JPS6114215A - Block copolymer and its production - Google Patents

Abstract

PURPOSE:To obtain a block copolymer having a high function of selectively separating ions and being useful for an ionpermselective film, etc., by introducing cation-selective ion exchange groups into one structural component of a specified block copolymer. CONSTITUTION:5-95mol% monomer selected from among vinylpyridine, vinylpyrimidine, etc., is block-copolymerized with 95-5mol% (alpha-methyl)styrene and, optionally, a diene monomer to prepare a block copolymer comprising a polymer block A to which anion exchange groups can be introduced, a polymer block B to which cation-selective ion exchange groups can be introduced and, optionally a diene polymer block C. Next, anion exchange groups are introduced into polymer blocks A of the copolymer, and then polymer block B is halomethylated or acetylated to introduce cation-selective ion exchange groups (e.g., formula I or II) thereinto. In this way, the aimed block copolymer is obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION A novel method comprising, as a part or whole of the components, and a cation-selective ion-exchange group or a polymer poly B having a functionality that allows easy introduction of a cation-selective ion-exchange group. related to block copolymers.

Block copolymers that form a unique microphase-separated structure are known to 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, cation exchange groups (sulfonic acid groups and carboxyl groups)
A multi-block copolymer consisting of a polymer having a ion exchange group, a polymer having an anion exchange group (quaternary amino group), and a polymer having no ion exchange group (Patent Publication No. 1976-76408)
It has been reported that when used as a separation membrane, inorganic and organic low molecular weight ions can be separated and removed from an aqueous solution.

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 arrived at the present invention. .

In other words, the block copolymer of the present invention has a polymer poly A having an anion exchange group and a cation-selective ion exchange group or a functional group into which a cation-selective ion exchange group can be easily introduced. High molecular weight poly.

B is a part or whole of the component.

A polymer into which a cation-selective ion exchange group can be easily introduced is represented by the general formula, where R is hydrogen or a methyl group, and Rx is 1CH*X (21 (X is chlorine or bromine) or -COC111 group (3) or a functional group derived from this having the following chemical structure.

CklzNPb 141 t CHO (sl,
COCH, Br letCH* COt Re 17
1 COC)hN(CIrICN)t (IQ-COCHIN(CHtCOtRt)t)t (91.

-CHtN (CyH40fl)- (1-COCHt
N(CHtC)ttcN)t(lit(However, R2
is an alkyl group having 1 to 6 carbon atoms) A polymer having a cation-selective ion exchange group is one derived from a polymer represented by the above formula (1), and has a functional group Rxb''-
It has the structure shown below.

■ @ Gl) (However, X is an integer from 1 to 6) In addition, in general formula (1), the monomer units having a functional group Rx account for 20 mol% or more, and all monomer units have a functional group Rx. It's okay.

The polymer polyX having an anion exchange group of the block copolymer of the present invention is obtained by quaternizing a polymer of monomers selected from the following monomer group A by a known method, for example. Nanatsuma Group A: Vinylpyridine such as 2-vinylpyridine, 4-vinylpyridine, 2-methyl-5-, and vinylpyridine, vinylpyrimidine, vinylquinoline, vinylcarbazole, vinylimidazole, and those having 1 to 12 carbon atoms. Compounds with hydrocarbon substituents, o
, m, p-vinylphenylalkylenedialkylamine, (wherein R3 and R4 each have 1 to 12 carbon atoms
an alkyl group, a is an integer from 1 to 6. ) In poly^, the monomer units into which anion exchange groups are introduced account for 20 mol % or more, and may be introduced into all of them.

In addition to poly A and poly B, the block copolymer of the present invention contains, in its component blocks, up to 90 mol% of polymer poly C, which does not have an ion-exchangeable functional group, in terms of monomer units. But that's fine. This polyC
The monomers constituting may be diene monomers such as butadiene, isofrene, pentadiene, and cyclohexadiene. Polymers made of such diene monomers can be easily crosslinked using the double bonds present in the polymer using a known method. Therefore, if these are included in the component blocks of a block copolymer, the resulting When performing crosslinking, which can improve the solvent resistance of the material being used, depending on the functionality required of the material,
It can be done to any degree to completeness.

The block copolymer of the present invention comprises a polymer polyA having an anion exchange group of 20 mol% or more per monomer unit and a cation-selective ion exchange group or a cation-selective ion exchange group of 20 mol% or more per monomer unit. It is necessary to contain 5 to 95 mol % of monomer units of polymer poly B having a functional group into which it can be easily introduced. If it is outside this range, there is a risk that the function of the block copolymer material will not be fully demonstrated. It is preferable to contain 60 to 90 mol % of a polymer polyC made of diene monomers in terms of monomer units.

A desirable method for obtaining the block copolymer of the present invention is to introduce an anion exchange group prepared by block copolymerizing a monomer selected from the monomer group A above with styrene or α-methylstyrene by a stripping anionic polymerization method. An original block copolymer consisting of possible high molecular weight polyA and polystyrene or poly(α-methylstyrene) (referred to as polyB), or three types of heptamers in which a diene monomer is added in addition to the above monomers. The method involves chemically treating the original block copolymer prepared in the same manner as described above, consisting of poly A, poly B, and diene polymer poly C.

The component polymer po constituting these original block copolymers
It is desirable that the molecular weight of lyA, polyBepolyC is 103 to 10°I/mol.

More preferably 10゛~5 x 10'j'/im
It is l. As is generally well known, in a block copolymer, as the molecular weight decreases, the ratio of compatible interface regions formed between domains formed by microphase separation increases. According to the experimental facts published so far, the molecular weight of each component block is 108g/rr.
+o l or less, no clear phase separation structure is formed.

On the other hand, if the molecular weight of a sample is too large, molding becomes extremely difficult due to the high viscosity in the melt or solution state. Toga,
For example, (poly, A-polyB)x, (po
lyA −poly 13+XpolyA + pol
yB(polyA-polyB)x, (po
l) rA-polyB-polyc)x, (p
olyB-polyA-polyc)x + (poly
A polyc - poly B )x, (po
lyA-polyC-polyB-polyc)x,
(polyc-polyA-polyC-poly
B) x j poly C-poly A-poly B-po
ly C, poly C-polyA -poly C
-poly B -poly C, poly A -p
oly C-poly B-poly Cpoly
A, poly B-poly C-poly A
-poly Cpoly B, poly A -p
oly B-poly C-poly B-pol
yA, polyB-polyApol
y C-polyA-polyB, poly
C-poly A-poly B-poly A
-poly C, poly C-poly B -po
It is sufficient that they are bonded in an arrangement of ly A poly B −' polyC (where X is an integer of 1 or more). Also, poly B which has poly A as a branch,
poly A with poly B as a branch, poly
poly C, poly with A and polyB as branches
A poly C type (or poly B-po
ly C type) poly B with block copolymer branches
(or polyA), poly C-poly
A-poly C type (or poly C-poly
B-poly It may be poly B (or poly A) having a C) type block copolymer as a branch.

Among these, poly A and poly B are pol
y are separated from each other by C and are bonded together (for example, poly A poly C-'poly
B) When the content of polyc is appropriate, the microphase-separated anion exchange region and the cation-selective ion exchange region are isolated from each other in the final ion exchanger, so that the micro Since the phase separation structure is stable, it is preferable for use as a functional material.

The block copolymer of the present invention can be prepared by adding the above original block copolymer to pol before, after, or simultaneously with molding.
After quaternizing the nitrogen atom of the yA portion to obtain a polymer polyX having an anion exchange group, the polyc portion is crosslinked as necessary to form polyC, and the poly B portion is further chloromethylated or acetylated, and then the known A cation-selective ion exchange group may be introduced into them by the method described in the following. Crosslinking of the poly C moiety introduced as necessary may be carried out at any stage within the range possible.

The quaternization reaction of nitrogen atoms is performed using Br (4Htt-s and ICI
Ht! Alkyl halogen compound represented by ++ (l is an integer from 1 to 12) or Br-+CH-+1 Br
It can be easily carried out using vapor or solution of alkylene cybarides represented by I-(-CH).
The polychef part is exposed to peroxide, sulfur, -sulfur chloride, ultraviolet light, or AlC15, SbC1m, FeC15+
TaCA! t1SnCJa, TiC4-, BF
It can be easily crosslinked using Friedel-Craft catalysts such as S, HtSα, etc. Moreover, hydrogenation can also be carried out.

Polystyrene or poly(α-methylstyrene) halomethylation can be easily carried out using formaldehyde and hydrogen halide, and chloromethylation can be easily carried out using chloromethyl methyl ether. Further, their acetylation can be carried out by a known method using acetyl chloride and the above-mentioned Friedel-Krach catalyst.

Furthermore, if ammonia is applied to the functional group of (4), it becomes the functional group of (4).

(5) (Sommel
et reaction).

If iminophosphoric acid is used, σ), aminophosphoric acid is used (2B), and reethanolamine is used, 0 is obtained.

In addition, if Br1 acts on the acetyl group (3), (6)
.

) If ISC le cooH is applied, Tsukuda) and PCl are applied, (25) will be obtained, respectively.

If hydrolyzed, it will be +141. (5) to NH, OH and KCN
and +1 if treated with acid. (C51)h(COO
H), if treated with NH4OH, sea bream or aη, if (8) is hydrolyzed, it will be al, if a4 is treated with (J-CNxCOONm, it will be co, if CICHxCOONm is applied to as, it will be al, ai K CI C )hcOONa
, al can be obtained respectively.

Furthermore, if we process (6) with NH(CH*C00QHs)t, we get (9).

If (9) is hydrolyzed, (22) is obtained (61 is NH(C
If treated with hCN) 1, it becomes a ring, 0 (if I is hydrolyzed (22), +61 is N) ((CHtC)hCN),
If treated with , aη, if aυ is hydrolyzed, (23),
If (22) is processed with PCla, (24) becomes C2
If 2) is treated with H8CHtCOOH, (26)
If (23) is treated with PCl5, (30) (23)
When treated with H8C and C0OH, (31) can be obtained in drops. Moreover, (29) can be obtained by oxidizing aa.

The above-mentioned individual reactions are known, and representative documents are listed below.

■ Written by R.B. Wagner and H.D. Zook,
[5yn-thetic Organic Chemi
atryJ, New York.

John Wiley & 5ons, Inc.
(1953) Volume 81, Page 377 (1959) ■ E. B. Trostyanskaya et al.
Journal of Polymer Sc'1enc
e, vol. 59, p. 379 (j962) ■ M, Marshall, L, Cheng
, Ta1anta.

Volume 21, page 751 (1974) ■ Edited by Shumasa Hojo, [Chelate Resin/Ion Exchange Resin],
Kodansha University Press (1976) The original block copolymer used in the present invention can be produced, for example, by a living anionic polymerization method. In this case, the polymerization initiator is known butyllithium (n
+ Bee Hjerj), 2-methylbutyllithium, sodium naphthalene, sodium anthracene, α-methylstyrene tetramer sodium, sodium biphenyl, etc. are used, and aromatic hydrocarbons, cyclic ethers, aliphatic hydrocarbons (generally, Polymerization is carried out in a vacuum or an inert gas atmosphere such as nitrogen gas or argon gas (benzene, toluene, tetrahydrofuran, n-hexane, cyclohexane, etc.). ! 1.
.

The block copolymer of the present invention has a region having an anion exchange group and a region having a cation-selective ion-exchange group or a functional group into which a cation-selective ion-exchange group can be easily introduced; It has a microphase-separated structure consisting of 102 regions and a region without ion exchange groups. Each region exists as a lamella, sphere, rod, or matrix phase, and these forms are copolymerized into original blocks.

Because it has a micro-heterogeneous structure, it can be molded into any desired shape, and is expected to have many uses, including ion selective permeation membranes used in ion analysis and waste liquid treatment, as well as conductive materials and biomedical materials. be done.

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 immersed in a dilute aqueous sodium hydroxide solution (pH: 12) containing 1 mol/l of glutinous acid for 20 hours.
After washing with water, the membrane was immersed in 0.5N hydrochloric acid for 20 hours, and the sodium ions released from the membrane were quantified. In addition, to measure the anion exchange capacity (quantitative determination of quaternary amine groups), the membrane was treated with a dilute aqueous sodium hydroxide solution, then immersed in a 1 mol/l aqueous potassium chloride solution for 20 hours, washed with water, and then soaked in a dilute aqueous solution of sodium hydroxide.
The membrane was immersed in mo1/l sodium nitrate for 20 hours, and the chlorine ions released from the membrane were quantified. Here, the quantification of sodium ions and chloride ions was carried out by a conventional method. Quantification of -grade amine groups (-NH,) was performed by treating the film with 2N hydrochloric acid containing an excess amount of sodium nitrite standard solution (0, IN) for 20 hours, and then removing unreacted sodium nitrite with sulfanilic acid. The standardization was carried out using a known method.

Example 1 In benzene purified through a sodium mirror, 5ec-
Using butyl lithium 5.5 x 10-' rnol as an initiator, styrene, 4-vinylbenzyldimethylamine (hereinafter abbreviated as 4-VBDMA), and putadiene, butadiene 6511 styrene 12 g, butadiene 7,01
? , 4-VBDMA, 191i1, butadiene 6.
Polymerization was carried out by adding 5I every 20 hours in 5 steps to form poly C-polyA -poly C-pol.
A y B -poly C type original block copolymer was synthesized. The polymerization temperature was 20°C for 4-VBDMA;
For other monomers, the temperature was 30° C., and the polymerization was carried out in a vacuum-sealed glass container. The polymerization yield was V1100%. The molecular weight per block of the final polymer was determined from the number average molecular weight of the intermediate polymer and final polymer determined by the membrane osmotic pressure method, and the first polybutadiene block was 1.9 x 10' g/mol.

Polystyrene block is 6.5 X 10' 9/mo
1. The central polybutadiene block is 2. ΩX ID
' , 9/mol, the poly(4-VBDMA) block was 5.5 x 10' g/mol, the last polymerized polybutadiene block was 1.8 x 1.0' gkol, and the monomer weight and initiator The value almost agreed with the value calculated from the number of moles.

5% by weight of the original block copolymer thus obtained
A film with a thickness of about 60 μm obtained by a solvent evaporation method on a mercury surface using a benzene solution of , and poly(4
-VBDMA) layer (the existence of a three-phase lamellar structure in which the repeating units of -B-8-B-A-) were regularly arranged.

Film 0 similarly produced from this original block copolymer
．． 3.9 was left in an indoor source of methyl iodide vapor for 10 hours to quaternize part A, and then part B was immersed in 100 d of a 20 volume percent sulfur monochloride solution in nitromethane at room temperature for 3 hours. Crosslinked.

As a result of this crosslinking reaction, the infrared absorption band caused by the double bond of polybutadiene almost disappeared, and it was confirmed that the degree of crosslinking of the polybutadiene moiety was close to 100%. This film was further coated with 45% chloromethyl methyl ether. 'F')'-, vy□ by immersing in F and keeping at 3°C, adding 15 g of aluminum chloride as a catalyst and leaving at the same temperature for 5 hours. 2°. 7a, 2a, □9e. The anion exchange capacity of the obtained film was determined by a conventional titration method, and the measured value was 85% of the calculated value. Further, as a result of 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 Thickness 6 made from the original block obtained in Example 1
A 0 μm film 0.519 was coated with poly(
The 4-VBDMA) moiety was quaternized and the polybutadiene moiety was crosslinked.

Further, this film was immersed in 50 mJ of carbon disulfide, 159 aluminum chloride and 1oII acetyl chloride were added, and reaction was carried out for 5 hours under reflux to introduce acetyl groups into the polystyrene portion. The film obtained through chemical treatment showed an infrared absorption band characteristic of carbonyl groups near 1690 cm-', and 13C-NMR measurements revealed that it had 0.81 acetyl groups per styrene monomer unit. Ta. Furthermore, as a result of transmission electron microscopy, it was confirmed that the initial lamellar structure was basically maintained.

Example 3 A 0.3 F film with a thickness of 60 μm 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. I did it. Furthermore, after chloromethylating the polystyrene portion in the same manner as in Example 1, the film was
It was treated with a weight percent hexamethylenetetramine solution in chloroform for 5 hours under reflux, washed with methanol, and finally treated 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 found that the chloromethyl group is a formyl group (-C
It was confirmed that it was converted to HO).

That is, in the "H-NMR spectrum, the peak derived from the hydrogen of the chloromethyl group around δ = 4 to 5 disappears, and the peak derived from the hydrogen of the formyl group newly appears around δ = 10, and the infrared absorption spectrum In this case, an absorption band derived from C-0 of aldehyde appeared around 1700 cm'.The anion exchange capacity of this film was 72% of the calculated value.

Example 4 A 60 μm thick film 0.51 produced 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 The polystyrene moiety was chloromethylated. Furthermore, this film was mixed with 67 g of iminoniacetic acid disodium salt and 3.3.9 g of sodium hydroxide. After treatment with a mixture of 50% dioxane and 50% water at 60°C for 1 hour, the film obtained using chloromethyl
A strong infrared absorption band characteristic of carboxylic acid groups was observed in the vicinity, and when this carboxylic acid group was measured by sodium quantification, it was found that 12
(8,2×10-' equivalents) of carboxylic acid groups were found to be present. In addition, the anion exchange capacity is the calculated value of 60
% (4,2 x 10-' equivalents).

Example 5 A 60 trm-thick film 0.39 mm made from the original block copolymer obtained in Example 1 was possesed in the same manner as in Example 1. The J(4-VBDMA) moiety was quaternized, the polybutadiene moiety was crosslinked, and the polystyrene moiety was chloromethylated.

The obtained film was immersed in 100 ml of benzene, left for one day and night, then ammonia was passed through it to saturate it at 20°C, the film was gradually heated to 40°C for another 5 hours, and further left at 20°C for one day and night. Complete amination of methylated polystyrene moiety
The film thus aminated was immersed in a 2019 □/a ether solution of diethyl maleate, and the reaction was carried out at 30°C for 7 days to convert the aminomethyl groups to -CH*NHCHCOtC*Hs groups. Subsequently, the CHtCO-beating CtHs film was immersed in acetone, concentrated hydrobromic acid was added dropwise thereto, and the mixture was refluxed for 20 hours to hydrolyze the ester.
) ICHCOOH group.

CH, COOH The obtained film showed a strong infrared absorption band characteristic of carboxylic acid groups around 1700 cm''. In addition, when this carboxylic acid group was measured by sodium quantification,
It was found that there were 15 carbo/acid groups per styrene monomer unit. In addition, the quaternary amino group is the calculated value of 6
It was 2%.

Example 6 Film 04I obtained by acetylation in Example 2 was
After 2 hours of immersion in 00d phosphorus trichloride, C) h was used as a base. Next, this film was immersed in water at 0°C and washed with water and dilute alkali.

The obtained film had a temperature of 1250-130 oCm-'
A strong infrared absorption band characteristic of the phosphorus-oxygen double bond was observed in the region. Furthermore, when the number of phosphoric acid groups introduced into the film was quantified, it was found that there were 065 phosphoric acid groups per styrene monomer unit.

Example 7 In benzene purified through a sodium mirror, 5ec-
Using 2.9 X 10-' mol of butyllithium as an initiator, Imprene 9I! , 15 g of styrene, 18 # of butadiene, and 1819 of 2-vinylpyridine in this order.
Polymerization is carried out by adding the polymer every 20 hours at
An original block copolymer of type C-poly B-poly C-poly A was synthesized. The polymerization temperature was 20°C for 2-vinylpyridine and 3°C for other monomers.
Polymerization was carried out in a glass container kept at 0° C. and sealed in vacuum.

The polymerization yield was approximately 10'0%. The molecular weight per block of the final polymer was determined from the number average molecule of the intermediate polymer and final polymer determined by membrane osmotic pressure method, and the polyisoprene block was 3.OX 10' 9/mol
, the polystyrene block is 55x 1o' 9/mol
, polybutadiene C7 is 6.2 x 10' I!
ko1, poly(2-vinylpyridine) block is 6.3
X 10' JF/n1o1, which almost coincided with the value calculated from the monomer weight and the number of moles of initiator.

5% by weight of the original block copolymer thus obtained
A film with a thickness of approximately 60 μm obtained by solvent evaporation on a mercury surface using a benzene solution of
The existence of a three-phase lamellar structure in which D), the polystyrene layer (S), and the poly(2-vinylpyridine) layer (P) were regularly arranged in repeating units of -D-8-D-P- was confirmed.

Film 0 similarly produced from this original block copolymer
．． 69 was left in short propane vapor at 40 °C for 8 days to quaternize the P portion, and then immersed in a 20 volume percent sulfur monochloride solution in nitromethane 100-100 at room temperature for 3 hours to crosslink the D portion. did. Furthermore, this film was immersed in 100 d of carbon disulfide, and 3 ap of aluminum chloride was added.
and 20 g of acetyl chloride were added thereto, refluxed for 2 hours, and then left at 30° C. for 2 days to introduce acetyl groups into the polystyrene portion. From the results of C-NMR measurement of the film thus obtained, it was found that 085 acetyl groups were introduced per styrene monomer unit. Further, as a result of observation using a transmission electron microscope, it was confirmed that the lamellar structure was basically maintained.

Example 8 0.4 g of the film acetylated in Example 7 was immersed in 100% of glacial acetic acid, and while cooling using an ice bath,
10I of bromine in this! was added dropwise and left for 8 hours to bromine the acetyl group.

This film was immersed in 100-0N, N'-dimethyl-dimethylhydrochloride. After adding 20 J' of Imi, Ziaya, and Trihetryl and keeping it at 90°C for 6 hours and washing with water and acetone, the film was further heat-treated with 100-concentrated hydrochloric acid for 5 hours, and then the film was soaked in water som. /, 30d of ethanol and 9I of barium hydroxide at 80°C for 6 hours to hydrolyze the cyano group. Through the above operations, the acetyl group was converted into -cocN(CH
1cOOHh group. The obtained film was 170
A strong infrared absorption band characteristic of carboxylic acids was observed near 0 cm-'. Further, when the carboxylic acid groups were quantified, it was confirmed that there were 1.1 carboxylic acid groups per unit of styrene resin.

Example 9 A 0.3 F film with a thickness of approximately 60 μm prepared from a benzene solution of the original block copolymer obtained in Example 7 was subjected to quaternization of the poly(2-vinylpyridine) portion in the same manner as in Example 7. and crosslinking of the polydiene portion. Furthermore, the polystyrene portion was chloromethylated in the same manner as in Example 1. Thereafter, 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 1H-NMR spectrum.

Example 10 The film finally obtained in Example 9 was mixed with 5.4y1 of ammonium chloride, 5.119% of sodium cyanide, 10% of concentrated aqueous ammonia, 2syrl of methanol, and 30% of water.
It was immersed in a mixed solution consisting of the following, and left at 35°C for about 6 hours. Next, a mixed solution of 1,611 L of sodium hydroxide, 2,511 L of methanol, and 100 L of water was added to this liquid, and the mixture was left to stand under reflux for 2 hours.

Thereafter, the film was taken out and washed with dilute hydrochloric acid.

Converted. When the primary amino groups and carboxylic acid groups contained in the obtained film were quantified, they were found to be equivalent to 025 and 024 groups, respectively, per styrene monomer unit. Further, the amount of quaternary amine 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 treated with malonic acid 191
After soaking in a mixture of 9g of concentrated ammonia water and 80% of ethanol and leaving under reflux for 6 hours, the ethanol was removed by distillation, and the film was soaked in a solution of 0.1% of sodium carbonate.
It was immersed in an aqueous solution of M (45°C).

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 was converted to -CHCH,C0OH group. The amounts of primary amine groups and carboxylic acid groups contained in the obtained film are approximately equal to 0.32 and 0.31' per styrene monomer unit, respectively, and the amount of quaternary amine groups is about 55 of the calculated value. %Met.

Example 12 Film 0.4 obtained by acetylation in Example 7
1 was subjected to bromination of the acetyl group in the same manner as in Example 8. Next, this film was immersed in 50-d ethyl acetate, and while refluxing, a solution obtained by mixing 50-d ethyl acetate and 3011-iminodiacetate was added dropwise over 1 hour. It was left at a slightly lower temperature for 20 hours. By the above procedure, the acetyl group is converted to -COCI and N(
It was converted into a C00CtH-)w group. Furthermore, this ester group is hydrolyzed to -COC&N (ClC00H
), the film was immersed in acetone, to which concentrated hydrobromic acid was added dropwise and refluxed for 20 hours.

The obtained film showed a strong infrared absorption band characteristic of carboxylic acid groups around 170 ocm-', and when this carboxylic acid group was quantified, it was found to be 13% per styrene monomer unit.
It turns out that there are. Further, the amount of quaternary amino groups was 60% of the calculated value.

Example 13 The film 0.31 finally obtained in Example 12 was subjected to a phosphorylation reaction in the same manner as in Example 6 to convert it into Suh. The obtained film showed a strong infrared absorption band of the C-0 bond near 1700 cm-' and a strong infrared absorption band of the phosphorus-oxygen double bond in the region of 1250 to 1300 cm-'. In addition, as a result of elemental analysis, the phosphorus atom is 3.6 times the carbon atom.
% by weight. If we calculate the phosphate group 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.
1X10-'' equivalent, consistent with that.

Example 14 03 g of a 6011 m thick film prepared from a benzene solution of the original block copolymer obtained in Example 1 was left in methyl iodide vapor at room temperature for 10 hours to form poly(4-VB).
The DMA ) moiety was quaternized and treated with a 2 g/a solution of stannic chloride in n-hexane at room temperature for 4 hours to crosslink the polyptage di/moiety. Furthermore, the polystyrene portion was acetylated in the same manner as in Example 2. Subsequently, the film was placed in a mixture of 10 J' of anhydrous zinc chloride and 100 m/h of chloroform, and 30 g of thioglycolic acid was added to the mixture for 1 hour. The mixture was added gradually over the course of the reaction and left under reflux for 15 hours.

After cooling, the film was washed with acetone, dioxane, and water. Through these steps, the styrene part was immersed in 1N hydrochloric acid for 20 hours to change the counter ion of the amine part to chlorine, dried, and elemental analysis revealed that carbon was 70.9
Weight%, nitrogen 21% by weight, hydrogen 82% by weight, oxygen 7.2%
% by weight, 6.1% by weight of sulfur, and 55% by weight of chlorine.

The number of 1-3CutCOOH groups is calculated from this carbon to sulfur weight ratio to be about 1.2 per styrene monomer unit. In addition, this film exhibits an infrared absorption band specific to C=O bonds, and the number of carboxylic acid groups is approximately 1 per styrene monomer unit, as determined by the sodium quantitative method described above.
．． There were 2 of them.

Claims (1)

[Scope of Claims] 1 A polymer poly■ having an anion exchange group of 20 mol % or more per monomer unit and a cation-selective ion exchange group or a cation-selective ion exchange group of 20 mol % or more per monomer unit Consisting of polymer poly■ and polymer polyC, which have functional groups that can be easily introduced, pol
y■, poly■ are monomer units, each having a value of 5 to 95
Contains mol%, poly■ is monomer unit poly■
Contains 0 to 90 mol% based on the total amount of and poly■,
Molecular weight of each block unit is 10^3~10^6g/mo
A block copolymer in which the polymer polyC is crosslinked with a double bond contained in polyC or is not crosslinked. (Here, poly■ is a polymer of monomers selected from the following monomer group A with an anion exchange group introduced, (monomer group A: vinylpyridine, vinylpyrimidine, vinylquinoline, vinylcarbazole, vinyl Imidazole and these compounds having a hydrocarbon substituent having 1 to 12 carbon atoms, ▲Mathematical formulas, chemical formulas, tables, etc. are available. are each an alkyl group with a carbon number of 1 to 12, and a is an integer of 1 to 3.)) Poly■ is a polymer represented by the following general formula, and there are ▲mathematical formulas, chemical formulas, tables, etc.▼ ( However, R_1 is hydrogen or a methyl group, and Rx is a cation-selective ion exchange group selected from the following or a functional group into which a cation-selective ion exchange group can be easily introduced. (1) -CH_2X, -COCH_3, (X is chlorine or bromine) (2) -CH_2NH_2, -CHO, -C
OCH_2Br(3)▲There are mathematical formulas, chemical formulas, tables, etc.▼ -COCH_2N(CH_2CO_2R_2)_2, -
COCH_2N(CH_2CN)_2-COCH_2N
(CH_2CH_2CN)_2, -CH_2N^+(C
_2H_4OH)_3 (However, R_2 is an alkyl group having 1 to 6 carbon atoms) (4) ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ (However, x is an integer from 1 to 6)) The polymer polyC is the diene shown below. It is a polymer of monomers of the system. (Diene monomers: phtadiene, isoprene, cyclohexadiene, pentadiene)) 2. Polymer polyA that can introduce 20 mol% or more anion exchange groups per monomer unit and polystyrene or poly( α-methylstyrene), consisting of polyB and high molecular weight polyC, polyA,
polyB is 5 to 95 mol% of each monomer unit
Contains polyC, which contains 0 to 90 mol% in monomer units, and the molecular weight of each block unit is 10^3 to 10^6 g.
/mol After introducing an anion exchange group into the polyA part of the block copolymer, the polyB part is halomethylated or acetylated, and then the halomethylated or acetylated polyB part is subjected to cation-selective ion exchange. A method for producing a block copolymer, which comprises introducing a functional group into which a group or a cation-selective ion exchange group can be easily introduced, or further crosslinking with a double bond contained in polyC at an arbitrary step. (Here, polyA is a polymer of monomers selected from the following monomer group A. Compounds with hydrocarbon substituents ▲ Numerical formulas, chemical formulas, tables, etc. ▼
In the alkyl group of 2, a is an integer from 1 to 3. ), cation-selective ion exchange groups or functional groups into which cation-selective ion exchange groups can be easily introduced are (1) -CH_2X, -COCH_3, (X is chlorine or bromine) (2) -CH_2NH_2, -CHO ,-C
OCH_2Br(3)▲There are mathematical formulas, chemical formulas, tables, etc.▼ -COCH_2N(CH_2CO_2R_2)_2, -
COCH_2N(CH_2CN)_2-COCH_2N
(CH_2CH_2CN)_2, -CH_2N(C_2
H_4OH)_3 (where R_2 is an alkyl group having 1 to 6 carbon atoms), and polyC is a polymer of the following diene monomer. (butadiene, isoprene, cyclohexadiene, pentadiene))