Accelerating the crystallization kinetics of linear polylactides by adding cyclic poly ( -lactide): Nucleation, plasticization and topological effects

Ruiz, Marina Betegón; Pérez-Camargo, Ricardo A.; López, José Antonio Fernández; Penott-Chang, Evis K.; Múgica, Agurtzane; Coulembier, Olivier; Müller, Alejandro J.

doi:10.1016/j.ijbiomac.2021.07.028

Cited by 20 publications

(22 citation statements)

References 65 publications

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“…Then, the extrapolation to an infinite l, i.e., 1/l ~0, leads to T m °. Independently of the stereochemistry, it was found T m °(linear) ~159 °C and T m °(cyclic) ~164 °C, probing that the T m °(cyclic) > T m °(linear), in line with other cyclic and linear polymers (Tezuka et al, 2008;Kitahara et al, 2011;Takeshita et al, 2012;Su et al, 2013;Ruiz et al, 2021). This result also proves that stereochemistry does not influence the T m °.…”

Section: Topology Effects: Cyclic Vs Linear Topologysupporting

confidence: 57%

“…The threading effect was firstly reported by Kapnistos et al (2008) in blends of cyclic/linear polystyrene, PS. Later, threading effects have been found in c-PCL/MWCNT-g-l-PCL (Pérez et al, 2014b), c-PCL/l-PCL (López et al, 2016), and c-PLLA/l-PLLA blends (Ruiz et al, 2021). In all the cases, the most significant threading effect was found with a small amount of cyclic chains.…”

Section: Topology Effects: Threading Effect Provoked By Small Amounts...mentioning

confidence: 94%

“…Frontiers in Soft Matter frontiersin.org (Zaldua et al, 2018). Figure 4D Adapted from (Ruiz et al, 2021), and Figure 4E Adapted from (López et al, 2016).…”

Section: Intermolecular Interactions In Homopolymersmentioning

confidence: 99%

“…Blending cyclic polymers with small amounts of linear ones generates the so-called threading effect. The cartoon in Figure 4D illustrates the threading effect: "threading refers to the action of linear chains that can reptate and thread through cyclic ones, thereby joining several chains together thus affecting diffusion and relaxation times" (Ruiz et al, 2021). This hinders or limits the nucleation and diffusion of the chains.…”

Section: Topology Effects: Threading Effect Provoked By Small Amounts...mentioning

confidence: 99%

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Recent applications of the Successive Self-nucleation and Annealing thermal fractionation technique

Pérez-Camargo

Cavallo²,

Müller³

2022

Front. Soft. Matter

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Successive Self-nucleation and Annealing (SSA) is a thermal fractionation technique that is performed by Differential Scanning Calorimetry (DSC). The combination of non-isothermal and isothermal steps applied during SSA achieves efficient molecular segregation during polymer crystallization. Such molecular segregation magnifies the effect of defects in polymer chain crystallization, thereby providing information on chain structure. The technique was created and implemented by Müller and co-workers in 1997, becoming a powerful resource for studying ethylene/α-olefin copolymers. The different variables to design the SSA protocol: fractionation window, fractionation time, scanning rate, sample mass, and the first self-nucleation temperature to be applied (Ts, ideal), have been previously reviewed, together with the different applications of SSA. SSA versatility, simplicity (when properly applied), and short times to produce results have allowed its use to study novel and more complex polymeric systems. This review article explores the most recent applications of SSA of the past decade. First, the principles of the technique are briefly explained, covering all the relevant variables. Next, we have selected different cases that show how SSA is employed in various novel fields, such as studying intermolecular interactions and topological effects in homopolymers; supernucleation and antinucleation effects in nanocomposites, including the pre-freezing phenomenon; crystallization modes in random copolymers; solid-solid transitions; miscibility, co-crystallization and composition in blends; evaluation of polymer synthesis variables; and the novel information that could be gained by using fast scanning chip-based calorimetry. Finally, we offer a perspective on SSA, a technique that has become a powerful method for studying the distribution of defects affecting crystallization in semi-crystalline polymers.

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Section: Topology Effects: Cyclic Vs Linear Topologysupporting

confidence: 57%

Section: Topology Effects: Threading Effect Provoked By Small Amounts...mentioning

confidence: 94%

“…Frontiers in Soft Matter frontiersin.org (Zaldua et al, 2018). Figure 4D Adapted from (Ruiz et al, 2021), and Figure 4E Adapted from (López et al, 2016).…”

Section: Intermolecular Interactions In Homopolymersmentioning

confidence: 99%

Section: Topology Effects: Threading Effect Provoked By Small Amounts...mentioning

confidence: 99%

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Recent applications of the Successive Self-nucleation and Annealing thermal fractionation technique

Pérez-Camargo

Cavallo²,

Müller³

2022

Front. Soft. Matter

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“…Linear OLA plasticized PLA and accelerated the growth rate of spherulitics, while cyclic OLA also increased the nucleation rate and consequently the overall crystallization rate of PLA. 21 Moreover, linear OLA resulted in larger water uptake and more rapid migration than cyclic OLA during hydrolytic degradation. 22 Another studied structural variation is enantiomerism.…”

Section: Introductionmentioning

confidence: 99%

Tailoring Oligomeric Plasticizers for Polylactide through Structural Control

Xuan¹,

Odelius²,

Hakkarainen³

2022

ACS Omega

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Structural variations (oligolactide segments, functionalized end groups, and different plasticizer cores) were utilized to tailor the performances of biobased plasticizers for polylactide (PLA). Six plasticizers were developed starting from 1,4-butanediol and isosorbide as cores: two monomeric (1,4-butanediol levulinate and isosorbide levulinate) and four oligomeric plasticizers with hydroxyl or levulinate ester end groups (1,4-butanediol-based oligolactide, isosorbide-based oligolactide, 1,4-butanediol-based oligomeric levulinate, and isosorbide-based oligomeric levulinate). Structural variations in plasticizer design were reflected in the thermal stability, plasticizing efficiency, and migration resistance. The monomeric plasticizer 1,4-butanediol levulinate decreased the glass-transition temperature of PLA from 59 to 16 °C and increased the strain at break substantially from 6 to 227% with 20 wt % addition. 1,4-Butanediol-based oligomeric levulinate exhibited better thermal stability and migration resistance, though the plasticizing efficiency was slightly lower (glass-transition temperature = 28 °C; strain at break = 202%). Compared to PLA films plasticized by plasticizers with flexible butanediol cores, those plasticized by plasticizers with rigid isosorbide cores exhibited higher Young’s modulus and thermal stability and lower plasticizing efficiency. Furthermore, plasticizers with levulinate ester end groups had improved thermal stability, plasticizing efficiency, and migration resistance compared to the corresponding plasticizers with hydroxyl end groups. Hence, a set of controlled structural variations in plasticizer design were successfully demonstrated as a potent route to tailor the plasticizer performances.

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Rotaxane Formation of Multicyclic Polydimethylsiloxane in a Silicone Network: A Step toward Constructing “Macro‐Rotaxanes” from High‐Molecular‐Weight Axle and Wheel Components

Ebe,

Soga,

Fujiwara

et al. 2023

Angewandte Chemie

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Rotaxanes consisting of a high‐molecular‐weight axle and wheel components (macro‐rotaxanes) have high structural freedom, and are attractive for soft‐material applications. However, their synthesis remains underexplored. Here, we investigated macro‐rotaxane formation by the topological trapping of multicyclic polydimethylsiloxanes (mc‐PDMSs) in silicone networks. mc‐PDMS with different numbers of cyclic units and ring sizes was synthesized by cyclopolymerization of a α,ω‐norbornenyl‐functionalized PDMS. Silicone networks were prepared in the presence of 10–60 wt % mc‐PDMS, and the trapping efficiency of mc‐PDMS was determined. In contrast to monocyclic PDMS, mc‐PDMSs with more cyclic units and larger ring sizes can be quantitatively trapped in the network as macro‐rotaxanes. The damping performance of a 60 wt % mc‐PDMS‐blended silicone network was evaluated, revealing a higher tan δ value than the bare PDMS network. Thus, macro‐rotaxanes are promising as non‐leaching additives for network polymers.

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Accelerating the crystallization kinetics of linear polylactides by adding cyclic poly ( -lactide): Nucleation, plasticization and topological effects

Cited by 20 publications

References 65 publications

Recent applications of the Successive Self-nucleation and Annealing thermal fractionation technique

Recent applications of the Successive Self-nucleation and Annealing thermal fractionation technique

Tailoring Oligomeric Plasticizers for Polylactide through Structural Control

Rotaxane Formation of Multicyclic Polydimethylsiloxane in a Silicone Network: A Step toward Constructing “Macro‐Rotaxanes” from High‐Molecular‐Weight Axle and Wheel Components

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