POLY(CARBONATE)

CROSS REFERENCE TO RELATED APPLICATIONS

This application claims priority to and benefit of U.S. Provisional Application No. 62/863,354 filed on June 19, 2019, the contents of which is incorporated by reference herein in its entirety.

BACKGROUND

[0001] Poly (carbonate) s are useful in the manufacture of articles and components for a wide range of applications, from automotive parts to electronic appliances. However, poly (carbonate) s are not readily biodegradable and can present a significant bulk waste disposal problem. Accordingly, efforts have been made to recover valuable resources from polycarbonate wastes.

[0002] Poly (carbonate) s can be depolymerized to generate the corresponding small molecule constituents, for example 4,4’-isopropylidenediphenol (also referred to as bisphenol A) and dimethyl carbonate. There remains a continuing need for an improved process for depolymerizing poly(carbonate)s where bisphenol A can be appropriately purified for further use. It would be a further advantage to provide a process which employed solvent recycle techniques to improve the cost-effectiveness of the process.

SUMMARY

[0003] A process for isolation of bisphenol A from depolymerization of a

poly (carbonate) comprises: depolymerizing a poly (carbonate) comprising repeating units derived from bisphenol A in the presence of a base, a Ci- ₆ alcohol, and an organic cosolvent that is miscible with the Ci- ₆ alcohol and has a boiling point that is greater than 90°C, to provide a depolymerized reaction mixture comprising bisphenol A, a di(Ci- ₆ alkyl) carbonate, the Ci- ₆ alcohol, the organic cosolvent, and optionally, residual base; separating the di(Ci- ₆ alkyl) carbonate, the Ci- ₆ alcohol, and optionally, at least a portion of the organic cosolvent from the depolymerized reaction mixture, preferably by distillation, to provide a di(Ci- ₆ alkyl) carbonate mixture; combining the di(Ci- ₆ alkyl) carbonate mixture with an aqueous base under conditions effective to hydrolyze the di(Ci- ₆ alkyl) carbonate to a corresponding Ci- ₆ alcohol; and crystallizing bisphenol A from the residual depolymerized reaction mixture to provide a purified bisphenol A. [0004] A bisphenol A made by the process is described.

[0005] A thermoplastic polymer comprises repeating units derived from the bisphenol A.

[0006] A method of making a poly(etherimide) comprises isolating bisphenol A from depolymerization of a poly(carbonate) according to the process described herein; forming an aromatic bis(ether anhydride) from the isolated bisphenol A; and reacting the aromatic bis(ether anhydride) with an organic diamine to form the poly(etherimide).

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

DETAILED DESCRIPTION

[0008] Described herein is a process for the depolymerization of a poly(carbonate) which can advantageously provide bisphenol A having a purity suitable for use in making new thermoplastic materials. In an additional advantageous feature, the process can effectively recover and recycle the solvent, thus improving the cost-effectiveness of the process. In particular, the present inventors have determined that the dialkyl carbonate byproduct of the depolymerization can be hydrolyzed to the corresponding alcohol, thus simplifying the purification and solvent recovery. In a further advantageous feature, the bisphenol A recovered from the depolymerization can be purified according to the process described herein to a purity of greater than 99.8%, with low color, and in good yield.

[0009] Accordingly, an aspect of the present disclosure is a process for isolation of bisphenol A from depolymerization of a poly (carbonate).“Poly(carbonate)” as used herein means a homopolymer or copolymer having repeating structural carbonate units of the formula (1)

o

- R ¹ — o— c— O - (1)

wherein at least 60 percent of the total number of R ¹ groups are aromatic, or each R ¹ contains at least one C6-30 aromatic group. Each occurrence of R ¹ can be the same or different.

Poly (carbonate) s and their methods of manufacture are known in the art, being described, for example, in WO 2013/175448 Al, US 2014/0295363, and WO 2014/072923. Poly(carbonate)s are generally manufactured from bisphenol compounds such as 2,2-bis(4-hydroxyphenyl) propane (“bisphenol-A” or“BPA” or“4,4’-isopropylidenediphenol”), 3,3-bis(4-hydroxyphenyl) phthalimidine, l,l-bis(4-hydroxy-3-methylphenyl)cyclohexane, or l,l-bis(4-hydroxyphenyl)- 3,3,5-trimethylcyclohexane (isophorone), or a combination thereof can also be used. [0010] The poly(carbonate) of the present disclosure comprises repeating units derived from bisphenol A. For example, the poly(carbonate) is a homopolymer derived from bisphenol A; a copolymer derived from bisphenol A and another bisphenol or dihydroxy aromatic compound such as resorcinol; or a copolymer derived from bisphenol A and optionally another bisphenol or dihydroxy aromatic compound, and further comprising non-carbonate units, for example aromatic ester units such as resorcinol terephthalate or isophthalate, aromatic-aliphatic ester units based on Ce-2o aliphatic diacids, polysiloxane units such as polydimethylsiloxane units, or a combination thereof. Some illustrative examples of other dihydroxy compounds that can be used in combination with bisphenol A are described, for example, in WO 2013/175448 Al, US 2014/0295363, and WO 2014/072923, incorporated herein by reference in their entirety.

[0011] In a specific aspect, the poly (carbonate) is a linear homopolymer containing bisphenol A carbonate units (BPA-PC).

[0012] The poly(carbonate)s can have an intrinsic viscosity, as determined in chloroform at 25°C, of 0.3 to 1.5 deciliters per gram (dl/gm), preferably 0.45 to 1.0 dl/gm. The

poly (carbonate) s can have a weight average molecular weight (Mw) of 10,000 to 200,000 grams per mole (Daltons), preferably 17,000 to 35,000 Daltons, as measured by gel permeation chromatography (GPC), using a crosslinked styrene-divinylbenzene column and calibrated to bisphenol A homopoly (carbonate) references. GPC samples are prepared at a concentration of 1 mg per ml, and are eluted at a flow rate of 1.5 ml per minute.

[0013] Poly (carbonate) s useful for the process of the present disclosure can include virgin poly(carbonate)s, post-consumer recycled poly(carbonate)s, post-industrial recycled poly(carbonate)s, and combinations thereof. In an aspect, the poly(carbonate) can be obtained from multiple sources, and can therefore comprise a combination of poly(carbonate)s having slight variances in structure, including different comonomers or end groups. For example, poly (carbonate) s can be produced using various end-capping agents (also referred to as a chain stopper agent or chain terminating agent) which can be included during polymerization to provide particular end groups, for example monocyclic phenols such as phenol, p-cyanophenol, and Ci -22 alkyl-substituted phenols such as p-cumyl-phenol, resorcinol monobenzoate, and p-and m-tertiary-butyl phenol, monoethers of diphenols, such as p-methoxyphenol, monoesters of diphenols such as resorcinol monobenzoate, and functionalized chlorides of aliphatic

monocarboxylic acids such as acryloyl chloride and methacryloyl chloride. In an aspect, the poly(carbonate) can have an end group derived from at least one of phenol, p-cumylphenol, p- tert-butylphenol, and p-tert-octylphenol. Combinations of different end groups can be used. Thus the poly(carbonate) used in the present process can be a combination of bisphenol A- containing poly (carbonate) s having different end groups.

[0014] It is also understood that when a post-consumer recycled poly(carbonate) or post industrial recycled poly(carbonate) are used, the poly(carbonate) stream can optionally containing one or more additives or additional thermoplastic polymers different from the poly (carbonate).

[0015] The process of the present disclosure comprises depolymerizing the

poly(carbonate) in the presence of a base, a Ci- ₆ alcohol, and an organic cosolvent.

[0016] The base can be, for example, an alkoxide or hydroxide. Suitable alkoxides and hydroxides are those that are soluble in the reaction mixture. Exemplary alkoxides can include Ci-4 alkoxides, and exemplary hydroxides can include, for example, alkali metal hydroxides, alkaline-earth metal hydroxides, tetra-alkyl ammonium hydroxides, and ammonium hydroxide. In an aspect, the base comprises an alkali metal hydroxide, for example sodium hydroxide. In an aspect, the base can be in the form of an aqueous solution for example an aqueous alkali metal hydroxide, preferably an aqueous sodium hydroxide solution. When provided as an aqueous solution, the base (e.g., the alkali metal hydroxide) can be present in an amount sufficient to provide a 10 to 50 weight percent solution of the base in water (based on the total weight of the base and the water), preferably a 20 to 50 weight percent solution, more preferably a 30 to 50 weight percent solution, even more preferably a 35 to 45 weight percent solution.

[0017] The Ci- ₆ alcohol can include, for example, methanol, ethanol, n-propanol, isopropanol, n-butanol, iso-butanol, and the like, or a combination thereof. In an aspect, the Ci- ₆ alcohol preferably comprises methanol. In a specific aspect, the Ci- ₆ alcohol consists of methanol.

[0018] The organic cosolvent is miscible with the Ci- ₆ alcohol, and thus forms a homogenous, single liquid phase. The organic cosolvent further has a boiling point that is greater than 90°C. Organic cosolvents having boiling points less than 90°C are not preferred as they can hinder the later separation of the di(Ci- ₆ alkyl) carbonate byproduct from the BPA. For example, the organic cosolvent can comprise toluene, chlorobenzene, xylene, and the like, or a combination thereof. In a specific aspect, the organic cosolvent comprises toluene.

[0019] In an aspect, the Ci- ₆ alcohol and the organic cosolvent can be present in a weight ratio of 0.1:1 to 1:0.1, or 0.25:1 to 1:0.25, or 0.5:1 to 1:0.5, or 0.75:1 to 1:0.75, or 0.8:1 to 1:0.8, or 0.9:1 to 1:0.9, or 0.95:1 to 1:0.95. In a specific aspect, the Ci- ₆ alcohol and the organic cosolvent can be present in a weight ratio of 1:1. [0020] In an aspect, the base can be present in an amount of 0.1 to 10 weight percent, based on the total weight of the Ci- ₆ alcohol, the organic cosolvent, and the base, for example 0.1 to 5 weight percent, or 0.1 to 1 weight percent, or 0.1 to 0.5 weight percent.

[0021] The poly(carbonate) is present in an amount of 10 to 30 weight percent, based on the total weight of the reaction mixture (e.g., the total weight of the Ci- ₆ alcohol, the organic cosolvent, the base and the poly(carbonate)). Within this range, the poly(carbonate) can be present in an amount of 15 to 25 weight percent, or 17 to 23 weight percent, or 18 to 21 weight percent.

[0022] The poly(carbonate) is depolymerized in the presence of the Ci- ₆ alcohol, the organic cosolvent, and the base to provide a depolymerized reaction mixture comprising bisphenol A, a di(Ci- ₆ alkyl) carbonate, the Ci- ₆ alcohol, the organic cosolvent, and optionally, residual base. The depolymerizing can be conducted at a temperature of 40 to 70°C, or 45 to 65°C, or 50 to 60°C, and atmospheric pressure. The depolymerization can be conducted for a time effective to depolymerize the poly (carbonate). The degree of depolymerization can be monitored, for example, by ultra-performance liquid chromatography (UPLC), as further described in the working examples below. For example, the depolymerizing can be for a time of 1 to 24 hours, preferably 1 to 18 hours, more preferably 1 to 10 hours, even more preferably 1 to 6 hours.

[0023] The identity of the di(Ci- ₆ alkyl) carbonate present in the depolymerized reaction mixture can be dictated by the particular Ci- ₆ alcohol selected for the depolymerization reaction. For example, in an aspect, the di(Ci- ₆ alkyl) carbonate can be dimethyl carbonate when methanol is selected as the alcohol.

[0024] The process of the present disclosure further comprises separating the di(Ci- ₆ alkyl) carbonate, the Ci- ₆ alcohol, and optionally, at least a portion of the organic cosolvent from the depolymerized reaction mixture to provide a di(Ci- ₆ alkyl) carbonate mixture. Preferably, this separation can be by distillation. The separation can be conducted at, for example, a temperature of greater than 90 to 115°C, or 100 to 110°C at atmospheric pressure. The separation can be as described in the working examples below.

[0025] The process further comprises combining the di(Ci- ₆ alkyl) carbonate mixture with an aqueous base under conditions effective to hydrolyze the di(Ci- ₆ alkyl) carbonate to the corresponding Ci- ₆ alcohol. For example, dimethyl carbonate can be hydrolyzed to form methanol and carbon dioxide (CO2). The aqueous base used for the hydrolysis of the di(Ci- ₆ alkyl) carbonate can be a hydroxide as described above, for example an alkali metal hydroxide, such as sodium hydroxide. The base-catalyzed hydrolysis of the di(Ci- ₆ alkyl) carbonate can be conducted, for example, at a temperature of 100 to 150°C, or 110 to 140°C, or 115 to 135°C, or 120 to 130°C, at a pressure of 100 to 150 psig, or 115 to 135 psig, or 120 to 130 psig, and for a time of 1 to 24 hours, or 5 to 20 hours, or 10 to 20 hours, or 12 to 18 hours. Various techniques can be used to monitor the progress of the hydrolysis, for example, ¹ H NMR spectroscopy, as described in the working examples below. Advantageously, the hydrolyzed product, which comprises the Ci- ₆ alcohol, and optionally the organic cosolvent, can be directly recycled back to a depolymerization reaction without the need for additional purification.

[0026] The process of the present disclosure further comprises crystallizing bisphenol A from the residual depolymerized reaction mixture (i.e., the residual reaction mixture that is left following the removal of the di(Ci- ₆ alkyl) carbonate, the Ci- ₆ alcohol, and the organic cosolvent. One or more crystallization steps can be conducted. In an aspect, crystallizing the residual depolymerized reaction mixture comprises adding an aqueous solution comprising an acid to the residual depolymerized reaction mixture. The acid can preferably be an organic acid, such as acetic acid. Upon addition of the acidic aqueous solution, the bisphenol A can crystallize from the mixture in a first crystallization step. The crystallized bisphenol A can be isolated, for example by filtration. The recovered bisphenol A can be crystallized again in a second, subsequent crystallization step. For example, a crystallization solvent can be added to the isolated crystallized bisphenol A from the first crystallization step to provide a second crystallization mixture, which can be heated to a suitable temperature to effect dissolution of the bisphenol A, and the solution can then be cooled. Upon cooling, bisphenol A can crystallized from the second crystallization mixture, and can further be isolated, preferably by filtration.

[0027] The crystallization solvent can comprise, for example, a mixture of toluene, isopropanol, and optionally, an organic acid such as acetic acid.

[0028] Advantageously, the isolated bisphenol A can have a high purity. For example, the isolated bisphenol A can have a purity of greater than 99.8%. In an aspect, the isolated bisphenol A can be 4,4’-isopropyiidenediphenoI having a purity of greater than 99.8%. The process described herein can effectively remove many types of additives (e.g., heat stabilizers, mold release agents, and the like), that can be present, in particular when the poly(carbonate) stream is at least partially derived from a post-consumer recycled poly (carbonate). The isolated bisphenol A can also advantageously comprise less than 0.2 weight percent of a monophenol, for example a monophenol typically used as an end-capping agent, as described above. This represents an important advantage of the present process because the minimization of monophenol compounds present in the bisphenol A can allow for production of high molecular weight polymers when the bisphenol A is used for subsequent polymerization reactions. Stated another way, the presence of excess monophenol compounds in the bisphenol A can undesirably limit the molecular weight of the polymer.

[0029] Thus, another aspect of the present disclosure is a thermoplastic polymer comprising repeating units derived from the bisphenol A made by the process described herein. The thermoplastic polymer can be any polymer which can have repeating units derived from bisphenol A, and can include, for example, poly (carbonates), poly(etherimides), poly(sulfones), epoxies, and the like. Preferably, the thermoplastic polymer can be a poly(carbonate), a poly(sulfone), or a poly(etherimide), more preferably a poly(etherimide).

[0030] In an aspect, the bisphenol A made from the process described herein can be used to provide a poly(carbonate). The poly(carbonate) can be a homopolymer or copolymer having the repeating structural carbonate units according to formula (1) described above. At least a portion (e.g., at least 10%) of the R ¹ groups of formula (1) are derived from the bisphenol A obtained by the method described herein. The remainder of the R ¹ groups can be derived from a dihydroxy compound such as an aromatic dihydroxy compound of formula (2) or a bisphenol of formula (3).

In formula (2), each R ^h is independently a halogen atom, for example bromine, a Ci-io hydrocarbyl group such as a Ci-io alkyl, a halogen-substituted Ci-io alkyl, a Ce-io aryl, or a halogen-substituted Ce-io aryl, and n is 0 to 4.

[0031] In formula (3), R ^a and R ^b are each independently a halogen, C i-12 alkoxy, or C i-12 alkyl, and p and q are each independently integers of 0 to 4, such that when p or q is less than 4, the valence of each carbon of the ring is filled by hydrogen. In an aspect, p and q is each 0, or p and q is each 1, and R ^a and R ^b are each a C 1-3 alkyl group, preferably methyl, disposed meta to the hydroxy group on each arylene group. X ^a is a bridging group connecting the two hydroxy- substituted aromatic groups, where the bridging group and the hydroxy substituent of each Ce arylene group are disposed ortho, meta, or para (preferably para) to each other on the Ce arylene group, for example, a single bond, -0-, -S-, -S(O)-, -S(0) ₂ -, -C(O)-, or a C 1-18 organic group, which can be cyclic or acyclic, aromatic or non-aromatic, and can further comprise heteroatoms such as halogens, oxygen, nitrogen, sulfur, silicon, or phosphorous. For example, X ^a can be a substituted or unsubstituted C3-18 cycloalkylidene; a C i-25 alkylidene of the formula -C(R ^c )(R ^d ) - wherein R ^c and R ^d are each independently hydrogen, C i-12 alkyl, Ci-12 cycloalkyl, C7-12 arylalkyl, Ci-12 heteroalkyl, or cyclic C7-12 heteroarylalkyl; or a group of the formula -C(=R ^e )- wherein R ^e is a divalent Ci-12 hydrocarbon group. Bisphenols of formula (3) can include bisphenol A that has not been recovered from a depolymerization process.

[0032] Examples of bisphenol compounds include 4,4'-dihydroxybiphenyl, 1,6- dihydroxynaphthalene, 2,6-dihydroxynaphthalene, bis(4-hydroxyphenyl)methane, bis(4- hydroxyphenyl)diphenylmethane, bis(4-hydroxyphenyl)-l-naphthylmethane, l,2-bis(4- hydroxyphenyl)ethane, l,l-bis(4-hydroxyphenyl)-l-phenylethane, 2-(4-hydroxyphenyl)-2-(3- hydroxyphenyl)propane, bis(4-hydroxyphenyl)phenylmethane, 2,2-bis(4-hydroxy-3- bromophenyl)propane, 1,1 -bis (hydroxyphenyl)cyclopentane, l,l-bis(4- hydroxyphenyl)cyclohexane, 1 , 1 -bis(4-hydroxyphenyl)isobutene, 1 , 1 -bis(4- hydroxyphenyl)cyclododecane, trans-2,3-bis(4-hydroxyphenyl)-2-butene, 2,2-bis(4- hydroxyphenyl)adamantane, alpha, alpha'-bis(4-hydroxyphenyl)toluene, bis(4- hydroxyphenyl)acetonitrile, 2,2-bis(3-methyl-4-hydroxyphenyl)propane, 2,2-bis(3-ethyl-4- hydroxyphenyl)propane, 2,2-bis(3-n-propyl-4-hydroxyphenyl)propane, 2,2-bis(3-isopropyl-4- hydroxyphenyl)propane, 2,2-bis(3-sec-butyl-4-hydroxyphenyl)propane, 2,2-bis(3-t-butyl-4- hydroxyphenyl)propane, 2,2-bis(3-cyclohexyl-4-hydroxyphenyl)propane, 2,2-bis(3-allyl-4- hydroxyphenyl)propane, 2,2-bis(3-methoxy-4-hydroxyphenyl)propane, 2,2-bis(4- hydroxyphenyl)hexafluoropropane, 1 , 1 -dichloro-2,2-bis(4-hydroxyphenyl)ethylene, 1,1- dibromo-2,2-bis(4-hydroxyphenyl)ethylene, l,l-dichloro-2,2-bis(5-phenoxy-4- hydroxyphenyl)ethylene, 4,4'-dihydroxybenzophenone, 3,3-bis(4-hydroxyphenyl)-2-butanone,

1.6-bis(4-hydroxyphenyl)-l,6-hexanedione, ethylene glycol bis(4-hydroxyphenyl)ether, bis(4- hydroxyphenyl)ether, bis(4-hydroxyphenyl)sulfide, bis(4-hydroxyphenyl)sulfoxide, bis(4- hydroxyphenyl)sulfone, 9,9-bis(4-hydroxyphenyl)fluorene, 2,7-dihydroxypyrene, 6,6'- dihydroxy-3,3,3',3'- tetramethylspiro(bis)indane ("spirobiindane bisphenol"), 3,3-bis(4- hydroxyphenyl)phthalimide, 2,6-dihydroxydibenzo-p-dioxin, 2,6-dihydroxythianthrene, 2,7- dihydroxyphenoxathin, 2,7-dihydroxy-9, 10-dimethylphenazine, 3,6-dihydroxydibenzofuran,

3.6-dihydroxydibenzothiophene, and 2,7-dihydroxycarbazole; resorcinol, substituted resorcinol compounds such as 5-methyl resorcinol, 5-ethyl resorcinol, 5-propyl resorcinol, 5-butyl resorcinol, 5-t-butyl resorcinol, 5-phenyl resorcinol, 5-cumyl resorcinol, 2,4,5,6-tetrafluoro resorcinol, 2,4,5,6-tetrabromo resorcinol, or the like; catechol; hydroquinone; substituted hydroquinones such as 2-methyl hydroquinone, 2-ethyl hydroquinone, 2-propyl hydroquinone, 2-butyl hydroquinone, 2-t-butyl hydroquinone, 2-phenyl hydroquinone, 2-cumyl hydroquinone,

2.3.5.6-tetramethyl hydroquinone, 2,3,5,6-tetra-t-butyl hydroquinone, 2,3,5,6-tetrafluoro hydroquinone, 2,3,5,6-tetrabromo hydroquinone, or the like. [0033] Specific dihydroxy compounds include resorcinol, 2,2-bis(4-hydroxyphenyl) propane (“bisphenol A” or“BPA”), 3,3-bis(4-hydroxyphenyl) phthalimidine, 2-phenyl-3,3’- bis(4-hydroxyphenyl) phthalimidine (also known as N-phenyl phenolphthalein bisphenol, “PPPBP”, or 3,3-bis(4-hydroxyphenyl)-2-phenylisoindolin-l-one), l,l-bis(4-hydroxy-3- methylphenyl)cyclohexane, and 1 , 1 -bis(4-hydroxyphenyl)-3 ,3 ,5-trimethylcyclohexane

(isophorone bisphenol).

[0034] The poly(carbonate)s prepared from the bisphenol A obtained by the method described herein can also include copolymers comprising carbonate units and ester units (“poly(ester-carbonate)s”. Poly(ester-carbonate)s further contain, in addition to recurring carbonate chain units of formula (1), repeating ester units of formula (4)

wherein J is a divalent group derived from a dihydroxy compound (which includes a reactive derivative thereof), and can be, for example, a Ci-io alkylene, a Ce-2o cycloalkylene, a C5-20 arylene, or a polyoxyalkylene group in which the alkylene groups contain 2 to 6 carbon atoms, preferably, 2, 3, or 4 carbon atoms; and T is a divalent group derived from a dicarboxylic acid (which includes a reactive derivative thereof), and can be, for example, a Ci-20 alkylene, a C5-20 cycloalkylene, or a C6-20 arylene. Copolyesters containing a combination of different T or J groups can be used. The polyester units can be branched or linear.

[0035] Dihydroxy compounds can be used in addition to the bisphenol A obtained by the process of the present disclosure and can include aromatic dihydroxy compounds of formula (2) (e.g., resorcinol), bisphenols of formula (3) (e.g., bisphenol A), a Ci-s aliphatic diol such as ethane diol, n-propane diol, i-propane diol, 1,4-butane diol, 1,4-cyclohexane diol, 1,4- hydroxymethylcyclohexane, or a combination thereof dihydroxy compounds. Aliphatic dicarboxylic acids that can be used include C5-20 aliphatic dicarboxylic acids (which includes the terminal carboxyl groups), preferably linear Cs-i2 aliphatic dicarboxylic acid such as decanedioic acid (sebacic acid); and alpha, omega-Ci2 dicarboxylic acids such as dodecanedioic acid

(DDDA). Aromatic dicarboxylic acids that can be used include terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid, 1,4-cyclohexane dicarboxylic acid, or a combination thereof acids. A combination of isophthalic acid and terephthalic acid wherein the weight ratio of isophthalic acid to terephthalic acid is 91:9 to 2:98 can be used.

[0036] Specific ester units include ethylene terephthalate units, n-proplyene terephthalate units, n-butylene terephthalate units, ester units derived from isophthalic acid, terephthalic acid, and resorcinol (ITR ester units), and ester units derived from sebacic acid and bisphenol A. The molar ratio of ester units to carbonate units in the poly (ester-carbonate) s can vary broadly, for example 1:99 to 99:1, preferably, 10:90 to 90:10, more preferably, 25:75 to 75:25, or from 2:98 to 15:85. In some aspects the molar ratio of ester units to carbonate units in the poly(ester- carbonate)s can vary from 1:99 to 30: 70, preferably 2:98 to 25:75, more preferably 3:97 to 20:80, or from 5:95 to 15:85.

[0037] In another aspect, the poly(carbonate) is a poly(carbonate-siloxane) copolymer comprising bisphenol A carbonate units and siloxane units, for example blocks containing 5 to 200 dimethylsiloxane units.

[0038] Other specific poly(carbonate)s that can be prepared from the bisphenol A of the present disclosure can include poly(aromatic ester-carbonate) s comprising bisphenol A carbonate units and isophthalate-terephthalate-bisphenol A ester units, also commonly referred to as poly (carbonate-ester) s (PCE) or poly(phthalate-carbonate)s (PPC), depending on the relative ratio of carbonate units and ester units. Another specific poly (ester-carbonate) comprises resorcinol isophthalate and terephthalate units and bisphenol A carbonate units.

[0039] In an aspect, the bisphenol A obtained by the process of the present disclosure can be particularly useful for the preparation of poly(etherimides). Poly(etherimides) comprise more than 1, for example 2 to 1000, or 5 to 500, or 10 to 100 structural units of formula (5)

wherein each R is independently the same or different, and is a substituted or unsubstituted divalent organic group, such as a substituted or unsubstituted Ce-2o aromatic hydrocarbon group, a substituted or unsubstituted straight or branched chain C4-20 alkylene group, a substituted or unsubstituted C3-8 cycloalkylene group, in particular a halogenated derivative of any of the foregoing. In an aspect R is divalent group of one or more of the following formulas (6)

wherein Q ¹ is -0-, -S-, -C(0)-, -SO2-, -SO-, -P(R ^a )(=0)- wherein R ^a is a Ci-s alkyl or C6-12 aryl, - C _y th _y - wherein y is an integer from 1 to 5 or a halogenated derivative thereof (which includes perfluoroalkylene groups), or -(CeH j _z - wherein z is an integer from 1 to 4. In an aspect R is m- phenylene, p-phenylene, or a diarylene sulfone, in particular bis(4,4’-phenylene)sulfone, bis(3,4’-phenylene)sulfone, bis(3,3’-phenylene)sulfone, or a combination comprising at least one of the foregoing. In an aspect, at least 10 mole percent or at least 50 mole percent of the R groups contain sulfone groups, and in an aspect no R groups contain sulfone groups.

[0040] Further in formula (5), T is a group derived from the bisphenol A obtained by the process of the present disclosure. Optionally, the poly(etherimide) can further comprise additional repeating units where T is a group of the formula -O-Z-O- wherein the divalent bonds of the -O-Z-O- group are in the 3,3', 3,4', 4,3', or the 4,4' positions, and Z is an aromatic Ce-24 monocyclic or polycyclic moiety optionally substituted with 1 to 6 Ci-s alkyl groups, 1 to 8 halogen atoms, or a combination comprising at least one of the foregoing, provided that the valence of Z is not exceeded. Exemplary groups Z include groups of formula (7)

wherein R ^a and R ^b are each independently the same or different, and are a halogen atom or a monovalent Ci- ₆ alkyl group, for example; p and q are each independently integers of 0 to 4; c is 0 to 4; and X ^a is a bridging group connecting the hydroxy-substituted aromatic groups, where the bridging group and the hydroxy substituent of each Ce arylene group are disposed ortho, meta, or para (specifically para) to each other on the Ce arylene group. The bridging group X ^a can be a single bond, -0-, -S-, -S(O)-, -S(0) ₂ -, -C(O)-, or a Ci-is organic bridging group. The Ci-18 organic bridging group can be cyclic or acyclic, aromatic or non-aromatic, and can further comprise heteroatoms such as halogens, oxygen, nitrogen, sulfur, silicon, or phosphorous. The Ci-is organic group can be disposed such that the Ce arylene groups connected thereto are each connected to a common alkylidene carbon or to different carbons of the Ci-is organic bridging group. A specific example of a group Z is a divalent group of formula (7a)

wherein Q is -0-, -S-, -C(O)-, -SO2-, -SO-, -P(R ^a )(=0)- wherein R ^a is a Ci-s alkyl or C6-12 aryl, or -C _y th _y - wherein y is an integer from 1 to 5 or a halogenated derivative thereof (including a perfluoroalkylene group). In an aspect Z is a derived from bisphenol A, such that Q in formula (7a) is 2,2-isopropylidene.

[0041] In an aspect in formula (5), R is m-phenylene, p-phenylene, or a combination comprising at least one of the foregoing, and T is a divalent group derived from the bisphenol A of the present disclosure. Alternatively, the poly(etherimide) can be a copolymer comprising additional structural poly(etherimide) units of formula (5) wherein at least 50 mole percent (mol%) of the R groups are bis(4,4’-phenylene)sulfone, bis(3,4’-phenylene)sulfone, bis(3,3’- phenylene)sulfone, or a combination comprising at least one of the foregoing and the remaining R groups are p-phenylene, m-phenylene or a combination comprising at least one of the foregoing; and T is a divalent group derived from the bisphenol A of the present disclosure.

[0042] In an aspect, the poly(etherimide) is a copolymer that optionally comprises additional structural imide units that are not poly(etherimide) units, for example imide units of formula (8)

wherein R is as described in formula (5) and each V is the same or different, and is a substituted or unsubstituted C6-20 aromatic hydrocarbon group, for example a tetravalent linker of the formulas

wherein W is a single bond, -0-, -S-, -C(O)-, -SO2-, -SO-, a Ci-is hydrocarbylene group, - P(R ^a )(=0)- wherein R ^a is a Ci-s alkyl or C6-12 aryl, or -C _y th _y - wherein y is an integer from 1 to 5 or a halogenated derivative thereof (which includes perfluoroalkylene groups). These additional structural imide units preferably comprise less than 20 mol% of the total number of units, and more preferably can be present in amounts of 0 to 10 mol% of the total number of units, or 0 to 5 mol% of the total number of units, or 0 to 2 mole % of the total number of units. In an aspect, no additional imide units are present in the poly(etherimide).

[0043] The poly(etherimide) can also be a poly(siloxane-etherimide) copolymer comprising poly(etherimide) units of formula (5) and siloxane blocks of formula (9)

wherein E has an average value of 2 to 100, 2 to 31, 5 to 75, 5 to 60, 5 to 15, or 15 to 40, each R’ is independently a Ci-13 monovalent hydrocarbyl group. For example, each R’ can

independently be a Ci-13 alkyl group, Ci-13 alkoxy group, C2-13 alkenyl group, C2-13 alkenyloxy group, C3-6 cycloalkyl group, C3-6 cycloalkoxy group, Ce-i ₄ aryl group, Ce-io aryloxy group, C7-13 arylalkylene group, C7-13 arylalkylenoxy group, C7-13 alkylarylene group, or C7-13

alkylaryleneoxy group. The foregoing groups can be fully or partially halogenated with fluorine, chlorine, bromine, or iodine, or a combination comprising at least one of the foregoing. In an aspect no bromine or chlorine is present, and in an aspect no halogens are present.

Combinations of the foregoing R groups can be used in the same copolymer. In an aspect, the polysiloxane blocks comprises R’ groups that have minimal hydrocarbon content. In an aspect, an R’ group with a minimal hydrocarbon content is a methyl group.

[0044] The poly(etherimide) can be prepared by any of the methods known to those skilled in the art, including the reaction of an aromatic bis(ether anhydride) of formula (10) or a chemical equivalent thereof, with an organic diamine of formula (11)

H2N-R-NH2 (11)

wherein T and R are defined as described above. Copolymers of the poly(etherimides) can be manufactured using a combination of an aromatic bis(ether anhydride) of formula (10) and an additional bis(anhydride) that is not a bis(ether anhydride), for example pyromellitic dianhydride or bis(3,4-dicarboxyphenyl) sulfone dianhydride. At least a portion of the aromatic bis(ether anhydride) of formula (10) can be formed from the isolated bisphenol A of the present disclosure according to methods that are generally known. A combination of different aromatic bis(ether anhydride)s can be used, for example an aromatic bis(ether anhydride) derived from the isolated bisphenol A of the present disclosure and one or more aromatic bis(ether anhydride)s that are derived from bisphenol A made by a different process, are derived from a different dihydroxy aromatic compound, or both.

[0045] Examples of organic diamines include 1,4-butane diamine, 1,5-pentanediamine, 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10- decanediamine, 1,12-dodecanediamine, 1,18-octadecanediamine, 3- methylheptamethylenediamine, 4,4-dimethylheptamethylenediamine, 4- methylnonamethylenediamine, 5-methylnonamethylenediamine, 2,5- dimethylhexamethylenediamine, 2,5-dimethylheptamethylenediamine, 2, 2- dimethylpropylenediamine, N-methyl-bis (3-aminopropyl) amine, 3- methoxyhexamethylenediamine, l,2-bis(3-aminopropoxy) ethane, bis(3-aminopropyl) sulfide, 1,4-cyclohexanediamine, bis-(4-aminocyclohexyl) methane, m-phenylenediamine, p- phenylenediamine, 2,4-diaminotoluene, 2,6-diaminotoluene, m-xylylenediamine, p- xylylenediamine, 2-methyl-4, 6-diethyl- 1 ,3-phenylene-diamine, 5-methyl-4, 6-diethyl- 1,3- phenylene-diamine, benzidine, 3,3’-dimethylbenzidine, 3,3’-dimethoxybenzidine, 1,5- diaminonaphthalene, bis(4-aminophenyl) methane, bis(2-chloro-4-amino-3,5-diethylphenyl) methane, bis(4-aminophenyl) propane, 2,4-bis(p-amino-t-butyl) toluene, bis(p-amino-t- butylphenyl) ether, bis(p-methyl-o-aminophenyl) benzene, bis(p-methyl-o-aminopentyl) benzene, 1, 3-diamino-4-isopropylbenzene, bis(4-aminophenyl) sulfide, bis-(4-aminophenyl) sulfone (also known as 4,4'-diaminodiphenyl sulfone (DDS)), and bis(4-aminophenyl) ether.

Any regioisomer of the foregoing compounds can be used. Ci-4 alkylated or poly(Ci-4)alkylated derivatives of any of the foregoing can be used, for example a polymethylated 1,6- hexanediamine. Combinations of these compounds can also be used. In an aspect the organic diamine is m-phenylenediamine, p-phenylenediamine, 4,4'-diaminodiphenyl sulfone, 3,4'- diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, or a combination comprising at least one of the foregoing.

[0046] The poly(etherimides) can have a melt index of 0.1 to 10 grams per minute (g/min), as measured by American Society for Testing Materials (ASTM) D1238 at 340 to 370°C, using a 6.7 kilogram (kg) weight. In an aspect, the poly(etherimide) has a weight average molecular weight (Mw) of 1,000 to 150,000 grams/mole (Dalton), as measured by gel permeation chromatography, using polystyrene standards. In an aspect the poly(etherimide) has an Mw of 10,000 to 80,000 Daltons. Such poly(etherimides) typically have an intrinsic viscosity greater than 0.2 deciliters per gram (dl/g), or, more specifically, 0.35 to 0.7 dl/g as measured in m-cresol at 25 °C. [0047] Thus the process of the present disclosure advantageously combines poly(carbonate) depolymerization, bisphenol A purification, and solvent recovery and recycle to provide an improved process for the isolation of bisphenol A from depolymerization of poly (carbonate). Careful selection of the bisphenol A purification employed has allowed for the bisphenol A to be obtained with high purity, making it desirable for subsequent use of the preparation of various thermoplastic polymers such as poly(carbonate) and poly(etherimide). Therefore a significant improvement is provided by the process of the present disclosure.

[0048] This disclosure is further illustrated by the following examples, which are non limiting.

EXAMPLES

Poly(carbonate) Depolymerization

[0049] To a one liter, three-necked round bottom flask equipped with a thermocouple- controlled external heater, mechanical agitation, and a condenser, under nitrogen, the following components were added: methanol (250 grams), toluene (250 grams), a 40 wt% solution of sodium hydroxide in water (4 grams), and poly(carbonate) powder (100 grams, obtained as LEXAN 100 grade from SABIC). The resulting slurry was stirred at 250 rpm and a temperature of 55°C for 16 hours to dissolve the poly (carbonate). The homogenous reaction mixture was sampled and analyzed by ultraperformance liquid chromatography (UPLC), which indicated complete depolymerization, with no significant level of bisphenol A carbonate dimer.

[0050] The reactor contents were then heated to 105°C at atmospheric pressure to remove methanol and dimethyl carbonate, with some toluene also removed as an azeotrope. The removed components were collected as a single fraction. The total weight of the collected fraction was 367.7 grams. Proton nuclear magnetic resonance (¾ NMR) spectroscopy indicated that the composition of this fraction was 58 wt% methanol, 35 wt% toluene, and 7 wt% dimethyl carbonate.

[0051] After removal of the methanol, dimethyl carbonate, and toluene, the remaining mixture was allowed to cool to 90°C, at which point 100 grams of room temperature water including 5 grams of glacial acetic acid was added. The reactor was allowed to continue cooling to room temperature while stirring. As the contents cooled, formation of solids was observed.

[0052] The contents of the reactor were vacuum filtered using a Buchner funnel with glass fiber filter cloth. The 120-gram wet cake was dried under vacuum to give 84.2 grams of a solid material. UPLC analysis showed that the isolated solid material was 99.83 wt% 4,4’- isopropylidenediphenol. The remaining filtrate weighed 193.7 grams. The overall mass yield at this stage was calculated to be 96 % (((193.7+120+367.7)/(100+250+250+4+100+5)) = 96%). BPA Purification

[0053] 84.2 grams of the crude isolated BPA from above was heated to 100°C to dissolve in a mixture of 140.5 grams of toluene, 56.3 grams of isopropyl alcohol, and 0.9 grams of acetic acid. The solution was then cooled to room temperature with stirring, and then filtered to provide a 73.7 gram wet cake and 183.9 grams of filtrate. The wet cake was dried under vacuum to give 48.9 grams of high purity BPA. The purity was determined by UPLC, and determined to be 99.97 4,4’-isopropylidenediphenol.

DMC Hydrolysis

[0054] The 367.7 grams of methanol, toluene, and dimethyl carbonate (DMC) isolated above after depolymerization was added to 10 grams of water and 4 grams of a 40 wt% aqueous solution of sodium hydroxide, and was heated to 125°C for 16 hours at a pressure of 125 psig. The reactor was cooled and vented to relieve excess pressure. The resulting product contained small amounts of white solids (presumably sodium carbonate), which can be removed by filtration and optionally recycled into a subsequent depolymerization reaction. ¹ H NMR spectroscopy indicated that the composition was 58 wt% methanol and 42 wt% toluene. No dimethyl carbonate was detected.

Poly(carbonate) Depolymerization with Recycled Methanol

[0055] To demonstrate the ability to recycle the methanol/toluene mixture obtained by hydrolysis of DMC, 355.3 grams of the recovered methanol/toluene mixture, 42.6 grams of methanol, 102.25 grams of toluene, 4 grams of a 40 wt% aqueous solution of sodium hydroxide, and 100 grams of the poly(carbonate) powder was added to a reactor. The slurry was stirred at 250 rpm and a temperature of 55°C for 16 hours. UPLC indicated complete depolymerization with no significant levels of BPA carbonate dimer.

[0056] The contents of the reactor were then stripped at a temperature of 105°C at atmospheric pressure to remove methanol and dimethyl carbonate, with some toluene also removed as an azeotrope. The removed components were collected as a single fraction having a weight of 358 grams.

[0057] After removal of the methanol, dimethyl carbonate, and toluene, the remaining mixture was allowed to cool to 90°C, at which point 100 grams of room temperature water including 5 grams of glacial acetic acid was added. The reactor was allowed to continue cooling to room temperature while stirring. As the contents cooled, formation of solids was observed. [0058] The contents of the reactor were vacuum filtered using a Buchner funnel with glass fiber filter cloth. The 123-gram wet cake was dried under vacuum to give 89.77 grams of a solid material. UPLC analysis showed that the isolated solid material was 99.62 wt% 4,4’- isopropylidenediphenol. The remaining filtrate weighed 152.4 grams. The overall mass yield at this stage was calculated to be 96 % (((152.4+123+358)/(100+355+42+102+4+100+5)) = 89%).

[0059] Thus an advantageous method for depolymerizing poly(carbonate) and recycling the solvent used in the depolymerization after a base-catalyzed hydrolysis of the DMC byproduct has been demonstrated.

[0060] This disclosure further encompasses the following aspects, which are non limiting.

[0061] Aspect 1: A process for isolation of bisphenol A from depolymerization of a poly (carbonate), the process comprising: depolymerizing a poly(carbonate) comprising repeating units derived from bisphenol A in the presence of a base, a Ci- ₆ alcohol, and an organic cosolvent that is miscible with the Ci- ₆ alcohol and has a boiling point that is greater than 90°C, to provide a depolymerized reaction mixture comprising bisphenol A, a di(Ci- ₆ alkyl) carbonate, the Ci- ₆ alcohol, the organic cosolvent, and optionally, residual base; separating the di(Ci- ₆ alkyl) carbonate, the Ci- ₆ alcohol, and optionally, at least a portion of the organic cosolvent from the depolymerized reaction mixture, preferably by distillation, to provide a di(Ci- ₆ alkyl) carbonate mixture; combining the di(Ci- ₆ alkyl) carbonate mixture with an aqueous base under conditions effective to hydrolyze the di(Ci- ₆ alkyl) carbonate to a corresponding Ci- ₆ alcohol; and crystallizing bisphenol A from the residual depolymerized reaction mixture to provide a purified bisphenol A.

[0062] Aspect 2: The process of aspect 1, wherein the process further comprises recycling the corresponding Ci- ₆ alcohol obtained from hydrolysis of the di(Ci- ₆ alkyl) carbonate mixture and, when present, the cosolvent, directly to a poly(carbonate) depolymerization step.

[0063] Aspect 3: The process of aspect 1 or 2, wherein the poly(carbonate) is a virgin poly (carbonate), a post-consumer recycled poly(carbonate), post-industrial recycled

poly (carbonate), or a combination thereof.

[0064] Aspect 4: The process of any one of aspects 1 to 3, wherein the Ci- ₆ alcohol is methanol.

[0065] Aspect 5: The process of aspect 4, wherein the di(Ci- ₆ alkyl) carbonate is dimethyl carbonate.

[0066] Aspect 6: The process of any one of aspects 1 to 5, wherein the organic cosolvent comprises toluene, chlorobenzene, xylene, or a combination thereof. [0067] Aspect 7: The process of any one of aspects 1 to 6, wherein the organic cosolvent comprises toluene.

[0068] Aspect 8: The process of any one of aspects 1 to 7, wherein the depolymerizing is in the presence of an aqueous base, preferably aqueous sodium hydroxide.

[0069] Aspect 9: The process of any one of aspects 1 to 8, wherein the depolymerizing is for a time of 1 to 24 hours, preferably 1 to 18 hours, more preferably 1 to 10 hours, even more preferably 1 to 6 hours.

[0070] Aspect 10: The process of any one of aspects 1 to 9, wherein the di(Ci- ₆ alkyl) carbonate mixture is combined with an aqueous base comprising sodium hydroxide at a temperature of 100 to 150°C, a pressure of 100 to 150 pounds per square inch, and for a time of 1 to 24 hours to provide the corresponding Ci- ₆ alcohol.

[0071] Aspect 11: The process of any one of aspects 1 to 10, wherein crystallizing the residual depolymerized reaction mixture comprising bisphenol A comprises adding an aqueous solution comprising an acid, preferably acetic acid, to the residual depolymerized reaction mixture to crystallize bisphenol A in a first crystallization step; isolating the crystallized bisphenol A from the first crystallization step; adding a crystallization solvent to the crystallized bisphenol A from the first crystallization step to provide a second crystallization mixture;

heating the second crystallization mixture under conditions effective to provide a homogenous solution; cooling the second crystallization mixture; and isolating purified bisphenol A from the second crystallization mixture, preferably by filtration.

[0072] Aspect 12: The process of aspect 11, wherein the crystallization solvent comprises a mixture of toluene, isopropanol, and optionally, an organic acid, preferably acetic acid.

[0073] Aspect 13: The process of any one of aspects 1 to 12, wherein the purified bisphenol A is 4,4’-isopropylidenediphenol having a purity of greater than 99.8%.

[0074] Aspect 14: A bisphenol A made by the process of any one of aspects 1 to 13.

[0075] Aspect 15: The bisphenol A of aspect 14, wherein the bisphenol A is 4,4’- isopropylidenediphenol having a purity of greater than 99.8% and comprising less than 0.2 wt% of a monophenol.

[0076] Aspect 16: A thermoplastic polymer comprising repeating units derived from the bisphenol A of aspects 14 or 15, or isolated by the process of any one or more of aspects 1 to 13.

[0077] Aspect 17: The thermoplastic polymer of aspect 16, wherein the thermoplastic polymer is a poly(etherimide) or a poly (carbonate). [0078] Aspect 18: The thermoplastic polymer of aspect 16, wherein the thermoplastic polymer is a poly(etherimide).

[0079] Aspect 19: A method of making a poly(etherimide), the method comprising: isolating bisphenol A from depolymerization of a poly(carbonate) according to the process of any one or more of aspects 1 to 13; forming an aromatic bis(ether anhydride) from the isolated bisphenol A; and reacting the aromatic bis(ether anhydride) with an organic diamine to form the poly (etherimide) .

[0080] The compositions, methods, and articles can alternatively comprise, consist of, or consist essentially of, any appropriate materials, steps, or components herein disclosed. The compositions, methods, and articles can additionally, or alternatively, be formulated so as to be devoid, or substantially free, of any materials (or species), steps, or components, that are otherwise not necessary to the achievement of the function or objectives of the compositions, methods, and articles.

[0081] 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 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, and may or may 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 may be combined in any suitable manner in the various aspects.

[0082] 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.

[0083] 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.

[0084] 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.

[0085] As used herein, the term“hydrocarbyl”, whether used by itself, or as a prefix, suffix, or fragment of another term, refers to a residue that contains only carbon and hydrogen. The residue can be aliphatic or aromatic, straight-chain, cyclic, bicyclic, branched, saturated, or unsaturated. It can also contain combinations of aliphatic, aromatic, straight chain, cyclic, bicyclic, branched, saturated, and unsaturated hydrocarbon moieties. However, when the hydrocarbyl residue is described as substituted, it may, optionally, contain heteroatoms over and above the carbon and hydrogen members of the substituent residue. Thus, when specifically described as substituted, the hydrocarbyl residue can also contain one or more carbonyl groups, amino groups, hydroxyl groups, or the like, or it can contain heteroatoms within the backbone of the hydrocarbyl residue. The term "alkyl" means a branched or straight chain, saturated aliphatic hydrocarbon group, e.g., methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, t-butyl, n- pentyl, s-pentyl, and n- and s-hexyl. “Alkenyl” means a straight or branched chain, 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-)).“Cycloalky lene” means a divalent cyclic alkylene group, -CiTbn-x, wherein x is the number of hydrogens replaced by cyclization(s). “Cycloalkenyl” means a monovalent group having one or more rings and one or more carbon-carbon double bonds in the ring, wherein all ring members are carbon (e.g., cyclopentyl and cyclohexyl). "Aryl" means an aromatic hydrocarbon group containing the specified number of carbon atoms, such as phenyl, tropone, indanyl, or naphthyl.“Arylene” means a divalent aryl group. “Alkylarylene” means an arylene group substituted with an alkyl group. “Arylalkylene” means an alkylene group substituted with an aryl group (e.g., benzyl). The prefix "halo" means a group or compound including one more of a fluoro, chloro, bromo, or iodo substituent. A combination of different halo groups (e.g., bromo and fluoro), or only chloro groups can be present. The prefix“hetero” means that the compound or group includes at least one ring member that is a heteroatom (e.g., 1, 2, or 3 heteroatom(s)), wherein the heteroatom(s) is each independently N, O, S, Si, or P. “Substituted” means that the compound or group is substituted with at least one (e.g., 1, 2, 3, or 4) substituents that can each independently be a C _1-9 alkoxy, a C _1-9 haloalkoxy, a nitro (-NO ₂ ), a cyano (-CN), a Ci- ₆ alkyl sulfonyl (-S(=0) ₂ -alkyl), a Ce-n aryl sulfonyl (-S(=0) ₂ -aryl), a thiol (-SH), a thiocyano (-SCN), a tosyl (CH3C6H4SO2-), a C3-12 cycloalkyl, a C2-12 alkenyl, a C5-12

cycloalkenyl, a Ce-u aryl, a C _7-13 arylalkylene, a C _4-12 heterocycloalkyl, and a C _3-12 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 - CH ₂ CH ₂ CN is a C ₂ alkyl group substituted with a nitrile.

[0086] While particular aspects have been described, alternatives, modifications, variations, improvements, and substantial equivalents that are or may be presently unforeseen may arise to applicants or others skilled in the art. Accordingly, the appended claims as filed and as they may be amended are intended to embrace all such alternatives, modifications variations, improvements, and substantial equivalents.