JPH0256362B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention uses monoallylamine (CH ₂ =
The present invention relates to a method for producing a polymer of CHCH ₂ NH ₂ ). As is well known, allyl compounds are difficult to polymerize using common radical initiators, and generally only polymers with a low degree of polymerization are produced in low yields. This is no exception for monoallylamine, which is a type of allyl compound; monoallylamine hardly polymerizes with ordinary radical or ionic initiators, and under special conditions such as the following. Only a few polymerization examples below have been reported. 1. A method for obtaining brown resinous poly-monoallylamine (hereinafter simply referred to as polyallylamine) by gas phase polymerization using tetrafluorohydrazine as a catalyst (US Pat. No. 3,062,798). 2. Add a small amount of water to monoallylamine hydrochloride, bring it to a molten state at 80-85℃, and polymerize while adding hydrogen peroxide little by little to obtain resin-like (blackish brown) polyallylamine hydrochloride with a molecular weight of 950-1000. How to obtain [VVZykova et al. Tr.Inst.Khim
Nauk, Akad.Nauk Kaz.SSR, 11 , 89–94.
(1964), Chem.Abst. 61 , 14855 (1964)]. 3 A method in which monoallylamine hydrochloride is dissolved in a mixed solvent of tert-butyl alcohol and chlorobenzene in the coexistence of diethyl phosphite, and polymerized at the reflux temperature of the solvent using azobisisobutyronitrile as an initiator [Germany method] Patent publication no.
2946550 and its corresponding Japanese application, JP-A-56-82807]. Methods 1, 2, and 3 above are examples of monoallylamine polymerization using a catalyst such as a radical initiator, but in methods 1 and 2, the resulting polymers are all sticky. A resin-like product with a high degree of polymerization has not been obtained. Method 3 described in the German publication is a homopolymerization and copolymerization method of monoallylamine hydrochloride, but all of the examples described in the publication, with the exception of one, are based on easily polymerized vinyl monomers. This is an example of copolymerization with polymers (acrylamide, acrylic acid, acrylic ester, acrylonitrile, etc.), and the only homopolymerization example described on page 36 of the same publication, polyallylamine hydrochloride was produced with a yield of 85%. is obtained. However, there is no description of the shape or degree of polymerization of the obtained polymer.
It simply states that it is water-soluble over the entire PH range. As a result of additional tests by the present inventors, contrary to the description, only a hygroscopic low molecular weight product was obtained with a yield of about 0.6% (see Comparative Example described below). Incidentally, no examples of homopolymerization of allyl ammonium salts are found in the specification of the above-mentioned corresponding Japanese patent application (JP-A-56-82807). Next, as a method for polymerizing monoallylamine, the following radiation polymerization method has also been proposed, and according to this method, a monoallylamine polymer having a higher degree of polymerization can be obtained than a method using a radical catalyst. Namely, 4. A method of polymerizing monoallylamine by irradiation with gamma rays in protonic acid (phosphoric acid, sulfuric acid, hydrochloric acid) or ultraviolet rays in the presence of hydrogen peroxide [V.
A. Kabanov et al., Vysokomol.Soed., 18 , No.9
1957-1962 (1976) and 18 , No. 10, 2233-
2238 (1976)]. 5. Monoallylamine, allyl cyanide or allyl mercaptan in the presence of an inorganic acid or an inorganic acid salt of a metal of group 1 or group of the periodic table,
Polymerization method by irradiation with various radiations (gamma rays, electron beams, X-rays, ultraviolet rays) (LSPolak,
VAKabanov et al., USSR Patent No. 296423). This patent also includes a radical-catalyzed polymerization method, but examples include polymerization of allyl cyanide with benzoyl peroxide in the presence of zinc chloride and hydrogen peroxide in the presence of calcium chloride. It only describes a method for polymerizing allyl mercaptan, but does not describe an example of polymerizing monoallyl amine using a radical catalyst. None of the monoallylamine polymerization methods described above can be said to be methods for easily obtaining polyallylamine in large quantities. Very recently, one of the inventors (Harada) developed an inorganic acid salt of monoallylamine in a polar solvent using an azo radical initiator containing a group with a cationic nitrogen atom in the molecule. They discovered that a polymer could be easily obtained by polymerizing the same, and filed a patent application for this in Japanese Patent Application No. 58-54988. This Japanese Patent Application No. 58-54988 states that "it is important that both the monomer and the initiator have an electric charge in the polymerization system" as a condition for facilitating the polymerization of inorganic acid salts of monoallylamine. It is stated that. In this case, it is clear from the claims that the initiator refers to a positively charged nitrogen atom. The present inventors searched for a more effective polymerization initiator when polymerizing an inorganic acid salt of monoallylamine in a polar solvent, and found that compounds represented by the following general formulas [] and [] were used as radical initiators. The present invention was completed based on the discovery that it is very effective when used as a compound. (In the general formulas [] and [], n represents an integer of 0 to 4, R ₁ and R ₂ are the same or different groups, and are a straight chain or branched alkyl group having 1 to 4 carbon atoms, a straight chain or branched alkyl group having 3 carbon atoms, -6 represents a cycloalkyl group, phenyl group or benzyl group.) By the way, the radical initiators represented by the above general formulas [] and [] are disclosed in the above-mentioned Japanese Patent Application No. 1983-
It differs from the radical initiator used in the invention of No. 54988 in the following points. That is, in the radical initiator of the present invention, the nitrogen atom other than the azo group is an amidoxime group or a nitrogen atom contained in a hydroxamic acid. Its basicity is significantly lower than that of a nitrogen atom, and rather it has the properties of a negative charge. In addition, the initiators [ ] and [ ] of the present invention contain a -COOH group that exhibits acidic properties. Of course, since polymerization is mainly carried out in a polar solvent in the presence of a strong acid, the carboxyl groups of the initiators [] and [] are unlikely to exist in the form of a negative charge like -COO +H. This does not mean that there is no ion dissociation of species. Considering the above properties, it was predicted that the initiators [ ] and [ ] of the present invention would have no effect at all even if applied as an initiator to the polymerization of an inorganic acid salt of monoallylamine. It is truly surprising that such an effect has been observed. Next, the present invention will be specifically described. 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, poly-phosphoric acid, etc.) or their aqueous solutions, organic acids (formic acid, acetic acid, propionic acid, lactic acid, etc.) or their aqueous solutions, alcohols. ,
dimethyl sulfoxide, dimethyl formamide,
It is carried out in an aqueous solution of 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. Among the initiators represented by the general formulas [] and [] used in the present invention, particularly desirable compounds are: 2,2'-Azobis-(2-carboxymethyl-propioamidoxime) 2,2'-azobis-(2-carboxyethyl-propioamidoxime) 3,3'-azobis-(3-carboxyethyl-butyroamidoxime) 2,2'-azobis-(2-carboxymethyl-propionhydroxamic acid) 2,2'-azobis-(2-carboxyethyl-propionhydroxamic acid) 3,3'-azobis-(3-carboxyethyl-butylhydroxamic acid) and the like. 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 usually 30° to 100°C, usually 40° to 70°C. Polymerization time is usually within 100 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. 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. Examples and comparative examples of the present invention are described below.
The fraction with a boiling point of 52.5-53°C obtained by drying MAA over granulated caustic soda and rectifying it under nitrogen was used.
As a result of gas chromatography, it was found that this fraction contained no diallylamine or triallylamine at all. Example 1 This example uses 2,2'-azobis-(2-carboxyethyl-propioamidoxime) (initiator-
An example of producing a monoallylamine polymer by polymerizing monoallylamine in phosphoric acid using 1) as an initiator will be shown. First, the method for synthesizing initiator-1 will be explained. Dissolve 12 g (0.3 mol) of caustic soda in 200 ml of water, cool on ice, and add 24.6 g (0.15 mol) of hydroxylamine sulfate while stirring. In this system, 4,4′-azobis(4-cyanovaleric acid) 16.8
g (0.06 mol) and reacted at 30-35°C for 20 hours. After the reaction, the mixture is concentrated to dryness under reduced pressure below 30°C. Dissolve this in 500 ml of acetone, and distill off the acetone from the resulting acetone solution. The residue is washed with ethyl acetate and dried under reduced pressure. Yield 10.2g (49
%). Elemental analysis, IR and NMR analysis, and acidity measurements confirmed that this product was initiator-1. Next, 922.3 g (8 moles) of 85% phosphoric acid are placed in two round bottom flasks equipped with a stirrer, thermometer, countercurrent condenser, and addition funnel. 224.8 g (4 mol) of monoallylamine (MAA) is added dropwise to this while stirring. At this time, set the temperature of the system to 10 to 30
Keep at ℃. After dropping, heat to 60℃ while stirring. In this way, 11.0 g of initiator-1 was added to the phosphoric acid solution of the obtained MAA-phosphate at 85%
Dissolve in 40g of phosphoric acid and add. Then at 60±2℃
Polymerize for 72 hours. After polymerization, a colorless, transparent and viscous solution is obtained. When this solution is added to a large amount of water, the polymer (polyallylamine-phosphate) becomes cake-like and precipitates. After thoroughly washing this precipitate with water, it was dissolved in 550 ml of concentrated hydrochloric acid and polyallylamine-
Converts phosphate to hydrochloride. This solution is added to a large amount of methanol, the precipitate is collected by filtration, and extracted with methanol using a Soxhlet extractor to remove unpolymerized monomers and phosphoric acid. The precipitate was dried under reduced pressure at 50°C to obtain 225g (about 60%) of a polymer.
This polymer was analyzed by elemental analysis, infrared spectroscopy,
As a result of ¹ H-NMR analysis, it was confirmed that it was polyallylamine hydrochloride (PAA-HCl).
¹ H-NMR spectrum of this polymer (in heavy water,
270MHz (TSP internal standard) is shown in the attached drawing. In addition, this value was determined by measuring osmotic pressure in a saline solution.
The number average molecular weight n of PAA-HCL was 22,000. This PAA-HCl is well soluble in water and acid aqueous solutions, but insoluble in organic solvents. The viscosity of the aqueous solution exhibits typical polyelectrolyte behavior. Furthermore, when heated in air, this PAA-HCl decomposes at temperatures above 300°C without melting. Next, free polyallylamine (PAA) was prepared from PAA-HCl. That is, PAA−HCl,
Dissolve 30g in 270g of distilled water, remove hydrochloric acid through a strongly basic ion exchange resin (Amberlite-IRA-402), and freeze-dry the filtrate.
16.5g of PAA is obtained. This PAA is easily soluble in water and methanol, swells with dimethyl sulfoxide and pyridine, but is insoluble in common organic solvents. When left in the air, this PAA absorbs carbon dioxide and moisture and produces carbonates. Example 2 This example describes the polymerization of monoallylamine by polymerization in an aqueous solution of monoallylamine hydrochloride using 2,2'-azobis-(2-carboxyethyl-propionhydroxamic acid) (initiator-2) as an initiator. An example of manufacturing the combination is shown below. Synthesis of initiator-2: 2,2'-azobis-(2-
carboxyethyl-propioamidoxime) (initiator-1, the synthesis method of which was shown in Example 1) 5.19 g
(0.015 mol), add 15 g of cooled concentrated hydrochloric acid,
Stir for 20 minutes at °C. After the reaction, the reaction mixture is poured into about 1 liter of acetone. The resulting precipitate was collected by filtration,
After washing with acetone and drying under reduced pressure, the result is 2.77
g (53%) of white powder is obtained. Elemental analysis, IR and NMR analysis, and acidity measurements of this powder confirmed that it was Initiator-2. Next, 570 g (10 mol) of MAA is added dropwise to 1.1 kg of concentrated hydrochloric acid (35% by weight) at 5 to 10° C. under ice cooling with stirring. After the dropwise addition is completed, water and excess hydrogen chloride are distilled off at 60°C under a reduced pressure of 20 mm of mercury using a rotary evaporator to obtain white crystals. The crystals were dried on silica gel with 5 mercury columns.
Dry at 80℃ under vacuum of mm, MAA-HCl980g
get. This MAA-HCl contains approximately 5% water. In a 500 ml round-bottomed flask equipped with a stirrer, thermometer, countercurrent condenser, and nitrogen gas inlet tube, add the above MAA.
- Add 98 g of HCl and 36 g of distilled water and stir to dissolve to make a 70% aqueous solution of MAA-HCl. Heat to 50°C while passing nitrogen gas. Next, 24.5 g of the above initiator was directly added, and polymerization was allowed to stand at 48 to 50°C for 70 hours. When the colorless, transparent and viscous solution thus obtained is added to a large amount of methanol, a white polymer precipitates out. This precipitate was collected by filtration, washed with methanol, and dried at 50°C under reduced pressure.
74.5%) of PAA-HCl is obtained. The number average molecular weight n of this PAA-HCl determined by osmotic pressure measurement in a saline solution was 5500. Example 3 100g of the 70% aqueous solution of MAA-HCl prepared in Example-2 was placed in a 200ml Erlenmeyer flask with a stopper, and initiator 1 synthesized in Example-1 or initiator- synthesized in Example-2 was added. 2 was added thereto, and polymerization was allowed to stand at 60°C for 50 hours. After polymerization, the same operation as in Example 2 was carried out to obtain polyallylamine hydrochloride. The results are summarized below.

[Table] Next, as a comparative example, in the coexistence of diethyl phosphite, as shown in German Patent Publication No. 2946550,
With 2,2'-azobisisobutyronitrile
The results of a follow-up test by the inventor of the polymerization example of MAA-HCl are shown. Comparative Example According to the method described on page 36 of German Patent Publication No. 2946550, 100 ml of t-butanol was added to a round bottom flask while nitrogen was being introduced, and the mixture was heated to reflux with stirring. A solution obtained by dissolving 46.8 g MAA-HCl and 0.5 g diethyl phosphite in 500 ml t-butanol and a solution obtained by dissolving 0.3 g azobisisobutyronitrile (AIBN) in 50 ml chlorobenzene. was simultaneously dropped into the t-butanol in the flask. The time required for dropping the two solutions was approximately 60 minutes. The reaction mixture was then refluxed for 3 hours. During the first two hours of this three hour period, a further solution of 0.3 g of AIBN in 50 ml of chlorobenzene was added. The reaction mixture was cooled to 20° C., filtered, washed with ethyl acetate, and dried under reduced pressure at 60° C. to obtain 0.25 g (0.53% yield) of a yellow hygroscopic product. Due to the small amount of product, it was not possible to measure the degree of polymerization of the product, but the hygroscopic nature of the product means that it has a relatively low degree of polymerization. .

[Brief explanation of the drawing]

The drawing is a ¹ H-NMR spectrum of a monoallylamine polymer obtained by the method of the present invention.

Claims (1)

[Scope of Claims] 1. A monoallylamine inorganic acid salt characterized by polymerizing an inorganic acid salt of monoallylamine in a polar solvent in the presence of an azo initiator represented by the following general formula [] or []. Method for producing polymers. (In the general formulas [] and [], n represents an integer of 0 to 4, R ₁ and R ₂ are the same or different groups, and are a straight chain or branched alkyl group having 1 to 4 carbon atoms, a carbon number 3 to 6 cycloalkyl group, phenyl group or benzyl group.)