CS229038B3 - Method of polymerizing and copolymerizing lactams of om - Google Patents

Description

The invention relates to a process for the polymerization and copolymerization of omege-amino acid lactams.

The polymerization and copolymerization of the lactams of the general formula (H-CH3) -O-O can be carried out in several ways, which differ according to the polymerization mechanism used according to the catalysts used. Tzv. The hydrolytic polymerization is catalysed by omega-emino acids, water or water-releasing agents and lasts from several hours to several hundred hours depending on the lactams used, the temperature, the concentration and the type of catalyst. By contrast, anionic polymerization of lactams is catalyzed by strong bases and proceeds in the presence of activators with an N-acyllactam structure several orders of magnitude faster than hydrolytic polymerization, even at low temperatures below the melting point of the polymer. Both methods are used technologically.

In contrast, the cationic polymerization of lactams catalysed by organic or inorganic acids or their lactase salts has not yet found technological application for the slow speed and complexity of the individual phases of the reaction.

Recently, novel initiators of cationic polymerization of lactams - equimolar anhydrous phosphoric acid compound with lactams of the homogeneous amino acids of the formula H 2 PO 4 have been described. The polymerization of omege-amino acid lactams initiated by these compounds, depending on the type of lactams, the initiator concentration and the temperature, is at a rate equal to or higher than the hydrolytic polymerization. In addition, a portion of phosphoric acid remains chemically bound in the polyamide reduced flammability, increased hydrophilicity.

The present invention does not bind the above results. In essence, the polymerization and copolymerization of lactams is initiated with 0.1 to 20 moles SK of the equimolar anhydrous arsenic acid compound with the lactams of the omega-amino acids of the formula H 2 AsO 4. HH- (CHg) _x -fco, where x is 3 to 11, according to Art. No. 227784 at temperatures of 200 to 330 ° C.

The effect of the process according to the invention is that the polymerization or copolymerization of the lactams initiated by the compounds takes place at temperatures common, e.g. The polymerization degree of the resulting polymers increases with decreasing initiator content so that polyamides and copolyamides can be prepared from low molecular weight, suitable for preparing polyamide powders for sorption materials and dispersions, to high molecular weight, suitable for spinning, injection molding and extrusion.

In addition to the initiating effect, the compounds have H 2 AsO 4. ΝΗ- (ΟΗ ₂ ) _χ - <} θ yet another advantageous property. Indeed, arsenic acid remains partially incorporated into the polyamide or copolyamide chain and is therefore the carrier of the novel properties of these polymers, e.g. antibactericidal, etc.

The process according to the invention is described in more detail below on several exemplary embodiments.

He did

6-Caprolactam was polymerized in the presence of 2 mol. % of the compound HytsO4. HH- (CH ₂ ) ₅ -CO at 260 ° C in a sealed evacuated glass vial. After 1 hour 40% of the polymer having a viscosimetric polymerization degree of Pg = 36 was obtained, after 3 hours 78% of the polymer with Pg = 66. An equilibrium polymer of P- = 67 was obtained after 8 hours of polymerization. (The polymer content was determined after extraction with water.)

Example 2

Polymerization of 6-caprolactam, initiated with 20 moles of XH ^O AsO ^. NH- _(CH2) ^ - has been performed as described in Example 1. After 30 min of polymerization, the ampoule was cooled and the contents extracted with water, and dried zfiltrovén. 70% of the polymer powder with P = 15 were obtained.

Example 3

Polymerization of 8-octanlactam, initiated with 2 moles of XH ^O AsO ^. 1 H- (CH ₂ ) ₂ -CO at 200 ° C was carried out as in Example 1. Equilibrium polyamide 8 o P _f; = 70 was obtained after 100 hours of polymerization.

Example 4

Polymerization of 12-dodecenlektem, initiated with 0.1 mol XH2O2O4. The? - (CH ₂ ) 4 -CO ₂ at 330 ° C was carried out as in Example 1 except that the polymer content was determined after the reaction mixture was extracted with methanol. After three hours of polymerization, 90% of polyamide 12 having P = 320 were obtained.

Example 5

Copolymerization of an equimolar mixture of 6-caprolactam and li-dodecanlectam, initiated with 2 mol X of HjAsO ^. 1 H- (CH ₂ ) i -CO at 260 ° C was carried out according to Example 4, an equilibrium copolymer with an intrinsic viscosity [7] = 1.0 (m-cresol, 25 ° C) was obtained after 20 hours.

Example 6

Terpolymerization of an equimolar mixture of 6-caprolactam, 12-dodecalactam and a mixture of 6-caprolactam C-methyl isomers, initiated with 10 mole of H HA AsO ^. The -H-CHg)) ^-00 was carried out as described in Example 4. After 90 minutes of polymerization at 260 ° C and extraction with methanol, the resulting terpolyamide was> [?] 0.4 in a yield of 48%.

Claims (1)

SUBJECT OF THE INVENTION Process for polymerization and copolymerization of lactams of omega-amino acids of the general formula r-1 NH- (CHg) _x -CO, 1; de x is from 3 to 11, characterized in that the copolymerization of β polymerization is initiated with 0.1 to 20 mol% of an equimolar compound of anhydrous arsenic acid with lactams of oraege-amino acids of the formula . NH- (CHg) _x -CO, where x is 3 to 11 protected by copyright certificate No. 227784 at temperatures of 200 to 330 ° C.