通过交联改性改善聚乳酸对映体共混物的结晶性能和发泡行为

高梦菊; 吴保钩; 周春晖; 汪龙

doi:10.14028/j.cnki.1003-3726.2025.25.136

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通过交联改性改善聚乳酸对映体共混物的结晶性能和发泡行为

研究论文 | 更新时间：2025-09-23

- 通过交联改性改善聚乳酸对映体共混物的结晶性能和发泡行为
- Improving the Crystallization Properties and Foaming Behavior of Poly(lactic acid) Enantiomeric Blends through Cross-linking Modification
- 高分子通报 2025年38卷第10期页码：1500-1510
- 作者机构：
  
  1.浙江工业大学化学工程学院，杭州 310014
  2.中国科学院宁波材料技术与工程研究所，宁波 315201
- 作者简介：
  
  wanglong@nimte.ac.cn
- 基金信息：
  
  国家自然科学基金(52003280)
- DOI：10.14028/j.cnki.1003-3726.2025.25.136
  中图分类号：
- 收稿日期：2025-05-03，
  
  录用日期：2025-07-07，
  
  网络出版日期：2025-08-27，
  
  纸质出版日期：2025-10-20
- 稿件说明：
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高梦菊, 吴保钩, 周春晖, 汪龙. 通过交联改性改善聚乳酸对映体共混物的结晶性能和发泡行为. 高分子通报, 2025, 38(10), 1500–1510.

Gao, M. J.; Wu, B. G.; Zhou, C. H.; Wang, L. Improving the crystallization properties and foaming behavior of poly(lactic acid) enantiomeric blends through cross-linking modification. Polym. Bull. (in Chinese), 2025, 38(10), 1500–1510.
高梦菊, 吴保钩, 周春晖, 汪龙. 通过交联改性改善聚乳酸对映体共混物的结晶性能和发泡行为. 高分子通报, 2025, 38(10), 1500–1510. DOI： 10.14028/j.cnki.1003-3726.2025.25.136.

Gao, M. J.; Wu, B. G.; Zhou, C. H.; Wang, L. Improving the crystallization properties and foaming behavior of poly(lactic acid) enantiomeric blends through cross-linking modification. Polym. Bull. (in Chinese), 2025, 38(10), 1500–1510. DOI： 10.14028/j.cnki.1003-3726.2025.25.136.

摘要

在聚乳酸(PLA)泡沫中构建高含量立构复合(SC)晶体，目前仍面临较大挑战。本研究利用引发剂双叔丁基过氧化二异丙基苯(BIPB)和交联剂三烯丙基异氰脲酸酯(TAIC)对左旋聚乳酸/右旋聚乳酸(PLLA/PDLA)共混物的分子链进行交联，并结合环保CO

发泡技术制备了PL

LA/PDLA/BIPB/TAIC发泡材料。结果表明：交联网络改善了PLLA/PDLA共混物的结晶性能，促进了SC晶体的形成并改善了SC晶体的熔体记忆效应。与此同时，交联网络提高了PLA的熔体强度，改善了PLA的发泡性能，从而制备出了泡孔结构良好且SC晶体质量分数高达35.2%的PLA泡沫。高含量SC晶体赋予交联PLA泡沫高耐热性，使其在200 ℃下的储能模量达到264.3 kPa，显著高于未交联泡沫的31.4 kPa。

Abstract

Constructing poly(lactic acid) (PLA) foams with a high stereocomplex (SC) crystallite content remains a significant challenge. In this study

we employed di-tert-butyl diisopropylbenzene peroxide (BIPB) as the initiator and triallyl isocyanurate (TAIC) as the cross-linker to induce cross-linking in poly(

-lactic acid)/poly(

-lactic acid) (PLLA/PDLA) blends. These modified blends were subsequently processed using an environmentally friendly CO

foaming technique to produce PLLA/PDLA/BIPB/TAIC foams. The results demonstrated that the crosslinked network enhanced the crystallization behavior of the PLLA/PDLA blends

facilitated the formation of SC crystallites

and improved the melt memory effect. Additionally

the crosslinked structure increased the melt strength and foaming performance of PLA

enabling the fabrication of PLA foams with a uniform cell structure and SC crystallite mass fraction of up to 35.2%. The increased SC content significantly enhanced the thermal resistance of the crosslinked PLA foam

resulting in a storage modulus of 264.3 kPa at 200 ℃

which is considerably higher than that of the uncrosslinked counterpart (31.4 kPa).

关键词

Keywords

references

Shalem, A. ; Yehezkeli, O. ; Fishman, A . Enzymatic degradation of polylactic acid (PLA) . Appl. Microbiol. Biotechnol. , 2024 , 108 ( 1 ), 413 .

Nofar, M. ; Park, C. B . Poly(lactic acid) foaming . Prog. Polym. Sci. , 2014 , 39 ( 10 ), 1721 – 1741 .

Zhao, X. P. ; Liu, J. C. ; Li, J. C. ; Liang, X. Y. ; Zhou, W. Y. ; Peng, S. X . Strategies and techniques for improving heat resistance and mechanical performances of poly(lactic acid) (PLA) biodegradable materials . Int. J. Biol. Macromol. , 2022 , 218 , 115 – 134 .

Gao, J. C. ; Wu, Y. D. ; Li, J. ; Peng, X. Q. ; Yin, D. W. ; Wang, J. C. ; Wang, X. H. ; Jin, M. J. ; Yao, Z. W. ; Shen, X. J. ; Wang, S. ; Jin, H. L . Toughening and heat-resistant modification of degradable PLA/PBS-based composites by using glass fiber/silicon dioxide hybrid fillers . Polymers , 2022 , 14 ( 16 ), 3237 .

Li, Y. ; Mi, J. G. ; Fu, H. ; Zhou, H. F. ; Wang, X. D . Nanocellular foaming behaviors of chain-extended poly(lactic acid) induced by isothermal crystallization . ACS Omega , 2019 , 4 ( 7 ), 12512 – 12523 .

Yang, S. ; Zhong, G. J. ; Xu, J. Z. ; Li, Z. M . Preferential formation of stereocomplex in high-molecular-weight polylactic acid racemic blend induced by carbon nanotubes . Polymer , 2016 , 105 , 167 – 171 .

Han, L. L. ; Pan, P. J. ; Shan, G. R. ; Bao, Y. Z . Stereocomplex crystallization of high-molecular-weight poly( l -lactic acid)/poly( d -lactic acid) racemic blends promoted by a selective nucleator . Polymer , 2015 , 63 , 144 – 153 .

Yan, Z. H. ; Liao, X. ; He, G. J. ; Li, S. J. ; Guo, F. M. ; Li, G. X . Green method to widen the foaming processing window of PLA by introducing stereocomplex crystallites . Ind. Eng. Chem. Res. , 2019 , 58 ( 47 ), 21466 – 21475 .

Ikada, Y. ; Jamshidi, K. ; Tsuji, H. ; Hyon, S. H . Stereocomplex formation between enantiomeric poly(lactides) . Macromolecules , 1987 , 20 ( 4 ), 904 – 906 .

Tsuji, H . Poly(lactide) stereocomplexes: formation, structure, properties, degradation, and applications . Macromol. Biosci. , 2005 , 5 ( 7 ), 569 – 597 .

Liu, Z. W. ; Fu, M. R. ; Ling, F. W. ; Sui, G. P. ; Bai, H. W. ; Zhang, Q. ; Fu, Q . Stereocomplex-type polylactide with bimodal melting temperature distribution: toward desirable melt-processability and thermomechanical performance . Polymer , 2019 , 169 , 21 – 28 .

Yang, C. F. ; Huang, Y. F. ; Ruan, J. ; Su, A. C . Extensive development of precursory helical pairs prior to formation of stereocomplex crystals in racemic polylactide melt mixture . Macromolecules , 2012 , 45 ( 2 ), 872 – 878 .

Huang, Y. F. ; Zhang, Z. C. ; Li, Y. ; Xu, J. Z. ; Xu, L. ; Yan, Z. ; Zhong, G. J. ; Li, Z. M . The role of melt memory and template effect in complete stereocomplex crystallization and phase morphology of polylactides . Cryst. Growth Des. , 2018 , 18 ( 3 ), 1613 – 1621 .

Cui, J. M. ; Yang, S.-G. ; Zhang, Q. L. ; Liu, F. ; Ungar, G . Poisoning by purity: what stops stereocomplex crystallization in polylactide racemate? Macromolecules , 2023 , 56 ( 3 ), 989 – 998 .

Sun, C. X. ; Zheng, Y. ; Xu, S. S. ; Ni, L. L. ; Li, X. ; Shan, G. R. ; Bao, Y. Z. ; Pan, P. J . Role of chain entanglements in the stereocomplex crystallization between poly(lactic acid) enantiomers . ACS Macro Lett. , 2021 , 10 ( 8 ), 1023 – 1028 .

Mi, M. M. ; Yu, J. ; Li, X. Y. ; Zhou, M. ; Xiu, H. ; Bai, H. W . Excl usive stereocomplex crystallization of high-molecular-weight poly( l -lactide)/poly( d -lactide) blends enabled by nucleating agent . Polymer , 2023 , 288 , 126451 .

Deng, S. H. ; Yao, J. ; Bai, H. W. ; Xiu, H. ; Zhang, Q. ; Fu, Q . A generalizable strategy toward highly tough and heat-resistant stereocomplex-type polylactide/elastomer blends with substantially enhanced melt processability . Polymer , 2021 , 224 , 123736 .

Feng, L. D. ; Bian, X. C. ; Li, G. ; Chen, X. S . Thermal properties and structural evolution of poly( l -lactide)/poly( d -lactide) blends . Macromolecules , 2021 , 54 ( 21 ), 10163 – 10176 .

Shi, Z. Z. ; Fan, Z. Y. ; Ma, L. ; Gong, P. J. ; Bao, R. Y. ; Yang, M. B. ; Yang, W . Simultaneously enhanced stereocomplexation and melt strength by dynamic polylactide toward heat-resistant green foams . Macromolecules , 2023 , 56 ( 21 ), 8735 – 8746 .

Hachana, N. ; Wongwanchai, T. ; Chaochanchaikul, K. ; Harnnarongchai, W . Influence of crosslinking agent and chain extender on properties of gamma-irradiated PLA . J. Polym. Environ. , 2017 , 25 ( 2 ), 323 – 333 .

da Silva Barbosa Ferreira, E. ; Luna, C. B. B. ; dos Santos Filho, E. A. ; Wellen, R. M. R. ; Araújo, E. M . Use of crosslinking agent to produce high-performance PLA/EVA blends via reactive processing . J. Vinyl Addit. Technol. , 2023 , 29 ( 1 ), 161 – 175 .

Cui, W. W. ; Wei, X. Y. ; Luo, J. Y. ; Xu, B. ; Zhou, H. F. ; Wang, X. D . CO 2 -assisted fabrication of PLA foams with exceptional compressive property and heat resistance via introducing well-dispersed stereocomplex crystallites . J. CO2 Util. , 2022 , 64 , 102184 .

Ahmed, J. ; Auras, R. ; Kijchavengkul, T. ; Varshney, S. K . Rheological, thermal and structural behavior of poly(ε-caprolactone) and nanoclay blended films . J. Food Eng. , 2012 , 111 ( 4 ), 580 – 589 .

Zhao, M. M. ; Ding, X. Y. ; Mi, J. G. ; Zhou, H. F. ; Wang, X. D . Role of high-density polyethylene in the crystallization behaviors, rheological property, and supercritical CO 2 foaming of poly(lactic acid) . Polym. Degrad. Stab. , 2017 , 146 , 277 – 286 .

Yu, K. S. ; Wang, D. ; Hou, J. J. ; Zhang, X. L. ; Chen, J. B . Fabrication of poly(lactic acid) foam with high expansion ratio and oriented cellular structure by restricting cold crystallization . Int. J. Biol. Macromol. , 2023 , 251 , 126463 .

Oyama, H. T. ; Abe, S . Stereocomplex poly(lactic acid) alloys with superb heat resistance and toughness . ACS Sustainable Chem. Eng. , 2015 , 3 ( 12 ), 3245 – 3252 .

Wu, B. G. ; Yang, W. J. ; Niu, D. Y. ; Dong, W. F. ; Chen, M. Q. ; Liu, T. X. ; Du, M. L. ; Ma, P. M . Stereocomplexed poly(lactide) composites toward engineering plastics with superior toughness, heat resistance and anti-hydrolysis . Chinese J. Polym. Sci. , 2020 , 38 ( 10 ), 1107 – 1116 .

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