交联壳聚糖/聚乙烯醇/蜗牛黏液复合膜的制备及性能研究

doi:10.19491/j.issn.1001-9278.2022.05.010

中国塑料 ›› 2022, Vol. 36 ›› Issue (5): 53-61.DOI: 10.19491/j.issn.1001-9278.2022.05.010

交联壳聚糖/聚乙烯醇/蜗牛黏液复合膜的制备及性能研究

李福杰¹, 齐斌¹^,², 徐华亭², 王立梅¹^,²()

^1.苏州大学药学院，江苏苏州 215127
^2.常熟理工学院生物与食品工程学院苏州市食品生物技术重点实验室，江苏苏州 215500

收稿日期:2022-01-06 出版日期:2022-05-26 发布日期:2022-05-26
通讯作者: 王立梅（1964—），女，教授，从事食品生物技术研究，wlmqb@126.com
E-mail:wlmqb@126.com
基金资助:
江苏省科技厅重点研发计划(BE2020386);苏州市科技计划项目(SS202120)

Preparation and properties of chitosan/polyvinyl alcohol/snail mucus composite films

LI Fujie¹, QI Bin¹^,², XU Huating², WANG Limei¹^,²()

^1.College of Pharmacy，Soochow University，Suzhou 215127，China
^2.Suzhou Key Laboratory of Food Biotechnology，School of Biological and Food Engineering，Changshu Institute of Technology，Suzhou 215500，China

Received:2022-01-06 Online:2022-05-26 Published:2022-05-26
Contact: WANG Limei E-mail:wlmqb@126.com

摘要/Abstract

摘要：

采用延流法制备了香兰素（V）交联的壳聚糖/聚乙烯醇/蜗牛黏液（CS/PVA/SM）复合膜，并通过热重分析仪（TG）、扫描电子显微镜（SEM）和万能材料试验机等研究了不同CS/SM配比对复合膜光学性能、水蒸气和氧气阻隔能力、力学性能、热力学性能及生物降解性能等的影响。结果表明，CS/PVA/SM复合膜为可降解的亲水性薄膜，当CS溶液/SM溶液体积比为5/3时，复合膜性能优良，其抗氧化活性为87.51 %，其水蒸气透过率比纯CS膜降低了75.16 %，不透明度降低了87.74 %，拉伸强度提高了16.04 %，断裂伸长率提高了28.26倍；随着SM含量的增加，复合膜的热稳定性有所降低；CS溶液/SM溶液体积比为5/1、5/2和5/3时，复合膜表现出良好的相容性；SM的添加使复合膜具有很好的延展性和柔韧性，V的添加提高了复合膜的拉伸强度和抗氧化能力；所制备的CS/PVA/SM复合膜在食品包装领域中有潜在的应用前景。

关键词: 壳聚糖, 聚乙烯醇, 蜗牛黏液, 香兰素, 食品包装

Abstract:

Chitosan （CS）/poly（vinyl alcohol）（PVA）/snail mucus （SM） composite films were prepared through crosslin?king with vanillin using a casting method. The effect of CS/SM mass ratio on the optical properties， water vapor permeability， water vapor， oxygen barrier capability， and mechanical and biodegradable properties of the composite films were investigated using a thermogravimetric analyzer， a scanning electron microscope， and a universal material testing machine. The results indicated that the composite films were biodegradable and hydrophilic， and their properties were optimal when the volume ratio of CS solution to SM solution was set to 5/3， presenting an antioxidant activity of 87.51%. Comparing to pure CS film， the composite films showed a decrease not only in water vapor transmission rate by 75.16 % but also in opacity by 87.74 %. However， they showed an increase in tensile strength by16.03 % and in elongation at break by a factor of 28.26. The thermal stability of the composite films decreased with an increase in the proportion of SM. In addition， the composite films exhibited good compatibility at CS/SM volume ratios of 5/1， 5/2， and 5/3. The addition of SM endowed the composite films with good ductility and flexibility， whereas the addition of vanillin improved their tensile strength and antioxidant activity. The CS/PVA/SM composite films exhibit potential prospects in the application for food packaging.

Key words: chitosan, poly（vinyl alcohol）, snail mucus, vanillin, food packaging

中图分类号:

TQ325.9

李福杰, 齐斌, 徐华亭, 王立梅. 交联壳聚糖/聚乙烯醇/蜗牛黏液复合膜的制备及性能研究[J]. 中国塑料, 2022, 36(5): 53-61.

LI Fujie, QI Bin, XU Huating, WANG Limei. Preparation and properties of chitosan/polyvinyl alcohol/snail mucus composite films[J]. China Plastics, 2022, 36(5): 53-61.

图/表 12

参考文献 32

1	EL⁃MEKAWY R E， ELHADY H A， AL⁃SHAREEF H F， et al. Highly stretchable， smooth， and biodegradable hydrogel films based on chitosan as safety food packaging［J］. Polymers and Polymer Composites， 2021， 29 （6）： 563⁃573.
2	KHALID M N， AGNELY F， YAGOUBI N， et al. Water state characterization， swelling behavior， thermal and mechanical properties of chitosan based networks［J］. European Journal of Pharmaceutical Sciences， 2002， 15（5）：425⁃432.
3	EDIYILYAM S， GEORGE B， SHANKAR S S， et al. Chitosan/gelatin/silver nanoparticles composites films for biodegradable food packaging applications［J］. Polymers， 2021， 13（11）：1680.
4	ZHANG Z D， LIU Y， LIN S D， et al. Preparation and properties of glutaraldehyde crosslinked poly（vinyl alcohol） membrane with gradient structure［J］. Journal of Polymer Research， 2020， 27：228.
5	AMMARA R， KHALID M Z， MOHAMMAD Z， et al. Chitosan functionalized poly（vinyl alcohol） for prospects biomedical and industrial applications： a review［J］. International Journal of Biological Macromolecules， 2016， 87：141⁃154.
6	BAHRAMI S B， KORDESTANI S S， MIRZADEH H， et al. Poly （vinyl alcohol）⁃chitosan blends： preparation， mechanical and physical properties［J］. Iranian Polymer Journal， 2003， 12（2）：139⁃146.
7	BEPPU M M， VIEIRA R S， AIMOLI C G， et al. Crosslinking of chitosan membranes using glutaraldehyde： effect on ion permeability and water absorption［J］. Journal of Membrane Science， 2007， 301（1/2）：126⁃130.
8	KOWALCZYK D， KORDOWSKA⁃WIATER M， NOWAK J， et al. Characterization of films based on chitosan lactate and its blends with oxidized starch and gelatin［J］. International Journal of Biological Macromolecules， 2015， 77：350⁃359.
9	ZHANG Z H， HAN Z， ZENG X A， et al. Enhancing mechanical properties of chitosan films via modification with vanillin［J］. International Journal of Biological Macromolecules， 2015， 81：638⁃643.
10	SOUZA V G L， FERNANDO A L， PIRES J R A， et al. Physical properties of chitosan films incorporated with natural antioxidants［J］. Industrial Crops & Products， 2017， 107：565⁃572.
11	DOMINGUEZ⁃MARTINEZ B M， MARTÍNEZ⁃FLORES H E， BERRIOS J D J， et al. Physical characterization of biodegradable films based on chitosan， polyvinyl alcohol and opuntia mucilage［J］. Journal of Polymers and the Environment， 2017， 25（3）：683⁃691.
12	DI FILIPPO M F， PANZAVOLTA S， ALBERTINI B， et al. Functional properties of chitosan films modified by snail mucus extract［J］. International Journal of Biological Macromolecules， 2019， 143：126⁃135.
13	CLAUDIO T， ROBERTA R， STEFANIA G， et al. Helix complex snail mucus exhibits pro⁃survival， proliferative and pro⁃migration effects on mammalian fibroblasts［J］. Scientific Reports，2018，8（1）：1834.
14	ABDULLAH K， TALIP K. Characterization of a new biodegradable edible film made from salep glucomannan［J］. Carbohydrate Polymers， 2014， 104：50⁃58.
15	UBONRAT S， BRUCE R H. Physical properties and antioxidant activity of an active film from chitosan incorpora⁃ted with green tea extract［J］. Food Hydrocolloids， 2010， 24（8）：770⁃775.
16	VERNON L S， RUDOLF O， LAMUELA⁃RAVENTÓS R M. Analysis of total phenols and other oxidation substrates and antioxidants by means of folin⁃ciocalteu reagent［J］. Methods in Enzymology， 1999， 299：152⁃178.
17	CONSIDINE G D. American Society for Testing and Materials （ASTM）［M］. New York： American Cancer Socie⁃ty， 2005：142⁃147.
18	FIRESTONE D， SOCIETY A. Official methods and recommended practices of the AOCS［J/OL］. AOCS， 2009. .
19	KUMAR D P， MAHADEVAN R， SIVARAMAN G K， et al. Biomodulation of poly（vinyl alcohol）/starch polymers into composite⁃based hybridised films： physico⁃chemical， structural and biocompatibility characterization［J］. Journal of Polymer Research， 2021， 28（7）：1⁃12.
20	US Department of Defense. Standard test method for tensile properties of thin plastic sheeting：［S］. West Conshohoken： ASTM International， 2012.
21	MENG W， SHI J， ZHANG X， et al. Effects of peanut shell and skin extracts on the antioxidant ability， physical and structure properties of starch⁃chitosan active packaging films［J］. International Journal of Biological Macromolecules， 2020， 152：137⁃146.
22	SOPHIE G， WALTRAUD K， NORBERT C， et al. Snail mucus⁃glandular origin and composition in helix pomatia［J］. Zoology， 2017， 122：126⁃138.
23	刘敏. 蜗牛粘液/丝素蛋白复合材料的制备与性能研究［D］.苏州：苏州大学，2018.
24	ZHANG Z H， HAN Z， LIU Y J， et al. Enhancing mechanical properties of chitosan films via modification with vanillin［J］. International Journal of Biological Macromolecules， 2015， 81：638⁃643.
25	WU Y， YE 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： 2 131⁃2 137.
26	ABDELGHANY A M， MENAZEA A A， ISMAIL A M. Synthesis characterization and antimicrobial activity of chitosan/polyvinyl alcohol blend doped with hibiscus sabdariffa L. extract［J］. Journal of Molecular Structure，2019，1 197： 603⁃609.
27	LIU Y W， WANG S Y， LAN W T. Fabrication of antibacterial chitosan⁃PVA blended film using electrospray technique for food packaging applications［J］. Internatio⁃nal Journal of Biological Macromolecules， 2017：848⁃854.
28	FU F N， SINGH B R， DEOLIVEIRA D B， et al. Secondary structure estimation of proteins using the amide III region of fourier transform infrared spectroscopy： application to analyze calcium⁃binding⁃induced structural changes in calsequestrin［J］. Applied Spectroscopy， 1994， 48（11）：1 432⁃1 441.
29	XIE M X， LIU Y. Studies on amide Ⅳ infrared bands for the secondary structure determination of proteins［J］. Chemi⁃cal Research in Chinese Universities， 2003，2：226⁃231.
30	WANG X， YONG H， GAO L， et al. Preparation and characterization of antioxidant and pH⁃sensitive films based on chitosan and black soybean seed coat extract［J］. Food Hydrocolloids， 2019， 89：56⁃66.
31	ZHEN Y， LI B， CHU J， et al. Silica in situ enhanced PVA/chitosan biodegradable films for food packages［J］. Carbohydrate Polymers， 2018， 184：214.
32	DI FILIPPO M F， SILVIA P， BEATRICE A， et al. Functional properties of chitosan films modified by snail mucus extract［J］. International Journal of Biological Macromolecules， 2020， 143：126⁃135.

样品	厚度/mm	W_C/%	S_D/%	W_S/%
CS	0.210±0.015^a	7.48±0.30ⁱ	1680.50±36.28^a	18.77±0.74^e
CS/PVA	0.196±0.011^a	10.75±0.18^g	710.61±24.42^b	25.65±1.16^c
CPV	0.180±0.003^b	8.95±0.34^h	38.32±0.56^f	20.58±0.95^d
CSP	0.119±0.022^c，d	58.10±0.98^a	106.02±0.85^c	29.68±1.74^a
CSPV1	0.174±0.016^b	16.46±0.16^f	42.13±0.27^f	25.20±0.66^c
CSPV2	0.167±0.018^b	36.91±0.46^e	53.48±0.94^e，f	26.82±0.72^b，c
CSPV3	0.136±0.031^c	42.09±0.67^d	63.02±0.59^e，f	27.64±0.47^b，c
CSPV4	0.126±0.021^c，d	49.03±0.38^c	74.65±0.58^d，e	28.30±1.34^a，b
CSPV5	0.110±0.008^d	56.48±0.58^b	91.06±1.14^c，d	29.76±1.00^a

样品	厚度/mm	W_C/%	S_D/%	W_S/%
CS	0.210±0.015^a	7.48±0.30ⁱ	1680.50±36.28^a	18.77±0.74^e
CS/PVA	0.196±0.011^a	10.75±0.18^g	710.61±24.42^b	25.65±1.16^c
CPV	0.180±0.003^b	8.95±0.34^h	38.32±0.56^f	20.58±0.95^d
CSP	0.119±0.022^c，d	58.10±0.98^a	106.02±0.85^c	29.68±1.74^a
CSPV1	0.174±0.016^b	16.46±0.16^f	42.13±0.27^f	25.20±0.66^c
CSPV2	0.167±0.018^b	36.91±0.46^e	53.48±0.94^e，f	26.82±0.72^b，c
CSPV3	0.136±0.031^c	42.09±0.67^d	63.02±0.59^e，f	27.64±0.47^b，c
CSPV4	0.126±0.021^c，d	49.03±0.38^c	74.65±0.58^d，e	28.30±1.34^a，b
CSPV5	0.110±0.008^d	56.48±0.58^b	91.06±1.14^c，d	29.76±1.00^a

样品	拉伸强度/MPa	断裂伸长率/%
CS	24.57±1.65^f	2.25±0.59ⁱ
CS/PVA	28.29±1.82^d	24.43±2.18^g
CPV	36.44±2.22^a	15.37±1.79^h
CSP	15.53±1.09^g	85.67±2.16^a
CSPV1	34.41±1.26^b	82.40±2.67^b
CSPV2	30.14±1.42^c	78.00±1.44^c
CSPV3	28.51±1.28^c，d	65.84±2.19^d
CSPV4	26.56±1.13^e	53.27±1.18^e
CSPV5	25.19±1.05^e，f	34.13±1.95^f

样品	拉伸强度/MPa	断裂伸长率/%
CS	24.57±1.65^f	2.25±0.59ⁱ
CS/PVA	28.29±1.82^d	24.43±2.18^g
CPV	36.44±2.22^a	15.37±1.79^h
CSP	15.53±1.09^g	85.67±2.16^a
CSPV1	34.41±1.26^b	82.40±2.67^b
CSPV2	30.14±1.42^c	78.00±1.44^c
CSPV3	28.51±1.28^c，d	65.84±2.19^d
CSPV4	26.56±1.13^e	53.27±1.18^e
CSPV5	25.19±1.05^e，f	34.13±1.95^f

[1]	杨笑春, 于静, 张青. 壳聚糖对PVC热稳定性能影响研究[J]. 中国塑料, 2022, 36(7): 68-73.
[2]	周舒毅, 朱敏, 刘忆颖, 曹舒惠, 蔡启轩, 聂慧, 张玉霞, 周洪福. 高分子止血材料研究进展[J]. 中国塑料, 2022, 36(7): 74-84.
[3]	刘伟, 吴显, 陈小澄, 成晓琼, 张纯. 羧基化填料对聚乙烯醇/纳米纤维素水凝胶力学、导电和传感性能的影响[J]. 中国塑料, 2022, 36(6): 16-23.
[4]	隋振全, 毛金超, 范金石. 壳聚糖/聚乙烯醇液态地膜的制备与应用[J]. 中国塑料, 2022, 36(3): 21-25.
[5]	谢玉, 王立梅, 齐斌. 交联壳聚糖/蒙脱土复合膜的制备及性能研究[J]. 中国塑料, 2022, 36(3): 58-63.
[6]	张婷, 张彩丽, 宋鑫宇, 翁云宣. PBAT薄膜的制备及应用研究进展[J]. 中国塑料, 2021, 35(7): 115-125.
[7]	沙金, 陈欣, 陈冬平, 马玉录, 谢林生. 基于EHD的PVA薄膜图案化及其在玻璃表面微结构制造中的应用[J]. 中国塑料, 2021, 35(6): 53-59.
[8]	郭金强, 王富玉, 张玉霞. 高阻隔高分子材料研究进展[J]. 中国塑料, 2021, 35(5): 146-155.
[9]	马超群, 师文钊, 崔杉杉, 张曼妍, 周红娟. 聚乙烯醇基多孔复合材料研究进展[J]. 中国塑料, 2021, 35(4): 116-123.
[10]	吴首昂, 涂征, 刘北军, 龚兴厚. PAAS/PVA/Zn_0.2Fe_2.8O₄磁性复合水凝胶的合成及其性能研究[J]. 中国塑料, 2021, 35(4): 12-17.
[11]	程龙, 郝艳玲, 宋小双. 壳聚糖对玉米淀粉可食膜性能的影响[J]. 中国塑料, 2021, 35(4): 35-41.
[12]	徐萌, 高达利, 张师军. 食品包装高分子材料技术进步与升级[J]. 中国塑料, 2021, 35(3): 74-82.
[13]	银鹏, 马宏鹏, 郭斌, 李盘欣. 聚乳酸纤维/聚乙烯醇纤维协同增强热塑性淀粉复合材料[J]. 中国塑料, 2021, 35(12): 16-20.
[14]	宗琳, 陈晨伟, 陈智杰, 谢晶. 淀粉/聚乙烯醇活性包装薄膜及其在食品包装应用中的研究进展[J]. 中国塑料, 2020, 34(8): 101-112.
[15]	陈秀玲, 高山俊, 沈春晖, 齐宏生, 刘洒文. 改性魔芋葡甘聚糖纳米晶对聚乙烯醇薄膜性能的影响[J]. 中国塑料, 2020, 34(5): 38-44.

交联壳聚糖/聚乙烯醇/蜗牛黏液复合膜的制备及性能研究

Preparation and properties of chitosan/polyvinyl alcohol/snail mucus composite films

RichHTML

PDF

可视化

摘要/Abstract

引用本文

使用本文

图/表 12

参考文献 32

相关文章 15

编辑推荐

Metrics

本文评价