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Oligomers and polymers containing sulfinate groups, and methods for producing the sameRelated Patent Categories: Synthetic Resins Or Natural Rubbers -- Part Of The Class 520 Series, Natural Rubber Compositions Having Nonreactive Materials (dnrm) Other Than: Carbon, Silicon Dioxide, Glass Titanium Dioxide, Water, Hydrocarbon, Halohydrocarbon, Ethylenically Unsaturated Reactant Admixed With A Preformed Reaction Product Derived From: (a) At Least One Polycarboxylic Acid, Ester, Or Anhydride; (b) At Least One Polyhydroxy Compound; And (c) At Least One Fatty Acid Glycerol Ester, Or A Fatty Acid Or Salt Derived From A Naturally Occurring Glyceride, Tall Oil, Or A Tall Oil Fatty Acid, At Least One Solid Polymer Derived From Ethylenic Reactants Only, Chemical Treating Agent Contains A Sulfur AtomOligomers and polymers containing sulfinate groups, and methods for producing the same description/claimsThe Patent Description & Claims data below is from USPTO Patent Application 20080090972, Oligomers and polymers containing sulfinate groups, and methods for producing the same. Brief Patent Description - Full Patent Description - Patent Application Claims
SUMMARY [0001] The invention relates to polymers obtained by S-alkylation of sulfinated polymers with alkylation agents, and AB-cross-linked polymers obtained by reacting polymers containing alkylation groups with low-molecular sulfinates, under S-alkylation, or AB-cross-linked polymers obtained by S-alkylation of sulfinated polymers with polymers containing alkylation groups, whereby sulfinated polymers are reacted with alkylation agents (I) wherein R represents alkyl, aryl, or any organic radicals; [0002] M represents alkali ions or alkaline-earth ions or any monovalent or bivalent metal cation or ammonium cation; ALK represents any alkylation group or polymer; Poly represents any polymer main chain; Hal represents F, Cl, Br or Iodine; x represents a number between 2 and 20; X represents electron-attracting groups and [0003] n represents the number of repeat units of the base polymer; and whereby polymers containing alkylation groups are reacted with sulfinated compounds. [0004] The invention also relates to the polymers obtained by reacting sulfinated polymers with mixtures of various monofunctional alkylation agents. Furthermore, the invention relates to polymers obtained by reacting sulfinated polymers with mixtures of monofunctional and difunctional or oligofunctional alkylation reagents (cross-linking agents), in addition to membranes and other moulded bodies. Disclosed are also the polymers obtained by reacting polymers containing alkylation groups with low-molecular or high-molecular sulfinates, whereby mixtures of various sulfinates can also be used. [0005] Finally, the invention relates to methods for producing said sulfinate-alkylated polymers, and for producing membranes and other moulded bodies from said sulfinate-alkylated polymers. STATE-OF-THE-ART [0006] It is known from the literature, that low-molecular sulfinates can be S- or O-alkylated.sup.1. Thus the alkylation of sulfinates with methyl iodide with formation of a methyl sulfone has been described. It is known, that polymers containing sulfinate groups can be cross-linked using dihalogen or oligohalogen alkanes by sulfinate-S-alkylation.sup.2,3. It is also known, that sulfinate groups can be alkylated via nucleophilic aromatic substitution.sup.4. Furthermore it is known, that sulfinate ions are able to do a Michael-typ-addition on olefines carrying electron-attracting groups.sup.5. .sup.1 T. Okuyama, Sulfinate ions as nucleophiles, in "The Chemistry of Sulphinic Acids, Esters and their Derivatives (Ed. S. Patai), John Wiley and Sons, 1990, S. 639-664 .sup.2 J. Kerres, W. Zhang, W. Cui, J. Polym. Sci.: Part A: Polym. Chem. 36, 1441-1448 (1998) .sup.3 Jochen Kerres, Wei Cui, Martin Junginger, J. Memb. Sci. 139, 227-241 (1998) .sup.4 A. Ulman, E. Urankar, J. Org. Chem. 54, 4691-4692 (1989) .sup.5 S. Oae, N. Kunieda, in Organic Chemistry of Sulfur (Ed. S. Oae), Plenum, New York, 1977, S. 625-637 [0007] The introduction of functional groups according to the invention (especially anion exchange groups, cation exchange groups as well as their non-ionic precursors without cross-linking reactions) in polymeric sulfinates via sulfinate alkylation with halogen compounds or with sultones or other electrophilic groups, which react with sulfinate groups, e.g. olefines with electron-attracting groups, using methods according to the invention has not been described so far to our knowledge in the literature. DESCRIPTION OF THE INVENTION [0008] Surprisingly it has been found, that sulfinated polymers can be modified versatile via sulfinate-S-alkylation. By means of this reaction functional groups can be introduced in polymers, which can not be introduced by other methods. A selection of the newly-discovered reactions is shown in FIG. 1. [0009] The first set concerns the reaction of sultones with polymeric sulfinates, as shown e.g. in FIG. 2. However in principle there is no limitation for the selection of the sultones. Any sultone can be used. The small ring sultones (4- and 5-rings) are more reactive due to their high ringtension than the big ring-sultones (6-rings and bigger). The highest reactivities are shown by the perfluorinated small-ring sultones such as for the perfluorinated sultone in FIG. 2. Also lactames, lactones and sultames as well as mixed compounds from these components can be reacted with sulfinates. [0010] The second set of reactions is the surprisingly possible alkylation of polymeric sulfinates with halogen aryl-, halogen alkyl- and halogen benzyl-ammonium- and phosphonium salts, as shown e.g. in FIG. 3. [0011] There is in principle no limitation to the selection of the respective ammonium- or phosphonium salt, however preferred are such ammonium- or phosphonium salts, which carry either long alkyl (longer than propyl)- or phenyl groups on the ammonium or phosphonium group, because such salts are better soluble in these organic solvents, in which also the polymeric sulfinates are soluble (dipolar-aprotic solvents such as N,N-dimethylformamide DMF, N-methylformamide, N,N-dimethylacetamide DMAc, N,N-dimethylpyrrolidinone NMP, dimethylsulfoxide DMSO, sulfolane). To further improve the compatibility of the solutions of sulfinated polymers with the ammonium-/phosphonium salts crown ethers can be added to the polymer solution such as 18-crown-6,15-crown-5 oder 12-crown-4, which coordinate the cation of the sulfinate group. For the halogen leaving group of halogen alkyl or benzyl compounds the following order of reactivity for the alkylation of the sulfinate group has been observed: I>>Br>Cl>>F. For the halogen leaving group of halogen aryl compounds the following order of reactivity for the alkylation of the sulfinate group has been observed: F>>Cl>Br>I. [0012] Surprisingly, a further group of halogen compounds, which react with polymeric sulfinates, are halogenated primary, secondary and tertiary aliphatic, aromatic and/or benzylic amines as well as halogen benzyl amines and their hydrohalogenides, some of these are shown in FIG. 4. Hereby the amino group can be protected with an amino protection group. Especially surprising is also the introduction of imidazole groups according to the invention possible, as shown in FIG. 4a and FIG. 4b. FIG. 4a shows the reaction of fluorinated aryl imidazole derivatives with polymeric sulfinates, whereas in FIG. 4b is shown the reaction of halogen alkyl imidazoles with polymeric sulfinates. [0013] A fourth set of reactions concerns the surprisingly possible S-alkylation of sulfinates with halogen alkyl- or halogen aryl- or halogen benzyl-sulfonates, phosphonates, carboxylates, boronates or their non-ionic precursors, some of which are shown in FIG. 5a. [0014] Hereby are preferred the non-ionic precursors of sulfonates, phosphonates and carboxylates (acid halides, acid esters, acid amides, acid imides, acid anhydrides), because they are better soluble in the organic solvents which are used to dissolve the polymeric sulfinates, and also do not show undesirable interactions with sulfinate groups (such as e.g. formation of ion pairs). If necessary, crown ethers can be added to the sulfinated polymer solutions and the halogen aryl-, halogen alkyl- or halogen benzyl carboxylates, halogen aryl-, halogen alkyl- or halogen benzyl phosphonates or halogen aryl-, halogen alkyl- or halogen benzyl sulfonates or halogen aryl-, halogen alkyl- or halogen benzyl boronates, to complex the cations of the salts. [0015] As already mentioned, amongst the aromatic halogens the aromatic fluorine compounds react best with sulfinates via S-alkylation. It has been found surprisingly, that the addition of calcium compounds to the reaction mixture and/or the after-treatment of the polymers, polymer blends, polymer (blend) membranes or other bodies obtained from the reaction products according to the invention with aqueous solutions of calcium compounds favours the sulfinat-S-alkylation reaction. Presumably the fluoride anions liberated during the S-alkylation are precipitated from the reaction equilibrium by formation of very sparingly soluble calcium fluoride: 2Ar--F+2MO.sub.2S--R'+Ca.sup.2+.fwdarw.2Ar--S(O).sub.2--R'+CaF.sub.2 [0016] If the S-alkylation reaction is conducted in organic solvents, calcium compounds are preferred, which are soluble in organic solvents, such as e.g.: [0017] calcium acetylacetonate (Bis-(2,4-pentanedionato)-calcium) [0018] calcium-bis-(6,6,7,7,8,8,8-heptafluor-2,2-dimethyl-3,5-octandionate) [0019] calcium-1,1,1,5,5,5-hexafluoracetylacetonate [0020] calciummethylate [0021] calciumoxalate [0022] calcium-D-gluconate [0023] calcium-(2,2,6,6-tetramethyl-3,5-heptandionate) [0024] calciumtriflate (Trifluormethanesulfonic acid calcium salt) [0025] However for some reactions it is sufficient to add to the reaction mixture an in the used solvent sparingly soluble calcium salt, because already small quantities of calcium ions and fluoride ions in the reaction mixture are sufficient to precipitate calcium fluoride. Thus to the reaction mixture can be added inorganic calcium salts: calcium halogenides, calcium sulfate, calcium hydrogensulfate, calcium phosphate and -hydrogenphosphates, calcium oxide, calcium hydroxide and other calcium salts. [0026] It is also wise to post-treat the reaction products of the S-alkylation of sulfinates with aryl fluor compounds with aqueous solutions of calcium salts, on the one hand to complete the S-alkylation reactions and on the other hand to precipitate the toxic fluoride ions liberated during the reaction with calcium ions as CaF.sub.2, which is important for an industrial production process. [0027] Surprisingly it has been found, that during the reaction of difluorinated and higher fluorinated aromatic sulfonic acid halides with polymeric sulfinates simultaneously cross-linking reactions take place, because the reaction product is no longer soluble in organic solvents. In FIG. 5B the postulated course of the reaction of a polymeric Li-sulfinate with pentafluorobenzene sulfochloride is shown. The covalently cross-linked ionomer membranes obtained show a surprisingly low ionic resistance at a surprisingly low water up-take (swelling) (see examples). [0028] Surprisingly it has been found, that a mixture of: [0029] low-molecular difluorinated and higher fluorinated aromatic sulfonic acid halides carbonic acid halides or phosphonic acid halides or other non-ionic precursors of corresponding acids (ester, amides, imides) and [0030] low-molecular perfluorinated aromatic compounds as perfluorodiphenylsulfone, perfluorobenzophenone, perfluorotriphenylphosphinoxide, perfluorodiphenyl, perfluorodiphenylether and other perfluorinated aromatic compounds (FIG. 5c) leads via reaction with polymeric or oligomeric sulfinates to cross-linked ionomer membranes with particularly high chemical stability and low swelling also at high temperatures. [0031] Surprisingly it has been found, that also mixtures of polymeric or oligomeric sulfinates with the following low-molecular compounds lead to covalently cross-linked ionomer membranes with a particular advantageous profile of properties: [0032] low-molecular perfluorinated or partly fluorinated precursor of aromatic carbonic acids, phosphonic acids or sulfonic acids or their non-ionic precursor (acid halides, acid amides, acid imides, acid ester) and [0033] dihalogen alkanes Hal(CH.sub.2).sub.xHal (x=1-20, Hal=I, Br, Cl) [0034] A further, fifth set of compounds, which reacts surprisingly via S-alkylation with polymeric sulfinates, are hetaryl halogen compounds, a selection of which is shown in FIG. 6. [0035] In particular it has been found, that by the reaction according to the invention reactive dyes can be bound to sulfinated polymers. In FIG. 7 exemplary reactive groups of dyes are shown, which react with sulfinate groups by S-Alkylation. The order of affinity of (het)aromatic halogen compounds for the S-Alkylation reaction is F>Cl>Br>I. Thereby the reactive groups are not limited to halogen radicals, but can be also protected or unprotected vinylsulfone groups or other unsaturated olefine groups. Olefines with electron-attracting groups (e.g. sulfone groups, sulfonate group, sulfonamide group, sulfonimide group, nitro group, halogen group, nitroso group, carbonyl group, carboxyl group) are preferred. Continue reading about Oligomers and polymers containing sulfinate groups, and methods for producing the same... 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