Polymerization of lactide initiated by primary amines and catalyzed by a protic acid

Bednarek, Melania; Baśko, Małgorzata; Biedroń, Tadeusz; Wojtczak, Edyta; Michalski, Adam

doi:10.1016/j.eurpolymj.2015.08.012

Cited by 12 publications

(7 citation statements)

References 42 publications

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“…These features lead mainly to a poor control of the polymerization especially when high DPs were targeted. In contrast, acids have been poorly explored with only two studies in bulk [29], [30] over the past 20 years. It is noteworthy that the only acid catalyst which has been found to be active for the ROP of LLA in solvent is trifluoromethane sulfonic acid (HOTf).…”

Section: Basic and Nuceophilic Catalystsmentioning

confidence: 99%

“…[31] This synthetic molecule has been found to be a bifunctional catalyst acting as a proton shuttle via its acidic hydrogen and basic oxygen atoms. [32] Bednarek et al [29] tried to use this feature in combination with amine initiators for the polymerization of LLA in bulk at 120°C. However, besides the fact that secondary amines can potentially initiate two PLLA chains, only oligomers with high dispersities (between 1.87 and 3.8) resulted.…”

Section: Basic and Nuceophilic Catalystsmentioning

confidence: 99%

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Organocatalytic ring-opening polymerization of l-lactide in bulk: A long standing challenge

Mezzasalma

Dove

Coulembier

2017

European Polymer Journal

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Section: Basic and Nuceophilic Catalystsmentioning

confidence: 99%

Section: Basic and Nuceophilic Catalystsmentioning

confidence: 99%

Organocatalytic ring-opening polymerization of l-lactide in bulk: A long standing challenge

Mezzasalma

Dove

Coulembier

2017

European Polymer Journal

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“…No precaution of stoichiometry is mandatory as the case for polyaddition between diiocyanate and diol precursors. In the literature, ROP-amine has been already investigated for the polymerization of lactide and ε-caprolactone monomers [ 22 , 23 , 24 ]. ROP-amine for polyesters allows to generate amide groups and shows to modify the properties of the polyester compared to hydroxyl initiation [ 25 ].…”

Section: Introductionmentioning

confidence: 99%

Synthesis of Poly(Trimethylene Carbonate) from Amine Group Initiation: Role of Urethane Bonds in the Crystallinity

Brossier

Volpi²,

Lapinte

et al. 2021

Polymers

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Semi-crystalline poly(trimethylene carbonate) (PTMC) can be efficiently prepared by ring-opening polymerization (ROP) initiated by amine using various catalysts. More promising results were reached with the one-step process of stannous octanoate unlike the two-step one-pot reaction using TBD and MSA catalysts. The ROP-amine of TMC consists in a simple isocyanate free process to produce polycarbonate-urethanes, compatible with the large availability of amines ranging from mono- to multifunctional until natural amino acids. ROP-amine of TMC leads to urethane bonds monitored by FTIR spectroscopy. The relationship between the nature of amines and the crystallinity of PTMC was discussed through X-ray diffraction and thermal studies by DSC and TGA. The impact of the crystallinity was also demonstrated on the mechanical properties of semi-crystalline PTMC in comparison to amorphous PTMC, synthesized by ROP initiated by alcohol. The semi-crystalline PTMC synthesized by ROP-amine opens many perspectives.

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“…Bulk conditions for lactide ROP with basic organocatalysts have been widely investigated displaying however serious drawbacks, related to their low thermal stability and racemization of L-lactide [ 20 ]. On the other hand, acidic organocatalysts have been scarcely explored until now, with only a few recent studies in bulk, exploiting triflic acid (TfOH) [ 21 ] and diphenylphosphate (DPP) [ 22 , 23 ] respectively, as Brønsted acid catalysts.…”

Section: Introductionmentioning

confidence: 99%

1,3-Dioxolan-4-Ones as Promising Monomers for Aliphatic Polyesters: Metal-Free, in Bulk Preparation of PLA

et al. 2020

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The first example of solvent-free, organocatalyzed, polymerization of 1,3-dioxolan-4-ones, used as easily accessible monomers for the synthesis of polylactic acid (PLA), is described here. An optimization of reaction conditions was carried out, with p-toluensulfonic acid emerging as the most efficient Brønsted acid catalyst. The reactivity of the monomers in the tested conditions was studied following the monomer conversion by 1H NMR and the molecular weight growth by SEC analysis. A double activation polymerization mechanism was proposed, pointing out the key role of the acid catalyst. The formation of acetal bridges was demonstrated, to different extents depending on the nature of the aldehyde or ketone employed for lactic acid protection. The polymer shows complete retention of stereochemistry, as well as good thermal properties and good polydispersity, albeit modest molecular weight.

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Polymerization of lactide initiated by primary amines and catalyzed by a protic acid

Cited by 12 publications

References 42 publications

Organocatalytic ring-opening polymerization of l-lactide in bulk: A long standing challenge

Organocatalytic ring-opening polymerization of l-lactide in bulk: A long standing challenge

Synthesis of Poly(Trimethylene Carbonate) from Amine Group Initiation: Role of Urethane Bonds in the Crystallinity

1,3-Dioxolan-4-Ones as Promising Monomers for Aliphatic Polyesters: Metal-Free, in Bulk Preparation of PLA

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