SU576325A1

SU576325A1 - Method of preparing oligomeric polyoxyphenylene

Info

Publication number: SU576325A1
Application number: SU7502106975A
Authority: SU
Inventors: Сергей Александрович Апостолов; Галина Федоровна Михайлова; Людмила Александровна Монахова
Original assignee: Северо-Западный Заочный Политехнический Институт
Priority date: 1975-01-07
Filing date: 1975-01-07
Publication date: 1977-10-15

Description

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Изобретение относитс к технологии получени олигомерных полиоксифениленов и может быть использовано в химической промышленности , а полученные олигомеры - в качестве полупродуктов дл получени термостойких полимеров.The invention relates to the technology of producing oligomeric polyoxyphenylene and can be used in the chemical industry, and the resulting oligomers as intermediates for the production of heat-resistant polymers.

Известен способ получени полиоксифениленов термической дегидратацией фенолов, в частности резорцина или гидрохинона, при 200-350°С в присутствии 3-4-х кратного избытка (по отношению к фенолу) хлористого цинка 1.A known method for producing polyoxyphenylene by thermal dehydration of phenols, in particular resorcin or hydroquinone, at 200-350 ° C in the presence of a 3-4-fold excess (relative to phenol) zinc chloride 1.

Наиболее близким к описываемому изобретению по технической суш,ности вл етс способ получени олигомерных полиоксифениленов , заключаюш,ийс в окислении фенола (оксибензола) в водном растворе под действием избытка хлорного железа по отношению к фенолу 2. Недостатком этого способа вл етс большое количество образующихс сточных вод, загр зненных фенолом и хлоридами железа (около 5 т на 1 т целевого нродукта). Кроме того, в процессе выдел етс на 1 моль фенола 2 моль хлористого водорода, что требует значительных затрат на его утилизацию и заш,иту оборудовани от коррозии.The closest to the described invention by technical drying is the method of producing oligomeric polyoxyphenylene, which consists in the oxidation of phenol (hydroxybenzene) in aqueous solution under the action of excess ferric chloride in relation to phenol 2. The disadvantage of this method is the large amount of wastewater contaminated with phenol and iron chlorides (about 5 tons per 1 ton of the target product). In addition, 2 mol of hydrogen chloride is released per 1 mol of phenol in the process, which requires significant costs for its utilization and protection of equipment from corrosion.

С целью повышени экономичности процесса и упрощени его технологии в предлагаемом способе процесс окислени фенолаIn order to improve the efficiency of the process and simplify its technology in the proposed method, the process of oxidation of phenol

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провод т в расплаве при барботировании через него воздуха в присутствии в качестве катализатора 0,5-4,0 вес. % (от фенола) порошкообразного железа.conducted in the melt by bubbling air through it in the presence of 0.5-4.0 weight as a catalyst. % (from phenol) powdered iron.

Нроцесс предпочтительно проводитс в реакторе , заполненном стальной насадкой. Учитыва , что в процессе синтеза не образуютс коррозионноактивные соединени , синтез может быть осуществлен в реакторе из обычной углеродистой стали. Отделение полученных олигомеров от непрореагировавшего фенола может быть осуществлено отгонкой последнего с вод ным паром или ректификацией . Примен емый катализатор не загр зн ет продукты реакции, что упрощает их очистку и разделение. Выделенне низкомолекул рных олигомеров фенола из продуктов окислени осуществл етс их экстракцией четыреххлористым углеродом. Выход составл ет около 90% на прореагировавший фенол.The process is preferably carried out in a reactor filled with a steel nozzle. Taking into account that no corrosion compounds are formed in the synthesis process, the synthesis can be carried out in a reactor of ordinary carbon steel. The separation of the oligomers obtained from unreacted phenol can be carried out by stripping the latter with steam or rectification. The catalyst used does not contaminate the reaction products, which simplifies their purification and separation. Selection of low molecular weight phenol oligomers from oxidation products is carried out by their extraction with carbon tetrachloride. The yield is about 90% for the phenol reacted.

Claims

Is an example. The synthesis is carried out in a steel reactor with a bubbler for air flow and a nozzle of steel rings. 1 kg of phenol is loaded into the reactor, after which the temperature of the phenol is raised to 200 ° C. After heating the reactor, air is fed through a bubbler at a pressure of 1.5 kg / cm in an amount of 120 l / h. The exhaust air passes through a reflux condenser and, after washing with a solution of sodium hydroxide solution, is discharged into the atmosphere. Oxidation produces water in an amount of 0.5 mol per 1 mol of reacted phenol. The rate of the oxidation reaction depends on the temperature, air flow rate and surface area of the steel nozzle. The table shows the dependence of the yield of phenol oligomers on the reaction time and the amount of iron introduced into the reaction volume (iron was introduced in the form of a powder with a grain size of 0.5-1.0 mm). The yield of purified phenol oligomers is about 90% for the refined phenol. The resulting phenol oligomers are characterized by the following parameters. Elementary composition, weight. %: C, 75.76; 30 H 5.15; About 19.09. 5 10 15 20 25 The content of hydroxyl groups, weight. %: 16.3 carbonyl group content, wt. % 1.3 Molecular weight278 Thus, a low yield of sewage (about 200 kg per 1 ton of phenol), the use of available oxidant (oxygen of the air) and the absence of corrosive compounds in this case leads to an increase in efficiency and simplification of technology compared with the known method. Claims of the method for producing oligomeric polyoxyfenlenes by phenol oxidation, characterized in that, in order to simplify the process, the latter is carried out in the melt of phenol while air is bubbled through it in the presence of 0.5 to 4.0 wt.% As a catalyst. % (from phenol) powdered iron. Sources of information taken into account during the examination 1. Paushkin Ya. M., Omarov O. Yu. Synthesis of ioliphenylenes and polyoxyphenylenes from mono- and diatomic phenols, "High-molecular compounds, A 9, N ° 6, 1293-1297, 1967 .

2. Copyright certificate № 363725, M, Cl.2 C 08G 61/10, 1973.