RU2506280C1 - Aromatic block copolyesters - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: present invention relates to high-molecular weight compounds, particularly block copolyesters which can be used as heat-resistant, high-strength film materials. Described are aromatic block copolyesters of formula

where R=

n=1-20; m=2-50; z=2-30.

EFFECT: obtaining aromatic block copolyesters with improved thermal and mechanical properties.

1 tbl, 3 ex

Description

The invention relates to macromolecular compounds, in particular to block copolyester forms, which may find application as heat and heat resistant high-strength film materials.

Block copolymers based on various oligomers are known.

1. Shustov G.B., Temiraev K.B., Mikitaev A.K., Chasgova A.G. Aromatic oligoformals. 7th Int. conf. in chemistry, physical chemistry of oligomers. ″ Oligomers 2000 ″. Thes. doc. Moscow-Perm-Chernogolovka. 2000. P.111.

2. Pat. US 3069386 - GLC. 18S209P. 1964.

3. Carnahan J.C. Polyethersulfoneformals. Pat. 4310654 (USA), publ. in РЖХ1982, 20С 467П.

4. Williams F.I., Hay A.S., Relies N.M. et al. The synthesis of aromatic polyformals. HLC 1984. 23 C451.

5. Hay A.S., Williams F.I., Relies H.M., Bonlette B.M., Donahne P.E., Sohnson D.S. / J. Polymer sci. Polymer letters. 1983. V.21. No. 6. P.449.

6. Khasbulatova Z. C., Asueva L. A., Nasurova M. A., Shustov G. B., Mikitaev A. K. Aromatic polyformals. Plast.massa. 2008. No8. C31-34.

The main disadvantage of these polymers is the low heat and heat resistance.

The closest to the proposed structure and properties are polyformals based on diane. Temiraev K.B., Shustov G.B., Mikitaev A.K. Synthesis and properties of copolyethersulfonformals. High mole. conn. B, 1988.V. 30. No. 6.C.412-415.

However, these polyformals have low physico-chemical properties, low heat and heat resistance.

The objective of the invention is the creation of polyester formal block structure with increased values of thermal and mechanical characteristics.

The problem is solved by obtaining block copolyesters of the following structure:

where R =

n is 1-20; m is 2-50; z = 2-30

the interaction of equimolar amounts of phenolphthalein oligoketones (OK) of the formula

where n = 1-20,

and oligoformals (RP) based on phenolphthalein and methylene chloride with degrees of condensation n = 1-20 with an equimolar mixture of iso- and terephthalic acid chlorides.

The proposed block copolyesters are characterized by high rates of heat and heat resistance, as well as mechanical characteristics.

Example 1

3.24 g (0.005 mol) OF-1F, 4.07 g (0.005 mol) OK-1F, 50 ml of methylene chloride, 2.80 ml (0.02 mol) are charged into a 250 ml two-necked flask equipped with a mechanical stirrer. ) triethylamine and stirred. After the oligomers are dissolved, 2.03 g (0.01 mol) of a mixture (50:50) of iso- and terephthalic acid dichlorides are added to the mixture. The reaction is carried out for 1 hour, then the reaction mixture is diluted with 50 ml of methylene chloride and the polymer is precipitated in isopropyl alcohol. The precipitated polymer is filtered off and washed with water until chlorine ions disappear.

The reduced viscosity of a 0.5% solution in chloroform is 1.19 dl / g. The yield is 96%.

Example 2

In a two-necked flask with a capacity of 250 ml equipped with a mechanical stirrer, load 18.11 g (0.005 mol) OF-10F, 26.42 g (0.005 mol) OK-10F, 100 ml of methylene chloride 2.8 ml (0.02 mol) triethylamine and stirred. After the oligomers are dissolved, 2.03 g (0.01 mol) of a mixture (50:50) of iso- and terephthalic acid dichlorides are added to the mixture. The reaction is carried out for 1 hour, then the reaction mixture is diluted with 100 ml of methylene chloride and the polymer is precipitated in isopropyl alcohol. The precipitated polymer is filtered off and washed with water until chlorine ions disappear. The reduced viscosity of a 0.5% solution in chloroform is 1.06 dl / g. The yield is 96%.

Example 3

In a two-necked flask with a capacity of 250 ml equipped with a mechanical stirrer, load 18.14 g (0.00262 mol) OF-20F, 26.85 g (0.00262 mol) OK-20F, 100 ml of methylene chloride 1.4 ml (0 , 01 mol) of triethylamine and stirred. After the oligomers are dissolved, 0.213 g (0.00105 mol) of a mixture (50:50) of iso- and terephthalic acid dichlorides are added to the mixture. The reaction is carried out for 1 hour, then the reaction mixture is diluted with 100 ml of methylene chloride and the polymer is precipitated in isopropyl alcohol. The precipitated polymer is filtered off and washed with water until chlorine ions disappear. The reduced viscosity of a 0.5% solution in chloroform is 0.80 dl / g. The yield is 97%.

Table Block copolymer properties Based block copolymers T _s , ° C T _tech , ° C δ _p , MPa ε _p ,% Heat resistance, ° С 2% 10% fifty% OF-1F OK-1F 167 218 70.1 12.1 360 410 427 OF-10F OK-10F 155 210 68.6 12,4 377 421 442 OF-10F OK-20F 151 210 69.8 15.8 383 430 479

The polymer structure is confirmed by IR spectroscopy and turbidimetric titration. The presence of one maximum on the differential curves of turbidimetric titration, as well as absorption bands for ester groups and the absence of bands for OH groups in the spectra confirm the structure of the polymers.

The technical result of the invention is to obtain block copolyesters with high heat and heat resistance, as well as high mechanical characteristics.

Claims (1)

Aromatic block copolyesters of the formula

where R =

n is 1-20; m is 2-50; z = 2-30.