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1.天津工业大学材料科学与工程学院
2.省部共建分离膜与膜过程国家重点实验室 天津 300387
Published:2019-1,
Published Online:9 November 2018,
Received:23 July 2018,
Revised:27 September 2018,
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Jun Song, Jun-nan Li, Yuan-fu Hou, Bo-wen Cheng, Lei Hao, Xue-xue Guo. Preparation and Properties of Antibacterial Cellulose Sorbate Films. [J]. Acta Polymerica Sinica 50(1):62-70(2019)
Jun Song, Jun-nan Li, Yuan-fu Hou, Bo-wen Cheng, Lei Hao, Xue-xue Guo. Preparation and Properties of Antibacterial Cellulose Sorbate Films. [J]. Acta Polymerica Sinica 50(1):62-70(2019) DOI: 10.11777/j.issn1000-3304.2018.18168.
以木浆纤维素为原材料、山梨酸为抗菌剂、二环己基碳二亚胺为脱水缩合剂,通过一步原位反应和相转化成膜技术制得抗菌纤维素山梨酸酯膜. 采用傅里叶红外光谱(FTIR)、X-射线光电子能谱(XPS)、固体核磁分析(NMR)、X-射线衍射光谱(XRD)、热重分析(TG-DTG)、示差扫描量热分析(DSC)等对其结构和性能进行表征. FTIR和XPS的测试结果表明通过酯化反应成功制得纤维素山梨酸酯膜. 但是酯化反应过程会导致纤维素的晶胞类型和晶体结构发生改变. TG和DSC的研究结果显示,山梨酰基的引入一定程度上降低或破坏了纤维素分子内及分子间的氢键作用,使得改性后的纤维素山梨酸酯膜的热稳定性略有降低. 动态接触抗菌测试结果表明,纤维素山梨酸酯对大肠杆菌和金黄色葡萄球菌均具有明显的抑菌作用,对大肠杆菌和金黄色葡萄球菌的抑菌率分别达到90.4% ~ 100%和99.2% ~ 100%,特别地,对金黄色葡萄球菌的抑菌效果优于对大肠杆菌的抑菌效果.
Cellulose has attracted considerable attention due to its unique advantages such as abundant availability
renewability
non-pollution
and biocompatibility. However
β
-glucose units in cellulose backbone are vulnerable to erosion and degradation by aquatic microorganisms. The antibacterial modification of cellulose was proposed by covalently introducing sorbic acid through esterification process. Antibacterial cellulose sorbate films were prepared by one-step
in situ
reaction and immersion precipitation phase inversion process with wood-pulp cellulose as raw material
sorbic acid as antibacterial agent
and
N
N'
-dicyclohexylcarbodiimide (DCC) as dehydrating agent to improve its antibacterial performance. Among them
the molar ratio of hydroxyl in cellulose to sorbic acid was 1:2
the reaction temperature was 80 °C and the reaction time was 4
6
8
10 and 12 h
respectively. The casting solutions were casted with casting knife of 250 μm thickness. And then antibacterial cellulose sorbate films were obtained after solvents evaporation and immersion precipitation process. The structure and performances of the obtained cellulose sorbate films were characterized by various methods such as Fourier transform infrared spectroscopy (FTIR)
X-ray photoelectron spectroscopy (XPS)
X-ray diffraction (XRD)
thermogravimetric analysis (TG-DTG) and differential scanning calorimetry analysis (DSC). The new characteristic peak of ester group (1715 cm
−1
) in FTIR spectra indicated that cellulose sorbate films were successfully prepared by esterification reaction. XPS and
13
C-NMR analysis results also showed the synthesis of cellulose sorbate. However
the crystal type and structure of cellulose had changed during esterification process. The results of TG and DSC showed that the effect of intra- and inter-molecular hydrogen bonds in cellulose were reduced or destroyed by the introduction of sorbic-acyl
leading to slightly lower thermal stability of the cellulose sorbate films. The dynamic contact antibacterial test results indicated that cellulose sorbate films had inhibitory effect on
E. coli
and
S. aureus
and possessed higher inhibition rate against
S. aureus
(99.2% − 100%) than that of
E. coli
(90.4% − 100%) due to different cell wall structures of
E. coli
and
S. aureus
. Therefore
the synthesized cellulose sorbate may have some potential applications in packing
environmental coatings
as well as some functional materials.
纤维素山梨酸二环己基碳二亚胺抗菌相转化
CelluloseSorbic acidNN'-dicyclohexyl car bodiimideAntibacterialImmersion precipitation phase inversion
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