Research progress of carbon material in the stereocomplex crystallization of poly (lactic acid)
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摘要: 聚乳酸是一种原料广泛、可生物降解的绿色高分子材料,具有力学性能好、热塑性强等优点,在替代石油基塑料方面具有极大潜力。然而,聚乳酸结晶速率慢、结晶度低、耐热性能差等问题,严重限制着其应用和发展。立构复合结晶(SC)已被证实是提高聚乳酸各方面性能的有效方法。但是在聚乳酸的实际生产与应用中SC晶体很难可控生成。碳材料作为一种绿色环保的成核剂,能够有效的调控SC生成。本文介绍了聚乳酸形成的同质晶体(HC)与SC的晶体结构,对近年来不同碳材料作为成核剂促进聚乳酸SC结晶的研究成果进行了综述,并探讨了碳材料成核剂促进聚乳酸SC结晶可能的机制,最后进行了总结与展望,指出目前存在的挑战并为未来的发展提供了思路。Abstract: Polylactic acid (PLA) is a biodegradable and biocompatible polymer. Because of its good mechanical properties and outstanding thermoplasticity, it has excellent potential for substitution of petroleum-based polymers. However, the slow crystallization rate, low crystallization and poor heat resistance of PLA, seriously restrict its wide application and development. It has been established that formation of stereocomplex (SC) crystallites is an effective way to improve the various performance of PLA. Nevertheless, SC crystallites are difficult to controllable formation in the actual production and application of PLA. As a green nucleating agent, carbon material could adjust the SC crystallization. This paper describes the crystal structures of HC and SC formed by PLA, sorts out the researches about carbon additives on the effect of SC crystallization and discusses the possible mechanism for carbon additives promoting SC crystallization of PLA. Finally, the current challenges are pointed out and the future research directions are prospected.
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Key words:
- Carbon material /
- Poly(lactic acid) /
- stereocomplex crystallization /
- nucleating agent /
- mechanism
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Crystal Form Space Group Helical
conformationa/nm b/nm c/nm α/(°) β/(°) γ/(°) Ref PLLA-α Pseudo-orthorhombic 103 1.07 0.645 2.78 90 90 90 [30] PLLA-α Pseudo-orthorhombic 103 1.06 0.61 2.88 90 90 90 [14] PLLA-α Orthorhombic 103 1.05 0.61 2.88 90 90 90 [31] PLLA-β Orthorhombic 31 1.031 1.821 0.90 90 90 90 [14] PLLA-β Trigonal 31 1.052 1.052 0.88 90 90 90 [32] PLLA-γ Orthorhombic 31 0.995 0.625 0.88 90 90 90 [19] SC Orthorhombic 31 0.916 0.916 0.870 109.2 109.2 109.8 [20] SC Triclinic 31 1.498 1.498 0.870 90 90 120 [21] 表 2 各种碳纳米成核剂对PLA SC形成和占比的影响总结
Table 2. Summary of the effect of carbon nano nucleating agent on the SCs formation and fraction in PLA blends
Nucleating agent Crystallinity (xSC) and fraction (fSC)
of SCComments Ref CB:10 wt% PX
30 wt% P35fSC=100% CB particles can adsorb PLLA and PDLA chains in their surface. The nucleation capacity of CB is related to its surface. [33] CQD-1 wt%
(200 Mpa, 200℃,4 h)xSC= 27.5%
fSC=78.5%CQD nanoparticles effectively regulate the size, distribution, stacking and hierarchical architecture of granular SC. [36] CQDs-g-PDLA- 30 wt% xSC= 41.4%
fSC≈100%The grafted CQDs as active foreign heterogeneities can enhance the
heterogeneous nucleation and facilitate the formation of SC[37] C70-1 wt% xSC= 23.3%
fSC≈100%Due to CH-π interactions,PLLA and PDLA chains epitaxially adhere to the surfaces of C70, which significantly increasing the chances of interactions between enantiomers [41] CNTs-0.2 wt% xSC= 51%
fSC=100%CNTs acted as the anchor to promote intermolecular nexus and shortened the chain coupling distance between PLLA and PDLA. [42] MWCNTs-1 wt% xSC= 61.8% On the one hand, the strong nucleation ability of MWCNTs accelerated the nucleation and growth of spherulite; On the other hand, MWCNTs have dynamic and spatial effects on crystal growth. [44] CNTs-0.001 wt% and sintering-assisted methos xSC= 60.4% SC crystallization induced by CNTs at the interface can overcome the restriction of chain diffusion [45] CNF-4 wt% xSC= 20.7% CNFs provide nucleation surface and facilitate the arrangement of PLLA/PDLA chains [51] GNPs-3 wt% xSC= 21.7% The surface induction process of GNPs greatly shorens the crystallization induction period. [57] GO-0.05 wt% fSC=100% Plane- and edge induced crystallization caused by randomly anchoring and oriented arrangement of the chains, respectively [59] GO-g-PDLA-20 wt% xSC= 76.9%±2.5
fSC=98.7%In the GO-g-PDLA-filled system, GO can only promote SC formation due to the presence of grafted PDLA, while GO can both promote Hc and Sc formation in PLLA/PDLA/GO mixtures. [62] G-g-PDLA-5 wt% xSC= 24,5%
fSC=80.9%SC is mainly generated at the interface of G-g-PDLA and PLLA [63] GO@CNT nanohybrid-0.05 wt%% 25.1% HC and SC Due to the strong interfacial interaction and uniform dispersion of GO@CNT nanohybrid in PLA, a large number of crystal nuclei are induced and stabilized [65] Notes: CB—Carbon black;CQD—Carbon quantum dots; CNTs—Carbon nanotubes; MWCNTs—Multiwall carbon nanotubes; CNF—Carbon nanofiber; GNPs—Graphene nanosheets; GO—Graphene Oxide; GO-g-PDLA—PDLA-graft- graphene oxide;-g-PDLA—PDLA-graft-graphene nanoplatelets. -
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