乙酰化纳米纤维素纤维的制备及其凝胶机制研究Preparation of Acetylated Cellulose Nanofibrils and its Gelation Behavior
李英豪,耿延训,徐化能
摘要(Abstract):
纳米纤维素纤维(cellulosenanofibrils,CNF)凝胶以其独特的生物亲和性、生物降解性和力学性能,可以广泛地应用到生物医药、食品等领域。然而,CNF在水溶液中易聚集而发生相分离,为了调控其聚集性能,有必要对其进行化学改性。今以商业化微晶纤维素为原料,采取无溶剂体系对其进行化学修饰,结合高压均质作用制备乙酰化纳米纤维素纤维(acetylated cellulose nanofibrils,ACNF)。利用流变仪、小角X射线散射仪、激光共聚焦显微镜等测试方法考察盐离子、温度对ACNF凝胶微观结构和宏观力学性能的影响。结果表明,ACNF呈现弯曲和无晶形的结构特征;其凝胶强度随着温度的升高先缓慢下降,而后急剧增加;而盐的加入能增强其凝胶强度,降低温度敏感性。无盐条件下,ACNF凝胶化主要基于纤维间热运动引起的物理缠结;而盐能促进体系发生浓度涨落,纤维因局部团聚经相互连接形成凝胶。
关键词(KeyWords): 乙酰化;纳米纤维素纤维;流变;缠结;凝胶特性
基金项目(Foundation): 国家自然科学基金(21576116)
作者(Author): 李英豪,耿延训,徐化能
参考文献(References):
- [1]Fang W,Paanaen A,Vitikainen M,et al.Elastic and p H-responsive hybrid interfaces created with engineered resilin and nanocellulose[J].Biomacromolecules,2017,18(6):1866-1873.
- [2]P??kk?M,Ankerfors M,Kosonen H,et al.Enzymatic hydrolysis combined with mechanical shearing and high-pressure homogenization for nanoscale cellulose fibrils and strong gels[J].Biomacromolecules,2007,8(6):1934-1941.
- [3]Wang M,Olszewska A,Malho J M,et al.Colloidal ionic assembly between anionic native cellulose nanofibrils and cationic block copolymer micelles into biomimetic nanocomposites[J].Biomacromolecules,2011,12(6):2074-2081.
- [4]Jowkarderis L,Van De Ven T G.Rheology of semi-dilute suspensions of carboxylated cellulose nanofibrils[J].Carbohydrate Polym,2015,123:416-423.
- [5]Le G K J,Jouanneau D,Garnier C,et al.Gelling of cellulose nanowhiskers in aqueous suspension[J].Journal of Applied Polymer Science,2014,131(17):8476-8481.
- [6]Zhang Y X,Carbonel R G,Rojas O J.Bioactive cellulose nanofibrils for specific human Ig G binding[J].Biomacromolecules,2013,14(12):4161-4168.
- [7]Nechyporchuk O,Belgacem M N,Pignon F.Current progress in rheology of cellulose nanofibril suspensions[J].Biomacromolecules,2016,17(7):2311-2320
- [8]Li M C,Wu Q,Song K,et al.Cellulose nanoparticles:structure-morphology-theology relationships[J].Acs Sustainable Chemistry&Engineering,2015,3(5):821-832.
- [9]Lee K Y,Quero F,Blaker J J,et al.Surface only modification of bacterial cellulose nanofibres with organic acids[J].Cellulose,2011,18(3):595-605.
- [10]Espino P E,Domenek S,Belgacem N,et al.Green process for chemical functionalization of nanocellulose with carboxylic acids[J].Biomacromolecules,2014,15(12):4551-4560.
- [11]Avila R J A,Fortunati E,Kenny J M,et al.Simple citric acid-catalyzed surface esterification of cellulose nanocrystals[J].Carbohydrate Polym,2017,157:1358-1364.
- [12]Yuwawech K,Wootthikanokkhan J,Tanpichai S.Enhancement of thermal,mechanical and barrier properties of EVA solar cell encapsulating films by reinforcing with esterified cellulose nanofibres[J].Polymer Testing,2015,48:12-22.
- [13]Jonoobi M,Harun J,Mathew A P,et al.Preparation of cellulose nanofibrilss with hydrophobic surface characteristics[J].Cellulose,2010,17(2):299-307.
- [14]Rodionova G,Lenes M,Eriksen O,et al.Surface chemical modification of microfibrillated cellulose:improvement of barrier properties for packaging applications[J].Cellulose,2011,18(1):127-134.
- [15]Moon R J,Martini A,Nairn J,et al.Cellulose nanomaterials review:structure,properties and nanocomposites[J].Chemical Society Reviews,2011,40(7):3941-3994.
- [16]Salas C,Nypel?T,Rodriguez A C,et al.Nanocellulose properties and applications in colloids and interfaces[J].Current Opinion in Colloid&Interface Science,2014,19(5):383-396.
- [17]Qi W,Xu H N,Zhang L.The aggregation behavior of cellulose micro/nanoparticles in aqueous media[J].RSC Advances,2015,5(12):8770-8777.
- [18]Martola F,Dumont P J,Orgeas L,et al.Micro-mechanics of electrostatically stabilized suspensions of cellulose nanofibrils under steady state shear flow[J].Soft Matter,2016,12(6):1721-1735.
- [19]Boromand A,Jamali S,Maia J M.Structural fingerprints of yielding mechanisms in attractive colloidal gels[J].Soft Matter,2017,13(2):458-473.
- [20]Bozic M,Vivod V,Kavcic S,et al.New findings about the lipase acetylation of nanofibrillated cellulose using acetic anhydride as acyl donor[J].Carbohydrate Polym,2015,125:340-351.
- [21]Davoudpour Y,Hossain S,Khalil H P S A,et al.Optimization of high pressure homogenization parameters for the isolation of cellulosic nanofibrilss using response surface methodology[J].Industrial Crops and Products,2015,74:381-387.
- [22]LIN Feng-cai(林凤采),LU Qi-lin(卢麒麟),LIN Yong-mei(林咏梅),et al.Preparation and characterization of acetylated nanocellulose by one-step method(一步法制备乙酰化纳米纤维素及其性能表征)[J].Chemical Industry and Engineering Progress(化工进展),2016,35(2):559-564.
- [23]Tian Z,Duan L,Wu L,et al.Rheological properties of glutaraldehyde-crosslinked collagen solutions analyzed quantitatively using mechanical models[J].Materials Science&Engineering C,2016,63:10-17.
- [24]Bodvik R,Dedinaite A,Karlson L,et al.Aggregation and network formation of aqueous methylcellulose and hydroxypropylmethyl cellulose solutions[J].Colloids Surface A,2010,354(1):162-171.
- [25]Rashad A,Mustafa K,Heggset E B,et al.Cytocompatibility of wood-derived cellulose nanofibril hydrogels with different surface chemistry[J].Biomacromolecules,2017,18(4):1238-1248.
- [26]ZHUANG Wen-chang(庄文昌),CHEN Xiao(陈晓),ZHAO Ji-kuan(赵继宽),et al.Small angle X-ray scattering studies on colloid dispersive systemsand organized molecular assemblies(胶体分散体系与有序分子组合体的小角X射线散射研究)[J].Progress in Chemistry(化学进展),2005,17(5):881-888.
- [27]Arvidson S A,Lott J R,Mcallister J W,et al.Interplay of phase separation and thermoreversible gelation in aqueous methylcellulose solutions[J].Macromolecules,2013,46(1):300-309.
- [28]Villetti M A,Soldi V,Rochas C,et al.Phase-separation kinetics and mechanism in a methylcellulose/salt aqueous solution studied by time-resolved small-angle light scattering(SALS)[J].Macromolecules,2011,212(10):1063-1071.