A simple and general approach for the synthesis of biodegradable triblock copolymers by organocatalytic ROP from poly(lactide) macroinitiators

Toshikj, Nikola; Robin, Jean‐Jacques; Blanquer, Sébastien

doi:10.1016/j.eurpolymj.2020.109599

Cited by 17 publications

(17 citation statements)

References 27 publications

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“…In fact, in agreement with recent work obtained with PLA [ 25 ], direct anionic polymerization with TBD leads to uncontrolled polymerization of the TMC, with a huge dispersity of 2.8. In addition, we also noticed a significantly longer reactivity with ROP-amine route compared to ROP initiated with hydroxy groups, with respectively only 10% of conversion against 100% after 1 h of reaction [ 26 ] ( Figure S2, from the supplementary materials ). Nevertheless, as proposed by Alba et al [ 25 ], the polymerization can be done in two successive steps one-pot, with first the ring opening of one TMC unit in absence of catalyst, followed by classic ROP initiated by the generated hydroxy groups.…”

Section: Resultsmentioning

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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Section: Resultsmentioning

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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“…Nucleophilic activation is one the most efficient way to homopolymerize DL-LA and was consequently used for synthesizing the first PDLLA block with terminal OH groups. Nucleophilic catalysts, such as N-heterocyclic carbenes (NHCs, e.g.,6, Scheme 5 ) and 1,5,7-Triazabicyclodec-5-ene (TBD) [ 65 ] as a guanidine type molecule are frequently applied to catalyze the ROP of lactide by this mechanism [ 63 , 66 , 67 ]. The free carbene functions as a nucleophile, which attacks the carbonyl group of the lactide to form the zwitterionic intermediate 7.…”

Section: Synthesis Of Plamentioning

confidence: 99%

Poly(lactic Acid): A Versatile Biobased Polymer for the Future with Multifunctional Properties—From Monomer Synthesis, Polymerization Techniques and Molecular Weight Increase to PLA Applications

et al. 2021

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Environmental problems, such as global warming and plastic pollution have forced researchers to investigate alternatives for conventional plastics. Poly(lactic acid) (PLA), one of the well-known eco-friendly biodegradables and biobased polyesters, has been studied extensively and is considered to be a promising substitute to petroleum-based polymers. This review gives an inclusive overview of the current research of lactic acid and lactide dimer techniques along with the production of PLA from its monomers. Melt polycondensation as well as ring opening polymerization techniques are discussed, and the effect of various catalysts and polymerization conditions is thoroughly presented. Reaction mechanisms are also reviewed. However, due to the competitive decomposition reactions, in the most cases low or medium molecular weight (MW) of PLA, not exceeding 20,000–50,000 g/mol, are prepared. For this reason, additional procedures such as solid state polycondensation (SSP) and chain extension (CE) reaching MW ranging from 80,000 up to 250,000 g/mol are extensively investigated here. Lastly, numerous practical applications of PLA in various fields of industry, technical challenges and limitations of PLA use as well as its future perspectives are also reported in this review.

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“…Copolymers with two miscible states of PDLLA and PT and segregated domains were detected, depending on their M n . Toshikj et al, proposed the synthesis of biodegradable triblock copolymers with PLA as the central building block, using three mechanisms (coordination-insertion, anionic and cationic) and also varying the nature of the catalysts (organometallic and organic) [145]. Two triblock polymers were prepared: poly(trimethylene carbonate) (PTMC): PTMC-b-PDLLA-b-PTMC; Poly(ε-caprolactone)s (PCL): PCL-b-PDLLA-b-PCL.…”

Section: Synthesis Of Blends Copolymers and Composites Using Pdllamentioning

confidence: 99%

Polymers Based on PLA from Synthesis Using D,L-Lactic Acid (or Racemic Lactide) and Some Biomedical Applications: A Short Review

et al. 2022

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Poly(lactic acid) (PLA) is an important polymer that is based on renewable biomass resources. Because of environmental issues, more renewable sources for polymers synthesis have been sought for industrial purposes. In this sense, cheaper monomers should be used to facilitate better utilization of less valuable chemicals and therefore granting more sustainable processes. Some points are raised about the need to study the total degradability of any PLA, which may require specific composting conditions (e.g., temperature, type of microorganism, adequate humidity and aerobic environment). Polymerization processes to produce PLA are presented with an emphasis on D,L-lactic acid (or rac-lactide) as the reactant monomer. The syntheses involving homogeneous and heterogeneous catalytic processes to produce poly(D,L-Lactic acid) (PDLLA) are also addressed. Additionally, the production of blends, copolymers, and composites with PDLLA are also presented exemplifying different preparation methods. Some general applications of these materials mostly dedicated to the biomedical area over the last 10–15 years will be pointed out.

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A simple and general approach for the synthesis of biodegradable triblock copolymers by organocatalytic ROP from poly(lactide) macroinitiators

Cited by 17 publications

References 27 publications

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

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

Poly(lactic Acid): A Versatile Biobased Polymer for the Future with Multifunctional Properties—From Monomer Synthesis, Polymerization Techniques and Molecular Weight Increase to PLA Applications

Polymers Based on PLA from Synthesis Using D,L-Lactic Acid (or Racemic Lactide) and Some Biomedical Applications: A Short Review

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