RU2145966C1 - Method of preparing poly-(n-phenylimino)carbophenyleneoxides - Google Patents

Abstract

FIELD: chemistry of high molecular compounds, more particularly highly thermostable and high-strength polymeric materials used in various fields of engineering and technology. SUBSTANCE: described is method of preparing poly-(N- phenylimino)carbophenyleneoxides of general formula I:

wherein R,R¹,n are as defined in claim 1, by polycondensation of diphenyloxide. Original reactants include N-pheniliminochlorides of aromatic dicarboxilic acids of formula:

with bisphenols of formula: HO-R¹-OH wherein R¹ is defined in claim 1, in amide solvents in inert gas current at 0-160 C for 13-15 hours. EFFECT: wider range of polyphenylene oxides of complicated structure, improved physico-mechanical characteristics and cheaper materials based thereon. 1 ex, 2 tbl

Description

 The invention relates to the chemistry of macromolecular compounds, and in particular to a method for producing poly- (N-phenylimino) carbophenylene oxides, which can be used to produce high-strength, heat-resistant polymer materials suitable in various fields of engineering and technology.

 A known method of producing polyphenylene oxide by the method of oxidative dehydro-polycondensation of 2,6-dimethylphenol in a medium of pyridine and copper (I) chloride [Eng. US Pat. 930993 (1963)]. The polymers synthesized by this method have high heat resistance and good solubility, however, the use of pyridine as a solvent and copper (I) chloride in a ratio of 1: 5 by weight of the monomer makes this method expensive and inefficient.

The closest in technical essence is the method for the synthesis of aromatic polyketones, the electrophilic substitution reaction in the form of precipitation polycondensation of dicarboxylic acid chlorides with diphenyl oxide in nitrobenzene or chlorinated hydrocarbons in the presence of aluminum chloride [MG Zolotukhin et al. Some patterns of precipitation polycondensation polyketones synthesis. (High-molecular compounds. 1989, T.31, N 12 (prototype)]. Polyketones obtained by the above method do not have significant differences in physicochemical characteristics from similar polyphenylene oxides. However, this method has some, in our opinion, significant disadvantages, such as the need to create a low (-30 ^o C) initial temperature, the use of a large amount of aluminum chloride, the duration (up to 24 hours) of the synthesis.The aim of the present invention is to simplify and reduce the cost of the production method, improved ia physical and mechanical properties, as well as expanding the range of polymeric materials.

для высокопрочных термостойких полимерных материалов.This goal is achieved in that in the method for producing poly (N-phenylimino) carbophenylene oxides by polycondensation of bisphenol with an acylating reagent, where N-phenyliminochlorides of aromatic dicarboxylic acids of the formula are used as the acylating reagent:

for high-strength heat-resistant polymer materials.

где (x= σ-связь; -CH₂-; -O-; -C(CH₃)₂).Poly- (N-phenylimino) carbophenylene oxides are obtained by polycondensation of equimolecular amounts of N-phenyliminochlorides (1) with bisphenols (2), according to the scheme:

where (x = σ-bond; -CH ₂ -; -O-; -C (CH ₃ ) ₂ ).

The process of producing polyphenylene oxides is carried out in amide solvents such as N, N'-dimethylformamide (DMF), N, N'-dimethylacetamide (DMA) and N-methyl-2-pyrrolidone (N-MP), which simultaneously serve as acceptors of low molecular weight condensates, in inert gas flow, at a temperature of 0-160 ^o C, for 13-15 hours

Carrying out the process beyond the limits of 0-160 ^o C and the synthesis time of more than 15 hours is not advisable, since, at temperatures below 0 ^o C, the rate of the ongoing reaction slows down, and at temperatures above 160 ^o C there is an alternative side process leading to the interaction of the component 1) with solvent. Polymers with maximum values of reduced viscosity are obtained within 13-15 hours, during the process more than 15 hours there is no increase in the values of reduced viscosity.

The resulting poly- (N-phenylimino) carbophenylene oxides, with a yield of 75-91% of theory, are readily soluble in organic solvents such as tetrachloroethane, dioxane, m-cresol, dimethyl sulfoxide and in amide solvents, forming highly viscous concentrated polymer solutions with reduced viscosity values from 0.45 to 0.72 dl / g (DMA solvent, C = 0.5%, T = 20 ^° C).

The structure of the obtained polymers is confirmed by the data of elemental analysis (Table 1) and IR spectroscopy. In the IR spectrum of polymers there are absorption bands in the range of 3060-3010 cm ^-1 (CH _arom ), 2950, 2870 cm ^-1 (CH _alif ), 2000-1790 cm ^-1 (C ₆ H ₅ ), 1665-1635 cm ^{- 1} (C = N), 1600 cm ^-1 (CC _arom ), 1420 cm ^-1 (CN), 1390, 1285-1265 cm ^-1 (CO), 1225-1175, 1125-1090, 1070-1000 cm ^-1 (CH _arom ), 1030 cm ^-1 (Ar-O-Ar), 900-860 cm ^-1 (CH _arom ), 840-810, 760, 700 cm ^-1 (CH _arom ), characteristic for stretching and bending functional vibrations groups of poly- (N-phenylimino) carbophenylene oxides. In these absorption bands, the characteristic absorption bands in the region of 1665–1635 cm ^–1 (C = N), 1420 cm ^–1 (CN), 1390, 1285–1265 cm ^–1 (CO) are well distinguished, indicating the formation of ether and imino groups .

Transparent, flexible films were obtained from 10-15% polymer solutions in DMA by pouring onto a glass substrate and drying at 80 ^° C for 48 hours. Pressing powders of poly- (N-phenylimino) -carbophenylene oxides at a pressure of 70-75 MPa and a temperature of 250-380 ^o C, obtained press products. The properties of the films and press products are given in table. 2. The heat resistance of poly- (N-phenylimino) carbophenylene oxides is 380-495 ^o C.

 The invention is confirmed by the following example.

Example. B a solution of 2.2829 g (0.01 mol) of 4,4'-dioxidiphenylpropane in 30 ml of N-MP, at 0-10 ^o C, with continuous passing of nitrogen into the solution and vigorous stirring, 3.5325 g are introduced in small portions 0.01 mol) N, N'-diphenylisophthaliminochloride for 30 minutes Then, the temperature of the reaction mixture was raised to 160 ^° C. over 5 hours. The mixture was stirred at this temperature for 10-12 hours. A viscous polymer solution with a reduced viscosity of 0.7 dl / g (C = 0.5%, DMA solvent, T = 20 ^o C). The polymer is isolated by precipitation in 500 ml of water, filtered, washed with water, dried. Yield 90% of theoretical. The data of elemental analysis are in good agreement with the calculated ones (see table. 1). The polymer structure was identified by IR spectrometry. The polymer is highly soluble in organic solvents, forming highly viscous polymer solutions. The temperature of the onset of polymer decomposition is 385 ^o C, in air, at a temperature rise rate of 5 deg / min. Strong elastic films were obtained from a 15% solution in DMA by pouring onto a glass substrate and drying at 70-80 ^° C for 48 hours. The breaking stress of non-oriented films is σ _p = 150-750 kgf / cm ² , H _p = 20-28%. Press materials obtained by pressing polymer powders at a specific pressure of 70-75 MPa and a temperature of 250-500 ^o C.

 Poly- (N-phenylimino) carbophenylene oxides based on various N-phenyliminochlorides of dicarboxylic acids (1) and bisphenols (2) are obtained analogously to the example. As can be seen from the data table. 1 and 2, the proposed substituted polyphenylene oxides have high viscosity properties, good solubility in organic solvents, good processability into polymeric materials by traditional methods, high values of the physicomechanical properties of materials based on them, and high resistance to thermal oxidative degradation.

 The above complex of practically useful properties of substituted polyphenylene oxides determines the positive effectiveness of the proposed invention. Substituted polyphenylene oxides can be used in various fields of technology and technology as highly heat-resistant coatings, carbon and fiberglass binders, adhesives, press materials, films with high values of physical and mechanical characteristics.

Claims (1)

The method of producing poly- (N-phenylimino) carbophenylene oxides by polycondensation, characterized in that the starting reagents are N-phenylimino chlorides of aromatic dicarboxylic acids of the formula

with bisphenols of the formula
HO-R'-OH,
Where

x is the σ bond; -CH ₂ -, -O-, -C (CH ₃ ) ₂ ),
to obtain poly- (N-phenylimino) carbophenylene oxides of the general formula

in an amide solvent, in an inert gas stream, at a temperature of 0 - 160 ^o C, for 13 - 15 hours

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