JPH08134114A - Method for polymerizing diallyldialkylammonium compound - Google Patents

Abstract

PURPOSE: To industrially, economically and stably produce a high-molecular weight polymer containing masked heavy metallic ions by adding a chelating agent to a diallyldialkylammonium compound and polymerizing the compound. CONSTITUTION: A chelating agent is added to chelate heavy metallic ions in a solution in polymerizing a monomer of the formula (R<1> and R<2> are each hydrogen, a 1-6C alkyl, benzyl or a cycloalkyl; X is F, Cl, Br, I, NO3 , HSO4 or H2 PO4 ) and providing a polymer. Heavy metallic ions are copper or iron ions. The chelating agent is selected from ethylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, glycol ether diaminetetraacetic acid, ethyl ether diaminetetraacetic acid, diethylenetriaminetetraacetic acid and alkali metallic salts thereof, dihydroxyethylglycine, tetraethylpentamine, triethylenetetramine and triethanolamine.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for polymerizing a diallyldialkylammonium compound.

[0002]

2. Description of the Related Art As a conventional method for polymerizing a polymer of diallylamine and its derivative (hereinafter abbreviated as diallylamine-based polymer), for example, a monomer represented by the following general formula (I) is persulfated in an aqueous medium. It is carried out using a radical polymerization initiator such as a salt or a water-soluble azo compound. At that time, even though the monomer is a polyfunctional unsaturated compound, it does not exhibit behavior such as three-dimensional structuring, and polymerizes with intramolecular cyclization reaction in one molecule, and the piperidine ring is formed in the molecule. It is generally known to produce a polymer having: and the resulting polymer is soluble in water.

Heretofore, when trying to obtain a high-molecular-weight diallylamine-based polymer, the molecular weight was influenced by the method of producing the monomer and the method of purification. Therefore, it was important to control the production method, but nevertheless, only a low molecular weight polymer could be obtained, and the influence of heavy metal ions was found to be the cause.

[0004]

When heavy metal ions such as copper and iron are present in the water-soluble medium of the diallylamine-based monomer, the polymerization reaction of the monomer is inhibited and a high-molecular weight polymer is obtained. I can't. These heavy metal ions may be contained in the activated carbon used for decolorizing the monomer solution or may be mixed in due to the corrosion of the reaction device or the like, which poses a serious problem in stabilizing the product quality.

[0005]

The present invention has been made by paying attention to the above problems, and as a result of earnest research, it is possible to stably produce a high-molecular-weight diallylamine polymer industrially and economically. It became possible to do.

In the present invention, when a monomer represented by the following general formula (I) is polymerized to produce a polymer, a chelating agent is added to a solution of the monomer and a heavy metal contained in the solution is added. A method for polymerizing a diallyldialkylammonium compound, which comprises chelating ions.

[0007]

[Chemical 2](R in the formula¹, R²Are independently hydrogen atoms and carbon atoms of 1 to 6
It represents a alkyl group, a benzyl group or a cycloalkyl group. X
Is F, Cl, Br, I, NO₃, HSO_FourOr H ₂PO
_FourRepresents )

In carrying out the present invention, the general formula (I)
The monomers shown in 1 may be used alone or in a mixture of 2 or more kinds. Preferred is a monomer in which R ¹ and R ² are methyl groups and X is Cl.

It is not clear by what mechanism heavy metal ions hinder the assembly in the polymerization reaction, but in the case of copper ions, the degree of polymerization is reduced by a small amount of about 0.01 ppm, and in the case of iron ions it is polymerized at 10 ppm or more. I lose my degree. It was found that when these heavy metal ions were made into chelate compounds, the degree of polymerization was hardly inhibited. Examples of chelating agents used include ethylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, glycol etherdiaminetetraacetic acid, ethyletherdiaminetetraacetic acid, diethylenetriaminepentaacetic acid, dihydroxylethylglycine, tetraethylpentamine, triethylenetetramine or Triethanolamine or the like may be used. Such acetic acid type chelating agents include alkali metal salts such as sodium salt and potassium salt. The chelating agent may be used in an amount equivalent to the heavy metal ion, but if it is more than that, chelation is completely carried out.

As other production conditions, the production conditions of the diallylamine polymer may be used as they are. That is, the concentration of the monomer is appropriately about 10% by weight to 80% by weight, but usually about 30% by weight to 55% by weight is appropriate in consideration of the cooling capacity and reactivity of the manufacturing apparatus.

As the radical polymerization initiator, persulfates such as potassium persulfate and ammonium persulfate, water-soluble azo compounds and the like can be used without particular limitation. As the water-soluble azo compound, 2,2'-azobis (2
-Amidinopropane) dihydrochloride, 2,2'-azobis (2-amidinobutane) dihydrochloride, 2,
2'-azobis (N-phenylaminodinopropane) dihydrochloride, 2,2'-azobis (N, N-dimethylamidinopropane) dihydrochloride, 2,2'-azobis (N-hydroxyethylamidinopropane) dihydrochloride, 2,2'-azobis (2-imidazolylamidinopropane) dihydrochloride, azobisvaleronitrile and the like are exemplified.

The reaction temperature, the pH during the reaction, and the like may be the same as when the chelating agent is not added, and the reaction temperature is usually
30 ° C to 100 ° C is suitable, and the temperature may be raised depending on the degree of progress of polymerization. A pH of 5 to 9 is usually suitable during the reaction. The reaction time may be the same as when the chelating agent is not added. In other words, one of the characteristics is that the chelating agent used in the present invention does not affect the polymerization conditions such as the polymerization temperature of the monomer.

Generally, in consideration of economic efficiency and ease of controlling the polymerization reaction, the concentration of the monomer is 40 to 42% by weight, water is used as a reaction solvent, and ammonium persulfate is polymerized as a radical polymerization initiator. It is preferable to use 0.1 to 1% by weight based on the charged amount, and polymerize at a reaction temperature of about 50 to 65 ° C. for production.

[0014]

EXAMPLES The present invention will now be described in more detail by way of examples. In the examples, composition% indicates weight%. Example 1 In a 100 ml reactor, 60 g of 60% diallyldimethylammonium chloride aqueous solution, 40 g of distilled water, 0.213 mg of cupric chloride (C
1.0 ppm as u ²⁺ ) and 4.0 mg of disodium ethylenediamine tetraacetate were charged, the temperature was raised to 55 ° C., 10 g of 3% ammonium persulfate was added, and the reaction was carried out for 10 hours. The viscosity of the obtained polymer was 1500 cp (measured by a B-type rotational viscometer at 25 ° C.).

Example 2 In a 100 ml reactor, 60 g of 60% diallyldimethylammonium chloride aqueous solution, 40 g of distilled water, 21 mg of ferric chloride (Fe ³⁺
100 mg) and 80 mg of disodium nitrilotriacetate were charged, the temperature was raised to 55 ° C., 10 g of 3% ammonium persulfate was added, and the mixture was reacted for 10 hours. The viscosity of the obtained polymer is 1600 cp
(Measurement at 25 ° C. by a B type rotational viscometer).

Comparative Example 1 A polymerization reaction was carried out for 10 hours in exactly the same manner as in Example 1 except that disodium ethylenediaminetetraacetate was not added. The viscosity of the obtained polymer was 20 cp (25 ° C measured by a B-type rotational viscometer).
Was measured).

Comparative Example 2 Example 2 except that disodium nitrilotriacetate was not added.
The polymerization reaction was carried out for 10 hours in the same manner as in. The viscosity of the obtained polymer was 400 cp (measured by a B-type rotational viscometer at 25 ° C.).

[0018]

Industrial Applicability According to the present invention, a polymer of a high-molecular-weight diallyldialkylammonium compound can be produced industrially and economically by hiding a heavy metal ion contained in a monomer solution and adversely affecting the polymerization reaction with a chelating agent. It can be manufactured in an advantageous manner.

Claims (4)

[Claims] 1. A monomer represented by the following general formula (I)
When producing the polymer by combining them,
Heavy metal ions contained in solution by adding chelating agent
Chelating a diallyldialkyl
Method for polymerizing ammonium compound. [Chemical 1](R in the formula¹, R²Are independently hydrogen atoms and carbon atoms of 1 to 6
It represents a alkyl group, a benzyl group or a cycloalkyl group. X
Is F, Cl, Br, I, NO₃, HSO_FourOr H ₂PO
_FourRepresents ) 2. The polymerization method according to claim ¹ , wherein in the general formula (I), R ¹ and R ² are methyl groups and X is Cl. 3. The polymerization method according to claim 1, wherein the heavy metal ion is at least one metal ion of copper and iron. 4. The chelating agent is ethylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid,
Glycol ether diamine tetraacetic acid, ethyl ether diamine tetraacetic acid, diethylenetriamine pentaacetic acid and the above alkali metal salts, and dihydroxyethylglycine,
The polymerization method according to any one of claims 1 to 3, which is at least one selected from tetraethylpentamine, triethylenetetramine, and triethanolamine.