JPH10330427A - Allylamine polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an allylamine polymer having high inherent viscosity or a water-insoluble highly polymerized jelly allylamine polymer at a high yield by polymerizing a salt of allylamine in the presence of an azo-based radical initiator by using a salt of a specific polyfunctional allylamine derivative as a crosslinking agent. SOLUTION: This polymer is obtained by polymerizing an allylamine salt in a polar solvent by using a salt of a polyufunctional allylamine derivative having an allylamine unit expressed by formula I and a part of the unit expressed by formula II (R<1> is H, etc.; X is NH, etc.; Y is a bifunctional organic group) as a crosslinking agent and in the presence of a radical initiator having an azo group in a molecule (e.g. 2,2'-diamidinyl-2,2'- azopropane.monohydrochloride). Preferably, a molar ratio of the polyfunctional allylamine derivative unit to the allylamine unit is 0.01-0.02.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a novel allylamine polymer, a method for producing the same, and a crosslinking agent. More specifically, the present invention relates to an allylamine polymer having a high intrinsic viscosity and a water-insoluble polymer gel-like allylamine polymer, a method for producing these in a high yield, and a cross-linking agent used for producing the above-mentioned allylamine polymer. It is about.

[0002]

2. Description of the Related Art An allylamine polymer is an olefin polymer containing an amino group in a side chain, is well soluble in water, and is known as a cationic polymer which is positively charged in water. As a method for producing such an allylamine polymer, there is known a method of polymerizing an aqueous solution of monoallylamine using hydrogen peroxide, potassium persulfate or a compound having an azo group in a molecule as a radical polymerization initiator. I have.

However, in such a method, the obtained allylamine polymer usually has a problem that it is difficult to produce an allylamine polymer having a small molecular weight and a high intrinsic viscosity or a water-insoluble polymer gel-like allylamine polymer. there were. On the other hand, in the fields of dye fixing agents for reactive dyes, polymer flocculants, and paper processing agents, cationic polymers such as allylamine polymers having a high intrinsic viscosity are required.
In the field of medicine such as a cholesterol lowering agent and a phosphoric acid removing agent, a cationic polymer such as a water-insoluble polymer gel-like allylamine polymer is required at present.

[0004]

SUMMARY OF THE INVENTION Under such circumstances, the present invention provides an allylamine polymer having a high intrinsic viscosity, a water-insoluble high molecular gel-like allylamine polymer, and a high yield thereof. It is intended to provide a method.

[0005]

Means for Solving the Problems As a result of intensive studies to achieve the above object, the present inventors have used a salt of a polyfunctional allylamine derivative having a specific structure as a cross-linking agent, In the presence of a system radical initiator, by polymerizing the salt of allylamine, found that an allylamine polymer having a high intrinsic viscosity or a water-insoluble polymer gel-like allylamine polymer can be obtained in a high yield, Based on this finding, the present invention has been completed.

That is, the present invention relates to the following formula (I)

Embedded image Having at least a part of the allylamine unit represented by the general formula (II):

Embedded image (Wherein R ¹ is a hydrogen atom or CH ₂ ＣＨCHCH ₂ —, X
Represents O, NH or CH ₂ ＣＨCHCH ₂ N, and Y represents a divalent organic group. An allylamine polymer characterized by being crosslinked with a polyfunctional allylamine derivative represented by the general formula (II), and an allylamine polymer comprising a salt of the polyfunctional allylamine derivative represented by the general formula (II) It also provides a manufacturing crosslinker.

Further, according to the present invention, according to the present invention, the allylamine polymer is a salt of a polyfunctional allylamine derivative represented by the following general formula (II) in a polar solvent, and a radical-initiated compound having an azo group in the molecule. It can be produced by polymerizing an allylamine salt in the presence of an agent.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The allylamine polymer of the present invention has the formula (I)

Embedded image Having at least a part of the allylamine unit represented by the general formula (II):

Embedded image (In the formula, R ¹ , X and Y are the same as described above.)

The allylamine polymer may be in a free form or a salt form. In the case of the salt type, there is no particular limitation on the kind of salt, and for example, inorganic salts such as hydrochloride, sulfate, nitrate, sulfite, and phosphate, p-toluenesulfonate, formate, acetate, and propionate Organic acid salts such as acid salts. Of these, the hydrochloride is preferred. In the case of the salt form, it may be in the form of a complete salt or in the form of a partial salt.

In the allylamine polymer of the present invention,
When the molar ratio of the polyfunctional allylamine derivative unit to the allylamine unit in the molecule is small, the polymer becomes a water-soluble polymer, and as the molar ratio increases, the intrinsic viscosity of the polymer increases. As the molar ratio increases, the polymer eventually becomes a water-insoluble polymer gel.

The molar ratio of the polyfunctional allylamine derivative unit to the allylamine unit in the allylamine polymer of the present invention is appropriately selected depending on the desired properties of the allylamine polymer and the structure of the polyfunctional allylamine derivative unit. Typically, 0.001 to 0.02
Range.

The method for producing the allylamine polymer of the present invention is not particularly limited, but according to the following method of the present invention, the allylamine polymer can be produced in a high yield.

In the method of the present invention, a salt of the polyfunctional allylamine derivative represented by the above general formula (II) and an allylamine salt in a polar solvent in the presence of a radical initiator having an azo group in the molecule are provided. Is polymerized to produce a desired allylamine polymer.

Although the reason why a high-molecular-weight allylamine polymer can be obtained in the method of the present invention is not necessarily clear, it is important that allylamine and a difunctional allylamine derivative have a positive charge in the polymerization system. Conceivable. This means that if allylamine is not in a salt state, it is difficult to polymerize, and furthermore, if a nonionic analogous compound usually used as a cross-linking agent, for example, N, N'-methylenebisacrylamide, is used. This is also supported because a molecular polymer cannot be obtained.

In the method of the present invention, a charged allylamino group (NCH ₂ CH ＝ C) is added to one end of a salt of a polyfunctional allylamine derivative used as a crosslinking agent.
H ₂ ) and, apart from it, at the other end, an allylamino group (NCH ₂ CH CH ₂ ) which is a hydrophilic group
It is also considered important to have an allyloxy group (OCH ₂ CH ＝ CH ₂ ). This is because even those which do not have such two groups independently, for example, N, N'-diallylacetamidine hydrochloride, N, N, N-triallylamine hydrochloride, etc., are used as a crosslinking agent. This is also supported because a polymer having a high viscosity cannot be obtained.

The structures of N, N'-methylenebisacrylamide, N, N'-diallylacetamidine and triallylamine are shown below.

N, N'-methylenebisacrylamide CH ₂ ＣＨCHCONHCH ₂ NHCOCH ＝ CH ₂ N, N'-diallylacetamidine

Embedded image Triallylamine N (CH ₂ CH ＝ CH ₂ ) _{3 In} the method of the present invention, examples of the salt of the allylamine salt used as a raw material monomer include inorganic salts such as hydrochloride, sulfate, nitrate, sulfite, and phosphate. Acid salt, p
Organic salts such as toluenesulphonate, formate, acetate, propionate and the like. Of these, the hydrochloride is preferred.

In the method of the present invention, the polymerization is carried out in a polar solvent. Examples of the polar solvent include water, acid (hydrochloric acid, sulfuric acid, phosphoric acid, poly-phosphoric acid) or an aqueous solution thereof, organic acid (formic acid, acetic acid, propionic acid, lactic acid, etc.) or an aqueous solution thereof, alcohol, dimethyl sulfoxide, It is carried out in an aqueous solution of dimethylformamide or a salt of an inorganic acid (zinc chloride, calcium chloride, magnesium chloride, etc.). In the polymerization, the above-mentioned allylamine salt is usually used in the form of isolated crystals, but the salt may be formed in the system by adding monoallylamine and an acid to the above-mentioned polar solvent. Needless to say, when an acid or an aqueous solution thereof is used as a polymerization solvent, a predetermined amount of allylamine is added to the acid or an aqueous solution thereof, and further, a polyfunctional allylamine derivative is added and polymerization can be performed as it is.

In the method of the present invention, a compound having an azo group in the molecule is used as the radical polymerization initiator because a high molecular weight allylamine polymer can be provided at a high conversion. Examples of the radical initiator having an azo group in the molecule include JP-B-2-14364, JP-B-2-56361, JP-B2-56362, JP-B-2-57082, and JP-B2- 5708
No. 3 publication and the like can be mentioned. The typical ones among them are as follows.

2,2'-diamidinyl-2,2'-azopropane monohydrochloride, 2,2'-diamidinyl-2,2
2'-azobutane monohydrochloride, 2,2'-diamidinyl-2,2'-azopentane monohydrochloride, 2,2'-bis (N-phenylamidinyl) -2,2'-azopropane.hydrochloric acid Salt, 2,2'-bis (N-phenylamidinyl)
-2,2'-azobutane hydrochloride, 2,2'-bis (N, N-dimethylamidinyl) -2,2'-azopropane hydrochloride, 2,2'-bis (N, N-dimethyl Amidinyl) -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. The obtained 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;

2,2'-azobis- (2-methyl-propioamidoxime), 2,2'-azobis- (2-methyl-propion-hydroxamic acid), 2,2'-azobis- (2-methyl- Butyroamidoxime), 2,2'-
Azobis- (2-methyl-butylhydroxamic acid),
2,2'-azobis- (2-isobutyl-2-methyl-
Propioamidoxime), 2,2'-azobis- (2-
Isobutyl-2-methyl-propion-hydroxamic acid), 2,2'-azobis- (2-cyclohexyl-
Propioamidoxime), 2,2'-azobis- (2-
Cyclohexyl-propion-hydroxamic acid), 2,
2'-azobis- (2-phenyl-propioamidoxime), 2,2'-azobis- (2-phenyl-propion-hydroxamic acid), 2,2'-azobis- (2-benzyl-propioamidoxime), 2,2'-azobis- (2-benzyl-propion-hydroxamic acid),
1,1'-azobis- (cyclohexyl-carbamidoxime, 1,1'-azobis- (cyclohexyl-carbohydroxamic acid);

2,2'-azobis- (2-carboxymethyl-propioamidoxime), 2,2'-azobis-
(2-carboxyethyl-propioamidoxime),
3,3'-azobis- (3-carboxyethyl-butyroamidoxime), 2,2'-azobis- (2-carboxymethyl-propionhydroxamic acid), 2,2'-azobis- (2-carboxyethyl-propion) Hydroxamic acid), 3,3'-azobis- (3-carboxyethyl-butylhydroxamic acid);

2,2'-azobis- (2-methylpropionic acid methyl ester), 2,2'-azobis- (2-methylpropionate)
Methyl propionic acid ethyl ester), 2,2'-azobis- (2-ethyl propionic acid methyl ester),
2,2'-azobis- (2-ethylbutyric acid methyl ester), 2,2'-azobis- (2-acetoxy-propane), 2,2'-azobis- (2-acetoxy-butane), 1,1 ' -Azobis (1-formoxy-cyclohexane);

2,2'-azobis- (2-methylpropionic hydrazide), 2,2'-azobis- (2-methylbutyric hydrazide), 2,2'-azobis- (2-ethylbutyric hydrazide), 1,1'-azobis- (1-cyclohexylcarboxylic acid hydrazide), 4,4'-azobis- (4-hydroxyvaleric acid hydrazide), 4,4'-
Azobis- (4-hydroxycaproic acid hydrazide).

These polymerization initiators may be used alone or in combination of two or more.

In the method of the present invention, as a crosslinking agent,
General formula (II)

Embedded image A salt of a polyfunctional allylamine derivative represented by the following formula is used.

In the general formula (II), R ¹ is a hydrogen atom or CH ₂ ＣＨCHCH ₂ —, X is O, NH or CH
₂ ＣＨCHCH ₂ N, Y represents a divalent organic group.

As the divalent organic group represented by the above Y,
It is composed of at least one group selected from an alkylene group and an alkylidene group which may be interrupted by an oxygen atom and a cycloalkylene group and a cycloalkylidene group, and has 2 to 2 carbon atoms to which a hydroxyl group may be introduced.
A divalent organic group of 0 is preferred.

Examples of the kind of the salt include the same as those exemplified above as the kind of the salt of the allylamine salt, and among these, the hydrochloride is particularly preferable.

The salts of the polyfunctional allylamine derivative represented by the general formula (II) include the following.

(1) R ¹ is a hydrogen atom, X is NH, and Y is-
(CH _{2) p} - allylamine derivatives is, that the general formula _{(II-1) CH 2 =} CHCH 2 NH (CH 2) p NHCHCH 2 = CH 2 (II-1) ( wherein, p is from 2 to 20 A salt of an allylamine derivative represented by the following general formula (II-1):
p is preferably an integer of 2 to 8 from the viewpoint of solubility at the time of polymerization, and specifically, N, N'-diallyl-ethylenediamine dihydrochloride, N, N'-diallyl-1,3-diamino Propane dihydrochloride, N, N'-diallyl-1,4-
Diaminobutane dihydrochloride, N, N'-diallyl-1,
5-diaminopentane dihydrochloride, N, N'-diallyl-1,6-diaminohexane dihydrochloride, N, N'-diallyl-1,7-diaminoheptane dihydrochloride,
N'-diallyl-1,8-diaminooctane dihydrochloride can be exemplified.

(2) R ¹ is a hydrogen atom, X is NH, and Y is-
An allylamine derivative in which a group of (CH ₂ ) _q — and —CH (R ² ) — are bonded, for example, a general formula (II-2)

Embedded image (Wherein R ² is an alkyl group having 1 to 9 carbon atoms, q is 1 to 1)
Indicates an integer of 0. In the above general formula (II-2), q is an integer of 1 to 4 and R ² is 1 to 4 carbon atoms from the viewpoint of good solubility during polymerization.
The alkyl group is preferably N, N'-diallyl-1,2-diaminopropane dihydrochloride, N, N '
Diallyl-1,2-diaminobutane dihydrochloride, N,
N'-diallyl-1,3-diaminobutane dihydrochloride,
N, N'-diallyl-1,2-diaminopentane dihydrochloride, N, N'-diallyl-1,3-diaminopentane dihydrochloride, N, N'-diallyl-1,4-diaminopentane. Dihydrochloride, N, N'-diallyl-1,2-diaminohexane dihydrochloride, N, N'-diallyl-1,3
-Diaminohexane dihydrochloride, N, N'-diallyl-
Examples thereof include 1,4-diaminohexane dihydrochloride and N, N'-diallyl-1,5-diaminohexane dihydrochloride.

(3) R ¹ is a hydrogen atom, X is NH, and Y is 1
A cycloalkylene group having 5 to 7 carbon atoms and 0 to _2- (CH ₂ ) _r- (r is an integer of 1 to 10) is bonded;
And a salt of an allylamine derivative having 2 to 20 carbon atoms; specifically, N, N'-diallyl-1,4-diaminocyclohexane dihydrochloride, N, N'-diallyl-4
-Aminomethyl-cyclohexylamine dihydrochloride,
Examples thereof include N, N'-diallyl-4-aminomethyl-cyclohexylmethylamine dihydrochloride, N, N'-diallyl-di (4-aminocyclohexyl) methane dihydrochloride, and the like.

(4) R ¹ is CH ₂ ＣＨCHCH ₂ — and X is C
H ₂ ＣＨCHCH ₂ N, an allylamine derivative in which Y is — (CH ₂ ) _s —, that is, general formula (II-3) (CH ₂ CHCH ₂ ) ₂ N (CH ₂ ) _s N (CH ₂ CH ＝ CH ₂ ) ₂ (II-3) (wherein s represents an integer of 2 to 20); a salt of an allylamine derivative represented by the following general formula (II-3): , S is preferably an integer of 2 to 8, and specifically, N, N, N ', N'-tetraallyl-
Ethylenediamine dihydrochloride, N, N, N ', N'-tetraallyl-1,3-diaminopropane dihydrochloride,
N, N, N ', N'-tetraallyl-1,4-diaminobutane dihydrochloride, N, N, N', N'-tetraallyl-1,5-diaminopentane dihydrochloride, N, N,
N ', N'-tetraallyl-1,6-diaminohexane dihydrochloride, N, N, N', N'-tetraallyl-1,
7-diaminoheptane dihydrochloride, N, N, N ', N'
-Tetraallyl-1,8-diaminooctane dihydrochloride.

(5) R ¹ is a hydrogen atom or CH ₂ ＣＨCHC
H ₂ -, X is O, NH or CH ₂ = CHCH ₂ N, Y is _{- [CH 2 CH (OH)} CH 2] t - [OCH 2 CH (O
H) CH ₂ ] _u − (wherein, t represents an integer of 1 to 6, and u represents an integer of 0 to 3,
The sum of t and u is 1-6. )); Specifically, 1-allylamino-2-hydroxy-3-allyloxy-propane.hydrochloride, 1- (diallyl) amino-2-hydroxy-3-
Allyloxy-propane hydrochloride, 1- (3'-allylamino-2'-hydroxy-propyloxy) -2-hydroxy-3-allyloxy-propane hydrochloride, 1-
[3 '-(Diallyl) amino-2'-hydroxy-propyloxy] -2-hydroxy-3-allyloxy-propane hydrochloride can be exemplified.

(6) R ¹ is a hydrogen atom or CH ₂ ＣＨCHC
H ₂ —, X is O, NH or CH ₂ ＣＨCHCH ₂ N, and Y is — [CH ₂ CH (OH) CH ₂ ] _v — [OCH ₂ CH (OH) CH ₂ ] _w —— [O (CH ₂ ) _X ] _y − (where v is an integer of 1 to 6, w is an integer of 0 to 3, x is 2
Or 3, y represents an integer of 1 to 3, and the sum of v, w, and y is 2 to 6. )); Specifically, N, N, N ', N'-tetraallyl-bis (3-amino-2-hydroxy-n-propyloxy) ethane dihydrochloride , N, N, N ', N'-
Tetraallyl-bis (3-amino-2-hydroxy-n
-Propyloxy) propane dihydrochloride.

In the method of the present invention, the amount of the radical initiator used is generally selected within the range of 0.1 to 20% by weight, preferably 1 to 10% by weight, based on the allylamine salt of the raw material monomer.

The amount of the salt of the polyfunctional allylamine derivative used is usually such that the molar ratio to the allylamine salt is 0.0
It is chosen to be between 01 and 0.02. As the molar ratio of the salt of the polyfunctional allylamine derivative increases, the intrinsic viscosity of the obtained allylamine polymer increases, but when it reaches a certain molar ratio, it becomes a polymer gel.

The total concentration of the allylamine salt and the salt of the polyfunctional allylamine derivative in the polymerization system is preferably as high as possible within the range of its solubility, but is usually from 10 to 85% by weight.
Is selected in the range.

The polymerization temperature varies depending on the kind of the radical initiator and the like, but is usually 30 to 100 ° C., preferably 40 to 100 ° C.
~ 80 ° C. The polymerization time depends on the polymerization temperature and the like, and cannot be unconditionally determined.
Within 00 hours is sufficient. In addition, since this polymerization is slightly inhibited by oxygen in the air, it is advantageous to carry out the polymerization in an atmosphere of an inert gas such as nitrogen.

If a salt-type allylamine polymer is desired after the completion of the polymerization reaction, for example, without neutralizing the reaction mixture, the reaction mixture is directly introduced into a poor solvent such as methanol,
The precipitated solid is taken out by means such as filtration, washed if necessary, and dried to obtain a desired salt-type allylamine polymer.

When a free allylamine polymer is desired, the reaction mixture is neutralized with an appropriate alkali and then treated in the same manner as described above to obtain a free allylamine polymer. Can be

The present invention also provides a crosslinking agent for producing an allylamine polymer comprising a salt of the polyfunctional allylamine derivative represented by the general formula (II). By using this crosslinking agent in the production of the allylamine polymer, as described above, an allylamine polymer having a high intrinsic viscosity and a water-insoluble allylamine polymer on a polymer gel can be obtained in a high yield.

[0046]

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

Example 1 N, N'-diallyl-1,3-
Synthesis of diaminopropane dihydrochloride (crosslinking agent A) 74.13 g of 1,3-diaminopropane in a five-neck round bottom flask equipped with a stirrer, reflux condenser, dropping funnel, and thermometer.
(1.0 mol), 50 ml of ether was added under ice cooling, and allyl chloride 168.3 was stirred and dissolved.
g (2.2 mol) and 220 g (2.2 mol) of a 40% by weight aqueous solution of sodium hydroxide were slowly dropped at the same time so that both of the drops ended simultaneously. During this time, the reaction was continued for 5 hours while maintaining the reaction temperature at 20 to 30 ° C. The temperature was further raised to 50 to 60 ° C., and the reaction was carried out for 8 hours under reflux of allyl chloride.

After completion of the reaction, the precipitated white crystals were separated by filtration.
Further, the oil layer was separated, the aqueous layer was extracted with ether, the oil layer and the ether layer were mixed, and dehydrated with sodium hydroxide overnight. Next, the ether was distilled off, and the residue was distilled under reduced pressure to obtain 107.86 g of N, N'-diallyl-1,3-diaminopropane having a bp of 70 to 74 ° C. (2 mmHg).

107.86 g (0.78 mol) of N, N'-diallyl-1,3-diaminopropane and ether 25
After putting 0 ml into a 1-liter four-neck separable flask equipped with a thermometer, a reflux condenser and a dropping funnel, 460 m of a 14.91 wt% hydrogen chloride ether solution under ice-cooling was added.
1 (1.88 mol) was added dropwise. The precipitated crystals were separated by filtration, sufficiently washed with ether, and vacuum-dried at 50 ° C. for 24 hours to obtain 122.20 g of crude crystals.
It was recrystallized from a mixed solution of methanol and ethanol at a weight ratio of 2: 1 to give N, N'-diallyl-1,3-diaminopropane dihydrochloride having a decomposition point of 251 ° C. in 25.6.
2 g were obtained. The results of elemental analysis were: C = 47.54%, H =
9.10%, N = 12.14%. These values are calculated C = 47.58%, H = 8.87%, N = 12.
This was 33%.

Example 2 N, N'-diallyl-1,2-
Synthesis of diaminopropane dihydrochloride (crosslinking agent B) Except that 1,2-diaminopropane was used in place of 1,3-diaminopropane, treatment was performed in the same manner as in Example 1, and b
N, N'-diallyl of p54-60 ° C (2 mmHg)
Via 1,2-diaminopropane, mp 176-1
21.82 g of N, N'-diallyl-1,2-diaminopropane dihydrochloride at 77 ° C. was obtained. The results of the elemental analysis
C = 47.39%, H = 9.17%, N = 12.22%
Met. These values are calculated C = 47.58%, H =
8.87% and N = 12.33%.

Example 3 N, N'-diallyl-1,6-
Synthesis of diamino-n-hexane dihydrochloride (crosslinking agent C) Instead of 1.0 mol of 1,3-diaminopropane, 1,6
-Diamino-n-hexane, except that 1.0 mol was used.
The same treatment as in Example 1 was carried out, and via N, N'-diallyl-1,6-diamino-n-hexane at bp 98 ° C (2 mmHg), N, N'-diallyl-
1,6-diamino-n-hexane dihydrochloride was 38.8.
8 g were obtained. The results of elemental analysis were: C = 52.13%, H =
10.23%, N = 11.30%, calculated value C = 53.
53%, H = 9.73%, and N = 10.40%.

Example 4 N, N'-diallyl-di (4-
Aminocyclohexyl) methane dihydrochloride (crosslinking agent D)
300 equipped with a synthetic stirrer, reflux condenser, dropping funnel and thermometer
52.59 g (0.25 mol) of di (4-aminocyclohexyl) methane was placed in a 5-ml round-bottomed flask, 50 ml of methylene chloride was added thereto under ice-cooling, and 46.27 g of allyl chloride (0. .60 mol) and 60.46 g of a 40% by weight aqueous sodium hydroxide solution (0.60 mol).
(60 mol) was slowly dropped at the same time so that both droppings ended simultaneously.

During this period, the reaction was continued for 5 hours while maintaining the reaction temperature at 20 to 30 ° C. The temperature was further raised to 50 to 60 ° C., and the mixture was reacted for 38 hours under reflux of allyl chloride.

After completion of the reaction, the precipitated white crystals were separated by filtration.
After separating the oil layer, the aqueous layer was extracted with ether, the oil layer and the ether layer were mixed, and dried with sodium hydroxide overnight. Next, the ether was distilled off to give 5 g as an oil.
4.51 g of N, N'-diallyl-di (4-aminocyclohexyl) methane were obtained.

52.45 g (0.18 mol) of this oil
Was placed in a 500 ml four-neck separable flask equipped with a thermometer, a reflux condenser and a dropping funnel, and 37.62 g (0.36 mol) of a 35% by weight aqueous hydrochloric acid solution was added dropwise under ice-cooling. After completion of the reaction, the aqueous solution was used as it was as an aqueous solution of N, N'-diallyl-di (4-aminocyclohexyl) methane dihydrochloride. Decomposition point 190-205C.

FIG. 1 shows the IR spectrum of this crosslinking agent.

Example 5 N, N, N ', N'-tetraa
Synthesis of Lil-ethylenediamine dihydrochloride (crosslinking agent E) 97.84 g of 1,2-dibromoethane was placed in a 1-liter five-necked round-bottomed flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer. 0.5 mol) and 116.6 g (1.2 mol) of diallylamine at a concentration of 40 under ice-cooling.
120 g (1.2 mol) of a weight% aqueous sodium hydroxide solution
Was slowly dropped simultaneously so that both drops were completed at the same time.

During this period, the reaction was continued for 5 hours while maintaining the reaction temperature at 20 to 30 ° C. Raise the temperature to 50-60
The reaction was carried out for 38 hours while maintaining the temperature at ° C.

After completion of the reaction, the precipitated crystals were separated by filtration, the oil layer was separated, the aqueous layer was extracted with ether, and the oil layer and the ether layer were mixed and dried with sodium hydroxide overnight. Next, the ether was distilled off under reduced pressure, and the residue was distilled under reduced pressure to obtain N, N, bp of bp 86 ° C. (3 mmHg).
53. N ', N'-tetraallyl-ethylenediamine
75 g were obtained.

50.98 g (0.23 mol) of N, N,
N ', N'-tetraallyl-ethylenediamine and 50m
of acetone was placed in a 300 ml four-necked separable flask equipped with a thermometer, a reflux condenser and a dropping funnel, and 136 ml of a 14.91% by weight hydrochloric acid ether solution was added under ice-cooling.
(0.56 mol) was added dropwise. After completion of the reaction, the solvent was distilled off under reduced pressure, and further dried at 50 ° C. for 24 hours under reduced pressure to obtain N, N, N ′, N ′ at mp 138 to 140 ° C.
-Tetraallyl-ethylenediamine dihydrochloride was obtained.
The result of elemental analysis was: C = 56.16%, H = 10.19
%, N = 9.49%. These values are calculated C =
57.34%, H = 8.94%, and N = 9.55%.

Example 6 N, N, N ', N'-tetraa
Lil-1,3-diaminopropane dihydrochloride (crosslinking agent
Synthesis of F) Instead of 0.5 mol of 1,2-dibromoethane, 1,3
-The same treatment as in Example 5 was carried out except that 0.5 mol of dibromopropane was used, and N, bp of 92 ° C (2 mmHg) was used.
Via N, N ′, N′-tetraallyl-1,3-diaminopropane, N, N, N ′, mp 74-76 ° C.
22.29 g of N'-tetraallyl-1,3-diaminopropane dihydrochloride was obtained. The result of elemental analysis was C = 5
7.90%, H = 10.20%, N = 8.84%. These values are calculated C = 58.63%, H = 9.1.
8% and N = 9.12%.

Example 7 N, N, N ', N'-tetraa
Lil-1,4-diaminobutane dihydrochloride (crosslinking agent G)
Synthesis Koei Chemical Co., Ltd. N, N, N ', N'- tetraallyl -
24.84 g (0.10 mol) of 1,4-diaminobutane
Was placed in a 300 ml four-neck separable flask equipped with a thermometer, a reflux condenser and a dropping funnel, and under ice-cooling, 7.29 g (0.20 mol) of a 35% by weight aqueous hydrochloric acid solution was added dropwise. After completion of the reaction, the aqueous solution was used as it was as a crosslinking agent.
The yield was 44.67 g.

Example 8 N, N, N ', N'-tetraa
Lil-1,6-diaminohexane dihydrochloride (crosslinking agent
Synthesis of H) Instead of 0.05 mol of 1,2-dibromoethane,
Except that 0.05 mol of 6-diaminohexane was used, treatment was carried out in the same manner as in Example 5, and bp 108 to 112 ° C (1 mm
Hg) N, N, N ', N'-tetraallyl-1,6-
Via diaminohexane, 7.19 g of N, N, N ', N'-tetraallyl-1,6-diaminohexane dihydrochloride having an mp of 137 to 138 ° C was obtained. The results of elemental analysis were: C = 61.78%, H = 10.00%, N = 7.9.
3%. These values are calculated C = 61.88%,
H = 9.81% and N = 8.02%.

Example 9 1-allylamino-2-hydro
Xy-3-allyloxy-propane hydrochloride (crosslinking agent
Synthesis of I) 62.82 g (1.1 mol) of monoallylamine was charged into a 300 ml four-neck separable flask equipped with a thermometer, a reflux condenser and a dropping funnel, and 114.15 g (1) of allyl glycidyl ether was added under ice cooling. 2.0 mol) was added dropwise. The reaction was continued for 5 hours while maintaining the reaction temperature at 20 to 30 ° C during this time. The temperature was further raised to 50 to 60 ° C, and the reaction was continued for 16 hours under reflux of monoallylamine. After the reaction,
The solvent and unreacted monoallylamine were removed by distillation, and the residue was distilled under reduced pressure to a bp of 101 to 104 ° C (2 mm
89.65 g of 1-allylamino-2-hydroxy-3-allyloxy-propane of Hg) was obtained. The results of elemental analysis were: C = 62.78%, H = 10.32%, N = 8.
22%, these values are calculated C = 63.13%,
H = 10.01% and N = 8.18%.

1-allylamino-2-hydroxy-3-
77.65 g (0.45 mol) of allyloxy-propane
Was placed in a 300 ml four-necked separable flask equipped with a thermometer, a reflux condenser and a dropping funnel, and further 140 ml (0.59%) of a 15.3% by weight hydrochloric acid ether solution under ice-cooling.
Mol) was added dropwise. After completion of the reaction, the solvent was removed by decanting, and the obtained residue was dried at 50 ° C. for 24 hours to obtain 96.45 g of 1-allylamino-2-hydroxy-3-allyloxy-propane.hydrochloride. This was used as it was as a crosslinking agent.

Example 10 1- (Diallyl) amino-2
-Hydroxy-3-allyloxy-propane hydrochloride
Synthesis of (Crosslinking Agent J) 72.87 g (0.75 mol) of diallylamine was placed in a 300 ml four-necked flask equipped with a thermometer, a reflux condenser and a dropping funnel, and then 57.08 g of allyl glycidyl ether under ice-cooling. (0.50 mol) was added dropwise. The reaction was continued for 5 hours while maintaining the reaction temperature at 20 to 30 ° C during this time. Further, the reaction temperature was raised to 50 to 60 ° C., and the reaction was continued for 24 hours. After unreacted diallylamine is removed by distillation, the residue is distilled under reduced pressure to obtain a bp of 101 to 102 ° C.
84.51 g of (2 mmHg) 1- (diallyl) amino-2-hydroxy-3-allyloxy-propane was obtained. The results of elemental analysis were: C = 67.83%, H = 10.
26%, N = 6.78%. These values are calculated C = 68.21%, H = 10.02%, N = 6.63%
And matched.

83.63 g of 1- (diallyl) amino-2-hydroxy-3-allyloxy-propane (0.40 g)
Mol) with a thermometer, reflux condenser and dropping funnel
ml of a 4-neck separable flask, and 151 g (0.79 wt.
Mol) was added dropwise. After decanting off the solvent, the residue was vacuum dried at 50 ° C. for 24 hours,
53.75 g of 1- (diallyl) amino-2-hydroxy-3-allyloxy-propane dihydrochloride was obtained.

Example 11 N, N, N ', N'-tetra
Allyl-bis (3-amino-2-hydroxy-n-pro
Synthesis of pyroxy) ethane dihydrochloride (crosslinking agent K) 64.12 g (0.66 mol) of diallylamine was placed in a 300 ml four-necked separable flask equipped with a thermometer, a reflux condenser and a dropping funnel, and then cooled with ice. Ethylene diglycidyl ether (Denacol EX manufactured by Nagase Kasei Co., Ltd.)
-811) 52.26 g (0.30 mol) was added dropwise.
The reaction was continued for 5 hours while maintaining the reaction temperature at 20 to 30 ° C during this time. Further, the reaction was continued for 8 hours while keeping the reaction temperature raised to 50 to 60 ° C.

After completion of the reaction, unreacted diallylamine was removed by distillation, and 94.27 g of N, N,
N ', N'-Tetraallyl-bis (3-amino-2-hydroxy-n-propyloxy) ethane was obtained. The results of elemental analysis were as follows: C = 76.14%, H = 11.14%, N
= 12.72%. These values are calculated C = 7
6.31%, H = 10.98%, and N = 12.71%.

94.27 g (0.26 mol) of this oil
Was placed in a 500 ml four-necked separable flask equipped with a thermometer, a reflux condenser, and a dropping funnel, and the concentration was 9.85 under ice cooling.
208.3 g (0.56 mol) of a weight% hydrochloric acid ether solution
Was added dropwise. After completion of the reaction, the solvent was decanted off and the resulting residue was dried in vacuo at 50 ° C. for 24 hours to give 86.74 g of N, N, N ′, N′-tetraallyl-bis (3-amino-2- Hydroxy-n-propyloxy) ethane dihydrochloride was obtained.

FIG. 2 shows the IR spectrum of this crosslinking agent.

Tables 1 and 2 show the structural formulas of the crosslinking agents A to K obtained as described above.

[0073]

[Table 1]

[0074]

[Table 2]

Examples 12 to 43 of allylamine polymer
Production concentration 62% or 70% by weight monoallylamine (M
AA) A predetermined amount of a crosslinking agent and 2,2′-azobis (2-amidinopropane) dihydrochloride as a radical initiator are added to 10 g of an aqueous solution of hydrochloride, and the resulting mixture is mixed with 5
The polymerization was carried out by heating at 5 ° C. for 72 hours.

After completion of the polymerization, regardless of whether the reaction mixture was liquid or gel, the reaction mixture was poured into 200 ml of methanol, and the resulting precipitate was collected by filtration to obtain an allylamine polymer of the present invention.

The results of the elemental analysis of the allylamine polymer hydrochloride (Example 13) synthesized using the cross-linking agent A were as follows:
C = 37.99%, H = 9.56%, N = 14.55%
Met. Note that the calculated values C = 38.51%, H = 8.6.
2%, N = 14.97%.

The IR spectrum of this polymer is shown in FIG.
Shown in

The molar ratio of the crosslinking agent to MAA in the polymerization, the yield of the obtained polymer, and its intrinsic viscosity (when the reaction mixture is a liquid) or water-insoluble gel (when a water-insoluble gel is generated) The results are shown in Tables 3 and 4.
The intrinsic viscosity was 0.5% by weight of the allylamine polymer.
The resulting solution was dissolved in a 0.1 mol / liter sodium chloride aqueous solution so as to have a concentration, and the obtained solution was measured at 30 ° C. for determination.

[0080]

[Table 3]

[0081]

[Table 4]

From Tables 3 and 4, it was found that in the method for producing an allylamine polymer of the present invention, a high-molecular-weight allylamine polymer can be obtained at a high conversion.

Comparative Examples 1 to 7 Allylamine polymers were produced in the same manner as in Examples, except that a crosslinking agent other than the crosslinking agent used in the present invention was used. Table 5 shows the results.

[0084]

[Table 5]

(Note)

Embedded image From Table 5, it was found that, in the case of using a compound other than the crosslinking agent used in the present invention, either the polymerization yield was poor or a high-viscosity (high-molecular) allylamine polymer could not be obtained. did.

[0086]

According to the present invention, an allylamine polymer having a high intrinsic viscosity or a water-insoluble polymer gel-like allylamine polymer, which has been difficult to produce conventionally, can be obtained in high yield.

[Brief description of the drawings]

FIG. 1 is a diagram of an IR spectrum of a crosslinking agent produced in Example 4.

FIG. 2 is a view of an IR spectrum of a crosslinking agent produced in Example 11.

FIG. 3 shows I of an allylamine polymer produced in Example 13.
It is a figure of an R spectrum.

Claims (4)

[Claims] 1. A compound of the formula (I) Having at least a part of the allylamine unit represented by the general formula (II): (Wherein R ¹ is a hydrogen atom or CH ₂ ＣＨCHCH ₂ —, X
Represents O, NH or CH ₂ ＣＨCHCH ₂ N, and Y represents a divalent organic group. An allylamine polymer which is crosslinked with the polyfunctional allylamine derivative represented by the formula (1). 2. A polyfunctional allylamine derivative,
Y in the general formula (II) is constituted by at least one group selected from an alkylene group and an alkylidene group which may be interrupted by an oxygen atom, and a cycloalkylene group and a cycloalkylidene group, wherein a hydroxyl group is introduced. The allylamine polymer according to claim 1, which is a divalent organic group having 2 to 20 carbon atoms. 3. In a polar solvent, a compound represented by the general formula (II): (Wherein R ¹ is a hydrogen atom or CH ₂ ＣＨCHCH ₂ —, X
Represents O, NH or CH ₂ ＣＨCHCH ₂ N, and Y represents a divalent organic group. 3. The method for producing an allylamine polymer according to claim 1, wherein the allylamine salt is polymerized in the presence of a salt of the polyfunctional allylamine derivative represented by the formula) and a radical initiator having an azo group in the molecule. Method. 4. The following formula (II): (Wherein R ¹ is a hydrogen atom or CH ₂ ＣＨCHCH ₂ —, X
Represents O, NH or CH ₂ ＣＨCHCH ₂ N, and Y represents a divalent organic group. A) a crosslinking agent for producing an allylamine polymer comprising a salt of a polyfunctional allylamine derivative represented by the following formula: