JPS62230806A - Guanidine group-containing polymer and production thereof - Google Patents

Abstract

PURPOSE:To industrially and advantageously produce a novel polymer useful as a germicide, high-polymer medicine, paper treating agent, flocculant, etc., at a low cost, by polymerizing a specific guanidine derivative in the presence of a polymerization initiator. CONSTITUTION:A guanidine group-containing polymer, obtained by polymerizing a guanidine derivative expressed by formula I (R1 and R2 are H, 1-18C alkyl, alkoxycarbonylalkylene, alkylenecarboxylic acid or 6-8C aryl; X is inorganic or organic group) alone or together with an allylamine expressed by formula II in the presence of a polymerization initiator having azo group and nitrogen- atom-containing group which is cationic or capable of forming cation in the molecule, e.g. 2,2'-diamidinyl-2,2'-azopropane hydrochloride, etc., and, as necessary, reacting the resultant polymer with an acid and containing guanidine group expressed by formula III (Y may be absent and indicates acid; m>=10; 0<j<=1).

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a novel guanidine group-containing polymer and a method for producing the same.

The novel guanidine group-containing polymer of the present invention can be used, for example, as a bactericide, an algaecide, a preservative, an antibacterial agent, a polymeric drug, a post-treatment agent for fibers or textiles, a paper treatment agent, a flocculant, an antistatic agent, and a shampoo. It is expected to be used as an auxiliary agent for detergents and detergents.

Prior art and its problems Alkylguanidine type compounds have been well known as bactericidal and antibacterial agents. Furthermore, since it is expected that a polymer having a guanidine group in its side chain will have both the properties of a guanidine group and the properties of a polymer, attempts have been made to produce this, ,
A so-called allylguanidine polymer in which the amino group in the side chain of this polymer is replaced with a guanidine group has not yet been obtained.

On the other hand, as similar compounds, for example, US Patent No. 3734
No. 939 discloses a method for producing a copolymer of N,N-diallylguanidine salts and acrylamide. However, this method is limited to monomeric N
, N-diallylguanidine salts are difficult to obtain (see Comparative Example 1 below).

In addition, this copolymer has a structure different from the above-mentioned allylguanidine polymer, and since it has a lower guanidine group content in the molecule than the above-mentioned allylguanidine polymer, it has an effect based on the guanidine group, For example, it is thought that the above-mentioned sterilization, algae, antiseptic, antibacterial effects, etc. are inferior. Furthermore, if a monoallylguanidine homopolymer can be obtained by direct polymerization reaction of a monoallylguanidine compound, this polymer is preferable because it has a high guanidine content in the molecule, but it is also possible to obtain this polymer. Not successful.

Therefore, an object (problem) of the present invention is to provide industrially a novel polymer containing a guanidine group.

Means for Solving the Problems The present inventors have conducted intensive research in order to economically obtain a novel polymer containing a guanidi group, which has not been obtained industrially in the past.As a result, (i) General formula (In the formula, RSR2 may be the same or different and represent a hydrogen atom, a C-C18 linear or branched alkyl group, an alkoxycarbonylalkylene group, an alkylenecarbonyl group, and X is an inorganic or organic acid The compound represented by the formula % () is used alone or together with the allylamine represented by the formula If desired, the final product, in which Y is absent from the combined product and Y is present, is further reacted with inorganic or organic 1aM (hereinafter referred to as method (c)). or (ii) to polyallylamine or its organic or non-acid salt represented by the general formula (wherein m is an integer of 10 or more) - or which may be different, represents a hydrogen atom, a C-C18 linear or branched alkyl group, an alkoxycarbonylalkylene group, an alkylenecarboxylic acid group, or a C6-C8 aryl group,
(represents an inorganic or organic acid, RG; tc represents an alkyl group of C5, 2 represents an oxygen or sulfur atom) or a compound that imparts a guanidine group to polyallylamine in the same way as the compound (III). (iii. ) General formula (wherein R , R , X, m are as defined above, Y is absent or, when present, represents Myl or m-acid, and j represents O<j≦1. The present invention was completed based on the discovery that a guanidine group-containing polymer having the following formula can be obtained.

That is, the present invention provides a novel guanidine-containing polymer having the general formula (1) described in (iii) above, and the novel guanidine-containing polymer described in (iii) above.
i) and (11) of the novel guanidine group-containing polymer having the general formula (I)? This relates to method i (c) and e).

First, the general formula that is a material invention The guanidine group-containing polymer represented by will be explained.

In the above general formula (I), R. R2 may be the same or different and represents a hydrogen atom, a C-C18 straight or branched alkyl group, a flukoxycarbonyl alkylene group, an alkylene carbon-C8 aryl group, and the above-mentioned C-C
As the alkyl group of 18, methyl, ethyl, propyl, hexyl, dodecyl, stearyl group, etc. are preferable; as the alkoxycarbonylalkylene group, methoxycarbonylmethylene group, 1-oxycarbonylmethylene group, etc. are preferable; as the alkylenecarboxylic acid group, methylene Preferred are carboxylic acid groups and the like: As the C-C8 aryl group, phenyl, tosyl, xylyl and the like are preferred.

In addition, when X is absent or present, it represents an inorganic or organic acid, examples of which include hydrogen halides such as hydrogen chloride, hydrogen bromide, and hydrogen iodide, sulfuric acid, and methyl hydrogen Examples include sulfuric acid, phosphoric acid, p-toluenesulfonic acid, and the like. In general, Y is absent or, when present, indicates inorganic or organic acid, and the inorganic or organic acids include the inorganic or organic acids exemplified as X above, but if X and Y in the same molecule may be the same or different.

Furthermore, m represents an integer of 10 or more, preferably 10
~5000.

Further, j is selected from any number satisfying O<j≦1.

Next, a method for producing a guanidine group-containing polymer of general formula (I), which is a production method invention, will be explained.

As mentioned above, methods for producing the guanidine group-containing polymer of general formula (I) of the present invention include method (c) and method (3), and each will be explained individually below.

Method (c) In this method, first, as a preliminary step, a vi salt of allylamine represented by the formula
, R , R , X. Z is as defined above) to obtain a compound of the general formula (wherein R.R2.X is as defined above). .

This reaction is preferably carried out in the presence of a solvent inert to the compound of formula (II) and the compound of formula (1), which are the reaction components. As the inert m'fi,
Examples include water, lower alcohols such as methanol and ethanol, and aromatic hydrocarbons such as benzene and toluene, with methanol and ethanol being particularly preferred. It is of course possible to carry out the reaction without using the above inert solvent,
In this case, the reaction component monoallylamine simultaneously serves as a solvent.

The reaction of the M salt of the compound of formula (It>) with the compound of formula (Ill) to obtain the compound of formula (IV)
) to the molar ratio of the compound of formula (I[[) to 1
It is preferable to use a ratio of 0/1 to 1/1, usually 2/1 to 3/1.

The reaction temperature for this reaction is appropriately determined depending on the reactivity of the solvent and reaction components, but is generally between -10°C and 100°C.
, more typically from 10<0>C to 80<0>C. Generally, the reaction proceeds satisfactorily at room temperature, but when it generates a lot of heat, it is necessary to cool it. A reaction time of 1 minute to 50 hours, preferably 10 minutes to 8 hours is sufficient. After the completion of the reaction, the general formula (IV
) is IIjlill.

Therefore, although it can be obtained, it is not better than the above-mentioned method.

■ The acid salt of the compound of formula (I[) and cyanamide (CNNI
-12) Preferably, water is used as the solvent and the reaction is carried out at 100 to 150°C for several hours.Since the reaction conditions are harsh, thermal decomposition tends to occur and the yield decreases. It has the disadvantage of being awkward.

■ Compound of formula (II) and Genocyan (XCN).

Formation of allylguanidine by reaction with X=C1,I) The reaction requires high temperatures and side reactions are likely to occur.

■ Formation of allylguanidate by melt reaction between dicyandiamide and the acid salt of the compound of formula (IF) or reaction of dicyandiamide and the compound of formula (I[) by heating (150 to 200°C) in water High-temperature heating reaction Therefore, thermal decomposition easily occurs and the yield is extremely low.

■ Formation of allyl alkylguanidine by reaction of allyl cyanamide, ammonia, and alkyl amines A high temperature is required, and if the amine is at a low temperature, an autoclave or the like must be used.

■ Allyl alkyl (or aryl) is formed by heating reaction between allyl guanidate and alkyl or arylamine.
Production of guanidine■ Class A heating reaction of allyldiA cyanide 1- or heating reaction with cyanamide■ In methods h to ■ of the reaction of the MW of the compound of formula (1 [>) with nitrosoguanidines, the reaction is Generally, the reaction is carried out in water, alcohol, dimethylformamide, dimethylsulfoxide, formamide, or a mixed solvent thereof.

Further, depending on the case, the reaction may be carried out without a solvent under heating and melting. The reaction temperature and time must be appropriately selected depending on the reaction temperature, but a pressure cooker such as a tocrepe of formula (n) may be required in some cases.

In method (c), the formula (IV
) alone or together with an inorganic or organic M salt of 7lylamine of formula (II), containing an azo group and a cationic or cationizable nitrogen atom-containing group in the molecule.
Polymerization is carried out in the presence of an initiator to obtain a guanidine group-containing polymer of general formula (I).

This polymerization reaction is carried out in an aqueous solvent. That is, a 10 to 90% aqueous solution, usually a 30 to 80% aqueous solution, of a monolinear compound of formula (IV) is mixed with a 20 to 100% aqueous solution, optionally in the presence of an inorganic or organic acid salt of allylamine of formula (II).
1 to 2 °C, particularly preferably at a polymerization temperature of 30 to 80 °C.
The polymerization treatment is carried out for 00 hours, usually from 5 to 90 hours.

The polymerization initiator used in this polymerization reaction is a radical initiator having an azo group and a cationic or cationizable nitrogen atom-containing group in the molecule, and such an initiator is Japanese Patent Application Publication No. 58-201811
＠ and Japanese Unexamined Patent Publication No. 60-104107, representative ones are as follows.

2.2'-Diaminyl-2,2'-azopropane hydrochloride, 2.2'-azobis(N,N'-dimethyleneisobutyramidine) dihydrochloride, 2.2'-azobis-(2-methylpropionamidoxime) ).

This initiator is added in an amount of 0.1 to 5 mol %, usually 0.2 to 2 mol %, based on the temperature of the 700 molar temperature.

After the polymerization reaction is completed, the produced iQ polymer is generally precipitated using a solvent such as A, dissolved using a suitable solvent such as methanol, and repeated reprecipitation with a poor solvent to obtain the polymer formula ( I) containing guanidine groups can be obtained as a solid.

A compound of formula (IV) is an allylamine of formula (II)
When copolymerizing with B, inorganic l! of allylamine is used. I
Salts, such as hydrogen halides, sulfates, phosphorus a t=
It is preferable to use the following. In this case, the molar ratio of the allylamine acid salt (inorganic or organic acid salt) to the compound of formula (IV) can be freely selected depending on the purpose, and copolymerization can be carried out at any ratio.

When Y does not exist in the guanidine group-containing polymer of the general formula (I) tentatively given above, by reacting it with an inorganic or right acid, Y'/fi is a general inorganic or organic acid. A guanidine group-containing FJi combination of formula (i) can be prepared. In addition, when Y exists in the polymer of general formula (I), if a polymer of general formula (I) without Y is desired, it may be treated with alkali, but in this case, depending on the treatment conditions, It should be noted that there is a possibility that the

Method 0 The guanidine group-containing polymer having the general formula (I>) of the present invention can also be obtained by method (2).

In this method, first, as a preliminary step, an inorganic or organic acid salt of allylamine having the formula Preferably, an inorganic or organic MMA of polyallylamine of the general formula % is obtained by combining the polyallylamine in the presence of %.

This polymerization reaction is carried out in accordance with the method described above (III) for the polymerization reaction in ~. In other words, the formula (II
) of allylamine (for example, hydrogen halide salt, (if salt, phosphate p-toluene sulfonate, etc.) is polymerized in water F8tIJA at a predetermined temperature for a predetermined time. Also, this polymerization reaction are JP-A-58-201811 and JP-A-60-1 related to this applicant's application.
It is described in detail in each publication of No. 04107.

The polymerization initiator used, which has an azo group and a cationic or cationizable nitrogen atom-containing group in the molecule, is also the same as that used in the above method (c), and is disclosed in the above two publications. detailed in.

In method (f), the inorganic or organic acid salt of polyallylamine of general formula (V) obtained above is reacted as it is or after being liberated with an alkali, for example, with a guanidine compound of general formula (III). A guanidine-based T1 polymer of formula (I) is obtained.

In this reaction, water, a lower alcohol such as methanol or ethanol, an inert solvent such as formamide, N,N-dimethylformamide, or tetrahydrofuran is used as a solvent for the polyallylamine of general formula (V) or its inorganic or organic acid salt. It will be done.

This reaction usually proceeds at room temperature, but may be heated. Generally room temperature is sufficient. The reaction time is sufficient to cause substitution of the guanidine group, and is usually 1 hour to
It is 72 hours.

When the free polyallylamine of formula (V) is used for the reaction with the compound of formula (I[[), the product of formula (1) contains Y
does not exist. Therefore, if a final product in which Y is desired is desired, it is necessary to skip the reaction with an inorganic or organic acid. Furthermore, when an inorganic or organic salt of polyallylamine of formula (V) is used in the reaction with a compound of formula (III), a product of formula (I) in which Y is present is obtained. Therefore, the Y-free final product can be treated with alkali if desired.

As described above, the guanidine U-containing polymer of the general formula (I>) can be obtained using either the polyallylamine of the general formula (V) or its inorganic or organic acid salt.

By adding an inert solvent in which the polymer is insoluble, such as acetone, to the reaction solution of the guanidine group-containing polymer thus obtained, the guanidine group-containing polymer of general formula (I) is converted into a solid. It is possible to obtain. Others, -
・By directly heating and condensing the acid salt of polyallylamine of general formula (V), such as hydrochloride, sulfate, etc. with urea or diourea and their derivatives according to a conventional method, the polyallylamine of general formula (1) can be obtained. It is also possible to directly perform coalescence, and this can be selected as appropriate.

Furthermore, the guanidine group-containing polymer of the general formula (I) is obtained by reacting the polyallylamine of the general formula (V) or its inorganic or organic acid salt with halogenocyanide, cyanamide, guanidine salts, nitrosoguanidines, disia, etc. You can do it.

The present invention will be further explained below with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.

Comparative Example IN, Production of N-diallylguanidine hydrobromide 30 g of diallylamine was added to 25.0 g of S-ethylisothiourea and stirred at room temperature. The reaction components did not dissolve easily and no ethyl mercaptan was generated. Therefore, 50 g of diallylamine was further added and the mixture was heated to 60°C.
Although the mixture was stirred for 7 hours, an insoluble portion remained. The insoluble portion (unreacted urea derivative) is filtered off, washed with a small amount of diallylamine, ether is added to the filtrate, and the decantation process is repeated.
Since the precipitate was precipitated in the form of glass, it was thoroughly washed repeatedly with ether by the decant method and dried under vacuum for 4 days.

This is a non-crystallizing fluid yellow-orange Pace 1-
(Yield: 123.8g). The infrared absorption spectrum shows CN absorption probably due to an abnormal reaction22
Doublet absorption was observed at 00CIR-1. Therefore, this pasty product cannot be said to be a pure product. Therefore,
N,N-diallylguanidine hydrobromide fk acid j! cannot be easily synthesized.

Preparation of polyallylguanidine depleted hydrogen salt by method) Concentrated hydrochloric acid (35% by weight) 1.17 (g)
At 0°C, 570 g (10 mol) of allylamine is added dropwise while stirring. After completion of the dropping, water and excess hydrogen chloride were distilled off at 60°C under a reduced pressure of 2 ONR of mercury using a rotary evaporator to obtain white crystals.The crystals were placed on silica gel for drying under reduced pressure of 5 m of mercury , and dried at 80° C. to obtain 980 g of allylamine hydrochloride. This contains about 5% water.

Into a 21 round bottom flask equipped with a stirrer, a thermometer, a backflow condenser, and a nitrogen gas inlet tube, allylamine salt M salt 59
0! Add J (6 moles) and 210 g of distilled water and stir to dissolve to obtain a 70% aqueous solution of allylamine hydrochloride.

The solution is heated to 50° C. while passing nitrogen gas. Next, an azo initiator having a group containing a cationic Nitrogen atom: 2
．． 2'-bis(N-phenylaminenyl)-2,2'
- Add 14 g of azopropane dihydrochloride dissolved in 201 d of distilled water. It will generate heat after about 2 hours, so cool while stirring to maintain the liquid temperature at 48-52°C.

Since the heat generation stopped about 10 hours after the addition of the initiator, stirring was stopped and the polymerization was continued at 50°±1°C for another 60 hours. A colorless, transparent and viscous solution is thus obtained. When this solution is added to a large amount of methanol, a white polymer precipitate is obtained. This precipitate is filtered off through a glass filter and washed with methanol.

The precipitate thus obtained is finely crushed without drying,
Using a Soxhlet extractor, extract with methanol for 15 hours to remove unpolymerized allylamine hydrochloride. After extraction, 5
It was dried under reduced pressure at 0°C to obtain 5339 (90%) polymer. This polymer was examined by elemental analysis and various magnetic resonance spectroscopy methods (270H11Z in heavy water), and it was found that this polymer was polyallylamine! ! It was confirmed that it was an acid salt.

Polyallylamine salt M salt obtained above [repeat unit molecule ta93.557, η1nh=0.35 (c=o, 5
J/dJ! , N/1ONaC! Medium, 30℃)) 100!
7 (1,069 mol) was dissolved in 11 methanol, 207 g of a 28% methanol solution of sodium methylate was added, and the mixture was stirred at room temperature for several hours. The generated sodium chloride was filtered off, and the excess methanol was removed at 30°C by 500ml.
After concentrating to c, the precipitated thorium chloride is filtered off again to obtain a methanol solution of poly7lylamine. This solution was diluted with methanol to give 12.412% polyallylamine.
Obtain a methanol solution of polyallylamine with a matching percentage.

S-
Add 18.5 g of ethylisothiourea hydrobromide.

When stirred at room temperature, the odor of ethyl mercaptan is generated.
It can be seen that the reaction is progressing. The reaction mixture dissolves in about 2 hours when diluted with 50 cc of methanol to facilitate stirring.

- After the overnight reaction, add the reaction solution to 700cc of acetone to obtain a white sticky precipitate. This material turned into a brittle solid over time, so it was thoroughly crushed to obtain a solid powder. When purified using a method of dissolving in methanol and precipitating with 7 cycles, a white solid is obtained. Vacuum drying over phosphorus pentoxide yielded 15.6 g of purified product. The Dtl of a solution obtained by dissolving this product in water was 9 to 10. It is thought that some free polyallylamine remains in the reaction product.

The infrared absorption spectrum of this material is λmax 3350.1650.1460°1360 as shown in Figure 1.
．． It showed characteristic absorption at 600cIR-1.

Further, the guanidine group content in the polymer was determined by potentiometric titration to be 92.5 mo1%.

Roughness ηinh is 0.35 (c=0.5g/dj, N
/10 in saline solution at 30°C), and the number average molecule ffi of this polymer was determined by osmotic pressure measurement in a saline solution.
(Mn) was 9,800.

Furthermore, this polymer began to decompose at about 220°C.

Production of polyallylguanidine hydrobromide by method (c) Thiourea 152.2SF and ethylbromide 2629,
Ethanol 200 dr: Dilute and reflux at 40°C.

The clear solution obtained after 5 hours of reaction is concentrated to produce a solid. Dissolve the Vi solid in 300 cc of ethanol, add ether, and prepare 2j! Bind, cold IJI L, TeJ3 <
and crystallize. White granular solid, melting point 88-89
S-ethylisothiourea depleted hydrochloride at °C 348.6
9 (94,2%).

Take 50 g of this isodiA urea hydrobromide, put it in an Erlenmeyer flask, attach a calcium chloride tube, and add 100 id of distilled allylamine. Immediately, ethyl mercaptan is generated and the urea derivative begins to melt exothermically. It melts in about 2-3 minutes to give a clear solution. To complete the reaction, the reaction was further stirred at room temperature for 5 hours, excess allylamine was decanted by adding ether, and the resulting solid was recrystallized from ethanol and ether to give N-allylguanidine hydrobromide in a yield of 47. 9 g (98.5%) were obtained. Melting point 70-71°C.

Elemental analysis Calculated value for C4H1oN3Br C=2
6.68 8=5.66 N=23.34% actual value
C=26.72 1-1=5.72 N=23.04
% N-allylguanidine hydrobromide obtained above was dissolved in water to make a 70% aqueous solution, and the polymerization initiator (X, Y shown below) used in the method of the present invention was prepared.

Polymerization was carried out using various radical catalysts other than the polymerization initiator used in the present invention. The results are shown in Table 1. Polymerization examples using the azo catalyst used in the present invention are Nα
1 to 11 and 25.26. Examples using other general polymerization catalysts are shown in Orders 12 to 24 for comparison.

After the polymerization reaction, polyarylguanidine hydrobromide is produced by pouring the polymerization solution into a large amount of acetone to solidify it, reprecipitating the polymer using methanol and acetone, and vacuum-drying the polymer over phosphorus pentoxide. I got it.

According to the infrared absorption spectrum of the polymer obtained by the polymerization reaction using the catalyst used in the present invention, the absorption of 930α-1,990IJ-1 based on the double bond of the olefin has disappeared. , it can be seen that there are no unreacted monomorphs.

This fact is shown in FIG. 2 as a representative example of the IR absorption spectrum of the polymer obtained in Example 2, NQl.

Further, the small polymer obtained in Example 2.1lk11 decomposed at 215°C and was quite serious, but the polymers of Example 2 and Nα1 to 26 all decomposed at around 220°C.

+g target item's'nonoa: 1cOa) mouth ω nononoyuki V
Ma size size? ! Dimension Ma Dimension Ma Dimension 1 ＾ N − ＼′のノノノノノノノののの5 −0 ゞ 00 ゝ■ 〇 −〇 − ζq C4のr r F” r r−r r r C 'Jhehehehe LN
11. N1 Table 1 Note 1) FFI! Medium X: 2.2'-diamidinyl-2.2
'-Azopropane hydrochloride Y: 2.2'-azobis(N,N'-dimethyleneisobutyramidine) dihydrochloride Z: 2.2'-azobis(N,N'-dimethyleneisobutyramidine) ACPA: 4.4' azobis(4-cyanopentane M
) AIBN: azohisisobutylnitrile Bl) Onidibenzoyl peroxide APS: ammonium peroxysulfate 2) Intrinsic viscosity: C=0.59/dj! , measured at 30°C in N/10 saline.

3) l average molecular weight = measured by osmotic pressure method in saline solution.

Example 3 Preparation of polyallylguanidine medyl hand sulfate by method C 1809 urea and 208 g of dimedyl sulfate are heated at 110° C. for 5 hours and decanted with acetone and ether to obtain an oil. When 250 g of allylamine is added to this, an exothermic reaction occurs at room temperature. After thoroughly decanting with acetone, benzene, and ether to remove excess allylamine, a 70% aqueous solution of the resulting viscous liquid allylguanidine methyl bisulfate is prepared. Take this aqueous solution in a test tube or Erlenmeyer flask, and add the polymerization initiators X and Y used in the present invention (see Table 1).
The results of polymerization at 60°C for 48 hours (order 1 to
9) and the results of polymerization using various other radical catalysts (Nα10 to 13) for comparison are also shown in Table 2.

Example 4 Preparation of copolymer of allylamine and allylguanidine by method (c) Allylamine hydrochloride (1.59 in 70% aqueous solution) and allylguanidine bromate (1.59 in 70% aqueous solution) were combined. Put 2,2'-diamidinyl 2,2' in a test tube.
-Add 0.0609g of azopropane dihydrochloride and 60℃
Polymerization was carried out for 48 hours. The solid obtained by pouring into 200 d of acetone was filtered, washed with acetone, and dried to obtain a copolymer of 1.879. Absorption of guanidine groups was observed in the infrared absorption spectrum. Intrinsic viscosity (ηinh) is 0.3
0 (c=o, 5, N/1O-NaCJ!). Table 3 shows the yield and intrinsic viscosity of copolymers obtained under the same polymerization conditions but with different weight ratios of monomers.

Example 5 Preparation of polyallyl guanidine rototoluene sulfonate by method 66 g of urea and 1 p-toluene sulfonic acid methyl ester
When 86 g of the mixture is mixed and heated on a steam bath at 80 to 90°C for 7 hours, crystals will precipitate. Cool the mixture to 70° C., add 400 ml of acetone, cool to 0° C., filter the crystals, and dry to obtain 325 g (66%) of 0-methylisourea-p-toluenesulfonate. 80.0g of this salt
When allylamine 100IIi is added to the solution, it generates heat and becomes a solution. After stirring for 2 hours, decant and drain with ether.

Dry, oily allylguanidine-p-toluenesulfone GL is obtained actionally, and then a 70% aqueous solution thereof is prepared.

Furthermore, 7 of allylguanidine P-toluenesulfonate
After polymerizing a 0% aqueous solution with X and Y (see Table 1) as a polymerization initiator at 60°C for 5 hours, the polymerization solution was ace1-
A solid was precipitated, filtered and dried to obtain polyallylguanidine rototoluenesulfonate. The polymerization conditions and results are shown in Table 4.

Effects of the Invention The present invention uses starting materials (monomers) that are cheaper and easier to obtain than existing methods for producing N,N-diallylguanidine salts-acrylamide copolymers. There is an advantage that a novel guanidine group-containing polymer can be obtained extremely efficiently. The obtained polymer is also superior to existing N,N-diallylguanidine salt-acrylamide copolymers in that it has a higher guanidine content ω in the molecule.

[Brief explanation of drawings]

Figures 1 and 2 show infrared spectra of the guanidine group-containing polymer of the present invention.

Claims (3)

[Claims] (1) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (I) (In the formula, R_1 and R_2 may be the same or different, hydrogen atom, C_1-C_1_8 straight chain or branched alkyl group, It represents an alkoxycarbonylalkylene group, an alkylenecarboxylic acid group, or a C_6-C_8 aryl group, X represents an inorganic or organic acid when absent or present, and Y represents an inorganic or organic acid when absent or present. represents an inorganic or organic acid, m represents an integer of 10 or more,
j is a number satisfying 0<j≦1) A guanidine group-containing polymer. (2) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (IV) (In the formula, R_1 and R_2 may be the same or different, hydrogen atom, C_1-C_1_8 straight chain or branched alkyl group, represents an alkoxycarbonylalkylene group, an alkylenecarboxylic acid group, or a C_6-C_8 aryl group, and X represents an inorganic or organic acid) alone or together with an allylamine represented by the formula CH_2=CHCH_2NH_2(II) , polymerized in the presence of a polymerization initiator having an azo group and a cationic or cationizable nitrogen atom-containing group in the molecule, and a final product in which Y is not present in the obtained polymer and Y is present. There are general formulas ▲mathematical formulas, chemical formulas, tables, etc.▼(I) (wherein R_1, R_2, and X are as defined above Y is absent or, when present, represents an inorganic or organic acid, m represents an integer of 10 or more, and j is 0<j
A method for producing a guanidine group-containing polymer (indicates a number satisfying ≦1). (3) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (V) (In the formula, m represents an integer of 10 or more) Polyallylamine or its organic or inorganic acid salt has the general formula ▲ Numerical formula, chemical formula , tables, etc.▼(III) (In the formula, R_1 and R_2 may be the same or different, and are a hydrogen atom, a C_1-C_1_8 linear or branched alkyl group, an alkoxycarbonylalkylene group, an alkylenecarboxylic acid group or represents a C_6-C_8 aryl group, X represents an inorganic or organic acid, and R_3 represents C_1-C_
5 and Z represents an oxygen or sulfur atom) or a compound that imparts a guanidine group to polyallylamine in the same manner as compound (III), and Y is added to the resulting polymer. There are general formulas ▲ mathematical formulas, chemical formulas, tables, etc. ▼ (I) (where R_1 , R_2, X, m are as defined above, Y is absent or, when present, represents an inorganic or organic acid, and j represents a number satisfying 0<j≦1) A method for producing a guanidine group-containing polymer.