Sustainable Polymers from Biomass‐Derived α‐Methylene‐γ‐Butyrolactones

Gowda, Ravikumar R.; Chen, Eugene Y.‐X.

doi:10.1002/0471440264.pst606

Cited by 26 publications

(38 citation statements)

References 182 publications

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“…Biomass-derived renewable methylene butyrolactones, such as α-methylene-γ-butyrolactone (MBL), γ-methyl-α-methylene-γ-butyrolactone ( γ MMBL) and β-methyl-α-methylene-γ-butyrolactone ( β MMBL) monomers, have gained increased attention as sustainable alternatives to fossil resource-based methacrylate monomers such as methyl methacrylate (MMA) for the production of specialty chemicals and polymers [32][33][34][35]. The corresponding polymers, poly(αmethylene-γ-butyrolactone) (PMBL), poly(γ-methyl-α-methylene-γ-butyrolactone) (P γ MMBL) and poly(β-methyl-α-methylene-γ-butyrolactone (P β MMBL), have been shown to display superior materials properties, such as a high glass-transition temperature (T g ) of 195°C for PMBL [36] (227°C, P γ MMBL; 288°C, P β MMBL) [37], but it is still difficult to fabricate these polymers for applications due to their characteristic brittleness.…”

Section: Introductionmentioning

confidence: 99%

Chemoselective Lewis pair polymerization of renewable multivinyl-functionalized γ-butyrolactones

Gowda

Chen

2017

Phil. Trans. R. Soc. A.

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Multivinyl-functionalized γ-butyrolactones, γ-vinyl-γ-methyl-α-methylene-γ-butyrolactone (VMMBL) and γ-allyl-γ-methyl-α-methylene-γ-butyrolactone (AMMBL), have been synthesized from biorenewable ethyl levulinate and effectively polymerized by Lewis pairs consisting of an organic -heterocyclic carbene Lewis base and a strong organo-Lewis acid E(CF) (E = Al, B). This Lewis pair polymerization is quantitatively chemoselective, proceeds exclusively via polyaddition across the conjugated α-methylene double bond without participation of the γ-vinyl or γ-allyl double bond, and produces high-molecular-weight functionalized polymers with unimodal molecular-weight distributions. The Al-based Lewis pair produces a polymer with approximately 5.5 times higher molecular weight than that produced by the B-based Lewis pair. The resulting vinyl-functionalized polymers are soluble in common organic solvents and stable at room temperature, and can be thermally cured into crosslinked materials.This article is part of the themed issue 'Frustrated Lewis pair chemistry'.

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Section: Introductionmentioning

confidence: 99%

Chemoselective Lewis pair polymerization of renewable multivinyl-functionalized γ-butyrolactones

Gowda

Chen

2017

Phil. Trans. R. Soc. A.

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“…Degassed VAc (1.20 mL, 1.08 g, 12.5 mmol) was injected under argon at 40 °C. After 3 h, a sample was picked out of the tube and added with traces of TEMPO (~10 mg/mL) in order to quench the polymerization for determining the monomer conversion by1 H NMR in CDCl3 (conversion = 27 %) and the molecular parameters of the PVAc precursor mL, 0.86 g, 10 mmol) were injected under argon. The polymerization medium was heated at 40 °C for 15 h and samples were regularly taken and added with traces of TEMPO in order to quench the polymerization.…”

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confidence: 99%

Organometallic-Mediated Radical (Co)polymerization of γ-Methylene-γ-Butyrolactone: Access to pH-Responsive Poly(vinyl alcohol) Derivatives

et al. 2019

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Conjugated vinyl lactones commonly serve as precursors of polymers with pendant cyclic esters, which can undergo several chemical modifications. They have notably been copolymerized with "more activated monomers" (MAMs) like (meth)acrylates. By contrast, the radical polymerization of the non-conjugated methylene lactone analogs has been disregarded as well as their copolymerization with "less activated monomers" (LAMs) such as acyclic vinyl esters. The present work explores the conventional radical polymerization and the reversible deactivation radical polymerization of γ-methylene-γ-butyrolactone (γMγBL) and its copolymerization with vinyl acetate (VAc). Statistical P(MBL-co-VAc) copolymers with predictable molar mass, low dispersity and precise compositions were notably achieved by organometallic-mediated radical polymerization based on cobalt complexes via both reversible termination (RT), also referred to as 2 reversible chain deactivation, and degenerative chain transfer (DT) pathways. Upon hydrolysis, these MBL-containing (co)polymers release one alcohol moiety and one carboxylic group per repeating unit leading to unprecedented carboxylic acid-functionalized poly(vinyl alcohol) derivatives. A preliminary study emphasizes the pH-responsiveness of the latter in water. poly(αMγBL)s exhibit higher Tg as well as increased optical properties. 19,26 The conventional radical copolymerization of αMγBL 22,23,27-29 or γMαMγBL 24,25 with various conjugated vinyl monomers like MMA, 22-24 styrene, 22,24,28 acrylamide, 27 butyl acrylate, 24 exomethylene lactide 25 and methacrylated oleic acid, 29 is also reported. Interestingly, these α-methylene lactones exhibit greater reactivity compared to their acyclic MMA counterpart due to the higher degree of delocalization of their radical species onto the carbonyl group of the rigid lactone. 21 The synthesis of well-defined α-methylene lactone-based (co)polymers was also achieved via reversible deactivation radical polymerization (RDRP). For example, αMγBL-containing homopolymers 30 and block copolymers 30-33 with predictable molar masses and low dispersities were prepared via copper catalyzed atom transfer radical polymerization (ATRP). High-density poly(αMγBL) brushes were also produced by surface-initiated ATRP of αMγBL. 34 On the other hand, αMγBL as well as its γ-substituted derivatives were polymerized in a controlled manner via reversible addition fragmentation chain transfer (RAFT). 35 The RAFT polymerization of γMαMγBL and copolymerization with styrene was also performed under miniemulsion 36 and from ab initio emulsion 37 conditions.

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“…The recent development of powerful catalytic/initiating systems also allowed the ROP of γBL derivatives as well as their copolymerization. The thermal or chemical depolymerization of some resultant polyesters back to the corresponding monomer was also achieved, which not only highlights the advantage of these materials, but also satisfies the rising demand of sustainable/recyclable polymers [27][28][29][30][31][32][33][34][35][36].…”

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confidence: 73%

Ring-opening polymerization of γ-lactones and copolymerization with other cyclic monomers

Song

Pascouau

Zhao

et al. 2020

Progress in Polymer Science

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Triggered by raised environmental awareness and the rising requirements for sustainable polymers such as degradable or recyclable polymers, studies on ring-opening (co)polymerization (ROP/ROCP) of (bio-based) cyclic monomers (e.g., cyclic esters, lactides, epoxides etc.) have been booming in recent years. Renewable five-membered γ-butyrolactone (γBL) and derivatives would thus be a desirable feedstock to produce poly(γ-butyrolactone) (PγBL) and different (bio-based) functional polyesters. Their copolymerization with other cyclic monomers could also afford an alternative to tune the properties of the resulting materials.Although γBL was traditionally regarded "non-polymerizable", some progresses were made recently concerning the ROP/ROCP of γBL and derivatives. More importantly, some polyesters could be totally depolymerized back to their monomers by thermal or chemical treatment. This review is specially focused on ROP of γ-lactones and their copolymerization with other cyclic monomers by different catalytic/initiating systems, including Lewis/Brønsted acids, organic bases and alkali metal compounds, organometallic compounds, and cooperative bicomponent catalytic systems. The depolymerization process of some obtained polyesters is also discussed.

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Sustainable Polymers from Biomass‐Derived α‐Methylene‐γ‐Butyrolactones

Cited by 26 publications

References 182 publications

Chemoselective Lewis pair polymerization of renewable multivinyl-functionalized γ-butyrolactones

Chemoselective Lewis pair polymerization of renewable multivinyl-functionalized γ-butyrolactones

Organometallic-Mediated Radical (Co)polymerization of γ-Methylene-γ-Butyrolactone: Access to pH-Responsive Poly(vinyl alcohol) Derivatives

Ring-opening polymerization of γ-lactones and copolymerization with other cyclic monomers

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