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EP3986850A1 - Dépolymérisation d'un poly(carbonate) et isolement de bisphénol a à partir d'un poly(carbonate) dépolymérisé - Google Patents

Dépolymérisation d'un poly(carbonate) et isolement de bisphénol a à partir d'un poly(carbonate) dépolymérisé

Info

Publication number
EP3986850A1
EP3986850A1 EP20735824.3A EP20735824A EP3986850A1 EP 3986850 A1 EP3986850 A1 EP 3986850A1 EP 20735824 A EP20735824 A EP 20735824A EP 3986850 A1 EP3986850 A1 EP 3986850A1
Authority
EP
European Patent Office
Prior art keywords
poly
bisphenol
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.)
Pending
Application number
EP20735824.3A
Other languages
German (de)
English (en)
Inventor
James Lawrence GORMAN III
Andrew Thomas PINGITORE
Caroline Elizabeth SCALES
Gregory Paul Shankwitz
James Alan Mahood
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.)
SHPP Global Technologies BV
Original Assignee
SHPP 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 SHPP Global Technologies BV filed Critical SHPP Global Technologies BV
Publication of EP3986850A1 publication Critical patent/EP3986850A1/fr
Pending legal-status Critical Current

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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
    • C08J11/14—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
    • 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

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
  • 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 other byproducts.
  • 4,4’-isopropylidenediphenol also referred to as bisphenol A
  • a process for depolymerization of poly(carbonate) comprises combining a poly(carbonate) comprising repeating units derived from bisphenol A; bisphenol A; water; and a base; under conditions effective to form a single liquid phase and to depolymerize the
  • a process for isolation of bisphenol A from a depolymerized poly(carbonate) comprises depolymerizing a poly (carbonate); isolating bisphenol A; and crystallizing the isolated bisphenol A with a crystallization solvent to provide a purified bisphenol A; wherein the purified bisphenol A is 4,4’-isopropylidenediphenol having a purity of greater than 99.8%.
  • a 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 depolymerization of a poly(carbonate) which can advantageously provide bisphenol A having a purity suitable for use in making new thermoplastic materials.
  • the process provided by the present disclosure is advantageously a base-catalyzed hydrolysis which has the advantage of depolymerizing the poly(carbonate) to bisphenol A and carbon dioxide, which is easily removed. This is in contrast to other processes such as ammonolysis (which produces a urea byproduct), alcoholysis (which produces dialkyl carbonates), and phenolysis (which produces diaryl carbonates).
  • the process of the present disclosure can advantageously provide completely depolymerized poly(carbonate) in short times, and using mild conditions.
  • 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.
  • the bisphenol A isolated from the depolymerization process described herein can find use in providing new thermoplastic materials.
  • an aspect of the present disclosure is a process for 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”), 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”), 3,3-bis(4-hydroxyphenyl) phthalimidine, l,l-bis(4- hydroxy-3-methylphenyl)cyclohexane, or l,
  • 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 C6-20 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 or compositions, for example having different comonomers or end groups or additives.
  • poly(carbonate)s can be produced using various end-capping agents (also referred to as a chain stopper agent or chain terminating agent) which can be included during polymerization to provide particular end groups, for example monocyclic phenols such as phenol, p-cyanophenol, and Ci-22 alkyl-substituted phenols such as p-cumyl- phenol, resorcinol monobenzoate, and p-and m-tertiary-butyl phenol, monoethers of diphenols, such as p-methoxyphenol, monoesters of diphenols such as resorcinol monobenzoate, and functionalized chlorides of aliphatic monocarboxylic acids such as acryloyl chloride and methacryoyl chloride,.
  • end-capping agents also referred to as a chain stopper agent or chain terminating agent
  • the poly(carbonate) can have an end group derived from at least one of phenol, p-cumylphenol, p-t-butylphenol, and p-t-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 contain one or more additives or additional thermoplastic polymers different from the poly (carbonate).
  • the process of the present disclosure comprises combining the poly(carbonate) comprising repeating units derived from bisphenol A, bisphenol A, water, a base, and optionally an organic solvent, under conditions effective to form a single liquid phase and depolymerize the poly (carbonate).
  • the organic solvent when present, can generally be any organic solvent that can swell the poly(carbonate) to assist in depolymerization, and has a boiling point high enough such that excessive pressure builds up can be avoided at elevated temperatures during the
  • the organic solvent can preferably allow for crystallization of the crude bisphenol A that results from the depolymerization step without requiring a solvent exchange.
  • the organic solvent can comprise toluene, chlorobenzene, xylene, and the like, or a combination thereof.
  • the organic solvent comprises toluene.
  • the base can comprise an alkali metal carbonate, an alkali metal hydroxide, an alkaline earth metal hydroxide, an ammonium hydroxide, a phosphonium hydroxide, or a combination thereof.
  • the base can be an alkali metal carbonate, for example sodium carbonate.
  • the poly(carbonate) can be present in an amount of 10 to 30 weight percent; the bisphenol A can be present in an amount of 1 to 65 weight percent; the organic solvent can be present in an amount of 5 to 65 weight percent; and the water can be present in an amount of 5 to 35 weight percent; wherein weight percent of each component is based on the total weight of the poly (carbonate), the organic solvent, water, bisphenol A, and the base.
  • the depolymerizing can be conducted at a temperature of 110 to 130°C, preferably 115 to 125°C, and a pressure of 10 to 75 psig, for example 15 to 50 psig, for example 20 to 40 psig.
  • 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 24 hours or less, preferably 16 hours or less, more preferably 10 hours or less, even more preferably 6 hours or less.
  • the depolymerizing can be for a time of 1 to 24 hours, or 1 to 18 hours, or 1 to 10 hours, or 1 to 6 hours.
  • the process of the present disclosure can optionally further comprise isolating bisphenol A, and crystallizing the isolated bisphenol A with a crystallization solvent to provide a purified bisphenol A. Following addition of the crystallization solvent, the resulting mixture can be heated to a suitable temperature to effect dissolution of the bisphenol A, and the solution can then be cooled. Upon cooling, the bisphenol A can be crystallized from the crystallization solution, and can further be isolated, for example by filtration.
  • the crystallization solvent can comprise, for example, a mixture of toluene, isopropanol, and optionally, acetic acid. Crystallization of the bisphenol A from the
  • Another aspect of the present disclosure is a process for isolation of bisphenol A from a depolymerized poly (carbonate).
  • the process comprises depolymerizing a
  • poly(carbonate) according to the process described herein; isolating bisphenol A; and crystallizing the isolated bisphenol A with a crystallization solvent to provide a purified bisphenol A; wherein the purified bisphenol A is 4,4’-isopropylidenediphenol having a purity of greater than 99.8%.
  • 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’-isopropylidenediphenol 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.
  • the isolated bisphenol A can comprise less than 0.2 weight percent of a monophenol comprising p-cumylphenol, t-butylphenol, p-t-octylphenol, or a combination thereof.
  • a monophenol comprising p-cumylphenol, t-butylphenol, p-t-octylphenol, or a combination thereof.
  • thermoplastic polymer comprising repeating units derived from the bisphenol A made by the process described herein.
  • the thermoplastic polymer can be any polymer having repeat units derived from bisphenol A, and can include, for example, poly(carbonate)s, poly(etherimide)s, polysulfones, epoxies, and the like.
  • the thermoplastic polymer can be a poly(carbonate) 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 CMO alkyl, a halogen-substituted Ci-io alkyl, a C6-10 aryl, or a halogen-substituted C 6 -io aryl, and n is 0 to 4.
  • a Ci-io hydrocarbyl group such as a CMO alkyl, a halogen-substituted Ci-io alkyl, a C6-10 aryl, or a halogen-substituted C 6 -io aryl
  • n is 0 to 4.
  • R a and R b are each independently a halogen, Ci-12 alkoxy, or Ci-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 C1-3 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 MS 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 CHO alkylene, a C6-20 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 C i-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(etherimide)s.
  • Poly(etherimide)s 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 C6-20 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 C6-24 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 C MS 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-18 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 mol% 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, C6-14 aryl group, C6-10 aryloxy group, C7-13 arylalkylene group, C7-13 arylalkylenoxy group, C7-13 alkylarylene group, or C7-13 alkylaryleneoxy group.
  • the foregoing groups can be fully or partially halogenated with fluorine, chlorine, bromine, or iodine, or a combination comprising at least one of the foregoing. In an aspect no bromine or chlorine is present, and in an aspect no halogens are present.
  • 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(etherimide)s 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.
  • C 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(etherimide)s 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 (Daltons), as measured by gel permeation chromatography, using polystyrene standards.
  • the poly(etherimide) has an Mw of 10,000 to 80,000 Daltons.
  • Such poly(etherimide)s 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.
  • Poly(carbonate) pellets obtained as LEXAN 100 from SABIC
  • bisphenol A (BPA) bisphenol A
  • toluene water
  • sodium carbonate (NaiCCE) sodium carbonate
  • the amounts of each component are provided in Table 1 below, where the amount of each component is provided in grams.
  • the reaction tubes were sealed and placed into an oil bath that was heated to 120°C. Mixing was accomplished with a magnetic stir bar, and the stir rate for each example was 535 rpm.
  • Example 3 After 6 hours, each reaction mixture was analyzed by Fourier Transform Infrared (FTIR) spectroscopy to determine the extent of the polymerization.
  • Example 3, 4, 11 and 12 were each observed to have been completely depolymerized within 6 hours, with no pellets remaining suspended in the reaction mixture, and no detectable carbonate stretch by FTIR.
  • Example 2, 5-10, 13-15 and 17-25 either still contained undissolved PC pellets in the reaction mixture after 6 hours, or FTIR analysis indicated a measurable carbonate stretch. So these Examples will obtain complete depolymerization at longer times (i.e., greater than 6 hours).
  • poly(carbonate) depolymerization was also scaled up, as described below.
  • the BPA (64 grams) was recrystallized by heating in a mixture of 358 grams of toluene, 26 grams of isopropyl alcohol, and 0.3 grams of acetic acid (to neutralize the residual sodium carbonate). The mixture was allowed to cool to give 53 grams of white solids after drying with purity of 99.99% 4,4’-isopropyiidenediphenol.
  • the initial solids isolated are a BPA-IPA adduct, which is converted to BPA by heating during the drying step.
  • Aspect 2 The process of aspect 1, wherein the process comprises combining the poly (carbonate), the bisphenol A, the water, the base, and an organic solvent
  • Aspect 3 The process of aspect 1 or 2, wherein the process further comprises isolating bisphenol A, and crystallizing the isolated bisphenol A with a crystallization solvent to provide a purified bisphenol A.
  • Aspect 4 The process of aspect 3, wherein the crystallization solvent comprises a mixture of toluene, isopropanol, and optionally, an organic acid, preferably acetic acid.
  • Aspect 5 The process of any one of aspects 1 to 4, wherein the poly(carbonate) is a virgin poly(carbonate), a post-consumer recycled poly(carbonate), post-industrial recycled poly (carbonate), or a combination thereof.
  • Aspect 6 The process of any one of aspects 2 to 5, wherein the organic solvent comprises toluene, xylene, chlorobenzene, or a combination thereof.
  • Aspect 7 The process of any one of aspects 1 to 6, wherein the base comprises an alkali metal carbonate, an alkali metal hydroxide, an alkaline earth metal hydroxide, an ammonium hydroxide, a phosphonium hydroxide, or a combination thereof.
  • Aspect 8 The process of any one of aspects 1 to 7, wherein the poly(carbonate) is present in an amount of 10 to 30 weight percent; the 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 the water is present in an amount of 5 to 35 weight percent; wherein weight percent of each component is based on the total weight of the poly(carbonate), the organic solvent, water, bisphenol A, and the base.
  • Aspect 9 The process of any one of aspects 1 to 8, wherein conditions effective to depolymerize the poly(carbonate) comprise a temperature of 110 to 130°C, preferably 115 to 125°C, and a pressure of 15 to 50 psig.
  • Aspect 10 The process of 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 process of any one of aspects 3 to 10, wherein the purified bisphenol A is 4,4’-isopropylidenediphenol having a purity of greater than 99.8%.
  • a bisphenol A obtained the process of any one of aspects 3 to 12.
  • Aspect 14 The bisphenol A of aspect 13, 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.
  • a thermoplastic polymer comprising repeating units derived from the bisphenol A of aspects 13 or 14, or isolated by the process 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).
  • 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 (-(CH2)3- )).
  • Cycloalky lene means a divalent cyclic alkylene group, -CiThn-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.
  • 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.
  • a heteroatom e.g., 1, 2, or 3 heteroatom(s)
  • 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- 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.

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Abstract

Un procédé de dépolymérisation de poly(carbonate) comprend la combinaison d'un poly(carbonate) comprenant des unités de répétition dérivées du bisphénol A ; du bisphénol A ; de l'eau ; et une base dans des conditions efficaces pour dépolymériser le poly(carbonate). Un bisphénol A purifié peut être obtenu à partir du procédé de dépolymérisation. Le bisphénol A purifié peut être particulièrement utile pour la production de polymères thermoplastiques contenant du bisphénol A.
EP20735824.3A 2019-06-19 2020-06-17 Dépolymérisation d'un poly(carbonate) et isolement de bisphénol a à partir d'un poly(carbonate) dépolymérisé Pending EP3986850A1 (fr)

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US201962863355P 2019-06-19 2019-06-19
PCT/US2020/038069 WO2020257237A1 (fr) 2019-06-19 2020-06-17 Dépolymérisation d'un poly(carbonate) et isolement de bisphénol a à partir d'un poly(carbonate) dépolymérisé

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US20230383089A1 (en) * 2021-09-13 2023-11-30 Lg Chem, Ltd. Monomer composition for synthesizing recycled plastic, preparation method thereof, recycled plastic, and molded product using the same
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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 (fr) 2012-11-07 2016-10-12 SABIC Global Technologies B.V. Procédé de production de compositions de polycarbonate
PE20142190A1 (es) * 2013-05-15 2015-01-11 Univ Pontificia Catolica Peru Metodo para la obtencion de bisfenol-a a partir de desechos de policarbonato utilizando radiacion de microondas
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