Organocatalyzed Synthesis of Aliphatic Polyesters from Ethylene Brassylate: A Cheap and Renewable Macrolactone

Pascual, Ana; Sardón, Haritz; Veloso, António; Ruipérez, Fernando; Mecerreyes, David

doi:10.1021/mz500401u

Cited by 75 publications

(93 citation statements)

References 53 publications

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“…Ethylene brassylate (EB) is one of the most commonly seen macrolactones. Fortunately, a novel catalyst such as triphenyl bismuth has been applied for the ROP of macrolactones and high molecular weights have been achieved . Poly(ethylene brassylate) (PEB) has poly(ε‐caprolactone)‐like properties with low T g (−30 °C) and excellent toughness (elongation at break higher than 1000%), which makes PEB an ideal mid‐block component of triblock copolymers.…”

Section: Introductionmentioning

confidence: 99%

Fully biobased biodegradable poly(l‐lactide)‐b‐poly(ethylene brassylate)‐b‐poly(l‐lactide) triblock copolymers: synthesis and investigation of relationship between crystallization morphology and thermal properties

Jin

Leng

Zhang

et al. 2020

Polymer International

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Well‐defined poly(l‐lactide‐b‐ethylene brassylate‐b‐l‐lactide) (PLLA‐b‐PEB‐b‐PLLA) triblock copolymer was synthesized by using double hydroxyl‐terminated PEBs with different molecular weights. Gel permeation chromatography and NMR characterization were employed to confirm the structure and composition of the triblock copolymers. DSC, wide‐angle X‐ray diffraction, TGA and polarized optical microscopy were also employed to demonstrate the relationship between the composition and properties. According to the DSC curves, the cold crystallization peak vanished gradually with decrease of the PLLA block, illustrating that the relatively smaller content of PLLA may lead to the formation of a deficient PLLA type crystal, leading to a decrease of melting enthalpy and melting temperature. Multi‐step thermal decompositions were determined by TGA, and the PEB unit exhibited much better thermal stability than the PLLA unit. Polarized optical microscopy images of all the triblock samples showed that spherulites which develop radially and with an extinction pattern in the form of a Maltese cross exhibit no ring bond. The growth rate of the spherulites of all triblock samples was investigated. The crystallization capacity of PLLA improved with incorporation of PLLA, which accords with the DSC and wide‐angle X‐ray diffraction results. © 2019 Society of Chemical Industry

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Section: Introductionmentioning

confidence: 99%

Fully biobased biodegradable poly(l‐lactide)‐b‐poly(ethylene brassylate)‐b‐poly(l‐lactide) triblock copolymers: synthesis and investigation of relationship between crystallization morphology and thermal properties

Jin

Leng

Zhang

et al. 2020

Polymer International

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“…A c c e p t e d M a n u s c r i p t ABSTRACT: 23 In this paper, a "graft from" Ring-Opening Polymerization (ROP) technique was used to 24 synthesize a lignin-graft-poly (ε-caprolactone) copolymer (BBL-g-PCL) using 25 biobutanol lignin (BBL) as raw material recovered from lignocellulosic butanol residue. 26 Polymerizations were carried out with various mass ratios of BBL and CL monomer BBL-g-PCL copolymers were characterized by differential scanning calorimetry (DSC) 33 and thermogravimetric analysis (TGA).…”

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confidence: 99%

“…However, changes in the biobutanol production Although the above publications showed that CL was successfully performed on the 90 lignin backbone by "graft from" ROP, the problem is that little metal residues will be 91 remain in the resulting products when using inorganocatalyst (e.g. zinc chloride and 92 stannous octanoate) for catalytic ring-opening polymerization (cROP) [23,24]. 93 However, that is an important factor restricting the application in packaging and 94 biomedical [24].…”

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confidence: 99%

Preparation and characterization of Lignin-graft-poly (ɛ-caprolactone) copolymers based on lignocellulosic butanol residue

Liu¹,

Zong

Jiang

et al. 2015

International Journal of Biological Macromolecules

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“…12−14 The ROP of macrolactones, viz. ω-pentadecalactone (PDL), can be catalyzed using enzymes, 14,15 organic catalysts, 13,16 and organometallic catalysts. 12,17−20 Polypentadecalactone (PPDL) has been compared with linear low-density polyethylene (LLDPE) due to the similar stiffness and molecular structure, in which the ester groups are compared with short-chain branches (SCBs).…”

Section: ■ Introductionmentioning

confidence: 99%

Mimicking (Linear) Low-Density Polyethylenes Using Modified Polymacrolactones

et al. 2015

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This paper presents a new approach toward the introduction of both short-(SCB) and long-chain branching (LCB) in polyethylene-like polyesters via the ring-opening polymerization of macrolactones. Macrolactones containing an alkyl (S1) or alcohol (S2) branch were obtained using radical thiol−ene chemistry of ambrettolide (Amb). Kinetic studies revealed the need for an excess of thiol to achieve a high conversion of the double bond. Even though homopolymerization of the three monomers Amb, S1, and S2 revealed comparable reactivities, the molecular weight buildup during polymerization of S2 differs drastically from that of Amb and S1. Instead of the linear increase of M n with conversion observed for Amb and S1, the molecular weight buildup for the ring-opening polymerization of S2 resembles that of a step-growth polymerizationslow buildup at low and moderate conversion followed by a rapid increase in molecular weight at high conversions. This disparity was attributed to the possibility of S2 to function as both an initiator and a monomer, leading to oligomers during the first part of the reaction that are subsequently connected to each other at the final stage of the reaction. Copolymerization of pentadecalactone (PDL) with various ratios of Amb, S1, and S2 in bulk led to the associated random copolymers containing double bonds, short-chain branches, and long-chain branches. The trans-double bonds in poly(PDL-coAmb) are included in the crystal lattice, leading to a slight decrease in the melting temperature, melting enthalpy and yield stress, while up to 20 double bonds/1000 backbone atoms the crystallinity and lamellar thickness remain similar to those of polypentadecalactone. In contrast, SCBs are fully excluded from the crystal lattice, leading to a more significant decrease in melting temperature and enthalpy as well as crystallinity and lamellar thickness with increasing branching density. The stiffness of these SCB-copolymers exponentially decreases as a function of branching content, effectively changing the mechanical behavior from semicrystalline to elastomeric. The LCB-containing polymers show an even larger linear decrease in melting temperature with increasing branching density than their SCB equivalents, likely due to the particular topology of the polymers consisting of a brush to a hyperbranched structure. However, a rapid decrease of molecular weight as was observed upon increasing the S2 content is also likely to play a role. The observed low molecular weight can be ascribed to both the fact that (macrocycles of) S2 can function as initiator, effectively increasing the amount of polymer chains, and the change of molecular weight buildup.

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Organocatalyzed Synthesis of Aliphatic Polyesters from Ethylene Brassylate: A Cheap and Renewable Macrolactone

Cited by 75 publications

References 53 publications

Fully biobased biodegradable poly(l‐lactide)‐b‐poly(ethylene brassylate)‐b‐poly(l‐lactide) triblock copolymers: synthesis and investigation of relationship between crystallization morphology and thermal properties

Fully biobased biodegradable poly(l‐lactide)‐b‐poly(ethylene brassylate)‐b‐poly(l‐lactide) triblock copolymers: synthesis and investigation of relationship between crystallization morphology and thermal properties

Preparation and characterization of Lignin-graft-poly (ɛ-caprolactone) copolymers based on lignocellulosic butanol residue

Mimicking (Linear) Low-Density Polyethylenes Using Modified Polymacrolactones

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