JPH062780B2 - Method for producing low molecular weight polymer of monoallylamine hydrochloride - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for efficiently producing a low molecular weight polymer of monoallylamine hydrochloride.

2. Description of the Related Art As is well known, allyl compounds are generally difficult to polymerize with conventional radical initiators and only produce a polymer having a low degree of polymerization in an extremely low yield. It is explained that this is because a self-termination reaction occurs due to the reaction between a hydrogen atom of an allyl group and a radical, and this reaction is usually called an allyl-type destructive chain transfer [eg CESchildknecht, "Allyl Co
mpounds and their Polymers "Wiley-Interscience19
73pp 29-30; and RC Laible, Chem. Rev., 58 , p.
p807-843 (1958)].

This is not an exception for monoallylamines, which is a type of allyl compound. Conventionally, monoallylamines have been obtained with high yields by using ordinary radical initiators or ionic initiators. That document has never happened.

Recently, one of the inventors of the present invention (Harada) has reported that the polymerization of a monoallylamine inorganic acid salt in a polar solvent using an azo radical initiator containing a group having a cationic nitrogen atom in the molecule results in It has been found that a coalesced product can be obtained in a high yield (see JP-A-58-201811).

However, when polyallylamine hydrochloride is synthesized using these polymerization initiators, the average molecular weights of the produced polymers are all about 10,000 (polymerization degree is about 100).

By the way, when polyallylamine hydrochloride and its dechlorinated product are used for applications such as sterilization, algaecides, post-treatment agents for fibers or fabrics, paper processing agents, metal surface treatment agents, coagulants, curing agents for epoxy resins, etc. However, it has been found that those having an average molecular weight of 10,000 or less, preferably 5,000 or less (polymerization degree of 50 or less) and belonging to a relatively low molecular weight region are effective in terms of performance. The polymers obtained with the initiator cannot be used for these applications.

Generally, in the polymerization using a radical initiator, it is theoretically possible to reduce the molecular weight of the polymer by increasing the polymerization concentration and the polymerization temperature and increasing the addition amount of the radical initiator. This is a known fact.

However, when the polymerization is carried out by this method, it is actually difficult to control the heat of polymerization because the reaction proceeds rapidly, and further, even if these conditions are overcome, the average molecular weight is 5 It is difficult to obtain a polymer of 1,000 or less in a high yield. Further, if the polymerization concentration is lowered, the molecular weight of the polymer can be reduced, but the yield is lowered and the practicality is lost.

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

Means for Achieving the Objects The above-mentioned objects of the present invention include monoallylamine hydrochloride,
Polymerization is performed in the presence of (i) an excess of hydrogen chloride with respect to monoallylamine hydrochloride and (ii) a polymerization initiator composed of an azo compound represented by the following general formula (I) and / or (II). Was achieved by a method for producing a low molecular weight polymer of monoallylamine hydrochloride.

[In the formula, R ₁ and R ₂ are the same or different groups and are hydrogen or a substituted or unsubstituted hydrocarbon group having 1 to 10 carbon atoms, and R ₁ and R ₂ form a ring. A substituted or unsubstituted hydrocarbon group having 1 to 8 carbon atoms,
HY is an inorganic or organic acid) or Is an inorganic acid or an organic acid, m is a number of 2-3); and n is a number of 1-2. The present invention makes it essential to carry out the polymerization in the presence of excess hydrogen chloride with respect to the starting monomer, monoallylamine hydrochloride.

When the amount of hydrogen chloride added to the monoallylamine hydrochloride is gradually increased, the average molecular weight of the low-molecular weight polymer produced tends to be gradually decreased, but the decrease rate of the average molecular weight decreases with the increase of the added amount. And then converges to a certain value. Therefore, from an industrial point of view, 0.2 to 1.0 times mol of hydrogen chloride is added to monoallylamine hydrochloride (hence 1.2 to 2.0 times mol of monoallylamine is added). Is enough.

According to the present invention, by carrying out the polymerization in the presence of excess hydrogen chloride, it becomes possible to easily obtain a desired low-molecular weight polymer in a high yield. It is not affected by other factors such as high or low temperature and the amount of polymerization initiator added. Therefore, there are advantages that the strictness is not required for setting the monomer concentration, the polymerization temperature, and the amount of the polymerization initiator added before the polymerization, and the control during the polymerization operation is easy.

Next, as a method of adding hydrogen chloride, a predetermined amount of hydrochloric acid may be added to an aqueous solution of monoallylamine hydrochloride.
It is of course possible to blow hydrogen chloride gas directly into the polymerization system. Generally, monoallylamine hydrochloride is subjected to polymerization without isolation. That is, it is common practice to add an equimolar amount of allylamine to concentrated hydrochloric acid to prepare an aqueous solution of allylamine hydrochloride. Therefore, it is industrially advantageous to drop allylamine into a reaction tank in which a concentrated excess amount of concentrated hydrochloric acid has been charged and to use this as a polymerization system as it is. If excess hydrogen chloride is added as hydrochloric acid,
The monomer concentration in the polymerization system is lower than that in the case of blowing hydrogen chloride gas, but if the monomer concentration is about 45% or more, the yield of the low-molecular weight polymer produced is
Since it is quantitative, it does not need to be considered so strictly.

In the present invention, another essential requirement is to carry out the polymerization in the presence of a polymerization initiator composed of the azo compound represented by the general formula (I) and / or (II).

The preferred examples of the azo compounds represented by the general formulas (I) and (II) are as follows. In addition, (1) ~
Of the compounds of group (7), only the compound of group (4) corresponds to the compound of general formula (II), and the other compounds all correspond to the compound of general formula (I).

(1) 2,2'-azobis (2-amidinopropane) dihydrochloride, 2,2'-azobis (2-amidinobutane) dihydrochloride, 2,2'-azobis (2-amidinopentane) dihydrochloride, 2,2'-azobis (2-amidinohexane)
Dihydrochloride, 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-
Dimethyl butane) dihydrochloride, 2,2'-azobis (2-
Amidino-4-methylpentane) dihydrochloride, 2,2'-
Azobis (2-amidino-4,4-dimethylpentane)
Dihydrochloride, 2,2'-azobis (2-amidino-3-phenylpropane) dihydrochloride (2) 2,2'-azobis [2- (N-phenylamidino) propane] dihydrochloride, 2,2 ′ -Azobis [2-
(N-phenylamidino) butane] dihydrochloride, 2,2 ′
-Azobis [2- (N-methylamidino) propane] dihydrochloride, 2,2'-azobis [2- (N-ethylamidino) propane] dihydrochloride, 2,2'-azobis [2-
(N-propylamidino) propane] dihydrochloride, 2,
2'-azobis [2- (N-butylamidino) propane] dihydrochloride, 2,2'-azobis [2- (N-cyclohexylamidino) propane] dihydrochloride, 2,2'-azobis [2- ( N-hydroxyethylamidino) propane] dihydrochloride, 2,2′-azobis [2- (N-dimethylaminopropylamidino) propane] tetrahydrochloride, 2,
2'-azobis [2- (N-benzylamidino) propane] dihydrochloride, 2,2'-azobis [2- (N, N-dimethylamidino) propane] dihydrochloride, 2,2'-azobis [2 -(N, N-Diethylamidino) propane] dihydrochloride, (3) 2,2'-azobis [2- (imidazolinyl) propane] dihydrochloride, 2,2'-azobis [2- (imidazolinyl) butane] Dihydrochloride, 2,2'-azobis [2-
(3,4,5,6-Tetrahydropyrimidinyl) propane] dihydrochloride, 2,2′-azobis [2- (3,4,
5,6-Tetrahydropyrimidinyl) butane] dihydrochloride, (4) 3,5-diamidinyl-1,2-diazo-1-cyclopentene dihydrochloride, 3-methyl-3,4-diamidinyl-1,2-diazo -1-cyclopentene dihydrochloride, 3
-Ethyl-3,5-diamidinyl-1,2-diazo-1
-Cyclopentene dihydrochloride, 3,5-dimethyl-3,5
-Diamidinyl-1,2-diazo-1-cyclopentene dihydrochloride, 3,6-diamidinyl-1,2-diazo-1
-Cyclohexene dihydrochloride, 3-phenyl-3,5-diamidinyl-1,2-diazo-1-cyclopentene dihydrochloride, 3,5-diphenyl-3,5-diamidinyl-
1,2-diazo-1-cyclopentene dihydrochloride, (5) 2,2′-azobis (2-methylpropionhydroxamic acid), 2,2′-azobis (2-ethylbutylhydroxamic acid), 2,2 ′ -Azobis (2-propylpentylhydroxamic acid), 2,2'-azobis (2-carboxymethylpropion hydroxamic acid), 2,2 '
-Azobis (2-carboxyethylpropion hydroxamic acid), (6) 2,2'-azobis (2-methylpropanamide oxime), 2,2'-azobis (2-ethylbutanamide oxime), 2,2'- Azobis (2-propylpentanamide oxime), 3,3'-azobis (3-acetamidooxime butyric acid), 4,4'-azobis (4-acetamidooxime valeric acid) (7) 2,2'-azobis (2- Methylpropionic acid hydrazide), 2,2'-azobis (2-ethylbutyric acid hydrazide), 2,2'-azobis (2-propylvaleric acid hydrazide) The production method of these azo compounds is described in US Patent No. 2,599,299. No. 2,599,300 and JP-A No. 60-104107.

Although the addition amount of these initiators tends to decrease the molecular weight of the low-molecular weight polymer produced, the effect thereof is extremely small as compared with the effect by addition of hydrogen chloride.
Therefore, the amount of the initiator added is 1 for the yield of the low molecular weight polymer.
The minimum amount required to reach 00% is sufficient, and although it varies slightly depending on the type of initiator, about 1 mol% is sufficient with respect to the monomer.

It is difficult to unconditionally determine the polymerization temperature and the polymerization time because there is a slight difference in the decomposition temperature of the initiator, but in any case, the polymerization temperature is 50 to 70 ° C., the polymerization time is 48 to 72 hours, and it is quantitative. Moreover, a low molecular weight polymer can be obtained.

In the polymerization, if the system is sufficiently replaced with nitrogen gas, the polymerization rate can be increased, but a low molecular weight polymer can be obtained almost quantitatively without strict replacement.

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) under ice cooling, 5 to 10 ° C
571 g (10 mol) of monoallylamine with stirring
Is dripped. After completion of dropping, water and excess hydrogen chloride were distilled off at 60 ° C. under reduced pressure of 200 mm of mercury using a rotary evaporator to obtain white crystals. The crystals were dried on silica gel for drying under reduced pressure of 5 mm in mercury at 80 ° C. to obtain 980 g of monoallylamine hydrochloride (hereinafter referred to as MAA-HCl). This MAA-HCl contains about 5% water.

Add 70% water to the above-obtained 5% water content MAA-HCl.
After preparing the aqueous solution, 10 g of this MAA-HCl aqueous solution was weighed into a test tube with a stopper, and 2,2 'in the above-mentioned initiator (1) group was measured.
-Azobis (2-amidinopropane) dihydrochloride was added to MAA
-After adding and dissolving 1 mol% with respect to HCl, a predetermined amount of concentrated hydrochloric acid was added. After the test tube was capped, static polymerization was carried out at 60 ° C. for 50 hours. After the polymerization, the system was poured into a 20-fold mixed solvent of acetone-methanol (18-1), and the generated precipitate was collected by filtration. After washing the precipitate twice with the above mixed solvent,
It was dried under reduced pressure. Yield of the obtained polymer and 1 / 10M
Table 1 shows the intrinsic viscosities (η _inh ) measured at 30 ° C. in 5% concentration of NaCl water.

The intrinsic viscosity (η _inh ) and average molecular weight (w) of polyallylamine hydrochloride were determined as follows. That is, η _inh = 0.36, η _inh = 0.10 and η _inh =
The average molecular weight of a hand-held polymer having an inherent viscosity of 0.05 was calculated to obtain the intrinsic viscosity [η] in a 3.5M / NaCl solution, respectively, and the relational expression [η] = 1.41 × 10 ⁻³ × w ^0.5 , w = 10,000 and 3,40, respectively.
It becomes 0, 2,070. From this value, the degree of polymerization is 1
07, 36 and 22. Therefore, as a standard for the molecular weight of 5,000 or less in the present invention, η _inh 0.
Corresponding to 14.

Example 2 The results of polymerizing 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 were shown in Table 2, Table 3 and Table 4. Shown in.

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

From this figure, it can be seen 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 Results obtained under the same conditions as in Example 1 except that 2,2′-azobis [2- (imidazolinyl) propane] dihydrochloride in the above-mentioned initiator (3) group was used as an initiator. Table 5
Shown in.

Example 4 The results obtained under the same conditions as in Example 2 except that 2,2′-azobis [2- (imidazolinyl) propane] dihydrochloride was used as the initiator are shown in Tables 6, 7 and 8.

FIG. 2 shows a plot of the relationship between the added amount of hydrogen chloride and the intrinsic viscosity (η _inh ) of the produced polymer in Examples 3 and 4.

From this figure, it is understood that in the polymerization method of the present invention, the intrinsic viscosity depends on the amount of added hydrogen chloride rather than the polymerization concentration.

Example 5 The polymerization temperature was set to 50 under the conditions according to Example 1 and Example 2.
The results when the temperature was set to ° C are shown in Table 9 and Fig. 3.

Example 6 A 1-necked three-necked flask equipped with a stirrer, a reflux condenser, and a nitrogen inlet tube was charged with 70% monoallylamine hydrochloride (MAA-HCl).
700 g of an aqueous solution and 165.2 g of 35% concentrated hydrochloric acid were added,
After adding 13.8 g of 2,2'-azobis [2-amidinopropane] dihydrochloride as an initiator and substituting with nitrogen, 60
Polymerized at ° C.

About 2 g of a sample was sampled and weighed at regular intervals after the initiation of polymerization, and treated in the same manner as in Example 1 to determine the degree of polymerization and the degree of polymerization. The results are shown in Table 10.

The charging ratio of hydrogen chloride to MAA-HCl in this polymerization system was 0.3 times mol.

Example 7 Using the apparatus used in Example 6, 600 g of 70% monoallylamine hydrochloride (MAA-HCl) aqueous solution, 35% concentrated hydrochloric acid 31
8.6 g of initiator, 2,2'-azobis [2-amidinopropane] dihydrochloride 11.7 g were added, and after nitrogen substitution, polymerization was carried out at 60 ° C., and polymerization was carried out after a certain period of time according to the method of Example 6. The rate and degree of polymerization were investigated. The results are shown in Table 11.

The charging ratio of hydrogen chloride to MAA-HCl in this polymerization system was 0.78 mol.

Example 8 By changing the initiator, monoallylamine hydrochloride (MAA-HC
Table 12 shows the results of polymerization under the same conditions as in Example 1 except that the charging ratio of hydrogen chloride to l) was 0.3 times mol.

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

Comparative Examples 1 to 4 The MAA inorganic acid salt was polymerized in various solvents using various radical initiators other than the radical initiator used in the present invention and without using excess hydrogen chloride.

All of these polymerization treatments were carried out in a 50 ml 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 described in the above Example, but extraction by a Soxhlet extractor was not carried out. The results are summarized in Table 13 below. The abbreviations in the table have the following meanings.

(l) n: number average molecular weight measured by osmometry in saline (m) APS: ammonium peroxysulfate (n) DMSO: dimethylsulfoxide (o) AIBN: azobisisobutyronitrile (p) DMF: dimethylformamide (q ) CHP: cumene hydroperoxide Effect of the Invention As described above, the method of the present invention has an effect that a low molecular weight polymer of monoallylamine hydrochloride can be obtained in a high yield.

This effect of the present invention is not affected by factors such as the polymerization temperature, the monomer concentration, and the amount of the polymerization initiator added. Therefore, the strictness of the setting of these factors is not required, and the polymerization operation is not required. There are advantages such as easy control.

[Brief description of drawings]

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

Claims (2)

[Claims] 1. Initiation of polymerization of monoallylamine hydrochloride from (i) an excess of hydrogen chloride with respect to monoallylamine hydrochloride and (ii) an azo compound represented by the following general formula (I) and / or (II). A method for producing a low molecular weight polymer of monoallylamine hydrochloride, which comprises polymerizing in the presence of an agent. [In the formula, R ₁ and R ₂ are the same or different groups and are hydrogen or a substituted or unsubstituted hydrocarbon group having 1 to 10 carbon atoms, and R ₁ and R ₂ form a ring. A substituted or unsubstituted hydrocarbon group having 1 to 8 carbon atoms,
HY is an inorganic or organic acid) or Is an inorganic acid or an organic acid, m is a number of 2-3); and n is a number of 1-2. ] 2. From 0.2 to monoallylamine hydrochloride.
A process according to claim 1, wherein 1.0 times the molar equivalent of hydrogen chloride is present.