JPH0379610A - Amphoteric polymer and production thereof - Google Patents

Abstract

PURPOSE:To obtain the subject copolymer useful for antistatic agent, chelate resin, treating agent of waste water and recovering agent of petroleum, etc., by mixing a monoallylamine derivative, etc., and itaconic acid in a specific ratio and copolymerizing in a solvent using a radical polymerization initiator. CONSTITUTION:(A) Monoallylamine derivative expressed by formula I (R1 and R2 are H, 1-12C alkyl or 5-6C cycloalkyl) or diallylamine derivative expressed by formula II (R3 is H, 1-12C alkyl or aralkyl) is mixed with (B) itaconic acid so as molar ratio of both to be 2/1-1/5 and copolymerization is performed in water or a polar solvent using a radical polymerization initiator (e.g., ammonium persulfate) to afford the aimed copolymer.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention provides an amphoteric polymer copolymer useful as an antistatic agent, a chelate resin, a wastewater treatment agent, an oil recovery agent, a paper manufacturing agent, etc. This article relates to a method for producing a molecular polymer, in particular a method for producing a new copolymer of monoallylamine and itaconic acid, a copolymer of diallylamine and itaconic acid, and a copolymer of a monoallylamine derivative or a diallylamine derivative and itaconic acid. It is.

[Prior Art] Conventionally, the basic method for producing ampholytic polymer electrolytes has been to copolymerize vinyl acidic monomers and basic monomers. However, copolymerization of vinyl monomers with extremely good polymerizability has usually been carried out, and copolymerization with allylamine derivatives has not been carried out.

In general, allylamine derivatives have an allyl group in the molecule, so they undergo so-called degenerative chain transfer and cannot be said to have high polymerization activity, and mono-arylamine is particularly susceptible to this tendency. Homopolymerization of monoallylamine has been thought to be impossible for many years, but polymerization can be achieved in high yield when monoallylamine is converted into a salt of a strong inorganic acid such as hydrochloric acid, phosphoric acid, or sulfuric acid and a specific azo catalyst is used. In recent years, it has been discovered that it is possible to obtain (Japanese Patent Application Laid-Open No. 58-201811). However, regarding copolymerization, it is recognized that copolymerization can occur with specific monomers that have a close chemical structure (Japanese Patent Laid-Open No. 6
O-088018) only.

In other words, even if monoallylamine is used as an inorganic acid salt as in the above homopolymerization, the same catalyst used in the homopolymerization is used, and highly polymerizable acrylamide or acrylonitrile is used as a comonomer, no copolymerization occurs and the polymerization rate is low. It is. In these copolymerization systems, allylamine is thought to act as a polymerization inhibitor for the comonomer.

As described above, it is currently considered difficult to copolymerize allylamine and its derivatives.

On the other hand, itaconic acid has been known to polymerize, but its polymerizability is not high. Therefore, it was considered extremely difficult to copolymerize allylamine or its derivatives with itaconic acid.

[Means to accomplish the task]

The present invention involves mixing monoallylamine derivatives or diallylamine derivatives with itaconic acid as free amines without converting them into salts of strong acids such as hydrochloric acid, as is done to ensure polymerizability during polymerization. Moreover, it was developed based on the discovery that copolymerization easily occurs when the proportions of both monomers are set to a specific ratio.

That is, the problem of the present invention is to combine a monoallylamine derivative represented by the general formula <1) or a diallylamine derivative represented by the general formula () and itaconic acid in a molar ratio of 2/1 to 115. This can be achieved by mixing the mixture so that it becomes the same and polymerizing it in water or a polar solvent using a radical polymerization initiator.

Examples of the monoallylamine derivative represented by the general formula (1) include monoallylamine, N-methylalylamine, N-ethylallylamine, N-n-propylarylamine, N-4so-propylarylamine, N- n-butylallylamine, N-is.

-butylallylamine, N-5ec-butylallylamine, N-tart-butylallylamine, N-hexylallylamine, N-cyclohexylallylamine, N,
N-dimethyl aryolamine, N, N-diethyl aryolamine, N, N-dipropylarylamine, N, N-
Examples include dibutylallylamine.

Examples of diallylamine derivatives represented by general formula (I[) include diallylamine, N-methyldiallylamine, N-ethyldiallylamine, N-propyldiallylamine, N-butyldiallylamine, N-hexyldiallylamine, N-octyldilylamine, Examples include N-dodecyldiallylamine and N-penzyldiallylamine.

In the homopolymerization of these monomers, polymerization usually does not occur unless they are neutralized with hydrochloric acid, sulfuric acid, etc. to form mineral acid salts. However, in the present invention, it is not preferable to use mineral acid salts because the yield decreases significantly, and free The amine is used as is for polymerization.

In the present invention, the molar ratio of monoallylamine derivative or diallylamine derivative to itaconic acid is 2/1 to 115.
It is necessary to do so. If it is outside this range, the yield will drop significantly and it will be of little practical value.

The solvent used in the present invention is preferably water or a polar solvent. Examples of polar solvents include methanol, ethanol, dimethylformamide, dimethyl sulfoxide, and the like.

Further, the radical polymerization initiator used in the present invention is not particularly limited, and includes ammonium persulfate, potassium persulfate, hydrogen peroxide, tert-butyl hydroperoxide, di-tart-butyl peroxide, cumene hydroperoxide, benzoyl peroxide. Azo compounds such as azobisisobutyronitrile and 2,2'-azobis(2-amidinopropane) dihydrochloride can be used as appropriate.

In addition, when using peroxide as a polymerization initiator, pe*
*It can also be used as a redox polymerization initiator in combination with metal ions, sulfites, amines, etc. 0 The polymerization initiator is 0.05 to 5 moles per copolymerization monomer.
It is within the range of χ.

The polymerization temperature is usually in the range of 40 to 100°C,
When using the above redox polymerization initiator, 0 to 4
Polymerization is possible even in the 0°C range.

Monomer concentration is 10-80%, preferably 40-75%
However, if the monomer concentration is too low, the polymerization reaction tends to be slow.

In the present invention, basic substances such as caustic soda, caustic potash, soda carbonate, ammonia, and amines may be added.

Example 1 130.1 g of itaconic acid (abbreviated as IA) was added to 187 g of water.
．． After dissolving in 2g of monoallylamine (A) under water cooling,
A monomer mixture having a molar ratio of AA and IA of 1:1 and a monomer concentration of 50% was prepared by dropping 57.1 g of the solution (abbreviated as A) at a temperature not exceeding 5°C. The temperature of this monomer mixture was raised to 55° C., and 2.28 g of ammonium persulfate (0.5 mol % based on the sum of both monomers) was added as a polymerization initiator, followed by polymerization at 55° C. for 24 hours. After the polymerization was completed, 10g was taken and precipitated in acetone.
It was filtered and dried by heating under reduced pressure to obtain 4.63 g of white powder. The polymerization rate was 92.6%. This one has a pH of 1,
If it is between 8 and 4, it is insoluble in water, and outside this range, it is soluble in water and exhibits properties as a typical polymer ampholyte.

N/10 in NaCl, 30°C, concentration 0.5g/d! The intrinsic viscosity measured inside was 0.32. The infrared absorption spectrum of this copolymer is shown in FIG. Elemental analysis value is C
=55.12%, H=7.38%, N=7.16%
It can be seen that the copolymer has a molar ratio of AA and IA of approximately 1:1. The melting point of this copolymer was measured, and it decomposed at temperatures above 220°C, which showed a clear melting point.

Examples 2 to 6, Comparative Examples 1 to 7 The molar ratio of allylamine and itaconic acid in Example 1 was changed from 1:1 to 1:2. Copolymerization was carried out in the same manner as in Example 1 except that te3,1:4°1:5 and 2:1 were used. These results are summarized in Table 1.For comparison, the molar ratio of allylamine and itaconic acid was 3:1,
Polymerization was carried out under the same polymerization conditions in the case of 1:8, in the case of allylamine alone, and in the case of itaconic acid alone.

Furthermore, for comparison, the molar ratios of allylamine hydrochloride obtained by neutralizing allylamine with hydrochloric acid and itaconic acid are 1:1, 1:2, and 2:1, other conditions being the same. Copolymerization was attempted using These results are also summarized in Table 1. Table 2 also shows the elemental analysis values and melting points of the copolymers obtained in each example.

Table 2 Figure 2 shows the results shown in Table 1 and Example 1, with the horizontal axis representing the mole fraction of itaconic acid in the monomer mixture and the vertical axis representing the polymerization rate. The mole fraction is from 0.3 to
It shows a peak effect in the range of 0.85, indicating that a high polymerization rate can be obtained. However, even if the molar fraction is within this range, only a low polymerization rate can be obtained when allylamine is neutralized to form allylamine hydrochloride.

Examples 7 to 10 The polymerization initiator ammonium persulfate in Example 1 was
Polymerization was carried out under the same conditions as in Example 1, except that potassium persulfate, tert-butyl hydroperoxide, hydrogen peroxide, and 2,2'-azobis(2-amidinopropane) dihydrochloride were used.

These polymerization conditions and results are shown in Table 3.

Examples 11 to 15 The monomer concentration in Example 1 was increased from 50% to 74.5
%, 60%, 40%, 30%, and 20%, respectively, and copolymerization was carried out under the same conditions as in Example 1. Polymerization conditions and results are shown in Table 4.

Table 3 Monomer molar ratio: allylamine:itaconic acid-1:l Monomer concentration: 50 wt% Polymerization temperature: 55°C Polymerization time: 24 hr Intrinsic viscosity: N/10 NaCl at 30°C.

Value at concentration 0.5 g/a Table 4 Monomer molar ratio: 1:1 Polymerization initiator: Ammonium persulfate Q, 55 tol
eχ Polymerization temperature: 55°C Polymerization time: 24 hr Intrinsic viscosity: N/10 NaCj! Medium, 30℃.

Value at a concentration of 0.5 g/a Examples 16 to 18 Instead of monoallylamine in Example 1, N-ethylallylamine, N-tert-butylallylamine,
A monomer mixture of N-cyclohexylallylamine and itaconic acid was prepared in a molar ratio of 1:1, and copolymerization was carried out in the same manner as in Example 1. acid copolymer,
A copolymer of N-tert-butylallylamine and itaconic acid and a copolymer of N-cyclohexylallylamine and itaconic acid were obtained. These polymerization conditions and results are shown in Table 5.

Seven months molar ratio 1; l Monomer concentration 50-t% Polymerization initiator Ammonium persulfate 0.5 molJ
Polymerization temperature: 55°C Polymerization time: 24 hours Intrinsic viscosity: N/10 NaCl at 30°C.

Value at a concentration of 0.5 g/a Example 19 97.2 g of diallylamine (abbreviated as DAA) was added dropwise to a mixture of 130.1 g of itaconic acid (IA) and 227.3 g of water while cooling with water. A monomer mixture solution having a molar ratio of 1:1 to IA and a monomer concentration of 50% was prepared. The temperature of this monomer mixture was raised to 55°C, 2.28g of ammonium persulfate (0.5+wolχ based on the sum of both monomers) was added as a polymerization initiator, and 2.28g of ammonium persulfate was added as a polymerization initiator.
Polymerization was carried out for 4 hours. After the polymerization was completed, 10 g was taken, precipitated in acetone, filtered, and dried under reduced pressure to give 4.99 g.
A white powder was obtained. The polymerization rate was 99.8%. This substance is insoluble in water at a pH of approximately 1.8 to 3.8, and becomes soluble in water outside this range, exhibiting properties as a typical polymer ampholyte. At 30℃, N/10
The intrinsic viscosity measured in NaCl at a concentration of 0.5 g/a is 0.
．． It was 25.

The infrared absorption spectrum of this copolymer is shown in FIG. Elemental analysis values are C=58.10%, H=7.86%, N=6
．． 09%, indicating that it is a copolymer with a molar ratio of DAA and IA of approximately 1:1. The melting point of this copolymer was measured, but it did not show a clear melting point and decomposed at temperatures above 250°C.

Examples 20 to 23 Diallylamine was prepared in the same manner as in Example 19 except that the molar ratio of diallylamine and itaconic acid in Example 19 was 2:1, 1:2.1:3, and 1:5 instead of 1:1. was copolymerized with itaconic acid.

Table 6 shows the polymerization conditions and results, and Table 7 shows the elemental analysis values and melting point of the obtained copolymer.

Table 6 Monomer concentration Polymerization initiator Polymerization temperature Polymerization time intrinsic viscosity 50wt% Ammonium persulfate 0.5 mole 255℃ 4 hours N/10 in NaCj, 30°C.

Value at concentration 0.5 g/dI Table Examples 24 to 25 Same as Example 19 except that N-methyldiallylamine (MDA) and N-butyldiallylamine (BDA) were used instead of diallylamine in Example 19. Copolymerization was carried out to obtain a copolymer of N-methyldiallylamine and itaconic acid and a copolymer of N-butyldiallylamine and itaconic acid, respectively. These polymerization conditions and results are summarized in Table 8.

No. table Monomer molar ratio; l:1 Monomer concentration ・50wt% Polymerization initiator; ammonium persulfate Polymerization temperature, 55°C Polymerization time: 24 hours Intrinsic viscosity N/10 in NaCl at 30°C.

Value at a concentration of 0.5 g/a (effect) The present invention enables copolymerization of allylamine derivatives and itaconic acid, which was previously thought to be impossible, and provides a novel amphoteric polymer.

[Brief explanation of drawings]

Figure 1 shows the infrared absorption spectrum (Br di
Figure 2 shows the relationship between the molar fraction of itaconic acid in the monomer mixture and the polymerization rate in the copolymerization of monoallylamine and itaconic acid. FIG. 3 shows an infrared absorption spectrum (KBr disk) of a copolymer of diallylamine and itaconic acid (molar ratio 1:1).

Claims (1)

[Claims] 1. An amphoteric polymer copolymer in which the molar ratio of both monoallylamine and itaconic acid components is 2/1 to 1/5. 2. The molar ratio of both components of diallylamine and itaconic acid is 2: Amphoteric polymer copolymer 3 which is 2/1 to 1/5, general formula ▲ Numerical formula, chemical formula, table, etc. ▼ Here, R_1 and R_2 are the same or different, hydrogen, alkyl having 1 to 12 carbon atoms or a monoallylamine derivative represented by a cycloalkyl group having 5 to 6 carbon atoms, or a general formula ▲ Numerical formula, chemical formula, table, etc. ▼ [Here, R_2 is hydrogen or an alkyl group having 1 to 12 carbon atoms] , or an aralkyl group. ] By mixing the diallylamine derivative represented by and itaconic acid so that the molar ratio of the two is 2/1 to 1/5, and copolymerizing the mixture using a radical polymerization initiator in water or a polar solvent. Method for producing amphoteric polymer