羧甲基半纤维素/壳聚糖/氧化石墨烯复合膜的制备及性能研究

doi:10.3969/j.issn.0253-2417.2019.06.002

林产化学与工业 ›› 2019, Vol. 39 ›› Issue (6): 13-20.doi: 10.3969/j.issn.0253-2417.2019.06.002

羧甲基半纤维素/壳聚糖/氧化石墨烯复合膜的制备及性能研究

关莹^1,²(),饶俊¹,吴玉乐¹,杨冉¹,高慧^1,*()

1. 安徽农业大学林学与园林学院, 安徽合肥 230036
2. 安徽农业大学生物质分子工程中心, 安徽合肥 230036

收稿日期:2019-07-09 出版日期:2019-12-28 发布日期:2019-12-21
通讯作者: 高慧 E-mail:xiaomi1231@163.com;huigaozh@163.com
作者简介:关莹(1985-),女,安徽蚌埠人,讲师,博士生,主要从事生物质多糖基功能材料的研究工作; E-mail:xiaomi1231@163.com
基金资助:
安徽省高等学校自然科学研究项目(KJ2018A0152);生物质分子工程中心开放课题基金资助项目(无编号);安徽省自然科学基金资助项目(1808085MC68)

Preparation and Characterization of Carboxymethyl Hemicelluloses/Chitosan/Graphene Oxide Composite Film

Ying GUAN^1,²(),Jun RAO¹,Yule WU¹,Ran YANG¹,Hui GAO^1,*()

1. School of Forestry and Landscape, Anhui Agricultural University, Hefei 230036, China
2. Biomass Molecular Engineering Center, Anhui Agricultural University, Heifei 230036, China

Received:2019-07-09 Online:2019-12-28 Published:2019-12-21
Contact: Hui GAO E-mail:xiaomi1231@163.com;huigaozh@163.com
Supported by:
安徽省高等学校自然科学研究项目(KJ2018A0152);生物质分子工程中心开放课题基金资助项目(无编号);安徽省自然科学基金资助项目(1808085MC68)

摘要/Abstract

摘要：

以毛竹半纤维素为原料，对其进行羧甲基化改性制备羧甲基半纤维素（CMH）；再将CMH与壳聚糖（CS）、氧化石墨烯（GO）共混制备具有良好力学及阻氧性能的半纤维素/壳聚糖/氧化石墨烯复合膜；采用FT-IR、XRD、SEM、TGA、力学强度和阻氧测试对复合膜材料进行分析，并探讨了不同GO添加量对复合膜结构及性能的影响。结果表明：CMH、CS、GO之间主要通过离子键和氢键作用，GO在CMH/CS基质中分散均匀，使得膜表面平整致密，断面具有层状结构。GO在整个复合体系中起增强作用，GO的添加使复合膜的力学性能和热稳定性明显提高，同时还改善了复合膜的氧气阻隔能力。当GO添加量为0.5%时，复合膜力学性能最佳，拉伸应力为73.63 MPa、应变为20.24%、杨氏模量为2.28 GPa，断裂能为1 293.24 N/m；同时，其阻氧性能也最佳，气体透过系数为3.793 cm³·cm/（m²·s·Pa）；此时膜材料的初始分解温度为242.4℃，最大热失重速率温度为274.5℃。

关键词: 羧甲基半纤维素, 壳聚糖, 氧化石墨烯, 复合膜

Abstract:

Carboxymethyl hemicellulose was modified by the carboxymethylation reaction which extracted from bamboo. The hemicellulose/chitosan/graphene oxide composite films were prepared from the obtained carboxymethyl hemicelluloses, chitosan and grapheme oxide, which possessed excellent mechanical and oxygen barrier properties. The properties of the composite films were analyzed by FT-IR, XRD, SEM, TGA, mechanical strength and oxygen barrier tests. The different contents of graphene oxide were detected to analyze the effects of structure and properties of the composite films. The matrix of CMH, CS, GO were combined mainly through ion bond and hydrogen bond, and the GO was dispersed uniformly in CMH/CS matrix. Therefore, the surface of the film was smooth and dense with regular layered structure. The mechanical properties and thermal stability of the composite films were obviously improved by the addition of GO, which was due to the enhancement of GO in the whole composite system. The oxygen barrier ability of the composite film was also increased. The best mechanical properties of composite membranes were as follows:the tensile stress was 73.63 MPa, the tensile strain was 20.24%, and Young's modulus was 2.28 GPa when the content of graphene oxide was 0.5%. Meanwhile, it performed the best oxygen barrier property when the content of graphene oxide was 0.5%, and the gas permeation coefficient of the film was reached to 3.793 cm³·cm/(m²·s·Pa). The initial decomposition and maximum loss ratio temperature of the FG_0.5 were 242.4 and 274.5℃, respectively.

Key words: carboxymethyl hemicelluloses, chitosan, graphene oxide, composite film

中图分类号:

TQ35

关莹,饶俊,吴玉乐,杨冉,高慧. 羧甲基半纤维素/壳聚糖/氧化石墨烯复合膜的制备及性能研究[J]. 林产化学与工业, 2019, 39(6): 13-20.

Ying GUAN,Jun RAO,Yule WU,Ran YANG,Hui GAO. Preparation and Characterization of Carboxymethyl Hemicelluloses/Chitosan/Graphene Oxide Composite Film[J]. Chemistry and Industry of Forest Products, 2019, 39(6): 13-20.

图/表 10

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参考文献 26

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样品 samples	拉伸应力/MPa tensile stress	拉伸应变/% tensile strain	杨氏模量/GPa Young's modulus	断裂能/(N·m^-1) breaking energy
FG₀	47.21±3.52	3.62±1.21	1.30±0.29	141.34
FG_0.25	67.53±2.23	10.13±1.65	1.92±0.14	627.02
FG_0.5	73.63±5.06	20.24±3.22	2.28±0.16	1293.24
FG_0.75	69.60±1.06	15.55±2.11	2.25±0.05	945.05
FG₁	55.23±2.83	13.98±1.46	1.71±0.19	671.17

样品 samples	初始分解温度(T₀)/℃ initial decomposition temp.	最大热失重速率温度/℃ maximum loss ratio temp.		最大热失重速率/(%· ℃^-1) the maximum loss ratio	残渣率/% residuals
样品 samples	初始分解温度(T₀)/℃ initial decomposition temp.	T₁	T₂	最大热失重速率/(%· ℃^-1) the maximum loss ratio	残渣率/% residuals
CMH	261.8	290.2	—	-10.18	24.47
CS	276.5	295.4	—	-10.44	34.91
GO	194.6	210.9	565.7	-6.95	37.86
FG₀	233.0	256.6	—	-5.69	33.23
FG_0.25	244.0	269.2	—	-7.07	34.12
FG_0.5	242.4	274.5	—	-6.72	34.96
FG_0.75	239.3	262.6	—	-6.71	35.64
FG₁	241.5	264.9	—	-7.08	35.77

样品 sample	气体透过率/ (cm³·m^-2·d^-1·Pa^-1) gas permeation rate	气体透过系数/ (cm³·cm·m^-2·s^-1·Pa^-1) gas permeation coefficient	厚度/mm thickness
FG₀	2514466	22931.930	0.0912
FG_0.25	492	6.002	0.1220
FG_0.5	430	3.793	0.0882
FG_0.75	571	4.619	0.0809
FG₁	752	9.490	0.1262

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羧甲基半纤维素/壳聚糖/氧化石墨烯复合膜的制备及性能研究

Preparation and Characterization of Carboxymethyl Hemicelluloses/Chitosan/Graphene Oxide Composite Film

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