SU1279533A3 - Method of producing polyhexamethylenadipamide - Google Patents

Abstract

The invention relates to the synthesis of polyhexamethylene adipamide, used for the manufacture of fibers. The invention allows to reduce the duration of the process, which consists in the interaction of equimolar amounts of adipic acid and hexamethylenediamine at 225-290 C and a pressure of 22-24 bar at the beginning and 0.335-6 bar at the end of the process in the presence of a ammonia, 16-45 wt.% Water and 0.01-1. , 0 wt.% catalyst vybrannogoiz group consisting fosfornuyukislotu, phosphorous acid, tris-nonilfosfit, 2-ethylhexyl-di-phenyl phosphate, tris-nonilfenilfosfit, difenilizooktilfosfit, dilaurilfosfit, tris-izooktilfosfit, fenilfosfonovuyukislotu, di ammonium phosphate ,, three enilfosfat, 4-ts1luolsulfokislo§tu, 2-naphthalenesulfonic acid, sulfaaminoammiachnuyu salt, boric acid, hydrogen iodide and ammonium iodide. with 1 tab.

Description

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00 to 1, 1 The invention relates to the synthesis of polymers, namely to the preparation of the complete hexamethylacadipamide used to make fibers. The purpose of the invention is to reduce the duration of the process of obtaining polymers. Example 1. A mixture of equimolar amounts of adipic acid nitrile and hexamethylenediamine containing 45% by weight of water and 0, May,% of phosphoric acid as a catalyst is loaded into a 2 liter autoclave with stainless steel, for 45 minutes the mixture is heated to 225 C, the pressure then rises to 22 bar. Over the next 50 minutes, the ammonia formed is continuously released through a reflux condenser, and the evaporated water is returned to the apparatus using the same reflux condenser. Then, for J 35 minutes, the temperature is raised to 275-285 C. And a gradual decrease in pressure is started, which in 60 minutes is reduced to 1 bar. The reaction mixture is kept under these conditions for 45 minutes and then discharged from the apparatus under nitrogen pressure. The polyamide is granulated or directly used to produce fibers. The molecular weight achieved is controlled by measuring the viscosity of a solution of 1 g of polymer in 100 mg of 96% sulfuric acid at 25 ° C. The results are shown in the table, Examples 2-23. According to the procedure described in Example 1f, the polymer is synthesized using different amounts of water and a catalyst. The results are shown in the table. Example 24. A homogenous mixture consisting of 38.0% adipoylstripe, 40.8% hexamethylenediamine, 21.1% water and 0.1% phosphorous whipping is discharged from the vessel that was in the preparation vessel using purified nitrogen, and continuously fed to the reactor cascade at a rate of kg / h. The reactor cascade contains two reactors equipped with partial condensers and a common gas system (filling level 75%). During the process, the following conditions are maintained in the reactors; 1 reactor - II reactor Pressure, bar 2424 242 265-270 Temperature, C 32 Temperature of reflux condenser, C 5590 At the same time, released ammonia is continuously removed from the reactors in an amount of 173 l / h at 30 ° C). The reaction product from the second reactor enters the autoclave, having a temperature of 280 Cj where the pressure is reduced to 5-6 bar, and the water vapor is condensed with a cooler. Next, the mixture enters the final polycondensation reactor, where the discharge is carried out to a residual pressure of L bar, and the temperature rises to 290 C. Nitrogen (5 l / h under normal conditions) is continuously fed into this apparatus, with which Noah pairs. The finished polymer using a gear pump in the amount of 0.795 kg / h is supplied for cooling and granulation. The granulation is dried at 105 ° C under vacuum for 12 hours until a residual moisture content of 0.08% is reached. The polymer obtained has a relative viscosity of a solution of 2.43. The table shows the process parameters and properties of the obtained polymers. Formula. The method of producing polyhexamethylene adipamide by reacting equimolar amounts of dinnitril adipic acid and hexamethylenediamine in the presence of water and ammonia with. 225-. 290 C and a pressure of 22-24 bar at the beginning and 0.335-6 bar in the end of the process, characterized in that, in order to reduce the duration of the process, water is used in an amount of 645% by weight of the mixture and additionally a catalyst selected from the group comprising a sponge s, boric acid, hydrogen iodide and ammonium iodide in an amount of 0.01-1.0% by weight of the reaction mixture. Priority by featured; 05/18/81 - use of phosphoric and phosphorus as a catalyst312795334

of acids, tris-nonylphosphite, 2-20.04.82 - use in c-ethylhexyl-diphenyl phosphate, tri-catalyst of 4-toluene-sulphononyl-phenylphosphite, diphenyl-isooctyl-acid, 2-naphthalene-sulphonic acid,

phosphite, dilauryl phosphite, tris-iso-sulfamines, boric acid, iothyl phosphite, phenylphosphonic acid, hydrogen hydroxide, iodide am

diammonium phosphate, triphenyl phosphate.monium.

Table continuation

Here and in Examples 2-19, the total reaction time is 5 hours. Here and in Examples 21 and 22, it takes more than 8 hours to achieve a polymer viscosity sufficient to produce fibers.

Claims (3)

^ Formula, inventions The method of obtaining polyhexamethylene "adipamide by the interaction of equimolar amounts of adipic dinitrile 3 acids and hexamethylenediamine in the presence of water and ammonia. 225-. 290 ° C and a pressure of 22-24 bar at the beginning and 0.335-6 bar at the end of the process, characterized in that, with 4Q in order to reduce the duration of the process, water is used in an amount of 1645% by weight of the mixture and an additional catalyst is used, selected from the group consisting of phosphoric acid, 45 phosphorous acid, tris-nonylphosphite, diphenylisooctylphosphite, dilaurylphosphite, tris-isooctylphosphite, 2-ethylhexylphosphate, tris-nonylphenylphosphite, phenylphosphonic acid, 5Q diammonium phosphate, triphenyl phosphate, 4-toluenesulfonic acid, 2-naphthalenesulfonic acid, sulfamino ammonium salt, boric acid, hydrogen iodide and ammonium iodide, in an amount of 0.01-1.0% by weight of the reaction 55. mixtures. Priority by feature; 05/18/81 - use of phosphoric and phosphoric acids, tris-nonylphosphite, 2-ethylhexyl-diphenyl phosphate, tris-nonylphenylphosphite, diphenyl isooctylphosphite, dilauryl phosphite, tris-isooctylphosphite, phenylphosphonate, and phenylphosphonate as a catalyst. 20.04.82 - the use of 4-toluenesulfonic acid as a catalyst, 2-n aphthium alium of sulfonic acid, sulfamino salt, boric acid, ionized hydrogen, ammonium iodide. Example Amount of water % Catalyst Amount of catalyst % Pressure bar Relative viscosity Suitability FOR NII half-fiber one 2 3 four 5 6 7 one*  45 Phosphoric acid 0.018 22 2,53 Good 2 ²¹ Phenylphosphonic acid 0,044 22 2.60 Conditional 3 28.6 Diammonium phosphate 0.024 22 2.75 Good four 28.6 Triphenyl Phosphate 0,072 ²² 2.65 5 22 4-T olu ol sul'foki sl o ta 0.1 24 2,50 ' 6 22 2-Naphthalenesulfokis- lot 0.14 24 2,51 7 22 Boric acid 0.08 24 • 2.25 8 22 Hydrogen iodide 0,085 24 2.45 - ^{, g} - 9 22 Sul Famino Ammi Ach salt 0.11 24 . 2.42 • P__ 10 22 Ammonium iodide 0,096 24 2.48 eleven 22 Phosphoric acid 0.01 24 2.45 12 16 0.018 24 2.47 - 13 22 tris nonylphenyl phosphite 0.29 24 2.54 fourteen 22 Diphenyl isooctylphosphite 0.13 24 2,55 fifteen 22 Tris nonylpheni phosphate 0.16 24 2,51 16 22 Dyl auryl phosphite 0.16 24 2.54 1 7 22 2-9type hexyl diphenyl phosphate 0.14 24 2,52 eighteen 22 tris isooctylfo sphit 1,0 24 2,55 Very good 19 22 Phosphoric acid 0.017 24 2.81 Good Examples for comparison * * * twenty 45 No catalyst - 22 2.15 Conditional