JPS6099308A - Permselective membrane based on polybenzimidazolone having pendant sulphonic acid group - Google Patents

Abstract

PURPOSE:To realize high water permeability preserving high chemical resistance by introducing pendant sulphonic acid groups to polybenzimidazolone polymer. CONSTITUTION:Permselective membrane consisting essentially of polybenzimidazolone having pendant sulphonic acid groups with at least 50mol% content of recurrent unit (basing on the whole recurrent units) expressed by the formula [wherein Ar1 is a tetravalent 6-40C aromatic group; Ar2 is a (2+m) valent 6- 40C aromatic group; m is an integer zero or 1-4; N and N, N and N are located in ortho position on an aromatic ring, to each other]. The pendant sulphonic acid groups are introduced by using an aromatic diamine having pendant sulphonic acid group as the starting material, or by using a diamine having a sulphonamide group or sulphonic ester group and hydrolyzing at an appropriate stage, or by first synthesizing polybenzimidazolone and sulphonating it with a suitable sulphonating agent.

Description

[Detailed description of the invention]

The present invention relates to an improved polybenzimitazolone thread waste combination having excellent practicality for use in reverse osmosis membranes, a method for producing the same, and a permselective membrane obtained therefrom. The present inventors have previously found a method for synthesizing a new conglomerate in which a benzimidazolone ring represented by the following formula (1m) is attached to the main chain (e.g., % Application No. 49-60964), and furthermore, it is an excellent choice. It has been discovered that it can be used as a permeable reverse osmosis membrane (for example, Japanese Patent Application No. 110427/1983). 1 However, in the formula, A' is an aromatic group, and N and N are located at ortho positions in the aromatic Group 11 group. It not only has at least the same water permeability as membranes and aromatic polyamide membranes (and various inorganic salts), but also has the ability to exclude organic matter.

[In addition, heat resistant,
It has been confirmed that it has better acid resistance, alkali resistance, and stability against certain oxidizing agents, so it can be used only in limited applications such as the conventional desalination of can water and the production of ultrapure water.
, cleaning water paste in metal surface treatments such as various plating a-
Practical use in industrial processes such as industrial processing, concentration processing of juices, broth, etc., and various food processing that requires heating, alkaline or oxidizing agent treatment, etc. I found out something. However, depending on the application, there are many cases where it is desired to obtain effective water permeation waves even if the rejection ability is sacrificed to some extent. Therefore, it has been difficult to achieve high water permeability while maintaining high chemical resistance as described above. The present inventors have developed polybenzimidasilon with such performance (as a result of intensive studies, we have found that either an aromatic diamine having a pendant sulfonic acid group is used as a raw material monomer, or polybenzimidacylon is used as a raw material monomer). By sulfonating the main polymer, polybenzimidacylon having pendant sulfonic acid groups in a certain specific allocation can be easily obtained, and such a monomer membrane can meet the above objectives. The present invention was achieved by discovering the repeating unit represented by the following formula (1) [However, the total average value of m is 0.0
A value in the range of 5 to 2, Ar in each unit, and Ar,
may be two or more different groups each satisfying the above conditions. ] with a pendant sulfonic acid group containing a small number of total repeating units (both 50 moles), an intrinsic viscosity of 0.
This is a selectively permeable membrane mainly composed of one or more polybenzimidacylons. As a preferable example of Ar in formula (1) of the present invention,
As the basic skeleton that forms it; the following formula [A], (-
) The basic skeleton of the compound (hereinafter abbreviated as A)t. ) can be given. [a] 0 (benzene) [a] (naphthalene) Further, the above iir: A It can also be suitably used when two or more of them are combined as in the following formulas [) to] to [ch]. [C) A R-A R [2J A It -A R-A R [E) AR-Q-AR [F] AH-q-AR-Q [H] AH-Q-AR -AR In the formula, [E] and [E] are preferred. However, the above formula [...] ~ [chi] ic o(・te, -(-
Examples include -so, -, -8-, -o-, -c-, a fullylene group having 1 to 3 carbon atoms, an oxadiazole group, a hytantoin group, a lanokun bond, an imide bond, a triazole bond. etc. at least one camphor: ll*desirable. The above-mentioned aromatic group AR may have an amorphous substituent such as a lower alkyl group, a lower alkoxy group, or an a-gen atom. Also, with regard to Arc, compounds similar to Ar can be cited as suitable examples. As a specific preferred example of Ar, 1 As a specific preferred example of Ar, when m = 1 to 4, etc. can be given, and when m = 00, *brt3゜-o- O-o-8q-o-o- etc. can be mentioned. These can be suitably selected to be la or more in the range where the average of m is O, (15 to 2, particularly preferably 0.1 to 1.5. In the polybenzimitazone a related to the present invention, the formula (1
) is at least 50 moles or more,
Preferably it is 70 molar or more, more preferably 90 molar or more. Other structural units include precursor units before benzimitazolone is produced, such as represented by the F-formula (V). (2) In addition, when Y is -NH, the -NH1 can be reacted with sulfonyl chloride or the like to form a phenylsulfonamide group or a methanesulfonamide group. Introduction of such a sulfonamide group results in water permeability 'kkt! /In some cases, it may have the effect of increasing As structural units other than the above precursor units, a part of the aromatic diamines (ill) may be aliphatic diamines (for example, hexamethylene diamine, dodecamethylene diamine, etc.),
Alicyclic diamines (e.g. piperazine, 4,4-disyc a
(hexylmethanediamine, etc.).
1), structural units corresponding to (V); Also, aromatic diamines [1) aminophenols (e.g. m-aminephenol, p-7 minophelate, etc.) and/or bisphenols (e.g. is hisphenol A. Bisphenol S, resorcinol, etc." is substituted with the lower hi" = formula [■]. ] Naru Nido a/J
An amide structural unit obtained by replacing a part of the C+ compound with a dicarphonyl a-noide (e.g., in7tal acid a-ride, terephthalic acid a2-ide, cepatic acid chloride, etc.), disulfonic acid halide (e.g. The sulfonamide structural unit obtained at °C is replaced with tricarboxylic acid monoanhydride monohalide (e.g., 4-chloroformylphthalic acid). Amide-imide or 1-amic acid structural unit [■] obtained by replacing with anhydride), amidic acid or imide structural unit LXJ obtained by replacing with tetracarboxylic dianhydride (e.g. bilome'J acid dianhydride), etc.; I can give Jlf. These are soluble, R water-based, etc.! It can be appropriately copolymerized and used for the purpose of making four sections. The polybenzimidazolone with pendant sulfonic acid groups according to the invention K has a %U of 5.9/lo. -Intrinsic viscosity measured at 30°C in N-methylpyrrolidone S liquid is at least 0.1 or more, preferably 0.4 or more,
More preferably, it is 6 or more. As a method for producing such a polymer, at least one of the aromatic nido If / Furthermore, if necessary, the above-mentioned copolymerization components are added as appropriate, and the polynitroimine represented by the formula (XI) is prepared by reacting with an inert polar solvent and an acid acceptor by heating. Hari]
It starts by obtaining the. [However, in the formula, ArI+ Ar and m are the same as above. ]
Dimethyl sulfoxide is used as an inert solvent. N-methyl vicritone, N,N-dimethylaceto'r
So-called aprotic polar solvents such as Mido are preferred. Although it is possible to use the above aprotic polar solvent as the acid acceptor, it is preferable to use it separately.As such acceptor, alkaline earth or alkali metal carbonate are particularly preferred, and specific examples include soda carbonate, potassium carbonate, charcoal lithium, calcium carbonate, etc.
I can give you. The reaction conditions are generally a reaction temperature of 7 ()
~21) QC, preferably 1011~180''G. Reaction time 0.5~3() hours, preferably 4~20 hours.The polynide aimine (Xl) thus obtained
The following formula [■] can be obtained by reducing the nitro group.
It is converted into a polyaminoimine represented by [However, in the formula, Ar, , Ar, and m are the same as @. ] Such reduction is carried out by dissolving the polymer in the above-mentioned heterogeneous solvent and homogenizing it.
System method, water, methanol 5. An example of this method is suspension in a medium such as tetrahydrofuran. Examples of the reduction method include a method using a chemical reducing agent such as hydrogen sulfide, soot chloride, and sodium chloride, and a method using catalytic hydrogenation using palladium-carbon or the like. Furthermore, the polyaminoimine (■) K pair (2,
Depending on the type of active carbonate derivative [■], the amino group can be converted to penzimitazolone V (via a urethane group or urea group).Such an activated carbonate derivative [■] is 關x'-c-x' ...... [■]' or 0C=N-bird ...... , a rate compound, and /'% of x' and and () are preferably bonded to pengtylene, ethylene, imitazole residues, etc., and R4 is preferably ethylene, etc. Also, phenyl, etc. is suitable as R3 in the above formula [Xl]. Examples include phosgene, ethyl chloroformate, phenylchloroformate,
Diphenyl carbonate, engineered carbonate, N,
N-dimethylcarnomate, o-ethyl-N
, N'-dimethylcarbamate. N-ri-a-formylpiveridine, N-phenyl O-
Examples include phenyl urethane + urine X, -y enyl isocyanate, and carbonyl diimitazolide. The chemical formula for using the compound is chemically represented by the formula CXI)
The amount may be equimolar to the aminoimine structure represented by, but it may be more than that, or less than equimolar if it is not necessary to convert all of the aminoimine structure to benzimitazolone. Costume. The reaction between the above-mentioned compound and a polymer having a 7-mininoimine structure must be carried out keeping in mind that one of the reaction components is in the Jll, Q form. IIL is preferably carried out in the presence of a medium that dissolves or moderates the polymer.Also, when the compound itself acts as a solvent, it is also preferable to carry out the reaction. The reaction can proceed. Such solvents include N-methyl biaridone, amide thread solvents such as dimethylacetamide, hexamethylphosphoramide, etc., or sulfoxide or sulfone solvents such as dimethyl sulfoxide, tetramethylene sulfone, etc. In some cases, organic acidic solvents such as cresol and 1v!S may also be used.The reaction varies depending on the reactivity of the cinnabar derivative or incyanate compound, but in general, 0-phenylenediamines and charcoal 111M are used. First, it does not follow the conditions of the known bennimitazolone formation reaction by reaction with a conductor or incyanate compound. Such a reaction can be expressed in the general formula as follows: 1 (II) 1X'-C-X'(Xm)'→(1) [■) 10QC;NRs (■]" → (1) Generally, a primary amino group is a secondary amino group (imino group)
(especially when C8 is an aromatic nuclear carbon atom). Therefore, the primary amino group and the more reactive side of x' and
1) VL ring closure. Therefore, if the reactivity of the primary amino group and the secondary amino group differ greatly, and/or if the reactivity of x' and It can be stably extracted using an intermediate polymer having the following properties. In addition, the structure (1
) can also be used. Examples of vertical acid derivatives and incyanate compounds from which intermediate polymers having bonds of structures (V)' and (V)' can be stably extracted include ethyl chloropomate, phenyl Qc1 formate, and N-chloro lj formyl dimethyl. 7μ, including chloraphorkyl derivatives such as amines and isocyanates, and stabilized incyanates such as phenylwallethane, etc. are produced. These compounds are generally 1oo
(V)', (V)' bond-containing intermediate polymer can be obtained by reacting with the primary I' mino group at a temperature of 50° C. or less, preferably 50° C. or less. The intermediate polymer can be converted to polybenzimidasilon by heating at 50°C or higher, preferably from 100°C to 300°C. Of course, when using the above-mentioned chloroformyl wire conductor wincyanate and stabilized isocyanates, the same structure (v)' as when using compounds having the same reactivity of x and x' such as phosgene, urea, diphenyl carbonate, etc. ,
Without taking out the intermediate polymer having (V)', it can be converted into polybenzimidacylon all at once and taken out as polybenzimidacylon h1. When using a carbonic acid derivative with a small number of x and ,)
Since this inhibits the reactivity of the group, it is preferable to carry out this reaction in the presence of an acid acceptor. Such acid acceptors include alkali metal or alkaline earth metal hydroxides, carbonates, bicarbonates. Examples include inorganic acid acceptors such as salts and organic acid acceptors such as tertiary amines. Further, among the reaction solvents mentioned above, the 7-mide solvent and the sulfoxide solvent have an acid-accepting ability and can also serve as an acid-accepting agent. In the present invention, the progress of the reaction can be monitored by measuring the infrared absorption spectrum or NMR spectrum of the polymer. The polybenzimidacylones thus obtained are generally N-methyl biolidone, dimethyl sulfoxide, etc. &'Lvs 1? +, and they can be formed into films, fibers, etc. The polybenzimidacylones obtained by the present invention have a high melting point and good heat resistance, and can be used as heat-resistant resins. It can also be suitably used as a membrane. Furthermore, it maintains a certain degree of reactivity as an original document bond.C
Since it also has a sulfonic acid group, it can be used as a functional polymer that can perform six reactions. In addition, as another method for producing polybenzimidacylon having pendant sulfonic acid groups according to the present invention, initially, as the diamine used for polymerization, a diamine having a sulfoxide or a sulfonic acid ester is used instead of a sulfonic acid group. It is also possible to obtain polybenzimidacylon having pendant sulfonic acid groups by subsequent hydrolysis at an appropriate stage. Furthermore, as a method for producing polybenzimidacylon having other pendant sulfonic acid groups, once polybenzimidacylon having no pendant sulfo/acid groups has been synthesized, preferably in the presence of a small active solvent "F". Chlorsulfone 1
F1. It is also possible to introduce the desired sulfonic acid group using a sulfonating agent such as fuming sulfuric acid. Therefore, m=
In this method, polybenzimidacylon corresponding to No. 0 is once synthesized by the method described above, and then sulfonated. As such a sulfonating agent, alkali sulfonic acid oleum is preferred. At that time, as fuming sulfuric acid, 2
~3Uffid%, preferably 5-20% fLJ1 of 3
It is advantageous to use a fuming 4iIt acid containing sulfur oxide. In the sulfonation by this method, the inert solvent used may be any solvent that does not react with chlorosulfonic acid and fuming sulfuric acid. The bath additives include carbon tetrachloride, methylene chloride, methylene bromide, and lye+cy.
Halogenated hydrocarbon threads such as form, dichloroethane, and trifluoroethane are preferably used. Generally, sulfonation with sulfuric acid is carried out without a solvent, and sulfonation with real sulfonate is carried out without a solvent or with an inert bath agent in order to control the reaction. When sulfuric acid is used, it is generally used in excess relative to the polypene/nimita/kun polymer, since it also serves as a bath agent, as described above. In addition, when using chlorsulfonic acid, the amount is 1% to 50% based on the polybenzimidacylon polymer.
The range of 1 kqb to 20 times is preferable. Generally, polybenzimidazo [1] is dissolved in chlorosulfonic acid as described above. Polybenzimitazocune is often not dissolved, and usually reacts with vigorous stirring while making polybenzimitazocune cloudy. Therefore, the reaction temperature is -10'C~I
The reaction time is preferably in the range of 50'C to 120'C.The reaction time depends on the required degree of sulfonation and the concentration of the reaction reagent, but is generally 5 minutes to 20 hours, preferably The period of time is from 10 minutes to 15 hours.The structure and degree of sulfonation of the polybenny!-dacinopolymers having pentanant sulfonic acid groups obtained by these methods are determined by infrared absorption spectra and nuclear magnetism. This can be confirmed by methods such as resonance spectroscopy and elemental analysis.Particularly when used as a membrane, the reactivity as the original bond and the reaction of the pendant sulfonic acid groups can be confirmed as described in the separately filed invention by the present inventors. Taking advantage of this property, it is also possible to crosslink the film by reaction with a crosslinking agent during or after film formation, resulting in a film with improved compaction properties, chemical resistance, etc.Next, the polymer related to the present invention The permselectivity using the membrane and its production method will be described below.The polymer used for the membrane in the present invention preferably has film-forming ability itself, and its intrinsic viscosity is generally (1.4 or more, preferably, (A value of 0.6 or more is preferably used.) However, as mentioned above, when a crosslinking agent is present during film formation to form a 1!8! film without crosslinking, this is not the case. The selectively permeable membrane of the present invention is usually obtained by #! membrane from a solution mainly containing an organic F14 medium.The organic solvent may be any organic solvent as long as it is inactive and can substantially dissolve the polymer VC. -4-7 (In other words, it is preferable to use a material that can be dissolved in a bath at room temperature as well as in a heated state to form a homogeneous shape, but a material that leaves some uneven areas is also acceptable.Also, if necessary, lithium chloride, The solubility can also be increased by adding an inorganic salt such as calcium chloride. In order to obtain the selectively permeable membrane of the present invention, suitable solvents that can be preferably used during membrane formation include N-methyl Pyrrolidone, N-methylsololactam, N,N-
dimethylacetamide, hexmethylbosphoramide,
Examples include amide-based solvents such as tetramethylene iodine; sulfoxide-based solvents such as dimethylsulfogycete; Also, using these solvents, polymer bath liquid f/
When adjusting, add an appropriate diluent to improve the properties of rice cake, dryness,
Coagulability etc. can be investigated. In addition, if the polymer is obtained as a uniform bath liquid at the layer end of the polymer mentioned above, It can be used as is as a stock solution for book binding. The selectively permeable membrane of the present invention may be formed into various forms, such as a flat plate or a tubular film, or a hollow fiber, depending on the form of use. When used in the form of a film, a method can be adopted in which, for example, a porous flat plate or a ridge-shaped base material and a thin film made of the polymer of the present invention are integrated. Such a thin film usually has a thickness of 0.06μ or more and IOβ or less.
C is used. Conventionally known techniques can be used for forming the thin film and for contacting or integrating the thin film with the porous substrate. For example, a stock solution for a membrane is cast onto a belt or a flat support to a desired thickness, the solvent is removed by drying or other means, and the resulting thin film is peeled off from the support. If necessary, a method of integrating with the porous material using an adhesive or the like may be used. Further, other methods for integration with the porous substrate include roll coating and coating. A method of directly coating the base material with the stock solution by dipping or the like may also be adopted. For the production of such thin films, it is advantageous to use stock solutions containing at least 0.5% by weight of the polymer, particularly preferably at least 1.11% by weight and not more than 10% by weight. However, the drying temperature varies depending on the whaling solvent, but the drying time is 5 o
~25 fl'C is preferably used. Other forms that can be used as a film include the above-mentioned L
Asymmetric structure similar to cellulose acetate membrane by oeb etc.
That is, there is a membrane with a smooth epithelial layer and a relatively porous lower layer with a 2m structure. To obtain such an asymmetric structure, for example, a wet membrane e
In this method, only one side of the membrane surface is brought into contact with the coagulation liquid to cause coagulation from that side; in dry membrane formation, the solvent is similarly evaporated from one side of the membrane surface, and some of the solvent remains. Immerse the partially solidified film in leachate with residual
Any method that extracts and removes the remaining solvent etc. may be used. In this case, inorganic salts, organic salts, or other organic compounds with a molecular weight of 5 (10 or less) that has an average size and volatilization rate different from those of the organic solvent used should be added to the film-forming stock solution. By removing it during extraction, the permselectivity can be greatly improved. Examples of effective additives include lithium chloride and odour-11S lithium. Inorganic materials such as calcium chloride and lithium nitrate. Examples include salts and organic substances such as formamide.The ratio of the additive to the polymer varies depending on the aI group of the heptamer and the static medium used, but is generally preferably 5 to 60% by weight.Partial solidification The membrane can be obtained by hardening the film-forming stock solution on a flat plate (cast to the desired thickness on a tubular support and opened on one side) for 1 hour. The suitable film forming temperature is the unique solvent and casting temperature.It may vary depending on the drying time and wind speed, etc., or the general VC40~
A range of 200° C., preferably 60 to s 5o C is reasonable. Partially solidified membranes contain 200 to 25
Preferably, a weight-related solvent and cooling agent remain. The partially solidified membrane thus obtained can be immersed in a leachate to remove most of the solvent J6 and additives remaining in the membrane, thereby obtaining the desired selectively permeable membrane. . The leachate used in this case is a liquid V that is compatible with the organic solvent and additives (and has a soluble level of -4 and is chemically inert with respect to the polymer). It is necessary to add k 74. Specific examples thereof include water, methanol, ethanol, or a mixture thereof, but water is the most suitable. The leaching temperature is generally -20 The temperature range is from ℃ to 50℃.If the leaching operation is performed at too high a temperature, the leaching rate will increase, but devitrification and other non-uniform areas may occur, which may seriously impair the performance of the membrane. In general, it is preferable for the leaching time to take about 10 minutes for most of the remaining substances in the partially solidified membrane, such as the solvent and added salt, to be leached out.After leaching, the membrane is hydrated in water. It is preferable to store the membrane as it is.After most of the above-mentioned residues have been leached out, the membrane can be treated with hot water at 50 to 95°C for a short period of time to further improve performance such as salt rejection rate. (The thickness of the selectively permeable membrane with an asymmetric structure obtained by this method is generally 1() to 500μ, preferably 4() to 2rO1).
Used in the μ range. Another example of the membrane type used is hollow fiber. In this case, the above-mentioned stock solution is extruded using a spinneret in the inner wall, and a film is formed by a known method such as a wet method, a dry method, or a combination of both methods. be able to. Further, in the case of SO&J, a diameter of 20 to 150μ, a wall thickness of 5 to 40μ, and a hole size of $0.1 to $0.6 are generally used. The selectively permeable membrane containing pentantosulfone #1M as a main component over the sulfur-polypenne imidazolone has superior chemical properties of the corresponding polypenneimidazolone selectively permeable membrane without pentantosulfone #1M. However, the water transport rate has been greatly improved due to the increased hydrophilicity fL', and it is possible to secure a lower pressure °C water permeation rate, making the original model υ) and I) more economical. This allows easy operation and can be suitably used in a wide range of applications as mentioned above. The present invention will be described in more detail below with reference to Examples, but the Examples are for illustration only and are not intended to be limiting. In addition, the intrinsic viscosity in the examples is 11.5 j// 111
am/polymer roughness 0N-methylpyrrolidone (hereinafter NMP
+%i") 8M, measured at 30'C.' Also, the inverse &a actual g is 4t+ky/oA, 1
% NaC6 aqueous solution.
This is the amount obtained by titration with 0.1NH (J) after HfjL concentration. 18.02 parts of di-7minodiphenyl ether, 3.44 parts of 2.2'-benzidine disulfonic acid, and 21.2 parts of anhydrous carbonic acid sorter were mixed with 2 s of dimethyl sulfoxide (roughly translated to 1 m, 1
(Heating and stirring were continued at 10°C for 20 hours. After the reaction, reaction f# was added to a large excess of water to obtain 51.0 parts of an orange-red polymer. The intrinsic viscosity of this polymer σ) was 0.43. there were. The polymer was suspended in a mixed medium of 11)0 parts of Meknol and 15) parts of water, and sodium I-itrosulfite 7.
5 parts were added and stirred for 2 hours at 75'C. C) After l>r, add to the large spear of water and thoroughly bathe with inorganic salt) After washing with water for 1 time,
40 parts of a gray-white polymer with an intrinsic viscosity of +1.7517 J after drying was obtained. σ) Polymer with N-methylpyrrolidone 200%
23 parts of carbonic acid sorter was added thereto, and 30 parts of chlorine acid salt was added dropwise, and the mixture was stirred for about 4 hours.
The reaction solution was added to the water containing a large amount of water to form a brown polymer 5.
I got 0@S. The intrinsic viscosity of this polymer g kA, 11
, li :4 Te1-. Tsuta. Based on the elemental analysis value and 7/I(YIlk II!) spectrum of this polymer, it was confirmed that it is polyether imine sulfone as shown by the following formula. [However, -CL) OEt is -COOC, bird represent. ]
50tfl of this polymer was converted into N-methylbi, 1/4
5 () parts, heated at 160°C ((stirred) for 3 hours, cooled and then added to a large excess of water for 441 hours. 42 parts of polymer was obtained. Polymer υ) L, 4 ; I viscosity was 0.62. Elemental analysis values were C: 48.+12%, H2: 2.32%. H: 29.97918. 8: 5.87, expressed by the following formula. Calculated values when considering polybenzimidacylon C: 47,96 units, If: 2,48 units, N: 3
11.124. S: There was good agreement with Sections 5 and 91. The infrared absorption spectrum of a film prepared from a solution of this polymer in N-methyl bichloride contains 2500~
370 (l cm-', 1080 c
m-', 1020 tx-'l' The first absorption based on sulfonic acid groups was observed. Before ion exchange, it was 0.32 milJ/i#, /11. Kyo combination 15s obtained in this way, lithium chloride 4.
A film-forming stock solution consisting of 5 parts of N-methylpyrrolidone and 85 parts of N-methylpyrrolidone was subjected to ilJ treatment. The stock solution was cast onto a glass plate using a doctor blade with an aperture of 50 ()μ, and heated at 14 (1'C, 9
After drying for a minute, the membrane was immediately immersed in ion-exchanged water for 24 hours to remove any residue in the membrane and obtain an asymmetric membrane. This membrane was subjected to a reverse osmosis experiment.
rrt-hr and desalination rate of 96.7 qb was obtained. Work 912 4.4'-Diquaru: 37.73 parts of 3'-dinitrodiphenyl sulfone, 6,02 parts of 1,4'-di-minodiphenyl ether, 2.2'-benzidine sulfone l! l! 6.89 parts and disaster acid suchiu A, I1.
In addition to 200 parts of 76 1kN-methylpyrrolidone, 14
Continue heating and stirring at 0°C for 16 hours. [Reaction] 1) At the end of the experiment, add the reactant to a large excess of water to form an orange-red borine (53
part) was collected. The intrinsic viscosity of this polymer is 0.41
Met. 50 parts of this polymer was mixed with Example 1 (
A reduction reaction was carried out in the same manner, followed by a urethane reaction using ethyl alkyl carbonate, and then heating to obtain 49 parts of a brown polymer. The elemental analysis value of this polymer is C:
5111.53chi, H: 3.17%, N: 10.
lJ2'l S: 8.43, calculated value when considering polybenzimitazolone shown by the following formula, C:
59.44%, )l: 3.08%, N: 10.
67%, 8:8.54%, which showed good agreement. In addition, the ion concentration of the stiff polymer was 0.772 mm/y. This value is a calculated value, 0.761 milliequivalent/
Good agreement was shown for the value of l. In addition, the infrared absorption spectrum is 1020 F-', 1080
Slightly strong absorption based on sulpon was observed in α-1. When this polymer was formed into a film in the same manner as in Example 1 and subjected to a reverse osmosis experiment, water permeability j#451/m'- hr, desalination rate was 93.7 qb. Example 3 494'-dichloro-3937-dinito a diphenyl 7
Polymerization reaction, reduction reaction, Lanthanization reaction. After a ring-closing reaction, the following formula was obtained: The ion exchange rate of this polymer was 1,295 JlJ/
I, showing good agreement with the calculated value of 1,280 mm/t/v. This polymer was formed into a film in the same manner as in Example 1, and subjected to a reverse osmosis experiment. The water permeability Ji was 53 liter/hr and the salt removal rate was 93.5.
He was in charge. Example 4 4.4'-dichloro-3,3'-dinito a diphenyl sulfone 37.73% (i, 4,4'-diaminodiphenyl ether 13.02 g 11.315-diaminopencensulfone ['iZ 6.59 parts and 1m of charcoal) 11.76 parts of lithium was dissolved in 200 parts of 1m of N-methyl birydium, and the polycondensation reaction, reduction reaction, and polymer reaction using carbonized ethyl were carried out in accordance with Example 2, followed by heating and ring-closing. After treatment, a polybenzimitazolone copolymer as shown in the figure was obtained. The intrinsic viscosity of this polymer is 0.47, and the elemental analysis value C
: 63.11%, J(: 3,37%, ・N:
3.04%, S: 9.43%, total Nli
tC: 63.75%. Good agreement was shown with H: 3.27%, N: 3.31%, and S: 9.61%. This polymer was formed into a film in the same manner as in Example 1 to obtain an asymmetric film. According to reverse osmosis experiments, this membrane has a water permeability of 41551
/rrt-hr, and the desalination rate was 94.1%. Example 5 Stir 10 parts by weight of glue and sulfonic acid using a 150 m thick J-rutaf while cooling with water. Polybenzimitazolone (hereinafter abbreviated as P Is l L) having the structural formula of
(Intrinsic viscosity 0.73) Add 10.83 parts (21 parts). At the same time as the addition, PBIL changed color from pale yellow to black IL. By decantation, you can get even fresher 1,
After washing with 2 g of 2-dicumyl ethane and decantation, the washing was repeated twice with 2oo=u methanol. Thereafter, the polymer was dissolved in 10 parts of N-methylpyrrolidone, and the small amount of insoluble portion was separated by 11=l, then added to a large amount of water, and the polymer was recovered by sedimentation. The intrinsic viscosity of this polymer was 0.98. The ionic father exchange potential of this polymer is 11.697 miIJ equivalent/g, which is m-0
, 366 polybenzimidacylon. Elemental analysis of this polymer +: a is c: 6+
1.21%, H: 3.279b, N: 7,8
5%. S: 8.29 qri, 61 staves considering m = 0, 37. 1st shift C: 59.35%, H: 3,07φ, N
Near, 99%: showed good agreement at 8.35%. Using this left combination, an asymmetric membrane was formed by V straining in the same manner as in Example 1, and a reverse osmosis experiment was conducted.
rr'hr, the salt removal rate was 94.31%. or,
After 200 hours of continuous operation, the water permeation rate was 461 parts.
'hr, and it was confirmed that good compaction performance was exhibited. Example 6 PHIL with intrinsic viscosity 0.73 10. o part 1-f-L
/7 Add a turbidity to 150 parts of chloride. 150 parts of dichloroethane containing 10 f[alpha]sulfonic acid is dissolved under vigorous stirring under ice cooling. After stirring for 4 hours under water cooling, the suspended polymer was filtered through a glass filter, washed with methylene chloride, washed with methanol, dissolved in 90% of N-methylpyrrolidone, and dissolved in a large excess of water. A precipitate of the polymer was obtained by adding to the solution. The intrinsic viscosity of this polymer was 0.63, and the ion exchange equivalent was 0.579 mm/yth. This value is m=(
It was confirmed to be polybenzimidacylon corresponding to 1,3. This left coalescence was formed into a film in the same manner as in Example 1 and subjected to a reverse osmosis experiment.
%, and the amount of water permeation is 411 after approximately 20 () hours of continuous operation.
/rK·klr, and it was recognized that good consolidation resistance was exhibited. Example 7 37.73 parts of 4.4'-dichloro-3,3'-dinitrodiphenyl sulfone, 20.03 parts of 4.4'-diaminodiphenyl ether, and 21.2 parts of sodium carbonate were dissolved in 250 parts of dimethyl sulfoxide, A polymerization reaction similar to that in Example 1 was carried out to obtain 50 parts of an orange-red polymer. The intrinsic viscosity of this polymer was 0.8:4. This polymer was subjected to a reduction reaction with idrosulfite in the same manner as in Example 1, and the obtained reduced polymer 40
1 part was dissolved in 400 parts of N-methylpyrrolidone, 42.4 parts of charcoal soda was added, and ice-cooled FK was added.First, 2.28 parts of methanesulfonic acid arid was added and stirring was continued for 1 hour. Added 29 parts. After stirring continuously for 2 hours, the bath temperature was raised to 160° C., and after stirring at the same temperature for 2 hours and cooling, the polymer was recovered by adding a large excess of water. The intrinsic viscosity of this left coalescence was 0.93, and it was confirmed from the intensity ratio of methyl groups and all benzene rings in the NMR spectrum that it was polybenzimidacylon having the structure of the following formula. The polymer obtained by sulfonation L5 in the same manner as in Example 6 has an intrinsic viscosity Q of 99° and an ion exchange equivalent of 0,565 milJ/N/jl, which means that m is 0.
．． The g equivalent to 30 is Lung G and J. When this polymer was subjected to reverse osmosis experiments using seven asymmetric membranes (as in Example 1), water permeability was 1 t56.(JJ/m'・hr,
It showed a performance of desalination rate of 94.29&. Ma+, +9.゛

Claims (1)

[Claims] A repeating unit represented by the following formula CI) (however, the total average value of m is +1,
Values range from 05 to 2, Ar in each unit, and Ar
, may be two or more different groups each satisfying the above condition. ] of the total repeating units (both 50 mol%
A selectively permeable membrane mainly composed of polybenzimitazo U having pentantosulfonic acid groups.