Controlled ring‐opening polymerization of lactide by bis‐sulfonamide/amine associations: Cooperative hydrogen‐bonding catalysis

Alba, Aurélie; Schopp, Aurélia; Delgado, Anne-Paula De Sousa; Cherif, Chokri; Martin‐Vaca, B.; Bourissou, Didier

doi:10.1002/pola.23852

Cited by 42 publications

(29 citation statements)

References 70 publications

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“…For the monosulfonamides, it was suggested that low catalyst activity might arise from reduced H-bond donation versus the bis donors. 111 This account is consistent with observations for the mono-, bis-and tris-(thio)urea H-bond donors. 105 Phosphoric and phosphoramidic acids, the weak acidity of which contrasts with strong acids used for electrophilic monomer activated ROP, 13 can act as bifunctional organocatalysts for ROP.…”

Section: Non-(thio)urea Lewis Acid/base Catalysis Sulfonamides Phospsupporting

confidence: 89%

“…The 18/DMAP cocatalysts produced the most rapid ROP of LA of the HBDs examined, and it was well-controlled. 111 Structurally similar catalysts, 19 and 20, were less active, and no monosulfonamide/base cocatalyzed ROPs of LA have been shown to reach full conversion in 24 h. Neither mononor bis-sulfonamides promoted the ring opening of LA in the absence of an amine cocatalyst. For the monosulfonamides, it was suggested that low catalyst activity might arise from reduced H-bond donation versus the bis donors.…”

Section: Non-(thio)urea Lewis Acid/base Catalysis Sulfonamides Phospmentioning

confidence: 98%

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Organocatalytic Pathway to the Creation of Polymeric Materials with Some Mechanistic Investigations

Datta¹

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The overarching theme of my research work involves understanding the mechanistic aspects of dually activated hydrogen-bonding catalyst systems and applying that knowledge to synthesize polymers from some of the less explored monomers. This entailed a thorough approach to some of the already hypothesized mechanisms in the polymer community and building on that with additional perspective on catalytic interactions. The other aspect of my research encompassed the application of these H-bond mediated catalysts in controlled ring-opening polymerization (ROP) of sulfur-based lactones. This allowed the growth in monomer scope using these catalysts for the first time. H-bonding catalysis, particularly the ones involving ureas and thioureas, began about a decade or so ago. The tremendous rise in organocatalytic ring-opening polymerization has sparked a wide range of catalysts developments in the past few years. Due to their lower cost, reduced toxicity and greener approach, the field has been booming vii

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Section: Non-(thio)urea Lewis Acid/base Catalysis Sulfonamides Phospsupporting

confidence: 89%

Section: Non-(thio)urea Lewis Acid/base Catalysis Sulfonamides Phospmentioning

confidence: 98%

Organocatalytic Pathway to the Creation of Polymeric Materials with Some Mechanistic Investigations

Datta¹

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“…5). [18][19][20][21][22] In order to assess the efficiency of these co-catalysts in (Fig. 6) enabled the determination of K app values ( Table 3).…”

Section: Bispidine Synthesis and Lactide Ropmentioning

confidence: 99%

Benzyl bispidine as an efficient replacement for (−)-sparteine in ring opening polymerisation

et al. 2013

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The synthesis and application of a dibenzyl-functionalized bispidine, in combination with 1-(3,5bis(trifluoromethyl)phenyl)-3-cyclohexylthiourea (TU) co-catalyst, has been demonstrated to be an excellent catalyst for the controlled ring-opening polymerisation (ROP) of lactide and cyclic carbonate monomers. Notably, the polymerisation proceeds with negligible transesterification or epimerisation, with the polymerisation of stereopure L-lactide affording highly crystalline poly(lactide) with a T m of 156 C. ROP of racemic lactide results in the observation of a modest degree of stereocontrol such that the probability of isotactic enchainment, P m ¼ 0.74. Comparison of a range of alternative hydrogen bond donor co-catalysts revealed that TU displayed the highest polymerisation rates in combination with the dibenzyl-functionalized bispidine.

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“…For the ROPs of cyclic monomers, such as δ‐valerolactone (δ‐VL), ε‐caprolactone (ε‐CL), LA, and trimethylene carbonate (TMC), the nucleophilic catalysts activated the carbonyl group in the monomers and basic catalysts activated the hydroxyl group in the alcohol initiators and/or polymer chain ends through hydrogen bonding, that is, the chain‐end activation mechanism. In addition, the “bifunctional activation” of a monomer and an initiator was achieved by binary catalyst systems consisting of electrophiles and amines, such as thiourea/amine, sulfonamide/amine, and fluorinated alcohol/amine . In order to achieve the controlled/living ROPs, suitable organocatalysts should be selected according to the type of monomers.…”

Section: Introductionmentioning

confidence: 99%

Diphenyl phosphate/4-dimethylaminopyridine as an efficient binary organocatalyst system for controlled/living ring-opening polymerization ofL-lactide leading to diblock and end-functionalized poly(L-lactide)s

Makiguchi

Kikuchi

Yanai

et al. 2014

J. Polym. Sci. Part A: Polym. Chem.

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The ring-opening polymerizations (ROPs) of e-caprolactone (e-CL) and L-lactide (LLA) have been studied using the organocatalysts of diphenyl phosphate (DPP) and 4dimethylaminopyridine (DMAP). The "dual activation" property of DPP and the "bifunctional activation" property of DPP/DMAP were confirmed by the NMR measurement for e-CL and its chain-end model of poly(e-caprolactone) and for LLA and its chain-end model of poly(L-lactide) (PLLA), respectively. The molar ratio of DPP/DMAP was optimized as 1/2 for the ROP of LLA leading to the well-defined PLLA, such as the molecular weight determined from 1 H NMR measurement of 19,200 g mol 21 and the narrow polydispersity of 1.10. Additionally, functional initiators were utilized for producing the end-functionalized PLLAs. The DPP-catalyzed ROPs of e-CL and its analogue cyclic monomers and then the DPP/DMAP-catalyzed ROP of LLA produced block copolymers.

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Controlled ring‐opening polymerization of lactide by bis‐sulfonamide/amine associations: Cooperative hydrogen‐bonding catalysis

Cited by 42 publications

References 70 publications

Organocatalytic Pathway to the Creation of Polymeric Materials with Some Mechanistic Investigations

Organocatalytic Pathway to the Creation of Polymeric Materials with Some Mechanistic Investigations

Benzyl bispidine as an efficient replacement for (−)-sparteine in ring opening polymerisation

Diphenyl phosphate/4-dimethylaminopyridine as an efficient binary organocatalyst system for controlled/living ring-opening polymerization ofL-lactide leading to diblock and end-functionalized poly(L-lactide)s

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