聚合物接枝二氧化硅纳米粒子协同调控聚(3-羟基丁酸酯-<italic style="font-style: italic">co</italic>-3-羟基戊酸酯)力学性能与热加工稳定性

姜瓯铄; 朱杰; 张绮琛; 邱绍恩; 赵欣然; 吴栋; 马佳睿; 李羿麒; 黄霞芸; 聂志鸿

doi:10.11777/j.issn1000-3304.2026.26216

您当前的位置：

首页 >

文章列表页 >

聚合物接枝二氧化硅纳米粒子协同调控聚(3-羟基丁酸酯-co-3-羟基戊酸酯)力学性能与热加工稳定性

研究论文 | 更新时间：2026-11-03

- 聚合物接枝二氧化硅纳米粒子协同调控聚(3-羟基丁酸酯-co-3-羟基戊酸酯)力学性能与热加工稳定性
- Polymer-grafted Silica Nanoparticles Enable Synergistic Enhancement of Mechanical Performance and Thermal Processing Stability in Poly(3-hydroxybutyrate-co-3-hydroxyvalerate)
- 高分子学报 2026年页码：1-12
- 作者机构：
  
  复旦大学高分子科学系聚合物分子工程全国重点实验室上海 200438
- 作者简介：
  
  E-mail: huangxiayun@fudan.edu.cn
- 基金信息：
- DOI：10.11777/j.issn1000-3304.2026.26216
  中图分类号：
- 收稿：2026-06-18，
  
  录用：2026-07-21，
  
  网络首发：2026-11-02，
- 稿件说明：
移动端阅览
姜瓯铄, 朱杰, 张绮琛, 邱绍恩, 赵欣然, 吴栋, 马佳睿, 李羿麒, 黄霞芸, 聂志鸿. 聚合物接枝二氧化硅纳米粒子协同调控聚(3-羟基丁酸酯-co-3-羟基戊酸酯)力学性能与热加工稳定性. 高分子学报, doi: 10.11777/j.issn1000-3304.2026.26216.

Jiang, O. S.; Zhu, J.; Zhang, Q. C.; Qiu, S. E.; Zhao, X. R.; Wu, D.; Ma, J. R.; Li, Y. Q.; Huang, X. Y.; Nie, Z. H. Polymer-grafted silica nanoparticles enable synergistic enhancement of mechanical performance and thermal processing stability in poly(3-hydroxybutyrate-co-3-hydroxyvalerate). Acta Polymerica Sinica (in Chinese), doi: 10.11777/j.issn1000-3304.2026.26216.
姜瓯铄, 朱杰, 张绮琛, 邱绍恩, 赵欣然, 吴栋, 马佳睿, 李羿麒, 黄霞芸, 聂志鸿. 聚合物接枝二氧化硅纳米粒子协同调控聚(3-羟基丁酸酯-co-3-羟基戊酸酯)力学性能与热加工稳定性. 高分子学报, doi: 10.11777/j.issn1000-3304.2026.26216. DOI： CSTR： 32057.14.GFZXB.2026.7702.

Jiang, O. S.; Zhu, J.; Zhang, Q. C.; Qiu, S. E.; Zhao, X. R.; Wu, D.; Ma, J. R.; Li, Y. Q.; Huang, X. Y.; Nie, Z. H. Polymer-grafted silica nanoparticles enable synergistic enhancement of mechanical performance and thermal processing stability in poly(3-hydroxybutyrate-co-3-hydroxyvalerate). Acta Polymerica Sinica (in Chinese), doi: 10.11777/j.issn1000-3304.2026.26216. DOI： CSTR： 32057.14.GFZXB.2026.7702.

摘要

为解决生物基塑料聚(3-羟基丁酸酯-

-3-羟基戊酸酯) (PHBV)在实际应用中存在的脆性、热稳定性差及循环加工性能衰减等问题，本研究提出一种基于聚合物接枝纳米粒子的界面调控策略. 通过表面引发可逆加成-断裂链转移聚合在二氧化硅(SiO

)纳米粒子表面共价接枝聚甲基丙烯酸缩水甘油酯(PGMA)，制备了SiO

@PGMA纳米粒子，并将其引入PHBV基体中构筑复合膜. 结果表明，当SiO

@PGMA添加量为10%时，复合膜表现出最佳综合性能，拉伸强度由18.29 MPa提高至36.94 MPa，韧性由0.23 MJ·m

-3

提高至0.69 MJ·m

-3

，起始热分解温度由261.4 ℃提高至275.6 ℃. 经过20次回收重塑后其仍能保持44.7%的拉伸强度，显著优于纯PHBV. 机制研究表明，PGMA界面层能够改善纳米粒子与基体的界面相容性，并促进PHBV异相成核、提高结晶度并细化球晶. 同时，PGMA可与PHBV降解过程中产生的羧基反应，从而抑制

-消除反应. 界面相容化、异相成核以及热稳定化的协同调控实现了PHBV力学性能、热稳定性和循环加工性能的同步提升. 本研究为可降解塑料的界面设计提供了一种新的策略.

Abstract

To address the intrinsic brittleness

poor thermal stability

and deterioration of recycling performance of the biobased plastic poly(3-hydroxybutyrate-

-3-hydroxyvalerate) (PHBV)

an interfacial regulation strategy based on polymer-grafted nanoparticles was developed. Poly(glycidyl methacry

late) (PGMA) was covalently grafted onto the surface of silica (SiO

) nanoparticles

via

surface-initiated reversible addition-fragmentation chain transfer polymerization to obtain SiO

@PGMA nanoparticles

which were subsequently incorporated into a PHBV matrix to fabricate composite films. The results showed that the composite film containing 10% SiO

@PGMA exhibited the best overall performance. The tensile strength increased from 18.29 MPa to 36.94 MPa

while the toughness increased from 0.23 MJ·m

-3

to 0.69 MJ·m

-3

. Meanwhile

the onset decomposition temperature (

onset

) increased from 261.4 ℃ to 275.6 ℃. After 20 recycling and reprocessing cycles

the composite film still retained 44.7% of its original tensile strength

significantly outperforming neat PHBV. Mechanistic studies revealed that the covalently grafted PGMA interfacial layer improved the compatibility between nanoparticles and the PHBV matrix

promoted heterogeneous nucleation

increased crystallinity

and refined the spherulitic structure of PHBV. In addition

the epoxy groups on the PGMA side chains could react with carboxyl groups generated during PHBV degradation

thereby suppressing the

-elimination reaction. The synergistic effects of interfacial compatibilization

heterogeneous nucleation

and thermal stabilization simultaneously enhanced the mechanical properties

thermal stability

and recycling performance of PHBV. This work provides a new interfacial design strategy for high-performance biodegradable plastics.

关键词

Keywords

references

Agrawala S. ; Börkey P. ; Lanzi E. Global Plastics Outlook: Economic Drivers , Environmental Impacts and Policy Options . Paris : OECD Publishing , 2022 , p 20 . doi: 10.1787/de747aef-en http://dx.doi.org/10.1787/de747aef-en

Li Z. B. ; Yang J. ; Loh X. J. Polyhydroxyalkanoates: opening doors for a sustainable future . NPG Asia Mater. , 2016 , 8 ( 4 ), e 265 . doi: 10.1038/am.2016.48 http://dx.doi.org/10.1038/am.2016.48

Rivera-Briso A. L. ; Serrano-Aroca Á. Poly(3-hydroxybutyrate- co -3-hydroxyvalerate): enhancement strategies for advanced applications . Polymers , 2018 , 10 ( 7 ), 732 . doi: 10.3390/polym10070732 http://dx.doi.org/10.3390/polym10070732

Gamboa-Suárez M. A. ; Rubiano N. C. P. ; Suárez-Rodríguez S. J. ; Blanco-Tirado C. ; Sierra C. A. ; Quintero-Silva M. J. ; Combariza M. Y. Modified biogenic nanocellulose and PHB from cacao fruit waste for enhanced mechanical and barrier performance of PHBV films . Carbohydr. Polym. Technolog. Appl. , 2025 , 12 , 101010 . doi: 10.1016/j.carpta.2025.101010 http://dx.doi.org/10.1016/j.carpta.2025.101010

Fang C. X. ; Shao T. R. ; Ji X. X. ; Wang F. F. ; Zhang H. ; Xu J. Y. ; Miao W. J. ; Wang Z. B. High mechanical property and antibacterial poly(3-hydroxybutyrate- co -3-hydroxyvalerate)/functional enzymatically-synthesized cellulose biodegradable composite . Int. J. Biol. Macromol. , 2023 , 225 , 776 - 785 . doi: 10.1016/j.ijbiomac.2022.11.140 http://dx.doi.org/10.1016/j.ijbiomac.2022.11.140

Liu Q. S. ; Zhu M. F. ; Wu W. H. ; Qin Z. Y. Reducing the formation of six-membered ring ester during thermal degradation of biodegradable PHBV to enhance its thermal stability . Polym. Degrad. Stabil. , 2009 , 94 ( 1 ), 18 - 24 . doi: 10.1016/j.polymdegradstab.2008.10.016 http://dx.doi.org/10.1016/j.polymdegradstab.2008.10.016

Zhou L. ; Zhang Z. ; Shi C. X. ; Scoti M. ; Barange D. K. ; Gowda R. R. ; Chen E. Y. Chemically circular, mechanically tough, and melt-processable polyhydroxyalkanoates . Science , 2023 , 380 ( 6640 ), 64 - 69 . doi: 10.1126/science.adg4520 http://dx.doi.org/10.1126/science.adg4520

Wang L. ; Guo Y. ; Chen Y. X. ; Chen T. ; Zhu S. L. ; Zhang T. T. ; Liu S. Q. Enhanced mechanical and water absorption properties of rice husk-derived nano-SiO 2 reinforced PHBV composites . Polymers , 2018 , 10 ( 9 ), 1022 . doi: 10.3390/polym10091022 http://dx.doi.org/10.3390/polym10091022

Dai Z. X. ; Li B. ; He M. ; Li J. ; Zou X. Y. ; Wang Y. W. ; Shan Y. R. Biodegradable and high-performance composites of poly(butylene adipate- co -terephthalate) with PHBV chain-functionalized nanocellulose . Prog. Org. Coat. , 2024 , 187 , 108136 . doi: 10.1016/j.porgcoat.2023.108136 http://dx.doi.org/10.1016/j.porgcoat.2023.108136

Esmizadeh E. ; Gupta A. ; Asrat S. ; Mekonnen T. H. Crystallization and performance evolution of PHBV nanocomposites through annealing: the role of surface modification of CNCs . Polymer , 2024 , 308 , 127352 . doi: 10.1016/j.polymer.2024.127352 http://dx.doi.org/10.1016/j.polymer.2024.127352

Malmir S. ; Montero B. ; Rico M. ; Barral L. ; Bouza R. Morphology, thermal and barrier properties of biodegradable films of poly(3-hydroxybutyrate- co -3-hydroxyvalerate) containing cellulose nanocrystals . Compos. Part A Appl. Sci. Manuf. , 2017 , 93 , 41 - 48 . doi: 10.1016/j.compositesa.2016.11.011 http://dx.doi.org/10.1016/j.compositesa.2016.11.011

Zheng T. ; Clemons C. M. ; Pilla S. Comparative study of direct compounding, coupling agent-aided and initiator-aided reactive extrusion to prepare cellulose nanocrystal/PHBV (CNC/PHBV) nanocomposite . ACS Sustainable Chem. Eng. , 2020 , 8 ( 2 ), 814 - 822 . doi: 10.1021/acssuschemeng.9b04867 http://dx.doi.org/10.1021/acssuschemeng.9b04867

Zhang H. ; Yu H. Y. ; Wang C. ; Yao J. M. Effect of silver contents in cellulose nanocrystal/silver nanohybrids on PHBV crystallization and property improvements . Carbohydr. Polym. , 2017 , 173 , 7 - 16 . doi: 10.1016/j.carbpol.2017.05.064 http://dx.doi.org/10.1016/j.carbpol.2017.05.064

Ma P. M. ; Wang R. Y. ; Wang S. F. ; Zhang Y. ; Zhang Y. X. ; Hristova D. Effects of fumed silica on the crystallization behavior and thermal properties of poly(hydroxybutyrate- co -hydroxyvalerate) . J. Appl. Polym. Sci. , 2008 , 108 ( 3 ), 1770 - 1777 . doi: 10.1002/app.27577 http://dx.doi.org/10.1002/app.27577

Du J. ; Zhao G. M. ; Pan M. Z. ; Zhuang L. L. ; Li D. G. ; Zhang R. Crystallization and mechanical properties of reinforced PHBV composites using melt compounding: effect of CNCs and CNFs . Carbohydr. Polym. , 2017 , 168 , 255 - 262 . doi: 10.1016/j.carbpol.2017.03.076 http://dx.doi.org/10.1016/j.carbpol.2017.03.076

Yin L. ; Wang L. ; Tan L. Y. ; Huang Z. ; Zhou J. ; Wang L. Y. ; Chen Y. X. ; Guo Y. Mechanical properties of modulus-graded bamboo fiber-reinforced PHBV composites and their thermal stability properties . Polym. Compos. , 2025 , 46 ( 12 ), 11494 - 11508 . doi: 10.1002/pc.29699 http://dx.doi.org/10.1002/pc.29699

Antunes A. ; Popelka A. ; Aljarod O. ; Hassan M. K. ; Kasak P. ; Luyt A. S. Accelerated weathering effects on poly(3-hydroxybutyrate- co -3-hydroxyvalerate) (PHBV) and PHBV/TiO 2 nanocomposites . Polymers , 2020 , 12 ( 8 ), 1743 . doi: 10.3390/polym12081743 http://dx.doi.org/10.3390/polym12081743

Zhao H. B. ; Cui Z. X. ; Wang X. F. ; Turng L. S. ; Peng X. F. Processing and characterization of solid and microcellular poly(lactic acid)/polyhydroxybutyrate-valerate (PLA/PHBV) blends and PLA/PHBV/Clay nanocomposites . Compos. Part B Eng. , 2013 , 51 , 79 - 91 . doi: 10.1016/j.compositesb.2013.02.034 http://dx.doi.org/10.1016/j.compositesb.2013.02.034

Karbowniczek J. E. ; Ura D. P. ; Stachewicz U. Nanoparticles distribution and agglomeration analysis in electrospun fiber based composites for desired mechanical performance of poly(3-hydroxybuty-rate- co -3-hydroxyvalerate (PHBV) scaffolds with hydroxyapatite (HA) and titanium dioxide (TiO 2 ) towards medical applications . Compos. Part B Eng. , 2022 , 241 , 110011 . doi: 10.1016/j.compositesb.2022.110011 http://dx.doi.org/10.1016/j.compositesb.2022.110011

Pal A. K. ; Wu F. ; Misra M. ; Mohanty A. K. Reactive extrusion of sustainable PHBV/PBAT-based nanocomposite films with organically modified nanoclay for packaging applications: compression moulding vs . cast film extrusion . Compos. Part B Eng. , 2020 , 198 , 108141 . doi: 10.1016/j.compositesb.2020.108141 http://dx.doi.org/10.1016/j.compositesb.2020.108141

Samaniego-Aguilar K. ; Sánchez-Safont E. ; Pisa-Ripoll I. ; Gámez-Pérez J. ; Cabedo L. Reactive compatibilization of PHBV/PCL blends: structure-property relationships, thermoformability and industrial compostability . Polym. Test. , 2026 , 158 , 109164 . doi: 10.1016/j.polymertesting.2026.109164 http://dx.doi.org/10.1016/j.polymertesting.2026.109164

Mokoena L. S. ; Mofokeng J. P. Preparation of poly(lactic acid) (PLA)/poly(3-hydroxybutyrate- co -3-hydroxyvalerate) (PHBV)/graphene oxide (GO) polymeric composites for the selective removal of lead ions (Pb(II)) in water . Polym. Compos. , 2024 , 45 ( 9 ), 8527 - 8542 . doi: 10.1002/pc.28358 http://dx.doi.org/10.1002/pc.28358

da Silva F. A. G. S. ; Matos M. ; Dourado F. ; Reis M. A M; Branco, P.C; Poças, F.; Gama, M. Development of a layered bacterial nanocellulose-PHBV composite for food packaging. J. Sci. Food Agric., 2023 , 103 ( 3 ), 1077 - 1087 . doi: 10.1002/jsfa.11839 http://dx.doi.org/10.1002/jsfa.11839

Stöber W. ; Fink A. ; Bohn E. Controlled growth of monodisperse silica spheres in the micron size range . J. Colloid Interface Sci. , 1968 , 26 ( 1 ), 62 - 69 . doi: 10.1016/0021-9797(68)90272-5 http://dx.doi.org/10.1016/0021-9797(68)90272-5

Mukherjee N. ; Das A. ; Dhara M. ; Jana T. Surface initiated RAFT polymerization to synthesize N -heterocyclic block copolymer grafted silica nanofillers for improving PEM properties . Polymer , 2021 , 236 , 124315 . doi: 10.1016/j.polymer.2021.124315 http://dx.doi.org/10.1016/j.polymer.2021.124315

Kuzmyn A. R. ; de Beer S. Polymer brushes by SI-PET-RAFT: synthesis and applications . Polymer, 2025 , 323 , 128155 . doi: 10.1016/j.polymer.2025.128155 http://dx.doi.org/10.1016/j.polymer.2025.128155

Park B. R. ; Nabae Y. ; Surapati M. ; Hayakawa T. ; Kakimoto M. A. Poly( N -isopropylacrylamide)-modified silica beads with hyperbranched polysiloxysilane for three-dimensional cell cultivation . Polym. J. , 2013 , 45 ( 2 ), 210 - 215 . doi: 10.1038/pj.2012.124 http://dx.doi.org/10.1038/pj.2012.124

Zhu H. ; Lv Y. ; Shi D. ; Li Y. G. ; Wang Z. B. Origin of the double melting peaks of poly(3-hydroxybutyrate- co -3-hydroxyvalerate) with a high HV content as revealed by in situ synchrotron WAXD/SAXS analyses . J. Polym. Sci. Part B Polym. Phys. , 2019 , 57 ( 21 ), 1453 - 1461 . doi: 10.1002/polb.24890 http://dx.doi.org/10.1002/polb.24890

Miao Y. S. ; Fang C. X. ; Shi D. ; Li Y. G. ; Wang Z. B. Coupling effects of boron nitride and heat treatment on crystallization, mechanical properties of poly(3-hydroxybutyrate- co -3-hydroxyvalerate) (PHBV) . Polymer , 2022 , 252 , 124967 . doi: 10.1016/j.polymer.2022.124967 http://dx.doi.org/10.1016/j.polymer.2022.124967

Zhang Z. ; Quinn E. C. ; Olmedo-Martínez J. L. ; Caputo M. R. ; Franklin K. A. ; Müller A. J. ; Chen E. Y. X. Toughening brittle bio-P3HB with synthetic P3HB of engineered stereomicrostructures . Angew. Chem. Int. Ed. , 2023 , 62 ( 49 ), e 202311264 . doi: 10.1002/anie.202311264 http://dx.doi.org/10.1002/anie.202311264

Xiang H. X. ; Wen X. S. ; Miu X. H. ; Li Y. ; Zhou Z. ; Zhu M. F. Thermal depolymerization mechanisms of poly(3-hydroxybutyrate- co -3-hydroxyvalerate) . Prog. Nat. Sci. Mater. Int. , 2016 , 26 ( 1 ), 58 - 64 . doi: 10.1016/j.pnsc.2016.01.007 http://dx.doi.org/10.1016/j.pnsc.2016.01.007

Al-Itry R. ; Lamnawar K. ; Maazouz A. Improvement of thermal stability, rheological and mechanical properties of PLA, PBAT and their blends by reactive extrusion with functionalized epoxy. Polym. Degrad. Stabil., 2012 , 97 ( 10 ), 1898 - 1914 . doi: 10.1016/j.polymdegradstab.2012.06.028 http://dx.doi.org/10.1016/j.polymdegradstab.2012.06.028

浏览量

下载量

CSCD

文章被引用时，请邮件提醒。

提交

工具集

关联资源

富氧空位的取向纳米纤维增强聚合物复合固态电解质的离子传输性能

补丁纳米粒子聚合诱导自组装行为的模拟研究

不同侧基耐热聚硅乙炔树脂的制备及其热性能

直链淀粉衍生物对聚甲基丙烯酸甲酯热性能的影响研究

热重分析技术及其在高分子表征中的应用

聚合物接枝二氧化硅纳米粒子协同调控聚(3-羟基丁酸酯-co-3-羟基戊酸酯)力学性能与热加工稳定性

Polymer-grafted Silica Nanoparticles Enable Synergistic Enhancement of Mechanical Performance and Thermal Processing Stability in Poly(3-hydroxybutyrate-co-3-hydroxyvalerate)

DOI：10.11777/j.issn1000-3304.2026.26216

摘要

Abstract

关键词

Keywords

references