SU998469A1 - Block-copolymers as film formers for gas separating membranes - Google Patents

Description

This invention relates to a high molecular weight compound based on a triazine-containing diol, oligodimethylsiloxanediol and organic diisocyanate, which can be used as film-forming materials for gas distribution membranes.

Known polytriazine siloxanes obtained by the interaction of 2-diphenylamino-4, b-dichloro-1,3,5-triazine with bis (fenylaminomethyl) dimethylsiloxanes

As a result, oligomers are obtained, which are powder or rubbery mass and do not have film-forming properties, which limits the range of their possible use.

Also known polysiloxane, obtained by the interaction of the silicone diol with organic diisocyanates, followed by curing the obtained prepolymer with organic diamines. The resulting β-films can be used to separate gases. 23 The disadvantages of polymers are their insolubility in organic solvents in the cured state of the scientific research institute, as well as low selectivity coefficients.

Triazine-containing polybutadiene-urethane block copolymers are known, obtained by reacting a mixture of oligobutadienediol and a triazine-containing diol with a diisocyanate in an organic solvent medium at 40-80 ° C in the presence of a ylovo annon-

10 ounces. These polysimers have film-forming properties and horizon solubility in organic solvents, which allows them to be used to obtain a gas separator 5 Membrane Z.

However, the membranes based on them are characterized by insufficiently high gas permeability and sepa ration values.

20

The purpose of the invention is to obtain static block copolymers - polytriazinesiloxanurethanes, which can be used as film-forming materials for gas-distributing dividing membranes based on them, which have high values of gas permeability and selectivity

The goal is achieved by a new chemical structure, which is expressed

30 formula

. -NH-5-NCH3-; (CH2) i, -1ts (Gusi2- /; J - (ong) b to 1-5; P 1-2 p 6-40; m 1-3; e - 6.8-43.0,. Molecular masses 34000-78000. Polymers are obtained by reacting a triazine-containing diol and oligo-dimethylsiloxane diol with an organic diisocyanate at 50-90 ° C in a dipolar aprotic solvent in the presence of an organotin. diphenylmethane-, 2, 4-toluene 1,6-hexamethylene diisocyanates. Aprotic dipolar solvent is used as a solvent, for example p dioxane or chlorobenzene. If dioxane is used, the polymer from the reaction mass is precipitated with water, and if chlorobenzene is used, hexane is used. The reaction is carried out depending on the nature of the reagents used at 50-90 ° C for Hb in the presence of 0.01 -0.1% by weight of an organotin compound, for example, dibutyl dilaurinate tin. Polyriazine siloxanurethanes are synthesized by fast dosing of a solution of diisocyanate into the diol mixture in a solvent. Under these conditions, polymers with a statistically distributed triazine and are obtained. silicon organic fragments in the chain. Block copolymers (Regularly distributed fragments can be obtained by reacting oligodimethylsiloxane diol with a preliminarily obtained macrodisocyanate based on a triazine-containing diol and diisocyanate, taken in a desired ratio. Polyriazine siloxanurethanes have a good solubility in a wide range of organic organic solvents.

; m. form, acetone, dimethylformamide, etc.), from the solution of which get durable elastic transparent films. The structure of the obtained polytriazinesiloxanes is confirmed by the data of elemental analysis and IR spectroscopy. The IR spectra of polymers contain absorption bands corresponding to vibrations of CrN bonds in the (1550, 1420) cycle, in the C-0 2,4-substituents of the triazine cycle (1080 cm-); N-H in the urethane group (3450-3250 cm-); C "0 in the urethane group (1720 cm); С-Н. . in CH ,, - groups (2960, 2870 cm); Si-O in oligodimethylsiloxanediol (1050-1012 cm-) and Si-CH in oligocymethylsiloxanediol (1260, 810 cm). Example 1. Synthesized polymer PGS-1 of general formula 1, where B 43. In a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, a protected calcium chloride tube, a dropping funnel and a tube for the introduction of argon are placed 1.3720 g (3.73-U mol) 2,4-bis (2-hydroxyethoxy) -6-diphenylamino1, 3,5-triazine; 2.1720 g (3.73 oO mol) of oligodimethylsiloxane (OKD) with a molecular mass of 946, previously evacuated at 80 ° C for 3 hours; 2, O-10-g dibutyl-dylaurinate tin (DBDLO) and 4 ml of freshly dissolved dioxane. To the mixture, heated to, for 5 minutes, a solution of 1.8641 g (7.46.) Of 4,4-diphenylmethane diisocyanate (DFMDI) in 7 ml of dioxane is metered from the dropping funnel. The reaction mixture was kept at 50 ° C for 3 hours, and then at another 2 hours. After cooling, the contents of the flask were diluted with dioxane and planted in distilled water. The polymer obtained is filtered off, washed with water and dried under vacuum at constant weight. The polymer yield is 6.4 g (-94.6% of theoretical yield); Reduced viscosity: 0.86 dl / g (determined for a solution of 0.5 g of polymer in 100 ml of ocean at); molecular weight 78,000. Elemental analysis. Found,%: C, 51.45; H 6.61; S | 16.13. Calculated,%: C 50.88; H, 6.20; Si 16.96. Example 2. Synthesis of polymer PTS-2 of General formula 1, where p-1; (, 5.. To a flask was charged 2.4071 g (6.50-10 mol) 2/4-bis (2-hydroxy ethoxy) -6-diphenylamino-1,3,5-triazine; 3.1005 g (3, 29 -10 mol), a molecular weight of 946; 3.2 k DBLO and 14 ml of dioxane. To this mixture, 1.6573 g (9.87: 10 mol) of 1,6-hexamethylene diisocyanate are added over 5 minutes. The mixture was stirred at 50 ° C for 3 hours and for another 2 hours. After isolating the product by the method described in Re 1, 6.7 g (93.0% of theory) of a polymer having 0.56 dl / g and a molecular weight of 55,200 are obtained. Elemental analysis. Found,%: C 49.72; H 6.9; SI 13.82. Identified,%: C 49.48; H 7.10; Si 14.02. P r and measures 3. Synthesis of PTS polymer -3 total f rmules 1, pt1; Br28.4. iJ flask placed J., 3578 g (5.03) 2,4-bis (2-hydroxyethyl but) -6-diethylamino-1,3,5-triazine; 4.7572 g (5.03.) OKD molecular weight of 946; l, 8ilOr DBDLO. And 4 ml of dioxane. To this mixture is added a solution of 2.5144 g (10.1.) DFDMN in 7 m of dioxane for 5 minutes The reaction mixture was stirred at 50 ° C for 3 hours and then at 70 ° C for another 2 hours. After separation of the product, 8.2 g (95.5% of theory of a polymer having 0.54 dl / g and a molecular weight of 51500 are obtained). Elemental angshiz. Found,%: C 48.71; H 7.16; Si 16.98. Calculated,% C 48.19; H 7.10; Si 17/80. Example 4. Synthesis of polymer PTS-4 of General formula 1, where Pfl; p-10; , 2. 1.0302 g (3.65 (10 mol) to 2,4-bis (2-hydroxyethyl but) -6-piperidino-1,3,5-triazine; 3.4602 g (3.65. Icr mol A) a molecular weight of 946, 3.0-10 dBDLO and 5 ml of dioxane. Then, a solution of 1.8275 g (7.31 mol) DDMDI in 6 ml of dioxane is dosed into this mixture, heated to 6 ml. At this temperature, the reaction mixture is kept 4 h. 6.0 g (95.3% of theory) of polymer having fJppHb of 0.62 dl / g and molecular weight of 64,000 were isolated. Elemental analysis Found:% C 48.83; H 6.87; Si 17.41.% Calculated: C 48.55; H 7.05; Si 17.82. Example 5. Synthesis of the polymer PTS-5 of the general formula 1, where p2, pgbb; 19.5. 9446 g- (3.82 u) 2,4-bi (hydroxymethylamino) -6-phenyl-1,3,5-triazine; 4.981 g (7.64 {O mol) OKD with a molecular weight of 652; 2.0010 g (11.5 ") of 2,4-toluene diisocyanate and 12 ml of dioxane. The reaction mass is heated to 70 ° C for 10 minutes, 4.0 are added. DDODO in 2 ml of dioxane and the reaction is continued at this temperature for 5 hours. 4.3 g are obtained (92.8% of theory) of a polymer having G of 0.43 dl / g and a molecular weight of 40,500. Elemental analysis. Found,%: C 48.05; H 7.29; Si 20.82. Calculated,%: C, 48.70; H 7.02; Si 20.39. Example 6. Synthesis of polymer PTS-6 of General formula 1, where m 3; ,eight. . Into the flask is charged 1,3359, g (4.47-lQ mol) 2,4-bis (3-hydroxypropyl-M-methylamino) -6-ethoxy-1, T, 5-triazine; 1.3410 g (5.36-) DFMDI and 10 ml of freshly distilled chlorobenzene. The mixture is heated to and kept at this temperature for 3 hours. After this, a solution of 2.8195 g (O, mol) of molecular weight 3168 and 3.8 AC 10 DBLO in 3 ml of chlorobenzene is added dropwise. Then the reaction mixture is heated to and stirred at this temperature for 5 hours. The resulting reaction mixture is treated with 1 ml of ethanol and planted in hexane. 4.3 g (78.4% of theory) of polymer are obtained, having a V of 0.36 dl / g and a molecular weight of 34,000. Elemental analysis. Found,% C 53.16; H 6.89; Si 19.62. Calculated,%: C 54., 65; H 6.01; Si 21.55. Durable elastic films are obtained from the polymers obtained by casting from a solution in chloroform. The gas permeability of the indicated membranes with a thickness of 80-100 Cosm for CO, 0 and Nj is tested by the manometric method. Values of gas and gas coefficients. Cement properties and selectivity for polytriazinsiloxanurethanes are presented in Table. one.

The physicomechanical characteristics of polytriazinesiloxanurethanes are given in table. 2

As can be seen from the table. 2, the synthesized static block-comolomers polytriazinsiloxanurethanes have high values of selectivity gas permeability coefficients. Use of Source Triazine-Containing Diols with Various Substituents

allows wide variations. To improve both gas permeability and selectivity, as well as physical and mechanical characteristics of membranes based on them. Thus, polytriazinesiloxanurethanes possess a complex of prices; properties that allow them to be used as film-forming materials for gas distribution membranes, which have high values of gas permeability and selectivity coefficients.

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Famous

Table 1

10.2

5.2

4.7

Polytrienesiloxanurethane

PTS-1 PTS-2 PTS-3 PTS-4 PTS-5 PTS-6

Claims (1)

Invention Formula Statistical block copolymer of the general formula table 2 Relative extension, % 55 160 245 220 275 320