Synthesis and characterization of poly(p‐phenylene)‐graft‐poly(ε‐caprolactone) copolymers by combined ring‐opening polymerization and cross‐coupling processes

Abstract

2,5‐Dibromo‐1,4‐(dihydroxymethyl)benzene was used as initiator in ring‐opening polymerization of ε‐caprolactone in the presence of stannous octoate (Sn(Oct)2) catalyst. The resulting poly(ε‐caprolactone) (PCL) macromonomer, with a central 2,5‐dibromo‐1,4‐diphenylene group, was used in combination with 1,4‐dibromo‐2,5‐dimethylbenzene for a Suzuki coupling in the presence of Pd(PPh3)4 as catalyst or using the system NiCl2/bpy/PPh3/Zn for a Yamamoto‐type polymerization. The poly(p‐phenylenes) (PPP) obtained, with PCL side chains, have solubility properties similar to those of the starting macromonomer, ie soluble in common organic solvents at room temperature. The new polymers were characterized by 1H and 13C NMR and UV spectroscopy and also by GPC measurements. The thermal behaviour of the precursor PCL macromonomer and the final poly(p‐phenylene)‐graft‐poly(ε‐caprolactone) copolymers were investigated by thermogravimetric analysis and differential scanning calorimetry analyses and compared. Copyright © 2004 Society of Chemical Industry

Organocatalyzed ring-opening copolymerization of α-bromo-γ-butyrolactone with ε-caprolactone for the synthesis of functional aliphatic polyesters – pre-polymers for graft copolymerization

“…A commonly used technique to prepare aliphatic polyesters is controlled ring-opening polymerization (CROP) which can construct well-defined polymers. However, up to now, many CROPs of εCL are catalyzed by metal-containing catalysts, such as stannous octoate [Sn(Oct) 2 ] [8,9], zinc-containing catalyst [10], iron-containing catalyst [11], magnesium-containing catalyst [12] and aluminum-containing catalyst [13], to name a few. It is attractive that the recent development of metal-free organocatalysts for CROP brings a new horizon of preparing aliphatic polyesters.…”

Synthesis, characterization, and hydrolytic degradation of graft copolymers of polystyrene and aliphatic polyesters

“…This methodology affords possibility to incorporate functional groups into polyesters provided that in addition to the hydroxyl groups, the initiator contains desired functionality. Previously, we have prepared thermal- [21][22][23][24][25][26][27], photo- [28,29], and electro-functional [30] polymers of biocompatible polymers by taking advantage of the functional initiator approach [31].…”

A QSPR Study on the Physical Properties of Substituted Polypyrroles and Poly(paraphenylenes)

“…Polypyrroles (PPy) with high conductivity [4,8] and environmental stability [4,7,8], and poly(para-phenylene)s (PPP) with excellent mechanical [8][9][10][11][12] and thermal stability [9][10][11], are widely studied. These polymers consitute rigid-rod structures with extended π-conjugation which qualifies them as electronic materials with stiff backbones and outstanding mechanical properties [12].…”

“…The experimental studies mentioned above [9][10][11][12][13][14][15][16][17][18][19] motivated us to study the effect of side-chain chemistry on the physical properties such as the glass transition temperature, cohesive energy and dielectric constants of the same systems by using empirical methods. The effect of the length and the type of the linearly extended side-chains grafted to the rigid backbone of PPP and PPy have been investigated by the quantitative structure-property relationship (QSPR) methodology.…”

“…Poly(ε-caprolactone) [9][10][11][12][13][14][15][16][17][18][19] (PCL) and polystyrene [9,15,17] (PSt) substituted poly(p-phenylene) co-polymers have been synthesized and characterized several times by 1 H-NMR, IR, GPC and DSC (Fig. 1).…”