SU739068A1 - Aromatic diamines containing urea groups - Google Patents

Description

The volume is a 0.1 Hi perchloric acid solution in dioxane, the titer of which was determined by a specially synthesized model compound.

Example 1. In a 0.5 L chemical beaker, place a solution of 26 g of m-phenylenediamine {0.25 mol) in 24 ml of acetone. Under vigorous stirring, a solution of 3.5 P1 (4.27 g, i.e. 0.024 mol) of 2,4-toluene diisocyanate in -21 ml of acetone is added to this solution drop by drop from a dropping funnel. After the addition, close the glass with a film and leave it overnight. Then 200 ml of water are added to the semi-liquid contents of the glass, allowed to stand i ° h and filtered through a large-porous (160) glass filter. The filter cake is washed with 300 ml of water and then dried in air and at 60 ° C in a vacuum oven (at 8-20 mm Hg). For bh, a constant be reached is 8.78 g (calculated yield, based on the receipt of the power of fault, p 1, is 9.35 g). Melting point 284 C. Found,%: C 63.95; H 6.19; N 20.2. Equivalent to 202.

Calculated (for diamamine, n 1),%: C 64.60; H 5.60; N 21.5. Equivalent to 195.

Example 2. In a 2 L chemical beaker, place a solution of 44.5 g of 2,4-toluenediamine (0.365 mol) in 120 ml of acetone. To this solution, with vigorous stirring, a solution of 10.4 ml (12.7 g, i.e., 0.073 col.) Of 2,4-toluene diisocyanate in 60 ml of acetone is added dropwise from the dropping Voroki. After the addition of this solution is completed, stirring is continued for another 15 minutes, after which the beaker is covered with a film and left overnight. Then, 900 ml of water is added to the contents of the glass, which is a solution with precipitate, stirred and left to stand for 5 hours. The precipitated yellowish precipitate is filtered off, washed with 100 m of water and dried in air, and then under vacuum. cabinet for 6 hours. Yield 30.8 g. Estimated yield, based on diamultipurity, p 1, is 30.5 g. Melting point 272 ° C. Found,%: C 65.4; H 6.50; N 19.48. Equivalent to 211.5.

Calculated (for diamamine, n),.%: C 66.0; H 6.20; N 20.0, Equivalent to 209.

Example 3. A solution of 14.8 g of 2,4-toluylene diamine (0.12 mol) in 40 ml of acetone is placed in a 0.8-liter beaker. With it under vigorous stirring, a solution of 3.5 ml (4.27 g, i.e., 0.034 ml) of toluylene diisocyanate (a mixture of isomers 2.4 and 2.6 in a ratio of 80:20

in 20 ml of acetone. After closing the glass with a film, let it stand for 1.5 hours, then 300 ml of water are added to the thick contents of the glass and stirred. After 2 hours, the precipitate is filtered off, washed with 100 ml of water, dried in air (day) and then in a vacuum cabinet at 60 ° C to a constant weight (6 hours), the product flow was 10.4 g (Estimated. Yield, based on diamine authority, item 1, was 0, 10.1 g).

Melting point 285 s.

Found,%: C 66.2; H 6.53; N 19.85, Equivalent to 213.

Calculated (for the diamparmer,

5 p l},%: C 66, OJ H 6.20; N 20.0. Equivalent to 209.

PI and me 4, Synthesis is carried out analogously to example 3, but 4,4-diiso-cyanate diphenylmethane (5.5 g, i.e. 0.022 mol) is used as the diisocyanate, and 2,4-toluene di-1IN (13.6 g, i.e. 0.11 mol) ,. The reaction product is obtained in the form of a fine white powder. The product yield of 10.6 g. Calculated

5 yield, based on diamoline, is 10.8 g.

Found,%: C 70.0; H 6.25; N 16.45. Equivalent to 228.

Calculated (for the diamparmer,

0 p 1),%: C 70.05; H 6.10; N 17.0. Equivalent to 247.

Example 5. In a chemical glass with a capacity of 0.6 l, 21.2 g of a diamine-urethane (claim 1), prepared as described in Example 2, are placed. It is dissolved in 180 ml of dimethylformamide and to this solution is added dropwise with stirring 1.45 ml (1, 77. D) of 2, 4-toluylenes.zo0 cyanate in 45 ml of dimethylformamide.

After 2 hours, the fine precipitated precipitate is filtered through a glass filter (40), washed with 15 ml of dimethylformamide and dried at 60-80 ° C in a vacuum cabinet to constant weight.

5 Product yield 1.61 g. Equivalent to 775. Melting point.

Found,%: C 59.4; H 6.95; N 18.4,

The value of the equivalent indicates

0 that the product is obtained from 5. The estimated equivalent for such a product is 801.

180 ml of ethyl alcohol is added to the obtained filtrate, the solution is placed in a 2-liter beaker, and slowly added with a mechanical stirrer, a solution of 270 ml of water and 180 ml of acetone. At the end of the addition

0 solution precipitates, which is filtered off, washed on the filter with a mixture of solvents (dimethylformamide 22.5 ml, alcohol 18 ml, acetone 18 ml, water 27 ml) and dried first in air and then at

in a vacuum oven to constant weight. Yield 7.7 g. Equivalent to 523. Melting point.

Found,%: with 62.94; H 6.25; | N 18,47.

 The value of the equivalent indicates that the product with item 3 is highlighted. The calculated equivalent for such a product is 505.

From the solvent mixture, the initial diamine catechevine (step 1), taken for synthesis in excess, is regenerated as follows.

To a mixture of solvents placed in a 2l beaker are added 500 ml of water, stirred, stirred for 1 hour and filtered through a paper filter. The precipitate is washed with water and air dried, and then in a vacuum oven with

 to constant weight. 12.9 g of product are obtained. Equivalent to 215., which corresponds to the original diamine authority ().

Thus, from 21.2 g of 0.05 mol of diamine of urea (p 1) and 1.77 g (0.01 mol) of 2,4-toluene diisocyanate. get 1.61. d diamine authority (p 5), 7.7 g diamine authority (p 3) and regenerate 12: 9 g diamine authority (p 13. The loss is 0.76 g {0.05 mol).

. Films of a thickness of 0.15-0.20 mm are cast from solutions of polymers obtained on the basis of new aromatic diamines containing urea groups and m-phenylenediamine, and their physical and mechanical properties are tested. The results are shown in the table.

520

230 747

287

Claims (1)

1. Saunders D.H. and others. Chemistry of polyurethanes. M., Mir, 1969, p. 365-366.