CS256557B1 - Process for preparing hexamethylenetetraminic quaternary salts - Google Patents

Abstract

A method of preparing hexamethylenetetramine quaternary salts of the formula: N·N CH?COOR X -N Θ by reacting hexamethylenetetramine with haloacetates of the formula: X—CH?—COOR, where X is Br, CI or I and R is alkyl with 1 to 4 carbon atoms. The essence of the invention is the fact that at a temperature of 0 to 120 °C, in the process of wet grinding, for a period of 1 to 120 minutes, 1 molar part of liquid haloacetate is treated with 1 molar part of hexamethylenetetramine in the absence of a solvent. The obtained products are suitable as bactericidal and fungicidal additives for coatings, latexes, adhesives, vegetable oils, etc.

Description

The above-mentioned drawbacks are solved by the present invention, according to which method for the preparation of quaternary salts of the formula:

N-Νχ \ V-CHfCOQRX ι V / <by reaction of hexamethylenetetramine with haloacetates of formula:

X - CH 2 - COOR, wherein, X is Br, Cl or I and R is alkyl of 1 to 4 carbon atoms, is carried out such that at 0 ° to 120 ° C, in a wet milling process, for 1 to 120 minutes, 1 molar part of liquid haloacetate is treated with 1 molar part of hexamethylenetetramine in the absence of solvent.

The progress of the invention is manifested by technical effects, in particular by reducing the reaction time and eliminating the problems of working with solvents.

The economic progress of the solution is reflected in the reduction of production costs, reduction of products, reduction of labor, saving of raw materials, energy etc.

Increasing work safety and hygiene conditions in connection with contamination of work and the environment with haloderivatives are also important from the social point of view.

In this so-called. According to the "slurry process", depending on the nature of the haloacetate, a small excess of one of the incoming reactants can be selected which does not result in a reduction in the product's effect.

The preparation of quaternary salts according to the invention is illustrated by the following examples, which in no way exclude the possibility of variability in the preparation of the subject substances.

Example 1

140.0 g of hexamethylenetetramine (1 mol) are poured into a 500 cm ³ stainless steel screw malaxer. 167.0 g (1 mol) of ethyl bromoacetate are successively metered in at room temperature 24 ° C with stirring and heated to 70 ° C by the liberated quaternization heat. After an hour of malaxing, the product is ground. This results in 306.0 g of quaternary salt, which is 99.7% of theory.

Note: the released heat of reaction may cause an increase in temperature that exceeds the decomposition temperature of the product.

Using differential thermal analysis (DTA), operating at a linear temperature rise rate of 5 ° C. min ^-1 , with a measuring range of 1 mV per scale scale and weighing 50 to 70 mg of sample, the onset of exothermic solid state decomposition at 117.0 ° C is found. Furthermore, the first peak of exo-decomposition at 142.4 ° C; endo-peak at 146.0 ° C and second exo-decomposition peak at 150.6 ° C. The decomposition pattern changes at 135.2 ° C.

The melting point of the specimen on the "Boetius" micro-heating plate is 142-143 degrees C.

The product has a pair of ester bands of approx. 1,740 and 1,290 cm ^-1 in the IR spectrum and four "urotropin" bands (with a slight shift). Bands between 3,000-2,800 cm ^-1 belong to the valence vibrations of the C-H bonds, and as expected, the strongest are i> as CH2 pca of 2,920 cm ^-1 . In the area of deformation vibrations of the C — H bonds, the strongest belt S Chi sciccor is also approximately 1,470 cm ^-1 and a belt called so-called. active CH2 groups of about 1410 cm ^-1 (actively = led to groups with - I effect)

The procedure is as in Example 1, except that esters with different R-values are used. The results are summarized in Table 1.

Table 1

attempt

no.

Yield (%)

Melting point (° C)

1 methyl 99.9 146 Second 2-propyl 99.7 140 Third 2-bromoallyl 99.0 141 4th allyl 99.8 149 5 2-chloroallyl 99.5 144

J

251557

Under similar conditions with the same effect, quaternary ester salts are formed in which R is 2,3-dichloroallyl, n-butyl and isobutyl, respectively, for X = Cl or I.

The products obtained by the process according to the invention are suitable as bacteriocidal and fungicidal additives for coatings, latexes, adhesives, cutting oils and the like.

Claims (1)

SUBJECT We claim: Process for the preparation of hexamethylenetetramine quaternary salts of the formula: by reacting hexamethylenetetramine with the haloacetates of the formula X-CH-COOR N · Nkde X is Br, Cl or 1, and R is C 1 -C 4 alkyl, characterized in that at a temperature of 0 ° C to 120 ° C, v. in a wet milling process, for 1 to 120 minutes, 1 molar part of liquid haloacetate, in the absence of solvent, is treated with 1 molar part of hexamethylenetetramine.