SU1180367A1 - - active non-symbos of thyptigendiol-2,5 as monomers for producing polycondensating polymers - Google Patents

Abstract

Halogen derivatives of tripticeniol-2, 5 of the general formula OH where X is chlorine, bromine, as monomers for the preparation of S polycondensation polymers. sl with:

Description

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about soyu

The invention relates to new compounds, namely to halogen derivatives tripticene-2.5, which can be used as monomers for the synthesis of soluble polycondensation polymers with improved strength characteristics.

 The aim of the invention is to create new monomers for the synthesis of polycondensation polymers with high strength characteristics.

Example 1. K5g (17.5 mmol trypticenediol-2.5 and 100 ml of glacial acetic acid add 5.72 g (36 mmol) of bromine over 0.5 h. Then the reaction mixture is boiled for 2 h until the tripty dissolves - Cendiol-2.5 and termination of HBg release. The reaction mixture is precipitated into water, 3,4-dibromo trypthycenediol-2, 5 is filtered off. Yield: 97%; T. S1. 268 ° C (from benzene). IR spectrum 3420- 3470 (OH); 1620 (anthracene radical), 875 (hexane substitution in the benzene ring), 365 cm (C-Vg); PMR spectrum: 2H — singlet of OH protons at O 7.97 ppm, 4H multiplet on -protons of unsubstituted aromatic rings with Centralized 6 MD 7.37, 4H, multiplet jb -proton unsubstituted aromatic rings with center S 6,92 ppm, singlet 2H bridging protons at about 5.98 ppm

Found,%: C 54.04; H 2.78, Br 35.85.

Cd, H, 2Bg2 O

Calculated,%: C 53.96} H 2.72; Br 35.90.

Example 2. K5g (17.5 mmol trypticenediol-2.5 and 70 ml was added 5.72 (36 mmol) of bromine over 0.5 h. Then the reaction mixture was boiled for 2 h until the dissolution of tripticendiol-2 was completely dissolved. , 5, and termination of HBg cleavage. After cooling the reaction mixture, everything is planted in water. 3,4-Dibromo trypthycenediol-2, 5 is filtered off.

Yield: 94%; m.p. (from benzene). The data of elemental analysis, IR, PMR spectra, as in example 1.

Example 3 Into a boiling mixture of 5 g (17.5 mmol) of tripticenedi2, 5, 100 ml of glacial acetic acid and 1.5 ml of 48% HBg is passed

40 mmol of gaseous chlorine for 1.5 hours. Then they are planted in water, 3,4-dichlorotripticenediol-2.5 is filtered off. Yield: 96%; m.p. 256 (from 1,4-dioxane). IR spectrum: 34203470 - (OH), 1620 (anthracene radical)} 875 (hexane replacement in the benzene ring); 780 (C-C1). PMR spectrum: 2H singlet of protons of OH groups at S 8.00 ppm; 4H multiplet ob-protons of unsubstituted aromatic rings with a center of 8 7.37 ppm, 4H multiplet of j -protons of unsubstituted aromatic rings with a center of S 6.88 ppm 2H singlet of bridge protons at S 5.95 ppm

Found,%: C 67.67; H 3.45, C1 19.91.

,,

Calculated,%: C 67.62; H 3.41; C1 19.96.

IR spectra are taken on a Regkin-Elmer-283 instrument. The PMR spectra were measured on a Tesla BS-467 instrument in deuteroacetone, internal standard of the CMT.

The numbering of carbon atoms in triptycene according to Bartlett 8

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PMR spectrum; tripticeniol-2.5: 2H singlet of protons of OH groups with

S 7.80 MD; 4H multiplet pro-protons with a center about 7.33 ppm, 4H multiplet / -protons with a center

S 6.89 ppm, 2H singlet of protons of methine groups at about 5.88 ppm, 2H singlet of protons of a substituted aromatic ring at 5 6.33 ppm

Based on new monomers, a series of polymers has been synthesized. As examples, a method for the preparation of copolyester is given. Copolyesters are obtained by low-temperature polycondensation of terephthalic acid dichlorohydride with a mixture of 3,4-dichlorotripti-cendiol-2,5 (or 3,4-dibromo-tripty3

cendiol-2,5) and bis-phenol-A in an organic solvent medium, in the presence of triethylamine and can be used as film and structural materials.

Example 4. To 0.4135 g (20 mol.%) Of 3,4-dibromo tripripenediol-2, 5 and 0.8696 g (80 mol.%) Of bis-phenol A in 15 ml of 1,2-dsloretane is added (200 mol.%) triethylamine. Then, with stirring, 1 g (100 mol.%) Of terephthalic acid dichloride is added. The reaction is carried out for 1 hour. The polymer is precipitated in isopropanol, filtered, washed with isopropanol and water. The polymer is dried at 100 ° C under vacuum to constant weight. The yield is 98% of the theoretical, the reduced viscosity of its 0.5% aqueous solution in tetrachloroethane at 20 C is 0.13.

Transparent films are obtained from the solution in t ° trachloroethane by a method of irrigation. Their properties are listed in Table 1.

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EXAMPLE 5 A copolymer is prepared analogously to example 4, but instead of a mixture of 20 mol.% 3,4-dibromo-tri-tcenediol-2, 5 and 80 mol.% Of bis-phenbla A, a mixture of 0.3499 g is taken.

(20 mol.%) 3,4-dichlorothriptycene 1ola-2, 5 IO, 8996 g. (80 mol.%) Bisphenol A; “P 0.23 0.5% s solution in tetrachloroethane at 20 ° С, polymer yield 98% of theoretical.

The properties of the polymer are given in table.1.

The data of IR spectroscopy and elemental analysis confirm the formation and structure of the obtained copolymers.

In tab. 2 shows the same properties for known polymers of the proposed compounds.

Thus, the proposed compounds allow to obtain on their basis polycondensation polymers with enhanced strength characteristics.

Table 1

3,4-Dibromotriptyceniol-2, 5,100: 20: 80

3,4-Dichlorotripticene-2, 5,100: 20: 80

0.054

100: 20: 80

360 116

11.8 1.96 360 109 13 2.05

table 2

20

78

310-317

0.072

100: 20: 80

.Continuation ta6p.2.

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Claims (2)

Halogen derivatives of tripticeniol-2,5 General formula as monomers for the preparation of polycondensation polymers. $ one .1180367 2