PL133746B2 - Method of manufacture of copolyamides - Google Patents

Method of manufacture of copolyamides Download PDF

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Publication number
PL133746B2
PL133746B2 PL24388683A PL24388683A PL133746B2 PL 133746 B2 PL133746 B2 PL 133746B2 PL 24388683 A PL24388683 A PL 24388683A PL 24388683 A PL24388683 A PL 24388683A PL 133746 B2 PL133746 B2 PL 133746B2
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Prior art keywords
laurinolactam
copolyamides
weight
carried out
catalyst
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PL24388683A
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Polish (pl)
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PL243886A2 (en
Inventor
Piotr Biernacki
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Politechnika Lodzka
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Priority to PL24388683A priority Critical patent/PL133746B2/en
Publication of PL243886A2 publication Critical patent/PL243886A2/en
Publication of PL133746B2 publication Critical patent/PL133746B2/en

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Description

Przedmiotem wynalazkujest sposób otrzymywania kopoliamidów stosowanych do wytwarza¬ nia wlókien oraz folii.Znane sa sposoby otrzymywania kopoliamidów z laktamów polegajace na ogrzewaniu subs- tratów z dodatkiem wody i kwasów organicznych lub nieorganicznych w temperaturze 290 — 330°C, pod zwiekszonym cisnieniem rzedu od kilku do kilkudziesieciu atmosfer, a nastepnie w atmosferze gazu obojetnego pod normalnym lub zmniejszonym cisnieniem. Reakcje prowadzi sie w czasie od kilku do kilkudziesieciu godzin, przy czym zwykle stosuje sie mieszanie.Niedogodnoscia znanych sposobów jest stosowanie podwyzszonego cisnienia, stosunkowo wysokich temperatur i dosc dlugich czasów reakcji dla osiagniecia duzego stopnia przereagowania laktamów.Sposób otrzymywania kopoliamidów wedlug wynalazku polega na tym, ze do mieszaniny koprolaktamu i laurynolaktamu wprowadza sie zwiazek o wzorze ogólnym przedstawionym na rysunku, w ilosci 1-3% wagowych, a nastepnie mieszanine reakcyjna ogrzewa sie w atmosferze gazu obojetnego, w srodowisku bezwodnym pod cisnieniem atmosferycznym, w temperaturze 280- 282°C, w czasie 8-16 godzin. W sposobie wedlug wynalazku stosuje sie 35-36 czesci wagowych kaprolaktamu na 65-64 czesci wagowe laurynolaktamu. Zwiazek o wzorze ogólnym, przedstawio¬ nym na rysunku, spelnia w sposobie wedlug wynalazku funkcje katalizatora i regulatora masy czasteczkowej i jest otrzymywany w reakcji miedzy laurynolaktamem a kwasem fosforowym, przy czym stosunek molowy laurynolaktamu do kwasu jest najkorzystniejszy przy 1:1.Sposób wedlug wynalazku zapewnia otrzymanie kopoliamidów z duza wydajnoscia rzedu 95-96% o dobrych wlasnosciach wlóknotwórczych, nadajacych sie równiez do otrzymywania folii, w procesie, w którym wyeliminowano nadcisnienie, wysokie temperatury i dlugi czas reakcji.Zmiana ilosci katalizatora zezwala na regulowanie masa czasteczkowa i lepkoscia otrzymanego kopoliamidu. Lepkosc wzgledna, mierzona w 0,5% roztworze m-krezolu, w temperaturze 25°C, wynosi 1,5-1,9. Zmiana skladu wyjsciowej mieszaniny zezwala na regulowanie wlasnosciami otrzymywanego kopoliamidu, a zwlaszcza jego temperature topnienia w zakresie 134-220°C.Sposób wedlug wynalazku ilustruje podany nizej przyklad.2 133746 Przyklad. 0,1 mola laurynolaktamu rozpuszczono w 0,7 mola benzenu w temperaturze wrzenia pod chlodnica zwrotna. Po ostygnieciu roztworu do 50°C wprowadzono 0,1 mola kwasu fosforowego w postaci 85% kwasu fosforowego. Mieszanine ogrzewano w temperaturzqwrzenia w czasie 30 minut. Oddestylowano azeotrop benzen-woda, a nastepnie 0,1 mola odwodnionego benzenu. Mieszanine pozostawiono do stygniecia, po czym rozdzielono na dwie warstwj. Zdekan- towano górna warstwe benzenowa, przy czym dolna warstwa przechodzila ze stanu dieklego w twarde krystaliczne, higroskopijne, biale cialo stale katalizatora o wzorze ogólnym przedstawio¬ nym na rysunku.Do reaktora wprowadzono 36 czesci wagowych kaprolaktamu i 64 czesci wagowe laurynolak¬ tamu. Przez 20 minut przepuszczano azot. Powoli stopiono mieszanine laktamów w atmosferze azotu i dodano 1,5 czesci wagowej otrzymanego wyzej katalizatora. Mieszanine reakcyjna, w atmosferze azotu i pod cisnieniem atmosferycznym ogrzewano w temperaturze 280°C w czasie 11 godzin. Otrzymano przezroczysty kopoliamid, w którym ilosc nieprzereagowanych laktamów nie przekraczala 5%, o temperaturze topnienia 134°C i lepkosc wzglednej 1,7-1,9 (oznaczenie w m-krezolu w temperaturze 25°C przy stezeniu 0,5g/100cm3 roztworu).Zastrzezenie patentowe Sposób otrzymywania kopoliamidów droga kapolimeryzacji kaprolaktamu i laurynolak¬ tamu, w atmosferze gazu obojetnego, znamienny tym, ze kopolimeryzacje prowadzi sie w obecnosci 1-3% wagowych katalizatora o wzorze ogólnym, przedstawionym na rysunku, otrzymanego w reakcji miedzy laurynolaktamem a kwasem fosforowym, najkorzystniej przy stosunku molowym 1:1, przy czym kopolimeryzacje prowadzi sie w srodowisku bezwodnym, pod cisnieniem atmosfe¬ rycznym przez ogrzewanie w temperaturze 280-282°C w czasie 8—16 godzin. c=o CH + NH PO, Pracownia Poligraficzna UP PRL. Naklad 100 cgz.Cena 100 zl PLThe subject of the invention is a method of obtaining copolyamides used for the production of fibers and films. There are known methods of obtaining copolyamides from lactams consisting in heating the substrates with the addition of water and organic or inorganic acids at a temperature of 290-330 ° C, under increased pressure from a few to several dozen atmospheres, and then in an inert gas atmosphere under normal or reduced pressure. The reactions are carried out in the period from several to several dozen hours, and usually mixing is used. The disadvantage of the known methods is the use of increased pressure, relatively high temperatures and rather long reaction times to achieve a high degree of conversion of lactams. The method of obtaining copolyamides according to the invention consists in the following: that a compound of the general formula shown in the figure is introduced into the mixture of coprolactam and laurinolactam in the amount of 1-3% by weight, and then the reaction mixture is heated in an inert gas atmosphere, in an anhydrous environment under atmospheric pressure, at a temperature of 280-282 ° C, in 8-16 hours. In the process according to the invention, 35-36 parts by weight of caprolactam are used for 65-64 parts by weight of laurinolactam. The compound of the general formula shown in the figure performs the functions of a catalyst and a molecular weight regulator in the process according to the invention and is obtained by the reaction between laurinolactam and phosphoric acid, the molar ratio of laurin lactam to acid being the most preferred at 1: 1. ensures the production of copolyamides with a high efficiency of 95-96% with good fiber-forming properties, also suitable for the production of films, in a process in which overpressure, high temperatures and long reaction time are eliminated. Changing the amount of the catalyst allows you to adjust the molecular weight and viscosity of the obtained copolyamide . Relative viscosity, measured in 0.5% m-cresol solution at 25 ° C, is 1.5-1.9. The change in the composition of the starting mixture allows to control the properties of the obtained copolyamide, especially its melting point in the range of 134-220 ° C. The method according to the invention is illustrated by the following example.2 133746 Example. 0.1 mole of laurinolactam was dissolved in 0.7 mole of benzene under reflux. After the solution had cooled to 50 ° C, 0.1 mole of phosphoric acid in the form of 85% phosphoric acid was introduced. The mixture was heated to reflux for 30 minutes. The benzene-water azeotrope was distilled off, followed by 0.1 mole of dehydrated benzene. The mixture was allowed to cool and then separated into two layers. The upper benzene layer was decanted, the lower layer changing from the diocese to a hard crystalline, hygroscopic white catalyst solid of the general formula shown in the figure. 36 parts by weight of caprolactam and 64 parts by weight of laurinolacam were introduced into the reactor. Nitrogen was bubbled through for 20 minutes. The lactam mixture was slowly melted under a nitrogen atmosphere and 1.5 parts by weight of the catalyst obtained above were added. The reaction mixture was heated at 280 ° C for 11 hours under an atmosphere of nitrogen atmosphere. A transparent copolyamide was obtained, in which the amount of unreacted lactams did not exceed 5%, with a melting point of 134 ° C and a relative viscosity of 1.7-1.9 (determination in m-cresol at 25 ° C at a concentration of 0.5 g / 100 cm3 of the solution) Patent claim A method of obtaining copolyamides by capolymerization of caprolactam and laurinolactam in an inert gas atmosphere, characterized in that the copolymerization is carried out in the presence of 1-3% by weight of a catalyst of the general formula shown in the figure, obtained by the reaction between laurinolactam and phosphoric acid. most preferably in a molar ratio of 1: 1, the copolymerizations being carried out in an anhydrous environment under atmospheric pressure by heating at 280-282 ° C for 8-16 hours. c = o CH + NH PO, Printing Studio of the UP PRL. Mintage 100 cgz Price PLN 100 PL

Claims (1)

Zastrzezenie patentowe Sposób otrzymywania kopoliamidów droga kapolimeryzacji kaprolaktamu i laurynolak¬ tamu, w atmosferze gazu obojetnego, znamienny tym, ze kopolimeryzacje prowadzi sie w obecnosciPatent claim A method of obtaining copolyamides by capolymerization of caprolactam and laurinolactam in an inert gas atmosphere, characterized in that the copolymerization is carried out in the presence of 1. -3% wagowych katalizatora o wzorze ogólnym, przedstawionym na rysunku, otrzymanego w reakcji miedzy laurynolaktamem a kwasem fosforowym, najkorzystniej przy stosunku molowym 1:1, przy czym kopolimeryzacje prowadzi sie w srodowisku bezwodnym, pod cisnieniem atmosfe¬ rycznym przez ogrzewanie w temperaturze 280-282°C w czasie 8—16 godzin. c=o CH + NH PO, Pracownia Poligraficzna UP PRL. Naklad 100 cgz. Cena 100 zl PL1. -3% by weight of a catalyst of the general formula shown in the figure, obtained by the reaction between laurinolactam and phosphoric acid, most preferably in a molar ratio of 1: 1, the copolymerization being carried out in an anhydrous environment under atmospheric pressure by heating at temperature 280-282 ° C for 8-16 hours. c = o CH + NH PO, Printing Studio of the UP PRL. Mintage 100 cg. Price PLN 100 PL
PL24388683A 1983-09-22 1983-09-22 Method of manufacture of copolyamides PL133746B2 (en)

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PL24388683A PL133746B2 (en) 1983-09-22 1983-09-22 Method of manufacture of copolyamides

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PL243886A2 PL243886A2 (en) 1984-08-13
PL133746B2 true PL133746B2 (en) 1985-06-29

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