JPS62172007A - Production of low-molecular-weight polymer of monoallylamine hydrochloride - Google Patents

Abstract

PURPOSE:To obtain a low-molecular-weight polymer of polyallylamine hydrochloride useful as a germicide, an algicidal agent, a paper processing agent, etc., effectively, by polymerizing a monoallylamine hydrochloride in the presence of a polymerization initiator consisting of HCl and a specific azo compound. CONSTITUTION:Monoallylamine hydrochloride is polymerized in the presence of a polymerization initiator consisting of (A) an excess amount, usually 0.2-1.0mol equivalent based on 1mol monoallylamine hydrochloride of HCl and (B) an azo compound [e.g., 2,2'-azobis(2-amidinopropane) dihydrochloride, etc.,] shown by formula I and/or formula II [R1 and R2 are H, 1-10C hydrocarbon or R1 and R2 may form ring; X is -CONHOH, -CONHNH2, formula III, formula IV (R3 is H or 1-8C hydrocarbon; HY is acid) or group shown by formula V (m is 2-3; n is 1-2)].

Description

DETAILED DESCRIPTION OF THE INVENTION Technical Field The present invention relates to a method for efficiently producing a low molecular m11 complex of monoallylamine hydrochloride.

Prior Art and Problems As is well known, allyl compounds are generally difficult to polymerize using conventional radical initiators and only produce polymers with a low degree of polymerization in very low yields. This is explained to be due to a self-termination reaction occurring due to the reaction between the hydrogen atom of the allyl group and the radical, and this reaction is usually called allyl-type destructive chain transfer [for example, C, E, 5 child kn
echt, “811yICompounds a
nd their Polymers”Wiley-I
interscience 973 pl) 29-30
: and R,C.

Able, Chel, Rev,, 5
8, pD807-843 (195
8)).

This is no exception for monoallylamines, which are a type of allyl compound; conventionally, the corresponding polymers of monoallylamines could be obtained in high yields using ordinary radical or ionic initiators. There was no such document.

Recently, one of the inventors of the present invention (Harada) has found that when monoallylamine inorganic acid salts are polymerized in a proprietary solvent using an azo radical initiator containing a group having a cationic nitrogen atom in the molecule, It has been found that the polymer can be obtained in high yield (see JP-A-58-2 Q 1811).

However, when polyallylamine hydrochloride is synthesized using these polymerization initiators, the average molecular weight of the resulting polymer is about 10.000<about 100 (degree of polymerization).

By the way, when polyallylamine hydrochloride and its dechlorinated product are used for purposes such as sterilization, algaecide, mu or textile post-treatment agent, paper processing agent, metal surface treatment agent, flocculant, and hardening agent for epoxy resin, It has been found that those belonging to a relatively low molecular weight region with an average molecular weight of io, ooo or less, preferably 5;00 or less (polymerization degree of 50 or less) are effective in terms of performance. Polymers prepared 1q using initiators cannot be used in these applications.

In general, in polymerization using a radical initiator, it is theoretically possible to reduce the molecular weight of the polymer by increasing the polymerization concentration and temperature, and increasing the amount of radical initiator added. It has become a known fact.

However, when polymerization is carried out by this method, in reality, the reaction proceeds rapidly, making it difficult to control the polymerization heat, and furthermore, even if these conditions are overcome, the average molecular weight is 5,000. It is difficult to obtain the following polymers in high yields. Furthermore, if the polymerization concentration is lowered, the distance between the polymer molecules can be reduced, but the yield will be low and this will be impractical.

OBJECT OF THE INVENTION Accordingly, an object of the present invention is to provide a method that enables efficient production of a low molecular weight polymer of polyallylamine hydrochloride, which has been difficult with any conventional method.

Means for achieving the object The object of the present invention as described above is to prepare monoallylamine hydrochloride (
i) excess hydrogen chloride with respect to monoallylamine hydrochloride and (ii) the following general formula <I) and/or (II>
This was achieved by a method for producing a low-molecular-weight monopolymer of monoallylamine hydrochloride, which is characterized by polymerization in the presence of a polymerization initiator consisting of an azo compound represented by:

R1R1 is a hydrogen group, R and R2 form a ring and are a substituted or unsubstituted hydrocarbon group having 1 to 8 carbon atoms, HY is a non-Nada acid or an R acid), or an inorganic acid or an organic acid. , m is 2
~3); n is a number from 1 to 2. The present invention requires that the polymerization be carried out in the presence of an excess of hydrogen chloride relative to the starting material, monoallylamine hydrochloride.

When the amount of hydrogen chloride added to monoallylamine hydrochloride is gradually increased, the average molecular weight of the low molecular weight polymer produced tends to gradually decrease. The amount decreases and converges to a constant value 1. Therefore, from an industrial standpoint, hydrogen chloride is 0.2 to 1.0 times the mole of monoallylamine hydrochloride (therefore, 1 mole of hydrogen chloride is needed for monoallylamine hydrochloride). .2~2.0
It is sufficient to add (2 times the mole).

According to the present invention, by carrying out polymerization in the presence of excess hydrogen chloride, it is possible to easily obtain a desired low molecular weight polymer in high yield, but this depends on the high or low concentration of heptamer, the polymerization It is not affected by other factors such as high temperature, polymerization [1] amount of initiator addition, etc. Therefore, there are advantages that the monomer concentration, polymerization temperature, and amount of polymerization initiator added are not strictly required to be set at 1 before polymerization, and that control during O polymerization operation is easy.

Next, as a method for adding hydrogen chloride, a predetermined amount of hydrochloric acid may be added to an aqueous solution of monoallylamine hydrochloride.
Of course, it is also possible to directly blow hydrogen chloride gas into the polymerization system. Generally, monoallylamine hydrochloride is subjected to polymerization without being isolated.

That is,! It is common practice to prepare an aqueous solution of allylamine hydrochloride by dropping the equimolar amount of 7lylamine into 11-hydrochloric acid. Therefore, it is industrially advantageous to drop 7lylamine into a reaction vessel previously charged with an excess of concentrated hydrochloric acid and use this as it is as a polymerization system. When excess hydrogen chloride is added as hydrochloric acid, the monomer concentration in the polymerization system increases compared to when hydrogen chloride gas is blown into the system.
However, if the heptome is 14 degrees or higher, which is around 45%, the yield of the produced low-molecular polymer is quantitative, so it is not necessary to consider it so strictly.

Another essential requirement of the present invention is that the polymerization is carried out in the presence of a polymerization initiator consisting of an azo compound represented by the above general formula <I) and/or (II).

Preferred examples of the azo compounds of formulas (I) and <II) are as follows. In addition, the following is an example (1
) to -+7) Among the compounds of l' and ¥, only the compounds of group (4) correspond to the compounds of general formula (II), and all the others correspond to the compounds of general formula (I).

fl+2.2'-azodos(2-amidinopropane) dihydrochloride, 2.2'-azobis(2-amidinobutane) dihydrochloride, 2,2'-azobis(2-amidinobentane)
Dihydrochloride, 2,2'-azobis(2-amidinohexane) bilayer'Pli salt, 2゜2'-azobis(2-amidino-4-methyl-4methoxypentane> dihydrochloride, 1
．． 1'-Azobis(1-amidinocyclohexane) dihydrochloride, 2,2'-azobis(2-amidino-3-methylbutane) dihydrochloride, 2,2'-azobis(2-amidino-3,3-dimedylbutane) Dihydrochloride, 2.2'-Azobis(2-7midino-4-methylpentane) dihydrochloride, 2.2'-Azobis(2-amidino-4,8methylpentane) dihydrochloride, 2.2'- Azobis(2-amidino-3-phenylpropane) dibase M salt (212,2'
-azobis(2-(N-phenylamidino)propane) diJu Mff salt, 2.2′-azobis(2-(N-
phenylamidino)butane) dihydrochloride, 2.2'-azobis(2-(N-methylamidino)propane) dihydrochloride, 2.2'-azobis(2-(N-ethylamidino)propane) dihydrochloride Hydrochloride, 2.2'-Azobis[2-(N-
propylamidino)propane] dihydrochloride, 2,2'-azogos(2-(N-butylamidino)propane) 2 groups 8
11.2.2'-AzobisC2-(N-cyclobexylamidino)propane] dibase M salt, 2'-Azobis(
2-(N-hydroxyethylamidino)propane] dihydrochloride, 2,2'-azobis(2-(N-dimethylaminepropylamidino)propane) tetrabasic acid salt, 2,2'-azobis(2-(N -benzylamidino)propane] dihydrochloride, 2.2'-azobis(2-(N,N-dimethylamidino)propane) di-salt tolerant, 2.2'-azobis[2-(N,N-diethylamidino) Propane] dihydrochloride, +312.2'-azobis[2-(imidazolinyl)propane] di[f salt, 2.2'-azobis[2-(imidazolinyl)butane] dihydrochloride, 2゜2'- Azobis (
2-(3,4,5,6-tetrahydromidinyl)propane] dihydrochloride, 2,2'-azobis(2-(3,4
,5,6-titrahydrobyrimidinyl)butane) dihydrochloride, 9.

(413,5-Diamminyl-1,2-azo-1-enclopentene dihydrochloride, 3-methyl-3,4-diaminyl-1,2-diazo-1-cyclobentene dihydrochloride, 3
-ethyl-3,5-diaminyl-1,2-diazo-1
-cyclopentene dihydrochloride, 3,5-dimethyl-3,5
-Diaminyl-1,2-diazo-1-cyclopentene dihydrochloride, 3,6-diaminyl-1,2-diazo-1
-cyclohexene dihydrochloride, 3-)♀ Engineering diru-3,5diamidinyl-1,2-diazo-1-cyclobenthene dihydrochloride, 3,5-diphenyl-3,5-
Diaminenyl-1,2-diazo-1-cyclobenthene dihydrochloride, (512,2'-azobis(2-methylpropionhydroxamic acid), 2.2'-azobis(2-ethylbutylhydroxam 110), 2.2 ' - Azobis (2
-propylpentylhydroxamic acid), 2.2'-azobis(2-carboxymethylpropionhydroxamus (2-carboxyethylpropionhydroxam f6)), 2.2'-azobis(2-methylpropanamide oxime), 2.2'- Azobis(2-ethylbutanamidoxime), 2,2'-azobis(2-propylpentanamide oxime), 3,3'-azobis(3
-acetamidoxime acetic acid), 4,4'-azobis(
4-7cetamidoxime valerate) +712.2'-azobis(2-methylpropionic acid hydrazide), 2,2'-azobis(2-ethyl acetic acid hydrazide), 2.2'-azobis(2-propyl valerate) The production method of these azo compounds (hydrazide) is described in U.S. Patent No. 2.599.299 and U.S. Pat.
No. 60-104107 of Japanese Patent Publication No. 60-104107.

The addition of these initiators, ω, tends to lower the molecular weight of the resulting low-molecular group polymer, but this effect is extremely small compared to the effect of adding hydrogen chloride.

The amount of initiator added increases the production yield of low molecular weight polymer by 1
The minimum amount of crushing needed to achieve 0.00% is sufficient, and although it varies slightly depending on the type of initiator, around 1 mol % is sufficient based on 70%.

Since there are slight differences in the decomposition temperature of the initiator, it is a national difficulty to define the polymerization temperature and time, but in all cases, the polymerization temperature is 50 to 70°C and the polymerization time is 48 to 72 hours. It is possible to form a combination of low molecular weight ffiff1.

During polymerization, if the system is sufficiently replaced with nitrogen gas, the polymerization rate can be increased, but even if the replacement is not carried out strictly, a low molecular weight polymer can be obtained almost constantly.

EXAMPLES In order to further clarify the present invention, Examples are shown below, but the present invention is not limited to these Examples.

Example 1 In 1.1 kg of concentrated hydrochloric acid (35% by weight), 55 to 1 kg of concentrated hydrochloric acid was added under water cooling.
571 g (10 moles) of monoallylamine are added dropwise with stirring at 0°C. After the dropwise addition was completed, water and excess hydrogen chloride were distilled off at 60° C. under a reduced pressure of 200 m of mercury using a rotary evaporator to obtain white crystals. The crystals were dried on silica gel in mercury under a vacuum of 5 mm at 80°C.
and monoallylamine jg-acid (hereinafter referred to as MAA-H)
(denoted as 1) 9803 was obtained. This MAA-
HC1 contains about 5% water.

After adding water to the above-obtained MAA-HCl with a water content of 5% to prepare a 70% aqueous solution, this MAA-1'' CI aqueous solution 109 was weighed into a stoppered test tube, and the above-mentioned initiator ( 1
) group, 2,2'-azobis(2-amidinopropane) dihydrochloride was added in an amount of 1 mol% relative to MAA-HCi.
After addition and dissolution, a prescribed amount of concentrated hydrochloric acid was added. After capping the test tube, polymerization was allowed to stand at 60° C. for 50 hours. After the polymerization, the system was poured into a 20 times acetone-methanol (18-1) mixed solvent, and the resulting precipitate was collected by filtration. Precipitate above U
After washing twice with a combined solvent, it was dried under reduced pressure. 111 yield of polymer and 1/IOM Na C
The average intrinsic viscosity molecule m (Mw) measured at 30'C at a concentration of 1 water and 5% was determined as follows.

That is, η = 0.36, ηinh = +nh 0.10, and +nh the average molecule ω of the polymer on hand, each with an intrinsic viscosity of -0.05, is 3.5M/
The intrinsic viscosity (Fη) of the NaCl solution is calculated from the equation 1 of the relationship between the intrinsic viscosity and the average molecular weight. Mw=10,000.3.4, respectively.
00.2,070. From these values, the degrees of polymerization are obtained as 107.36 and 22, respectively. Therefore, as a guideline for the molecular weight of 5,000 or less in the present invention, η1r
Corresponds to ih≦0,14.

Example 2 Tables 2, 3 and 4 show the results of polymerization under the same conditions as in Example 1, except that 6N-hydrochloric acid, 3N-hydrochloric acid and 1N-hydrochloric acid were added instead of adding concentrated hydrochloric acid. Shown below.

FIG. 1 shows a plot of the relationship between the amount of hydrogen chloride added and the intrinsic viscosity (η·) of the produced polymer in Examples 1 and 2.

This figure shows that in the method of the present invention, the intrinsic viscosity depends more on the amount of hydrogen chloride added than on the polymerization concentration.

Example 3 As an initiator, 2°2'- from the group of initiators (3) mentioned above
Table 5 shows the results obtained under the same conditions as in Example 1 except that azobis[2-(imidazolinyl)propane) dihydrochloride was used.

Example/1 2,2'-azobis(2-(imidazolinyl)propane) dibase R salt was used as the initiator; except for this, Example 2
Same as - by ordinance? The results are shown in Tables 6, 7, and 8.

The relationship between the amount of hydrogen chloride added and the intrinsic viscosity (η, ) of the produced polymer in Example PA3 and Example 4 is shown in FIG.

From this figure, it can be seen that in the polymerization method of the present invention, the intrinsic viscosity depends more on the suspension of JQ hydrogen hydride added than on the polymerization concentration.

Example 5 Table 9 and FIG. 3 show the results when the polymerization temperature was set to 50°C under the same conditions as in Examples 1 and 2.

Example 6 70% monoallylamine hydrochloride (MAA-H
After adding 700 y of CJ aqueous solution and 165.29 y of 35% concentrated hydrochloric acid, and adding 13.8 g of 2゜2'-azobis[2-amidinopropane] dihydrochloride as an initiator and replacing the atmosphere with nitrogen, the car was placed under a car at 60°C. .

After the start of polymerization, about 2 g of Zamble was collected at regular intervals, weighed, and treated in the same manner as in Example 1 to determine the Φ content and degree of polymerization. The results are shown in Table 10.

In this polymerization system, the charging ratio of hydrogen chloride to MAA-HCJ was 0.3 times by mole.

Table 10 Example 7 Using the apparatus used in Example 6, 70% monoallylamine hydrochloride (MAA-HCj aqueous solution 600 g, 35% concentrated hydrochloric acid 318.6 g, initiator 2.2'-azogos[2 -amidinopropane) dihydrochloride was added, the mixture was replaced with nitrogen, and then polymerized at 60°C, and the polymerization rate and degree of polymerization after a certain period of time were examined according to the method of Example 6. Table 1 shows the results.
Shown in 1.

In this polymerization system, the charging ratio of hydrogen chloride to MAA-HC1 was 0.78 times by mole.

Table 11 Example 8 Monoallylamine hydrochloride (MAA-
Table 12 shows the results of polymerization conducted under the same conditions as in Example 1, except that the charging ratio of hydrogen chloride to HCj was 0.3 times the mole.

The amount of initiator added was constant at 1 mol % to monomer.

Comparative Examples 1 to 4 Using various radical initiators other than the radical initiator used in the present invention, and without using excess hydrogen chloride, MAΔinorganic m-type combinations were carried out in various solvents.

All of these polymerization treatments were carried out in a 50Id test tube with a stopper under nitrogen by a static method. Separation and purification of the polymer after the polymerization treatment was carried out by the method explained in the previous example, but extraction using a Soxhlet extractor was not carried out. The results are summarized in Table 13 below. The abbreviations in the table have the following meanings.

(1) Mn: Number average molecular weight measured by osmotic pressure method in saline (m) APS: Ammonium peroxysulfate (n) DM
SO dimethyl sulfoxide (o) AIBN: azobisisobutyronitrile (p) DMF dimethylformamide (Q) CHP: cumenhyde peroxide Effects of the Invention As described above, the method of the present invention provides a low molecular weight monoallylamine salt M salt. This has the effect that the polymer is 114-produced in high yield.

This effect of the present invention is not affected by factors such as polymerization temperature, monomer concentration, amount of polymerization initiator added, and therefore does not require strict settings of these factors.
Further, there are advantages such as ease of controlling the polymerization operation.

[Brief explanation of drawings]

1 to 3 are graphs showing the relationship between the hydrogen chloride addition port and the intrinsic viscosity of the produced polymer in the method of the present invention.

Claims (1)

[Claims] (1) Monoallylamine hydrochloride is treated with a polymerization initiator consisting of (i) hydrogen chloride in excess of monoallylamine hydrochloride and (ii) an azo compound represented by the following general formula (I) and/or (II). 1. A method for producing a low molecular weight polymer of monoallylamine hydrochloride, which comprises polymerizing in the presence of monoallylamine hydrochloride. ▲There are mathematical formulas, chemical formulas, tables, etc.▼---(I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼---(II) [In the formula, R_1 and R_2 are the same or different groups,
It is hydrogen or a substituted or unsubstituted hydrocarbon group having 1 to 10 carbon atoms, and R_1 and R_2 may form a ring; etc. ▼ (In the formula, R_3 is hydrogen or a substituted or unsubstituted hydrocarbon group having 1 to 8 carbon atoms,
HY is an inorganic or organic acid) or ▲There is a mathematical formula, chemical formula, table, etc.▼ (wherein HY is an inorganic or organic acid, m is a number from 2 to 3); n is The number is 1-2. (2) The method according to claim 1, wherein hydrogen chloride is present in an amount of 0.2 to 1.0 times the molar equivalent of monoallylamine hydrochloride.