类沸石咪唑酯骨架ZIF-L/PVA复合薄膜的制备与性能

王保营; 丁艳红; 李璐瑶; 郭冉冉; 夏知星; 张岩

doi:10.13801/j.cnki.fhclxb.20211103.001

类沸石咪唑酯骨架ZIF-L/PVA复合薄膜的制备与性能

河南牧业经济学院　包装与印刷工程学院，郑州 450046

基金项目: 河南省科技攻关项目(212102110195，202102210243)；河南省高等学校重点科研项目(19A430016)；河南省高等学校大学生创新创业训练计划项目(S202010469007)；河南牧业经济学院科研创新基金(XKYCXJJ2017011)；河南牧业经济学院博士启动基金(53000160)

详细信息

通讯作者:
张岩，博士，副教授，硕士生导师，研究方向为复合包装材料及包装安全　E-mail: yanzhang12@yeah.net

中图分类号: TB332
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出版历程
- 收稿日期: 2021-09-09
- 修回日期: 2021-10-18
- 录用日期: 2021-10-23
- 网络出版日期: 2021-11-02
- 刊出日期: 2022-08-21

Preparation and properties of zeolitic imidazolate framework ZIF-L/PVA composite films

School of Packaging and Printing Engineering, Henan University of Animal Husbandry and Economy, Zhengzhou 450046, China

摘要

摘要: 类沸石咪唑酯骨架材料(ZIFs)因具有独特的结构和功能，使得利用ZIFs增强改性高分子材料的性能，制备新型功能复合材料，日益受到人们的重视。为研究ZIFs对聚乙烯醇(PVA)的增强改性作用，本研究以类沸石咪唑酯骨架ZIF-L为增强剂，采用溶液流延法制备了系列类沸石咪唑酯骨架ZIF-L/PVA复合薄膜，并对复合薄膜的结构、光学性能、力学性能、颜色、阻隔性能及热稳定性进行了表征。结果表明：ZIF-L的加入增强了复合薄膜的抗紫外性能；随着ZIF-L含量的增加，复合薄膜拉伸强度先增大后降低，水蒸气透过率及最大热分解温度先降低后升高，氧气透过量逐渐增大。当ZIF-L的质量分数为1wt%时，拉伸强度可提高约15%，水蒸气透过率降低1.8%，ZIF-L对PVA具有明显的增强作用，复合薄膜的综合性能较好；当ZIF-L的质量分数大于5wt%时，复合薄膜的最大热分解温度开始升高，最高可达297.84℃。制备的ZIF-L增强改性PVA复合材料为新型功能性包装复合薄膜的开发应用提供了有益借鉴。
- 类沸石咪唑酯骨架 /
- ZIF-L /
- 复合薄膜 /
- 抗紫外性能 /
- 力学性能 /
- 热稳定性
Abstract: Because of the unique structure and function of zeolitic imidazolate frameworks (ZIFs), the utilization of ZIFs to enhance the properties of polymer and prepare new functional composites have attracted growing attention. To clarify the reinforcing effects of ZIFs on poly(vinyl alcohol) (PVA), zeolitic imidazolate framework ZIF-L was used as reinforcer and series of PVA composite films with different concentrations of ZIF-L were prepared by solution casting process. The structure, optical properties, mechanical properties, color, barrier performance and thermostability of the composite films were analyzed. The results indicate that the composite films show an enhanced anti-ultraviolet property with the addition of ZIF-L. The tensile strength initially increases and then decreases with increasing content of ZIF-L while the water vapor permeability and thermal degradation temperature show an opposite tendency. In addition, the incorporation of ZIF-L increases the oxygen permeability of the films gradually. When the ZIF-L content is 1wt%, the tensile strength of the composite film is increased by about 15%, while the water vapor permeability is reduced by 1.8%, ZIF-L significantly enhances the properties of PVA and the composite film show good comprehensive performance. When the ZIF-L content is larger than 5wt%, the maximum decomposition temperature begins to increase and reaches up to 297.84℃. The ZIF-L reinforced PVA composites in the present work will advance the development of new functional packaging composite films.
- zeolitic imidazolate framework /
- ZIF-L /
- composite film /
- anti-ultraviolet property /
- mechanical property /
- thermostability

HTML全文

图 1 类沸石咪唑酯骨架材料/聚乙烯醇(ZIF-L/PVA)复合薄膜的制备过程示意图

Figure 1. Schematic diagram of the preparation process for zeolitic imidazolate frameworks/poly(vinyl alcohol) (ZIF-L/PVA) composite film

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图 2 ZIF-L (a)及不同ZIF-L含量的ZIF-L/PVA复合薄膜的SEM图像：((b)~(f)) 表面；((g)~(h)) 断面

Figure 2. SEM images of ZIF-L (a) and ZIF-L/PVA composite films with different concentrations of ZIF-L: ((b)-(f)) Surface; ((g)-(h)) Cross-section

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图 3 ZIF-L及不同ZIF-L含量的ZIF-L/PVA复合薄膜的XRD图谱

Figure 3. XRD patterns of ZIF-L and ZIF-L/PVA composite films with different concentrations of ZIF-L

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图 4 不同ZIF-L含量的ZIF-L/PVA复合薄膜的FTIR图谱：(a) 40 00~500 cm⁻¹范围内的ATR-IR图谱；(b) 19 00~400 cm⁻¹范围内FTIR图谱

Figure 4. FTIR spectra of ZIF-L/PVA composite films with different concentrations of ZIF-L: (a) ATR-IR spectra in the range of 40 00-500 cm⁻¹; (b) FTIR spectra in the range of 19 00-400 cm⁻¹

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图 5 不同ZIF-L含量的ZIF-L/PVA复合薄膜的紫外可见光谱

Figure 5. UV-Vis spectra of ZIF-L/PVA composite films with different concentrations of ZIF-L

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图 6 不同ZIF-L含量的ZIF-L/PVA复合薄膜的力学性能

Figure 6. Mechanical performance of ZIF-L/PVA composite films with different concentrations of ZIF-L

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图 7 不同ZIF-L含量的ZIF-L/PVA复合薄膜的水蒸气透过率

Figure 7. Water vapor permeability of ZIF-L/PVA composite films with different concentrations of ZIF-L

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图 8 不同ZIF-L含量的ZIF-L/PVA复合薄膜的氧气透过量

Figure 8. Oxygen permeability of ZIF-L/PVA composite films withdifferent concentrations of ZIF-L

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图 9 不同ZIF-L含量的ZIF-L/PVA复合薄膜的TG曲线 (a) 及DTG曲线 (b)

Figure 9. TG curves (a) and DTG curves (b) of ZIF-L/PVA composite films with different concentrations of ZIF-L

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表 1 ZIF-L/PVA复合薄膜的光学性能

Table 1 Optical properties of the ZIF-L/PVA composite films

Mass fraction of ZIF-L/wt%	Light transmittance/%	Haze/%	L*	a*	b*	∆E
0	92.83±0.16^a	0.21±0.03^e	94.56±0.04^b	−0.87±0.03^bc	1.43±0.01^b	2.13±0.04^d
1	92.63±0.16^a	0.91±0.01^d	94.28±0.02^c	−0.84±0.03^ab	1.61±0.01^a	2.45±0.02^c
5	92.73±0.06^a	10.47±0.57^c	93.19±0.00^e	−0.78±0.04^a	1.64±0.03^a	3.52±0.01^a
10	92.73±0.12^a	26.61±0.53^b	94.07±0.01^d	−0.93±0.06^c	1.14±0.01^d	2.60±0.01^b
15	91.53±0.16^b	59.92±0.08^a	95.04±0.06^a	−0.90±0.02^bc	1.29±0.14^c	1.65±0.04^e
Notes: Value(means±stand deviation); Same letters in the column are not significant; P>0.05; L, a, b—Color parameters; L—Brightness, black-white; a—Greenness-redness; b—Blueness-yellowness; ΔE—Total color difference.

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