SU1016317A1 - Process for producing polyaminoesters - Google Patents

Abstract

METHOD OF OBTAINING POLYAMINOATHER by the interaction of aliphatic. diamines and diacryl diesters, in that, in order to simplify and speed up the process, the interaction is carried out in an aqueous medium at (-20) - (-5) with constant stirring.

Description

This invention relates to the synthesis of high molecular weight compounds, namely polyamino esters, which can be used in medical research and in the chemical industry. . Methods are known for the preparation of polyamino esters by the interaction of aliphatic (divoric) diamines and diakrilovy diesters under conditions characteristic only for each pair of comonomers. The reaction is carried out in a rat thief, as a solvent, soldered. ethanol. The temperature cutting of the polyreaction depends on the properties of the starting components, such as the basicity of the diamines, the activity of double bonds, steric factors, and, as a rule, lies in the range from room temperature to the boiling point of the solution (and above). The same factors as the temperature regime determine the reaction time: a sufficient degree of conversion is achieved in the range from several hours to a day. It should be noted that identifiable poly products were obtained only with the use of divoric diamines Cl. The disadvantages of these methods are the need for thorough purification of the solvent, carrying out the reaction in an inert gas atmosphere, and a sufficiently long reaction time. The closest to the proposed technical essence and the achieved result is the method of obtaining polyamino esters of the interaction of aliphatic diamines and diakryl diesters. The ethylene dicrylate solution of icol in anhydrous ethanol is freed from dissolved air by repeatedly blowing nitrogen into the solution followed by evacuation. Then, in a stream of nitrogen, the amount of piperazine, strictly equimole with respect to the diester, is added to the reaction medium. The mixture is incubated for four hours at room temperature under a nitrogen atmosphere, then poured into an excess of anhydrous ether, the precipitate is filtered and dried at 50 ° C and 0.5 mm Hg. 2. The disadvantages of the known method are the necessity of using an inert gas, dry solvents of the precipitant, a longer reaction time, the method does not provide an opportunity to obtain a polymer based on primary aliphatic diamines. The aim of the invention is to simplify and speed up the process. This goal is achieved by the fact that, according to the method of obtaining polyamino esters by the interaction of aliphatic diamines and diacryl diesters, the interaction was carried out in an aqueous medium at (-20) - (-5) ° C with constant stirring. The method is carried out as follows. A solution of the amine in water is poured into a flask or a glass with a stirrer, cooled in a bath with a temperature of (-20) -. (-5) ° C, then with constant stirring, an exactly equivalent amount of diester is added. Stirring is continued for 15-30 minutes. The formed polymer is isolated in two ways: the reaction mass is acidified by adding hydrochloric acid to pH 3-4 and poured into acetone, the precipitated precipitate is washed with acetone and filtered, or the acetone is decanted; the polymer is dried under vacuum; from the reaction mass, the water is removed by freeze drying. Our studies have shown that the implementation of this polyreaction in an aqueous medium at temperatures that are common for such reactions, is impossible due to the hydrolysis of the resulting polymer. Conducting the reactions at sub-zero temperatures below (-2) - (-5) ° C makes it possible to isolate high molecular weight polyaminoesters with practically quantitative yield. The reaction rate with decreasing temperature increases. At temperatures below (-20) ° (-25) ° C, it is not practical to carry out the reaction, because, firstly, it complicates the cooling process, secondly, at (-20) ° C, the polyreaction rate is so high that after 5-10 min after discharging the reagents, detecting double bonds in the reaction system is not possible. The need for constant mixing (at least at the moment of mixing the reactants) is associated with heterogeneity. Both the amine group and the ether group enter the unit of the obtained polyaminoether, which predetermines the unique properties of these substances: depending on the pH of the medium, keep its structure completely without any changes, or quickly expand to low molecular weight products. In addition, these compounds are ionic polymers, which also has a significant impact on both their properties, namely the process of their self-destruction, and the scope of their application. In other words, in this case, we are dealing with ionic-polymer compounds that are self-degradable and manageable, which makes it possible to use these compounds in the chemical industry (as complexons, coagulants, surfactants, and so on. e.) and in medicine, for example, in quality carriers for drug paraty. In particular, the proposed allows to obtain a polyamine of the formula i-iiN-Br "H-H2 CHg-CH 0 (3 II 0-B2-0,,"; where R2 (2) n.,. FiH2-CK, "112-II about: B2-o, where,. V a 4HC2H4 n. "-Tsrif-dHx-CHa- o (; II

1H2-JH2-, d -Sh-K1-: K11 CH2-CIl2-H2-JH2-ra.-Bt- «HC-0-R2-01i0 (

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-1TH-E1-MH-eH2-CHj-C-OH + OH-Bj-OH + HO-C-CHf CHj-Hli The break time of 40% of the ester bonds in the polymer at pH 9 is 20-30 minutes (Fig .one). Fig. 1 shows the dependence of the degree of conversion in the reaction of polyaminoesters on time (polyaminoesters based on: 1-piperazine and three ethylene glycol diacrylate; 2-ethylene diamine and trite ethylene glycol diacrylate; 3-piperazine and diacrylate lat butanediol. T) j in Fig. 2 PMR spectra of piperazine and triethyl glycol diacrylate; figure 3 - the same on the basis of ethylenediamine and diacrylate triethylene glycol; figure 4 is the same, based on piperazine and butanediol diacrylate. PRI mere. 50 ml of a 1 M solution of piperazine in water are cooled in a bath of {-20) ° C, 12.9 g of triethylene glycol diacrylate are added with constant stirring, followed by stirring. After 5-7 minutes, the reaction mixture turns into a thick paste. Then dilute the portion of the product.

I t Q-O-O. Polymers are white crystalline powders (with the exception of gels derived from polyamines and glycol and ethyl glycol diesters), soluble in organic polar solvents and in water, with a characteristic viscosity measured in chloroform, Laying in the range of 0.3-0.8 dl / g. The data of elemental analysis and GSR spectra completely confirm the proposed structure. In addition, the complete hydrolysis of polymers leads to the isolation of products - the corresponding alcohol and acid, which are easily identified -. c. These polymers readily hydrolyze in a neutral and alkaline medium, while in an acidic environment, oii are relatively stable. The destruction of the polymer proceeds according to the scheme. toj I hydrochloric acid to pH 3-4; and the acidified reaction mixture is poured into acetone. The precipitated polymer is washed with acetone and dried under vacuum at an acid temperature. The second part of the reaction mass is subjected to freeze drying. The non-salt form of the polyamino ether has fi when in chloroform 0.6 dl / g. The total polymer yield is quantitative. Example 2. The entire procedure for mixing equimrillant amounts of pea gates is similar to that described in Example 1. Ethylenediamine is used as the diamine, and ethylene glycol diacrylate is used as the diamine. The reaction is carried out at a temperature of (-15) € for 20 minutes. The resulting product is also isolated in acetone and / or by freeze drying "with 0.4 dl / g in chloroform. Both p and m 3. 50 ml of a -0.1 M solution of} 1-ethyleneimine in water is cooled to (-5) ° C and then 12.9 g of triethylene glycol diacrylate are added with stirring. After 10-15 minutes, the reaction mass turns into an elastic dense gel. It is treated with water, acidified with hydrochloric acid to pH 3-4, and then with acetone, and then dried in vacuum at room temperature. The reaction product is a swollen, water-insoluble gel. . Example 4. Mixing of reagents is carried out in a manner similar to what was described in Example 1. Piperazine is used as the diamine; butane diol diacrylate is used as the diester. The reaction is carried out with constant stirring for 30 minutes at a temperature of (-10) ° C. A portion of the product is isolated in acetone, the other portion by freeze drying. 1 when in chloroform 0.35 DL / g Polyproduct yield is quantitative. Example 5. The entire procedure for mixing the reagents is similar to that described in Example 1. In this example, ethylene 1 is used as the diamine. diamine; triethylene glycol diacrylate as diester. The obtained polyproduct was isolated both in acetone and by freeze drying, t.t at 30 ° C in chloroform 0.43 dl / g. The elemental composition of the poly product is theoretically & 1 theoretically calculated. The destruction of the polymer is shown in curve 2 (figure 1), the spectrum of the PMR {figure 2). The proposed method allows to obtain a series of ionic polymers having a controlled property of self-destruction. Oco6Qe attention should be paid in this case to the high possibility of obtaining identifiable polyamino esters based on primary diamines, which could not be done by a known method. The proposed method allows to simplify the process (zgilen ethyl alcohol as a solvent for water, no need to use an inert gas and dry solvents and a precipitant) and speed it up compared to the known method.

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Claims (1)

METHOD FOR PRODUCING POLYAMINOESTERS by aliphatic interaction. diacrylate diamines and diethers of tlichayuschiys I that, _hours in order to simplify and expedite the process, the reaction is carried out in an aqueous medium at (-20) - (-5) ° C with constant stirring. m th ('ns'' ⁰ FIG. /