ATRP法接枝卤胺分子制备纤维素共聚物抗菌材料

doi:10.11949/j.issn.0438-1157.20180291

化工学报 ›› 2018, Vol. 69 ›› Issue (S1): 155-160.DOI: 10.11949/j.issn.0438-1157.20180291

• 材料化学工程与纳米技术 • 上一篇下一篇

ATRP法接枝卤胺分子制备纤维素共聚物抗菌材料

韩瑞涛¹, 赵磊², 唐二军², 赵雄燕¹, 赵聪思²

1 河北科技大学材料科学与工程学院, 河北石家庄 050018;
2 河北科技大学化学与制药工程学院, 河北石家庄 050018

收稿日期:2018-03-19 修回日期:2018-07-18 出版日期:2018-09-30 发布日期:2018-09-30
通讯作者: 唐二军,E-mail:ejtang@sohu.com
基金资助:
国家自然科学基金项目（21304030）；河北省重点基础研究计划课题项目（20182018183）。

Preparation of cellulose antimicrobial materials grafted halamnie by ATRP

HAN Ruitao¹, ZHAO Lei², TANG Erjun², ZHAO Xiongyan¹, ZHAO Congsi²

1 College of Material Science and Engineering, Shijiazhuang 050018, Hebei, China;
2 Chemical and Pharmaceutical Engineering, Hebei University of Science and Technology, Shijiazhuang 050018, Hebei, China

Received:2018-03-19 Revised:2018-07-18 Online:2018-09-30 Published:2018-09-30
Supported by:
supported by the National Natural Science Foundation of China (21304030) and the Key Basic Research Project of Hebei Province(20182018183).

摘要/Abstract

摘要：

以氯化1-烯丙基-3-甲基咪唑（[AMIM]Cl）离子液体为溶剂，采用原子转移自由基聚合法（ATRP）在微晶纤维素上接枝功能单体N-羟甲基丙烯酰胺，制备了卤胺化合物中间体，应用卤化法将接枝共聚物中的N-H转化为N-Cl键获得具有抗菌性的共聚物材料，并对其抗菌性能进行研究。通过FT-IR、¹H NMR、SEM以及抗菌测试等分析手段表征分析了聚合物的结构、表面形貌和抗菌性能等。结果表明该工艺合成了纤维素接枝N-羟甲基丙烯酰胺共聚物，接枝后表面明显变得粗糙，有利于材料与细菌的接触进而充分发挥其抗菌性能，制备的材料对金黄色葡萄球菌和大肠杆菌均表现出良好抗菌性能，在抗菌材料领域具有较好的应用前景。

关键词: 离子液体, 卤胺, 纤维素, ATRP, 抗菌

Abstract:

Functional monomer N-methylolacrylamide was grafted onto microcrystalline cellulose to prepare the intermediates MCC-g-PHAM by atom transfer radical polymerization (ATRP) in ionic liquid 1-allyl-3-methyl-imidazole chloride. Halogenation was used to convert N-H in graft copolymer into N-Cl bond to obtain antibacterial copolymer, and its antibacterial properties were studied. The obtained polymer structure, surface morphology and antibacterial properties were characterized by FT-IR, ¹H NMR, SEM and antibacterial test. The result showed that the cellulose graft copolymer has been successfully synthesized and the surface after grafting became noticeably rougher. Therefore, the contact between the material and the bacteria is facilitated and the antibacterial performance is fully exerted. The material exhibits perfect antibacterial performance against Staphylococcus aureus and Escherichia coli. Thus the obtained material presents a better application prospect on the antibacterial field.

Key words: ionic liquid, halamine, cellulose, ATRP, antibacterial

中图分类号:

TQ352.77

韩瑞涛, 赵磊, 唐二军, 赵雄燕, 赵聪思. ATRP法接枝卤胺分子制备纤维素共聚物抗菌材料[J]. 化工学报, 2018, 69(S1): 155-160.

HAN Ruitao, ZHAO Lei, TANG Erjun, ZHAO Xiongyan, ZHAO Congsi. Preparation of cellulose antimicrobial materials grafted halamnie by ATRP[J]. CIESC Journal, 2018, 69(S1): 155-160.

参考文献 30

[1]	GABRIEL G J, SOM A, MADKOUR A E, et al. Infectious disease:connecting innate immunity to biocidal polymers[J]. Mater. Sci. Eng. R, 2007, 57(9):28-64.
[2]	甄志超, 胡燕, 李朝顺, 等. 抗菌纺织品的发展[J].新材料产业, 2009, 21(7):28-31. ZHEN Z C, HU Y, LI C S, et al. The development of antibacterial textile[J]. Adv. Mater. Ind., 2009, 21(7):28-31.
[3]	REN X H,ZHU C Y,KOU L, et al. Acyclic N-halamine polymeric bbiocidal films[J]. Bioact. Compat. Polym., 2010, 25(4):392-405.
[4]	ZHAO N, ZHANEL G G, LIU S, et al. Regenerability of antibacterial activity of interpenetrating polymeric N-halamineandpoly(ethylene terphthalate)[J]. J. Appl. Polym. Sci., 2011, 120(1):611-622.
[5]	BARNELA S B, WORLEY S D, WILLIAMS D E. Syntheses and antibacterial activity of new N-halamine compounds[J]. J. Pharm. Sci., 1987, 76(3):245-247.
[6]	AKDAG A, MCKEE M L, WORLEY S D. Mechanism of formation of biocidal imidazolidin-4-one derivatives:an ab initio density-functional theory study[J]. Phys. Chem. A, 2006, 110(24):7621-7627.
[7]	赵洁, 安秋凤, 李献起, 等. 有机硅在抗菌整理剂中的应用[J]. 化学进展, 2014, 26(2/3):310-319. ZHAO J, AN Q F, LI X Q, et al. Organosilicon in antimicrobial agent[J]. Progress in Chemistry, 2014, 26(2/3):310-319.
[8]	李平, 董阿力德尔图, 孙梓嘉, 等. N-卤胺类高分子与纳米抗菌材料的制备及应用[J].化学进展, 2017, 29(2/3):318-328. LI P, DONG A, SUN Z J, et al. Synthesis and applications antibacterial N-halamine polymers and nanomaterials[J]. Progress in Chemistry, 2017, 29(2/3):318-328.
[9]	SUN Y Y, SUN G. Novel refreshable N-halamine polymeric biocides:grafting hydantoin-containing monomers onto high performance fibers by a continuou sprocess[J]. J. Appl. Polym. Sci., 2003, 88(4):1032-1039.
[10]	SUN Y Y, SUN G. Durable and regenerable antimicrobial textile materials prepared by a continuous grafting process[J]. J. Appl. Polym. Sci., 2002, 84(8):1592-1599.
[11]	任联振, 任鹏刚, 张晓亮. 天然纤维素/PVA复合水凝胶的形成机理及力学性能研究[J]. 高校化学工程学报, 2015, 29(4):1003-1009. REN L Z, REN P G, ZHANG X L. Preparation and mechanical properties of natural cellulose/PVA composite hydrogels[J]. Journal of Chemical Engineering of Chinese Universities, 2015, 29(4):1003-1009.
[12]	杜煌, 薛腾, 唐二军, 等. 离子液体中ATRP合成MCC-g-P4VP分子及其药物控释应用[J]. 高校化学工程学报, 2017, 31(2):352-360. DU H, XUE T, TANG E J, et al. Atom transfer radical polymerization of MCC-g-P4VP in ionic liquids and its application in controlled drug release[J]. Journal of Chemical Engineering of Chinese Universities, 2017, 31(2):352-360.
[13]	杜煌, 常达, 唐二军, 等. 离子液体中ATRP合成MCC-g-PMAA及其分子对阿司匹林控释的应用[J]. 化工学报, 2016, 67(S2):164-170. DU H, CHANG D, TANG E J, et al. Synthesis of MCC-g-PMAA by ATRP in ILs and its application in controlled release to Aspirin[J]. CIESC Journal, 2016, 67(S2):164-170.
[14]	叶代勇, 黄洪, 傅和青, 等. 纤维素化学研究进展[J]. 化工学报, 2006, 57(8):1782-1791. YE D Y, HUANG H, FU H Q, et al. Advances in cellulose chemistry[J]. Journal of Chemical Industry and Engineering (China), 2006, 57(8):1782-1791.
[15]	尹婵, 魏晓奕, 李积华, 等. 天然植物纤维素的改性技术及研究进展[J]. 广东化工, 2012, 39(15):17-19. YIN C, WEI X Y, LI J H, et al. The research progress of cellulose modification technology[J]. Guangdong Chemical Industry, 2012, 39(15):17-19.
[16]	LIN J, WINKLEMAN C, WORLEY S D, BROUGHTON R M, et al. Antimicrobial treatment of nylon[J]. J. Appl. Polym. Sci.,2001, 81(4):943-947.
[17]	JIE Z Q, YAN X F, ZHAO L H, et al. A high-efficacy and regenerable antimicrobial resin containing quaternarized N-halamine groups[J]. React. Funct. Polym., 2013, 73(11):1580-1587.
[18]	LI R, HU P, REN X H, et al. Antimicrobial N-halamine modified chitosan films[J]. Carbohydrate Polymers,2013, 92(1):534-539.
[19]	KOCER H B, CERKEZ I, WORLEY S D,et al. Polymeric antimicrobial N-halamine epoxides[J]. ACS Appl. Mater. Inter., 2011, 3(8):2845-2847.
[20]	LIU S, SUN G. Functional modification of poly(ethylene terephthalate) with an allyl monomer:chemistry and structure characterization[J].Polymer, 2008, 49(24):5225-5232.
[21]	MATYJASZWSKI K, GAYNOR S, WANG J S. Controlled radical polimerizations:the use of alkyl iodides in degenerative transfer[J]. Macromolecules, 1995, 28(6):2093-2095.
[22]	IKEDA T, TAZUKE S. Biologically active polycations:antimicrobial activities of poly[trialkyl (vinylbenzyl) ammonium chloride]-type polycations[J]. Die Makromolekulare Chemie, Rapid Communications, 1983, 4(7):459-461.
[23]	李蓉, 刘颖, 任学宏. 卤胺类抗菌剂和抗菌材料研究进展[J]. 化工新材料, 2013, 41(11):19-22. LI R, LIU Y, REN X H. Development of N-halamine based antibacterial agent and antibacterial materials[J]. New Chemical Materials, 2013, 41(11):19-22.
[24]	李晓林, 成晓莉, 李琳, 等. N-羟甲基丙烯酰胺在棉织物抗菌整理中的应用[J].材料导报, 2015, 29(10):23-27. LI X L, CHENG X L, LI L, et al. The application of N-methylol acrylamidein antibacterial finishing of cotton fabric[J]. Materials Review, 2015, 29(10):23-27.
[25]	杜凯迪, 唐二军, 袁淼, 等.[AMIM]Cl离子液体中纤维素接枝PDEAEMA分子刷的均相可控聚合李蓉, 刘颖, 任学宏. 卤胺类抗菌剂和抗菌材料研究进展[J]. 化工学报, 2015, 66(10):4275-4280. DU K D, TANG E J, YUAN M, et al. Controlled synthesis of cellulose grafting PDEAEMA brushes by ATRP in ionic liquid[AMIM]Cl[J]. CIESC Journal, 2015, 66(10):4275-4280.
[26]	成晓莉, 马会燕, 刘殷, 等. 卤胺类单体接枝汉麻纤维及抗菌性能研究[J]. 化工新型材料, 2016, 44(5):249-251. CHENG X L, MA H Y, LIU Y, et al. Antibacterial treatment of hemp fiber by grafting N-halamine momer[J]. New Chemical Materials, 2016, 44(5):249-251.
[27]	卢生昌, 巫龙辉, 林新兴, 等. ATRP法均相改性纤维素的研究进展[J]. 纤维素科学与技术, 2016, 24(4):56-67. LU S C, WU L H, LIN X X, et al. Progress in cellulose modification under homogeneous reaction condition via ATRP[J]. Journal of Cellulose Science and Technology, 2016, 24(4):56-67.
[28]	QIU X Y, REN X Q, HU S W. Fabrication of dual-responsive cellulose-based membrane via simplified surface-initiated ATRP[J]. Carbohydrate Polymers, 2013, 92(2):1887-1895.
[29]	MENG T, GAO X, ZHANG J, et al. Graft copolymers prepared by atom transfer radical polymerization (ATRP) from cellulose[J]. Polymer, 2009, 50(2):447-454.
[30]	LIU Y, LI L, WANG Y F,MENG T, et al. Antibacterial modification of microcrystalline cellulose by grafting copolymerization[J]. Bioresources, 2015, 11(1):519-529.

ATRP法接枝卤胺分子制备纤维素共聚物抗菌材料

Preparation of cellulose antimicrobial materials grafted halamnie by ATRP

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

参考文献 30

相关文章 15

编辑推荐

Metrics

本文评价

[1]	王琪, 张斌, 张晓昕, 武虎建, 战海涛, 王涛. 氯铝酸-三乙胺离子液体/P₂O₅催化合成伊索克酸和2-乙基蒽醌[J]. 化工学报, 2023, 74(S1): 245-249.
[2]	车睿敏, 郑文秋, 王小宇, 李鑫, 许凤. 基于离子液体的纤维素均相加工研究进展[J]. 化工学报, 2023, 74(9): 3615-3627.
[3]	陈美思, 陈威达, 李鑫垚, 李尚予, 吴有庭, 张锋, 张志炳. 硅基离子液体微颗粒强化气体捕集与转化的研究进展[J]. 化工学报, 2023, 74(9): 3628-3639.
[4]	程业品, 胡达清, 徐奕莎, 刘华彦, 卢晗锋, 崔国凯. 离子液体基低共熔溶剂在转化CO₂中的应用[J]. 化工学报, 2023, 74(9): 3640-3653.
[5]	王俐智, 杭钱程, 郑叶玲, 丁延, 陈家继, 叶青, 李进龙. 离子液体萃取剂萃取精馏分离丙酸甲酯+甲醇共沸物[J]. 化工学报, 2023, 74(9): 3731-3741.
[6]	陈杰, 林永胜, 肖恺, 杨臣, 邱挺. 胆碱基碱性离子液体催化合成仲丁醇性能研究[J]. 化工学报, 2023, 74(9): 3716-3730.
[7]	米泽豪, 花儿. 基于DFT和COSMO-RS理论研究多元胺型离子液体吸收SO₂气体[J]. 化工学报, 2023, 74(9): 3681-3696.
[8]	宋明昊, 赵霏, 刘淑晴, 李国选, 杨声, 雷志刚. 离子液体脱除模拟油中挥发酚的多尺度模拟与研究[J]. 化工学报, 2023, 74(9): 3654-3664.
[9]	杨绍旗, 赵淑蘅, 陈伦刚, 王晨光, 胡建军, 周清, 马隆龙. Raney镍-质子型离子液体体系催化木质素平台分子加氢脱氧制备烷烃[J]. 化工学报, 2023, 74(9): 3697-3707.
[10]	陆俊凤, 孙怀宇, 王艳磊, 何宏艳. 离子液体界面极化及其调控氢键性质的分子机理[J]. 化工学报, 2023, 74(9): 3665-3680.
[11]	郑佳丽, 李志会, 赵新强, 王延吉. 离子液体催化合成2-氰基呋喃反应动力学研究[J]. 化工学报, 2023, 74(9): 3708-3715.
[12]	张缘良, 栾昕奇, 苏伟格, 李畅浩, 赵钟兴, 周利琴, 陈健民, 黄艳, 赵祯霞. 离子液体复合萃取剂选择性萃取尼古丁的研究及DFT计算[J]. 化工学报, 2023, 74(7): 2947-2956.
[13]	毛磊, 刘冠章, 袁航, 张光亚. 可捕集CO₂的纳米碳酸酐酶粒子的高效制备及性能研究[J]. 化工学报, 2023, 74(6): 2589-2598.
[14]	董茂林, 陈李栋, 黄六莲, 吴伟兵, 戴红旗, 卞辉洋. 酸性助水溶剂制备木质纳米纤维素及功能应用研究进展[J]. 化工学报, 2023, 74(6): 2281-2295.
[15]	龙臻, 王谨航, 任俊杰, 何勇, 周雪冰, 梁德青. 离子液体协同PVCap抑制天然气水合物生成实验研究[J]. 化工学报, 2023, 74(6): 2639-2646.