Controlled synthesis of cellulose grafting PDEAEMA brushes by ATRPin ionic liquid [AMIM]Cl

doi:10.11949/j.issn.0438-1157.20150055

Abstract

Abstract:

The microcrystalline cellulose-g-poly[2-(diethylamino)ethyl methacrylate] (MCC-g-PDEAEMA) polymer brushes were synthesized under control by atom transfer radical polymerization (ATRP) in the ionic liquid 1-allyl-3-methylimidazolium chloride ([AMIM]Cl). Ethyl alcohol was used as the cosolvent to form a homogeneous system and solve the problem that the functional monomer N,N-diethylamino-2-ethyl methacrylate (DEAEMA) hardly dissolved in [AMIM]Cl. The synthetic mechanism of heterogeneous system and homogeneous system in [AMIM]Cl was analyzed. The experiments showed that the byproduct PDEAEMA in the homogeneous system was reduced and the grafting efficiency of the polymer brushes was improved. Meanwhile, the molecular weight distribution was narrow and ATRP was easily controlled. Optimum reaction conditions in the homogeneous system were attained at CuBr/PMDETA/DEAEMA/ethyl alcohol molar ratio of 1:15:150:300. The grafting efficiency could reach to 78.1%. MCC-g-PDEAEMA was characterized through FTIR spectroscopy, ¹H NMR spectroscopy and GPC. The results proved that the PDEAEMA side chains were covalently bonded to the MCC backbone and the molecular weight distribution of the polymer brushes were even.

Key words: ionic liquid, ATRP, microcrystalline cellulose, interface, homogenization

摘要：

在氯化1-烯丙基-3-甲基咪唑([AMIM]Cl)离子液体中,采用原子转移自由基(ATRP) 法接枝改性微晶纤维素,合成了微晶纤维素-g-甲基丙烯酸二乙氨基乙酯(MCC-g-PDEAEMA)聚合物分子刷。通过加入助溶剂形成均相反应体系,解决了功能性单体甲基丙烯酸二乙氨基乙酯(DEAEMA)在[AMIM]Cl离子液体中的溶解问题。分别研究了离子液体中均相与非均相的反应机理,结果表明:在均相体系中,生成的反应副产物PDEAEMA较少,聚合物分子刷的接枝效率较高,分子量分布窄,ATRP反应可控性好。实验确定了均相体系最佳反应条件:CuBr/PMDETA/DEAEMA/乙醇的摩尔比为1:15:150:300, MCC-g-PDEAEMA的接枝效率可达78.1%。通过红外、核磁和GPC对聚合物表征发现,侧链PDEAEMA成功地接枝到微晶纤维素骨架上,生成的聚合物分子刷的分子量分布均匀。

关键词: 离子液体, ATRP, 微晶纤维素, 界面, 均化作用

CLC Number:

TQ028.8

DU Kaidi, TANG Erjun, YUAN Miao, LIU Shaojie, ZHAO Dishun. Controlled synthesis of cellulose grafting PDEAEMA brushes by ATRPin ionic liquid [AMIM]Cl[J]. CIESC Journal, 2015, 66(10): 4275-4280.

杜凯迪, 唐二军, 袁淼, 刘少杰, 赵地顺. [AMIM]Cl离子液体中纤维素接枝PDEAEMA分子刷的均相可控聚合[J]. 化工学报, 2015, 66(10): 4275-4280.

References 23

[1]	Klemm D, Heublein B, Fink H P, Bohn A. Cellulose: fascinating biopolymer and sustainable raw material [J]. Angew Chem. Int. Ed., 2005, 44: 3358-3393.
[2]	Zhuang Zhiliang (庄志良), Zhu Li (祝黎), Wu Weibing (吴伟兵), Dai Hongqi (戴红旗). Progress on the heterogeneous cellulose grafting polymerization by ATRP [J]. Chemistry and Industry of Forest Products (林产化学与工业), 2014, 34 (3): 121-129.
[3]	Heinze T, Schwikal K, Banhel S. Ionic liquids as reaction medium in cellulose functionalization [J]. Macromol. Biosci., 2005, (5): 520-525.
[4]	Liu Chuanfu (刘传富), Zhang Aiping (张爱萍), Li Weiying (李维英), Sun Runcang (孙润仓). Dissolution of cellulose in novel green solvent ionic liquids and its application [J]. Progress in Chemistry (化学进展), 2009, 21 (9):1800-1806.
[5]	Kubisa P. Ionic liquids as solvents for polymerization processes— progress and challenges [J]. Prog. Polym. Sci., 2009, 34: 1333-1347.
[6]	Li Changzhi (李昌志), Wang Aiqin (王爱琴), Zhang Tao (张涛). Progress of conversion of cellulose resource in ionic liquids [J]. CIESC Journal (化工学报), 2013, 64 (1): 182-197.
[7]	Halidan Maimaiti (哈丽丹·买买提), Kalbinur Arken (开比努尔·艾尔肯), Minawar Wumaier (米娜瓦尔·乌买尔). Preparation of cellulose graft poly (butyl methacrylate) copolymers by homogeneous ATRP [J]. CIESC Journal (化工学报), 2014, 65 (3): 1111-1117.
[8]	Chen Jinghuan (陈京环), Wang Kun (王堃), Xu Feng (许凤), Sun Runcang (孙润仓). Progress of preparing regenerated cellulose fibers using novel dissolution process [J]. CIESC Journal (化工学报), 2014, 65 (11): 4213-4221.
[9]	Wang J S, Matyjaszewski K. Controlled living radical polymerization in the presence of transition-metal complexes [J]. J. Am. Chem. Soc., 1995, 117 (20): 5614-5615.
[10]	Zampano G, Bertoldo M, Bronco S. Poly(ethyl acrylate) surface-initiated ATRP grafting from wood pulp cellulose fibers [J]. Carbohyd. Polym., 2009, 75: 22-31.
[11]	Wang M, Yuan J, Huang X B, Cai X M, Li L, Shen J. Grafting of carboxybetaine brush onto cellulose membranes via surface-initiated ARGET-ATRP for improving blood compatibility [J]. Colloids and Surf. A, 2013, (103): 52-58.
[12]	Meng T, Gao X, Yuan J, Zhang Y, He J. Graft copolymers prepared by atom transfer radical polymerization (ATRP) from cellulose [J]. Polymer, 2009, 50 (2): 447-454.
[13]	Sui X F, Yuan J Y, Zhou M, Zhang J, Yang H J, Yuan W Z, Wei Y, Pan C Y. Synthesis of cellulose-graft-poly(N,N-dimethylamino-2-ethylmethacrylate) copolymers via homogeneous ATRP and their aggregates in aqueous media [J]. Biomacromolecules, 2008, 9: 2615-2620.
[14]	Wu Lianbin (吴连斌), Hu Ziqiang (胡自强). “Living” radical polymerization of methyl methacrylate using CuBr as catalyst in [Hmim][CH3COO] [J]. Journal of Functional Polymers (功能高分子学报), 2008, 4 (21): 427-431.
[15]	Clare H W, Kristina T C, Milena G M, Rachel J P, Janis G M. Surface modification of commercial cellulose acetate membranes using surface-initiated polymerization of 2-hydroxyethyl methacrylate to improve membrane surface biofouling resistance [J]. J. Membrane Sci., 2011: 385-386.
[16]	Xu A R, Wang J J, Wang H Y. Effects of anionic structure and lithium salts addition on the dissolution of cellulose in 1-butyl-3-methylimidazolium-based ionic liquid solvent systems [J]. Green Chem., 2010, 12: 268-275.
[17]	Yuan Miao (袁淼). Study on self-assembly of cellulose graft copolymer synthesized by ATRP in ionic liquids. [D]. Shijiazhuang: Hebei University of Science and Technology, 2013.
[18]	Gualandi C, Duan C, Focarete M L, Scandola M. Advantages of surface-initiated ATRP (SI-ATRP) for the functionalization of electrospun materials [J]. Macromol. Rapid Comm., 2013, 34 (1): 51-56.
[19]	Ren Nannan (任楠楠). Measurement and research for density viscosity and surface tension of ionic liquid system [D]. Beijing: Beijing University of Chemical Technology, 2013.
[20]	Shi Jiahua (石家华), Sun Xun (孙逊), et al. The research progress of ionic liquid [J]. Chemistry Online (化工通报), 2002, 4: 243-250.
[21]	Guo Kai (郭锴), Tang Xiaoheng (唐小恒), Zhou Xumei (周绪美). Chemical Reaction Engineering (化学反应工程) [M]. Beijing: Chemical Industry Press, 2000: 9-19.
[22]	Song Jin (宋瑾), Ni Jian (倪健), et al. Self-initiated oxidative radical polymerization of 2-(N,N-diethylamino) ethyl methacrylate [J]. Acta Polymerica Sinica (高分子学报), 2011, 12: 1445-1453.
[23]	Ge Wenjiao (葛文娇), Guo Yanzhu (郭延柱), Zhang Xia (张霞), et al. Synthesis of amphiphilic cellulose graft copolymers and their applications in drug delivery [J]. Paper Science&Technology, 2014, 33 (1): 39-43.