A New Insight Into the Mechanism of the Ring‐Opening Polymerization of Trimethylene Carbonate Catalyzed by Methanesulfonic Acid

Campos, Jorge; Ribeiro, M. Rosário; Deffieux, Alain; Peruch, Frédéric

doi:10.1002/macp.201200433

Cited by 18 publications

(7 citation statements)

References 19 publications

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“…As observed with other macrolactones, although the analysis of chain-ends by MALDI-ToF mass spectrometry indicated an initiation by BnOH, the presence of species generated by Step-growth polymerization ROP BnOH inter-and intra-molecular transesterifications were also detected, in agreement with the broad dispersity observed. [43] Theoretically, in the case of MSA, only the AMM was predicted to be operative instead of the two distinct and competitive mechanisms observed experimentally by Bourissou et al [39] and Peruch et al [40]. Indeed, an activation barrier of 17 kcal.mol -1 and 45 kcal.mol -1 were calculated for the ring-opening of the monomer, in the case of the AMM and ACEM, respectively.…”

Section: Methodsmentioning

confidence: 90%

Update and challenges in organo-mediated polymerization reactions

Ottou

Sardón

Mecerreyes

et al. 2016

Progress in Polymer Science

304

223

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International audienceOrganocatalysis has become a very powerful tool for precision macromolecular chemistry, as judged by the number of articles published in this field in the past decade. A variety of small organic molecules, including Bronsted/Lewis bases and acids, based on amines, phosphines or carbenes, but also on bi-component systems, have been employed as a means to catalyze the polymerization of miscellaneous monomers. Not only can organocatalysts be employed to promote the ring-opening polymerization of various heterocyclics (e.g. lactones, lactide, cyclic carbonates, epoxides, lactams, cyclocarbosiloxanes), but some of them also allow activating vinylic monomers such as (meth)acrylics, or triggering the step growth polymerization of monomers such as diisocyanates and diols for polyurethane synthesis. The reduced toxicity of organocatalysts in comparison to their metallic counterparts is also driving their development in some sensitive applications, such as biomedical or microelectronics. Overall, organocatalysts display specific monomer activation modes, thereby providing a unique opportunity to control the polymerization of various functional monomers, under mild conditions. This review article focuses on advances of the past 4 years (>150 publications) in polymerization reactions utilizing small organic molecules either as direct initiators or as true catalysts, with a special emphasis on monomer activation modes, as well as polymerization mechanism aspects

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Section: Methodsmentioning

confidence: 90%

Update and challenges in organo-mediated polymerization reactions

Ottou

Sardón

Mecerreyes

et al. 2016

Progress in Polymer Science

304

223

View full text Add to dashboard Cite

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“…Concerns over the toxic metal residues in the prepared polymers have motivated the development of a metal‐free organocatalytic ROP, which has seen great progress in the last decade since Hedrick et al reported the use of 4‐(dimethylamino)pyridine as the catalyst for the ROP of lactones. Basic organocatalysts tertiary amines, guanidines, amidines, phosphazenes, N ‐heterocyclic carbine, and thiourea (TU)/amines, and the organic acidic catalysts diphenyl phosphate, methanesulfonic acid, and triflic acid (TFA) have all been found to be effective in catalyzing the ROP of cyclic carbonates. Lipases as a class of biofriendly enzyme catalysts have also been explored for ROP .…”

Section: Progress On Apc Polymerization Techniquesmentioning

confidence: 99%

Renaissance of aliphatic polycarbonates: New techniques and biomedical applications

Feng

Song

2013

J of Applied Polymer Sci

133

122

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Aliphatic polycarbonates were discovered a long time ago, with their conventional applications mostly limited to low molecular weight oligomeric intermediates for copolymerization with other polymers. Recent developments in polymerization techniques have overcome the difficulty in preparing high molecular weight aliphatic polycarbonates. These in turn, along with new functional monomers, have enabled the preparation of a wide range of aliphatic polycarbonates with diverse chemical compositions and structures. This review summarizes the latest polymerization techniques for preparing well-defined functional aliphatic polycarbonates, as well as the new applications of those aliphatic polycarbonates, esecially in the biomedical field.

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“…MSA is an effective organocatalyst for ROP of both CL and TMC as it has been demonstrated previously. [32][33][34][35] The ROP of CL and TMC was performed in chloroform at 40°C. After a reaction time of 1 hour, the conversion of both monomers reached 97% as determined by 1 H NMR.…”

Section: Resultsmentioning

confidence: 99%

“…This synthetic procedure has enabled us to prepare well-defined homopolypeptides and polypeptidebased hybrid block copolymers by using the hydroxyl functionalized (macro)initiators. Herein, we report on a sequential synthetic procedure that combines the sulfonic acid-based organocatalyzed ROP of cyclic esters or carbonates [29][30][31][32][33][34][35] and our synthetic method for ROP of NCA initiated by the hydroxyl group in order to synthesize the polyester/polycarbonate-bpolypeptide hybrid block copolymers in a one-pot manner.…”

Section: Introductionmentioning

confidence: 99%