pH响应性气体渗透CNC/PBAT复合膜的制备与性能

doi:10.11949/0438-1157.20231133

摘要/Abstract

摘要：

具有可调控气体渗透的薄膜对包装保鲜领域发展具有重要意义，而设计具有pH响应性渗透和高力学性能的薄膜仍然是一个挑战。设计琥珀酸酐酯化与二乙烯三胺酰胺化的两步取代反应，实现纤维素纳米晶表面胺基（A-CNC）与羧基（S-CNC）功能化修饰，进一步与聚对苯二甲酸-己二酸丁二醇酯（PBAT）复合，制备具有互反pH响应性气体渗透的复合薄膜。结果表明，通过扫描电镜（SEM）、红外光谱（FTIR）和核磁共振¹³C谱（¹³C NMR）对纤维素纳米晶及其功能化修饰进行表征，证实改性成功。对复合薄膜性能表征：在力学性能方面，S-CNC/PBAT（3/97）与A-CNC/PBAT（5/95）复合薄膜拉伸强度达到最高，比PBAT分别增加40.44%与50.56%，但断裂伸长率下降，断裂模式由韧性向脆性断裂转变。在气体渗透性方面，复合薄膜展现出互反pH响应渗透特征。S-CNC/PBAT（5/95）复合薄膜渗透性出现正响应变化趋势，随着缓冲液pH（3~12）升高，CO₂与O₂渗透性分别增加67.98%和48.34%，水蒸气渗透性从2.467×10^-13变化到3.039×10^-13 g·cm/（cm²·s·Pa）；而A-CNC/PBAT（5/95）复合薄膜渗透出现pH负响应性现象，CO₂与O₂渗透性分别降低63.00%与54.61%，水蒸气渗透性从2.747×10^-13变化到2.043×10^-13 g·cm/（cm²·s·Pa）。这种具有pH响应性渗透的复合薄膜在智能包装领域具有广阔的前景。

关键词: 纤维素纳米晶, 功能化修饰, 复合材料, 力学性能, 响应性渗透

Abstract:

Films with tunable gas permeation are important for the development of the packaging and preservation field, while designing films with pH-responsive permeation and high mechanical properties remains a challenge. In this paper, a two-step substitution reaction of succinic anhydride esterification and diethylenetriamine amidation was designed to achieve functionalized modification of amine group (A-CNC) and carboxyl group (S-CNC) on the surface of cellulose nanocrystals, which was further composited with poly(butylene adipate-co-terephthalate) (PBAT) to prepare composite films with pH-responsive gas permeation. The results showed that the cellulose nanocrystals and their functionalisation were characterised by scanning electron microscopy (SEM), infrared spectroscopy (FTIR) and nuclear magnetic resonance ¹³C spectroscopy (¹³C NMR), confirming the success of the modification. Characterisation of the composite film properties: in terms of mechanical properties, the tensile strength of S-CNC/PBAT (3/97) and A-CNC/PBAT (5/95) composite films reached the highest, which was 40.44% and 50.56% higher than PBAT respectively, whereas the elongation at break decreased and the fracture mode shifted from ductile to brittle fracture. In terms of gas permeability, the composite films showed mutual inverse pH response permeability characteristics. The permeability of S-CNC/PBAT (5/95) composite films showed a positive response to the trend of change, with the increase of buffer pH (3—12), CO₂ and O₂ permeability increased by 67.98% and 48.34%, respectively, and the water vapour permeability varied from 2.467×10^-13 to 3.039×10^-13 g·cm/(cm²·s·Pa), and A-CNC/PBAT (5/95) composite film permeation appeared pH negative responsive phenomenon, CO₂ and O₂ permeability decreased by 63.00% and 54.61%, respectively, and the water vapour permeability changed from 2.747×10^-13 to 2.043×10^-13 g·cm/(cm²·s·Pa). This composite film with pH-responsive permeability has a broad prospect in the field of smart packaging.

Key words: cellulose nanocrystals, functionalized modification, composite material, mechanical properties, responsive permeation

中图分类号:

TS 206.4

丁相斐, 丘晓琳, 朱喜成, 张佳伟, 陈锦华. pH响应性气体渗透CNC/PBAT复合膜的制备与性能[J]. 化工学报, 2024, 75(3): 1040-1051.

Xiangfei DING, Xiaolin QIU, Xicheng ZHU, Jiawei ZHANG, Jinhua CHEN. Preparation and properties of pH-responsive gas permeable CNC/PBAT composite membranes[J]. CIESC Journal, 2024, 75(3): 1040-1051.

图/表 11

图1 CNC及其表面功能化修饰示意图

Fig.1 Schematic diagram of CNC and its surface functionalisation modification

图2 硫酸水解前后制备的CNC的SEM图像与激光粒度测试结果

Fig.2 SEM images and laser particle size test results of CNC prepared before and after sulphuric acid hydrolysis

图3 CNC及其表面功能化修饰的表征结果

Fig.3 Characterisation results of CNC and its surface functionalisation modifications

图4 不同含量的功能化CNC/PBAT复合薄膜的力学性能测试

Fig.4 Mechanical properties testing of functionalized CNC/PBAT composite films with different contents

图5 不同含量的功能化CNC/PBAT复合薄膜的DSC测试:（a）、（b）一次降温曲线；（c）、（d）二次升温曲线

Fig.5 DSC tests of functionalized CNC/PBAT composite films with different contents: (a), (b) primary cooling curves; (c), (d) secondary heating curves

表1 功能化CNC/PBAT复合薄膜的DSC曲线参数

Table 1 The DSC curve parameters of functionalized CNC /PBAT composite films

样品名称	T_m/℃	T_c/℃	T_c-onset/℃	ΔH_m/(J/g)	ΔX_c/%
PBAT	125.51	82.43	93.04	13.32	11.68
S-CNC/PBAT(1/99)	128.29	94.86	103.89	9.261	8.21
S-CNC/PBAT(3/97)	127.43	89.48	96.82	9.505	8.60
S-CNC/PBAT(5/95)	126.45	91.08	104.18	8.143	7.52
S-CNC/PBAT(7/93)	128.95	98.70	107.31	7.296	6.88
A-CNC/PBAT(1/99)	126.96	89.31	97.16	10.94	9.69
A-CNC/PBAT(3/97)	127.60	92.43	101.54	10.39	9.59
A-CNC/PBAT(5/95)	127.84	92.66	101.76	9.858	8.91
A-CNC/PBAT(7/93)	128.53	93.21	103.23	9.36	8.83

图6 不同含量的功能化CNC/PBAT复合薄膜的表面性能测试

Fig.6 Surface property test of functionalized CNC/PBAT composite films with different contents

图7 功能化CNC/PBAT复合薄膜截面的低、高倍下扫描电镜SEM表征结果

Fig.7 SEM characterisation results at low and high magnification of functionalised CNC/PBAT composite film cross section

图8 功能化CNC/PBAT复合薄膜的pH响应性气体渗透原理示意图

Fig.8 Schematic representation of the principle of pH-responsive gas permeation of functionalized CNC/PBAT composite films

图9 功能化CNC/PBAT复合薄膜的pH响应性CO2/O2气体渗透的测试结果

Fig.9 Test results of pH-responsive CO2/O2 gas permeation of functional composite films

图10 S-CNC/PBAT(5/95)与A-CNC/PBAT(5/95)复合薄膜的pH响应性水蒸气渗透的测试结果

Fig.10 Test results of pH-responsive water vapor permeability of S-CNC/PBAT (5/95) and A-CNC/PBAT (5/95) composite films

参考文献 36

1	Opara U L, Caleb O J, Belay Z A. Modified atmosphere packaging for food preservation[M]//Food Quality and Shelf Life. Amsterdam: Elsevier, 2019: 235-259.
2	Turan D, Sängerlaub S, Stramm C, et al. Gas permeabilities of polyurethane films for fresh produce packaging: response of O₂ permeability to temperature and relative humidity[J]. Polymer Testing, 2017, 59: 237-244.
3	Zhao Y, Qiu X L, Wang J, et al. Preparation and characterization of CO₂/O₂ selective facilitated transport films by coating polyvinyl alcohol/polyethylene glycol/aminated sodium lignosulfonate on TiO₂/ZnO-modified LDPE[J]. Journal of Applied Polymer Science, 2023, 140(21): e53877.
4	Kim D, Seo J. A review: breathable films for packaging applications[J]. Trends in Food Science & Technology, 2018, 76: 15-27.
5	Osada Y, Honda K, Ohta M. Control of water permeability by mechanochemical contraction of poly(methacrylic acid)-grafted membranes[J]. Journal of Membrane Science, 1986, 27(3): 327-338.
6	Tufani A, Ozaydin Ince G. Smart membranes with pH-responsive control of macromolecule permeability[J]. Journal of Membrane Science, 2017, 537: 255-262.
7	Houben S J A, Kloos J, Borneman Z, et al. Switchable gas permeability of a polypropylene-liquid crystalline composite film[J]. Journal of Polymer Science, 2022, 60(5): 803-811.
8	Siracusa V, Rocculi P, Romani S, et al. Biodegradable polymers for food packaging: a review[J]. Trends in Food Science & Technology, 2008, 19(12): 634-643.
9	Sousa F M, Cavalcanti F B, Marinho V A D, et al. Effect of composition on permeability, mechanical properties and biodegradation of PBAT/PCL blends films[J]. Polymer Bulletin, 2022, 79(7): 5327-5338.
10	Kian L K, Jawaid M, Mahmoud M H, et al. PBAT/PBS blends membranes filled with nanocrystalline cellulose for heavy metal ion separation[J]. Journal of Polymers and the Environment, 2022, 30(12): 5263-5273.
11	Lamsaf H, Singh S, Pereira J, et al. Multifunctional properties of PBAT with hemp (Cannabis sativa) micronised fibres for food packaging: cast films and coated paper[J]. Coatings, 2023, 13(7): 1195.
12	Sonchaeng U, Promsorn J, Bumbudsanpharoke N, et al. Polyesters incorporating Gallic acid as oxygen scavenger in biodegradable packaging[J]. Polymers, 2022, 14(23): 5296.
13	Pagno V, Módenes A N, Dragunski D C, et al. Heat treatment of polymeric PBAT/PCL membranes containing activated carbon from Brazil nutshell biomass obtained by electrospinning and applied in drug removal[J]. Journal of Environmental Chemical Engineering, 2020, 8(5): 104159.
14	Thangudu S. Next generation nanomaterials: smart nanomaterials, significance, and biomedical applications[M]//Khan F. Applications of Nanomaterials in Human Health. Singapore: Springer, 2020: 287-312.
15	Fourati Y, Tarrés Q, Delgado-Aguilar M, et al. Cellulose nanofibrils reinforced PBAT/TPS blends: mechanical and rheological properties[J]. International Journal of Biological Macromolecules, 2021, 183: 267-275.
16	Hung Y J, Chiang M Y, Wang E T, et al. Synthesis, characterization, and physical properties of maleic acid-grafted poly(butylene adipate-co-terephthalate)/cellulose nanocrystal composites[J]. Polymers, 2022, 14(13): 2742.
17	Isogai A. Emerging nanocellulose technologies: recent developments[J]. Advanced Materials, 2021, 33(28): 2000630.
18	Nasseri R, Deutschman C P, Han L, et al. Cellulose nanocrystals in smart and stimuli-responsive materials: a review[J]. Materials Today Advances, 2020, 5: 100055.
19	Way A E, Hsu L, Shanmuganathan K, et al. pH-responsive cellulose nanocrystal gels and nanocomposites[J]. ACS Macro Letters, 2012, 1(8): 1001-1006.
20	Li Y, Chen H M, Liu D, et al. pH-responsive shape memory poly(ethylene glycol)-poly(ε-caprolactone)-based polyurethane/cellulose nanocrystals nanocomposite[J]. ACS Applied Materials & Interfaces, 2015, 7(23): 12988-12999.
21	Chen Y X, Abdalkarim S Y H, Yu H Y, et al. Double stimuli-responsive cellulose nanocrystals reinforced electrospun PHBV composites membrane for intelligent drug release[J]. International Journal of Biological Macromolecules, 2020, 155: 330-339.
22	Luo Q Y, Hossen A, Sameen D E, et al. Recent advances in the fabrication of pH-sensitive indicators films and their application for food quality evaluation[J]. Critical Reviews in Food Science and Nutrition, 2023, 63(8): 1102-1118.
23	Thambiraj S, Ravi Shankaran D. Preparation and physicochemical characterization of cellulose nanocrystals from industrial waste cotton[J]. Applied Surface Science, 2017, 412: 405-416.
24	Mazlita Y, Lee H V, Hamid S B A. Preparation of cellulose nanocrystals bio-polymer from agro-industrial wastes: separation and characterization[J]. Polymers and Polymer Composites, 2016, 24(9): 719-728.
25	Habibi Y, Lucia L A, Rojas O J. Cellulose nanocrystals: chemistry, self-assembly, and applications[J]. Chemical Reviews, 2010, 110(6): 3479-3500.
26	Hu Y, Tang L R, Lu Q L, et al. Preparation of cellulose nanocrystals and carboxylated cellulose nanocrystals from borer powder of bamboo[J]. Cellulose, 2014, 21(3): 1611-1618.
27	Zafari R, Mendonça F G, Baker R T, et al. Technology, efficient SO₂ capture using an amine-functionalized, nanocrystalline cellulose-based adsorbent[J]. Separation and Purification Technology, 2023, 308: 122917.
28	Chatterjee S, Nafezarefi F, Tai N H, et al. Size and synergy effects of nanofiller hybrids including graphene nanoplatelets and carbon nanotubes in mechanical properties of epoxy composites[J]. Carbon, 2012, 50(15): 5380-5386.
29	Wu C Q, Zhang X Z, Wang X H, et al. Surface modification of cellulose nanocrystal using succinic anhydride and its effects on poly(butylene succinate) based composites[J]. Cellulose, 2019, 26(5): 3167-3181.
30	Liu X, Shao X Y, Fang G B, et al. Preparation and properties of chemically reduced graphene oxide/copolymer-polyamide nanocomposites[J]. e-Polymers, 2017, 17(1): 3-14.
31	Huang W J, Lv G F, Wei L J, et al. Preparation and performance study of pbat/microcrystalline cellulose composite materials[J]. 2021, 49(9): 12-16.
32	Wang Z F, Wang B, Qi N, et al. Influence of fillers on free volume and gas barrier properties in styrene-butadiene rubber studied by positrons[J]. Polymer, 2005, 46(3): 719-724.
33	Torstensen J Ø, Liu M, Jin S A, et al. Swelling and free-volume characteristics of TEMPO-oxidized cellulose nanofibril films[J]. Biomacromolecules, 2018, 19(3): 1016-1025.
34	Moon J D, Borjigin H, Liu R, et al. Impact of humidity on gas transport in polybenzimidazole membranes[J]. Journal of Membrane Science, 2021, 639: 119758.
35	Kedia P, Badhe Y, Gupta R, et al. Modeling the effect of pH on the permeability of dried chitosan film[J]. Journal of Food Engineering, 2023, 358: 111682.
36	Zhang F, Yu L J, Liu J, et al. pH-responsive laminar WSe₂ membrane with photocatalytic antifouling property for ultrafast water transport[J]. Chemical Engineering Journal, 2022, 435:135159.

[1]	徐文杰, 贾献峰, 王际童, 乔文明, 凌立成, 王任平, 余子舰, 张寅旭. 有机硅/酚醛杂化气凝胶的制备和性能研究[J]. 化工学报, 2023, 74(8): 3572-3583.
[2]	胡兴枝, 张皓焱, 庄境坤, 范雨晴, 张开银, 向军. 嵌有超小CeO₂纳米粒子的碳纳米纤维的制备及其吸波性能[J]. 化工学报, 2023, 74(8): 3584-3596.
[3]	张澳, 罗英武. 低模量、高弹性、高剥离强度丙烯酸酯压敏胶[J]. 化工学报, 2023, 74(7): 3079-3092.
[4]	王杰, 丘晓琳, 赵烨, 刘鑫洋, 韩忠强, 许雍, 蒋文瀚. 聚电解质静电沉积改性PHBV抗氧化膜的制备与性能研究[J]. 化工学报, 2023, 74(7): 3068-3078.
[5]	刘杰, 吴立盛, 李锦锦, 罗正鸿, 周寅宁. 含乙烯基胺酯键聚醚类可逆交联聚合物的制备及性能研究[J]. 化工学报, 2023, 74(7): 3051-3057.
[6]	蔡斌, 张效林, 罗倩, 党江涛, 左栗源, 刘欣梅. 导电薄膜材料的研究进展[J]. 化工学报, 2023, 74(6): 2308-2321.
[7]	崔张宁, 胡紫璇, 吴雷, 周军, 叶干, 刘田田, 张秋利, 宋永辉. 可降解纤维素基材料的耐水性能研究进展[J]. 化工学报, 2023, 74(6): 2296-2307.
[8]	杨琴, 秦传鉴, 李明梓, 杨文晶, 赵卫杰, 刘虎. 用于柔性传感的双形状记忆MXene基水凝胶的制备及性能研究[J]. 化工学报, 2023, 74(6): 2699-2707.
[9]	李振, 张博, 王丽伟. PEG-EG固-固相变材料的制备和性能研究[J]. 化工学报, 2023, 74(6): 2680-2688.
[10]	代佳琳, 毕唯东, 雍玉梅, 陈文强, 莫晗旸, 孙兵, 杨超. 热物性对混合型CPCMs固液相变特性影响模拟研究[J]. 化工学报, 2023, 74(5): 1914-1927.
[11]	陈韶云, 徐东, 陈龙, 张禹, 张远方, 尤庆亮, 胡成龙, 陈建. 单层聚苯胺微球阵列结构的制备及其吸附性能[J]. 化工学报, 2023, 74(5): 2228-2238.
[12]	刘瑞琪, 周栖桐, 张悦, 贺莹, 高静, 马丽. 基于金纳米颗粒修饰二氧化硅纳米花的生物传感器构建及应用[J]. 化工学报, 2023, 74(3): 1247-1259.
[13]	徐东, 田杜, 陈龙, 张禹, 尤庆亮, 胡成龙, 陈韶云, 陈建. 聚苯胺/二氧化锰/聚吡咯复合纳米球的制备及其电化学储能性[J]. 化工学报, 2023, 74(3): 1379-1389.
[14]	陈瑞哲, 程磊磊, 顾菁, 袁浩然, 陈勇. 纤维增强树脂复合材料化学回收技术研究进展[J]. 化工学报, 2023, 74(3): 981-994.
[15]	王帅, 杨富凯, 徐新宇. 阻燃型全生物基多元醇聚氨酯泡沫的制备及性能研究[J]. 化工学报, 2023, 74(3): 1399-1408.