SU811750A1 - Bis-bicarbonates of aliphatic diols as monomers for preparing polyurethanes and process for producing the same - Google Patents

Description

This invention relates to the synthesis of new chemical compounds - bis-carbonates of the general formula: x-o-c-c-c-s-comp. where b cnH cH2 cn cCHg cH 2 cn, X-4O W2; - p -N02-, ci .ei Cl Gl and choco6 are used to obtain them. Activated bis carbonates of aliphatic diols are highly reactive bifunctional compounds and can be used to produce high molecular weight polyurethanes and polycarbonates. These compounds, their properties and the method of their preparation are not described in the literature. . Cl 3 bifunctional compounds based on aliphatic dioles — diols bis chloroformates, used as monomers under polycondensation conditions for the synthesis of polyurethanes and polycarbonates are known. The use of bis-chloroformates as i monomers in the polycondensation of the pIJ deficiencies of 2 3 "-bis-chloroformates toxic substances causing corrosion; - they hydrolyze easily and their storage is difficult, during hydrolysis 2 moles of carbon dioxide and 2 "OLA of hydrogen chloride are released and the danger of pressure increase must be taken into account; - bis-chloroformates are practically unsuitable for the synthesis of polyurethanes by solution polycondensation, they react with many organic solvents, which makes it difficult to select solvents for carrying out polycondensation; 8P7 5 "О 15 20 25 02 -bis-chlorofrmimates also react violently with tertiary amines used as an acceptor of hydrogen chloride, which leads to the death of functional groups and the formation of low-molecular polymers - the synthesis of bis-chloroformates of various diols requires repeated use of phosgene, which complicates the process technology; Most of the bis-chloroformates of aliphatic diols, liquids, which cause inconvenience in working with them, they have high boiling points and are purified only by distillation in a vacuum; - during the synthesis of a series of bis-chloroformates, cyclic carbonates are formed as by-products with a short hydrocarbon chain, which leads to a violation of the equimolecularity during the polycondensation reaction. The aim of the invention is the synthesis of activated bis-carbonates of aliphatic diols, which can be used to obtain high molecular weight polyurethanes and polycarbonates. The goal is achieved by the structure of the chemical compounds of the formula: x-0-coKoc-oXi gze R -cHrCH2-cH2-v -sHz CH2-CH2-SNSH C1 These compounds are obtained by the interaction of an aliatic diol bis-chloroformate with a compound made from the following groups: nitrophenol, dinitophenol, trichlorophenol, pentachlorophenrel, or an aliphatic diol with chloroformate 3 of the compounds from t oh same group, in the environment of an Organic solvent in the presence of a tertiary amine in kaO / -L and Oglo / °

30 ml of dry chlorobenzene and 2.8 ml {0.02 mol) of triethylamine are added to 2.783 g (0.02 mol) of p-nitrophenol at room temperature. After the complete dissolution of p-nitrophenol, the solution is cooled down to -15 and slowly, mixed (the solution js 7.0t g (o, 01 mol) of li bischloroformate, 3 propanediol in 5 ml of chlorobenzene. After the total amount of bis -urformate, the reaction mixture is stirred for 15 min, after which the cooling 2o

Ooh

51 "/

; About o-c-o- (sn 213-o-c-o-r. Tch W. Synthesis is carried out in accordance with the procedure described in Example 1, with the difference that 2, -dinitrophenol is taken instead of p-nitro-phenol. Product is obtained in the sediment in a mixture with hydrochloric triethylamine, it is filtered, washed with alcohol, and the synthesis is carried out in accordance with the procedure described in example 1, with the difference that 2,4,6-trichlorophenol is taken instead of p-nitrophenol. reactions in solution, therefore, the reaction mixture is filtered from the expelled triethylamine hydrochloride, the precipitate is washed twice We use small O - oy-Q- - (() Cl Cl Synthesis is carried out in accordance with the procedure described in Example 1, with the difference that pentachlorophenol is taken instead of p-nitro and phenol. The product falls out of the reaction solution along with the salt triethylamine, acidic precipitate is filtered off, washed with ethinuid and stirring is continued at room temperature for 1 hour. The product together with triethylamine hydrochloride precipitates, which is filtered off and washed with ethyl alcohol to remove triethylamine and dried. Get it. almost pure white crystalline substance with so pl. 1,31132 ° C. The output after recrystallization mz toluene, mp 132-133 ° C. Example 2. 8P750 car1 catalyst and hydrogen chlorine acceptor at -15 -. . Example 1. about 1, dried. An almost pure, white crystalline substance is obtained with m.p. 87-88 e, yield 65%, after recrystallization from a mixture of toluene with: hexane so pl. . PRI me R 3.) Cr-o-o (5 ml) in portions of chlorobenzene. The combined filter is evaporated in vacuo. A white crystalline substance is obtained with a mp. 107-110 ° C, yield 50, after recrystallization from hexane so pl. 110-112 C. Example t. C1 C1 -Q. SG C1 lov alcohol and dried. A white, crystalline, practically pure substance is obtained. , exit 75. After recrystallization from a mixture of toluene with hexane so pl. 17b-178 s. Froze

 OSKz Oh

Yu) -o-s-o-Shg CNG sa-o-s-o

The synthesis is carried out in cooTBetciBHM with the procedure given in example t, with the difference that it is used instead of bis-chloroformate 1,3-prbpandiol using bis-chlorofrmiate t, 3-butanediol. The product precipitates from the reaction solution as a precipitate along with hydroxys

CHO) -o-s-o-sngsN2 - C-o-s o

The synthesis is carried out in accordance with the procedure described in Example 1,. with the difference that BMeicto bischloroformate 1 13-propanediol use bis-chloroformate 1,3-butanediol, and

instead of p-nitrophenol, petachlorophenol 5 The reaction product is in solution, therefore, the reaction mixture is filtered from the precipitated hydrochloric triethylamine.

solid triethylamiomy, the precipitate is filtered off, washed with ethyl alcohol and dried. A white, crystalline substance is obtained. , yield 6k% t after recrystallization from tolu and so pl. l47-lA8 t, Synthesis 6.

SNZ Oh

I u

the precipitate is washed twice with small portions of 5 ml of chlorobenzene. The combined filtrate was evaporated in vacuo. A white, crystalline substance is obtained. 137-139 0, yield 72%, after recrystallization from N-butanol so pl. UO-Ua S.

PRI me R 7.

| 0

II

0-с-о- (о- с-0

to a solution of 0.76 g (P, 01 mol) of 1,3-propanediol and 1, B2 ml (0.02 mol) of anhydrous pyridine in 30 ml of dry tetrahydrofuran while cooling is added g (0.02 mol) of chloroformate G) -nitrophenol. After adding the total amount of chloroformate, cooling off and stirring

2лО / -о с-о (сН2) г sn-о-с-о-О)

The synthesis is carried out in accordance with the procedure given in example 7, with the difference that instead of 1,3-propanediol

Continue at room temperature for 2 hours. The precipitate formed is dried, washed with ethyl alcohol and dried. M.p. the obtained substance 130-132 C, yield 85, after recrystallization from toluene, so pl. 132-133 ° C. Example 8

Snch about

use 1,3-butanediol, t. pl. product yield 82. After recrystallization from toluene

m.p. , Basic A 71 132-133 1770 Toluene (recrystall A 65 88-90 1755 Toluene + hexane A 50 110-112 1765 Hexay (recrystall A 75 176-178 1765 Toluene + Hex A6. I7-1 8 1760- Toluene (by recrystallization 1750). . (pEmoo) A72 1770 N-butanol (before 1780 by crystallisation) (PLV) by lyse) (by recrystallization by crystallization) (by recrystallization of 7-in 750g characteristics of activated bis-carbonates of the general formula 50.16 3.23 6.61 (50.2 " |) (3,) (6.9) "0.96 2.21 11.26 (1st, 13) (2.2) (11.29) 38.92 1.76 - U.N (39.0 ) (1, 73) 3.78, 0.76 -53.18. (30.86) (0.91) - (53.7) 51.2 "3.68 6.58 (51." "H) (3.81) (6.67) 31.92 V, 02-52.03 (32.0) (1, tS) 152.6)

Claims (2)

BIS-CARBONATES OF ALIPHATIC MON FISHING-MONOMERS FOR POLYURETHANES AND Polycarbonates and a method for their preparation. (57) 1. Bis-carbonates of aliphatic Diols of the general formula where -monomers for polyurethanes and polycarbonates. 2. The method for producing compounds according to claim 1, wherein the aliphatic diol bischloroformate is reacted with a compound selected from the group: nitrophenol, dinitrophenol, trichporphenol, pentachlorophenol, or an aliphatic diol with chloroformate of compounds from the same group in an organic solvent in presence of a tertiary amine as a catalyst and hydrogen chloride scavenger at -15 ~ 25 ^minutes C.