Preparation and properties of crosslinked chitosan/montmorillonite composite films

doi:10.19491/j.issn.1001-9278.2022.03.010

Abstract

Abstract:

Crosslinked chitosan （CS）/montmorillonite （MMT） composite films were prepared through a solution intercalation method using CS as a matrix， MMT as a filler， and glutaraldehyde （GA） as a crosslinking agent. Their structure and properties were characterized using infrared spectroscopy， scanning electron microscopy， X?ray diffraction， and thermogravimetric analysis. The effect of MMT content on the water uptake， water vapor barrier and mechanical properties of the composite films were investigated. The results indicated that the composite films exhibited an improvement in water resistance， and their water uptake ratio decreased by 9.6 % compared to that of pure CS film. The introduction of MMT improved the water resistance， water vapor barrier property， mechanical performance， and thermal stability of the composite films. The composite films exhibited better comprehensive properties at a MMT content of 5 wt% in the CS domain. Compared to pure CS film， the composite films presented a decrease in water uptake ratio， water vapor transmission rate， and elongation at break by 37.3 %， 36.7 %， and 41.9 %， respectively. Their tensile strength increased by 160.5 %. The composite films exhibit potential applications as a food packaging material.

Key words: crosslinked chitosan, montmorillonite, composite film, water resistance, thermal stability

CLC Number:

TQ325.

XIE Yu, WANG Limei, QI Bin. Preparation and properties of crosslinked chitosan/montmorillonite composite films[J]. China Plastics, 2022, 36(3): 58-63.

Figures/Tables 8

Fig.1. SEM of CS and its composite films（×5 000）

Fig.2. XRD patterns of MMT，CS and its composite films

Fig.3. FTIR spectra of MMT，CS and its composite films

Fig.4. TG curves of CS and its composite films

样品编号	T_{5 %}/℃	T_{30 %}/℃	T_{50 %}/℃
CS	56.9	181.7	282.5
CS/GA	54.9	179.8	279.4
CS/GA/MMT1	85.8	235.0	295.9
CS/GA/MMT3	97.1	265.1	307.4
CS/GA/MMT5	97.5	278.7	351.2

Tab.1. TGA data of CS and its composite films

Fig.5. Water absorption ration of CS and its composite films

Fig.6. Water vapor transmission rate of CS and its composite films

Fig.7. Mechanical properties of CS and its composite films

References 25

1	LIU Y， SONG R， ZHANG X， et al. Enhanced antimicrobial activity and pH⁃responsive sustained release of chitosan/poly （vinyl alcohol）/graphene oxide nanofibrous membrane loading with allicin［J］. International Journal of Biological Macromolecules， 2020，161：1 405⁃1 413.
2	MOHEBALI A， ABDOUSS M. Layered biocompatible pH⁃responsive antibacterial composite film based on HNT/PLGA/chitosan for controlled release of minocycline as burn wound dressing［J］. International Journal of Biological Macromolecules， 2020，164：4 193⁃4 204.
3	SAMEH S A， EL⁃REFAIE K， FATMA I S， et al. Pharmaceutical potential of a novel chitosan derivative schiff base with special reference to antibacterial， anti⁃biofilm， antioxidant， anti⁃inflammatory， hemocompatibility and cytotoxic activities［J］. Pharmaceutical Research， 2019，36（1）：1⁃18.
4	CHAN L W， KIM C H， WANG X， et al. PolySTAT⁃modified chitosan gauzes for improved hemostasis in external hemorrhage［J］. Acta Biomater， 2016，31：178⁃185.
5	EHSAN S， PARISA D， AHMAD A S. A review on chitosan⁃based adsorptive membranes［J］. Carbohydrate Polymers， 2016， 152：419⁃432.
6	Dongying H， Lijuan W. Fabrication of antibacterial blend film from poly （vinyl alcohol） and quaternized chitosan for packa⁃ging［J］. Materials Research Bulletin， 2016，（78）：46⁃52.
7	WU Y， YING Y， LIU Y， et al. Preparation of chitosan/poly vinyl alcohol films and their inhibition of biofilm formation against Pseudomonas aeruginosa PAO1.［J］. International journal of biological macromolecules， 2018， 118：S0141813018328411.
8	ROCÍO Y A， ADRIANA I R， EDUARDO M， et al. Effect of equilibrium moisture content on barrier， mechanical and thermal properties of chitosan films［J］. Food Chemistry， 2016， 196：560⁃566.
9	MARIANA P， GUILLERMINA A， NORMA E M. Development and characterization of edible chitosan/olive oil emulsion films［J］. Carbohydrate Polymers， 2012， 87（2）：1 318⁃1 325.
10	PAVONI J M F， ZDOS SANTOS N， MAY I C， et al. Impact of acid type and glutaraldehyde crosslinking in the physicochemical and mechanical properties and biodegradability of chitosan films［J］. Polymer Bulletin， 2021，78（2）：981⁃1 000.
11	FRICK J M， AMBROSI A， POLLO L D， et al. Influence of Glutaraldehyde Crosslinking and Alkaline Post⁃treatment on the Properties of Chitosan⁃Based Films［J］. Journal of Polymers and the Environment， 2018，26（7）：2 748⁃2 757.
12	汪希铭，程凤，高晶，等. 交联改性对敷料用壳聚糖/聚氧化乙烯纳米纤维膜性能的影响［J］. 纺织学报， 2020，41（12）：31⁃36.
	WANG X M， CHENG F， GAO J， et al. Effect of cross⁃linking modification on properties of chitosan/polyoxyethylene nanofiber membranes towards wound care［J］. Journal of Textile Research， 2020，41（12）：31⁃36.
13	LIM J W， LIM W S， LEE M H， et al. Barrier and structural properties of polyethylene terephthalate film coated with poly（acrylic acid）/montmorillonite nanocomposites［J］. Packaging Technology and Science， 2021，34（3）：141⁃150.
14	AMBROGI V， PIETRELLA D， NOCCHETTI M， et al. Montmorillonite⁃chitosan⁃chlorhexidine composite films with antibiofilm activity and improved cytotoxicity for wound dressing［J］. J Colloid Interface Sci， 2017，491：265⁃272.
15	ANA B， ESPERANZA C， CAROLA A， et al. Biopharmaceutical improvement of praziquantel by interaction with montmorillonite and sepiolite［J］. Applied Clay Science， 2018， 160（Aug.）：173⁃179.
16	JUNJIE C， LONGFEI Y， WENYA S， et al. Interfacial characteristics of carbon nanotube⁃polymer composites： a review［J］. Composites Part A， 2018， 114：149⁃169.
17	JIANG Y， YIN H， ZHOU X， et al. Antimicrobial， antioxidant and physical properties of chitosan film containing Akebia trifoliata （Thunb.） Koidz. peel extract/montmorillonite and its application［J］. Food Chem， 2021，361：130111.
18	MIN Z， QIN L， SHUAISHUAI W， et al. Starch/chitosan films reinforced with polydopamine modified MMT： Effects of dopamine concentration［J］. Food Hydrocolloids， 2016， 61：678⁃684.
19	YING Y， WU Y， HUANG J. Preparation and characte⁃rization of chitosan/poly（vinyl alcohol）/graphene oxide films and studies on their antibiofilm formation activity［J］. Journal of Biomedical Materials Research Part A， 2020，108（10）：2 015⁃2 022.
20	TIAN H， WANG K， LIU D， et al. Enhanced mechanical and thermal properties of poly （vinyl alcohol）/corn starch blends by nanoclay intercalation［J］. Int J Biol Macromol， 2017，101：314⁃320.
21	BANO I， ARSHAD M， YASIN T， et al. Chitosan： a potential biopolymer for wound management［J］. Int J Biol Macromol， 2017，102：380⁃383.
22	RASHID A， MUHAMMAD T， IMRAN A， et al. No⁃vel electrospun chitosan/polyvinyl alcohol/zinc oxide nanofibrous mats with antibacterial and antioxidant properties for diabetic wound healing［J］. International Journal of Bio⁃logical Macromolecules， 2018， 120：385⁃393.
23	GIERSZEWSKA M， JAKUBOWSKA E， OLEWNIK⁃KRUSZKOWSKA E. Effect of chemical crosslinking on properties of chitosan⁃montmorillonite composites［J］. Polymer Testing， 2019，77：105872.
24	TOMASZ J， URSZULA F， PAULA S， et al. Effect of ionic and covalent crosslinking agents on properties of chitosan beads and sorption effectiveness of reactive black 5 dye［J］. Reactive and Functional Polymers， 2017，（114）：58⁃74.
25	GIANNAKAS A， GRIGORIADI K， LEONTIOU A， et al. Preparation， characterization， mechanical and barrier properties investigation of chitosan⁃clay nanocomposites［J］. Carbohydrate Polymers， 2014，108：103⁃111.

[1]	TAN Liqin, LIU Weiqu, LIANG Liyan, WANG Shuo, FENG Zhiqiang, LIN Jiaming. Preparation and performance of epoxy resin modified with mercaptan polysiloxane [J]. China Plastics, 2022, 36(7): 21-29.
[2]	ZHANG Shucheng, TANG Wenbin, YU Tianjiao, XU Zhenzhen, XING Jian. Preparation and properties of polyurethane foams with different contents of polyether polyol [J]. China Plastics, 2022, 36(3): 104-109.
[3]	LI Yongqing, YANG Xiaolong, CHEN Wenjing, YAN Xiaokun, MA Xiuqing. Molecular dynamics simulation of modifier and high⁃density polyethylene intercalate and exfoliate montmorillonite [J]. China Plastics, 2022, 36(2): 67-74.
[4]	WANG Yazhen, LIU Xinyu, DONG Shaobo, LAN Tianyu, ZU Liwu. Compatibilizing effect on performance of PE⁃HD/corn stalk biochar composites [J]. China Plastics, 2022, 36(1): 128-134.
[5]	SUN Zhengmeng, ZHANG Mingxu, ZHANG Xinning, LIANG Ce, ZHANG Hailiang, LI Yunhui, MA Yuqin. Study on Thermal Stability of Bisphenol⁃A⁃Type Epoxy Matrix Composites Doped with Nano Glass Powders [J]. China Plastics, 2021, 35(9): 15-20.
[6]	WU Chaoting, CHEN Huayan, ZHANG Wenxin, LYU Xiaolong. Study on Thermal Conductivity of Carbon Nanotube Dispersion Strengthened PVDF Composite Film [J]. China Plastics, 2021, 35(7): 25-31.
[7]	LYU Qiang. Preparation of Glass⁃fiber Reinforced Polyamide 6 with Halogen⁃free Flame Retardant and Permanent Antistatic Performance [J]. China Plastics, 2021, 35(7): 58-62.
[8]	HE Yintong, LIANG Jiaqi, LIU Lubin, XU Yue, WANG Kezhu, YU Hang, WANG Shuhui, XU Miaojun. Preparation and Applications of Water⁃resistant Flame⁃retardant Transparent Epoxy Resins [J]. China Plastics, 2021, 35(5): 6-10.
[9]	YE Jinlun, YANG Liting, LI Yantao, ZENG Cong, LI Zhen, HUANG Wenjie, GUAN Jiawei. Effect of Modified Boehmite on Properties of Polypropylene [J]. China Plastics, 2021, 35(3): 16-22.
[10]	GU Lin, ZHU Yuting, HE Jialong, ZHU Huihao, MA Yulu, XIE Linsheng. Preparation and Properties of Poly（lactic acid）/Polycaprolactone Degradable Multilayered Films Based on Micro⁃nano Multiplayer Coextrusion [J]. China Plastics, 2021, 35(11): 7-14.
[11]	ZHU Yuting, GU Lin, HE Jialong, JI Huajian, WANG Yu, ZHU Huihao, MA Yulu, XIE Linsheng. Preparation and Properties of PP/PA6/CNTs In⁃situ Microfiber Composite Films Based on Microlayer Coextrusion [J]. China Plastics, 2021, 35(10): 1-7.
[12]	TIE Rui, WU You, HAN Xiaolong, SONG Jiajie, WANG Yuchen, KAN Chunyi, YUAN Mengju, JIN Yujuan. Modification of PHBV/EVA Blends with OMMT [J]. China Plastics, 2021, 35(10): 60-67.
[13]	Xiwei XIE, Yunxuan WENG, Caili ZHANG, Xinyu SONG. Compatibilization Modification of Bamboo Powders with Aluminic Acid Ester and Its Effect on Properties of PBAT Matrix Composites [J]. China Plastics, 2020, 34(4): 78-83.
[14]	Xiangyu WANG, Yuxia ZHANG. Tuning of Microstructure of PLA/PBAT/OMMT Nanocomposite [J]. China Plastics, 2020, 34(4): 35-41.
[15]	. Study on Enhancement of Heat Resistance for PMMA Resin with α-methylstyrene [J]. China Plastics, 2019, 33(8): 12-17.