纺织学报 ›› 2020, Vol. 41 ›› Issue (09): 8-15.doi: 10.13475/j.fzxb.20191203408

• 纤维材料 • 上一篇    下一篇

聚(3-羟基丁酸-co-3-羟基戊酸共聚酯)复合膜的制备及其性能

唐峰1, 余厚咏2(), 周颖2, 李营战2, 姚菊明1, 王闯1, 金万慧3   

  1. 1.浙江理工大学 材料科学与工程学院, 浙江 杭州 310018
    2.浙江理工大学纺织科学与工程学院(国际丝绸学院), 浙江 杭州 310018
    3.湖北省纤维检验局, 湖北 武汉 430000
  • 收稿日期:2019-12-06 修回日期:2020-06-02 出版日期:2020-09-15 发布日期:2020-09-25
  • 通讯作者: 余厚咏
  • 作者简介:唐峰(1995—),男,硕士。主要研究方向为生物基高分子材料的制备与应用。
  • 基金资助:
    浙江省重点自然科学基金项目(LZ20E030003);中国科协青年人才托举工程项目(2018QNRC001);浙江省科技厅公益项目(2017C37014);浙江理工大学科研启动基金项目(19012099-Y)

Preparation and property of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) composite films

TANG Feng1, YU Houyong2(), ZHOU Ying2, LI Yingzhan2, YAO Juming1, WANG Chuang1, JIN Wanhui3   

  1. 1. School of Materials Science and Engineering, Zhejiang Sci-Tech University, Hangzhou, Zhejiang 310018, China
    2. College of Textiles Science and Engineering (International Institute of Silk), Zhejiang Sci-Tech University, Hangzhou, Zhejiang 310018, China
    3. Hubei Province Fibre Inspection Bureau, Wuhan, Hubei 430000, China
  • Received:2019-12-06 Revised:2020-06-02 Online:2020-09-15 Published:2020-09-25
  • Contact: YU Houyong

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摘要：

为提高聚(3-羟基丁酸-co-3-羟基戊酸共聚酯)(PHBV)膜的抗菌性能,拓展其在食品包装领域的应用,首先利用纤维素纳米纤丝(CNF)表面的不同极性基团,采用原位还原法制备了不同形貌的CNF-Ag杂化材料;然后将其与PHBV复合制得高阻隔性抗菌复合膜材料,并对复合膜材料的微观形貌、结晶性能、热稳定性、化学结构和抗菌性能进行表征与分析。结果表明:引入柠檬酸与抗坏血酸后,CNF-Ag杂化材料表面羧基含量最高可达1.21 mmol/g;CNF-Ag杂化材料和PHBV基体形成了较强的氢键作用,改善了PHBV的结晶性能和抗菌性能,使复合膜的拉伸强度高达66.7 MPa,弹性模量达7.6 GPa,且对金黄色葡萄球菌抗菌率达到99%。

关键词: 复合膜, 纤维素纳米纤丝, 聚(3-羟基丁酸-co-3-羟基戊酸共聚酯), 纳米银, 抗菌性, 高阻隔性

Abstract:

Aiming to improve the antibacterial properties of poly (3-hydroxybutyrate-co-3-hydroxyvalerate copolyester) (PHBV) film, cellulose nanofibril (CNF) with different polar groups was used to produce CNF-Ag hybrid materials with different morphologies via the in situ reduction method, which was incorporated into poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) matrix to get antibacterial high-barrier composite films. The morphology, crystallinity, thermal stability, chemical structure and antibacterial properties of samples were investigated and analyzed. The results show that the surface carboxyl group content of CNF-Ag hybrid can reach up to 1.21 mmol/g by introducing citric acid and ascorbic acid. CNF-Ag not only induces PHBV to generate hydrogen bond network, but also improves the crystallization behavior, with the tensile strength of the composite film being 66.7 MPa, the modulus of elasticity 7.6 GPa, and the antibacterial activity against Staphylococcus aureus 99%.

Key words: composite film, cellulose nanofibril, poly (3-hydroxybutyrate-co-3-hydroxyvalerate), nano silver, antibacterial ability, high barrier property

中图分类号: 

  • TQ352.8

图1

实验流程图"

图2

不同PHBV复合膜截面扫描电镜照片"

图3

不同PHBV复合膜的紫外-可见光谱图"

图4

不同PHBV复合膜的红外光谱图"

图5

PHBV复合膜的X射线衍射图谱"

图6

PHBV复合膜的DSC曲线"

表1

PHBV复合膜的氢键系数及结晶度"

样品名称 羧基含量/
(mmol·g-1)		 氢键系数 结晶度/%
PHBV/CNF-Ag 0.11 0.12±0.03 67.3±3.12
PHBV/CNF (4.5)-Ag 1.03 0.12±0.02 52.6±2.15
PHBV/CNF (7.5)-Ag 1.12 0.13±0.03 52.1±3.43
PHBV/CNFA-Ag 0.13 0.13±0.02 46.6±6.02
PHBV/CNFC-Ag 1.11 0.16±0.03 46.2±3.57
PHBV/CNFAC-Ag 1.21 0.18±0.03 35.4±1.89
PHBV/CNF(7.5)A-Ag 0.91 0.17±0.04 42.6±2.65

图7

PHBV复合膜的TGA和DTG曲线"

表2

PHBV复合膜的力学性能和透湿迁移性能"

样品名称 拉伸强度/MPa 弹性模量/GPa 断裂伸长率/% 迁移量/(μg·kg-1) 吸水率/% 水蒸气透过率/
(10-14 kg·m·m-2·s-1·Pa-1)
异辛烷 乙醇
PHBV 10.2±0.3 0.1±0.3 1.78±0.13 107.0±0.5 83.9±9.8 10.06±0.02 7.63±0.04
PHBV/CNF-Ag 22.2±0.8 2.3±0.2 1.85±0.15 25.5±0.2 38.9±0.2 0.18±0.05 1.57±0.02
PHBV/CNF (4.5)-Ag 42.8±0.5 5.6±0.5 1.74±0.25 18.9±0.3 31.5±0.6 2.01±0.08 5.62±0.05
PHBV/CNF (7.5)-Ag 53.3±0.7 6.8±0.3 1.57±0.38 16.2±0.5 27.4±0.7 2.25±0.01 5.96±0.08
PHBV/CNFA-Ag 55.3±0.05 7.1±0.2 1.49±0.02 34.5±0.2 68.6±0.8 3.18±0.05 7.15±0.07
PHBV/CNFC-Ag 57.6±0.2 7.3±0.3 1.31±0.57 44.2±0.1 86.9±0.4 3.23±0.03 6.83±0.04
PHBV/CNFAC-Ag 66.7±0.6 7.6±0.3 1.29±0.89 35.4±0.6 61.5±0.3 3.91±0.09 8.13±0.06
PHBV/CNF (7.5)A-Ag 36.1±0.8 4.8±0.4 1.48±0.65 38.5±0.7 67.2±0.1 3.57±0.03 5.89±0.04

图8

PHBV复合膜在金黄色葡萄球菌中的抑菌圈面积"

表3

PHBV复合膜对金黄色葡萄球菌的抗菌率测试结果"

样品名称 抗菌率/%
PHBV/CNF-Ag 100.0
PHBV/CNF (4.5)-Ag 100.0
PHBV/CNF (7.5)-Ag 99.9
PHBV/CNFA-Ag 99.9
PHBV/CNFC-Ag 99.5
PHBV/CNFAC-Ag 99.9
PHBV/CNF(7.5)A-Ag 99.9
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