SU1016314A1 - Process for producing polyester urethanes - Google Patents

Abstract

METHOD OF OBTAINING POLYESTERURATANANV through interaction c. (a melt of a hydroxyl-containing glycosyl ester with hexamethylene diisocyanate in the presence of a diol, characterized in that, in order to impart biodegradable properties to the final product, a hydroxyl-containing oligoester is used as a hydroxyl-containing oligoester with a compound of the general formula pf-f 0-ch-co) co-ch-O ti n, where c 0-20; E 0-20 (where L 0, t О,, 1. 0); R-Mi CHjiliK rn, or R R-CH5V. CHv § -№) 2r {l «2i3, SI, H ca2) (CH2-o-i

Description

This invention relates to the synthesis of polyether urethanes that can be used in medicine, for example; as a samorasshansmidkhs surgical materials. A known method of producing polyether urethanes by reacting hydroxyl-containing oligomers of an ester- type, with a diisocyanate in the presence of a diol l3. A disadvantage of the known method of producing polyether urethanes is their unsuitability for use in medicine as biodegradable materials. The most similar in technical essence to the proposed method is the method of obtaining polyether urethanes by melting complex hydroxyl-containing oligophira with the hexamethyleni-iso-isocyanate iannidar i'm i'm i'm io4 i4i4i4i4i-4y; As a complex hydroxyl-bearing oligo-efir, a condensation product of dicarboxylic acids and a diol, for example, adipic acid and ethylene glycol in the C2 melt, is used. A disadvantage obtained in a known manner, polyetheruretans, is the absence of bonds in their macromolecules capable of undergoing enzymatic biodegradation. The aim of the invention is to impart biodegradable properties to the final product. This goal is achieved by the fact that, according to the method for obtaining polyetheruretans, by using a compound of the formula RK II Jlf (Jfl CO- (H - O -) - H, de H 0-20 0-20 (1C O , С О,) е О, 1 О R - H R - CHj or RRH, or Р Р - СНэ,, .СНз R- - 1 5Н21г rl iHjts, (jHj iCH2) 2-iH -, - ( SH2) f-0- (and the process is carried out in steps: at 90-120 s for 0.5-1 h, at 160190 ° C for 4-5 h. The block-polymer structure of the obtained polymers is confirmed by studying their solubility in organic solvents and by comparison with solubility with the corresponding homopolymers, as well as the study of their IR and NMR spectra. The synthesized polyfiruretans exhibit film- and fiber-forming properties. They dissolve in many organic diluents, forming highly concentrated solutions, and elastic films were obtained from these solutions by pouring onto glass substrates. having a tensile strength of 300,400 kg / cm2 and a tensile elongation of 100,200%. The structure and characteristics of used polyester resins are given. in table.1. Table 1

Example 1. In a three-necked, equipped with a stirrer, the input and output for argon is placed 0.005 mol of oligomer SE-1-0 (table 1) and the flask is heated to 120-125 ° C. To the resulting melt, half (0.05 mol) of hexamethylene diisocyanate is added (the total amount of hexamethylene diisocyanate is 0.1 mol). The melt is stirred for 30 minutes, after which the temperature is lowered to 90-10 ° C and Qf095 mol of the extender (diol) S 1,3-propanediol is introduced. The mixture is refilled again and stirred for another 30 missions, then carefully, at times, the remaining amount (0.05 mol of di-isocyanate) is added. The reaction mixture thickens rapidly and is not stirred. The temperature is slowly raised until the reaction mixture is easily stirred and kept at this temperature for 4 hours. The melt is poured onto a Petri dish and cooled. The reduced viscosity is 0.64 dl / g in m-cresol, t 2US, С at 0.5 g / dL. . Example 2. In a three-necked flask equipped with a stirrer, an inlet for argon was placed with 0.0–5 mo of SE-06-04 oligomer, the flask was heated to 9Q ° C, and half of 0.05 mole of hexamethylene diisocyanate was added to the melt. The reaction mixture is heated to 30 minutes, then cooled to 90 ° C and 0 mol of propane diol is introduced, heated to 120 ° C again for 30 min to 90 ° C and the remaining amount of diisocyanate is carefully added. The mixture is slowly heated to 1 ° C, and the temperature is increased so that the flask has a well mixed melt. The reaction mixture: you are kept at for 5 h after it is poured onto a Petri dish and cooled. Chpr 0,58 dl / g in a mixture of tetrachlorotane: phenol (3: 1), t ° 25s, With 0.5 g / dl. Example 3. Synthesis of the polymer was carried out in accordance with the procedure given in c. Example 2, with the only difference that instead of oligo-, measure СЭ-Об-04 (table), use oligomer СЭ-05-05 (table 1), and as a chain extender instead of 1.3 propandiol use ethylene glycol 0.52 dl / g in a mixture of tetrachloride ztan: enol (3: 1), t 25 "s, C 0.5 g / dl. Example 4. Synthesis of the polymer was carried out in accordance with the procedure described in example 2, with the difference that instead of the opomer SE-06-04; take oligomer SE-05-05,. 0.5d dl / g in a mixture of tetroyelorethan with phenol 3: l, t ° 25 ° C, 0.5 g / dL, Example 5 Polymer synthesis is carried out in accordance with the procedure given in Example 2 with the difference that instead of an oligomer of SE-06-04 an oligomer of SE-04-05 is taken, “Injp 0.4 dl / g in a mixture of tetrachloroethane With phenol 3: 1, t, C 0.5 g / dl. EXAMPLE 6 Polymer Synthesis was carried out in accordance with the procedure described in Example 2, with the difference that instead of the SE-06-04 oligomer, the SE-0-1 oligomer was taken to be 0.48 dl / g in a mixture of tvtssloroethane and phenol ( 3: 1), t® 25 ° С, С 0.5 g / dl. Example 7. Synthesis of catalyst size is 1 according to the procedure described in example 1, with the difference that instead of oligomer СЭ-1-0 take SP-1-0 oligomer (Table 1) H «p 0.60 dl / g in m-cresol, C 0.5 g / dl. The synthesis conditions and the main characteristics of the polyether urethanes obtained are given in Table 2.

Thus, the proposed method of producing polyether urethanes containing oligoester blocks on the chain of ici-hydroxy acids in the chains of macromolecules provides the following advantages: using polyhydric esters based on polyhydroxy esters as the starting resin allows zi capable of underwater fermentation biodegradation

The resulting polyesterutanes are useful in medicine as self-absorbing materials, since they contain biodegradable cl-spherical bonds in the chains of macromolecules;

the solubility of the obtained polyether urethane in organic solvents, which facilitates their processing into articles - films, porous materials, etc.

Claims (1)

METHOD FOR PRODUCING POLYETHYRETHRETANES by reacting in a (melt of a complex hydroxyl-containing oligoester with hexamethylene diisocyanate in the presence of a diol), characterized in that, in order to give the final product biodegradable properties, a complex hydroxyl-containing oligoester is used as the complex compound. "B * ^ - (0 - ^ - 60) ^ 0 ^ 0 - (- 00 - ^ - 0¼ ^ where k = e = (and R-wj 0-20; 0-20 x = o, him, e = o, k * o); or R = R'-H, or a ”- - (“ ЧЬ 6Й ₃ 4 ^ 2) 2 - (^ 1 -, - ^ 2-0- ^ 2) 2, and the process is carried out stepwise: 90-120 ° С for 0.5-1 hours _at a 160 190 ° C for 4-5 hours.