Convenient Method of Chain‐Growth Polycondensation for Well‐Defined Aromatic Polyamides

Abstract

Summary: For the convenient synthesis of well‐defined poly(N‐octyl‐p‐benzamide)s with low polydispersities, the polycondensation of methyl 4‐octylaminobenzoate (1) was investigated. Methyl ester monomer 1 polymerized with lithium 1,1,1,3,3,3‐hexamethyldisilazide (LHMDS) in the presence of an initiator in tetrahydrofuran at −10 °C. The highly pure polyamide with a defined molecular weight and a low polydispersity is obtained after simple treatment of the reaction mixture with aqueous NaOH solution, followed by evaporation.The chain‐growth polycondensation of 4‐octylaminobenzoic acid methyl ester (1) with lithium 1,1,1,3,3,3‐hexamethyldisilazide (LHMDS) to yield poly(N‐octyl‐p‐benzamide).magnified imageThe chain‐growth polycondensation of 4‐octylaminobenzoic acid methyl ester (1) with lithium 1,1,1,3,3,3‐hexamethyldisilazide (LHMDS) to yield poly(N‐octyl‐p‐benzamide).

Synthesis of Well‐Defined Polybenzamide‐block‐Polystyrene by Combination of Chain‐Growth Condensation Polymerization and RAFT Polymerization

“…Methyl 4-(octylamino)benzoate 2 p , [7] ethyl 3-(octylamino)benzoate 2 m , [9] and N-octyl-p-toluidine 3 [17] were prepared according to the established procedures. …”

“…We have employed chain-growth condensation polymerization to obtain N-alkylated poly( p-benzamide) [6][7][8] and poly(m-benzamide) [9,10] with controlled molecular weight and narrow polydispersity, and have synthesized block copolymers including these aromatic polyamides. For example, block copolymers of poly(N-alkyl-p-benzamide) with poly(ethylene glycol) [11] and poly(tetrahydrofuran) [12] were synthesized by coupling reaction of the aromatic polyamide with these coil polymers.…”

Polycondensation of ‘a − bn’ or ‘a2 + + bn’ Monomers ‐ A Comparison

“…[48] Most of Yokozawa's work [45,47,50,53] was focused on the syntheses of aromatic polyamides. [54,58,[60][61][62]65,66] In numerous experiments phenyl N-alkyl-4-aminobenzoates were used as monomers. The N-substitution served two purposes.…”

Well‐defined star‐shaped poly(p‐benzamide) via chain‐growth condensation polymerization: Use of tetra‐functional porphyrin initiator to optimize star polymer formation

“…In our previous report, 7 LiHMDS, which is a stronger base, was effective for the synthesis of linear poly(N-octyl-p-benzamide)s with defined molecular weight and narrow molecular weight distribution by polymerization of the methyl ester monomer 1b. Therefore, the polymerization of 1b was carried out by using LiHMDS in the presence of…”