JPS6375031A - Production of sulfonated poly(arylether) resin - Google Patents

Abstract

(57) [Abstract] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION; Technical Field of the Invention The present invention relates to a novel method for sulfonating poly(arylether) resins, particularly the combination of silyl halosulfonates or halosulfonic acids with silyl halides as sulfonating agents. Concerning the use of things. In general, the present invention relates to sulfonated poly(arylether) resins and membranes processed therefrom.

PRIOR ART Poly(arylether) resins are a class of resins that have a variety of uses in forming wire coatings, wire insulation, and electrical connectors. Once sulfonated, these resins can be used to form osmosis and reverse osmosis membranes useful in a wide variety of liquid purification methods, such as desalination methods for purifying salt aqueous solutions such as seawater. . A typical poly(arylether) resin is a polysulfone having a repeating unit structure of the formula: The polysulfones mentioned above are often referred to herein as PSEs.

PSF has been sulfonated by various methods.

For example, U.S. Patent No. 3.709.84 to Quentin.
An earlier method disclosed in publication no. [Johnson et al., Journal Polymer Science, Polymer Chemistry Edition, Vol. 22, p. 721 (1984)]. In general, this reaction is heterogeneous, which can affect the reproducibility and degree of sulfonation.

Nociei and Robson [Journal Applied Polymer Science, Vol. 20, p. 1885 <1976
) J is a complex of SO3 and triethyl phosphate, S
have reported a mild sulfonation method using O3.PO(OCI-120H3)3, which can minimize side reactions. However, this method
is troublesome due to the reactivity and toxicity of SO3 and the exothermic reaction of SO3 with triethyl phosphate.

Sulfonated polysulfones are often converted into the salt form for use in membranes by reaction with a base such as sodium hydroxide: No. 3,875,096 to Grayhue et al. and Johnson et al. and Noshiei et al. (supra).

Several papers have appeared reporting on the sulfonation of various organic compounds using trimethylsilylchlorosulfonate as the sulfonating agent. For example, Hoffman et al., Synthesis, September 1979, pp. 699-700;
), pp. 282-297: Grignon-Dubois et al., Journal Organometallic Chemistry, No. 12
Volume 4 (1977), pp. 135-142: Duhou et al., Brechin Nchete Himica Français (1963)
, pp. 512-517: Felix et al., Angewante Chemie International Edition, Vol. 18 (1979), pp. 402-403;
and Fuerix et al., Angewante Chemie International Edition, Vol. 16 (1).
977), pp. 488-489. However, none of these papers discloses the sulfonation of the conjugate. In general, none of these articles discloses the use of a combination of silyl halide and halosulfonic acid in the sulfonation process.

[Summary of the Invention] In one aspect, the present invention provides a novel method for sulfonating poly(arylether) resins, which method comprises: (i) in a first step, poly(arylether) resins are silylated; intermediate by reacting with a halosulfonate or a combination of a silyl halide and a halosulfonic acid to form a poly(arylether) resin in which a portion of the repeating units in the resin backbone are derivatized with decorated silyl sulfonate groups. sulfonate salts of poly(arylether) resins by making an intermediate resin product and then (ii) reacting the intermediate resin product so produced with a base to cleave the silyl moieties from the silyl sulfonate groups. It is characterized by generating.

In another aspect, the present invention provides novel intermediate resins, i.e., poly(arylether)'s derivatized with modified silyl sulfonate groups or some of the repeating units in the resin backbone.
The P4 fat extends from the aromatic ring portion of the raised ring R0 R-3i-0-8- RO where R has the following meaning.

These intermediate resins are poly(arylether) resins having the formula: % where X is 0.3r or I, preferably
and the R groups may be the same or different and are inert organic groups.

Furthermore, these intermediate resins are a crude combination of a halosulfonic acid: 0-3-X and a silyl halide having the structure: R-3r -x [wherein X and R have the above meanings]. It can also be produced by reacting with The use of this combination to make intermediate resins is often described herein as "in situ" sulfonation, which is different from sulfonation using preformed silylhalosulfonates.

The terms "combination" and/or "halogenated silyl halide/halosulfonic acid combination" refer to the halogenated silyl halide and halosulfonic acid combination used together or supplied as a mixture or as separate components to a solution of poly(arylether) resin. intend to.

The products obtained from the reaction of poly(arylether) resins with silyl halosulfonates or halogenated silyl/halosulfonic acid combinations, described herein as intermediates or derivatives, contain modified silyl sulfonate groups along the resin backbone. , R3-8i 0-302-. The poly(arylether) resin is then prepared in the (sulfonate) salt form, i.e., the -S○3M+ group (this L ~1 is a cation derived from the base, which will be explained further below)
It is possible to obtain a resin having the following properties.

As a specific example, equations A and B below illustrate the sulfonation process according to the invention as a flow diagram for a single repeating unit of PSF, using trimethylsilylchlorosulfonate as the sulfonating agent, where Me represents a methyl group. ): + 80-80-5i Same as above if instead of using trimethylsilylchlorosulfonate (i.e. silylsulfonate) trimethylsilyl chloride is used in combination with chlorosulfonic acid (V silyl halide/halosulfonic acid combination) able to achieve results.

That is, the sulfonated poly(arylether) resins and intermediate resins provided by the present invention can be prepared in situ by using a halogenated silyl/halosulfonic acid combination as the sulfonating agent. Additionally, these resins can be made using a silyl halosulfonate as the sulfonating agent, which can then be preformed as a reaction product of a halogenated silyl/halosulfonic acid combination. The sulfonating agents useful in this invention thus form a functionally equivalent reactant.

The present invention avoids many of the problems associated with previously known sulfonation methods. For example, the sulfonating agents of the present invention generally result in homogeneous reaction systems, unlike the heterogeneous systems obtained with halosulfonic acids. When a halosulfone solution, such as chlorosulfonic acid, is dissolved in a solution of a poly(arylether) resin, such as PSF, a single-phase reaction solution is initially obtained. However, as the reaction proceeds, two phases develop, one of which is a thick and relatively viscous phase rich in sulfonated polymer. This thick phase is difficult to stir effectively and presents other processing problems, such as difficulty in filtration. On the other hand,
When the silyl halosulfonate or the halogenated silyl/halosulfonic acid combination is dissolved in a solution of the polymer, the initially obtained homogeneous solution is maintained as a homogeneous single phase throughout the course of the reaction, and the silyl sulfonate polymer is yields an intermediate. Addition of base to cleave the silyl moieties does not destroy this single phase (ie homogeneity of the reaction medium), but turbidity may be observed. Stirring and filtration are relatively easy. In general, the better mixing that can be achieved in homogeneous reaction systems allows for a more uniform distribution of sulfonation along the backbone of the polymer, as well as the less uniform distribution that occurs due to difficult mixing in heterogeneous systems. Unlike sulfonation, it appears to result in a more uniform sulfonated polymer product. This homogeneity is believed to be due to the silyl moiety acting as a solubilizing group, allowing the silylhalosulfonate polymer derivative to dissolve in the solvent used to dissolve the non-sulfonated polymer.

Importantly, the sulfonating agents of the present invention generally provide less chain scission than occurs when using halosulfonic acids alone. Thus, the present invention is advantageous in other aspects in providing higher molecular weight sulfonated polymers than would be obtained using chlorosulfonic acid under the same reaction conditions. High molecular weight is an important characteristic needed to create membranes with good mechanical strength for tear and burst resistance.

sulfonated poly(aryl ether) with a higher molecular weight than that obtained using chlorosulfonic acid alone,
The ability of halogenated silyl/'halosulfone combinations to form resins is particularly surprising. The reaction of poly(aryl needle) resin with halosulfonic acid alone produces one equivalent of hydrogen halide, which is exemplified by reaction (T) above. The reaction of the poly(aryl ether) resin with the halogenated silyl/halosulfonic acid combination produces the dihydrogen halide as follows: HO-3○2-X+R3-3i -X→ PSF
+2HX SO2-0-3i -R3 However, higher polymer molecular weights are obtained than those obtained with halosulfonic acids. Sulfonation, @ in the reaction medium where twice the amount of hydrogen halide is expected to be produced and therefore greater acid decomposition of the resin occurs.
It was unexpected that a high molecular weight could be obtained for the fat.

Furthermore, the toxicity and pyrogenicity problems that arise using the SO3 phosphate method described above can be avoided using the method of the present invention.

Hereinafter, the present invention will be explained in more detail with reference to specific examples.

A. Polyarylether Resins Poly(arylether) suitable for use in the present invention
The resin has the following formula: % formula % [where E is a residue of a dihydric phenol and E' is a benzenoid compound having an inert electron-withdrawing group in at least one of the ortho and para positions with respect to the valence bond. A linear thermoplastic poly(arylene polyether) having a repeating unit of 100%, both of which are bonded to the ether oxygen via an aromatic carbon atom.This type of aromatic polyether The ethers are
For example, U.S. Pat. Nos. 3.264.536 and 11.
It is included in the polyarylene polyether resins of the type described in Publication No. 175.175. Bi-6-phenols are trinuclear phenols, such as dihydroxydiphenylalkanes or their nuclear halogenated derivatives, such as 2,2-
Preference is given to bis(4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)2-phenylethane or bis(4-hydroxyphenyl)methane. Because the sulfonation reaction is electrophilic, at least one of the rings in the divalent trinuclear phenol is preferably "undeactivated", meaning that it is not replaced by a deactivated electron-withdrawing group. means. The other ring can have a deactivating group. Additionally, other materials commonly referred to as bisphenols are also highly useful and suitable. These substances are, for example, ether oxygen (-0
-) or bisphenols having a hydrocarbon residue in which two phenolic nuclei are bonded to the same or different carbon atoms of the residue.

This trinuclear phenol has the formula: %formula%) [wherein Ar is an aromatic group, preferably a phenylene group, and R1 and R'1 are the same or different inert substituents, such as 1 to 4 carbon atoms. an alkyl group having an atom, an aryl, a halogen atom, i.e. fluorine, chlorine, bromine or iodine, or an alkoxy group having from 1 to 4 carbon atoms, C independently being an integer having a numerical value from O to 4; , R2 represents a bond between aromatic carbon atoms, such as in dihydroxy-diphenyl, or divalent radicals, including groups such as -0-1-S-1-S-S-, and e.g. alkylene, Indicates a divalent hydrogen oxide group such as alkylidene, cycloalkylene, cycloalkylidene or alkylene substituted with halogen, alkyl, aryl, etc., alkylidene and cycloaliphatic group, and a ring fused to an aromatic group and both Ar groups. ] It can be characterized as having the @ structure.

Examples of specific divalent polynuclear phenols include: bis-(hydroxyphenyl) alkanes, such as 2,2-bis(4-hydroxyphenyl>propane, 2,2-bis(4-hydroxyphenyl) 3,5-dimethylphenyl)propane, 2,4'-dihydroxydiphenylmethane, bis-(2
-hydroxyphenyl)methane, bis-(4-Ilnitroxyphenyl)methane, his-(4-hydroxy-2
,6-dimethyl-3-methoxyphenyl)methane, 1.1-bis-(4-hydroxy-phenyl>ethane, 1.2-bis-(4-hydroxyphenyl)ethane, 1.1-bis-(4-hydroxy) -2-chlorophenyl)ethane, 1.1-bis-(3-methyl-4-hydroxyphenyl)propane, 1.3-bis-(3-methyl-41-hydroxyphenyl)propane, 2.2-bis- (3-phenyl-4-hydroxyphenyl)propane, 2.2-bis-(3-isopropyl-4-hydroxyphenyl)propane, 2.2-bis-(2-isopropyl-4-hydroxyphenyl)propane, 2. 2-bis-(4-hydroxy-naphthyl)propane, 2.2-bis-(4-hydroxyphenyl)pentane, 3.3-bis-(4-hydroxyphenyl)pentane, 2.2-bis-(4- hydroxyphenyl)hebutane, bis=(4-hydroxyphenyl)phenylmethane, 2.2-his-(4-hydroxyphenyl)-1-phenyl-propane, 2.2-bis-(4-hydroxyphenyl)-1 ,1,
di(hydroxyphenyl)ethers such as 1,3,3,3-hexafluoropropane, even bis-(
4-hydroxyphenyl)ether, 4.2'-12,
2'- and 2,3'-dihydroxyphenyl ether, 4.3'- and 4,4'-dihydroxy-2゜6-dimethyldiphenyl ether, bis-(4-hydroxy-3-isobutylphenyl) ether , bis-(4-hydroxy-3-isopropylphenyl)
Ether, Bis-(4-hydroxy-3-chlorophenyl) ether, Bis-(4-hydroxy-3-fluorophenyl) ether, Bis-(4-hydroxy-3-bromophenyl) ether, Bis-(4-hydroxy naphthyl) ether, bis(
4-hydroxy-3-chlornaphthyl) needle and 4,4'-dihydroxy-3,6-cymethoxydiphenyl ether.

Additionally, suitable useful dihydric phenyls are: As used herein, the term E defined as "residue of a dihydric phenol" refers to the term E defined as "residue of a dihydric phenol", in which two aromatic hydroxyl groups have been removed. Of course, it means the residue of the dihydric phenol mentioned below. That is, as can be easily seen, these polyarylene polyethers have a repeating group in which a dihydric phenol residue and a benzenoid compound residue are bonded via an aromatic ether radical.

Any dihalopenpinoid or dinitropeipinoid compound or mixture thereof can be used to form E' in the present invention.
A benzenoid residue can be generated, the compound having two halogen or nitro groups attached to a benzene ring with an electron-withdrawing group in at least one of the positions ortho and para to the halogen or nitro groups. Dihalobenzenoid or dinitrobenzenoid compounds are
It can be either mononuclear, in which the halogen or nitro groups are attached to the same benzene ring, or polynuclear, in which they are attached to different benzene rings, provided that the activating electron-withdrawing group is present in the ortho or para position of these benzene nuclei. exist. Fluorine and chlorine-substituted benzenoid reactants are preferred, with fluorine compounds exhibiting rapid reactivity and chlorine compounds being preferred because of their low cost.

In these compounds, electron-withdrawing groups can be used as activating groups. Of course, it must be inert under the reaction conditions, but the other structure is not critical.

Preferred are strong activating groups, such as sulfonic groups (-3-) linking two halogen or nitro-substituted benzene nuclei, such as 4,4'-dichlorodiphenylsulfone and 4,4'-di Although chlordiphenyl sulfone, other strong attraction groups can also be used, such as those described below.

Preferably, the ring does not have an electron-donating group on the same benzene nucleus as the halogen or nitro group. However, other groups may be present in the nucleus or in the residue of the compound.

Activating groups can be essentially one of two types: (a) activating one or more halogen or nitro groups in the same ring, e.g. other nitro or halo groups; , phenylsulfone or alkylsulfone, cyano, trifluoromethyl, nitroso and heteronitrogens such as in pyridine; (b) monovalent groups such as halogens present in two different rings, e.g. sulfone; Group-8-;0
H ++ 1 carbonyl group -C-; vinylene group -C=C-nide 1 sulfoxide group -8-diazo group -N-N-:F3 ■ Saturated fluorocarbon group -C-1 CF3 -CF2-CF2 CF2-: Organic Phosphine oxide -P-: (wherein R3 is a hydrocarbon group), as well as ethylidene groups A-C-A- (where A can be hydrogen or =C- can be halogen). The basis of valence.

If desired, mixtures of two or more dihalobenzenoid or dinitrobenzenoid compounds can be used to make the polymer.

That is, the E' residues of the benzenoid compounds in Polymer 1@ may be the same or different.

Examples of hempinoid compounds useful for imparting E' residues to poly(arylether) resins are: 4.4'-dichlorodiphenyl sulfone, 4.4'-difluorodiphenylsulfone, 4. 4'-bis(4-chlorophenylsulfonyl)biphenyl, 4.4'-bis(4-fluorophenylsulfonyl)biphenyl, 4.4'-difluorobenzophenone, 4.4'-dichlorobenzophenone, 4.4'- Bis(4-fluorobenzoyl)benzene, 4,4'-bis(4-chlorobenzoyl)benzene, 2,6-dichlorobenzonitrile, and its isomers.

Furthermore, the term E' defined as [residue of benzenoid compound] as used herein means an aromatic or benzenoid residue of the compound after removal of the halogen atom or nitro group in the benzene nucleus. You can understand that too.

The polyarylene polyethers of the present invention can be obtained in approximately equimolar amounts of, for example, a double alkali metal salt of a dihydric phenol and a dihalopenzenoid compound under approximately anhydrous conditions in the presence of a specific liquid organic sulfoxide or sulfone solvent. It is produced by a method well known in the art as a one-step reaction.

In general, these polymers are made by first converting the dihydric phenol into an alkali by reacting it in situ with an alkali metal, alkali metal hydride, alkali metal hydroxide, alkali metal alkoxide, or alkali metal alkyl compound in a first reaction solvent. It can also be produced by a two-step method in which metal salts are also converted. Preferably, alkali metal hydroxides are used.

After removing any water present or produced to ensure anhydrous conditions, the dialkali metal salt of the dihydric phenol is mixed and reacted with an approximately stoichiometric amount of the dihalobenzenoid or dinitrobenzenoid compound.

Additionally, polyethers may be used, for example in U.S. Pat.
76.222, in which a substantially equimolar mixture of at least one bisphenol and at least one dihalopengenoid is heated at a temperature of about 100 to about 400°C. and a mixture of sodium carbonate or bicarbonate and a second alkali metal carbonate or bicarbonate having an atomic number higher than sodium.

Additionally, these polyethers are described in Canadian Patent No. 847
．． It can also be produced by the method described in Publication No. 963, in which bisphenol and a dihalobenzenoid compound are heated in the presence of potassium carbonate using a high-boiling solvent such as diphenylsulfone or sulfolane. .

Preferred polyarylene polyethers of the present invention are those produced using the following types of divalent polynuclear phenols:
Includes derivatives thereof substituted with inert substituents: [wherein R4 groups are independently hydrogen, lower alkyl, ali,
(d) HO+0-@-OH and substituted derivatives thereof.

Furthermore, it is also conceivable in the present invention to use a mixture of two or more different dihydric phenols to achieve the same objective as described above.

That is, in the above case, one E-residue in the polymer structure can actually be the same or different aromatic residues. For example, when using a mixture of polynuclear dihydric phenols, such as a binary mixture of trinuclear bisphenols, each ring in one of the trinuclear phenol components can be deactivated if desired to form a deactivated (hard to sulfonate) Units can be incorporated into the polymer backbone. Representative of this type of inactivated divalent polynuclear phenol is one in which Meizon is connected by an electron-withdrawing group, and includes, for example, the following dihydric phenols.

When using this type of phenol that has been inactivated by Meien, they have a copolymer backbone of about 95
Preferably, it is limited to less than mol%.

The poly(aryl ether) has a poly(aryl ether) of from about 0.2 to about 2, as measured in a suitable solvent at a suitable temperature depending on the particular polyether, for example, in methylene chloride at 25°C.
, preferably having a reduced viscosity of about 0.35 to about 1.5.

Preferred poly(aryl ethers) have one or more repeating units or subunits of the formula: The term "subunit" means that any of the above may also be included as part of a larger repeating unit, acting as an entire repeating unit.

Polymers having repeating units or subunits as described above are described, for example, in U.S. Pat. No. 4,175,175;
No. 320.224: No. 4.108.837: No. 4.0
No. 09.149: No. 3,455.866; No. 3,51
No. 8,067: No. 3,764.583: No. 3.400
．． No. 065: No. 3.647.751: 19B2 Year 3
European Patent Application Box No. 81107193.5, published with publication number 0047999 on the 24th of May -
and Publication No. 00296 dated June 3, 1981.
European Patent Application Box 8020 published as No. 33
No. 1194.0, respectively.

For ease of explanation, PSE
are often specifically mentioned herein. However, this illustration is in no way meant to be limiting.

B. Process Conditions The sulfonation reaction is carried out in a suitable solvent, the suitability of which is determined by the ability of the solvent to dissolve the polymer and the sulfonating agent and its inertness toward the sulfonating agent.

Suitable are loraliphatic hydrocarbons such as chloroform, methylene chloride and 1,2-dichloroethane. Chlorinated aromatic hydrocarbons such as chlorobenzene are less desirable. This is because, although acceptable for dissolving the polymer, they can be reactive towards sulfonating agents. Inactivated aromatic hydrocarbons, such as trichlorobenzene and nitrobenzene, appear to be suitable solvents.

The amount of solvent used to carry out the reaction is not critical, but
The amount of solvent used should not be so great as to dilute the reaction mixture to the point that the rate of reaction is unfavorably slowed. The minimum amount of solvent is just enough to dissolve the polymer and sulfonating agent. For example methylene chloride or 1.2
- When using loraliphatic hydrocarbons such as dichloroethane, it is possible to use from 5 to 20 ml of solvent per gram of polymer, preferably from 10 to 15 ml per gram of polymer.

Preferably, the reaction is carried out at about room temperature, i.e. from about 0°C to about 30°C.
It is carried out at a temperature in the range of . This is because running the reaction at higher temperatures increases chain scission to levels that are unacceptable compared to the extent of chain scission that occurs at lower temperatures. Although the reaction can be carried out at temperatures below O'C,
Since the reaction rate decreases, it becomes necessary to carry out the reaction for a longer time.

Although there is no need to take particular pressure into account, the reaction is generally carried out at atmospheric pressure.

When a halogenated silyl/halosulfonic acid combination is used to make a sulfonated poly(arylether) resin, the halosulfonic acid is an acid 20■0-3-X [wherein X is α or 8r or ■, preferably 5 is Cl].

As mentioned above, the silyl halide may be any compound having the structure of the formula: % where X is a halogen selected from the group consisting of α, Br and I, preferably Cl. Can be done.

The R groups can generally be the same or different M groups and are inert, i.e. not reactive towards the polymer, do not render the sulfonating agent insoluble in the reaction medium, and preferably contain 5r-o bonds. Any group that does not inhibit base cleavage can be used. For example, R can be: aliphatic or cycloaliphatic alkyl or alkoxy having 1 to 10 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, cyclohexyl and alkoxy thereof. Homologues (e.g. methoxy, ethoxy, etc.) Fluorinated alkyl and cycloalkyl, cyanoalkyl and cycloalkyl, etc.: Aryl having 6 to 18 carbon atoms, such as phenyl or naphthyl, where said aryl group is optionally 1
one or more electron-withdrawing (i.e. inactivating) groups, such as halogen (F, C1, Br or I)
, -NO2, -CN or 10OR5 (R5=01
-1o alkyl)).

Other suitable radicals include (siloxy or) oligosiloxy groups of the formula: wherein W is from O to about 10 and the R groups may be the same or different and have the same meaning as R above. do.

Representative silyl halides include: chlortrimethylsilane, chlortriethoxysilane, chlortriethylsilane, chlorethoxydimethylsilane, chlortripropylsilane, chlormethoxydimethylsilane, chlortri, methoxysilane, tributylchlor. Silane, Chlorjethoxymethylsilane, Butylchlorodimethylsilane, Chlorpentamethyldisiloxane, Chlortriisopropylsilane, Chlorisopropyldimethylsilane, Chlormethylbis(3,3,3-trifluoro10pyr)silane, Tri-t-butyl Chlorsilane, chlortriisopropoxysilane, dimethyldecylchlorosilane, 4-(chlordimethylsilyl)butylonitrile, tributoxychlorosilane, 2-(chlordimethylsilyl)propionitrile, chlortrihexylsilane, chlordimethyl(m-nitrophenethyl) ) silane, chlordimethyl(2,3,4,5,6-pentafluorophenethyl)silane, chlordimethyl[2,4,6-tris(1,1-dimethylethyl)phenoxycosilane, chlordimethyl(2-
nitropropoxy)silane, chloro(isooctyloxy)dimethylsilane.

The amount of halosulfonic acid used is 1. Generally, it can vary from about 0.005 to about 2 moles per mole of polymer repeat unit. The amount of silyl halide used can vary from about 0.50 to about 2 moles, preferably from about 0.9 to about 1.4 moles per mole of halosulfonic acid. In a preferred embodiment, molar equivalents of silyl halosulfonate and halosulfonic acid are provided to the reaction medium. The molar ratio between the sulfonating agent and the polymer repeating unit or Zab unit! ! l! The desired degree of sulfonation can be obtained by adjusting the temperature.

For purposes of explanation, the term "degree of sulfonation" refers to the individual polymer repeat units that are sulfonated -0-E-0-E
The number of '- is expressed as a proportion of the total number of polymer repeat units available in the reaction mixture solution containing the reactive polymer. For example, a degree of sulfonation of about 33% indicates that about 1 out of every 3 repeating units of the polymer is sulfonated.

When producing a sulfonated poly(arylether) resin using a silyl halosulfonate, that is, a reaction product of a silyl halide and a halosulfonic acid, the silyl halosulfonate has the formula: % formula % [wherein X and R are as described above] It can be any compound having the structure:

As mentioned above, silylhalosulfonates can be synthesized by reacting the corresponding halosulfonic acid 1: HO-3-.X with silyl chloride: R3-3i-α, where all symbols in the formula have the above meanings. and according to the general principles disclosed, for example, by Schmidt et al. in Chemical Berichte, Vol. 95, p. 47 (1962). Representative silyl chlorides are the same as those listed above.

The amount of silylhalosulfonate reacted with the poly(arylether) resin is about 0 per mole of polymer repeating units -〇-E-0-E'-, depending on the degree of sulfonation desired.
．． 0.005 to about 2 moles.

For a given reaction time, temperature and polymer repeat unit concentration, increasing the concentration of sulfonating agent generally increases the degree of sulfonation. The number of moles of silylhalosulfonate used per mole of polymeric repeat unit -0-E-0-E' - can be greater than 2, but no significant advantage is obtained.

The reaction time can vary widely from less than 1 hour to as long as desired, and can be increased to increase the degree of sulfonation, but the rate of sulfonation, other reaction conditions being held constant, can vary widely. does not increase linearly with reaction time.

The sulfonating agent can also be added directly to the reaction mixture,
Alternatively, it can be dissolved first in a solvent, preferably in the solvent used to dissolve the polymer. Since hydrogen halides are generated by the substitution reaction, it is preferable to add 2 mb of the sulfonating agent to the dissolved polymer, but the addition time can vary widely from several minutes to hours or more. can.

The reaction can be carried out to form the polymer, for example in the form of powder, feathers or penta-
The reaction can be carried out by dissolving the polymer solution in a solvent and charging the polymer solution and sulfonating agent to a suitable reaction vessel which is non-corrosive to HG. Advantageously, the container may be glass or glass lined, or fabricated from a non-corrosive metal such as Hastelloy (a registered trademark of Kapot Corporation). In general, the container must be provided with means for mechanical mixing or agitation. Although the reaction is not expected to be particularly exothermic or endothermic, it may be desirable to provide heating and/or cooling means. Additionally, it may be desirable to provide means for supplying an inert atmosphere, such as nitrogen or argon, to the reaction solution. It is best to use dry gas. This is because excessive water or water vapor inhibits sulfonation.

Since HCJ is generated on the spot due to the reaction, Ha! is removed from the reaction solution. Means for cleaning or capturing may also be used. To remove the HCl, the gas may be passed gently over the surface of the reaction solution using the means used to provide an inert gas atmosphere, or the gas may be bubbled into the solution a day later. The gaseous effluent can also be washed or captured, for example by passing the effluent through a solution of base.

If the reaction is carried out using a relatively volatile solvent, e.g. methylene chloride, the solvent vapor may be recondensed using a condenser supplied with a coolant, e.g. dry ice/acetone or chilled brine. It can also be returned to the reaction medium.

After the reaction has run for the desired time, the intermediate product (i.e.
An intermediate solution is obtained which contains, for example, in particular in the case of the PSE mentioned above, a polymer having silylsulfonate groups): in which all the symbols have the meanings given above. If desired, the silyl sulfonate derivative can be isolated by coagulating the polymer in a non-solvent such as methanol, acetone or water.

Cleavage of the silyl group can be accomplished by addition of base to yield the desired sulfonated polymer product. A solution of the base in a suitable solvent is added to the reaction solution and mechanical stirring is continued for a sufficient time to substantially complete cleavage. Upon addition of base, some turbidity is initially observed if the solvent in which the base is dissolved may cause the polymer to aggregate, but generally no precipitation occurs.

The base used to cleave the trimethylsilyl group can be any suitable organic or inorganic base, such as ammonium hydroxide or an alkali or alkaline earth metal hydroxide or a base having 1 to 15 carbon atoms, preferably 1 to 3 carbon atoms. Sodium, lithium and potassium hydroxides: sodium, lithium and potassium methoxides: sodium, lithium and potassium ethoxides, and the corresponding magnesium;
Calcium and barium hydroxides and alkoxides are included, which are dissolved in a suitable solvent such as, for example, an alcohol. For example, bases such as alkali metal amides (e.g. KNH2, NaNH2 or LiNH2) can also be used, or e.g.
Alternatively, alkyl congeners such as NaNR2 (where R is an alkyl group of Cl-15) can also be used. Inorganic hydride bases can also be used, for example lithium, sodium or potassium hydrides or calcium hydride.

Alkali metal hydroxides and alkoxides are preferred.

Preferably, the base should be added in an amount sufficient to cleave the modified silyl group and neutralize any acid still present in the solution. Although an excess of base can be used,
This excess should be minimized to prevent unfavorable base cleavage of the resin chain backbone. Base cleavage of the silyl group is preferably carried out with continuous stirring for a sufficient period of time to substantially complete the cleavage reaction. Depending on base concentration, polymer concentration, etc., base cleavage is generally almost complete within about 1 hour, but this cleavage reaction may be continued for a longer period of time if desired, taking care to avoid chain cleavage of the resin. You can also do it.

Advantageously, the cleavage reaction leaves the sulfonated polymer with the formula:
M+ is a cation generated from the base that cleaves the silyl moiety (
For example, NH4'', Na+, Li+, K+, Mg2+ or Ba2'')]. This polymer salt makes asymmetric membranes more useful and membranes with better desalting properties than membranes made from acid-form polymers, such as those disclosed in U.S. Pat. No. 3,875,096. Can be processed. The salt type is more stable than the acid type, especially at high temperatures, and is an acidic sulfone? Prevents self-decomposition as could occur due to the presence of in.

However, sulfonated poly(aryl ether)
! If it is desired to obtain the acid form for membrane processing or any other application from the sulfone H (-3O3H> form of the 8I fat), the resin sulfonate salt can be readily converted by simply exposing it to a dilute solution of the acid. For example, suitable acids include carboxylic acids such as acetic acid, propionic acid and its halogenated homologs (such as trichloroacetic acid and trifluoroacetic acid), sulfonic acids such as p-toluenesulfonic acid, methane, etc. Sulfonic acids and their halogenated congeners (e.g. trifluoromethanesulfonic acid, trichloromethanesulfone r!i)
, and inorganic acids such as hydrochloric acid, sulfuric acid and nitric acid.

The above is representative and in no way is meant to be limiting.

This salt can be converted to an acid by addition of a compound in a suitable solvent that is miscible with the solvent in which the resin salt is dissolved after base cleavage of the silyl group and before aggregation. Care should be taken to add enough acid not only to convert the salt, but also to neutralize any base remaining after base cleavage of the silyl group.

The resin should be washed after flocculation to remove any remaining free particles.

Alternatively, the resin salt can be first added to the resulting resin salt solution after base cleavage as is known in the art with an excess of non-solvent (e.g., water,
Acetone or alcohol) can also be added to cause flocculation and isolation, for example by filtration. The resin thus isolated can then be washed directly with, or even immersed in, an acidic solution of a non-solvent (eg water). Conversion to an acid is also possible by permeating the sulfonated poly(arylether) resin salt obtained as a filtrate with an acid. This is because the filtrate is generally a feather-like porous product that allows effective surface contact for acid non-solvent solutions, such as regeneration of ion exchange resins. However, immersion is preferred.

Alternatively, the resin salt can be aggregated, isolated, for example by filtration, and then redissolved in fresh loraliphatic hydrocarbon solvent. Acids can also be dissolved in solution and converted to salts.

The amount and degree of acidity to be added to the resin salt solution or used to wash or soak the aggregated resin salt is not critical, but depends to some extent on the degree of sulfonation.

Generally, a molar ratio of acid to sulfonate salt groups of about 10:1 is sufficient to convert nearly all of the sulfonate salt groups to the acid form. By adding enough acid to the resin salt solution to bring the solution to 1N (1N) or less, or by soaking or washing the aggregated polymer with an acid having a concentration of 1N (or less), It is sufficient to carry out the conversion independently of the degree of sulfonation. Acid solutions with concentrations greater than 1N may be used, but may lead to acid cleavage of the resin, uncontrolled sulfonation, such as when using high concentrations of sulfuric acid, or undue oxidation, such as when using high concentrations of nitric acid. Care should be taken to avoid decomposition.

As mentioned above, flocculation of sulfonated resins in acid or salt form is possible in amounts sufficient to flocculate a solution of the resin as desired, whereas a miscible but solvent for the sulfonated resin It can also be added to any liquid that is not
This is known in the art.

Membranes are prepared using sulfonated poly(aryl ether ) Can be processed from resin. Suitable solvents are generally polar organic solvents such as dimethylformamide, dimethylsulfoxide, methylpyrrolidone and diethylene glycol monoethyl ether, with dimethylformamide being preferred.

Reinforced membranes can also be obtained by casting onto screens, such as woven fabrics or grids. Methods of this type are disclosed and illustrated, for example, in US Pat. No. 3,709.841 and US Pat. No. 3,875,096.

[Examples] Hereinafter, the present invention will be further explained with reference to Examples, but the present invention is not limited thereto.

C0 Experimental Example 1 40 (P-1700, the name of a commercially available polysulfone manufactured by Union Carbide Corporation) was mixed with 300rr11 methylene chloride (CI-12CJ1).
2). The solution was placed in a four-necked glass flask equipped with a mechanical stirrer, thermometer, reflux condenser, and nitrogen inlet. Nitrogen circulation to the surface of the solution was started and maintained throughout the experiment. A separate solution of 11.95 moles of trimethylsilylchlorosulfonate in 100 methylene chloride was made and added dropwise to the stirred polymer solution over 10 minutes at room temperature.

Stirring was continued overnight (20 hours).

A 25% by weight solution of sodium methoxide in methanol (J) was added. A slight development of turbidity was observed. However, no precipitation of the polymer was observed. After stirring for approximately 1 hour, the reaction mixture in an excess (5:1 volume) of methanol; the white fluffy precipitate was filtered and washed once with water and once with methanol. This was done by stirring in a Waring blender for 5 minutes.

The reduced viscosity was: 0.37 dl 7g for starting material P-1700 (
25 °C, 0.2 (J/100 rnl, in N-methylpyrrolidone), and 1. for the final sulfonated salt.
12dl 7g.

Sulfur analysis indicates that this material contains 0.3
083 SO3N a units, indicating a degree of sulfonation of about 31%.

Compared to the above results, the effect of shorter reaction time (i.e. stirring time before adding the sodium methoxide/methanol solution) is shown in the table of reduced viscosity (RV) and degree of sulfonation as follows: There is: 4 0.98 14.54 5 1.03 13.78 (1) 0.2g / 100rd,: 25℃,
N-Methylpyrrolidone (NMP> (2) The two results appear to be virtually identical, with any differences due to experimental errors inherent in the analysis.

Example 2 The general procedure of Example 1 using P-1700 was followed except that 8.54 g (0.0d53 mol) of (CH
3) 3S i SO3C1 (using D Mira). The reaction was carried out under reflux (40° C.) for only 4 hours.

The polymer was isolated as in Example 1. This sulfonated product is 1.15 (0.2 g/100s?, 2
5°C, NMP> RV and its degree of sulfonation is 32.
．． It was 2%.

This result indicates that fewer expensive silyl reagents and shorter reaction times are required to achieve a comparable degree of sulfonation at higher temperatures. However, if the reaction is continued under reflux overnight (20 hours), degradation of the polymer is observed.

The degraded material becomes more highly sulfonated. That is, the degraded product had an RV of 0.58 and a degree of sulfonation of 40.7%.

EXAMPLE 3-21 Additional data and results obtained following the general procedure of Example 1 and using the reaction times, temperatures and amounts of starting materials described above are summarized in Table 3. EXAMPLE 22 Dry 409 P- 1700 was dissolved in 370 ml of methylene chloride in a 10100 O three-necked flask equipped with a mechanical stirrer, condenser and nitrogen sparge. The solution was purged with nitrogen for 1 hour and trimethylsilyl chloride (7.57 g, 0.0697 mol) was added via addition funnel over 5 minutes and rinsed with 15 mL of methylene chloride. Then, chlorsulfonic acid (7,39()
, 00.0634 mol was added dropwise over 1 hour and rinsed with 15 d of methylene chloride. The solution was then stirred at room temperature overnight. The reaction solution was homogeneous throughout this time. 2 of sodium methoxide in methanol
A 5% solution (40c+) was added to the reaction. After 1 hour, this homogeneous solution was added to a large excess of methanol in a blender to aggregate the polymer. The recovered polymer was washed with water and methanol in a blender and dried in a vacuum oven. Reduced viscosity of polymer (RV, N to 0 in IP
．． 2%) was 0.98. Original cumulative, fold is 8.92%
of sulfur and 1.64% of sodium, the degree of sulfonation was 32.3%>. The glass transition temperature of this product is 22
The temperature was 4°C.

The polymer of this example exhibited improved resistance to solvents such as acetone, ethyl acetate, and toluene compared to polysulfone.

Example 23 The sulfonation reaction was carried out in a total of 400 d of methylene chloride containing 1.6 mmol (>29 mg) of water.
10g (P-1700) polysulfone and 6.88C](
0,0634 mol) of trimethylsilyl chloride and 7.39
9 (0,0634 moles) of chlorosulfonic acid.

A dry ice/acetone condenser was used. After 4 hours, the sample taken showed an RV of 0.80.

After 22 hours at room temperature, the reaction was treated with base and Example 22
The polymer was recovered in the same manner as in. This product is 1.
14 RVs and 8.85%! Comparative Example A The sulfonation of Example 22 was repeated without trimethylsilyl chloride. That is, 3857! 40(](]p-1700 polysulfone in methylene chloride of 7.38
(] (00,0634 moles of chlorsulfonic acid (15
d solvent washing). The reactants are heterogeneous and 2
It had two distinct phases. After 22 hours, the lower phase became thick and the stirrer was turned on. A sodium methoxide/methanol solution was added to cause partial dissolution of the lower phase. The polymer was recovered as in Example 1, but was extremely difficult to filter due to the fineness of the particles. The recovered polymer is 0.6
It had an RV of 1 and analyzed 9.47% sulfur and 2.39% sodium (nominal degree of sulfonation 43.
9%).

The glass transition temperature of this polymer was 264°C.

Samples taken after 4 hours had an RV of 0.98.

Compared to Examples 22 and 23, this example shows that sulfonation with chlorosulfonic acid may result in an apparently better degree of sulfonation or a product of significantly lower molecular weight. Decrease in molecular weight (R
> indicated by a decrease in V indicates chain cleavage of the polymer. Furthermore, this example shows that in the presence of trimethylsilyl chloride, the reaction becomes homogeneous, whereas chlorosulfonic acid alone leads to a heterogeneous two-phase system.

Comparative Example B The sulfonation was repeated substantially as in Example 22, except that 40 (p-1
700> using polysulfone and methylene chloride 100
A solution of trimethylsilylchlorosulfonate (11.95 g, 0.0634 mol) obtained from Full Force AG in ml was added over 10 minutes.

After stirring overnight at room temperature, the homogeneous reaction medium was treated with sodium methoxide and the polymer was recovered as in Example 22. This polymer had an RV of 1.11 and an elemental analysis of 8.86% sulfur and 0.439% sodium (degree of sulfonation 31.0%).

This example shows that the use of the trimethylsilylchlorosulfonate reagent also results in polymers with good molecular weights and degrees of sulfonation similar to those obtained in Examples 22 and 23. However, the in situ methods in Examples 22 and 23 are cheaper.

Example 24 The reaction was repeated in substantially the same manner as in Example 22, except that trimethylsilyl chloride (8.25 g, 0.076 mol) in methylene chloride 257 was added via addition funnel to chlorsulfone I (7, 39(], 0,
0634 mol). After 2 hours at room temperature, the mixture was then added to polysulfone (40 g) dissolved in 300 ml of solvent. After 22 hours, homogeneous coalescence R
V was 0.96 and elemental analysis showed 8.56% sulfur and 1.07% sodium (degree of sulfonation 2
4.9%).

Premixing of these reagents also resulted in a homogeneous reaction and the final molecular weight was comparable to that found in Examples 22 and 23. However, the degree of sulfonation is slightly lower.

This example illustrates an alternative way of implementing the invention, whereas Examples 22 and 23 illustrate the preferred method of implementing the in-situ method.

Claims (75)

[Claims] (1) When producing a silyl sulfonate derivative of poly(arylether) resin, the formula: -O-E-O-E'
- [wherein E is a residue of a dihydric phenol, and E' is a residue of a benzenoid compound having an electron-withdrawing group at at least one of the ortho and para positions with respect to the valence bond, and these residues E and E' are bonded to the ether oxygen via an aromatic carbon atom] under reaction conditions sufficient to form said derivative. 1. A method for producing a silyl sulfonate derivative of a poly(arylether) resin, comprising reacting it with an effective amount of silyl halosulfonate. (2) The method according to claim 1, wherein the dihydric phenol residue is a bisphenol residue. (3) Formula for dihydric phenol: ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, and ▲Mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, the R_4 group independently represents hydrogen, lower alkyl, aryl, and a halogen-substituted group thereof.] The method according to claim 1, wherein R_4 is selected from the group consisting of: (4) Formulas for benzenoid compounds: ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, and ▲ Mathematical formulas, chemical formulas, tables, etc. ▼ The method according to claim 1, wherein Y is halogen or nitro. (5) The method according to claim 4, wherein Y is F or Cl. (6) Poly(arylether) resin has a formula: ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas, tables, etc. There are ▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ ▲There are mathematical formulas, chemical formulas, tables, etc.▼, and ▲ The method according to claim 1, having a repeating unit or subunit selected from the group consisting of mathematical formulas, chemical formulas, tables, etc. (7) The method according to claim 6, wherein the poly(arylether) resin is polysulfone. (8) Poly(aryl ether) resin from about 0℃ to about 35℃
A method according to claim 1, characterized in that the reaction is carried out with a silylhalosulfonate at a temperature of .degree. (9) Silylhalosulfonate has a structure with the formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, X is a halogen selected from Cl, Br and I, and R is an inert organic group] The method according to claim 1. (10) The method according to claim 9, wherein the silylhalosulfonate is trimethylsilylchlorosulfonate. (11) The method of claim 1, wherein a poly(arylether) resin is reacted with a silyl halosulfonate in an inert chloroaliphatic hydrocarbon solvent. (12) The amount of silylhalosulfonate reacted with the poly(arylether) resin is the repeating unit -O-E-O-E.
2. The method of claim 1, wherein the amount is from about 0.005 to about 2.0 moles per mole of -. (13) A silyl sulfonate derivative produced by the method according to any one of claims 1 to 12. (14) When poly(arylether) resin is sulfonated, A, the formula: -O-E-O-E'- [wherein E is a residue of a dihydric phenol and E' is a valence bond] is a residue of a benzenoid compound having an electron-withdrawing group in at least one of the ortho and para positions,
Both residues E and E' are linked to the ether oxygen via an aromatic carbon atom. B. reacting this derivative with a base to form a sulfonate salt of the poly(arylether) resin; aryl ether) resin sulfonation method. (15) The method according to claim 14, wherein the dihydric phenol residue is a bisphenol residue. (16) Formula for dihydric phenol: ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, and ▲ Mathematical formulas, chemical formulas, tables, etc. 15. The method according to claim 14, wherein the R_4 group independently represents hydrogen, lower alkyl, aryl, or a halogen-substituted group thereof. (17) Formulas for benzenoid compounds: ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, and ▲ Mathematical formulas, chemical formulas, tables, etc. 15. The method according to claim 14, wherein Y is selected from the group consisting of ▼ [wherein Y is halogen or nitro]. (18) Claim 1 in which Y is F or Cl
The method described in Section 7. (19) Poly(aryl ether) resin has the formula: ▲ Formula,
There are chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc. From the group consisting of ▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, and ▲There are mathematical formulas, chemical formulas, tables, etc.▼ 15. The method of claim 14 with selected repeating units or subunits. (20) The method according to claim 19, wherein the poly(arylether) resin is polysulfone. (21) Poly(arylether) resin from about 0°C to about 3°C
15. A process according to claim 14, characterized in that the reaction is carried out with a silylhalosulfonate at a temperature of 5[deg.]C. (22) The method of claim 14, wherein a poly(arylether) resin is reacted with a silyl halosulfonate in an inert chloroaliphatic hydrocarbon solvent. (23) Silylhalosulfonate has a structure with the formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, X is a halogen selected from Cl, Br and I, and R is an inert organic group] 15. The method according to claim 14. (24) The method according to claim 23, wherein the silylhalosulfonate is trimethylsilylchlorosulfonate. (25) The amount of silylhalosulfonate reacted with the poly(arylether) resin is the repeating unit -O-E-O-E.
15. The method of claim 14, wherein from about 0.005 to about 2 moles per mole of -. (26) The method according to claim 14, wherein the base is an alkali or alkaline earth metal hydroxide or an alkali metal alkoxide. (27) The method according to claim 26, wherein the alkali metal is sodium, potassium, or lithium. (28) The method of claim 26, wherein the alkali metal alkoxide has 1 to 15 carbon atoms. (29) The method according to claim 28, wherein the alkali metal alkoxide has 1 to 3 carbon atoms. (30) Claim 29, wherein the alkali metal alkoxide is an alkali metal methoxide or ethoxide.
The method described in section. (31) The method of claim 14, wherein the poly(arylether) resin sulfonate salt is exposed to an acid to convert the resin sulfonate salt to a resin sulfonic acid. (32) A sulfonated poly(arylether) resin produced by the method according to any one of claims 14 to 31. (33) The resin according to claim 32, which is in the form of a film. (34) When producing a silyl sulfonate derivative of poly(arylether) resin, the formula: -O-E-O-E
'- [wherein E is a residue of a dihydric phenol, and E' is a residue of a benzenoid compound having an electron-withdrawing group at at least one of the ortho and para positions with respect to the valence bond,
Both residues E and E' are linked to the ether oxygen via an aromatic carbon atom. A method for producing a silyl sulfonate derivative of a poly(arylether) resin, characterized in that the silyl sulfonate derivative of a poly(arylether) resin is reacted with a combination of a silyl halide and a halosulfonic acid in effective amounts, respectively. (35) The method according to claim 34, wherein the dihydric phenol residue is a bisphenol residue. (36) Formula for dihydric phenol: ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, and ▲Mathematical formulas, chemical formulas, tables, etc. 35. The method according to claim 34, wherein the R_4 group independently represents hydrogen, lower alkyl, aryl, or a halogen-substituted group thereof. (37) Formulas for benzenoid compounds: ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, and ▲ Mathematical formulas, chemical formulas, tables, etc. 35. The method according to claim 34, wherein Y is halogen or nitro. (38) Claim 3 in which Y is F or Cl
The method described in Section 7. (39) Poly(aryl ether) resin has the formula: ▲ Formula,
There are chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc. From the group consisting of ▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, and ▲There are mathematical formulas, chemical formulas, tables, etc.▼ 35. The method of claim 34 with selected repeating units or subunits. (40) The method according to claim 39, wherein the poly(arylether) resin is polysulfone. (41) Poly(arylether) resin from about 0°C to about 3°C
35. The method of claim 34, wherein the reaction is carried out with the combination at a temperature of 5<0>C. (42) The halogenated silyl has a structure of the formula: R_3-Si-X [wherein X is a halogen selected from Cl, Br, and I, and the R groups are independently inert organic groups] 35. The method of claim 34. (43) The method according to claim 42, wherein the silyl halide is trimethylsilyl chloride. (44) The method according to claim 34, wherein the halosulfonic acid is chlorosulfonic acid. 45. The method of claim 34, wherein a poly(arylether) resin is reacted with the combination in an inert chloroaliphatic hydrocarbon solvent. (46) Claim 3 wherein an amount of the halosulfonic acid from about 0.005 to about 2 moles per mole of repeating units -O-E-O-E'- is reacted with the poly(arylether) resin.
The method described in Section 4. 47. The method of claim 46, wherein an amount of silyl halide from about 0.5 to about 2 moles per mole of halosulfonic acid is reacted with the poly(arylether) resin. (48) A silyl sulfonate derivative produced by the method according to any one of claims 34 to 41. (49) When poly(arylether) resin is sulfonated, A, the formula: -O-E-O-E'- [wherein E is a residue of a dihydric phenol and E' is a valence bond] is a residue of a benzenoid compound having an electron-withdrawing group in at least one of the ortho and para positions,
Both residues E and E' are linked to the ether oxygen via an aromatic carbon atom. B. making a silyl sulfonate derivative by reacting with a combination of an effective amount of a silyl halide and a halosulfonic acid, respectively; and B. reacting said derivative with a base to form a sulfonate salt of said poly(arylether) resin. A method for sulfonating a poly(arylether) resin, the method comprising: (50) The method according to claim 49, wherein the dihydric phenol residue is a bisphenol residue. (51) Formula for dihydric phenol: (a) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, (b) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, (c) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ , and (d) ▲ Numerical formulas, chemical formulas, tables, etc. The method according to scope item 49. (52) Formulas for benzenoid compounds: ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, and ▲ Mathematical formulas, chemical formulas, tables, etc. 49. The method according to claim 49, wherein Y is halogen or nitro. (53) Claim 5 in which Y is F or Cl
The method described in Section 2. (54) Poly(aryl ether) resin has the formula: ▲ Formula,
There are chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc. From the group consisting of ▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, and ▲There are mathematical formulas, chemical formulas, tables, etc.▼ 50. The method of claim 49 with selected repeating units or subunits. (55) The method according to claim 54, wherein the poly(arylether) resin is polysulfone. (56) Poly(arylether) resin from about 0°C to about 3°C
50. The method of claim 49, wherein the reaction is carried out with the combination at a temperature of 5<0>C. 57. The method of claim 49, wherein a poly(arylether) resin is reacted with the combination in an inert chloroaliphatic hydrocarbon solvent. (58) The silyl halide has the structure of the formula: R_3-Si-X, where X is a halogen selected from Cl, Br, and I, and the R groups are independently inert organic groups. A method according to claim 49. (59) The method according to claim 58, wherein the silyl halide is trimethylsilyl chloride. (60) The method according to claim 49, wherein the halosulfonic acid is chlorosulfonic acid. (61) The amount of halosulfonic acid reacted with the poly(arylether) resin is 1 of the repeating unit -O-E-O-E'-
50. The method of claim 49, wherein from about 0.005 to about 2.0 moles per mole. (62) The amount of halogenated silyl to be reacted with the poly(arylether) resin is about 0.0% per mole of halosulfonic acid.
50. The method of claim 49, wherein the amount is from 5 to about 2 moles. (63) The method according to claim 49, wherein the base is an alkali or alkaline earth metal hydroxide or an alkali metal alkoxide. (64) The method according to claim 63, wherein the alkali metal is sodium, potassium, or lithium. (65) The method of claim 63, wherein the alkali metal alkoxide has 1 to 15 carbon atoms. (66) The method of claim 65, wherein the alkali metal alkoxide has 1 to 3 carbon atoms. (67) Claim 66, wherein the alkali metal alkoxide is an alkali metal methoxide or ethoxide.
The method described in section. 68. The method of claim 49, wherein the poly(arylether) resin sulfonate salt is exposed to an acid to convert the resin sulfonate salt to a resin sulfonic acid. (69) A sulfonated poly(arylether) resin produced by the method according to any one of claims 49 to 68. (70) The resin according to claim 69, which is in the form of a film. (71) Formula: -O-E-O-E'- [In the formula, E is a residue of a dihydric phenol, and E' has an electron-withdrawing group at at least one of the ortho and para positions with respect to the valence bond. is a residue of a benzenoid compound having
Both of these residues E and E' are bonded to the ether oxygen via an aromatic carbon atom. A linear poly(arylether) resin characterized by having a modified silyl sulfonate group having the following structure: [In the formula, the R groups are the same or different inert organic groups.] (72) The repeating unit or subunit is a formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲Mathematical formulas, chemical formulas, tables, etc. There are ▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, and ▲There are mathematical formulas, chemical formulas, tables, etc.▼ The resin according to claim 71, which is selected from the group consisting of. (73) The resin according to claim 71, wherein the silylsulfonate group is a trimethylsilylchlorosulfonate group. (74) Silyl halosulfonate is produced by introducing silyl halide and halosulfonic acid in claim 34.
A method according to claim 1, which is derived similarly to the method according to claim 1. (75) The method according to claim 14, in which silyl halosulfonate is derived in the same manner as the method according to claim 49, by introducing a silyl halide and a halosulfonic acid.