JPH0257082B2 - - 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 produce resin-like (blackish brown) polyallylamine hydrochloride with a molecular weight of 950-1000. How to obtain salt [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. [German Patent Publication No.
2946550 and its corresponding Japanese application, JP-A-56-82807]. The above methods (1), (2) and (3) are examples of monoallylamine polymerization using a catalyst such as a radical initiator. All of the polymers were sticky and resinous, and no polymers with a high degree of polymerization were obtained. Method (3) described in the German publication is a method for homopolymerization and copolymerization of monoallylamine hydrochloride, but all of the examples described in the publication, with the exception of one, are easy to polymerize. This is an example of copolymerization with vinyl monomers (acrylamide, acrylic acid, acrylic ester, acronitrile, etc.),
In the only homopolymerization example described on page 36 of the publication, polyallylamine hydrochloride was obtained with a yield of 85%. However, there is no description of the shape or degree of polymerization of the obtained polymer, only that it is water-soluble in the entire pH range. As a result of further testing by the inventors, it was found that, contrary to that description, approximately
Only a hygroscopic low molecular weight product was obtained with a yield of 0.6% (see Comparative Example 2 below). By the way, the above-mentioned corresponding Japanese patent application
No. 82807), there are no examples of homopolymerization of allyl ammonium salts. 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. That is, (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 group or group metal 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 of the present invention (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. He discovered that a polymer could be easily obtained by polymerization, and filed a patent application for this in Japanese Patent Application No. 54988-1988. In it, he 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. In this case, it is clear from the claims that the "charge" regarding the initiator refers to the positive charge of the cationic nitrogen atom. The present inventors searched for a more effective polymerization initiator and polymerization reaction system when polymerizing an inorganic acid salt of monoallylamine in a polar solvent, and found that in the presence of an inorganic acid salt, the following general The present invention was completed based on the discovery that the polymerization reaction can be carried out very well when an azo compound represented by the formula [] or [] is used as a radical initiator. (In the general formulas [] and [], R ₁ and R ₂ are
Same or different hydrocarbon groups, R ₁ , R ₂
may be taken together to form a ring, R ₃ represents a hydrogen atom or an alkyl group, and m represents 0 or 1. ) By the way, the radical initiator represented by the above general formula [] or [] is applicable to the invention described above (Japanese Patent Application No.
Compared to the radical initiator No. 54988), it is significantly different in the following points. That is, the radical initiator of the present invention does not contain any nitrogen atoms other than an azo group, and is a completely neutral substance,
Insoluble in water, general alkaline water and inorganic acid water. In fact, it has been found that, for example, even if a compound of the above general formula [] or [] is added to monoallylamine hydrochloride and a polymerization reaction is carried out, there is no effect (see Comparative Example 1 described below). However, when polymerization is carried out by adding and dissolving an inorganic acid salt, such as zinc chloride, in the above reaction system, a remarkable effect is observed. It is well known that acrylonitrile (AN) is polymerized in a concentrated solution of zinc chloride, an inorganic acid salt, using azobisisobutyronitrile (ABIN) as an initiator. When directly applied to the polymerization of monoallylamine; for example, if we consider that there is no effect at all even if neutral ABIN is used as a radical initiator in a zinc chloride aqueous solution of monoallylamine hydrochloride. (Please refer to Comparative Example 1 described below),
It is truly surprising that remarkable effects are observed in the polymerization system of the present invention. Next, the present invention will be specifically described. In the present invention, monoallylamine is used in the form of an inorganic acid salt, preferably a hydrochloride. Other inorganic acid salts, such as sulfates, sulfites and phosphates, may be used as well, but may not give better results than the hydrochloride. The polymerization is carried out in an aqueous solution containing salts of inorganic acids, such as zinc chloride, calcium chloride and magnesium chloride. Particularly preferred is an aqueous solution of zinc chloride.
Generally speaking, the amount of the inorganic acid salt to be added is preferably large, but the solubility of the salt in water and solutions containing monoallylamine hydrochloride at various concentrations varies depending on the polymerization temperature, so it is not uniformly regulated. It is difficult to do so. However, in any case, it is preferable that the inorganic acid salt is contained in an amount of 5 to 500% by weight based on monoallylamine hydrochloride. During polymerization, an inorganic acid salt (e.g., hydrochloride) of monoallylamine is usually used in the form of an isolated crystal, but after adding a predetermined amount of monoallylamine to an inorganic acid (e.g., hydrochloric acid) in water. It is also possible to directly add and dissolve the above-mentioned inorganic acid salt (for example, zinc chloride) and subject it to polymerization as it is. In the present invention, among the initiators represented by the general formulas [] and [], particularly desirable compounds are:

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

[Formula] etc. The amount of initiator used in the invention is from 0.1 to 15% by weight, usually from 1 to 8% 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. In these examples, monoallylamine (hereinafter sometimes abbreviated as MAA) as a raw material monomer was manufactured by Shell Chemical Co., Ltd.
MAA (USA) was dried over granulated caustic soda,
A fraction with a boiling point of 52.5 to 53°C obtained by rectification 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 describes the polymerization of monoallylamine hydrochloride in an aqueous zinc chloride solution using 2,2'-azobis(2-methylpropionic acid methyl ester) (hereinafter referred to as initiator-1) as an initiator. An example of producing an allylamine polymer will be shown. As initiator-1, a reagent manufactured by Wako Pure Chemical Industries, Ltd. was used as it was. In 1.1Kg of concentrated hydrochloric acid (35% by weight), 5 to 10 minutes under ice cooling.
570 g (10 moles) of monoallylamine (MAA) are added dropwise with stirring at °C. After dropping, use a rotary evaporator to reduce the amount of mercury to 20
Water and excess hydrogen chloride are distilled off at 60° C. under a reduced pressure of 1 mm to obtain white crystals. The crystals were dried on silica gel for drying at 80°C under a reduced pressure of 5 mm of mercury,
Monoallylamine hydrochloride (MAA-HCl) 980g
get. This MMA-HC1 contains approximately 5% water. Add water to MAA-HC1 obtained above to make 85%
It was made into an aqueous solution and used in the following examples. 85% MAA in a 500 ml round bottom flask equipped with a stirrer, thermometer, countercurrent condenser, and nitrogen gas inlet tube.
-100g of HC1 aqueous solution and 200g of 70% zinc chloride aqueous solution
After making a homogeneous solution, heat it to 60℃ while passing nitrogen gas. Next, the above initiator-1
Add 2.09g directly and dissolve, then heat to 58-60℃48
Polymerize by standing for a while. When the viscous solution thus obtained is poured into a large amount of methanol, a white polymer precipitates out. This precipitate is collected by filtration and extracted with methanol using a Soxhlet extractor to remove unreacted monomers and zinc chloride. Precipitate at 50℃
The mixture was dried under reduced pressure to obtain 62.5 g (73.5%) of a polymer. As a result of elemental analysis, infrared spectrum analysis, and ¹ H-NMR analysis, this polymer was confirmed to be polyallylamine hydrochloride (PAA-HC1). The ¹ H-NMR spectrum (in deuterated water, 270 MHz, TSP internal standard) of this polymer 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-HC1 was 9800. This PAA-HC1 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-HC1 decomposes at temperatures above 300°C without melting. Next, free polyallylamine (PAA) was prepared from PAA-HC1. That is, PAA−HC1,
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 In this example, monoallylamine hydrochloride was prepared by polymerizing monoallylamine hydrochloride in an aqueous zinc chloride solution using 2,2'-azobis(2-acetoxy-propane) (hereinafter referred to as initiator-2) as an initiator. An example of producing a salt polymer is shown below. Synthesis of initiator-2: Dissolve 33.6 g of sodium acetate in 300 ml of acetic acid, add 11.2 g of ketazine synthesized from hydrazine and acetone, and slowly pass through chlorine gas while stirring at 10-20°C. After passing through an equivalent amount of chlorine gas, the mixture was further stirred at 20°C for 30 minutes.
Pour the reaction mixture into 5-8 times the volume of ice-water mixture,
The product is extracted with ether. Distilling off the ether gives 17.3 g (about 75%) of solid material. This substance was confirmed to be initiator-2 from the analysis values of elemental analysis, IR spectrum, and NMR spectrum. (Other initiators can also be obtained using the corresponding ketone and hydrazine as starting materials according to the above synthesis example.) Production of polyallylamine hydrochloride: Stirrer, thermometer, countercurrent condenser, nitrogen gas 300ml with introduction tube
In a round bottom flask, add 50% 85% MAA-HC1 aqueous solution.
g and 150 g of 70% zinc chloride aqueous solution to make a homogeneous solution, and then heated to 60°C while passing nitrogen gas. Next, 1.05 g of the above-mentioned initiator-2 was directly added to the system and polymerized at 58 to 60° C. for 70 hours. The resulting viscous solution was poured into a large amount of methanol to obtain a white polymer, which was then purified in the same manner as in Example 1 to obtain polyallylamine hydrochloride (PAA-
28.9 g (68%) of HC1) is obtained. The number average molecular weight n of this PAA-HC1 determined by osmotic pressure measurement in a saline solution was 8,000. Example 3 85% MAA-HC1 aqueous solution prepared in Example 1 10
g into a 50 ml or 100 ml Erlenmeyer flask with a stopper, add a predetermined amount of 70% zinc chloride aqueous solution, dissolve it, add initiator-1 or initiator-2, and incubate at 60°C for 70 hours. After standing polymerization, the same operation as in Example 1 was performed to obtain polyallylamine hydrochloride (PAA-HC1). These results are summarized in Table 1 below. Comparative Example 1 For comparison, polymerization examples using initiator -1 or -2 without the addition of zinc chloride (Comparative Examples 1a and 1b) and polymerization examples using azobisisobutyronitrile (ABIN) as an initiator. The results of (Comparative Example 1c) are also shown in Table-1. As is clear from the table, PAA-HC1 was substantially not obtained in Comparative Example 1, whereas PAA-HC1 with a high degree of polymerization was obtained in good yield in Example 3.

【table】

[Table] Example 4 Take 5 g of MAA-H ₃ PO ₄ aqueous solution in which the concentration of monoallylamine (MAA) in phosphoric acid is 19.85% in an Erlenmeyer flask with a stopper, and add 5 g of 70% zinc chloride aqueous solution.
After adding and dissolving, initiator-1 0.04g
(1 mol%) and polymerize at 60°C for 48 hours.
When the solution thus obtained is poured into a large amount of methanol, the polymer precipitates. This precipitate was collected by filtration,
Polyallylamine hydrochloride (PAA-
Take out as HC1). The yield was 0.1g, the yield was 6.2%, and the intrinsic viscosity ηinh0.5g/100ml was 0.1. Comparative Example 2 The present inventor's follow-up results of the polymerization example of MMA-HC1 using 2,2'-azoisobutyronitrile in the coexistence of diethyl phosphite, which was shown in German Published Publication No. 2946550, are shown. According to the method described on page 36 of German Publication No. 2946550, 100 ml of t-butanol was added to a round-bottomed flask while nitrogen was being introduced, and the mixture was heated to reflux with stirring. 46.8 in 500ml t-butanol
A solution obtained by dissolving g of MAA-HC1 and 0.5 g of diethyl phosphite and 0.3 g of azobisisobutyronitrile (AIBN) in 50 ml of chlorobenzene.
At the same time, the solution obtained by dissolving t
-Dropped into butanol. The time required for dropping the two solutions was approximately 60 minutes. The reaction mixture was then refluxed for 3 hours. The first 2 out of the last 3 hours
0.3 g in 50 ml of chlorobenzene per hour
A solution obtained by dissolving AIBN was further 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 suggests that
This means that the product has a relatively low degree of polymerization.

[Brief explanation of drawings]

The figure is a ¹ H-NMR spectrum diagram of polyallylamine hydrochloride obtained according to the present invention.

Claims (1)

[Claims] 1. A method characterized by polymerizing an inorganic acid salt of monoallylamine in an aqueous solution of an inorganic acid salt in the presence of an azo initiator represented by the following general formula [] or []. A method for producing a monoallylamine polymer. (In the general formulas [] and [], R ₁ and R ₂ are
R ₁ and R ₂ may be the same or different hydrocarbon groups and may form a ring together, and R ₃ is
Indicates a hydrogen atom or an alkyl group, and further m
represents 0 or 1. )