A Cascade Polymerization Method for the Property Modification of Poly(butylene terephthalate) by the Incorporation of Isosorbide

Abstract

Poly(butylene terephthalate) (PBT) is an important engineering plastic with good mechanical properties. We report herein the incorporation of biobased isosorbide into PBT by a green in situ cascade polycondensation-coupling ring-opening polymerization (PROP) method via the melt polymerization of commercially available isosorbide as initiator and cyclic oligo(butylene terephthalate)s (COBTs) as monomer. By varying the feeding weight ratio of isosorbide to COBTs, poly(butylene-coisosorbide terephthalate) (PBIT) copolyesters with different content of isosorbide (5−20%) were synthesized. The structure of the PBIT copolyesters was characterized by 1 H quantitative and 2D 1 H− 1 H gCOSY NMR spectra. Kinetics studies confirm the PROP mechanism, which shows the advantage of high atom economy (89−99%). Property investigation of the sustainable PBIT copolymers shows that their thermal decomposition temperature increased slightly compared to PBT homopolymers, and the glass transition temperature increases with isosorbide content, while the melting and crystallization temperatures, crystallinity, and storage modulus decrease accordingly. Our PROP method provides a facile method for the synthesis of biodegradable and sustainable PBIT copolymers, with improved properties that could extend their applications in engineering plastics.

Mono-acrylated isosorbide as a bio-based monomer for the improvement of thermal and mechanical properties of poly(methyl methacrylate)

“…Comparing with the linear PMMA chain, the incorporation of MAI with the free hydroxyl group increased the intramolecular interactions via a hydrogen bond. These enhanced interactions could inhibit the chain cleavage, improve impact strength, and contribute to a better toughness, which are in agreement with the results reported by Tu et al 38 In addition, the introduction of a fused ve-member rings of isosorbide into the PMMA linear chains has increased the free volume of the polymer chains, which could further improve the PMMA toughness.…”

Short-process synthetic strategies of sustainable isohexide-based polyesters towards higher molecular weight and commercial applicability

“…PROP is a combination of ROP and condensation polymerization (CP) processes, and can synthesize copolyesters with both high molecular weight and high functional group content, combining the advantages of both ROP and CP. 172,173 An early example of PROP is reported by Kricheldorf et al 174 They tried to obtain high-performance isosorbide-based polyester in one pot: firstly, isosorbide initiated the ring opening of lactide by using ZnCl 2 or SnCl 2 catalyst, and the resulting hydroxyl-terminated oligomer was polycondensed with isophthaloyl chloride (IPCl) in different solvents (chlorobenzene, xylene and toluene) to obtain the products (Scheme 6). The metal chlorides are effective catalysts to afford the copolyesters with relatively high molecular weight (M n : 11 000-25 500 g mol −1 ).…”

Effect of Block Number and Weight Fraction on the Structure and Properties of Poly(butylene terephthalate)-block-Poly(tetramethylene oxide) Multiblock Copolymers

“…Recently, we have developed a cascade polycondensation-coupling ring-opening polymerization (PROP) method for the facile synthesis of poly­(ether ester) mBCPs, utilizing polyether diols as an initiator and cyclic oligoesters as a monomer. − Due to the cascade coupling of two polymerizations, poly­(ether ester) mBCPs with high molecular weights can be obtained quickly (about 1 h). The side reactions in traditional condensation polymerization are deeply suppressed in PROP by reducing the polymerization time, and mBCPs with a better controlled structure are obtained.…”