JP2002047316A - Allylamines polymer with mercapto group at terminal and method of manufacturing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide allylamines polymer which has mercapto groups at terminals and is expected to be a functional polymer having new applications, and method of manufacturing the same. SOLUTION: The allylamines polymer contains at least one selected from a constitutional unit shown in general formula (I), (II-a) and (II-b) (wherein, R1, R2 is H or C1-C10 alkyl group, R3 is H or C1-C10 alkyl group that may contain hydroxyl group), its salt adduct and its quaternary ammonium salt, and mercapto groups at terminals. In a polar solvent and in the presence of a water-soluble azo catalyst and a thio acid, a salt adduct of monoalkylamines and/or diallylamines or quaternary ammonium salt are polymerized and hydrolyzed to provide allylamines polymer with mercapto groups at terminals.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an allylamine polymer having a mercapto group at a terminal and a method for producing the same. More specifically, the present invention provides a monoallylamine polymer or a diallylamine polymer having a mercapto group as a functional group at a terminal, which is expected to have a new use as a functional polymer, and a method for efficiently producing the polymer. It is about.

[0002]

2. Description of the Related Art Polymers having a mercapto group at the terminal are:
From the viewpoint of the reactivity of the mercapto group, various uses can be expected as a functional polymer. Conventionally, as a method for producing a polymer having a mercapto group at a terminal, for example, a method of subjecting a radically polymerizable monomer to radical polymerization in the presence of a thioacid such as thioacetic acid, and then subjecting the resulting polymer to hydrolysis treatment. Is known (Japanese Patent Publication No. 2-7325).
In this method, a thioacid acts as a chain transfer agent, is introduced into the terminal of the polymer in the form of a thioacid ester, and is hydrolyzed with an alkali or an acid to obtain a polymer having a mercapto group at the terminal. Is the way.

In this method, as monomers capable of radical polymerization, α-olefins, (meth) acrylic acid or its esters, (meth) acrylamide or its N-substituted products, styrenes, and (meth) acrylonitrile , N-vinylpyrrolidone and fluorinated monomers, but no mention is made of allylamines. It is generally known that allylamines are hardly polymerized by destructive chain transfer. Therefore, it is the actual situation that no allylamine polymers having a mercapto group at the terminal have been found so far.

[0004] The applicant of the present invention has conducted intensive studies on the polymerization of allylamines, and has been able to obtain a polymer having a high degree of polymerization by using a specific radical initiator and polymerizing the allylamine under specific conditions. For example, it was found that an inorganic acid salt of monoallylamine was obtained in a polar solvent in the presence of a radical initiator containing an azo group and a group having a cationic nitrogen atom in the molecule. (Japanese Patent Application Laid-Open No. 58-201811).

[0005]

SUMMARY OF THE INVENTION Under these circumstances, the present invention provides an allylamine polymer having a mercapto group as a functional group at a terminal and expected to have a new use as a functional polymer. It is an object of the present invention to provide a method for efficiently manufacturing this.

[0006]

Means for Solving the Problems The present inventors have conducted intensive studies to achieve the above object, and as a result, have found that monoallylamines can be obtained in a polar solvent in the presence of a water-soluble azo catalyst and a thioacid. After polymerizing an addition salt and / or an addition salt of diallylamines or a quaternary ammonium salt, it was found that an allylamine polymer having a mercapto group at a terminal can be efficiently obtained by hydrolysis treatment. The present invention has been completed based on the findings.

That is, the present invention provides a compound represented by the general formula (I)

[0008]

Embedded image

(Wherein, R ¹ and R ² each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms)
And the addition salt thereof, and the general formulas (II-a) and (II-b)

[0010]

Embedded image

(In the formula, R ³ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may have a hydroxyl group.)
And at least one selected from addition units and quaternary ammonium salts thereof, and having a mercapto group at the terminal.

According to the present invention, the allylamine polymer having a mercapto group at the terminal can be prepared by reacting a compound represented by the general formula (III) in a polar solvent in the presence of a water-soluble azo catalyst and a thioacid.

[0013]

Embedded image

(Wherein, R ¹ and R ² each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms)
And / or an addition salt of a monoallylamine represented by the general formula (IV)

[0015]

Embedded image

(In the formula, R ³ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may have a hydroxyl group.)
Can be produced by polymerizing an addition salt or quaternary ammonium salt of a diallylamine represented by the formula (1), followed by hydrolysis.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION The allylamine polymer having a mercapto group at the terminal of the present invention is represented by the following general formula (I):

[0018]

Embedded image

A unit represented by the general formula (II-a) or (II-b):

[0020]

Embedded image

And at least one selected from the group consisting of an addition salt thereof and a quaternary ammonium salt. That is, it may be a homopolymer having only one type of each unit, or a copolymer including two or more types of each unit, and the copolymer may be random or block. There may be.

In the structural unit represented by the general formula (I), R ¹ and R ² each represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, which may be the same or different. . As the alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 4 carbon atoms, specifically, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, various butyl groups, and more preferably a cyclohexyl group Can be mentioned. Examples of the addition salt of the structural unit represented by the general formula (I) include hydrochloride, hydrobromide, sulfate, nitrate, sulfite, and phosphate.

On the other hand, the general formulas (II-a) and (II-b)
In the structural unit represented by, R ³ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may have a hydroxyl group. As the alkyl group having 1 to 10 carbon atoms which may have a hydroxyl group, an alkyl group having 1 to 4 carbon atoms which may have a hydroxyl group, specifically, a methyl group, an ethyl group, and n -Propyl group, isopropyl group, various butyl groups, 2-hydroxyethyl group, 2-hydroxypropyl group, 3-hydroxypropyl group and the like.

The compounds of the general formulas (II-a) and (II-b)
As the addition salt of the structural unit represented by, for example, hydrochloride,
Examples thereof include hydrobromide, sulfate, nitrate, sulfite, and phosphate. Examples of the quaternary ammonium salt include N, N-dimethylallylammonium chloride, N, N
-Diethylallylammonium chloride, N, N-dipropylallylammonium chloride, N, N-dibutylallylammonium chloride, N, N-methylbenzylallylammonium chloride, N, N-ethylbenzylallylammonium chloride, and chlorides thereof And bromides, iodides, methyl sulfates, and the like corresponding to the compounds.

The molecular weight of the allylamine polymer having a mercapto group at the terminal is usually from 500 to 20.
000, preferably in the range of 1,000 to 10,000. Therefore, the SH equivalent value is usually 0.05 to 2 me.
It is in the range of q / g, preferably in the range of 0.1 to 1 meq / g. An allylamine polymer having the above constitutional unit and having a mercapto group at a terminal can be efficiently produced by the method of the present invention described below.

In the method of the present invention, an addition salt of a monoallylamine and / or an addition salt of a diallylamine or a quaternary ammonium salt is first prepared in a polar solvent in the presence of a water-soluble azo catalyst and a thioacid. Polymerize.

The polar solvent is particularly preferably an aqueous solvent. Examples of the aqueous solvent include water, an inorganic acid (hydrochloric acid, sulfuric acid, phosphoric acid, polyphosphoric acid), an organic acid aqueous solution, and an inorganic acid salt (zinc chloride, calcium chloride, magnesium chloride, etc.) aqueous solution.

As the water-soluble azo catalyst, a radical polymerization initiator having an azo group and a group having a cationic nitrogen in the molecule is preferable. Any of these can be selected and used. Among them, a compound represented by the general formula (V): R ⁴ —NＮNR ⁵ (V) wherein at least one of R ⁴ and R ⁵ is an aminohydrocarbyl group, an amino group with groups comprising isoxazolidinyl hydrocarbyl group and a nitrogen atom that can be cationized is selected from cyano amino hydrocarbyl groups, the remainder is a hydrocarbyl group or a cyano hydrocarbyl group, R ⁴ and R ^5, they together general formula (VI)

[0029]

Embedded image

(R is an alkylene group, X is a group containing a cationizable nitrogen atom, and the covalent bonds (a) and (b) are each bonded to a nitrogen atom of the azo group to form a ring containing an azo group. ) May be formed. The inorganic acid salt or the organic acid salt of the azo compound represented by the formula [1] is practically used in terms of ease of synthesis and the like.

In R ⁴ and R ⁵ in the formula (V), examples of the aminohydrocarbyl group include an aminoalkyl group, an aminoaryl group, an aminoalkaryl group and an aminoaralkyl group. Examples of the hydrocarbyl group include an amidinylalkyl group, an amidinylaryl group, an amidinylalkaryl group, and an amidinylaralkyl group.Examples of the cyanoaminohydrocarbyl group include a cyanoaminoalkyl group and a cyanoamino group. Examples include an aryl group, a cyanoaminoalkaryl group, and a cyanoaminoaralkyl group. Examples of the hydrocarbyl group include an alkyl group, an aryl group, an alkaryl group, and an aralkyl group.Examples of the cyanohydrocarbyl group include a cyanoalkyl group, a cyanoaryl group, a cyanoalkaryl group, and a cyanoaralkyl group. No.

On the other hand, examples of the alkylene group represented by R in the general formula (VI) include a linear alkylene group, an alkylalkylene group and an arylalkylene group.

Examples of the radical polymerization initiator represented by the general formula (V) include 2,2'-diamidinyl-2,
2'-azopropane hydrochloride, 2,2'-diamidinyl-2,2'-azobutane hydrochloride, 2,2'-diamidinyl-2,2'-azopentane hydrochloride, 2,2'-bis (N -Phenylamidinyl) -2,2'-azopropane hydrochloride, 2,2'-bis (N-phenylamidinyl) -2,2'-azobutane hydrochloride, 2,2'-bis (N , N-Dimethylamidinyl) -2,2'-azopropane hydrochloride, 2,2'-bis (N, N-dimethylamidinyl) -2,2'-azobutane hydrochloride, 2,2 ' −
Bis (N, N-diethylamidinyl) -2,2'-azopropane hydrochloride, 2,2'-bis (N, N-diethylamidinyl) -2,2'-azobutane hydrochloride, ,
2'-bis (N-di-n-butylamidinyl) -2,2 '
-Azopropane hydrochloride, 2,2'-bis (N-di-n-
Butylamidinyl) -2,2'-azobutane hydrochloride,
3,3'-bis (N, N-di-n-butylamidinyl)-
3,3'-azopentane hydrochloride, azo-bis-N,
N'-dimethyleneisobutylamidine hydrochloride; 2,
2'-azo-bis (2-methyl-4-diethylamino)
-Butyronitrile hydrochloride, 2,2'-azo-bis (2
-Methyl-4-dimethylamino) -butyronitrile hydrochloride, 2,2'-azo-bis (2-methyl-4-diethylamino) -butyronitrile hydrochloride, 2,2'-azo-bis (2-methyl- 4-diethylamino) -butyronitrile or 2,2'-azo-bis (2-methyl-4-
Dimethylamino) -butyronitrile is quaternized with dimethyl sulfate or methyl p-toluenesulfonate, for example; quaternary ammonium salt type azonitrile; 3,5-diamidinyl-1,2-diazo-1-cyclopentene hydrochloride; 3-methyl-3,4-diamidinyl-1,2-diazo-1-cyclopentene hydrochloride, 3-ethyl-3,5
-Diamidinyl-1,2-diazo-1-cyclopentene hydrochloride, 3,5-dimethyl-3,5-diamidinyl-
1,2-diazo-1-cyclopentene hydrochloride, 3,6
-Diamidinyl-1,2-diazo-1-cyclohexene hydrochloride, 3-phenyl-3,5-diamidinyl-1,
2-diazo-1-cyclopentene hydrochloride, 3,5-diphenyl-3,5-diamidinyl-1,2-diazo-1
-Cyclopentene hydrochloride.

Further, as a water-soluble azo catalyst, a compound represented by the general formula (VII):

[0035]

Embedded image

Wherein R ^{6 to} R ⁹ are each independently a lower alkyl group, and R ¹⁰ and R ¹¹ are each independently a general formula (VIII)

[0037]

Embedded image

(Where, Z is an alkylene group having 1 to 12 carbon atoms), which represents a hydroxyalkylamide group or a hydroxyalkylester group. ] Can also be used.

In the above general formula (VII), examples of the lower alkyl group represented by R ^{6 to} R ⁹ include a saturated or unsaturated alkyl group having 1 to 10 carbon atoms. It may be branched or cyclic, and one or more carbon atoms may be substituted by O, S or N. For example, R ^{6 to} R ⁹ may be an alkoxyalkyl group having 2 to ⁹ carbon atoms.

In the compound represented by the general formula (VII), R ^{6 to} R ⁹ are all methyl groups, and Z in the general formula (VIII) is an ethylene group as R ¹⁰ and R ^11. Some are preferred, and 2,2'-azobis [2-methyl-N- (2-hydroxyethyl) propionamide] is particularly preferred.

One of these water-soluble azo catalysts may be used alone, or two or more of them may be used in combination. %, More preferably 3 to 15 mol%.

On the other hand, thioacid refers to a compound having a -COSH group, and examples thereof include thioacetic acid, thiopropionic acid, thiobutyric acid, and thiovaleric acid. Of these, thioacetic acid is particularly preferred because the thioacid ester at the polymer terminal has good hydrolyzability.

This thioacid may be used alone or in combination of two or more.
The amount of the catalyst used is 0. 0 based on the water-soluble azo catalyst used.
5 to 3.0 equivalents are preferred, and 0.8 to 2.5 equivalents are particularly preferred.

In the method of the present invention, the starting monomer is represented by the general formula (III):

[0045]

Embedded image

(Wherein R ¹ and R ² are the same as described above), and / or an addition salt of a monoallylamine represented by the general formula (IV)

[0047]

Embedded image

(Wherein R ³ is the same as described above), or an addition salt or quaternary ammonium salt of diallylamine.

Examples of addition salts of monoallylamines represented by the above general formula (III) include monoallylamine, N
-Methylallylamine, N-ethylallylamine, N-
Propylallylamine, N-cyclohexylallylamine, N, N-dimethylallylamine, N, N-diethylallylamine, N, N-dipropylallylamine,
N-dicyclohexylallylamine, N, N- (methyl) cyclohexylallylamine, N, N- (ethyl)
Hydrochloride such as cyclohexyl allylamine, hydrobromide, sulfate, nitrate, sulfite, phosphate and the like can be mentioned.

On the other hand, examples of diallylamine addition salts represented by the above general formula (IV) include diallylamine, N
-Methyldiallylamine, N-ethyldiallylamine,
N-propyldiallylamine, N-butyldiallylamine, N-2-hydroxyethyldiallylamine, N-2
Hydrochloride such as -hydroxypropyldiallylamine, N-3-hydroxypropyldiallylamine, hydrobromide, sulfate, nitrate, sulfite, phosphate and the like. Examples of the quaternary ammonium salts of diallylamines represented by the general formula (IV) include diallyldimethylammonium chloride, diallyldimethylammonium bromide, diallyldimethylammonium iodide, diallyldimethylammonium methylsulfate, and diallyldiethyldiethyl chloride. Ammonium, diallyl diethylammonium bromide, diallyl diethylammonium iodide, diallyl diethylammonium methylsulfate, diallylmethylbenzylammonium chloride, diallylmethylbenzylammonium bromide,
Diallylmethylbenzylammonium iodide, diallylmethylbenzylammonium methylsulfate, diallylethylbenzylammonium chloride, diallylethylbenzylammonium bromide, diallylethylbenzylammonium iodide, diallylethylbenzylammonium methylsulfate and the like.

In the present invention, one of the raw material monomers may be selected for homopolymerization, or two or more may be selected for copolymerization. The polymerization temperature is not particularly limited,
The range is preferably from 30 to 90 ° C, particularly preferably from 40 to 80 ° C.

After the completion of the polymerization reaction, the thioate group at the terminal of the polymer is hydrolyzed to introduce a mercapto group. In the present invention, an acid such as hydrochloric acid is used in the hydrolysis treatment. However, it is preferable to perform the reaction at a temperature of about 20 to 60 ° C. by adding a substantially stoichiometric amount.

Since the allylamine polymer having a mercapto group at the terminal thus formed forms an addition salt and / or a quaternary ammonium salt, the addition salt and / or quaternary ammonium salt is formed by a known method. It may be taken out and purified in the form of a quaternary ammonium salt, or, if desired, treated with an alkali and then taken out and purified in a free form. Further, a desired acid can be added to the thus-purified free-form polymer to obtain a complete addition salt or a partial addition salt.

[0054]

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

The measurement of the weight average molecular weight of the polymer, the determination of the mercapto (SH) group at one terminal and the calculation of the molecular weight were carried out according to the following methods.

(1) Measurement of Weight Average Molecular Weight of Polymer The weight average molecular weight (Mw) of the polymer was determined by Hitachi L-6000.
It was measured by gel permeation chromatography (GPC method) using a high-performance liquid chromatograph. The eluent flow path pump is Hitachi L-6000, the detector is Shodex RI SE-61 differential refractive index detector, and the column is Asahi Pack's aqueous gel filtration type GS-22.
0HQ (exclusion limit molecular weight 3,000) and GS-620H
Q (exclusion limit molecular weight: 2,000,000) was used in double connection. Sample is 0.5g / 100ml as eluent
And used 20 μl. The eluent contains 0.
A 4 mol / l aqueous sodium chloride solution was used. The column temperature was 30 ° C. and the flow rate was 1.0 ml / min.
Molecular weights 106, 194, 440, 6 as standard samples
00, 1470, 4100, 7100, 10300, 1
A calibration curve was determined using polyethylene glycol such as 2600 or 23000, and the M of the polymer was determined based on the calibration curve.
w was determined.

(2) Quantification of Mercapto (SH) Group at One Terminal and Calculation of Molecular Weight To determine the mercapto group at one terminal, a certain amount of a standard solution of iodine was added to a sample, and the remaining iodine was added to a standard solution of sodium thiosulfate. Was determined by iodine oxidation titration, and the molecular weight was calculated from the value. That is, the purified polymer is
Approximately 0.1 g is weighed in a volumetric flask, and distilled water 40 ml
Was added, stirred and dissolved, and about 0.9 ml of a 0.1 N iodine solution was accurately added to the polymer solution with a 1 ml measuring pipette. Then, add distilled water to this solution up to the marked line,
For 2 hours. Add a few drops of starch solution to this sample,
Titration with 0.01 N sodium thiosulfate solution was completed when the blue color just disappeared. The molecular weight was calculated from the SH equivalent value (eq / g).

Examples 1 to 6 In a 30-ml test tube with a stopper, 20 mmol of a 20% by weight aqueous solution of diallylamines and thioacetic acid (based on monomer 1)
Then, 2,2′-azobis (2-amidinopropane) hydrochloride (ABAP) (5 to 10 mol% based on monomer) was added, and the mixture was allowed to stand still at 60 ° C. for 72 hours. After completion of the polymerization, the polymerization yield and Mw were determined by the GPC method. The results are shown in Table 1.

After completion of the polymerization, thioacetic acid and an equimolar amount of 35% by weight hydrochloric acid were added, and the mixture was hydrolyzed at 40 ° C. for 24 hours. The polymer after hydrolysis was concentrated, reprecipitated with isopropanol (IPA), filtered off with a 1G5 glass filter, and vacuum dried at 40 ° C. for 72 hours or more. The sample obtained by reprecipitation was subjected to iodine oxidation titration to determine the terminal group, and the molecular weight was determined. The results are shown in Table 1.

[0060]

[Table 1]

(Note) DAA.HCl: diallylamine hydrochloride DAMA.HCl: N-methyldiallylamine hydrochloride

Example 7 801.73 g of a 20% by weight DAA.HCl aqueous solution
To this was added 4.57 g of thioacetic acid (5 mol% based on the monomer). When the internal temperature of the solution reaches 60 ° C., about 50 r
16.27 g of ABAP as initiator under stirring speed of pm
(5 mol% with respect to monomer) was added all at once, and polymerization was started. After 72 hours, the polymerization was terminated, and the polymerization yield and Mw were determined by the GPC method. As a result, the polymerization yield was 96% and M
w was 5,000.

After completion of the polymerization, 35% by weight hydrochloric acid in an equimolar amount to thioacetic acid was added to the polymerization solution, and hydrolysis was carried out at 40 ° C. for 24 hours. After the hydrolysis, a part of the solution was taken out, concentrated, reprecipitated with IPA, filtered off with a 1G5 glass filter, and vacuum-dried at 40 ° C. for 72 hours or more. The sample obtained by reprecipitation was subjected to terminal group quantification by iodine oxidation titration. As a result, the SH equivalent value was 2.26 × 10 ⁻¹ meq.
/ G, and the molecular weight was 4,400.

Example 8 833.63 DAMA · HCl aqueous solution having a concentration of 15% by weight
3.23 g of thioacetic acid (5 mol% with respect to the monomer) was added to g. When the internal temperature of the solution reaches 60 ° C., about 50
ABAP 11.53 as initiator under stirring speed of rpm
g (based on the monomer 5 mol%) was added all at once, and polymerization was started. After 72 hours, the polymerization was terminated, and the polymerization yield and Mw were determined by the GPC method. As a result, the polymerization yield was 84% and Mw was 6,000. Hydrolysis was carried out in the same manner as in Example 7, and the SH equivalent value was determined to be 1.73 by iodine oxidation titration.
× 10 ^-1 meq / g, and the molecular weight was 5,800.

Example 9 To 808.38 g of an aqueous solution of diallyldimethylammonium chloride (DADMAC) having a concentration of 15% by weight, 2.85 g of thioacetic acid (5 mol% based on monomer) was added. When the internal temperature of the solution reached 60 ° C., 10.17 g (5 mol% based on monomer) of ABAP was added as an initiator at a time under a stirring speed of about 50 rpm to initiate polymerization. 72
After a lapse of time, the polymerization is terminated, and the polymerization yield and Mw are determined by the GPC method.
As a result, the polymerization yield was 92% and Mw was 6,100. Hydrolysis was carried out in the same manner as in Example 7, and titration was difficult, but the SH equivalent value was 1.3 by iodine oxidation titration.
It was 9 × 10 ⁻¹ meq / g, and the molecular weight was 7,200.

Example 10 Monoallylamine hydrochloride (MAA.H) having a concentration of 60% by weight
9.38 g of thioacetic acid (5 mol% based on monomer) was added to 389.82 g of an aqueous solution of Cl). When the internal temperature of the solution is 60
When the temperature reached 0 ° C., 33.90 g of ABAP (5 mol% based on monomer) was used as an initiator under a stirring speed of about 50 rpm.
Was added all at once to initiate polymerization. After 72 hours, the polymerization was terminated, and the polymerization yield and Mw were determined by the GPC method.
The polymerization yield was 95% and Mw was 2,100. Hydrolysis was carried out in the same manner as in Example 7, and the sulfur content was determined by iodine oxidation titration.
The H equivalent value was 4.47 × 10 ⁻¹ meq / g, and the molecular weight was 2,200.

[0067]

According to the method of the present invention, an allylamine polymer having a mercapto group at a terminal (a homopolymer or a copolymer of monoallylamine or diallylamine)
Can be produced in good yield. Since this allylamine polymer has a SH group which is a functional group at a terminal,
New applications can be expected as functional polymers.

Claims (5)

[Claims] 1. A compound of the general formula (I) (Wherein, R ¹ and R ² each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms) and an addition salt thereof, and a compound represented by the general formula (II-a) or ( II-b) (Wherein R ³ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may have a hydroxyl group), an addition salt thereof and a quaternary ammonium salt. An allylamine polymer comprising at least one of the above, and having a mercapto group at a terminal. 2. The allylamine polymer according to claim 1, wherein the SH equivalent value is 0.05 to 2 meq / g. 3. A compound of the formula (III) in a polar solvent in the presence of a water-soluble azo catalyst and a thioacid. (Wherein, R ¹ and R ² each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms), and / or an addition salt of a monoallylamine represented by the general formula (I
V) (Wherein, R ³ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may have a hydroxyl group.) An addition salt or quaternary ammonium salt of diallylamine represented by Characterized by a hydrolysis treatment,
A method for producing an allylamine polymer according to claim 1. 4. The method according to claim 3, wherein the thioacid is thioacetic acid. 5. The method according to claim 3, wherein the polar solvent is an aqueous solvent.