SU1154267A1 - Diquaternary ammonium salts of methylenediamines as softeners of cloth and cellulose,chemical and mixed fibre articles - Google Patents

Abstract

D-quaternary ammonium salts of methylenediamines of the general formula CH NRCORi CHi HCORi

Description

"115A267

The invention relates to new chemical compounds, specifically to R, CONHCHjCHg-K-CHg CH NHCOR,

I, COMNH2CH2 -K - CHgCHsNHCOR,

where RI is alksh,

X is the anion CHE504 or, which can be used as fabric softeners from whole RiCONH-Cn, H, Q, -ljr-CnH n-NHCORj R CONH-CpHjp - N CpH2j .-- l HCOR7 where R, R R ., J - Cd-C aliphatic radicals, 2 6 arylalkyl, alkyl or polyalkylene glycol groups; alkylene, g an alkylating agent anion proposed as fabric softener l. However, these polyamide-ammonium compounds, according to the conditions of their synthesis, cannot contain as a bridging element R methylene group CHj. In addition, the synthesis of compounds of formula II is technically difficult, it involves the alkylation of the secondary amino group Soc-acyldialkylene triamine by adding Kj unsaturated substances, alkylene oxides or reductive methylation, and subsequent quaternization of the resulting tertiary amine with inaccessible bi-functional alkylating agents. A known polyethylene emulsion, which is also used as a fabric softener for textile textile enterprises 2J. A disadvantage of the known preparation is the imparting to them tissues of moderate-converting ammonium salts of substituted methylenediamines of the general formula

SI,

4- +

2X

Syz

lulose, chemical and mixed fibers,

f5 Polyamide ammonium compounds of the general formula are known.

+ 4Pa

2A, but with a soft fingerboard, significantly deteriorating after washing. The purpose of the invention is the synthesis from the secondary amines of di-quaternary ammonium salts of substituted methylenediamines, which could be used as effective softeners in the final finishing of textile materials. This goal is achieved by using the quaternary ammonium salts of methylenediamines of the general formula (I) .3 as a fabric softener and cellulose, chemical: and mixed fiber products. The compounds of formula (D) are obtained by reacting 2 moles of a secondary amine with 1 mole of formaldehyde and quaternizing the resulting tetra-alkyl methylenediamine with apycliculants. Condensation of diacyl diethylenetriamine and formaldehyde can be carried out using both formaldehyde aqueous solution formalin and paraformaldehyde (paraform). The reaction is carried out with minimal heating of the mixture, ensuring the liquid state of the initial diacyl diethylenetriamine. For quaternization of the obtained methylenediamine derivative, it is advisable to use dimethylcyrr, phat or benzene sulphospot methyl ester, which are most accessible and provide quaternary salts that easily form stable aqueous solutions or dispersions. The presence of the methylene fragment between the two nitrogen atoms in the obtained compounds (1) is especially beneficial in the case of using these substances as fabric softeners, since the derivatives of methylenediamine, in addition to increased affinity for the fiber, are inherent in all cationic compounds, also have amymemethylose and, thus, they enter into a chemical interaction with active groups of fibers. This makes it possible to apply compounds (I) as softeners of a persistent effect, which retain their effectiveness. s after repeated washings. Compounds (II) do not exhibit such properties. Example 1. N, dimethyl-N, N, S, N-tetrakis- (2-stear-ilaminostil) methylenediamine (I, Cj C, H, 5, ..., 60) bismetosulfate N A. To 284 g (1 mol) of stearic acid at 80-100 s is added dropwise 51.5 g (0.5 mol) of diethylene amine, the mixture is heated for 1.5-2 hours in a stream of nitrogen to ISO- lbO C and stirred at this temperature for 6 hours with distillation of the water liberated during the reaction. Light yellow distearoyl ethylene triamine is obtained with a freezing point of 93-105 ° C and a residual acid number of 4.2 mg KOH / H. The product is used for further reaction without purification. The dp of the compound identification is recrystallized from isopropyl alcohol. Distearoylistilienes triamine obtained. M.p. 115-11b ° C. Found,%: C 75.74; H 12.79, N 6.77. C..HgNpj Calculated,%: C 75.53; H 12.84, N 6.61. Amine number, mg HCP / g: found 57.6J calculated 57.38. B. To melt the product of the interaction of stearic acid with dystilitriamine at 100-110 ° C, add 15 g portions (0.5 mol) of paraform. The mixture is stirred at this temperature for 2 hours until a clear melt is obtained and no formaldehyde is present in the product. Tetrakis (2-stiraoylaminoethyl) methylenediamine is obtained in the form of a light yellow melt, which is boiled when cooled to a waxy mass. The product is used for further reaction without purification. Instead of paraforma, an equivalent amount of formalin can be obtained. For analysis, the resulting batch is recrystallized from isopropyl alcohol, to obtain colorless microcrystals of tetrakis (2-stearo1-amino-ethyl) methylenediamine, do not have a clear temperature of ap., Found,%: C 76.01; H 1., 60, N 6,79. Calculated,%: C 75.7 6, Calculated,%: C 73.76 "N 12.72} N 6.54. Amine number, mg ISB / g: found 57.1; calculated 56.84. There are no bands characteristic of R2NH in the IR spectrum. B, To the melt of tetrakis (2-stearoyl aminoethyl) methylenediamine at 126 ° C, add 126 g (1 mol) of dimethyl sulfate. The mixture is heated for 2 hours at 100 ° C and N, N -dimethyl-N, N, N, N -tetrakis (2 stearoylaminoethyl) methylenediammonium bismetosulphate is obtained, which, on cooling, is cooled to a waxy, light yellow color. The identification of the quaternary salt is carried out by the method based on the formation of water-insoluble plex from three bications of salt and two ferricyanide anions during the processing of the product with iron solution of potassium pedigree. According to this method, the mass fraction of the quaternary salt in the quaternization product is 98.8%. For the use of the di-quaternary salt as a tetrakis (2-stearonpaminoethyl) methylenediamine softener, it is advisable to dilute with heating an equal weight of ethylene glycol by heating before quaternization. After the completion of the reaction, the solution is diluted at 60-80 ° C with water to a salt concentration of 20-40%. A water or water-glycolic paste of N, N-dimethyl-N, N, N, N-tetrakis bismethosulfate (2-stearoylaminostip) methylenediammonium white or creamy color, easily mixing with a warm wave with the formation of stable non-stratifying dispersions is obtained. Examples 2-26. According to the method of example 1 get quaternary salts of General formula (1), are given in table. 1. Example 27. The compound of example 1 is tested as a softener with high-quality cotton poplin finishing in combination with carbomol TsEM, a preparation that imparts low wrinkle and low shrinkage to the fabric. Samples of poplin treated with a dispersion containing, wt.%: The compound according to example 13.0 Carbamol CEM 25.0 magnesium chloride. hexahydrate 1.5 Water Up to 100 Fabric is squeezed to a residual moisture content of 60-70%, dried in air and subjected to heat treatment at 15 and for 3 minutes. Examples 28-29. Analogously to example 27, with high-quality finishing of cotton poplin (art. 714), the compounds obtained according to examples 1-3,6,7,12, 13,15-17, 20, 21 and 25 are tested. Table 2 shows the softness estimate. samples (tissue neck) on a 5-point scale and the physicomechanical properties of the fabric. Example 40. The compound of example 1 is tested as a chitale with a low-abrasive finish of flax-and-nap tissue together with carbamol (no brand). Samples of fabric are treated with a dispersion containing, in wt.%: Compound according to Example 13.0 Carbamol25.0 Ammonium Chloride Urea1 0 Water 100 Fabric is squeezed to a residual moisture content of 80-90%, air-dried and heat treated at 150-160 ° C for 3 min Examples 41-55. The compounds of examples 1,2,4,5,8-11, 14-16, 18, 19, 22-24 are tested as in Example 40 with a low-gloss finish of flax-and-nap tissue (art. 062256). The test results are shown in Table 3. Examples 56-61. The compounds of Examples 1, 2, 7, 8, 15 and 16 are tested as softeners and antistatic agents when finishing fabrics from chemical fibers. Samples of polyamide, polyester, and acetate fabrics are impregnated with a dispersion of the compounds obtained in Examples 1,2,7,8,15 or 16 (20 g / l), pressed to a residual moisture content of 80-90% and dried in air. The fabric neck and anti-electrostatic properties, measured in electrical resistance, measured on a teraommeter at a relative humidity of 65%, are evaluated. The treated samples acquire a soft silky neck, estimated at 45 points. The electrical resistance data is given in table 4. Thus, the testing of the di-quaternary ammonium salts of methylenediamines in the decoration of textile materials shows that these compounds impart very soft, silky neck resistant to washes to fabrics and products made from natural, chemical and mixed fibers. As follows from the data, the compounds of the general Formula (l) are superior to the known compounds in terms of the effect of softening and permanence. Substances are easily combined with other non-ionic and cation-type finishing agents, and do not cause a change in the color of the colored tissues.

Table 1

,

CH, 504

SO

, СН, 604, СН, 50, SO, С1Ц504

, 90z

, CH, 504,

CH, 504,

CH, 50 C.

CH 604

Ce, Hj50

SbN5vO, SNz904

,

K, -K, P5 K7 "1z5 K (, 0 ((: H2) 2;,; fft2; A-Cl

Table 2

R ,, H, 5i RI-RC H; R (.) 0 (Cl {j); .

Table 3

Table 4

Claims (2)

(56) 1. Switzerland patent R 553150, cl. C 07 C 87/30, published. 1974. 2. Legchilina L.M. and others. Improving the quality of cotton fabrics through the use of low-crease socks in the processes of final finishing. Review, ser. Cotton industry, vol. 3, I., TSNIITEIlegprom, 1979. (54) DETURBERTIC AMMONIUM SALTS OF METHYLENEDIAMINS AS SOFTENERS OF TISSUES AND ARTICLES OF CELLULOSE, CHEMICAL AND MIXED FIBERS. (57) Methylenediamines di-quaternary ammonium salts of the general formula 'sn ₃ RjCONHCHjCH ^ - N— CH _g I CH ₃ + + • 2X “where is the alkyl C ^ -St, X - anion CH ₃ bO ₄ or C ₆ H ₅ 50 ^, as softeners for fabrics and products from cellulose, mastic and mixed fibers.