JPH0543733B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a polymer polyA having an anion exchange group.
The present invention relates to a novel block copolymer comprising, as a part or whole, a cation-selective ion-exchange group or a polymer polyB having a functionality that allows easy introduction of a cation-selective ion-exchange group. It is known that block copolymers that form a unique microphase-separated structure exhibit novel properties due to their heterogeneous structure. For example, block copolymers consisting of polyisoprene or polybutadiene chains and polystyrene chains have found use as thermoplastic rubbers and impact-resistant materials, and block copolymers consisting of polyurethane and polyether, poly( A block copolymer consisting of 2-hydroxyethyl methacrylate (2-hydroxyethyl methacrylate) and polystyrene is expected to be an anticoagulant material. Recently, multi-block copolymers consisting of polymers with cation exchange groups (sulfonic acid groups and carboxylic acid groups), polymers with ion exchange groups (quaternary amine groups), and polymers without ion exchange groups have been developed. It has been reported that inorganic and organic low molecular weight ions can be separated and removed from an aqueous solution by using the combination (Publication of Patent Publication No. 1976-76408) as a separation membrane. However, with this membrane, highly selective separation between ions cannot be expected. After extensive research, the present inventors came up with the idea of imparting a new function to a block copolymer by introducing a selective ion exchange group into one component of the block copolymer, and thus arrived at the present invention. . That is, the block copolymer of the present invention consists of a polymer polyA having an anion exchange group and a polymer having a cation-selective ion exchange group or a functional group into which a cation-selective ion exchange group can be easily introduced.
polyB as a part or whole of the component. The general formula for polymers into which cation-selective ion exchange groups can be easily introduced is , R ₁ is hydrogen or a methyl group,
Rx is _-CH2X (2) (X is chlorine or bromine) or _-COCH3 group(3), or a functional group derived therefrom having the following chemical structure. −CH ₂ NH ₂ (4), −CHO (5), −COCH ₂ Br (6) −COCH ₂ N(CH ₂ CO ₂ R ₂ ) ₂ (9), −COCH ₂ N(CH ₂ CN) ₂ (10) −COCH ₂ N(CH ₂ CH ₂ CN) ₂ (11) −CH ₂ N ⁺ (C ₂ H ₄ OH) ₃ (12) (However, R ₂ is an alkyl group having 1 to 6 carbon atoms) A polymer having a cation-selective ion exchange group is represented by the above formula (1). It is derived from a polymer, and the functional group Rx has the structure shown below. -CH=C(COOH) ₂ (17) −COCH ₂ N(CH ₂ COOH) ₂ (22) −COCH ₂ N(CH ₂ CH ₂ COOH) ₂ (23) −CH ₂ −NH(CH ₂ ( _x --PO(OH) ₂ (28) (However, x is an integer from 1 to 6) Furthermore, in the general formula (1), the monomer units having the functional group Rx account for 20 mol % or more, and all may be monomer units having the functional group Rx. The polymer polyA~ having an anion exchange group of the block copolymer of the present invention is, for example, a polymer of monomers selected from the following monomer group A, which is quaternized by a known method. Monomer group A: 2-vinylpyridine, 4-vinylpyridine, 2-methyl-5-
Vinylpyridine such as vinylpyridine, vinylpyrimidine, vinylquinoline, vinylcarbazole, vinylimidazole and these with 1 carbon number
a compound having 12 hydrocarbon substituents from o, m, p-vinylphenylalkylenedialkylamine represented by (however, R ₃ and R ₄ are each an alkyl group having 1 to 12 carbon atoms, and a is an integer of 1 to 3) in polyA~ The proportion of monomer units into which anion exchange groups are introduced is 20 mol % or more, and the anion exchange group may be introduced into all of the monomer units. The block copolymer of the present invention has the above-mentioned polyA and
In addition to polyB, the component block may contain up to 90 mol % of a polymer polyC having no ion-exchangeable functional group in monomer units. This polyC
The monomers constituting may be diene monomers such as butadiene, isoprene, pentadiene, and cyclohexadiene. Polymers made of such diene monomers can be easily crosslinked using the double bonds present in the polymer by a known method, so if these are included in the component blocks of a block copolymer, the resulting material can be It is possible to improve the solvent resistance of When crosslinking is carried out, it can be carried out to any degree or completely depending on the functionality required of the material. The block copolymer of the present invention has a polymer having an anion exchange group of 20 mol% or more per monomer unit.
polyA and a polymer polyB having 20 mol% or more of cation-selective ion-exchange groups per monomer unit or a functional group that can easily introduce cation-selective ion-exchange groups are 5% or more per monomer unit for each.
It is necessary to contain ~95 mol%. If it is outside this range, the function of the block copolymer material may not be fully exhibited. In addition, in order to increase the solvent resistance of the block copolymer material and stabilize the microphase-separated structure formed, it is preferable to contain 30 to 90 mol% of the polymer polyC made of diene monomers in monomer units. . A preferred method for obtaining the block copolymer of the present invention is a living anionic polymerization method in which an anion exchange group prepared by block copolymerizing a monomer selected from monomer group A and styrene or α-methylstyrene is introduced. Possible polymers
An original block copolymer consisting of polyA and polystyrene or poly(α-methylstyrene) (referred to as polyB), or the above polyA prepared in the same way from three types of monomers in which a diene monomer is added in addition to the above monomers. The first step is to chemically treat the original block copolymer consisting of polyB and diene polymer polyC. The molecular weights of the component polymers polyA, polyB, and polyC that make up these original block copolymers are 10 ³ to 10 ⁶
g/mol is desirable. More preferably, it is 10 ⁴ to 5×10 ³ g/mol. As is generally well known, in a block copolymer, as the molecular weight decreases, the proportion of compatible interface areas formed between domains formed by microphase separation increases. According to experimental facts published so far, the molecular weight of each component block is 10 ³ g/
A clear phase separation structure is not formed below mol.
On the other hand, if the molecular weight of the sample is too large, the viscosity of the molten or solution state will be high, making it extremely difficult to mold the sample. The original block copolymer used in the present invention has the above polymers polyA, polyB, and polyC, for example, (polyA-polyB) x, (polyA-polyB) _x ---
polyA, polyB (-polyA-polyB) x, (polyA-
polyB−polyC) _x , (polyB−polyA−polyC)x,
(polyA−polyC−polyB)x, (polyA−polyC−
polyB−polyC)x, (polyC−polyA−polyC−
polyB)x, polyC−polyA−polyB−polyC, polyC−
polyA−polyC−polyB−polyC, polyA−polyC
−polyB−polyC−polyA, polyB−polyC−
polyA−polyC−polyB, polyA−polyB−polyC
−polyB−polyA, polyB−polyA−polyC−
polyA−polyB, polyC−polyA−polyB−polyA
−polyC, polyC−polyB−polyA−polyB−
Any combination of polyC (where x is an integer of 1 or more) may be used. Also, polyB with polyA as a branch, polyA with polyB as a branch, and polyA.
polyC with polyB as a branch, polyA-polyC type (or polyB-polyC type) polyB (or polyA) with a block copolymer as a branch, polyC-polyA
- polyB (or
polyA). Among these, polyA and polyB are separated from each other by polyC and bonded together (for example, polyA-polyC-polyB), when the content of polyC is appropriate, the final ion exchange When the microphase-separated anion exchange region and the cation-selective ion exchange region are isolated from each other in the body, the microphase-separated structure becomes stable, which is preferable for use as a functional material. The block copolymer of the present invention can be produced by quaternizing the nitrogen atom of the polyA portion of the original block copolymer described above before, after, or simultaneously with molding to form a polymer polyA~ having an anion exchange group. Cross-link the polyC part according to
After chloromethylating or acetylating the polyB moiety, a cation-selective ion exchange group may be introduced therein by a known method. Crosslinking of the polyC moiety introduced as necessary may be carried out at any stage to the extent possible. You can go. The quaternization reaction of nitrogen atoms is BrC _l H _2l+1 and IC _l H _2l+1
(l is an integer from 1 to 12) or Br(-CH ₂ ) _l Br or I(-CH ₂
) It can be easily carried out using a vapor or solution of an alkylene dihalide represented by _l ---I. Polydiene moieties are exposed to peroxides, sulfur, sulfur monochloride, ultraviolet light, or AlCl ₃ , SbCl ₃ , FeCl ₃ ,
Crosslinking can be easily carried out using Friedel-Crafts catalysts such as TeCl ₂ , SnCl ₄ , TiCl ₄ , BF ₃ , H ₂ SO ₄ and the like. Moreover, hydrogenation can also be carried out. Halomethylation of polystyrene or poly(α-methylstyrene) can be easily performed using formaldehyde and hydrogen halide, and chloromethylation can be easily performed using chloromethyl methyl ether. Further, their acetylation can be carried out by a known method using acetyl chloride and the above-mentioned Friedel-Crafts catalyst. Furthermore, in the halomethyl group, If we act on the functional group of (13), If you act on it, you will get the functional group (8), if you act on it with ammonia you will get the functional group (4), and if you act on it with (CH ₂ ) ₆ N ₄ you will get the functional group (5).
(Sommelet reaction), (27), aminophosphoric acid (28), and triethanolamine (12) can be obtained. In addition, if Br ₂ acts on the acetyl group (3), (6),
When HSCH ₂ COOH is used, (21) and PCl ₃ are used to obtain (25). Furthermore, in (4) If we act on it, we get (7), and if we hydrolyze (7), we get (14) and (5).
Treatment with NH ₄ OH, KCN and acid yields (15) and (5).
When treated with CH ₂ (COOH) ₂ and NH ₄ OH, (16) and (17),
Hydrolyzing (3) gives (13), (14) gives (20), and (15 ₎ gives (18) and ₍ 16). By acting with ClCH ₂ COONa, (19) can be obtained. Furthermore, if (6) is treated with NH (CH ₂ COOC ₂ H ₃ ) ₂ , it becomes (9), and if (9) is hydrolyzed, (22), (6) becomes NH
If treated with (CH ₂ CN) ₂ , (10), if (10) is hydrolyzed, (22), if (6) is treated with NH (CH ₂ CH ₂ CN) ₂ , (11),
If (11) is hydrolyzed, (23) is obtained, (22) is treated with PCl ₂ (24), (22) is treated with HSCH ₂ COOH (26), and (23) is treated with PCl _3. ba (30), (23)
When treated with HSCH ₂ COOH, (31) can be obtained. Moreover, (29) can be obtained by oxidizing (12). The above-mentioned individual reactions are known, and representative documents are listed below. RB Wagner and HDzook, “Synthetic
Organic Chemistry”, New York, John
Wiley & Sons, Inc. (1953) LRMorris et al., Journal of American
Chemical Society, Volume 81, Page 377 (1959
) EB Trostyanskaya et al., Journal of
Polymcr Science, Volume 59, Page 379 (1962) M. Marshall and KLCheng, Talanta, Volume 21,
Page 751 (1974) Edited by Shumasa Hojo, "Chelate Resin/Ion Exchange Resin", Kodansha Scientific (1976) The original block copolymer used in the present invention is produced by, for example, a living anionic polymerization method. be able to. In this case, as the polymerization initiator, known butyllithium (n, sec, tert), 2-methylbutyllithium, sodium naphthalene, sodium anthracene, α-methylstyrene tetramer sodium, sodium biphenyl, etc. are used. , aromatic hydrocarbons, cyclic ethers, aliphatic hydrocarbons (generally benzene,
Toluene, tetrahydrofuran, n-hexane,
Polymerization is carried out in a vacuum or an inert gas atmosphere such as nitrogen gas or argon gas (for example, cyclohexane is used). The block copolymer of the present invention has a region A having an anion exchange group and a region B having a cation-selective ion exchange group or a functional group into which a cation-selective ion exchange group can be easily introduced, or A~, B~
It has a micron phase separation structure consisting of two regions and a region C~ having no ion exchange group. Each region exists as a lamella, sphere, rod, or matrix phase, but these forms depend on the composition and molecular structure of the original block copolymer. In addition, the width of the lamella and the diameter of the sphere or rod are usually from several nm to several hundred nm.
It is. In this way, due to the micro-heterogeneity structure,
The block copolymer of the present invention exhibits unique functions. They can be arbitrarily formed into films, tubes, fibers, gels, etc. In addition to ion selective permeable membranes used for ion analysis and waste liquid treatment, they can also be made from conductive materials,
It is expected to have many uses such as biomedical materials. The present invention will be explained below with reference to Examples. In addition, in order to quantify the phosphoric acid group or carboxylic acid group introduced into the film in the examples, the film was soaked in a dilute aqueous sodium hydroxide solution (PH
≒12) for 20 hours, washed with water, and then soaked in 0.5N hydrochloric acid for 20 hours.
After soaking for an hour, the sodium ions released from the membrane were quantified. In addition, to measure the anion exchange capacity (quantification of quaternary amino groups), after treating the membrane with a dilute aqueous sodium hydroxide solution, immerse the membrane in a 1 mol/aqueous potassium chloride solution for 20 hours, and then immerse the membrane in a 1 mol/aqueous potassium chloride solution. This was done by soaking the membrane in water for 20 hours and quantifying the amount of chlorine ions released from the membrane. here,
Quantification of sodium ions and chloride ions was performed by conventional methods. For the determination of primary amino groups (-NH ₂ ), use an excess amount of sodium nitrite standard solution (0.1N).
After treating the film for 20 hours with 2N hydrochloric acid containing
This was carried out by standardizing unreacted sodium nitrite using sulfanilic acid by a known method. Example 1 In benzene purified through a sodium mirror,
Using 3.5 x 10 ^-4 mol of sec-butyllithium as an initiator, styrene, 4-vinylbenzyldimethylamine (hereinafter abbreviated as 4-VBDMA), and butadiene were mixed into 6.5 g of butadiene, 12 g of styrene, 7.0 g of butadiene, and 19 g of 4-VBDMA. , 6.5 g of butadiene were added every 20 hours in 5 steps to carry out polymerization.
An original block copolymer of polyC-polyA-polyC-polyB-polyC type was synthesized. The polymerization temperature is 4-
Polymerization was carried out at 20°C for VBDMA and 30°C for other monomers in a vacuum-sealed glass vessel. The polymerization yield was approximately 100%. The molecular weight per block of the final polymer was determined from the intermediate polymer, final polymer, and number average molecular weight determined by membrane osmotic pressure method, and the first polymerized polybutadiene block was 1.9 x 10 ⁴ g/mol, and the polystyrene block was 3.5. ×10 ⁴ 2/mol, the central polybutadiene block contains 2.0 × 10 ⁴ g/mol, poly(4-
VBDMA) block is 5.5×10 ⁴ g/mol, and the final polymerized polybutadiene block is 1.8×10 ⁴ g/mol.
mol, which almost agreed with the value calculated from the monomer weight and the number of moles of initiator. Using a 5% by weight benzene solution of the original block copolymer thus obtained, a film with a thickness of about 60 μm obtained by solvent evaporation on a mercury surface was stained with an osmic acid aqueous solution and then subjected to transmission electron microscopy. When observed, a three-phase lamellar structure was observed in which the polybutadiene layer (B), polystyrene layer (S), and poly(4-VBDAM) layer (A) were regularly arranged in -B-S-B-A- repeating units. existence was confirmed. 0.3 g of a film similarly prepared from this original block copolymer was left in methyl iodide vapor at room temperature for 10 hours to quaternize the A portion, and then placed in 100 ml of a 20 volume percent sulfur monochloride solution in nitromethane. Part B was crosslinked by soaking at room temperature for 3 hours. This crosslinking reaction caused the infrared absorption band caused by the double bonds in polybutadiene to almost disappear, confirming that the degree of crosslinking in the polybutadiene portion was close to 100%. Further, this film was immersed in 45 g of chloromethyl ether, kept at 3°C, 15 g of aluminum chloride was added as a catalyst, and the film was left at the same temperature for 5 hours to chloromethylate the polystyrene portion. When the anion exchange capacity of the obtained film was determined using a conventional method, the measured value was 85% higher than the calculated value.
It was %. Furthermore, as a result of ¹³ C-NMR measurement, the presence of 0.82 chloromethyl groups per styrene monomer unit was confirmed. When this film was treated with a 1% aqueous solution of osmic acid and observed under a transmission electron microscope, it was found that the original lamellar structure was maintained without being significantly disturbed. Example 2 0.3 g of a 60 μm thick film prepared from the original block copolymer obtained in Example 1 was subjected to quaternization of the poly(4-VBDMA) portion and crosslinking of the polybutadiene portion in the same manner as in Example 1. Ivy. Furthermore, this film was immersed in 50 ml of carbon disulfide, and 15 g of aluminum chloride and 10 g of acetyl chloride were added.
was added, and the reaction was carried out under reflux for 5 hours to introduce acetyl groups into the polystyrene portion. The film obtained through this chemical treatment exhibits an infrared absorption band characteristic of carbonyl groups around 1690 cm ^{-1 13} C-NMR.
From the measurement results, 0.81 per styrene monomer unit
It was found that it has several acetyl groups. Furthermore, as a result of transmission electron microscopy, it was confirmed that the initial lamellar structure was basically maintained. Example 3 0.3 g of a 60 μm thick film prepared from the original block copolymer obtained in Example 1 was subjected to quaternization of the poly(4-VBDMA) portion and crosslinking of the polybutadiene portion in the same manner as in Example 1. Ivy. Furthermore, Example 1
After chloromethylating the polystyrene portion in the same manner as above, the film was refluxed with a 20 weight percent hexamethylenetetramine solution in chloroform for 5 minutes.
Treatment was performed for a period of time, washing with methanol, and finally treatment with water at 90°C for 5 hours. From the measurement results of the infrared absorption spectrum and H-NMR spectrum of the obtained film, it was confirmed that the chloromethyl group was converted to a formyl group (-CHO). That is, in the ¹ H-NMR spectrum, δ=4
The peak derived from the hydrogen of the chloromethyl group around ~5 disappears, and a new peak derived from the hydrogen of the formyl group around δ = 10 appears, and in the infrared absorption spectrum, the C=O of the aldehyde appears around 1700 cm ^-1 . An absorption band originating from this appeared. Further, the anion exchange capacity of this film was 72% of the calculated value. Example 4 0.3 g of a 60 μm thick film prepared from the original block copolymer obtained in Example 1 was subjected to quaternization of the poly(4-VBDMA) portion, crosslinking of the polybutadiene portion, and polystyrene treatment in the same manner as in Example 1. Partial chloromethylation was performed. Furthermore, this film was treated with a mixture of 6.7 g of iminodiacetic acid disodium salt, 3.3 g of sodium hydroxide, 50 ml of dioxane, and 50 ml of water at 60°C for 1 hour to remove the chloromethyl groups. Converted to base. The obtained film showed a strong infrared absorption band near 1700 cm ^-1 that is characteristic of carboxylic acid groups.
When this carboxylic acid group was measured by sodium quantification, it was found that 1.2
It was found that there were 8.2×10 ⁻⁴ equivalents of carboxylic acid groups. Further, the anion exchange capacity was 60% of the calculated value (4.2×10 ^-4 equivalent). Example 5 0.3 g of a 60 μm thick film prepared from the original block copolymer obtained in Example 1 was subjected to quaternization of the poly(4-VBDMA) portion, crosslinking of the polybutadiene portion, and Chloromethylation of the polystyrene moiety was performed. The obtained film was immersed in 100ml of benzene,
After leaving it for a day and night, add ammonia to it for 20 minutes.
After saturation at 40°C, the mixture was gradually heated to 40°C for another 5 hours, and then left at 20°C overnight to complete amination of the chloromethylated polystyrene moiety. 20g/20g of film aminated in this way
dl was immersed in an ether solution of diethyl maleate and reacted at 30℃ for 7 days to remove the aminomethyl group. Converted to base. Next, the film was immersed in acetone, concentrated hydrobromic acid was added dropwise to it, and the film was refluxed for 20 hours to hydrolyze the ester. Based on. The obtained film showed a strong infrared absorption band near 1700 cm ^-1 that is characteristic of carboxylic acid groups. Also,
When this carboxylic acid group was measured by sodium quantification, it was found that there were 1.5 carboxylic acid groups per styrene monomer unit. Also,
The quaternary amino group was 62% of the calculated value. Example 6 Film obtained by acetylation in Example 2
After 2 hours of soaking 0.4g in 100ml of phosphorus trichloride,
Add 60g of glacial acetic acid to this and leave it for 10 days to phosphorylate the acetyl group. Based on. Next, this film was immersed in water at 0°C and washed with water and dilute alkali. The obtained film showed a strong infrared absorption band characteristic of the phosphorus-oxygen double bond in the region of 1250 to 1300 cm ^-1 . Furthermore, when the number of phosphoric acid groups introduced into the membrane was quantified, it was found that there were 0.65 phosphoric acid groups per styrene monomer unit. Example 7 In benzene purified through a sodium mirror,
Using 2.9×10 ^-4 mol of sec-butyllithium as an initiator, 9 g of isoprene, 15 g of styrene, and butadiene.
Polymerization was carried out by adding 18 g of 2-vinylpyridine and 18 g of 2-vinylpyridine in this order every 20 hours in 4 steps.
A polyB-polyC-polyA type original block copolymer was synthesized. The polymerization temperature was 20°C for 2-vinylpyridine and 30°C for other monomers.
Polymerization was carried out in a glass container sealed under vacuum. The polymerization yield was approximately 100%. The molecular weight per block of the final polymer was determined from the number average molecules of the intermediate polymer and the final polymer determined by the membrane osmotic pressure method, and the polyisoprene block was found to be 3.0×10 ⁴ g/
mol, polystyrene block is 5.3×10 ⁴ g/mol,
Polybutadiene block is 6.2×10 ⁴ g/mol, poly(2-vinylpyridine) block is 6.3×10 ⁴
g/mol, which almost coincided with the value calculated from the monomer weight and the number of moles of initiator. Using a 5% by weight benzene solution of the original block copolymer thus obtained, a film with a thickness of about 60 μm obtained by solvent evaporation on a mercury surface was stained with an osmic acid aqueous solution and examined using a transmission electron microscope. Upon observation, the polydiene layer (D) and polystyrene layer
(S) and the poly(2-vinylpyridine) layer (P) were confirmed to have a three-phase lamellar structure in which repeating units of -D-S-D-P were regularly arranged. 0.3 g of a film similarly prepared from this original block copolymer was placed in diiodopropane vapor at 40°C.
After leaving for 8 days to quaternize the P moiety, a solution of 20 volume percent sulfur monochloride in nitromethane was added.
ml for 3 hours at room temperature to crosslink portion D.
Furthermore, this film was immersed in 100 ml of carbon disulfide, and 30 g of aluminum chloride and 20 g of acetyl chloride were added.
was added to this, refluxed for 2 hours, and then heated to 30°C.
This was left for 2 days to introduce acetyl groups into the polystyrene portion. The film obtained in this way
From the results of ¹³ C-NMR measurement, it was found that 0.85 acetyl groups were introduced per styrene monomer unit. In addition, as a result of transmission electron microscopy,
It was confirmed that the lamellar structure was basically maintained. Example 8 0.4g of film acetylated in Example 7
was immersed in 100 ml of glacial acetic acid, and while cooling using an ice bath, 10 g of bromine was added dropwise thereto, and the mixture was left to stand for 8 hours to remove bromine from the acetyl groups. This film was immersed in 100 ml of N,N'-dimethylformamide, 20 g of iminodiacetonitrile was added thereto, kept at 90°C for 6 hours, washed with water and acetone, and then immersed in 100 ml of concentrated hydrochloric acid. Heat treated for 50 hours, followed by watering the film for 50 hours.
ml, 30 ml of ethanol, and 9 g of barium hydroxide at 80° C. for 6 hours to hydrolyze the cyano groups. Through the above operations, the acetyl group was converted into ₂ -COCH ₂ N(CH ₂ COOH) groups. The obtained film showed a strong infrared absorption band characteristic of carboxylic acids around 1700 cm ^-1 . Furthermore, when this carboxylic acid group was quantified, it was confirmed that there were 1.1 carboxylic acid groups per styrene monomer unit. Example 9 A film with a thickness of approximately 60 μm (0.3 μm) was prepared from a benzene solution of the original block copolymer obtained in Example 7.
In the same manner as in Example 7, the poly(2-vinylpyridine) moiety was quaternized and the polydiene moiety was crosslinked. Furthermore, the polystyrene moiety was chloromethylated in the same manner as in Example 1, and then the chloromethyl group was converted into a formyl group in the same manner as in Example 3. The introduction of formyl groups into the film was confirmed by infrared absorption spectrum and ¹ H-NMR spectrum. Example 10 The film finally obtained in Example 9 was mixed with 5.4 g of ammonium chloride, 5.1 g of sodium cyanide, 10 ml of concentrated ammonia water, 25 ml of methanol, and 30 ml of water.
ml of the mixed solution and left at 35°C for about 3 hours. Next, add 16g of sodium hydroxide to this liquid.
A mixed solution of 25 ml of methanol and 100 ml of water was added thereto, and the mixture was left to stand under reflux for 2 hours. Thereafter, the film was taken out and washed with dilute hydrochloric acid. By the above operations, the formyl group is Converted to base. When the primary amino groups and carboxylic acid groups contained in the obtained film were quantified, they were found to be 0.25 and 0.24 per styrene monomer unit, respectively.
It was about the same amount as Ko. Further, the amount of quaternary amino groups was about 50% of the value calculated from the weight of the film before chemical treatment and the monomer composition. Example 11 The film finally obtained in Example 9 was immersed in a mixture of 19 g of malonic acid, 9 g of concentrated aqueous ammonia, and 80 ml of ethanol, left to stand under reflux for 3 hours, the ethanol was removed by distillation, and the film was soaked in sodium carbonate. immersed in a 0.1M aqueous solution (45°C) of Further, this film was immersed in dilute hydrochloric acid at 2 to 5° C. for 5 hours, and washed with dilute aqueous alkaline solution and water. By the above operations, the formyl group is Converted to base. The amounts of primary amino groups and carboxylic acid groups contained in the obtained film were approximately equal to 0.32 and 0.31 per styrene monomer unit, respectively, and the amount of quaternary amino groups was about 55% of the calculated value. Example 12 0.4 g of the film obtained by acetylation in Example 7 was subjected to bromination of acetyl groups in the same manner as in Example 8. Next, this film was immersed in 50 ml of ethyl acetate, and while refluxing, a solution obtained by mixing 50 ml of ethyl acetate and 30 g of ethyl iminodiacetate was added dropwise over 1 hour. It was left at a low temperature for 20 hours. By the above procedure, the acetyl group is converted to −COCH ₂ N(CH ₂ COOC ₂ H ₃ ) ₂
Converted to base. Furthermore, in order to hydrolyze this ester group to make -COCH ₂ N (CH ₂ COOH) ₂ groups,
The film was immersed in acetone, concentrated hydrobromic acid was added dropwise thereto, and the mixture was refluxed for 20 hours. The obtained film showed a strong infrared absorption band near 1700 cm ^-1 that is characteristic of carboxylic acid groups, and when the number of carboxylic acid groups was quantified, it was found that there were 1.3 carboxylic acid groups per styrene monomer unit. Also, 4
The number of grade amino groups was 60% of the calculated value. Example 13 0.3 g of the film finally obtained in Example 12 was subjected to a phosphorylation reaction in the same manner as in Example 6, and -
COCH ₂ N (CH ₂ COOH) ₂ units Converted to base. The obtained film showed strong infrared absorption bands of C=O bonds near 1700 cm ^-1 and strong infrared absorption bands of phosphorus-oxygen double bonds in the region of 1250 to 1300 cm ^-1 . In addition, elemental analysis shows that phosphorus atoms are carbon atoms.
It was 3.6% by weight. If the number of phosphate groups is calculated from this value, it will be about 0.5 groups per styrene monomer unit, and the cation exchange capacity determined from the sodium determination method described above is 1.4 ₁ × 10 ^-3 equivalents, which is consistent with this. Example 14 0.3 g of a 60 μm thick film prepared from a benzene solution of the original block copolymer obtained in Example 1
was allowed to stand in methyl iodide vapor at room temperature for 10 hours to quaternize the poly(4-VBDMA) portion, resulting in a concentration of 2 g/dl.
The polybutadiene portion was crosslinked by treatment with a solution of stannic chloride in n-hexane at room temperature for 4 hours. Furthermore, the polystyrene portion was acetylated in the same manner as in Example 2. Next, the film was placed in a mixture of 10 g of anhydrous zinc chloride and 100 ml of chloroform.
To this, 30 g of thioglycolic acid was gradually added over 1 hour, and the mixture was left to stand under reflux for 15 hours. After cooling, the film was washed with acetone, dioxane, and water. These steps will make the styrene part introduced a group. This film was immersed in 1N hydrochloric acid for 20 hours to change the counterion of the amine portion to chlorine, then dried and elemental analysis revealed that carbon was 70.9% by weight, nitrogen was 2.1% by weight, hydrogen was 8.2% by weight, and oxygen was 7.2% by weight. % by weight, 6.1% by weight of sulfur, and 5.5% by weight of chlorine.
Calculating the number of -SCH ₂ COOH groups from this carbon to sulfur weight ratio gives approximately
It will be 1.2 pieces. Further, this film exhibited an infrared absorption band specific to C=O bonds, and the number of carboxylic acid groups was determined to be about 1.2 per styrene monomer unit, as determined by the sodium quantitative method described above.

Claims (1)

[Claims] 1. Consisting of a polymer polyA capable of introducing 20 mol% or more of anion exchange groups per monomer unit and polystyrene or poly(α-methylstyrene),
A polymer capable of introducing cation-selective ion-exchange groups of 20 mol% or more per monomer unit or exchange groups into which cation-selective ion-exchange groups can be easily introduced.
Consisting of polyB and polyC, polyA and polyB each contain 5 to 95 mol% as monomer units,
After introducing an anion exchange group into the polyA part of a block copolymer containing 30 to 90 mol% of polyC monomer units and a molecular weight of each block unit of 10 ³ to 10 ⁶ g/mol, the polyB part is converted to halomethyl. or acetylated, and then introducing a cation-selective ion exchange group or an exchange group into which a cation-selective ion exchange group can be easily introduced into the halomethylated or acetylated polyB moiety,
A method for producing a block copolymer, which is characterized in that crosslinking is carried out using double bonds contained in polyC, if necessary. (Here, polyA is a polymer of monomers selected from the following monomer group A, (monomer group A:
Vinylpyridine, vinylpyrimidine, vinylquinoline, vinylcarbazole, vinylimidazole, and compounds thereof having a hydrocarbon substituent having 1 to 12 carbon atoms, o, m, p-vinylphenyl alkylene diamine represented by (however, R ₃ and R ₄ are each an alkyl group having 1 to 12 carbon atoms, and a is an integer of 1 to 3) Cation selectivity Functional groups into which ion exchange groups or cation-selective ion exchange groups can be easily introduced are (1) -CH ₂ X, -COCH ₃ , (X is chlorine or bromine) (2) -CH ₂ NH ₂ , -CHO , −COCH ₂ Br (3) −COCH ₂ N(CH ₂ CO ₂ R ₂ ) ₂ , −COCH ₂ N
(CH ₂ CN) ₂ −COCH ₂ N (CH ₂ CH ₂ CN) ₂ , −CH ₂ N ⁺
(C ₂ H ₄ OH) ₃ (However, R ₂ is an alkyl group having 1 to 6 carbon atoms) (4) -CH=C(COOH) ₂ −COCH ₂ N(CH ₂ COOH) ₂ , −COCH ₂ N
(CH ₂ CH ₂ COOH) ₂ −CH ₂ −NH(CH ₂ ) _x PO(OH) ₂ , (However, x is an integer from 1 to 6)),
PolyC is a polymer of the following diene monomers. (butadiene, isoprene, cyclohexadiene, pentadiene))