Polymerization of Racemic β-Butyrolactone Using Gold Catalysts: A Simple Access to Biodegradable Polymers

Brûlé, Emilie; Gaillard, Sylvain; Rager, Marie‐Noëlle; Roisnel, Thierry; Guérineau, Vincent; Nolan, Steven P.; Thomas, Christophe M.

doi:10.1021/om200271q

Cited by 38 publications

(14 citation statements)

References 45 publications

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“…The most efficient method for synthesizing PLAs and PCLs is the ring‐opening polymerization (ROP) of cyclic esters catalyzed by metal complexes, organic or enzyme catalysts. ROP processes offer excel control in terms of molecular weight ( M n ), polydispersity (MWDs) and microstructure . Several complexes have been successfully employed in the ROP of lactide, including lithium, sodium, potassium, magnesium, calcium, strontium, aluminum, tin, zinc, some transition metals, and rare‐earth metals .…”

Section: Introductionmentioning

confidence: 99%

Cubane‐Type Polynuclear Zinc Complexes Containing Tridentate Schiff Base Ligands: Synthesis, Characterization, and Ring‐Opening Polymerization Studies of rac‐Lactide and ε‐Caprolactone

Ghosh

Spannenberg

Mejía

2017

Helvetica Chimica Acta

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New polynuclear zinc complexes containing tridentate Schiff base ligands were successfully synthesized and fully characterized. The solid‐state structure of the complexes was determined using single crystal X‐ray diffraction. The complexes display a tetranuclear cubane‐like core structure [Zn4O4] and sowed good catalytic activity towards the ring‐opening polymerization (ROP) of rac‐lactide (rac‐LA) and ε‐caprolactone (ε‐CL) under solvent‐free conditions. The polylactic acid (PLA) obtained from rac‐LA showed isotactic enrichment, as proved by homonuclear decoupled 1H‐NMR analysis. These complexes also showed good activity and superior control towards the ROP of rac‐LA and ε‐CL in the presence of benzyl alcohol as a co‐initiator. Furthermore, kinetic studies demonstrated that the ROP of rac‐LA and ε‐CL has a first order dependence on both monomer (rac‐LA and ε‐CL) and catalyst concentration.

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Section: Introductionmentioning

confidence: 99%

Cubane‐Type Polynuclear Zinc Complexes Containing Tridentate Schiff Base Ligands: Synthesis, Characterization, and Ring‐Opening Polymerization Studies of rac‐Lactide and ε‐Caprolactone

Ghosh

Spannenberg

Mejía

2017

Helvetica Chimica Acta

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“… [20–22] Significant advancements in catalyst and methodology development have resulted in improved yields, turn‐over frequencies (TOF), and functionality tolerance, enabling the synthesis of structurally diverse and complex organic molecules. Access to new macromolecular chemistries could be obtained directly from aryl‐containing building blocks and various alkyne comonomers if an analogous polymerization chemistry was developed; however, the use of Au as a polymerization catalyst remains essentially unexplored [23–27] …”

Section: Methodsmentioning

confidence: 99%

Gold‐Catalyzed C−H Functionalization Polycondensation for the Synthesis of Aromatic Polymers

et al. 2020

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Homogeneous gold (Au) complexes have demonstrated tremendous utility in modern organic chemistry; however, their application for the synthesis of polymers remains rare. Herein, we demonstrate the first catalytic application of Au complexes toward the polycondensation of alkyne-containing comonomers and heteroarene nucleophiles. Polymerization occurs through successive intermolecular hydroarylation reactions to produce high molecular weight aromatic copolymers with 1,1-disubstituted alkene backbone linkages. Clear correlations between the rate and degree of polymerization (DP) were established based on catalyst structure and counterion pairing, thus enabling polymerization reactions that proceeded with remarkable efficiency, high reactivity, and exceptional DPs. The reactivity is broad in scope, enabling the copolymerization of highly functionalized aromatic and aliphatic monomers. These results highlight the untapped utility of Au catalysis in providing access to new macromolecular constructs. A principal strategy to achieve materials with robust mechanical, chemical, electronic, and thermal properties involves the incorporation of planar, rigid aromatic, or pseudo-aromatic units within the polymer backbone. [1-3] These aromatic polymers form the basis for many highperformance materials applied in demanding applications. While these materials are primarily derived from traditional step-growth polymerizations, late transition metal (i.e., Ni, Pd, Ru, Rh) mediated polycondensations have matured to high levels in recent years, enabling the synthesis of novel aromatic polymers which impact an innumerable number of emerging technologies. [4-7] In order to broaden the scope of polymers that can be prepared, there remains an ongoing need for new catalytic approaches that overcome limitations that define these reactions such as multistep monomer syntheses, harsh reaction conditions, stoichiometric byproduct generation, and intolerance toward oxygen and water. Consequently, widespread efforts have focused on metal catalyzed C À H activation and functionalization processes, where C À C bond formation occurs directly between C(sp 2) À

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“…Therefore, development of a synthesis method producing PHBs with controlled molecular weight, lower melting temperature, and lower brittleness would be a solution for industrial manufacturing and practical use of ideal bio-based polymers (Li et al, 2016). One of the most effective approaches for the controlled synthesis of PHB is ring-opening polymerization (ROP) of β-butyrolactone (BBL) (Kricheldorf and Eggerstedt, 1997; Hori and Hagiwara, 1999; Rieth et al, 2002; Ajellal et al, 2010; Brulé et al, 2011, 2013; Li et al, 2016). ROP of β-butyrolactone mediated by metal systems has attracted much attention in recent years and had considerable achievements (Kricheldorf and Eggerstedt, 1997; Hori and Hagiwara, 1999; Rieth et al, 2002; Ajellal et al, 2010; Brulé et al, 2011).…”

Section: Introductionmentioning

confidence: 99%

Stereoselective Ring-Opening (Co)polymerization of β-Butyrolactone and ε-Decalactone Using an Yttrium Bis(phenolate) Catalytic System

et al. 2019

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An effective route for ring-opening copolymerization of β-butyrolactone (BBL) with ε-decalactone (ε-DL) is reported. Microstructures of the block copolymers characterized by 13 C NMR spectroscopy revealed syndiotactic-enriched poly(3-hydroxybutyrate) (PHB) blocks. Several di- and triblock copolymers (PDL- b -PHB and PDL- b -PHB- b -PDL, respectively) were successfully synthesized by sequential addition of the monomers using (salan)Y(III) complexes as catalysts. The results from MALDI-ToF mass spectrometry confirmed the presence of the copolymers. Moreover, thermal properties of the block copolymers were also investigated and showed that the microphase separation of PDL- b -PHB copolymers into PHB- and PDL-rich domains has an impact on the glass transition temperatures of both blocks.

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Polymerization of Racemic β-Butyrolactone Using Gold Catalysts: A Simple Access to Biodegradable Polymers

Cited by 38 publications

References 45 publications

Cubane‐Type Polynuclear Zinc Complexes Containing Tridentate Schiff Base Ligands: Synthesis, Characterization, and Ring‐Opening Polymerization Studies of rac‐Lactide and ε‐Caprolactone

Cubane‐Type Polynuclear Zinc Complexes Containing Tridentate Schiff Base Ligands: Synthesis, Characterization, and Ring‐Opening Polymerization Studies of rac‐Lactide and ε‐Caprolactone

Gold‐Catalyzed C−H Functionalization Polycondensation for the Synthesis of Aromatic Polymers

Stereoselective Ring-Opening (Co)polymerization of β-Butyrolactone and ε-Decalactone Using an Yttrium Bis(phenolate) Catalytic System

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