Investigation of Chain Folding and Traversing during Melt Crystallization of Poly(L-lactide) Based on Selective Alkali Hydrolysis of Its Amorphous Regions

Yu-Fei Dong; Xin-Yang Zhou; Zhao-Hua Ren; Jia-Chen Zhang; Man Xi; Jia-Yao Wang; Ji-Chun You

doi:10.1007/s10118-025-3436-1

Your Location：

Home >

Browse articles >

Investigation of Chain Folding and Traversing during Melt Crystallization of Poly(L-lactide) Based on Selective Alkali Hydrolysis of Its Amorphous Regions

RESEARCH ARTICLE | Updated：2025-12-03

- Investigation of Chain Folding and Traversing during Melt Crystallization of Poly(L-lactide) Based on Selective Alkali Hydrolysis of Its Amorphous Regions
- Chinese Journal of Polymer Science Vol. 43, Issue 12, Pages: 2395-2402(2025)
- Affiliations：
  
  a.College of Material, Chemistry and Chemical Engineering, Key Laboratory of Organosilicon Chemistry and Material Technology, Ministry of Education, Hangzhou Normal University, Hangzhou 311121, China
  b.Key Laboratory of Yarn Materials Forming and Composite Processing Technology of Zhejiang Province, Jiaxing University, Jiaxing 314001, China
- Author bio：
  
  xixi123456@zjxu.edu.cn (M.X.)
  jiayaowang@hznu.edu.cn (J.Y.W.)
  you@hznu.edu.cn (J.C.Y.)
- Funds：
- DOI：10.1007/s10118-025-3436-1
  CLC：
- Received：22 June 2025，
  
  Accepted：17 August 2025，
  
  Published Online：12 November 2025，
  
  Published：15 December 2025
- Accepted：
Scan QR Code
Dong, Y. F.; Zhou, X. Y.; Ren, Z. H.; Zhang, J. C.; Xi, M.; Wang, J. Y.; You, J. C. Investigation of chain folding and traversing during melt crystallization of poly(L-lactide) based on selective alkali hydrolysis of its amorphous regions. Chinese J. Polym. Sci. 2025, 43, 2395–2402

Yu-Fei Dong, Xin-Yang Zhou, Zhao-Hua Ren, et al. Investigation of Chain Folding and Traversing during Melt Crystallization of Poly(L-lactide) Based on Selective Alkali Hydrolysis of Its Amorphous Regions[J]. Chinese Journal of Polymer Science, 2025, 43(12): 2395-2402.
Dong, Y. F.; Zhou, X. Y.; Ren, Z. H.; Zhang, J. C.; Xi, M.; Wang, J. Y.; You, J. C. Investigation of chain folding and traversing during melt crystallization of poly(L-lactide) based on selective alkali hydrolysis of its amorphous regions. Chinese J. Polym. Sci. 2025, 43, 2395–2402 DOI： 10.1007/s10118-025-3436-1.

Yu-Fei Dong, Xin-Yang Zhou, Zhao-Hua Ren, et al. Investigation of Chain Folding and Traversing during Melt Crystallization of Poly(L-lactide) Based on Selective Alkali Hydrolysis of Its Amorphous Regions[J]. Chinese Journal of Polymer Science, 2025, 43(12): 2395-2402. DOI： 10.1007/s10118-025-3436-1.

摘要

By utilizing the selective hydrolysis of polymer chains in the amorphous regions of melt-crystallized PLLA

the maximum folding number and minimum cluster number within a single chain were quantitatively determined. Our work provides a strategy for investigating chain folding and traversing during the melt crystallization of polymers.

Abstract

An efficient strategy has been developed to reconstruct chain folding and traversing of poly(L-lactide) (PLLA) during melt crystallization based on the selective hydrolysis of its amorphous regions. The molecular weights of the pristine PLLA (crystalline part)

single stem

and single cluster were determined by gel permeation chromatography (GPC) according to their evolution during alkali hydrolysis. The maximum-folding-number (in a single cluster) and minimum-cluster-number (in one polymer chain) were obtained using these molecular weights. With the help of two numbers

the chain folding and traversing during the melt crystallization process (at 120 °C) of PLLA can be described as follows. Statistically

in a single polymer chain

there are at least 2 clusters consisting of up to 6.5 stems in each of them

while the rest of the polymer chain contributes to amorphous regions. Our results provide a new strategy for the investigation and fundamental understanding of the melt crystallization of PLLA.

关键词

Keywords

references

Tang, X.; Chen, W.; Li, L. The tough journey of polymer crystallization: battling with chain flexibility and connectivity. Macromolecules 2019 , 52 , 3575−3591..

[Neufeld, L.; Stassen, F.; Sheppard, R.; Gilman, T. The new plastics economy: rethinking the future of plastics; World Economic Forum: 2016 .

[Geyer, R.; Jambeck, J. R.; Law, K. L.; Production, use, and fate of all plastics ever made. Sci. Adv . 2017 , 3 , e1700782..

[Lodge, T. P. Celebrating 50 years of macromolecules. Macromolecules 2017 , 50 , 9525–9527..

Keller, A. A note on single crystals in polymers: evidence for a folded chain configuration. Phils. Mag. 1957 , 2 , 1171−1175..

Sadler, D. M.; Keller, A. Neutron scattering of solution-grown polymer crystals: molecular dimensions are insensitive to molecular weight. Science 1979 , 203 , 263−265..

Ungar, G.; Stejny, J.; Keller, A.; Bidd, I. Whiting, M. C. The crystallization of ultralong normal paraffins: the onset of chain folding. Science 1985 , 229 , 386−391..

Yuki, O.; Jiro, O. K. In situ real-time observation of polymer folded-chain crystallization by atomic force microscopy at the molecular level. Macromolecules 2018 , 51 , 7629−7636..

Anzai, T.; Kawauchi, M.; Kawauchi, T.; Kumaki, J. Crystallization behavior of single isotactic poly(methyl methacrylate) chains visualized by atomic force microscopy. J. Phys. Chem. B 2015 , 119 , 338−347..

Ma, Z.; Yang, P.; Zhang, X.; Jiang, K.; Song, Y.; Zhang, W. Quantifying the chain folding in polymer single crystals by single-molecule force spectroscopy. ACS Macro Lett. 2019 , 8 , 1194−1199..

Yang, P.; Song, Y.; Feng, W.; Zhang, W. Unfolding of a single polymer chain from the single crystal by air-phase single-molecule force spectroscopy: toward better force precision and more accurate description of molecular behaviors. Macromolecules 2018 , 51 , 7052−7060..

Flory, P. J. On the morphology of the crystalline state in polymers. J. Am. Chem. Soc. 1962 , 84 , 2857−2867..

Spells, S. J.; Sadler, D. M.; Keller, A. Chain trajectory in solution grown polyethylene crystals: correlation between infra-red spectroscopy and small-angle neutron scattering. Polymer 1980 , 21 , 1121−1128..

Yoon, D. Y.; Flory, P. J. Small-angle neutron scattering by semicrystalline polyethylene. Polymer 1977 , 18 , 509−513..

Jing, X.; Krimm, S. Mixed-crystal infrared studies of chain folding in melt-crystallized polyethylene. J. Polym. Sci. C. 1983 , 21 , 123−130..

Fischer, E. W. Neutron scattering studies on the crystallization of polymers. Polym. J. 1985 , 17 , 307−320..

Fischer, E. W. The conformation of polymer chains in the semicrystalline state. Makromol. Chem. Symp. 1988 , 20 , 277−291..

Schelten, J. D.; Ballard, G. H.; Wignall, G. D.; Longman, G.; Schmatz, W. Small-angle neutron scattering studies of molten and crystalline polyethylene. Polymer 1976 , 17 , 751−757..

Keith, H. D.; Padden, F. J.; Vadimsky, R. G. Intercrystalline links in polyethylene crystallized fr om the melt. J. Polym. Sci. A-2: Polym. Phys. 1966 , 4 , 267−281..

Keith, H. D.; Padden, F. J.; Vadimsky, R. G. Intercrystalline links in bulk polyethylene. Science 1965 , 150 , 1026−1027..

Hoffman, J. D. Regime III crystallization in melt-crystallized polymers: the variable cluster model of chain folding. Polymer 1983 , 24 , 3−26..

You, J. C.; Dong, W. Y.; Zhao, L. P.; Cao, X. J.; Qiu, J. S.; Sheng, W. J.; Li, Y. J. Crystal orientation behavior and shape-memory performance of poly(vinylidene fluoride)/acrylic copolymer blends. J. Phys. Chem. B 2012 , 116 , 1256−1264..

Yuan, S.; Li, Z.; Hong, Y.; Ke, Y.; Kang, J.; Kamimura, A.; Otsubo, A.; Miyoshi, T. Folding of polymer chains in the early stage of crystallization. ACS Macro Lett. 2015 , 4 , 1382−1385..

Wang, S.; Yuan, S.; Wang, K.; Chen, W.; Yamada, K.; Barkley, D.; Koga, T.; Hong, Y.; Miyoshi, T. Intramolecular and intermolecular packing in polymer crystallization. Macromolecules 2019 , 52 , 4739−4748..

Hong, Y.; Miyoshi, T. Chain-folding structure of a semicrystalline polymer in bulk crystals determined by 13 C- 13 C double quantum NMR. ACS Macro Lett. 2013 , 2 , 501−505..

Hu, W. B. The physics of polymer chain-folding. Phys. Rep. 2018 , 747 , 1−50..

Hu, W. B.; Frenkel, D.; Mathor, V. B. F. Intramolecular nucleation model for polymer crystallization. Macromolecules 2003 , 36 , 8178−8183..

Williams, T.; Blundell, D. J.; Keller, A.; Ward, I. M. Gel permeation chromatographic studies of the degradation of polyethylene with fuming nitric acid. I. Single crystals. J. Polym. Sci A-2: Polym. Phys 1968 , 6 , 1613−1619..

Williams, T.; Keller, A.; Ward, I. M. Gel permeation chromatographic studies of the degradation of polyethylene with fuming nitric acid. II. Bulk polyethylene. J. Polym. Sci A-2: Polym. Phys 1968 , 6 , 1621−1625..

Tsuji, H.; Ikada, Y. Properties and morphology of poly(L-lactide). II. Hydrolysis in alkaline solution. J. Polym. Sci. A 1998 , 36 , 59−66..

Tsuji, H.; Mizuno, A.; Ikada, Y. Properties and morphology of poly (L-lactide). III. Effects of initial crystallinity on long-term in vitro hydrolysis of high molecular weight poly (L-lactide) film in phosphate-buffered solution. J. Appl. Polym. Sci. 2000 , 77 , 1452−1464..

Tsuji, H.; Ikada, Y. Properties and morphology of poly (L-lactide) 4. Effects of structural parameters on long-term hydrolysis of poly (L-lactide) in phosphate-buffered solution. Polym. Degrad. Stab. 2000 , 67 , 179−181..

Heeley, E. L.; Billimoria, K.; Parsons, N.; Figiel, Ł.; Keating, E. M.; Cafolla, C. T.; Crabb, E. M. D.; Hughes, J. In-situ uniaxial drawing of poly-L-lactic acid (PLLA): following the crystalline morphology development using time-resolved SAXS/WAXS. Polymer 2020 , 193 , 122353..

Zhang, L.; Zhao, G.; Wang, G. Investigation on the α / δ crystal transition of poly(L-lactic acid) with different molecular weights. Polymers 2021 , 13 , 3280..

Garlotta, D. A literature review of poly(lactic acid). J. Polym. Environ. 2001 , 9 , 63−84..

Takahashi, A.; Tsunoda, S.; Yuzaki, R.; Kameyama, A. Thioacyl-transfer ring-expansion polymerization of thiiranes based on a cyclic dithiocarbamate initiator. Macromolecules 2020 , 53 , 5227−5236..

Nagarajan, S.; Gowd, E. B. Cold crystallization of PDMS and PLLA in poly(L-lactideb-dimethylsiloxane-b-L-lactide) triblock copolymer and their effect on nanostructure morphology. Macromolecules 2015 , 48 , 5367−5377..

Nurkhamidah, S.; Woo, E. M. Phase separation and lamellae assembly below UCST in poly(l-lactic acid)/poly(1,4-butylene adipate) blend induced by crystallization. Macromolecules 2012 , 45 , 3094−3103..

Jaime-Azuara, A.; Longo, E.; Boselli, E.; Baratieri, M.; Pedersen, T. H. Exploratory DSC investigation on the solvolytic depolymerization of PET in varied solvent systems and in the presence of model additives and contaminants. Polym. Degrad. Stab. 2024 , 224 , 11075 1..

Ye, C.; Zhao,J.; Ye, L.; Jiang, Z.; You, J.; Li, Y. Precise inter-lamellar/inter-fibrillar localization and consequent fabrication of porous membranes with crystallization-modulated pore-size. Polymer 2018 , 142 , 48−51..

Ge, J.; He, M.; Xie, N.; Yang, X. B.; Ye, Z.; Qiu, F. Microphase separation and crystallization in all-conjugated poly(3-alkylthiophene) diblock copolymers. Macromolecules 2015 , 48 , 279−286..

Lee, J. K.; Choi, M. J.; Im, J. E.; Hwang, D. J.; Lee, K. H. Spherulite morphology and crystallization behavior of poly(trimethylene terephthalate)/poly(ether imide) blends. Polymer 2007 , 48 , 2980−2987..

De Santis, P.; Kovacs, A. J. Molecular conformation of poly(S-lactic acid). Biopolymers 1968 , 6 , 299−306..

Noor, M. A. M.; Sendijarevic, V.; Hassan, H. A.; Sendijarevic, I.; Ismail, T. N. M. T.; Soi,H. S.; Hanzah, N. A.; Ghazali, R. Polyether polyols as GPC calibration standards for determination of molecular weight distribution of polyether polyols. J. Appl. Polym. Sci. 2015 , 132 , 42698..

Ping, B. T. Y.; Hanzah, N. A. Conventional gel permeation chromatography vs. gel permeation chromatography with combined detectors for analyses of palm oil-based polyols. J. Oil Palm Res. 2012 , 24 , 1421−1431..

Views

Downloads

CSCD

Alert me when the article has been cited

Submit

Tools

Publicity Resources

Enhanced Crystallization Kinetics of PLLA by Ethoxycarbonyl Ionic Liquid Modified Graphene

Foaming of Poly(3-hydroxybutyrate-co-3-hydroxyvalerate) Foams with Double Melting Peaks

Simultaneous Improvement of Strength and Toughness of Poly(lactic acid) via Multiple Dynamic Pressure

Related Author

Pei Xu

Zhao-Pei Cui

Gang Ruan

Yun-Sheng Ding

Ming-Hui Wu

Dan Shi

Li Zhang

Zong-Bao Wang

Related Institution

Department of Polymer Science and Engineering, School of Chemistry and Chemical Engineering, and Anhui Key Laboratory of Advanced Functional Materials and Devices, Hefei University of Technology

School of Materials Science and Chemical Engineering, Key Laboratory of Impact and Safety Engineering, Ministry of Education, Ningbo University

National Engineering Research Center of Novel Equipment for Polymer Processing, Key Laboratory of Polymer Processing Engineering, Ministry of Education, Guangdong Provincial Key Laboratory of Technique and Equipment for Macromolecular Advanced Manufacturing, School of Mechanical and Automotive Engineering, South China University of Technology

Daqing Petrochemical Research Center, Petrochemical Research Institute of PetroChina

Biomaterials Research Axis, Sirius University of Science and Technology, 1 Olympic Ave, Sochi

⁰