Effect of Nucleating Agent on Crystallization and Properties of Poly（butylene succinate）

doi:10.19491/j.issn.1001-9278.2021.08.021

Abstract

Abstract:

This paper focused on the effect of hydrazide nucleating agent （TMC?300） on the crystallization and properties of poly（butylene succinate）（PBS）. The effect of TMC?300 on the crystallization process， mechanical properties， thermal properties and shrinkage of PBS were investigated with differential scanning calorimeter， polarizing microscope， electron tension universal test machine， digital impact meter and thermal deformation micro?card temperature meter. The results indicated that the crystallization speed and crystallinity of PBS increased with the addition of TMC?300， and its crystal size was reduced significantly. Moreover， the crystallization temperature increased by 4.74 %， and the half?crystal time was shortened to 57 s with a decreased by 71.88 %. The nucleated PBS achieved a flexural modulus of 689.4 MPa， a heat distortion temperature of 89.6 °C and impact strength of 17.75 MPa， which increased by 9.5 %， 5.5 %， and 171.4 % respectively. This indicates a good balance among the rigidity and toughness and heat resistance. Although the shrinkage of PBS increased in the presence of TMC?300， the shrinkage ratio was closer to 1. This is easier to resolve the deformation and warpage problems occurring in PBS.

Key words: nucleating agent, poly（butylene succinate）, biodegradable plastic, crystallization

CLC Number:

TQ 323.6

LI Xiangyang, YANG Linzhu, ZHAI Guoqiang, GAO Wanqin, WANG Kezhi, LI Xungang. Effect of Nucleating Agent on Crystallization and Properties of Poly（butylene succinate）[J]. China Plastics, 2021, 35(8): 146-151.

Figures/Tables 11

References 18

1	魏家瑞.热塑性聚酯及其应用［M］.北京：化学工业出版社，2011：372⁃375.
2	翁云宣，付烨.生物分解塑料与生物基塑料［M］.北京：化学工业出版社，2020：117⁃125.
3	RUNGLAWAN S，NARINYA M.Isothermal and Non⁃isothermal Crystallization Kinetics of PLA/PBS Blends with Talc as Nucleating Agent［J］.Journal of Thermal Analysis and Calorimetry，2020，139（3）：1 941⁃1 948.
4	RUNGSIMA H，NATTAKARN H.Mechanical and Thermal Properties of PLA/PBS Co⁃continuous Blends Adding Nucleating Agent［J］.Energy Procedia，2013， 34（1）：871⁃879.
5	TAN L C，CHEN Y W，ZHOU WH，et al.Novel Approach toward Poly（butylene succinate）/Single⁃walled Carbon Nanotubes Nanocomposites with Interfacial⁃induced Crystallization Behaviors and Mechanical Strength［J］.Polymer，2011，52（16）：3 587⁃3 596.
6	高利斌，陈宇，许国志.成核剂对PBS结晶性能及力学性能的影响［J］.北京工商大学学报（自然科学版），2006，24（02）：5⁃8.
	GAO L B ，CHEN Y，XU G Z.Effects of Nucleating Agent on Crystallization Properties and Mechanical Properties of PBS［J］.Journal of Beijing Technology and Business University（Natural Science Edition），2006，24（02）：5⁃8.
7	魏志勇，周城，宋平，等. 聚丁二酸丁二醇酯/笼型低聚倍半硅氧烷纳米复合材料的结晶行为研究［J］. 高分子学报， 2013，（10）： 1253⁃1261.
	WEI Z Y，ZHOU C，SUN Ping，et al.Retarded Crystallization in Poly （butylene succinate）/Polyhedral Oligomeric Silsesquioxanes Nanocomposites ［J］.Acta Polymerica Sinica， 2013，（10）： 1 253⁃1 261.
8	FAN M，QIU Z.Enhanced Crystallization Rate of Biodegradable Poly（butylene succinate⁃co⁃ethylene succinate） by Poly（butylene fumarate） as an Efficient Polymeric Nucleating Agent［J］.Rsc Advances， 2015，5（117）：96 290⁃96 296.
9	何曼君，张东红，陈维孝，等.高分子物理［M］.上海：复旦大学出版社，2007：181⁃186
10	MARIJA S N，JASNA D.Synthesis and Characterization of Biodegradable Poly（butylene succinate⁃ co ⁃butylene adipate）s［J］.Polymer Degradation and Stability，2001，74（2）：263⁃270.
11	MELVIN A.Kinetics of Phase Change.I General Theory［J］.Journal ofChemical Physics，1939，7（12）：1 103⁃1 113.
12	周卫华，吕美娟，张丽.用SALS法研究PET的结晶机理和结晶动力学［J］.北京化纤工学院学报，1985，（2）：32⁃44.
	ZHOU W H，LV M J，ZHANG L.An Investlgation of the Crystallization Mechanism and Kinetics of PET by SALS Method［J］.Journal of Beijing Institute of Clothing，1985，（2）：32⁃44.
13	GÜMTHER B，ZACHMANN H G.Influence of Molar Mass and Catalysts on the Kinetics of Crystallization and on the Orientation of Poly（ethylene terephthalate）［J］.Elsevier，1983，24（8）：1 008⁃1 014.
14	关家玉，王兰兰，安宝珠，等.不同催化剂PET树脂结晶动力学讨论［J］.影像技术，1992（4）：6⁃8.
	GUAN J Y，WANG Y L，AN B Z，et al. On the Crystallization Kinetics of PET Resins Copolymerized Using Different Catalysts［J］.Image Technology， 1992，（4）：6⁃8.
15	杨始堃，刘佑习，赵冬升，黎少桦，陈玉君.缩聚催化剂用量对PET结晶性能的影响［J］.合成纤维工业，1988，11（6）：34⁃38.
	YANG S K，LIU Y X，ZHAO D S. Effect of the Amount of Condensation Catalyst ON The PET Crystallization［J］.Synthetic Fiber Industry， 1988，11（6）：34⁃38.
16	TAKASHI F.Processability and Properties of Aliphatic Polyesters， ‘BIONOLLE’， Synthesized by Polycondensation Reaction［J］. Polymer Degradation and Stability，1998，59（1）：209⁃214.
17	张洪军，梁晓雯，崔子怡，等.基于Moldflow的手机壳成形翘曲分析及优化设计［J］.机电工程技术，2020，49（8）：196⁃198.
	ZHANG H J，LIANG X W，CUI Z Y，et al.Warpage Analysis and Optimization Design of Mobile Phone Shell Based on Moldflow［J］. Mechanical & Electrical Engineering Technology， 2020，49（8）：196⁃198.
18	苏彬，董斌斌.热塑性材料产品的收缩与翘曲［J］.国外塑料，2006，24（06）：42⁃44.
	SU B，DONG B B.Shrinkage and Warpage of Thermoplastic Material Part［J］. World Plastics， 2006，24（06）：42⁃44.

样品	添加量/ %	T_c/℃	ΔH_c / J?g^?1	T_m/℃	ΔH_m/ J?g^?1	X_t/%
TMC?300	0	83.88	85.9	114.82	65.34	59.23
TMC?300	0.5	86.11	84.9	115.39	76.06	68.96
TMC?300	0.8	87.22	88.3	115.56	75.11	68.1
TMC?300	1	87.86	78.56	114.79	71.14	64.5

样品	添加量/ %	T_c/℃	ΔH_c / J?g^?1	T_m/℃	ΔH_m/ J?g^?1	X_t/%
TMC?300	0	83.88	85.9	114.82	65.34	59.23
TMC?300	0.5	86.11	84.9	115.39	76.06	68.96
TMC?300	0.8	87.22	88.3	115.56	75.11	68.1
TMC?300	1	87.86	78.56	114.79	71.14	64.5

样品	添加量/%	等温温度/℃	lnk	n	t_1/2/s	k/s^?n
TMC?300	0	95	-13.848 66	2.536 08	203.595 74	9.673 94×10^-7
TMC?300	0.5	95	-12.596 52	2.658 27	99.557 88	3.383 77×10^-6
TMC?300	0.8	95	-11.933 28	2.709 30	71.470 34	6.568 14×10^-6
TMC?300	1	95	-11.583 44	2.771 34	57.252 66	9.319 14×10^-6

样品	添加量/%	等温温度/℃	lnk	n	t_1/2/s	k/s^?n
TMC?300	0	95	-13.848 66	2.536 08	203.595 74	9.673 94×10^-7
TMC?300	0.5	95	-12.596 52	2.658 27	99.557 88	3.383 77×10^-6
TMC?300	0.8	95	-11.933 28	2.709 30	71.470 34	6.568 14×10^-6
TMC?300	1	95	-11.583 44	2.771 34	57.252 66	9.319 14×10^-6

样品	添加量/%	平行于熔体流动方向的收缩率/%	垂直于熔体流动方向的收缩率/%	双向收缩率比值
TMC?300	0	0.77	0.65	1.18
TMC?300	0.5	1.02	0.88	1.15
TMC?300	0.8	0.99	0.92	1.08
TMC?300	1	0.94	0.91	1.04