功能性乙基纤维素-松香复合膜的合成与性能表征

doi:10.3969/j.issn.0253-2417.2020.02.005

林产化学与工业 ›› 2020, Vol. 40 ›› Issue (2): 42-48.doi: 10.3969/j.issn.0253-2417.2020.02.005

功能性乙基纤维素-松香复合膜的合成与性能表征

丘雨玲^1,²,郭晓亮^1,²,卢传巍^1,²,王春鹏^1,²,王基夫^1,^2,*(),储富祥^1,²

1. 中国林业科学研究院林产化学工业研究所; 生物质化学利用国家工程实验室; 国家林业和草原局林产化学工程重点实验室; 江苏省生物质能源与材料重点实验室, 江苏南京 210042
2. 南京林业大学江苏省林业资源高效加工利用协同创新中心, 江苏南京 210037

收稿日期:2019-09-27 出版日期:2020-04-28 发布日期:2020-04-27
通讯作者: 王基夫 E-mail:wjf118@126.com
作者简介:丘雨玲(1993-),女,广西贵港人,硕士生,主要从事生物质材料功能化研究工作
基金资助:
国家自然科学基金资助项目(31570579)

Synthesis and Characterization of Functional Ethyl Cellulose-rosin Hybrid Membrane

Yuling QIU^1,²,Xiaoliang GUO^1,²,Chuanwei LU^1,²,Chunpeng WANG^1,²,Jifu WANG^1,^2,*(),Fuxiang CHU^1,²

1. Institute of Chemical Industry of Forest Products, CAF; National Engineering Lab. for Biomass Chemical Utilization; Key Lab. of Chemical Engineering of Forest Products, National Forestry and Grassland Administration; Key Lab. of Biomass Energy and Material, Jiangsu Province, Nanjing 210042, China
2. Jiangsu Co-Innovation Center of Efficient Processing and Utilization of Forest Resources, Nanjing Forestry University, Nanjing 210037, China

Received:2019-09-27 Online:2020-04-28 Published:2020-04-27
Contact: Jifu WANG E-mail:wjf118@126.com

摘要/Abstract

摘要：

以松香衍生物马来海松酸（MPA）为原料，通过酯化反应将其接枝到乙基纤维素（EC）骨架上合成乙基纤维素-松香基聚合物（EC-g-MPA），然后采用环氧大豆油（ESO）对其进行改性和内增塑，制备了生物基复合膜（EC-g-MPA-ESO），并对EC-g-MPA的结构和EC-g-MPA-ESO的结构及性能进行表征。研究结果表明：FT-IR、¹H NMR和UV-Vis证实MPA已成功接枝到EC分子上；复合膜EC-g-MPA-ESO具有一定的紫外吸收能力，且相比于EC和EC-g-MPA，复合膜的玻璃化转变温度（T_g）有所降低，同时具有较好的韧性；当ESO用量（以EC-g-MPA质量计）达到20%时，其拉伸强度达到最大值12.07 MPa，力学性能最佳；循环拉伸实验证实EC-g-MPA-ESO的弹性恢复系数随着伸长率的增加而增加，当伸长率达到80%时，其弹性恢复系数可以达到54.6%，表明EC-g-MPA-ESO具有优异的回弹性，可作为一种热塑性弹性体。该复合膜具有纤维素骨架和松香结构官能团，有望应用于紫外吸收和可降解薄膜材料领域。

关键词: 松香, 乙基纤维素, 环氧大豆油, 聚合物, 复合膜

Abstract:

A class of bio-based hybrid membranes named EC-g-MPA-ESO were prepared by the esterification reaction between the epoxidized soybean oil (ESO) and the ethyl cellulose-rosin-based polymer (EC-g-MPA), synthesized by grafting rosin derivative maleopimaric acid (MPA) onto the ethyl cellulose (EC) backbone via esterification reaction. The chemical structure of EC-g-MPA was characterized by FT-IR, ¹H NMR, and UV-Vis spectrophotometer, by which have confirmed the successful preparation of EC-g-MPA. Then, TGA, DSC, UV-Vis spectrophotometer, and tensile test were applied to investigate the thermal stability, curing properties, UV absorption properties, and mechanical properties of bio-based hybrid membrane EC-g-MPA-ESO with different ESO content. The results showed that the bio-based hybrid membrane exhibited UV absorption property. Compared with EC and EC-g-MPA, EC-g-MPA-ESO exhibited low glass transition temperature and excellent toughness. Mechanical test showed that when ESO content was 20% (based on the mass of EC-g-MPA), the blend film shows the best mechanical properties, and tensile strength reaches the maximum value of 12.07 MPa. Cyclic tensile test confirmed that the elastic restitution coefficient of EC-g-MPA-ESO increased with the increase of elongation. As the elongation reached 80%, the elastic restitution coefficient reached 54.6%, indicating that EC-g-MPA-ESO had good elastomer behavior and could be used as a thermoplastic elastomer. The hybrid membrane consists of cellulose matrix and rosin functional groups, and could find potential application in UV absorption and degradable plastic film.

Key words: rosin, ethyl cellulose, epoxidized soybean oil, polymer, hybrid film

中图分类号:

TQ35
TQ326.4

丘雨玲,郭晓亮,卢传巍,王春鹏,王基夫,储富祥. 功能性乙基纤维素-松香复合膜的合成与性能表征[J]. 林产化学与工业, 2020, 40(2): 42-48.

Yuling QIU,Xiaoliang GUO,Chuanwei LU,Chunpeng WANG,Jifu WANG,Fuxiang CHU. Synthesis and Characterization of Functional Ethyl Cellulose-rosin Hybrid Membrane[J]. Chemistry and Industry of Forest Products, 2020, 40(2): 42-48.

图/表 9

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参考文献 21

1	简春梅.基于乙基纤维素/壳聚糖的刺激响应性超分子体系的构筑[D].北京:清华大学, 2014.
	JIAN C M.The construction of stimuli-responsive supramolecular system base on ethyl cellulose/chitosan[D]. Beijing: Tsinghua University, 2014.
2	田银彩, 杨倩. 凝固剂对玉米淀粉/棉纤维素薄膜降解性能的影响[J]. 塑料工业, 2019, 47 (8): 124- 127, 137.
	TIAN Y C , YANG Q . Effect of coagulant on degradation performance of corn starch/cotton cellulose film[J]. Plastics Industry, 2019, 47 (8): 124- 127, 137.
3	张德健, 方志强, 刘宇, 等. PET纤维增强纳米纤维素薄膜撕裂性能的研究[J]. 造纸科学与技术, 2019, 38 (4): 21- 26.
	ZHANG D J , FANG Z Q , LIU Y , et al. Study on tear properties of PET fiber reinforced nanocellulose film[J]. Paper Science and Technology, 2019, 38 (4): 21- 26.
4	朱朋辉, 陈港, 欧华杰, 等. 纳米纤维素/碳纳米管复合薄膜的制备及湿敏性能[J]. 华南理工大学学报(自然科学版), 2019, 47 (8): 129- 135.
	ZHU P H , CHEN G , OU H J , et al. Preparation and humidity sensitivity of nanocellulose/carbon nanotube composite films[J]. Journal of South China University of Technology(Natural Science Edition), 2019, 47 (8): 129- 135.
5	谭温珍.再生纤维素基复合薄膜的制备及阻隔性研究[D].西安:西安理工大学, 2019.
	TAN W Z.Preparation and barrier properties of regenerated cellulose-based composite films[D]. Xi'an: Xi'an University of Technology, 2019.
6	杨胜都, 孙鑫, 李毅, 等. 石墨烯/碳纳米管协同增强再生纤维素复合薄膜的导热性能研究[J]. 塑料工业, 2019, 47 (9): 147- 153, 163.
	YANG S D , SUN X , LI Y , et al. Study on thermal conductivity of regenerated cellulose composite film synergistically enhanced by graphene/carbon nanotubes[J]. Plastics Industry, 2019, 47 (9): 147- 153, 163.
7	汪艳杰, 许国权, 郭瑞, 等. 醋酸纤维素薄膜电泳法分离血清蛋白质实验方法优化[J]. 亚太传统医药, 2019, 15 (8): 38- 40.
	WANG Y J , XU G Q , GUO R , et al. Optimization of experimental methods for separation of serum proteins by cellulose acetate membrane electrophoresis[J]. Asia-Pacific Traditional Medicine, 2019, 15 (8): 38- 40.
8	蒋革, 杨铭, 唐川. 纤维素硫酸酯制备研究进展[J]. 功能材料, 2019, 50 (7): 07035- 07039.
	JIANG G , YANG M , TANG C . Research progress in preparation of cellulose sulfate[J]. Journal of Functional Materials, 2019, 50 (7): 07035- 07039.
9	许玉芝.内塑化纤维素酯的制备、性能和结构研究[D].北京:中国林业科学研究院, 2009.
	XU Y Z.Study on preparation, properties and structures of cellulose internal plasticization[D]. Beijing: Chinese Academy of Forestry, 2009.
10	LIU Y P , YAO K J , CHEN X M , et al. Sustainable thermoplastic elastomers derived from renewable cellulose, rosin and fatty acids[J]. Polymer Chemistry, 2014, 5 (9): 3109- 3280.
11	GOLDMANN A S , TISCHER T , BARNER L , et al. Mild and modular surface modification of cellulose via hetero Diels-Alder (HDA) cycloaddition[J]. Biomacromolecules, 2011, 12 (4): 1137- 1145.
12	CHEN J X , WU D F , PAN K R . Effects of Ethyl Cellulose on the crystallization and mechanical properties of poly(β-hydroxybutyrate)[J]. International Journal of Biological Macromolecules, 2016, 88, 120- 129.
13	沈一丁, 赖小娟, 王磊. 聚乳酸/乙基纤维素复合膜的制备及其性能[J]. 复合材料学报, 2007, 24 (3): 40- 44.
	SHEN Y D , LAI X J , WANG L . Preparation and properties of poly(lactic acid)/ethyl cellulose composite films[J]. Acta Materlae Compositae Sinica, 2007, 24 (3): 40- 44.
14	董文苑.机械球磨辅助静电纺丝制备壳聚糖/乙基纤维素复合膜及血液相容性[D].海口:海南大学, 2017.
	DONG W Y.Preparation of chitosan/ethyl cellulose composite membrane by mechanical ball milling and electrospinning and blood compatibility[D]. Haikou: Hainan University, 2017.
15	ROY D , SEMSARIlAR M , GUTHRIE J T , et al. Cellulose modification by polymer grafting:A review[J]. Chemical Society Reviews, 2009, 38 (7): 2046- 2064.
16	YU J , LIU Y P , LIU X H , et al. Integration of renewable cellulose and rosin towards sustainable copolymers by "grafting from" ATRP[J]. Green Chemistry, 2014, 16 (4): 1854- 1864.
17	徐静.乙基纤维素衍生物储氢材料的研究[D].绵阳:西南科技大学, 2013.
	XU J.Study on hydrogen storage materials of ethyl cellulose derivatives[D]. Mianyang: Southwest University of Science and Technology, 2013.
18	雷岚.松香基表面活性剂的合成及自组织研究[D].无锡:江南大学, 2017.
	LEI L.Study on the synthesis and self-assembly of rosin-based surfactants[D]. Wuxi: Jiangnan University, 2017.
19	SHEN D , YU H , HUANG Y . Densely grafting copolymers of ethyl cellulose through atom transfer radical polymerization[J]. Journal of Polymer Science Part A Polymer Chemistry, 2005, 43 (18): 4099- 4108.
20	WANG J F , CHEN Y P , YAO K J , et al. Robust antimicrobial compounds and polymers derived from natural resin acids[J]. ChemicalCommunications, 2012, 48 (6): 916- 918.
21	LU C W , YU J , WANG C P , et al. Fabrication of UV-absorbent cellulose-rosin based thermoplastic elastomer via "graft from" ATRP[J]. Carbohydrate Polymers, 2018, 188, 128- 135.

样品 samples	ESO用量/% ECO dosage	拉伸强度/MPa tensile strength	断裂伸长率/% elongation at break
EC-g-MPA	0	2.08	0.41
EC-g-MPA-5%ESO	5	5.52	1.41
EC-g-MPA-10%ESO	10	6.68	3.75
EC-g-MPA-15%ESO	15	7.54	8.94
EC-g-MPA-20%ESO	20	12.07	60.84
EC-g-MPA-25%ESO	25	8.91	88.31
EC-g-MPA-30%ESO	30	7.01	93.02

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功能性乙基纤维素-松香复合膜的合成与性能表征

Synthesis and Characterization of Functional Ethyl Cellulose-rosin Hybrid Membrane

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