Polymerization of <i>rac</i>‐Lactide Using Achiral Iron Complexes: Access to Thermally Stable Stereocomplexes

Marin, Paul; Tschan, Mathieu J.‐L.; Isnard, Florence; Robert, Carine; Haquette, Pierre; Trivelli, Xavier; Chamoreau, Lise‐Marie; Guérineau, Vincent; Rosal, Iker del; Maron, Laurent; Venditto, Vincenzo; Thomas, Christophe M.

doi:10.1002/ange.201903224

Cited by 9 publications

(2 citation statements)

References 68 publications

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“…It is, indeed, well documented in the literature that stereocomplexation between poly(D-lactide) and poly(Llactide) can take place in solution. 37,38 Photophysical properties…”

Section: Resultsmentioning

confidence: 99%

Ruthenium-initiated polymerization of lactide: a route to remarkable cellular uptake for photodynamic therapy of cancer

et al. 2020

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“…It is, indeed, well documented in the literature that stereocomplexation between poly(D-lactide) and poly(Llactide) can take place in solution. 37,38 Photophysical properties…”

Section: Resultsmentioning

confidence: 99%

Ruthenium-initiated polymerization of lactide: a route to remarkable cellular uptake for photodynamic therapy of cancer

et al. 2020

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“…41 Blending syndiotactic PLA or alternating stereocopolymer poly(L-lactic acid-alt-D-lactic acid) with isotactic PLA, PLLA, was found not to form SC, 42 in contrast with isotactic and syndiotactic poly(methyl methacrylate) blends. Marin et al synthesized stereo-multiblock PLA from DL-lactide at ambient temperature using achiral iron complexes, 43 whereas Chen et al fabricated PLA stereocomplexed microspheres during synthesis of miktoarm copolymers of PLLA and PDLA. 44 Pan et al prepared PLA stereocomplexed materials with different memory shape effects by incorporation of elastomeric block and network formation 45 or supramolecular formation, 46 whereas Li et al effectively utilized SC formation between PLLA and SiO 2 -g-poly(εcaprolactone-co-meso-lactide)-b-PDLA particles for rubber toughening.…”

Section: ■ Introductionmentioning

confidence: 99%

Stereocomplex Formation between Enantiomeric Alternating Lactic Acid-Based Copolymers as a Versatile Method for the Preparation of High Performance Biobased Biodegradable Materials

Tsuji

Yamasaki

Arakawa

2019

ACS Appl. Polym. Mater.

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Enantiomeric alternating lactic acid-based copolymers, i.e., poly(L-lactic acid-alt-glycolic acid) [P(LLA-alt-GA)] and poly(Dlactic acid-alt-glycolic acid) [P(DLA-alt-GA)], with the number-average molecular weights (M n ) of 5 × 10 3 g mol −1 were synthesized, and their stereocomplex (SC) formation was reported for the first time. Wideangle X-ray diffractometry indicated that the SC crystalline modification of P(LLA-alt-GA) and P(DLA-alt-GA) is different from those reported for enantiomeric homopolymers of poly(L-lactic acid) (PLLA) and poly(D-lactic acid) (PDLA). The SC crystallizability of copolymer blends was much higher than the homocrystallizability of neat copolymers, as evidenced by the higher crystallinity and melting enthalpy values. The melting temperature values of the stereocomplexed blends (187.6 and 187.8 °C) were much higher than those of the neat copolymers (74.6−83.2 °C) and that reported for poly(Llactic acid-alt-6-hydroxycaproic acid)/poly(D-lactic acid-alt-6-hydroxycaproic acid) SC (45.7 °C) but slightly lower than those reported for PLLA and PDLA homopolymer blends with the similar average M n values of 2.9 × 10 3 and 7.0 × 10 3 g mol −1 (196.6 and 224.2 °C, respectively). The P(LLA-alt-GA)/P(DLA-alt-GA) blends are expected to have higher thermal stability compared to that of neat P(LLA-alt-GA) and P(DLA-alt-GA), since the melting temperature values of the former were higher than those of the latter. The radial growth rates of spherulites of SC crystallites in the blends were in the range 0.49−9.4 μm min −1 , with which the maximum value was much lower, by 2 orders, than those reported for enantiomeric PLLA and PDLA homopolymer blends with the similar average M n values of 2.9 × 10 3 and 7.0 × 10 3 g mol −1 (247.7 and 120.8 μm min −1 , respectively). SC formation did not largely affect the FTIR peak shape and frequency, suggesting that the helical structure of the alternating copolymer chains was not so largely altered by SC formation. The sufficiently high melting temperature values of P(LLA-alt-GA)/P(DLA-alt-GA) blends compared to those of the neat polymers as well as the reported high mechanical performance and high thermal stability reported for stereocomplexed PLLA/PDLA blends compared to the neat polymers strongly suggest that SC crystallization between enantiomeric alternating lactic acid-based copolymers with various counterparts of lactic acid units is a versatile method for the preparation of high performance biobased biodegradable materials with diverse physical properties and biodegradability.

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Highly Efficient Synthesis of Poly(silylether)s: Access to Degradable Polymers from Renewable Resources

et al. 2021

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The design of new materials with tunable properties and intrinsic recyclability, derived from biomass under mild conditions, stands as a gold standard in polymer chemistry. Reported herein are platinum complexes which catalyze the formation of poly(silylether)s (PSEs) at low catalyst loadings. These polymers are directly obtained from dual-functional biobased building blocks such as 5-hydroxymethylfurfural (HMF) or vanillin, coupled with various dihydrosilanes. Access to different types of copolymer architectures (statistical or alternating) is highlighted by several synthetic strategies. The materials obtained were then characterized as low T g materials (ranging from À 60 to 29 °C), stable upon heating (T À 5% up to 301 °C) and resistant towards uncatalyzed methanolysis. Additionally, quantitative chemical recycling of several PSEs could be triggered by acid-catalyzed hydrolysis or methanolysis. These results emphasize the interest of biobased poly(silylether)s as sustainable materials with high recycling potential.

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Polymerization of rac‐Lactide Using Achiral Iron Complexes: Access to Thermally Stable Stereocomplexes

Cited by 9 publications

References 68 publications

Ruthenium-initiated polymerization of lactide: a route to remarkable cellular uptake for photodynamic therapy of cancer

Ruthenium-initiated polymerization of lactide: a route to remarkable cellular uptake for photodynamic therapy of cancer

Stereocomplex Formation between Enantiomeric Alternating Lactic Acid-Based Copolymers as a Versatile Method for the Preparation of High Performance Biobased Biodegradable Materials

Highly Efficient Synthesis of Poly(silylether)s: Access to Degradable Polymers from Renewable Resources

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