Oligomers and Polymers Containing Sulfinate Groups, and Methods for Producing the Same

Abstract

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.

1 . Modified polymers or polymer blends or polymer (blend) membranes or polymer moulded bodies, characterized in that a polymer containing at least sulfinate groups SO 2 M, a polymer blend containing at least sulfinate groups SO 2 M, a polymer(blend)membrane containing at least sulfinate groups SO 2 M or other moulded bodies containing at least sulfinate groups SO 2 M (M represents 1-, 2- or 3-valent metal cation or ammonium ion NR 4   +  (R represents H and/or alkyl and/or Aryl or imidazolium ion or pyrazolium ion or pyridinium ion) are subjected to S-alkylation reactions of the sulfinate group, wherein ALK represents any alkylation agent or mixture of different alkylation agents, that react by S-Alkylation either by substitution or by addition (with olefins with electron-attracting groups) with the sulfinate group:  
       
         
           
           
               
               
           
         
       
       thereby the alkylation agent shows 1 or 2 or >2 alkylation groups.  
     
     
         2 . Modified polymers or polymer blends or polymer (blend) membranes or polymer moulded bodies, characterized in that a polymer containing at least alkylation groups, a polymer blend containing at least alkylation groups, a polymer(blend)membrane containing at least alkylation groups or other moulded bodies containing at least alkylation groups ALK reacts with a low-molecular or high-molecular sulfinate compound R—SO 2 M (R=any organic radical resp. polymer repeat unit) by S-alkylation of the sulfinate groups, wherein ALK represents any alkylation agent or mixture of different alkylation agents, that react by S-Alkylation either by substitution or by addition (with olefins with electronen-attracting groups) with the sulfinate group:  
       
         
           
           
               
               
           
         
       
     
     
         3 . Modified polymers or polymer blends or polymer (blend) membranes or polymer moulded bodies according to  claim 1  and  2  characterized in that M represents alkali ions (Li + , Na + , K + , Rb + , Cs + ) or other monovalent cations such as Cu +  or Ag + , that 0.1 to 8 alkylation groups resp. sulfinate groups per polymer repeat unit are present, and that the alkylation agent or mixture of alkylation agents shows 1 or 2 groups, which can be alkylated.  
     
     
         4 . Modified polymers or polymer blends or polymer (blend) membranes or polymer moulded bodies according to  claim 1  and  2  characterized in that as alkylation agents 
 high-molecular or low-molecular halogen compounds (Hal) n -Al or (Hal) n -Ar or (Hal-CH 2 ) n —Ar or (Hal-Ar) n -Al, n represents a number between 1 and 1000    or    sultones    or    epoxy groups containing high-molecular or low-molecular compounds    or    alkoxy groups containing high-molecular or low-molecular compounds    or    tosylate groups containing high-molecular or low-molecular compounds    or    other nucleophilic leaving groups    or    olefin groups with electron-attracting groups containing high-molecular or low-molecular compounds    containing organic compounds are used (R=alkyl, aryl, hetaryl, any organic radicals, M represents alkali ions or alkaline-earth ions or any monovalent or bivalent metal cation or ammonium cation, polymer represents any polymer main chain, Hal represents F, Cl, Br, I, x represents a number between 2 and 20, X represents electron-attracting-groups, n represents the number of repeat units (RU) of the base polymer):                          
     
     
         5 . Modified polymers or polymer blends or polymer (blend) membranes or polymer moulded bodies according to  claim 4  characterized in that as sultone 4-, 5- 6- or 7-ring-sultones are preferred, in which also benzosultones can be used:  
       
         
           
           
               
               
           
         
       
     
     
         6 . Modified polymers or polymer blends or polymer (blend) membranes or polymer moulded bodies according to  claim 4  and  5  characterized in that as sultone 4- or 5-ring-(benz)sultones are preferred.  
     
     
         7 . Modified polymers or polymer blends or polymer (blend) membranes or polymer moulded bodies according to  claim 4  characterized in that as halogen containing compounds those compounds are preferred that contain one or more anion exchange groups:  
       
         
           
           
               
               
           
         
       
     
     
         8 . Modified polymers or polymer blends or polymer (blend) membranes or polymer moulded bodies according to  claim 7  characterized in that m represents a number between 1 and 10, R 1  represents C n H 2n-1  with n represents a number between 1 and 12 and/or phenyl and Hal represents Cl, Br or I and Ar represents 1,4-phenylen.  
     
     
         9 . Modified polymers or polymer blends or polymer (blend) membranes or polymer moulded bodies according to  claim 4  characterized in that as halogen compound a benzyl compound is used (R represents any organic radical):  
       
         
           
           
               
               
           
         
       
     
     
         10 . Modified polymers or polymer blends or polymer (blend) membranes or polymer moulded bodies according to  claim 9  characterized in that as benzyl compound the following compounds are preferred:  
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
       
     
     
         11 . Modified polymers or polymer blends or polymer (blend) membranes or polymer moulded bodies according to  claim 4  characterized in that as halogen compound a haloamine is used:  
       
         
           
           
               
               
           
         
       
     
     
         12 . Modified polymers or polymer blends or polymer (blend) membranes or polymer moulded bodies according to  claim 4  characterized in that as halogen compound a compound is used, which contains cation exchange groups or their non-ionic precursor:  
       
         
           
           
               
               
           
         
       
     
     
         13 . Modified polymers or polymer blends or polymer (blend) membranes or polymer moulded bodies according to  claim 12  characterized in that as halogen compound the following compounds are preferred:  
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
       
     
     
         14 . Modified polymers or polymer blends or polymer (blend) membranes or polymer moulded bodies according to  claim 4  characterized in that as halogen compounds arylhalogen compounds or hetarylhalogen compounds are used.  
     
     
         15 . Modified polymers or polymer blends or polymer (blend) membranes or polymer moulded bodies according to  claim 14  characterized in that as halogen compounds, compounds are preferred, which contain the following sub-structures:  
       
         
           
           
               
               
           
         
       
     
     
         16 . Modified polymers or polymer blends or polymer (blend) membranes or polymer moulded bodies according to  claim 14  characterized in that as halogen compounds, reactive dyes are preferred containing the following reactive groups: dichlorotriazine, difluoropyrimidine, monofluorotriazine, dichlorochinoxaline, monochlortriazine, trichloropyrimidine, mononicotinic acid triazine, Michael-acceptors such as vinylsulfone or their sulphuric acid ester  
       
         
           
           
               
               
           
         
       
     
     
         17 . Modified polymers or polymer blends or polymer (blend) membranes or polymer moulded bodies according to  claim 15  characterized in that the reactive dyes may contain the following chromophores: 
 Azo with arylpyrazol-5-one as coupling component    Azo with I-acid as coupling component (CC)    Azo with H-acid as CC    Azo-copper complex with H-acid as CC    Coppercomplex-formazane    Phtalocyanine    Anthrachinone    Triphendioxazine    Disazo with H-acid as CC    Azo-Coppercomplex with 1-aryl-pyrazol-5-on as CC    
     
     
         18 . Modified polymers or polymer blends or polymer (blend) membranes or polymer moulded bodies according to  claim 17  characterized in that as base polymers of the modified polymers, polymer blends, polymer (blend) membranes are preferred: 
 polyolefines such as polyethylene, polypropylene, polyisobutylene, polynorbornene, polymethylpentene, polyisoprene, poly(1,4-butadiene), poly(1,2-butadiene)    styrol(co)polymers such as polystyrol, poly(methylstyrol), poly(α,β,β-trifluorstyrol), poly(pentafluorostyrol)    perfluorinated ionomers such as Nafion® or the SO 2 Hal-precursor or the SO 2 M-precursor of Nafion® (Hal represents F, Cl, Br, I), Dow®-membrane, GoreSelect®-membrane    sulfonated PVDF and/or the SO 2 Hal-precursor, in which Hal represents fluorine, chlorine, bromine or iodine    (het)aryl mainchain polymers such as: 
 polyetherketones such as polyetherketone PEK Victrex®, polyetheretherketone PEEK Victrex®, polyetheretherketonketone PEEKK, polyetherketonether-ketonketone PEKEKK Ultrapek®, polyetheretherketonketone PEEKK, polyetherketonketone PEKK  
 polyethersulfone such as polysulfone Udel®, polyphenylsulfone Radel R®, polyetherethersulfone Radel A®, polyethersulfone PES Victrex® polyethersulfone Ultrason® 
 poly(benz)imidazole such as PBI Celazol® and other oligomers and polymers containing the (benz)imidazol-unit, in which the (benz)imidazol group can be present in the main chain or in the side chain  
 polyphenylenether such as poly(2,6-dimethyloxyphenylen), poly(2,6-diphenyloxyphenylen)  
 polyphenylensulfide and copolymers  
 poly(1,4-phenylene) or poly(1,3-phenylene), which can be modified in the side chain with benzoyl-, napthoyl- or o-phenyloxy-1,4-benzoyl groups, m-phenyloxy-,1,4-benzoyl groups or p-phenyloxy-1,4-benzoyl groups,  
 poly(benzoxazole) and copolymers  
 poly(benzthiazole) and copolymers  
 poly(phtalazinone) and copolymers  
 polyaniline and copolymers  
   
     
     
         19 . Modified polymers or polymer blends or polymer (blend) membranes or polymer moulded bodies according to  claim 18  characterized in that as base polymers (Het)aryl main chain polymers are preferred, which consist of the following construction units (R represents construction units, BrG represents bridging groups between construction units (n represents the number of polymer repeat units (RE) 
 (—(R—BrG) n -):                                            
     
     
         20 . Modified polymers or polymer blends or polymer (blend) membranes or polymer moulded bodies according to  claim 19  characterized in that as polymer rests the following types of aryl main chain polymers are preferred: 
 polyethersulfones such as PSU Udel®, PES Victrex®, PPhSU Radel R®, PEES Radel A®, Ultrason®;    polyphenylene such as poly-p-phenylene, poly-m-Phenylene and poly-p-stat-m-phenylene;    polyphenyleneether such as poly(2,6-dimethylphenyleneether) and poly(2,6-diphenylphenyleneether);    polyphenylensulfide    polyetherketone such as polyetheretherketone PEEK, Polyetherketone PEK, polyetheretherketoneketone PEEKK, polyetherketoneketone PEKK, polyetherketonetherketoneketone PEKEKK    
     
     
         21 . Modified polymers or polymer blends or polymer (blend) membranes or polymer moulded bodies according to  claim 20  characterized in that the polymers can carry in addition the following functional groups in any position: NO 2 , Hal, R 2 , N(R 2 ) 2 , SO 2 R 2 , NO, SO 2 Hal, SO 2 N(R 2 ) 2 , R 9 ═C n (C n H 2n-1 ) 2n-1 , R 9 ═C n (Hal) 2n-1 , R 9 ═C n (C n (Hal) 2n-1 ) 2n-1 , (n=1-20), H, Hal (Hal=F, Cl, Br, I), R 9 , OR 9  mit R 9 ═C n H 2n-1 , R 9 ═C n (C n H 2n-1 ) 2n-1 , R 9 ═C n (Hal) 2n-1 , R 9 ═C n (C n (Hal) 2n-1 ) 2n-1  (n=1-20), phenyl, naphtyl, anthracenyl, aryl, hetaryl, N(R 3 ) 2 , N 3 , NO 2 , ONO, nitroalkyl, nitroaryl, COOR 9 .  
     
     
         22 . Process for the production of modified polymers according to  claim 21  characterized in that the polymer containing sulfinate groups are reacted if necessary together with other polymers in a reaction vessel if necessary under inert gas and if necessary dissolved or suspended in a solvent suitable for the respective alkylation reaction with the organic alkylation agents according to the invention or mixtures of alkylation agents and if necessary with in the reaction mixture soluble or sparingly soluble calcium compounds at temperatures between 0° C. to +200° C. if necessary under inert gas with stirring, the reaction mixture is stirred at temperatures between 0° C. and +200° C., until the reaction is finished and then the work-up of the reaction mixture is carried out as follows: 
 (a) water-soluble products:    1) (optionally) addition of a 2 to 10-fold excess of water, aqueous calcium salt solution such as calcium chloride solution or calcium gluconate solution and/or aqueous base solution (1-30% NaOH, KOH, LiOH, Ca(OH) 2 , 1-30% ammonia solution or amine solution), based on the molar mass of alkylation agent, under stirring to the reaction mixture to deactivate alkylation agent in excess and if necessary precipitate the fluoride ions liberated during the reaction as CaF 2 ;    2) -precipitation resp. suspension of the reaction mixture in a 2 to 20-fold excess (based on the volume of the reaction mixture or the modified polymer) of an alcohol (methanol, ethanol, i-propanol, n-propanol) or of water or an aqueous mineral salt solution (NaCl, NaHCO 3 , Na 2 SO 4 , CaCl 2 , etc.) or other common precipitation agents (acetone, methylethylketone etc.) and filtration;    3) washing of the precipitate until the wash water is free of ions;    4) drying at higher temperatures and if necessary reduced pressure;    5) (optionally) redissolution of the modified polymer in a suitable solvent and work-up as above (from 2)).    (b) water-soluble products:    1) mixing of the reaction mixture with a 2 to 10-fold excess of water, aqueous calcium salt solution such as calcium chloride solution or calcium gluconate solution and/or aqueous base solution (1-30% NaOH, KOH, LiOH, Ca(OH) 2 , 1-30% ammonia solution or amine solution), based on the molar mass of alkylation agent, under stirring to the reaction mixture to deactivate alkylation agent in excess and if necessary precipitate the fluoride ions liberated during the reaction as CaF 2 ;    2) mixing of the reaction mixture with a 5 to 20-fold excess of water and dialysis until all low-molecular substances are removed;    3) filtration of all water-insoluble parts of the dialysate;    4) drying at higher temperatures and if necessary reduced pressure.    
     
     
         23 . Process for the production of polymer (blend) membranes according to  claim 21  characterized in that the polymers containing sulfinate groups are mixed if necessary together with other polymers in a reaction vessel if necessary under inert gas and if necessary dissolved or suspended in a for the respective alkylation reaction suitable dipolar-aprotic solvent or protic solvent or ether solvent with the organic alkylation agents according to the invention or mixtures of alkylation agents and if necessary with in the reaction mixture soluble or sparingly soluble calcium compounds at temperatures between 0° C. to +200° C. if necessary under inert gas with stirring, the reaction mixture is stirred at temperatures between 0° C. and +200° C., until the reaction has started or is finished and then direct from the reaction mixture a thin film is cast with a doctor knife on a support (e.g. glass plate or metal plate or textile support or nonwoven), the solvent is removed from the film by a temperature increase and if necessary a pressure reduction and then the polymer(blend)film is posttreated as follows, in which the number and order of the posttreatment steps can be varied: 
 (1) if necessary 1-50% aqueous calcium salt solution at temperature between 0° C. and 90° C. for 1 to 48 hours    (2) 1-50% aqueous base at temperature between 0° C. and 90° C. for 1 to 48 hours    (3) 1-20% aqueous mineral acid at temperature between 0° C. and 90° C. for 1 to 48 hours    (4) water at a temperature between 0° C. and 100° C. for 1 to 48 hours    
     
     
         24 . Process for the production of either on the surface or in the bulk modified polymer (blend) membranes or other polymer moulded bodies according to  claim 21  characterized in that the polymermembranes or polymer moulded bodies containing sulfinate groups, which are if necessary in an organic solvent, are alkylated in a reaction vessel with an alkylation agent or a mixture of different alkylation agents if necessary under inert gas and if necessary with addition of in the reaction mixture soluble or sparingly soluble calcium compounds at temperatures between 0° C. to +200° C. either on the surface or in the bulk until the end of the alkylation reaction, and are then post-treated as follows: 
 1) addition of a 2 to 10-fold excess of water, aqueous calcium salt solution such as calcium chloride solution or calcium gluconate solution and/or aqueous base solution (1-30% NaOH, KOH, LiOH, Ca(OH) 2 , 1-30% ammonia solution or amine solution), based on the molar mass of alkylation agent, to the polymer moulded body to deactivate alkylation agent in excess and if necessary precipitate the fluoride ions liberated during the reaction as CaF 2 ;    2) washing of the polymer moulded body in a 2 to 20-fold excess (based on the volume of the reaction mixture or the modified polymer) of an alcohol (methanol, ethanol, i-propanol, n-propanol) or of water or an aqueous mineral salt solution (NaCl, NaHCO 3 , Na 2 SO 4 , CaCl 2 , etc.) or other common organic solvents (acetone, methylethylketon etc.);    3) washing with water until the wash water is free of ions;    4) drying at higher temperatures and if necessary reduced pressure.    
     
     
         25 . Process for the production of modified polymers according to  claim 21  characterized in that the polymers containing alkylation groups are reacted if necessary together with other polymers in a reaction vessel if necessary under inert gas and if necessary dissolved or suspended in a for the respective alkylation reaction suitable solvent with the low-molecular or high-molecular sulfinates according to the invention or mixtures of sulfinates and if necessary with in the reaction mixture soluble or sparingly soluble calcium compounds at temperatures between 0° C. to +200° C. if necessary under inert gas with stirring, the reaction mixture is stirred at temperatures between 0° C. and +200° C., until the reaction is finished and then the work-up of the reaction mixture is carried out as follows: 
 (a) water-soluble products:    1) (optionally) addition of a 2 to 10-fold excess of water, aqueous calcium salt solution such as calcium chloride solution or calcium gluconate solution and/or aqueous base solution (1-30% NaOH, KOH, LiOH, Ca(OH) 2 , 1-30% ammonia solution or amine solution), based on the molar mass of alkylation agent, under stirring to the reaction mixture to deactivate alkylation agent in excess and if necessary precipitate the fluoride ions liberated during the reaction as CaF 2 ;    2) -precipitation resp. suspension of the reaction mixture in a 2 to 20-fold excess (based on the volume of the reaction mixture or the modified polymer) of an alcohol (methanol, ethanol, i-propanol, n-propanol) or of water or an aqueous mineral salt solution (NaCl, NaHCO 3 , Na 2 SO 4 , CaCl 2 , etc.) or other common precipitation agents (acetone, methylethylketon etc.) and filtration;    3) washing of the precipitate until the wash water is free of ions;    4) drying at higher temperatures and if necessary reduced pressure;    5) (optionally) redissolution of the modified polymer in a suitable solvent and work-up as above (from 2)).    (b) water-soluble products:    1) mixing of the reaction mixture with a 2 to 10-fold excess of water, aqueous calcium salt solution such as calcium chloride solution or calcium gluconate solution and/or aqueous base solution (1-30% NaOH, KOH, LiOH, Ca(OH) 2 , 1-30% ammonia solution or amine solution), based on the molar mass of alkylation agent, under stirring to the reaction mixture to deactivate alkylation agent in excess and if necessary precipitate the fluoride ions liberated during the reaction as CaF 2 ;    2) mixing of the reaction mixture with a 5 to 20-fold excess of water and dialysis until all low-molecular substances are removed;    3) filtration of all water-insoluble parts of the dialysate;    4) drying at higher temperatures and if necessary reduced pressure.    
     
     
         26 . Process for the production of polymer(blend) membranes according to  claim 21  characterized in that the polymers containing alkylation groups are mixed if necessary together with other polymers in a reaction vessel if necessary under inert gas and if necessary dissolved or suspended in a for the respective alkylation reaction suitable solvent with the low-molecular or high-molecular sulfinates according to the invention or mixtures of sulfinates and if necessary with in the reaction mixture soluble or sparingly soluble calcium compounds at temperatures between 0° C. to +200° C. if necessary under inert gas with stirring, the reaction mixture is stirred at temperatures between 0° C. and +200° C., until the reaction has started or is finished and then direct from the reaction mixture a thin film is cast with a doctor knife on a support (e.g. glass plate or metal plate or textile support or nonwoven), the solvent is removed from the film by a temperature increase and if necessary a pressure reduction and then the polymer(blend)film is posttreated as follows, in which the number and order of the posttreatment steps can be varied: 
 (1) if necessary 1-50% aqueous calcium salt solution at temperature between 0° C. and 90° C. for 1 to 48 hours    (2) 1-50% aqueous base at temperature between 0° C. and 90° C. for 1 to 48 hours    (3) 1-20% aqueous mineral acid at temperature between 0° C. and 90° C. for 1 to 48 hours    (4) water at a temperature between 0° C. and 100° C. for 1 to 48 hours    
     
     
         27 . Process for the production of either on the surface or in the bulk modified polymer (blend) membranes or other polymer moulded bodies according to  claim 21  characterized in that the alkylation groups containing polymermembranes or polymer moulded bodies, which are if necessary in an organic solvent, are alkylated in a reaction vessel if necessary under inert gas and if necessary with in the reaction mixture soluble or sparingly soluble calcium compounds at temperatures between 0° C. to +200° C. either on the surface or in the bulk with the low-molecular or high-molecular sulfinates according to the invention or mixtures of sulfinates until the alkylation reaction has finished and then the work-up of the reaction mixture is carried out as follows: 
 1) addition of a 2 to 10-fold excess of water, aqueous calcium salt solution such as calcium chloride solution or calcium gluconate solution and/or aqueous base solution (1-30% NaOH, KOH, LiOH, Ca(OH) 2 , 1-30% ammonia solution or amine solution), based on the molar mass of alkylation agent, to the polymer moulded body to deactivate alkylation agent in excess and if necessary precipitate the fluoride ions liberated during the reaction as CaF 2 ;    2) washing of the polymer moulded body in a 2 to 20-fold excess (based on the volume of the reaction mixture or the modified polymer) of an alcohol (methanol, ethanol, i-propanol, n-propanol) or of water or an aqueous mineral salt solution (NaCl, NaHCO 3 , Na 2 SO 4 , CaCl 2 , etc.) or other common organic solvents (acetone, methylethylketon etc.);    3) washing with water until the wash water is free of ions;    4) drying at higher temperatures and if necessary reduced pressure.    
     
     
         28 . Process according to the  claim 27  characterized in that are used either in pure form or as a mixture as reaction medium or as solvent for the alkylation reaction: 
 dipolar-aprotic solvents such as dimethylsulfoxide, sulfolane, N-methylpyrrolidinone, N,N-dimethylacetamide, N,N-dimethylformamide, N-methylformamide, N-methylacetamide, acetonitrile, dimethylcarbonate, diethylcarbonate or mixtures of these solvents with each other;    an ether solvent such as diethylether, tetrahydrofurane, glyme, diglyme, triglyme, dioxane or mixtures of these solvents with each other;    an alkylalcohol such as methanol, ethanol, n-propanol, i-propanol or mixtures of these solvents with each other;    a ketone such as methylethylketon or acetone or mixtures of these solvents with each other    water or its mixtures with the above solvents    Any mixtures of above solvents.    
     
     
         29 . Process according to  claim 28  characterized in that as soluble or sparingly-soluble calcium compounds in the reaction mixture the following calcium compounds are preferred: 
 calciumacetylacetonate (Bis-(2,4-pentandionato)-calcium)    calcium-bis-(6,6,7,7,8,8,8-heptafluor-2,2-dimethyl-3,5-octandionate)    calcium-1,1,1,5,5,5-hexafluoracetylacetonate    calciummethylate    calciumoxalate    calcium-D-gluconate    calcium-(2,2,6,6-tetramethyl-3,5-heptandionate)    calciumtriflate (calcium salt of trifluoromethansulfonic acid)    
     
     
         30 . Forming of modified polymers produced according to  claim 29  to membranes for use in membran processes or if necessary membrane fuel cells, membran electrolysis.  
     
     
         31 . Use of modified polymers produced according to  claim 29  as a blend component for proton conducting blend membranes for membrane fuel cells or membran electrolysis, in which the blend membranes if necessary can be cross-linked physically and/or covalently.  
     
     
         32 . Use of modified polymer membranes produced according to  claim 29  in membrane separation processes, membrane fuel cells or membrane electrolysis.