WO2004078345A1 - Method for producing bisphenol catalysts and bisphenols - Google Patents

Method for producing bisphenol catalysts and bisphenols Download PDF

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Publication number
WO2004078345A1
WO2004078345A1 PCT/US2003/006435 US0306435W WO2004078345A1 WO 2004078345 A1 WO2004078345 A1 WO 2004078345A1 US 0306435 W US0306435 W US 0306435W WO 2004078345 A1 WO2004078345 A1 WO 2004078345A1
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functionality
carbon atoms
group
ring
aliphatic
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PCT/US2003/006435
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French (fr)
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Jimmy Lynn Webb
James Lawrence Spivack
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General Electric Company
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Priority to AU2003219982A priority Critical patent/AU2003219982A1/en
Priority to JP2004569165A priority patent/JP2006513848A/en
Priority to EP03716269A priority patent/EP1601460A1/en
Priority to PCT/US2003/006435 priority patent/WO2004078345A1/en
Priority to CN03826406.4A priority patent/CN100551532C/en
Publication of WO2004078345A1 publication Critical patent/WO2004078345A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/62—Oxygen or sulfur atoms
    • C07D213/70—Sulfur atoms
    • 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
    • B01J31/0218—Sulfides
    • 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
    • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
    • 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
    • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
    • B01J31/0235—Nitrogen containing compounds
    • B01J31/0244—Nitrogen containing compounds with nitrogen contained as ring member in aromatic compounds or moieties, e.g. pyridine
    • 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
    • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
    • B01J31/0255—Phosphorus containing compounds
    • B01J31/0267—Phosphines or phosphonium compounds, i.e. phosphorus bonded to at least one carbon atom, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, the other atoms bonded to phosphorus being either carbon or hydrogen
    • B01J31/0268—Phosphonium compounds, i.e. phosphine with an additional hydrogen or carbon atom bonded to phosphorous so as to result in a formal positive charge on phosphorous
    • 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
    • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
    • B01J31/0271—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds also containing elements or functional groups covered by B01J31/0201 - B01J31/0231
    • 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
    • B01J31/08—Ion-exchange resins
    • B01J31/10—Ion-exchange resins sulfonated
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/28—Radicals substituted by singly-bound oxygen or sulphur atoms
    • C07D213/32—Sulfur atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/66—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D233/84—Sulfur atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D235/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings
    • C07D235/02—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings condensed with carbocyclic rings or ring systems
    • C07D235/04—Benzimidazoles; Hydrogenated benzimidazoles
    • C07D235/24—Benzimidazoles; Hydrogenated benzimidazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 2
    • C07D235/26—Oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D235/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings
    • C07D235/02—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings condensed with carbocyclic rings or ring systems
    • C07D235/04—Benzimidazoles; Hydrogenated benzimidazoles
    • C07D235/24—Benzimidazoles; Hydrogenated benzimidazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 2
    • C07D235/28—Sulfur atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
    • C07D277/62—Benzothiazoles
    • C07D277/68—Benzothiazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 2
    • C07D277/70—Sulfur atoms
    • C07D277/74—Sulfur atoms substituted by carbon atoms

Definitions

  • This disclosure relates to a method for producing and using catalysts for the production of bisphenols, and in particular to a method for producing catalysts which contain attached poly-sulfur mercaptan promoters, and using these catalysts in the production of bisphenol-A, and its derivatives.
  • Typical bisphenols such as 4,4'-isopropylidenediphenol, e.g., bisphenol-A (BPA) are widely employed as monomers in the manufacture of polymeric materials, such as engineering thermoplastics.
  • BPA is a principal monomer used in the manufacture of polycarbonate.
  • Bisphenols are generally prepared by the electrophilic addition of aldehydes, or ketones such as acetone, to aromatic hydroxy compounds such as phenol, in the presence of an acidic catalyst compositions. These types of reactions are also referred to as acid catalyzed condensation reactions.
  • sulfonated polystyrene resin cross-linked with divinylbenzene e.g., PS-DVB
  • PS-DVB divinylbenzene
  • Reaction promoters can also be employed as part of a catalyst composition to improve the reaction rate, and selectivity, of the desired condensation reaction; in the case of BPA, the desired selectivity is for the para-para isomer (pp-BPA).
  • Promoters can be present as unattached molecules in the bulk reaction matrix, e.g., "bulk-promoters", or can be attached to the resin through ionic linkages, e.g., "attached-promoters".
  • a useful class of promoter is the mercaptans, specifically thiols, e.g., organosulfur compounds which are derivatives of hydrogen sulfide.
  • Typical mercaptan protomers contain only a single sulfur atom, and result in catalyst compositions that catalyze bisphenol formation with poor isomer selectivity; in the case of BPA, the undesired selectivity if for the ortho-para isomer (op-BPA). Consequently, a long felt yet unsatisfied need exists for new and improved catalyst compositions, and a method to produce them, which are selective in the production of bisphenols.
  • a method to produce catalyst compositions comprising poly-sulfur mercaptan promoters is disclosed. The use of poly-sulfur mercaptan promoters results in catalyst compositions that are highly selective in the formation of bisphenols.
  • the present disclosure pertains to a method for producing a catalyst composition which catalyzes the formation of bisphenols from aromatic hydroxy compounds and carbonyl containing compounds, said method comprising the step of attaching a poly-sulfur mercaptan promoter component to a solid acid support component comprising a protic acid functionality, said poly-sulfur mercaptan promoter component having the following structure (I),
  • Ri is a functionality selected from the group consisting of a positively charged ammonium functionality, a positively charged guanidinium functionality, a positively charged phosphonium functionality, and a neutral amine;
  • a is between about 0 and about 11 ;
  • b is between about 1 and about 11 ;
  • c is between about 1 and about 11 ;
  • d is between about 1 and about 5;
  • X is a linking functionality which is one member selected from the group consisting of a linear aliphatic chain comprising between about 1 and about 11 carbon atoms, a cyclic aliphatic ring comprising at least 5 carbon atoms, a cyclic aromatic ring comprising at least 6 carbon atoms, a cyclic aliphatic heterocycle comprising at least 3 carbon atoms, and a cyclic aromatic heterocycle comprising at least 3 carbon atoms;
  • Y is a linking functionality which is one member selected from the group consisting of a linear aliphatic chain comprising between about 1 and about 11 carbon atoms, a cyclic aliphatic ring comprising at least 5 carbon atoms, a cyclic aromatic ring comprising at least 6 carbon atoms, a cyclic aliphatic heterocycle comprising at least 3 carbon atoms, and a cyclic aromatic heterocycle comprising at least 3 carbon atoms; and
  • R 2 is one member selected from the group consisting of a hydrogen, a tertiary aliphatic functionality, an ester functionality, a carbonate functionality, and a benzyl functionality which is attached via the benzylic methylene carbon.
  • the present disclosure relates to a method for forming bisphenols, comprising the step of reacting an aromatic hydroxy compound with a carbonyl containing compound in the presence of a catalyst composition, said catalyst composition comprising a solid acid component and a poly-sulfur mercaptan promoter component having the following structure (I),
  • Ri is a functionality selected from the group consisting of a positively charged ammonium functionality, a positively charged guanidinium functionality, a positively charged phosphonium functionality, and a neutral amine;
  • a is between about 0 and about 11 ;
  • b is between about 1 and about 11 ;
  • c is between about 1 and about 11 ;
  • d is between about 1 and about 5;
  • X is a linking functionality which is one member selected from the group consisting of a linear aliphatic chain comprising between about 1 and about 11 carbon atoms, a cyclic aliphatic ring comprising at least 5 carbon atoms, a cyclic aromatic ring comprising at least 6 carbon atoms, a cyclic aliphatic heterocycle comprising at least 3 carbon atoms, and a cyclic aromatic heterocycle comprising at least 3 carbon atoms;
  • Y is a linking functionality which is one member selected from the group consisting of a linear aliphatic chain comprising between about 1 and about 11 carbon atoms, a cyclic aliphatic ring comprising at least 5 carbon atoms, a cyclic aromatic ring comprising at least 6 carbon atoms, a cyclic aliphatic heterocycle comprising at least 3 carbon atoms, and a cyclic aromatic heterocycle comprising at least 3 carbon atoms; and
  • R 2 is one member selected from the group consisting of a hydrogen, a tertiary aliphatic functionality, an ester functionality, a carbonate functionality, and a benzyl functionality which is attached via the benzylic methylene carbon.
  • the present disclosure is directed to a method for producing and using catalysts for the production of bisphenols, and is suitable for the preparation of attached-promoter catalysts, which can effectively catalyze the formation of bisphenols from aromatic hydroxy compounds and carbonyl containing compounds.
  • catalyst refers to a composition, wherein the individual constituents of the composition are referred to as "components".
  • a typical catalyst comprises a "support” component that is generally a polymeric material, also referred to as a "resin”, comprising a protic acid functionality, and a "promoter” component that is generally an organic compound.
  • a “protic acid functionality” is defined as a group of atoms that are covalently attached to the polymeric support component of the catalyst, which can act as a source of protons, e.g., a Bronsted acid, and upon deprotonation the counter-anion can serve as an anionic moiety of an ionic bond with a cationically charged promoter component.
  • a support component is a polystyrene resin, cross-linked with up to 12 percent of divinylbenzene.
  • Suitable examples of protic acid functionalities which are attached to the support component, are a sulfonic acid functionality, which upon deprotonation produces a sulfonate anion functionality, a phosphonic acid functionality, which upon deprotonation produces a phosphonate anion functionality, and a carboxylic acid functionality, which upon deprotonation produces a carboxylate anion functionality.
  • the support component is a polystyrene resin, cross-linked with 4% of divinylbenzene, and functionalized with sulfonic acid groups.
  • Promoter components are typically organic compounds, which can readily form stable cationic species.
  • Typical promoter components comprise at least one mercaptan chain functionality, and an organic skeletal functionality, to which the mercaptan chain functionality is covalently bound.
  • the term "mercaptan chain functionality" is defined as an organosulfur functionality, which is a derivative of hydrogen sulf ⁇ de.
  • a typical mercaptan chain functionality i.e. - ⁇ [(X) a -S] b ⁇ (Y) c -S-R ⁇ , comprises at least two (2) sufur atoms.
  • up to twelve sulfur atoms can be present in a single mercaptan chain, e.g., b is between about 1 and about 12 in a chain defined by the following formula, - ⁇ [(X) a -S] b -(Y) c -S-R ⁇ .
  • the sulfur atoms in a typical mercaptan chain functionality are linked by various organic linkers functionalities, e.g., X and Y.
  • typical linker functionalities include, but are not limited to, a linear aliphatic chain comprising between about 1 and about 11 carbon atoms, a cyclic aliphatic ring comprising at least 5 carbon atoms, a cyclic aromatic ring comprising at least 6 carbon atoms, a cyclic aliphatic heterocycle comprising at least 3 carbon atoms, and a cyclic aromatic heterocycle comprising at least 3 carbon atoms.
  • organic skeletal functionality is defined as an organic functionality, which is capable of forming a covalent bond with at least one mercaptan chain functionality, and can form a stable cationic species that can act as a cationic moiety of an ionic bond.
  • Suitable examples of organic skeletal functionalities include, but are not limited to, an alkylammonium functionality, an alkylguanidinium functionality, an alkylphosphonium functionality, and an amino functionality.
  • amino skeletal functionalities include, but are not limited to, monocyclic aromatic amino compounds, and polyciclic aromatic amino compounds.
  • suitable amino skeletal functionalities include, but are not limited to, pyridyl functionalities, benzimidazole functionalities, benzothiazole functionalities, and imidazole functionalities.
  • a mercaptan chain functionality can be bonded to the ring system at any one of the ring locations that is capable of covalently bonding a substituent.
  • a mercaptan chain functionality can be appended to pyridine ring at any one of the 2, 3, or 4 ring positions.
  • mercaptan promoter i.e. alkylammonium mercaptans, alkylguanidinium mercaptans, alkylphosphonium mercaptans, and amino mercaptans, more than one mercaptan chain can be present in the promoter.
  • the pyridine ring can be substituted with up to 5 mercaptan chain functionalities, with one chain covalently bonded to each of the five carbon ring positions of the pyridine ring.
  • Substituent groups which are typically represented by the symbol R in chemical structures, can also be attached to a promoter to adjust the promoter's electronic properties, steric properties, and combinations thereof, to affect the reactivity of the overall catalyst composition.
  • Suitable promoter substituent groups include, but are not limited to, a hydrogen, a fluoride, a bromide, a chloride, an iodide, a vinyl group, a hydroxide, an alkoxide functionality comprising between about 1 and about 11 carbon atoms, an aryloxide functionality comprising at least about 6 carbon atoms, an aliphatic functionality comprising between about 1 and about 11 carbon atoms, and an aromatic functionality comprising at least about 6 carbon atoms.
  • a substituent group can also be a cycloaliphatic ring comprising at least about 5 carbon atoms, said cycloaliphatic ring being fused to the amino ring through an adjacent ring substituent, or a cycloaromatic ring comprising at least about 6 carbon atoms, said cycloaromatic ring being fused to the amino ring through an adjacent ring substituent.
  • Attachment of a promoter component to the polymeric support component is typically made via an ionic linkage between a cationically charged promoter component, which in the case of an aminomercaptan results from the protonation at the nitrogen atom, and the anionically charged deprotonated acid functionality on the resin backbone.
  • the attachment of an aminomercaptan promoter to an acid functionalized polymeric support can be performed in an aqueous solution.
  • aqueous solution includes those solutions where water is present as a solvent.
  • a protected mercaptan promoter such as [2-((CH 2 ) 2 -S-(CH 2 ) -S-( t -Bu))pyridine]
  • a sulfonic acid functionalized PS-DVB resin through an ionic linkage formed between a [2-((CH 2 ) -S-(CH 2 ) 3 -S-( t -Bu))pyridinium] + cation, and a sulfonate anion on the polymeric support, by mixing the PS-DVB resin and the mercaptan promoter together in water.
  • the aminomercaptan promoter can be attached to an acid functionalized polymeric support in an organic medium comprising an aromatic hydroxy compound, such as phenol.
  • the mercaptan promoter is protected at the sulfur atom, before it is attached to the support with a typical protecting group functionality used to protect Group 16 elements, such as oxygen and sulfur, from oxidation.
  • protecting group refers to a functionality which inhibits a specific type of reactivity, and in the context of the present disclosure, the protecting group attached to the terminal sulfur atom of the mercaptan promoter is present in order to inhibit the oxidation of the terminal sulfur atom; typically, unprotected mercaptan sulfhydryl groups are readily oxidized to disulfides, or more highly oxidized groups, during synthesis or under the conditions in which the promoters are attached to the polymeric supports.
  • suitable examples of sulfur protecting groups include, but are not limited to, aliphatic functionalities that form stable carbocations, ester functionalities, carbonate functionalities, and benzylic functionalities.
  • aliphatic refers to an organic compound composed of hydrogen atoms and carbon atom arranged in a branched chain, capable of forming a stable carbocation species.
  • the aliphatic protecting group is a tertiary butyl group, e.g., -C(CH 3 ) 3 .
  • aliphatic refers more broadly to an organic compound composed of hydrogen atoms and carbon atoms which contains between about 1 and about 11 carbon atoms, arranged in either a linear or branched chain.
  • aromatic is defined as an organic compound composed of hydrogen atoms and carbon atoms, which contains at least about 6 cyclic conjugated carbon atoms.
  • ester functionalities e.g., -C(O)R wherein R can be either an aliphatic substituent or an aromatic substituent
  • R can be either an aliphatic substituent or an aromatic substituent
  • esters which contain between about 1 and about 11 carbon atoms, such as an acetate group, e.g., - C(O)CH 3
  • carbonate functionalities e.g., -C(O)OR
  • carbonates with aliphatic substituents or aromatic substituents An example of a suitable aliphatic carbonate protecting group is as a tert-butoxy carbonate, e.g., - C(O)O- t Bu.
  • a suitable aromatic carbonate protecting group is as a phenyl carbonate group, e.g., -C(O)OPh.
  • the present application relates to a method for using the catalysts disclosed herein, to catalyze the formation of bisphenols, such as 4,4'- isopropylidenediphenol.
  • the term "catalyze”, when used in reference to a catalyst composition refers to the facilitation of a specific chemical transformation between one or more chemical species, at a reaction rate or selectivity, which is greater than, or equal to, a predetermined reference reaction rate, or reference selectivity, under a specific set of reaction conditions.
  • the reaction that is being catalyzed is a condensation reaction between an aromatic hydroxy compound and carbonyl-comprising compound to form a bisphenol, which typically occurs in a liquid reaction mixture.
  • liquid reaction mixture is defined as a mixture of compounds, which are present predominantly in a liquid state at ambient room temperature and pressure (e.g., about 25°C and about 0.1 MPa).
  • Liquid reaction mixtures can be homogeneous liquid mixtures composed of one of more phases (e.g., biphasic liquid reaction mixtures), or heterogeneous liquid-solid mixtures comprising components that are present in the solid state (e.g., precipitates).
  • the components which are present in a typical liquid reaction mixture of a condensation reaction to produce bisphenols include, but are not limited to, the desired bisphenol, byproducts of the condensation reaction such as water, and bisphenols other than the desired bisphenol, soluble components of the catalyst composition, insoluble components of the catalyst composition, and unreacted starting materials, e.g. an aromatic hydroxy compound, and a carbonyl containing compound.
  • Suitable types of aromatic hydroxy compounds include, but are not limited to, monocyclic aromatic compounds comprising at least one hydroxy group, and polycyclic aromatic compounds comprising at least one hydroxy group.
  • Suitable aromatic hydroxy compounds include, but are not limited to, phenol, alkylphenols, alkoxyphenols, naphthols, alkylnaphthols, and alkoxynaphthols.
  • carbonyl containing compounds refers to organic compounds which contain an sp 2 hybridized carbon which is double bonded to an oxygen atom, and includes aldehydes, and ketones.
  • An example of a suitable aldehyde is acetaldehyde.
  • An example of a suitable ketone is acetone.
  • the condensation reaction can be influenced by various reaction conditions including, but not limited to, reactor vessel pressure, reaction temperature, agitation rate, the pH of the reaction mixture, catalyst concentration, the weight % of various components of the liquid reaction mixture including, but not limited to, the weight % of an aromatic hydroxy compound, the weight % of a carbonyl containing compound, the weight % of a desired bisphenol, and the weight % of water.
  • typical reaction conditions for the catalytic production of BPA using the catalysts described herein and an incremental flow reactor include, but are not limited to, temperatures between about 55°C and about 85°C, acetone concentrations of between about 1% and about 10%, and space velocities between about 0.1 pounds of feed per pound of solid catalyst per hour and 10 pounds of feed per pound of solid catalyst per hour.
  • the resulting mixture of catalyst in phenol had a mass of about 3.5 times the mass of the initial dry resin.
  • a condensation reaction was performed by feeding a solution of about 9 wt% acetone in phenol, while maintaining a reactor temperature of 70°C in an incremental flow reactor run at a space velocity of about 2.7 mg feed/ mg dry resin/ hr and a liquid residence time of about 0.9 hr.
  • Table 1 summarizes the results by tabulating the wt% p,p-BPA produced, and the ratio of pp-BPA to o,p-BPA ("pp/op ratio") and the overall pp-BPA selectivity, which is defined as the weight % p,p-BVA as a fraction of all products measured. Table 1.
  • the p,p-BFA produced amounts to about 22.5 wt%, with app selectivity of about 93.7%, and a.pp/op ratio of about 23.9.

Abstract

This disclosure relates to a method for producing and using catalysts in the production of bisphenols, and in particular to a method for producing catalysts which contain poly-sulfur mercaptan promoters, and using these catalysts in the production of bisphenol-A and its derivatives. The poly-sulphur groups are pendant fro a positively charged functionality comprising nitrogen or phosphorous, preferably a nitrogen heterocycle. The catalysts also comprise a solid acid support component comprising a protic acid functionality, preferably a sulfonated polymeric resin.

Description

METHOD FOR PRODUCING BISPHENOL CATALYSTS AND BISPHENOLS
BACKGROUND OF THE INVENTION
This disclosure relates to a method for producing and using catalysts for the production of bisphenols, and in particular to a method for producing catalysts which contain attached poly-sulfur mercaptan promoters, and using these catalysts in the production of bisphenol-A, and its derivatives.
Typical bisphenols, such as 4,4'-isopropylidenediphenol, e.g., bisphenol-A (BPA), are widely employed as monomers in the manufacture of polymeric materials, such as engineering thermoplastics. For example, BPA is a principal monomer used in the manufacture of polycarbonate. Bisphenols are generally prepared by the electrophilic addition of aldehydes, or ketones such as acetone, to aromatic hydroxy compounds such as phenol, in the presence of an acidic catalyst compositions. These types of reactions are also referred to as acid catalyzed condensation reactions. Commercially, sulfonated polystyrene resin cross-linked with divinylbenzene, e.g., PS-DVB, is typically used as a solid acid component of the catalyst composition. Reaction promoters can also be employed as part of a catalyst composition to improve the reaction rate, and selectivity, of the desired condensation reaction; in the case of BPA, the desired selectivity is for the para-para isomer (pp-BPA). Promoters can be present as unattached molecules in the bulk reaction matrix, e.g., "bulk-promoters", or can be attached to the resin through ionic linkages, e.g., "attached-promoters". A useful class of promoter is the mercaptans, specifically thiols, e.g., organosulfur compounds which are derivatives of hydrogen sulfide. Typical mercaptan protomers contain only a single sulfur atom, and result in catalyst compositions that catalyze bisphenol formation with poor isomer selectivity; in the case of BPA, the undesired selectivity if for the ortho-para isomer (op-BPA). Consequently, a long felt yet unsatisfied need exists for new and improved catalyst compositions, and a method to produce them, which are selective in the production of bisphenols. Herein, a method to produce catalyst compositions comprising poly-sulfur mercaptan promoters is disclosed. The use of poly-sulfur mercaptan promoters results in catalyst compositions that are highly selective in the formation of bisphenols.
SUMMARY OF THE INVENTION
In one embodiment, the present disclosure pertains to a method for producing a catalyst composition which catalyzes the formation of bisphenols from aromatic hydroxy compounds and carbonyl containing compounds, said method comprising the step of attaching a poly-sulfur mercaptan promoter component to a solid acid support component comprising a protic acid functionality, said poly-sulfur mercaptan promoter component having the following structure (I),
Figure imgf000003_0001
(I)
wherein Ri is a functionality selected from the group consisting of a positively charged ammonium functionality, a positively charged guanidinium functionality, a positively charged phosphonium functionality, and a neutral amine;
wherein a is between about 0 and about 11 ;
wherein b is between about 1 and about 11 ;
wherein c is between about 1 and about 11 ;
wherein d is between about 1 and about 5;
wherein X is a linking functionality which is one member selected from the group consisting of a linear aliphatic chain comprising between about 1 and about 11 carbon atoms, a cyclic aliphatic ring comprising at least 5 carbon atoms, a cyclic aromatic ring comprising at least 6 carbon atoms, a cyclic aliphatic heterocycle comprising at least 3 carbon atoms, and a cyclic aromatic heterocycle comprising at least 3 carbon atoms; wherein Y is a linking functionality which is one member selected from the group consisting of a linear aliphatic chain comprising between about 1 and about 11 carbon atoms, a cyclic aliphatic ring comprising at least 5 carbon atoms, a cyclic aromatic ring comprising at least 6 carbon atoms, a cyclic aliphatic heterocycle comprising at least 3 carbon atoms, and a cyclic aromatic heterocycle comprising at least 3 carbon atoms; and
wherein R2 is one member selected from the group consisting of a hydrogen, a tertiary aliphatic functionality, an ester functionality, a carbonate functionality, and a benzyl functionality which is attached via the benzylic methylene carbon.
In another embodiment, the present disclosure relates to a method for forming bisphenols, comprising the step of reacting an aromatic hydroxy compound with a carbonyl containing compound in the presence of a catalyst composition, said catalyst composition comprising a solid acid component and a poly-sulfur mercaptan promoter component having the following structure (I),
Figure imgf000004_0001
(I)
wherein Ri is a functionality selected from the group consisting of a positively charged ammonium functionality, a positively charged guanidinium functionality, a positively charged phosphonium functionality, and a neutral amine;
wherein a is between about 0 and about 11 ;
wherein b is between about 1 and about 11 ;
wherein c is between about 1 and about 11 ;
wherein d is between about 1 and about 5; wherein X is a linking functionality which is one member selected from the group consisting of a linear aliphatic chain comprising between about 1 and about 11 carbon atoms, a cyclic aliphatic ring comprising at least 5 carbon atoms, a cyclic aromatic ring comprising at least 6 carbon atoms, a cyclic aliphatic heterocycle comprising at least 3 carbon atoms, and a cyclic aromatic heterocycle comprising at least 3 carbon atoms;
wherein Y is a linking functionality which is one member selected from the group consisting of a linear aliphatic chain comprising between about 1 and about 11 carbon atoms, a cyclic aliphatic ring comprising at least 5 carbon atoms, a cyclic aromatic ring comprising at least 6 carbon atoms, a cyclic aliphatic heterocycle comprising at least 3 carbon atoms, and a cyclic aromatic heterocycle comprising at least 3 carbon atoms; and
wherein R2 is one member selected from the group consisting of a hydrogen, a tertiary aliphatic functionality, an ester functionality, a carbonate functionality, and a benzyl functionality which is attached via the benzylic methylene carbon.
DETAILED DESCRIPTION
The present disclosure is directed to a method for producing and using catalysts for the production of bisphenols, and is suitable for the preparation of attached-promoter catalysts, which can effectively catalyze the formation of bisphenols from aromatic hydroxy compounds and carbonyl containing compounds. In the context of the present disclosure, the term "catalyst" refers to a composition, wherein the individual constituents of the composition are referred to as "components". In the context of the present disclosure, a typical catalyst comprises a "support" component that is generally a polymeric material, also referred to as a "resin", comprising a protic acid functionality, and a "promoter" component that is generally an organic compound. As used herein, the term "functionality" is defined as an atom, or group of atoms acting as a unit, whose presence imparts characteristic properties to the molecule to which the functionality is attached. In the context of the present disclosure, a "protic acid functionality" is defined as a group of atoms that are covalently attached to the polymeric support component of the catalyst, which can act as a source of protons, e.g., a Bronsted acid, and upon deprotonation the counter-anion can serve as an anionic moiety of an ionic bond with a cationically charged promoter component. A suitable example of a support component is a polystyrene resin, cross-linked with up to 12 percent of divinylbenzene. Suitable examples of protic acid functionalities, which are attached to the support component, are a sulfonic acid functionality, which upon deprotonation produces a sulfonate anion functionality, a phosphonic acid functionality, which upon deprotonation produces a phosphonate anion functionality, and a carboxylic acid functionality, which upon deprotonation produces a carboxylate anion functionality. For example, in one embodiment of the present disclosure, the support component is a polystyrene resin, cross-linked with 4% of divinylbenzene, and functionalized with sulfonic acid groups.
Promoter components are typically organic compounds, which can readily form stable cationic species. Typical promoter components comprise at least one mercaptan chain functionality, and an organic skeletal functionality, to which the mercaptan chain functionality is covalently bound. As used herein, the term "mercaptan chain functionality" is defined as an organosulfur functionality, which is a derivative of hydrogen sulfϊde. In the context of the present disclosure, a typical mercaptan chain functionality, i.e. -{[(X)a-S]b~(Y)c-S-R}, comprises at least two (2) sufur atoms. In one embodiment up to twelve sulfur atoms can be present in a single mercaptan chain, e.g., b is between about 1 and about 12 in a chain defined by the following formula, - {[(X)a-S]b-(Y)c-S-R}. The sulfur atoms in a typical mercaptan chain functionality are linked by various organic linkers functionalities, e.g., X and Y. In the context of the present disclosure, typical linker functionalities include, but are not limited to, a linear aliphatic chain comprising between about 1 and about 11 carbon atoms, a cyclic aliphatic ring comprising at least 5 carbon atoms, a cyclic aromatic ring comprising at least 6 carbon atoms, a cyclic aliphatic heterocycle comprising at least 3 carbon atoms, and a cyclic aromatic heterocycle comprising at least 3 carbon atoms. The term "organic skeletal functionality" is defined as an organic functionality, which is capable of forming a covalent bond with at least one mercaptan chain functionality, and can form a stable cationic species that can act as a cationic moiety of an ionic bond. Suitable examples of organic skeletal functionalities include, but are not limited to, an alkylammonium functionality, an alkylguanidinium functionality, an alkylphosphonium functionality, and an amino functionality. Typically amino skeletal functionalities include, but are not limited to, monocyclic aromatic amino compounds, and polyciclic aromatic amino compounds. For example, suitable amino skeletal functionalities include, but are not limited to, pyridyl functionalities, benzimidazole functionalities, benzothiazole functionalities, and imidazole functionalities. In the case of skeletal functionalities that comprise ring systems, a mercaptan chain functionality can be bonded to the ring system at any one of the ring locations that is capable of covalently bonding a substituent. For example, in the case of a pyridyl-mercaptan promoter, a mercaptan chain functionality can be appended to pyridine ring at any one of the 2, 3, or 4 ring positions. Furthermore, in each of the classes of mercaptan promoter described above, i.e. alkylammonium mercaptans, alkylguanidinium mercaptans, alkylphosphonium mercaptans, and amino mercaptans, more than one mercaptan chain can be present in the promoter. For example, in the case of pyridyl-mercaptans, the pyridine ring can be substituted with up to 5 mercaptan chain functionalities, with one chain covalently bonded to each of the five carbon ring positions of the pyridine ring.
Substituent groups, which are typically represented by the symbol R in chemical structures, can also be attached to a promoter to adjust the promoter's electronic properties, steric properties, and combinations thereof, to affect the reactivity of the overall catalyst composition. Suitable promoter substituent groups include, but are not limited to, a hydrogen, a fluoride, a bromide, a chloride, an iodide, a vinyl group, a hydroxide, an alkoxide functionality comprising between about 1 and about 11 carbon atoms, an aryloxide functionality comprising at least about 6 carbon atoms, an aliphatic functionality comprising between about 1 and about 11 carbon atoms, and an aromatic functionality comprising at least about 6 carbon atoms. In the case of aminomercaptans that comprise ring systems, a substituent group can also be a cycloaliphatic ring comprising at least about 5 carbon atoms, said cycloaliphatic ring being fused to the amino ring through an adjacent ring substituent, or a cycloaromatic ring comprising at least about 6 carbon atoms, said cycloaromatic ring being fused to the amino ring through an adjacent ring substituent.
Attachment of a promoter component to the polymeric support component is typically made via an ionic linkage between a cationically charged promoter component, which in the case of an aminomercaptan results from the protonation at the nitrogen atom, and the anionically charged deprotonated acid functionality on the resin backbone. The attachment of an aminomercaptan promoter to an acid functionalized polymeric support can be performed in an aqueous solution. Herein, the term "aqueous solution" includes those solutions where water is present as a solvent. For example, a protected mercaptan promoter, such as [2-((CH2)2-S-(CH2) -S-(t-Bu))pyridine], can be attached to a sulfonic acid functionalized PS-DVB resin through an ionic linkage formed between a [2-((CH2) -S-(CH2)3-S-(t-Bu))pyridinium]+ cation, and a sulfonate anion on the polymeric support, by mixing the PS-DVB resin and the mercaptan promoter together in water. Alternatively, the aminomercaptan promoter can be attached to an acid functionalized polymeric support in an organic medium comprising an aromatic hydroxy compound, such as phenol.
In one embodiment of the present disclosure, the mercaptan promoter is protected at the sulfur atom, before it is attached to the support with a typical protecting group functionality used to protect Group 16 elements, such as oxygen and sulfur, from oxidation. As used herein, the term "protecting group" refers to a functionality which inhibits a specific type of reactivity, and in the context of the present disclosure, the protecting group attached to the terminal sulfur atom of the mercaptan promoter is present in order to inhibit the oxidation of the terminal sulfur atom; typically, unprotected mercaptan sulfhydryl groups are readily oxidized to disulfides, or more highly oxidized groups, during synthesis or under the conditions in which the promoters are attached to the polymeric supports. In the context of the present disclosure, suitable examples of sulfur protecting groups include, but are not limited to, aliphatic functionalities that form stable carbocations, ester functionalities, carbonate functionalities, and benzylic functionalities. When used in conjunction with the term protecting group, the term "aliphatic" refers to an organic compound composed of hydrogen atoms and carbon atom arranged in a branched chain, capable of forming a stable carbocation species. For example, in one embodiment the aliphatic protecting group is a tertiary butyl group, e.g., -C(CH3)3. However, when used in conjunction with the term "substituent", the term "aliphatic" refers more broadly to an organic compound composed of hydrogen atoms and carbon atoms which contains between about 1 and about 11 carbon atoms, arranged in either a linear or branched chain. Furthermore, when used in conjunction with the term "substituent", the term "aromatic" is defined as an organic compound composed of hydrogen atoms and carbon atoms, which contains at least about 6 cyclic conjugated carbon atoms.
Suitable examples of ester functionalities, e.g., -C(O)R wherein R can be either an aliphatic substituent or an aromatic substituent, include those esters which contain between about 1 and about 11 carbon atoms, such as an acetate group, e.g., - C(O)CH3. Suitable examples of carbonate functionalities, e.g., -C(O)OR, include carbonates with aliphatic substituents or aromatic substituents. An example of a suitable aliphatic carbonate protecting group is as a tert-butoxy carbonate, e.g., - C(O)O-tBu. An example of a suitable aromatic carbonate protecting group is as a phenyl carbonate group, e.g., -C(O)OPh. Suitable examples of benzylic functionalities, e.g., -CH2(aryl), include those benzylic groups which contain at least 7 carbon atoms, such as a benzyl group, e.g., -CH (C6H6).
In another embodiment, the present application relates to a method for using the catalysts disclosed herein, to catalyze the formation of bisphenols, such as 4,4'- isopropylidenediphenol. In the context of the present disclosure, the term "catalyze", when used in reference to a catalyst composition, refers to the facilitation of a specific chemical transformation between one or more chemical species, at a reaction rate or selectivity, which is greater than, or equal to, a predetermined reference reaction rate, or reference selectivity, under a specific set of reaction conditions. In the context of the present disclosure, the reaction that is being catalyzed is a condensation reaction between an aromatic hydroxy compound and carbonyl-comprising compound to form a bisphenol, which typically occurs in a liquid reaction mixture. Herein, the term "liquid reaction mixture" is defined as a mixture of compounds, which are present predominantly in a liquid state at ambient room temperature and pressure (e.g., about 25°C and about 0.1 MPa). Liquid reaction mixtures can be homogeneous liquid mixtures composed of one of more phases (e.g., biphasic liquid reaction mixtures), or heterogeneous liquid-solid mixtures comprising components that are present in the solid state (e.g., precipitates).
The components which are present in a typical liquid reaction mixture of a condensation reaction to produce bisphenols include, but are not limited to, the desired bisphenol, byproducts of the condensation reaction such as water, and bisphenols other than the desired bisphenol, soluble components of the catalyst composition, insoluble components of the catalyst composition, and unreacted starting materials, e.g. an aromatic hydroxy compound, and a carbonyl containing compound. Suitable types of aromatic hydroxy compounds include, but are not limited to, monocyclic aromatic compounds comprising at least one hydroxy group, and polycyclic aromatic compounds comprising at least one hydroxy group. Illustrative examples of suitable aromatic hydroxy compounds include, but are not limited to, phenol, alkylphenols, alkoxyphenols, naphthols, alkylnaphthols, and alkoxynaphthols. As used herein, the term "carbonyl containing" compounds refers to organic compounds which contain an sp2 hybridized carbon which is double bonded to an oxygen atom, and includes aldehydes, and ketones. An example of a suitable aldehyde is acetaldehyde. An example of a suitable ketone is acetone.
The condensation reaction can be influenced by various reaction conditions including, but not limited to, reactor vessel pressure, reaction temperature, agitation rate, the pH of the reaction mixture, catalyst concentration, the weight % of various components of the liquid reaction mixture including, but not limited to, the weight % of an aromatic hydroxy compound, the weight % of a carbonyl containing compound, the weight % of a desired bisphenol, and the weight % of water. For example, typical reaction conditions for the catalytic production of BPA using the catalysts described herein and an incremental flow reactor include, but are not limited to, temperatures between about 55°C and about 85°C, acetone concentrations of between about 1% and about 10%, and space velocities between about 0.1 pounds of feed per pound of solid catalyst per hour and 10 pounds of feed per pound of solid catalyst per hour. The following examples are included to provide additional guidance to those skilled in the art in practicing the claimed disclosure. The examples provided are merely representative of the present disclosure. Accordingly, the following examples are not intended to limit the disclosure, as defined in the appended claims, in any manner.
Examples in Table 1 : For each of the examples listed in Table 1 , the following synthetic procedure was used to prepare the catalyst with the promoters listed in Table 1. About 30 mg to about 55 mg of dry Rohm and Haas A131 resin beads (sulfonated polystyrene, cross linked with about 4% divinylbenzene) with about 4 times it's mass of molten phenol were heated at about 70°C for about one hour. To this mixture was added a 540 mM phenol solution of the promoter, in an amount sufficient to yield a reaction mixture, which was about 1 mmole of promoter per gram of dry resin. The resulting reaction mixture was stirred for about 4 hours, after which time a portion of the phenol was removed. The resulting mixture of catalyst in phenol had a mass of about 3.5 times the mass of the initial dry resin. To demonstrate the catalytic activity of the catalyst prepared by the procedure described above, a condensation reaction was performed by feeding a solution of about 9 wt% acetone in phenol, while maintaining a reactor temperature of 70°C in an incremental flow reactor run at a space velocity of about 2.7 mg feed/ mg dry resin/ hr and a liquid residence time of about 0.9 hr. After about 40 cycles of alternate feeding and reactor mixture removal, the composition in the reactor was near steady state and samples were taken and analyzed for 4,4'-isopropylidenediphenol (p,p- IΑ), and 4,2'-isopropylidenediphenol (ø^-BPA), ) and eight other compounds known to sometimes be formed in smaller amounts. Table 1 summarizes the results by tabulating the wt% p,p-BPA produced, and the ratio of pp-BPA to o,p-BPA ("pp/op ratio") and the overall pp-BPA selectivity, which is defined as the weight % p,p-BVA as a fraction of all products measured. Table 1. Formation of pp-BPA, using a 9% acetone in phenol solution, at 70°C for 1 hour, catalyzed by Rohm & Haas A131 resin (1 meq/g, 19% neutralized), functionalized with the following attached promoters.
Figure imgf000013_0001
From the results presented in Table 1, it is evident that the catalysts prepared by the method of the present disclosure using the attached promoters listed in Table 1 , can effectively catalyze the formation of pp-BPA from phenol and acetone. For comparison, when Rohm and Haas A131 resin beads are used under similar conditions as described above, but without an attached promoter, the p,p-BFA produced amounts to about 9.9 wt%, with &pp selectivity of about 83.8%, and a pp/op ratio of about 7.5. Furthermore, when Rohm and Haas A131 resin beads are used under similar conditions as described above, except with a tert-butoxy carbonyl sulfur protected cysteamine promoter, the p,p-BFA produced amounts to about 22.5 wt%, with app selectivity of about 93.7%, and a.pp/op ratio of about 23.9.
While the disclosure has been illustrated and described, it is not intended to be limited to the details shown, since various modifications and substitutions can be made without departing in any way from the spirit of the present invention. As such, further modifications and equivalents of the disclosure herein disclosed can occur to persons skilled in the art using no more than routine experimentation, and all such modifications and equivalents are believed to be within the spirit and scope of the disclosure as defined by the following claims.

Claims

WHAT IS CLAIMED IS:
1. A method for producing a catalyst composition which catalyzes the formation of bisphenols from aromatic hydroxy compounds and carbonyl containing compounds, said method comprising the step of attaching a poly-sulfur mercaptan promoter component to a solid acid support component comprising a protic acid functionality, said poly-sulfur mercaptan promoter component having the following structure (I),
Figure imgf000015_0001
(I)
wherein Ri is a functionality selected from the group consisting of a positively charged ammonium functionality, a positively charged guanidinium functionality, a positively charged phosphonium functionality, and a neutral amine;
wherein a is between about 0 and about 11 ;
wherein b is between about 1 and about 11 ;
wherein c is between about 1 and about 11 ;
wherein d is between about 1 and about 5;
wherein X is a linking functionality which is one member selected from the group consisting of a linear aliphatic chain comprising between about 1 and about 11 carbon atoms, a cyclic aliphatic ring comprising at least 5 carbon atoms, a cyclic aromatic ring comprising at least 6 carbon atoms, a cyclic aliphatic heterocycle comprising at least 3 carbon atoms, and a cyclic aromatic heterocycle comprising at least 3 carbon atoms;
wherein Y is a linking functionality which is one member selected from the group consisting of a linear aliphatic chain comprising between about 1 and about 11 carbon atoms, a cyclic aliphatic ring comprising at least 5 carbon atoms, a cyclic aromatic ring comprising at least 6 carbon atoms, a cyclic aliphatic heterocycle comprising at least 3 carbon atoms, and a cyclic aromatic heterocycle comprising at least 3 carbon atoms; and
wherein R2 is one member selected from the group consisting of a hydrogen, a secondary aliphatic functionality, a tertiary aliphatic functionality, an ester functionality, a carbonate functionality, and a benzyl functionality which is attached via the benzylic methylene carbon.
2. The method of claim 1, wherein said tertiary aliphatic functionality is one member selected from the group consisting of a branched aliphatic functionality, and a cyclic aliphatic functionality.
3. The method of claim 1, wherein said R2 functionality is one member selected from the group consisting of an isopropyl functionality, an isobutyl functionality, a tertiary butyl functionality, a tertiary amyl functionality, a cyclopentyl functionality, a benzyl, a 4-methoxybenzyl functionality, a 1-methylcyclohexyl functionality, and a cyclohexyl functionality.
4. The method of claim 1, wherein said ester functionality is one member selected from the group consisting of an acetate functionality, a propionate functionality, and a benzoate functionality.
5. The method of claim 1, wherein said carbonate functionality is one member selected from the group consisting of an alkyl carbonate functionality, and an aromatic carbonate functionality.
6. The method of claim 1 , wherein the bisphenol which is being formed is 4,4'-isopropylidenediphenol.
7. The method of claim 1 , wherein the carbonyl containing compound is a ketone or an aldehyde.
8. The method of claim 1, wherein the aromatic hydroxy compound is phenol, and the carbonyl containing compound is acetone.
9. The method of claim 1, wherein the attachment step is performed in an aqueous solution comprising water.
10. The method of claim 1, wherein said solid acid comprises at least one member selected from the group consisting of polystyrene, a zeolite, and silica.
11. A method for producing a catalyst composition which catalyzes the formation of bisphenols from aromatic hydroxy compounds and carbonyl containing compounds, said method comprising the step of attaching a poly-sulfur mercaptan promoter component to a polymeric resin component comprising a protic acid functionality, wherein said poly-sulfur mercaptan promoter component is one member selected from the group consisting of a functionalized pyridine mercaptan, a functionalized benzimidazole mercaptan, a functionalized benzothiazole mercaptan, and a functionalized imidazole mercaptan.
12. The method of claim 11, wherein said functionalized pyridine mercaptan has the following the structure (II),
Figure imgf000017_0001
(II)
wherein e is between about 0 and about 11;
wherein f is between about 1 and about 11 ;
wherein s is between about 1 and about 11 ;
wherein h is between about 1 and about 5; wherein X is a linking functionality which is one member selected from the group consisting of a linear aliphatic chain comprising between about 1 and about 11 carbon atoms, a cyclic aliphatic ring comprising at least 5 carbon atoms, a cyclic aromatic ring comprising at least 6 carbon atoms, a cyclic aliphatic heterocycle comprising at least 3 carbon atoms, and a cyclic aromatic heterocycle comprising at least 3 carbon atoms;
wherein Y is a linking functionality which is one member selected from the group consisting of a linear aliphatic chain comprising between about 1 and about 11 carbon atoms, a cyclic aliphatic ring comprising at least 5 carbon atoms, a cyclic aromatic ring comprising at least 6 carbon atoms, a cyclic aliphatic heterocycle comprising at least 3 carbon atoms, and a cyclic aromatic heterocycle comprising at least 3 carbon atoms;
wherein R3 is a hydrogen or a sulfur-protecting functionality which is one member selected from the group consisting of an aliphatic functionality comprising at least about 4 carbon atom, an ester functionality comprising between about 1 and about 11 carbon atoms, a carbonate functionality comprising between about 1 and about 11 carbon atoms, and a benzylic functionality comprising at least about 7 carbon atoms which is attached to the terminal sulfur atom via the benzylic methylene carbon; and
wherein at least one member selected from the group consisting of R_j, R5, R6, R7, and R8 is a {[(X)eS]f[(Y)gS-R3]} chain, and each of R4, R5, R6, R7, and R8 that is not a {[(X)eS]f{(Y)gS-R3]} chain is independently one member selected from the group consisting of a hydrogen, a fluoride, a bromide, a chloride, an iodide, a vinyl group, a hydroxide, an alkoxide functionality comprising between about 1 and about 11 carbon atoms, an aryloxide functionality comprising at least about 6 carbon atoms, an aliphatic functionality comprising between about 1 and about 11 carbon atoms, an aromatic functionality comprising at least about 6 carbon atoms, a cycloaliphatic ring comprising at least about 5 carbon, said cycloaliphatic ring being fused to the pyridine ring through an adjacent ring substituent, and a cycloaromatic ring comprising at least about 6 carbon atoms, said cycloaromatic ring being fused to the pyridine ring through an adjacent ring substituent.
13. The method of claim 11, wherein said a functionalized benzimidazole mercaptan has the structure (III),
Figure imgf000019_0001
(III)
wherein i is between about 0 and about 11 ;
wherein j is between about 1 and about 11 ;
wherein k is between about 1 and about 11 ;
wherein R9 is a hydrogen atom or a sulfur-protecting functionality which is one member selected from the group consisting of an aliphatic functionality comprising at least about 4 carbon atom, an ester functionality comprising between about 1 and about 11 carbon atoms, a carbonate functionality comprising between about 1 and about 11 carbon atoms, and a benzylic functionality comprising at least about 7 carbon atoms which is attached to the terminal sulfur atom via the benzylic methylene carbon;
wherein Rio is one member selected from the group consisting of a hydrogen, an aliphatic carbonyl functionality comprising about 1 to about 11 carbon atoms, an aliphatic functionality comprising between about 1 and about 11 carbon atoms, an aromatic carbonyl functionality comprising at least about 7 carbon atoms, and an aromatic functionality comprising at least about 6 carbon atoms; and
wherein each of Ru, n, Rι3 and 14 are independently one member selected from the group consisting of a hydrogen, a fluoride, a bromide, a chloride, an iodide, a vinyl group, a hydroxide, an alkoxide functionality comprising between about 1 and about 11 carbon atoms, an aryloxide functionality comprising at least about 6 carbon atoms, an aliphatic functionality comprising between about 1 and about 11 carbon atoms, an aromatic functionality comprising at least about 6 carbon atoms, a cycloaliphatic ring comprising at least about 5 carbon atoms, said cycloaliphatic ring being fused to the benzimidazole arene ring through an adjacent ring substituent, and a cycloaromatic ring comprising at least about 6 carbon atoms, said cycloaromatic ring being fused to the benzimidazole arene ring through an adjacent ring substituent.
14. The method of claim 11, wherein said a functionalized benzothiazole mercaptan has the structure (IV),
Figure imgf000020_0001
(IV)
wherein 1 is between about 0 and about 11 ;
wherein m is between about 1 and about 11 ;
wherein n is between about 1 and about 11 ;
wherein R15 is a hydrogen atom or a sulfur-protecting functionality which is one member selected from the group consisting of an aliphatic functionality comprising at least about 4 carbon atom, an ester functionality comprising between about 1 and about 11 carbon atoms, a carbonate functionality comprising between about 1 and about 11 carbon atoms, and a benzylic functionality comprising at least about 7 carbon atoms which is attached to the terminal sulfur atom via the benzylic methylene carbon; and wherein each of R16, R17, Ris, and R19 are independently one member selected from the group consisting of a hydrogen, a fluoride, a bromide, a chloride, an iodide, a vinyl group, a hydroxide, an alkoxide functionality comprising between about 1 and about 11 carbon atoms, an aryloxide functionality comprising at least about 6 carbon atoms, an aliphatic functionality comprising between about 1 and about 1 1 carbon atoms, an aromatic functionality comprising at least about 6 carbon atoms, a cycloaliphatic ring comprising at least about 5 carbon atoms, said cycloaliphatic ring being fused to the benzothiazole arene ring through an adjacent ring substituent, and a cycloaromatic ring comprising at least about 6 carbon atoms, said cycloaromatic ring being fused to the benzothiazole arene ring through an adjacent ring substituent.
15. The method of claim 11, wherein said and a functionalized imidazole mercaptan has the structure (V),
Figure imgf000021_0001
(V)
wherein o is between about 0 and about 11 ;
wherein p is between about 1 and about 11 ;
wherein q is between about 1 and about 11 ;
wherein R2o is a hydrogen atom or a sulfur-protecting functionality which is one member selected from the group consisting of an aliphatic functionality comprising at least about 4 carbon atom, an ester functionality comprising between about 1 and about 11 carbon atoms, a carbonate functionality comprising between about 1 and about 11 carbon atoms, and a benzylic functionality comprising at least about 7 carbon atoms which is attached to the terminal sulfur atom via the benzylic methylene carbon; wherein R2ι is one member selected from the group consisting of a hydrogen, an aliphatic carbonyl functionality comprising about 1 to about , 11 carbon atoms, an aliphatic functionality comprising between about 1 and about 11 carbon atoms, an aromatic carbonyl functionality comprising at least about 7 carbon atoms, and an aromatic functionality comprising at least about 6 carbon atoms; and
wherein each of R22 and R23 are independently one member selected from the group consisting of a hydrogen, a fluoride, a bromide, a chloride, an iodide, a vinyl group, a hydroxide, an alkoxide functionality comprising between about 1 and about 11 carbon atoms, an aryloxide functionality comprising at least about 6 carbon atoms, an aliphatic functionality comprising between about 1 and about 11 carbon atoms, an aromatic functionality comprising at least about 6 carbon atoms, a cycloaliphatic ring comprising at least about 5 carbon atoms, said cycloaliphatic ring being fused to the imidazole ring through an adjacent ring substituent, and a cycloaromatic ring comprising at least about 6 carbon atoms, said cycloaromatic ring being fused to the imidazole ring through an adjacent ring substituent.
16. The method of claim 11 , wherein the bisphenol which is being formed is 4,4'-isopropylidenediphenol.
17. The method of claim 11, wherein the carbonyl containing compound is a ketone or an aldehyde.
18. The method of claim 11, wherein the aromatic hydroxy compound is phenol, and the carbonyl containing compound is acetone.
19. The method of claim 11, wherein the attachment step is performed in an aqueous solution comprising water.
20. The method of claim 11, wherein said polymeric resin comprises at least one member selected from the group consisting of polystyrene, a zeolite, and silica.
21. The method of claim 20, wherein said polymeric resin further comprises divinylbenzene.
22. The method of claim 21, wherein the amount of divinylbenzene is up to about 12 percent of the total weight of the polymeric resin.
23. The method of claim 11, wherein said protic acid functionality comprises at least one member selected from the group consisting of a sulfonic acid functionality, a phosphonic acid functionality, and a carboxylic acid functionality.
24. The method of claim 12, wherein the linking functionality X, is the same as the linking functionality Y.
25. The method of claim 12, wherein X is a -CH2- group, e is 2, f is 1, Y is a -CH2- group, g is 3, and R4 is the {[(X)eSM(Y)gS-R3]} chain.
26. The method of claim 12, wherein X is a -CH2- group, e is 2, f is 1 , Y is a -CH2- group, g is 3, and Rs is the {[(X)eS]f[(Y)gS-R3]} chain.
27. The method of claim 12, wherein X is a -CH2- group, e is 2, f is 1 , Y is a -CH2- group, g is 3, and R6 is the {[(X)eSM(Y)gS-R3] } chain.
28. The method of claim 12, wherein the bisphenol is 4,4'- isopropylidenediphenol, the aromatic hydroxy compound is phenol, the carbonyl containing compound is acetone, and said promoter component is,
Figure imgf000023_0001
wherein R24 is a hydrogen atom or a sulfur-protecting functionality which is one member selected from the group consisting of an aliphatic functionality comprising at least about 4 carbon atom, an ester functionality comprising between about 1 and about 11 carbon atoms, a carbonate functionality comprising between about 1 and about 11 carbon atoms, and a benzylic functionality comprising at least about 7 carbon atoms which is attached via the benzylic methylene carbon; and
wherein r is 3 or 6.
29. The method of claim 12, wherein the bisphenol is 4,4'- isopropylidenediphenol, the aromatic hydroxy compound is phenol, the carbonyl containing compound is acetone, and said promoter component is,
Figure imgf000024_0001
wherein R2s is a hydrogen atom or a sulfur-protecting functionality which is one member selected from the group consisting of an aliphatic functionality comprising at least about 4 carbon atom, an ester functionality comprising between about 1 and about 11 carbon atoms, a carbonate functionality comprising between about 1 and about 11 carbon atoms, and a benzylic functionality comprising at least about 7 carbon atoms which is attached via the benzylic methylene carbon; and
wherein t is 3 or 6.
30. The method of claim 12, wherein the bisphenol is 4,4'- isopropylidenediphenol, the aromatic hydroxy compound is phenol, the carbonyl containing compound is acetone, and said promoter component is,
Figure imgf000025_0001
wherein R26 is a hydrogen atom or a sulfur-protecting functionality which is one member selected from the group consisting of an aliphatic functionality comprising at least about 4 carbon atom, an ester functionality comprising between about 1 and about 11 carbon atoms, a carbonate functionality comprising between about 1 and about 11 carbon atoms, and a benzylic functionality comprising at least about 7 carbon atoms which is attached via the benzylic methylene carbon; and
wherein is 3 or 6.
31. The method of claim 12, wherein the bisphenol is 4,4'- isopropylidenediphenol, the aromatic hydroxy compound is phenol, the carbonyl containing compound is acetone, and said promoter component is,
Figure imgf000025_0002
wherein R27 is a hydrogen atom or a sulfur-protecting functionality which is one member selected from the group consisting of an aliphatic functionality comprising at least about 4 carbon atom, an ester functionality comprising between about 1 and about 1 1 carbon atoms, a carbonate functionality comprising between about 1 and about 11 carbon atoms, and a benzylic functionality comprising at least about 7 carbon atoms which is attached via the benzylic methylene carbon; and wherein v is 3 or 6.
32. The method of claim 12, wherein the bisphenol is 4,4'- isopropylidenediphenol, the aromatic hydroxy compound is phenol, the carbonyl containing compound is acetone, and said promoter component is,
Figure imgf000026_0001
wherein R2g is a hydrogen atom or a sulfur-protecting functionality which is one member selected from the group consisting of an aliphatic functionality comprising at least about 4 carbon atom, an ester functionality comprising between about 1 and about 11 carbon atoms, a carbonate functionality comprising between about 1 and about 11 carbon atoms, and a benzylic functionality comprising at least about 7 carbon atoms which is attached via the benzylic methylene carbon; and
wherein w is 3 or 6.
33. The method of claim 12, wherein the bisphenol is 4,4'- isopropylidenediphenol, the aromatic hydroxy compound is phenol, the carbonyl containing compound is acetone, and said promoter component is,
Figure imgf000026_0002
wherein R29 is a hydrogen atom or a sulfur-protecting functionality which is one member selected from the group consisting of an aliphatic functionality comprising at least about 4 carbon atom, an ester functionality comprising between about 1 and about 11 carbon atoms, a carbonate functionality comprising between about 1 and about 1 1 carbon atoms, and a benzylic functionality comprising at least about 7 carbon atoms which is attached via the benzylic methylene carbon; and
wherein x is 3 or 6.
34. The method of claim 13, wherein the bisphenol is 4,4'- isopropylidenediphenol, the aromatic hydroxy compound is phenol, the carbonyl containing compound is acetone, and said promoter component is,
Figure imgf000027_0001
wherein R30 is a hydrogen atom or a sulfur-protecting functionality which is one member selected from the group consisting of an aliphatic functionality comprising at least about 4 carbon atom, an ester functionality comprising between about 1 and about 11 carbon atoms, a carbonate functionality comprising between about 1 and about 11 carbon atoms, and a benzylic functionality comprising at least about 7 carbon atoms which is attached via the benzylic methylene carbon.
35. The method of claim 13, wherein the bisphenol is 4,4'- isopropylidenediphenol, the aromatic hydroxy compound is phenol, the carbonyl containing compound is acetone, and said promoter component is, 1
Figure imgf000028_0001
wherein R3ι is a hydrogen atom or a sulfur-protecting functionality which is one member selected from the group consisting of an aliphatic functionality comprising at least about 4 carbon atom, an ester functionality comprising between about 1 and about 11 carbon atoms, a carbonate functionality comprising between about 1 and about 11 carbon atoms, and a benzylic functionality comprising at least about 7 carbon atoms which is attached via the benzylic methylene carbon.
36. The method of claim 13, wherein the bisphenol is 4,4'- isopropylidenediphenol, the aromatic hydroxy compound is phenol, the carbonyl containing compound is acetone, and said promoter component is,
Figure imgf000028_0002
wherein R32 is a hydrogen atom or a sulfur-protecting functionality which is one member selected from the group consisting of an aliphatic functionality comprising at least about 4 carbon atom, an ester functionality comprising between about 1 and about 11 carbon atoms, a carbonate functionality comprising between about 1 and about 11 carbon atoms, and a benzylic functionality comprising at least about 7 carbon atoms which is attached via the benzylic methylene carbon.
37. The method of claim 14, wherein the bisphenol is 4,4'- isopropylidenediphenol, the aromatic hydroxy compound is phenol, the carbonyl containing compound is acetone, and said promoter component is,
Figure imgf000029_0001
wherein R33 is a hydrogen atom or a sulfur-protecting functionality which is one member selected from the group consisting of an aliphatic functionality comprising at least about 4 carbon atom, an ester functionality comprising between about 1 and about 11 carbon atoms, a carbonate functionality comprising between about 1 and about 11 carbon atoms, and a benzylic functionality comprising at least about 7 carbon atoms which is attached via the benzylic methylene carbon; and
wherein y is 3 or 6.
38. A method for forming bisphenols, comprising the step of reacting an aromatic hydroxy compound with a carbonyl containing compound in the presence of a catalyst composition, said catalyst composition comprising a solid acid component and a poly-sulfur mercaptan promoter component having the following structure (I),
Figure imgf000029_0002
(I) wherein Ri is a functionality selected from the group consisting of a positively charged ammonium functionality, a positively charged guanidinium functionality, a positively charged phosphonium functionality, and a neutral amine;
wherein a is between about 0 and about 11 ;
wherein b is between about 1 and about 11 ;
wherein c is between about 1 and about 11 ;
wherein d is between about 1 and about 5;
wherein X is a linking functionality which is one member selected from the group consisting of a linear aliphatic chain comprising between about 1 and about 11 carbon atoms, a cyclic aliphatic ring comprising at least 5 carbon atoms, a cyclic aromatic ring comprising at least 6 carbon atoms, a cyclic aliphatic heterocycle comprising at least 3 carbon atoms, and a cyclic aromatic heterocycle comprising at least 3 carbon atoms;
wherein Y is a linking functionality which is one member selected from the group consisting of a linear aliphatic chain comprising between about 1 and about 11 carbon atoms, a cyclic aliphatic ring comprising at least 5 carbon atoms, a cyclic aromatic ring comprising at least 6 carbon atoms, a cyclic aliphatic heterocycle comprising at least 3 carbon atoms, and a cyclic aromatic heterocycle comprising at least 3 carbon atoms; and
wherein R2 is one member selected from the group consisting of a hydrogen, a secondary aliphatic functionality, a tertiary aliphatic functionality, an ester functionality, a carbonate functionality, and a benzyl functionality which is attached via the benzylic methylene carbon.
39. The method of claim 38, wherein said tertiary aliphatic functionality is one member selected from the group consisting of a branched aliphatic functionality, and a cyclic aliphatic functionality.
40. The method of claim 38, wherein said R2 is one member selected from the group consisting of a, an isopropyl functionality, an isobutyl functionality, a tertiary butyl functionality, a tertiary amyl functionality, a cyclopentyl functionality, a benzyl, a 4-methoxybenzyl, a 1-methylcyclohexyl functionality, and a cyclohexyl functionality.
41. The method of claim 38, wherein said ester functionality is one member selected from the group consisting of an acetate functionality, a propionate functionality, and a benzoate functionality.
42. The method of claim 38, wherein said carbonate functionality is one member selected from the group consisting of an alkyl carbonate functionality, and an aromatic carbonate functionality.
43. The method of claim 38, wherein the bisphenol which is being formed is 4,4'-isopropylidenediphenol.
44. The method of claim 38 wherein the aromatic hydroxy compound is phenol.
45. The method of claim 38, wherein the carbonyl containing compound is a ketone or an aldehyde.
46. The method of claim 45 wherein the ketone is acetone.
47. The method of claim 38, wherein said solid acid comprises at least one member selected from the group consisting of polystyrene, a zeolite, and silica.
48. The method of claim 38, wherein said solid acid is a sulfonic acid functionalized polymeric resin.
49. The method of claim 48, wherein said polymeric resin further comprises divinylbenzene.
50. The method of claim 49, wherein the amount of divnylbenzene is up to about 12 percent of the total weight of the polymeric resin.
51. The method of claim 38 wherein said solid acid component comprises at least one member selected from the group consisting of a sulfonic acid functionality, a phosphonic acid functionality, and a carboxylic acid functionality.
52. The method of claim 38, wherein the linking functionality X, is the same as the linking functionality Y.
53. A method for foπning bisphenols, comprising the step of reacting an aromatic hydroxy compound with a carbonyl containing compound in the presence of a catalyst composition, said catalyst composition comprising a polymeric resin component comprising a protic acid functionality, and a poly-sulfur mercaptan promoter component, wherein said poly-sulfur mercaptan promoter component is one member selected from the group consisting of a functionalized pyridine mercaptan, a functionalized benzimidazole mercaptan, a functionalized benzothiazole mercaptan, and a functionalized imidazole mercaptan.
54. The method of claim 53, wherein said functionalized pyridine mercaptan has the structure (II),
Figure imgf000032_0001
(II)
wherein e is between about 0 and about 11 ;
wherein f is between about 1 and about 11 ;
wherein g is between about 1 and about 11 ;
wherein h is between about 1 and about 5; wherein X is a linking functionality which is one member selected from the group consisting of a linear aliphatic chain comprising between about 1 and about 11 carbon atoms, a cyclic aliphatic ring comprising at least 5 carbon atoms, a cyclic aromatic ring comprising at least 6 carbon atoms, a cyclic aliphatic heterocycle comprising at least 3 carbon atoms, and a cyclic aromatic heterocycle comprising at least 3 carbon atoms;
wherein Y is a linking functionality which is one member selected from the group consisting of a linear aliphatic chain comprising between about 1 and about 11 carbon atoms, a cyclic aliphatic ring comprising at least 5 carbon atoms, a cyclic aromatic ring comprising at least 6 carbon atoms, a cyclic aliphatic heterocycle comprising at least 3 carbon atoms, and a cyclic aromatic heterocycle comprising at least 3 carbon atoms;
wherein R3 is a hydrogen or a sulfur-protecting functionality which is one member selected from the group consisting of an aliphatic functionality comprising at least about 4 carbon atom, an ester functionality comprising between about 1 and about 11 carbon atoms, a carbonate functionality comprising between about 1 and about 11 carbon atoms, and a benzylic functionality comprising at least about 7 carbon atoms which is attached to the terminal sulfur atom via the benzylic methylene carbon; and
wherein at least one member selected from the group consisting of R4, R5, R6, R7, and R8 is a {[(X)eS]f[(Y)gS-R3]} chain, and each of R4, R5, R6, R7, and Rg that is not a {[(X)eS]f{(Y)gS-R3]} chain is independently one member selected from the group consisting of a hydrogen, a fluoride, a bromide, a chloride, an iodide, a vinyl group, a hydroxide, an alkoxide functionality comprising between about 1 and about 11 carbon atoms, an aryloxide functionality comprising at least about 6 carbon atoms, an aliphatic functionality comprising between about 1 and about 11 carbon atoms, an aromatic functionality comprising at least about 6 carbon atoms, a cycloaliphatic ring comprising at least about 5 carbon atoms, said cycloaliphatic ring being fused to the pyridine ring through an adjacent ring substituent, and a cycloaromatic ring comprising at least about 6 carbon atoms, said cycloaromatic ring being fused to the pyridine ring through an adjacent ring substituent.
55. The method of claim 53, wherein said functionalized benzimidazole mercaptan has the structure (III),
Figure imgf000034_0001
(in)
wherein i is between about 0 and about 11 ;
wherein j is between about 1 and about 11 ;
wherein k is between about 1 and about 11 ;
wherein R9 is a hydrogen atom or a sulfur-protecting functionality which is one member selected from the group consisting of an aliphatic functionality comprising at least about 4 carbon atom, an ester functionality comprising between about 1 and about 11 carbon atoms, a carbonate functionality comprising between about 1 and about 11 carbon atoms, and a benzylic functionality comprising at least about 7 carbon atoms which is attached to the terminal sulfur atom via the benzylic methylene carbon;
wherein R10 is one member selected from the group consisting of a hydrogen, an aliphatic carbonyl functionality comprising about 1 to about 11 carbon atoms, an aliphatic functionality comprising between about 1 and about 11 carbon atoms, an aromatic carbonyl functionality comprising at least about 7 carbon atoms, and an aromatic functionality comprising at least about 6 carbon atoms; and
wherein each of n, R12, R13 and R14 are independently one member selected from the group consisting of a hydrogen, a fluoride, a bromide, a chloride, an iodide, a vinyl group, a hydroxide, an alkoxide functionality comprising between about 1 and about 11 carbon atoms, an aryloxide functionality comprising at least about 6 carbon atoms, an aliphatic functionality comprising between about 1 and about 11 carbon atoms, an aromatic functionality comprising at least about 6 carbon atoms, a cycloaliphatic ring comprising at least about 5 carbon atoms, said cycloaliphatic ring being fused to the benzimidazole arene ring through an adjacent ring substituent, and a cycloaromatic ring comprising at least about 6 carbon atoms, said cycloaromatic ring being fused to the benzimidazole arene ring through an adjacent ring substituent.
56. The method of claim 53, wherein said functionalized benzothiazole mercaptan has the structure (IV),
Figure imgf000035_0001
(IV)
wherein 1 is between about 0 and about 11 ;
wherein m is between about 1 and about 11 ;
wherein n is between about 1 and about 11 ;
wherein R15 is a hydrogen atom or a sulfur-protecting functionality which is one member selected from the group consisting of an aliphatic functionality comprising at least about 4 carbon atom, an ester functionality comprising between about 1 and about 11 carbon atoms, a carbonate functionality comprising between about 1 and about 11 carbon atoms, and a benzylic functionality comprising at least about 7 carbon atoms which is attached to the terminal sulfur atom via the benzylic methylene carbon; and wherein each of Rι6, R17, Rig, and R19 are independently one member selected from the group consisting of a hydrogen, a fluoride, a bromide, a chloride, an iodide, a vinyl group, a hydroxide, an alkoxide functionality comprising between about 1 and about 11 carbon atoms, an aryloxide functionality comprising at least about 6 carbon atoms, an aliphatic functionality comprising between about 1 and about 1 1 carbon atoms, an aromatic functionality comprising at least about 6 carbon atoms, a cycloaliphatic ring comprising at least about 5 carbon atoms, said cycloaliphatic ring being fused to the benzothiazole arene ring through an adjacent ring substituent, and a cycloaromatic ring comprising at least about 6 carbon atoms, said cycloaromatic ring being fused to the benzothiazole arene ring through an adjacent ring substituent.
57. The method of claim 53, wherein said functionalized imidazole mercaptan has the structure (V),
Figure imgf000036_0001
(V)
wherein o is between about 0 and about 11 ;
wherein p is between about 1 and about 11 ;
wherein q is between about 1 and about 11 ;
wherein R20 is a hydrogen atom or a sulfur-protecting functionality which is one member selected from the group consisting of an aliphatic functionality comprising at least about A carbon atom, an ester functionality comprising between about 1 and about 11 carbon atoms, a carbonate functionality comprising between about 1 and about 11 carbon atoms, and a benzylic functionality comprising at least about 7 carbon atoms which is attached to the terminal sulfur atom via the benzylic methylene carbon; wherein R2ι is one member selected from the group consisting of a hydrogen, an aliphatic carbonyl functionality comprising about 1 to about 11 carbon atoms, an aliphatic functionality comprising between about 1 and about 11 carbon atoms, an aromatic carbonyl functionality comprising at least about 7 carbon atoms, and an aromatic functionality comprising at least about 6 carbon atoms; and
wherein each of R22 and R23 are independently one member selected from the group consisting of a hydrogen, a fluoride, a bromide, a chloride, an iodide, a vinyl group, a hydroxide, an alkoxide functionality comprising between about 1 and about 11 carbon atoms, an aryloxide functionality comprising at least about 6 carbon atoms, an aliphatic functionality comprising between about 1 and about 11 carbon atoms, an aromatic functionality comprising at least about 6 carbon atoms, a cycloaliphatic ring comprising at least about 5 carbon atoms, said cycloaliphatic ring being fused to the imidazole ring through an adjacent ring substituent, and a cycloaromatic ring comprising at least about 6 carbon atoms, said cycloaromatic ring being fused to the imidazole ring through an adjacent ring substituent.
58. The method of claim 53, wherein the bisphenol which is being formed is 4,4'-isopropylidenediphenol.
59. The method of claim 53, wherein the aromatic hydroxy compound is phenol.
60. The method of claim 53, wherein the carbonyl containing compound is a ketone or an aldehyde.
61. The method of claim 60, wherein the ketone is acetone.
62. The method of claim 53, wherein said polymeric resin comprises at least one member selected from the group consisting of polystyrene, a zeolite, and silica.
63. The method of claim 62, wherein said polymeric resin further comprises divinylbenzene.
64. The method of claim 63, wherein the amount of divinylbenzene is up to about 12 percent based on the total weight of the polymeric resin.
65. The method of claim 53, wherein said protic acid functionality comprises at least one member selected from the group consisting of a sulfonic acid functionality, a phosphonic acid functionality, and a carboxylic acid functionality.
66. The method of claim 54, wherein the linking functionality X, is the same as the linking functionality Y.
67. The method of claim 54, wherein X is a -CH2- group, e is 2, f is 1 , Y is a -CH2- group, g is 3, and 4is the {[(X)eS]f[(Y)gS-R3]} chain.
68. The method of claim 54, wherein X is a -CH2- group, e is 2, f is 1, Y is a -CH2- group, g is 3, and R5is the {[(X)eS]f[(Y)gS-R3]} chain.
69. The method of claim 54, wherein X is a -CH2- group, e is 2, f is 1, Y is a-CH2- group, g is 3, and R6 is the {[(X)eSM(Y)gS-R3]} chain.
70. The method of claim 54, wherein the bisphenol is 4,4'- isopropylidenediphenol, the aromatic hydroxy compound is phenol, the carbonyl containing compound is acetone, and said promoter component is,
Figure imgf000038_0001
wherein R24 is a hydrogen atom or a sulfur-protecting functionality which is one member selected from the group consisting of an aliphatic functionality comprising at least about 4 carbon atom, an ester functionality comprising between about 1 and about 11 carbon atoms, a carbonate functionality comprising between about 1 and about 1 1 carbon atoms, and a benzylic functionality comprising at least about 7 carbon atoms which is attached to the terminal sulfur atom via the benzylic methylene carbon; and
wherein r is 3 or 6.
71. The method of claim 54, wherein the bisphenol is 4,4'- isopropylidenediphenol, the aromatic hydroxy compound is phenol, the carbonyl containing compound is acetone, and said promoter component is,
Figure imgf000039_0001
wherein R2s is a hydrogen atom or a sulfur-protecting functionality which is one member selected from the group consisting of an aliphatic functionality comprising at least about 4 carbon atom, an ester functionality comprising between about 1 and about 11 carbon atoms, a carbonate functionality comprising between about 1 and about 11 carbon atoms, and a benzylic functionality comprising at least about 7 carbon atoms which is attached to the terminal sulfur atom via the benzylic methylene carbon; and
wherein t is 3 or 6.
72. The method of claim 54, wherein the bisphenol is 4,4'- isopropylidenediphenol, the aromatic hydroxy compound is phenol, the carbonyl containing compound is acetone, and said promoter component is,
Figure imgf000040_0001
wherein R26 is a hydrogen atom or a sulfur-protecting functionality which is one member selected from the group consisting of an aliphatic functionality comprising at least about 4 carbon atom, an ester functionality comprising between about 1 and about 11 carbon atoms, a carbonate functionality comprising between about 1 and about 11 carbon atoms, and a benzylic functionality comprising at least about 7 carbon atoms which is attached to the terminal sulfur atom via the benzylic methylene carbon; and
wherein u is 3 or 6.
73. The method of claim 54, wherein the bisphenol is 4,4'- isopropylidenediphenol, the aromatic hydroxy compound is phenol, the carbonyl containing compound is acetone, and said promoter component is,
Figure imgf000040_0002
wherein R27 is a hydrogen atom or a sulfur-protecting functionality which is one member selected from the group consisting of an aliphatic functionality comprising at least about 4 carbon atom, an ester functionality comprising between about 1 and about 11 carbon atoms, a carbonate functionality comprising between about 1 and about 11 carbon atoms, and a benzylic functionality comprising at least about 7 carbon atoms which is attached to the terminal sulfur atom via the benzylic methylene carbon; and
wherein v is 3 or 6.
74. The method of claim 54, wherein the bisphenol is 4,4''- isopropylidenediphenol, the aromatic hydroxy compound is phenol, the carbonyl containing compound is acetone, and said promoter component is,
Figure imgf000041_0001
wherein R28 is a hydrogen atom or a sulfur-protecting functionality which is one member selected from the group consisting of an aliphatic functionality comprising at least about 4 carbon atom, an ester functionality comprising between about 1 and about 11 carbon atoms, a carbonate functionality comprising between about 1 and about 11 carbon atoms, and a benzylic functionality comprising at least about 7 carbon atoms which is attached to the terminal sulfur atom via the benzylic methylene carbon; and
wherein is 3 or 6.
75. The method of claim 54, wherein the bisphenol is 4,4'- isopropylidenediphenol, the aromatic hydroxy compound is phenol, the carbonyl containing compound is acetone, and said promoter component is,
Figure imgf000042_0001
wherein R29 is a hydrogen atom or a sulfur-protecting functionality which is one member selected from the group consisting of an aliphatic functionality comprising at least about 4 carbon atom, an ester functionality comprising between about 1 and about 11 carbon atoms, a carbonate functionality comprising between about 1 and about 11 carbon atoms, and a benzylic functionality comprising at least about 7 carbon atoms which is attached to the terminal sulfur atom via the benzylic methylene carbon; and
wherein x is 3 or 6.
76. The method of claim 55, wherein the bisphenol is 4,4'- isopropylidenediphenol, the aromatic hydroxy compound is phenol, the carbonyl containing compound is acetone, and said promoter component is,
Figure imgf000042_0002
wherein R3o is a hydrogen atom or a sulfur-protecting functionality which is one member selected from the group consisting of an aliphatic functionality comprising at least about 4 carbon atom, an ester functionality comprising between about 1 and about 11 carbon atoms, a carbonate functionality comprising between about 1 and about 11 carbon atoms, and a benzylic functionality comprising at least about 7 carbon atoms which is attached to the terminal sulfur atom via the benzylic methylene carbon.
77. The method of claim 55, wherein the bisphenol is 4,4'- isopropylidenediphenol, the aromatic hydroxy compound is phenol, the carbonyl containing compound is acetone, and said promoter component is,
Figure imgf000043_0001
wherein R31 is a hydrogen atom or a sulfur-protecting functionality which is one member selected from the group consisting of an aliphatic functionality comprising at least about 4 carbon atom, an ester functionality comprising between about 1 and about 11 carbon atoms, a carbonate functionality comprising between about 1 and about 11 carbon atoms, and a benzylic functionality comprising at least about 7 carbon atoms which is attached to the terminal sulfur atom via the benzylic methylene carbon.
78. The method of claim 55, wherein the bisphenol is 4,4'- isopropylidenediphenol, the aromatic hydroxy compound is phenol, the carbonyl containing compound is acetone, and said promoter component is,
Figure imgf000044_0001
(XIV)
wherein R32 is a hydrogen atom or a sulfur-protecting functionality which is one member selected from the group consisting of an aliphatic functionality comprising at least about 4 carbon atom, an ester functionality comprising between about 1 and about 11 carbon atoms, a carbonate functionality comprising between about 1 and about 11 carbon atoms, and a benzylic functionality comprising at least about 7 carbon atoms which is attached to the terminal sulfur atom via the benzylic methylene carbon.
79. The method of claim 56, wherein the bisphenol is 4,4'- isopropylidenediphenol, the aromatic hydroxy compound is phenol, the carbonyl containing compound is acetone, and said promoter component is,
Figure imgf000044_0002
wherein R33 is a hydrogen atom or a sulfur-protecting functionality which is one member selected from the group consisting of an aliphatic functionality comprising at least about 4 carbon atom, an ester functionality comprising between about 1 and about 11 carbon atoms, a carbonate functionality comprising between about 1 and about 11 carbon atoms, and a benzylic functionality comprising at least about 7 carbon atoms which is attached to the terminal sulfur atom via the benzylic methylene carbon; and
wherein y is 3 or 6.
80. A pyridine compound having the following structure (II),
Figure imgf000045_0001
(II)
wherein e is between about 0 and about 11 ;
wherein f is between about 1 and about 11 ;
wherein g is between about 1 and about 11 ;
wherein h is between about 1 and about 5;
wherein X is a linking functionality which is one member selected from the group consisting of a linear aliphatic chain comprising between about 1 and about 11 carbon atoms, a cyclic aliphatic ring comprising at least 5 carbon atoms, a cyclic aromatic ring comprising at least 6 carbon atoms, a cyclic aliphatic heterocycle comprising at least 3 carbon atoms, and a cyclic aromatic heterocycle comprising at least 3 carbon atoms;
wherein Y is a linking functionality which is one member selected from the group consisting of a linear aliphatic chain comprising between about 1 and about 11 carbon atoms, a cyclic aliphatic ring comprising at least 5 carbon atoms, a cyclic aromatic ring comprising at least 6 carbon atoms, a cyclic aliphatic heterocycle comprising at least 3 carbon atoms, and a cyclic aromatic heterocycle comprising at least 3 carbon atoms;
wherem R3 is a hydrogen or a sulfur-protecting functionality which is one member selected from the group consisting of an aliphatic functionality comprising at least about 4 carbon atom, an ester functionality comprising between about 1 and about 11 carbon atoms, a carbonate functionality comprising between about 1 and about 11 carbon atoms, and a benzylic functionality comprising at least about 7 carbon atoms which is attached to the teπriinal sulfur atom via the benzylic methylene carbon; and
wherein at least one member selected from the group consisting of R4, R5s R6, R7, and Rg is a {[(X)eS]f[(Y)gS-R3]} chain, and each of R4, R5, R6, R7, and Rg that is not a {[(X)eS]t{(Y)gS-R ]} chain is independently one member selected from the group consisting of a hydrogen, a fluoride, a bromide, a chloride, an iodide, a vinyl group, a hydroxide, an alkoxide functionality comprising between about 1 and about 11 carbon atoms, an aryloxide functionality comprising at least about 6 carbon atoms, an aliphatic functionality comprising between about 1 and about 11 carbon atoms, an aromatic functionality comprising at least about 6 carbon atoms, a cycloaliphatic ring comprising at least about 5 carbon atoms, said cycloaliphatic ring being fused to the pyridine ring tlirough an adjacent ring substituent, and a cycloaromatic ring comprising at least about 6 carbon atoms, said cycloaromatic ring being fused to the pyridine ring through an adjacent ring substituent.
81. A benzimidazole compound having following the structure (III),
Figure imgf000046_0001
(III) wherein i is between about 0 and about 11 ;
wherein j is between about 1 and about 11 ;
wherein k is between about 1 and about 11 ;
wherein R9 is a hydrogen atom or a sulfur-protecting functionality which is one member selected from the group consisting of an aliphatic functionality comprising at least about 4 carbon atom, an ester functionality comprising between about 1 and about 11 carbon atoms, a carbonate functionality comprising between about 1 and about 11 carbon atoms, and a benzylic functionality comprising at least about 7 carbon atoms which is attached to the terminal sulfur atom via the benzylic methylene carbon;
wherein Rio is one member selected from the group consisting of a hydrogen, an aliphatic carbonyl functionality comprising about 1 to about 11 carbon atoms, an aliphatic functionality comprising between about 1 and about 11 carbon atoms, an aromatic carbonyl functionality comprising at least about 7 carbon atoms, and an aromatic functionality comprising at least about 6 carbon atoms; and
wherein each of Rn, Rn, R13 and R14 are independently one member selected from the group consisting of a hydrogen, a fluoride, a bromide, a chloride, an iodide, a vinyl group, a hydroxide, an alkoxide functionality comprising between about 1 and about 11 carbon atoms, an aryloxide functionality comprising at least about 6 carbon atoms, an aliphatic functionality comprising between about 1 and about 11 carbon atoms, an aromatic functionality comprising at least about 6 carbon atoms, a cycloaliphatic ring comprising at least about 5 carbon atoms, said cycloaliphatic ring being fused to the benzimidazole arene ring through an adjacent ring substituent, and a cycloaromatic ring comprising at least about 6 carbon atoms, said cycloaromatic ring being fused to the benzimidazole arene ring through an adjacent ring substituent.
82. A benzothiazole compound having the following structure (IV),
Figure imgf000048_0001
(IV)
wherein 1 is between about 0 and about 11 ;
wherein m is between about 1 and about 11 ;
wherein n is between about 1 and about 11 ;
wherein R15 is a hydrogen atom or a sulfur-protecting functionality which is one member selected from the group consisting of an aliphatic functionality comprising at least about 4 carbon atom, an ester functionality comprising between about 1 and about 11 carbon atoms, a carbonate functionality comprising between about 1 and about 11 carbon atoms, and a benzylic functionality comprising at least about 7 carbon atoms which is attached to the terminal sulfur atom via the benzylic methylene carbon; and
wherein each of Rι6, R17, Ris, and R19 are independently one member selected from the group consisting of a hydrogen, a fluoride, a bromide, a chloride, an iodide, a vinyl group, a hydroxide, an alkoxide functionality comprising between about 1 and about 11 carbon atoms, an aryloxide functionality comprising at least about 6 carbon atoms, an aliphatic functionality comprising between about 1 and about 11 carbon atoms, an aromatic functionality comprising at least about 6 carbon atoms, a cycloaliphatic ring comprising at least about 5 carbon atoms, said cycloaliphatic ring being fused to the benzothiazole arene ring through an adjacent ring substituent, and a cycloaromatic ring comprising at least about 6 carbon atoms, said cycloaromatic ring being fused to the benzothiazole arene ring tlirough an adjacent ring substituent.
83. An imidazole compound having the following structure (V),
Figure imgf000049_0001
(V)
wherein o is between about 0 and about 11 ;
wherein p is between about 1 and about 11 ;
wherein q is between about 1 and about 11 ;
wherein R 0 is a hydrogen atom or a sulfur-protecting functionality which is one member selected from the group consisting of an aliphatic functionality comprising at least about 4 carbon atom, an ester functionality comprising between about 1 and about 11 carbon atoms, a carbonate functionality comprising between about 1 and about 11 carbon atoms, and a benzylic functionality comprising at least about 7 carbon atoms which is attached to the terminal sulfur atom via the benzylic methylene carbon;
wherein R21 is one member selected from the group consisting of a hydrogen, an aliphatic carbonyl functionality comprising about 1 to about 11 carbon atoms, an aliphatic functionality comprising between about 1 and about 11 carbon atoms, an aromatic carbonyl functionality comprising at least about 7 carbon atoms, and an aromatic functionality comprising at least about 6 carbon atoms; and
wherein each of R22 and R23 are independently one member selected from the group consisting of a hydrogen, a fluoride, a bromide, a chloride, an iodide, a vinyl group, a hydroxide, an alkoxide functionality comprising between about 1 and about 11 carbon atoms, an aryloxide functionality comprising at least about 6 carbon atoms, an aliphatic functionality comprising between about 1 and about 11 carbon atoms, an aromatic functionality comprising at least about 6 carbon atoms, a cycloaliphatic ring comprising at least about 5 carbon atoms, said cycloaliphatic ring being fused to the imidazole ring through an adjacent ring substituent, and a cycloaromatic ring comprising at least about 6 carbon atoms, said cycloaroamtic ring being fused to the imidazole ring through an adjacent ring substituent.
PCT/US2003/006435 2003-03-03 2003-03-03 Method for producing bisphenol catalysts and bisphenols WO2004078345A1 (en)

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