| PATENT ASSIGNEE'S COUNTRY | USA |
| UPDATE | 04.00 |
| PATENT NUMBER | This data is not available for free |
| PATENT GRANT DATE | 18.04.00 |
| PATENT TITLE |
Polymeric substrate containing mercapto and sulfonic groups |
| PATENT ABSTRACT |
A catalyst useful for the condensation of an aldehyde or ketone starting material with a phenol is an insoluble mercaptosulfonic acid compound. The heterogeneous catalysts comprise catalytically-active species represented by the formula: ##STR1## L is an optional linking group and -- is a bond, which catalytically-active species is attached by the bond -- to an insoluble organic or inorganic support; or a catalytically-active species represented by the formula: ##STR2## wherein L' is an optional linking group, -- is a bond and .theta.' and .theta." are residues of .theta., and a and b are independently selected from integers equal to or greater than 1. |
| PATENT INVENTORS | This data is not available for free |
| PATENT ASSIGNEE | This data is not available for free |
| PATENT FILE DATE | 27.04.98 |
| PATENT REFERENCES CITED |
Camps et al.; "Separation of a commercial mixture of isomers of chloromethylstyrene into its constituents, 3-chloromethyl styrene and 4-chloromethylstyrene", 1982; Fr. Makromol. Chem., Rapid Commun.; 3(1), pp. 35-40, Pham Quang Tho Lab Chim Org Macromol, Unites Enseign Rech Sci, Saint-Etienne, 42023. Chemical Abstract 32290x (1970). Selva et al., "Improved Selectivity in the Chloromethyllation of Alkylbenzenes in the Presence of Quaternary Ammonium Salts", Synthesis, pp. 1003-1004. Shinkai et al., "Enhanced Reactivity and Affinity of Polymeric 3-Carbamoylpyridinium toward Cyanide Ion", Polymer Letters Edition, John Wiley and Sons, vol. 14, pp. 1-3, (1976). Ellis et al., "The Preparation and Properties of a Double Series of Aliphatic Mercaptans," J. Am. Chem. Soc., vol. 54 (1932), pp. 1674-1687. Schramm et al., "The Synthesis of mercaptoalkanesulfonic Acids," J. Am. Chem. Soc., vol. 77 (1955), pp. 6231-6233. Frank et al., "The Preparation of Mercaptans from Alcohols," J. Am. Chem. Soc., vol. 68 (1946), pp. 2103-2104. Chem. Abs., 90:86742m (1979) (Bruszewski). R. Fischer, "Propanesultone," Ind. Eng. Chem., vol. 56 (1964), pp. 41-45. A. Mustafa, "The Chemistry of Sultones and Sultams," Chemical Reviews, vol. 54 (1954), pp. 195-223. G. Manecke et al., Chem. Abs. 53:2083c (1959). E. Goethals, "Synthesis and Polymerization of Allyl Vinyl Sulfonate," Polymer Letters, vol. 4, (1966), pp. 691-693. E. Goethals et al., "Polymerization and Copolymerization of Allyl Allyl Sulfonate," J. Macromol. Sci.-Chem., vol. A5 (1971), pp. 63-72. A. Warshawsky et al., "Functionalization of Polystyrene. I. Alkylation wiwth Substituted Benzyl Halide and Benzyl Alcohol Compounds," J. Org. Chem., vol. 43 (1978), pp. 3151-3157. Akelah et al., "Application of Functionalized Polymers in Organic Synthesis," Chem. Rev., vol. 81 (1981), pp. 557-587. Frechet et al., "Functionalization of Crosslinked Polystyrene Resins by Chemical Modification: A Review," in "Chemistry and Properties of Crosslinked Polymers" S. Labana, ed., Academic Press, New York (1977), pp. 59-83. Marechal, "Chemical Modification of Synthetic Polymers," in "Comprehensive Polymer Science," vol. 6, Allen, ed., Pergamon Press, New York, pp. 1-47. M. B. Smith et al., "Lithium Aluminum Hydride-Aluminum Hydride Reduction of Sultones," J. Org. Chem., vol. 46 (1981), pp. 101-106. T. Durst et al., "Metallation of 5- and 6-membered ring sultones," Can. J. Chem., vol. 47 (1969), pp. 1230-1233. T. Durst et al., "A new route to 5- and 6-membered ring sultones," Can. J. Chem., vol. 48 (1970), pp. 845-851. Tomoi et al., "A Novel One-pot Synthesis of Spacer-modified Polymer Supports and Phase-transfer Catalytic Activity of Phosphonium Salts Bound to the Polymer Supports," Reactive Polymers, vol. 3 (1985), pp. 341-349. M. S. Chiles et al., "Phase Transfer Catalysts Anchord to Polystyrene," Tetrahedron Letters (1979), pp. 3367-3370. M. Tomoi et al., "Novel Synthesis of Spacer-Modified Polymer Supports and Activity of Phase-Transfer Catalysts Derived from the Polymer Supports," J. Polymer. Sci. Polymer Chem. Ed., vol. 20 (1982), pp. 3015-3019. M. J. Farrall et al., "Bromination and Lithiation: Two Important Steps in the Functionalization of Polystyrene Resins," J. Org. Chem., vol. 41 (1976), pp. 3877-3882. S. P. McManus et al., "Reactions of Cyclic Halonium Ions and Alkylene Dihalides with Polystyryllithium. Preparation of haloalkylated Polystyrene," J. Org. Chem., vol. 45 (1980), pp. 2717-2719. M. Haratake et. al. "Sorption of Phenols on Anion-Exchange Resins Having .omega.-Oxoalkyl or .omega.-Hydroxyalkyl Spacer," Analytical Sciences, vol. 4 (1988), pp. 591-594. M. Gauthier et al., "Alkylated Styrene Ionomers with Variable Length Spacers. I. Synthesis," J. Polymer Sci.: Part A: Polymer Chem., vol. 28 (1990), pp. 1549-1568. P. Tundo, "Easy and Economical Synthesis of Widely Porous Resins; Very Efficient Supports for Immobilized Phase-Transfer Catalysts," Synthesis (1978), pp. 315-316. G. Zheng, et. al. "Synthesis of Bromoalkylated Crosslinked Polystyrene," Xinan Shifan Daxue Xuebao, Ziran Kexueban, vol. 2 (1986) pp. 68-70 Chem. Abs. 105:192049. M. L. Hallensleben, "Preparation of Poly(p-(.omega.-lithiumalkyl)styrenes) and Their use as Polymer Metalating Agents," Angew. Makromol. Chem., vol. 31 (1973), pp. 147-159 Chem. Abs. 79:54020. F. Doscher et al., "Synthesis of Sulfoalkylated Styrene-Divinylbenzene Copolymers," Makromol. Chem., Rapid Commun., vol. 1 (1980), pp. 297-302. E. De Witte et al ., Telomerization Studies with Allyl Ethene Sulfonate and Allyl Allyl Sulfonate, J. Makromol. Sci.-Chem., vol. A5 (1975), pp. 73-88. |
| PATENT PARENT CASE TEXT | This data is not available for free |
| PATENT CLAIMS |
We claim: 1. A catalytically-active material comprising an insoluble organic or inorganic support in which is incorporated a polystyrene resin having a mercaptosulfonic acid residue represented by the formula ##STR31## wherein n is an integer of from 0 to 10. 2. The catalytically-active material of claim 1, wherein n is 2 or 3. ##STR32## |
| PATENT DESCRIPTION |
BACKGROUND OF THE INVENTION This invention relates to preparation of polyphenols, more particularly to the preparation of polyphenols from ketones or aldehydes and phenols. Acid-catalyzed condensation of phenols with aldehydes or ketones is well known. Acid catalysts include acidic ion exchange resin catalysts and soluble acid catalysts. Soluble acid catalysts can be, for example, hydrogen chloride, sulfuric acid, hydrochloric acid, phosphoric acid, hydrobromic acid, nitric acid, dimethyl sulfate, sulfur dioxide, 4-toluenesulfonic acid, boron trifluoride, alkanesulfonic acids, boron trifluoride complexes and other acid-acting compounds, including compounds which are hydrolyzed by water to form acids, e.g. aluminum chloride, sulfonyl chloride and phosgene. A number of compounds are known to promote such an acid-catalyzed condensation. These promoters include mercaptan groups which are either free or bound to a resin. Alkyl mercaptans and bis-mercaptoethanolamine are examples of reported promoters. It has been proposed by Scriabine et al. (U.S. Pat. No. 2,923,744) to produce Bisphenol A using sulfuric acid, promoted by mercaptoalkanesulfonic acids or salts or corresponding sulfonate esters at a level of 0.1-5% by weight of the base charge, to catalyze condensation of acetone and phenols, when used in amounts of 0.1 to 5 percent by weight based on total charge. Sulfuric acid is used in amounts of about 2 moles per mole of acetone. Riemann et al. (U.S. Pat. No. 4,675,458) have proposed making 9,9-bis-(4-hydroxyphenyl)fluorene in the presence of sulfuric acid, preferably concentrated sulfuric acid, and a mercaptan, particularly 3-mercaptopropionic acid, as promoter. Massirio et al. (U.S. Pat. No. 5,248,838) have disclosed the use of a combination of methanesulfonic acid and a mercaptan/mercaptoalkanoic acid for catalyzing the condensation of phenols with fluorenone. High levels of methanesulfonic acid with respect to the feed and the mercaptan/mercaptoalkanoic acid, are used. The reactions can be run in halogenated hydrocarbon solvents. Bottenbruch et al. (U.S. Pat. No. 4,996,373) have proposed a process for producing dihydroxyaryl compounds from carbonyl compounds and phenols under high pressure, in the presence of various catalysts, including sulfonic acid resins. Catalysts containing sulfhydryl functionality, e.g. ion exchangers treated with mercapto compounds, have been disclosed for this use. Meyer et al. (U.S. Pat. No. 4,387,251) have proposed processes for making 4,4'-dihydroxydiphenyl alkanes using aromatic sulfonic acids as condensing agents. Mercapto groups are included within the definition of R.sub.3 and are characterized as being inert. Freitag et al. (U.S. Pat. No. 5,210,328) disclose using the same types of sulfonic acid catalysts for making cycloalkylidene bisphenols. Jansen (U.S. Pat. No. 2,468,982) has proposed preparation of bisphenols using anhydrous hydrogen chloride in combination with a mercaptoalkanoic acid, which may be formed in situ by reaction of a mercaptol with the ketone, as condensing agent. Knebel et al. (U.S. Pat. No. 4,931,594) disclose the use of large amounts of sulfonic acid resin, mixed with uncombined 3-mercaptopropionic acid, to cause the condensation to occur. It has been proposed in British Patent 1,185,223 to use a mixture of insoluble resins, one a sulfonic acid resin and the other a resin containing mercapto groups, for making bisphenols. Randolph et al. (U.S. Pat. No. 5,212,206) disclose a catalyst, made by treating a sulfonated ion-exchange resin with a dialkylaminomercaptan. Other references, representative of references on modification of sulfonic acid ion-exchange resins, include Wagner (U.S. Pat. No. 3,172,916). McNutt et al. (U.S. Pat. No. 3,394,089), Faler et al. (U.S. Pat. Nos. 4,455,409; 4,294,995 and 4,396,728); Heydenrich et al. (U.S. Pat. No. 4,369,293); Berg et al. (U.S. Pat. No. 5,302,774) and Maki et al. (U.S. Pat. No. 4,423,252). The reactive catalysts generally include mercapto-functions attached to a sulfonic acid group in the form of a sulfonamido or ammonium sulfonate salt. Shaw (U.S. Pat. No. 4,859,803) discloses preparing bis-phenols from phenol and a ketone in the presence of an acidic (sulfonic acid) ion-exchange resin and a mercaptan, the mercaptan being added at particular locations of a specified reactor configuration to prevent the formation of cyclic dimers. Li has disclosed (U.S. Pat. No. 4,825,010) isomerization of by-products of condensates of phenols and ketones, using a catalytic amount of acidic sulfonated cationic-exchange resin having sulfonic acid sites ionically bonded to alkylmercaptoamines. Other patents by Li (U.S. Pat. Nos. 4,822,923 and 5,001,281) further suggest the state of the art of using ion-exchange resins to isomerize by-products of bisphenol syntheses. Powell et al. (U.S. Pat. No. 5,105,026) disclose using acidic ion-exchange resins to isomerize undesirable products of bisphenol synthesis to desirable products, e.g. to Bisphenol A. Morgan (U.S. Pat. No. 3,546,165) has disclosed condensation of phenol with various ketones, including fluorenone and indanone, using high levels of hydrochloric acid or hydrogen chloride, in the presence of minor amounts of 3-mercapto-propionic acid. The products are used for the preparation of polyester resins. Szabolcs (U.S. Pat. Nos. 4,467,122 and 4,503,266) discloses washing crude product, containing BHPF, from a hydrochloric acid/zinc chloride catalyzed process, to B remove HCl, ZnCl.sub.2 and excess phenol, prior to recrystallization from dichloroethane. See also the abstract for DE OLS 2,948,222 (7/30/81). Korshak et al. (SU 172,775) disclose washing a mixture of phenol, BHPF and HCl with water, after which phenol is removed by distillation. The following references, herein incorporated by reference, disclose the preparation of resins, containing sulfonic acid functionality, introduced either by copolymerization or by sulfonation after polymerization: ______________________________________ U.S. Pat. No. 3,205,285 Turbak et al. U.S. Pat. No. 3,366,711 Mazzolini et al. U.S. Pat. No. 3,426,104 Masson U.S. Pat. No. 4,587,304 Thaler et al. U.S. Pat. No. 4,764,557 Eichenauer et al. ______________________________________ Trapasso (U.S. Pat. No. 3,706,707) discloses the preparation of adducts from a polymerized cyclic ether and a sultone. Dean (U.S. Pat. No. 4,568,724) is of similar interest with respect to reaction products from an EPDM rubber and a sultone. Welch (U.S. Pat. No. 3,029,221) and Niwa et al. (U.S. Pat. No. 4,912,170) disclose processes for modifying polystyrene resins. It is an object of this invention to provide a process for the condensation of aldehydes or ketones with phenols, to achieve high yields of preferred bis-(4-hydroxyaryl) isomers with low reaction times while avoiding use of strong inorganic acids. Further objects of the invention include the development of processes for the synthesis of polyphenols, characterized by high yields of high purity products under reaction conditions, which are not corrosive to vessels in which the processes are conducted. In addition, avoiding the use of sulfuric acid, eliminates the possibility of side reactions, including sulfonation of phenols. DISCLOSURE OF THE INVENTION In one aspect, this invention relates to a process for the condensation of an aldehyde or ketone starting material with a phenol, unsubstituted in at least one position, comprising reacting the aldehyde or ketone starting material with the phenol in a reaction mixture in the presence of a soluble or insoluble mercaptosulfonic acid compound under conditions sufficient to bring about formation of a geminal bisphenolic moiety at each aldehyde or ketone moiety in the starting material; provided that the soluble mercaptosulfonic acid compound is characterized by the formula (HS).sub.a --.theta.--(SO.sub.3 H).sub.b wherein .theta. is an alkylene, cycloaliphatic, arylene, alkylenearylene, alkylenecycloaliphatic, alkylenearyl, heterocyclic or alkyleneheterocyclic residue and a and b are independently selected from integers from 1 to about 20; and the insoluble mercaptosulfonic acid comprises a catalytically-active species represented by the formula ##STR3## in which .theta.' is an alkylene, cycloaliphatic, arylene, alkylenearylene, alkylenecycloaliphatic, alkylenearyl, heterocyclic or alkyleneheterocyclic residue; a and b are independently selected from integers from 1 to about 20; L is an optional linking group and--is a bond, which catalytically-active species is attached by the bond--to an insoluble organic or inorganic support; or a catalytically-active species represented by the unit formula ##STR4## wherein .theta." is an alkylene, arylene, cycloaliphatic, alkylenearylene, alkylenecycloaliphatic, alkylenearyl, heterocyclic or alkyleneheterocyclic residue; a and b are independently selected from integers from 1 to about 20; L' is an optional linking group and--is a bond. This invention further relates to novel catalytically-active polystyrene resins, characterized by bearing at least one of each of a mercapto function and a sulfonic acid function on some individual styrene units of a polymer chain. In yet another aspect, this invention relates to processes for preparing the catalytically-active polystyrene resins. These processes preferably comprise steps of (b) sulfonating a haloalkylpolystyrene to produce an intermediate having sulfo functional groups; (c) optionally converting the sulfo functional groups to corresponding alkali metal salts; (d) thiolating the thus-produced sulfostyrene intermediate by reacting the halo function with a reactive thiolate to produce a corresponding mercapto group or precursor thereof;(e) optionally hydrolyzing the thus-thiolated intermediate with an acid or base when the thiolated group so requires and (f) optionally acidifying (if so required) to produce sulfonic acid functional groups units. The process of the invention permits use of very low levels of a single acidic condensing agent. The process permits simplified product isolation procedures, recycle procedures, and/or waste management. The process does not require a neutralization step to remove hydrochloric or sulfuric acid and does not produce a waste salt stream. The acidic condensing agents used in the process of this invention are readily removed from the reaction mixtures and can be recovered and recycled. The process of this invention results in high selectivity toward preferred bis-(4-hydroxyaryl) isomers and very fast reaction rates. The process of this invention is particularly useful for the preparation of bis(hydroxyaryl) compounds, such as bisphenol A and 9,9-bis-(4-hydroxyphenyl)fluorene, both of which are useful in the preparation of polycarbonates and other commercially significant polymers. The heterogeneous catalysts disclosed herein advantageously are more reactive than heterogeneous catalysts currently used. They advantageously allow using lower temperatures with correspondingly greater selectivity for desired product than is currently experienced. Greater selectivity reduces purification necessary to produce a desired or preselected purity of product. Thus for a commercially produced bisphenol like Bisphenol A, a heterogeneous catalyst disclosed herein can be advantageously substituted in an existing commercial process, run with the same or higher throughput at a lower temperature with less purification to achieve at least equally pure product. |
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| PATENT PHOTOCOPY | Available on request |
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