JPS6068056A - Ion-exchange body - Google Patents

Abstract

PURPOSE:To obtain a novel ion-exchange body by constituting of a block copolymer which is composed of wholly or partly of a high molecular yolyA<+> having an anion exchanging group and a high molecular pol6B having a phenolic hydroxyl group. CONSTITUTION:The ion-exchange body is constituted of a block copolymer which is composed wholly or partly of a high molecular polyA<+> having an anion exchanging group and a high molecular polyB having a phenolic hydroxyl group, and whose content of each component is regulated to >=5wt%. The different component blocks in the block copolymer are immiscible with each other and present as a separated microphase, and the molded material acts as an anion exchanging body under nearly-neutral or acidic conditions and as an amphoteric ion exchanging body under alkaline conditions. When only a part of block copolymer is composed of said polyA<+> and polyB, the remaining part consists of a high molecular polyC without any polar group.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides polymer polyA+ having anion exchange groups.
and a polymer poly4 having a phenolic hydroxyl group as a whole or a part of its constituent components.

Block copolymers that form a unique microphase-separated structure are known to exhibit novel properties due to their microscopically heterogeneous structure, and various uses have been found for them. For example, block copolymers consisting of long polyisogrene or polyptadiene chains and short polystyrene chains are known as thermoplastic rubbers, while block copolymers consisting of long polystyrene chains and short polyisoprene or polybutadiene chains are known as impact-resistant materials, and polyurethane Block copolymers consisting of polyether and hydrophilic poly(2-hydroxyethyl methacrylate) and hydrophobic polystyrene are expected to be anticoagulant materials. It is also known that a block copolymer containing a polymer having a barfluoroalkyl group as one component is effective for surface modification of plastics and the like.

Recently, polymers into which cation exchange groups can be introduced (e.g., polystyrene and polymethyl methacrylate) and polymers into which anion exchange groups can be introduced (e.g., poly(2-vinylpyridine) and poly(4-vinylbenzyl) dimethylamine))
It has been reported that an amphoteric ion exchanger can be obtained from a multi-block copolymer consisting of a polymer having no ion exchange group and a polymer having no ion exchange group (for example, polyisoprene or polybutadiene). (Publication of Patent Publication No. 56-76408) These amphoteric ion exchangers have a sulfone group or a carboxyl group as a cation exchange group and a quaternary ammonium base as an anion exchange group, and have a fairly wide range of properties ranging from acidic to alkaline. It functions as an amphoteric ion exchanger in the pH range, and is expected to be used as a membrane to separate low-molecular-weight organic substances and inorganic salts.

After extensive research, the present inventors discovered a polymer polyA+ having an anion exchange group and a polymer polyj? having a phenolic hydroxyl group. We have come up with a new block copolymer that contains part or all of the components and succeeded in its synthesis. In molded products of these block copolymers, different component blocks do not mix with each other and exist as microphase separated, and these molded products can be used as anion exchangers under near-neutral or acidic conditions. It was found that it acts as an amphoteric ion exchanger under alkaline conditions. There is no doubt that these facts promise to provide ion exchangers as new functional materials.

The present invention will be explained in more detail below.

The ion exchanger in the present invention is a polymer poly/l+ having an anion exchange group and a polymer poly2? having a phenolic hydroxyl group. It can be obtained from a block copolymer comprising part or all of the constituent components.

In the block copolymer used here, the above po
When ly, 4+ and polyZl are part of the constituent components, the remaining part is a polymer polyc that does not have a polar group.
Consisting of These block copolymers include, for example, polymers po17A and po1yJ into which anion exchange groups can be introduced.
? Polymer p017B whose hydroxyl group is protected with an appropriate protecting group
and, if necessary, a block copolymer composed of a polymer p017C that does not have a polar group, is subjected to a protective group elimination reaction and an anion exchange group introduction reaction before, after, or simultaneously with molding. and, if necessary, a crosslinking reaction.

The ion exchanger of the present invention has a phase-separated structure consisting of microdomains having anion exchange groups, microdomains having phenolic hydroxyl groups, or both microdomains and microdomains having no polar group. In block copolymers made of non-polar polymers such as polyisoprene and polystyrene, different component blocks do not mix with each other in the solid state, but phase separate into microdomains with spherical, columnar, or lamellar shapes depending on the composition. It is known to do. In this case, the diameter of the spherical domain, the diameter of the columnar domain, the distance between the centers of these domains, or the width of the lamellar domain is limited by the fact that the component blocks are intertwined with each other. Spread and coroot if (usually,
(tens to hundreds of angstroms).

The present inventors have found a method to finally arrive at the ion exchanger of the present invention while utilizing such a microphase separation phenomenon.

In the block copolymer used in the present invention, the component block having a phenolic hydroxyl group is the following bonding unit 7 (where R4 is hydrogen or a methyl group + RM to R
It is a polymer having 0) in which one of o is a hydroxyl group and the others are hydrogen atoms or methyl groups. The hydroxyl group of such a polymer is p
Ka (pKa=-10gKa, Ka is the dissociation constant) is 1
It is around 0, hardly dissociates under acidic or neutral conditions, and dissociates only under alkaline conditions. Therefore, the ion exchanger of the present invention has a multiphase structure consisting of microdomains with anion exchange groups and microdomains with undissociated phenolic hydroxyl groups under acidic and near-neutral conditions, and under alkaline conditions. It has a multiphase structure consisting of microdomains with anion exchange groups and microdomains with dissociated phenolic hydroxyl groups (i.e., cation exchange groups).

Furthermore, when the block copolymer used in the present invention contains a component block po17C that does not have a polar group, it has a multiphase structure including microdomains that do not have a polar group under any pH condition. .

Component block PO of the block copolymer used in the present invention
The anion exchange group having 174" power may be an ammonium group, a sulfonium group, a haphosphonium group, etc. Among these, the ammonium group is a polymer polyA consisting of a monomer χ selected from the following monomer group A. Obtained by grading.

Monomer group A: 2-vinylpyridine, 4-vinylpyridine.

Vinylpyridine compounds such as 2-methyl-5-vinylpyridine, vinylpyrimidines, vinylquinolines, vinyl carnocylates 7+/[, vinylimidazo-/l/].

o, m, p-vinylphenylalkylenedialkylamines represented by:

Dialkylaminoalkyl acrylates represented by:

Dialkyl acrylamides represented by (where R
I and R2 are each an alkyl group having 1 to 12 carbon atoms,
R3 is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms; n is an integer of 1 to 6; 1m is 2 or 5; ) Polymer p017F having a phenolic hydroxyl group can be obtained by overlaying a monomer represented by the following chemical formula having a phenolic hydroxyl group protected with an appropriate protecting group, and then removing the protecting group.

Here, R4 is a hydrogen atom or a methyl group r''M to R,
Any one of is -0-CH,+2l -O-(3H,R,,+31 -0-0-R,. (4) Kichi 1, IO ■ -0-C-R,, (5) 12 tts -O-S i-R,4(61 15 (However, RI(+ + RII * RIt + R
13T R141RH+R8° represents an alkyl group having 1 to 12 carbon atoms. ) etc., and the others are hydrogen atoms or methyl groups.

The remaining monomer blocks constituting the polymer polyC having no polar groups may be selected from the following monomer group C, for example.

Monomer group C: Monomers having an aromatic ring such as styrene, α-methylstyrene, and vinyltoluene; diene monomers such as butadiene, isoprene, pentadiene, cyclohexadiene, and diphenylbutadiene; By constructing a block copolymer in addition to the polymer poly〆 having an ion exchange group and the polymer p017β having a phenolic hydroxyl group, the mechanical strength of the material can be increased and the microphase separation structure can be stabilized. becomes possible. In particular, polymers made of diene monomers can be easily crosslinked, so their use can improve the solvent resistance of the material.

A desirable method for obtaining the ion exchanger of the present invention is to combine a monomer selected from the above monomer group A, a hexamer represented by the chemical formula (1), or both of these and monomer group C.
Polymer pol into which an anion exchange group can be introduced prepared using the living anion protein method
Polymer pol capable of introducing y/l and phenolic hydroxyl groups
After molding the original block copolymer consisting of yB or both of these polymers and po17C, a polymer without polar groups,
Alternatively, anion exchange groups may be introduced (quaternization of nitrogen atoms) and hydrolysis may be carried out before or simultaneously with molding.

When obtaining an original block copolymerized polymer by a living anionic polymerization method, among the monomers represented by the chemical formula fi+, monomers having a protecting group represented by the chemical formula +41, (51 or (6)) are desirable, and more preferably those having a protecting group represented by the chemical formula (4)
) or (5), most preferably a monomer having the chemical formula (5).

Initiators for living anionic polymerization include known butyl thirium (n, sθc, tθrt, etc.), 2-methylbutyllithium, sodium naphthalene, sodium anthracene, α-methylstyrene tetramer sodium, sodium biphenyl, cumyl potash, butyl cesium ( n, sθC2tert@), etc. are used.

As the polymerization solvent, aromatic hydrocarbons, cyclic ethers, aliphatic hydrocarbons (generally benzene, toluene, tetrahydrofuran, n-hexane, cyclohexane, etc. are used) are used, and vacuum or nitrogen gas, argon gas, etc. Polymerization is carried out under an active gas atmosphere.

The original block copolymer used in the present invention is the polymer P described above.
017A+ polyB, pO17', for example,
(po:LyJ-polyB)z, (polyA-po
lyZl-)-, polyA+polyB+polyA
-polyZ? ), , (polyA-polyB-p
oly(1”),, + (pO17B-pO17A-
pO17C)z j(polyA-poly'-pol
yB) 2H+ (pol-74-po'1yC-pol
yB-poly(”)x+ (polyC-polyA
-polyC-polyB), .

p017C-polyA-p017B-polyC,p
olyC-po':tyA-polyC-polyB-
polyC, polyA-poly'-pO1yJ?
-1) 017 C-p OlyA, p(i ly
Z? -p Oly C-p OlyA -p Oly
'-polyB, poly4-polyZl-po
lyc-polyB-polyA.

pQ17E-po17A-po17cmpo17A-p
Q': L7E, polyC-p017A, -T"17B
-1"17A-I"17'+ T"17C-polyB
-pOXyA -po 1yII -pc) 1yc (
However, it is sufficient if X is an integer of 1 or more) connected in an array.

Among these, polyA and po'17B are polyc
Things that are separated from each other and connected by.

'P017A-pO17'-1)017B+ (pol
yA-po'1yC-polyB-polyG),
, (polyC-polyA-polyC-polyB
)x.

pOlyC-polyA-p017'-p017B-1
"17C+ T"17A-pO13"'-1)017"
-p017”-1)017”l polyB-poly
In C-po'1y4-polyC-polyB, if the content of pO171Z' is appropriate (usually about 60% or more of the block copolymer by weight), the microphase will not be present in the final ion exchanger. Domains with separate anion exchange groups and domains with phenolic hydroxyl groups are separated from each other by domains without polar groups.

Such an ion exchanger has a stable microphase-separated structure in a wide pH range from acidic to alkaline, so it can be said to be preferable for use as a functional material.

Component polymer pol constituting the above original block copolymer
yA, 1; lo'17B, the molecular weight of polyc is 1
0m-10'? /rno1 is desirable. More preferably, the amount is 104 to 5Xil15 mol. As is generally well known, in a block copolymer, as the molecular weight decreases, the volume fraction of the compatible interface region generated between two adjacent domains formed by microphase separation increases. For this reason, in a sample with a low molecular weight, the formation of polyion complexes is large in the alkaline region (and the characteristics of the ion exchanger of the present invention are weakened).

According to the experimental facts published so far for various block copolymers, the molecular weight of each component block is 103
It is considered that a clear phase separation structure is hardly formed below r/mo1. On the other hand, if the molecular weight of the sample is too large, molding becomes difficult due to its high viscosity in the melt or solution state.

In the original block copolymer used in the present invention, the weight fraction of the region having an anion exchange group and the region having a phenolic hydroxyl group in the ion exchanger finally obtained is 5% or more of the ion exchanger. The molecular weight and content of polyA and polyB must be as follows.

This is because if their weight fraction is less than 5%, the characteristics of the ion exchanger will be significantly impaired.

The nitrogen molecules of the polymer polyA used in the present invention into which an anion exchange group can be introduced can be quaternized using an alkyl halogen compound or an alkylene cybaride.

As an alkyl halogen compound, XctH2t+1° As an alkylene cybaride, X+c2H4+-X
(However, X is an atom or an iodine) and has a t value of 1 to 12.

Furthermore, this quaternization can be carried out using a chloromethylated aromatic compound such as chloromethylbenzene or an acid halide such as benzenesulfonyl chloride or acetyl chloride.

The 12g grading reaction can be carried out in the vapor or solution of these compounds. On the other hand, these nitrogen atoms of polyA can also be converted into tertiary ammonium salts with hydrochloric acid or the like.

K, which is used to obtain a polymer having a phenolic hydroxyl group from a polymer consisting of a monomer represented by the chemical formula (1), may be subjected to a protective group elimination reaction using a known method. (Reference: T
+W, Greene, “Protective Gr.
upsin Organic 5 synthesis,
”John Wiley k 5oz.

New York, 1981) For example, in the presence of a protecting group represented by chemical formula (5), a sample is treated with hydrochloric acid, hydrobromic acid, or iodide-based acid under heating in a d-media such as dioxane, acetone, methyl ethyl ketone, or acetonitrile. The elimination reaction can be easily carried out by adding dropwise. Also, anhydrous 1.1.1
This reaction can be carried out at relatively low temperatures using trifluoroacetic acid or a mixture of acetic acid and hydrobromic acid or a solution of trimethylsilyl iosite in carbon tetrachloride or chloroform.

Ion exchangers with phenolic hydroxyl groups as described above are used as highly selective separation membranes and biomedical materials.

It is expected to have a wide range of applications as a gel for liquid chromatography, a surface modification material, etc.

Hereinafter, the present invention will be explained by examples.

Example 1 Tetrahydrofuran 600ml 1K purified using n-butyllithium after dehydration with calcium hydride
2. Add n-butyllithium, an initiator for anionic polymerization.
After adding 1 x 10-4 mol, 12 J' of p-tert-butoxystyrene was added and left for about 20 hours. (1st stage) After collecting a part of the polymer, 11.8y
of isoprene was added and left for about 20 hours. (Second stage) After collecting a portion of the polymer, 11.5j' of 4-vinylbenzyldimethylamine (4-VBDMA) was added and left to stand for about 20 hours. (Third step) Among the three types of monomers used here, p-tert butomokukuri was purified in advance using sodium benzophenone, and then
It was further purified by treatment with a mixture of triphenylmethyllithium and lithium bromide and by vacuum distillation.

4-VBDMA was dehydrated with calcium hydride, distilled under reduced pressure, and then treated with a mixture of triphenylmethyllithium and lithium bromide to perform Makabe distillation.

After drying isoprene with calcium hydride and sodium,
Distillation was performed.

The number average molecular weight of the polymer obtained at each stage of polymerization was determined by membrane osmotic pressure method, and it was found that the first stage TE was 5.6.
x 10'S'/mol, 1, 10 in the second stage
x 10' f/mo1. 1.66X10 in the third stage
'f/mol, which agreed well with the value calculated from the weight of the initiator and monomers charged. In addition, the polymerization yield was approximately 1
00%, and the weight ratios of carbon, hydrogen, and nitrogen contained in the final polymer were 85.8% and 10%, respectively.
．． 1% and 2.8%, which agreed well with the calculated values.

Regarding this final weight, Toyo Soda GPO column GM
Using H6 (length 6ocm, inner diameter 15 m), 3% (
7) When GPO measurement was performed using tetrahydrofuran containing N,N-dimethylbenzylamine as an eluent, a single peak was observed, indicating that the molecular weight distribution of this sample was quite narrow.

(FIG. 1) Furthermore, FIG. 2 shows the infrared absorption spectrum of the final polymer.

From the above results, in this example, poly(4-VBD
MA), polyisoprene, and poly(p-tert-butoxystyrene) polyA-polyc-poly
It is certain that a type B ternary block copolymer was obtained.

A 60 μm thick film prepared from a benzene solution of the final polymer was stained with osmium tetroxide and observed with a transmission electron microscope, revealing polyisoprene domains (1) and poly(p-tert-butoxystyrene) domains (B).
and poly(4-VBDMA) domain (A) is -■-B
A lamellar microphase-separated structure in which repeating units of -knee A- were regularly arranged was confirmed. The thickness of one layer was approximately 150 angstroms.

The anion exchange group and phenolic hydroxyl group were introduced as follows.

A similarly produced film [1302] with a thickness of 60 μm was treated with 1.3 shots of propane vapor at room temperature for 40 hours to quaternize and crosslink the poly(4-VBD, MA) portion. This film was immersed in acetone at 50°C, and a small amount of concentrated bromide-based acid was added to make poly(p-tert).
butoxystyrene) to start the elimination of the tert-butyl group, and then add an appropriate cap of dilute aqueous hydrogen bromide solution for about 1 hour.
The tert-butyl group was completely eliminated by standing for 0 hours.

Complete elimination of the tertbutyl group results in H'-NMRlc
I checked it out. That is, the t observed before the elimination reaction
The peak attributable to the -butyl group completely disappeared after the elimination reaction, and a new large peak that was considered to be a phenolic hydroxyl group appeared.

The film thus obtained was immersed in a 1N Kct aqueous solution for a day and night, and after washing with water, it was soaked in a 1N NaNO3 aqueous solution for 2 hours.
When the chlorine ions liberated after being immersed for one day were quantified, it was found that 5.6 moles of anion exchange groups were present in the membrane. Furthermore, this film was immersed in 1N hydrochloric acid for one day and night, and after washing with water, it was immersed in a 1N NaCZ aqueous solution for 2 days.
No release of hydrogen ions was observed. On the other hand, the film treated with 1N hydrochloric acid and washed with water was treated with a mixture of common salt and sodium hydroxide (11
(added 15 ml of N aqueous sodium hydroxide solution) to 2
When immersed for one day, it was found that 5.3 m01 of hydrogen ions were liberated. Thus, the poly(p-hydroxystyrene) moiety dissociates only under alkaline conditions.

Therefore, the ion exchanger obtained in this example is referred to as an amphoteric ion exchanger only in the alkaline region.

Example 2 Tetrahydrofuran 70rJ purified in the same manner as Example 1
mllCn-butyllithium 1.7 x 10-4
After adding moles, butadiene 18 f, p-ter
t-butoxystyrene9. Of, Imprene A7r,
4-VBDMAa9t and 5.7f of butadiene were added in five stages to carry out block copolymerization. Polymerization time is 1
It took about 20 hours per stage.

p-tertbutoxystyrene, imprene and 4-
VBDMA was purified in the same manner as in Example 1, and 1-butadiene was purified in the same manner as isoprene.

The number average molecular weight determined by the membrane osmotic pressure method for the polymer obtained at each stage of polymerization almost matches the value calculated from the number of moles of initiator and the total weight of monomers added up to each stage of polymerization. did.

Furthermore, the polymerization yield was approximately 100%, the elemental analysis results of the final polymer agreed well with the calculated values, and the GPC measurement results also showed that the molecular weight distribution was narrow.

From the above results, in this example, poly(4-VBD
MA), polyisoprene, polybutadiene, and poly(p-
tert-butoxystyrene)
It is certain that a five-element block copolymer of lyA-p017'-po'1yB-polyc type (wherein polyc at both ends is polybutadiene and pop-yC at the center is polyisoprene) was obtained.

60 μm thick made from dioxane solution of final polymer
When stained with a film of osmium tetroxide and observed with a transmission electron microscope, polydiem domain (D), poly(p-tart butoxystyrene) domain (B), and poly(4-*BDMA) domain (4) were observed. Toga-D-B-
A microphase-separated structure in which repeating units of DA- were regularly arranged in a lamellar manner was confirmed.

A similarly produced film (L30t) with a thickness of 60 μm was subjected to quaternization of the amine moiety and removal of the t-butyl group in the same manner as in Example 1, resulting in an anion exchange group of 5.2 × 104 moles. A membrane with phenolic hydroxyl groups of 4.9 x 1 (1' mole) was obtained.

Example 3 Tetrahydrofuran 6 purified in the same manner as Example 1
00m1! 2.0 x 10''' n-butyllithium inside
After adding 4 mol, 112 mol of 2-methyl-4-tertbutoxystyrene was added and left to stand for about 20 hours. (First stage) After collecting a portion of the polymer, 4-vinylpyridine was then added at 10.5F and left for about 20 hours. (Second Step) The two types of monomers used here were purified in advance in the same manner as p-tert-butoxystyrene described in Example 1.

When the number average molecular weight of the polymer obtained at each stage of polymerization was measured, it was 5.6 x 10' in the first stage. /
rno1. In the second stage, t 06X 10' P/mo
1, which was in good agreement with the value calculated from the weight of the initiator and monomer charged. The polymerization yield was approximately 100%, and the GPc elution curve measured in the same manner as in Example 1 showed a single narrow peak.

These facts indicate that in this example, a poly, 4-polyB type binary block copolymer consisting of poly(4-vinylpyridine) and poly(2-methyl-4-tartbutoxystyrene) was obtained. It shows. The results of elemental analysis and infrared absorption spectrum were also consistent with such a block copolymer.

A film with a thickness of 60 μm prepared from a solution of this block copolymer was stained with osmium tetroxide and observed using a transmission electron microscope.
A microphase-separated structure in which 4-tartbutoxystyrene) domains (M) and poly(4-vinylpyridine) domains ('P) were arranged alternately in a lamellar shape was confirmed. The thickness of this single layer was 150-200 Angstroms.

The obtained block copolymer Q, 50 if 100 m
1 was dissolved in benzene, 2 ml of methyl iodide was added, and the mixture was left to stand for 2 hours with stirring. After drying the recovered polymer at 50℃
was dissolved in 1 orul of acetone, a small amount of concentrated hydrobromic acid was added, and after stirring for 5 minutes, 5 ml of gold hydrobromic acid was added and the mixture was left stirring for 5 hours. A 40 μm thick film cast from this solution at room temperature was irradiated with ultraviolet rays for several hours to make it insoluble in water, and the anion exchange groups and phenolic hydroxyl groups were quantified in the same manner as in Example 1. As a result, 1.05 X 10-3 mol and Z
It was 42 x 10-4 mol.

[Brief explanation of the drawing]

FIG. 1 is a GPC bath separation curve of the final polymer obtained in Example 1, which was detected with a differential refractometer (R-nee 8 manufactured by Toyo Soda Co., Ltd.). Column GMH6 (length 60c++, inner diameter 7.5'i') 18 manufactured by Toyo Soda Co., Ltd. Measurements were made at a flow rate of 1 ml/min using tetrahydrofuran containing 6% N,N-dimethylbenzylamine as a synergist. Figure 2 is an infrared absorption spectrum of the same polymer. Patent applicant: Toyo Soda Kogyo Co., Ltd. Engraving of drawings (no changes in content) 12 14 16 18 20 22 24 26 hours
Time (minutes) Written amendment October 24, 1980 q, J7, 3i, Office J, + Mr. Kazuo Kanwakasugi 1. Indication of r'i 1988 Patent Application No. 173234 2. Name of the invention Ion exchanger 4. Date of amendment order 1. Spontaneous 6. Subject of amendment: “Description” and “Drawings” 7. Contents of amendment

Claims (1)

[Claims] 1) A polymer p0174+ having an anion exchange group and a polymer poly! having a phenolic hydroxyl group. An ion exchanger made of a four-block copolymer in which these are all or part of the constituent components, and the content of each is 5% by weight or more. 2) The ion exchanger according to claim 1, wherein the anion exchange group is an ammonium base, phosphonium kM, Ti- or sulfonium base. 3) An anion exchange group is introduced into a polymer po17J having an anion exchange group or a polymer made of a monomer selected from the following Nanatsuma Group A, or The ion exchanger according to item 2. Nanatsuma Group A: 2-vinylpyridine, 4-vinylpyridine. Vinylpyridines such as 2-methyl-5-vinylpyridine, vinylpyrimidines, vinylquinolines, vinylcarbazoles, and vinylimidazoles. o+m+p-vinylphenylalkylenedialkylamines represented by: Dialkylaminoalkyl acrylates represented by: Dialkyl acrylamides represented by 82. (However, n-=1 to 5, m=2 or 3, R and R are each an alkyl group having 1 to 12 carbon atoms, and R3 is hydrogen or an alkyl group having 1 to 12 carbon atoms.) 4) Polymer polyjL having a phenolic hydroxyl group has the following formula R4 1 R7 (where R4 is hydrogen or a methyl group, R5 to R.
One of them is a hydroxyl group, and the others are hydrogen or methyl groups. ) Claims 1 to 3 have a bonding unit represented by
The ion exchanger according to any one of Item 3. 5》Polymer p01 whose block copolymer does not have a polar group
Claim 1 containing 7G in an amount of 30% or more
The ion exchanger according to any one of items 1 to 4. 6) Polymer polyC without polar groups is putadiene,
The ion exchanger according to claim 5, characterized in that it is made of a diene monomer such as isoprene, pentadiene, cyclohexadiene, diphenylptadiene, etc. and 7) Polymer p01yC without polar groups is styrene,
The ion exchanger according to claim 5, characterized in that it is made of a monomer having an aromatic ring, such as α-methylstyrene or vinyltoluene.