JP2000128836A - Cationizing agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a cationizing agent improving the stability of epoxy groups on a cationizing reaction, capable of inhibiting the elimination of the epoxy groups by their decomposition reactions, having effects such as the improvement of a yield, and having good stability on reactions. SOLUTION: This cationizing agent of formula I X is a halogen; Z is a structure of formula II; Y is an alkylene, a cycloalkylene, phenylene, a hydroxyalkylene or a group of formula III [R1 to R8 are each a 1-3C alkyl; (m) is 2-6; (n1), (n2) and (p) are each an integer including zero]). The cationizing agent is obtained, for example, by reacting 1 mole of an oligomer with 2 moles of an N,N,N',N'-tetraalkyl-α,ω-alkanediamine and then further with 2 moles of an epihalohydrin such as epichlorohydrin and 2 moles of a hydrogen halide such as hydrochloride.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a cationizing agent having good stability during a reaction.

[0002]

2. Description of the Related Art As a reason for introducing a cationic group into a compound such as starch, cellulose, PVA (meaning polyvinyl alcohol; the same applies hereinafter), for example, when the compound is a fiber, improvement in dyeability is cited. In this case, it is known that the dyeability is improved as more cationic groups are introduced (increased cation). As a cationizing agent in the case of high cationization, a general formula (in the formula,
R9 and R10 are an alkyl group having 1 to 3 carbon atoms, X is a halogen group, and r is an integer of 1 to 5), having halohydrin groups at both ends of the molecule, and having a plurality of cationic groups in the molecule. It has been proposed that an oligomer-type cationizing agent having the following formula is effective (JP-A-6-87799).
This oligomer is obtained by the reaction of a dialkylamine with epihalohydrin.

As a cationization method using a cationizing agent having a halohydrin group, a cationizing agent is generally reacted with an alkali to close the halohydrin group to an epoxy group, and then to form a desired compound such as starch, cellulose or PVA. Is preferable from the viewpoint of reactivity.

[0004]

However, the above oligomer type cationizing agent has a poor stability of an epoxy group generated by the action of an alkali, so that the cationizing reaction is difficult.
In addition to being consumed by the reaction with the target substance, it has a disadvantage that it is decomposed and consumed by a side reaction, so that the yield is poor and the productivity is not satisfactory.

The present invention has been made in view of such conventional problems, and aims to provide a cationizing agent having good stability during the reaction.

[0006]

The present inventors have made intensive studies on the stability of the epoxy group of the oligomer type cationizing agent, and as a result, have found that the cationizing agent shown in FIG. 1 shows extremely good stability. The present invention has been completed.

That is, the present invention relates to a compound represented by the general formula shown in FIG. 1 wherein X is a halogen atom, Z is a structure represented by the general formula shown in FIG. This is a structure represented by the general formula of FIG. 3, where R1, R2, R3, R
4, R5, R6, R7 and R8 are alkyl groups having 1 to 3 carbon atoms, m is an integer of 2 to 6, and n1, n2 and p are integers including 0. R1, R2, R3, R4, R5, R
6, R7 and R8 may be the same or different. ) Is a cationizing agent characterized by the following.

When an alkali acts on the cationizing agent of the present invention, the halohydrin group in the cationizing agent is closed to form an epoxy group. There is no hydroxyl group near this epoxy group. Therefore, intramolecular decomposition caused by the side reaction does not occur. Therefore, the epoxy group of the cationizing agent generated after the alkali action is stable during the cationization reaction. Therefore, the cationizing agent of the present invention has excellent stability during the reaction.

In the formula of FIG. 1, Y represents an alkylene group, a cycloalkylene group, a phenylene group, a hydroxyalkylene group,
Or a structure represented by the general formula in FIG. When the purpose is to introduce many cationic groups, the structure represented by the general formula in FIG. 3 is preferable. In the formula of FIG. 3, Z is a structure represented by the general formula of FIG.

In the equations of FIGS. 2 and 3, R1, R2, R3,
R4, R5, R6, R7 and R8 are alkyl groups having 1 to 3 carbon atoms. When the number of carbon atoms is 4 or more, there is a problem that the reactivity with epihalohydrin is poor when preparing the cationizing agent of the present invention and the oligomer as a raw material. When the number of carbon atoms is 0, it becomes an amine type, which is extremely unstable. In the equations of FIGS. 2 and 3,
X is a halogen atom.

In the formula of FIG. 2, m is an integer of 2 to 6. m
When the value is 7 or more, there is a problem that the density of the cationizing agent is reduced. Further, when m is 0 or 1, there is a problem that stability during the cationization reaction is poor.

In the equation of FIG. 3, n1, n2 and p are integers including 0. The preferred range of n1 and n2 is 1 to 20 depending on the relationship with the molecular weight of the cationizing agent. The preferred range of p is from 0 to 0 depending on the relationship with the molecular weight of the cationizing agent.
It is one.

Examples of the method for producing the cationizing agent of the present invention include:
1 mol of the oligomer (A) represented by the general formula in FIG. 4 is reacted with 2 mol of (B) N, N, N ′, N′-tetraalkyl-α, ω-alkanediamine represented by the general formula in FIG. After that, it is obtained by further reacting (C) epihalohydrin with (D) hydrogen halide in 2 moles each.

In the equations of FIGS. 4 and 5, R11, R12, R
13, R14, R15, R16, R17 and R18 are
It is an alkyl group having 1 to 3 carbon atoms. X and m in the equations of FIGS. 4 and 5 are the same as X and m in the equations of FIGS. 2 and 3. Q in the equations of FIGS. 4 and 5 is an integer including 0.

The oligomer as the component (A) can be usually obtained as an aqueous solution by a known method using dialkylamine, epihalohydrin and hydrogen halide as raw materials. Examples of the above-mentioned dialkylamine include dimethylamine, diethylamine, dipropylamine, methyletheramine and the like. Of these, dimethylamine is preferred for economic reasons. Examples of the epihalohydrin include epichlorohydrin, epibromohydrin, epiiodohydrin and the like. Of these, epichlorohydrin is preferred for economic reasons. Examples of the hydrogen halide include hydrogen chloride, hydrogen bromide, hydrogen iodide, and an aqueous solution thereof, but hydrochloric acid is preferred from the viewpoint of availability and handling.

The above components (B), N, N, N ', N'
-Tetraalkyl-α, ω-alkanediamine includes N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetramethylpropylenediamine, N, N, N ′, N '-Tetramethylhexamethylenediamine and the like. Of these, N,
N, N ', N'-tetramethylethylenediamine and N,
N, N ', N'-tetramethylpropylenediamine is preferred.

The epihalohydrin as the component (C) includes the same epihalohydrin as the raw material for the component (A), and epichlorohydrin is preferable for the same reason.

Examples of the hydrogen halide as the component (D) include the same ones as the raw material for the component (A), and hydrochloric acid is preferred for the same reason.

Examples of the use of the cationizing agent of the present invention include cationizing agents for papermaking, cosmetics, fibers and the like.
It is not limited to this.

[0020]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the present invention will be described with reference to Examples 1 to 4 and Comparative Examples 1 and 2. Note that the present invention is not limited to these examples.

Example 1 Dimethylamine, epichlorohydrin and hydrochloric acid were used in the following manner:
The reaction was carried out at a molar ratio of 2: 1 to obtain a 40% by weight aqueous solution of the oligomer. After reacting 1.72 mol of N, N, N ', N'-tetramethylethylenediamine with 0.86 mol of the oligomer in this aqueous oligomer solution, 1.72 mol of 35% by weight hydrochloric acid and 1.72 epichlorohydrin are obtained.
The moles were reacted, and further diluted water was added to adjust the concentration. Thus, a 50% by weight aqueous solution of the cationizing agent of this example was obtained. As a result of measuring the inorganic chlorine content and the chlorohydrin group content of this reaction product, 3,353
mmol / g and 0.805 mmol / g.

The aqueous solution of the reaction product was added to the aqueous solution so that the molar ratio of NaOH to chlorohydrin groups was 0.95.
An 8% by weight aqueous solution of NaOH was added, and the mixture was further diluted with pure water so that the concentration of the cationizing agent became 30% by weight to obtain a bath of the cationizing agent. The bath was kept at 30 ° C., and the epoxy group content after 1, 3, and 5 hours was measured. Obtain the ratio of the measured value to the theoretical value as the epoxy group residual rate,
The stability of the epoxy group was evaluated. The results are shown in Table 1.

Example 2 The same procedure as in Example 1 was carried out except that a 50% by weight aqueous solution of the oligomer obtained by reacting dimethylamine, epichlorohydrin and hydrochloric acid at a molar ratio of 5: 4: 1 was used as the raw material aqueous oligomer solution. The operation was performed to obtain a 50% by weight aqueous solution of a reaction product. As a result of measuring the content of inorganic chlorine and the content of chlorohydrin group of the reaction product, each was 3.
519 mmol / g and 0.513 mmol / g. The stability of the epoxy group of this reaction product was evaluated in the same manner as in Example 1. The results are shown in Table 1.

Example 3 N, N, N ', N'-tetraalkyl-α, ω-
The same operation as in Example 1 was carried out except that N, N, N ', N'-tetramethylpropanediamine was used as the alkanediamine, to obtain a 50% by weight aqueous solution of a reaction product. As a result of measuring the inorganic chlorine content and the chlorohydrin group content of this reaction product, each was 3.247 mmol / g.
And 0.787 mmol / g. The stability of the epoxy group of this reaction product was evaluated in the same manner as in Example 1. The results are shown in Table 1.

Example 4 N, N, N ', N'-tetraalkyl-α, ω-
Example 1 except that N, N, N ', N'-tetramethylhexamethylenediamine was used as the alkanediamine.
The same operation as described above was performed to obtain a 50% by weight aqueous solution of the reaction product. As a result of measuring the inorganic chlorine content and the chlorohydrin group content of this reaction product, 3.519 mmol each was obtained.
1 / g and 0.513 mmol / g. The stability of the epoxy group of this reaction product was evaluated in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 1 The stability of the epoxy group of the aqueous oligomer solution used as a raw material in Example 1 was evaluated. The results are shown in Table 1.

Comparative Example 2 The stability of the epoxy group in the aqueous oligomer solution used as a raw material in Example 2 was evaluated. The results are shown in Table 1.

Cationization performance Starch is cationized using the bath of the cationization agent shown in Examples 1-4 and Comparative Examples 1-2, and the degree of cationization is measured by colloid titration to perform the cationization. It was confirmed. The results are shown in Table 2.

[0029]

[Table 1]

[0030]

[Table 2]

[0031]

As described above, the cationizing agent of the present invention comprises:
Shows cationization performance equivalent to or better than conventional oligomeric cationizing agents, and improves the stability of epoxy groups during cationization reactions, which is a drawback of conventional oligomeric cationizing agents, and reduces the loss due to decomposition reactions. Since it can be suppressed, effects such as improvement in yield can be expected in the reaction with compounds such as starch, cellulose, and PVA. Therefore, it is suitable as a cationizing agent.

[Brief description of the drawings]

FIG. 1 is an explanatory diagram showing a general formula of a cationizing agent of the present invention.

FIG. 2 is an explanatory view showing a structure of Z in the present invention.

FIG. 3 is an explanatory view showing a structure of Y in the present invention.

FIG. 4 is an explanatory view showing a general formula of an oligomer which is a raw material of the cationizing agent of the present invention.

FIG. 5: N, N, which is a raw material of the cationizing agent of the present invention.
Explanatory drawing of N ', N'-tetraalkyl-α, ω-alkanediamine.

FIG. 6 is an explanatory view of a conventional alkylating agent.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Koji Mase 710, Orokuromicho, Yokkaichi-shi, Mie Yokkaichi Gosei Co., Ltd. F-term (reference) 4C048 AA01 BB03 BB04 CC01 UU10 XX03 4H006 AA03 AB81 BN10 BU50 4H057 AA01 CA03 CA37 CA38 CB08 CB13 CB18 CC01 DA01 DA24 DA29

Claims (1)

[Claims] 1. X is a halogen atom, Z is a structure represented by the general formula in FIG. 2, Y is an alkylene group, a cycloalkylene group, a phenylene group, a hydroxyalkylene group in FIG. 2 and FIG. 3, wherein R1, R2, R3, R4, R5
R6, R7 and R8 are alkyl groups having 1 to 3 carbon atoms, m is an integer of 2 to 6, and n1, n2 and p are integers including 0. R1, R2, R3, R4, R5, R6, R7 and R8 may be the same or different. A cationizing agent characterized by the following.