Polymerization of lactams, 88. Copolymers poly(ϵ‐caprolactam)‐block‐polybutadiene prepared by anionic polymerization, part III. Model polymerizations initiated with potassium salt of ϵ‐caprolactam and accelerated with isocyanates and their derivatives

Abstract

Anionic polymerization of e-caprolactam was initiated with the potassium salt of Ecaprolactam and accelerated with phenyl isocyanate, toluylene diisocyanate, 4,4'-diphenylmethane diisocyanate, some derivatives of these isocyanates (urethanes, ureas, and allophanates), or combinations of phenyl isocyanate with its derivatives at 150°C. The effect of individual structures on the polymerization kinetics and their contribution to the preparation of block copolymers of e-caprolactam with hydroxy-terminated prepolymers, in-situ functionalized with diisocyanates, are discussed on the basis of a detailed analysis of time functions of polymer yield and degree of polymerization.

Activated anionic ring-opening polymerization of ε-caprolactam with magnesium di(ε-caprolactamate) as initiator: effect of magnesium halides

“…S2) are linear at least up to 80-85% of the monomer conversion indicating that the polymerization of e-caprolactam exhibits zero-order kinetics in respect of the monomer concentration under investigated conditions. According to [15,16,23], the rate of activated anionic polymerization of e-caprolactam exhibiting zero-order kinetics could be expressed by following equations: As shown in Fig. 2, the zero-order plots are linear up to high monomer conversions (80-85%) and pass trough the origin.…”

“…Sodium salt of e-caprolactam (CLNa) or its precursors (sodium hydride, sodium methoxide) are a most used initiator in the (co)polymerization of lactams [7,9,[11][12][13][14][15][16][17]. The main disadvantages of this initiator are rather high content of cyclic oligomers [18][19][20] in obtained polymers and relatively low thermal stability [5] of resulting polyamides.…”

Synthesis of nylon-6 triblock copolymers with bifunctional polymeric activators

“…7 The ampules, prepolymer, and monomer HL were added to a glass reactor in a nitrogen atmosphere and were molten at 90°C with continuous stirring for 10 min (the PAC was prepared in situ). After the homogenization of the mixture, the initiator (Na-HL) was added with vigorous stirring, and the mixture was forced into ampules with N 2 .…”

“…In the literature, there are reported elastomeric blocks based on different polyethers [polyethyleneoxide, polypropyleneoxide, and polytetrahydrofuran (PTHF)], [1][2][3][4][5] polybutadiene, [6][7][8] butadiene-acrylonitryl copolymer diols, 9 styrene-butadiene, 10 and polyethersulfone. 11 In addition, a commercial multiblock copolymer (PEBAX) based on polyamide and PTHF prepared by polycondensation is well known.…”

Polymerization of lactams, 94. Formation of cyclic oligomers in anionic polymerization of 6-hexanelactam

“…The content of polymer was determined by a fourfold extraction of the polymerization products with methanol (100 mL per 1 g of the polymerization product) under reflux for 20 min. The average molar masses were determined by viscometry according to 16) . The analyses of the cyclic oligomers were performed using a HPLC apparatus: HP pumps Consta Metric 3500, Consta Metric 3200, injector Rheodyne 7225i (sample loop 20 …”