JPS60108405A - Manufacture of n-methylated allylamine polymer - Google Patents

Abstract

PURPOSE:To obtain the titled polymer in high yield by polymerization of inorganic acid salt of monoallylamine using radial initiator containing azo group followed by reaction of both formic acid and HCHO with the resulting compound (polymer) or one derived therfrom by subjecting alkali. CONSTITUTION:An inorganic acid salt of monoallylamine is polymerized using pref. 1-6wt% based on said salt, of a radical initiator containing azo group [e.g. a compound of formula R1-N=N-R2 (R1 and R2 are each aminoalkyl, aminoaryl, amidinylalkyl, amidinylaryl, cyanoaminoalkyl, etc.), II or III (R3-R6 are each hydrocarbon)]. The resulting polyallylamine salt or polyallylamine derived from said salt by subjecting alkali is made to react with both formic acid and HCHO, thus obtaining the objective N-methyl allylamine- and N,N- dimethyl allylamine polymer.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing N-methylated allylamine polymers.

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 allyl compounds.
There are no reports of obtaining methylallylamine and N,N-dimethylallylamine polymers 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 polymer and N,N-dimethylallylamine polymer. 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 inner ring of the obtained polyallylamine or the like is obtained. The present inventors have completed the present invention by discovering that N-methylated allylamine polymers can be obtained in high yield by reacting polyallylamine obtained by reacting with an alkali with yadic acid and formaldehyde.

That is, the method for producing an N-methylated allylamine polymer of the present invention involves enriching an inorganic acid salt of monoallylamine □ using a radical polymerization initiator containing an azo group in the molecule, and then enriching the resulting polyallylamine salt. Alternatively, the process of reacting formic acid and formaldehyde with polyallylamine obtained by reacting with an alkali is called imitation.

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 typical example thereof is an azo compound represented by the following general formula (1). Mention may be made of inorganic or organic acid salts such as hydrochlorides, sulfates, phosphates, alkyl sulfates, para-toluenesulfonates, formates, acetates and zolopionates.

R1-N-N-R2(I) [wherein at least one of R1 and R2, preferably both, are aminoalkyl, aminoaryl, aminonylalkyl, aminoalkaryl, aminoalkaryl, aminoaralkyl, aminylaralkyl , is a group containing a cationizable nitrogen atom selected from the group consisting of aminenylarkaryl, cyanoaminoalkaryl, and cyanoaminoalkaryl, and when only one of R1 and R2 is a group containing a cationizable nitrogen atom (Well, on the other hand,
It is a group selected from the group consisting of alkyl, aryl, alkaryl, aralkyl, cyanoalkyl, cyanoaryl, cyanoalkaryl, and cyanoaralkyl, and R1 and R2 together represent the following general formula: [
A single alkylene group shown in [11] may be formed.

(In the formula, R is a group selected from the group consisting of alkylene, alkylalkylene, and arylalkylene, and a covalent bond (a8 (b) is bonded to each nitrogen atom of the azo group,
An azo group-containing ring is formed, and X is a group containing a cationizable nitrogen atom. )].

Among the initiators represented by the general formula (1), particularly desirable compounds are those having a secondary or tertiary carbon atom adjacent to an azo group. It is as follows: 2,2'-diaminonyl-2,2'
-azopropane-salt [ffl, 2゜2'-diaminyl-2,2'-azobutane-hydrochloride, 2,2'-diaminyl-2,2'-azopentane hydrochloride, 2,2'-his(N-phenyl aminonyl)-2,2'-azopropane hydrochloride, 2,2'-bis-(N-phenylamidinyl), 2,2'-azozotane hydrochloride, 2,2'-bis(N
, N-dimethylamyl)-2,2'-azopropane hydrochloride, 2,2'-bis-(N,N-dimethylamyl)-2゜2'-azobutane hydrochloride, 2,2'-bis( N,N-diethylaminenyl)-2,2'-azopropane hydrochloride, 2,2'-bis(N,N-diethylaminenyl)-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)
-6,6'-azopentane hydrochloride, azo-bis-N.

N'-dimethyleneisobutyramicine hydrochloride; 2.2'
-Azo-bis(2-methyl-4-gelamino)-butyronitrile hydrochloride, 2.2'-Azo-bis(2-methyl-4-dimethylamino)-butyronitrile hydrochloride, 2.
2'-Azo-bis-(2-methyl-4-diethylamino)-butyronitrile hydrochloride, 2'-Azo-bis-(
2-Methyl-4-diethylamino)-butyronitrile or 2,2'-azo-bis-(2-methyl-4-dimethylamino)-butyronitrile in dimethyl sulfate or p
-) Quaternary ammonium salt type azonitrile obtained by quaternization with methyl luenesulfonate etc.: 6.5-diaminonyl-1,2-diazo 1=cyclopentene hydrochloride, 6-methyl-6,4-diaminonyl-1, 2-Diazo-1-cyclopente 7 salt dk salt, 3-ethyl-6,5-diamidinyl-1,2-diazo-1-cyclopentene hydrochloride, 6
゜5-dimethyl-6,5-diamidinyl-1,2-diazo-1-cyclopentene hydrochloride 1.6.6-diamidinyl-1,2-diazo-1-cyclohexene hydrochlorideffl,
3-phenyl-6,5-di1 midinyl-1,2-diazo-1-cyclopentene hydrochloride, 6,5-diphenyl-6
, 5-diamidinyl-1°2-diazo-1-cyclopentene hydrochloride.

Inorganic or M of the azo compound represented by the above general formula CI)
A method for polymerizing an inorganic acid salt of monoallylamine using an organic acid salt as a polymerization initiator is disclosed in Japanese Patent Application No. 58-54 filed by the same applicant.
The details are described in the specification of No. 988.

As another representative example of the initiator used in the polymerization of the inorganic acid salt of monoallylamine in the present invention, the following general formula [1]
Or an azo compound represented by [■] can be mentioned.

C1) [IY) (In general formulas (1) and (IV), R3, R4, R5 and R6 are the same or different hydrocarbon groups.) R3+
Particularly preferred R4s R5 and R6 are a straight chain or branched alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 6 to 6 carbon atoms, a phenyl group, and a benzyl group. R3 and R4 or/and R5 and R6 may form a compound together with the carbon atom to which they are bonded. Particularly preferable compounds of the initiators of general formulas (1) and (IV) include [sulfuric acid] and [■], but are not limited thereto.

A method for polymerizing an inorganic acid salt of monoallylamine using the compound of the above general formula [lid] or (IV) as an initiator is disclosed in a patent application filed on November 10, 1982 by the same applicant (title of invention: polymerization of monoallylamine). The details are described in ``Coalescence manufacturing method''.

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, ranging from A60° to
100°0, usually 40° to 85'0. The polymerization time is usually within 100 hours, preferably 20 to 40 hours.

The starting monomer concentration is desirably as high as within the range of 1 degree of resolution, but is usually in the range of 10 to 85 percent by weight.

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 their water bath solutions, organic acids (
Formic acid, acetic acid, propionic acid, lactic acid, etc.) or their aqueous solutions, alcohol, dimethyl sulfoxide, dimethyl formamide, 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 the polymerization medium, a predetermined amount of monoallylamine is
It can be added to S organic acid or its aqueous solution and polymerized as it is.

Polymerization is slightly inhibited by vIl in the air, so
Preferably, this is carried out under an inert gas such as nitrogen.

In the N-methylation reaction using formaldehyde and diacid, which will be described later, 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. In order to remove by-product salt (hydrochloride is used as the allylamine salt, or table salt when caustic soda is used as the strong alkali), it is subjected to dialysis, ultrafiltration, del 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 ic acid and formaldehyde will be described.

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, fd is then added dropwise to a formaldehyde water bath. In the case of N-methylallylamine polymer, the amount of diacid and formaldehyde to be added is 1 as the amine of polyallylamine.
Per mole, 1 to 1.5 mole of formaldehyde, 1 mole of sulfuric acid
．． Requires 5-4 moles. N.

In the case of N-dimethyl amine polymer, 2 to 6 moles of formaldehyde and 3 to 8 moles of formaldehyde are similarly required. The degree of methylation can be controlled by varying the amounts of formaldehyde and jalic acid.

After the dropwise addition of phosphoric acid and formaldehyde is completed, the temperature is gradually raised to 70 to 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, unreacted formaldehyde and sulfuric acid are removed by precipitation by adding a large amount of acetone.
Filtered and dried to obtain N-methylallylamine polymer or N,
A formate salt of N-dimethylallylamine polymer is obtained. The formate salt is optionally converted to free N-methyl phosphorylamine polymer or N,N-dimethyl phosphorylamine polymer.

2 Next, Examples are given below to further clarify the present invention.

Example 1 104.2 J of 65% hydrochloric acid to 57.1 g of allylamine
was added dropwise at 10 to 20°C to obtain an aqueous solution of amine hydrochloride having a concentration of 59.1%. This was concentrated using a rotary evaporator to a concentration of 75%. Heat this solution
2,2'-diaminonyl-2,2'
-Azopropane hydrochloride 2.3411 (to monomer 2.5
%) was added dropwise over 3 hours, and the temperature was maintained 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 86I.

Polyallylamine hydrochloride obtained above 20. li'vc water 3
Add 0g of water and dissolve 0g of it, add 40% caustic soda 21.4
Added to g'. To remove the generated salt, dialysis was carried out for 24 hours using hollow fibers, and the total weight was 100 g, which was then freeze-dried to obtain polyallylamine II.
,6. I got v.

11.4 g of polyallylamine (0.2 mol as amine) was dissolved in 30 g of water, and heated to 90°C while keeping the temperature below 60°C.
40.99 (0.8 mol) of 0% sulfuric acid was added dropwise, followed by 6
67.7 g (0.44 mol) of 5% formalin was added dropwise. After the addition was completed, the temperature was gradually raised to 80''C.

Carbon dioxide gas was generated freely. 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 amethane to precipitate, and the mixture was filtered and dried to obtain a white powder. The yield was 24.29.

The elemental analysis values of this product were as follows.

Actual value (theoretical value) C55,10% (54,94%) H9,91% (9,99%) N10.44% (10,68%) The numbers in parentheses are N, N-dimethylallylamine polymer formate. It is a theoretical value.

Moreover, it was confirmed from lH-NMR-spectral analysis that this polymer was poly-(N,N-dimethylallylamine).

Example 2 Polyallylamine ii obtained in the same manner as in Example 1, 4.
20. 90% reduction in the same manner as in Example 1 using p.
5 N (0.4 mol), 65% forrin 18.9.
9 (0.22 mol). Yield is 22, ON
Met.

The first elemental analysis of this product was as follows.

Measured values (actual values) C50,73% (51,26%) H9,18% (9,47%) N12.24% (11,96%) The values in parentheses are the formate of N-methylallylamine fraternate. This is a theoretical value.

Furthermore, it was confirmed from 1H-NMR-spectral analysis that this polymer was poly-(N-methyl l-allylamine).

Agent Akira Asamura 5 Procedural amendment Showa 59% July 18th, Mr. Commissioner of the Japan Patent Office 2. Invention 0 Name N-jflly A, A, 2 A, 7 Process for producing polymer 3, Person making amendment Related Patent Applicant Address Name (397) Nitto Boseki Co., Ltd. (Name) 4. Agent 5. Date of Amendment Order Month, Day, 6, Showa (1) -1 Azopropane on page 5, line 5 of the specification.” of"
Corrected to "Azopropane".

(2) "Azobutane-" on page 5, line 6 of the same book is corrected to "azobutane."

(3) In the same book, page 5, line 10, “aminir),” was replaced with “
aminyl)-J.

(4) "Fourth" on page 6, line 14 of the same book is corrected to "Grade 4."

Claims (1)

[Claims] (1) A polyallylamine salt obtained by polymerizing an inorganic acid salt of monoallylamine using a radical polymerization initiator containing an azo group in the molecule, or a polyallylamine obtained by treating the same with an alkali. 1. A method for producing an N-methylated allylamine polymer, characterized in that it is made to react with jalic acid and formaldehyde.