JP2009263673A - Oligomer and polymer containing sulfinate group, and their production method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a membrane in which a functional group impossible to be introduced with a past method is introduced into high molecular sulfinate by sulfinate alkylation. <P>SOLUTION: A modified polymer, a polymer blend, a polymer (blend) membrane, or a polymer formed product is provided by S-alkylating with a sulfinate group including a sulfinate group SO<SB>2</SB>M, a polymer blend containing the sulfinate group, a polymer (blend) membrane, or a polymer formed product containing the other sulfinate group as in a chemical formula 1 and Fig.1 (wherein M=monovalence, divalence, trivalence metallic ion, ammonium ion NR<SB>4</SB><SP>+</SP>(R=H, alkyl, aryl, imidazole ion, pyrazole ion, or pyridinium ion)). <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

From the literature, ¹ that the low-molecular sulfinate is S- alkylated or O- alkylation is known. The alkylation of sulfinates with methyl iodide to form methylsulfone has been described. It is known that polymers containing sulfinate groups are covalently crosslinked with dihalogenalkanen or oligohaloalkanes by sulfinate-S-alkylation ^2,3 . It is also known that sulfinate groups can be alkylated by aromatic nucleophilic substitution reactions ⁴ . Subsequently, Michael to olefins containing electron withdrawing groups sulfinate of - Type - added is also known that it is possible ^5.

  To the best of our knowledge, the functional groups of the present invention (especially anion exchange groups, cation exchange groups, and their non-ionic precursors without cross-linking reaction) can be halogenated, or sultone, or other, The introduction to polymeric sulfinates using the preparation method of the present invention by sulfinate alkylation with electrophilic groups that react with sulfinate groups (eg olefins containing electron withdrawing groups) has been described in the literature. Absent.

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 J. Kerres, W. Zhang, W. Cui, J. Polym. Sci .: Part A: Polym. Chem. 36, 1441-1448 (1998) Jochen Kerres, Wei Cui, Martin Junginger, J. Memb. Sci. 139, 227-241 (1998) A. Ulman, E. Urankar, J. Org. Chem. 54, 4691-4692 (1989) S. Oae, N. Kunieda, in Organic Chemistry of Sulfur (Ed. S. Oae), Plenum, New York, 1977, S. 625-637 Kerres et al., J. Polym. Sci., Part A °: Polym. Chem., 39, 2874-2888 (2001)

It has been surprisingly found that sulfinate polymers are variably mutated by sulfinate-S-alkylation. By this reaction, functional groups that cannot be introduced by other methods can be introduced into the polymer. Some of the new reactions discovered are shown in FIG.
The first group corresponds to sultone and polymeric sulfinates, as shown by way of example in FIG. There are no fundamental restrictions on the choice of sultone. Any sultone can be used. However, 4-ring and 5-ring sultone has higher ring stress and is therefore more reactive than polycyclic sultone (6 rings and higher). The highest reactivity is perfluorinated microcyclic sultone, such as the perfluorinated sultone shown in FIG. Lactams, lactones, sultams and complex compounds composed of these components can react with sulfinates.

  The second reaction group is a surprisingly possible alkylation of halogenaryl-, halogenalkyl-, halogenbenzyl-ammonium salts of polymeric sulfinates with these phosphonium salts, as FIG. 3 shows by example. .

Here, there is basically no limitation on the selection of ammonium salt and phosphonium salt, but organic solvents (N, N-dimethylformamide DMF, N-methylformamide, N, N-dimethylacetamide DMAc, in which polymer sulfinate is dissolved) N, N-methylpyrrolidinone NMP, dimethyl sulfoxide DMSO, or ammonium salt containing a long chain alkyl group (propyl group or more) or phenyl group in an ammonium group / phosphonium group that is easy to dissolve in a dipolar-aprotic solvent such as sulfolene) Preference is given to phosphonium salts. To further improve the compatibility of the sulfinate polymer solution with ammonium / phosphonium salts, 18-crown-6, 15-crown-5 or 12-crown-4 complexing the sulfinate group cation to this polymer solution Etc. can be added. The order of reactivity of alkylation of sulfinate groups in the halogen leaving groups of halogen alkyl compounds or benzyl compounds was confirmed as follows:
I >>Br> Cl >> F.
For the halogen leaving groups of halogenaryl compounds, the order of reactivity of alkylation of sulfinate groups was confirmed as follows:
F >>Cl>Br> I.

Some of the further halogen compounds that react with the polymeric sulfinate are surprisingly halogenated primary, secondary, tertiary aliphatic amines, aromatic amines, and / or benzylamines, as listed in FIG. Halogen benzylamine and their hydrogen halides.
In this case, the amino group may be protected by an amine protecting group (Aminschutzgruppe). Even more surprising, it is possible to work with imidazole groups using the method of the present invention, as listed in FIGS. 4a and 4b. FIG. 4a shows the reaction of a fluorinated arylimidazole derivative with a polymeric sulfinate, and FIG. 4b shows the reaction of a halogen alkylimidazole with a polymeric sulfinate.

The fourth reaction group is surprisingly possible, as listed in part in FIG. 5a, sulfinates and halogen alkyl sulfonates or halogen aryl sulfonates, or halogen benzyl sulfonates, or these. Relates to S-alkylation of phosphonates, carboxylates, boronates, or their nonionic precursors.
At that time, it is easy to dissolve in the organic solvent used for dissolving the polymer sulfinate, and it does not cause an unfavorable interaction with the sulfinate group (eg, ion pair formation), so that sulfonate, phosphonate, and carvone Preference is given to nonionic precursors of acid salts (acid halides, acid esters, acid amides, acid imides, acid anhydrides).
In some cases, a polymer sulfinate solution and a halogen aryl carboxylate, halogen alkyl carboxylate, halogen benzyl carboxylate, or halogen aryl phosphonate, halogen alkyl are used to complex the base cation. Incorporating a crown ether into a phosphonate, halogen benzyl phosphonate, or halogen aryl sulfonate, halogen alkyl sulfonate, halogen benzyl sulfonate, halogen aryl boronate, halogen alkyl boronate, halogen benzyl boronate I can do it.

As already mentioned, aromatic fluorine compounds of aromatic halides react best with sulfinates on S-alkylation. Surprisingly, the addition of calcium compounds to the reaction compounds and / or other formed bodies consisting of formed polymers, polymer blends, polymer (blend) films, or reactants with aqueous solutions of calcium compounds of the present invention. It was confirmed that the post-treatment promoted the sulfinate-S-alkylation reaction. It is presumed that the fluoride anion liberated during S-alkylation leaves the reaction equilibrium with the formation of extremely insoluble calcium fluoride.
2 Ar-F + 2 MO ₂ SR´ + Ca ²⁺ → 2 Ar-S (O) ₂ -R´ + CaF ₂
When the S-alkylation reaction is performed in an organic solution, calcium compounds that are soluble in the organic solution are preferred, as in the following example:
・ Calcium acetylacetonate (Bis- (2,4-pentandionato) -calcium)
Calcium-bis- (6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octandionato) = Calcium-bis- (6,6,7,7 , 8,8,8-heptafluor-2,2-dimethyl-3,5-octandionat)
・ Calcium-1,1,1,5,5,5-hexafluoroacetylacetonate = Calcium-1,1,1,5,5,5-hexafluoracetylacetonat
・ Calcium methylat
・ Calcium oxalate = Calciumoxalat
・ Calcium-D-gluconat
・ Calcium- (2,2,6,6-tetramethyl-3,5-heptandionat) = Calcium- (2,2,6,6-tetramethyl-3,5-heptandionat)
・ Calcium triflate (= Calcium trifluoromethanesulfonate) = Calciumtriflat (Trifluormethansulfonsaure Calciumsalz)

However, the calcium ion concentration and fluoride ion concentration in the reaction compound precipitate calcium fluoride at a minimum, so in some reactions, a calcium salt that is sparingly soluble in the organic solvent used is added to the reaction compound. Just enough. There, it is possible to add a calcium mineral salt to the reaction compound:
Calcium halides, calcium sulfate, calcium hydrogen sulfate, calcium phosphate, and calcium hydrogen phosphate, calcium oxide, calcium hydroxide, and other calcium salts.

S-alkylation of sulfinates and aryl fluorine compounds to complete the S-alkylation reaction and, on the other hand, precipitate the highly toxic fluoride ions liberated during the reaction as CaF ₂ with calcium ions, making them harmless It is also meaningful to post-treat the reaction product of the conversion with an aqueous solution of calcium salt, which is important in industrial production processes.

  As the reaction product is insoluble in organic solution, it is surprising that a cross-linking reaction occurs simultaneously in the reaction of difluorinated aromatic sulfonic acid chloride, higher fluorinated aromatic sulfonic acid chloride and polymer sulfinate. Was confirmed. FIG. 5b shows the reaction course premised on the polymer Li-sulfinate and Pentafluorbenzolsulfochlorid. Covalently crosslinked ionomer membranes exhibit surprisingly low ionic resistance with surprisingly low water swellability (see practical examples).

It was unexpectedly confirmed that the following mixture formed a cross-linked ionomer membrane having a high chemical stability and a low swelling property even at a high temperature by the reaction with a polymer sulfinate or an oligomeric sulfinate.
· Low molecular difluorination and higher fluorinated aromatic sulfonic acid halides, carboxylic acid halides, or phosphonic acid halides, or other nonionic precursors of the corresponding acids (esters, amides, imides) )
· Perfluorinated diphenyl sulfone, perfluorinated benzophenone, perfluorinated triphenylphosphine oxide, perfluorinated diphenyl, perfluorinated diphenyl ether, and other perfluorinated aromatic mixtures (Fig. 5c), such as low-molecular perfluorinated aromatic compounds

Surprisingly, it has also been found that mixtures of polymeric or oligomeric sulfinates with the following small molecules also form covalently crosslinked ionomer membranes with particularly advantageous properties:
・ Low molecular perfluorinated precursors or partially fluorinated precursors of aromatic carboxylic acids, phosphonic acids, sulphonic acids or non-ionic precursors (acid halides, acid amides, acid imides, acid esters) Dihalogenalkane Hal (CH ₂ ) _x Hal (x = 1-20, Hal = I, Br, Cl)

Furthermore, unexpectedly, a fifth group that undergoes an S-alkylation reaction with a polymeric sulfinate is a hetarylhalogenverbindungen, some examples of which are given in FIG.
It has been unexpectedly confirmed that a reactive dye can be bound to a polymer containing a sulfinate group due to the reaction of the present invention. FIG. 7 shows some examples of reactive dyes that undergo S-alkylation reaction with sulfinate groups. The order of affinity of the heteroaromatic halogen compounds (het (aromatische Halogenverbindungen)) for the S-alkyl reaction is F>Cl>Br> I. At this time, the reactive group is not limited to a halogen group, but can also indicate a temporary or non-fancy vinyl sulfone group or other unsaturated olefin group. Preference is given to olefins containing electron withdrawing groups (eg sulphone groups, sulphonate groups, sulphonamide groups, sulphonimide groups, nitro groups, halogen groups, nitroso groups, carbonyl groups, carboxyl groups).

FIG. 8 shows an example of a reactive dye that reacts according to the present invention. One of the applicable areas of polymers colored using such reactive dyes is nonlinear optics. The advantage of these polymers is that the dye is permanently attached to the polymer due to the alkylation reaction of the present invention.
A further surprising discovery is that the method of the present invention allows the incorporation of functional groups that cannot normally be introduced into the polymer. This allows functional groups to be incorporated into conductive metallizable polymers through metalation reactions (Figure 9) (Kerres et al., J. Polym. Sci., Part A °: Polym. Chem). ., 39, 2874-2888 (2001)).
To date, it has not been possible to incorporate these functional groups into polymers that cannot be metallated. One group of polymers that cannot be metallated is polyetherketone because an organometallic compound (eg, n-butyllithium) is added to the carbonyl group. The method of the present invention opens the way for incorporation of conductive groups into polyether ketones. For this purpose, the sulfochloride group of the polyetherketone containing a sulfochloride group is reduced to a sulfinate group using, for example, sodium sulfite. This sulfinate group can then be alkylated with a compound containing a conductive functional group and containing a halogen (FIG. 10).

A further surprising finding is that polymers containing alkyl groups react with small or high molecular sulfinates in S-alkylation. Examples of alkylating groups according to the invention are as follows (Hal = F, Cl, Br, I):
・ Halogen alkyl group Hal-Al (Al = aliphatic group) Halogenalkylgruppen
Halogen aryl group Hal-Ar Halogenarylgruppen
Halogen benzyl group Hal-CH ₂ -Ar Halogenbenzylgruppen
Examples of polymers of the invention containing alkyl groups are in particular halogenmethylated polymers (eg chloromethylated polystyrol, bromoethylated polysulfone).

  A further surprising discovery is that thin membranes (membranes) and other formations can also be deformed from the sulfinate-based polymers on the surface or in bulk (bulk) due to the sulfinate-S-alkylation of the present invention: membranes When swelled in a suitable solvent containing an alkylating agent, it is possible to alkylate all sulfinate groups of the membrane or formation; in the unswelled state only the surface of the membrane or formation is deformed by alkylation (This includes the inner surface of the porous membrane).

  Surprisingly, the opposite case is also possible: membranes or other formations containing alkylating groups are swollen by suitable organic solvents containing low or high molecular weight sulfinate compounds. Superficial or bulk (bulk) alkylation is possible.

Even more surprising, by forming the next reaction mixture in a single process, thin films (membranes) and other formations that are optionally covalently crosslinked can be converted from polymers using sulfinate-S-alkylation. Can be created in a single process:
1) The sulfinate group polymer is dissolved in a suitable solvent. The alkylating agent or a mixture of different alkylating agents is then added to the solvent. At this time, the alkylating agent can have two or more alkylating groups (crosslinking agent). At this time, the alkylating agent may further have other functional groups such as a cation exchange group or a nonionic precursor thereof, or an anion exchange group or a nonionic precursor thereof.
2) A polymer containing an alkylated group (eg, halogen methylated polymer) is dissolved in a suitable solvent. Next, a low or high molecular weight compound containing one or more sulfinate groups is added to the solvent. At this time, the sulfinate may further have other functional groups such as a cation exchange group and a nonionic precursor thereof, or an anion exchange group and a nonionic precursor thereof.

The reactive compound is thinned on the foundation in the next step (glass plate, metal plate, plastic plate, fabric, fleece). The temperature is then raised and / or low pressure is applied to evaporate the solvent. An alkylation reaction takes place while the solvent evaporates.
In order to cross-link the membrane covalently, a high-molecular or low-molecular compound containing two or more alkylating groups must be added to the reactive compound 1). One example of a polymeric crosslinking agent that can be used in accordance with the present invention is a halomethylated polymer (chloromethylated polystyrol, bromethylated polysulfone). Examples of low molecular crosslinkers are given in FIG. In this case, the cross-linking agent is arranged alongside the functional group that reacts with the sulfinate group, and further functional groups such as basic and acidic functional groups (FIG. 11) and their precursors.

Reaction of sulfinate polymers with alkylating agents Changes in polymeric sulfinates by sulfinate alkylation with sultone. Alkylation of polymeric sulfinates, halogenalkyl-ammonium salts and halogenalkyl-phosphonium salts Polymer sulfinates, halogen alkyl amines and halogen alkyl hydrogen halides Reactions of aromatic fluorinated arylimidazole derivatives with polymeric sulfinates. Reaction of halogenalkylimidazoles with polymeric sulfinates. S-alkylating agents for sulfinates of halogen alkyl sulfonates or halogen aryl sulfonates, or halogen benzyl sulfonates, or their phosphonates, carboxylates, boronates, or nonionic precursors thereof Reaction process based on polymer Li-sulfinate and pentafluorobenzenesulfochloride Perfluorinated aromatic crosslinking agent Alkylation of sulfinate groups of polymer sulfinates and halogen hetaryl compounds Reactive groups of pigments capable of reacting with sulfinate groups Examples of reactive dyes that react with polymers containing sulfinate groups Incorporating conductive groups into Polysulfon Udel® Incorporating conductive functional groups into sulfinate polyetherketone Examples of cross-linking agents of the present invention

1. Reaction of Polysulfon-Lithiumsulfinat with (3-Brompropyl) trimethzlammoniumbromid 10g of 5% by weight PSU-lithium sulfinate dissolved in dimethylsulfoxide DMSO (structural unit 1 sulfinate group) and 10,179 g of 5 wt% (3-bromopropyl) trimethylammonium bromide in DMSO are mixed with stirring. This mixture is stored in a dry glass rack in a sealed glass bottle at a temperature of 80 degrees for 48 hours. The solution is then poured into a glass dish and the solution is evaporated. Then peel off the thin film in the glass dish and treat as follows:
24 hours at room temperature in 10% aqueous NaOH, 24 hours at 60 ° C. in water

2. Reaction of Polysulfon-Lithiumsulfinat with (3-Brompropyl) triphenylphosphoniumbromid 10 g of 5% by weight PSU-lithium sulfinate solution in dimethylsulfoxide DMSO (structure) 1 sulfinate group per unit repeat) and 18,104 g of 5 wt% (3-bromopropyl) triphenylphosphonium bromide in DMSO are mixed with stirring. This mixture is stored in a dry glass rack in a sealed glass bottle at a temperature of 80 degrees for 48 hours. The solution is then poured into a glass dish and the solution is evaporated. Then peel off the thin film in the glass dish and treat as follows:
24 hours at room temperature in 10% aqueous NaOH, 24 hours at 60 ° C. in water

3. Reaction of Polysulfon-Lithiumsulfinat with 2-Chlormethylbenzimidazole
5 g of a 10 wt% PSU-lithium sulfinate solution in N-methylpyrrolidinone (one sulfinate group per repeating structural unit) and 0,325 g of 5 wt% 2-chloromethylbenzimidazole in DMSO are mixed with stirring. . This mixture is stored in a dry glass rack in a sealed glass bottle at a temperature of 80 degrees for 48 hours. A clear solution is formed here. The solution is then poured into a glass dish and the solution is evaporated. Then peel off the thin film in the glass dish and treat as follows:
24 hours at room temperature in 10% aqueous NaOH, 24 hours at 60 ° C. in water

4). Reaction of polysulfone-lithium sulfinate with Cibacron® Brilliantgelb CI 18972 10 g of a 5 wt% PSU-lithium sulfinate solution in dimethyl sulfoxide DMSO (1 sulfinate group per repeat of structural unit), 1,7 g Cibacron® Brilliantgelb CI 18972 is mixed with stirring. This mixture is stored in a sealed glass bottle for 48 hours at a temperature of 80 ° C. on a drying shelf. The solution is then poured into a glass dish and the solution is evaporated. Then peel off the thin film in the glass dish and treat as follows:
24 hours at 90 ° C in 7% aqueous HCl 24 hours at 60 ° C in water

5. Reaction of polysulfone-lithium sulfinate with Cibacron® Brilliantrot CI 18105 10 g of a 5 wt% PSU-lithium sulfinate solution in dimethyl sulfoxide DMSO (one sulfinate group per repeat of structural units), 3,88 g Cibacron® Brilliantrot CI 18105 is mixed with stirring. This mixture is stored in a sealed glass bottle for 48 hours at a temperature of 80 ° C. on a drying shelf. The solution is then poured into a glass dish and the solvent is evaporated. Then peel off the thin film in the glass dish and treat as follows:
24 hours at 90 ° C in 7% aqueous HCl 24 hours at 60 ° C in water

6). Covalently crosslinked anion exchange membrane and quaternary ammonium salt
11 g of 15% by weight PSU (SO ₂ Li) ₂ solution in N-methylpyrrolidinone (NMP) (2 sulfinate groups per repeat of PSU-structural units) and 0.51 g of (3-bromopropyl) trimethylammonium bromide Lightly warm until the salt dissolves and mix with stirring. Thereafter, 0,38 ml of 1,4, diiodobutane (crosslinking agent) and 5 g of NMP are added to the solution.
The reaction mixture is thinned onto a glass plate and evaporated in a vacuum drying cabinet at 140-150 degrees, initially at 700 mbar and then <10 mbar. While the membrane is made, an alkylation reaction takes place. The film is then peeled off in water and post-treated as follows:
48 hours at room temperature −90 ° C. in 1N NaOH 48 hours at room temperature −60 ° C. in water

7). Covalently crosslinked anion exchange membrane and quaternary phosphonium salt
994 g of PSU (SO ₂ Li) ₂ solution in 15% by weight in N-methylpyrrolidinone (NMP) (2 sulfinate groups per repeat of structural unit) and 1,026 g of (3-bromopropyl) triphenyl bromide Lightly warm the phosphonium until the low molecular weight salt is dissolved and mix with stirring. Thereafter, 0,34 ml of 1,4, diiodobutane (crosslinking agent) and 5 g of NMP are added to the solution.
The reaction mixture is thinned onto a glass plate and evaporated in a vacuum drying cabinet at 140-150 degrees, initially at 700 mbar and then <10 mbar. While the membrane is made, an alkylation reaction takes place. The film is then peeled off in water and post-treated as follows:
48 hours at room temperature −90 ° C. in 1N NaOH 48 hours at room temperature −60 ° C. in water

8). Covalently crosslinked cation exchange membrane comprising (2-bromoethyl) sulfonic acid Na salt ((2-Bromethyl) sulfonsaeure Na salz) and PSU-sulfinate
15 wt% PSU (SO ₂ Li) ₂ solution in N-methylpyrrolidinone (NMP) (PSU—2 sulfinate groups per repeating structural unit) 6,67 g and 0,38 g (2-bromoethyl) sulfonic acid Na salt Lightly warm until the low molecular weight salt is dissolved and mix with stirring. Thereafter, 0,05 ml of 1,4, diiodobutane (crosslinking agent) and 8 g of NMP are added to the solution.
The reaction mixture is thinned onto a glass plate and evaporated in a vacuum drying cabinet at 140-150 degrees, initially at 700 mbar and then <10 mbar. While the membrane is made, an alkylation reaction takes place. The film is then peeled off in water and post-treated as follows:
48 hours at room temperature-90 ° C. in 10% HCl 48 hours at 60 ° C. in water

9. Covalently crosslinked cation exchange membrane composed of (2-chloroethane) chlorosulfonic acid ((2-Chlorethan) sulfonsaeurechlorid) and PSU-sulfinate
A solution of 15 wt% PSU (SO ₂ Li) _{2 in} N-methylpyrrolidinone (NMP) (PSU-two sulfinate groups per repeating structural unit) and 6,67 g and ((2-chloroethane) chlorinated sulfonic acid (2-Chlorethan ) Sulfosaeurechlorid) 0,545g is lightly warmed until low molecular weight sulfochloride is dissolved and mixed with stirring. Then, add 0,05 ml 1,4, diiodobutane (crosslinking agent) and 8 g NMP to the solution.
The reaction mixture is thinned onto a glass plate and evaporated in a vacuum drying cabinet at 140-150 degrees, initially at 700 mbar and then <10 mbar. While the membrane is made, an alkylation reaction takes place. Thereafter, the membrane is peeled off in water and post-treated as follows. This causes sulfochloride to hydrolyze to sulfonic acid:
48 hours at room temperature -90 ° C in 10% HCl 48 hours at room temperature-60 ° C in water

10. Covalently crosslinked cation exchange membrane comprising (2-bromoethane) phosphonic acid diethyl ester ((2-Bromethan) phosphonsaeurediethylester) and PSU-sulfinate
15% by weight PSU (SO ₂ Li) ₂ solution in N-methylpyrrolidinone (NMP) (PSU—2 sulfinate groups per repeating structural unit) 6,67 g and 0,819 g (2-bromoethane) phosphonic acid diethyl ester ( Lightly warm (2-Bromethan) phosphonsaeurediethylester) until the low molecular weight ester is dissolved and mix with stirring. Thereafter, 0,05 ml of 1,4, diiodobutane (crosslinking agent) and 8 g of NMP are added to the solution.
The reaction mixture is thinned onto a glass plate and evaporated in a vacuum drying cabinet at 140-150 degrees, initially at 700 mbar and then <10 mbar. While the membrane is made, an alkylation reaction takes place. Thereafter, the membrane is peeled off in water and post-treated as follows. This causes the phosphonate to hydrolyze to phosphonic acid:
48% in 10% NaOH at room temperature -90 ° C 48 hours in 1N HCl at room temperature -90 ° C 48 hours in water at room temperature -60 ° C

11. Ionomer membranes of 4-Fluorbenzolsulfochlorid and Calciumtrifluormethansulfonat
RadelR (SO ₂ Li) ₂ is dissolved in 3 g and NMP 17 g. Next, 1,184 g of calcium 3 fluoromethanesulfonate (Calciumtriflat) is added to the solution, followed by 3,32 g of 4-fluorobenzenesulfochloride. Stir until the solution is clear. The start of the aromatic nucleophilic substitution reaction can be confirmed by an increase in viscosity. The reaction mixture is thinned onto a glass plate and evaporated at 130-140 degrees, 700 mbar to 1 mbar. Thereafter, the membrane is peeled off in water and post-treated as follows.
24 hours in 10% CaCl ₂ at room temperature -90 ° C 24 hours in 1N HCl at room temperature -90 ° C 48 hours in water at room temperature -90 ° C

12 Pentafluorbenzolsufonsauerechlorid ionomer blend membrane (Membran 1296)
Dissolve the following polymer to 15% weight in NMP:
2,258 g PSU (SO ₂ Li) ₂
0,828 g Radel R (SO ₂ Li) ₁
1,805 g sPEKCl (IEC = 3,49 meq SO ₃ H / g after hydrolysis)
1,335 g sPEEKCl (IEC = 1,8 meq SO ₃ H / g after hydrolysis)
Thereafter, 1,843 g pentafluorobenzene chlorosulfonic acid is added to the polymer solution. Stir until homogenized. Thereafter, 0,75 g of bis (4-fluorophenyl) sulfone) (Bis (4-fluorphenyl) sulfon) is added and dissolved. The reaction mixture is thinned onto a glass plate and evaporated at 130-140 degrees, 700 mbar to 1 mbar. The film is then peeled off in water and post-treated as follows:
24 hours at 10% CaCl ₂ at room temperature-90 ° C. 24 hours at 10% NaOH at room temperature-90 ° C. 48 hours at room temperature-90 ° C. in 1N HCl 48 hours at room temperature-90 ° C. in water The post-processing steps can be omitted or the order can be changed.
Instead of pentafluorobenzene chlorosulfonic acid, difluorobenzene chlorosulfonic acid, trifluorobenzene chlorosulfonic acid, tetrafluorobenzene chlorosulfonic acid, etc. ) Can be added in equimolar amounts or in excess. Further, bis (3-nitro-4-fluorophenyl) sulfone (Bis (3-nitro-4-fluorophenyl) sulfon), bis (4-fluorophenyl) phenylphosphinoxid), or correspondingly Other cross-linking agents such as bis (3-chlorosulfo-4-fluorophenyl) sulfone (Bis (3-chlorosulfo-4-fluorphenyl) sulfon) and dihaloalkanes and halogens can be added. Benzyl chloride can also be added.
Characteristic results:
IEC (meq SO ₃ H / g): 1,52
R _sp ^{H +} , 0,5N HCl (Ω * cm): 13,33
SW 25 ℃ (%): 108,6
SW 90 ℃ (%): 190

13. Different fluorinated benzolsulfonsaeurechloride ionomer membranes Polymer sulfinates are dissolved in NMP (see Table 1). To this is added fluorinated benzene chlorosulfonic acid or chlorofluorobenzene (see Table 1). Stir until homogenized. The reaction mixture is thinned onto a glass plate and evaporated at 130-140 degrees, 700 mbar to 1 mbar. The film is then peeled off in water and post-treated as follows:
24 hours at 10% CaCl ₂ at room temperature-90 ° C. 24 hours at 10% NaOH at room temperature-90 ° C. 48 hours at room temperature-90 ° C. in 1N HCl 48 hours at room temperature-90 ° C. in water The post-processing steps can be omitted or the order can be changed.

b. Polysulfon Udel (製作者BP Amoco)
c. Polyphenylsulfon Radel R (製作者 BP Amoco)
d. Poly(etheretherketon) (製作者 Victrex)

b. Polysulfon Udel (by BP Amoco)
c. Polyphenylsulfon Radel R (by BP Amoco)
d. Poly (etheretherketon) (author Victrex)

14 Add different fluorierte Pentafluorbenzolsulfonsaeurechlorid and ionomer membrane of crosslinker 3g of polymer sulfinate is dissolved in NMP (see Table 2). To this is added 1,95 g of pentafluorobenzene chlorosulfonic acid (see Table 2). Add aromatic crosslinker. Stir until homogenized. The reaction mixture is thinned onto a glass plate and evaporated at 130-140 degrees, 700 mbar to 1 mbar. The film is then peeled off in water and post-treated as follows:
24 hours at 10% CaCl ₂ at room temperature-90 ° C. 24 hours at 10% NaOH at room temperature-90 ° C. 48 hours at room temperature-90 ° C. in 1N HCl 48 hours at room temperature-90 ° C. in water The post-processing steps can be omitted or the order can be changed.

b. Polysulfon Udel (製造者 BP Amoco)

b. Polysulfon Udel (Manufacturer BP Amoco)

  Surprisingly, it was confirmed that when the calcium salt was added to the reaction mixture in an equimolar amount with respect to the sulfinate group, the reaction was further accelerated. This is presumed to be due to the fact that the fluoride ions produced during the nucleophilic substitution reaction move away from the reaction equilibrium due to the precipitation of calcium fluoride. When calcium fluoride is produced, they remain in the membrane matrix, resulting in an increase in the thermal and mechanical resistance of the membrane. The calcium salt that can be used in the reactions of Examples 13 and 14 is calcium triflat which is soluble in NMP and other dipolar-aprotic solvents.

15. Ionomer membrane of pentafluorobenzene chlorinated sulfonic acid (Petanfluorbenzolsulfonsaeurechlorid) (Membran 1289)
Dissolve PSU (SO ₂ Li) ₂ in 3 g NMP. To this is added 2,5 g of pentafluorobenzene chlorosulfonic acid. Stir until homogenized. The reaction mixture is thinned onto a glass plate and evaporated at 130-140 degrees, 700 mbar to 1 mbar. The film is then peeled off in water and post-treated as follows:
In 10% CaCl ₂ at room temperature -90 ° C for 24 hours In 1N HCl at room temperature -90 ° C for 48 hours In water at room temperature -90 ° C for 48 hours Characteristic results:
IEC (meq SO ₃ H / g): 0,89
R _sp ^{H +} , 0,5N HCl (Ω * cm): 38,05
SW 25 ℃ (%): 24,6
SW 90 ℃ (%): 32,6

16. 2,6-Difluorobenzolsufonsaeurechlorid ionomer membrane (Membran 1297)
Dissolve PSU (SO ₂ Li) ₂ in 3 g NMP. To this, 3,06 g of 2,6-difluorobenzene chlorosulfonic acid is added. Stir until homogenized. The reaction mixture is thinned onto a glass plate and evaporated at 130-140 degrees, 700 mbar to 1 mbar. The film is then peeled off in water and post-treated as follows:
In 10% CaCl ₂ at room temperature -90 ° C for 24 hours In 1N HCl at room temperature -90 ° C for 48 hours In water at room temperature -90 ° C for 48 hours Characteristic results:
IEC (meq SO ₃ H / g): 0,29
R _sp ^{H +} , 0,5N HCl (Ω * cm): 67,8
SW 25 ℃ (%): 13,8
SW 90 ℃ (%): 25,5

17. Ionomer membrane of 2,3,4-Trifluorbenzolsulfonsaeurechlorid (Membran 1289)
Dissolve PSU (SO ₂ Li) ₂ in 3 g NMP. To this, 3,32 g of 2,3,4-fluorobenzene chlorosulfonic acid is added. Stir until homogenized. The reaction mixture is thinned onto a glass plate and evaporated at 130-140 degrees, 700 mbar to 1 mbar. The film is then peeled off in water and post-treated as follows:
In 10% CaCl ₂ at room temperature -90 ° C for 24 hours In 1N HCl at room temperature -90 ° C for 48 hours In water at room temperature -90 ° C for 48 hours Characteristic results:
IEC (meq SO ₃ H / g): 0,10
R _sp ^{H +} , 0,5N HCl (Ω * cm): 21,8
SW 25 ℃ (%): 14,8
SW 90 ℃ (%): 45,6

18. Pentafluorbenzolsulfonsaeurechlorid ionomer membrane (Membran 1299)
Dissolve PSU (SO ₂ Li) ₂ in 3 g NMP. To this is added 1,92 g of pentafluorobenzene chlorosulfonic acid. Stir until homogenized. The reaction mixture is thinned onto a glass plate and evaporated at 130-140 degrees, 700 mbar to 1 mbar. The film is then peeled off in water and post-treated as follows:
In 10% CaCl ₂ at room temperature -90 ° C for 24 hours In 1N HCl at room temperature -90 ° C for 48 hours In water at room temperature -90 ° C for 48 hours Characteristic results:
IEC (meq SO ₃ H / g): 0,99
R _sp ^{H +} , 0,5N HCl (Ω * cm): 26,1
SW 25 ℃ (%): 14,8
SW 90 ℃ (%): 44

19. Ionomer membrane of pentafluorbenzolsulfonsaeurechlorid (Membran 1300)
Dissolve PSU (SO ₂ Li) ₂ in 3 g NMP. To this is added 1,92 g of pentafluorobenzene chlorosulfonic acid, followed by 1,184 g of calcium trifluorosulfonate. Stir until homogenized. The reaction mixture is thinned onto a glass plate and evaporated at 130-140 degrees, 700 mbar to 1 mbar. The film is then peeled off in water and post-treated as follows:
In 10% CaCl ₂ at room temperature -90 ° C for 24 hours In 1N HCl at room temperature -90 ° C for 48 hours In water at room temperature -90 ° C for 48 hours Characteristic results:
IEC (meq SO ₃ H / g): 1.01
R _sp ^{H +} , 0,5N HCl (Ω * cm): 12,2
SW 25 ℃ (%): 27
SW 90 ℃ (%): 69,6

20. Pentafluorbenzolsulfonsaeurechlorid ionomer membrane (Membran 1301)
Dissolve PSU (SO ₂ Li) ₂ in 3 g NMP. To this, 3,84 g of pentafluorobenzene chlorosulfonic acid is added. Stir until homogenized. The reaction mixture is thinned onto a glass plate and evaporated at 130-140 degrees, 700 mbar to 1 mbar. The film is then peeled off in water and post-treated as follows:
In 10% CaCl ₂ at room temperature -90 ° C for 24 hours In 1N HCl at room temperature -90 ° C for 48 hours In water at room temperature -90 ° C for 48 hours Characteristic results:
IEC (meq SO ₃ H / g): 1.25
R _sp ^{H +} , 0,5N HCl (Ω * cm): 8,3
SW 25 ℃ (%): 41,4
SW 90 ℃ (%): 136

21. Pentafluorbenzolsulfonsaeurechlorid ionomer membrane (Membran 1302)
PSU (SO ₂ Li) ₂ is dissolved in 2,693 g NMP. To this, 3,45 g of pentafluorobenzene chlorosulfonic acid is added, and then 0.5 g of bis (3-nitro-4-fluorophenyl) sulfon is added. Stir until homogenized. The reaction mixture is thinned onto a glass plate and evaporated at 130-140 degrees, 700 mbar to 1 mbar. The film is then peeled off in water and post-treated as follows:
In 10% CaCl ₂ at room temperature -90 ° C for 24 hours In 1 N HCl at room temperature -90 ° C for 48 hours In water at room temperature -90 ° C for 48 hours Characteristic results:
IEC (meq SO ₃ H / g): 1.16
R _sp ^{H +} , 0,5N HCl (Ω * cm): 7,5
SW 25 ℃ (%): 30,8
SW 90 ℃ (%): 207,8

22. Pentafluorobenzolsulfonsaeurechlorid ionomer membrane (Membran 1307)
RadelR (SO ₂ Li) ₁ is dissolved in 2,822 g NMP. To this, 1,79 g of pentafluorobenzene chlorosulfonic acid is added. Stir until homogenized. The reaction mixture is thinned onto a glass plate and evaporated at 130-140 degrees, 700 mbar to 1 mbar. The film is then peeled off in water and post-treated as follows:
In 10% CaCl ₂ at room temperature -90 ° C for 24 hours In 1N HCl at room temperature -90 ° C for 48 hours In water at room temperature -90 ° C for 48 hours Characteristic results:
IEC (meq SO ₃ H / g):
R _sp ^{H +} , 0,5N HCl (Ω * cm): 36,8
SW 25 ℃ (%):
SW 90 ℃ (%):

23. Pentafluorbenzolsulfonsaeurechlorid ionomer membrane (Membran 1309)
RadelR (SO ₂ Li) ₂ is dissolved in 3 g NMP. To this is added 2 ml of pentafluorobenzene chlorosulfonic acid. Stir until homogenized. The reaction mixture is thinned onto a glass plate and evaporated at 130-140 degrees, 700 mbar to 1 mbar. The film is then peeled off in water and post-treated as follows:
In 10% CaCl ₂ at room temperature -90 ° C for 24 hours In 1N HCl at room temperature -90 ° C for 48 hours In water at room temperature -90 ° C for 48 hours Characteristic results:
IEC (meq SO ₃ H / g):
R _sp ^{H +} , 0,5N HCl (Ω * cm):
SW 25 ℃ (%):
SW 90 ℃ (%):

24. Pentafluorbenzolsulfonsaeurechlorid ionomer membrane (Membran 1310)
PEEK (SO ₂ Li) _0,5 (SO ₃ Li) _0,5 is dissolved in 3 g NMP. To this is added 0.5 ml of pentafluorobenzene chlorosulfonic acid. Stir until homogenized. The reaction mixture is thinned onto a glass plate and evaporated at 130-140 degrees, 700 mbar to 1 mbar. The film is then peeled off in water and post-treated as follows:
In 10% CaCl ₂ at room temperature -90 ° C for 24 hours In 1N HCl at room temperature -90 ° C for 48 hours In water at room temperature -90 ° C for 48 hours Characteristic results:
IEC (meq SO ₃ H / g):
R _sp ^{H +} , 0,5N HCl (Ω * cm):
SW 25 ℃ (%):
SW 90 ℃ (%):

25. Pentafluorbenzolsulfonsaeurechlorid ionomer membrane (Membran 1312)
RadelR (SO ₂ Li) ₂ is dissolved in 4 g NMP. To this is added 2,2 ml of pentafluorobenzene chlorosulfonic acid, followed by 1,337 g of decafluorobenzophenone. Stir until homogenized. The reaction mixture is thinned onto a glass plate and evaporated at 130-140 degrees, 700 mbar to 1 mbar. The film is then peeled off in water and post-treated as follows:
10% CaCl ₂ at room temperature -90 ° C for 24 hours 1N HCl in room temperature at -90 ° C for 48 hours Water in room temperature at -90 ° C for 48 hours
IEC (meq SO ₃ H / g):
R _sp ^{H +} , 0,5N HCl (Ω * cm):
SW 25 ℃ (%):
SW 90 ℃ (%):

26. Decafluorobenzophenon ionomer membrane (Membran 1313)
PEEK (SO ₂ Li) _0,5 (SO ₃ Li) _0,5 is dissolved in 4,486 g NMP. To this is added 0,235 g of decafluorobenzophenone. Stir until homogenized. The reaction mixture is thinned onto a glass plate and evaporated at 130-140 degrees, 700 mbar to 1 mbar. The film is then peeled off in water and post-treated as follows:
In 10% CaCl ₂ at room temperature -90 ° C for 24 hours In 1N HCl at room temperature -90 ° C for 48 hours In water at room temperature -90 ° C for 48 hours Characteristic results:
IEC (meq SO ₃ H / g):
R _sp ^{H +} , 0,5N HCl (Ω * cm):
SW 25 ℃ (%):
SW 90 ℃ (%):

Claims (31)

Polymer formation containing polymer, or polymer blend comprising at least sulfinate groups SO ₂ M, or polymers (blends) film containing at least sulfinate groups SO ₂ M, or other at least sulfinate groups SO ₂ M containing at least sulfinate groups SO ₂ M (M = monovalent-, divalent- or trivalent metal cation or ammonium ion NR ₄ ⁺ (R = H and / or alkyl and / or aryl or imidazole ion or pyrazole ion or pyridinium ion)), a sulfinate group A modified polymer, polymer blend, polymer (blend) film, or polymer former characterized by S-alkylation with
At this time, ALK can be an optional alkylating agent or a mixture of different alkylating agents (electron-withdrawing group in the case of olefins) modified polymer, polymer that undergoes substitution or addition reaction with sulfinate groups while S-alkylating. Blend, polymer (blend) film, or polymer former.

At this time, the alkylating agent represents one, two, or two or more alkylating groups. M is an alkali metal cation (Li ⁺ , Na ⁺ , K ⁺ , Rb ⁺ , Cs ⁺ ) or other monovalent cation such as Cu ⁺ or Ag ⁺ , resulting in 0.1 per polymer repeat unit. The modified polymer according to claim 1, characterized in that there are 1 to 8 alkylating groups or sulfinate groups, wherein the alkylating agent or mixture of alkylating agents has one or two alkylatable groups, Polymer blend, polymer (blend) film, or polymer former. As an alkylating agent ・ From a polymer or a low-molecular halogen compound (Hal) _n -Al or (Hal) _n -Ar or (Hal-CH ₂ ) _n -Ar or (Hal-Ar) _n -Al, n = 1 Integer of 1000 or ・ Sultone or ・ High molecular compound or low molecular compound containing epoxy group or ・ High molecular compound or low molecular compound containing alkoxy group or ・ High molecular compound or low molecular compound containing tosyl group or other demand The modified polymer, polymer blend, polymer (blend) film, or polymer according to claim 1, wherein a high molecular compound containing a nuclear leaving group or an electron withdrawing group or an organic compound containing an olefin group having a low molecular compound can be used. Formation.
(R = alkyl, aryl, hetaryl, optional organic group, M = alkaline or alkaline earth ion or any monovalent or divalent metal ion, or ammonium cation, Polymer = optional polymer. Main chain, Hal = F, Cl, Br, I, x = 2-20, X = electron withdrawing group, n = number of repeating units of main polymer (WE)):

A modified polymer, polymer blend, polymer (4) characterized in that a tetracyclic, pentacyclic, hexacyclic or heptacyclic sultone is preferred as the sultone, and benzsultone can also be used. Blend) film, or polymer former.

R ₁ = H and / or Hal, C _n H _2n-1 , C _n Hal _2n-1
n = 1-30, Hal = F, Cl, Br, I   The modified polymer, polymer blend, polymer (blend) film, or polymer-formation product according to claim 3 or 4, characterized in that tetracyclic and pentacyclic (benz) sultone are preferred as sultone. The modified polymer, polymer blend, polymer (blend) film, or polymer-formation product according to claim 3, characterized in that a compound containing one or more anion exchange groups is preferred as the halogen-containing compound.

m = 1-30,
R ₁ = H and / or C _n H _2n-1 and / or aryl, hetaryl, phenyl, n = 1-30,
A = Hal (F, Cl, Br, I), OH, any anion,
Ar = any arylene group m is 1-10, R ₁ = C _n H _2n-1 , n = 1-12 and / or phenyl and Hal Cl, Br or I, Ar = 1,4-phenyl, Item 7. The modified polymer, polymer blend, polymer (blend) film, or polymer formed product of Item 6. The modified polymer, polymer blend, polymer (blend) film, or polymer-formed product according to claim 3, wherein a benzyl compound is used as the halogen compound.
(R = any organic group)

The modified polymer, polymer blend, polymer (blend) film, or polymer-formation product according to claim 8, characterized in that the following compounds are preferred as benzyl compounds.

4. The modified polymer, polymer blend, polymer (blend) film, or polymer formed product according to claim 3, wherein halogenamine is used as the halogen compound.

m = 1-30,
R ₁ = H and / or C _n H _2n-1 and / or aryl, hetaryl, phenyl, n = 1-30,
Ar = any arylene group The modified polymer, polymer blend, polymer (blend) film, or polymer formed product according to claim 3, wherein a compound containing a cation exchange group or a nonionic precursor thereof is used as the halogen compound. .

m = 1-30,
Hal = F, Cl, Br, I,
Ar = any arylene group,
X = OM (M = H or any cation), Hal, OR ₁ , N (R ₁ ) ₂ ,
R ₁ = H and / or C _n H _2n-1 and / or aryl, hetaryl, phenyl, n = 1-30, NHR ₂ (R ₂ = C _n F _{2n + 1} and n = 1-30) The modified polymer, polymer blend, polymer (blend) film, or polymer-formation product according to claim 11, characterized in that the following compound is preferred as the halogen compound.

  The modified polymer, polymer blend, polymer (blend) film, or polymer-formation product according to claim 3, wherein an aryl halogen compound or a hetaryl halogen compound (Hetarylhalogenverbindungen) is used as the halogen compound. 14. The modified polymer, polymer blend, polymer (blend) film or polymer formed product according to claim 13, characterized in that halogen compounds containing the following basic structure are preferred.

14. The modified polymer, polymer blend, polymer (blend) film, or polymer-formation product according to claim 3 or 13, wherein a reactive dye containing the following reactive group is preferred as the halogen compound.
Reactive groups: Michael-acceptors such as dichlorotriazine, difluoropyrimidine, monofluorotriazine, dichloroquinoxaline, monochlorotriazine, trichloropyrimidine, trinicotinic acid triazine, vinyl sulfone and sulfate thereof.

15. A modified polymer, polymer blend, polymer (blend) film, or polymer former according to claim 14, characterized in that the reactive dye comprises the following chromophores.
・ Azo and arylpyrazol-5-one as linking component ・ Azo and I acid as linking component ・ Azo and H acid as linking component ・ Azo-copper complex and H acid ・ copper complex -formazan ・ phthalocyanine as linking component・ Anthraquinone ・ Triphendioxazin
・ Disazo ・ Azo-copper complex and 1-aryl-pyrazol-5-one as linking components 17. Modified polymer, polymer blend, polymer (blend) film or polymer formation according to any of claims 1 to 16, characterized in that it is preferred as a base polymer for a modified polymer, polymer blend, polymer (blend) film object.
・ Polyolefins such as polyethylene, polypropylene, polyisobutylene, polynorbornene, polymethylpentene, polyisoprene, poly (1,4-butadiene), poly (1,2-butadiene), and the like, poly (methylstyrene), poly (a , B, b-trifluorostyrol), poly (pentafluorostyrol) and other styrol (co) polymers, Nafion® or Nafion® SO ₂ Hal-precursor or SO ₂ M-precursor ( Hal = F, Cl, Br, I), Dow®-Membrane, GoreSelect®-Membran and other perfluorinated ionomer sulfonated PVDF and / or SO ₂ Hal-precursors, Hal is fluorine, Means chlorine, bromine and iodine.
・ (Heta) aryl main chain polymer:
Polyether ketone PEK Victrex (registered trademark), polyether ether ketone PEEK Victrex (registered trademark), polyether ether ketone ketone PEEKK, polyether ketone ether-ketone ketone PEKEKK Ultrapek (registered trademark), polyether ether ketone ketone PEEKK, poly Polyether ketones such as ether ketone ketone PEKK ・ Polysulfone Udel (registered trademark), polyphenylsulfone Radel R (registered trademark), polyether ether sulfone Radel A (registered trademark), polyether sulfone PES Victrex (registered trademark), poly Polyethersulfones such as ethersulfone Ultrason® Poly (benz) imidazoles such as PBI Celazol® and other oligomers and polymers containing benzimidazole components. (Benz) imidazole groups may be included in the main chain or polymer side chain.
Polyphenylene ethers such as poly (2,6-dimethyloxyphenylene), poly (2,6-diphenyloxyphene), etc.polyphenylene sulfide and copolymers side chain, optionally benzoyl-, naphthoyl-, or Poly (1,4-phenylene) deformed due to o-phenyloxy-1,4-benzoyl group, m-phenyloxy-1,4-benzoyl group or p-phenyloxy-1,4-benzoyl group Or poly (1,3-phenylene)
・ Poly (benzoxazole) and copolymer ・ Poly (benzthiazole) and copolymer ・ Poly (phthalazinone) and copolymer ・ Polyaniline and copolymer 18. A modified polymer, polymer blend, polymer (blend) film or polymer former according to claim 17, characterized in that a (het) aryl main chain polymer which can consist of the following constituents is preferred as the base polymer.
(R = constituent group, BrG = crosslinking group between constituent elements (n = number of polymer repeating units (WE) (-(R-BrG) _n- )):

R ₁ = C _n H _2n-1 or aryl, n = 1-30,
R ₂ = C (C _n H _2n-1 ) ₂ or C (C _n F _2n-1 ) ₂ , n = 1-30,
m = 0 or 1
X = N
Y = O, S, NH 19. A modified polymer, polymer blend, polymer (blend) film or polymer former according to claim 18, characterized in that the following types of aryl main chain polymers are preferred as polymer groups.
-Polyethersulfones such as PSU Udel (registered trademark), PES Victrex (registered trademark), PPhSU Radel R (registered trademark), PEES Radel A (registered trademark), Ultrason (registered trademark)-Poly-p-phenylene, poly -M-phenylene and polyphenylenes such as poly-p-stat-m-phenylene, polyphenylene ethers such as poly (2,6-dimethylphenylene ether) and poly (2,6-diphenylphenylene ether), and polyphenylene sulfides・ Polyether ketones such as polyether ether ketone PEEK, polyether ketone PEK, polyether ether ketone ketone PEEKK, polyether ketone ketone PEKK, polyether ketone ether ketone ketone PEKEKK 20. The modified polymer, polymer blend, polymer (blend) film, or polymer formation according to any one of claims 17 to 19, characterized in that the polymer can further have the following functional groups at any place: object.
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, naphthyl, anthracenyl, aryl, hetaryl, N (R ₃ ) ₂ , N ₃ , NO ₂ , ONO, nitroalkyl, nitroaryl, COOR ₉ . A method for producing a modified polymer according to any one of claims 1 to 20,
A polymer containing a sulfinate group is optionally suspended in a flask together with other polymers, optionally using a protective gas, and optionally suspended in a solvent suitable for the dissolution or each alkylation reaction. It is characterized by reacting with an easily or slightly soluble calcium compound in an alkylating agent, or a mixture of alkylating agents, and in some cases in a reaction mixture, with stirring at 0 to 200 ° C. using a protective gas in some cases. At this time, the reaction mixture is stirred between 0 ° C. and 200 ° C. until the reaction is completed, and the reaction mixture is purified as follows.
(A) Water-insoluble matter (1) (Optional) In order to destroy excess alkylating agent and possibly precipitate fluoride ions released due to the reaction as CaF ₂ , the molar amount of alkylating agent On the other hand, the reaction mixture contains 2-10 times the amount of water, calcium chloride solution, calcium salt aqueous solution such as calcium gluconate solution, and / or alkaline aqueous solution (1-30% NaOH, KOH, LiOH, Ca (OH) _2. 1-30% ammonia solution or amine solution) is added to the reaction mixture with stirring.
(2) 2-20 times in alcohol (methanol, ethanol, i-propanol, n-propanol) (in the reaction mixture or modified polymer volume), or in water or in an aqueous mineral salt solution (NaCl, NaHCO ₃ , Na ₂ SO ₄ , CaCl _2, etc.) or other common precipitating agents (acetone, methyl ethyl ketone, etc.) are precipitated or suspended and filtered.
(3) Wash the precipitate until no ions are present in the wash water. (4) Raise the temperature and reduce the pressure depending on the case. (5) (Optional) Re-dissolve the modified polymer in a suitable solvent, as above. Purify (after (2)).
(B) Water-soluble substances (1) In order to destroy the excess amount of the alkylating agent and in some cases to precipitate fluoride ions liberated due to the reaction as CaF ₂ , the reaction mixture relative to the molar amount of the alkylating agent 2-10 times water, calcium chloride solution, calcium salt aqueous solution such as calcium gluconate solution, and / or alkaline aqueous solution (1-30% NaOH, KOH, LiOH, Ca (OH) ₂ , 1-30% Ammonia solution or amine solution) is added with stirring.
(2) Combine the reaction mixture with 5-20 volumes of water and dialyze until all low molecular weight material is removed.
(3) Filter the non-water soluble components of the dialysate that may be present.
(4) Increase the temperature, and depending on the case, reduce the pressure and dry. A method for producing a polymer (blend) film according to any one of claims 1 to 20,
A polymer containing sulfinate groups, optionally in a reaction vessel with other polymers, optionally using a protective gas, and optionally a dipolar-aprotic solvent or protic suitable for each alkylation reaction Suspend in a solvent or ether solvent and stir using an organic alkylating agent of the present invention, or a mixture of alkylating agents, and, in some cases, a reaction mixture, using a readily soluble or slightly soluble calcium compound and optionally a protective gas. Mix together,
Stir the reaction mixture from 0 ° C. to 200 ° C. until the beginning or end of the alkylation reaction. Immediately afterwards, spread the reaction mixture as a thin film on the underlay (glass plate, metal plate, cloth or fleece), increase the temperature, optionally Is a method for producing a polymer (blend) film in which the low pressure is removed, and then the polymer (blend) film is post-treated as follows, and the number of post-treatments and the order of the post-treatment steps can be changed.
(1) 1 to 48 hours at a temperature of 0 ° C. to 90 ° C. 1-50% calcium salt aqueous solution (2) 1 to 48 hours at 0 ° C. to 90 ° C. 1-50% aqueous alkali (3) from 0 ° C. 1 to 48 hours at 100 ° C 1-20% aqueous mineral acid (4) 0 to 100 ° C for 1 to 48 hours water A method of making a superficially or largely (bulk) modified polymer (blend) film or other polymer formation according to any of claims 1 to 20, comprising
The polymer film containing the sulfinate group, or the polymer-formation product, is used in the reaction vessel with an alkylating agent or a mixture of different alkylating agents and, in some cases, a protective gas, and in some cases is easily soluble or hardly soluble in the reaction mixture. Polymer (blend), characterized by adding calcium compound, alkylating superficially or mostly (bulk) from 0 ° C to 200 ° C until the end of the alkylation reaction and then washing as follows Method for making a film or other polymer formation.
(1) 2-10 times the amount of the alkylating agent relative to the molar amount of the alkylating agent in order to destroy the excess amount of the alkylating agent and in some cases to precipitate fluoride ions liberated due to the reaction as CaF _2. Water, calcium chloride solution, calcium salt aqueous solution such as calcium gluconate solution, and / or alkaline aqueous solution (1-30% NaOH, KOH, LiOH, Ca (OH) ₂ , 1-30% ammonia solution or amine) Solution) is added to the polymer formation with stirring.
(2) 2-20 times in alcohol (methanol, ethanol, i-propanol, n-propanol) (in the reaction mixture or modified polymer volume), or in water or in an aqueous mineral salt solution (NaCl, NaHCO ₃ , Na ₂ SO ₄ , CaCl ₂ , Ca (NO ₃ ) ₂ ), or other common organic precipitating agents (acetone, methyl ethyl ketone, etc.).
(3) Wash with water until no ions are present in the wash water. (4) Increase the temperature and reduce the pressure depending on the case. A method for producing a modified polymer according to any one of claims 1 to 20,
The polymer containing the alkylating group is optionally in a flask together with other polymers, optionally using a protective gas, and optionally suspended or suspended in a solvent suitable for each alkylation reaction. In low-molecular or high-molecular sulfinates, or a mixture of different sulfinates, and in some cases, in a reaction mixture, react with an easily or slightly soluble calcium compound at 0 to 200 ° C. with stirring using a protective gas in some cases. A method for producing a modified polymer, characterized in that, at this time, the reaction mixture is stirred between 0 ° C. and 200 ° C. until the reaction is completed, and the reaction mixture is purified as follows.
(A) Water-insoluble matter (1) (Optional) In order to destroy excess alkylating agent and possibly precipitate fluoride ions released due to the reaction as CaF ₂ , the molar amount of alkylating agent On the other hand, the reaction mixture contains 2-10 times the amount of water, calcium chloride solution, calcium salt aqueous solution such as calcium gluconate solution, and / or alkaline aqueous solution (1-30% NaOH, KOH, LiOH, Ca (OH) _2. 1-30% ammonia solution or amine solution) is added to the reaction mixture with stirring.
(2) 2-20 times in alcohol (methanol, ethanol, i-propanol, n-propanol) (in the reaction mixture or modified polymer volume), or in water or in an aqueous mineral salt solution (NaCl, NaHCO ₃ , Na ₂ SO ₄ , CaCl ₂ , Ca (NO ₃ ) ₂ etc.) or other general precipitating agents (acetone, methyl ethyl ketone, etc.) are precipitated or suspended and filtered.
(3) Wash the precipitate until no ions are present in the wash water. (4) Raise the temperature and reduce the pressure depending on the case. (5) (Optional) Re-dissolve the modified polymer in a suitable solvent, as above. Purify (after (2)).
(B) Water-soluble substances (1) In order to destroy the excess amount of the alkylating agent and in some cases to precipitate fluoride ions liberated due to the reaction as CaF ₂ , the reaction mixture relative to the molar amount of the alkylating agent 2-10 times water, calcium chloride solution, calcium salt aqueous solution such as calcium gluconate solution, and / or alkaline aqueous solution (1-30% NaOH, KOH, LiOH, Ca (OH) ₂ , 1-30% Ammonia solution or amine solution) is added with stirring.
(2) Combine the reaction mixture with 5-20 volumes of water and dialyze until all low molecular weight material is removed.
(3) Filter the non-water soluble components of the dialysate that may be present.
(4) Increase the temperature, and depending on the case, reduce the pressure and dry. A method for producing a polymer (blend) film according to any one of claims 1 to 20,
A polymer containing an alkylating group is optionally combined with other polymers in a reaction vessel, optionally using a protective gas, and optionally dissolved or suspended in a solvent suitable for each alkylation reaction. A low-molecular sulfinate or a high-molecular sulfinate, or a mixture of different sulfinates and, in some cases, a slightly soluble or slightly soluble calcium compound in the reaction mixture, and optionally a protective gas and mixed with stirring.
Stir the reaction mixture from 0 ° C. to 200 ° C. until the beginning or end of the alkylation reaction. Immediately afterwards, spread the reaction mixture as a thin film on the underlay (glass plate, metal plate, cloth or fleece), increase the temperature, optionally Is a method for producing a polymer (blend) film in which the low pressure is removed, and then the polymer (blend) film is post-treated as follows, and the number of post-treatments and the order of the post-treatment steps can be changed.
(1) 1 to 48 hours at a temperature of 0 ° C. to 90 ° C. 1-50% calcium salt aqueous solution (2) 1 to 48 hours at 0 ° C. to 90 ° C. 1-50% aqueous alkali (3) from 0 ° C. 1 to 48 hours at 100 ° C 1-20% aqueous mineral acid (4) 0 to 100 ° C for 1 to 48 hours water A method of making a superficially or largely (bulk) modified polymer (blend) film or other polymer formation according to any of claims 1 to 20, comprising
A polymer film containing an alkylating group or a polymer-forming product may be used in the reaction vessel, possibly using a protective gas, and in some cases, a surface of the reaction mixture at 0 ° C. to 200 ° C. with a calcium compound that is easily or hardly soluble in the reaction mixture. A polymer characterized in that it is alkylated with the low molecular weight sulfinates of the present invention or polymeric sulfinates or mixtures of different sulfinates until the end of the alkylation reaction, in bulk or in bulk, and then washed as follows: (Blend) A method of making a film or other polymer formation.
(1) 2-10 times the amount of the alkylating agent relative to the molar amount of the alkylating agent in order to destroy the excess amount of the alkylating agent and in some cases to precipitate fluoride ions liberated due to the reaction as CaF _2. Water, calcium chloride solution, calcium salt aqueous solution such as calcium gluconate solution, and / or alkaline aqueous solution (1-30% NaOH, KOH, LiOH, Ca (OH) ₂ , 1-30% ammonia solution or amine) Solution) is added to the polymer formation with stirring.
(2) 2-20 times in alcohol (methanol, ethanol, i-propanol, n-propanol) (in the reaction mixture or modified polymer volume), or in water or in an aqueous mineral salt solution (NaCl, NaHCO ₃ , Na ₂ SO ₄ , CaCl ₂ , Ca (NO ₃ ) ₂ ), or other common organic precipitating agents (acetone, methyl ethyl ketone, etc.).
(3) Wash with water until ions disappear from the wash water.
(4) Increase the temperature, and depending on the case, reduce the pressure and dry. A creation method according to any one of claims 21 to 26, wherein:
A production method characterized by using the following solvent as a pure solvent or a mixture as a reaction solvent or a solvent for an alkylation reaction.
Dimethyl sulfoxide, sulfolene, N-methylpyrrolidinone, N, N-dimethylacetamide, N, N-dimethylformamide, N-methylformamide, N-methylacetamide, acetonitrile, dimethyl carbonate, diethyl carbonate, or a mixture of these solvents Dipolar-aprotic solvents such as diethyl ether, tetrahydrofuran, glyme, diglyme, diglyme, triglyme, dioxane, or a mixture of these solvents, etc. Ether solvents such as methanol, ethanol, n-propanol, i-propanol Or alkyl alcohols such as a mixture of these solvents, methyl ethyl ketone and acetone, or ketones such as a mixture of these solvents, water or a mixture with the above solvents, and any mixtures of the above solvents A creation method according to any one of claims 21 to 27,
A production method characterized in that the following calcium compound is preferred as an easily soluble or hardly soluble calcium compound in the reaction mixture.
・ Calcium acetylacetonate (bis- (2,4-pentandionato) -calcium) = Calciumacetylacetonat (Bis- (2,4-pentandionato) -calcium)
Calcium-bis- (6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octandionato) = Calcium-bis- (6,6,7,7 , 8,8,8-heptafluor-2,2-dimethyl-3,5-octandionat)
・ Calcium-1,1,1,5,5,5-hexafluoroacetylacetonate = Calcium-1,1,1,5,5,5-hexafluoracetylacetonat
・ Calcium methylat
・ Calcium oxalate = Calciumoxalat
・ Calcium-D-gluconat
・ Calcium- (2,2,6,6-tetramethyl-3,5-heptanedionato) = Calcium- (2,2,6,6-tetramethyl-3,5-heptandionat)
・ Calcium triflate (= Calcium trifluoromethanesulfonate) = Calciumtriflat (Trifluormethansulfonsaure Calciumsalz)   A modification of a modified polymer according to any of claims 1 to 28 into a membrane for use in a membrane process or optionally a membrane fuel cell, membrane electrolysis.   29. Blend component of a blended membrane of a modified polymer according to any of claims 1 to 28, which is proton-conductive, optionally physically covalently crosslinked, for membrane fuel cell or membrane electrolysis Use as.   29. Use of a modified polymer membrane prepared according to any of claims 1 to 28 in a membrane process, a membrane separation process, a membrane fuel cell or membrane electrolysis.

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