Study on microstructure and properties of ST⁃NAB3 nucleating agent⁃modified chain⁃extended polylactic acid

doi:10.19491/j.issn.1001-9278.2024.09.008

Abstract

Abstract:

PLA was melt⁃blended with a chain extender （CEAX8840） and a nucleating agent （ST⁃NAB3） by using a torque rheometer， and the microstructure， crystallization behavior， mechanical properties， and heat resistance of the modified PLA were characterized by suing scanning electron microscope， hot⁃plate polarizing microscope， differential scanning calorimeter， thermal deformation meter， universal testing machine， and impact tester. The results indicated that the modified PLA obtained the smallest crystal size at CEAX8840 and ST⁃NAB3 contents of 6 and 1 wt%， respectively； however， its crystal density was the highest. Moreover， the crystallization temperature and crystallinity degree of the modified PLA were increased to 123.9 ℃ and 44.9 %， respectively. In addition， its impact strength and thermal deformation temperature were increased to 64.7 kJ/m² and 84.9 ℃， respectively.

Key words: poly（lactic acid）, chain extender, nucleating agent, impact strength, thermal deformation temperature

CLC Number:

TQ321

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.

Figures/Tables 9

References 22

1	Feng T， Li R， Zhang H， et al. Induction mechanism and optimization of tradable green certificates and carbon emission trading acting on electricity market in China ［J］. Resour Conserv Recycl， 2021， 169： 105487.
2	Liao Q， Peng X， Fang H， et al. Fabrication of poly（lactic acid）/silkworm excrement composite with enhanced crystallization， toughness and biodegradation properties ［J］. J Polym Environ， 2020， 28（1）： 295⁃303.
3	Cui W， Wei X， Luo J， et al. CO₂⁃assisted fabrication of PLA foams with exceptional compressive property and heat resistance via introducing well⁃dispersed stereocomplex crystallites ［J］. J CO₂ Util， 2022， 64： 102184.
4	Guo X， Luo C， Fang M， et al. Effects of self‐assembled nucleating agent on the crystallization behavior， thermal properties， and mechanical properties of polylactic acid ［J］. J Appl Polym Sci， 2023， 140（31）： e54222.
5	Wang G， Zhao G， Wang S， et al. Injection molded microcellular PLA/graphite nanocomposite with dramatically enhanced mechanical and electrical properties for ultra⁃efficient EMI shielding applications ［J］. J Mater Chem C， 2018， 6（25）： 6 847⁃6 859.
6	Kuang T， Ju J， Liu T， et al. A facile structural manipulation strategy to prepare ultra⁃strong， super⁃tough， and thermally stable polylactide/nucleating agent composites ［J］. Adv Compos Hybrid Mater， 2022， 5（2）： 948⁃959.
7	Wang X， Gao Y， Li X， et al. Selective localization of graphene oxide in electrospun polylactic acid/poly（ε⁃caprolactone） blended nanofibers ［J］. Polym Test， 2017， 59： 396⁃403.
8	Kuang T， Ju J， Chen F， et al. Coupled effect of self⁃assembled nucleating agent， Ni⁃CNTs and pressure⁃driven flow on the electrical， electromagnetic interference shielding and thermal conductive properties of poly （lactic acid） composite foams ［J］. Compos Sci Technol， 2022， 230： 109736.
9	Luo J， Meng X， Gong W， et al. Improving the stability and ductility of polylactic acid via phosphite functional polysilsesquioxane ［J］. RSC Adv， 2019， 9（43）： 25 151⁃25 157.
10	Barczewski M， Mysiukiewicz O， Matykiewicz D， et al. Development of polylactide composites with improved thermomechanical properties by simultaneous use of basalt powder and a nucleating agent ［J］. Polym Compos， 2020， 41（7）：2 947⁃2 957.
11	Xu X， Zhen W. Preparation， performance and non⁃isothermal crystallization kinetics of poly（lactic acid）/amidated humic acid composites ［J］. Polym Bull， 2017， 75（8）： 3 753⁃3 780.
12	Petchwattana N， Naknaen P， Narupai B. Combination effects of reinforcing filler and impact modifier on the crystallization and toughening performances of poly（lactic acid）［J］. eXPRESS Polym Lett， 2020， 14（9）： 848⁃859.
13	Bai H， Huang C， Xiu H， et al. Enhancing mechanical performance of polylactide by tailoring crystal morphology and lamellae orientation with the aid of nucleating agent ［J］. Polymer， 2014， 55（26）： 6 924⁃6 934.
14	Xu H， Xie L， Chen Y， et al. Strong shear flow⁃driven simultaneous formation of classic shish⁃kebab， hybrid shish⁃kebab， and transcrystallinity in Poly（lactic acid）/Natural fiber biocomposites ［J］. ACS Sustainable Chem Eng， 2013， 1（12）： 1 619⁃1 629.
15	Ema Y， Ikeya M， Okamoto M. Foam processing and cellular structure of polylactide⁃based nanocomposites ［J］. Polymer， 2006， 47（15）： 5 350⁃5 359.
16	Yin D， Mi J， Zhou H， et al. Simple and feasible strategy to fabricate microcellular poly（butylene succinate） foams by chain extension and isothermal crystallization induction ［J］. J Appl Polym Sci， 2020， 137（26）： 48850.
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］. Polym Degrad Stab， 2022， 198： 109891.
18	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］. Polym Adv Technol， 2016， 27（4）： 550⁃560.
19	Ageyeva T， Kovacs JG， Tabi T. Comparison of the efficiency of the most effective heterogeneous nucleating agents for Poly（lactic acid）［J］. J Therm Anal Calorim， 2021， 147（15）： 8 199⁃8 211.
20	Ji H， Zhou X， Chen X， et al. Deformation⁃induced crystallization behavior of isotactic polypropylene sheets containing a β⁃Nucleating agent under solid⁃State stretching ［J］. Polymers， 2020， 12（6）： 1 258.
21	Singh AA， Wei J， Herrera N， et al. Synergistic effect of chitin nanocrystals and orientations induced by solid⁃state drawing on PLA⁃based nanocomposite tapes ［J］. Compos Sci Technol， 2018， 162： 140⁃145.
22	Dun D， Bai Y， Wang L， et al. Crystallization behaviors of poly （Lactic Acid） modified with ST⁃NAB3 and its improved mechanical and thermal properties ［J］. J Polym Environ， 2023， 31（12）： 5 166⁃5 184.

样品名称	PLA/%	ST⁃NAB3/%	CEAX8840/%
纯PLA	100.00	0	0
BPLA	94.00	0	6
PLA⁃0.5	99.50	0.5	0
BPLA⁃0.5	93.50	0.5	6
BPLA⁃0.75	93.25	0.75	6
BPLA⁃1	93.00	1	6

样品名称	PLA/%	ST⁃NAB3/%	CEAX8840/%
纯PLA	100.00	0	0
BPLA	94.00	0	6
PLA⁃0.5	99.50	0.5	0
BPLA⁃0.5	93.50	0.5	6
BPLA⁃0.75	93.25	0.75	6
BPLA⁃1	93.00	1	6

样品名称	T_cc/°C	H_cc/J·g^-1	T_c1/°C	T_c2/°C	H_c1/J·g^-1	H_c2/J·g^-1	T_m1/°C	T_m2/°C	H_m/J·g^-1	χ_c/%
纯PLA	112.8	29.6	-	-	-	-	164.4	171.7	30.1	0.6
BPLA	110.1	22.8	-	-	-	-	162.2	169.2	32.9	2.6
PLA⁃0.5	-	-	-	108.1	-	32.4	163.2	169.6	36.4	35.2
BPLA⁃0.5	-	-	78.2	111.8	0.9	32.6	163.6	169.9	37.1	37.5
BPLA⁃0.75	-	-	78.3	123.3	1.1	37.9	165.6	-	39.1	43.8
BPLA⁃1	-	-	78.5	123.9	1.6	38.8	165.7	-	42.4	44.9

样品名称	T_cc/°C	H_cc/J·g^-1	T_c1/°C	T_c2/°C	H_c1/J·g^-1	H_c2/J·g^-1	T_m1/°C	T_m2/°C	H_m/J·g^-1	χ_c/%
纯PLA	112.8	29.6	-	-	-	-	164.4	171.7	30.1	0.6
BPLA	110.1	22.8	-	-	-	-	162.2	169.2	32.9	2.6
PLA⁃0.5	-	-	-	108.1	-	32.4	163.2	169.6	36.4	35.2
BPLA⁃0.5	-	-	78.2	111.8	0.9	32.6	163.6	169.9	37.1	37.5
BPLA⁃0.75	-	-	78.3	123.3	1.1	37.9	165.6	-	39.1	43.8
BPLA⁃1	-	-	78.5	123.9	1.6	38.8	165.7	-	42.4	44.9

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