Modification of Polylactic Acid by Reactive Blending with Functionalized Imidazolium-based Ionomers and Epoxy-containing Additives

doi:10.19894/j.issn.1000-0518.220055

Chinese Journal of Applied Chemistry ›› 2022, Vol. 39 ›› Issue (12): 1870-1879.DOI: 10.19894/j.issn.1000-0518.220055

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Modification of Polylactic Acid by Reactive Blending with Functionalized Imidazolium-based Ionomers and Epoxy-containing Additives

Yi-Lian MA¹, Hao-Dong HU¹, Ying-Li DING², Xiang-Jian CHEN², Liang CUI³(), Kun-Yu ZHANG³()

^1.School of Chemical Engineering and Technology，Tianjin University，Tianjin 300350，China
^2.Tianjin Key Laboratory of Composite and Functional Materials，School of Materials Science and Engineering，Tianjin University，Tianjin 300350，China
^3.Advanced Materials Research Center，Petrochemical Research Institute，Petro China Company Limited，Beijing 102206，China

Received:2022-03-03 Accepted:2022-07-25 Published:2022-12-01 Online:2022-12-13
Contact: Liang CUI,Kun-Yu ZHANG
About author:cuiliang@petrochina.com.cn
kyzhang@tju.edu.cn
Supported by:
the National Natural Science Foundation of China(51573130)

Abstract

Abstract:

Aiming to tackle the serious brittleness problem of polylactic acid （PLA）， PLA-based multiphase blends are prepared by melting reactive blending with hydroxyl functionalized ionomer as the toughening agent and compatibilizer containing epoxy groups. The structures and properties of the blends are characterized by scanning electron microscopy （SEM）， Fourier transform infrared spectrometer （FT-IR）， differential scanning calorimetry （DSC） and mechanical properties tests. The synergistic compatibilization and toughening effects of epoxy soybean oil （ESO）， polyethylene glycol diglycidyl ether （PEGDE） and ethylene-methyl acrylate-glycidyl methacrylate （AX8900） terpolymer are compared and analyzed. The results show that the compatibilization effect is closely related to the content and position of the epoxy group in the additives， which presenting different toughening effects. The addition of AX8900 can effectively improve the toughness of the blend system to obtain balanced mechanical properties. However， ESO tends to lead to crosslinking， which limits the toughening efficiency. PEGDE mainly shows a plasticizing effect， leading to the reduction of tensile strength. The results demonstrate modification of the PLA blends by reactive blending with different epoxy additives and hydroxy-containing polymers is an effective strategy for the development of high-performance biobased PLA materials.

Key words: Polylactide, Reactive blending, Toughening, Ionomer

CLC Number:

O631

Yi-Lian MA, Hao-Dong HU, Ying-Li DING, Xiang-Jian CHEN, Liang CUI, Kun-Yu ZHANG. Modification of Polylactic Acid by Reactive Blending with Functionalized Imidazolium-based Ionomers and Epoxy-containing Additives[J]. Chinese Journal of Applied Chemistry, 2022, 39(12): 1870-1879.

Figures/Tables 8

Fig.1 The structures of ESO， PEGDE and AX8900

Table 1 Blend compositions and the corresponding codes

样品 Sample	质量比 Mass ratio
PLA/ECO-OH-PF₆	m（PLA）/m（ECO-OH-PF₆）=90/10
PLA/ECO-OH-PF₆	m（PLA）/m（ECO-OH-PF₆）=80/20
PLA/ECO-OH-PF₆	m（PLA）/m（ECO-OH-PF₆）=70/30
PLA/ESO/ECO-OH-PF₆	m（PLA）/m（ESO）/m（ECO-OH-PF₆）=80/5/20
PLA/ESO/ECO-OH-PF₆	m（PLA）/m（ESO）/m（ECO-OH-PF₆）=80/10/20
PLA/ESO/ECO-OH-PF₆	m（PLA）/m（ESO）/m（ECO-OH-PF₆）=80/15/20
PLA/AX8900/ECO-OH-PF₆	m（PLA）/m（AX8900）/m（ECO-OH-PF₆）=80/5/20
PLA/AX8900/ECO-OH-PF₆	m（PLA）/m（AX8900）/m（ECO-OH-PF₆）=80/10/20
PLA/AX8900/ECO-OH-PF₆	m（PLA）/m（AX8900）/m（ECO-OH-PF₆）=80/15/20
PLA/PEGDE/ECO-OH-PF₆	m（PLA）/m（PEGDE）/m（ECO-OH-PF₆）=80/5/20
PLA/PEGDE/ECO-OH-PF₆	m（PLA）/m（PEGDE）/m（ECO-OH-PF₆）=80/10/20
PLA/PEGDE/ECO-OH-PF₆	m（PLA）/m（PEGDE）/m（ECO-OH-PF₆）=80/15/20

Fig.2 SEM images for cryo-fractured surfaces of the ternary blends

Fig.3 FT-IR spectra and partial enlarged of the blending samples：（A，A'，A"） the blends PLA/AX8900/ECO-OH-PF6；（B，B'，B"） the blends of PLA/ESO/ECO-OH-PF6；（C，C'，C"） the blends of PLA/PEGDE/ECO-OH-PF6

Fig.4 DSC curves of neat PLA and the blends：（A） neat PLA， the blends of PLA/ECO-OH-PF6 and PLA/ESO/ECO-OH-PF6；（B） neat PLA， the blends of PLA/ECO-OH-PF6 and PLA/AX8900/ECO-OH-PF6；（C） neat PLA， the blends of PLA/ECO-OH-PF6 and PLA/PEGDE/ECO-OH-PF6

Fig.5 Tensile stress-strain curves of the blends：（A） the blends of PLA/ECO-OH-PF6；（B） the blends of PLA/ESO/ECO-OH-PF6；（C） the blends of PLA/AX8900/ECO-OH-PF6；（D） the blends of PLA/PEGDE/ECO-OH-PF6

Fig.6 Impact strength of the blends：（A） the blends of PLA/ECO-OH-PF6；（B） the blends of PLA/ESO/ECO-OH-PF6；（C） the blends of PLA/AX8900/ECO-OH-PF6；（D） the blends of PLA/PEGDE/ECO-OH-PF6

Fig.7 SEM images for impact section of the blends

References 18

1	MEHRABI M M， EDALAT A， BERAHMAN R， et al. Highly-toughened polylactide-（PLA-） based ternary blends with significantly enhanced glass transition and melt strength： tailoring the interfacial interactions， phase morphology， and performance［J］. Macromolecules， 2018， 51（11）： 4298-4314.
2	曹友錋，庞烜，项盛，等. 溶剂诱导的聚乳酸/聚乳酸衍生物共结晶行为［J］. 应用化学， 2021， 38（1）： 60-68.
	CAO Y P， PANG X， XIANG S， et al. Solution-induced co-crystallization in poly（lactic acid）/substituted poly（lactic acid） blends［J］. Chinese J Appl Chem， 2021， 38（1）： 60-68.
3	YU H Y, ZHANG H, SONG M L， et al. From cellulose nanospheres， nanorods to nanofibers： various aspect ratio induced nucleation/reinforcing effects on polylactic acid for robust-barrier food packaging［J］. ACS Appl Mater Interfaces， 2017， 9（50）： 43920-43938.
4	胡宽，江海，黄冬，等. 聚丁二酸丁二醇酯与氯醚弹性体协同增韧改性聚乳酸多元共混体系［J］. 应用化学， 2019， 36（9）： 996-1002.
	HU K， JIANG H， HUANG D， et al. Synergetic modification of polybutylene succinate and poly（epichlorohydrin-co-ethylene oxide） elastomer in toughening poly（lactic acid）［J］. Chinese J Appl Chem， 2019， 36（9）： 996-1002.
5	DANIELE B， ALBERTO F， TOBIAS A， et al. Epoxy coupling agent for PLA and PHB copolymer-based cotton fabric bio-composites［J］. Compos Part B-Eng， 2018， 148： 188-197.
6	HIROFUMI K， NANAKA M， HIROKI S， et al. Effect of surface treatment of cellulose fiber （CF） on durability of PLA/CF bio-composites［J］. Carbohydr Polym， 2019， 203： 95-102.
7	WON J C， KI S H， HYUK J K， et al. Rapid development of dual porous poly（lactic acid） foam using fused deposition modeling （FDM） 3D printing for medical scaffold application［J］. Mater Sci Eng， 2020， 110： 110693.
8	YAN Z， BOHUA Z， BOLEI W， et al. Enhanced compatibility between poly（lactic acid） and poly（butylene adipate-co-terephthalate） by incorporation of N-halamine epoxy precursor［J］. Int J Biol Macromol， 2020， 165： 460-471.
9	王行，胡浩东，陈相见，等. 含功能化咪唑鎓离聚物增韧改性聚乳酸的研究［J］. 高分子学报， 2021， 52（10）： 1323-1333.
	WANG H， HU H D， CHEN X J， et al. Functionalized imidazolium-based ionomers as effective toughening agents for poly（lactic acid）［J］. Acta Polym Sin， 2021， 52（10）： 1323-1333.
10	SUN S， WANG H， HUANG D， et al. Refractive index engineering as a novel strategy toward highly transparent and tough sustainable polymer blends［J］. Chinese J Polym Sci， 2020， 38（12）： 1335-1344.
11	HUANG D， DING Y， JIANG H， et al. Functionalized elastomeric ionomers used as effective toughening agents for poly（lactic acid）： enhancement in interfacial adhesion and mechanical performance［J］. ACS Sustainable Chem Eng， 2019， 8（1）： 573-585.
12	HOU A L， QU J P. Super-toughened poly（lactic acid） with poly（epsilon-caprolactone） and ethylene-methyl acrylate-glycidyl methacrylate by reactive melt blending［J］. Polymers， 2019， 11： 771.
13	GANDINI A， LACERDA T M， CARVALHO A， et al. Progress of polymers from renewable resources： furans， vegetable oils， and polysaccharides［J］. Chem Rev， 2016， 116（3）： 1637-1669.
14	JIA P Y， ZHANG M， HU L H， et al. Green plasticizers derived from soybean oil for poly（vinyl chloride） as a renewable resource material［J］. Korean J Chem Eng， 2016， 33（3）： 1080-1087.
15	WANG H， CHEN X， DING Y， et al. Combining novel polyether-based ionomers and polyethylene glycol as effective toughening agents for polylactide［J］. Polymer， 2021， 229： 123964.
16	QUILES-CARRILLO L， DUART S， MONTANES N， et al. Enhancement of the mechanical and thermal properties of injection-molded polylactide parts by the addition of acrylated epoxidized soybean oil［J］. Mater Des， 2018， 140： 54-63.
17	KILIC N T， CAN B N， KODAL M， et al. Compatibilization of PLA/PBAT blends by using Epoxy-POSS［J］. J Appl Polym Sci， 2019， 136： 47217.
18	ZHAO X， LI K， WANG Y， et al. High-strength polylactic acid （PLA） biocomposites reinforced by epoxy-modified pine fibers［J］. ACS Sustainable Chem Eng， 2020， 8（35）： 13236-13247.

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[2]	LI Fei, JIANG Guowei, ZHOU Guangyuan, SUN Xiuyun, SUN Chunrong, SHANG Xue, DONG Yan, WANG Yiming. Halogen Free Flame Retardant Modification of Polytrimethylene Terephthalate [J]. Chinese Journal of Applied Chemistry, 2017, 34(4): 436-442.
[3]	ZHANG Han, SUN Zhiqiang, PANG Xuan, ZHOU Linyao, LI Shuai, SUN Haibo, CHEN Wenqi, CHEN Xuesi. Structure and Properties of Polylactide/Polycaprolactone/Poly(ε-caprolactone-L-lactide) Ternary Blends [J]. Chinese Journal of Applied Chemistry, 2016, 33(9): 1026-1032.
[4]	SUN Bin, LIU Yanlong, BIAN Xinchao, ZHANG Bao, ZHOU Linyao, FENG Lidong, LI Gao, CHEN Zhiming. Preparation of High Heat Resistance Polylactide by Stereocomplexation [J]. Chinese Journal of Applied Chemistry, 2016, 33(9): 1033-1039.
[5]	BIAN Xinchao, FENG Lidong, CHEN Zhiming, CHEN Xuesi. Non-Isothermal Crystallization Behavior of Polylactide [J]. Chinese Journal of Applied Chemistry, 2016, 33(7): 766-773.
[6]	YANG Lixin, HU Xiuli, HUANG Yubin, JING Xiabin. Synthesis and Characterization of Retardant Polyurethanes Based on Polylactide [J]. Chinese Journal of Applied Chemistry, 2016, 33(1): 47-52.
[7]	ZHANG Han, SUN Zhiqiang, PANG Xuan, LI Shuai, SUN Jingru, CHEN Wenqi, CHEN Xuesi. Preparation and Properties of Blends from Poly(ε-caprolactone-ran-L-lactide) Random Copolymer and Amorphous Poly(lactic acid) [J]. Chinese Journal of Applied Chemistry, 2015, 32(11): 1268-1274.
[8]	ZOU Yinjiang, SHENG Yu, ZHU Deqin. Influential Factors of Toughening Polypropylene via* the Incorporation of Inorganic Rigid Particles [J]. Chinese Journal of Applied Chemistry, 2013, 30(03): 245-251.
[9]	DONG Yanlei1,2, CHEN Lijie1, QIN Yusheng1, WANG Xianhong1*, ZHAO Xiaojiang1, WANG Fosong1,3. Effect of Linear Poly(ester amide) on Properties of Blends with Poly(propylene carbonate) [J]. Chinese Journal of Applied Chemistry, 2012, 29(10): 1107-1110.
[10]	ZHONG Yinhua, LUO Yan*, ZENG Jian, WEI Yinglin, WU Yehui. Epoxy Resin Toughened by Polyester Hot Melt Adhesive [J]. Chinese Journal of Applied Chemistry, 2012, 29(07): 745-750.
[11]	HU Yuexin1,2, FENG Yulin1,2, JIANG Wei1*. High-density Polyethylene Toughened with Calcium Carbonate Filler Particles--Applicability of Wu′ Criterion for Brittle-Ductile Transition of Polymer Blends [J]. Chinese Journal of Applied Chemistry, 2011, 28(05): 500-503.
[12]	CHENG Hai-Bo1,2, CHEN Xue-Si1, XIAO Hai-Hua1,2, HU Xiu-Li1, JING Xia-Bin1*. Promotion of Crystallization in Linear Polylactide by Multiarm-polylactide [J]. Chinese Journal of Applied Chemistry, 2010, 27(07): 754-758.
[13]	Zhang Jie, Gan Zhihua, Liang Qizhi, Jing Xiabin. The Morphology of Poly(ε-caprolactone)/Poly(d,l-lactide) Blends Film in the Course of Enzymatic Degradation [J]. Chinese Journal of Applied Chemistry, 1998, 0(3): 91-93.
[14]	Zhang Huixuan, Yang Haidong, Dai Ying, Feng Zhiliu. Impact Modification of PVC with PBA/PMMA Core/Shell Composite Particles [J]. Chinese Journal of Applied Chemistry, 1997, 0(3): 16-18.
[15]	Zhuo Renxi, Yin Chao, Wu Yinnan, Zhu Lei, Zhen Shuiqing. Synthesis and Degradation Behavior of Poly(DL-Lactide)for Ophthalmic Application [J]. Chinese Journal of Applied Chemistry, 1997, 0(2): 102-104.

Modification of Polylactic Acid by Reactive Blending with Functionalized Imidazolium-based Ionomers and Epoxy-containing Additives

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