CN113993831A - Depolymerization of poly (carbonate) and separation of bisphenol A from depolymerized poly (carbonate) - Google Patents

Depolymerization of poly (carbonate) and separation of bisphenol A from depolymerized poly (carbonate) Download PDF

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CN113993831A
CN113993831A CN202080044318.3A CN202080044318A CN113993831A CN 113993831 A CN113993831 A CN 113993831A CN 202080044318 A CN202080044318 A CN 202080044318A CN 113993831 A CN113993831 A CN 113993831A
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bisphenol
carbonate
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詹姆斯·艾伦·马胡德
詹姆斯·劳伦斯·戈尔曼三世
安德鲁·托马斯·平吉托雷
卡罗琳·伊丽莎白·斯凯尔斯
格雷戈里·保罗·尚克维茨
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SABIC Global Technologies BV
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J11/00—Recovery or working-up of waste materials
    • C08J11/04—Recovery or working-up of waste materials of polymers
    • C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
    • C08J11/14—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with steam or water
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
    • C07C37/01—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis
    • C07C37/055—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis the substituted group being bound to oxygen, e.g. ether group
    • C07C37/0555—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis the substituted group being bound to oxygen, e.g. ether group being esterified hydroxy groups
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
    • C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
    • C07C37/70—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment
    • C07C37/84—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment by crystallisation
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    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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    • C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J11/00—Recovery or working-up of waste materials
    • C08J11/04—Recovery or working-up of waste materials of polymers
    • C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
    • C08J11/18—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material
    • C08J11/22—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material by treatment with organic oxygen-containing compounds
    • C08J11/24—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material by treatment with organic oxygen-containing compounds containing hydroxyl groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J2369/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/62—Plastics recycling; Rubber recycling

Abstract

The method for depolymerization of poly (carbonate) s comprises: combining a poly (carbonate) comprising repeat units derived from bisphenol a, water, and a base under conditions effective to depolymerize the poly (carbonate). Purified bisphenol a can be obtained from a depolymerization process. Purified bisphenol a may be particularly useful for the production of thermoplastic polymers containing bisphenol a.

Description

Depolymerization of poly (carbonate) and separation of bisphenol A from depolymerized poly (carbonate)
Citations to related applications
This application claims priority and benefit of U.S. provisional application No. 62/863,355 filed on 19/6/2019, the contents of which are incorporated herein by reference in their entirety.
Background
Poly (carbonates) are useful in the production of articles and components for a wide range of applications, from automotive parts to electronic devices. However, poly (carbonates) are not readily biodegradable and can present a number of waste disposal problems. Accordingly, efforts have been made to recover valuable resources from poly (carbonate) waste.
Poly (carbonates) can be depolymerized to produce the corresponding small molecule components, e.g., 4,4 '-isopropylidenediphenol (4, 4' -isopropylidenediphenol) (also known as bisphenol a) and other by-products. There is a continuing need for improved methods of depolymerizing poly (carbonates) wherein bisphenol a can be suitably purified for further use. It would be a further advantage to provide a process that minimizes the formation of by-products to facilitate easy purification of bisphenol a. It would be a further advantage to carry out the depolymerization under mild conditions.
Disclosure of Invention
A method for depolymerization of a poly (carbonate) includes combining a poly (carbonate) including repeat units derived from bisphenol a, water, and a base under conditions effective to form a single liquid phase and depolymerize the poly (carbonate).
A method for isolating bisphenol a from depolymerized poly (carbonate) comprises depolymerizing the poly (carbonate), isolating bisphenol a, and crystallizing the isolated bisphenol a with a crystallization solvent to provide purified bisphenol a, wherein the purified bisphenol a is 4,4' -isopropylidene diphenol with a purity of greater than 99.8%.
A process for obtaining bisphenol A is also described.
The thermoplastic polymer includes repeating units derived from bisphenol a.
A method of making a poly (ether imide) includes isolating bisphenol a from a poly (carbonate) depolymerized according to the method 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 (ether imide).
The above described and other features are exemplified by the following detailed description.
Detailed Description
Described herein are methods for the depolymerization of poly (carbonates) that can advantageously provide bisphenol-a having a purity suitable for use in the preparation of new thermoplastic materials. The process provided by the present disclosure is advantageously base-catalyzed hydrolysis, which has the advantage of depolymerizing the poly (carbonate) to bisphenol a and carbon dioxide which is easily removed. This is in contrast to other processes such as aminolysis (which produces urea by-product), alcoholysis (which produces dialkyl carbonate), and phenolysis (which produces diaryl carbonate). The methods of the present disclosure can advantageously provide fully depolymerized poly (carbonates) in a short time and using mild conditions. In other advantageous features, bisphenol a recovered from depolymerization according to the methods described herein can be purified to greater than 99.8% purity, light in color, and good in yield. Thus, bisphenol a isolated from the depolymerization processes described herein can be used to provide new thermoplastic materials.
Accordingly, an aspect of the present disclosure is a method for depolymerization of poly (carbonate). As used herein, "poly (carbonate)" means a homopolymer or copolymer of carbonate units having a repeating structure of formula (1)
Figure BDA0003415021350000021
Wherein R is1At least 60% of the total number of radicals being aromatic, or R1Each containing at least one C6-30An aromatic group. Each occurrence of R1May be the same or different. Poly (carbonates) and methods for their preparation are known in the art, for example in WO 2013/175448 a1, US 2014/0295363 and WO 2014Described in/072923. The poly (carbonates) are usually prepared from bisphenol compounds, such as 2, 2-bis (4-hydroxyphenyl) propane ("bisphenol-A" or "BPA"), 3-bis (4-hydroxyphenyl) phthalimidine, 1-bis (4-hydroxy-3-methylphenyl) cyclohexane or 1, 1-bis (4-hydroxyphenyl) -3,3, 5-trimethylcyclohexane (isophorone), or else using combinations thereof.
The poly (carbonates) of the present disclosure comprise repeat units derived from bisphenol a. For example, poly (carbonates) are homopolymers derived from bisphenol a; copolymers 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, e.g., aromatic ester units such as resorcinol terephthalate or isophthalate, based on C6-20Aromatic-aliphatic ester units of aliphatic diacids, polysiloxane units, such as polydimethylsiloxane units, or combinations thereof. Some illustrative examples of other dihydroxy compounds that may be used in combination with bisphenol a are described, for example, in WO 2013/175448 a1, US 2014/0295363, and WO 2014/072923 (incorporated herein by reference in their entirety).
In a particular aspect, the poly (carbonate) is a linear homopolymer containing bisphenol a carbonate units (BPA-PC).
The poly (carbonate) may have an intrinsic viscosity of 0.3 to 1.5 deciliters per gram (dl/gm), preferably 0.45 to 1.0dl/gm, as determined in chloroform at 25 ℃. The poly (carbonate) 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 homopolymer (carbonate) references. GPC samples were prepared at a concentration of 1 mg/ml and eluted at a flow rate of 1.5 ml/min.
The poly (carbonate) s used in the methods of the present disclosure may include virgin poly (carbonate), post-consumer recycled poly (carbonate), post-industrial recycled poly (carbonate), and combinations thereof. In one aspect, the poly (carbonate) s canObtained from a variety of sources and may therefore comprise combinations of poly (carbonates) with slight variations in structure or composition, for example, with different co-monomers or end groups or additives. For example, poly (carbonate) s can be produced using a variety of end-capping agents (also known as chain terminators (chain stoppers)) that can be included during polymerization to provide specific end groups, e.g., monocyclic phenols such as phenol, p-cyanophenol, and C1-22Alkyl-substituted phenols such as p-cumylphenol, resorcinol monobenzoate and p-and m-tert-butylphenol, monoethers of diphenols such as p-methoxyphenol, monoesters of diphenols such as resorcinol monobenzoate and chlorides of functionalized aliphatic monocarboxylic acids such as acryloyl chloride and methacryloyl chloride. In one aspect, the poly (carbonate) can have terminal groups derived from at least one of phenol, p-cumylphenol, p-tert-butylphenol, and p-tert-octylphenol. Combinations of different end groups may be used. Thus, the poly (carbonate) used in the process of the present invention may be a combination of bisphenol a-containing poly (carbonates) having different terminal groups.
It is also understood that when post-consumer recycled poly (carbonate) or post-industrial recycled poly (carbonate) is used, the poly (carbonate) stream may optionally contain one or more additives or other thermoplastic polymers other than poly (carbonate).
The method of the present disclosure includes combining a poly (carbonate) comprising repeat units derived from bisphenol a, water, a base, and optionally an organic solvent under conditions effective to form a single liquid phase and depolymerize the poly (carbonate).
When present, the organic solvent can generally be any organic solvent that can swell the poly (carbonate) to aid in depolymerization and has a sufficiently high boiling point so that excessive pressure build-up at elevated temperatures during depolymerization can be avoided. Further, the organic solvent may preferably crystallize the crude bisphenol a produced from the depolymerization step without solvent exchange. In one aspect, the organic solvent may include toluene, chlorobenzene, xylene, or the like, or combinations thereof. In a particular aspect, the organic solvent comprises toluene.
The base may comprise an alkali metal carbonate, an alkali metal hydroxide, an alkaline earth metal hydroxide, ammonium hydroxide, phosphonium hydroxide, or combinations thereof. In one aspect, the base can be an alkali metal carbonate, such as sodium carbonate.
In one aspect, the poly (carbonate) can be present in an amount of 10 to 30 weight percent; bisphenol a may be present in an amount of 1 to 65 weight percent; the organic solvent may be present in an amount of 5 to 65 weight percent; and water may be present in an amount of 5 to 35 weight percent; wherein the weight percent of each component is based on the total weight of the poly (carbonate), the organic solvent, the water, the bisphenol A, and the base.
The depolymerization can be carried out at a temperature of 110 to 130 ℃, preferably 115 to 125 ℃, and at a pressure of 10 to 75psig, e.g., 15 to 50psig, e.g., 20 to 40 psig. The depolymerization may be carried out for a period of 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, depolymerization may be continued for a period of 24 hours or less, preferably 16 hours or less, more preferably 10 hours or less, even more preferably 6 hours or less. Within this range, depolymerization may continue for a time period of 1 to 24 hours, or 1 to 18 hours, or 1 to 10 hours, or 1 to 6 hours.
The process of the present disclosure may optionally further comprise isolating bisphenol a and crystallizing the isolated bisphenol a with a crystallization solvent to provide purified bisphenol a. After addition of the crystallization solvent, the resulting mixture can be heated to a suitable temperature to effect dissolution of the bisphenol a, and then the solution can be cooled. Upon cooling, bisphenol a may be crystallized from the crystallization solution and may be further isolated, for example, by filtration.
The crystallization solvent may comprise, for example, a mixture of toluene, isopropanol, and optionally acetic acid. The crystallization of bisphenol a from the depolymerization reaction mixture is further described in the working examples below.
Another aspect of the disclosure is a method for separating bisphenol a from depolymerized poly (carbonate). The method comprises depolymerizing a poly (carbonate) according to the method described herein; separating the bisphenol A; and crystallizing the isolated bisphenol a using a crystallization solvent to provide purified bisphenol a; wherein the purified bisphenol-A is 4,4' -isopropylidene diphenol with a purity of greater than 99.8%.
Advantageously, the isolated bisphenol a can have a high purity. For example, the isolated bisphenol-a may have a purity of greater than 99.8%. In one aspect, the isolated bisphenol-A can be 4,4' -isopropylidene diphenol with a purity of greater than 99.8%. The methods described herein can be effective in removing various types of additives (e.g., thermal stabilizers, mold release agents, etc.), particularly additives that may be present when the poly (carbonate) stream is at least partially derived from post-consumer recycled poly (carbonate). The isolated bisphenol-a may also advantageously include less than 0.2 weight percent of monophenols, for example, monophenols commonly used as endcapping agents, as described above. Specifically, the isolated bisphenol-a may include less than 0.2 weight percent monophenols including p-cumyl phenol, t-butyl phenol, p-t-octyl phenol, or combinations thereof. This represents an important advantage of the process of the present invention, since the minimization of monophenol compounds present in bisphenol A may enable the production of high molecular weight polymers when bisphenol A is used in subsequent polymerization reactions. In other words, the presence of an excess of monophenol compound in bisphenol A may undesirably limit the molecular weight of the polymer.
Accordingly, another aspect of the present disclosure is a thermoplastic polymer comprising repeat units derived from bisphenol a prepared by the methods described herein. The thermoplastic polymer may be any polymer having repeating units derived from bisphenol a, and may include, for example, poly (carbonate), poly (etherimide), polysulfone, epoxy resin, and the like. Preferably, the thermoplastic polymer may be a poly (carbonate) or poly (etherimide), more preferably a poly (etherimide).
In one aspect, bisphenol a prepared by the methods described herein can be used to provide a poly (carbonate). The poly (carbonate) may be a homopolymer or a copolymer having a repeating structural carbonate unit according to formula (1) described above. R of formula (1)1Of a group toA minor portion (e.g., at least 10%) is derived from bisphenol a obtained by the methods described herein. R1The remainder of the group may be derived from a dihydroxy compound, such as an aromatic dihydroxy compound of formula (2) or a bisphenol of formula (3).
Figure BDA0003415021350000071
In the formula (2), RhEach independently being a halogen atom, e.g. bromine, C1-10Hydrocarbyl radicals, e.g. C1-10Alkyl, halogen substituted C1-10Alkyl radical, C6-10Aryl or halogen substituted C6-10Aryl, and n is 0 to 4.
In the formula (3), RaAnd RbEach independently is halogen, C1-12Alkoxy or C1-12And p and q are each independently an integer of 0 to 4 such that p or q is less than 4, the valences of each carbon of the ring being filled with hydrogen. In one aspect, p and q are each 0, or p and q are each 1, and RaAnd RbEach is C1-3An alkyl group, preferably a methyl group, disposed meta to the hydroxyl group on each arylene group. XaIs a bridging group linking two hydroxy-substituted aromatic groups, wherein the bridging group and each C6Hydroxy substituents of arylene radicals at C6Ortho, meta or para (preferably, para) to each other on the arylene group, e.g., single bond, -O-, -S-, -S (O) -, -S (O)2-, -C (O) -or C1-18An organic group, which may be cyclic or acyclic, aromatic or non-aromatic, and may also contain heteroatoms such as halogens, oxygen, nitrogen, sulfur, silicon, or phosphorus. For example, XaC which may be substituted or unsubstituted3-18A cycloalkylidene group; formula-C (R)c)(Rd) C of (A-C)1-25Alkylidene radical, wherein RcAnd RdEach independently is hydrogen, C1-12Alkyl radical, C1-12Cycloalkyl radical, C7-12Arylalkyl radical, C1-12Heteroalkyl or cyclic C7-12A heteroarylalkyl group; or formula-C (═ R)e) A group of (a) wherein ReIs divalent C1-12A hydrocarbyl group. The bisphenol of formula (3) may include bisphenol a that has not been recovered from the depolymerization process.
Examples of the bisphenol compound include 4,4' -dihydroxybiphenyl, 1, 6-dihydroxynaphthalene, 2, 6-dihydroxynaphthalene, bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) diphenylmethane, bis (4-hydroxyphenyl) -1-naphthylmethane, 1, 2-bis (4-hydroxyphenyl) ethane, 1-bis (4-hydroxyphenyl) -1-phenylethane, 2- (4-hydroxyphenyl) -2- (3-hydroxyphenyl) propane, bis (4-hydroxyphenyl) phenylmethane, 2-bis (4-hydroxy-3-bromophenyl) propane, 1-bis (hydroxyphenyl) cyclopentane, 1-bis (4-hydroxyphenyl) cyclohexane, 1-bis (4-hydroxyphenyl) isobutylene, 1, 6-dihydroxynaphthalene, 2, 6-dihydroxynaphthalene, bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) -1-naphthylmethane, 1, 2-bis (4-hydroxyphenyl) ethane, 1-bis (4-hydroxyphenyl) -1-phenylethane, 1, 1-bis (4-hydroxyphenyl) cyclododecane, trans-2, 3-bis (4-hydroxyphenyl) -2-butene, 2-bis (4-hydroxyphenyl) adamantane, α' -bis (4-hydroxyphenyl) toluene, bis (4-hydroxyphenyl) acetonitrile, 2-bis (3-methyl-4-hydroxyphenyl) propane, 2-bis (3-ethyl-4-hydroxyphenyl) propane, 2-bis (3-n-propyl-4-hydroxyphenyl) propane, 2-bis (3-isopropyl-4-hydroxyphenyl) propane, 2-bis (3-sec-butyl-4-hydroxyphenyl) propane, 2-bis (3-tert-butyl-4-hydroxyphenyl) propane, 2, 2-bis (3-cyclohexyl-4-hydroxyphenyl) propane, 2-bis (3-allyl-4-hydroxyphenyl) propane, 2-bis (3-methoxy-4-hydroxyphenyl) propane, 2-bis (4-hydroxyphenyl) hexafluoropropane, 1-dichloro-2, 2-bis (4-hydroxyphenyl) ethylene, 1-dibromo-2, 2-bis (4-hydroxyphenyl) ethylene, 1-dichloro-2, 2-bis (5-phenoxy-4-hydroxyphenyl) ethylene, 4' -dihydroxybenzophenone, 3-bis (4-hydroxyphenyl) -2-butanone, 1, 6-bis (4-hydroxyphenyl) -1, 6-hexanedione, ethylene glycol bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) sulfone, 9-bis (4-hydroxyphenyl) fluorene, 2, 7-dihydroxypyrene, 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-dihydroxyphenol flavin, 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-tert-butyl resorcinol, 5-phenyl resorcinol, 5-cumyl resorcinol, 2,4,5, 6-tetrafluoro resorcinol, 2,4,5, 6-tetrabromo resorcinol, and the like; catechol; hydroquinone; substituted hydroquinones, such as 2-methylhydroquinone, 2-ethylhydroquinone, 2-propylhydroquinone, 2-butylhydroquinone, 2-tert-butylhydroquinone, 2-phenylhydroquinone, 2-cumylhydroquinone, 2,3,5, 6-tetramethylhydroquinone, 2,3,5, 6-tetra-tert-butylhydroquinone, 2,3,5, 6-tetrafluorohydroquinone, 2,3,5, 6-tetrabromohydroquinone, and the like.
Specific dihydroxy compounds include resorcinol, 2-bis (4-hydroxyphenyl) propane ("bisphenol a" or "BPA"), 3-bis (4-hydroxyphenyl) phthalimidine, 2-phenyl-3, 3' -bis (4-hydroxyphenyl) phthalimidine (also known as N-phenylphenolphthalein bisphenol, "PPPBP" or 3, 3-bis (4-hydroxyphenyl) -2-phenylisoindolin-1-one), 1-bis (4-hydroxy-3-methylphenyl) cyclohexane, and 1, 1-bis (4-hydroxyphenyl) -3,3, 5-trimethylcyclohexane (isophorone bisphenol).
The poly (carbonate) s prepared from bisphenol a obtained by the methods described herein may also include copolymers comprising carbonate units and ester units ("poly (ester-carbonates)"). In addition to recurring carbonate chain units of the formula (1), the poly (ester-carbonates) contain recurring ester units of the formula (4)
Figure BDA0003415021350000091
Wherein J is a divalent radical derived from a dihydroxy compound (including reactive derivatives thereof) and may be, for example, C1-10Alkylene radical, C6-20Cycloalkylene radical, C5-20Arylene or polyoxyalkylene group in which the alkylene group contains 2 to 6 carbon atoms, preferably 2,3 or 4 carbon atoms; and T is a divalent radical derived from a dicarboxylic acid (including reactive derivatives thereof) and may be, for example, C1-20Alkylene radical, C5-20Cycloalkylene or C6-20An arylene group. Copolyesters containing a combination of different T or J groups may be used. The polyester units may be branched or linear.
In addition to bisphenol A obtained by the process of the present disclosure, there may beSo as to use a dihydroxy compound, and the dihydroxy compound may include an aromatic dihydroxy compound of formula (2) (e.g., resorcinol), a bisphenol of formula (3) (e.g., bisphenol A), C1-8Aliphatic diols such as ethylene glycol, n-propylene glycol, isopropylene glycol, 1, 4-butylene glycol, 1, 4-cyclohexanediol, 1, 4-hydroxymethylcyclohexane or combinations of dihydroxy compounds thereof. Aliphatic dicarboxylic acids which may be used include C5-20Aliphatic dicarboxylic acids (which include terminal carboxyl groups), preferably straight-chain C8-12Aliphatic dicarboxylic acids, such as sebacic acid (sebacylic acid); and alpha, omega-C12Dicarboxylic acids, such as dodecanedioic acid (DDDA). Aromatic dicarboxylic acids that may be used include terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid, 1, 4-cyclohexane dicarboxylic acid, or combinations of the acids thereof. A combination of isophthalic acid and terephthalic acid may be used with a weight ratio of isophthalic acid to terephthalic acid ranging from 91:9 to 2: 98.
Specific ester units include ethylene terephthalate units, n-propylene 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) can vary widely, for example, from 1:99 to 99:1, preferably from 10:90 to 90:10, more preferably from 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) can vary from 1:99 to 30:70, preferably 2:98 to 25:75, more preferably 3:97 to 20:80, or 5:95 to 15: 85.
In another aspect, the poly (carbonate) is a poly (carbonate-siloxane) copolymer comprising bisphenol a carbonate units and siloxane units, e.g., containing blocks of 5 to 200 dimethylsiloxane units.
Other specific poly (carbonates) that can be prepared from bisphenol a of the present disclosure can include poly (aromatic ester-carbonates) comprising bisphenol a carbonate units and ester units of bisphenol a isophthalate-bisphenol a terephthalate, also commonly referred to as poly (carbonate-ester) (PCE) or poly (phthalate-carbonate) (PPC), based on the relative ratio of carbonate units and ester units. Another specific poly (ester-carbonate) comprises resorcinol isophthalate and terephthalate ester units and bisphenol a carbonate units.
In one aspect, bisphenol a obtained by the methods of the present disclosure may be particularly useful for the preparation of poly (etherimides). The poly (etherimide) comprises greater than 1, e.g., 2 to 1000, or 5 to 500 or 10 to 100 structural units of formula (5)
Figure BDA0003415021350000101
Wherein each R is independently the same or different and is a substituted or unsubstituted divalent organic group, such as substituted or unsubstituted C6-20Aromatic hydrocarbon radicals, substituted or unsubstituted straight or branched C4-20Alkylene, substituted or unsubstituted C3-8Cycloalkylene groups, in particular halogenated derivatives of any of the above groups. In one aspect, R is a divalent group of one or more of the following formula (6)
Figure BDA0003415021350000111
Wherein Q1is-O-, -S-, -C (O) -, -SO2-、-SO-、-P(Ra) (═ O) - (wherein R)aIs C1-8Alkyl or C6-12Aryl), -CyH2y- (wherein y is an integer of 1 to 5) or halogenated derivatives thereof (including perfluoroalkylene) or- (C)6H10)z- (wherein z is an integer from 1 to 4). In one aspect, R is m-phenylene, p-phenylene, or diarylene sulfone, specifically bis (4,4 '-phenylene) sulfone, bis (3, 3' -phenylene) sulfone, or a combination comprising at least one of the foregoing. In one aspect, at least 10 mole percent or at least 50 mole percent of the R groups contain sulfone groups, and in one aspect, no R groups contain sulfone groups.
Further, in formula (5), T is derived from a compound obtained by the process of the present disclosureThe group of bisphenol A of (1). Optionally, the poly (etherimide) may further comprise other repeating units, wherein T is a group of the formula-O-Z-O-, wherein the divalent bond of-O-Z-O-is in the 3,3',3, 4', 4,3 'or 4,4' position, and Z is optionally substituted with 1 to 6C1-8Aromatic C substituted with alkyl groups, 1 to 8 halogen atoms, or a combination comprising at least one of the foregoing6-24A monocyclic or polycyclic moiety, provided that the valence of Z is not exceeded. Exemplary groups Z include groups of formula (7)
Figure BDA0003415021350000121
Wherein R isaAnd RbEach independently of the other, is the same or different and is a halogen atom or a monovalent C1-6Alkyl, for example, p and q are each independently integers of 0 to 4; c is 0 to 4; and XaA bridging group to connect the hydroxy-substituted aromatic group, wherein the bridging group and each C6Hydroxy substituents of arylene radicals at C6The arylene groups are in ortho, meta, or para (specifically para) arrangement to each other. Bridging group XaMay be a single bond, -O-, -S-, -S (O) -, -S (O)2-, -C (O) -or C1-18An organic bridging group. C1-18The organic bridging group may be cyclic or acyclic, aromatic or non-aromatic and may also contain heteroatoms such as halogens, oxygen, nitrogen, sulfur, silicon or phosphorus. C1-18The arrangement of the organic groups being such that C is attached thereto6Arylene radicals each bound to C1-18The same alkylidene carbon or a different carbon of the organic bridging group. Specific examples of the group Z are divalent groups of the formula (7a)
Figure BDA0003415021350000122
Wherein Q is-O-, -S-, -C (O) -, -SO2-、-SO-、-P(Ra) (═ O) - (wherein R)aIs C1-8Alkyl or C6-12Aryl) or-CyH2y- (wherein y is an integer of 1 to 5) or halogenated derivatives thereof (including perfluoroalkyleneA base). In one aspect, Z is derived from bisphenol A, such that Q in formula (7a) is 2, 2-isopropylidene.
In one 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 bisphenol a of the present disclosure. Alternatively, the poly (etherimide) can be a copolymer comprising poly (etherimide) units of other structure of formula (5), wherein at least 50 mole percent (mol%) of the R groups are bis (4,4 '-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 bisphenol a of the present disclosure.
In one aspect, the poly (etherimide) is a copolymer optionally comprising imide units of other structure than poly (etherimide) units, for example, imide units of formula (8)
Figure BDA0003415021350000131
Wherein R is as described for formula (5), and each V is the same or different and is substituted or unsubstituted C6-20Aromatic hydrocarbon radicals, e.g. tetravalent linkers of the formula
Figure BDA0003415021350000132
Wherein W is a single bond, -O-, -S-, -C (O) -, -SO2-、-SO-、C1-18Alkylene, -P (R)a) (═ O) - (wherein R)aIs C1-8Alkyl or C6-12Aryl) or-CyH2y- (wherein y is an integer of 1 to 5) or halogenated derivatives thereof (including perfluoroalkylene). These imide units of other structure preferably comprise less than 20 mol% of the total number of units, and more preferably may be present in an amount 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 mol% of the total number of units. In one aspect of the present invention,no other imide units are present in the poly (etherimide).
The poly (etherimide) may also be a poly (siloxane-etherimide) copolymer comprising poly (etherimide) units of formula (5) and siloxane blocks of formula (9)
Figure BDA0003415021350000141
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, and each R' is independently C1-13A monovalent hydrocarbon group. For example, each R' may independently be C1-13Alkyl radical, C1-13Alkoxy radical, C2-13Alkenyl radical, C2-13Alkenyloxy radical, C3-6Cycloalkyl radical, C3-6Cycloalkoxy, C6-14Aryl radical, C6-10Aryloxy radical, C7-13Arylalkylene radical, C7-13Arylalkyleneoxy group, C7-13Alkylarylene or C7-13An alkylarylene oxy group. The foregoing groups may be fully or partially halogenated with fluorine, chlorine, bromine, or iodine, or a combination comprising at least one of the foregoing. In one aspect, no bromine or chlorine is present, and in one aspect, no halogen is present. Combinations of the above R groups may be used in the same copolymer. In one aspect, the polysiloxane block comprises R' groups with minimal hydrocarbon content. In one aspect, the R' group with the smallest hydrocarbon content is methyl.
The poly (etherimide) s can be prepared by any method 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)
Figure BDA0003415021350000142
H2N-R-NH2 (11)
Wherein T and R are defined as described above. The combination of an aromatic bis (ether anhydride) of formula (10) and another bis (anhydride) other than bis (ether anhydride), for example, pyromellitic dianhydride or bis (3, 4-dicarboxyphenyl) sulfone dianhydride, may be used to produce copolymers of poly (etherimides). At least a portion of the aromatic bis (ether anhydride) of formula (10) may be formed from the isolated bisphenol a of the present disclosure according to generally known methods. Combinations of different aromatic bis (ether anhydrides) may be used, for example, an aromatic bis (ether anhydride) derived from isolated bisphenol a of the present disclosure and one or more aromatic bis (ether anhydrides) derived from bisphenol a prepared by different methods, derived from different dihydroxy aromatic compounds, or both.
Examples of the organic diamine include 1, 4-butanediamine, 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-dimethylheptamethylenediamine, 4-methylnonamethylenediamine, 5-methylnonamethylenediamine, 2, 5-dimethylhexamethylenediamine, 2, 5-dimethylheptamethylenediamine, 2-dimethylpropylenediamine, N-methyl-bis (3-aminopropyl) amine, 3-methoxyhexamethylenediamine, 1, 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 '-dimethylbenzidine, 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-aminophenyl) benzene), bis (p-methyl-o-aminophenyl) 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 positional isomer of the above compounds may be used. Any of the above C may be used1-4Alkylated or poly (C)1-4) Alkylated derivatives, for example, polymethylated 1, 6-hexanediamine. Combinations of these compounds may also be used. In one aspect, the organic diamine is m-phenylenediamine, p-phenylenediamine, 4' -diAminodiphenyl sulfone, 3,4 '-diaminodiphenyl sulfone, 3' -diaminodiphenyl sulfone, or a combination comprising at least one of the foregoing.
The poly (etherimide) can have a melt index of 0.1 to 10 grams per minute (g/min), as measured by the American Society for Testing and Materials (ASTM) D1238 at 340 to 370 ℃ using a weight of 6.7 kilograms (kg). In one aspect, the poly (etherimide) has a weight average molecular weight (Mw) of 1,000 to 150,000 grams/mole (daltons), as measured by gel permeation chromatography using polystyrene standards. In one aspect, the poly (etherimide) has a Mw of 10,000 to 80,000 daltons. These poly (etherimides) generally have an intrinsic viscosity greater than 0.2 deciliters per gram (dl/g), or, more specifically, 0.35 to 0.7dl/g, as measured in m-cresol at 25 ℃.
Thus, the methods of the present disclosure advantageously combine poly (carbonate) depolymerization, bisphenol a purification, and solvent recovery and recycle to provide an improved method for separating bisphenol a from poly (carbonate) depolymerization. The careful selection of bisphenol a purification used enables bisphenol a to be obtained with high purity, which makes it desirable for subsequent use in the preparation of a variety of thermoplastic polymers, such as poly (carbonates) and poly (etherimides). Thus, significant improvements are provided by the methods of the present disclosure.
The disclosure is further illustrated by the following examples, which are not limiting.
Examples
Depolymerization of poly (carbonate)
The same general procedure was used in each of the following examples. Particles of poly (carbonate) (obtained as LEXAN 100 from SABIC), bisphenol A (BPA), toluene, water and sodium carbonate (Na)2CO3) Added to a tubular reactor equipped with a stir bar. Table 1 below provides the amount of each component, wherein the amount of each component is provided in grams. The reaction tube was sealed and placed in an oil bath heated to 120 ℃. Mixing was accomplished by a magnetic stir bar and the stirring rate for each example was 535 rpm.
TABLE 1
Figure BDA0003415021350000161
"" denotes comparative examples
TABLE 1 (continuation)
Figure BDA0003415021350000162
Figure BDA0003415021350000171
"" denotes comparative examples
After 6 hours, each reaction mixture was analyzed by Fourier Transform Infrared (FTIR) spectroscopy to determine the degree of polymerization. Each of examples 3,4, 11 and 12 were observed to have completely depolymerized within 6 hours, with no particles remaining suspended in the reaction mixture, and no detectable carbonate stretching by FTIR (stretch). In contrast, examples 2, 5-10, 13-15, and 17-25 still contained undissolved PC particles in the reaction mixture after 6 hours, or FTIR analysis indicated measurable carbonate shrinkage. Thus, these examples will achieve complete depolymerization over a longer period of time (i.e., greater than 6 hours).
Poly (carbonate) depolymerization is also amplified, as described below.
To a 600 ml Parr reactor equipped with a magnetic stir bar, glass liner, and an internal thermocouple, 25 grams of poly (carbonate) particles (obtained as LEXAN 100 from SABIC), 10 grams deionized water, 30.42 grams of toluene, 45.01 grams of BPA, and 0.51 grams of sodium carbonate were added. The reactor was then placed in a heating mantle and sealed. The reactor was heated to 125 ℃ overnight to ensure complete depolymerization. The depolymerization was carried out at a pressure of 35 psig.
The reactor air was cooled to room temperature and the Parr reactor was opened. At the bottom of the glass sleeve, the crude BPA solidified into a solid mass. The liquid layer was poured (45 g of toluene, with some water and organic impurities, such as p-cumylphenol) and discarded. The solids were removed from the glass sleeve and allowed to dry to provide 67 grams of dry crude BPA with 4,4' -isopropylidenediphenol having a purity of 99.7%.
BPA purification
After the above large-scale depolymerization, crude BPA (67 g) was dissolved in 267 g of hot toluene and allowed to cool to room temperature. The cooled crystalline solid was isolated by filtration and dried to provide 64 grams of yellow-white BPA with 99.7% purity of 4,4' -isopropylidene diphenol.
BPA (64 g) was recrystallized by heating in a mixture of 358 g toluene, 26 g isopropanol and 0.3 g acetic acid to neutralize residual sodium carbonate. After drying, the mixture was cooled to provide 53 grams of a white solid with 4,4' -isopropylidene diphenol of 99.99% purity. The initial solid isolated was BPA-IPA adduct, which was converted to BPA by heating during the drying step.
The present disclosure also encompasses the following aspects.
Aspect 1: a method for depolymerization of a poly (carbonate), the method comprising: the method comprises combining a poly (carbonate) comprising repeat units derived from bisphenol a, water, and a base under conditions effective to form a single liquid phase and depolymerize the poly (carbonate).
Aspect 2: the method according to aspect 1, wherein the method comprises combining poly (carbonate), bisphenol a, water, a base, and an organic solvent.
Aspect 3: the method according to aspect 1 or 2, wherein the method further comprises isolating bisphenol a and crystallizing the isolated bisphenol a with a crystallization solvent to provide purified bisphenol a.
Aspect 4: the process according to aspect 3, wherein the crystallization solvent comprises a mixture of toluene, isopropanol and optionally an organic acid (preferably acetic acid).
Aspect 5: the method of any of aspects 1 to 4, wherein the poly (carbonate) is virgin poly (carbonate), post-consumer recycled poly (carbonate), post-industrial recycled poly (carbonate), or a combination thereof.
Aspect 6: the method according to any one of aspects 2 to 5, wherein the organic solvent comprises toluene, xylene, chlorobenzene, or a combination thereof.
Aspect 7: the method of any one of aspects 1 to 6, wherein the base comprises an alkali metal carbonate, an alkali metal hydroxide, an alkaline earth metal hydroxide, ammonium hydroxide, phosphonium hydroxide, or a combination thereof.
Aspect 8: the method of any of aspects 1 to 7, wherein the poly (carbonate) is present in an amount of 10 to 30 weight percent; bisphenol a is present in an amount of 1 to 65 weight percent; the organic solvent is present in an amount of 5 to 65 weight percent; and water is present in an amount of 5 to 35 weight percent; wherein the weight percent of each component is based on the total weight of the poly (carbonate), the organic solvent, the water, the bisphenol A, and the base.
Aspect 9: the method according to any one of aspects 1 to 8, wherein the conditions effective to depolymerize the poly (carbonate) comprise a temperature of 110 to 130 ℃, preferably 115 to 125 ℃, and a pressure of 15 to 50 psig.
Aspect 10: the method according to any one of aspects 1 to 9, wherein the depolymerization of the poly (carbonate) is completed in 24 hours or less, preferably 16 hours or less, more preferably 10 hours or less, even more preferably 6 hours or less.
Aspect 11: the method according to any one of aspects 3 to 10, wherein the purified bisphenol-a is 4,4' -isopropylidene diphenol with a purity of greater than 99.8%.
Aspect 12: a method for isolating bisphenol a from depolymerized poly (carbonate), the method comprising: the method according to any one of aspects 1 to 11, depolymerizing the poly (carbonate); separating the bisphenol A; and crystallizing the isolated bisphenol a using a crystallization solvent to provide purified bisphenol a; wherein the purified bisphenol-A is 4,4' -isopropylidene diphenol with a purity of greater than 99.8%.
Aspect 13: bisphenol a obtained by the method of any one of aspects 3 to 12.
Aspect 14: bisphenol a according to aspect 13, wherein bisphenol a is 4,4' -isopropylidene diphenol with a purity of greater than 99.8% and comprising less than 0.2 wt% monophenol.
Aspect 15: a thermoplastic polymer comprising repeat units derived from bisphenol a of aspect 13 or 14 or bisphenol a isolated by the method of any one or more of aspects 3 to 12.
Aspect 16: the thermoplastic polymer of aspect 15, wherein the thermoplastic polymer is a poly (etherimide) or a poly (carbonate).
Aspect 17: the thermoplastic polymer of aspect 15, wherein the thermoplastic polymer is a poly (etherimide).
Aspect 18: a method of making a poly (etherimide), the method comprising: isolating bisphenol a from the poly (carbonate) depolymerized according to the method of any one or more of aspects 1 to 10; forming an aromatic bis (ether anhydride) from the isolated bisphenol a; and reacting the aromatic bis (ether anhydride) with an organic diamine to form a poly (ether imide).
Alternatively, the compositions, methods, and articles of manufacture may comprise, consist essentially of, or consist of any suitable material, step, or component disclosed herein. Additionally or alternatively, the compositions, methods, and articles may be formulated so as to be devoid of, or substantially free of, any material (or materials), step, or component that is otherwise not necessary to the achievement of the function or goal of the compositions, methods, and articles.
All ranges disclosed herein include endpoints, and the endpoints are independently combinable with each other. "combination" includes 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," "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. Unless expressly stated otherwise, "or" means "and/or. Throughout the specification, references to "some aspects," "an aspect," and so forth, mean 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 "a combination thereof, as used herein, includes one or more of the listed elements, and is open-ended, thereby permitting the presence of one or more similar elements not already mentioned. In addition, it is to be understood that the described elements may be combined in any suitable manner in the various aspects.
Unless otherwise indicated herein, all test criteria are the latest criteria that come into effect by the date of filing of the present application, or if priority is claimed, by the date of filing of the earliest priority application in which the test criteria occurs.
Unless defined otherwise, technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary 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.
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 the carbonyl carbon.
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 may be aliphatic or aromatic, straight chain, cyclic, bicyclic, branched, saturated, or unsaturated. It may 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 may also contain one or more carbonyl groups, amino groups, hydroxyl groups, or the like, or it may contain heteroatoms within the backbone of the hydrocarbyl residue. The term "alkyl" denotes a branched or straight chain saturated aliphatic hydrocarbon group, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, sec-pentyl, and n-hexyl and sec-hexyl. "alkenyl" means a straight chain or branched chain having at least one carbon-carbon double bondBranched monovalent hydrocarbon groups (e.g., vinyl (-HC ═ CH)2)). "alkoxy" means an alkyl group (i.e., alkyl-O-) attached through an oxygen, for example, methoxy, ethoxy, and sec-butoxy. "alkylene" means a straight or branched chain saturated divalent aliphatic hydrocarbon group (e.g., methylene (-CH)2-) or propylene (- (CH)2)3-)). "cycloalkylene" denotes a divalent cycloalkylene radical, -CnH2n-xWherein x is the number of hydrogens replaced by cyclization. "cycloalkenyl" means a monovalent group having one or more rings with one or more carbon-carbon double bonds in the ring, where 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" refers to a divalent aryl group. "Alkylarylene" refers to an arylene group substituted with an alkyl group. "arylalkylene" refers to an alkylene group substituted with an aryl group (e.g., benzyl). The prefix "halo" denotes a group or compound comprising one or more fluoro, chloro, bromo or iodo substituents. Combinations of different halo groups (e.g., bromo and fluoro) may be present, or only chloro groups may be present. The prefix "hetero" indicates that the compound or group contains at least one ring member (e.g., 1,2, or 3 heteroatoms) as a heteroatom, wherein each heteroatom is 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) substituent, which may each independently be C1-9Alkoxy radical, C1-9Haloalkoxy, nitro (-NO)2) Cyano (-CN), C1-6Alkylsulfonyl (-S (═ O)2Alkyl), C6-12Arylsulfonyl (-S (═ O)2Aryl), thiol (-SH), thiocyanato (-SCN), tosyl (CH)3C6H4SO2-)、C3-12Cycloalkyl radical, C2-12Alkenyl radical, C5-12Cycloalkenyl radical, C6-12Aryl radical, C7-13Arylalkylene radical, C4-12Heterocycloalkyl and C3-12Heteroaryl groups are substituted for hydrogen, provided that the normal valency of the substituted atom is not exceeded. Base ofThe number of carbon atoms indicated in the group does not include any substituents. For example, -CH2CH2CN is C substituted by nitrile2An alkyl group.
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.

Claims (19)

1. A method for depolymerization of a poly (carbonate), the method comprising:
combining under conditions that form a single liquid phase and are effective to depolymerize the poly (carbonate)
A poly (carbonate) comprising repeat units derived from bisphenol a;
bisphenol A;
water; and
a base.
2. The method of claim 1, wherein the method comprises combining the poly (carbonate), bisphenol a, water, the base, and an organic solvent.
3. The method of claim 1 or 2, wherein the method further comprises isolating bisphenol a and crystallizing the isolated bisphenol a with a crystallization solvent to provide purified bisphenol a.
4. A process according to claim 3, wherein the crystallization solvent comprises a mixture of toluene, isopropanol and optionally an organic acid, preferably acetic acid.
5. The method of any of claims 1 to 4, wherein the poly (carbonate) is virgin poly (carbonate), post-consumer recycled poly (carbonate), post-industrial recycled poly (carbonate), or a combination thereof.
6. The method of any one of claims 2 to 5, wherein the organic solvent comprises toluene, xylene, chlorobenzene, or a combination thereof.
7. The method of any one of claims 1 to 6, wherein the base comprises an alkali metal carbonate, an alkali metal hydroxide, an alkaline earth metal hydroxide, ammonium hydroxide, phosphonium hydroxide, or a combination thereof.
8. The method of any one of claims 1 to 7, wherein
The poly (carbonate) is present in an amount of 10 to 30 weight percent;
bisphenol a is present in an amount of 1 to 65 weight percent;
the organic solvent is present in an amount of 5 to 65 weight percent; and is
Water is present in an amount of 5 to 35 weight percent;
wherein the weight percent of each component is based on the total weight of the poly (carbonate), the organic solvent, water, bisphenol A, and the base.
9. The process of any of claims 1-8, wherein the conditions effective to depolymerize the poly (carbonate) comprise a temperature of 110 to 130 ℃, preferably 115 to 125 ℃, and a pressure of 15 to 50 psig.
10. The method of any one of claims 1 to 8, wherein depolymerization of the poly (carbonate) is completed in 24 hours or less, preferably 16 hours or less, more preferably 10 hours or less, even more preferably 6 hours or less.
11. The process of any one of claims 3 to 10, wherein the purified bisphenol a is 4,4' -isopropylidene diphenol having a purity of greater than 99.8%.
12. A method for isolating bisphenol a from depolymerized poly (carbonate), the method comprising:
the method of any one of claims 1 to 11, depolymerizing the poly (carbonate);
separating the bisphenol A; and
crystallizing the isolated bisphenol a using a crystallization solvent to provide purified bisphenol a;
wherein the purified bisphenol-A is 4,4' -isopropylidene diphenol having a purity of greater than 99.8%.
13. Bisphenol a obtained by the process of any of claims 3 to 12.
14. The bisphenol-a of claim 13, wherein bisphenol-a is 4,4' -isopropylidene diphenol having a purity of greater than 99.8% and comprising less than 0.2 wt% monophenol.
15. The bisphenol-a of claim 14, wherein the monophenol comprises p-cumylphenol, t-butylphenol, p-t-octylphenol, or a combination thereof.
16. A thermoplastic polymer comprising repeat units derived from the bisphenol a of claims 13-15 or isolated by the method of any one or more of claims 3-12.
17. The thermoplastic polymer of claim 16, wherein the thermoplastic polymer is a poly (etherimide) or a poly (carbonate).
18. The thermoplastic polymer of claim 16, wherein the thermoplastic polymer is a poly (etherimide).
19. A method of making a poly (etherimide), the method comprising:
isolating bisphenol a from the poly (carbonate) depolymerized according to the method of any one or more of claims 1 to 12;
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 (ether imide).
CN202080044318.3A 2019-06-19 2020-06-17 Depolymerization of poly (carbonate) and separation of bisphenol A from depolymerized poly (carbonate) Pending CN113993831A (en)

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