Crystallization, thermal and mechanical properties of stereocomplexed poly(lactide) with flexible PLLA/PCL multiblock copolymer

In this work, the synthesized PLLA/PCL multi-block copolymers with different compositions were introduced into a stereocomplexed poly(lactide) (sc-PLA) matrix to accelerate the stereocomplexation of PLA enantiomers and improve its inherent brittleness. The PLLA/PCL multi-block copolymers were in different compositions to adjust the molecular weight of the PLLA block. The structure, molecular weight, crystallization behavior, crystal structure and thermal stability of PLLA/PCL multi-block copolymers were investigated. The results indicated that PLLA/PCL multi-block copolymers with controllable structure and composition were successfully synthesized. On this basis, the blends of sc-PLA and PLLA/PCL multi-block copolymers were prepared by solution casting, and characterized. The results revealed that the introduction of PLLA/PCL multi-block copolymers promoted the stereocomplexation of the PLA enantiomers during the melting crystallization process to obtain a complete stereocomplexed material. But the presence of the PCL block leads to a decrease in the melting temperature of the stereocomplex and difficulty in homogeneous nucleation. Compared with sc-PLA, the elongation at break of the blends was significantly improved and their tensile strengths were only slightly reduced. And the thermal stability and mechanical properties of the blends could be adjusted by controlling the content and composition of PCL/PLLA multi-block copolymers. These results revealed that the degree of stereocomplexation and toughness of sc-PLA were improved, which may expand the application fields of PLA-based materials.

[1]  Haiping Ye,et al.  Dependence of Crystallization Behavior of Interacting Telechelic Poly(butylene succinate) Oligomer on Molecular Weight , 2021, Crystals.

[2]  N. Shimizu,et al.  Enhanced formation of stereocomplex crystallites in Poly(l-lactic acid)/Poly(d-lactic acid) blends by silk fibroin nanodisc , 2021, Polymer.

[3]  E. Doganci,et al.  Preparation of hetero-armed POSS-cored star-shaped PCL-PLA/PLA composites and effect of different diisocyanates as compatibilizer. , 2021, Journal of the mechanical behavior of biomedical materials.

[4]  S. Techasakul,et al.  Development of bacterial cellulose and polycaprolactone (PCL) based composite for medical material , 2021 .

[5]  Q. Zhang,et al.  A generalizable strategy toward highly tough and heat-resistant stereocomplex-type polylactide/elastomer blends with substantially enhanced melt processability , 2021 .

[6]  Yaqi Wang,et al.  Preparation of different morphologies cellulose nanocrystals from waste cotton fibers and its effect on PLLA/PDLA composites films , 2021, Composites Part B: Engineering.

[7]  Jizhong Chen,et al.  Synergistic effects of chain dynamics and enantiomeric interaction on the crystallization in PDLA/PLLA mixtures , 2021 .

[8]  D. Pappalardo,et al.  Thermo-Rheological and Shape Memory Properties of Block and Random Copolymers of Lactide and ε-Caprolactone , 2021, Polymers.

[9]  Xiaofeng Song,et al.  Water-responsive shape memory PLLA via incorporating PCL-(PMVS-s-PAA)-PCL-PTMG-PCL-(PMVS-s-PAA)-PCL , 2021 .

[10]  H. Tsuji,et al.  Stereocomplex- and homo-crystallization behavior, structure, morphology, and thermal properties of crystalline and amorphous stereo diblock copolymers, enantiomeric Poly(l-lactide)-b-Poly(dl-lactide) and Poly(d-lactide)-b-Poly(dl-lactide) , 2020 .

[11]  Helan Xu,et al.  Influence of scPLA microsphere on the crystallization behavior of PLLA/PDLA composites , 2020 .

[12]  J. Chung,et al.  Arm-length-dependent phase transformation and dual dynamic healing behavior of supramolecular networks consisting of ureidopyrimidinone-end-functionalized semi-crystalline star polymers , 2020 .

[13]  A. Lendlein,et al.  Strain recovery and stress relaxation behaviour of multiblock copolymer blends physically cross-linked with PLA stereocomplexation , 2020 .

[14]  W. Zhou,et al.  A novel aryl hydrazide nucleator to effectively promote stereocomplex crystallization in high-molecular-weight poly(L-lactide)/poly(D-lactide) blends , 2020 .

[15]  Jafar Khademzadeh Yeganeh,et al.  Highly toughened poly(lactic acid) (PLA) prepared through melt blending with ethylene-co-vinyl acetate (EVA) copolymer and simultaneous addition of hydrophilic silica nanoparticles and block copolymer compatibilizer , 2020 .

[16]  Hao Wang,et al.  Enhanced toughness of PLLA/PCL blends using poly(d-lactide)-poly(ε-caprolactone)-poly(d-lactide) as compatibilizer , 2020 .

[17]  Xianming Zhang,et al.  Fractionated crystallization and fractionated melting behaviors of poly(ethylene glycol) induced by poly(lactide) stereocomplex in their block copolymers and blends , 2020 .

[18]  S. Mohanty,et al.  Synergistic effect of polylactic acid(PLA) and Poly(butylene succinate-co-adipate) (PBSA) based sustainable, reactive, super toughened eco-composite blown films for flexible packaging applications , 2020 .

[19]  Wei Yang,et al.  High-efficient crystallization promotion and melt reinforcement effect of diblock PDLA-b-PLLA copolymer on PLLA , 2020 .

[20]  Sachin Kumar,et al.  Effect of Block Length and Stereocomplexation on the Thermally Processable Poly(ε-caprolactone) and Poly(Lactic acid) Block Copolymers for Biomedical Applications , 2019, ACS Applied Polymer Materials.

[21]  Q. Fu,et al.  Toward Supertough and Heat-Resistant Stereocomplex-Type Polylactide/Elastomer Blends with Impressive Melt Stability via in Situ Formation of Graft Copolymer during One-Pot Reactive Melt Blending , 2019, Macromolecules.

[22]  Yahui Wang,et al.  Design high heat‐resistant stereocomplex poly(lactide acid) by cross‐linking and plasticizing , 2018 .

[23]  Y. Kimura,et al.  Influence of decomposition temperature of aromatic sulfonic acid catalysts on the molecular weight and thermal stability of poly(l-lactic acid) prepared by melt/solid state polycondenstaion , 2018, Polymer.

[24]  Xiaohong Wang,et al.  Largely improved mechanical properties of a biodegradable polyurethane elastomer via polylactide stereocomplexation , 2018 .

[25]  Wei Yang,et al.  Poly(l-lactic acid)-polyethylene glycol-poly(l-lactic acid) triblock copolymer: A novel macromolecular plasticizer to enhance the crystallization of poly(l-lactic acid) , 2017 .

[26]  Long Jiang,et al.  Enhanced crystallization kinetics of symmetric poly(l-lactide)/poly(d-lactide) stereocomplex in the presence of nanocrystalline cellulose , 2017 .

[27]  V. Siracusa,et al.  Design of biobased PLLA triblock copolymers for sustainable food packaging: Thermo-mechanical properties, gas barrier ability and compostability , 2017 .

[28]  M. Değirmenci,et al.  Two-arm PCL and PLLA macrophotoinitiators with benzoin end-functional groups by combination of ROP and click chemistry and their use in the synthesis of A2B2 type miktoarm star copolymers , 2017 .

[29]  Junwei Gu,et al.  Synthesis and properties of poly(lactide)/poly(ε-caprolactone) multiblock supramolecular polymers bonded by the self-complementary quadruple hydrogen bonding , 2017 .

[30]  R. Prud’homme,et al.  Crystallization and morphology of ultrathin films of poly(d-lactide) with BAB block copolymers in which the A block is made of poly(l-lactide) , 2017 .

[31]  Xuesi Chen,et al.  Synthesis of PLLA-based block copolymers for improving melt strength and toughness of PLLA by in situ reactive blending , 2017 .

[32]  Xuesi Chen,et al.  Toughening effect of poly(d-lactide)-b-poly(butylene succinate)-b-poly(d-lactide) copolymers on poly(l-lactic acid) by solution casting method , 2015 .

[33]  Dujing Wang,et al.  Role of PEG Segment in Stereocomplex Crystallization for PLLA/PDLA-b-PEG-b-PDLA Blends , 2015 .

[34]  Xiao Hu,et al.  Mechanical and thermal property characterization of poly-l-lactide (PLLA) scaffold developed using pressure-controllable green foaming technology. , 2015, Materials science & engineering. C, Materials for biological applications.

[35]  J. Kenny,et al.  Crystallization and thermal characterization of biodegradable tri-block copolymers and poly(ester-urethane)s based on PCL and PLLA , 2014 .

[36]  Xuesi Chen,et al.  Improved mechanical and thermal properties of PLLA by solvent blending with PDLA-b-PEG-b-PDLA , 2014 .

[37]  F. Bates,et al.  Sustainable Poly(lactide-b-butadiene) Multiblock Copolymers with Enhanced Mechanical Properties , 2013 .

[38]  Chul B. Park,et al.  Evidence of a dual network/spherulitic crystalline morphology in PLA stereocomplexes , 2012 .

[39]  Charles S. Golub,et al.  Effect of midblock on the morphology and properties of blends of ABA triblock copolymers of PDLA-mid-block-PDLA with PLLA , 2012 .

[40]  Youngmee Jung,et al.  Stereocomplexation of Poly(L-lactide) and Random Copolymer Poly(D-lactide-co-ε-caprolactone) To Enhance Melt Stability , 2012 .

[41]  M. Mariatti,et al.  Improvement of microstructures and properties of biodegradable PLLA and PCL blends compatibilized with a triblock copolymer , 2010 .

[42]  H. Tsuji,et al.  Stereocomplex crystallization and spherulite growth behavior of poly(l-lactide)-b-poly(d-lactide) stereodiblock copolymers , 2010 .

[43]  C. Fang,et al.  Additive manufacturing of CNTs/PLA composites and the correlation between microstructure and functional properties , 2021 .