JPH05320228A - Biguanide polymer and its production - Google Patents

Abstract

PURPOSE:To obtain a biguanide polymer by reacting a specified polyallylamine with a specified guanyl compound. CONSTITUTION:A biguanide polymer of general formula III [wherein R1 to R3 and X are the same as defined in formula II, provided that R1 to R3 are each other than alkoxycarbonylalkylene; m is an integer of 10 or greater; and 0<j<1] is obtained by adding a hydrochloride of a polyallylamine of general formula I (wherein m is the same as that of formula III) to a methanolic solution of an equimolar amount of sodium methoxide, removing the sodium chloride precipitated by the neutralization in a nitrogen stream, adding a biguanide compound of general formula II (wherein R1 to R3 are each H, 1-18C linear or branched group or 6-8C aryl; R4 is 1-5C alkyl; X is null or an organic or inorganic acid; and Z is O) to the obtained free polyallylamine solution, reacting them at 45-50 deg.C, acidifying the reaction mixture with dilute hydrochloric acid after the reaction, and pouring the resulting solution into acetone.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel biguanide group-containing polymer and a method for producing the same. The novel biguanide group-containing polymer of the present invention includes, for example, fungicides, algaecides, preservatives, antibacterial agents, polymer drugs, fibers or post-treatment agents for fibers, paper treating agents, coagulants, antistatic agents, It is used as an auxiliary agent for shampoos and detergents.

[0002]

2. Description of the Related Art Alkyl biguanide type compounds have been well known as fungicides and antibacterial agents. Further, since it is expected that a polymer having a biguanide group in the side chain will also have the properties of the biguanide group and the properties as a polymer, attempts have been made to produce it, but polyallylamine was used as the main chain. However, a so-called allyl biguanide polymer of the type in which the amino group of the side chain of this polymer is replaced with a biguanide group has not yet been obtained. On the other hand, as a compound containing a biguanide group in a polymer, Japanese Patent Publication No. 63-21
Some of them have a biguanide group in the polymer main chain as shown in Japanese Patent Publication No. 979, and some have a biguanide group in the side chain of the polyacrylate of Japanese Patent Publication No. 59-196303. It has a structure different from that of the biguanide polymer.

[0003]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a novel polymer containing a biguanide group and a method for producing the same.

[0004]

DISCLOSURE OF THE INVENTION The inventors of the present invention have conducted extensive studies in order to economically obtain a novel polymer containing a biguanide group, which has not been industrially obtained in the past. It came to completion.

That is, according to the present invention, there is provided a biguanide group-containing polymer represented by the following general formulas 1 and 2.

[0006]

[Chemical 1]

[0007]

[Chemical 2]

In the above formula, R ₁ , R ₂ and R ₃ may be the same or different and each is a linear or branched alkyl group having a hydrogen atom C ₁ -C ₁₈ , an alkylenecarboxylic acid group or C ₆ -C _8. And an aryl group of R ₄ is a C ₁ -C ₅ alkyl group,
X and Y may be the same or different and each represents an organic or inorganic acid, m represents an integer of 10 or more, and j represents 0 <j <.
A number that satisfies 1 is shown. X in the general formula 1 may not be present.

Further, according to the present invention, in order to produce the biguanide group-containing polymer represented by the general formula 1,
General formula

[0010]

Embedded image wherein polyallylamine represented by the formula:

(In the formula, R ₁ , R ₂ and R ₃ may be the same or different and may be a linear or branched alkyl group having a hydrogen atom C ₁ -C ₁₈ , an alkoxycarbonialkylene group, an alkylenecarboxylic group. Acid group or a C ₆ -C ₈ aryl group, R ₄ represents a C ₁ -C ₅ alkyl group, X is optionally present, represents an organic or inorganic acid, and Z represents oxygen). A method of reacting a compound is provided.

Further, according to the present invention, the general formula 2
In order to produce a biguanide group-containing polymer represented by the formula 1, there is provided a method of reacting a polyallylamine represented by the general formula 3 with a compound represented by the general formula 4, and further reacting with an organic or inorganic acid. ..

In the above general formula, R ₁ , R ₂ and R ₃ may be the same or different and each is a hydrogen atom, a C ₁ -C ₁₈ linear or branched alkyl group, an alkoxycarbonylalkylene group or an alkylenecarboxylic acid group. or while indicating aryl group C ₆ -C _8, C ₁ described above - the alkyl group of _18, methyl, ethyl, propyl, hexyl, dodecyl, preferably stearyl group; as alkoxycarbonyl alkylene group, Methoxycarbonylmethylene, ethoxycarbonylmethylene group and the like are preferable; methylenecarboxylic acid group and the like are preferable as alkylenecarboxylic acid group; phenyl, tolyl, and C ₆ -C ₈ aryl group,
A xylyl group and the like are preferable. X represents an inorganic or organic acid, and examples of the inorganic or organic acid include hydrogen halide such as hydrogen chloride, hydrogen bromide, hydrogen iodide, sulfuric acid, methyl bisulfate, phosphoric acid, p-toluenesulfonic acid. Etc.
Further, Y represents an inorganic or organic acid, and the inorganic or organic acid includes the inorganic or organic acid exemplified as the above X. X and Y may be the same or different in the same molecule.

Further, m represents an integer of 10 or more, preferably 10 to 5000. Furthermore, j is 0 <j <1.
Is selected from any number that satisfies

[0014]

EXAMPLES Next, a method for producing the biguanide group-containing polymer of the present invention will be described.

Example 1 Polyallylamine hydrochloride 0.98 g (0.01 mol;
5 wt% water content) is added to a solution of sodium methyl alcoholate (0.011 mol) in methanol and treated under stirring at 45-50 ° C. for 3-5 hours. During the treatment, the polyallylamine hydrochloride dissolves, and sodium chloride is deposited by neutralization. The sodium chloride was distinguished under a nitrogen stream, and the obtained free polyallylamine solution was added with guanyl-0-methylisourea hydrochloride 1.55 g (0.0
1 mol) is added and the reaction is performed at 45 to 50 ° C. for 0.5 to 24 hours. After the reaction, the solution is acidified with dilute hydrochloric acid, and this solution is poured into acetone to obtain the desired polyallyl biguanide hydrochloride. Yield 0.99-1.90 g. Elemental analysis C: 35.21%; H: 7.66%; N: 28.90
%; Cl: 21.39%. The IR spectrum is shown in FIG.

Example 2 4.83 g (0.05 mol) of polyallylamine hydrochloride
Was made into a free polyallylamine with an ion exchange resin IRA-402, and then guanyl-0-methylisourea 7.6 was obtained.
4g at 35 ° C in a nitrogen stream with 3g (0.05mol)
By reacting for 8 hours and treating the reaction solution, the target polyallylamine hydrochloride is obtained. Yield 3.24g.

Example 3 4.83 g (0.05 mol) of polyallylamine hydrochloride
Was treated with a 1N aqueous sodium hydroxide solution to give free polyallylamine, and then guanyl-0-methylisourea (7.63 g, 0.05 mol) and 35 ° C in a nitrogen stream.
At 48 hours, the reaction solution is treated to obtain the desired polyallylamine hydrochloride. Yield 5.30
g.

[Brief description of drawings]

FIG. 1 is an IR spectrum diagram of a polymer containing a biguanide group.

Claims (4)

[Claims] 1. A general formula: (In the formula, R ₁ , R ₂ and R ₃ may be the same or different and may be a linear or branched alkyl group having a hydrogen atom C ₁ -C ₁₈ , an alkylenecarboxylic acid group or a C ₆ -C ₈ aryl group. , X is present in some cases, represents an organic or inorganic acid, m represents an integer of 10 or more, and j represents a number satisfying 0 <j <1). 2. A general formula: (In the formula, R ₁ , R ₂ and R ₃ may be the same or different and may be a linear or branched alkyl group having a hydrogen atom C ₁ -C ₁₈ , an alkylenecarboxylic acid group or a C ₆ -C ₈ aryl group. X and Y may be the same or different and represent an organic or inorganic acid, m is an integer of 10 or more, and j is 0 <j.
A carbamoylguanidine group-containing polymer represented by <indicating a number satisfying <1>. 3. To prepare the biguanide group-containing polymer of claim 1, a compound of the general formula: (Wherein, m is an integer of 10 or more) is added to the polyallylamine represented by the general formula: (In the formula, R ₁ , R ₂ and R ₃ may be the same or different and each is a linear or branched alkyl group having a hydrogen atom C ₁ -C ₁₈ , an alkoxycarbonialkylene group, an alkylenecarboxylic acid group or C ₆ an aryl group -C _8, R ₄ represents an alkyl group of C ₁ -C _5, X is optionally present, represents an organic or inorganic acid, Z is reacting the compound represented by the indicating oxygen) How to make. 4. In order to produce the biguanide group-containing polymer of claim 2, a polyallylamine represented by the general formula: ## STR3 ## wherein m is an integer of 10 or more is added to the general formula: (In the formula, R ₁ , R ₂ and R ₃ may be the same or different and may be a linear or branched alkyl group having a hydrogen atom C ₁ -C ₁₈ , an alkoxycarbonialkylene group, an alkylenecarboxylic acid group or C ₆ -C ₈ aryl group is shown, and R ₄ is C ₁
Represents a -C ₅ alkyl group, X is optionally present,
A compound represented by an organic or inorganic acid, Z is oxygen) is reacted, and further an organic or inorganic acid is reacted.