[go: up one dir, main page]

CN113993831B - 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

Info

Publication number
CN113993831B
CN113993831B CN202080044318.3A CN202080044318A CN113993831B CN 113993831 B CN113993831 B CN 113993831B CN 202080044318 A CN202080044318 A CN 202080044318A CN 113993831 B CN113993831 B CN 113993831B
Authority
CN
China
Prior art keywords
bisphenol
poly
carbonate
bis
depolymerization
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202080044318.3A
Other languages
Chinese (zh)
Other versions
CN113993831A (en
Inventor
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
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
SABIC Global Technologies BV
Original Assignee
SABIC Global Technologies BV
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by SABIC Global Technologies BV filed Critical SABIC Global Technologies BV
Publication of CN113993831A publication Critical patent/CN113993831A/en
Application granted granted Critical
Publication of CN113993831B publication Critical patent/CN113993831B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • 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
    • 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
    • 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
    • C07C37/68—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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • 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
    • C08G73/1003—Preparatory processes
    • C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08J11/18—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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Sustainable Development (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Polyethers (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The method for depolymerization of poly (carbonate) comprises: the poly (carbonate) comprising repeating units derived from bisphenol a, water, and a base are combined under conditions effective to depolymerize the poly (carbonate). Purified bisphenol a can be obtained from a depolymerization process. Purified bisphenol a can 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)
Citation of related applications
The present application claims priority and benefit from U.S. provisional application No. 62/863,355 filed on 6/19 in 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.
The poly (carbonate) can be depolymerized to produce the corresponding small molecule components, e.g., 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) in which bisphenol a can be purified appropriately for further use. It would be further advantageous to provide a process that minimizes the formation of byproducts to aid in the easy purification of bisphenol a. Performing the depolymerization under mild conditions would have additional advantages.
Disclosure of Invention
A method for depolymerization of a poly (carbonate) includes 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).
A method for separating bisphenol a from depolymerized poly (carbonate) includes depolymerizing the poly (carbonate), separating bisphenol a, and crystallizing the separated bisphenol a with a crystallization solvent to provide purified bisphenol a, wherein the purified bisphenol a is 4,4' -isopropylidenediphenol having a purity of greater than 99.8%.
Methods of obtaining bisphenol A are also described.
The thermoplastic polymer comprises repeating units derived from bisphenol a.
A method of making a poly (etherimide) includes separating bisphenol a from poly (carbonate) depolymerized according to the methods described herein, forming aromatic bis (ether anhydride) from the separated bisphenol a, and reacting the aromatic bis (ether anhydride) with an organic diamine to form the poly (etherimide).
The above described and other features are exemplified by the following detailed description.
Detailed Description
Described herein are methods for depolymerization of poly (carbonates) that can advantageously provide bisphenol a with a purity suitable for use in the preparation of new thermoplastic materials. The process provided by the present disclosure is advantageously a base catalyzed hydrolysis, which has the advantage of depolymerizing poly (carbonate) to bisphenol a and carbon dioxide that is easy to remove. This is in contrast to other processes such as ammonolysis (which produces urea by-products), alcoholysis (which produces dialkyl carbonates) and phenolysis (which produces diaryl carbonates). The methods of the present disclosure can advantageously provide fully depolymerized poly (carbonate) in a short time and using mild conditions. In other advantageous features, bisphenol a recovered from depolymerization can be purified to greater than 99.8% purity, light in color and good in yield according to the methods described herein. Accordingly, bisphenol a isolated from the depolymerization process described herein can be used to provide new thermoplastic materials.
Accordingly, aspects of the present disclosure are methods for depolymerization of poly (carbonates). As used herein, "poly (carbonate)" means a homopolymer or copolymer having a repeating structural carbonate unit of formula (1)
Wherein at least 60% of the total number of R 1 groups are aromatic, or R 1 each contain at least one C 6-30 aromatic group. R 1 for each occurrence may be the same or different. Poly (carbonates) and methods for their preparation are known in the art and are described, for example, in WO 2013/175448 A1, US 2014/0295363 and WO 2014/072923. Poly (carbonates) are generally 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, 5-trimethylcyclohexane (isophorone), or may also be prepared using combinations thereof.
The poly (carbonate) of the present disclosure comprises repeat units derived from bisphenol a. For example, poly (carbonate) is a homopolymer derived from bisphenol a; copolymers derived from bisphenol a and another bisphenol or dihydroxyaromatic 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 resorcinol isophthalate, aromatic-aliphatic ester units based on C 6-20 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 (BPA-PC) containing bisphenol a carbonate units.
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) may 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 homo (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) used in the methods of the present disclosure can include virgin poly (carbonate), post-consumer recycled poly (carbonate), post-industrial (post-industrial) recycled poly (carbonate), and combinations thereof. In one aspect, the poly (carbonate) may be obtained from a variety of sources and thus may comprise a combination of poly (carbonates) with slight variations in structure or composition, e.g., with different comonomers or terminal groups or additives. For example, various end-capping agents (also known as chain terminators (chain stopper agent) or chain terminators (CHAIN TERMINATING AGENT)) may be used to produce the poly (carbonates), which may be included during polymerization to provide specific end groups, for example, monocyclic phenols such as phenol, p-cyanophenol and C 1-22 alkyl-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) may have a terminal group 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 end 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 methods of the present disclosure include 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 may generally be any organic solvent that can swell the poly (carbonate) to aid in depolymerization and has a boiling point high enough that excessive pressure build up at elevated temperatures during depolymerization can be avoided. Furthermore, 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, and the like, or combinations thereof. In a particular aspect, the organic solvent comprises toluene.
The base may include an alkali metal carbonate, an alkali metal hydroxide, an alkaline earth metal hydroxide, ammonium hydroxide, phosphonium hydroxide, or a combination thereof. In one aspect, the base may be an alkali metal carbonate, such as sodium carbonate.
In one aspect, the poly (carbonate) may 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 poly (carbonate), organic solvent, water, bisphenol A, and base.
Depolymerization may 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. Depolymerization may be carried out for a period of time effective to depolymerize the poly (carbonate). The degree of depolymerization may be monitored, for example, by ultra high performance liquid chromatography (UPLC), as further described in the working examples below. For example, the depolymerization may last for 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, the depolymerization may last for a time of 1 to 24 hours, or 1 to 18 hours, or 1 to 10 hours, or 1 to 6 hours.
The methods of the present disclosure may optionally further comprise isolating bisphenol a and crystallizing the isolated bisphenol a using a crystallization solvent to provide purified bisphenol a. After the addition of the crystallization solvent, the resulting mixture may be heated to a suitable temperature to effect dissolution of bisphenol A, and the solution may then be cooled. Once cooled, bisphenol a may be crystallized from the crystallization solution and may be further separated, for example, by filtration.
The crystallization solvent may comprise, for example, a mixture of toluene, isopropanol, and optionally acetic acid. Crystallization of bisphenol a from the depolymerization reaction mixture is further described in the working examples below.
Another aspect of the present disclosure is a method for separating bisphenol a from depolymerized poly (carbonate). The method comprises depolymerizing the poly (carbonate) according to the method described herein; separating 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' -isopropylidenediphenol having 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' -isopropylidenediphenol having a purity of greater than 99.8%. The methods described herein can be effective in removing various types of additives (e.g., heat 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 comprise less than 0.2 weight percent of monophenols, for example, monophenols commonly used as capping agents, as described above. Specifically, the isolated bisphenol a may comprise less than 0.2 weight percent of monophenols including p-cumylphenol, t-butylphenol, p-t-octylphenol, or combinations thereof. This represents an important advantage of the process of the present invention, since the minimization of the monophenolic 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 can 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 process 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, and the like. Preferably, the thermoplastic polymer may be a poly (carbonate) or a poly (etherimide), more preferably a poly (etherimide).
In one aspect, bisphenol a prepared by the methods described herein can be used to provide poly (carbonates). The poly (carbonate) may be a homopolymer or a copolymer having a repeating structure carbonate unit 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 bisphenol a obtained by the methods described herein. The remainder of the R 1 group may 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, e.g., bromine, a C 1-10 hydrocarbyl group, such as C 1-10 alkyl, halogen substituted C 1-10 alkyl, C 6-10 aryl, or halogen substituted C 6-10 aryl, and n is 0 to 4.
In formula (3), R a and R b are each independently halogen, C 1-12 alkoxy or C 1-12 alkyl, and p and q are each independently integers from 0 to 4 such that p or q is less than 4, the valence 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 R a and R b are each C 1-3 alkyl, preferably methyl, disposed meta to the hydroxy group on each arylene group. X a is a bridging group linking the two hydroxy-substituted aromatic groups, wherein the bridging group and the hydroxy substituent of each C 6 arylene group are ortho, meta, or para (preferably para) to each other on the C 6 arylene group, e.g., a single bond, -O-, -S (O) 2 -, -C (O) -or C 1-18 organic groups which may be cyclic or acyclic, aromatic or non-aromatic, and which may also contain heteroatoms such as halogen, oxygen, nitrogen, sulphur, silicon or phosphorus. For example, X a may be substituted or unsubstituted C 3-18 cycloalkylidene; C 1-25 alkylidene of the formula-C (R c)(Rd) -wherein R c and R d are each independently hydrogen, c 1-12 alkyl, C 1-12 cycloalkyl, C 7-12 arylalkyl, C 1-12 heteroalkyl, or cyclic C 7-12 heteroarylalkyl; Or a group of formula-C (=r e) -wherein R e is a divalent C 1-12 hydrocarbon group. The bisphenol of formula (3) may comprise bisphenol a that has not been recovered from the depolymerization process.
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) -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, 1-bis (4-hydroxyphenyl) cyclododecane, trans-2, 3-bis (4-hydroxyphenyl) -2-butene, 2-bis (4-hydroxyphenyl) adamantane, alpha, alpha' -bis (4-hydroxyphenyl) toluene, bis (4-hydroxyphenyl) acetonitrile, 2-bis (3-methyl-4-hydroxyphenyl) propane, 2-bis (3-ethyl-4-hydroxyphenyl) propane 2, 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, 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' -tetramethylspiro (bis) indane ("spirobiindane bisphenol"), 3-bis (4-hydroxyphenyl) phthalimide, 2, 6-dihydroxydibenzop-dioxin (2, 6-dihydroxydibenzo-p-dioxan), 2, 6-dihydroxythianthrene, 2, 7-dihydroxyphenolflavin, 2, 7-dihydroxy-9, 10-dimethylphenoxazine, 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-tetrafluororesorcinol, 2,4,5, 6-tetrabromoresorcinol, and 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, 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-phenylplphthalide 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, 5-trimethylcyclohexane (isophorone bisphenol).
The poly (carbonate) s prepared from bisphenol a obtained by the process described herein may also include copolymers comprising carbonate units and ester units ("poly (ester-carbonate)"). In addition to the recurring carbonate chain units of formula (1), the poly (ester-carbonate) also contains recurring ester units of formula (4)
Wherein J is a divalent group derived from a dihydroxy compound (including reactive derivatives thereof) and may be, for example, a C 1-10 alkylene group, a C 6-20 cycloalkylene group, a C 5-20 arylene group, or a 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 group derived from a dicarboxylic acid (including reactive derivatives thereof) and may be, for example, C 1-20 alkylene, C 5-20 cycloalkylene, or C 6-20 arylene. Copolyesters containing a combination of different T or J groups may be used. The polyester units may be branched or straight chain.
In addition to bisphenol a obtained by the methods of the present disclosure, dihydroxy compounds may be used, and the dihydroxy compounds may include aromatic dihydroxy compounds of formula (2) (e.g., resorcinol), bisphenols of formula (3) (e.g., bisphenol a), C 1-8 aliphatic diols such as ethylene glycol, n-propylene glycol, isopropyl glycol, 1, 4-butanediol, 1, 4-cyclohexanediol, 1, 4-hydroxymethyl cyclohexane, or combinations of dihydroxy compounds thereof. Aliphatic dicarboxylic acids that may be used include C 5-20 aliphatic dicarboxylic acids (which include terminal carboxyl groups), preferably straight chain C 8-12 aliphatic dicarboxylic acids, such as sebacic acid (sebaceous acid); and alpha, omega-C 12 dicarboxylic 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 acids thereof. Combinations of isophthalic acid and terephthalic acid having a weight ratio of isophthalic acid to terephthalic acid ranging from 91:9 to 2:98 may be used.
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) may 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) may 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., blocks containing 5 to 200 dimethylsiloxane units.
Other specific poly (carbonates) that may be prepared from bisphenol a of the present disclosure may include poly (aromatic ester-carbonates) containing bisphenol a carbonate units and ester units of bisphenol a isophthalate-bisphenol a terephthalate, also commonly referred to as poly (carbonate-esters) (PCE) or poly (phthalate-carbonates) (PPC), based 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.
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 (etherimides) comprise more than 1, for example from 2 to 1000, or from 5 to 500 or from 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 C 6-20 aromatic hydrocarbon group, a substituted or unsubstituted linear or branched C 4-20 alkylene group, a substituted or unsubstituted C 3-8 cycloalkylene group, specifically halogenated derivatives of any of the foregoing groups. In one aspect, R is a divalent group of one or more of the following formulas (6)
Wherein Q 1 is-O-, -S-, -C (O) -, -SO 2-、-SO-、-P(Ra) (=o) - (wherein R a is C 1-8 alkyl or C 6-12 aryl), -C yH2y - (wherein y is an integer from 1 to 5) or a halogenated derivative 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 diarylidene 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.
Furthermore, in formula (5), T is a group derived from bisphenol a obtained by the process of the present disclosure. 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 an aromatic C 6-24 monocyclic or polycyclic moiety optionally substituted with 1 to 6C 1-8 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 C 1-6 alkyl group, e.g., p and q are each independently integers from 0 to 4; c is 0 to 4; and X a is a bridging group linking the hydroxy-substituted aromatic groups, wherein the bridging group and the hydroxy substituent of each C 6 arylene group are disposed ortho, meta, or para (specifically para) to each other on the C 6 arylene group. The bridging group X a can be a single bond, -O-, -S (O) 2 -, -C (O) -, or C 1-18 organic bridging group. The C 1-18 organic bridging group may be cyclic or acyclic, aromatic or non-aromatic and may also contain heteroatoms such as halogen, oxygen, nitrogen, sulfur, silicon or phosphorus. The arrangement of the C 1-18 organic groups may be such that the C 6 arylene groups attached thereto are each attached to the same alkylidene carbon or different carbons of the C 1-18 organic bridging group. Specific examples of the group Z are divalent groups of the formula (7 a)
Wherein Q is-O-, -S-, -C (O) -, -SO 2-、-SO-、-P(Ra) (=o) - (wherein R a is C 1-8 alkyl or C 6-12 aryl) or-C yH2y - (wherein y is an integer from 1 to 5) or a halogenated derivative thereof (including perfluoroalkylene). In one aspect, Z is derived from bisphenol A, such that Q in formula (7 a) 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) may be a copolymer comprising other 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, 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 other structural imide units other than poly (etherimide) units, e.g., 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 C 6-20 aromatic hydrocarbon group, e.g., a tetravalent linker of the formula
Wherein W is a single bond, -O-, -S-, -C (O) -, -SO 2-、-SO-、C1-18 alkylene, -P (R a) (=o) - (wherein R a is C 1-8 alkyl or C 6-12 aryl) or-C yH2y - (wherein y is an integer from 1 to 5) or halogenated derivatives thereof (including perfluoroalkylenes). The imide units of these other structures preferably comprise less than 20 mole% of the total number of units, and more preferably may be present in an amount of 0 to 10 mole% of the total number of units, or 0 to 5 mole% of the total number of units, or 0 to 2 mole% of the total number of units. In one aspect, 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 a siloxane block 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 C 1-13 monovalent hydrocarbon group. For example, each R' may independently be C 1-13 alkyl, C 1-13 alkoxy, C 2-13 alkenyl, C 2-13 alkenyloxy, C 3-6 cycloalkyl, C 3-6 cycloalkoxy, C 6-14 aryl, C 6-10 aryloxy, C 7-13 arylalkylene, C 7-13 arylalkyleneoxy, C 7-13 alkylarylene, or C 7-13 alkylaryleneoxy. The above 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 can 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 minimal hydrocarbon content is methyl.
Poly (etherimides) may 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)
H2N-R-NH2 (11)
Wherein T and R are defined as described above. The copolymers of poly (etherimides) may be produced using a combination of aromatic bis (ether anhydride) of formula (10) and other bis (anhydride) than 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) 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, aromatic bis (ether anhydride) derived from the isolated bisphenol-a of the present disclosure and one or more aromatic bis (ether anhydride) derived from bisphenol-a prepared by different processes, 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-dimethylpropanediamine, N-methyl-bis (3-aminopropyl) amine, 3-methoxyhexamethylenediamine, 1, 2-bis (3-aminopropoxy) ethane bis (3-aminopropyl) sulfide, 1, 4-cyclohexane diamine, 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-tert-butyl) toluene, bis (p-amino-tert-butylphenyl) ether, bis (p-methylparaben) benzene (bis (p-methyl-o-aminophenyl) benzone), bis (p-methylparaben) 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 C 1-4 alkylated or poly (C 1-4) alkylated derivatives described above, for example, poly-methylated 1, 6-hexamethylenediamine, may be used. Combinations of these compounds may also be used. In one aspect, the organic diamine is meta-phenylenediamine, para-phenylenediamine, 4 '-diaminodiphenyl sulfone, 3' -diaminodiphenyl sulfone, or a combination comprising at least one of the foregoing.
The poly (etherimide) may have a melt index of 0.1 to 10 grams per minute (g/min), as measured by American Society for Testing and Materials (ASTM) D1238 using a 6.7 kilogram (kg) weight at 340 to 370 ℃. 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) typically have an intrinsic viscosity of 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 process of the present disclosure advantageously combines poly (carbonate) depolymerization, bisphenol a purification, and solvent recovery and recycle to provide an improved process for separating bisphenol a from poly (carbonate) depolymerization. Careful selection of the 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
Poly (carbonate) depolymerization
The same general procedure was used for each of the following examples. Poly (carbonate) pellets (available as LEXAN 100 from SABIC), bisphenol A (BPA), toluene, water and sodium carbonate (Na 2CO3) were added to a tubular reactor equipped with a stirring bar. The amounts of each component are provided in table 1 below, wherein the amounts of each component are provided in grams. The reaction tube was sealed and placed in an oil bath heated to 120 ℃. The mixing was done by a magnetic stirrer bar and the stirring rate for each example was 535rpm.
TABLE 1
"X" indicates comparative example
Table 1 (subsequent)
"X" indicates comparative example
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 was observed to have been completely depolymerized within 6 hours, no particles in the reaction mixture remained suspended, and no detectable carbonate extension (stretch) by FTIR. 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 extension. Thus, these embodiments 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.
A 600 ml Parr reactor equipped with a magnetic stir bar, glass liner, and internal thermocouple was charged with 25 grams of poly (carbonate) particles (available from SABIC as LEXAN 100), 10 grams of deionized water, 30.42 grams of toluene, 45.01 grams of BPA, and 0.51 grams of sodium carbonate. The reactor was then placed in a heating mantle and sealed. The reactor was heated to 125 ℃ overnight to ensure complete depolymerization. Depolymerization was carried out at a pressure of 35 psig.
The reactor was air cooled to room temperature and the Parr reactor was opened. At the bottom of the glass sleeve, the crude BPA solidifies into a solid material. The liquid layer (45 grams toluene, with some water and organic impurities such as p-cumylphenol) was poured and discarded. The solids were removed from the glass sleeve and dried to provide 67 grams of dried crude BPA having 99.7% purity 4,4' -isopropylidenediphenol.
Purification of BPA
After the above large scale depolymerization, crude BPA (67 g) was dissolved in 267 g hot toluene and allowed to cool to room temperature. The cooled crystallized solid was isolated by filtration and dried to provide 64 grams of yellow-white BPA having 99.7% purity 4,4' -isopropylidenediphenol.
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 g of a white solid having a purity of 99.99% of 4,4' -isopropylidenediphenol. The initial solid isolated is BPA-IPA adduct, which is converted to BPA during the drying step by heating.
The present disclosure also encompasses the following aspects.
Aspect 1: a method for depolymerization of poly (carbonate), the method comprising: the poly (carbonate) comprising repeating units derived from bisphenol a, water, and a base are combined 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 or2, 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 according to 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 one 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 poly (carbonate), organic solvent, water, bisphenol A, and base.
Aspect 9: the method of any 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 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' -isopropylidenediphenol having a purity of greater than 99.8%.
Aspect 12: a method for separating bisphenol a from depolymerized poly (carbonate), the method comprising: depolymerizing the poly (carbonate) according to the method of any one of aspects 1 to 11; separating 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' -isopropylidenediphenol having a purity of greater than 99.8%.
Aspect 13: bisphenol a obtained by the method of any of aspects 3 to 12.
Aspect 14: bisphenol a according to aspect 13, wherein bisphenol a is 4,4' -isopropylidenediphenol having a purity of greater than 99.8% and comprising less than 0.2 wt.% monophenols.
Aspect 15: a thermoplastic polymer comprising recurring units derived from bisphenol a of aspects 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 preparing a poly (etherimide), the method comprising: separating bisphenol a from the poly (carbonate) depolymerized by the method according to any one or more of aspects 1 to 10; forming 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 of, or consist essentially of any of the suitable materials, steps, or components disclosed herein. Additionally or alternatively, the compositions, methods, and articles of manufacture may be formulated so as to be devoid or substantially free of any material (or substance), step, or component otherwise unnecessary to achieve the function or goal of the compositions, methods, and articles of manufacture.
All ranges disclosed herein are inclusive of the 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 explicitly stated otherwise, "or" means "and/or". Throughout the specification, references to "some aspects," "one aspect," etc., 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 to allow the presence of one or more similar elements not mentioned. Additionally, it should be understood that the elements may be combined in any suitable manner in various aspects.
Unless indicated to the contrary herein, all test criteria are either by the date of filing of the present application, or if priority is required, by the latest criteria that are in effect at the date of filing of the earliest priority application in which the test criteria occur.
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 contradicts a term in the incorporated reference, then the term from the present application takes precedence over the contradictory 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 located between two letters or symbols is used to indicate a point of attachment for a substituent. For example, -CHO is linked through a 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 residues 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 a 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" means 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 or branched monovalent hydrocarbon group having at least one carbon-carbon double bond (e.g., vinyl (-hc=ch 2)). "alkoxy" means an alkyl group attached through oxygen (i.e., alkyl-O-), such as 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" means a divalent cycloalkylene radical, -C nH2n-x, where x is the number of hydrogens substituted by cyclization. "cycloalkenyl" means a monovalent group having one or more rings and 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" means a divalent aryl group. "Alkylarylene" means an arylene group substituted with an alkyl group. "arylalkylene" means an alkylene group (e.g., benzyl) substituted with an aryl group. The prefix "halo" refers to a group or compound that includes 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" means that the compound or group contains at least one ring member as a heteroatom (e.g., 1,2, or 3 heteroatoms), where the heteroatoms are 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) substituent that may each independently be C 1-9 alkoxy, C 1-9 haloalkoxy, nitro (-NO 2), nitro, cyano (-CN), C 1-6 alkylsulfonyl (-S (=o) 2 -alkyl), C 6-12 arylsulfonyl (-S (=o) 2 -aryl), Thiol (-SH), thiocyanato (-SCN), tosyl (CH 3C6H4SO2-)、C3-12 cycloalkyl, C 2-12 alkenyl, C 5-12 cycloalkenyl, C 6-12 aryl), C 7-13 arylalkylene, C 4-12 heterocycloalkyl, and C 3-12 heteroaryl replace hydrogen, provided that the normal valency of the substituted atoms is not exceeded. the indicated number of carbon atoms in the group does not include any substituents. For example, -CH 2CH2 CN is C 2 alkyl substituted by nitrile.
Although particular aspects have been described, applicant or other person skilled in the art may conceive of alternatives, modifications, variations, improvements, and substantial equivalents that are or may not be presently contemplated. 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 (12)

1. A method for depolymerization of poly (carbonate), the method comprising:
the following are combined at a temperature of 110 to 130 ℃ and a pressure of 15 to 50 psig to depolymerize the poly (carbonate):
a poly (carbonate) comprising repeat units derived from bisphenol a;
Bisphenol a;
Water; and
And (5) alkali.
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, 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.
5. The method of claim 1, 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 claim 2, wherein the organic solvent is selected from toluene, xylene, chlorobenzene, or a combination thereof.
7. The method of claim 1, 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 claim 2, 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, water, bisphenol a, and the base.
9. The method of claim 1, wherein depolymerization of the poly (carbonate) is completed in 24 hours or less.
10. A process according to claim 3, wherein the purified bisphenol a is 4,4' -isopropylidenediphenol having a purity of greater than 99.8%.
11. A method for separating bisphenol a from depolymerized poly (carbonate), the method comprising:
The method of any one of claims 1 to 10, depolymerizing poly (carbonate);
Separating 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' -isopropylidenediphenol having a purity of greater than 99.8%.
12. A method of preparing a poly (etherimide), the method comprising:
the poly (carbonate) is depolymerized by combining at a temperature of 110 to 130 ℃ and a pressure of 15 to 50 psig:
a poly (carbonate) comprising repeat units derived from bisphenol a;
Bisphenol a;
Water; and
A base;
isolating bisphenol a and crystallizing the isolated bisphenol a using a crystallization solvent to provide purified bisphenol a;
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) Active CN113993831B (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US201962863355P 2019-06-19 2019-06-19
US62/863,355 2019-06-19
PCT/US2020/038069 WO2020257237A1 (en) 2019-06-19 2020-06-17 Depolymerization of a poly(carbonate) and isolation of bisphenol a from a depolymerized poly(carbonate)

Publications (2)

Publication Number Publication Date
CN113993831A CN113993831A (en) 2022-01-28
CN113993831B true CN113993831B (en) 2024-07-02

Family

ID=71409590

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202080044318.3A Active CN113993831B (en) 2019-06-19 2020-06-17 Depolymerization of poly (carbonate) and separation of bisphenol A from depolymerized poly (carbonate)

Country Status (3)

Country Link
EP (1) EP3986850A1 (en)
CN (1) CN113993831B (en)
WO (1) WO2020257237A1 (en)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20230096984A (en) * 2020-10-30 2023-06-30 미쯔비시 케미컬 주식회사 Method for producing bisphenol, method for producing recycled polycarbonate resin, method for producing carbon dioxide, method for producing diester carbonate, method for producing epoxy resin, and method for producing cured epoxy resin product
WO2023038271A1 (en) * 2021-09-13 2023-03-16 주식회사 엘지화학 Monomer composition for synthesizing recycled plastic, preparation method therefor, and recycled plastic and molded product which use same
KR20240095417A (en) 2021-10-29 2024-06-25 코베스트로 도이칠란트 아게 Method of hydrolysis of (poly)carbonate
TWI872713B (en) * 2023-09-21 2025-02-11 國立中興大學 Carbonate-containing aldehyde derived compound, preparation method thereof, poly(carbonate imine) prepared thereby and method for remodeling, reprocessing and degrading poly(carbonate imine)

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4910288A (en) * 1989-02-07 1990-03-20 General Electric Company Process for the preparation of polyetherimides

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20140295363A1 (en) 2011-10-08 2014-10-02 Sabic Innovative Plastics Ip B.V. Plastic flame housing and method of making the same
US20130317142A1 (en) 2012-05-24 2013-11-28 Sabic Innovative Plastics Ip B.V. Flame retardant thermoplastic compositions, methods of manufacture thereof and articles comprising the same
EP2730618B1 (en) 2012-11-07 2016-10-12 SABIC Global Technologies B.V. Process for producing polycarbonate compositions
PE20142190A1 (en) * 2013-05-15 2015-01-11 Univ Pontificia Catolica Peru METHOD FOR OBTAINING BISPHENOL-A FROM POLYCARBONATE WASTE USING MICROWAVE RADIATION
CN105764878B (en) * 2013-11-11 2017-10-03 田冈化学工业株式会社 From the method that bisphenol fluorene class is reclaimed comprising fluorene structured resin

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4910288A (en) * 1989-02-07 1990-03-20 General Electric Company Process for the preparation of polyetherimides

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
Methanolysis and Hydrolysis of Polycarbonate Under Moderate Conditions;Fu-Sheng Liu等;J Polym Environ.(第17期);208-211 *
PHASE-SEPARATION BEHAVIOR IN POLY(ETHER IMIDE)-MODIFIED EPOXY BLENDS;SRIDHAR K. SIDDHAMALLI;Polymer-Plastics Technology and Engineering;第39卷(第4期);699-710 *
帝人化学开发从废PC回收高纯度双酚A技术;李正;精细与专用化学品;第14卷(第8期);44 *

Also Published As

Publication number Publication date
EP3986850A1 (en) 2022-04-27
WO2020257237A1 (en) 2020-12-24
CN113993831A (en) 2022-01-28

Similar Documents

Publication Publication Date Title
CN113993831B (en) Depolymerization of poly (carbonate) and separation of bisphenol A from depolymerized poly (carbonate)
EP3986851A1 (en) Isolation of bisphenol a from depolymerization of a poly(carbonate)
US8809486B2 (en) Methods for producing and purifying 2-aryl-3,3-bis(4-hydroxyaryl)phthalimidine compounds, the purified monomers, and polymers derived therefrom
EP2912099B1 (en) Phenolic compounds as end-capping agents for polysiloxanes in polycarbonate-polysiloxane block copolymers
US4757150A (en) Polyetherimide bisphenol compositions
WO2006066055A2 (en) Polycarbonate-ultem block copolymers
JPH02117919A (en) Composition
EP0469447A2 (en) Blocked amine terminated polycarbonates and products obtained thereof
EP3445748B1 (en) Methods of manufacture of 2-aryl-3,3-bis(4-hydroxyaryl) phthalimidines and polymers derived therefrom
EP3530700A1 (en) Polycarbonate copolymer blends, articles formed therefrom, and methods of manufacture
CN112074508A (en) Method for separating dianhydride and dianhydride prepared by same
EP3137551A1 (en) Fiber reinforced polyetherimide compositions
US20230111779A1 (en) Methods of manufacture of dianhydrides
US11078212B2 (en) 2-hydrocarbyl-3-(dihydroxyfluoresceinyl)phthalimidine monomers, methods of manufacture, and copolymers derived therefrom
EP3599233A1 (en) Methods of purification of 2-aryl-3,3-bis(4-hydroxyaryl)phthalimidines, and polymers derived therefrom
EP0257469A1 (en) Block copolyimidecarbonates and method for their preparation
WO2020100008A1 (en) Method of injection molding a thermoplastic article
KR20210123345A (en) Poly(etherimide), methods of making same, and articles comprising poly(etherimide)

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant