Food Sweetener Saccharin in Binary Organocatalyst for Bulk Ring‐Opening Polymerization of Lactide

Wei, Fulan; Zhu, Hai‐Liang; Li, Zhenjiang; Wang, Haixin; Zhu, Yun; Zhang, Lei; Yao, Zhiwei; Luo, Zikun; Zhang, Chan; Guo, Kai

doi:10.1002/adsc.201801319

Cited by 21 publications

(15 citation statements)

References 78 publications

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“…Study showed that DMAP$saccharinate (DMAP$Sac) catalyzed ROP of LLA at a fast rate (Scheme 100). 121 19 Tetrazole-amino-saccharin Tetrazole-amino-saccharin was synthesized from the reaction of saccharyl chloride (synthesized by saccharin) and 2methyl-2(H)-tertrazole-5-amine (derived from tetrazole-5-amine) under inert condition as described Scheme 101(a). 122 An anaerobic oxidation of benzyl alcohols was reported by Frija et al in the presence of tetrazole-amino-saccharin as organocatalyst under solvent free conditions and microwave assisted process comprising aqueous tert-butyl hydroperoxide (TBHP) as oxidant (Scheme 101b).…”

Section: Dmap-saccharinmentioning

confidence: 99%

Artificial sugar saccharin and its derivatives: role as a catalyst

Kaur

Srivastava

2020

RSC Adv.

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Section: Dmap-saccharinmentioning

confidence: 99%

Artificial sugar saccharin and its derivatives: role as a catalyst

Kaur

Srivastava

2020

RSC Adv.

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“…Following the same concept, a recent study used a DMAP and saccharin system 1:1 (DMAP:Sac) as a bifunctional catalyst for the ROP of LLA and δ-valerolactone (VL) in bulk at 140 °C (Figure 4a). 19 They first combined three commercial pyridines including DMAP, phenylpyridine (PPY), and pyridine with a stoichiometric ratio of saccharine. Among them, DMAP:Sac ionic mixture was the most efficient salt in the ROP of LLA.…”

Section: Acs Macro Lettersmentioning

confidence: 99%

“…In this Viewpoint, we summarize the results presented in the literature in the use of a family of thermally stable organocatalysts based on ionic compounds composed of mixtures of organic acids and bases. These catalysts have successfully been used in industrially relevant conditions, requiring high temperatures, both in chain growth and step-growth polymerizations of polyesters, polyesteramides or polyethers. ,− Moreover, this Viewpoint will also address the recent efforts in the use of these acid–base mixtures in polymer recycling by depolymerization which has nowadays raised significant attention from an economic and environmental perspective . It is worth to mention that we intend to keep the scope of this viewpoint as narrow as possible and it will be solely based on acid–base mixtures prepared by physical interaction (proton transfer reaction) not covering the extensive literature based on frustrated ion pairs, ionic liquids, or acidic ionic liquids as catalyst for polymerizations. , …”

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confidence: 99%

“…However, due to its high activity and poor thermal stability, DMAP promoted transesterification reactions on the PLA backbone, especially at elevated temperatures. Recent studies have overcome the strong activity of the DMAP and its lack of thermal stability by forming ionic complexes with organic acids. ,− Hence, the group of Peruch explored different NEMO formed by mixing 2 equiv of DMAP and 1 equiv of different acids for the ROP of LLA at 100 °C . From all the catalysts evaluated, the combination of DMAP and triflic acid (DMAP:HOTf) displayed an outstanding catalytic activity able to produce PLLA with M n of 14 kg mol –1 in 1 h. The reaction rates were quite competitive and no transesterification reactions were observed at monomer conversions up to 80% by MALDI-TOF.…”

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confidence: 99%

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Dual Organocatalysts Based on Ionic Mixtures of Acids and Bases: A Step Toward High Temperature Polymerizations

et al. 2019

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Organocatalysis provides a powerful alternative in many polymerization reactions and nowadays has become a valuable tool for polymer chemists. The key reason for transitioning to organocatalysts is not only their ability to be effectively removed from resultant products, but also, their potential to exquisitely control the catalytic activity and selectivity of the polymerization processes. While organocatalysis has been largely implemented in research laboratories, its use in industrial bulk polymerization processes is still scarce. This is mostly due to the poor thermal stability of organocatalysts at temperatures (150−250 °C) usually employed for industrial polymerizations. In this Viewpoint, we highlight the recent advances of the use of acid−base ionic mixtures in high temperatures bulk polymerization reactions. First, we will focus on the synthesis, characterization, difunctional catalytic properties, and thermal stability of these acid−base mixtures. Afterward, we will emphasize the recent literature describing their use in chain growth and step-growth polymerizations. Moreover, the highlight will also draw attention to recent efforts in the use of these acid−base mixtures in polymer recycling by means of depolymerization.

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“…Similarly, by use of DMAP and saccharin, a naturally occurring acid, in stoichiometric quantities, the ROP of L-LA provided stereoregular PLLA of moderate molecular weights ( M n = 4 kg mol –1 ) but narrow dispersity at 90 °C. 24 …”

Section: Introductionmentioning

confidence: 99%

Stereoretention in the Bulk ROP of l-Lactide Guided by a Thermally Stable Organocatalyst

et al. 2021

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Polylactide (PLA) has emerged as one of the most promising bio-based alternatives to petroleum-based plastics, mainly because it can be produced from the fermentation of naturally occurring sugars and because it can be industrially compostable. In spite of these benefits, the industrial ring-opening polymerization (ROP) of l -lactide (L-LA) still requires the use of highly active and thermally stable metal-based catalysts, which have raised some environmental concerns. While the excellent balance between activity and functional group compatibility of organic acid catalysts makes them some of the most suitable catalysts for the metal-free ROP of L-LA, the majority of these acids are highly volatile and subject to decomposition at high temperature, which limits their use under industrially relevant conditions. In this work we exploit the use of a nonstoichiometric acid–base organocatalyst to promote the solvent-free and metal-free ROP of L-LA at elevated temperatures in the absence of epimerization and transesterification. To do so, a stable acidic complex was prepared by mixing 4-(dimethylamino)pyridine (DMAP) with 2 equiv of methanesulfonic acid (MSA). Both experimental and computational results indicate that DMAP:MSA (1:2) not only is highly thermally stable but also promotes the retention of stereoregularity during the polymerization of L-LA, leading to PLLA with a molar mass of up to 40 kg mol –1 and a chiral purity in excess of 98%. This result provides a new feature to exploit in organocatalyzed polymerization and in the design of new catalysts to facilitate the path to market.

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Food Sweetener Saccharin in Binary Organocatalyst for Bulk Ring‐Opening Polymerization of Lactide

Cited by 21 publications

References 78 publications

Artificial sugar saccharin and its derivatives: role as a catalyst

Artificial sugar saccharin and its derivatives: role as a catalyst

Dual Organocatalysts Based on Ionic Mixtures of Acids and Bases: A Step Toward High Temperature Polymerizations

Stereoretention in the Bulk ROP of l-Lactide Guided by a Thermally Stable Organocatalyst

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