SU522205A1

SU522205A1 - Method for producing aromatic polysulfonamides

Info

Publication number: SU522205A1
Application number: SU2014642A
Authority: SU
Inventors: Валентина Ивановна Логунова; Лев Борисович Соколов; Валентин Михайлович Савинов; Людмила Михайловна Веселова
Original assignee: Предприятие П/Я Г-4059
Priority date: 1974-04-04
Filing date: 1974-04-04
Publication date: 1976-07-25

Description

Полученные полимеры имеют высокую мо лекул рную массу, аморфны, раствор51ютс в р де органических растворителей и в 96%ной серной кислоте, устойчивы к действию холодных концентрированных щелочей, перерабатываютс в пластмассу, волокна и плен ки. Температура разм гчени полимеров 20О-280 С {в зависимости от типа испопьзуемых диаминов и дисульфонилхлоридов). В случае проведени синтеза полисульфонамидов при некотором (0,5-3 моль.%) избытке дисульфонилхлорида получаютс полимеры , нерастворимые в органических растворител х , но способные перерабатыватьс в пластмассу. Пример 1.К интенсивно перемешиваемому раствору 0,7435 г (0,00375 мол 4,4 -диаминодифенилметана и О,795 г (О,О075 мол ) карбоната натри , растворенных в 2 мл тетрагидрофурана и 15 мл воды, добавл ют 1,317 г (О,ОО375 мол ) 4,4-дифенилдисульфонилхлорида в 8 мл тетрагидрофурана. Образующийс полимер выпадает в осадо в виде набухшей массы через 2-3 мин после добавлени сульфонилхлорида. Полимер от фильтровывают, промывают гор чей водой до отсутстви ионов с с и сушат при 100 в течение 5 час. Выход полимера составл ет-1ОО% . 11 1,3 ЦП/г, температура разм гчени 200 С. Полимер образует концентрированные (5-15%-ные) растворы в диметилацетамиде, диметилсульфохлориде, циклогексане с 6% воды, тетрагидрофуране с 10% воды, нерастворим в трифторуксусной кислоте, при комнатной температуре в 1О%ном водном и спиртовом растворе гидроокиси натри . При вьщержке полимера в 1О%-ном водном растворе гидроокиси кали в течение мес ца при комнатной температуре молекул рна масса (в зкость) полимера не измен етс . Из 1О%-ного раствора полимера в смеси тетрагвдрофурана с 10% воды были получены пленки со следующими свойствами: прочность на разрыв 230 кг/см, относительное удлинение при разрыве 1 %; 2-10 ом/см; tg-5 (V )PV () 10 гц)-2,8. -2,3-10 Образцы пластмассы, изготовленные методом пр мого прессовани при удельном давлении прессовани 500 кг/см и температуре 260°С, имели следующие механические свойства: удельна ударна в зкость 8 кГсм/см , прочность при раст жении 430 кг/см .Влагопотлощение образцов пластмассы при кип чении в воде до насыщени составл ет 5%. Примеры 2-4 получени полисульфонидов по методике, указанной выше (см. таблицу).The polymers obtained have a high molecular weight, are amorphous, dissolved in a number of organic solvents and in 96% sulfuric acid, resistant to cold concentrated alkalis, and processed into plastic, fibers and films. The softening temperature of polymers 20О-280 С {depending on the type of used diamines and disulfonyl chlorides). In the case of carrying out the synthesis of polysulfonamides with a certain (0.5-3 mol%) excess of disulfonyl chloride, polymers are obtained which are insoluble in organic solvents but can be converted into plastic. Example 1. To a vigorously stirred solution of 0.7435 g (0.00375 mol of 4,4-diaminodiphenylmethane and O, 795 g (O, O075 mol) of sodium carbonate, dissolved in 2 ml of tetrahydrofuran and 15 ml of water, was added 1.317 g ( O, OO375 mol) 4,4-diphenyldisulfonyl chloride in 8 ml of tetrahydrofuran. The polymer formed precipitated as a swollen mass 2-3 min after the addition of sulfonyl chloride. The polymer was filtered, washed with hot water until there were no ions with and dried at 100 within 5 hours. The polymer yield is -1OO%. 11 1.3 Cp / g, softening temperature 200 C. Polymer Forms concentrated (5-15%) solutions in dimethylacetamide, dimethylsulfochloride, cyclohexane with 6% water, tetrahydrofuran with 10% water, insoluble in trifluoroacetic acid, at room temperature in a 1O% aqueous and alcoholic solution of sodium hydroxide. in a 1O% aqueous solution of potassium hydroxide for a month at room temperature, the molecular weight (viscosity) of the polymer does not change. Films with the following properties were obtained from a 1O% polymer solution in a mixture of tetragvdrofuran with 10% water: tensile strength 230 kg / cm, elongation at break 1%; 2-10 ohm / cm; tg-5 (V) PV () 10 Hz) -2.8. -2.3-10 Plastic samples made by direct pressing at a specific pressing pressure of 500 kg / cm and a temperature of 260 ° C had the following mechanical properties: specific impact viscosity 8 kg / cm, tensile strength 430 kg / cm The moisture absorption of plastic samples during boiling in water until saturation is 5%. Examples 2-4 of the preparation of polysulfonides according to the procedure indicated above (see table).

Claims

Example 5. A polymer was prepared as described in Example 1, except that the solvents are distributed as follows: 4,4-diaminodiphenylmethane and sodium carbonate are dissolved in 2 ml of tetrahydrofuran and 16.6 ml of water, 4,4-diphenyl disulfonyl chloride solution are placed in 6.3 ml of tetrahydrofuran. The resulting polymer precipitates as a swollen mass after 1 min after the addition of sulfonyl chloride. Stirring is continued for a further 9 minutes. The polymer yield is-g 00%, 0.5 dl. Example 6. To a vigorously stirred solution of 0.7435 g (0.0075 mol), 4.4-diaminodiphenylmethane and O, 795 g ( 0.0075 mol of sodium carbonate, dissolved in 4.5 ml of tetrahydrofuran and 12.5 m of water, 1.33 g (0.00375 mol of excess 1%) of 4,4-diphenyl disulfonyl chloride in 8 ml of tetrahydrofuran are added. The resulting polymer precipitates as a swollen mass 3-4 minutes after the addition of sul fonipchloride. Stirring is continued for another 7 minutes and 100 ml of water is added to completely precipitate the polymer from the reaction medium. The polymer is treated as in Example 1. The polymer yield is 1OO%. The polymer is insoluble in dimethylaptamide, as well as other organic solvents, and is suitable for processing into plastic. The polymer softening temperature is 200 ° C. Plastics samples have the following mechanical properties: specific impact viscosity 8 kg / cm2 tensile strength 300 kg / cm2. The invention claims;} and a method for producing aromatic polysulfonamides by polycondensation of aromatic diamines and aromatic disulfonyl chlorides in the presence of a hydrogen chloride acceptor, characterized in that in order to obtain polymers with a high molecular weight and simplify the technology, the polycondensation is carried out in a mixture of water and an organic solvent , -, miscible with water, at a ratio of 1-2 in the presence of an alkali metal carbonate, with a molar concentration of 2 times the concentration of disulfonyl chloride. Sources of information taken into account in the examination: 1. US Patent N 3591559 Cl. 26O49, 1970 (prototype).