Catalytic Ring-Opening Polymerization of Renewable Macrolactones to High Molecular Weight Polyethylene-like Polymers

Meulen, Inge van der; Gubbels, Erik; Huijser, Saskia; Sablong, RJ Rafaël; Koning, Cor E.; Heise, Andreas; Duchateau, Robbert

doi:10.1021/ma200685u

Cited by 123 publications

(131 citation statements)

References 55 publications

Supporting

Mentioning

127

Contrasting

Order By: Relevance

“…In comparison to the step‐growth polycondensation processes, the chain‐growth ROP of large lactones enables the achievement of a high degree of control over molecular weight and their dispersity, end‐group fidelity, regio‐ and stereoselectivity, and architecture . More importantly, the ROP should enable the copolymerization of different monomers and allow to modulate carefully composition and topology (block, cyclic, star, and so forth) thus opening the scenario to different and programmed polymeric architectures . A further added value is the “green” origin of macrolactones, being derived from renewable resources, mostly isolated from plant oil, often used in the fragrance industries.…”

Section: Introductionmentioning

confidence: 99%

Tuning the thermal properties of poly(ethylene)‐like poly(esters) by copolymerization of ε‐caprolactone with macrolactones, in the presence of a pyridylamidozinc(II) complex

Naddeo

D’Auria

Viscusi

et al. 2020

Journal of Polymer Science

View full text Add to dashboard Cite

Linear aliphatic poly(ester)s, as thermoplastic materials, are more and more envisaged as the potential “green” alternative to traditional plastics. Aliphatic polyesters having long methylene chain behave as “polyethylene‐like” materials and can be prepared by ring‐opening polymerization (ROP) of macrolactones. A pyridylamidozinc(II) complex was used for the ROP of ε‐caprolactone (CL) and of two large ring size lactones, the ω‐6‐hexadecenlactone (6HDL) and the ω‐pentadecalactone (PDL). High turnover frequencies were observed for the CL polymerization, while for the macrolactones, an entropy‐driven behavior was recognized. Random copolymerizations of the PDL with 6HDL and of the macrolactones with CL were successfully achieved, and the copolymer microstructure was ascertained by NMR and MALDI analyses. The copolymer melting temperatures, measured by DSC, and the thermal degradation behavior, studied by TGA in nitrogen and air atmosphere, were dependent on the copolymer's composition. © 2020 Wiley Periodicals, Inc. J. Polym. Sci. 2020, 58, 528–539

show abstract

Section: Introductionmentioning

confidence: 99%

Tuning the thermal properties of poly(ethylene)‐like poly(esters) by copolymerization of ε‐caprolactone with macrolactones, in the presence of a pyridylamidozinc(II) complex

Naddeo

D’Auria

Viscusi

et al. 2020

Journal of Polymer Science

View full text Add to dashboard Cite

show abstract

“…Macrolactones are of interest in ROP as the longer uninterrupted ethylene chains with regular ester linkages could potentially serve as biodegradable alternatives to polyethylene. While there is very limited work on ROP of macrolactones with aluminum complexes, Duchateau has demonstrated its promise (64), using 4 and 13 to polymerize macrolactones decalactone (DL), undecalactone (UDL), pentadecalactone (PDL) and hexadecalactone (HDL), as shown in Figure 9. Polymerizations proceeded to high conversion (84 -98%) with relatively broad dispersities (1.6 -1.8) and molecular weights slightly higher than theoretical values.…”

Section: Monomer Scopementioning

confidence: 99%

Aluminum Salen and Salan Polymerization Catalysts: From Monomer Scope to Macrostructure Control

MacDonald

Shaver

2015

ACS Symposium Series

View full text Add to dashboard Cite

Tel +44 (0) 131 650 4726.Aluminum salen and salan complexes have been extensively employed as catalysts for the ring-opening polymerization of cyclic esters. The high tunability of the ligand framework has encouraged the systematic study of substituent effects on optimizing polymer and copolymer synthesis. Building on early work, designed catalysts are able to produce highly isotactic or heterotactic poly(lactic acid). The monomer scope has grown to include β-lactones, δ-valerolactone, lactide, (substituted) ε-caprolactones and macrolactones, with a significant level of control over molecular weight and dispersity (Đ). Polymer macrostructures have also been explored, often resulting in well-defined and predictable products. Macrostructures synthesized include random copolymers, AB diblock and ABA triblock copolymers and polymer stars.Polymer macrostructure control can tune properties not accessible through homopolymerization.

show abstract

“…Yet, a positive entropy of polymerization now dominates ROP, resulting in a net negative Gibbs free energy of polymerization and consequently in an entropy‐driven ROP (Δ

G_{polym}^{normal0}

= −8.0 kJ mol −1 ) . Apart from several metal based systems employed as ROP catalysts, especially enzymes exhibit high activity in ROP of pentadecalactone, resulting in molar masses as high as M w = 4.8 × 10 5 g mol −1 . Apart from this example, ROP of all‐aliphatic monolides of significantly larger ring sizes still is largely unexplored, presumably on account of the limited accessibility of these cycles.…”

Section: Introductionmentioning

confidence: 99%

No Strain, No Gain? Enzymatic Ring‐Opening Polymerization of Strainless Aliphatic Macrolactones

Witt

Häußler

Mecking

2017

Macromol. Rapid Commun.

View full text Add to dashboard Cite

Starting from readily available oleic and erucic acid, macrocyclic nonadecalactone (C ) and tricosalactone (C ) can be synthesized in polymerization grade purity in a four-step reaction sequence. Ring-opening polymerization (ROP) of these strainless macrolactones can be performed utilizing an enzyme as a catalyst. Despite the missing ring-strain as key driving force for smaller (strained) lactones, high molar masses (M ≈ 10 g mol ) can be accessed in an entropically driven ROP. Polyester-19 and polyester-23 prepared feature melting temperatures well above 100 °C. Further analysis of the mechanical properties of these materials displays the resemblance to polyethylene. For example, Young's moduli on the order of 600 MPa are observed as a result of the high crystallinity of the polymer.

show abstract

Catalytic Ring-Opening Polymerization of Renewable Macrolactones to High Molecular Weight Polyethylene-like Polymers

Cited by 123 publications

References 55 publications

Tuning the thermal properties of poly(ethylene)‐like poly(esters) by copolymerization of ε‐caprolactone with macrolactones, in the presence of a pyridylamidozinc(II) complex

Tuning the thermal properties of poly(ethylene)‐like poly(esters) by copolymerization of ε‐caprolactone with macrolactones, in the presence of a pyridylamidozinc(II) complex

Aluminum Salen and Salan Polymerization Catalysts: From Monomer Scope to Macrostructure Control

No Strain, No Gain? Enzymatic Ring‐Opening Polymerization of Strainless Aliphatic Macrolactones

Contact Info

Product

Resources

About