JPS6160703A - Production of polymer of monoallylamine or its salt - Google Patents

Abstract

PURPOSE:To produce the title polymer in good yield with the aid of a strong basic group-free polymerization initiator, by polymerizing an inorganic acid salt of a monoallylamine in the presence of a specified azoic polymerization initiator in a polar solvent. CONSTITUTION:In the presence of about 0.1-10wt% azoic polymerization initiator of formula I or II [wherein R1, R2, R3 and R4 are each a hydrocarbon group (R1 and R2 and/or R3 and R4 may be combined to form a ring)], e.g., 2,2'-azobis(2-methylpropionic acid hydrazine) or 4,4'-azobis(4-hydroxycaproic acid hydrazide), an inorganic acid salt of a monoallylamine is polymerized at 30-100 deg.C within about 100hr in a polar solvent (e.g., methanol).

Description

DETAILED DESCRIPTION OF THE INVENTION Technical Field The present invention relates to monoallylamine (0H2e 0HOH2N
This invention relates to a method for producing the polymer H2).

BACKGROUND OF THE INVENTION As is well known in the art, 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 true for monoallylamine, which is a type of allyl compound. Monoallylamine hardly polymerizes with ordinary radical or ionic initiators, but under special conditions as shown below. A few polymerization examples have been reported.

(1) A method for obtaining a brown resinous poly-monoallylamine (hereinafter simply referred to as "reallylamine") by gas phase polymerization using tetrafluorohydrazine as a catalyst (US Pat. No. 3,062,798).

(2) A small amount of water '4r:t to monoallylamine hydrochloride
A method of obtaining resin-like (blackish brown) polyallylamine hydrochloride with a molecular weight of 950 to 1000 by heating it to a melted state at 80 to 85 °C and polymerizing it while adding hydrogen peroxide little by little (v, v, z7kovaS, &Tr .

Engst, Khim Naulc, Mukad, N.
auk ICaz, BS only.

11.89-94 (19 (54), Ohem, mbst
.

61.14855 (1964)).

(3) Monoallylamine hydrochloride t1 In the presence of diethyl phosphite, it is dissolved in a mixed solvent of tert-butyl alcohol-florbenzene, and polymerized at the reflux temperature of the solvent using abbisisobutyronitrile as an initiator [ See German Patent Publication No. 2.946,550 and its corresponding Japanese application, JP-A-56-82807].

The above-mentioned methods (L), (2) and (3) are examples of monoallylamine polymerization using a catalyst such as a radical initiator, but in the methods (1) and (2), the obtained All of the polymers were viscous and resin-like, and none with a high degree of polymerization was obtained.

The method (3) described in the V-Itsu publication is a method for homopolymerization and copolymerization of monoallylamine hydrochloride, but all of the examples described in the publication, except for -,
This is an example of copolymerization with vinyl monomers that are easy to polymerize (acrylamizo-acrylic acid, acrylic ester, acronitrile, etc.), and the only homopolymerization example described on page 36 of the same publication shows a yield of 85%. However, there is no description of the shape or degree of polymerization of the obtained polymer, only that it is hydrophilic in all areas, and the book As a result of repeated experiments by the 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). By the way, the corresponding Japanese patent application mentioned above (
No examples of homopolymerization of allyl ammonium salts are found in the specification of JP-A-56-82807.

Next, as a method for polymerizing monoallylamine, the following radiation 11iIt method has 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 (v, A) in which monoallylamine is polymerized by ultraviolet irradiation in the presence of gamma rays or hydrogen peroxide in a protonic acid (phosphoric acid, sulfuric acid, hydrochloric acid).

Kabanov et al., Vysokomol, 5oed,
ldan, 厘91957-1962 (1976) and 18
, Fu 10.2236-2238 (1976)).

(5) Various types of radiation (gamma rays, electron beams, X-rays, Ultraviolet rays) + 7) [Polymerization method by irradiation (L, B, Po1ak.

V. A. Kabanov et al. USSR Patent No. 296.42
3 specification). This patent also includes a polymerization method using a radical catalyst, but the examples include a method for polymerizing allyl compound V with benzoyl peroxide in the presence of zinc chloride, and a method for polymerizing allyl compound V with benzoyl peroxide in the presence of zinc chloride, and hydrogen peroxide in the presence of calcium chloride. The method for polymerizing allyl mercaptan is only described, and no example of polymerizing monoallyl amine using a radical catalyst is described.

The method for polymerizing monoallylamine described above cannot be said to be a method for easily obtaining polyallylamine χ in large quantities.

Very recently, one of the inventors (Harada et al.) has developed an inorganic acid salt of monoallylamine, t, in a polar solvent, to initiate an a-based radical containing a group with a cationic nitrogen atom Z in the molecule. If polymerization is carried out using agent χ, a polymer can be easily obtained. This is the headline! A patent application has been filed as Japanese Patent Application No. 58-54988 (Japanese Unexamined Patent Publication No. 58-201811).

2'-azopropane dihydrochloride, 2
．． 2'-azobis(2-methyl-4-diethylamino)
These compounds are dethyronitrile dihydrochloride, and in addition to the azo group, these compounds have strongly basic amidino and alkylamino groups in their molecules, and these strong basic groups are cationized in the polymerization system, resulting in the formation of monoallylamine. It is thought that it is largely involved in the polymerization of inorganic acid salts.

Summary of the Invention The present inventors conducted seven searches for a more effective polymerization initiator when polymerizing an inorganic acid salt χ of monoallylamine in a polar medium, and unexpectedly found a polymerization initiator represented by the following general formula [I]. The azo compound represented by the formula [I] and/or the azo compound represented by the general formula [I] is disclosed in Japanese Patent Application No. 58-54 filed earlier by the present applicant.
Although it does not have a strong basic group in its molecule, unlike the azo compound disclosed in No. 988, it is an effective catalyst for polymerizing inorganic acid salts of monoallylamine. Heading The invention has been completed.

co c.

I HEME2NHNH2 co c.

NINE2NHNH2 (R + R2+ in general formula [I] and CI []
R5 and R4 are the same or different hydrocarbon groups,
In general formula (1), R and R2 and/or R3 and R4
may form a ring together with the carbon atoms to which they are bonded. ) That is, the method for producing a polymer of monoallylamine or a salt thereof of the present invention involves polymerizing monoallylamine in the presence of an inorganic initiator to eliminate monoallylamine. ! Obtaining a polymer of the acid salt yIl-, and further converting the polymer of the inorganic acid salt of monoallylamine into a polymer of monoallylamine or a polymer of the @acid acid salt of monoallylamine by a conventional method as necessary. do.

Preferred embodiments for carrying out the invention In the general formulas (I) and (IF) representing the azo initiator used in the method of the invention, "L + R2+
R3 and R4 are the same or different hydrocarbon groups as described above, and preferable examples of the hydrocarbon groups include carbon a1-
Examples include a straight chain or branched alkyl group having 4 carbon atoms, a cycloalkyl group having 6 to 6 carbon atoms, a phenyl group, and a benzyl group.

In addition, in general formula [I], R1 and R2 and/or R3
and R4 may form a ring together with the carbon atom to which they are bonded, and examples of such a ring include a cyclo(tane ring, a cyclohexane ring, etc.).

General formula (1) and [
Particularly preferred compounds of the azo initiators represented by I] are as follows.

Cl3 Initiator-1 Initiator-2 2,2'-azobis 2.2'-azobis(2(2
-Methylpro-methylbutyric acid F-radiionic acid V
V) Initiator-3 Initiator-4 2,7-azobis 1.1'-azobis(1(2-
Ethylbutyric acid - cyclohexylcarhydrazif)
Bonic acid hydrazide) (II) Initiator-5 Initiator-6 Acid hydrazide) Ronic acid hydrazide) The amount of the azo initiator used in the present invention is the absence of monoallylamine! ! For example, it is 0.1 to 10 parts by weight, more preferably 1 to 6 parts by weight, relative to the acid salt.

The azo radical initiators represented by the above general formulas (1) and [I] are known from the aforementioned earlier application by the present applicant (Japanese Patent Application No.
It differs from the azo radical initiator used in the invention of No. 54988) in the following points. That is, the radical initiator of the present invention has a nitrogen atom included in a hydrazide group as a nitrogen atom other than an azo group, but this nitrogen atom has a significantly lower basicity than the nitrogen atom in the prior invention described above. Therefore, its range is completely different from the nitrogen atom that constitutes a strong basic substance such as the amidino group or alkylamino group in the first invention. Therefore, although it was thought that there would be no effect even if the initiator (1) of the present invention was applied to the polymerization of the inorganic acid salt of [I] Y monoallylamine, the remarkable effect was observed. That can be said to be surprising.

By the way, the above-mentioned earlier application by the present applicant (Japanese Patent Application No. 58-5
No. 4988), it is known that the radical initiator effective for polymerizing allylamine inorganic acid salts is largely controlled by the structure of the substituent adjacent to the azo group.

On the other hand, it is well known that in general, amidino groups are easily hydrolyzed to produce amides and amines.

This is no exception for the amidino group-containing initiator (A) in the prior invention, which is immediately hydrolyzed to form amide I' (B).

This initiator (B) is ineffective against the polymerization of allylamine inorganic acid salt. By the way, the hydrazide group in the azo initiator in the present invention has significantly higher hydrolysis resistance than the amidino group, and hydrazide decomposes into acid more slowly, resulting in less loss of performance as an initiator. There is an advantage that a small amount (for example, about ⅓ of the amount of initiator used in the prior invention) is required.

This can be said to be a great advantage when producing polyallylamine industrially.

The azo initiator of the present invention has been described above in detail, and other points will be explained in detail below.

Suitable inorganic acid salts of monoallylamine used in the present invention include hydrochloride, sulfate, sulfite, and phosphate.

Polymerization takes place in polar media, i.e. water, inorganic acids (hydrochloric acid, sulfuric acid, phosphoric acid, polyphosphoric acid) or aqueous solutions thereof, organic acids (
It is carried out in an aqueous solution of formic acid, acetic acid, propionic acid, milk V salts (zinc chloride, calcium chloride, magnesium chloride, etc.).

During polymerization, the inorganic acid salt of monoallylamine is usually used in the form of single IlI crystals,
Monoallylamine and no tUt in the above polar solvent? In addition, salt may be generated in the system.

Needless to say, when an inorganic acid or an aqueous solution thereof is used as a polymerization medium, it can be added to a predetermined amount of monoallylamine-depleted inorganic acid or an aqueous solution thereof and polymerized as it is.

The degree of doai differs depending on the chemical structure of the initiator, but it is 30°
~100''O1 is usually 40' to 70°C. Polymerization time is usually within 100 hours.

The starting monomer concentration is preferably as high as possible within the range of its solubility, but is usually 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, but in these examples, monoallylamine (monoallylamine (
Shell chemistry (hereinafter abbreviated as MAA)
MAA4 manufactured by Chemical Co., USA)
A fraction having a boiling point of 52.5 DEG to 53 DEG C., obtained by drying over granular caustic soda and rectifying under nitrogen, was used. As a result of examination by schromatography, it was found that this region contained no diallylamine or triallylamine at all.

Example-1 This example includes 2. Production of monoallylamine salt polymer and monoallylamine polymer by polymerization of monoallylamine in phosphoric acid using z-azobis(2-methylpropionic acid hydrazide) (hereinafter referred to as initiator-1) as an initiator. Give an example.

First, the method for synthesizing initiator-1 will be explained.

13.8 g of 2,z-azobis(2-methylpropionic acid methyl ester) was dissolved in Y methanol 60111 and cooled with ice-water. System 7 Stir and add 30 g of hydrated hydrazine.
A solution dissolved in 100 d of methanol was added and reacted for 48 hours. The resulting precipitation fRyI? It was collected by filtration, washed with methanol, and then dried under reduced pressure. Yield 10.4 g (75.4%)
. This product was confirmed to be initiator-1 from elemental analysis, R spectrum, UV spectrum, and NMR spectrum measurements.

In the same manner, initiators-2 to 6 exemplified above were obtained from the corresponding esters or lactones.

Next, 85 tlI of phosphoric acid 922 was added to a 2 t round bottom flask equipped with a stirrer, thermometer, countercurrent condenser, and addition funnel.
．． 3 g (8 mol) 1- was added. Monoallylamine (MAA) 224.8F (4 mol) was added dropwise to this while stirring. At this time, the temperature of the reaction system was maintained at 10 to 60°C. After dropping, the system was heated to 60'O while stirring. 9.2 g of initiator-IY was directly added to the phosphoric acid solution of MAA phosphate obtained in this way, and then 60
Polymerization was carried out at ±2°C for 72 hours. After polymerization, a colorless, transparent and viscous solution was obtained. When this solution was added to a large amount of water, the polymer (polyallylamine-phosphate) precipitated in the form of a rice cake. This precipitate was thoroughly washed with water and then dissolved in 500 d of concentrated hydrochloric acid to convert polyallylamine phosphate to hydrochloride. This solution was added to a large amount of methanol, and the precipitate Y was collected 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 260 g (approximately 61 inches) of polymer χ.

This polymer was analyzed by elemental analysis, infrared spectroscopy, and IH-
As a result of NMR analysis, polyallylamine hydrochloride (FAA
-HOI). IH/NMR spectrum of this polymer (in heavy water, 270 MHz, T
SP internal standards) are shown in Figure 1.

In addition, this FAA determined by osmotic pressure measurement in a saline solution
-Mol had a number average molecular weight Mn of 23,000.

This FAA-HOl is well soluble in water and acid-water solutions, but is insoluble in organic solvents. The viscosity of the water II solution exhibits typical polyelectrolyte behavior.

Moreover, this FAA-HoI decomposes at 300° C. or higher without melting when heated in air.

Next, free polyallylamine (F
AA) +ik was prepared. That is, PAA-HC
! l, 30FY 270g of distilled water, strong basic ion exchange resin (Amparite RA-402)'
Hydrochloric acid was removed through a' and the filtrate was lyophilized to yield 16.5 g of white PAA. This FAA is easily soluble in water and methanol, swells with dimethyl sulfoxide and lysine, but is insoluble in common organic solvents.

When this FAA is left in the air, it absorbs carbon dioxide and moisture and produces carbonates.

Example-2 Salt production 1! #105 weight section) 1.1 #, under water cooling 5-1
At 0°C, 570 g (10 mol) of MAA was added dropwise while stirring. After the dropwise addition was completed, water and excess hydrogen chloride were distilled off at 60° C. under a reduced pressure of 201,311 mercury columns using a rotary evaporator to obtain white crystals. On this crystal t1 drying silica sol, under reduced pressure of 5 units of mercury, 80
It was dried at ℃ to obtain MAA-acx 9809. This M
AA-Hol contains about 5-water.

The above MAA-HC! 1.1
00 g and distilled water 27Nχ, stir to dissolve.
It was made into Amu HOI 75 ton water* solution. The mixture was heated to 60°C while nitrogen gas was passed through it. Then initiator-12,8
g' directly and polymerized by standing at 58 to 60°C for 72 hours. When the colorless, transparent and viscous solution thus obtained was added to a large amount of methanol, a white polymer precipitated. This precipitate was collected by filtration, washed with methanol, and dried at 50°C under reduced pressure to yield 53.5 g (56,3) of FAA-HO'.
l was obtained.

FAA-H determined by osmotic pressure measurement in saline solution (1!
The number average molecular weight Mn of 1 was 8,700, Example-
3 Example-2! lIIi adjusted MAA-HC! l 3
Q Q g, water 36. ! i'Y was added and dissolved by 50° OK to prepare an 85% aqueous solution of MAA-HCm.

Separately, weigh 210 g of zinc chloride and add water? In addition, the total concentration was set to 300.9, and a 70% water volume solution of zinc chloride was prepared.

MAA-HoI prepared above in a 1 L round bottom flask equipped with a stirrer, thermometer, countercurrent condenser, and nitrogen gas inlet tube.
300g of 85% aqueous solution of
g and heated to 60° C. while stirring while passing nitrogen gas through the mixture. Next, add 15.8 g of initiator and add 58-60 g of initiator.
The polymerization was allowed to stand at ℃ for 48 hours. The resulting colorless, transparent and viscous solution was poured into a large amount of methanol for 1JJ, and the resulting precipitate was collected by filtration. Using a Soxhlet extractor, the mixture was extracted with methanol and then with acetane to produce white FAA-Hol. was quantitatively weighed (250 g). The number average molecular weight of I'AA-)101 determined by osmotic pressure measurement in a saline solution is 1.
It was 2,000.

Example-4 gl1 85% aqueous solution of Shin A-HOl prepared in Example-3 5oIi and 70% zinc chloride aqueous solution 100Ji'Y2
It was placed in an O0d Erlenmeyer flask with a stopper, and the initiators 1 to 6 synthesized in Example 1 were added thereto, and polymerization was allowed to stand at 60° for 0.48 hours. After polymerization, the same operation as in Example-3 was carried out,
Pmumu HOI Y got it. The results are summarized below.

Type of initiator PAA-101 intrinsic viscosity addition amount of initiator Yield and yield l;. h Il g Chi initiator-10,41835,38 0 0.37t
t-10-62841,798,00,33 initiator-20,46934,180,20,28p-
20-70438, 390-00-25 initiator-30,
52032, 576, 50, 251-30, 781
37.6 88.5 0.24 Initiator-40.5
6429,970,40,26tt -40-84
654,080,10,23 initiator-50,52833
,278,10,21tt -50-79135
,483,30,20 initiator -60,5792B,6
67.3 0.25〃-60・868 30.2
71.1 0.23■,! J? 0.59Y
'/l. Shows the intrinsic viscosity at 60°C when M-NaC2100,..., PKh is dissolved.

Next, as a comparative example, 2.2/
- MAA-H using azoitudethyronitrile (The results of a follow-up test by the present inventor of polymerization example 11 are shown.

Comparative example released! According to the method described on page 36 of Publication No. 2,946.550, 100 d of t-butanol Z was added to a round bottom flask while nitrogen was introduced, and the mixture was heated to reflux with stirring. 46.89 for 500ju of t-butanol
of MAA-HOI and 0.5 J of diethylphosphite)
0 in the solution obtained by dissolving Y and 50d in chlorobenzene.
．． 3 g of azobisisodethyloni) IJru (N from A
) The solution obtained by dissolving Y was added to t-7 in the above flask at the same time.
Dropped into ethanol.

The time required for dropping the two solutions was about 60 minutes. The reaction mixture was then refluxed for 73 hours. In the first 2 hours of these 3 hours, 50d of chlorobenzene Ic
The solution obtained by dissolving N'2i1 from A of O, 3, and F 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 (yield 0.53%) 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 drawings]

The figure shows an LH-NMR spectrum of polyallylamine hydrochloride obtained by the method of the present invention.

Claims (1)

[Claims] (1) An inorganic acid salt of monoallylamine is polymerized in a polar solvent in the presence of an azo initiator represented by the following general formula [I] and/or an azo initiator represented by the general formula [II]. A polymer of an inorganic acid salt of monoallylamine is obtained, and if necessary, the polymer of the inorganic acid salt of monoallylamine is converted into a polymer of monoallylamine or a polymer of an organic acid salt of monoallylamine by a conventional method. A method for producing a polymer of monoallylamine or a salt thereof. ▲There are mathematical formulas, chemical formulas, tables, etc.▼[I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼[II] (R_1, R_2 in general formulas [I] and [II]
, R_3 and R_4 are the same or different hydrocarbon groups, but in the general formula [I], R_1 and R_2 and/or R_3 and R_4 may form a ring together with the carbon atoms to which they are bonded. )