JPS58174349A - Preparation of aqueous solution of 3-chloro-2- oxypropyltrimethylammonium chloride - Google Patents

Abstract

PURPOSE:To obtain the titled compound useful as an agent for making cellulose, etc. cationic, etc. in high yield, by mixing continuously equimolar amounts of an aqueous solution of trimethylamine hydrochloride and epichlorohydrin at a specific temperature successively. CONSTITUTION:Equimolar amounts of an aqueous solution of trimethylamine hydrochloride shown by the formula I and epichlorohydrin shown by the formula II are mixed continuously with keeping the reaction temperature at <=70 deg.C, to give an aqueous solution of 3-chloro-2- oxypropyltrimethylammonium chloride shown by the formula III. When the reaction is carried out by adding dropwise the compound shown by the formula II to the compound shown by the formula I , by-products shown by the formulas IV-VI are prepared as a molar ratio of the compound shown by the formula II/the compound shown by the formula I approaches 1, the yield of the desired compound shown by the formula III is reduced and the formation of alpha- dichlorohydrin shown by the formula IV as a by-product is increased. By mixing continuously the equimolar amounts of the compound shown by the formula I and the compound shown by the formula II and carrying out the reaction at <=70 deg.C with suppressing heat generation, the formation of the compounds shown by the formulas V and VI as the by-products will not occur, and the formation ratio of the compound shown by the formula III as the by-product is reduced.

Description

DETAILED DESCRIPTION OF THE INVENTION $ The present invention relates to a method for producing an aqueous solution of 3-chloro-2-oxypropylammonium chloride from an aqueous trimethylamine hydrochloric acid solution and epichlorohydrin with few by-products and a good yield.

3-Chlor-2-oxypropylammonium chloride (1) is widely used as a cationizing agent for starch, cellulose, etc., and the compound (I) is generally prepared by adding Epicure to an aqueous solution of trimethylazun hydrochloride (a). It is obtained by dropping hydrin and reacting, but the following side reaction occurs at this time.

l) Main reaction (a) (b) (1)2)
Side reaction HCl + (b) → CtCko(l CHCgo(鵞Ct ・・・-・■0f(a-dichlorohydrin value) ω 2-oxytrimethylene-1,3-bis(trimethylammonium chloride)(凰) 1 No. 7 Niwamcrophid (W) (a) ◆ (W) → (飄) ・・・・・・・・・
■α-Dichlorohydrin (
Since it has two functional groups, if it is mixed in even a small amount in a product, it will react with polymers such as starch and cellulose and form crosslinks, increasing the viscosity of the resulting cationic polymer and increasing the water content. Problems such as insolubility arise.

The present inventors proposed a method of first removing such by-products by adding water or steam to the reaction crude liquid and topping it under reduced pressure or normal pressure, or repeating the concentration operation.
JP-A No. 54-30109].

However, in the conventional method, several α-dichlorohydrin (1) is present in the reaction crude solution, and this is 10
0 pp! rc removing 11 or less requires a large amount of energy. Therefore, if it is possible to suppress the amount of by-product of a-dichlorohydrin, the removal process will be easier and the cost will be reduced. On the other hand, even if the compound (1M) produced in the side reaction of formula (■) remains in the product, it will not interfere with the reaction with the polymer, but if the amount of the above-mentioned metal compound is reduced in the washing process of the produced cationic compound 17,-. That much less cleaning solvent is required.

According to the findings of the present inventors, trimethylamine hydrochloride-
) When the reaction is carried out by dropping epichlorohydrin (b) into an aqueous solution, as the molar ratio of (b)/yam) approaches 1, reactions of formulas 0 to 0 occur in addition to the reactions of formulas 0 to 0. C,
It was found that as the yield of the target product (1) decreased, the brain production of a-dichlorohydrin (1) increased.

Furthermore, in the dropping reaction, it was found that the dropwise addition time of epichlorohydrin (@a dichlorohydrin) was short, the by-product rate of @a dichlorohydrin) was reduced, and the yield of the target product (summer) was improved. However, in batch reactions, trimethylamine hydrochloride (
The reaction between a) and epichlorohydrin) occurs rapidly and generates a very large amount of heat, so it is extremely difficult to perform the dropwise addition of (-) in a short period of time in an industrial batch reaction from the standpoint of thermal control. .11 Incidentally, as the reaction temperature increases, side reactions are more likely to occur.

In view of this, the inventors of the present invention considered and studied the possibility of continuously preparing an aqueous solution of 葽) and 佽), and found that they mixed equal moles of 葽) and 伽) and continuously introduced the solution into a reactor. Supply 70℃
When reacting at the following temperatures, use the above [Yes].

It has been found that almost no side reaction of formula 0 occurs, the yield of the target product (1) is improved, and the by-product rate of a-dichlorohydrin (a-dichlorohydrin) is reduced compared to the conventional O dropwise reaction. The present invention has been achieved.

That is, the present invention involves reacting trimethylamine hydrochloride (a water-resistant solution and epichlorohydrin (b),
and 6) in 1 equimolar amount at a time, and at a reaction temperature t.
The present invention provides a method for producing an aqueous solution of 3-chloro-2-oxy-10-pyltrimethylammonium chloride, which is maintained at a temperature of 70°C or lower.

The present invention will be explained in detail below. In the present invention, the aqueous solution (a) and (b) are continuously mixed in equimolar amounts and supplied to a coolable reactor. When the ratio of (resistance/to) becomes smaller than 1, the reaction of the above-mentioned formula 0 occurs and forms an a-dichlorohydrin button; When reacting with -, it reacts with an alkali to liberate trimethylamine, producing a bad odor, which is undesirable from a work standpoint.

The concentration Fi of (a) in the aqueous solution of (false) is not particularly limited, but is usually between 40 and 70. The reaction temperature is generally 0 to 70°C, preferably 20 to 50°C, because as the reaction temperature increases, the rate of side reactions increases, and as a result, the yield of the target product (1) decreases. The continuous reactor may be either a tank type or a tube type. The average residence time of the reaction solution in the continuous reactor is not particularly limited, but it is usually l
O to x8(1) rb preferably 30 to 120 minutes.

The reaction crude liquid coming out of the reactor is continuously treated in a batch manner as described in step 4 above. The by-product a-dichlorohydrin is removed and purified by the method disclosed in 1983-30109-Jj Zenkaiho.

According to the method of the present invention, the target object (1) 3
The yield of -chloro-2-oxypropyltrimethylammonium chloride is improved by 10 to 20 times, and the by-product rate of a-dichlorohydrin (1) is also reduced, making the subsequent removal and purification process easier. Also, you won't have to practice your reaction time.

Next, the present invention will be explained in more detail with reference to Examples.
The present invention is not limited to the following examples unless the gist of the invention is exceeded.

Example Epichlorohydrin (b) t 0.57 Kg Mixed continuously at a flow rate of 1 min (a) / (b) molar ratio 1.
0] supplied.

The average residence time in the reaction tank was 60 minutes, and the temperature in the reaction system was maintained at 3θ°C by cooling the hinoki cypress.

The composition of the reaction crude liquid is as follows.

2-oxytrimethylene-1,3-bis(trimethylammonium chloride X grave) 1.9wt%σ-
Dichlorohydrin (1) 0.3wt1
G water
3- to 25.3 wt% epichlorohydrin
The yield of chlor-2-oxypropyltrimethylammonium chloride was 97 mol%, and the by-product rate of a-dichlorohydrin was 0.57 mol%.

The reaction crude liquid was charged into an 80Jilt100j distillation can, and dichlorohydrin was removed to 100 ppra or less.

The product composition was as follows, and the amount of water added was 0.8 times the amount of reaction crude liquid charged.

2-oxytrimethylene-1,3-bis(trimethylammonium chloride) (1) 1.7wt% water
32.8w
tlG Comparative Example 60-trimethylamine hydrochloride (water resistant solution 40.0K4
The temperature in the reaction system was maintained at I°C while cooling, and 23.2 kg of epichlorohydrin (0) was added dropwise ((a)/(b) molar ratio 1.O). The dropping time was 5 hours. The reaction solution composition was as follows.

a-dichlorohydrin (1)
z, 7wt*water
25. : The yield of 3-chloro-2-oxypropyltrimethylammonium chloride was 85.3 mol % based on 4 wt % epichlorohydrin, and the by-product rate of a-dichlorohydrin was 5.4 mol %.

#100 was added to the reaction crude solution 60 into a distillation can, and a-dichlorohydrin tt-100p was added in the same manner as in the example.
It was removed to below p. For product compositions F1 and below, the amount of water added was 3.3 times the amount of reaction crude liquid charged.

Patent applicant: Yokkaichi Gosei Co., Ltd.

Claims (1)

[Claims] When reacting the trimethylamine hydrochloride (conversion) aqueous solution and epichlorohydrin (b), (a) and (b) are continuously mixed t times at a time, and the reaction temperature is maintained at t-70°C or lower. Production of 3-chloro-2-oxypropyltrimethylammonium chloride aqueous solution a:
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