Study on performance regulation of chain⁃extended poly（lactic acid） foams with diphenylhydrazide sebacic acid

doi:10.19491/j.issn.1001-9278.2024.11.011

Abstract

Abstract:

In this study， diphenylhydrazide sebacic acid （ST⁃NAB3） was used to regulate the properties of a chemical graft product （C⁃PLA） obtained from the chain⁃extension modification of polylactic acid （PLA） using styrene⁃acrylonitrile⁃glycidyl methacrylate （SAG） a chain extender. Then， C⁃PLA⁃ST⁃NAB3 foams were prepared by using supercritical CO₂， and their crystallization performance， thermal performance， rheological behavior， foaming properties， and microstructure were investigated by polarization light microscopy， differential scanning calorimetry， rotational rheometer， and scanning electron microscopy. The results indicated that the addition of ST⁃NAB3 increased the crystallization rate of C⁃PLA foams significantly， resulting in a reduction in the crystal size but an increase in the crystal density. With an increase in the ST⁃NAB3 content， the crystallinity degree of the C⁃PLA foam increased from 3.2 % to 20.2 %. When the content of ST⁃NAB3 was 0.3 and 0.4 wt%， the C⁃PLA⁃ST⁃NAB3 foams with a uniform cell size could be formed at different foaming temperature.

Key words: poly（lactic acid）, diphenylhydrazide sebacic acid, foaming material, crystallization performance, cell structure

CLC Number:

TQ321

WANG Aohua, DUN Dongxing, MENG Ruijing, ZHANG Yuxia. Study on performance regulation of chain⁃extended poly（lactic acid） foams with diphenylhydrazide sebacic acid[J]. China Plastics, 2024, 38(11): 64-69.

Figures/Tables 10

Fig.1. Structural formula of ST⁃NAB3

样品	PLA	SAG	ST⁃NAB3
PLA	100	0	0
C⁃PLA	97.0	3	0
C⁃PLA⁃0.1^a	96.9	3	0.1
C⁃PLA⁃0.2	96.8	3	0.2
C⁃PLA⁃0.3	96.7	3	0.3
C⁃PLA⁃0.4	96.6	3	0.4

Tab.1. Formula of the C⁃PLA⁃ST⁃NAB3 foaming material

Fig.2. PLM images of various foamed chain⁃extended PLA samples crystallized at 120 ℃ for various time at isothermal temperature

Fig.3. DSC curves of the chain⁃extended PLA with different ST⁃NAB3 contents

样品	T_cc/℃	H_cc/J·g^-1	T_c/℃	H_c /J·g^-1	T_m1/℃	T_m2/℃	H_m/J·g^-1	X_c/%
PLA	109.3	29.6	—	—	162.8	169.7	30.1	0.5
C⁃PLA	108.8	25.5	—	—	163.4	169.0	28.4	3.2
C⁃PLA⁃0.1	106.9	22.6	—	—	163.4	169.0	27.7	5.7
C⁃PLA⁃0.2	102.7	20.0	—	—	168.9	—	26.1	6.8
C⁃PLA⁃0.3	95.0	15.1	88.4	10.6	167.8	—	29.5	11.8
C⁃PLA⁃0.4	—	—	95.8	18.2	168.0	—	30.1	20.2

Tab.2. Crystallization and melting properties of the chain⁃extended PLA with different ST⁃NAB3 contents

Fig.4. Dynamic rheological curves of the C⁃PLA with different ST⁃NAB3 contents

Fig.5. SEM images of the chain⁃extended PLA foams with different ST⁃NAB3 contents

Fig.6. Cell characteristics of the chain⁃extended PLA foams with different ST⁃NAB3 contents

Fig.7. Cell nucleation mechanism of the C⁃PLA and C⁃PLA⁃ST⁃NAB3

Fig.8. Mechanical properties of the chain⁃extended PLA foams with different ST⁃NAB3 contents

References 21

1	Anton P， Patrik S， Miroslav Mrlík，et al. Foamy phase change materials based on linear low⁃density polyethylene and paraffin wax blends［J］. Emergent Materials， 2018， 1： 47⁃54.
2	Miroslav M， Sobolciak P， Krupa I， et al. Light⁃controllable viscoelastic properties of a photolabile carboxybetaine ester⁃based polymer with mucus and cellulose sulfate［J］. Emergent Materials， 2018， 1： 35⁃45.
3	Sarver J A， Kiran E.Foaming of polymers with carbon dioxide⁃the year⁃in⁃review-2019［J］. Journal of Supercritical Fluids， 2021， 173： 105166.
4	Nagarajan V， Mohanty A K， Misra M. Perspective on polylactic acid （PLA） based sustainable materials for durable applications： focus on toughness and heat resistance［J］. ACS Sustainable Chem Eng， 2016， 4（6）： 2 899⁃2 916.
5	Li X L， Wang R， Yang C F， et al. Effect of poly（D⁃lactic acid） block copolymers with soft chains on the tensile behavior of poly（L⁃lactic acid）［J］. Acta Polymerica Sinica， 2018（5）： 598⁃606.
6	Saeidlou S， Huneault M A， Li H， et al. Poly（lactic acid） crystallization［J］. Progress in Polymer Science， 2012， 37（12）： 1 657⁃1 677.
7	Qu X Z S. Cellular morphology evolution in nanocellular poly （lactic acid）/thermoplastic polyurethane blending foams in the presence of supercritical N-2［J］. European Polymer Journal， 2019， 116： 291⁃301.
8	Li Y， Mi J， Fu H， et al. Nanocellular foaming behaviors of chain⁃extended poly （lactic acid） induced by isothermal crystallization［J］. ACS Omega， 2019， 4（7）： 12 512⁃12 523.
9	Li Y， Yin D， Liu W， et al. Fabrication of biodegradable poly （lactic acid）/carbon nanotube nanocomposite foams： Significant improvement on rheological property and foamability［J］. International Journal of Biological Macromolecules， 2020， 163： 1 175⁃1 186.
10	张婧婧，黄汉雄，黄耿群.交联剂对聚乳酸流变性能及其发泡材料泡孔结构的影响［J］.化工学报，2015，66（10）：4 252⁃4 257.
	ZHANG J J， HUANG H X， HUANG G Q. Effects of crosslinking agent on rheological properties of poly（lactic acid） and cellular structure of its microcellular foams［J］. CIESC Journal， 2015， 66（10）： 4 252⁃4 257.
11	李成浪，窦强.PLA成核剂的研究进展［J］.塑料助剂，2014（02）：6⁃10，56.
	LI C L， DOU Q. Research progress on nucleating agents for poly（lactic acid）［J］. Plastics Additives， 2014（02）： 6⁃10，56.
12	Dun D X， Bai Y A， Wang L Z， et al. Crystallization behaviors of poly （lactic acid） modified with ST⁃NAB3 and its improved mechanical and thermal properties［J］. Polym Environ， 2023（31）： 5 166⁃5 184.
13	Li Y， Mi J G， Fu H， et al. Nanocellular foaming behaviors of chain⁃extended poly（lactic acid） induced by isothermal crystallization［J］. ACS Omega， 2019， 4（7）： 12 512⁃12 523.
14	张靖倩，曾广胜，彭军，等.酰肼成核剂对聚乳酸结晶和力学性能的影响［J］.材料科学与工程学报， 2024， 42（3）：427⁃434.
	ZHANG J J， ZENG G S， PENG J， et al. Effects of hydrazide nucleating agents on crystallization and mechanical properties of polylactic acid［J］. Journal of Materials Science and Engineering， 2024， 42（3）：427⁃434.
15	刘凤玉.成核剂和扩链剂对PLA/PBAT共混体系性能的影响［J］.工程塑料应用，2023，51（10）：154⁃159，166.
	LIU F Y. Effects of nucleating agent and chain extender on properties of PLA/PBAT blends［J］. Engineering Plastics Application， 2023，51（10）： 154⁃159，166.
16	师萌萌.聚乳酸的结晶及力学性能的调控［D］.宁夏：宁夏大学，2018.
17	Tang Y， Wang Y， Chen S， et al.Fabrication of low⁃density poly（lactic acid） microcellular foam by self⁃assembly crystallization nucleating agent［J］.Polymer Degradation and Stability， 2022， 198：109891.
18	Huang F， Liu W， Lai J， et al.Enhanced heat resistance and expansion ratio of biodegradable poly （lactic acid）/poly （butylene adipate⁃co⁃terephthalate） composite foams via synergistic effect of nucleating agent and chain extension［J］.Journal of Polymer Engineering， 2023， 43（4）： 297⁃309.
19	黄枫.高耐热聚乳酸复合材料的制备及发泡性能研究［D］.福建工程学院，2024.
20	Shi X， Zhang G， Liu Y， et al. Microcellular foaming of polylactide and poly（butylene adipate⁃co⁃terphathalate） blends and their CaCO₃ reinforced nanocomposites using supercritical carbon dioxide［J］.Polymers for Advanced Technologies， 2016， 27（4）： 550⁃560.
21	杨文杰，何佳文，朱寒宾等.石墨烯增强聚乳酸力学性能及其发泡行为研究［J］.中国塑料， 2021， 35（06）： 26⁃32.
	Yang J W， He J W， Zhu H B， et al. Mechanical properties and foaming behaviors of graphene⁃reinforced poly（lactic acid）［J］.China Plastics， 2021， 35（06）： 26⁃32.

[1]	CUI Bao, YANG Jianjun, WU Qingyun, WU Mingyuan, ZHANG Jianan, LIU Jiuyi. Research Progress in blending modification of polylactic acid composites and their applications [J]. China Plastics, 2024, 38(9): 129-136.
[2]	DING Xinyi, DUN Dongxing, QIN Junxi, CHEN Yulei, HAN Yufei, ZHANG Yuxia, ZHOU Hongfu. Study on microstructure and properties of ST⁃NAB3 nucleating agent⁃modified chain⁃extended polylactic acid [J]. China Plastics, 2024, 38(9): 41-46.
[3]	DONG Guang, HOU Yangzhe, YUAN Hongyue, LIU Xianhu, PAN Yamin. Progress in porous poly（lactic acid） material and their structure and performance optimization [J]. China Plastics, 2024, 38(8): 132-140.
[4]	HU Yongxiang, XIE Jiling, LI Weiming, ZHANG Lu, TANG Xianggang, LYU Yitong, SHEN Hongwang, JU Guannan. Effect of maleic anhydride graft⁃modified ground tire rubber on properties of poly（lactic acid） [J]. China Plastics, 2024, 38(7): 20-24.
[5]	WANG Jie, XIN Dehua, LI Hui, JIANG Hongshi, ZHOU Hongfu, ZHAO Jianguo. Effect of hybrid reinforcement of nanoclay and silica on properties of poly（lactic acid） [J]. China Plastics, 2024, 38(7): 43-48.
[6]	SHEN Qiangfeng, LYU Mingfu, XU Yaohui. Study on autoclave foaming properties of metallocene polypropylene [J]. China Plastics, 2024, 38(7): 55-61.
[7]	YANG Lian, JIANG Jing, JIA Caiyi, XIE Yuehan, WANG Xiaofeng, LI Qian. Preparation of polyamide 6 microfiber reinforced polypropylene composite and its property of chemical foam injection molding [J]. China Plastics, 2024, 38(6): 12-18.
[8]	YANG Chaoyong, GUO Jinqiang, WANG Fuyu, ZHANG Yuxia. Effect of extrusion blowing process on microstructure and properties of PBAT/PLA blend [J]. China Plastics, 2024, 38(5): 82-87.
[9]	BO Haiwa, ZHAO Zhongguo, WANG Chouxuan, XUE Rong. Structural design and properties of PLA/CNTs conductive composites with high conductivity and low percolation [J]. China Plastics, 2024, 38(4): 13-18.
[10]	JIANG Shuaihua, LI Zhuolun, LU Haofan, SUN Yibo, WANG Xiangdong, CHEN Shihong, WU Lili. Study on preparation and properties of high strength PS/PPO open cell foams induced by stabilized island structure [J]. China Plastics, 2024, 38(3): 49-53.
[11]	QI Shijie, YOU Xiangyu, WANG Ruichen, ZHOU Linfei, ZHANG Huijie. Preparation and properties of poly（lactic acid）/lignin blends with high lignin content [J]. China Plastics, 2024, 38(2): 45-51.
[12]	TAN Jing, WANG Zhi, WANG Shuo, FU Hongyan, LI Changjin, LI Haoyi, YANG Weimin, ZHANG Yang. Study on toughening modification of poly（lactic acid） melt differential electrospun fiber membrane by dendrimer [J]. China Plastics, 2024, 38(2): 7-13.
[13]	MA Xiuqing, LAO Zhichao, LI Mingqian, HAN Shuntao, HU Nan. Effect of 3D printing process parameters on mechanical properties of PLA/PTW blends [J]. China Plastics, 2024, 38(2): 70-75.
[14]	CUI Chengzhi, CAO Jinxing, LIU Jianlan, ZHANG Hui. Research progress in poly(lactic acid)/thermoplastic polyurethane blends [J]. China Plastics, 2023, 37(9): 75-82.
[15]	GUAN Guotao, LIU Chenze, HE Shiquan, SONG Chaoyang, ZHANG Xiang, ZHAO Na, WANG Chao. Preparation and properties of antibacterial biodegradable poly (lactic acid) membrane [J]. China Plastics, 2023, 37(9): 8-13.