Classifications

• • 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
  • 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
  • C07C37/74—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment by distillation
• • 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
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C39/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
  • C07C39/12—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic with no unsaturation outside the aromatic rings
  • C07C39/15—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic with no unsaturation outside the aromatic rings with all hydroxy groups on non-condensed rings, e.g. phenylphenol
  • C07C39/16—Bis-(hydroxyphenyl) alkanes; Tris-(hydroxyphenyl)alkanes
• • 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
  • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
• • 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
  • C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
• • 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
  • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
  • C08G75/20—Polysulfones
• • 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

Definitions

• Poly (carbonate) s are useful in the manufacture of articles and components for a wide range of applications, from automotive parts to electronic appliances.
• poly (carbonate) s are not readily biodegradable and can present a significant bulk waste disposal problem. Accordingly, efforts have been made to recover valuable resources from polycarbonate wastes.
• Poly (carbonate) s can be depolymerized to generate the corresponding small molecule constituents, for example 4,4’-isopropylidenediphenol (also referred to as bisphenol A) and dimethyl carbonate.
• 4,4’-isopropylidenediphenol also referred to as bisphenol A
• dimethyl carbonate dimethyl carbonate.
• poly (carbonate) comprises: depolymerizing a poly (carbonate) comprising repeating units derived from bisphenol A in the presence of a base, a Ci- 6 alcohol, and an organic cosolvent that is miscible with the Ci- 6 alcohol and has a boiling point that is greater than 90°C, to provide a depolymerized reaction mixture comprising bisphenol A, a di(Ci- 6 alkyl) carbonate, the Ci- 6 alcohol, the organic cosolvent, and optionally, residual base; separating the di(Ci- 6 alkyl) carbonate, the Ci- 6 alcohol, and optionally, at least a portion of the organic cosolvent from the depolymerized reaction mixture, preferably by distillation, to provide a di(Ci- 6 alkyl) carbonate mixture; combining the di(Ci- 6 alkyl) carbonate mixture with an aqueous base under conditions effective to hydrolyze the di(Ci- 6 alkyl) carbonate to a corresponding Ci- 6 alcohol; and crystall
• thermoplastic polymer comprises repeating units derived from the bisphenol A.
• a method of making a poly(etherimide) comprises isolating bisphenol A from depolymerization of a poly(carbonate) according to the process described herein; forming an aromatic bis(ether anhydride) from the isolated bisphenol A; and reacting the aromatic bis(ether anhydride) with an organic diamine to form the poly(etherimide).
• Described herein is a process for the depolymerization of a poly(carbonate) which can advantageously provide bisphenol A having a purity suitable for use in making new thermoplastic materials.
• the process can effectively recover and recycle the solvent, thus improving the cost-effectiveness of the process.
• the present inventors have determined that the dialkyl carbonate byproduct of the depolymerization can be hydrolyzed to the corresponding alcohol, thus simplifying the purification and solvent recovery.
• the bisphenol A recovered from the depolymerization can be purified according to the process described herein to a purity of greater than 99.8%, with low color, and in good yield.
• an aspect of the present disclosure is a process for isolation of bisphenol A from depolymerization of a poly (carbonate).“Poly(carbonate)” as used herein means a homopolymer or copolymer having repeating structural carbonate units of the formula (1)
• R 1 groups wherein at least 60 percent of the total number of R 1 groups are aromatic, or each R 1 contains at least one C6-30 aromatic group.
• Each occurrence of R 1 can be the same or different.
• Poly (carbonate) s and their methods of manufacture are known in the art, being described, for example, in WO 2013/175448 Al, US 2014/0295363, and WO 2014/072923.
• Poly(carbonate)s are generally manufactured from bisphenol compounds such as 2,2-bis(4-hydroxyphenyl) propane (“bisphenol-A” or“BPA” or“4,4’-isopropylidenediphenol”), 3,3-bis(4-hydroxyphenyl) phthalimidine, l,l-bis(4-hydroxy-3-methylphenyl)cyclohexane, or l,l-bis(4-hydroxyphenyl)- 3,3,5-trimethylcyclohexane (isophorone), or a combination thereof can also be used.
• bisphenol compounds such as 2,2-bis(4-hydroxyphenyl) propane (“bisphenol-A” or“BPA” or“4,4’-isopropylidenediphenol”), 3,3-bis(4-hydroxyphenyl) phthalimidine,
• the poly(carbonate) of the present disclosure comprises repeating units derived from bisphenol A.
• the poly(carbonate) is a homopolymer derived from bisphenol A; a copolymer derived from bisphenol A and another bisphenol or dihydroxy aromatic compound such as resorcinol; or a copolymer derived from bisphenol A and optionally another bisphenol or dihydroxy aromatic compound, and further comprising non-carbonate units, for example aromatic ester units such as resorcinol terephthalate or isophthalate, aromatic-aliphatic ester units based on Ce-2o aliphatic diacids, polysiloxane units such as polydimethylsiloxane units, or a combination thereof.
• the poly (carbonate) is a linear homopolymer containing bisphenol A carbonate units (BPA-PC).
• the poly(carbonate)s can have an intrinsic viscosity, as determined in chloroform at 25°C, of 0.3 to 1.5 deciliters per gram (dl/gm), preferably 0.45 to 1.0 dl/gm.
• poly (carbonate) s can have a weight average molecular weight (Mw) of 10,000 to 200,000 grams per mole (Daltons), preferably 17,000 to 35,000 Daltons, as measured by gel permeation chromatography (GPC), using a crosslinked styrene-divinylbenzene column and calibrated to bisphenol A homopoly (carbonate) references.
• Mw weight average molecular weight
• GPC gel permeation chromatography
• Poly (carbonate) s useful for the process of the present disclosure can include virgin poly(carbonate)s, post-consumer recycled poly(carbonate)s, post-industrial recycled poly(carbonate)s, and combinations thereof.
• the poly(carbonate) can be obtained from multiple sources, and can therefore comprise a combination of poly(carbonate)s having slight variances in structure, including different comonomers or end groups.
• poly (carbonate) s can be produced using various end-capping agents (also referred to as a chain stopper agent or chain terminating agent) which can be included during polymerization to provide particular end groups, for example monocyclic phenols such as phenol, p-cyanophenol, and Ci -22 alkyl-substituted phenols such as p-cumyl-phenol, resorcinol monobenzoate, and p-and m-tertiary-butyl phenol, monoethers of diphenols, such as p-methoxyphenol, monoesters of diphenols such as resorcinol monobenzoate, and functionalized chlorides of aliphatic end groups, for example monocyclic phenols such as phenol, p-cyanophenol, and Ci -22 alkyl-substituted phenols such as p-cumyl-phenol, resorcinol monobenzoate, and p-and m-tertiary-butyl phenol,
• the poly(carbonate) can have an end group derived from at least one of phenol, p-cumylphenol, p- tert-butylphenol, and p-tert-octylphenol. Combinations of different end groups can be used.
• the poly(carbonate) used in the present process can be a combination of bisphenol A- containing poly (carbonate) s having different end groups.
• the poly(carbonate) stream can optionally containing one or more additives or additional thermoplastic polymers different from the poly (carbonate).
• the process of the present disclosure comprises depolymerizing the
• poly(carbonate) in the presence of a base, a Ci- 6 alcohol, and an organic cosolvent.
• the base can be, for example, an alkoxide or hydroxide. Suitable alkoxides and hydroxides are those that are soluble in the reaction mixture. Exemplary alkoxides can include Ci-4 alkoxides, and exemplary hydroxides can include, for example, alkali metal hydroxides, alkaline-earth metal hydroxides, tetra-alkyl ammonium hydroxides, and ammonium hydroxide.
• the base comprises an alkali metal hydroxide, for example sodium hydroxide.
• the base can be in the form of an aqueous solution for example an aqueous alkali metal hydroxide, preferably an aqueous sodium hydroxide solution.
• the base e.g., the alkali metal hydroxide
• the base can be present in an amount sufficient to provide a 10 to 50 weight percent solution of the base in water (based on the total weight of the base and the water), preferably a 20 to 50 weight percent solution, more preferably a 30 to 50 weight percent solution, even more preferably a 35 to 45 weight percent solution.
• the Ci- 6 alcohol can include, for example, methanol, ethanol, n-propanol, isopropanol, n-butanol, iso-butanol, and the like, or a combination thereof.
• the Ci- 6 alcohol preferably comprises methanol.
• the Ci- 6 alcohol consists of methanol.
• the organic cosolvent is miscible with the Ci- 6 alcohol, and thus forms a homogenous, single liquid phase.
• the organic cosolvent further has a boiling point that is greater than 90°C.
• Organic cosolvents having boiling points less than 90°C are not preferred as they can hinder the later separation of the di(Ci- 6 alkyl) carbonate byproduct from the BPA.
• the organic cosolvent can comprise toluene, chlorobenzene, xylene, and the like, or a combination thereof.
• the organic cosolvent comprises toluene.
• the Ci- 6 alcohol and the organic cosolvent can be present in a weight ratio of 0.1:1 to 1:0.1, or 0.25:1 to 1:0.25, or 0.5:1 to 1:0.5, or 0.75:1 to 1:0.75, or 0.8:1 to 1:0.8, or 0.9:1 to 1:0.9, or 0.95:1 to 1:0.95.
• the Ci- 6 alcohol and the organic cosolvent can be present in a weight ratio of 1:1.
• the base can be present in an amount of 0.1 to 10 weight percent, based on the total weight of the Ci- 6 alcohol, the organic cosolvent, and the base, for example 0.1 to 5 weight percent, or 0.1 to 1 weight percent, or 0.1 to 0.5 weight percent.
• the poly(carbonate) is present in an amount of 10 to 30 weight percent, based on the total weight of the reaction mixture (e.g., the total weight of the Ci- 6 alcohol, the organic cosolvent, the base and the poly(carbonate)). Within this range, the poly(carbonate) can be present in an amount of 15 to 25 weight percent, or 17 to 23 weight percent, or 18 to 21 weight percent.
• the poly(carbonate) is depolymerized in the presence of the Ci- 6 alcohol, the organic cosolvent, and the base to provide a depolymerized reaction mixture comprising bisphenol A, a di(Ci- 6 alkyl) carbonate, the Ci- 6 alcohol, the organic cosolvent, and optionally, residual base.
• the depolymerizing can be conducted at a temperature of 40 to 70°C, or 45 to 65°C, or 50 to 60°C, and atmospheric pressure.
• the depolymerization can be conducted for a time effective to depolymerize the poly (carbonate).
• the degree of depolymerization can be monitored, for example, by ultra-performance liquid chromatography (UPLC), as further described in the working examples below.
• UPLC ultra-performance liquid chromatography
• the depolymerizing can be for a time of 1 to 24 hours, preferably 1 to 18 hours, more preferably 1 to 10 hours, even more preferably 1 to 6 hours.
• the identity of the di(Ci- 6 alkyl) carbonate present in the depolymerized reaction mixture can be dictated by the particular Ci- 6 alcohol selected for the depolymerization reaction.
• the di(Ci- 6 alkyl) carbonate can be dimethyl carbonate when methanol is selected as the alcohol.
• the process of the present disclosure further comprises separating the di(Ci- 6 alkyl) carbonate, the Ci- 6 alcohol, and optionally, at least a portion of the organic cosolvent from the depolymerized reaction mixture to provide a di(Ci- 6 alkyl) carbonate mixture.
• this separation can be by distillation.
• the separation can be conducted at, for example, a temperature of greater than 90 to 115°C, or 100 to 110°C at atmospheric pressure.
• the separation can be as described in the working examples below.
• the process further comprises combining the di(Ci- 6 alkyl) carbonate mixture with an aqueous base under conditions effective to hydrolyze the di(Ci- 6 alkyl) carbonate to the corresponding Ci- 6 alcohol.
• dimethyl carbonate can be hydrolyzed to form methanol and carbon dioxide (CO2).
• the aqueous base used for the hydrolysis of the di(Ci- 6 alkyl) carbonate can be a hydroxide as described above, for example an alkali metal hydroxide, such as sodium hydroxide.
• the base-catalyzed hydrolysis of the di(Ci- 6 alkyl) carbonate can be conducted, for example, at a temperature of 100 to 150°C, or 110 to 140°C, or 115 to 135°C, or 120 to 130°C, at a pressure of 100 to 150 psig, or 115 to 135 psig, or 120 to 130 psig, and for a time of 1 to 24 hours, or 5 to 20 hours, or 10 to 20 hours, or 12 to 18 hours.
• Various techniques can be used to monitor the progress of the hydrolysis, for example, 1 H NMR spectroscopy, as described in the working examples below.
• the hydrolyzed product which comprises the Ci- 6 alcohol, and optionally the organic cosolvent, can be directly recycled back to a depolymerization reaction without the need for additional purification.
• the process of the present disclosure further comprises crystallizing bisphenol A from the residual depolymerized reaction mixture (i.e., the residual reaction mixture that is left following the removal of the di(Ci- 6 alkyl) carbonate, the Ci- 6 alcohol, and the organic cosolvent.
• crystallizing the residual depolymerized reaction mixture comprises adding an aqueous solution comprising an acid to the residual depolymerized reaction mixture.
• the acid can preferably be an organic acid, such as acetic acid.
• the bisphenol A can crystallize from the mixture in a first crystallization step.
• the crystallized bisphenol A can be isolated, for example by filtration.
• the recovered bisphenol A can be crystallized again in a second, subsequent crystallization step.
• a crystallization solvent can be added to the isolated crystallized bisphenol A from the first crystallization step to provide a second crystallization mixture, which can be heated to a suitable temperature to effect dissolution of the bisphenol A, and the solution can then be cooled.
• bisphenol A can crystallized from the second crystallization mixture, and can further be isolated, preferably by filtration.
• the crystallization solvent can comprise, for example, a mixture of toluene, isopropanol, and optionally, an organic acid such as acetic acid.
• the isolated bisphenol A can have a high purity.
• the isolated bisphenol A can have a purity of greater than 99.8%.
• the isolated bisphenol A can be 4,4’-isopropyiidenediphenoI having a purity of greater than 99.8%.
• the process described herein can effectively remove many types of additives (e.g., heat stabilizers, mold release agents, and the like), that can be present, in particular when the poly(carbonate) stream is at least partially derived from a post-consumer recycled poly (carbonate).
• the isolated bisphenol A can also advantageously comprise less than 0.2 weight percent of a monophenol, for example a monophenol typically used as an end-capping agent, as described above.
• thermoplastic polymer comprising repeating units derived from the bisphenol A made by the process described herein.
• the thermoplastic polymer can be any polymer which can have repeating units derived from bisphenol A, and can include, for example, poly (carbonates), poly(etherimides), poly(sulfones), epoxies, and the like.
• the thermoplastic polymer can be a poly(carbonate), a poly(sulfone), or a poly(etherimide), more preferably a poly(etherimide).
• the bisphenol A made from the process described herein can be used to provide a poly(carbonate).
• the poly(carbonate) can be a homopolymer or copolymer having the repeating structural carbonate units according to formula (1) described above.
• At least a portion (e.g., at least 10%) of the R 1 groups of formula (1) are derived from the bisphenol A obtained by the method described herein.
• the remainder of the R 1 groups can be derived from a dihydroxy compound such as an aromatic dihydroxy compound of formula (2) or a bisphenol of formula (3).
• each R h is independently a halogen atom, for example bromine, a Ci-io hydrocarbyl group such as a Ci-io alkyl, a halogen-substituted Ci-io alkyl, a Ce-io aryl, or a halogen-substituted Ce-io aryl, and n is 0 to 4.
• a Ci-io hydrocarbyl group such as a Ci-io alkyl, a halogen-substituted Ci-io alkyl, a Ce-io aryl, or a halogen-substituted Ce-io aryl
• n is 0 to 4.
• R a and R b are each independently a halogen, C i-12 alkoxy, or C i-12 alkyl, and p and q are each independently integers of 0 to 4, such that when p or q is less than 4, the valence of each carbon of the ring is filled by hydrogen.
• p and q is each 0, or p and q is each 1
• R a and R b are each a C 1-3 alkyl group, preferably methyl, disposed meta to the hydroxy group on each arylene group.
• X a is a bridging group connecting the two hydroxy- substituted aromatic groups, where the bridging group and the hydroxy substituent of each Ce arylene group are disposed ortho, meta, or para (preferably para) to each other on the Ce arylene group, for example, a single bond, -0-, -S-, -S(O)-, -S(0) 2 -, -C(O)-, or a C 1-18 organic group, which can be cyclic or acyclic, aromatic or non-aromatic, and can further comprise heteroatoms such as halogens, oxygen, nitrogen, sulfur, silicon, or phosphorous.
• Bisphenols of formula (3) can include bisphenol A that has not been recovered from a depolymerization process.
• bisphenol compounds include 4,4'-dihydroxybiphenyl, 1,6- dihydroxynaphthalene, 2,6-dihydroxynaphthalene, bis(4-hydroxyphenyl)methane, bis(4- hydroxyphenyl)diphenylmethane, bis(4-hydroxyphenyl)-l-naphthylmethane, l,2-bis(4- hydroxyphenyl)ethane, l,l-bis(4-hydroxyphenyl)-l-phenylethane, 2-(4-hydroxyphenyl)-2-(3- hydroxyphenyl)propane, bis(4-hydroxyphenyl)phenylmethane, 2,2-bis(4-hydroxy-3- bromophenyl)propane, 1,1 -bis (hydroxyphenyl)cyclopentane, l,l-bis(4- hydroxyphenyl)cyclohexane, 1 , 1 -bis(4-hydroxyphenyl)
• 1.6-bis(4-hydroxyphenyl)-l,6-hexanedione ethylene glycol bis(4-hydroxyphenyl)ether, bis(4- hydroxyphenyl)ether, bis(4-hydroxyphenyl)sulfide, bis(4-hydroxyphenyl)sulfoxide, bis(4- hydroxyphenyl)sulfone, 9,9-bis(4-hydroxyphenyl)fluorene, 2,7-dihydroxypyrene, 6,6'- dihydroxy-3,3,3',3'- tetramethylspiro(bis)indane ("spirobiindane bisphenol"), 3,3-bis(4- hydroxyphenyl)phthalimide, 2,6-dihydroxydibenzo-p-dioxin, 2,6-dihydroxythianthrene, 2,7- dihydroxyphenoxathin, 2,7-dihydroxy-9, 10-dimethylphenazine, 3,6-dihydroxydibenzofuran,
• resorcinol substituted resorcinol compounds such as 5-methyl resorcinol, 5-ethyl resorcinol, 5-propyl resorcinol, 5-butyl resorcinol, 5-t-butyl resorcinol, 5-phenyl resorcinol, 5-cumyl resorcinol, 2,4,5,6-tetrafluoro resorcinol, 2,4,5,6-tetrabromo resorcinol, or the like; catechol; hydroquinone; substituted hydroquinones such as 2-methyl hydroquinone, 2-ethyl hydroquinone, 2-propyl hydroquinone, 2-butyl hydroquinone, 2-t-butyl hydroquinone, 2-phenyl hydroquinone, 2-cumyl hydroquinone,
• Specific dihydroxy compounds include resorcinol, 2,2-bis(4-hydroxyphenyl) propane (“bisphenol A” or“BPA”), 3,3-bis(4-hydroxyphenyl) phthalimidine, 2-phenyl-3,3’- bis(4-hydroxyphenyl) phthalimidine (also known as N-phenyl phenolphthalein bisphenol, “PPPBP”, or 3,3-bis(4-hydroxyphenyl)-2-phenylisoindolin-l-one), l,l-bis(4-hydroxy-3- methylphenyl)cyclohexane, and 1 , 1 -bis(4-hydroxyphenyl)-3 ,3 ,5-trimethylcyclohexane
• poly(carbonate)s prepared from the bisphenol A obtained by the method described herein can also include copolymers comprising carbonate units and ester units (“poly(ester-carbonate)s”.
• Poly(ester-carbonate)s further contain, in addition to recurring carbonate chain units of formula (1), repeating ester units of formula (4)
• J is a divalent group derived from a dihydroxy compound (which includes a reactive derivative thereof), and can be, for example, a Ci-io alkylene, a Ce-2o cycloalkylene, a C5-20 arylene, or a polyoxyalkylene group in which the alkylene groups contain 2 to 6 carbon atoms, preferably, 2, 3, or 4 carbon atoms; and T is a divalent group derived from a dicarboxylic acid (which includes a reactive derivative thereof), and can be, for example, a Ci-20 alkylene, a C5-20 cycloalkylene, or a C6-20 arylene.
• Copolyesters containing a combination of different T or J groups can be used.
• the polyester units can be branched or linear.
• Dihydroxy compounds can be used in addition to the bisphenol A obtained by the process of the present disclosure and can include aromatic dihydroxy compounds of formula (2) (e.g., resorcinol), bisphenols of formula (3) (e.g., bisphenol A), a Ci-s aliphatic diol such as ethane diol, n-propane diol, i-propane diol, 1,4-butane diol, 1,4-cyclohexane diol, 1,4- hydroxymethylcyclohexane, or a combination thereof dihydroxy compounds.
• aromatic dihydroxy compounds of formula (2) e.g., resorcinol
• bisphenols of formula (3) e.g., bisphenol A
• a Ci-s aliphatic diol such as ethane diol, n-propane diol, i-propane diol, 1,4-butane diol, 1,4-cyclohexane diol, 1,4
• Aliphatic dicarboxylic acids that can be used include C5-20 aliphatic dicarboxylic acids (which includes the terminal carboxyl groups), preferably linear Cs-i2 aliphatic dicarboxylic acid such as decanedioic acid (sebacic acid); and alpha, omega-Ci2 dicarboxylic acids such as dodecanedioic acid
• Aromatic dicarboxylic acids that can be used include terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid, 1,4-cyclohexane dicarboxylic acid, or a combination thereof acids.
• a combination of isophthalic acid and terephthalic acid wherein the weight ratio of isophthalic acid to terephthalic acid is 91:9 to 2:98 can be used.
• ester units include ethylene terephthalate units, n-proplyene terephthalate units, n-butylene terephthalate units, ester units derived from isophthalic acid, terephthalic acid, and resorcinol (ITR ester units), and ester units derived from sebacic acid and bisphenol A.
• the molar ratio of ester units to carbonate units in the poly (ester-carbonate) s can vary broadly, for example 1:99 to 99:1, preferably, 10:90 to 90:10, more preferably, 25:75 to 75:25, or from 2:98 to 15:85.
• the molar ratio of ester units to carbonate units in the poly(ester- carbonate)s can vary from 1:99 to 30: 70, preferably 2:98 to 25:75, more preferably 3:97 to 20:80, or from 5:95 to 15:85.
• the poly(carbonate) is a poly(carbonate-siloxane) copolymer comprising bisphenol A carbonate units and siloxane units, for example blocks containing 5 to 200 dimethylsiloxane units.
• poly(carbonate)s that can be prepared from the bisphenol A of the present disclosure can include poly(aromatic ester-carbonate) s comprising bisphenol A carbonate units and isophthalate-terephthalate-bisphenol A ester units, also commonly referred to as poly (carbonate-ester) s (PCE) or poly(phthalate-carbonate)s (PPC), depending on the relative ratio of carbonate units and ester units.
• poly (carbonate-ester) s PCE
• PPC poly(phthalate-carbonate)s
• Another specific poly (ester-carbonate) comprises resorcinol isophthalate and terephthalate units and bisphenol A carbonate units.
• the bisphenol A obtained by the process of the present disclosure can be particularly useful for the preparation of poly(etherimides).
• Poly(etherimides) comprise more than 1, for example 2 to 1000, or 5 to 500, or 10 to 100 structural units of formula (5)
• each R is independently the same or different, and is a substituted or unsubstituted divalent organic group, such as a substituted or unsubstituted Ce-2o aromatic hydrocarbon group, a substituted or unsubstituted straight or branched chain C4-20 alkylene group, a substituted or unsubstituted C3-8 cycloalkylene group, in particular a halogenated derivative of any of the foregoing.
• R is divalent group of one or more of the following formulas (6)
• R is m- phenylene, p-phenylene, or a diarylene sulfone, in particular bis(4,4’-phenylene)sulfone, bis(3,4’-phenylene)sulfone, bis(3,3’-phenylene)sulfone, or a combination comprising at least one of the foregoing.
• at least 10 mole percent or at least 50 mole percent of the R groups contain sulfone groups, and in an aspect no R groups contain sulfone groups.
• T is a group derived from the bisphenol A obtained by the process of the present disclosure.
• the poly(etherimide) can further comprise additional repeating units where T is a group of the formula -O-Z-O- wherein the divalent bonds of the -O-Z-O- group are in the 3,3', 3,4', 4,3', or the 4,4' positions, and Z is an aromatic Ce-24 monocyclic or polycyclic moiety optionally substituted with 1 to 6 Ci-s alkyl groups, 1 to 8 halogen atoms, or a combination comprising at least one of the foregoing, provided that the valence of Z is not exceeded.
• Exemplary groups Z include groups of formula (7)
• R a and R b are each independently the same or different, and are a halogen atom or a monovalent Ci- 6 alkyl group, for example; p and q are each independently integers of 0 to 4; c is 0 to 4; and X a is a bridging group connecting the hydroxy-substituted aromatic groups, where the bridging group and the hydroxy substituent of each Ce arylene group are disposed ortho, meta, or para (specifically para) to each other on the Ce arylene group.
• the bridging group X a can be a single bond, -0-, -S-, -S(O)-, -S(0) 2 -, -C(O)-, or a Ci-is organic bridging group.
• the Ci-18 organic bridging group can be cyclic or acyclic, aromatic or non-aromatic, and can further comprise heteroatoms such as halogens, oxygen, nitrogen, sulfur, silicon, or phosphorous.
• the Ci-is organic group can be disposed such that the Ce arylene groups connected thereto are each connected to a common alkylidene carbon or to different carbons of the Ci-is organic bridging group.
• a specific example of a group Z is a divalent group of formula (7a)
• Z is a derived from bisphenol A, such that Q in formula (7a) is 2,2-isopropylidene.
• R is m-phenylene, p-phenylene, or a combination comprising at least one of the foregoing
• T is a divalent group derived from the bisphenol A of the present disclosure
• the poly(etherimide) can be a copolymer comprising additional structural poly(etherimide) units of formula (5) wherein at least 50 mole percent (mol%) of the R groups are bis(4,4’-phenylene)sulfone, bis(3,4’-phenylene)sulfone, bis(3,3’- phenylene)sulfone, or a combination comprising at least one of the foregoing and the remaining R groups are p-phenylene, m-phenylene or a combination comprising at least one of the foregoing; and T is a divalent group derived from the bisphenol A of the present disclosure.
• the poly(etherimide) is a copolymer that optionally comprises additional structural imide units that are not poly(etherimide) units, for example imide units of formula (8)
• R is as described in formula (5) and each V is the same or different, and is a substituted or unsubstituted C6-20 aromatic hydrocarbon group, for example a tetravalent linker of the formulas
• additional structural imide units preferably comprise less than 20 mol% of the total number of units, and more preferably can be present in amounts of 0 to 10 mol% of the total number of units, or 0 to 5 mol% of the total number of units, or 0 to 2 mole % of the total number of units. In an aspect, no additional imide units are present in the poly(etherimide).
• the poly(etherimide) can also be a poly(siloxane-etherimide) copolymer comprising poly(etherimide) units of formula (5) and siloxane blocks of formula (9)
• each R’ is independently a Ci-13 monovalent hydrocarbyl group.
• each R’ can be any Ci-13 monovalent hydrocarbyl group.
• each R’ can be any Ci-13 monovalent hydrocarbyl group.
• Ci-13 alkyl group independently be a Ci-13 alkyl group, Ci-13 alkoxy group, C2-13 alkenyl group, C2-13 alkenyloxy group, C3-6 cycloalkyl group, C3-6 cycloalkoxy group, Ce-i 4 aryl group, Ce-io aryloxy group, C7-13 arylalkylene group, C7-13 arylalkylenoxy group, C7-13 alkylarylene group, or C7-13
• alkylaryleneoxy group can be fully or partially halogenated with fluorine, chlorine, bromine, or iodine, or a combination comprising at least one of the foregoing. In an aspect no bromine or chlorine is present, and in an aspect no halogens are present.
• the polysiloxane blocks comprises R’ groups that have minimal hydrocarbon content.
• an R’ group with a minimal hydrocarbon content is a methyl group.
• the poly(etherimide) can be prepared by any of the methods known to those skilled in the art, including the reaction of an aromatic bis(ether anhydride) of formula (10) or a chemical equivalent thereof, with an organic diamine of formula (11)
• Copolymers of the poly(etherimides) can be manufactured using a combination of an aromatic bis(ether anhydride) of formula (10) and an additional bis(anhydride) that is not a bis(ether anhydride), for example pyromellitic dianhydride or bis(3,4-dicarboxyphenyl) sulfone dianhydride. At least a portion of the aromatic bis(ether anhydride) of formula (10) can be formed from the isolated bisphenol A of the present disclosure according to methods that are generally known.
• a combination of different aromatic bis(ether anhydride)s can be used, for example an aromatic bis(ether anhydride) derived from the isolated bisphenol A of the present disclosure and one or more aromatic bis(ether anhydride)s that are derived from bisphenol A made by a different process, are derived from a different dihydroxy aromatic compound, or both.
• organic diamines examples include 1,4-butane diamine, 1,5-pentanediamine, 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10- decanediamine, 1,12-dodecanediamine, 1,18-octadecanediamine, 3- methylheptamethylenediamine, 4,4-dimethylheptamethylenediamine, 4- methylnonamethylenediamine, 5-methylnonamethylenediamine, 2,5- dimethylhexamethylenediamine, 2,5-dimethylheptamethylenediamine, 2, 2- dimethylpropylenediamine, N-methyl-bis (3-aminopropyl) amine, 3- methoxyhexamethylenediamine, l,2-bis(3-aminopropoxy) ethane, bis(3-aminopropyl) sulfide, 1,4-cyclohexanediamine,
• any regioisomer of the foregoing compounds can be used.
• Ci-4 alkylated or poly(Ci-4)alkylated derivatives of any of the foregoing can be used, for example a polymethylated 1,6- hexanediamine. Combinations of these compounds can also be used.
• the organic diamine is m-phenylenediamine, p-phenylenediamine, 4,4'-diaminodiphenyl sulfone, 3,4'- diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, or a combination comprising at least one of the foregoing.
• the poly(etherimides) can have a melt index of 0.1 to 10 grams per minute (g/min), as measured by American Society for Testing Materials (ASTM) D1238 at 340 to 370°C, using a 6.7 kilogram (kg) weight.
• the poly(etherimide) has a weight average molecular weight (Mw) of 1,000 to 150,000 grams/mole (Dalton), as measured by gel permeation chromatography, using polystyrene standards.
• Mw weight average molecular weight
• the poly(etherimide) has an Mw of 10,000 to 80,000 Daltons.
• Such poly(etherimides) typically have an intrinsic viscosity greater than 0.2 deciliters per gram (dl/g), or, more specifically, 0.35 to 0.7 dl/g as measured in m-cresol at 25 °C.
• dl/g deciliters per gram
• solvent recovery and recycle to provide an improved process for the isolation of bisphenol A from depolymerization of poly (carbonate).
• Careful selection of the bisphenol A purification employed has allowed for the bisphenol A to be obtained with high purity, making it desirable for subsequent use of the preparation of various thermoplastic polymers such as poly(carbonate) and poly(etherimide). Therefore a significant improvement is provided by the process of the present disclosure.
• Aspect 2 The process of aspect 1, wherein the process further comprises recycling the corresponding Ci- 6 alcohol obtained from hydrolysis of the di(Ci- 6 alkyl) carbonate mixture and, when present, the cosolvent, directly to a poly(carbonate) depolymerization step.
• Aspect 3 The process of aspect 1 or 2, wherein the poly(carbonate) is a virgin poly (carbonate), a post-consumer recycled poly(carbonate), post-industrial recycled
• Aspect 4 The process of any one of aspects 1 to 3, wherein the Ci- 6 alcohol is methanol.
• Aspect 5 The process of aspect 4, wherein the di(Ci- 6 alkyl) carbonate is dimethyl carbonate.
• Aspect 6 The process of any one of aspects 1 to 5, wherein the organic cosolvent comprises toluene, chlorobenzene, xylene, or a combination thereof.
• Aspect 7 The process of any one of aspects 1 to 6, wherein the organic cosolvent comprises toluene.
• Aspect 8 The process of any one of aspects 1 to 7, wherein the depolymerizing is in the presence of an aqueous base, preferably aqueous sodium hydroxide.
• Aspect 9 The process of any one of aspects 1 to 8, wherein the depolymerizing is for a time of 1 to 24 hours, preferably 1 to 18 hours, more preferably 1 to 10 hours, even more preferably 1 to 6 hours.
• Aspect 10 The process of any one of aspects 1 to 9, wherein the di(Ci- 6 alkyl) carbonate mixture is combined with an aqueous base comprising sodium hydroxide at a temperature of 100 to 150°C, a pressure of 100 to 150 pounds per square inch, and for a time of 1 to 24 hours to provide the corresponding Ci- 6 alcohol.
• Aspect 11 The process of any one of aspects 1 to 10, wherein crystallizing the residual depolymerized reaction mixture comprising bisphenol A comprises adding an aqueous solution comprising an acid, preferably acetic acid, to the residual depolymerized reaction mixture to crystallize bisphenol A in a first crystallization step; isolating the crystallized bisphenol A from the first crystallization step; adding a crystallization solvent to the crystallized bisphenol A from the first crystallization step to provide a second crystallization mixture;
• Aspect 12 The process of aspect 11, wherein the crystallization solvent comprises a mixture of toluene, isopropanol, and optionally, an organic acid, preferably acetic acid.
• Aspect 13 The process of any one of aspects 1 to 12, wherein the purified bisphenol A is 4,4’-isopropylidenediphenol having a purity of greater than 99.8%.
• Aspect 14 A bisphenol A made by the process of any one of aspects 1 to 13.
• Aspect 15 The bisphenol A of aspect 14, wherein the bisphenol A is 4,4’- isopropylidenediphenol having a purity of greater than 99.8% and comprising less than 0.2 wt% of a monophenol.
• Aspect 16 A thermoplastic polymer comprising repeating units derived from the bisphenol A of aspects 14 or 15, or isolated by the process of any one or more of aspects 1 to 13.
• Aspect 17 The thermoplastic polymer of aspect 16, wherein the thermoplastic polymer is a poly(etherimide) or a poly (carbonate).
• Aspect 18 The thermoplastic polymer of aspect 16, wherein the thermoplastic polymer is a poly(etherimide).
• compositions, methods, and articles can alternatively comprise, consist of, or consist essentially of, any appropriate materials, steps, or components herein disclosed.
• the compositions, methods, and articles can additionally, or alternatively, be formulated so as to be devoid, or substantially free, of any materials (or species), steps, or components, that are otherwise not necessary to the achievement of the function or objectives of the compositions, methods, and articles.
• test standards are the most recent standard in effect as of the filing date of this application, or, if priority is claimed, the filing date of the earliest priority application in which the test standard appears.
• hydrocarbyl refers to a residue that contains only carbon and hydrogen.
• the residue can be aliphatic or aromatic, straight-chain, cyclic, bicyclic, branched, saturated, or unsaturated. It can also contain combinations of aliphatic, aromatic, straight chain, cyclic, bicyclic, branched, saturated, and unsaturated hydrocarbon moieties.
• the hydrocarbyl residue when described as substituted, it may, optionally, contain heteroatoms over and above the carbon and hydrogen members of the substituent residue.
• the hydrocarbyl residue can also contain one or more carbonyl groups, amino groups, hydroxyl groups, or the like, or it can contain heteroatoms within the backbone of the hydrocarbyl residue.
• alkyl means a branched or straight chain, saturated aliphatic hydrocarbon group, e.g., methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, t-butyl, n- pentyl, s-pentyl, and n- and s-hexyl.
• Alkoxy means an alkyl group that is linked via an oxygen (i.e., alkyl-O-), for example methoxy, ethoxy, and sec-butyloxy groups.
• Alkylene means a straight or branched chain, saturated, divalent aliphatic hydrocarbon group (e.g., methylene (-CH2-) or, propylene
• “Cycloalky lene” means a divalent cyclic alkylene group, -CiTbn-x, wherein x is the number of hydrogens replaced by cyclization(s).
• “Cycloalkenyl” means a monovalent group having one or more rings and one or more carbon-carbon double bonds in the ring, wherein all ring members are carbon (e.g., cyclopentyl and cyclohexyl).
• “Aryl” means an aromatic hydrocarbon group containing the specified number of carbon atoms, such as phenyl, tropone, indanyl, or naphthyl.“Arylene” means a divalent aryl group.
• Alkylarylene means an arylene group substituted with an alkyl group.
• Arylalkylene means an alkylene group substituted with an aryl group (e.g., benzyl).
• halo means a group or compound including one more of a fluoro, chloro, bromo, or iodo substituent. A combination of different halo groups (e.g., bromo and fluoro), or only chloro groups can be present.
• the prefix“hetero” means that the compound or group includes at least one ring member that is a heteroatom (e.g., 1, 2, or 3 heteroatom(s)), wherein the heteroatom(s) is each independently N, O, S, Si, or P.
• substituents that can each independently be a C 1-9 alkoxy, a C 1-9 haloalkoxy, a nitro (-NO 2 ), a cyano (-CN), a
• cycloalkenyl a Ce-u aryl, a C 7-13 arylalkylene, a C 4-12 heterocycloalkyl, and a C 3-12 heteroaryl instead of hydrogen, provided that the substituted atom’s normal valence is not exceeded.
• the number of carbon atoms indicated in a group is exclusive of any substituents.
• - CH 2 CH 2 CN is a C 2 alkyl group substituted with a nitrile.

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Crystallography & Structural Chemistry (AREA)
• Life Sciences & Earth Sciences (AREA)
• Sustainable Development (AREA)
• Polyethers (AREA)

Priority Applications (2)

Applications Claiming Priority (2)

Publications (1)

Family

ID=71452788

Family Applications (1)

Country Status (3)

Cited By (3)

Citations (5)

Family Cites Families (1)

• 2020
  • 2020-06-17 EP EP20736541.2A patent/EP3986851A1/en active Pending
  • 2020-06-17 CN CN202080044273.XA patent/CN114008010A/zh active Pending
  • 2020-06-17 WO PCT/US2020/038063 patent/WO2020257234A1/en unknown

Patent Citations (5)

Non-Patent Citations (4)

Also Published As

Similar Documents

Legal Events