JPS6343402B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing an N-methylated allylamine polymer. As is well known, monoallyl compounds are difficult to polymerize using common radical polymerization initiators, and generally only polymers with a low degree of polymerization are produced in low yields. This is explained to be due to a self-termination reaction caused by the reaction between the allylic hydrogen atom and the radical, and is usually called allylic destructive chain transfer. This is true for N-methylallylamine and N,N-dimethylallylamine, which are a type of allyl compound, and with ordinary radical polymerization initiators, only a trace amount is obtained and almost no polymerization occurs. There are no reports of N-methylallylamine and N,N-dimethylallylamine polymers being obtained in high yields. In view of the current situation, the present inventors have conducted intensive studies to develop a practical method for producing N-methylallylamine polymers and N,N-dimethylallylamine polymers. When an inorganic acid salt of monoallylamine is polymerized using a polymerization initiator, the inorganic acid salt of allylamine is polymerized in high yield, and a salt of polyallylamine with a high degree of polymerization is obtained, and the obtained salt of polyallylamine or the same The present invention was completed based on the discovery that an N-methylated allylamine polymer can be obtained in high yield by reacting formic acid and formaldehyde with polyallylamine obtained by reacting with an alkali. That is, the method for producing an N-methylated allylamine polymer of the present invention involves polymerizing an inorganic acid salt of monoallylamine using a radical polymerization initiator containing an azo group in the molecule, and then polymerizing the resulting polyallylamine salt or It is characterized in that formic acid and formaldehyde are reacted on polyallylamine obtained by reacting an alkali with the polyallylamine. The polymerization initiator used in the polymerization of the inorganic acid salt of monoallylamine in the present invention is a radical initiator containing an azo group in the molecule, and a representative example thereof is hydrochloric acid of an azo compound represented by the following general formula []. salt, sulfate, phosphate, alkyl sulfate, para-
Mention may be made of inorganic or organic acid salts such as toluenesulfonate, formate, acetate and propionate. R ₁ −N=N−R ₂ ... [] [In the formula, at least one of R ₁ and R ₂ , preferably both, are aminoalkyl, aminoaryl, amidinylalkyl, amidinylaryl, aminoalkaryl , aminoaralkyl, amidinylalkaryl, amidinylalkaryl, cyanoaminoalkyl, and cyanoaminoalkaryl, and only one of R ₁ and R ₂ is a group containing a cationizable nitrogen atom. In the case of a group containing a cationizable nitrogen atom, the other
A group selected from the group consisting of alkyl, aryl, alkaryl, aralkyl, cyanoalkyl, cyanoaryl, cyanoalkaryl, and cyanoaralkyl, and R ₁ and R ₂ together represent the following: A single alkylene group represented by the general formula [] may be formed. (In the formula, R is a group selected from the group consisting of alkylene, alkylalkylene, and arylalkylene, and the covalent bonds (a) and (b) are bonded to each nitrogen atom of the azo group, and the azo group-containing ring and X is a group containing a nitrogen atom that can be cationized). Among the initiators represented by the general formula [], particularly desirable compounds are those having a secondary or tertiary carbon atom adjacent to an azo group. It is: 2,2'-diamidinyl-2,2'-azopropane hydrochloride, 2,
2′-diamidinyl-2,2′-azobutane hydrochloride,
2,2'-diamidinyl-2,2'-azopentane hydrochloride, 2,2'-bis(N-phenylamisonyl)
-2,2'-azopropane hydrochloride, 2,2'-bis-
(N-phenylamidinyl)-2,2'-azobutane hydrochloride, 2,2'-bis(N,N-dimethylamidinyl)-2,2'-azopropane hydrochloride, 2,
2'-bis-(N,N-dimethylamidinyl)-
2,2'-Azobutane hydrochloride, 2,2'-bis(N,
N-diethylamidinyl)-2,2'-azopropane hydrochloride, 2,2'-bis(N,N-diethylamidinyl)-2,2'-azobutane hydrochloride, 2,2'-
Bis-(N-n-butylamidinyl)-2,2'-
Azopropane hydrochloride, 2,2'-bis(N-n-butylamidinyl)-2,2'-azobutane hydrochloride,
3,3'-bis(N,N-di-n-butylamidinyl)-3,3'-azopentane hydrochloride, azo-bis-N,N'-dimethyleneisobutyramidine hydrochloride; 2,2'-azo- Bis(2-methyl-4-dielamino)-butyronitrile hydrochloride, 2,2'-azo-bis(2-methyl-4-dimethylamino)-butyronitrile hydrochloride, 2,2'-azo-bis-(2
-Methyl-4-diethylamino)-butyronitrile hydrochloride, 2,2'-azo-bis-(2-methyl-
Quaternary compound obtained by quaternizing 4-diethylamino)-butyronitrile or 2,2'-azo-bis-(2-methyl-4-dimethylamino)-butyronitrile with dimethyl sulfate or methyl p-toluenesulfonate, etc. Ammonium salt type azonitrile; 3,5-diamidinyl-1,2-diazo-1-
Cyclopentene hydrochloride, 3-methyl-3,4-diamidinyl-1,2-diazo-1-cyclopentene hydrochloride, 3-ethyl-3,5-diamidinyl-
1,2-diazo-1-cyclopentene hydrochloride,
3,5-dimethyl-3,5-diamidinyl-1,
2-Diazo-1-cyclopentene hydrochloride, 3,6
-Diamidinyl-1,2-diazo-1-cyclohexene hydrochloride, 3-phenyl-3,5-diamidinyl-1,2-diazo-1-cyclopentene hydrochloride, 3,5-diphenyl-3,5-diamidinyl-1 , 2-diazo-1-cyclopentene hydrochloride. A method for polymerizing an inorganic acid salt of monoallylamine using an inorganic or organic acid salt of an azo compound represented by the above general formula [] as a polymerization initiator is disclosed in Japanese Patent Application No. 58-54988 (Japanese Patent Application Laid-open No. 58-201811 filed by the same applicant). issue)
The details are described in the specification. Other representative examples of the initiator used in the polymerization of the inorganic acid salt of monoallylamine in the present invention include azo compounds represented by the following general formula [] or [].

【formula】

[Formula] (In the general formulas [] and [], R ₃ , R ₄ , R ₅ and R ₆ are the same or different hydrocarbon groups.) Particularly preferred ones of R ₃ , R ₄ , R ₅ and R ₆ is a straight chain or branched alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, a phenyl group, or a benzyl group. R ₃ and R ₄ or/and R ₅ and R ₆ may form a ring together with the carbon atom to which they are bonded. Particularly preferred compounds of the initiators of the general formulas [] and [] are: However, it is needless to say that the invention is not limited to these. A method for polymerizing an inorganic acid salt of monoallylamine using a compound of the above general formula [] or [] as an initiator is disclosed in a patent application filed on November 10, 1988 by the same applicant (Japanese Patent Application No. Showa 60-
No. 104107) (title of the invention: Method for producing a polymer of monoallylamine) describes the details thereof. The amount of initiator used in the present invention is 0.1 to 10% by weight, usually 1 to 6% by weight, based on the inorganic acid salt of monoallylamine. The polymerization temperature varies depending on the chemical structure of the initiator, but is generally 30° to 100°C, usually 40° to 85°C. The polymerization time is usually within 100 hours, preferably 20 to 40 hours. The concentration of the starting monomer is preferably as high as possible within the range of its solubility, but is usually in the range of 10 to 85% by weight. Suitable inorganic acid salts of monoallylamine used in the present invention include hydrochloride, sulfate,
These include sulfites and phosphates. Polymerization takes place in polar media, i.e. water, inorganic acids (hydrochloric acid, sulfuric acid, phosphoric acid, polyphosphoric acid) or their aqueous solutions, organic acids (formic acid, acetic acid, propionic acid, lactic acid, etc.) or their aqueous solutions, alcohol, dimethyl It is carried out in aqueous solutions of sulfoxides, dimethylformamide, salts of inorganic acids (zinc chloride, calcium chloride, magnesium chloride, etc.). During polymerization, the inorganic acid salt of monoallylamine is usually used in the form of an isolated crystal, but monoallylamine and an inorganic acid are added to the polar solvent to form a salt in the system. You may let them. Needless to say, when an inorganic acid or its aqueous solution is used as a polymerization medium, a predetermined amount of monoallylamine can be added to the inorganic acid or its aqueous solution and polymerized as it is. Since polymerization is somewhat inhibited by oxygen in the air, it is preferable to carry out the polymerization in an inert gas such as nitrogen. In the later-described N-methylation reaction using formaldehyde and formic acid, the salt of polyallylamine may be used as it is or may be used as polyallylamine. Polyallylamine can be obtained as follows. That is, a salt of polyallylamine is dissolved in water, and an equimolar amount of a strong alkali such as caustic soda is added. To remove by-product salt (salt when hydrochloride is used as the allylamine salt and caustic soda is used as the strong alkali), it is subjected to dialysis, ultrafiltration, gel filtration, etc., and then dehydrated and dried. Next, a method for producing an N-methylallylamine polymer and an N,N-dimethylallylamine polymer by reacting the obtained polyallylamine or its salt with formic acid and formaldehyde will be explained. Polyallylamine or a salt thereof is dissolved in water, methanol, or a mixed solvent of these and a polar solvent. The concentration is 5-60%. While cooling this and keeping the temperature below 30°C, formic acid and then formaldehyde aqueous solution are added dropwise. In the case of N-methylallylamine polymer, the amount of formic acid and formaldehyde to be added is 1 to 1.5 formaldehyde per mole of polyallylamine as amine.
1.5 to 4 moles of formic acid are required. N, N-
In the case of dimethylallylamine polymer, 2 to 3 moles of formaldehyde and 3 to 8 moles of formic acid are also required. The degree of methylation can be controlled by varying the amounts of formaldehyde and formic acid. After dropping formic acid and formaldehyde, the temperature is gradually raised to 70-90°C. Carbon dioxide gas is generated violently. If the temperature is kept at the same temperature for 4 to 6 hours and gas generation stops, the reaction can be considered to have ended. After the reaction is complete, it is precipitated in a large amount of acetone to remove unreacted formaldehyde and formic acid, filtered, dried, and
- Obtain a formate of a methylallylamine polymer or an N,N-dimethylallylamine polymer. The formate salt is converted to free N-methylallylamine polymer or N,N-dimethylallylamine polymer as required. Next, examples are given below to further clarify the present invention. Example 1 104.2 g of 35% hydrochloric acid was added to 57.1 g of allylamine.
It was added dropwise at ~20°C to obtain an aqueous allylamine hydrochloride solution with a concentration of 59.1%. This was concentrated using a rotary evaporator to a concentration of 75%. Heat this solution to 60
℃, and add 2,2′-diamidinyl-2,
2'-azopropane hydrochloride 2.34g (to monomer 2.5
%) was added dropwise over a period of 3 hours, and the temperature was kept at 60°C for 15 hours after the addition was completed. After the polymerization was completed, the polymer was precipitated by adding it to a large amount of methanol, followed by filtering and drying. The yield was 86g. 20g of polyallylamine hydrochloride obtained above and 30g of water
was added and dissolved, and 21.4 g of 40% caustic soda was added thereto. In order to remove the generated salt, the mixture was dialyzed for 24 hours using a hollow fiber, and the total weight was made up to 100 g, which was then freeze-dried to obtain 11.6 g of polyallylamine. Dissolve 11.4 g of polyallylamine (0.2 mol as amine) in 30 g of water, and heat the solution at 90°C while keeping the temperature below 30°C.
% formic acid (40.9 g (0.8 mol)), followed by 35%
37.7 g (0.44 mol) of formalin was added dropwise. After the addition was completed, the temperature was gradually raised to 80°C. A large amount of carbon dioxide gas was generated. The temperature was kept at the same temperature for 5 hours, and the reaction was completed when it was confirmed that gas generation had stopped. The reaction solution was added to a large amount of acetone to precipitate it, and the mixture was filtered and dried to obtain a white powder. The yield was 24.2g. The elemental analysis values of this product were as follows. Actual measured values (theoretical values) C 55.10% (54.94%) H 9.91% (9.99%) N 10.44% (10.68%) The values in this figure are theoretical values for the formate of N,N-dimethylallylamine polymer. Furthermore, ^1H -NMR-spectral analysis reveals that this polymer is poly-(N,N-dimethylallylamine).
It was confirmed that. Example 2 Polyallylamine obtained in the same manner as Example 1
20.5 g (0.4 mol) of 90% formic acid and 18.9 g of 35% formalin were prepared in the same manner as in Example 1 using 11.4 g.
(0.22 mol). The yield was 22.0g. The elemental analysis values of this product were as follows. Measured values (actual values) C 50.73% (51.26%) H 9.18% (9.47%) N 12.24% (11.96%) The figures in the brackets are theoretical values for the formate of N-methylallylamine polymer. Furthermore, ¹ H-NMR-spectral analysis confirmed that this polymer was poly-(N-methylallylamine).

Claims (1)

[Claims] 1. Polymerizing an inorganic acid salt of monoallylamine using a radical polymerization initiator containing an azo group in the molecule,
Next, a method for producing an N-methylated allylamine polymer, which comprises reacting the obtained polyallylamine salt or the polyallylamine obtained by reacting an alkali with formic acid and formaldehyde.