIBK (methyl isobutyl ketone) at 60 °C with stirring. To this solution was added 2 mol% of KOH (39.2g of a 50 wt% solution in water) and the solution dried by pulling a slight vacuum and distilling out on the order of 100 g of the solvent (until it ran clear.) This solution was then transferred under N2 into a 4L autoclave and ethylene oxide (4.5g, gas) was transferred into it. The autoclave was heated to 135 °C and held until the pressure drop stopped and was stable. The reactor was cooled to 25°C and the solution discharged. The resin was collected by precipitation with 5 equivalents of methanol, filtered and dried in a 100°C vacuum oven overnight.

[0095] This process was repeated with samples being removed after aliquots of ethylene oxide were sequentially added. The results are shown in the FIGURE, which is a plot of the Tgof each material produced vs. the number of equivalents of ethylene oxide added.1H-NMR was used to determine the equivalents of ethylene oxide from the ratio of peaks in the PPE backbone to the ethylene oxide groups.31P-NMR was used to check for remaining phenolic end-groups from the original oligomer. In all cases, the phenolic end groups if present, were less than the detection limit (~10ppm). As demonstrated by the data in the FIGURE, there was excellent linearity in the response of Tg to equivalents of ethylene oxide. Further, since the target Tg for customers was 80°C, this process can readily produce oligomers that satisfy the requirement.

[0096] This disclosure further encompasses the following aspects.

[0097] Aspect 1. A polyfunctional poly(arylene ether) including an end group, preferably 2-3 end groups, wherein each end group includes a linking group and a terminal functional group, wherein the terminal functional group includes a hydroxyl group, salt thereof, or a combination thereof, and the linking group includes a substituted or unsubstituted saturated hydrocarbylene, or a substituted or unsubstituted saturated poly(hydrocarbylene ether), wherein the linking group includes 0 to 5,000 ppm of a carbonate functional group, 0 to 5,000 ppm of an ester functional group, or a combination thereof, as determined byNMR.

[0098] Aspect 2. The polyfunctional poly (arylene ether) of aspect 1 including an average of at least 1.8 end groups.

[0099] Aspect 3. The polyfunctional poly(arylene ether) of aspect 1 or aspect 2, wherein the linking group independently includes the following formulas: -C(RI)(R2)-, or -[(C(RX)( Ry))mi-O]o-(C(RX)( Ry))-, wherein Rxand Ryare each independently hydrogen, halogen, or Ci-6 alkyl, m is 2 or more, preferably 2-4, and o is 1 or more.

[0100] Aspect 4. The polyfunctional poly(arylene ether) of aspect 3, wherein the linking group is -[(C(Rx)(Ry))m-O]o-(C(Rx)(Ry))-, mi s 2-4, and o is 1-25, preferably 15-25.

[0101] Aspect 5. The polyfunctional poly (arylene ether) of any one of the preceding aspects, wherein the linking groups further include units derived from a multifunctional polyol, wherein the multifunctional polyol includes two or more hydroxyl groups.

[0102] Aspect 6. The polyfunctional poly(arylene ether) of any one of the preceding aspects, wherein the poly(arylene ether) includes repeating units having the structure of formula (2)wherein each occurrence of Q1and Q2are independently 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; 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-g 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; L is 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-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, 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.

[0103] Aspect 7. The polyfunctional poly (arylene ether) of any one of the preceding aspects including a glass transition temperature of not more than 100°C, preferably not more than 80°C as determined according to differential scanning calorimetry as per ASTM D3418 with a 20°C / min heating rate.

[0104] Aspect 8. A composition including the polyfunctional poly (arylene ether) of any one of the preceding aspects, wherein the composition includes: 0 to 5,000 ppm of a carbonate-containing polyfunctional poly( arylene ether) including an end group, wherein the end group includes a linking group and a terminal functional group, wherein the terminal functional group includes a hydroxyl group, salt thereof, or a combination thereof, and wherein the linking group of the carbonate-containing polyfunctional poly(arylene ether) includes a carbonate group, 0 to 5,000 ppm of an ester-containing poly functional poly (arylene ether), including an end group, wherein the end group includes a linking group and a terminal functional group, wherein the terminal functional group includes a hydroxyl group, salt thereof, or a combination thereof, and wherein the linking group of the ester-containing polyfunctional poly(arylene ether) includes an ester group, or a combination thereof.

[0105] Aspect 9. A method for preparing the polyfunctional poly (arylene ether), the method including reacting a substituted or unsubstituted alkylene oxide and optionally, a multifunctional polyol with a poly(arylene ether) including a phenolic terminal functional groups under conditions effective to provide a reaction mixture including the polyfunctional poly (arylene ether), wherein the linking group of the polyfunctional poly(arylene ether) includes 0 to 5,000 ppm of a carbonate functional group, 0 to 5,000 ppm of an ester functional group, or a combination thereof.

[0106] Aspect 10. A method for decreasing the glass transition temperature of a polymer that is different from the polyfunctional poly(arylene ether) of any one of claims 1 to 7, the method including reacting the polyfunctional poly(arylene ether) with the polymer that isdifferent from the polyfunctional poly(arylene ether) under conditions effective to provide the copolymer, wherein the copolymer has a glass transition temperature lower than that of the polymer.

[0107] Aspect 11. A copolymer derived from the polyfunctional poly(arylene ether) of any one of aspects 1 to 7.

[0108] Aspect 12. The copolymer of aspect 11, wherein the copolymer is a poly(arylene-ether)-polycarbonate, poly(arylene-ether)-polyurethane, poly(arylene-ether)- polyurea, poly(arylene-ether)-polyester, poly(arylene-ether)-poly(ester-carbonate), or poly(arylene-ether)-poly(carbonate-siloxane); or wherein the copolymer is a poly( arylene etherurethane).

[0109] Aspect 13. A copolymer composition including the copolymer of aspect 10 or 11 and an additive composition.

[0110] Aspect 14. An article including the copolymer of aspect 11 to 12 or the copolymer composition of aspect 13.

[0111] Aspect 15. A method for manufacturing the article of aspect 14 including molding, casting, extruding, spinning fibers, or foaming the copolymer of aspect 11 to 12 or the copolymer composition of aspect 13 to provide the article.

[0112] The compositions, methods, and articles can alternatively include, consist of, or consist essentially of, any appropriate materials, steps, or components herein disclosed. The compositions, methods, and articles can additionally, or alternatively, be formulated so as to be devoid, or substantially free, of any materials (or species), steps, or components, which are otherwise not necessary to the achievement of the function or objectives of the compositions, methods, and articles.

[0113] All ranges disclosed herein are inclusive of the endpoints, and the endpoints are independently combinable with each other (e.g., ranges of “up to 25 wt%, or, more specifically, 5 wt% to 20 wt%”, is inclusive of the endpoints and all intermediate values of the ranges of “5 wt% to 25 wt%,” etc.). “Combinations” is inclusive of blends, mixtures, alloys, reaction products, and the like. The terms “first,” “second,” and the like, do not denote any order, quantity, or importance, but rather are used to distinguish one element from another. The 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”, “an aspect”, and so forth, means that a particular element described in connection with the aspect is included in at least one aspect described herein, andmay or may not be present in other aspects. In addition, it is to be understood that the described elements can be combined in any suitable manner in the various aspects. A “combination thereof’ is open and includes any combination including at least one of the listed components or properties optionally together with a like or equivalent component or property not listed

[0114] 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.

[0115] 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.

[0116] 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 dash that 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.

[0117] The term "alkyl" means a branched or straight chain, unsaturated aliphatic hydrocarbon group, e.g., methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, t-butyl, n-pentyl, s- pentyl, and n- and s-hexyl. “Alkenyl” means a straight or branched chain, monovalent hydrocarbon group having at least one carbon-carbon double bond (e.g., ethenyl (-HC=CH2)). “Alkoxy” means an alkyl group that is linked via an oxygen (i.e., alkyl-O-), for example methoxy, ethoxy, and sec-butyloxy groups. "Alkylene" means a straight or branched chain, saturated, divalent aliphatic hydrocarbon group (e.g., methylene (-CH2-) or, propylene (-(CH2)3- )). “Cycloalkylene” means a divalent cyclic alkylene group, -CnH2n-x, wherein x is the number of hydrogens replaced by cyclization(s). “Cycloalkenyl” means a monovalent group having one or more rings and one or more carbon-carbon double bonds in the ring, wherein all ring members are carbon (e.g., cyclopentyl and cyclohexyl). "Aryl" means an aromatic hydrocarbon group containing the specified number of carbon atoms, such as phenyl, tropone, indanyl, or naphthyl. “Arylene” means a divalent aryl group. “Alkylarylene” means an arylene group substituted with an alkyl group. “Arylalkylene” means an alkylene group substituted with an aryl group (e.g., benzyl). The prefix "halo" means a group or compound including one more of a fluoro, chloro, bromo, or iodo substituent. A combination of different halo groups (e.g., bromo and fluoro), oronly chloro groups can be present. The prefix “hetero” means that the compound or group includes at least one ring member that is a heteroatom (e.g., 1, 2, or 3 heteroatom(s)), wherein the heteroatom(s) is each independently N, O, S, Si, or P. “Substituted” means that the compound or group is substituted with at least one (e.g., 1, 2, 3, or 4) substituents that can each independently be a C1-9 alkoxy, a C1-9 haloalkoxy, a nitro (-NO2), a cyano (-CN), a C1-6 alkyl sulfonyl (-S(=O)2-alkyl), a C6-12 aryl sulfonyl (-S(=O)2-aryl)a thiol (-SH), a thiocyano (-SCN), a tosyl (CH3C6H4SO2-), a C3-12 cycloalkyl, a C2-12 alkenyl, a C5-12 cycloalkenyl, a C6-12 aryl, a C7-13 arylalkylene, a C4-12 heterocycloalkyl, and a C3-12 heteroaryl instead of hydrogen, provided that the substituted atom’s normal valence is not exceeded. The number of carbon atoms indicated in a group, e.g., an alkyl group, is exclusive of any substituents. For example, the group - CH2CH2CN is a C2 alkyl group substituted with a nitrile.

[0118] While particular aspects 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

CLAIMSWhat is claimed:

1. A polyfunctional poly(arylene ether) including an end group, wherein the end group includes a linking group and a terminal functional group, wherein the linking group includes a substituted or unsubstituted saturated hydrocarbylene or a substituted or unsubstituted saturated poly(hydrocarbylene ether), and the terminal functional group includes a hydroxyl group, salt thereof, or a combination thereof, and wherein the linking group includes 0 to 5,000 ppm of a carbonate functional group, 0 to 5,000 ppm of an ester functional group, or a combination thereof, each as determined by proton nuclear magnetic spectroscopy.

2. The polyfunctional poly(arylene ether) of claim 1 including an average of at least 1.8 end groups, or 1.8-2.0 end groups, or 1.8-3.0 end groups.

3. The polyfunctional poly(arylene ether) of claim 1 or claim 2, wherein the linking group independently comprises the following formulas-C(Rx)(Ry)- ,-[(C(Rx)(Ry))m-O]o-(C(Rx)(Ry))-, or a combination thereof, whereinRxand Ryare each independently hydrogen, halogen, or Ci-Ce alkyl, m is 2 or more, preferably 2-4, o is 1 or more.

4. The polyfunctional poly(arylene ether) of claim 3, wherein the linking group is - [(C(Rx)(Ry))m-O]o-(C(Rx)(Ry))-, mi s 2-4, and o is 1-25, preferably 15-25.

5. The polyfunctional poly(arylene ether) of any one of the preceding claims, wherein the linking group further includes units derived from a multifunctional polyol, wherein the multifunctional polyol includes two or more hydroxyl groups.

6. The polyfunctional poly(arylene ether) of any one of the preceding claims, wherein the poly(arylene ether) includes repeating units having the structure of formula (2)wherein each occurrence of Q1and Q2are independently 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; each occurrence of Q3and Q4are independently 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 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;L is 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 formulaor , wherein 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, 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, andR2is independently at each occurrence is a single bond, a unsubstituted or substituted Ci- 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.

7. The polyfunctional poly(arylene ether) of any one of the preceding claims having a glass transition temperature of not more than 100°C, preferably not more than 80°C as determined according to differential scanning calorimetry as per ASTM D3418 with a 20°C / min heating rate.

8. A composition including the polyfunctional poly (arylene ether) of any one of the preceding claims, wherein the composition includes0 to 5,000 ppm of a carbonate-containing polyfunctional poly(arylene ether) including an end group, wherein the end group includes a linking group and a terminal functional group, wherein the terminal functional group includes a hydroxyl group, salt thereof, or a combination thereof, and wherein the linking group of the carbonate-containing polyfunctional poly(arylene ether) includes a carbonate group,0 to 5,000 ppm of an ester-containing polyfunctional poly(arylene ether), including an end group, wherein the end group includes a linking group and a terminal functional group, wherein the terminal functional group includes a hydroxylgroup, salt thereof, or a combination thereof, and wherein the linking group of the ester-containing polyfunctional poly (arylene ether) includes an ester group, or a combination thereof.

9. A method for preparing the polyfunctional poly (arylene ether) of any of the preceding claims, the method including reacting a substituted or unsubstituted alkylene oxide and optionally, a multifunctional polyol with a poly(arylene ether) including a phenolic terminal functional groups under conditions effective to provide a reaction mixture including the polyfunctional poly(arylene ether), wherein the linking group of the polyfunctional poly(arylene ether) includes 0 to 5,000 ppm of a carbonate functional group, 0 to 5,000 ppm of an ester functional group, or a combination thereof.

10. A method for decreasing the glass transition temperature of a polymer that is different from the polyfunctional poly (arylene ether) of any one of claims 1-7, the method including reacting the polyfunctional poly( arylene ether) with the polymer that is different from the polyfunctional poly(arylene ether) under conditions effective to provide the copolymer, wherein the copolymer has a glass transition temperature lower than that of the polymer.

11. A copolymer derived from the polyfunctional poly(arylene ether) of any one of claims 1-7.

12. The copolymer of claim 11, wherein the copolymer is a poly(arylene-ether)- polycarbonate, poly(arylene-ether)-polyurethane, poly(arylene-ether)-polyurea, poly(arylene- ether)-polyester, poly(arylene-ether)-poly(ester-carbonate), or poly(arylene-ether)- poly(carbonate-siloxane); or wherein the copolymer is a poly(arylene ether-urethane).

13. A copolymer composition including the copolymer of claim 11 or 12 and an additive composition.

14. An article including the copolymer of claim 11-12 or the copolymer composition of claim 13.

15. A method for manufacturing the article of claim 14 including molding, casting, extruding, spinning fibers, or foaming the copolymer of claim 11-12 or the copolymer composition of claim 13 to provide the article.

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