Effects of chain⁃extension condition on properties of poly（butylene succinate⁃co⁃terephthalate）/talc blends

doi:10.19491/j.issn.1001-9278.2024.06.001

Abstract

Abstract:

A multifunctional epoxy polymer was used as a chain extender for poly（butylene succinate⁃co⁃terephthalate）（PBST）， and the effects of chain extension condition on the properties of PBST/Talc（talcum powder） blends were investigated during the melt⁃phase reactive extrusion process. The chain extender dosage， reaction temperature， and screw rotational speed were studied as main factors. The primary influence factors and their interactions were identified through an analysis of variance. The results indicated that the influence of chain extender dosage is most significant， followed with a reaction temperature， whereas the influence of screw speed is less. The melting and crystallization temperatures of PBST decreased with an increase in the chain extender dosage， and meanwhile its molecular weight， melt viscosity， and thermal stability increased. The modified PBST compounds presented an increase in the breaking stress but a decrease in the breaking strain with an increase in the chain extender dosage. Response surface analysis indicated that the optimal chain extension condition was a chain extender dosage of 0.66 %， a reaction temperature of 200 ℃， and a screw speed of 300 r/min.

Key words: biodegradable polyester, chain extender, chain extension conditions, poly（butylene succinate?co?terephthalate）, talc

CLC Number:

TQ323.4

LUO Jiawei, ZHOU Bing, WANG James H, JIA Qin. Effects of chain⁃extension condition on properties of poly（butylene succinate⁃co⁃terephthalate）/talc blends[J]. China Plastics, 2024, 38(6): 1-11.

Figures/Tables 19

Fig.1. Scheme of molecular structures of PBST and ECE and chain extension reaction between PBST and ECE

样品编号	PBST/份	滑石粉母料/份	ECE/%	白油/%	温度^*/℃	螺杆转速/r•min^-1
PBST⁃0	75	25	0	0	220	250
PBST⁃1/220/250	75	25	0.1	0.8	220	250
PBST⁃3/220/250	75	25	0.3	0.8	220	250
PBST⁃5/220/250	75	25	0.5	0.8	220	250
PBST⁃7/220/250	75	25	0.7	0.8	220	250
PBST⁃5/200/250	75	25	0.5	0.8	200	250
PBST⁃5/240/250	75	25	0.5	0.8	240	250
PBST⁃5/220/200	75	25	0.5	0.8	220	200
PBST⁃5/220/300	75	25	0.5	0.8	220	300

Tab. 1. The experimental recipes and chain extension conditions

Fig.2. FTIR spectra and enlarged FTIR spectra of PBST， PBST⁃0， PBST⁃7/220/250 and ECE

样品	ECE用量/%	温度/℃	螺杆转速/r•min^-1	$M n ¯$ /g·mol^-1	$M w ¯$ /g·mol^-1	PDI
PBST⁃0	0	220	250	50 084	73 874	1.47
PBST⁃1/220/250	0.1	220	250	45 751	67 990	1.49
PBST⁃3/220/250	0.3	220	250	46 489	68 390	1.47
PBST⁃5/220/250	0.5	220	250	49 402	75 053	1.52
PBST⁃7/220/250	0.7	220	250	49 607	74 822	1.51
PBST⁃5/200/250	0.5	200	250	47 637	71 717	1.51
PBST⁃5/240/250	0.5	240	250	48 271	72 157	1.49
PBST⁃5/220/200	0.5	220	200	50 048	74 519	1.49
PBST⁃5/220/300	0.5	220	300	47 727	71 167	1.49

样品	ECE用量/%	温度/℃	螺杆转速/r•min^-1	$M n ¯$ /g·mol^-1	$M w ¯$ /g·mol^-1	PDI
PBST⁃0	0	220	250	50 084	73 874	1.47
PBST⁃1/220/250	0.1	220	250	45 751	67 990	1.49
PBST⁃3/220/250	0.3	220	250	46 489	68 390	1.47
PBST⁃5/220/250	0.5	220	250	49 402	75 053	1.52
PBST⁃7/220/250	0.7	220	250	49 607	74 822	1.51
PBST⁃5/200/250	0.5	200	250	47 637	71 717	1.51
PBST⁃5/240/250	0.5	240	250	48 271	72 157	1.49
PBST⁃5/220/200	0.5	220	200	50 048	74 519	1.49
PBST⁃5/220/300	0.5	220	300	47 727	71 167	1.49

Tab.2. GPC results of unmodified PBST and chain extended PBSTs

Fig.3. Relationships between the number⁃average molecular weights of chain⁃extended PBST and ECE dosage， temperature， and screw speed

样品	ECE用量/%	温度/℃	螺杆转速/r•min^-1	熔体体积流动速率（MVR）/cm³·（10 min）^-1	熔体质量流动速率（MFR）/g·（10 min）^-1
纯PBST	-	-	-	21.05±0.19	23.24±0.18
PBST⁃0	0	220	250	19.33±0.25	22.07±0.25
PBST⁃1/220/250	0.1	220	250	17.70±0.20	20.09±0.20
PBST⁃3/220/250	0.3	220	250	13.62±0.04	15.62±0.09
PBST⁃5/220/250	0.5	220	250	10.69±0.31	12.36±0.33
PBST⁃7/220/250	0.7	220	250	5.59±0.40	6.28±0.39
PBST⁃5/200/250	0.5	200	250	12.82±0.25	14.61±0.24
PBST⁃5/240/250	0.5	240	250	9.06±0.16	10.32±0.32
PBST⁃5/220/200	0.5	220	200	7.70±0.42	8.90±0.49
PBST⁃5/220/300	0.5	220	300	9.11±0.34	10.47±0.30

Tab. 3. Melt flow rates of pure PBST， unmodified PBST and chain⁃extended PBSTs

样品	ECE用量/%	温度/℃	螺杆转速/r•min^-1	180 ℃下熔体黏度/Pa·s
样品	ECE用量/%	温度/℃	螺杆转速/r•min^-1	100 s^-1	1 000 s^-1
PBST⁃0	0	220	250	394	171
PBST⁃1/220/250	0.1	220	250	399	177
PBST⁃3/220/250	0.3	220	250	461	189
PBST⁃5/220/250	0.5	220	250	551	202
PBST⁃7/220/250	0.7	220	250	683	245
PBST⁃5/200/250	0.5	200	250	518	199
PBST⁃5/240/250	0.5	240	250	546	215
PBST⁃5/220/200	0.5	220	200	586	217
PBST⁃5/220/300	0.5	220	300	610	234

Tab. 4. Melt viscosities of unmodified PBST and chain⁃extended PBSTs modified by chain extension

Fig.4. Response surfaces of MVR and melt viscosity of chain⁃extended PBST at 250 r/min

来源	平方和（SST）	df	均方（MSE）	F值	p值
模型	159.73	3	53.24	35.77	0.000 8	显著
A（ECE用量）	151.67	1	151.67	101.9	0.000 2
B（温度）	7.07	1	7.07	4.75	0.081 2
C（螺杆转速）	0.994 1	1	0.994 1	0.667 9	0.451 0
残差	7.44	5	1.49	-	-
总相关系数	167.18	8	-	-	-

Tab.5. Analysis of variance of response values of MVR of chain⁃extended PBST

Fig.5. Relationships between the melt indexes of chain⁃extended PBST and ECE dosage， temperature and screw speed

Fig.6. Relationships between the viscosity of chain⁃extended PBST at 180 ℃/1 000 s-1 and ECE Level， temperature and screw speed

样品	T_g^a /℃	T_m^b /℃	ΔH_m^c /J·g^-1	T_c^d/℃	ΔH_c^e/J·g^-1	X_c^f /%
PBST⁃0	-20.4	115.2	8.4	72.8	11.5	6.08
PBST⁃1/220/250	-20.6	114.4	10.0	72.6	13.7	7.23
PBST⁃3/220/250	-20.3	113.6	10.8	70.5	13.4	7.81
PBST⁃5/220/250	-19.3	112.6	12.9	66.6	13.5	9.33
PBST⁃7/220/250	-19.9	110.0	13.2	63.9	13.4	9.55
PBST⁃5/200/250	-20.3	112.5	11.8	68.8	13.3	8.54
PBST⁃5/240/250	-20.2	112.0	10.8	67.3	13.1	7.81
PBST⁃5/220/200	-19.2	112.1	12.9	66.5	16.7	9.33
PBST⁃5/220/300	-20.2	113.1	11.3	69.3	12.4	8.18
ECE	51.2	67.2	9.77	-	-	-

Tab. 6. DSC analysis results of ECE， unmodified PBST and chain⁃extended PBSTs

Fig.7. Response surfaces of glass transition temperature， melting point， crystallization temperature and crystallinity of chain⁃extended PBST at 250 r/min

Fig.8. Relationships between DSC analysis results of chain⁃extended PBST and ECE dosage， temperature and screw speed

Fig.9. TG and DTG curves of chain⁃extended PBST

Fig.10. Relationships between the Td5 of chain⁃extended PBST and ECE dosage， temperature and screw speed， and its response surface

Fig.11. Comparison between the typical stretch curve of unmodified PBST and chain⁃extended PBSTs

Fig.12. Response surfaces of elongation at break and elastic modulus of chain⁃extended PBSTs modified by chain extension

Fig.13. Relationships between the tensile mechanical properties of chain⁃extended PBST and ECE dosage，temperature and screw rotational speed

References 30

1	Sudesh K， Iwata T. Sustainability of Biobased and Biodegradable Plastics［J］. CLEAN⁃Soil， Air， Water， 2010， 36（5/6）： 433⁃442.
2	Alvarez⁃Chavez C R， Edwards S， Moure⁃Eraso R， et al. Sustainability of bio⁃based plastics： general comparative analysis and recommendations for improvement［J］. Journal of Cleaner Production， 2012， 23（1）： 47⁃56.
3	Müller R J， Kleeberg I， Deckwer W D. Biodegradation of polyesters containing aromatic constituents［J］. Journal of Biotechnology， 2001， 86（2）： 87⁃95.
4	Witt U， Müller R J， Augusta J， et al. Synthesis， properties and biodegradability of polyesters based on 1，3⁃propanediol［J］. Macromolecular Chemistry and Physics， 1994， 195（2）： 793⁃802.
5	Witt U， Müller R J， Deckwer W D. Evaluation of the biodegradability of copolyesters containing aromatic compounds by investigations of model oligomers［J］. Journal of Environmental Polymer Degradation， 1996， 4（1）：9⁃20.
6	Müller R J， Witt U， Rantze E， et al. Architecture of biodegradable copolyesters containing aromatic constituents［J］. Polymer Degradation & Stability， 1998， 59（1）： 203⁃208.
7	Witt U， Yamamoto M， Seeliger U， et al. Biodegradable Polymeric Materials—Not the Origin but the Chemical Structure Determines Biodegradability［J］. Angewandte Chemie International Edition， 1999， 38（10）： 1 438⁃1 442.
8	Witt U， Einig T， Yamamoto M， et al. Biodegradation of aliphatic⁃aromatic copolyesters： evaluation of the final biodegradability and ecotoxicological impact of degradation intermediates.［J］. Chemosphere， 2001， 44（2）： 289⁃299.
9	Honda N， Taniguchi I， Miyamoto M， et al. Reaction Mechanism of Enzymatic Degradation of Poly（butylene succinate⁃co⁃terephthalate）（PBST） with a Lipase Originated from Pseudomonas cepacia［J］. Macromolecular Bioscience， 2003， 3（3/4）： 189⁃197.
10	Lee S H， Lim S W， Lee K H. Properties of potentially biodegradable copolyesters of （succinic acid-1，4⁃butanediol）/（dimethyl terephthalate-1，4⁃butanediol）［J］. Polymer International， 1999， 48（9）： 861⁃867.
11	祝桂香，叶文亮.生物可降解共聚酯PBST的合成，结构性能及应用研究进展［J］.化工与医药工程， 2022， 43（5）：1⁃6.
	ZHU G X， YE W L. Research progress in synthesis，structure，properties and application of biodegradable copolyester PBST［J］. Chemical and Pharmaceutical Engineering， 2022， 43（5）：1⁃6.
12	Shaik A A， Richter M， Kricheldorf H R， et al. New polymer syntheses. CIX. Biodegradable， alternating copolyesters of terephthalic acid， aliphatic dicarboxylic acids， and alkane diols［J］. Journal of Polymer Science Part A： Polymer Chemistry， 2001， 39（19）： 3 371⁃3 382.
13	舒梦莹，翁云宣，张彩丽.多元环氧扩链剂（ADR）对PBAT的扩链改性及其耐老化性能的影响［J］.中国塑料， 2020， 34（3）：33⁃39.
	SHU M Y， WENG Y X， ZHANG C L. Influence of multi⁃component epoxy chain⁃extension agent on aging resistance of chain⁃extension modified PBAT［J］. China Plastics， 2020， 34（3）：33⁃39.
14	Li H， Huneault M A. Effect of chain extension on the properties of PLA/TPS blends［J］. Journal of Applied Polymer Science， 2011， 122（1）： 134⁃141.
15	Eslami H， Kamal M R. Effect of a chain extender on the rheological and mechanical properties of biodegradable poly（lactic acid）/poly［（butylene succinate）⁃co⁃adipate］ blends［J］. Journal of Applied Polymer Science， 2013， 129（5）： 2 418⁃2 428.
16	Baimark Y， Cheerarot O. Effect of Chain Extension on Thermal Stability Behaviors of Polylactide Bioplastics［J］. Oriental Journal of Chemistry， 2015， 31（2）： 635⁃641.
17	Baimark Y， Srihanam P. Influence of chain extender on thermal properties and melt flow index of stereocomplex PLA［J］. Polymer Testing， 2015， 45： 52⁃57.
18	王勋林，张敬勋，赵保才，等.PPC/PBAT薄膜制品性能研究［J］.塑料科技， 2015， 43（5）： 70⁃72.
	WANG X L， ZHANG J X， ZHAO B C， et al. Research on PPC/PBAT film products［J］. Plastics Science and Technology， 2015， 43（5）： 70⁃72.
19	Freitas A L P， Filho L R T， Calvao P S， et al. Effect of montmorillonite and chain extender on rheological， morphological and biodegradation behavior of PLA/PBAT blends［J］. Polymer Testing， 2017， 62： 189⁃195.
20	宋敬思，王贤增，周洪福，等.PBAT的扩链反应及其微孔发泡行为研究［J］.中国塑料， 2018， 32（11）：42⁃48.
	SONG J S， WANG Z X， ZHOU H F， et al. Study on chain extension and microcellular foaming behaviors of poly（butyleneadipate⁃co⁃terephthlate）［J］. China Plastics， 2018， 32（11）：42⁃48.
21	Souza A G， Nunes E C D， Rosa D S. Understanding the effect of chain extender on poly（butylene adipate⁃co⁃terephthalate） structure［J］. Iranian Polymer Journal， 2019， 28（12）： 1 035⁃1 044.
22	Nunes E C， Souza A G， Rosa D S. Use of a chain extender as a dispersing agent of the CaCO₃ into PBAT matrix［J］. Journal of Composite Materials， 2019， 54（10）： 1 373⁃1 382.
23	王杰，吴卫东，周洪福.EMA对PBAT的扩链改性及其微孔发泡行为［J］.工程塑料应用， 2020， 48（3）：28⁃33.
	WANG J， WU W D， ZHOU H F. Chain extension of poly （butylene adipate⁃co⁃terephthalate） by ethylene⁃glycidyl methacrylate copolymer and its microcellular foaming behaviors［J］. Engineering Plastics Application， 2020， 48（3）：28⁃33.
24	Zhang T， Han W Y， Zhang C L， et al. Effect of chain extender and light stabilizer on the weathering resistance of PBAT/PLA blend films prepared by extrusion blowing［J］. Polymer Degradation and Stability， 2021， 183： 109455.
25	赵海鹏，胡顺朋，夏学莲，等.扩链剂增容PBAT/PLA共混体系结构及性能［J］.工程塑料应用， 2021， 49（10）：131⁃137.
	ZHAO H P， HU S P， XIA X L， et al. Structures and properties of PBAT/PLA composites with chain extender［J］. Engineering Plastics Application， 2021， 49（10）：131⁃137.
26	宋浩，白楠，宋立新，等.扩链剂对PBAT/TPS共混体系性能的影响［J］.塑料科技， 2022， 50（5）：23⁃28.
	Song H， Bai N， Song L X， et al. Effect of chain extender on properties of PBAT/TPS blends［J］. Plastics Science and Technology， 2022， 50（5）：23⁃28.
27	Jia S L， Wang X Y， Zhang Y，et al.Superior Toughened Biodegradable Poly（L⁃lactic acid）⁃based Blends with Enhanced Melt Strength and Excellent Low⁃temperature Toughness via In situ Reaction Compatibilization［J］. Chinese Journal of Polymer Science， 2023， 41（3）： 373⁃385.
28	Grcev S， Schoenmakers P， Iedema P. Determination of molecular weight and size distribution and branching characteristics of PVAc by means of size exclusion chromatography/multi⁃angle laser light scattering （SEC/MALLS）［J］. Polymer， 2004， 45（1）：39⁃48.
29	郭宝华，丁慧鸽，徐晓琳，等. 生物可降解共聚物聚丁二酸/对苯二甲酸丁二醇酯（PBST）的序列结构及结晶性研究［J］. 高等学校化学学报， 2003， 24（12）： 2 312⁃2 316.
	GUO B H， DING H G， XU X L， et al. Studies on the sequence structure and crystallinity of poly（butylene succinate） copolymers with terephthalic acid ［J］. Chemical Journal of Chinese Universities， 2003， 24（12）： 2 312⁃2 316.
30	Hwang I T， Jung C H， Kuk I S， et al. Electron beam⁃induced crosslinking of poly（butylene adipate⁃co⁃terephthalate）［J］.Nuclear Instruments & Methods in Physics Research， 2010， 268（21）： 3 386⁃3 389.

[1]	SHEN Dantong, XUE Yuting, LI Rongjie, XU Fang, WENG Yunxuan. Study on preparation of poly（lactic acid）⁃based waterborne polyurethane and its application in synthetic leathers [J]. China Plastics, 2024, 38(4): 19-25.
[2]	LI Xianming, ZHANG Ning, LI Gaihua, LIU Shuang, LIU Zhengyuan. Effect of sodium dodecyl sulfate surface⁃modified hydrotalcite on thermal stability of PVC [J]. China Plastics, 2024, 38(2): 82-86.
[3]	SUN Yibo, LIU Yaning, LU Haofan, CHEN Shihong, WANG Xiangdong, WU Lili. Study on chain⁃extending reaction of PA66 and its supercritical CO₂ microcellular foaming behavior [J]. China Plastics, 2023, 37(12): 41-46.
[4]	WU Wei, HU Huanbo, SHEN Hui, ZHAO Tianyu. Dual⁃synergistic effect of 4A zeolite and Ca⁃Mg⁃Al hydrotalcite on intumescent flame retardant PP and its mechanism [J]. China Plastics, 2022, 36(7): 1-7.
[5]	LIU Jinyu, JIA Yongxing, WEN Bianying, QIU Munan. Research progress in fully biodegradable polyester/straw plant fiber composites [J]. China Plastics, 2022, 36(11): 183-191.
[6]	LU Weixin, LU Chong, WANG Bin, HU Jing, WU Jingjing, ZHOU Qinpeng. Effect of Epoxy Modifiers on Properties of PA6/EVOH Blends [J]. China Plastics, 2021, 35(9): 8-14.
[7]	LIU Xianggui, FANG Wei, SHU Hongbin, ZHENG Genwen, LIU Hai. Preparation and Performance of Hydrotalcite⁃filled PVC Composites [J]. China Plastics, 2021, 35(7): 63-68.
[8]	CAI Xiaofang, YUAN Hang, DIAO Xiaoqian, LI Ziyi, FENG Di. Analysis of Talc Migration in Polylactic Acid Cup Cover for Food Contact [J]. China Plastics, 2021, 35(7): 91-96.
[9]	WANG Conglong, HAN Shuo, ZHANG Yihui, CHEN Shihong, WANG Xiangdong. Study on Foaming Behavior of PES Using Supercritical CO₂ as Foaming Agent [J]. China Plastics, 2021, 35(6): 13-19.
[10]	YING Jie, QIU Qihao, ZHANG Xing, GU Hainan, LUO Rui. Effect of Talc on Properties of Flame⁃retardant Polycarbonate [J]. China Plastics, 2021, 35(5): 107-112.
[11]	LI Xianming, ZHANG Ning, LIU Zhengyuan, LIU Luiyuan. Study on Synthesis and Properties of Butyl Stannate Intercalated Hydrotalcite⁃like Compound for PVC [J]. China Plastics, 2021, 35(3): 38-43.
[12]	Yu ZU, Yanan REN, Jing HU. Study on Modification of Polylactic Acid/Poly(3⁃Hydroxybutyric Acid⁃co⁃3⁃Hydroxyvalate) Blends as 3D⁃Printing Filament [J]. China Plastics, 2020, 34(7): 36-43.
[13]	DING Jianfeng, WANG Wei, LIU Yao, XIA Zhean, LI Xinxin∗. Structure and Properties of Polyamide 6/Carbon Fiber Composites Modified with Inorganic Nucleating Agents [J]. China Plastics, 2020, 34(12): 8-16.
[14]	HAN Shuo, WANG Xiangdong, CHEN Shihong, JIANG Can, WANG Yaqiao. Effect of Epoxy-based Chain Extender on Crystallization Behavior and Rheological Property of PET/PA6 Blends [J]. China Plastics, 2019, 33(10): 23-27.
[15]	. Study on Mechanical Behaviors of Thermoplastic Materials Used for Automobile Rear Door Panels [J]. China Plastics, 2017, 31(08): 84-87 .