纳米微晶纤维素制备*

纳米微晶纤维素（NCC）由于其大量、可再生、可生物降解以及优良的力学性能,成为纳米技术领域研究的热点。文章综述了NCC的制备方法,并对化学和机械法制备NCC纤维素作了重点介绍。同时对NCC的表面改性进行了综述。并对NCC在制备纳米复合材料领域的应用进行了总结,对其在增强复合材料中的应用作了较详细的介绍。最后对NCC未来的发展进行了展望。     

纳米微晶纤维素聚合物的研究现状及应用前景

纳米微晶纤维素(NCC)具有广泛的兼容性和独特的物理尺寸效应,通过硫酸化、氧化、阳离子化、接枝和甲硅烷基化等化学改性可获得NCC聚合物,并赋予其独特的光学性质、流变性能和机械性能。NCC及其复合材料可应用于生物医药、航天航空、军事、建筑、造纸等领域。文章综述了NCC聚合物的研究进展及应用前景。     

纳米纤维素的制备

纳米纤维素(NCC)由于其大量、可再生、可生物降解以及优良的力学性能,成为纳米技术领域研究的热点。文章综述了NCC的制备方法,对化学和机械法制备NCC纤维素做了重点介绍,同时,对NCC的表面改性进行了综述。并对NCC在制备纳米复合材料领域的应用进行了总结,对其在增强复合材料中的应用做了较详细的介绍。最后对NCC未来的发展进行了展望。     

纳米纤维素晶须的表面醋酸酯化改性及复合材料的力学性能

采用硫酸水解法制备纳米纤维素晶须, 再以冰醋酸为分散介质, 浓硫酸为催化剂, 醋酸酐为酯化剂对纳米纤维素晶须进行不同程度醋酸酯化改性, 得到醋酸酯化的纳米纤维素. 采用红外光谱(FTIR)、 X射线光衍射(XRD)、 透射电子显微镜(TEM)和X射线光电子能谱(XPS)等手段对改性产物进行分析和表征. 结果表明, 改性纳米纤维素晶须中醋酸酯基的平均取代度过小或过大时均不适宜用作复合材料的增强相. 当改性纳米纤维素晶须中醋酸酯基的平均取代度为0.05时, 醋酸酯化反应只发生在纳米纤维素晶须的表面. 此时, 晶须能在丙酮中稳定悬浮, 表现出流动双折射现象, 并保持了改性前纳米纤维素晶须的棒状形态和高结晶度. 将这种改性后的纳米纤维素晶须作为增强相与醋酸纤维素通过溶液浇铸法制成纳米复合膜, 结果显示, 与空白醋酸纤维素膜相比, 添加改性纳米纤维素晶须后, 纳米复合膜的拉伸强度、 杨氏模量和断裂伸长率都得到了提高. 在玻璃化转变区间纳米复合膜储能模量的降低幅度小于空白膜.     

纳米纤维素晶须的表面改性及其在环氧树脂中的应用

以棉纤维素为原料,采用硫酸水解法制备了纳米纤维素晶须.以N,N-二甲基甲酰胺(DMF)为分散介质,二甲基氨基吡啶(DMAP)为催化剂,十二烯基琥珀酸酐为酯化剂对纳米纤维素晶须进行化学改性,得到了一系列取代程度不同的改性产物(记为DCNW).采用红外光谱(FTIR)、X射线衍射(XRD)、透射电子显微镜(TEM)和X射线光电子能谱(XPS)等手段对DCNW的结构和性能进行了分析和表征.选择表面取代度为0.3的改性产物作为复合材料的增强相.该改性产物能在丙酮中均匀分散和稳定悬浮,并且保持了改性前纳米纤维素晶须的棒状形态和高结晶度.将其分散于环氧单体中,通过浇铸法制备了纳米复合材料,考察了改性纳米纤维素晶须添加量对纳米复合材料拉伸性能、动态力学性能及耐湿热性的影响规律.结果表明,与空白环氧树脂相比,添加了改性纳米纤维素晶须的纳米复合材料的拉伸强度、杨氏模量和断裂伸长率都得到了提高.玻璃化转变温度、耐湿热性也得到了显著改善.其中,当改性纳米纤维素晶须的添加量为3.5%时,拉伸强度从纯环氧的39.85 MPa提高到72.33 MPa,增加了82%;杨氏模量增大了21%;断裂伸长率从纯环氧树脂的2.45%提高到7.29%,增加了198%;Tg值从纯环氧的103.4℃,提高到134.1℃;吸水率从1.9%下降到1.4%.     

纳米微晶纤维素对炭黑补强天然橡胶力学性能和动态性能的影响

采用酸水解工业微晶纤维素(MCC)制备纳米微晶纤维素(NCC),将其与天然胶乳共凝沉,混炼时加入炭黑(CB),制备了天然橡胶(NR)/NCC/CB复合材料,研究了NR/NCC/CB和NR/NCC/CB/RH(间苯二酚-六亚甲基四胺络合物)复合材料的力学性能和动态性能,并与NR/CB体系的性能进行对比.结果表明NCC可以均匀分散在天然橡胶基体中,且依拉伸方向取向,随着NCC替代炭黑的份数增加,Payne效应减弱,说明NCC本身并不构成强的填料网络,NR/NCC/CB与NR/CB比较,前者整体的网络化程度减弱,体系的损耗因子变化不大,NCC的加入改善了NR/CB的力学性能和抗屈挠龟裂性能,降低压缩疲劳温升和压缩永久形变,当NCC取代5～20 phr CB后,仍然保持高耐磨炭黑补强天然橡胶的耐磨耗性能.动态力学性能显示NR/NCC/CB的玻璃化转变温度较NR/CB变化不大,0℃的tanδ略有下降的同时60℃的tanδ明显降低.NR/NCC/CB/RH体系的Payne效应较NR/NCC/CB明显减弱,力学性能、抗屈挠龟裂性能和耐磨耗性能进一步改善,体系的压缩疲劳温升和压缩永久形变更小.     

纳米/微米碳酸钙的结构表征和热分解行为

采用棕榈酸对纳米碳酸钙进行有机表面改性, 运用SEM﹑TEM、XRD、FTIR 及TG-DTG 对表面改性前后的纳米碳酸钙进行表征, 并与微米碳酸钙的微晶结构及热分解特性进行比较. FTIR 分析结果确证了棕榈酸与纳米碳酸钙表面是以化学键合和物理吸附方式相结合, 粒子表面存在羧基等有机官能团的红外吸收特征. 对比研究发现, 碳酸钙微晶纳米化后, 其红外V3特征吸收峰出现约35 cm-1 的蓝移现象, 并且明显窄化. 初步解释了纳米碳酸钙红外吸收峰蓝移的原因, 认为尺寸效应和晶体场效应是影响纳米碳酸钙红外光谱特征的主要因素. 微晶结构的变化使得纳米碳酸钙的热分解反应表现出反常特性, 热分解温度较微米碳酸钙下降了40.6 ℃.     

硫酸钡微晶改性毛细管柱的制备及其分离性能的研究（Ⅰ）

本文提出利用硫酸钡微晶对玻璃毛细管内表面进行改性,成功地将中、强极性固定液涂溃在这种改性表面上,制备出高效毛细管色谱柱。文中较详细地给出了硫酸钡微晶的制备方法以及微晶层的沉积方法,并对这种毛细管色谱柱的性能进行了考察。     

纳晶纤维素的功能化及应用

纳晶纤维素(NCC)是一种由价廉的可再生原料制备得到的棒状纳米材料。NCC表面存在的羟基使其可直接进行化学修饰,也可作为生物模板组装负载无机纳米粒子,这赋予了NCC更多的功能。本文对NCC表面组装负载无机纳米粒子的研究进行了重点归纳。NCC具有独特的尺寸结构,优异的强度性质和物理化学性质,毒性较低,没有明显的环境问题,在众多领域有重要的应用价值。本文全面阐述了NCC在复合增强、绿色催化、光电材料、酶固定化、抗菌和医用材料、生物传感器、荧光探针和药物释放等方面的应用,并对其稳定性、相容性和毒性等实际应用性能进行了相应的探讨。     

丁二酸酐接枝纳米纤维素负载木犀草素及其苷（英文）

将纳米纤维素(NCC)表面接枝丁二酸酐得到丁二酸酐化纳米纤维素(NCSA),再将阳离子表面活性剂十六烷基三甲基溴化铵(CTAB)负载到NCSA,得到一种新的纳米药物载体(CTAB@NCSA).考察了NCSA的物理化学性能,包括扫描、透射电镜,红外光谱,X射线粉末衍射及电位测定;同时研究了NCSA对CTAB的吸附行为.最后以CTAB@NCSA为药物载体,以LUT和LUS为模型药物,通过分子间作用力及疏水作用力得到负载LUT和LUS的纳米复合物微球CTAB@NCSA@LUT和CTAB@NCSA@LUS,并对其体外释药进行了研究.     

酸碱处理后纳米微晶纤维素的热行为分析

Nanocrystalline cellulose (NCC) was prepared from microcrystalline cellulose (MCC) by acid hydrolysis. It was observed that the diameter of NCC particles mainly distributed over 30-50nm by transmission electron microscope (TEM) . The crystal form and degree of crystallinity were detected by X-Ray diffraction. The results showed that NCC and MCC have the same crystal form of cellulose I, and that the reactions mainly occurred in the amorphous region of MCC during the acid hydrolysis process. The thermal behavior of NCC in different pH conditions was characterized by differential scanning calorimetry (DSC) . The consequences indicate that the thermal stability of NCC distinctly decreased by contrast with the thermal stability of MCC, and that the thermal stability of NCCs in alkali conditions was higher than that of NCCs in acid conditions. The specific surface area distinctly increased with sharp decreasing of the particle size of NCC. This induced the end carbons and active groups of surface of NCC to increase sharply, therefore caused the thermal stability of NCC to distinctly abate. That NCC has very strong adsorption affinity is the cause of the obvious difference of thermal behavior of NCC in different pH. In acid conditions the surface of NCC adsorbed a great lot of H^ , which induced the cellulose chains of surface of NCC to decompose at low temperature catalyzed by H^ . When adding sodium hydroxide solution, on one hand the H^ of surface of NCC was neutralized; on the other hand, the cellulose chains of low molecular weight were dissolved in sodium hydroxide solution and the defects of surface of NCC rearranged and stable structure formed. These factors improved the thermal stability of NCC in alkali conditions.     

Antibacterial membranes based on chitosan and quaternary ammonium salts modified nanocrystalline cellulose

Etherification of nanocrystalline cellulose (NCC) with three kinds of quaternary ammonium salts epoxypropyltrimethylammonium chloride, N,N‐dimethyl‐N‐dodecyl‐N‐(1,2‐epoxypropyl) ammonium chloride (DMDEPAC), and N,N‐dimethyl‐N‐octadecyl‐N‐(1,2‐epoxypropyl) ammonium chloride (DMOEPAC) was successfully performed via a nucleophilic addition reaction. The synthesized DMDEPAC and DMOEPAC were characterized by nuclear magnetic resonance. The modified NCC particles, NCC epoxypropyltrimethylammonium chloride, NCC‐DMDEPAC, and NCC‐DMOEPAC, were characterized by energy dispersive spectrometer. Nanocomposite films based on chitosan (CS) containing quaternary ammonium salts modified NCC were prepared with nanoparticle loadings of 5.0, 7.5, and 10.0%, respectively. The effect of nanoparticle content on the tensile strength of composite films was studied. The results indicated that the films with 5.0% nanoparticle loading exhibited the biggest increase in tensile strength. Surface morphology, smoothness, and antibacterial properties of composite films containing 5% modified NCC were also studied. CS/NCC‐DMDEPAC‐5.0 and CS/NCC‐DMOEPAC‐5.0 displayed excellent biocidal abilities against both Gram‐positive Staphylococcus aureus (ATCC 6538) and Gram‐negative Escherichia coli O157:H7 (ATCC 43895). The bio‐based nanocomposite films with increased mechanical strength and excellent antibacterial properties show great potential as food packaging materials. Copyright © 2017 John Wiley & Sons, Ltd.     

Optical and mechanical properties of polyurethane/surface-modified nanocrystalline cellulose composites

in order to improve the optical and mechanical performances of waterborne polyurethane （WPU）, nanocrystalline cellulose （NCC）/WPU composites were synthesized in this study. NCC （prepared by acid hydrolysis of cotton fiber） was modified by （3-aminopropyl）triethoxysilane （APTES） to enhance its compatibility with WPU, and the surface-modified NCC was characterized by grafting ratio, crystallinity and contact angle （CA）. NCC/WPU composites were examined by scanning electron microscopy （SEM）, X-ray powder diffraction （XRD） and thermogravimetric analysis （TG）. The anti-yellowing property, specular gloss, pencil hardness, and abrasion resistance of NCC/WPU composites were investigated by the methods of Chinese National Standards GB/T 23999-2009, GB/T 9754-2007, GB/T 6739-2006 and GB/T 1768-2006, respectively. The results showed that the grafting ratio of NCC modified by 6% APTES was 36.01% and the crystallinity of modified NCC was decreased with the enhancement of APTES. CA of the modified NCC was decreased by 28.8% and the nanoparticles were homogeneously dispersed in the WPU matrix. The XRD patterns of the NCC/WPU composites were relatively steady, while the thermal stability of the composites was enhanced by 6.7% with 1.0 wt% modified NCC. Modified NCC affected the specular gloss of NCC/WPU composites more obviously than the anti-yellowing property. The pencil hardness of NCC/WPU composites was increased from 2H to 4H by addition of NCC and the abrasion resistance of the composites was enhanced significantly. In general, NCC/WPU composites showed significant improvements in the optical and mechanical performances.     

表面亲水性粒度单分散交联PMMA树脂的合成及表征

用种子溶胀聚合方法 ,合成出了粒度单分散的交联聚甲基丙烯酸甲酯微球 .将微球通过水解 ,使其转化为表面带羧基的树脂 .分别用多糖化合物Dextran和DEAE Dextran对水解树脂表面进行包覆涂层 ,然后用n 丁二醇双环氧丙醚分别进行交联 ,制备出两种表面带高交联多糖覆盖层的树脂 .以两种改性树脂为填料 ,以人血清蛋白为试样 ,用HPLC方法对树脂的亲水性能进行了表征 .研究表明 ,两种改性树脂均有很好的亲水性 ,蛋白质的回收率分别在 97%和 99%以上 ,并有良好的机械强度和化学稳定性     

聚乙二醇和叶酸对层状双金属氢氧化物颗粒的表面修饰

以具有伪装隐形作用的聚乙二醇(PEG)和具有靶向作用的叶酸(FA)为修饰剂, 以氨丙基三甲氧基硅烷(APTMS)为连接剂, 对Mg₃Al-NO₃层状双金属氢氧化物(LDH)进行了表面修饰, 制备了LDH-PEG-FA纳米颗粒, 并通过X射线衍射(XRD)、 透射电子显微镜(TEM)、 紫外-可见光谱(UV-Vis)、 傅里叶变换红外光谱(FTIR)、 粒度分布分析和元素分析等技术对其结构进行了表征. 结果表明, PEG和FA的修饰量可由其原料配比调控, 修饰后的产物具有良好的水再分散性, 这主要源于修饰层的空间位阻效应. 预期LDH-PEG-FA同时具有伪装隐形性和靶向性, 可用于药物载体等领域.     

PREPARATION AND STRUCTURE OFFIVE DERIVATIVES OFβ-(1→3)-D-GLUCAN ISOLATED FROM PORIA COCOS SCLEROTIUM*

A new solvent of cellulose (1.5 mol/L NaOH/0.5 mol/L urea aqueous solution) was used as one of the homogeneous reaction media of polysaccharides for methylation, hydroxyethylation and hydroxypropylation. A water insoluble β-(1→3)-D-glucan, sample PCS3-Ⅱ, isolated from fresh sclerotium of Poria cocos was sulfated in dimethyl sulfoxide (Me2SO), carboxymethylated in NaOH, isopropanol solution, as well as methylated, hydroxyethylated and hydroxypropylated in the new solvent system, respectively, to obtain five water-soluble derivatives coded as S-PCS3-Ⅱ, C-PCS3-Ⅱ, M-PCS3-Ⅱ, HE-PCS3-Ⅱand HP-PCS3-Ⅱ. Their chemical structure and distribution of substitution were characterized by infrared spectroscopy (IR), elementary analysis (EA), ^1H-NMR, ^13C-NMR, 2D-COSY, 2D-TOCSY and 2D-^1H-detected ^1H ^13C HMQC spectra. The results reveal that the relative reactivity of hydroxyl groups of the β(1→3)-D-glucan is in the order C-6 ＞ C-4 ＞ C-2 on the whole. The substitution of the samples S-PCS3-Ⅱ, C-PCS3-Ⅱ and M-PCS3-Ⅱ occurred mainly at C-6 position and secondly at C-4 and C-2 positions, and that of HE-PCS3-Ⅱ occurred at C-6 and C-4 positions and of HP-PCS3-Ⅱ almost completely occurred at C-6 position. The degrees of substitution (DS) obtained from ^13C-NMR range from 0.23 to 1.27. The water solubility of the derivatives is in the order S-PCS3-Ⅱ ＞ C-PCS3-Ⅱ ＞ M-PCS3-Ⅱ ＞ HE-PCS3-Ⅱ ＞ HP-PCS3-Ⅱ. This work provides a novel and nonpolluting process for the methylation, hydroxyethylation and hydroxypropylation of β-(1→3)-D-glucan.     

Click-chemistry for surface modification of monodisperse-macroporous particles

In this study, click chemistry was proposed as a tool for tuning the surface hydrophilicity of monodisperse-macroporous particles in micron-size range. The monodisperse-porous particles carrying hydrophobic or hydrophilic molecular brushes on their surfaces were obtained by the proposed modification. Hydrophilic poly(glycidyl methacrylate-co-ethylene dimethacrylate), poly(GMA-co-EDM) particles were hydrophobized by the covalent attachment of poly(octadecyl acrylate-co-propargyl acrylate), poly(ODA-co-PA) copolymer onto the particle surface via triazole formation by click chemistry. In the second part, Hydrophobic poly(4-chloromethylstyrene-co-divinylbenzene), poly(CMS-co-DVB) particles were hydrophilized by the covalent attachment of poly(vinyl alcohol), PVA onto their surface also via triazole formation by click chemistry. The presence of PVA and poly(ODA-co-PA) copolymer on the corresponding particles was shown by FTIR-DRS. After click-coupling reactions applied for both hydrophobic poly(CMS-co-DVB) and hydrophilic poly(GMA-co-EDM) particles, the marked changes in surface polarity were shown by contact angle measurements. Protein adsorption characteristics of plain and modified particles were investigated for both materials. In the isoelectric point of albumin, the non-specific albumin adsorption decreased from 225 to 80 mg/g by grafting PVA onto the poly(CMS-co-DVB) beads. On the other hand, the non-specific albumin adsorption onto the plain poly(GMA-co-EDM) beads increased from 50 to 400 mg/g by the covalent attachment of poly(ODA-co-PA) copolymer onto the bead-surface via click chemistry. The protein adsorption behavior was efficiently regulated by the covalent attachment of appropriate molecular brushes onto the surfaces of selected particles. The results indicated that "click chemistry" was an efficient tool for controlling the polarity of monodisperse-macroporous particles.     

高分散性SiO2/PMMA复合材料的制备与表征——纳米SiO2在MMA中的分散

用硅烷偶联剂3-(甲基丙烯酰氧)丙基三甲氧基硅烷(MPS)对分散于乙醇中的纳米SiO2进行偶联改性,再通过介质置换和原位本体聚合制得SiO2/甲基丙烯酸甲酯(MMA)单体分散液和SiO2/PMMA复合材料.红外光谱分析(FTIR)和热重分析(TG)结合洗提实验考察了SiO2表面MPS的偶联率和偶联效率,透射电镜(TEM...     

Unique viscoelastic behaviors of colloidal nanocrystalline cellulose aqueous suspensions

Unique rheological and phase behaviors of rod-like nanocrystalline cellulose (NCC) suspensions in aqueous media are revealed in the present article. Specifically, the NCC aqueous suspension remained isotropic in a wide NCC concentration range in which the suspension underwent transition from dilute solution to gel, and the relative viscosity of the NCC suspension could be well fitted by the Sato-Teramoto theory in the full concentration range tested. Correspondingly, both zero-shear viscosity and complex viscosity increased monotonically with NCC concentration, and no maximum value was observed along the curves of zero-shear viscosity or complex viscosity versus NCC concentration, indicating a deviation from the lyotropic system. However, a shear-induced birefringence phenomenon was observed, indicating the NCC suspension formed a temporary ordered structure in the external force field but was unable to form an anisotropic (liquid crystalline) phase. The Cox-Merz rule was not applicable for the NCC suspension as a result of oriented domains, i.e., rod-like NCC particles. Moreover, time-concentration superposition was successfully applied to both the storage and loss modulus, attributed to the isotropic feature of the NCC suspension in the tested concentration range. The reason why this NCC suspension remained isotropic could be because of the strong electrostatic repulsions between NCC particles and the weak tendency or driving force of anisotropy formation as a result of the small aspect ratio of NCC particles, Na⁺ counterions and large amounts of negative charges along the NCC particles. The results suggested that not all the rod-like particles were able to form an anisotropic phase in aqueous suspension, but dominated by various factors.     

Dispersions of nanocrystalline cellulose in aqueous polymer solutions: structure formation of colloidal rods

The steady-state shear and linear viscoelastic deformations of semidilute suspensions of rod-shaped nanocrystalline cellulose (NCC) particles in 1.0% hydroxyethyl cellulose and carboxymethyl cellulose solutions were investigated. Addition of NCC at the onset of semidilute suspension concentration significantly altered the rheological and linear viscoelastic properties of semidilute polymer solutions. The low-shear viscosity values of polymers solutions were increased 20-490 times (depending on polymer molecular weight and functional groups) by the presence of NCC. NCC suspensions in polymer solutions exhibited yield stresses up to 7.12 Pa. Viscoelasticity measurements also showed that NCC suspended polymer solutions had higher linear elastic moduli than the loss moduli. All of those results revealed the gel formation of NCC particles and presence of internal structures. The formation of a weak gel structure was due to the nonadsorbing macromolecules which caused the depletion-induced interaction among NCC particles. A simple interaction energy model was used to show successfully the flocculation of NCC particles in the presence of nonadsorbing polymers. The model is based on the incorporation of the depletion interaction term between two parallel plates into the DLVO theory for cubic prismatic rod shaped NCC particles.