Effect of epoxy⁃terminated hyperbranched polyester on properties of poly（lactic acid）/talc blends

doi:10.19491/j.issn.1001-9278.2025.05.006

Abstract

Abstract:

In this paper， epoxy⁃terminated hyperbranched polyester （EHBP） were synthesized and then blended with poly（lactic acid）（PLA） and talc powders through melt blending to obtain PLA/talc/EHBP composites. The surface hydrophobic properties， crystallization properties， molecular structure， mechanical properties， thermal properties， and microstructures of the blends were characterized by contact angle measurement， differential scanning calorimetry， Fourier⁃transform infrared spectroscopy， universal testing machine， thermogravimetric analyzer， and scanning electron microscopy. The results indicated that the addition of EHBP reduced the degree of crystallinity of PLA. The compatibility between PLA and talc powders was best for the composites at a EHBP content of 2 phr. The addition of EHBP enhanced the mechanical properties and toughness of the composites. The composites obtained a significant improvement in the mechanical properties at a EHBP content of 2 phr， leading to an increase in elongation at break by 29.3 %， in impact strength by 49.8 %， and in tensile strength by 31.3 %.

Key words: poly（lactic acid）, talc, epoxy?terminated hyperbranched polyester, compatibility

CLC Number:

TQ321

FENG Shuo, ZHOU Shuyi, JIAO Yang, HU Miao, ZHANG Ruoxuan, JIN Yujuan. Effect of epoxy⁃terminated hyperbranched polyester on properties of poly（lactic acid）/talc blends[J]. China Plastics, 2025, 39(5): 36-42.

Figures/Tables 9

Fig.1. FTIR spectra of the （a） EHBP and （b） PLA/talc composites with different EHBP contents，and （c） schematic diagram of chemical reaction and hydrogen bonding of the PLA/talc/EHBP composites

Fig.2. DSC curves of different components

样品EHBP含量/份	T_C/℃	△H_C/J·g^-1	T_m1/℃	T_m2/℃	△H_m/J·g^-1	X_c/%	G/%
0	105.61	21.77	158.32	165.61	27.43	29.27	—
1	105.01	22.25	157.95	165.17	26.65	27.32	2.84
2	104.80	22.17	158.14	165.93	25.09	25.51	8.53
3	104.02	21.77	158.06	165.27	22.77	25.05	16.99
5	104.27	21.57	156.86	164.81	22.10	24.83	19.43
8	104.68	21.46	156.12	164.32	21.35	24.76	22.17

Tab.1. Thermodynamic parameters of composites with different EHBP content

Fig.3. Melt flow rate of the samples with different EHBP contents

Fig.4. （a）TG and （b）DTG curves of the composites with different EHBP contents

样品EHBP含量/份	T_d5/℃	T_d10/℃	T_dmax/℃
0	310.5	329.3	360.7
1	310.0	328.8	361.7
2	309.6	328.3	362.7
3	309.9	328.6	359.6
5	309.8	328.7	356.9
8	307.7	326.4	351.2

Tab.2. Thermal weight data of the PLA/talc/EHBP composites

Fig.5. （a） elongation at break and impact properties，（b） tensile strength，（c） stress⁃strain curve and （d） Shore hardness of the PLA/talc/EHBP

Fig.6. Contact angles of the samples

Fig.7. SEM images of PLA/talc/EHBP composites with different EHBP contents

References 39

1	丁燕，江驰，潘剑婷，等. 无机填料增强增韧聚乳酸基生物可降解材料的研究进展［J］. 云南化工， 2024， 51（06）： 18⁃21.
	DING Y， JIANG C， PAN J T， et al. Research progress on strengthening and toughening polylactic acid biodegradable materials by inorganic fillers ［J］. Yunnan Chemical Industry， 2024， 51（06）： 18⁃21.
2	BALDOWSKA⁃WITOS P， KRUSZELNICKA W， KASNER R， et al. Application of LCA method for assessment of environmental impacts of a polylactide （PLA） bottle shaping ［J］. Polymers， 2020， 12（2）：388.
3	ASGHER M， QAMAR S A， BILAL M， et al. Bio⁃based active food packaging materials： Sustainable alternative to conventional petrochemical⁃based packaging materials ［J］. Food Research International， 2020， 137：109625.
4	DING S， FANG C， WANG X， et al. Crystallization⁃driven microstructure changes during microphase separation for environment⁃friendly thermoplastic triblock copolymer elastomers ［J］. Polymer， 2020， 186：121993.
5	刘丰颉，李伟，彭新洋， et al. 聚乳酸的制备、改性及应用进展研究［J］. 塑料科技， 2024， 52（05）： 156⁃160.
	LIU F J， LI W， PENG X Y， et al. Preparation， modification and application of polylactic acid ［J］. Plastic Science and Technology， 2024， 52（05）： 156⁃160.
6	李羽佳，王喜明，姚利宏，等. 功能型植物纤维增强聚乳酸复合材料研究进展［J］. 塑料， 2024， 53（03）： 104⁃108.
	LI Y J， WANG X M， YAO L H， et al. Research progress of functional plant fiber reinforced polylactic acid composites ［J］. Plastics， 2024， 53（03）： 104⁃108.
7	王培，冯嘉玮，邓祎慧，等. 聚乳酸材料性能改进研究进展［J］. 安徽化工， 2024， 50（02）： 9⁃13.
	WANG P， FENG J W， DENG Y H， et al. Research progress on improving properties of polylactic acid materials ［J］. Anhui Chemical Industry， 2024， 50（02）： 9⁃13.
8	邓惠文. 生物降解聚乳酸增韧及其耐热改性研究［D］. 长春工业大学： 2024.
9	江闻欣，张广翔，杨可，等. 全生物降解高抗冲PLA/PBAT复合材料的制备与性能［J］. 辽宁石油化工大学学报，2024，44（05）：31⁃37.
	JIANG W X， ZHANG G X， Yang K， et al. Preparation and properties of fully biodegradable PLA/PBAT composites with high impact resistance ［J］. Journal of Liaoning Shihua University，2024，44（05）：31⁃37.
10	刘美意，张镇鹏，马凤国. 硅橡胶⁃聚丙烯酸酯微球增韧聚乳酸研究［J］. 合成材料老化与应用， 2024， 53（03）： 11⁃13.
	LIU M Y， ZHANG Z P， MA F G. Study on toughening polylactic acid with silicone rubber⁃polyacrylate microspheres ［J］. Aging and Application of Synthetic Materials， 2024， 53（03）： 11⁃13.
11	黄晓兰，李彩玲，刘幸琪，等. 绿色可降解生物高分子聚乳酸改性及应用研究进展［J］. 工程塑料应用， 2021， 49（07）： 162⁃166.
	HUANG X L， LI C L， LIU X Q， et al. Research progress on modification and application of green biodegradable polylactic acid ［J］. Engineering Plastics Application， 2021， 49（07）： 162⁃166.
12	胡晨曦，王宇韬，祝桂香，等. 无机填料在生物可降解塑料改性的应用进展［J］. 塑料科技， 2022， 50（08）： 83⁃87.
	HU C X， WANG Y T， ZHU G X， et al. Progress in the application of inorganic fillers to the modification of biodegradable plastics ［J］. Plastic Science and Technology， 2022， 50（08）： 83⁃87.
13	MAK S L， WU M Y T， TANG W F， et al. A review on mechanical properties modification of polymer with talc powder［C］//Proceedings of the IEEE international symposium on product compliance engineering ⁃ Asia （IEEE ISPCE⁃ASIA）.Taipei：2021.
14	孙闯闯，丁建萍，魏志和，等. 耐水解PLA/PBS/滑石粉复合材料的制备及性能［J］. 现代塑料加工应用， 2024， 36（02）： 33⁃36.
	SUN C C， DING J P， WEI Z H， et al. Preparation and properties of hydrolyzable PLA/PBS/talc composites ［J］. Modern plastics processing and application， 2024， 36（02）： 33⁃36.
15	韩嘉晖，黄汉雄，黄宇霄.滑石粉和PLA⁃g⁃MAH对聚乳酸结晶性能和熔体强度的改善［J］.高等学校化学学报，2018，39（09）：2 089⁃2 097.
	HAN J， HUANG H， HUANG Y. Improving crystallization behavior and meltstrength of poly（lactic acid）via·adding talc and PLA⁃g⁃MAH［J］. Chemical Journal of Chinese Universities， 2018，39（9）：2 089⁃2 097.
16	HAO Y， TIAN H， CHEN J， et al. Roles of physical filling and chemical crosslinking on the physico⁃mechanical properties of polylactic acid ［J］.Journal of Applied Polymer Science， 2022，139（34）：e52808.
17	XAY， QIANS， LU W， et al. Astrategy to prepare high⁃robust and ultra⁃toughpolylactic acid/polycaprolactone/talc composites with thermo⁃resistance ［J］.Polymer Composites，2023， 44（12）：8 750⁃8 765.
18	GHARSALLAHA， LAYACHI A， LOUAER A， et al. Thermal degradation kinetics of Opuntia Ficus Indica flour and talc⁃filled poly（lactic acid） hybrid biocomposites by TGA analysis ［J］. Journal of Composite Materials， 2021， 55（22）：3 099⁃3 118.
19	ZHU S， SUN M， MENG X， et al. Crystallization improvement of PLA by the talc with "grafting from" method of polymerization of lactide ［J］. Journal of Polymer Research， 2024， 31（1）：20.
20	HONG Y， CHEN L， SONG G， et al. Effect of in situ and mechanical properties of polylactide/talc composites ［J］. Polymer Composites， 2018， 39： 1 618⁃1 625.
21	LEE C， PANG M M， KOAY S C， et al. Talc filled polylactic⁃acid biobased polymer composites： tensile， thermal and morphological properties ［J］. Sn Applied Sciences， 2020， 2（3）：354.
22	PARK S BIN， LEE YJ KU K H， et al.Triallyl isocyanurate⁃assisted grafting of maleic anhydride to poly（lactic acid）： Efficient compatibilizers forpoly（lactic acid）/talc composites with enhanced mechanical properties ［J］.Journal ofApplied Polymer Science，2022.139（2）：e51488.
23	AVERSAC， BARLETTA M， PIZZI E， et al. Wear resistance of injectionmoulded PLA⁃talc engineered bio⁃composites： Effect of material design，thermal history and shear stresses during melt processing ［J］.Wear， 2017， 390/391：184⁃197.
24	SUN Z. Hyperbranched polymers in modifying natural plant fibers and their applications in polymer matrix composites⁃a review ［J］. J Agric Food Chem， 2019， 67（32）： 8 715⁃8 724.
25	FENG L， LI R， YANG H， et al. The hyperbranched polyester reinforced unsaturated polyester resin ［J］. Polymers （Basel）， 2022， 14（6）：1127.
26	XU W， WANG W， HAO L， et al. Effect of generation number on properties of fluoroalkyl‐terminated hyperbranched polyurethane latexs and its films ［J］. J Appl Polym Sci， 2020， 137（40）：e49215.
27	LIU M， ZHAO L B， YU L Y， et al. Structure and properties of PSf hollow fiber membranes with different molecular weight hyperbranched polyester using pentaerythritol as core ［J］. Polymers （Basel）， 2020， 12（2）：383.
28	孔祥临. 超支化聚酯/氧化石墨烯增韧环氧沥青的性能研究［D］.重庆交通大学，2024.
29	CHEN S， XU Z， ZHANG D. Synthesis and application of epoxy⁃ended hyperbranched polymers ［J］. Chemical Engineering Journal， 2018， 343： 283⁃302.
30	LI Z， WANG Y， LU H， et al. Stable nanoscale sea⁃island structure of biobased polyamide 56/poly （butylene adipate⁃co⁃terephthalate） blends compatibilized by interfacial hyperbranched structure： Toward biobased polymer blends with ultrahigh toughness ［J］. International Journal of Biological Macromolecules， 2024， 259：129310.
31	SI J， SHAO X， WEI W， et al. Epoxy⁃ended hyperbranched polymer⁃grafted graphene oxide for cold⁃mixed epoxy asphalt modification ［J］. International Journal of Pavement Engineering， 2024， 25（1）：2361344.
32	GUO M， JIN Y， HAN X， et al. Biodegradable poly （butylene adipate⁃co⁃terephthalate） and thermoplastic starch sustainable blends modified by epoxy⁃terminated hyperbranched polyester with excellent mechanical properties and high transparency ［J］. Starch⁃Starke， 2023， 75（3/4）：2200169.
33	GUO M， JIN Y， HAN X， et al. Simultaneously strengthening and toughening biodegradable polylactic acid/thermoplastic starch blends by compatibilizing with epoxy⁃terminated hyperbranched polyester ［J］. Journal of Polymers and the Environment， 2024， 32（7）： 3 025⁃3 038.
34	HAN X， HAN Y， JIN Y， et al. Tailoring compatibility and toughness of microbial poly （3⁃hydroxybutyrate⁃co-3⁃hydroxyvalerate）/bio⁃based polyester elastomer blends by epoxy⁃terminated hyperbranched polyester ［J］. International Journal of Biological Macromolecules， 2022， 220： 1 163⁃1 176.
35	HAN X， JIN Y， HUANG J， et al. Highly toughening modification of hyperbranched polyester with environment⁃friendly caprolactone as end group on poly （3⁃hydroxybutyrate⁃co-3⁃hydroxyvalerate）［J］. Journal of Polymers and the Environment， 2022， 30（8）： 3 209⁃3 217.
36	LI S， WU Q， LV T， et al. Synthesis and characterization of hyperbranched polymer with epoxide⁃terminated group and application as modifier for epoxy/polyamide system ［J］. Polymer Science Series B， 2017， 59（3）： 328⁃336.
37	ZHOU S， GUO M， JIN Y， et al. Synergistic toughening and reinforcement of poly（lactic acid） with epoxy⁃terminated hyperbranched polymers ［J］. Journal of Applied Polymer Science， 2024， 141（1）： 54740.
38	SOSNOWSKI S. Poly（L⁃lactide） microspheres with controlled crystallinity ［J］. Polymer， 2001， 42（2）： 637⁃643.
39	ZHANG J， LIU C， CHENG J， et al. Simultaneous toughening and strengthening of diglycidyl ether of bisphenol⁃a using epoxy⁃ended hyperbranched polymers obtained from thiol⁃ene click reaction ［J］. Polymer Engineering and Science， 2018， 58（10）： 1 703⁃1 709.

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