The paper presents the results of the systematic research into effects of 3d-metals acetates, acetylacetonates and double tartrategermanates/stannates on the modification of polyglycol maleine phthalate. The copolymerization parameters of the prepared modified oligoesters with methyl methacrylate monomer and threeethyleneglycoldimethacrylate oligomer were determined. Modifiers were added to the reaction mixture before the start of polycondensation of maleic and phthalic anhydrides with ethylene glycol at the temperature of 1750C. The kinetics of copolymerization at the initial stages was determined by the dilatometry at the temperatures of 500C to 600C. It was established that the modification of polyglycol maleinate phthalate with the studied compounds allows significantly increasing the rate and reducing the temperature coefficient of the copolymerization reaction. There advantages of the investigated double multi-metal mixed ligand coordination compounds as modifiers were proved as compared to the standard industrial systems, acetylacetonates and metal acetates. The presented modifiers are able to improve significantly the characteristics of the semi-finished products in the industrial manufacturing of copolymers without the significant change of the technological process.

The possibility of using a number of bimetallic complexes of germanium (IV) - zinc / cobalt (II) / nickel (II) / cuprum (II) with hydroxycarboxylic acids as modifiers of unsaturated oligoester in the processes of its copolymerization with methyl methacrylate has been investigated. The modification was carried out by adding the corresponding complex to the reaction mixture during the polycondensation of maleic and phthalic anhydride with ethylene glycol at 175 °C. The kinetics of copolymerization at the initial stages was studied by dilatometry at temperatures from 50 °C to 60 °C. It has been shown that the modified polyglycolmalenatephthalate with the studied complexes can significantly increase the rate and reduce the temperature coefficient of the reaction during its copolymerization with methyl methacrylate. The advantages of the studied coordination compounds as modifiers in comparison with unmodified systems and 1,10-phenanthroline have been proved. The effect of the modifier (1,10-phenanthroline), depending on its content in the modified polyglycolmalenatephthalate, on the kinetic characteristics of copolymerization with methylmethacrylate in the range from 0 to 0.5 mol/L was investigated. The calculations of the influence of the temperature coefficient of reaction on the maximum allowable diameter on the example of a spherical sample when reaching a critical temperature of 90 0C for non-isotremic copolymerization processes. Physico-mechanical characteristics have been studied and it has been shown that the addition of a modifier does not significantly change them.  In addition, germanium (IV) compounds retain a higher oxidation state, which makes it possible to use the finished polymer product as a biological material for special purposes. The proposed methods can be used to improve the characteristics of semi-finished products in the industrial production of copolymer products without significant changes in the technological process.

In the present work, the kinetics of radical copolymerization in solution at the initial stages of polyglycol maleinate phthalates modified with nitrogen-containing compounds with methyl methacrylate in a ratio of 1:1 was studied. Cyclohexanone was used as a solvent, and benzoyl peroxide was used as an initiator. The study was carried out at temperatures of 50 and 60 °C by dilatometry using collapsible dilatometers and a centrifuge. 13 amine-containing compounds of different types were chosen as modifiers. Also, for comparison, the possibility of using amides and hydrazines as modifiers was checked. Polycondensation was carried out in an oil bath at 175 °C and with vigorous stirring with water withdrawal until a constant acid number was reached. It is shown that the addition of 0.1 mol/l modifier during the polycondensation of a mixture of maleic and phthalic anhydrides with ethylene glycol makes it possible to obtain an unsaturated oligoester, for which the temperature coefficient of the reaction of its copolymerization with methyl methacrylate is significantly reduced. This allows for non-isothermal curing to increase the volume of the copolymer block without the risk of overheating and destruction. Of the studied amines, para-aminoacetophenone turned out to be the most effective; its use as a modifier makes it possible to reduce the temperature coefficient of the reaction from 2.1 to 1.7. The rate of copolymerization at the initial stages for the studied modified systems decreases from 2 to 20 times. The results of the work allow us to propose a technology for the production of polymeric materials by molding them in blocks of much larger sizes than with the use of traditional unsaturated oligomers. Also, calculations were carried out according to a special technique and the maximum size of a copolymer block in the form of a cylinder was determined, in which the height is equal to the radius, which can be obtained by forming it in a non-isothermal mode in a thin layer form with convection air cooling and the maximum allowable temperature in the system is 90 °C. It is shown that the volume of such a block, when using some modified oligomers, increases significantly. Some physical and mechanical characteristics of the obtained copolymers with methyl methacrylate were determined, and it was shown that modification with nitrogen-containing compounds does not improve or worsen the studied characteristics.

No abstract

1 Одесский национальный университет им. И.И. Мечникова, кафедра общей химии и полимеров, ул. Дворянская 2, Одесса, 65082, Украина 2 Одесский национальный медицинский университет, кафедра фармацевтической химии, Валиховский пер. 2, Одесса, 65082, Украина