JPH03109407A - Method for polymerizing diallylamine and derivative thereof - Google Patents

Abstract

PURPOSE:To obtain a low-molecular weight polymer without affecting polymerization rate, etc., by polymerizing a specific monomer using a hypophosphorous acid (salt) as a polymerization degree regulator. CONSTITUTION:The objective polymer obtained by polymerizing a monomer (e.g. diallydimethylammonium chloride) expressed by the formula (R1 and R2 are H, 1-5C alkyl, benzyl or cyclohexyl; X<-> is F<->, Cl<->, Br<->, I<->, NO, HSO or H2PO) using hypophosphorous acid and/or salt thereof (e.g. sodium hypophosphite) as a polymerization degree regulator.

Description

[Detailed description of the invention] [Industrial application field]

The present invention relates to a method for polymerizing diallylamine and its derivatives.

[Conventional technology]

Conventional methods for producing polymers of diallylamine and its derivatives (hereinafter referred to as diallylamine polymers) include, for example, adding the monomer represented by formula (I) to a persulfate or a water-soluble azo compound in an aqueous medium. This is carried out using a radical polymerization initiator. At that time, although the monomer is a polyfunctional unsaturated compound, it does not show any behavior such as becoming three-dimensional; - it polymerizes with an intramolecular cyclization reaction within the molecule, and a piperidine ring is formed in the molecule. It is generally known that the polymers obtained are soluble in water. Conventionally, when producing a diallylamine polymer having a desired molecular weight, the concentration of the monomer charged or the concentration of the polymerization initiator was changed. When trying to obtain a low molecular weight diallylamine polymer, the concentration of the monomer should be set low and the concentration of the initiator should be set high. The invention that attempts to control the molecular weight of diallylamine polymers is disclosed in Japanese Patent Application Laid-Open No. 63-23911.
The use of mercaptans, phosphorous acid or derivatives thereof has only been proposed.

[Problems to be solved by the invention] However, in such conventional methods for producing diallylamine-based polymers, ■If the concentration of monomer is lowered, it takes a very long time to complete the reaction, making it uneconomical. unfavorable to On the other hand, if the temperature is set too high, it becomes difficult to remove heat during polymerization.
As a result, the polymerization reaction thermally goes out of control. (2) Even when the amount of the polymerization initiator is changed, the same thing as (2) occurs, and it is impossible to obtain diallylamine polymers with different molecular weights within a wide range that is desired economically and industrially. ■The method described in JP-A No. 63-23911, that is,
When a mercaptan is used as a chain transfer agent, a polymer with a lower molecular weight than the desired one is obtained in the early stage of the reaction, and a polymer with a higher molecular weight is produced in the latter stage of the reaction. As a result, even if a polymer having a macroscopically desired molecular weight is obtained, the molecular weight distribution will be extremely wide. ■Also, in the method using phosphorous acid, the pH during the reaction is 2 to 3.
The problem was that the low corrosion rate caused corrosion of the manufacturing equipment, and that special materials were required for the manufacturing equipment. [Means for Solving the Problems] The present invention has been made by focusing on such conventional problems, and as a result of intensive research, it has been made to develop a diallylamine-based polymer that is industrially and economically advantageous and has a low molecular weight. It became possible to manufacture. That is, diallylamine and its derivatives are characterized in that hypophosphorous acid and/or its salts are used as a polymerization degree regulator when polymerizing the monomer represented by the general formula (I) to produce the corresponding polymer. This is a polymerization method. (Requirements constituting the means) The polymerization method of the present invention is characterized by polymerization in the presence of a polymerization degree regulator, and hypophosphorous acid and/or a salt thereof may be used as the polymerization degree regulator. This is a necessary condition. The hypophosphorous acid referred to here is a compound having the chemical formula HsPOa, and the free acid is colorless crystal and has a melting point of 26.5°C. The manufacturing method is to convert yellow phosphorus into NaOH%Ba(OH)
A method of making the corresponding hypophosphite by dissolving it in a strong alkali such as T is known. In addition, in order to obtain free acid, Ba ions may be precipitated and removed from a solution of Ba salt crystals using sulfuric acid.In addition to free hypophosphorous acid, in the present invention, Na,
Li, %N) 14, amine salts are used. Furthermore, it is known that these salts exist stably in the form of hydrates, but the use of hydrates does not impede the effects of the present invention. In carrying out the present invention, monomers represented by general formula (I) are used, but these may be used alone or in a mixture of two or more types @RI
I R1 each independently represents hydrogen, methyl group, or carbon number 1
-5 alkyl group, benzyl group or cyclohexyl group, preferably both R1 and R8 are methyl groups. Anions include F', Cl13. Br0. Io, N
OI. , )(SO4 or Hs PO4゜,
Preferably it is cX. Other production conditions are not particularly limited, and in general, the production conditions for diallylamine-based polymers may be used as they are.In other words, the monomer concentration depends on the cooling capacity of the production equipment, but from an economic point of view 40 thoughts from
Approximately 55% by weight is appropriate. Examples of radical polymerization initiators include water-soluble organic or inorganic peroxides such as hydrogen peroxide, ammonium persulfate, potassium persulfate, t-butyl hydroperoxide, and cumene hydroperoxide;
2°-azobis(2-amidinopropane) dihydrochloride, 2.2′-azobis(2-amidinobutane) dihydrochloride, 2.2°-azobis(N-phenylamidinopropane) dihydrochloride, 2,2°-azobisIN , N-dimethylamidinopropane) dihydrochloride, 2,2°-azobis(N-hydroxyethylamidinopropane) dihydrochloride, 2°2°-azobis(
Any commonly used radical polymerization initiator can be used without particular limitation, such as water-soluble azo compounds such as 2-imidazolinylpropane) dihydrochloride and azobisvaleronitrile. The reaction temperature, reaction time, pH during reaction, etc. may be the same as when no polymerization regulator is added. In other words, one of the characteristics of the polymerization regulator used in the present invention is that it does not affect the polymerization rate or polymerization state of monomers. Generally speaking, considering economic efficiency and ease of controlling the polymerization reaction, the monomer concentration is set at 50%, water is used as a reaction solvent, and ammonium persulfate is used as a radical polymerization initiator in the polymerization amount. Use 0.3% to 0.5% for
It is preferable to carry out the polymerization at a reaction temperature of about 60°C to 80°C for about 5 to 7 hours to complete the reaction. The amount of the polymerization degree regulator used in the present invention can be arbitrarily selected depending on the desired degree of polymerization, but usually 1 to 5% O, based on the weight of the monomer, is sufficient to achieve the purpose.

[Effect]

It is known that hypophosphorous acid or its salt, which is a polymerization degree regulator that is an essential condition for the production method of the present invention, contains a P-H bond in the molecule, but the dissociation energy of this P-H bond is small. It is considered that low molecular weight diallylamine polymers are efficiently synthesized due to the ease with which H atoms are extracted. In addition, since the molecular weight adjustment of the polymer by the abstraction of H atoms is based on the commonly referred to chain transfer reaction, 1) Even if the polymerization degree regulator used in the present invention is used, it will not affect the polymerization rate etc. considered to be a thing.

【Example】

Hereinafter, the present invention will be explained in more detail with reference to Examples.
These examples are not intended to limit the scope of the invention. In the examples, % indicates weight %. Example 1 666 g of 60% diallyldimethylammonium chloride aqueous solution 1 Potassium hypophosphite 4 129 g of ion-exchanged water was placed in a 1000rn J2 flask equipped with a thermometer, condenser, stirrer, and nitrogen inlet tube, and the flask was purged with nitrogen for 30 minutes. The temperature was raised to 60°C, 0.8g of ammonium persulfate was added under a nitrogen stream, and after reacting for 5 hours, 2g of ammonium persulfate was further added, the temperature was raised to 80°C, and the mixture was aged for 2 hours to complete the polymerization. Ta. The polymerization conditions, intrinsic viscosity and reaction rate (cation equivalent) of the obtained polymer are shown in Table 1. Example 2 666 g of 60% diallyldimethylammonium chloride aqueous solution, 8.5 g of potassium hypophosphite, and 129 g of ion-exchanged water were charged into the same reaction apparatus as in Example 1, and ammonium persulfate was used as an initiator in the same manner as in Example 1. was used and polymerized. Polymerization conditions, intrinsic viscosity of the obtained polymer, reaction rate (
cation equivalent) are shown in Table 1. Example 3 In the same reaction apparatus as in Example 1, 666 g of 60% diallyldimethylammonium chloride aqueous solution, 9.5 g of ammonium hypophosphite, and 129 g of ion-exchanged water were charged, and as in Example 1, ammonium persulfate was used as an initiator. was used and polymerized. The polymerization conditions, intrinsic viscosity and reaction rate (cation equivalent) of the obtained polymer are shown in Table 1. Example 4 Polymerization conditions were carried out in the same manner as in Example 1 except that a 60% aqueous solution of diallylmethylammonium chloride was used as the monomer, and the intrinsic viscosity and reaction rate (cation equivalent) of the obtained polymer are shown in Table 1. It was shown to. Example 5 Diallylamine hydrochloride 40 was added to the same reactor as Example 1.
0g, sodium hypophosphite 4.8g. After charging 395 g of ion-exchanged water and purging with nitrogen for 30 minutes, the temperature was raised to 60°C and 0.8 g of 2.2°-azobis(2-amidinopropane) dihydrochloride was added under a nitrogen stream.
After adding g and reacting for 4 hours, 1.6 g of 2.2°-azobis(2-amidinopropane) dihydrochloride was added.
After the addition, the temperature was raised to 80'C and aged for 2 hours to complete polymerization. The polymerization conditions and the intrinsic viscosity of the obtained polymer are shown in Table 1. Example 6 In the same reactor as in Example 1, 781 g of diallyl dibenzyl ammonium chloride and 4.8 g of sodium hypophosphite were added.
g and 215 g of ion-exchanged water were charged, and polymerization was carried out in the same manner as in Example 1 using ammonium persulfate as an initiator. Polymerization conditions,
The intrinsic viscosity and reaction rate (cation equivalent) of the obtained polymer are shown in Table 1. Comparative Example 1 In the same reaction apparatus as in Example 1, 666 g of 60% diallyldimethylammonium chloride aqueous solution and 12 g of ion-exchanged water were added.
9 g was charged and polymerized in the same manner as in Example 1. The polymerization conditions, intrinsic viscosity and reaction rate (cation equivalent) of the obtained polymer are shown in Table 1. Comparative Example 2 In the same reaction apparatus as in Example 1, 267 g of 60% diallyldimethylammonium chloride aqueous solution and 53 g of ion-exchanged water were added.
3 g was charged and polymerized in the same manner as in Example 1. The polymerization conditions, intrinsic viscosity and reaction rate (cation equivalent) of the obtained polymer are shown in Table 1. Comparative Example 3 4.8g of 2-mercaptoethanol as a polymerization regulator
The same procedure as in Example 1 was carried out except for the use. The polymerization conditions, intrinsic viscosity and reaction rate (cation equivalent) of the obtained polymer are shown in Table 1. From the results in Table 1, when hypophosphite is used, the intrinsic viscosity is small, so that the desired low molecular weight product can be produced. Also, from the cation equivalent, it can be seen that the reaction is almost 100% (margin below).

【Effect of the invention】

By the polymerization method of the present invention, the desired low molecular weight product can be produced, and it can be produced in a method that is industrially and economically advantageous.

Claims (1)

[Claims] 1. In producing a polymer by polymerizing a monomer represented by the following general formula (I), hypophosphorous acid and/or a salt thereof may be used as a polymerization degree regulator. Characteristic method for polymerizing diallylamine and derivatives thereof. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) [In the formula, R_1 and R_2 independently represent hydrogen, an alkyl group having 1 to 5 carbon atoms, a benzyl group, or a cyclohexyl group. X^■ is F^■, Cl^■, Br^■, I^■, N
O_3^■, HSO_4^■ or H_2PO_4^■
represents. ] 2. In general formula (I), R_1 is a methyl group, R_
2. The polymerization method according to claim 1, wherein 2 is a methyl group and X^■ is Cl^■.