JP2013151681A - Method for producing monomer, oligomer and polymer of phosphonic acid ester, phosphonic acid and sulfonic acid by aromatic nucleophilic substitution - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a monomer, oligomer and polymer of aromatic sulfonic acid or phosphonic acid (or these derivatives), wherein the monomer, oligomer and polymer are obtained by an aromatic nucleophilic substitution using a sulfur or phosphorus nucleophilic reagent.SOLUTION: The monomer, oligomer and polymer of unfluorinated, partially-fluorinated or perfluorinated (perfluoro) sulfonic acid are produced by a reaction of an oligomeric or polymeric arene, which is halogenated and has low molecular weight, with (hydrogen) sulfite, dithionite, sulfide or other reducing sulfur salt while using a suitable oxidizing agent by the sulfur oxidation degree of less than +6 as much as possible to oxidize a sulfur-containing arene intermediate formed together with the formation of corresponding sulfonic acid functional groups (the groups of a sulfonic acid, sulfohalogenide, sulfonamide and sulfonic acid ester).

Description

The methods currently performed to produce sulfonated poly (allyl) ethers can be divided into the following two groups (Non-patent Document 1):
i) Sulfonate the existing polymer later:
In the methods described in the literature, aromatic electrophilic substitution (SEAr) is always used. Typical sulfonation reagents in this case are concentrated sulfuric acid, fuming sulfuric acid, chlorosulfonic acid, sulfur trioxide and complex compounds thereof (for example, sulfur trioxide-pyridine, sulfur trioxide-triethyl phosphate complex, etc.) Is mentioned. An alternative sulfonation route is described in Kerres et al. Using polysulfone as an example (Non-Patent Documents 2, 3, and 4). According to this, the polymer is first lithiated and converted in the next step by a sulfur dioxide electrophile and finally the resulting sulfinic acid polymer is oxidized. The lithiated polymer can be converted to a sulfochloride polymer by sulfuryl chloride SO2Cl2, followed by hydrolysis of the sulfochloride group to a sulfonic acid group in an aqueous solvent (Non-Patent Document 5).
ii) directly polymerizing the sulfonated polymer (statistical copolymer):
Similarly, the monomer introduced for copolymerization is sulfonated by the above-described method, and particularly concentrated sulfuric acid or fuming sulfuric acid is added as a sulfonation reagent (Non-patent Documents 6 and 7).
In recent years, interest in phosphonation of polyallyl ether has increased year by year. However, covalently attaching phosphonic acid to a polymer chain is difficult in terms of synthesis and has been realized only with a few polymers so far (Non-patent Document 8). Some examples are described below. Phosphonation of the poly (phosphazene) backbone was successfully accomplished by Allcock et.al by lithiation followed by conversion of the chlorophosphonate (9). Similarly, Allcock et.al described phosphonation of the benzyl side chain by nucleophilic substitution (Michaelis-Becker reaction) in poly (phosphazenes) containing dimethyl sodium phosphite and dibutyl sodium phosphite. As another synthetic route for obtaining phosphonated polyallyl ether, there is phosphonation by a palladium catalyst (Non-patent Document 10 and Patent Document 1). In the area of low molecular weight compounds, the Michaelis-Becker reaction is also used for the production of aromatic (fluorinated) phosphonates (Non-Patent Document 11). This aromatic (fluorinated) phosphonic acid ester starts with various low molecular weight fluoroaromatics (pentafluorobenzonitrile, octafluorotoluene, hexafluorobenzole, pentafluorobenzole, pentafluoronitrobenzole, pentafluoroanisole). The yield is about 10-65%. This reaction has not been described to the best of our knowledge for partially fluorinated polymers.
Other methods of introducing (CF2) XPO (OR) 2 side chains (x = 1-20, R = any organic moiety) into aromatic systems have already been established in medicinal chemistry or medicinal chemistry, In the presence of Zn powder and CuBr of the group (mostly iodine aromatic or bromine aromatic) and X (CF2) XPO (OR) 2 (X = halogen, often bromine or iodine, R = any organic moiety) In the reaction in N, N-dimethylacetamide (DMAc) (Non-patent Documents 12 and 13). Partially and perfluorinated low molecular weight aromatics having the general chemical formula R-CF2X (R = non-partially or perfluorinated aromatic, X = Br, I) are described in Non-Patent Document 14 and Non-Patent Document 15 Can be transferred to a compound of the formula R—CF 2 SO 2 Y (Y═Cl, OH, OMe, Me = any cation) by the method described in (Sulfinate halogenation followed by oxidation). The reaction described above has not been described for polymers to the best of our knowledge.

  An object of the present invention is to obtain monomers, oligomers and polymers of sulfonic acid or phosphonic acid or sulfonic acid or phosphonic acid derivatives by aromatic nucleophilic substitution reaction (SNAr). To prepare monomers of sulfonic or phosphonic acids, starting from partially or perhalogenated (especially partially or perfluorinated) aromatics, while preparing oligomers and polymers of sulfonic or phosphonic acids Describes by way of example poly (allyl) ethers which are partially or perhalogenated (particularly partially or perfluorinated). This method can be surprisingly applied to other suitable partially and perhalogenated (particularly partially or perfluorinated) polymers. As the nucleophile for the production of the sulfonic acid mentioned above, metal sulfite, metal hydrogen sulfite, metal dithionite or metal sulfide is used. In the aromatic nucleophilic substitution reaction in the halogen coordination of halogenated arenes with metal dithionite or hydrogen dithionite or metal sulfite or hydrogen sulfite, a sulfur functional group having an oxidation number of sulfur of +6 or less is obtained. Thus, according to the present invention, these functional groups can be converted to halogen molecules (bromine, iodine, chlorine), metal hypochlorite, potassium permanganate, hydrogen peroxide or other suitable oxidizing agents, Raise the oxidation number to the appropriate required sulfonic acid functionality.

  When producing similar phosphonic acids, Michaelis-Becker reagents (eg, diethyl sodium phosphite, phenyl sodium phosphite, dibutyl sodium phosphite) are used as nucleophiles at reaction temperatures of -93 ° C to + 200 ° C. Use. In both cases, the enucleating group is a CSP2 bonded halogen (especially fluorine). In addition, functional non-partial or perfluorinated copolymers (alternative, statistical block and graft copolymers) can be partially or perfluorinated by suitable methods, such as suitable diphenols, dithios. Phenol or other suitable monomers (eg, low molecular weight sulfonic and / or phosphonic acids (or derivatives thereof) including derivatives of diphenols such as silyl ethers or carbamoyl protecting groups (Non-Patent Documents 16 and 17)) The production by nucleophilic polycondensation by charging is a component of the present invention, which is the most commonly used method (potassium carbonate as base, aprotic polar solvent, relatively high Temperature: 80-200 ° C., possibly benzol, toluene or xylol that pulls under water input In addition to organic solvents, it is also possible to apply methods that can be carried out under mild conditions, modified to have advantages (avoid dendritic branching and crosslinking of the polymer), in particular Robertson. Et. al describes a method for absorbing reaction water generated by introducing a molecular sieve at a relatively mild temperature (Non-Patent Document 18) and the above-described method using calcium hydride as a base and cesium fluoride as a catalyst. And a method in DMAc / benzol or propylene carbonate (Non-patent Document 19, Patent Document 2).

German Patent Application Publication No. 10148131 US Patent Application No. 60/433574 (filed in 2003)

M.M. A. Hicknell, W. Kui, H. Gassemi, Y.M. S. Kim, B. R. Ainsla, J.H. E. Chemical Review by McGrath et al. (Chem. Rev.), 2004 No. 104, pp. 4587-4612 J. et al. Ceres, W. Kui, S. "J. Polym. Sci., Part A: Polym. Chem", 1996, Vol. 34, p. 2421, by Richie et al. J. et al. Ceres, W. Tsang W. Kui et al., "J. Polym. Sci., Part A: Polym. Chem", 1996, Volume 36, page 1441 J. et al. Ceres, W. Kui, M.M. Jungergar et al., "J. Membr. Sci., Part A: Polym. Chem", 1996, Volume 36, page 1441 J. et al. Ceres, A. "J.Appl. Polym. Sci., Part A: Polym. Chem", 1999, 74, 428-438, by J. Van Zeil et al. F. Wang, M.M. Hicknell, Y.M. S. Kim, T. A. Zavotzinsky, J.M. E. "J. Membr. Sci., Part A: Polym. Chem", 2002, 197, 231 pages, by McGrath et al. F. Wang, M.M. Hicknell, Q. Ju W. Harrison, J McCam, T.W. A. Zavotzinsky, J.M. E. Macgrass et al., “Macromol. Symp.” 2001, 175, 387 A. Grussen, D.C. Struten et al., "Membranen fur Polymerelektorolyt-Brennstoffzellen, Chemie Ingenieur Technik", 2003, 75 (11), 1591-1597 H. R. Allcock, M.C. A. Hoffman, C.I. M.M. Ambler, R.A. V. A paper by Morford et al., “Macromolecules” 2002, 35, 3484 K. Miyatake, A. S. "Journal of Polymer Science: Part A: Polymer Chemistry", 2001, Vol. 39, pages 3770 to 3779 by Hai et al. L. N. Markovcy, G. G. Flynn, Y. G. Shell Morovic, G. G. Jacobson et al., “Bulletin of the Academy of Science of the USSR / Division of Chemical Science,” 1981, volume 30 (4), pages 646-648 T.A. Yokomatsu, H.C. Abe, T. Yamagi, K .; Sümne, S. Shibuya et al., “J. Org. Chem.” 1999, Vol. 64, pages 8413-8418 G. S Cockeryl, H.C. J. et al. Easter Field, J.M. M.M. Percy, S.M. "J. Chem. Soc., Perkin. Trans. 1", 2000, pages 2591 to 2599 by Pintat et al. J. et al. T.A. Louis, H.C. J. et al. "Chem. Lett." 2000, Vol. 11, No. 3, pp. 189-190, by Ryu Shin et al. G. K. Surya Prakash, J.A. Hugh, J.H. Simon, D.D. R. Bereu, G. A. "J. Fluorine Chem." 2004, Vol. 125, pp. 595-601, by Olah et al. A. Tiger, C.I. Vogel, D.C. Lehmann, W. Lenk, K. Schlenstedt, J.M. A paper on “Macromol. Symp.” 2004, Volume 210, pages 175-184, by Meyer-Haack et al. L. One, Y. Z. Men, S.M. J. et al. Wang, X. Y. Shan, L. Lee, A. S. "Macromolecules" 2004, volume 37, pages 3151 to 1158, by Hai et al. F. Liu, J. Din, M.D. Lee, M. Day, G. Robertson, M.C. Tsou et al., “Macromol. Rapid Commun.” 2002 Volume 23, 844-848 Y. Kui, J.H. Din, M.D. Day, J. Jean, C. L. Calender et al., “Chem. Mater.” 2005, Vol. 17, pp. 676-682 Professor of Chemistry at Thames Polytechnic in London, UK N. "Reactions of sulphone-stabilised carbanions with fluorinated aromatic compounds" by Sergis published in December 1990

  Surprisingly, the partial and perhalogenated (especially partially and perfluorinated) aromatics shown in FIG. 1 can be converted to sulfurous acid or hydrogen sulfite, or, for example, dithionite / hydrogen dithionite or sulfide / sulfurized. It has been discovered that it can be reacted by aromatic nucleophilic substitution with other sulfates such as hydrogen, possibly resulting in a suitable sulfonic acid or salt thereof after the oxidation step.

  The partially and perhalogenated (especially partially and perfluorinated) allyl backbone polymer shown in FIG. 2 can be reacted with metal sulfite or sodium bisulfite for aromatic nucleophilic substitution, with sulfone It has further been discovered to yield acid polymers or salts thereof.

  Hydrolysis of the phosphinate (Figure 3) (phosphoric acid ester produced by the Michaelis-Becker reaction) with a moiety containing metal phosphite and a perhalogenated aromatic monomer with HBr or other suitable hydrolysis reagent Can be converted into a free phosphonic acid (as described above (Non-patent Document 11)) in some low-molecular aromatics. Surprisingly, Michaelis replaced the moiety containing metal phosphite and perhalogenated oligo or polyallyl (polyallyl ether, polyallyl thioether, polyallyl sulfoxide, polyallyl sulfone and copolymers thereof) (see FIG. 4). It has been found that conversion can be carried out at a reaction temperature of −93 ° C. to + 200 ° C. by Becker reaction.

  It was surprisingly found that the reactions described for the following small molecule halogenated aromatics can also be performed with polymers (FIG. 5).

The following figures (FIG. 6, FIG. 7, FIG. 8, FIG. 9, FIG. 10, FIG. 11, FIG. 12, FIG. 13, FIG. 14, FIG. 15, FIG. 16, FIG. 17, FIG. 18, FIG. 21, FIG. 22, FIG. 23, FIG. 24, FIG. 25) shows parts of the invention suitable for nucleophilic substitution reactions with metal phosphites, metal sulfites or other metal sulfur compounds such as sodium dithionite. A halogenated, in particular partially fluorinated allyl polymer is shown.
6, 7, 8, 9, 9, 10, 11, 12, 13, 14, 15, 15, 16, 17, 18, 19, 20, 20, 21, 22 The statistical copolymers and block copolymers containing the repeating units shown in the diagrams of FIGS. 23, 24 and 25 are the metal phosphite, metal sulfite of the present invention, or others such as sodium dithionite. It was surprisingly shown to be suitable for nucleophilic substitution reactions with metal sulfur compounds.
Even more surprising, non-salt phosphite compounds are also suitable for aromatic nucleophilic substitution reactions. This allows nucleophilic substitution of the halogen atom bonded to the aromatic group by tris (trimethylsilyl) phosphite and any other silylphosphorous acid by phosphonic acid coordination (FIG. 26).
In addition, it is surprising that polymers modified by perfluorinated side chains, especially allyl backbone polymers, are suitable for nucleophilic substitution reactions with phosphorous acid, metal sulfites or other metal sulfur compounds such as sodium dithionite. It was shown in In this case, polymers having these perfluorinated aromatics as side chains can surprisingly be produced, for example, by lithiated polymers having suitable perfluorinated aromatics (see FIG. 27 for the schematic). So far, the literature only describes the reaction of low molecular weight, sulfone stabilized carbanions and partially or perfluorinated aromatics (Patent Document 22). To make this polymer from a lithiated polymer, for example, brominated PPSU Radel R and perfluorinated aromatic benzol are shown in FIG. A suitable moiety or perfluorinated aromatic for reaction with a lithiated polymer is shown in FIG.

SNAr reaction of sulfurous acid or hydrogen sulfite with partially or perhalogenated and optionally substituted halogen aromatics (especially fluorine aromatics). SNAr reaction of sulfurous acid or hydrogen sulfite with partially or perhalogenated polyallyl ether. It is a SNAr reaction (Michaelis-Becker reaction) between a metal phosphite and a partially or perhalogenated aromatic. SNAr reaction (Michaelis-Becker reaction) of metal phosphite and partially or perhalogenated oligo or polyallyl ether. N, N- in halogenated allyl polymer and X (CF2) XPO (OR) 2 (X = halogen, often bromine or iodine, R = any organic moiety) in the presence of Zn powder and CuBr Reaction in dimethylacetamide (DMAc). FIG. 5 is a continuation reaction of the present invention with metal phosphite, sulfurous acid or other suitable phosphorus or sulfur compound using decafluorobiphenyl as a polymer made from monomers. FIG. 5 is a continuation reaction of the present invention with metal phosphite, sulfurous acid or other suitable phosphorus or sulfur compound using decafluorobenzophenone as a polymer made from monomers. FIG. 5 is a continuation reaction of the present invention with metal phosphite, sulfurous acid or other suitable phosphorus or sulfur compound using decafluorodiphenylsulfone as a polymer made from monomers. FIG. 5 is a continuation reaction of the present invention with metal phosphite, sulfurous acid or other suitable phosphorus or sulfur compound using decafluorodiphenyl sulfide as a polymer made from monomers. FIG. 5 is a continuation reaction of the present invention with metal phosphite, sulfurous acid or other suitable phosphorus or sulfur compound using hexafluorobenzole as a polymer made from monomers. FIG. 3 is a continuation reaction of the present invention with metal phosphite, sulfurous acid or other suitable phosphorus or sulfur compound using octafluorotoluene as a polymer made from monomers. FIG. 4 is a continuation reaction of the present invention with metal phosphite, sulfurous acid or other suitable phosphorus or sulfur compound using pentafluorobenzoyl sulfonic acid as a polymer prepared from monomers. FIG. 4 is a continuation reaction of the present invention with metal phosphite, sulfurous acid or other suitable phosphorus or sulfur compound using heptafluorobenzyl sulfonic acid as a polymer made from monomers. FIG. 4 is a continuation reaction of the present invention with metal phosphite, sulfurous acid or other suitable phosphorus or sulfur compound using 4-trifluoromethylphenylphosphonic acid as a polymer made from monomers. Continued reaction of the partially fluorinated polymer prepared perfluorinated benzyl iodide by sulfinic acid halogenation-oxidation and / or with metal phosphite, sulfurous acid or other suitable phosphorus or sulfur compounds of the present invention It is. FIG. 5 is a continuation reaction of the present invention with metal phosphite, sulfurous acid or other suitable phosphorus or sulfur compound using pentafluorobenzonitrile as a polymer made from monomers. FIG. 5 is a continuation reaction of the present invention with metal phosphite, sulfurous acid or other suitable phosphorus or sulfur compound using tetrafluoroisophthalonitrile as a polymer made from monomers. FIG. 5 is a continuation reaction of the present invention with metal phosphite, sulfurous acid or other suitable phosphorus or sulfur compound using bis (4-hydroxyphenyl) phenylphosphine oxide as a polymer prepared from diphenol. A suitable polymer choice as an educt for aromatic nucleophilic substitution with metal hydrogen sulfite or metal phosphite. A suitable polymer choice as an educt for aromatic nucleophilic substitution with metal hydrogen sulfite or metal phosphite. A suitable polymer choice as an educt for aromatic nucleophilic substitution with metal hydrogen sulfite or metal phosphite. A suitable polymer choice as an educt for aromatic nucleophilic substitution with metal hydrogen sulfite or metal phosphite. A suitable polymer choice as an educt for aromatic nucleophilic substitution with metal hydrogen sulfite or metal phosphite. A suitable polymer choice as an educt for aromatic nucleophilic substitution with metal hydrogen sulfite or metal phosphite. A suitable polymer choice as an educt for aromatic nucleophilic substitution with metal hydrogen sulfite or metal phosphite. Reaction of tris phosphite (trimethylsilyl) with a partially fluorinated aromatic polymer. This is a method for producing a polymer having perfluorinated aromatics as side groups with a lithiated polymer showing polyphenylsulfone as an example. Perfluorinated aromatics suitable for reaction with lithiated polymers. It is a reaction formula of reaction which converts the partially fluorinated polymer PFS001 with sodium phosphite. It is a reaction formula of reaction which converts the partially fluorinated polymer PFS001 with sodium phosphite. 2 is a ¹ H-NMR spectrum of a phosphonated reaction product XFS001D. A comparison ¹ H-NMR spectrum of the educt PFS001D polymer. It is a ¹³ C-NMR spectrum of the reaction product XFS001D. It is a ¹⁹ F-NMR spectrum of reaction product XFS001D. (A = overall view, b = detailed view) ¹⁹ is a ¹⁹ F-spectrum of reaction free product PFS001. It is IR-spectrum of free substance PFS001. It is IR-spectrum of reaction product XFS001D and hydrolyzed product (free phosphonic acid group) XFX001D-H. It is IR spectrum for the comparison of PFS001, XFS001D, and XFS001D-H. It is a ¹ H-NMR spectrum of the reaction product AK51. It is a ¹³ C-NMR spectrum of reaction product AK51. It is a ¹⁹ F-NMR spectrum of reaction product AK51. It is a ¹⁹ F-NMR spectrum of reaction product A1179. (Measured in DMSO) A @ 19 F-NMR spectrum of the reaction product A1179 in CDCl _3. It is a reaction formula in which a polymer 1179 modified with hexafluorobenzol is phosphonated with sodium triethyl phosphite to produce a reaction product A1184. It is a ¹⁹ F-NMR spectrum of reaction product A1184 in CDCl ₃ . It is a ¹⁹ F-NMR spectrum of reaction product A1184 in DMSO. It is a ¹ H-NMR spectrum of the reaction product A1184 in DMSO. ^{1 is} a ¹ H-NMR spectrum of reaction product A1184 in CDCl ₃ . It is a ¹³ C-NMR spectrum of reaction product A1184 in DMSO. It is a ³¹ P-NMR spectrum of reaction product A1184 in DMSO. It is a ³¹ P-NMR spectrum of reaction product A1184 in CDCl ₃ . It is a reaction formula of reaction which obtains reaction product A1180 by lithiated PSU and decafluorobiphenyl. ^{1 is} a ¹ H-NMR spectrum of reaction product A1180 in CDCl ₃ . It is a ¹ H-NMR spectrum of reaction product A1180 in DMSO. It is a ¹³ C-NMR spectrum of reaction product A1180 in CDCl ₃ . It is a ¹⁹ F-NMR spectrum of the reaction product A1180 in CDCl _3. It is a ¹⁹ F-NMR spectrum of reaction product A1180 in DMSO. It is the reaction formula of reaction which converts lithiated PSU into reaction product A1181 by pentafluoropyridine. 2 is a ¹ H-NMR spectrum of reaction product A1181 in CDCl ₃ . _{3 is} a ¹³ C-NMR spectrum of reaction product A1181 in CDCl ₃ . It is a ¹⁹ F-NMR spectrum of the reaction product A1181 in CDCl _3. It is a ¹⁹ F-NMR spectrum of reaction product A1181 in DMSO.

  Next, preferred embodiments of the present invention will be described with reference to the drawings.

1. Sulfonated polysulfone obtained from sulfinated polysulfone, decafluorobiphenyl and sodium sulfite is cured according to the background art and converted to a polymer of sulfinic acid by sulfur dioxide. The sulfinic acid group is in the ortho position relative to the sulfonic acid group of the polysulfone. The sulfinic acid lithium salt polymer is filtered and vacuum dried at low temperature. For the next reaction, a polysulfone having 1.5 lithium sulfinate groups per polymer repeating unit is used. 10 grams of decafluorobiphenyl is mixed with 50 grams of NMP at room temperature. Ten grams of a sulfinic acid polymer having 1.5 sulfinic acid groups per repeating unit is dissolved in 90 grams of NMP. Stir the mixture of decafluorobiphenyl and NMP well (stirring speed is 300 rev / min) and add the sulfinic acid polymer slowly (1 ml / min) via the addition funnel. The mixture is further stirred and then heated slowly to 120 ° C. (heating rate is 1 ° C./min). Maintain a temperature of 120 ° C. for 10 hours. Then cool to 10 ° C. and add 500 ml of fully cooled (at T = 10 ° C.) hydrated sodium sulfite solution to the mixture. Thereafter, it is heated to 110 ° C. under backflow and maintained at this temperature for 10 hours.
After cooling, the product is evaporated in vacuo by a rotary evaporator. The resulting product is mixed with 1 liter of water and dialyzed into a dialysis hose to make demineralized water (dialysis membrane removal size for polymer is 3000 daltons). This allows separation of small molecules from the sulfonated polymer (which yields a sulfonate salt). After evaporating the dialysis hose residue, the sulfonated polymer is obtained in the sodium salt form.

2. Michaelis-Becker reaction of partially fluorinated allyl main chain polymer and sodium phosphite (synthesis of XFS001A)

ＰＦＳ００１Ｂに基づいて２ｅｑ ＮａＰＯ（ＯＭｅ）_２

₂ eq NaPO (OMe) ₂ based on PFS001B

The reaction formula of this reaction is shown in FIG. To a solution of 0.519 g (21.63 mmol) of sodium hydride in 40 ml of anhydrous THF, 21.3807 g (21.63 mmol) of dimethyl phosphite (40 ml of anhydrous THF) under protective gas at 0 ° C. ) Drip slowly. When the generation of hydrogen is finished, the reaction solution is warmed to room temperature, and 6.8180 g (10.815 mmol) of PFS001B dissolved in 80 ml of anhydrous THF is added dropwise (about 20 minutes) (PFS001B dissolved in THF: yellowish) The reaction solution becomes pink / orange upon the dropwise addition of dimethyl sodium phosphite). The reaction mixture is stirred overnight at RT and heated to 65 ° C. for an additional 3 hours (after which the solution appears yellow and a homogeneously dispersed solid—sodium fluoride? —Appears that can be filtered. Not) The solution is then concentrated in a rotary evaporator. Attempt to absorb the residue with about 300 ml of methylene chloride (to wash away with water and remove the resulting NAF). However, a yellowish (not salty) residue remains. The precipitate is filtered off, suspended in about 200 ml of water and dialyzed (XFS001A, CH ₂ Cl ₂ insoluble fraction XFS001A-UF).
The CH ₂ Cl ₂ filtrate is freshly concentrated and the residue is similarly resuspended in 200 ml of water and dialyzed (XFS001A, CH ₂ Cl ₂ insoluble fraction = XFS001A-LF).

Characteristic analysis:
A. Elemental analysis (XFS001A-UF):
Experimental formula: C ₃₁ H ₂₀ O ₈ F ₁₂ P ₂ (2 phosphonic acid group, M = 810.14 gmol ⁻¹ )
Experimental formula: C ₂₉ H ₁₄ O ₅ F ₁₃ P (1 phosphonic acid group, M = 720.37 gmol ⁻¹ )

B. Elemental analysis (XFS001A-LF):
Experimental formula: C ₃₁ H ₂₀ O ₈ F12P ₂ (2 phosphonic acid group)
Experimental formula: C ₂₉ H 14 O ₅ F ₁₃ P (1 phosphonic acid group, M = 689.40 gmol ⁻¹ )

3. Michaelis-Becker reaction of partially fluorinated allyl main chain polymer and sodium phosphite (synthesis of XFS001D)

括弧内の記述：理論値；その上の記述：実験値

註：使用したＴＨＦ(フィッシャー)は、計測したＮａＨにさらにＴＨＦを加えると多かれ少なかれはっきりと水素合成が起こったことから、高いＨ_２Ｏ濃度を有すると考えられる。このため、ポリマーＰＦＳ００１Ｄの量を実際に計測した量とは見込まない（実際に４倍の過剰量の原因がＮａＰＯ（ＯＥｔ）_２であることを確実にするため）。

ＰＦＳ００１Ｄに基づいて４ｅｑ ＮａＰＯ（ＯＭｔ）_２

Description in parentheses: theoretical value; description above: experimental value

Note: The THF (Fisher) used is considered to have a high H ₂ O concentration because hydrogen synthesis occurred more or less clearly when additional THF was added to the measured NaH. For this reason, the amount of polymer PFS001D is not expected to be the amount actually measured (to ensure that the cause of the 4-fold excess is actually NaPO (OEt) ₂ ).

4 eq NaPO (OMt) ₂ based on PFS001D

The reaction formula of this reaction is shown in FIG. Dissolve 1.155 g (48.15 mmol) of sodium hydride in 80 ml of anhydrous THF and slowly add 6.689 g (48.15 mmol) of dimethyl phosphite (in 80 ml of anhydrous THF) under protective gas at 0 ° C. And dripping. When the generation of hydrogen is completed, the reaction solution is warmed to room temperature and 6.8180 g (10.815 mmol) of PFS001D dissolved in 80 ml of anhydrous THF is added dropwise (about 20 minutes) (PFS001D dissolved in THF: yellowish) The reaction solution becomes pink / orange when dimethyl sodium phosphite is added dropwise). The reaction mixture is stirred for 72 hours by RT and heated to 65 ° C. for a further 6 hours. The solution is then concentrated on a rotary evaporator. The residue is absorbed with about 300 ml of water and dialyzed. After evaporating the solvent, the polymer is dried in an oven at 60 ° C. (overnight).
Characteristic analysis (XFS001D):
A. Elemental analysis empirical formula: C ₃₁ H ₁₈ O ₅ F ₁₃ P ( ₂ groups of 1PO (OEt) per RU, M = 748.42 gmol ⁻¹ )
Empirical formula: C ₃₅ H ₂₈ O ₈ F ₁₂ P ₂ (2PO (OEt) ₂ groups per RU, M = 866.52 gmol ⁻¹ )
Experimental formula: C ₃₉ H ₃₈ O ₁₁ F ₁₁ P ₃ (3PO (OEt) ₂ groups per RU, M = 984.62 gmol ⁻¹ )
Experimental formula: C ₄₃ H ₄₈ O ₁₄ F ₁₀ P ₄ ( ₂ groups of 4PO (OEt) per RU, M = 1102.71 gmol ⁻¹ )

溶媒： ＣＤＣｌ_３
基準： ＴＭＳ
δ[ｐｐｍ]（２００．１３ＭＨｚ）： ７．０６(ｄ，Ｊ＝８．５１Ｈｚ，^１Ｈ，^３Ｈ，
^６Ｈ^８Ｈ，４Ｈ)
７．４２(ｄ，Ｊ＝８．７２Ｈｚ，^２Ｈ，^４Ｈ，
^５Ｈ^７Ｈ，４Ｈ)

Ｃ．^１３Ｃ−ＮＭＲ 図３３参照。

Ｄ．^１９Ｆ−ＮＭＲ 図３４参照。

^１９Ｆ−ＮＭＲ比較スペクトルＰＦＳ００１Ｄ 図３５参照。 B. ¹ H-NMR
Reference spectrum PFS001D see FIG. 31 See FIG.

Solvent: CDCl ₃
Standard: TMS
δ [ppm] (200.13 MHz): 7.06 (d, J = 8.51 Hz, ¹ H, ³ H,
⁶ H ⁸ H, 4H)
7.42 (d, J = 8.72 Hz, ² H, ⁴ H,
⁵ H ⁷ H, 4H)

C. ¹³ C-NMR See FIG.

D. ¹⁹ F-NMR See FIG.

¹⁹ F-NMR comparative spectrum PFS001D See FIG.

F. IR-spectrum The FTIR-spectrum of the free product PFS001 is shown in FIG.
FIG. 37 shows IR spectra of the reaction product XFS001D and the hydrolyzed product (free phosphonic acid group) XFX01D-H.
FIG. 38 shows IR spectra of PFS001, XFS001D and XFS001D-H (free phosphonic acid groups) for comparison.
The band of 2983-2912 cm ⁻¹ (red curve is XFS001D-H) has the possibility of OH stretching vibration of phosphonic acid group. Similarly, a newly generated peak at 1394 cm ⁻¹ cannot be reliably classified. According to the literature (Hesse, Meier, Zeeh), the P = O-stretching vibration of phosphonic acid is located at 1240-1180 cm- ¹ . Such oscillations should also be seen in the ester form (green curve) (probably a little off due to different substitution patterns, but the peak should be relatively large).

Hydrolysis of XFS001D (XFS001D-H):
3. Suspend 50 g of XFS001D in 80 ml of 48% hydrobromic acid and heat to 100 ° C. for 16 hours. The reaction solution is diluted with about 800 ml of water and the precipitate is filtered. The precipitate resuspended in water is dialyzed for 5 days. The polymer is then dried in a circulating air dryer at 80 ° C. (drying temperature <110 ° C. to avoid phosphonic acid concentration).
Yield (after dialysis):
2.507g

Characterization of XFS001D-H:

A. Elemental analysis <br/> Empirical _{formula: C 27 H 10 O 5 F} 13 P (RU per 1PO _{(OH) 2} group, M = 692.32gmol ^-1)
Experimental formula: C ₂₇ H ₁₂ O ₈ F ₁₂ P ₂ (2PO (OH) ₂ groups per RU, M = 754.31 gmol ⁻¹ )

Ｂ．ＩＥＣ値の計測

B. Measurement of IEC value

［１］ポリマーは計測の際、上方で浮遊した（置換は完了？）

[1] The polymer floated above during measurement (replacement complete?)

4. Reaction of octafluorotoluene with lithiated PSU (AK-51) Materials:
22.1 g PSU Udel P 1800 (0.05 mol) dried 800 ml anhydrous THF
10 ml n-BuLi 10N (0.1 mol)
28.4 ml = 47.2 g octafluorotoluene (0.2 mol, MW = 236 g / mol)

Run:
Fill the reaction vessel with THF under protective gas. Then, the dried polymer is placed in the reaction vessel while stirring and intensive washing with argon. Once the polymer is dissolved, cool to -50 ° C (as much as possible) under strong argon. The polymer solution is then carefully titrated with 2.5N n-BuLi until the reaction mixture exhibits a light yellow / orange color indicating that it is no longer anhydrous. Add 10N n-BuLi within 10 minutes. Stir for a minimum of 2 hours. Wait for the color of the reaction mixture to change. If the color does not change, warm to -30 ° C overnight. Stir at −30 ° C. overnight at most until the reaction mixture is colorless.

  If the solution does not become colorless, raise the temperature the next morning up to -10 ° C (the solution remains highly viscous). 20 ml of methanol are added until the reaction mixture is colourless. Then warm to room temperature.

The polymer is poured into 2 l of methanol, filtered and washed with methanol.
The charged polymer is freshly filtered, dried and stirred in 800 ml MeOH. Then, it is filtered again, suspended again in 400 ml of MeOH, stirred and filtered, and vacuum dried at 50 ° C. Attempt to dissolve the dried polymer in NMP (if dissolved, the film-forming properties can be determined). The substitution temperature of the modified PSU is determined by ¹ H / ¹³ C-NMR and elemental analysis (C, H, S).

Yield: 35.4 g (81% of the theoretical yield 43.73 g ~)

Elemental analysis

Calculated as two units

C ₄₁ H ₂₀ F ₁₄ O ₄ S
874.64
874.085876
C 56.30% H 2.30% F 30.41% O 7.32% S 3.67%

Regarding fluorine content, 1.25 units / F. E. Joined!

See FIG. 39 for the 1H-NMR spectrum of reaction product AK51. The ¹³ C-NMR spectrum of the reaction product AK51 is shown in FIG. A ^19F- NMR spectrum of the reaction product AK51 is shown in FIG.

5. Reaction of hexafluorobenzole with lithiated PSU A1179 Materials:
11.05 g PSU Udel P 1800 (0.025 mol) dried 800 ml anhydrous THF
5 ml n-BuLi 10N (0.05 mol)
11.54 mol = 18.6 g hexafluorobenzole (0.1 mol, MW = 186.056 g / mol)

Run:
Fill the reaction vessel with THF under protective gas. Then, the dried polymer is placed in the reaction vessel while stirring and intensive washing with argon. Once the polymer is dissolved, cool to -50 ° C (as much as possible) under strong argon. The polymer solution is then carefully titrated with 2.5Nn-BuLi until a light yellow / orange stain appears, indicating that the reaction mixture is no longer anhydrous. Add 10N n-BuLi within 10 minutes. Stir for a minimum of 2 hours. Thereafter, hexafluorobenzole is added. Wait for the color of the reaction mixture to change. If the color does not change, warm to −30 ° C. overnight ( ¹⁹ F-NMR A 1179a acceptance: insoluble in CHCl ₃ and slightly soluble in DMSO). Stir at −30 ° C. overnight at most until the reaction mixture is colorless.

If the solution does not become colorless, the temperature is raised to -10 ° C up to the next morning ( ¹⁹ F-NMR A 1179b acceptance: insoluble in CHCl ₃ and moderately soluble in DMSO). 20 ml of methanol are added until the reaction mixture is colorless. Then warm to room temperature.

  The polymer is poured into 2 l of methanol, filtered, extracted with 0.5 liters of MeOH, filtered and post-washed with methanol on a frit.

The charged polymer is vacuum-dried at 50 ° C. Attempt to dissolve from dried polymer in NMP. The substitution temperature of the modified PSU is determined by ¹ H / ¹³ C / ¹⁹ F-NMR and elemental analysis (C, H, S, F).
The polymer is difficult to dissolve in NMP and takes 12 hours to completely dissolve! ! !

Yield: 16.8 g (theoretical yield 19.67% of 19.37 g)

Elemental analysis 1179a (-30 ° C)

Calculate as 2 units

C ₃₉ H ₂₀ F ₁₀ O ₄ S
774.62
774.009263
C 60.47% H2.60% F24.53% O8.26% S4.14%

Elemental analysis 1179b (-10 ° C)

Calculate as 2 units

C ₃₉ H ₂₀ F ₁₀ O ₄ S
774.62
774.009263
C 60.47% H2.60% F24.53% O8.26% S4.14%

Regarding the fluorine content, 1.59 groups / F. E. Joined!

  FIG. 42 shows a 19F-NMR spectrum of the reaction product A1179 in the solvent DMSO. It can be clearly seen that the reaction between hexafluorobenzole and lithiated PSU has weakened. Three peaks are seen with an approximate integration ratio of 2: 2: 1 (2 ortho-F: 2 meta-F: 1 para-F). FIG. 43 shows the 19F-NMR spectrum of the reaction product A1179 in the solvent CDCl3. It can be seen that the reaction product is very insoluble in CDCl3.

6. Reaction material of A1179 (PSU / hexafluorobenzole / n-BuLi) with sodium diethylphosphite (A1184):
A1179 having 5 g 1.59 groups (M = 774.62 g / mol, 6.45 mmol), 1.78 g diethylphosphorous acid (M = 138.10 g / mol, 12.9 mmol) dissolved / suspended in 100 ml THF ), Dissolved in 20 ml of THF.
Sdp = 2 mmHg, 50-51 ° C., density: 1.072 g / cm 3, refractive index: 1.407
0.31 g Sodium hydride (M = 24.0 g / mol, 12.9 mmol), dissolved in 20 ml THF.
Reaction formula: See FIG.

Run:
At 0 ° C. under protective gas, 1.78 g (12.9 mmol) of diethyl phosphorous acid dissolved in 20 ml of anhydrous THF is placed in a 250 ml three-necked flask. This three-necked flask contains 0.31 g (12.9 mmol) of NaH dissolved in 20 ml of THF. When no more hydrogen is generated (about 30 minutes), the solution is warmed at RT and compound 1 dissolved in 100 ml of THL is titrated with a dropping funnel for 20 minutes. The mixture is stirred for 6 hours at 65 ° C., then the reaction solution is hydrolyzed with 20 ml MeOh to remove THF in a rotary evaporator and taken up by dest. Add water (suspension) and dialyze for 48 hours (3 changes of water).
The water is evaporated in an oven at 80 ° C. in a large porcelain container and then further post-dried in a vacuum oven at 80 ° C.
The following analyzes are obtained from the product: ¹ H-, ¹⁹ F-, ¹³ C-NMR, elemental analysis (C, H, F, P).

Yield: 4.5 g to 6.52 g (69.1% of theoretical yield)

¹ H, ¹³ C, ¹⁹ F, ³¹ P-NMR: A1184C is difficult to dissolve in CDCl 3 where A1184D is moderately soluble in DMSO

FIG. 45 shows a 19F-NMR spectrum of reaction product A1184 in CDCl ₃ . The signal is very weak because the reaction product is difficult to dissolve in CDCl ₃ . FIG. 46 shows a 19F-NMR spectrum of reaction product A1184 in DMSO. Compared with the 19F-NMR spectrum of reaction product A1179 in DMSO (FIG. 43), one signal was found to disappear, indicating that the reaction of para-F with sodium diethylphosphite was weakened ( This indicates that a substitution reaction has occurred, and that the necessary substitution reaction has occurred. The Figure 47 shows the ¹ H-NMR spectrum of the reaction product A1184 in DMSO, in FIG. 48 shows the ¹ H-NMR spectrum of the reaction product A1184 in CDCl _3. FIG. 49 shows a ¹³ C-NMR spectrum of the reaction product A1184 in DMSO, and FIG. 50 shows a 13C-NMR spectrum of the reaction product A1184 in DMSO. In FIG. 51, the bond between phosphonate P and adjacent F is clearly seen.

Elemental analysis:
C ₃₇ H ₃₁ F ₄ O ₇ PS calculated as one unit
726.67
726.146426
C 61.16% H 4.30% F 10.46% O 15.41% P 4.26% S 4.41%

リンによれば、０．９３基／ＦＥ

According to phosphorus, 0.93 units / FE

C ₄₇ H ₄₀ F ₈ O ₁₀ P2S calculated as two units
1010.82
1010.168972
C 55.85% H 3.99% F 15.04% O 15.83% P 6.13% S 3.17%

リンによれば、１．２８基／ＦＥ

According to phosphorus, 1.28 units / FE

7. Reaction material of decafluorobiphenyl and lithiated PSU A1180:
5.53 g PSU UdelP1800 (0.0125 mol) dried 800 ml anhydrous THF
2.5 ml n-BuLi10N (0.025 mol)
16.7 g Decafluorobiphenyl (0.1 mol, MW = 334.11 g / mol)
Reaction formula: see FIG. 52
Fill the reaction vessel with THF under protective gas. Thereafter, the dried polymer is placed in the reaction vessel with stirring and vigorous washing with argon. When the polymer is dissolved, it is cooled to −60 ° C. under strong argon air. The polymer solution is then carefully titrated with 2.5N n-BuLi until a light yellow / orange stain appears, indicating that the reaction mixture is no longer anhydrous. Add 10N n-BuLi within 10 minutes. Stir for a minimum of 2 hours. Then, when decafluorobiphenyl is added (dissolved in 100 ml of THF, added by a dropping funnel), the color immediately changes to black. After reacting at -55 ° C for 15 hours, the color changes to light gray / light color, the reaction is interrupted and hydrolysis occurs. Now add 20 ml MeOH until the reaction mixture is colorless. Then warm to room temperature.

After adding the polymer to 2 l of MeOH, the methanol is removed by rotation, and the mixture is dialyzed by absorption in water. The water is then evaporated at 50 ° C. and the polymer is vacuum dried at 50 ° C. Attempt to dissolve the dried polymer in NMP. The substitution temperature of the modified PSU is determined by 1H / ¹³ C / ¹⁹ F-NMR and elemental analysis (C, H, S, F).

Yield: 8.8 g (corresponding to 63.5% of the theoretical yield of 13.86 g)
Solubility: Insoluble in acetonitrile
Slightly soluble in CHCl ₃ A1180 (NMR)
Gelation in CH ₂ Cl ₂
Insoluble in D ₂ O
Insoluble in acetone
Moderately soluble in DMSO A1180D (NMR)

Elemental analysis
C ₅₁ H20F ₂₀ O ₄ S calculated as two units
110.74
1108.076296
C 55.25% H1.82% F34.27% O 5.77% S2.89%

Regarding fluorine content, 1.24 groups / F. E. Joined!

The Figure 53 shows the ¹ H-NMR spectrum of the reaction product A1180 in CDCl _3, in FIG. 54 shows the ¹ H-NMR spectrum of the reaction product A1180 in DMSO. The Figure 55 shows a ¹³ C-NMR spectrum of the reaction product A1180 in CDCl _3, in FIG. 56 shows a ¹⁹ F-NMR spectrum of the reaction product A1180 in CDCl _3, in Figure 57 the reaction in DMSO ¹⁹ shows the ¹⁹ F-NMR spectrum of product A1180.

8. Reaction material of pentafluoropyridine and lithiated PSU A1181:
5.53 g dried PSU Udel P1800 (0.0125 mol) 800 ml anhydrous THF
2.5 ml n-BuLi 10N (0.025 mol)
8.45 g = 5.3 ml pentafluoropyridine (0.05 mol, MW = 169.05 g / mol)
Reaction formula: see FIG. 58 Execution:
Fill the reaction vessel with THF under protective gas. The dried polymer is then charged to the reaction vessel with stirring and vigorous washing with argon. Once the polymer is dissolved, cool to −60 ° C. under strong argon. The polymer solution is then carefully titrated with 2.5N n-BuLi until a light yellow / orange color appears, indicating that the reaction mixture is no longer anhydrous. Add 10N n-BuLi within 10 minutes. Stir for 2 hours. Thereafter, pentafluoropyridine is dropped by a dropping funnel (dissolved in 100 ml of THF). Observe how the color of the reaction mixture changes (reaction time: 4 hours, temperature: −60 ° C.). When the color does not change, the reaction is performed at -55 ° C for 96 hours or more. The color changes from dark red / dark orange to bright orange.

2 l of MeOH is added until the reaction mixture is colorless. Then warm to room temperature.
The polymer is poured into 2 l MeOH, filtered, extracted with 0.5 l MeOH, filtered on a frit with methanol and post-washed.
The charged polymer is vacuum-dried at 60 ° C. Attempt to dissolve the dried polymer in NMP. The substitution temperature of the modified PSU is determined by 1H / ¹³ C / ¹⁹ F-NMR and elemental analysis (C, H, S, F).

Yield: 9.1 g (corresponding to a theoretical yield of 13.86 g)
Solubility: Insoluble in acetonitrile
Insoluble in CHCl ₃
Gelation in CH ₂ Cl ₂
Insoluble in D ₂ O
Insoluble in acetone
1H, 13C-NMR moderately soluble in DMSO: A1181D in DMSO
A1181C in CDCl ₃

The Figure 59 shows the ¹ H-NMR spectrum of the reaction product A1181 in CDCl _3, in FIG. 60 shows a ¹³ C-NMR spectrum of the reaction product A1181 in CDCl _3. The Figure 61 shows the ¹⁹ F-NMR spectrum of the reaction product A1181 in CDCl3, in FIG. 62 shows a ¹⁹ F-NMR spectrum of the reaction product A1181 in DMSO.

Elemental analysis
_{C 37 H 20 F 10 N 2} O 4 S to calculate the 2 groups
778.62
778.009411
C 57.08% H2.59% F24.40% N3.60% O8.22% S4.12%

According to the fluorine content, 1.59 groups / F. E. Joined

Claims (9)

  Non-fluorinated, partially fluorinated or perfluorinated (especially non-, partially or perfluorinated), aromatic sulfonic acid or phosphonic acid (or derivatives thereof) monomers, oligomers and polymers, polymers Obtained by aromatic nucleophilic substitution with sulfur or phosphorus nucleophiles in the monomers, oligomers and polymers which can be provided with side chains or perfluorinated groups in the main chain as well as in the polymer. Monomers, oligomers, and polymers characterized by   The monomers, oligomers and polymers according to claim 1 have a broad substitution pattern in highly reactive halogen aromatics (especially fluoroaromatics), so that proton-conducting groups can be retained immediately (FIG. 1). And the halogenated monomer that can be input include bis (pentafluorophenyl) sulfone, bis (pentafluorophenyl) sulfide, decafluorobiphenyl, 4,4′-difluorobiphenyl, decafluorobenzophenone, 4,4 '-Difluorobenzophenone, bis (4-fluorophenyl) phenylphosphine oxide, decafluorodiphenyl sulfide, hexafluorobenzole, pentafluorobenzole, variously substituted di, tri and tetrafluorobenzoles, octafluoro Ruene, 2,2 ′, 3,3 ′, 5,5 ′, 6,6′-octafluorobiphenyl, pentafluoropyridine, variously substituted di-, tri- and tetrafluoropyridines (for example 2,3,5 , 6-tetrafluoropyridine, 2,6-difluoropyridine, 3,5-difluoropyridine, 2,5-difluoropyridine, 2,4-difluoropyridine, 2,4,6-trifluoropyridine), various triazines ( For example, 2,4,6-trifluoro-1,3,5-triazine, 3,5,6-trifluoro-1,2,4-triazine, 3,6-difluoro-1,2,4-triazine), pyrimidine (Eg, 2,4,6-trifluoropyrimidine), pyridazine (eg, 3,6-difluoropyridazine, 3,4,5,6-tetrafluoropyridazine), Pyrazine (eg 2,6-difluoropyrazine, 2,3,5,6-tetrafluoropyrazine), quinoline (eg heptafluoroquinoline), isoquinoline (eg heptafluoroisoquinoline), quinoxaline (eg hexafluoroquinoxaline), quinazoline (eg Hexafluoroquinazoline) and dihalogenated heteroallyl compounds such as non-, partially or perfluorinated imidazoles and benzimidazoles, pentafluorobenzoylsulfonic acid or salts thereof, pentafluorobenzoylphosphonic acid or salts thereof are suitable, Any possible diphenol can be used as the phenol, and in particular, the following diphenols: bisphenol A (4,4 ′-(isopropylidene) -diphenol), bisphenol S (biphenol). (4-hydroxyphenyl) sulfone), bis (4-hydroxyphenyl) thioether, bis (4-hydroxyphenyl) ether, 4,4 ′-(hexafluoroisopropylidene) -diphenol, bis (4-hydroxyphenyl) phenyl Monomers, oligomers and polymers where phosphine oxide and phenolphthalein are suitable and the monomers can optionally be combined with polymers such as homopolymers, statistical copolymers or block copolymers. 2. The oligomer and polymer according to claim 1, wherein a highly reactive halogen aromatic (especially fluoroaromatic) has a wide substitution pattern and can retain a proton conductive group (see FIGS. 2 and 4), and CSP. All polymers having _two bonded halogens (especially fluorine) are suitable, and suitable polymer options for this are shown in FIGS. 6, 7, 8, 9, 10, 11, 12, 13 for example. , 14, 15, 16, 17, 18, 19, 20, 21, 21, 22, 23, 24, and 25. The method for producing monomers, oligomers and polymers according to claims 1 to 3, wherein the solvent is a protic or polar aprotic solvent and water (only for sulfones), THF, according to the substitution pattern of the educt, respectively. , Aprotic solvents such as diethyl ether, dioxane, glyme, diglyme, triglyme, DMAc, DMF, NMP, sulfolane, propylene carbonate, dimethyl sulfoxide, acetonitrile, benzol, toluene, xylol and any mixtures thereof can be used together And the method.   The method for producing monomers, oligomers and polymers according to claims 1 to 4, wherein the reaction temperature is -93 ° C to + 200 ° C depending on the reactivity of the solvent and the free substance, and the reaction is carried out under a protective gas (argon, nitrogen) or protection. A method that can be performed in an environment without gas.   6. The method for producing monomers, oligomers and polymers according to claims 1-5, wherein the reactive nucleophile is a metal sulfite or metal bisulfite (e.g. sodium sulfite, sodium hydrogen sulfite, potassium sulfite, potassium hydrogen sulfite) or Metal phosphates (eg, dimethyl sodium phosphite, diethyl sodium phosphite, diphenyl sodium phosphite) or other phosphite compounds such as tris phosphite (trimethylsilyl) are used, which in the SNAr reaction One or more halide ions (especially fluoride ions) are liberated from a compatible, partially or perhalogenated (especially partially or perfluorinated) starting compound and the metal phosphite in situ, THF or Metal hydrides in other anhydrous solvents, Method can be produced by the following reaction with dialkyl or phosphorous acid diallyl.   In the method for producing monomers, oligomers and polymers according to claims 1-6, in the case of monomeric compounds, it is required by standard means (for example described in Yakobson et al. (Non-patent Document 12)) or similar treatments. In the case of liquid compounds, washing is performed by distillation; in the case of solid compounds, recrystallization is performed, and a non-partially or perhalogenated (especially non-partially or perfluorinated) aroma is obtained. In the case of polymers (oligomers) of aliphatic sulfonic acids or phosphonic acids (or their derivatives), the treatment and washing are carried out by repeated precipitation and redissolution, and in the case of water-soluble sulfonic and phosphonic acid polymers by dialysis.   Compounds, especially polymers and oligomers, produced by one or more methods according to claims 1-7.   Use of a compound produced by one or more methods according to claims 1-7, comprising membrane treatment (especially fuel cells, membrane electrolysis and electrodialysis treatment), coating (eg textile fibers), nano Usage in particles, paints, adhesives, packings, sensors, dyes, herbicides and pesticides.

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