WO1997008122A1 - Isomerization of bisphenols - Google Patents

Isomerization of bisphenols Download PDF

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Publication number
WO1997008122A1
WO1997008122A1 PCT/US1996/013683 US9613683W WO9708122A1 WO 1997008122 A1 WO1997008122 A1 WO 1997008122A1 US 9613683 W US9613683 W US 9613683W WO 9708122 A1 WO9708122 A1 WO 9708122A1
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Prior art keywords
acid
percent
reaction
phenol
mixture
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PCT/US1996/013683
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English (en)
French (fr)
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Emmett L. Tasset
Richard M. Wehmeyer
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The Dow Chemical Company
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Priority to EP96930593A priority Critical patent/EP0848693A4/en
Priority to CA002230272A priority patent/CA2230272A1/en
Publication of WO1997008122A1 publication Critical patent/WO1997008122A1/en

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    • 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
    • C07C37/11—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms
    • C07C37/20—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms using aldehydes or ketones
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0215—Sulfur-containing compounds
    • B01J31/0217—Mercaptans or thiols
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0215—Sulfur-containing compounds
    • B01J31/0225—Sulfur-containing compounds comprising sulfonic acid groups or the corresponding salts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
    • 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
    • C07C2603/00—Systems containing at least three condensed rings
    • C07C2603/02—Ortho- or ortho- and peri-condensed systems
    • C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
    • C07C2603/06—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members
    • C07C2603/10—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings
    • C07C2603/12—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings only one five-membered ring
    • C07C2603/18—Fluorenes; Hydrogenated fluorenes

Definitions

  • This invention relates to preparation of polyphenols, more particularly to the preparation of polyphenols from k ⁇ tones or aldehydes and phenols.
  • Acid catalysts include acidic ion exchange resin catalysts and soluble acid catalysts.
  • Soluble acid catalysts can be, for example, hydrogen chloride, sulfuric acid, hydrochloric acid, phosphoric acid, hydrobromic acid, nitric acid, dimethyl sulfate, sulfur dioxide,
  • promoters include mercaptan groups that were either free or bound to a resin.
  • Alkyl mercaptans and bis-mercaptoethanolamine were examples of reported promoters.
  • Hassirio et al. (U.S. Patent No. 5,248,838) have disclosed the use of a combination of methanesulfonic acid and a mercaptan/mercaptoalkanoic acid for catalyzing the condensation of phenols with fluorenone. High levels of methanesulfonic acid with respect to the feed and the mercaptan/mercaptoalkanoic acid, were used. The reactions can be run in halogenated hydrocarbon solvents.
  • Bottenbruch et al. (U. S. Patent No. 4,996,373) have proposed a process for producing dihydroxyaryl compounds from carbonyl compounds and phenols under high pressure, in the presence of various catalysts, including sulfonic acid resins. Catalysts containing sulfhydryl
  • Jansen U.S. Patent No. 2,468,982
  • a mercaptoalkanoic acid which may be formed in situ by reaction of a mercapton with the ketone, as condensing agent.
  • Knebel et al. (U.S. Patent No. 4,931,594) disclose the use of large amounts of sulfonic acid resin, mixed with uncombined 3-mercaptopropionic acid, to cause the condensation to occur.
  • the reactive catalysts generally include mercapto-functions attached to a sulfonic acid group in the form of a sulfonamido or ammonium sulfonate salt.
  • Shaw discloses preparing bisphenols from phenol and a ketone in the presence of an acidic (sulfonic acid) ion-exchange resin and a mercaptan.
  • the mercaptan being added at particular locations of a specified reactor configuration to prevent the formation of cyclic dimers.
  • Li has disclosed (U.S. Patent No. 4,825,010) isomerization of by-products of condensates of phenols and ketones, using a catalytic amount of acidic sulfonated cationic-exchange resin having sulfonic acid sites ionically bonded to alkylmercaptoamines.
  • Other patents by Li (U.S. Patent Nos. 4,822,923 and 5,001,281) further suggest the state of the art of using ion-exchange resins to isomerize by-products of bisphenol syntheses.
  • hydrochloric acid or hydrogen chloride in the presence of minor amounts of 3-mercaptopropionic acid.
  • the products were used for the preparation of polyester resins.
  • Szabolcs U.S. Patent Nos. 4,467,122 and 4,503,266 discloses washing crude product, containing BHPF, from a hydrochloric acid/zinc chloride catalyzed process, to remove HCl, ZnCl 2 and excess phenol, prior to recrystallization from dichloroethane. See also the abstract for DE OLS 2,948,222 (July 30, 1981).
  • Korshak et al., (SU 172,775) disclose washing a mixture of phenol, BHPF and HCl with water, after which phenol was removed by distillation.
  • Trapasso U.S. Patent No. 3,706,707 discloses the preparation of adducts from a polymerized cyclic ether and a sultone.
  • Dean U.S. Patent No. 4,568,724 was of similar interest with respect to reaction products from an EPDM rubber and a sultone.
  • this invention relates to a process for the condensation of an aldehyde or ketone starting material with a phenol, unsubstituted in at least one position, comprising reacting the aldehyde or ketone starting material with the phenol in a reaction mixture in the presence of a soluble or insoluble mercaptosulfonic acid compound under conditions sufficient to bring about formation of a geminal bisphenolic moiety at each aldehyde or ketone moiety in the starting material;
  • ⁇ was an alkylene, cycloaliphatic, arylene, alkylenearylene, alkylenecycloaliphatic, alkylenearyl, heterocyclic or alkyleneheterocyclic residue and a and b were independently selected from integers from 1 to
  • the insoluble mercaptosulfonic acid comprises a catalytically-active species represented by the formula
  • ⁇ ' was an alkylene, cycloaliphatic, arylene, alkylenearylene, alkylenecycloaliphatic, alkylenearyl, heterocyclic or alkyleneheterocyclic residue; a and b were independently selected from integers from 1 to 20; L was an optional linking group and - was a bond, which catalytically-active species was attached by the bond - to an insoluble organic or inorganic support; or a catalytically-active species represented by the unit formula wherein ⁇ " was an alkylene, arylene, cycloaliphatic, alkylenearylene, alkylenecycloaliphatic, alkylenearyl, heterocyclic or alkyleneheterocyclic residue; a and b were independently selected from integers from 1 to 20; L' was an optional linking group and - was a bond.
  • This invention further relates to novel catalytically-active polystyrene resins, characterized by bearing at least one of each of a mercapto-function and a sulfonic acid function on some individual styrene units of a polymer chain.
  • this invention relates to processes for preparing the catalytically-active polystyrene resins. These processes preferably comprise steps of (b) sulfonating a haloalkylpolystyrene to produce an intermediate having sulfo functional groups; (c) optionally converting the sulfo functional groups to corresponding alkali metal salts; (d) thiolating the thus-produced sulfostyrene intermediate by reacting the halo function with a reactive thiolate to produce a
  • the process of the invention permits use of very low levels of a single acidic condensing agent.
  • the process permits simplified product isolation procedures, recycle procedures, and/or waste management.
  • the process does not require a neutralization step to remove hydrochloric or sulfuric acid and does not produce a waste salt stream.
  • the acidic condensing agents used in the process of this invention were readily removed from the reaction mixtures and can be recovered and recycled.
  • the process of this invention results in high selectivity toward preferred bis-(4-hydroxyaryl) isomers and very fast reaction rates.
  • the process of this invention was particularly useful for the preparation of bis(hydroxyaryl) compounds, such as bisphenol A and 9,9-bis-(4-hydroxyphenyl)fluorene, both of which were useful in the
  • heterogeneous catalysts disclosed herein advantageously were more reactive than heterogeneous catalysts currently used. They
  • a heterogeneous catalyst disclosed herein can be advantageously substituted in an existing commercial process, run with the same or higher throughput at a lower temperature with less
  • Ketones or aldehydes and phenolic compounds (hereinafter phenol, phenols, a phenol or phenolic starting material) useful in process of the invention were known in the art and were described in the literature, for instance, Jansen '982, supra, Maki et al., '252, supra, Morgan '165, supra, and Knebel et al., '594, supra.
  • condensations of this invention can be represented by the equation for a representative condensation, that of phenol with 9-fluorenone:
  • the process for making bisphenol A can be represented by the equation:
  • Phenol starting materials were advantageously any aromatic hydroxy compounds which have at least one unsubstituted position, and optionally have one or more inert substituents, such as hydrocarbyl or halogen at the one or more ring positions.
  • An inert substituent was a substituent which does not interfere undesirably with the condensation of the phenol and ketone or aldehyde and which was not, itself, catalytic.
  • the phenols were unsubstituted in the position, para to the hydroxyl group.
  • Alkylene (alk), alkyl, cycloaliphatic, aryl, arylene (ar), alkylarylene (allkar), arylalkylene (aralk), alkylcycloaliphatic and alkylenecycloaliphatic were hydrocarbyl functions, that was, functions containing carbon and hydrogen atoms.
  • the alkylene functions can be straight-chain or branched-chain and saturated or unsaturated, that was alkylene, alkenylene, or alkynylene.
  • Cycloaliphatic hydrocarbon residues include both saturated and unsaturated cyclic residues, that was, cycloalkylene and cycloalkenylene.
  • Arylene includes mono- and polycyclic aromatic residues, for example, those of benzene, biphenyl, biaryl, naphthyl, phenanthrenyl, anthracenyl or aryl groups, including those bridged by an alkylene group.
  • Alkaryl residues include alkyl, alkenyl and alkynylsubstituted aromatic rings.
  • Aralkyl includes alkyl, alkenyl or alkynyl residues, substituted by one or more aromatic groups.
  • Alkyl groups include both straight-chain and branched-chain isomers of methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, nonadecyl and eicosyl groups, as well as the corresponding unsaturated (alkenyl or alkynyl) groups, as well as higher homologues.
  • the alkyl groups were of 1 to 20 carbon atoms, more preferably of 1 to 5 carbon atoms, most preferably those of 1 to 3 carbon atoms.
  • Alkyl of 1 to 5 carbon atoms includes the various methyl, ethyl, propyl, butyl and pentyl isomers.
  • Alkyl, aryl, alkaryl and aralkyl substituents were suitable hydrocarbyl substituents on the phenol reactant.
  • inert substituents on the phenols include, but were not limited to alkoxy, aryloxy or alkaryloxy, wherein alkoxy includes methoxy, ethoxy, propyloxy, butoxy, pentoxy, hexoxy, heptoxy, octyloxy, nonyloxy, decyloxy and polyoxyethylene, as well as higher homologues; aryloxy, phenoxy, biphenoxy, naphthyloxy and alkaryloxy includes alkyl, alkenyl and alkylnyl-substituted phenolics.
  • Additional inert substituents in phenols includes halo, such as bromo, chloro or iodo.
  • Cyano and nitro substituents may deactivate the phenols and aldehyde and carboxylic acid substituents may cause interfering reactions.
  • Preferred substituents include alkyl moieties containing from 1 to 10 carbon atoms, more preferably, lower alkyl moieties, containing from 1 to 5 carbon atoms, most preferably from 1 to 3 carbon atoms.
  • the alkyl substituents may be straight-chain or branched-chain isomers.
  • Exemplary phenols include, but were not limited to, phenol,
  • phenols include phenol, 2- or 3-cresol, 2,6-dimethylphenol, resorcinol, naphthols, and mixtures thereof. Most preferably, the phenol was unsubstituted.
  • the ketones can be substituted with substituents, which were inert under the conditions used. Inert substituents were as set forth above for the reactive phenols.
  • ketones were advantageously selected from aliphatic, aromatic, alicyclic or mixed aromatic-aliphatic ketones, diketones or polyketones, of which acetone, methyl ethyl ketone, diethyl ketone, benzil,
  • acetophenone, ethyl phenyl ketone, cyclohexanone, cyclopentanone, benzophenone, fluorenone, indanone, 3,3,5-trimethylcyclohexanone, anthraquinone, 4-hydroxyacetophenone, acenaphthenequinone, quinone, benzoylacetone and diacetyl were representative examples.
  • Ketones having halo, nitrile or nitro substituents can also be used; for example, 1,3-dichloroacetone or hexafluoroacetone.
  • Aliphatic ketones which were useful starting materials include, but were not limited to acetone, ethyl methyl ketone, isobutyl methyl ketone, 1,3-dichloroacetone, hexafluoroacetone.
  • a preferred aliphatic ketone was acetone, which condenses with phenol to produce 2,2-bis-(4-hydroxyphenyl)-propane, commonly known as bisphenol A.
  • Another preferred aliphatic ketone was hexafluoroacetone, which reacts with two moles of phenol to produce 2,2-bis-(4-hydroxyphenyl)-hexafluoropropane (bisphenol AF).
  • a preferred class of ketones has at least one hydrocarbyl group containing an aryl group, for example, a phenyl, tolyl, naphthyl, xylyl or 4-hydroxyphenyl group.
  • Other preferred ketones include those in which the hydrocarbon radicals connected to the carbonyl groups of the ketone was in a cycloaliphatic group. Examples of specific preferred ketones include 9-fluorenone, cyclohexanone, 3,3,5-trimethylcyclohexanone, indanone, indenone, and anthraquinone.
  • ketones include 9-fluorenone, benzophenone, acetone, acetophenone, 4-hydroxyacetophenone and 4,4'-dihydroxybenzophenone.
  • the process of this invention was used to make bisphenol A by reaction of phenol with acetone or to make 9,9-bis-(4-hydroxyphenyl)fluorene (BHPF) by reaction of phenol with 9-fluorenone.
  • BHPF 9,9-bis-(4-hydroxyphenyl)fluorene
  • the process of this invention can also be used for the condensation of phenols with aldehydes; for example, with formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde or higher homologues of the formula RCHO, wherein R was alkyl of 1 to 20 carbon atoms.
  • R was alkyl of 1 to 20 carbon atoms.
  • the condensation of two moles of phenol with one mole of formaldehyde produces bis-(4-hydroxyphenyl)methane, also known as Bisphenol F.
  • dialdehydes and ketoaldehdyes for example, glyoxal, phenylglyoxal or pyruvic aldehyde, can also be used.
  • the products were generally geminal bisphenols, that was, compounds having one or more single carbon atoms to which were attached nuclei of two phenolic moieties.
  • This single carbon atom corresponds to the carbonyl carbon of the ketone or aldehyde reactant.
  • the product will contain more than one geminal bisphenolic moiety.
  • the condensate from acetyl acetone and phenol was 2,2,4,4-tetrakis-(hydroxyphenyl)pentane and the condensate from benzoylacetone was 2,2,4,4-tetrakis-(hydroxyphenyl)-4-phenylbutane.
  • the mercaptosulfonic acid catalyst was any species, whether soluble or insoluble in the reaction mixture, containing at least one thiol (SH) group and at least one sulfonic acid (SO 3 H) group, including any group which can be converted to a sulfonic acid group under the reaction conditions used.
  • SH thiol
  • SO 3 H sulfonic acid
  • solubility in the reaction mixture means a compound which has some solubility in the reaction mixture and which can be removed from the mixture, at the end of the reaction, by extraction, ion-exchange, precipitation, absorption.
  • Insoluble mercaptosulfonic acid means a material, which was insoluble in the reaction mixture. These materials were generally polymeric organic resins, or catalyticallyactive compounds, bonded to an inorganic support.
  • the alkylene can be of 2 to 20 carbon atoms, including straight and branched chain alkylene moieties, corresponding heterochain moieties and alkylene substituted with inert substituents.
  • Inert substituents include, for example, alkoxy, alkenyl, alkynyl, halo, nitro, aryl.
  • Representative mercaptoalkanesulfonic acids include, but were not limited to, 2-mercaptoethanesulfonic acid, 3-mercaptopropanesulfonic acid, 4-mercaptobutanesulfonic acid, 4-mercaptopentanesulfonic acid, 3-mercapto-2,2-dimethylpropanesulfonic acid, 2,3-dimercaptopropanesulfonic acid, mercaptopropane-2,3-disulfonic acid, 2-benzyl-4-mercaptobutanesulfonic acid, 5-mercaptopentanesulfonic acid. Most preferred among this group of catalysts were 3-mercaptopropanesulfonic acid and 4-mercaptobutanesulfonic acids.
  • Q was an inert substituent and Y was an optional heteroelement, for example O, H-Q or S.
  • Q was H, hydrocarbyl, halo, carboxy, sulfonyl, as described above for inert substituents on the phenol, ketone or aldehyde starting materials. More than one Q may optionally be present.
  • the Q substituent can be at any position on the chain and more than one Q can be present.
  • more than one SH or sulfonic acid function were optionally present in the catalyst.
  • y was an integer from 0 to 20
  • z was an integer from 0 to 20
  • Q was an optional inert substituent and y + z ⁇ 1, up to a maximum of 40.
  • inert substituents, Q can be attached at any point along the carbon chain; wherein Y was a heteroelement, for example, -S-; each of y and z was at least 1 and y + z ⁇ 2, up to a maximum of 40.
  • Preferred linear mercaptoalkanesulfonic acids were those in which the distance between the mercapto and sulfonic acid functions were less than 20 atoms, including both carbon and heteroatoms.
  • Compounds of Formula Kb) can also have more than one SH and/or more than one sulfonic acid function.
  • Mercaptosulfonic acid precursors can also be used as catalysts, by conversion to active mercaptosulfonic acid catalysts in the reaction mixtures.
  • a precursor alkali metal sulfonate salt can be neutralized with a mineral acid to produce a free sulfonic acid.
  • Sulfonate ester precursors can be hydrolyzed by treatment with a strong base, for example, sodium or potassium hydroxide, and thus converted to a corresponding alkali metal salt.
  • a strong base for example, sodium or potassium hydroxide
  • a further precursor of sulfonic acids for the practice of this invention was a sulfonyl halide group, which can readily converted to a corresponding sulfonic acid.
  • Higher mercaptoalkanesulfonic acids can be prepared from higher olefinsulfonic acids, for example, oleyl sulfonic acid, by adding hydrogen sulfide across the olefinic bond.
  • the olefinic bond of an olefinic sulfonic acid can be halogenated, for example, chlorinated, and the halogen moiety replaced by a mercapto function, as above.
  • Mercaptoalkanesulfonic acids can also be made from corresponding sultones, for example, 1,4-butanesultone, in accordance with Chem. Abs., 90:86742m (1979); R. Fischer, "Propanesultone,” Ind. Eng. Chem., Volume 56 (1964), Pages 41-45; or A. Mustafa, "The Chemistry of Sultones and
  • mercaptosulfonic acids include 2-mercaptobenzenesulfonic acid, 3-mercaptobenzenesulfonic acid, 4-mercaptobenzenesulfonic acid, 2-mercaptonaphthalenesulfonic acid.
  • the aromatic residues can be
  • the active catalysts can contain more than one SH and/or more than one sulfonic acid function in each molecule.
  • Cycloaliphatic residues include those of cyclohexane, cyclopentane and cycloheptane; the aliphatic ring of indane, Tetralin or
  • cycloaliphatic mercaptosulfonic acids include, but were not limited to, 2-mercaptocyclohexanesulfonic acid, 2-mercaptocyclopentanesulfonic acid, 3-mercaptocyclohexanesulfonic acid, and 3-mercaptocyclopentanesulfonic acid.
  • the cycloaliphatic rings can also be substituted with inert substituents and can contain more than one SH group and/or more than one sulfonic acid group.
  • alkylenecycloaliphatic mercaptosulfonic acid compounds can be represented by the following formulas:
  • y and z were integers of 0 to 20; Q was an optional inert substituent selected from alkyl, aryl, halo, alkoxy or aryloxy and y + z ⁇ 1.
  • Typical compounds include (mercaptomethyl)cyclohexanesulfonic acid and (mercaptomethyl) (sulfomethyl)cyclohexane.
  • Typical alkylenearyl mercaptosulfonic acids can be represented by the formulas:
  • a typical compound of this group (mercaptomethyl)benzene-sulfonic acid, can be prepared from a corresponding chloromethyl- or bromomethylbenzenesulfonic acid.
  • Oligomers from vinylsulfonic acid can provide soluble materials, containing large numbers of mercapto and sulfonic acid groups.
  • This type of soluble catalyst can be prepared from oligomers containing
  • oligomeric catalysts containing a multiplicity of mercapto and sulfonic acid units
  • Propenesultone was prepared as described by G. Manecke et al., Chem. Abs. 53:2083c (1959), Helberger et al., DE 1,146,870 and Chem. Abs. 59:11259 (1963).
  • the sultone ring of the polymer can be opened, generally as above, to furnish mercaptosulfonic acid oligomers, containing a plurality of mercapto and sulfonic acid units.
  • oligomers containing a plurality of mercaptosulfonic acid functions can be prepared from oligomers of 4-allyl-1,4-butanesultone.
  • the monomer was prepared as described for 4-benzyl-1,4-butanesultone, using allyl chloride instead of benzyl chloride.
  • 4,4-Diallyl-1,4-butanesultone can be prepared by addition of a second allyl group.
  • the conversion can be represented by the equation:
  • Heterocyclic residues advantageously include cyclic residues, containing N, O, or S. These will generally correspond to aromatic compounds, for example, residues from pyridine, thiophene, quinoline, phenanthridine, as well as the corresponding partially or fully
  • Alkyleneheterocyclic residues otherwise correspond to aromatic residues of the same configuration, as do alkyl heterocyclic residues, as well as corresponding fully or partially hydrogenated compounds.
  • Preferred soluble mercaptosulfonic acids were compounds in which the mercaptan and sulfonic acid functions were separated by a chain of 2 to 10 atoms, whether the chain or linker arm was in an alkylene group or incorporated in an aromatic, cycloaliphatic or heterocyclic ring, whether or not the chain includes heteroelement, and whether or not the mercapto and sulfonic acid functions were attached directly or indirectly to the ring structures.
  • Preferred soluble catalysts for the practice of this invention were mercaptosulfonic acids in which a and b were independently from 1 to 4. More preferably, a and b were independently 1 or 2.
  • mercaptosulfonic acids containing mercapto and sulfonic acid functions in a 1:1 molar ratio, that was a and b were each 1, more particularly 3-mercaptopropanesulfonic acid and 4-mercaptobutanesulfonic acid.
  • the heterogeneous catalyst comprises a catalytically-active species represented by Formula II:
  • each of a and b was independently an integer from 1 to 20
  • ⁇ ' was an alkylene, cycloaliphatic, arylene, alkylenearylene, alkylenecycloaliphatic, alkylenearyl, heterocyclic or alkyleneheterocyclic residue
  • L was an optional linking group and - was a bond
  • catalytically-active species was attached by the bond - to an insoluble organic or inorganic support; or a catalytically-active species
  • ⁇ " was an alkylene, arylene, cycloaliphatic, alkylenearylene, alkylenecycloaliphatic, alkylenearyl, heterocyclic or alkyleneheterocyclic residue; a and b were independently selected from integers from 1 to 20; L' was an optional linking group and - was a bond.
  • Catalytically-active materials of Formula II were generally derived from polymers of ethylenic monomers, wherein the insoluble organic support was the main chain of a resulting polymer and -L- was a covalent bond or a linking group.
  • This type of polymer will include unit structures represented by the general formula:
  • the catalytically-active materials will include those having from 1 to 4 of each of mercapto and sulfonic acid groups per ⁇ '. More preferably, the catalytically-active materials will include those having 1 or 2 of each of mercapto and sulfonic acid groups per ⁇ ' . Most preferably, the catalytically-active materials contain 1:1 ratios of mercapto and sulfonic acid functions and will correspond to the general formula:
  • Exemplary polymers made from ethylenically unsaturated monomers and which can be used as carriers for the catalytically-active species, include, but were not limited to:
  • linking groups, -L- accordingly can include alkylene, a covalent bond, oxycarbonyl, carbonyloxy, oxy, ureido, amido, amino, thio (sulfur), sulfono or sulfoxo.
  • Preferred linking groups include a covalent bond, methylene, sulfur or oxygen, more particularly a covalent bond joining a phenyl ring to a carbon backbone in polystyrene or polystyrene derivatives, each containing SH and SO 3 H functions in single monomeric units of polystyrene.
  • One type of novel catalytically-active polystyrene resins includes unit structures represented by Formula IV:
  • R and R 1 were independently selected from H, alkyl or aryl, -C n H 2n - was straight or branched chain alkylene and n was an integer from 0 to 20.
  • the bridging group B can be selected from alkylene, generally as above.
  • Alkyl and aryl are defined above.
  • Polystyrene resins of Formula IV can be made by the steps of (a) reacting a haloalkystyrene polymer with a lithiated sultone, (b) treating a resulting sultone-functionalized polymer with a reactive thiolate and (c) acidifying the resulting intermediate to produce a polymer containing (mercaptosulfoalkyl)styrene units.
  • Haloalkylstyrene polymers include, but were not limited to poly(chloromethylstyrene), poly(bromomethylstyrene),
  • Representative starting materials can be made by copolymerization of vinylbenzyl chloride or vinylbenzyl bromide with styrene. Either starting material can be crosslinked with divinylbenzene or similar crosslinking monomers.
  • the polymers can contain other monomers, for example, styrene, ⁇ -methylstyrene, acrylonitrile, butadiene, maleic anhydride, ethylene or propylene.
  • haloalkylated polymers will advantageously contain from 0.5 meq/g to 10 meq/g of halomethyl groups.
  • Halomethylated or haloalkylated polymers normally comprise mixtures of polymers, substituted in the ortho, meta- and para-positions.
  • reaction sequence described above can be performed utilizing a variety of chloromethylated or bromomethylated styrene polymers or copolymers.
  • styrene/divinylbenzene copolymers in various forms for example, microporous or macroporous beads, powders, can be functionalized to provide the corresponding mercaptosulfonic acid polymers.
  • Beads were suitably of any size through which effective flow and contact was achieved. Physical forms including powders, beads, extruded shapes, macroporous and microporous configuration were; however, suitably used in the practice of the invention. In general smaller size provides more surface area for contact, but larger size permits greater flow through a bed. Optimizing these factors was within the skill of the art.
  • Reactive thiolates advantageously include, but were not limited to, sodium thioacetate, potassium thioacetate, ammonium thioacetate and lithium thioacetate and the corresponding hydrosulfides. Of these, lithium, sodium or potassium thioacetate was preferred.
  • the thioureas were advantageously selected from thiourea, N-methylthiourea, N-ethylthiourea, N-phenylthiourea.
  • sodium thiosulfate can be used.
  • catalytically-active polystyrene resin was made by reacting poly(chloromethyl)styrene with lithiated 1,4- butanesultone to produce an intermediate sultone, represented by the structural unit formula:
  • the resulting polymer contained ( ⁇ -mercapto- ⁇ sulfopentyl) styrene units, that was, n in Formula IV was 2 and B was -CH 2 -.
  • this type of resin was made from a slightly crosslinked polystyrene; the resulting catalytically active material was designated as PMBSA-MER.
  • catalytically-active polystyrene resins can be prepared by the steps of:
  • This process can be represented broadly by the reaction sequence: to produce intermediate haloalkyl sulfonated styrene polymers, of which halo functions were converted to mercapto-functions to produce the following types of products of Formula V:
  • Alkenyl halides optionally contain aryl and alkyl substituents, as defined above.
  • Representative alkenyl halides, useful for preparing the catalytically-active polymers include, but were not limited to, allyl chloride, allyl bromide, allyl iodide, methallyl chloride, methallyl bromide, crotyl chloride, crotyl bromide, 4-bromo-1-butene, 5-bromo-1-butene, 6-bromo-1-hexene or higher chloro or bromoalkenes.
  • the alkenyl halide was 5-bromo-1-pentene, 11-bromo-1-undecene or allyl bromide.
  • a particularly preferred product thus made can be characterized by the formula, in the case of a product from 5-bromo-1-pentene:
  • Reactive thiolates were as defined above. Most preferably, the reactive thiolate was an alkali metal thioacetate or hydrosulfide.
  • the basic procedure described above can also be used to prepare a variety of catalysts with varying chain lengths between the mercaptan and sulfonic acid moieties.
  • a number of catalysts with different amounts of mercaptosulfonic acid sites, depending upon the degree of functionalization in the alkylation and sulfonation steps in the process, and structural relationships between the mercaptan and sulfonic acid sites, depending upon the choice of bromo- or chloroalkylating agent, can accordingly be made.
  • this invention relates to novel
  • n was preferably an integer from 0 to 10, more preferably 2 or 3.
  • DPMSA-XE3C A representative member of this series of polymers, designated as DPMSA-XE3C was made from chloromethylstyrene polymer and 3-bromopropylbenzene, in accordance with the following reaction sequence:
  • haloalkyl polystyrene starting materials can advantageously be selected from chloromethylated polystyrenes, bromomethylated polystyrenes, chloroethylated polystyrenes, iodoethylated polystyrenes, generally as above, preferably the halomethylated polystyrenes.
  • chloromethylated polystyrenes bromomethylated polystyrenes
  • chloroethylated polystyrenes chloroethylated polystyrenes
  • iodoethylated polystyrenes generally as above, preferably the halomethylated polystyrenes.
  • haloalkylaryene compound can conveniently be selected from chlorobenzene, (chloromethyl)benzene, (chloroethyl)benzene,
  • chloropropyl)benzene (chlorobutyl)benzene, as well as the corresponding fluoro, bromo and iodo analogues.
  • Representative examples include (2- chloroethyl)benzene, (2-bromoethyl)benzene, (2-iodoethyl)benzene, 1-chloro-3-phenylpropane, 1-bromo-3-phenylpropane, and 1-iodo-3-phenylpropane.
  • the bromo compounds were preferred.
  • the alkylation was conveniently carried out in the presence of a Friedel-Crafts catalyst, of which aluminum trichloride, aluminum bromide, boron trifluoride, hydrogen fluoride, phosphoric acid, zinc chloride, titanium chloride, ethylaluminum dichloride and stannic chloride were representative.
  • a preferred catalyst was aluminum chloride in
  • haloalkylbenzene, solvent and catalyst in the admixture were removed from the alkylated polystyrene by means within the art such as filtration.
  • the admixture was recycled for reaction with additional haloalkyl polystyrene.
  • the alkylated polystyrene was optionally washed with a solvent such as dichloromethane and optionally dried.
  • the resulting alkylated polystyrene was sulfonated using
  • chlorosulfonic acid oleum or other known sulfonating agents.
  • halo moiety Prior to conversion of the halo moiety to the mercapto moiety, it was convenient to convert the sulfo moieties to corresponding alkali metal salts.
  • Chlorosulfonic acid, sulfuric acid or sulfur trioxide was conveniently used in an amount sufficient to achieve a predetermiend or desirable degree of sulfonation, advantageoul ⁇ y to avoid unnecessary workup, in an amount not in large excess of the sufficient amount which varies with each resin but was determined without undue experimentation.
  • the advantages of lower reaction temperatures were greater with chlorosulfonic acid.
  • the thiolating reagents were conveniently selected from those disclosed above. Sodium thioacetate was preferred. Excess sodium hydrosulfide was optionally used for thiolation. Hydrolysis was then unnecessary since a thio group rather than a thioacetate was formed.
  • the intermediate thiolated compound was, if necessary, acidified with a strong acid to convert sulfonate salt moieties to corresponding sulfonic acid moieties.
  • a mineral acid was used, as above.
  • the process comprises: (a) alkylating a polystyrene resin with a halomethyl haloalkylarylene compound to produce an intermediate having
  • the alkylating step was performed as in the preceding process optionally in a solvent such as chloroform, 1,2-dichloroethane,
  • the alkylating agent was any halomethyl haloalkylarylene preferably wherein the alkyl group has from 0 to 10 carbon atoms.
  • the arylene group preferably has from 6 to 14 carbon atoms. It was within the skill of the art to select halomethyl
  • haloalkylarylenes in which the haloalkyl and halomethyl groups have activities sufficiently different to achieve the desired result.
  • halomethyl haloalkylarylene compounds include
  • Chloromethyl haloalkylarlenes were conveniently prepared by means within the skill of the art such as described by Selva et al., Synthesis, 1991, 1003-1004, wherein haloalkylarylenes were reacted with formaldehyde in acid (for example, sulfuric or hydrochloric) in the presence of a quaternary ammonium phase transfer catalyst. Chloromethylation can also be performed using zinc chloride and paraformaldehyde in accordance with the method described by Daren in U.S. Patent No. 4,967,026.
  • chloromethyl ethers were used to chloromethylate a haloalkyl arylene by methods similar to that taught by Raley in U.S.
  • Patent No. 3,311,602 by Shinka, et al., J. Poly. Sci. Polym. Lett. Ed.
  • hydrohalogenating agents such as, HBr were added to alkenyl arylenes, such as, styrene under radical forming conditions such as taught by Martan in U.S. Patent No. 4,228,106 or Plesmid in U.S. Patent No. 3,321,536.
  • vinylbenzyl chloride was hydrobrominated by this method.
  • haloalkylated polystyrene resins include (but were not limited to) those described or discussed by: a) P. C. Reeves and M. S. Chiles, "Phase
  • haloalkylated polystyrene resin prepared in a manner such as that described in the above references could be further functionalized by the sulfonation and thiolation procedures previously described to provide a mercaptosulfonic acid polymer catalyst.
  • Catalysts derived from polystyrenes will advantageously contain from 0.2 to 5 meq of mercaptosulfonic acid functionality per g, most preferably from 2 to 4 meq/g.
  • polymers containing large amounts of mercaptosulfonic acid functionality on a given carrier, pendant from a hydrocarbon chain, can be prepared by grafting vinylsulfonic acid, propenesultone, to the pendant carrier function, and converting the grafted polymer to materials having mercapto/sulfonic acid functionality.
  • Catalytically-active polymers in which - was an ionic bond can advantageously be prepared from ion-exchange resins and reactive compounds, containing both mercapto and sulfonic acid functions.
  • a strongly basic ion-exchange resin such as
  • poly(vinylbenzyl amine) can be reacted with a compound such as 4-mercapto-1,2-butanesulfonic acid to produce catalytically-active material as represented by the equation:
  • Representative strongly basic ion-exchange resins include DOWEXTM 1X2-400, from The Dow Chemical Company, AmberlystTM A-21 from Rohm and Haas, DOWEXTM WGR-1, DOWEXTM WGR-2 and DOWEXTM MSA-1, from The Dow Chemical Company.
  • the WGR resins were polypropyleneimines, conveniently obtained by condensation of epichlorohydrin with ammonia.
  • Catalytically-active materials can also advantageously be prepared from an acidic ion-exchange resin, for example sulfonated polystyrene by reaction with an aminomercaptosulfonic acid, for example, 2-mercapto-4-aminobenzene sulfonic acid, as represented by the equation:
  • Representative strongly acidic cation-exchange resins include DOWEXTM 50X2-400, AmberlystTM A-21, from Rohm and Haas, and DOWEXTM MSC-1, from The Dow Chemical Company.
  • the catalytically-active species can be attached to an inorganic support, for example a mineral, such as silica, alumina, aluminosilicates or glass, through the linking group -L-.
  • an inorganic support for example a mineral, such as silica, alumina, aluminosilicates or glass.
  • a representative case was that wherein the linking group was -OSiO- or
  • Catalytically-active species of Formula III will conveniently be incorporated in the backbone of condensation polymers; for example, polyesters, polyamides, polycarbonates, polyurethanes, polysiloxanes, polyamines, polyethers, polyketones, polysulfones and polysulfoxides.
  • the divalent linking group, -L'- can be selected from such structures as polyoxy(alk-di-yl), polyoxy(ar-di-yl), dioxy(alkar-di-yl), polyoxy(aralk- di-yl), polythio(alk-di-yl), polythio(aralk-di-yl), polythio(ar-di-yl), polythio(alkar-di-yl), polythio(aralk-di-yl), polyamido(alk-di-yl), polyamido(ar-di-yl), polyamido-(aralk-di-yl), polycarbonyloxy(alk-di-yl), polycarbonyloxy(ar-di-yl), polycarbonyloxy(alkar-di-yl), polycarbonyldioxy(alk-di-yl), polycarbonyldioxy(alkar-di-yl), polycarbon
  • dithiohydrocarbylene and hydrocarbylene groups containing aromatic rings.
  • the mercaptosulfonic acid catalyst was suitably present in an amount sufficient to enable condensation of the phenol with the ketone/aldehyde in a reasonable time.
  • the amount of mercaptosulfonic acid ranges from 0.01 equivalents to 2.0 equivalents of catalyst per 1.00 equivalents of the ketone/aldehyde. More preferably, the amount of mercaptosulfonic acid catalyst was from 0.02 to 1.0 equivalent of mercaptosulfonic acid per equivalents of
  • reaction mixture will contain from 0.03 to 1.0 equivalent of mercaptosulfonic acid per equivalents of aldehyde or ketone under batch processing.
  • ketone/aldehyde When ketone/aldehyde was added over the course of a reaction (for example, a continuous reaction) the previously stated preferred amounts refer to total catalyst and reactants added rather than catalyst present in a reaction mixture at a given moment. Those skilled in the art recognize that when a reactant was added incrementally or continuously, there was often a large excess of catalyst.
  • the ratio of catalyst to ketone/aldehyde in the reaction mixture was advantageously greater than one, conveniently on the order of 20 equivalents to 1 equivalent. Due to the high activity of the mercaptosulfonic acid catalysts, good reaction rates and high selectivity can be obtained at temperatures below the melting point of phenol.
  • the phenol reactant can advantageously be kept in the liquid state by addition of solvents, for example, water, methylene chloride, diphenylmethane.
  • solvents for example, water, methylene chloride, diphenylmethane.
  • the reaction temperature will accordingly advantageously be selected in the range from 0°C to 100°C, preferably from 15°C to 60°C. Temperature ranges can be chosen by routine experimentation, depending upon the ketone/aldehyde and phenol feeds.
  • the temperature for the condensation was advantageously selected so that the phenol was in the liquid state.
  • the use of an inert solvent was preferred.
  • Diphenylmethane has been found to be particularly useful for this purpose.
  • Other useable inert solvents include, but were not limited to, the xylenes, mesitylene, the durenes, fluorobenzene, toluene, cyclohexane, chlorobenzene, halogenated aliphatic hydrocarbons and alkylnaphthalenes having low melting points.
  • the amount used conveniently ranges from 5 mL to 1 L per mole of ketone or aldehyde. Preferably, from 200 ml to 400 mL were used per mole of ketone or aldehyde.
  • the reaction can advantageously be carried out by stirring the ketone or aldehyde and mercaptosulfonic acid into molten phenol in such a way that the temperature in the reaction vessel will not rise above 150°C.
  • the molar ratio of phenolic reactant to ketone or aldehyde was advantageously selected so that at least two moles of phenol will condense with the ketone to produce a corresponding bisphenol or higher condensate. Therefore, molar ratios of 2:1 or higher will advantageously be selected. It was preferred to carry out the reactions using larger excesses of phenolic reactant, up to as much as 50 moles of phenol per mole of ketone or aldehyde. It will be understood that the excess phenol acts as a solvent or diluent, as well as a reactant.
  • the molar ratio was from 6:1 to 25:1.
  • the reactants instead of being mixed together all at once, were optionally progressively mixed together at a speed depending upon the intensity of the cooling employed to maintain the temperature of the reaction medium within the optimum limits. After the mixing of the reactants, they were preferably left in contact for some time in order to complete the condensation.
  • the duration of the introduction of the reactants during a batch process conveniently varies from 15 minutes to 1 hour.
  • the reactants and the catalyst were preferably thoroughly stirred mechanically to assure better mixing, and hence an improved space-time yield.
  • reaction time was advantageously in the range of 0.1 to 20 hours depending on the reaction conditions including the amount of the catalyst used, the reaction temperature, and specific reactants, solvents and products.
  • the process of this invention can also be run in a continuous mode, more preferably by use of a series of continuous stirred tank reactors, the use of which approximates plug flow reaction conditions. It was preferred to carry out the process of this invention under continuous reaction conditions.
  • the pressure in the reaction zone was not critical, but preferably ranges from 0.001 to 10 bar (0.1 to 1000 kPa), and more particularly from 0.5 to 3 bar (50 to 300 kPa). In many cases, it will be preferred to carry out the reactions under ambient pressure, that was, 1 bar (100 kPa).
  • the soluble mercaptosulfonic acid catalysts can advantageously be removed from the crude product by extraction with water.
  • the aqueous extracts can be concentrated and recovered
  • mercaptosulfonic acid catalyst can be optionally recycled to subsequent runs.
  • phenolic starting material was phenol
  • a solution of the mercaptosulfonic acid in phenol was conveniently recovered and was optionally recycled without further purification.
  • the acid concentration can be reduced below the limits of detection, and probably below 1 ppm by weight of acid, by repeated extractions with water.
  • the facile removal of catalyst from the reaction mixtures was a significant advantage over the prior art, using mixtures of condensing agents. It was within the practice of this invention to remove the mercaptosulfonic acid by continuous countercurrent extraction.
  • the time for phase separation during extraction of the acid catalyst was on the order of 10 to 15 minutes under batch conditions, without a drag layer. Stirring speed during the extraction in a mixer/settler was adjusted so as to avoid emulsion formation.
  • the soluble mercaptosulfonic acid catalysts can also be removed from reaction mixtures by extraction with a solution of an alkali metal hydroxide, carbonate or bicarbonate.
  • the soluble mercaptosulfonic acid catalysts can be removed from reaction mixtures by passing the reaction mixture through a column of anion-exchange resin or amine resin, such as DOWEXTM WGR, from The Dow Chemical Company.
  • a water purge from the process will contain phenol plus catalyst.
  • This purge was advantageously treated to remove phenol by extraction with methyl isobutyl ketone before being sent to a bio-pond for disposal.
  • a phenol/water mixture was preferably distilled from the water-washed mixture until the weight ratio of phenol:BHPF was below 1.5:1.
  • phenol was removed until the phenol:BHPF weight ratio was from 1.5:1 to 0.5:1. It has been found particularly advantageous to dissolve the resulting material in hot methylene chloride and cool the resulting solution to obtain crystalline BHPF.
  • Very highly purified BHPF accordingly can be obtained by a process wherein a resulting crude product was washed with water to remove (HS) a - ⁇ -(SO 3 H) b ; the resulting acid-free mixture was distilled to remove phenol and water until the phenol:9,9-bis-(4-hydroxyphenyl)fluorene weight ratio was less than 1.5; the resulting mixture was taken up in hot methylene chloride and the resulting solution was cooled to produce crystalline 9,9-bis-(4-hydroxyphenyl)fluorene.
  • BHPF purified in this way can be used to make ultrahigh quality polycarbonate resins.
  • Excess phenol can also be removed by boiling the reaction mixture repeatedly with water, optionally with the use of a water-miscible organic solvent such as methanol. The aqueous solution was separated each time and the product, then practically pure, was dried. Another effective method of removing excess phenol was by steam distillation.
  • reaction product solution was optionally then concentrated by evaporation and repeatedly extracted with boiling water for the removal of excess phenol.
  • the product so obtained was optionally then recrystallized for further purification.
  • BHPF can be isolated from the reaction mixtures in several
  • the method selected will depend on the degree of purification desired, as well as the composition of the reaction mixture, and the desired production rate.
  • the mixture after being treated to remove catalyst, can be treated with a volume of hot water sufficient to dilute the mixture and bring
  • the reaction mixture can be added to hot water and the phenol removed in the form of a water/phenol azeotrope until the phenol content was lowered sufficiently to permit precipitation of BHPF from the mixture.
  • the BHPF solids can be collected and dried before use or can be used in the form of a slurry.
  • the solids can be purified by precipitation from a solvent, for example, diphenylmethane or methylene chloride.
  • Another method for isolating BHPF comprises adding to the reaction mixture, at the end of the reaction, a solvent, boiling at a higher temperature than phenol, and removing phenol from the phenol/BHPF/solvent mixture until BHPF crystallizes or precipitates from the mixture.
  • This method can be carried out by adding diphenylmethane or triisopropylbenzene to a reaction mixture, from which catalyst has been extracted or removed, prior to distilling the mixture.
  • the solvents can be added to the initial reaction mixture so that the reactions were run in the presence of the solvent. The reaction mixture was worked up, by
  • BHPF can also be isolated by adding to a reaction mixture a solvent, which boils at a higher temperature than phenol and dissolves sufficient BHPF, in the absence of phenol, that removing phenol from the
  • phenol/BHPF/solvent mixture provides a homogeneous solution, cooling of which causes crystallization of BHPF.
  • Solvents meeting these requirements include diphenylmethane, diphenyl ether, dodecane, naphthalene, IsoparTM (hydrocarbon mixture commercially available from Exxon Corporation) and triisopropylbenzene.
  • Further purification can also be accomplished, after removing catalyst from the reaction mixture, by distilling to remove phenol to a level at which BHPF crystallizes from the phenol/BHPF mixture.
  • the BHPF solids obtained can be isolated by conventional means and then further treated, for example, by washing with water to remove phenol.
  • An alternative method for obtaining high purity BHPF comprises removing catalyst from the reaction mixture, distilling phenol from the reaction mixture to a phenol/BHPF level such that dilution of the distillation residue with a solvent induces crystallization of the BHPF from the phenol/BHPF/solvent mixture.
  • phenol can be removed by distillation until the distillation residue contained 50 percent by weight of phenol and 50 percent by weight of BHPF.
  • Methylene chloride, triisopropylbenzene or toluene can be added to the residue and the resulting solution can be cooled to bring about crystallization of highly purified BHPF.
  • Another procedure for isolating pure BHPF solid from the reaction comprises removing the mercaptosulfonic acid catalyst, distilling phenol from the resulting mixture, to produce a still residue, to which addition of a solvent induces crystallization of BHPF.
  • a still residue containing 80 percent by weight of phenol and 20 percent by weight of BHPF can be diluted with a solvent, for example dichloromethane or toluene, to induce crystallization of BHPF.
  • BHPF can be isolated from a reaction mixture, by removing the mercaptosulfonic acid catalyst, adding to the resulting reaction mixture a solvent, which forms an azeotrope with phenol and in which BHPF was soluble in the absence of phenol, and removing phenol from the mixture by azeotropic distillation.
  • Cyclohexanol was exemplary of a solvent, which will form an azeotrope with phenol and from which BHPF will precipitate upon cooling the still residue from the azeotropic
  • phenol can be removed from the reaction mixtures by addition of a solvent, which forms an azeotrope with phenol. After removing phenol by azeotropic distillation, the still residue was cooled and BHPF crystallizes out from the cooled mixture.
  • the catalyst was optionally not removed before crystallization of product but rather either tolerated in the product or removed from the crystals, for instance by washing or other means within the skill of the art, after crystallization.
  • condensation of phenol with ketones or aldehydes can be run in a solvent, for example, methylene chloride, from which the product will precipitate during the course of the reaction, as was described in more detail for the preparation of bisphenol A.
  • a solvent for example, methylene chloride
  • a representative solvent used for crystallization of BHPF, methylene chloride can be recovered from the mother liquors by batch distillation and recycled back to the process.
  • the still bottoms contain BHPF and methylene chloride and can be cooled to recover additional BHPF.
  • BHPF crystals thus formed were conveniently recovered using a basket centrifuge or pressure filter and can be recycled back to a main crystallizer. Crude mother liquor can also be recycled back to the phenol evaporation section.
  • vent header system When methylene chloride was used as solvent for crystallizing BHPF, a common vent header for collecting all vents from storage tanks and safety relief systems was recommended.
  • the vent header system
  • a complete effluent treating system will advantageously include means for removing organics from process waters and means for removal of particulates from vent gas, for example, a water venturi flow meter to scrub particulates from the vent header.
  • a further advantage of the catalysts used in the practice of this invention was that the catalysts can be used to isomerize the crude product mixture, which typically contained (4-hydroxyphenyl) (2-hydroxyphenyl) compounds, the major bis-(4-hydroxyphenyl) compounds, and condensates, to produce more of the bis-(4-hydroxyphenyl) compounds.
  • ⁇ ' was an alkylene, cycloaliphatic, arylene, alkylenearylene, alkylenecycloaliphatic, alkylenearyl, heterocyclic or alkyleneheterocyclic residue; a and b were independently selected from integers from 1 to 20; L was an optional linking group and - was a bond, which catalytically-active species was attached by the bond - to an insoluble organic or inorganic support; and heated sufficiently to result in formation of the p,p (bis(4-hydroxyphenyl) product from at least a portion of the o,p (2-hydroxyphenyl, 4-hydroxyphenyl product.
  • the catalyst was a compound (including polymer) of the formula (HS) a - ⁇ -(SO 3 H) b or of formula (a), preferably those preferred for the reaction of an aldehyde or ketone with a phenol as described herein, with 3-mercaptopropanesulfonic acid most preferred. It was noted that such catalysts result in conveniently fast isomerization and less formation of additional by-products than do acids such as methane sulfonic acid. Temperatures, which will vary with the compound being isomerized, were suitably any temperature at which isomerization takes place, and were conveniently at least room temperature (30°C), preferably at least 40°C, more preferably at least 50°C.
  • the temperature was preferably lower than that temperature at which an undesirable amount of additional by-product or polymer would form, conveniently less than 100°C, more preferably less than 85°C, most preferably less than 75°C. Seventy degrees centigrade was a convenient and preferred temperature. It was found that increasing the temperature within the range speeds isomerization. Likewise, increasing the temperature
  • the catalyst was present in the same amounts and preferred ranges as for preparation of a bisphenol by the process disclosed herein.
  • the pressure was not critical, but was also
  • Time for the isomerization was preferably that in which, under the conditions, results in isomerization of at least a portion, more preferably a predetermined or desired fraction of the o,p by-product being isomerized to the desired p,p product. More preferably the ratio of o,p to p,p product was less than 0.12, most preferably less than 0.1, even more preferably less than 0.075. The time to achieve this result varies with isomerization conditions but was conveniently less than a day, more preferably less than 12 hours, most preferably less than 8 hours, for conversion of half of the o,p product to p,p product.
  • the process of this invention was advantageously carried out under conditions such that the concentration of chloride was below 5000 ppm, preferably below 1000 ppm, most preferably below 100 ppm.
  • the insoluble catalysts of this invention can be filtered from the reaction mixtures, washed with a mixture of ketone/aldehyde and phenol, and recycled to subsequent runs.
  • the insoluble catalysts were used in fixed beds and the condensations of phenols with
  • aldehyde/ketone was done in continuous upflow, crossflow or downflow fashion.
  • the catalytically-active resins remain in the resin beds and need not be removed.
  • a particularly preferred process was one wherein the molar ratio of phenol:fluorenone was from 4:1 to 25:1; the reaction temperature was from 25°C to 50°C; the catalyst was mercaptopropanesulfonic acid or
  • mercaptobutanesulfonic acid used in an amount from 5 to 10 molar percent with respect to fluorenone; the process was carried out under ambient pressure or under vacuum to remove water of reaction and increase the reaction rate; no cosolvent was used; the catalyst was removed from the product by extraction with water using a wash column or by batch
  • a particularly preferred process was one wherein the molar ratio of phenol:fluorenone was from 4:1 to 25:1; the condensation was carried out at a temperature from 40°C to 60° C; no cosolvent was used; the catalyst was PMBSA; the condensation was carried out in a continuous plug flow reactor; the reaction was carried out at ambient pressure or under reduced pressure to remove water of reaction and increase the reaction rate; the product was isolated by removing excess phenol to a weight ratio from 1.5:1 to 0.5:1 of
  • the process for making BHPF can also be carried out at molar ratios of phenol:fluorenone from 7:1 to 5:1 in the presence of 0.05 to 0.15 equivalent of MPSA or MBSA per mole of fluorenone, wherein methylene chloride was added to the reaction mixture after conversion of at least 20 percent of fluorenone has occurred; heating the resulting mixture under reduced pressure to remove an azeotrope of methylene chloride and water; and cooling the mixture at the end of the condensation reaction to cause precipitation of BHPF.
  • the condensation of phenol with fluorenone can further be carried out using a feed containing from 5:1 to 3:1 molar ratio of
  • Crystalline BHPF can be collected from the cooled reaction mixture.
  • BHPF can be prepared from a reaction mixture
  • the phenol :acetone feed contained from 6:1 to 15:1 molar ratios of phenol:acetone; the condensation was carried out at a temperature from 25°C to 35°C; the reaction mixture contained up to 5 percent by weight of water to lower the freezing point of phenol; the catalyst was 3-mercaptopropanesulfonic or 4-mercaptobutanesulfonic acid in an amount from 0.05 to 0.50 equivalent per mole of acetone in the acetone:phenol feed; the reaction was carried out under ambient pressure; and the crystalline bisphenol A produced by the process was removed by filtration or centrifugation.
  • Further processing can include washing the bisphenol A with water to partially remove soluble catalyst, and removing additional soluble catalyst by treatment with an anion exchange resin. It was believed that a preferred reactor configuration for this process was a series of continuous stirred tank reactors, so as to approximate plug flow reaction conditions.
  • Such catalysts include soluble mercaptosulfonic acids in which a and b were each independently integers from 1 to 4.
  • Preferred conditions include reaction temperatures from 0°C to 50°C, more preferably from 20°C to 40°C.
  • complex-forming solvents for bisphenol A include diethyl ether, acetone, ethanol, propanol, dioxane, acetic acid, acetonitrile, methylene chloride or carbon tetrachloride.
  • the complex-forming solvents complex preferentially with the 4,4-diphenolic isomer so that the resulting complex has solubility properties, differing from that of the uncomplexed 2,4-diphenolic compound and can be readily separated therefrom.
  • a most preferred process of this invention was that wherein the ketone was 9-fluorenone, the phenol was unsubstituted and the product was 9,9-bis-(4-hydroxyphenyl)fluorene; the molar ratio of phenol to fluorenone was from 8:1 to 25:1; the reaction mixture contained from 0.05 to 0.20 equivalent of mercaptosulfonic acid per mole of fluorene; the mercaptosulfonic acid compound was 3-mercaptopropanesulfonic acid or 4-mercaptobutanesulfonic acid and the process was carried out at a temperature from 45°C to 60°C.
  • Reactor Design 1 A 500-mL reactor prepared from PFA Teflon ® (material from DuPont) was fitted with a thermocouple port, water condenser topped with nitrogen inlet, mechanical stirrer, drain port, and sampling port. Heating was provided with an infrared beat lamp and the temperature was controlled with an electronic thermometer/temperature controller.
  • Reactor Design 2 A capped 4-dram glass vial with a magnetic stirrer. Heating was regulated by placing the vial in a temperaturecontrolled aluminum block heater.
  • Reactor Design 3 A 100-mL jacketed glass reactor was fitted with a thermometer port, magnetic stirrer, nitrogen inlet, and sampling port. Heating was provided and the temperature was controlled by circulating glycol solution of the appropriate temperature through the jacketed flask using a Heslab Model RTE-220 circulating bath.
  • Reactor Design 4 A 1.5 L, 2 L, or 3 L jacketed glass reactor fitted with a thermometer/sampling port, nitrogen inlet, and mechanical stirrer. Heating was provided and the temperature was controlled by circulating glycol solution of the appropriate temperature, through the jacketed flask using a Neslab Model RTE-220 circulating bath.
  • Analytical Method 1 A Varian HPLC System (Model 9010 solvent delivery system, Model 9095 Autosampler, Model 9065 Polychrom diode array detector) interfaced with a Varian Star workstation was used for analysis. Area percent analysis was reported at 282 nm. Percent conversion was determined by an external standard method using calibrated concentration curves for each major component. Analytical HPLC samples were prepared by careful quantitative dilution of reaction samples (range: 400-500 times dilution). Column: Waters Nova-Pak C-18 (60 Angstrom, 4 micron, 3.9 X 150 mm).
  • Analytical Method 2 A Hewlett-Packard HPLC system (Model 1084B solvent delivery system. Model 79850B LC terminal) was used for analysis. Area percent analysis was reported at 254 nm. Percent conversion was determined by an external standard method using calibrated concentration curves for each major component. Analytical HPLC samples were prepared by careful quantitative dilution of reaction samples (range: 400-500 times dilution). Column: Waters Nova-Pak C-18 (60 Angstrom, 4 micron, 3.9 X 150 mm).
  • Analytical Method 3 A Varian HPLC system (Model 9010 solvent delivery system. Model 9095 Autosampler, Model 9065 Polychrom diode array detector) interfaced with a Varian Star workstation was used for analysis. Area percent analysis was reported at 282 nm. Percent conversion was determined by an internal standard method using a solution of 0.0508 weight percent acetophenone in 60/40 (weight/weight percent)
  • Analytical Method 5 The reaction mixture was diluted with acetonitrile to a concentration of 0.01-0.1 percent by weight of components and the diluted sample was analyzed by HPLC on a Waters NovaPak C18 column (10.16 cm ⁇ 0.635 cm inner diameter) connected to a VarianTM 9100 UV detector, set at 280 nm.
  • the auto sampler injects 20 microliters of sample onto the column every 36 minutes.
  • Reservoir A contained megapure water and reservoir B HPLC grade acetonitrile. The following protocol was used:
  • the peak area generated by each component in the sample was used with its known response factor, and the dilution ratio, to calculate the concentrations of each component in the sample solution.
  • Fluorenone (Aldrich 98 percent), about 0.5 percent fluorene and methyl-fluorenes
  • Acetone (Baker reagent, dried over molecular sieves)
  • Phenol (Dow Chemical 99+ percent), about 100 ppm H 2 O + 100 ppm impurities
  • Source B 90 percent purity (Raschig Corp.)
  • Source B Prepared from 90 percent Raschig Corp. sodium 3-mercaptopropanesulfonate
  • MBSA 4-Mercaptobutanesulfonic acid
  • 2,2-Bis(mercaptomethyl)-1,3-propanedisulfonic acid prepared from 2,2-bis(bromomethyl)-1,3-propanediol (Aldrich, 98 percent) as follows:
  • the mixture was cooled to room temperature and saturated with gaseous hydrogen chloride. An exotherm to 43°C was observed. The mixture becomes homogenous and yellow in color during the early stages of HCl addition. As the mixture becomes saturated with HCl, a voluminous white precipitate was formed.
  • the solution was cooled to room temperature and filtered to remove solid salts, which were primarily sodium chloride and sodium bromide. Water was removed from the filtrate to provide 2,2-bis- (hydroxymethyl)-1,3-propanedisulfonic acid (190.7 g) as a highly viscous amber oil (glass).
  • reaction mixture can be worked up by dilution with 200 mL of ethanol or methanol, after which the solid was removed by filtration. Solvent was removed from the filtrate on a rotary evaporator, to produce a white solid containing mainly disodium 2,2-bis-(hydroxymethyl)-1,3-propanedisulfonate. Concentrated hydrochloric acid can be added to the solid product to give the soluble disulfonic acid, plus insoluble sodium chloride and sodium bromide.
  • p-Xylene 400 mL was added to the 2,2-bis-(hydroxymethyl)-1,3-propanedisulfonic acid and the resulting two-phase mixture was heated under reflux (135°C to 150°C pot temperature) to remove water, produced by the dehydration, in the form of an azeotrope in a Dean-Stark trap. After 8 hours' heating under reflux, the mixture was allowed to cool to room temperature and the upper xylene phase was decanted from the lower viscous product phase. Water (300 mL) was added to the cooled, lower phase containing 2,2-bis-(hydroxymethyl)-1,3-propanedisulfonic acid bis-sultone to produce a large mass of white solid. The white solid (bis-sultone) was removed by filtration, slurry washed extensively with water and with methanol and dried in a vacuum oven
  • the thioacetate adduct (18.2 g) was hydrolyzed by stirring overnight at ambient temperature in a nitrogen-saturated mixture of 10 percent sodium hydroxide (20 g) and 100 g of water. The mixture was acidified to pH 3 with 10 percent aqueous hydrochloric acid solution. Solvent was removed from the resulting mixture in a fume hood, using a rotary evaporator. The residue was dissolved in 50 mL of water and saturated with hydrogen chloride gas. The resulting solid salt was removed by filtration and the filtrate was concentrated using a rotary evaporator to give 2,2-bis-(mercaptomethyl)-1,3-propane-disulfonic acid as a viscous dark-colored oil.
  • the thioacetate adduct can be hydrolyzed by stirring with concentrated hydrochloric acid, removing the solid salt product by filtration and removing water from the filtrate using a rotary evaporator.
  • nm nanometers
  • the 9-fluorenone was found to be completely consumed within 120 minutes with a product composition, determined by quantitative HPLC, of 98 percent of 9,9-bis-(4-hydroxyphenyl)-fluorene.
  • the product was further analyzed by a combination of HPLC and UV (282 nm) and contained:
  • Example 1 The procedure of Example 1 was repeated except that the catalyst was prepared in situ from 90 percent sodium
  • Example 2A The procedure of Example 2A was repeated except that 98 percent sodium 2-mercaptoethanesulfonate (0.779 g, 4.75 mmol, 0.0427 equivalents) and 95 to 98 percent sulfuric acid (0.48 g, 4.9 mmol, 0.044 equivalents) were used as catalysts. The reaction was conducted at 85°C.
  • reaction mixture was heated to 45°C with stirring under a pad of nitrogen.
  • 3-Mercaptopropanesulfonic acid (8.28 g, 53.0 mmol, 0.0692 equivalent) was added slowly over approximately 1 minute to the reaction mixture at 45°C.
  • the reaction was monitored throughout the reaction period by collecting samples and analyzing by HPLC.
  • 2,3-Dimercaptopropanesulfonic acid (0.021 g, 0.011 mmol, 0.050 equivalent) was added in one portion to the vial which was then tightly capped. The reaction was monitored throughout the reaction period by collecting samples and analyzing by HPLC (analytical method 2). The 9-fluorenone was found to be 5 percent consumed in 1.5 hours.
  • Example 5D The reaction conditions described in Example 5D were repeated substituting each of the following acids (each at 8 mol percent) for methanesulfonic acid in the reaction: sulfamic acid (Aldrich 98 percent), methylphosphonic acid (Aldrich 98 percent), and phenylphosphonic acid (Aldrich 98 percent). In each case, very little conversion of the fluorenone was observed in comparison with the use of methanesulfonic acid.
  • reaction mixture was heated to 45°C with stirring under a pad of nitrogen.
  • 3-Mercaptopropanesulfonic acid (5.53 g, 35.4 mmol, 0.0500 equivalent) was added slowly over approximately 1 minute to the reaction mixture at 45 °C.
  • the reaction was monitored throughout the reaction period by collecting samples and analyzing by HPLC.
  • HPLC analysis (analytical method 2) gives a relative area percent ratio of 97.0:3.0 for the desired reaction product 2,2-bis-(4-hydroxyphenyl)propane (4,4-bisphenol A) relative to the isomeric impurity 2-(2-hydroxyphenyl)-2-(4-hydroxyphenyl)-propane (2,4-bisphenol A) at 70 percent conversion.
  • 1,4-Butanesultone (3.00 g, 22.0 mmol, 1.00 equivalent) was added to dry THF (150 mL) under a nitrogen atmosphere. The solution was cooled to -78°C using a dry ice/acetone bath. n-Butyllithium (1.6 molar in hexanes, 13.8 mL, 1.00 equivalent) was added slowly dropwise to the -78°C solution via an addition funnel over approximately 40 minutes with vigorous stirring. The homogeneous reaction mixture was allowed to stir for an additional 10 to 15 minutes at -78°C.
  • the sultone-functional polymer from above (4.00 g, approximately 15.9 mmol sultone) was added to THF (125 mL).
  • Potassium thioacetate (2.20 g, 19.0 mmol, 1.20 equivalent) was added as a solid to the slurry of the polysultone in THF.
  • One drop of 50 percent tetrabutylammonium chloride was added to the rapidly stirred slurry. The temperature rose to 26°C over several minutes, then slowly dropped to 20°C. Two additional drops of 50 percent tetrabutylammonium chloride were added and the solution was warmed to 40°C for 15 minutes. Water (100 mL) was slowly added over 1 hour to the reaction mixture at 40°C.
  • the tan solid was slurried in a 2:1 (by volume) mixture of toluene/ethanol. Concentrated hydrochloric acid (50 mL) was added and the mixture was stirred at room temperature overnight. Most of the HCl was removed by sparging the mixture with nitrogen, then the solvents were removed by rotoevaporation. The light tan solid was slurry-washed extensively with 10 percent hydrochloric acid and with water. Drying overnight in a vacuum oven (60°C/full vacuum) provides 4.18 g of the polymer-supported mercaptosulfonic acid as a light tan solid.
  • a catalyst was prepared as above, starting with Merrifield® resin (200 to 400, 2 percent crosslinked, gel), treated with butanesultone. The product was identified as PMBSA-MER.
  • a catalyst was prepared as above, starting with bromomethylated AmberliteTM XE-305 macroporous resin (4 percent crosslinked, 20 to 50 mesh, 3.7 meq Br/g).
  • a catalyst was prepared as above, starting with chloromethylated AmberliteTM macroporous resin (4 percent crosslinked, 20 to 50 mesh, 4.3 meq Cl/g).
  • Catalyst was prepared above, by treating Merrifield® resin (2 percent crosslinked, 200 to 400 mesh, 4.3 meq Cl/g) with lithiated 1,3- propanesultone, which can be prepared in accordance with T. Durst et al., "A new route to 5- and 6-membered ring sultones", Can. J. Chem., Volume 48 (1970), Pages 845-851.
  • the reaction mixture consisted of a homogeneous liquid phase plus a separate heterogeneous polymer catalyst phase. The mixture was heated to 50°C for 18 hours. Monitoring of the reaction by HPLC showed approximately 17 percent conversion after 4 hours and 73 percent conversion after 18 hours at 50°C. HPLC analysis (analytical method 2) and gave the following relative area percent analysis for the products after 18 hours of reaction (73 percent conversion):
  • the reaction mixture from Example 10A was cooled to 40°C and the mixture was centrifuged. The upper liquid layer was decanted and additional warm (40 to 45°C) 20.8:1 mole ratio phenol/fluorenone solution (approximately 3 to 4 times the catalyst volume) was added. The mixture was stirred, centrifuged, and the warmed liquid layer was decanted. This wash procedure was repeated for a total of three washes, then the required amount of phenol /fluorenone reactant mixture was added and the reaction began.
  • Example 11A To the 4-dram vial containing the mercaptosulfonic acid polymer recovered (as described above) from Example 11A was added 4.33 grams of a 20.8:1 mole ratio mixture of phenol to fluorenone. The mixture was heated to 50°C for 4 hours. Monitoring of the reaction by HPLC showed
  • the amount of MPSA catalyst were related to the amount of 2,4- isomeric product formed.
  • High 2,4/4,4 ratios at high concentrations of MPSA were probably related to a shift toward an acid-catalyzed reaction to produce relatively higher amounts of 2,4-isomer.
  • Phenol was weighed and charged into the reaction vessel. Fluorenone was weighed and charged to the reaction vessel, followed by a weighed quantity of MPSA catalyst.
  • Reactions were done in stirred batch isothermal reactors (reactor design 2). To the reactor was charged a mixture of 83.2 percent by weight of phenol, 0.09 percent by weight of fluorenone, 13.2 percent by weight of BHPF, containing 0.92 percent by weight of 2,4-isomer and 0.68 percent by weight of 2:3 adduct. Various amounts of MPSA were charged to the reactor. The resulting mixtures were stirred and heated. The
  • compositions in the reactor at various times were determined by analytical method 4.
  • compositions of other reaction mixtures were given in Table V.
  • a synthetic reaction mixture (105.5 g: 63 percent by weight, 66.5 g of phenol; 20 percent by weight, 21.1 g of 4,4-BHPF and 17 percent by weight, 18 g of water) was placed in a 500-mL round-bottom three-neck flask equipped with a heating mantle/Variac, thermometer, stirring bar and distillation arm.
  • a "Therm-O-Watch” was used to control temperature of the liquid in the flask.
  • a separate thermometer was placed in the distillation tower to monitor temperature in the vapor phase. The mixture was stirred and heated at ambient pressure up to a temperature of 160°C, during which time distillation of phenol and water occurred. Analysis of the reaction mixture indicates the phenol:BHPF mass ratio was 1:1.
  • reaction mixture while still hot, was slowly added to 176 g of BHPF-saturated methylene chloride and the resulting mixture was slowly swirled to produce a homogeneous solution, clear and yellow in color. The mixture was allowed to cool to room temperature which causes crystallization to occur.
  • the rod-like crystals present in the magma were analyzed by
  • the crystal magma was filtered on a medium porosity glass frit, using a vacuum produced by water jet.
  • the filter cake was displacement-washed with 79 g of BHPF-saturated methylene chloride and then 72 g of hot (90°C) water. After drying at 65°C in air overnight, 12.9 g of white product was recovered. Isolated yield was 61 percent and HPLC purity was 99.8 percent.
  • Synthetic reaction mixture (105.5 g as in Example 17A) was combined with 100 mL of a 2 percent by weight aqueous solution of sodium
  • the mixture was stirred and heated at a pressure of 80 to 100 mm Hg, up to a temperature of 160°C, during which time distillation of phenol and water occurred.
  • BHPF-saturated phenol 100 g was then added to the reaction mixture and the temperature of the mixture was controlled at 65°C. Crystallization began within 1 hour.
  • the slurry was stirred overnight, after which the rod-like crystals present in the magma were analyzed by microscope before filtration. Approximately 30 percent of the crystals viewed have a length greater than 100 microns and a diameter between 10 and 30 microns.
  • the crystal magma was filtered on a medium porosity glass frit using a vacuum produced by a water jet. The brown filter cake was
  • Synthetic reaction mixture (149 g: 17.5 percent by weight, 24 g of
  • the resulting mixture was added while still hot, to 121 g of BHPF-saturated toluene.
  • the resulting homogeneous solution was allowed to cool to room temperature, during which crystallization occurred.
  • the resulting rod-like crystals present in the magma were analyzed by microscope prior to filtration. Approximately 20 percent of the crystals viewed had a length greater than 100 microns and a diameter between 10 and 50 microns.
  • the crystal magma was filtered on a medium porosity glass frit using a vacuum produced by a water jet.
  • the pink filter cake was treated similarly to other examples. After drying at 65°C in air overnight, 18.5 g of pink product were recovered. Isolated yield was 77 percent and HPLC purity was 98.1 percent.
  • Phenol and fluorenone were combined in the presence of 3-mercaptopropanesulfonic acid (MPSA) to produce a reaction mixture which, after washing to remove the acid catalyst, contained 20 weight percent of 4,4-BHPF, 64 weight percent of phenol and 16 weight percent water.
  • the reaction mixture was distilled under water jet vacuum (approximated 80 mm Hg) up to a temperature of 160°C to yield a residue, containing
  • a reaction mixture (55.8 g: 63.1 percent by weight, 35 g of phenol; 14 percent by weight of 4,4-BHPF and 23 percent by weight, 12.8 g of water) was charged to a 250-mL round bottom flask, otherwise fitted out as in Example 17A. Triisopropylbenzene (TIPB, 106.6 g) was added to the mixture in the flask, as a result of which the mixture separates into two phases, of which the yellow reaction mixture was the lower.
  • TIPB Triisopropylbenzene
  • reaction mixture (98.8 g: 61 percent by weight, 60.3 g of phenol; 19.4 percent by weight, 19.2 g of
  • Example 17F 4,4-BHPF and 19.6 percent by weight, 19.4 g of water was charged to an apparatus, described in Example 17F.
  • a collection flask was attached to the distillation arm and connected to a vacuum source (a water jet). The temperature set point was adjusted to 100°C and heating began.
  • the pot residue at 110°C was added to 172 g of fresh drum-grade methylene chloride in a bottle. The addition was done slowly in order to avoid excessive flashing or boiling of the methylene chloride. The resulting mixture more or less separated into two layers, of which the upper layer was richer in the phenol:BHPF component. The mixture was swirled and became homogeneous. The bottle was sealed and placed in a pan of cold water (approximately 10°C).
  • the crystallizer bottle was rinsed with 29.7 g of fresh methylene chloride (not all solids dissolve), the resulting mixture being used to displacement wash the filter cake, which improved slightly in color.
  • the filter cake was slurry washed with 49.4 g of fresh methylene chloride and the resulting slurry was filtered under vacuum. The color of the filter cake was unchanged.
  • the filter cake was displacement washed with 33 g of cold water, without a change in the color of the cake.
  • the filter cake was slurry-washed with 40 g of boiling water, without a change in the color of the cake.
  • the cake was dried in air under vacuum for approximately 2 hours, transferred to a watch glass and dried in an oven overnight at 65°C. The cake was slightly yellow.
  • the mixture was stripped at 140°C under nitrogen at ⁇ 80 mm Hg to give 4.2 g of white solid.
  • Phenol was distilled from the reaction mixtures to produce mixtures, containing less than 50:50 phenol:BHPF by weight.
  • the resulting materials can be washed with methylene chloride.
  • the products were inconsistent in color and contain small crystals, usually of the size of 10 to 70 microns.
  • the BHPF-phenol mixture was kept at 90°C and stirred prior to addition of methylene chloride or other crystallizing solvent.
  • BHPF was crystallized at room temperature under a nitrogen pad. A batch crystallizer was cooled to 5 to 10°C for several hours during which BHPF crystallizes. Solid BHPF was separated from the resulting slurry using a batch pressure filter or basket filter. Optionally, a pressure filter can be used. Methylene chloride or other solvent can be recycled to the process.
  • BHPF from Sloss (Birmingham, Alabama): The sample evaluated was a dry solid, from lot number 9307-03.
  • Corrosion tests were performed using a representative reaction mixture for the condensation of phenol with fluorenone using various catalysts. The tests were done using metal specimens 3.81 cm in length, 1.59 cm in width, 0.32 cm thick, and having a 0.64 cm hole centered in one end. The specimens were isolated from each other and the mounting rack using polytetrafluoroethylene shoulder washers. The specimens were exposed to both the liquid and vapor phases of each test cell. The contents of the cells were stirred continuously and were maintained at the selected temperature using YSI temperature controllers and GLASCOLTM heating mantles. The tests were run under a nitrogen pad. The chloride content of the test mixtures was ⁇ 500 ppm. The tests were run at 65°C for 13 days (312 hours). Compositions tested and results are presented in Table VIII.
  • Example 18A A mixture containing 94.35 percent by weight of phenol, 4.15 percent by weight of acetone and 1.50 percent of MPSA was evaluated as in Example 18A.
  • the corrosion rates in both the liquid and vapor phases was ⁇ 0.00254 cm/year. The corrosion was uniform. The rate of corrosion was below that for conventional reaction mixtures for making bisphenol A.
  • Bisphenol A was prepared from 14:1 phenol:acetone (mole ratio) at 50°
  • the PMBSA catalyst of Example 9B at a level of 6 percent by weight, gives 75 percent conversion after 5 hours.
  • the product contained 99.0:1.0 of 4,4:2,4-isomers (area percent).
  • the PMBSA was recovered and reused in a second cycle.
  • the conversion after 4 hours was 60 percent.
  • the product contained 99.1:0.9 of 4,4:2,4- isomers (area percent).
  • DOWEXTM 50WX4 from The Dow Chemical Company, (35 percent by weight as dry mass), promoted with 25 percent by weight of 2,2- dimethylthiazolidine, was used in a similar experiment. The conversion after 4 hours was 43 percent and the product contained 98.0:2.0 (as area percent) of 4,4:2.4-isomers.
  • the reactor comprised a vertical tube.
  • the bottom part of the tube was filled with glass beads, on top of which was provided a bed of PMBSA catalyst resin.
  • the remainder of the tube was filled with glass beads.
  • the tube was fitted with a pressure gauge, a pressure regulator, heating means external to the catalyst bed and feed means at the bottom of the tubular reactor for introducing the phenol and fluorenone reactants.
  • the feed was prepared in a container, provided with a nitrogen stream and heated externally by a fluid.
  • a valve was intermediate the feed preparation container and a pump for introducing the feed into the bottom of the reactor.
  • a relief valve was placed between the pump and the reactor.
  • the feed was introduced into the reactor at a predetermined rate and passes upwardly through the lower bed of glass beads, which functioned as a pre-heater, through the catalyst bed and the upper bed of glass beads, whereupon the product was removed from the top part of the reactor for analysis or further processing.
  • Catalyst was removed from the product by first melting the crystals and washing the resulting oil with water, and then extracting the organic layer with water, which reduces the acid concentration below 100 ppm after three equilibrium stages. The remaining catalyst was removed using an anion exchange bed ( ⁇ 50 ppm, the limit of detection). Bisphenol A, isolated by a single crystallization step, was of higher purity than products, generally obtained using two
  • the polymer containing 28 percent of alkylmercaptan functionality gives 75 percent conversion after 5 hours.
  • the product distribution was 96.8:3.2 of 4,4:2,4-isomers (area percent).
  • the reaction mixture (slurry) was allowed to slowly warm to room temperature in the cooling bath (over approximately 3 to 4 hours) and was allowed to stir at room temperature overnight.
  • the white precipitate which has formed in the reaction mixture during the n-butyllithium addition period remains insoluble as the mixture reaches room temperature.
  • the white (insoluble) solid was removed by vacuum filtration.
  • the polymer can be washed with water or water can be added to the THF/polymer slurry prior to filtration. Addition of water sometxmes results in increasing the time required for filtration.
  • the solid was slurry-washed with THF, then with methanol and finally with methylene chloride (causing some
  • the lithium thioacetate reagent was formed in situ by slowly adding solid lithium carbonate to a mixture of the sultone polymer and thiolacetic acid in a 3:2 volume ratio of nitrogen-saturated THF/water.
  • the polymer slurry was heated to 45 to 50°C, and slow, dropwise addition of the 5-bromo-1-pentene solution was begun.
  • the 5-bromo-1-pentene solution was added slowly over approximately 3 days to the stirred polymer slurry at 50°C. After the 5-bromo-1-pentene addition was complete, the reaction was allowed to stir an additional 1 day at 50°C.
  • the polymer slurry was very dark-colored throughout the addition period.
  • the polymer slurry (very dark red-brown) was cooled to room temperature and filtered. The beads were washed extensively with dichloromethane (still dark colored beads) and then were washed
  • the liquid layer was then removed from the polymer using a small-bore cannula.
  • the beads were then washed several times with dichloromethane. (The liquid layer and dichloromethane washes were slowly and carefully quenched in a separate vessel using ice.)
  • the polymer beads were then carefully transferred to a fritted-glass funnel, and the polymer beads were quenched by slow, careful addition of ice water.
  • aqueous polymer bead slurry from above was added sodium bicarbonate (60.5 g, 0.720 mol). The mixture was evacuated and back-filled with nitrogen three times. Thiolacetic acid (41.1 g, 0.540 mol) was added slowly dropwise over 1 hours 10 minutes to the polymer slurry at room temperature. The mixture was slowly warmed to 80°C over several hours and allowed to react at 80°C for 3 days. After cooling to 40°C, the supernatant solution was removed using a small-bore cannula. The polymer was washed several times with water, giving slightly off-white colored polymer beads. Concentrated hydrochloric acid (250 mL) was added to the polymer and the slurry was heated to 50°C for 3 hours.
  • the hydrochloric acid solution was removed using a small-bore cannula.
  • the polymer beads were then washed several times with diluted hydrochloric acid and the beads were transferred to a fritted-glass funnel.
  • the beads were again washed repeatedly with diluted hydrochloric acid followed by extensive washings with water, giving slightly off-white water-swollen beads. (The water-swollen volume of the polymer beads was approximately 900 mL.)
  • the beads were washed with methanol (methanol-swollen volume approximately 600 mL) and finally with dichloromethane. After drying in a vacuum oven at 60°C overnight, the dark-colored beads had a dry volume of approximately 200 mL. This product was identified as XEMSA-5C.
  • Catalyst was prepared as above, starting with macroporous
  • polystyrene (AmberliteTM XE-305) and 11-bromo-1-undecene.
  • Example 22A-C To a 4-dram vial equipped with a stirring bar was added 4.32 g of a 20.8:1 molar ratio mixture of phenol to fluorenone and 0.26 g (6 percent by weight of the reactant solution) of the mercaptosulfonic acid polymer (XEMSA-5C) prepared as described in Example 22A-C.
  • the reaction mixture consists of a homogeneous liquid phase plus a separate heterogeneous polymer catalyst phase.
  • the mixture was heated to 50°C for 5 hours.
  • the reaction was monitored throughout the reaction period by collecting samples and analyzing by HPLC.
  • the 9-fluorenone was found to be 36 percent consumed within 2 hours and 76 percent consumed within 5 hours.
  • HPLC analysis (analytical method 3) gives the following relative area percent analysis for the products after 5 hours of reaction (76 percent conversion): 9,9-bis-(4-hydroxyphenyl)fluorene (97.45 area percent) : 9-(2-hydroxyphenyl)-9-(4-hydroxyphenyl)fluorene (2.17 area percent) : adduct containing two fluorene units and three phenolic units (0.39 area percent).
  • heterogeneous polymer catalyst phase The mixture was heated to 50°C for 5 hours. The reaction was monitored throughout the reaction period by collecting samples and analyzing by HPLC. The 9-fluorenone was found to be 44 percent consumed within 2 hours and 75 percent consumed within 5 hours. HPLC analysis (analytical method 3) gives the following relative area percent analysis for the products after 5 hours of reaction (75 percent conversion): 9,9-bis-(4-hydroxyphenyl)fluorene (96.10 area percent): 9-(2-hydroxyphenyl)-9-(4-hydroxyphenyl)fluorene (3.52 area percent): adduct containing two fluorene units and three phenolic units (0.38 area percent).
  • reaction mixture consists of a homogeneous liquid phase plus a separate heterogeneous polymeric catalyst phase.
  • the mixture was heated at 50°C for 2 hours.
  • the reaction was monitored by collecting samples, which were analyzed by HPLC.
  • the 9-fluorenone was 99.5 percent consumed within 2 hours.
  • the product after 2 hours contained 96.83 area percent of 9,9-bis-(4-hydroxyphenyl)fluorene, 2.44 area percent of 9-(2-hydroxyphenyl)-9-(4-hydroxyphenyl)fluorene and 0.72 area percent of an adduct containing two fluorene units and three phenolic units by HPLC (analytical method 3).
  • Example 21B To a 4-dram vial equipped with a stirring bar was added 4.32 g of a 20.8:1 molar ratio mixture of phenol:fluorenone and 0.26 g (6 percent by weight of the reactant solution) of the polymer of Example 21B (PMBSA-SU).
  • the reaction mixture consisted of a homogeneous liquid phase plus a separate heterogeneous polymer catalyst phase. The mixture was heated to 50°C for 5 hours. The progress of the reaction was followed by HPLC. At the end of 2 hours, 67 percent of the fluorenone was consumed, and 85 percent at the end of 5 hours.
  • the reaction mixture contained 97.09 area percent of 9,9-bis-(4-hydroxyphenyl)fluorene, 2.25 area percent of 9-(2-hydroxyphenyl)-9-(4-hydroxyphenyl)fluorene and 0.66 area percent of an adduct containing two fluorene units and three phenolic units by HPLC analysis.
  • the reaction mixture (about 97 percent selectivity to 4,4-BHPF, little unreacted fluorenone) was split into two parts.
  • the first fraction (53.3 g) was filtered.
  • the filter cake was washed with methylene chloride (49 g) and then with hot water (55 g).
  • the recovery was 6.4 g (first crop) and 0.6 g (second crop) of white crystals, corresponding to 99 percent purity 4,4-BHPF (33 percent recovery).
  • Phenol (30.0 g, 0.32 mole), 9-fluorenone (16.41 g, 0.0911 mole) and
  • the crystalline solid was removed by filtration and the filter cake was washed with methylene chloride. A second crop of crystals was recovered from the mother liquors. The yield was 0.86 g (first crop), 8.66 g
  • the reaction was carried out in a 2-L jacketed baffled resin pot, equipped with a condenser and nitrogen purge. Isothermal temperature control was provided by a fluid material, circulated through the reactor jacket. Stirring was provided by a Lightnin Labmaster® TS2510 stirrer, equipped with an A-310 impeller.
  • the washed adduct contained 57.7 percent by weight of 4,4-bisphenol, 160 ppm of 2,4-bisphenol, 200 ppm of trisphenol, 2270 ppm of other trace bisphenolic impurities and 1170 ppm of MPSA, the balance being phenol.
  • the mother liquor contained 8.44 percent by weight of 4,4-bisphenol, 0.26 percent by weight of 2,4-bisphenol, 0.13 percent by weight of trisphenol 0.62 percent by weight of other bisphenolic impurities, 0.81 percent by weight of acetone, 2.95 percent by weight of water and 2.78 percent by weight of MPSA, the balance being phenol.
  • the mother liquor from (A) was charged to a rotary evaporator with make-up phenol (181 g) .
  • the evaporator was heated at 50°C for 30 minutes, at the end of which the conversion of acetone was 90 percent.
  • Pressure was reduced to 10 mm Hg absolute for 30 minutes, at the end of which the mixture contained 1.4 percent by weight of water.
  • the acetone content was below the detection limit.
  • the dried mother liquor was returned to the reactor, along with make-up phenol, acetone, water and MPSA to give a mixture containing 92.0 percent by weight of phenol, 4.0 percent by weight of acetone, 1.8 percent by weight of water and 2.2 percent by weight of MPSA.
  • the total mass corresponds to (A) minus the weight of samples removed.
  • the mixture was stirred and heated at 35°C for 3 hours. Crystallization of BPA was observed after the initial 30 minutes of heating. At the end of 3 hours heating, acetone conversion was 80 percent.
  • the reaction mixture was processed as in (A). Recycling of the mother liquors was repeated for 12 cycles. Results are given in Tables XIV and XV.
  • Crystalline product removed from the reaction mixture by filtration, constitutes 15 percent of the mixture.
  • the crystals a 1:1 adduct of BPA:phenol, were washed with phenol.
  • the washed crystals contain 51.8 percent by weight of the 4,4-isomer, 60 ppm of 2,4-isomer, ⁇ 20 ppm of trisphenol, 690 ppm of other trace bisphenols and 840 ppm of MPSA, the remainder being phenol.
  • the mother liquors contained 6.73 percent by weight of 4,4-isomer, 0.15 percent by weight of 2,4-isomer, 0.08 percent by weight of trisphenol, 0.76 percent by weight of other bisphenols, 5.71 percent by weight of acetone, 4.97 percent by weight of water and 2.66 percent by weight of MPSA, the remainder being phenol.
  • a 15.00 g sample of 200 to 400 mesh chloromethylated polystyrene/2 percent divinylbenzene copolymer beaded (approximately 4.3 mmol Cl/g resin, approximately 64.5 mmole Cl) known in the art as a Merrifield® resin (available from Fluka Chemie AG) was added to a round bottom glass flask (reactor) under a pad of plant nitrogen with a sodium hydroxide scrubber attached (to trap evolved HCl).
  • (3-Bromopropyl)benzene (102.7 g, 78.4 mL, 8.0 equivalents) was added to the dry resin beads.
  • nitrobenzene 50 mL was added, and the beads were slowly stirred at room temperature to allow for swelling of the beads.
  • the reactor was cooled to 0°C in an ice water bath.
  • a 20 mL sample of 1.0 M aluminum chloride in nitrobenzene available from Aldrich Chemical Co. was slowly added via syringe to the cold polymer slurry with rapid stirring over approximately 10 minutes. The mixture turns dark red as soon as the aluminum chloride solution was added and exotherms to approximately 4°C within the first 15 minutes of reaction with HCl being evolved from the solution.
  • the polymer beads from Example 27A (23.30 g, estimated 161.3 mmole of phenyl groups) were added to a glass reactor with addition funnel and NaOH scrubber attached.
  • Dichloromethane (100 mL) was added to the flask and the beads were allowed to swell (rapid swelling was observed).
  • the slurry was cooled to 0°C in an ice water bath.
  • Chlorosulfonic acid 37.6 g, 21.4 mL, 320 mmole, approximately 2.0 equivalents per equivalent phenyl groups was slowly added dropwise over approximately 2 hours to the polymer slurry at 0°C. The mixture was allowed to slowly warm to room temperature overnight in the water bath.
  • the mixture was slowly poured onto ice to quench the excess chlorosulfonic acid, then the beads were separated using a glass-fritted funnel with vacuum filtration. The beads were then washed extensively with water. Water was added to make a slurry, then solid sodium bicarbonate was slowly added in small portions over approximately 2 hours until no more bubbling was observed (all active acid sites neutralized). The mixture was allowed to stand 3 days in the aqueous sodium bicarbonate solution (some additional bead swelling was observed over this time period). The beads were washed with water and transferred to a glass reactor with 100 mL of water. The beads were then heated to 70-80°C over 2 hours to ensure hydrolysis of any residual sulfonyl chloride groups.
  • Example 27B The aqueous polymer slurry from Example 27B was cooled to room temperature. Sodium bicarbonate was slowly added until the slurry was neutral (no bubbling observed), then additional sodium bicarbonate (27.1 g, 323 mmol) was added to the aqueous bead slurry. Thiolacetic acid (24.6 g, 23.1 mL, 323 mmol) was added to an addition funnel. The reactor was evacuated and refilled with nitrogen several times to minimize the air content. The thiolacetic acid was slowly added over approximately 15 to 20 minutes to the aqueous bead slurry with rapid stirring. The addition rate was adjusted to control the effervescent evolution of carbon dioxide which was formed in the neutralization process.
  • the mixture was heated to 70°C and was allowed to react overnight with minimal stirring. The mixture was then cooled to room temperature and the beads were collected by filtration using a fritted-glass funnel. The beads were washed extensively with water, then with dichloromethane, and then washed again with water. The beads were transferred back to the glass reactor, then concentrated (12 molar) hydrochloric acid (100 mL) was added. The mixture was heated with mild stirring to 50°C for 4 to 5 hours, then was cooled to room temperature. Deionized water (100 mL) was added and the beads were again collected by filtration using a fritted-glass funnel.
  • the beads were washed with water, then were washed extensively (approximately 500 mL) with dilute (approximately 3 molar) aqueous hydrochloric acid. The beads were then washed again with deionized water and finally were washed with methanol to displace the water and shrink the polymer beads. The beads were dried overnight in a vacuum oven at 70 °C (dry mass 34.17 g).
  • the final polymer catalyst was designated as DPMSA-MER3C
  • Another mercaptosulfonic acid polymer was prepared using the procedure of steps A to C of Example 27, except using a chloromethylated polystyrene resin (2 percent divinylbenzene, 200 to 400 mesh,
  • Another mercaptosulfonic acid polymer was prepared using the procedure of steps A to C of Example 27, except using a chloromethylated 1.5 percent crosslinked polystyrene gel-resin (-30+70 mesh, approximately 4.3 mmol Cl/g resin) as the polymeric support and (3-bromopropyl) benzene in the alkylation step of the reaction.
  • This polymer was identified as DPMSA-1.5X3C.
  • F Preparation of Two-Carbon DPMSA Polymer From Chloromethylated Gel-Resin Beads
  • Another mercaptosulfonic acid polymer was prepared using the procedure of steps A to C of Example 27, except using a chloromethylated 1.5 percent crosslinked polystyrene gel-resin (-30+70 mesh, approximately 4.3 mmol Cl/g resin) as the polymeric support and (2-bromoethyl) benzene in the alkylation step of the reaction.
  • This polymer was identified as DPMSA-1.5X2C.
  • Another mercaptosulfonic acid polymer was using the procedure of steps A to C of Example 27, except using a chloromethylated 6 percent crosslinked macroporous polystyrene resin (approximately 30 to 70 mesh, approximately 4.3 mmol Cl/g resin) as the polymeric support and (3-bromopropyl)benzene in the alkylation step of the reaction.
  • This polymer was identified as DPMSA-6/42-3C.
  • Another mercaptosulfonic acid polymer was using the procedure of steps A to C of Example 27, except using a chloromethylated 6.5 percent crosslinked uniform particle size polystyrene gel-resin (380 micron, approximately 4.3 mmol Cl/g resin) as the polymeric support and
  • a fixed bed downflow reactor having a volume of 10-mL, was constructed from a vertical tube, filled with catalyst. External to the catalyst bed was a preheater area, packed with glass wool.
  • Ancillary equipment includes a pressure regulator, relief valve, pump and heater for the feed. The feed was heated by heating fluid, circulated through the feed pot, and was kept under a nitrogen pad.
  • the feed was phenol (99.9 percent) and fluorenone (about 99 percent) in a 21:1 molar ratio.
  • the heating fluid, heating tape and reactor were turned on.
  • the selected catalyst was slurried in phenol at about 45°C.
  • Catalyst-phenol mixture was pigetted into the reactor, at the bottom of which a plug of glass wool/glass beads was placed to prevent catalyst from leaving the reactor.
  • the phenol:fluorenone was added to the feed pot at 55°C. The pressure was adjusted to about 0.34 bars.
  • Phenol:fluorenone feed was introduced into the reactor and the composition of the effluent from the reactor was followed by HPLC.
  • the reactor comprises a three-staged continuous reactor (isothermal perfectly stirred type). The reaction was run at 46°C at a 21:1 molar ratio of phenol:fluorenone (98 percent, Aldrich), the amount of MPSA being
  • the reactor comprises a vertical upflow column of stainless steel tubing, packed with resin atop a screen and glass beads.
  • the column was heated by a water jacket.
  • the progress of the reaction was followed as above by HPLC.
  • Phenol and formaldehyde were reacted to produce bisphenol F. Similar results were obtained.
  • a small portion (approximately 10-15 mL) of the sulfuric acid was added to the reaction mixture from the addition funnel and the slurry was heated to 80°C with stirring at approximately 1000 rpm. After the reaction reaches 80°C, the remaining concentrated sulfuric acid was added dropwise over 3 hours. After an addition 1 hour reaction time, the reaction was less than 50 percent complete as determined by gas chromatographic analysis. The mixture was allowed to cool and was transferred to a separatory funnel. The organic phase was separated and saved for further reaction.
  • Styrene/divinylbenzene co-polymer resin beads (10.00 g, -30+70 mesh, 1.5 percent divinylbenzene, approximately 96.0 mmole styrene repeat units) were added to a round bottom glass flask (reactor) under a pad of nitrogen with a sodium hydroxide scrubber attached (to trap evolved HCl).
  • a solution of (2-bromoethyl)benzyl chloride (mixture of aromatic ring isomers, predominately para) (10.0 g, 0.238 equivalents based upon styrene repeating units) in
  • 1,2-dichloroethane 25 mL was added to the dry resin beads. The beads were allowed to swell for approximately 5 to 10 minutes, then additional 1,2-dichloroethane (35 mL) was added to the swollen beads.
  • Anhydrous tin(IV) chloride (2.5 mL, approximately 5.57 g, approximately 21.4 mmol) was slowly added via syringe to the polymer slurry at room temperature over approximately 10 minutes with rapid stirring. The mixture turned light yellow when the tin(IV) chloride was added. The mixture was slowly warmed (in 5°C increments) to 40°C over approximately 30 minutes and was allowed to react at 40°C for 1 hour.
  • the polymer beads from Exeunpl ⁇ 32B (13.89 g, estimated 116 mmole of phenyl groups) were added to a glass reactor with addition funnel and NaOH scrubber attached.
  • Dichloromethane (75 mL) was added to the flask and the beads were allowed to swell (rapid swelling was observed).
  • the slurry was cooled to approximately 3 to 5 °C in an ice water bath.
  • Chlorosulfonic acid (11.7 mL, approximately 20.5 g, approximately 176 mmol, approximately 1.5 equivalents per equivalent of phenyl groups) was slowly added dropwise over approximately 30 minutes to the cold polymer slurry with stirring. The mixture was allowed to react at approximately 3 to 5°C in an ice water bath for 1 hour.
  • the mixture was removed from the ice bath and allowed to warm to room temperature over 2 hours 45 minutes. At this time, the polymer slurry was again cooled to 3-5°C in an ice water bath, and water was slowly added with rapid stirring to quench the excess chlorosulfonic acid.
  • the beads were separated using a glass-fritted funnel with vacuum filtration. The beads were then washed extensively with water. Water was added to make a slurry, then solid sodium bicarbonate was slowly added in small portions with stirring until no more bubbling was observed (all active acid sites were neutralized). The beads were washed with water and transferred back to the glass reactor with 100 mL of water. The beads were then heated to 60 to 70°C over 2 hours to ensure hydrolysis of any residual sulfonyl chloride groups.
  • the aqueous polymer slurry from Example 32C (estimated approximately 20 mmole Br) was cooled to room temperature. Sodium bicarbonate was slowly added until the slurry was neutral (no bubbling observed), then additional sodium bicarbonate (5.30 g, 63.0 mmol, approximately 3 equivalents relative to estimated bromine content in beads) was added to the aqueous bead slurry. Thiolacetic acid (4.5 mL, approximately 4.8 g, approximately 63 mmol, approximately 3 equivalents relative to estimated bromine content in beads) was added to an addition funnel. The reactor was evacuated and refilled with nitrogen several times to minimize the air content.
  • the thiolacetic acid was slowly added over approximately 10-15 minutes to the aqueous bead slurry at room temperature with rapid stirring.
  • the thiolacetic acid addition rate was adjusted to control the effervescent evolution of carbon dioxide which was formed in the neutralization process.
  • the mixture was heated to 70°C and was allowed to react overnight with minimal stirring.
  • the mixture was then cooled to room temperature and the beads were collected by filtration using a fritted-glass funnel.
  • the beads were washed extensively with water, then with dichloromethane (optional), and then washed again with water.
  • the beads were transferred back to the glass reactor, then concentrated (12 molar) hydrochloric acid (100 mL) was added.
  • the mixture was heated with mild stirring to 50°C for 2-3 hours, then was cooled to room temperature.
  • Deionized water 100 mL was added and the beads were again collected by filtration using a fritted-glass funnel.
  • the beads were washed with water, then were washed extensively (approximately 500 mL) with dilute (approximately 3 molar) aqueous hydrochloric acid.
  • the beads were then washed again with deionized water and were transferred to a storage bottle without any additional drying.
  • the final polymer catalyst has a titrated water-wet (water swollen) acid capacity of 0.80 milliequivalent/mL catalyst.
  • the final polymer catalyst was designated as DPMSAA-0.25-1.5X2C
  • the mass yield of polymer obtained from the alkylation reaction corresponds to a 83 percent yield in the alkylation reaction and a degree of functionality of 0.59.
  • the final polymer catalyst has a titrated water-wet (water swollen) acid capacity of 0.94 milliequivalent/mL catalyst.
  • the final polymer catalyst was designated as DPMSAA-0.75-1.5X2C.
  • the mass yield of polymer obtained from the alkylation reaction corresponded to a 81 percent yield in the alkylation reaction and a degree of functionality of 0.35.
  • the final polymer catalyst has a titrated water-wet (water swollen) acid capacity of 0.85 milliequivalent/mL catalyst.
  • the final polymer catalyst was designated as DPMSAA-0.45-1.5X2C.
  • Another mercaptosulfonic acid polymer was prepared from 1.5 percent crosslinked styrene/divinylbenzene co-polymer beads (-30+70 mesh) using the procedure described in steps B-D of Example 32, except using 0.42 equivalents of (2-bromoethyl)benzyl chloride and 0.30 equivalents of benzyl chloride in the alkylation reaction. Chlorosulfonic acid (2.0 equivalents relative to the calculated total equivalents of phenyl groups in the polymer) was used in the sulfonation reaction. Thiolacetic acid and sodium bicarbonate (3.0 equivalents of each reagent relative to the calculated amount of bromine in the polymer) were used in the thiolation reaction.
  • the final polymer catalyst has a titrated water-wet (water swollen) acid capacity of 0.94 milliequivalent/mL catalyst. The final polymer catalyst was designated as DPMSAA-0.45/0.30-1.5X2C.
  • Another mercaptosulfonic acid polymer was prepared from 1.5 percent crosslinked styrene/divinylbenzene co-polymer beads (-30+70 mesh) using the procedure of steps B-D of Example 32, except using 0.423 equivalents of (2-bromoethyl)benzyl chloride in the alkylation reaction and directly carrying the polymer slurry obtained from the alkylation reaction directly on to the sulfonation reaction without any quenching, isolation, or washing steps after the alkylation reaction. Chlorosulfonic acid (1.25 equivalents relative to the total equivalents of phenyl groups present in all reactants) was added directly to the polymer slurry after the alkylation reaction was complete.
  • Example 32 Workup and subsequent isolation of the product after sulfonation was as in Example 32, except that more extensive washing was required to remove soluble reaction by-products from the polymer slurry.
  • Thiolacetic acid and sodium bicarbonate (3.0 equivalents of each reagent relative to the estimated maximum amount of bromine present in the polymer) were used in the thiolation reaction.
  • the final polymer catalyst has a titrated water-wet (water swollen) acid capacity of 0.78 milliequivalent/mL catalyst.
  • the final polymer catalyst was designated as DPMSAA-0.45NW-1.5X2C.
  • Another mercaptosulfonic acid polymer was prepared from 1.5 percent crosslinked styrene/divinylbenzene co-polymer beads (-30+70 mesh) using a variation of the procedure described in Example 32.
  • the alkylation and sulfonation reactions were performed in one step utilizing chlorosulfonic acid as the alkylation catalyst and sulfonation reagent.
  • Styrene/divinylbenzene co-polymer resin beads (10.00 g, -30+70 mesh, 1.5 percent divinylbenzene, approximately 96.0 mmol styrene repeat units) were added to a round bottom glass flask (reactor) under a pad of plant nitrogen with a sodium hydroxide scrubber attached (to trap evolved HCl).
  • a solution of (2-bromoethyl)benzyl chloride (mixture of aromatic ring isomers, predominately para) (5.32 g, 0.238 equivalents based upon styrene repeat units) in
  • 1,2-dichloroethane 25 mL was added to the dry resin beads.
  • the beads were allowed to swell for approximately 5 to 10 minutes, then additional
  • 1,2-dichloroethane 35 mL was added to the swollen beads.
  • the slurry was cooled 2 to 3°C in an ice bath, then chlorosulfonic acid (12.0 mL, approximately 21.0 g, 1.5 equivalents based upon total equivalents of phenyl groups in the mixture) was added slowly dropwise over approximately 1 hour 45 minutes.
  • the mixture was allowed to stir an additional 1 hour at 3 to 4°C, then was removed to room temperature and allowed to react an additional 1.5 hours.
  • the mixture was then cooled in an ice water bath and water was slowly added to quench the excess chlorosulfonic acid.
  • Example 32 Thereafter the beads were isolated according to the procedure described in part C of Example 32. Likewise, the thiolation reaction was as in part D of Example 32 using thiolacetic acid and sodium bicarbonate (3.0 equivalents of each reagent relative to the estimated maximum amount of bromine in the polymer).
  • the final polymer catalyst has a titrated water-wet (water swollen) acid capacity of 0.94 milliequivalent/mL catalyst.
  • the final polymer catalyst was designated as DPMSAA-2S-0.25-1.5X2C.
  • the final polymer catalyst has a titrated water-wet (water swollen) acid capacity of 1.75 milliequivalent/mL catalyst.
  • the final polymer catalyst was designated as DPMSAA-0.45-6.5X2C.
  • Another mercaptosulfonic acid polymer was prepared from 1.8 percent crosslinked styrene/divinylbenzene copolymer beads (-25+40 mesh) using the procedure described in steps B through D of Example 32, except using 0.25 equivalents of (2-bromoethyl)benzyl chloride in the alkylation reaction.
  • Chlorosulfonic acid (1.5 equivalents relative to the calculated total equivalents of phenyl groups in the polymer) was used in the sulfonation reaction.
  • Thiolacetic acid and sodium bicarbonate (3.0 equivalents of each reagent relative to the calculated amount of bromine in the polymer) were used in the thiolation reaction.
  • the mass yield of polymer obtained from the alkylation reaction corresponds to an 86 percent yield in the alkylation reaction and a degree of functionality of 0.22.
  • the final polymer catalyst had a titrated water-wet (water swollen) acid capacity of 0.85 milliequivalent/mL catalyst.
  • the final polymer catalyst was designated as DPMSAA-0.25-1.8X2C.
  • Another mercaptosulfonic acid polymer was prepared from 1.8 percent crosslinked styrene/divinylbenzene co-polymer beads (-25+40 mesh) using the procedure described in steps B to D of Example 32, except using 0.10 equivalents of (2-bromoethyl)benzyl chloride in the alkylation reaction. Chlorosulfonic acid (1.5 equivalents relative to the calculated total equivalents of phenyl groups in the polymer) was used in the sulfonation reaction. Thiolacetic acid and sodium bicarbonate (3.0 equivalents of each reagent relative to the calculated amount of bromine in the polymer) were used in the thiolation reaction.
  • the final polymer catalyst has a titrated water-wet (water swollen) acid capacity of 0.81 milliequivalent/mL catalyst. The final polymer catalyst was designated as DPMSAA-0.10-1.8X2C.
  • Another mercaptosulfonic acid polymer was prepared from 1.5 percent crosslinked styrene/divinylbenzene co-polymer beads (-30+70 mesh) using a variation of the procedure described in steps B to D of Example 32, except using 0.10 equivalents of (2-bromoethyl)benzyl chloride in the alkylation reaction and sodium hydrosulfide in the thiolation reaction.
  • the final polymer catalyst has a titrated water-wet (water swollen) acid capacity of 0.82 milliequivalent/mL catalyst.
  • the final polymer catalyst was designated as DPMSAA-AT-0.10-1.5X2C.
  • Another mercaptosulfonic acid polymer was prepared from 4 percent crosslinked styrene/divinylbenzene co-polymer beads (360 micron uniform particle size spheres) using the procedure described in steps B-D of
  • Example 32 except using 0.25 equivalents of (2-bromoethyl)benzyl chloride in the alkylation reaction.
  • Chlorosulfonic acid (1.5 equivalents relative to the calculated total equivalents of phenyl groups in the polymer) was used in the sulfonation reaction.
  • Thiolacetic acid and sodium bicarbonate (3.0 equivalents of each reagent relative to the calculated amount of bromine in the polymer) were used in the thiolation reaction.
  • the mass yield of polymer obtained from the alkylation reaction corresponds to a 73 percent yield in the alkylation reaction and a degree of functionality of 0.18.
  • the final polymer catalyst was designated as DPMSAA-0.25-4X2C.
  • a three-stage up-flow reactor was constructed from three vertical stainless steel tubes with sampling ports between each section. Each reactor stage was water jacketed for temperature control with all connecting lines heat-traced to prevent reactor line plugging. Likewise the 2L reactor feed tank was jacketed so that precise control of the reactor feed can be obtained. From the feed tank, feed flows through an electrically heat-traced section of tubing for control of feed input temperature.
  • Each reactor section was packed with 10-20 mL of water-wet catalyst.
  • the reactor feed consists of a solution of 4 weight percent acetone in phenol.
  • the acetone:phenol mixture was precisely metered into the temperature controlled reactor system at a defined combination of flow rate (1.0 mL/min to 2.0 mL/min) and reactor temperature (55°C to 65°C).
  • the feed passes through the catalyst for at least 12 hours before measurements were recorded to remove water from the catalyst.
  • Product composition of the reactor effluent from each of the three stages was analyzed by HPLC while gas chromatography was used to analyze for acetone and water.
  • Table XIX The results obtained from tests of the catalysts at various times of reaction (reactor residence times) were provided in Table XIX.
  • Productivity was expressed in terms of pounds of bisphenol A produced per hour per cubic foot of water-swollen catalyst charged into the reactor. (NOTE: Unless otherwise noted, all of the catalyst results were obtained at 55°C.)

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US6872860B1 (en) 2001-09-18 2005-03-29 General Electric Company Method for producing bisphenol catalysts and bisphenols
US6891073B2 (en) 2002-02-28 2005-05-10 General Electric Company Chemical reactor system and process
US7112702B2 (en) 2002-12-12 2006-09-26 General Electric Company Process for the synthesis of bisphenol
US7132575B2 (en) 2003-07-01 2006-11-07 General Electric Company Process for the synthesis of bisphenol
WO2014031019A1 (en) 2012-08-23 2014-02-27 Instytut Cieżkiej Syntezy Organicznej "Blachownia" Method of transforming by-products in the process of synthesis of bisphenol a
US8735634B2 (en) 2011-05-02 2014-05-27 Sabic Innovative Plastics Ip B.V. Promoter catalyst system with solvent purification
US9287471B2 (en) 2012-02-29 2016-03-15 Sabic Global Technologies B.V. Polycarbonate compositions containing conversion material chemistry and having enhanced optical properties, methods of making and articles comprising the same
US9290618B2 (en) 2011-08-05 2016-03-22 Sabic Global Technologies B.V. Polycarbonate compositions having enhanced optical properties, methods of making and articles comprising the polycarbonate compositions
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US9553244B2 (en) 2013-05-16 2017-01-24 Sabic Global Technologies B.V. Branched polycarbonate compositions having conversion material chemistry and articles thereof
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US9771452B2 (en) 2012-02-29 2017-09-26 Sabic Global Technologies B.V. Plastic composition comprising a polycarbonate made from low sulfur bisphenol A, and articles made therefrom
US9821523B2 (en) 2012-10-25 2017-11-21 Sabic Global Technologies B.V. Light emitting diode devices, method of manufacture, uses thereof
WO2018116219A1 (en) * 2016-12-20 2018-06-28 Sabic Global Technologies B.V. Method for manufacturing of bisphenol a
WO2020263195A3 (en) * 2019-06-28 2021-05-06 Ptt Global Chemical Public Company Limited An isomerization process of product obtained from bisphenol preparation from a condensation reaction of ketone and phenol

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* Cited by examiner, † Cited by third party
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2923744A (en) * 1960-02-02 Preparation of bis-z
US4675458A (en) * 1984-10-27 1987-06-23 Ronm GmbH Method for making 9,9-bis-(4-hydroxyphenyl)-fluorene
US4996373A (en) * 1988-10-15 1991-02-26 Bayer Aktiengesellschaft Process for producing dihydroxydiarylalkanes
US5248838A (en) * 1990-10-30 1993-09-28 Minnesota Mining And Manufacturing Company Process for preparing bisphenol fluorene compounds
US5463140A (en) * 1994-08-31 1995-10-31 The Dow Chemical Company Process for making polyphenols from ketones or aldehydes and phenols

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2923744A (en) * 1960-02-02 Preparation of bis-z
US4675458A (en) * 1984-10-27 1987-06-23 Ronm GmbH Method for making 9,9-bis-(4-hydroxyphenyl)-fluorene
US4996373A (en) * 1988-10-15 1991-02-26 Bayer Aktiengesellschaft Process for producing dihydroxydiarylalkanes
US5248838A (en) * 1990-10-30 1993-09-28 Minnesota Mining And Manufacturing Company Process for preparing bisphenol fluorene compounds
US5463140A (en) * 1994-08-31 1995-10-31 The Dow Chemical Company Process for making polyphenols from ketones or aldehydes and phenols

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP0848693A4 *

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US6872860B1 (en) 2001-09-18 2005-03-29 General Electric Company Method for producing bisphenol catalysts and bisphenols
US6992228B2 (en) 2001-09-18 2006-01-31 General Electric Company Method for producing bisphenol catalysts and bisphenols
US6995294B2 (en) 2001-09-18 2006-02-07 General Electric Company Method for producing bisphenol catalysts and bisphenols
US6891073B2 (en) 2002-02-28 2005-05-10 General Electric Company Chemical reactor system and process
US7112702B2 (en) 2002-12-12 2006-09-26 General Electric Company Process for the synthesis of bisphenol
US7132575B2 (en) 2003-07-01 2006-11-07 General Electric Company Process for the synthesis of bisphenol
US9056821B2 (en) 2011-05-02 2015-06-16 Sabic Global Technologies B.V. Promoter catalyst system with solvent purification
US8735634B2 (en) 2011-05-02 2014-05-27 Sabic Innovative Plastics Ip B.V. Promoter catalyst system with solvent purification
US9290618B2 (en) 2011-08-05 2016-03-22 Sabic Global Technologies B.V. Polycarbonate compositions having enhanced optical properties, methods of making and articles comprising the polycarbonate compositions
US9957351B2 (en) 2011-08-05 2018-05-01 Sabic Global Technologies B.V. Polycarbonate compositions having enhanced optical properties, methods of making and articles comprising the polycarbonate compositions
US9490405B2 (en) 2012-02-03 2016-11-08 Sabic Innovative Plastics Ip B.V. Light emitting diode device and method for production thereof containing conversion material chemistry
US9711695B2 (en) 2012-02-03 2017-07-18 Sabic Global Technologies B.V. Light emitting diode device and method for production thereof containing conversion material chemistry
US9771452B2 (en) 2012-02-29 2017-09-26 Sabic Global Technologies B.V. Plastic composition comprising a polycarbonate made from low sulfur bisphenol A, and articles made therefrom
US9287471B2 (en) 2012-02-29 2016-03-15 Sabic Global Technologies B.V. Polycarbonate compositions containing conversion material chemistry and having enhanced optical properties, methods of making and articles comprising the same
US9299898B2 (en) 2012-02-29 2016-03-29 Sabic Global Technologies B.V. Polycarbonate compositions containing conversion material chemistry and having enhanced optical properties, methods of making and articles comprising the same
WO2014031019A1 (en) 2012-08-23 2014-02-27 Instytut Cieżkiej Syntezy Organicznej "Blachownia" Method of transforming by-products in the process of synthesis of bisphenol a
US9821523B2 (en) 2012-10-25 2017-11-21 Sabic Global Technologies B.V. Light emitting diode devices, method of manufacture, uses thereof
US9346949B2 (en) 2013-02-12 2016-05-24 Sabic Global Technologies B.V. High reflectance polycarbonate
US9553244B2 (en) 2013-05-16 2017-01-24 Sabic Global Technologies B.V. Branched polycarbonate compositions having conversion material chemistry and articles thereof
US9772086B2 (en) 2013-05-29 2017-09-26 Sabic Innovative Plastics Ip B.V. Illuminating devices with color stable thermoplastic light transmitting articles
WO2018116219A1 (en) * 2016-12-20 2018-06-28 Sabic Global Technologies B.V. Method for manufacturing of bisphenol a
EP3558916B1 (en) * 2016-12-20 2021-06-09 SABIC Global Technologies B.V. Method for manufacturing of bisphenol a
WO2020263195A3 (en) * 2019-06-28 2021-05-06 Ptt Global Chemical Public Company Limited An isomerization process of product obtained from bisphenol preparation from a condensation reaction of ketone and phenol
JP2022539307A (ja) * 2019-06-28 2022-09-08 ピーティーティー グローバル ケミカル パブリック カンパニー リミテッド ケトンおよびフェノールの縮合反応からのビスフェノール調製から得られる生成物の異性化プロセス

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