CS229063B1 - Compound for cationizing polymeric materials and method of preparing same - Google Patents

Description

The invention relates to compounds of formula I

(I) where k is 1 or 2, n is 1, 2 or 3,

X is an anion of a strong organic or inorganic acid,

Y is OH-CH-CHa- or CHh-CH-CH _? \ 2/2 I 2 I 2

Cl OH bonded to the nitrogen atoms of the cyclic group M,

M is a five- or six-action two-nitrogen cycle derived from pyridazine, pyrimidine, pyrazine, piperazine, pyrazole, pyrazoline,. pyrazolidine or imidazole, wherein the individual hydrogen atoms may be substituted with alkyls or hydrides having a carbon number of 1 to 4.

Reactive quaternary ammonium salts, derived from tertiary amines and epichlorohydrin, have found application in the refining technology of cellulosic textile mattrials, in paper making technology and in the preparation of insoluble starches. They are compounds of the type:

Y-N-H ₂ ♦ Cl (II) where

Y is -CH ₂ -CH = H _2, or

OH Cl

Hp H ₂ and R 3 are alkyls ·

Trimethylammonium compounds of this type have found industrial application so far · Some environmental problems »especially unpleasant odor, prevents wider use ·

Therefore, new compounds have been protected where one of the methyls is replaced by benzyl;

The compounds according to the invention are characterized by a higher activity than the compounds of the general formula (II) and have no ecological disadvantages.

The introduction of two reactive groups Y significantly increases the use of preparations and allows them to be used for some other technologies, which are not feasible with one-function preparations · It is mainly the sulphurization of cellulose, improving its creasing and crease recovery properties and the ability to other than anionic dyes.

Compounds of the general formula (I) with the group -CH ₂ -CH-CH ₂ can be prepared from aqueous solutions

OH Cl salts of the heterocyclic compounds of Table 1 by treatment with epichlorohydrin

/ СН CH ^< \ iH f 1 CH CH | 2+ SO ₄ ² “+ 2 CH, -CH-CH, C1 V - z ^c 4 CH N-CH _O -CH-CH _O II 1 ² 1 1 ² CH CH OH OH CH ₀ -CH-CH, ² L or ² L or J

Compounds with a five-membered ring can be prepared, for example, from imidazole in an aqueous medium according to the scheme:

Cl + Cl

Compounds of formula (I) with CH ₂ -CH-CH ₂ - can most preferably be prepared by treating alkali hydroxides on compounds of formula (I) with CH ₂ -CH-CH ₂ -, Cl OH

The molar ratio of the reacting components produces compounds of the general formulas

CH ₀ -CH-CH ₀ -M-CH ₀ .

\ ^2/2 by ²

CH _O CH CH _O CH _O -N-CH-CH ² _O ² \ / ² O

k +

wherein the meaning of M, к, X, n is the same as that of formula (I).

Practical possibilities for preparing the compounds of the invention are set forth in the Examples.

Example 1

An enamelled duplicator of 100 L having a reflux condenser and stirrer was charged with 203 kg of 36% hydrochloric acid. While cooling, 80 kg of pyrimidine are gradually added so that the temperature does not exceed 70 ° C. After addition of the pyrimidine, the temperature of the solution was adjusted to 40 ° C and 184 kg of epichlorohydrin were gradually introduced at this temperature. Cooling keeps the temperature of the reaction mixture between 40 and 55 ° C. After all the epichlorohydrin was added, cooling was stopped and the temperature of the reaction mixture rose to 80-85 ° C. The reaction is then complete and after 30 minutes from reaching the maximum temperature, the reaction mixture is cooled to 25-30 ° C. The reaction resulted in an aqueous solution containing 70% 1,3-bis (3-chloro-2-hydroxypropyl) pyrimidinediyl chloride. Theoretical yield 72.3%.

The amount of active ingredient was determined by argenometry, based on the difference between total chlorine (after alkaline hydrolysis) and chloride ion determination.

Example 2

Place in a three-necked glass flask with reflux condenser, stirrer and thermometer

196 g of 50% sulfuric acid. Then 82 g of 1-methylimidazole are added gradually. The temperature of the reaction mixture is adjusted to 80 ° C and 184 g of epichlorohydrin are metered in at this temperature. The epichlorohydrin influx rate is selected such that the temperature is maintained at 80-90 ° C. After all the epichlorohydrin was added, the mixture was allowed to react for 60 minutes. The reaction mixture was cooled to 20 ° C and 160 g of 50% NaOH was gradually added at this temperature. During the reaction, the temperature must not exceed 25 ° C. After all the NaOH solution has been added, the mixture is allowed to react for 30 minutes while cooling. If the temperature of the reaction mixture does not increase spontaneously after cooling, the reaction is complete. Amount of active substance

The 1,3-bis (2,3-epoxypropyl) -1-methyl-imidazolinediyl chloride is determined by titration with a hydrochloric acid solution. The active substance content in this case is 67.2% - Theoretical yield 71.1%.

Example 3

In a glass bank according to Example 2, 80 g of pyrazine are dissolved in 120 g of 50% acetic acid. The temperature of the solution was adjusted by cooling to 25 ° C. 184 g of epichlorohydrin are slowly introduced at this temperature. The temperature of the reaction mixture begins to rise spontaneously. By reducing the epichlorohydrin inflow and cooling, the temperature is maintained at 25-30 ° C. After addition of the whole epichlorohydrin fluid, cooling is discontinued and the temperature rises spontaneously up to 65 ° C. The mixture is allowed to react for 60 minutes at this temperature. This completes the reaction. The retention mixture contained 72.3% 1,3-bi8 (3-halo-2-hydroxyolyl) pyoaziodiyliacetate. The theoretical yield was 76.1%.

Example 4

In the laboratory apparatus of Example 2, 116 g of 1,4-dimethylpiperazine are dissolved in 203 g of 36% hydrochloric acid. The temperature is adjusted to 30 ° C by cooling and 184 g of epichlorohydrin are gradually added over a period of 2 hours while maintaining the temperature of the reaction mixture between 30 and 40 ° C. After addition of the entire amount of epichlorohydrin, the cooling was interrupted and the temperature of the reaction mixture rises to 80 DEG C. As soon as the temperature of the mixture begins to decrease, the reaction is complete. The theoretical yield of 1,4-bis (3-chloro-2-lyrdroxyppoopyl) -1,4-diyleylpiperaziodiylSulfuride is 73.9%, actually found 71.1% ·

Example 5

In a glass apparatus according to Example 2, 80 g of pyridazine are dissolved in 203 g of hydrochloric acid. Ex. 184 g of epic-chlorohydrate are gradually added at 30 ° C. The temperature of the mixture is maintained at 35-45 ° C by cooling. Upon addition of the entire amount of epichlorohydrin (2 h), walking is stopped and the temperature spontaneously rises to 85 ° C. At this temperature, 30 more minutes are allowed to react. The theoretical yield of 1,2-bis (3-chloro-2-ydorxypropyl) pyridazinediyl Snlorides is 72.3% · Indeed found 65.7%.

Example 6

In a glass laboratory apparatus according to Example 2, 68 g of pyrazole is dissolved in 98 g of 50% sulfuric acid. The temperature of the sulfur is adjusted to 80 ° C and 184 g of epichlorohydrin are gradually added over 2 hours. The reaction temperature was maintained at 80-90 ° C by cooling. After addition of the entire mixture, the reaction mixture was allowed to react at 90 ° C for a further 30 minutes. The theoretical yield of 1,2-bi8 (Зc-hly-propyl) pyoazoline sulphate is 86.3% · Indeed found

79.2%.

Example 7

According to the procedure described in Example 6 and with the reduction of other chemicals, 70 g of pyrazoline were used instead of pyrazole. The theoretical yield of 1,2-bis (3-chloro-2-hydroxypropyl) pyrazolioisulfate is 86.1%, compared to 78.8%.

Example 8

In the apparatus of Example 2, 100 g of 1,2-diethylpyrazolidios were dissolved in 240 g of acetic acid 50%. At 50 [deg.] C., 184 g of epic-chlorohydria are gradually added over 2 hours. After adding the whole. The amount of epichlorohydrin is allowed to react for 30 minutes at 60 ° C. The theoretical yield of 1,2-bi8 (3-halo-22-hydroxypyropyl) pyoazolidinediylSuiacetyl is 76.8%. Found '69.2% «

Examples of compounds of the invention are shown in Tables I and 11.

Table I

1 R ^{/ C} % ^Z ' ^N IR ² J i 3 1 j ⁴ R VV ⁴ R 1 R R .R ^X C --- 2 V _r z ^R c ---- c R R R R V v R X Al ⁵ II II Л / I ⁶ Rj II R | c --- c ⁷ 4 i C --- N β II II cc R ^X R and R R 1 R 1 R

R is hydrogen or alkyl having 1-4 carbons

Table II

Examples of compounds of the invention:

1,2-bis (3-chloro-2-hydroxypropyl) pyridazinediyl sulphate,

1,2-biβ (2,3-epoxypropyl) pyridazinediyl chloride,

1,3-bis (3-chloro-2-hydroxypropyl) pyrimidinediyl sulphate _>

1,3-bis (2 _> 3-epoxypropyl) pyrimidinediyl chloride,

1,4-bis with (3-chloro-2-hydroxypropyl) pyrrole; jindiylium chloride,

1,4-bis (2,3-epoxypropyl) pyrazinediyl sulphate,

1,4-dimethyl-4-1,4-bis (3-chloro-2-hydroxypropyl) piperazinediamine sulphate,

1.2-bi g (3-chloro-2-hydroxypropyl) pyrazolinium chloride,

1,3-bis (2,3-epoxypropyl) pyrazolinium sulphate,

1- _> 3-bis (3-chloro-2-hydroxypropyl) imidazolinium acetate _>

1,3-bis (2,3-epoxypropyl) imidazolinium sulphate,

1,2-bis (3-chloro-2-hydroxypropyl) -1-methylpyrazolidinium chloride,

1,2-bis (3-chloro-2-hydroxypropyl) -1,2-dimethylpyrazolidinediamine sulphate ·

Claims (3)

SUBJECT OF THE INVENTION A compound for the cationization of polymeric materials of general formula (I) k _χ η (I) where k is an integer of 1 or 2, n is an integer of 1, 2 or 3, X is an anion of a strong inorganic or organic acid, M is a five-membered or six-membered two-nitrogen cycle, derived from pyrazine, piperazine, pyridazine, pyrimidine, pyrazole, pyrazoline, pyrazolidine and imidazole, wherein each hydrogen atom may be substituted with alkyl or hydroxyalkyl having a number of ulxLs of 1 to 4, Y is a group -CH _O -CH-CH ² R ² or -CH ₉ -CH-CH- Oh (C attached to the nitrogen atom of the group M. A process for the preparation of compounds of formula (I) wherein Y is -CHg-CH-CHg OH Cl and the other symbols are as defined in claim 1, characterized in that epichlorlydrin is treated with aqueous solutions of salts of strong inorganic or organic acids and of pridazine, pyrazine, pyrimidine, piperazine, pyrazole, pyrazoline, pyrazolidine or imidazole or their alkyl derivatives. or hydroxyalkyl derivatives wherein the alkyl or hydroxyalkyl has at most 4 carbons. 3. The process of Item 1 for preparing compounds. of formula (f), wherein Y is -CH 2 -CH-CH 2, characterized in that the compounds of formula (I) are treated with alkali, O wherein Y is -CH 2 -CH-C 1 OH 6 Cl