纤维素-[Amim]Cl浓溶液的稳态流变规律

对纤维素-氯代1-烯丙基-3-甲基咪唑([Amim]Cl)浓溶液在不同温度下的稳态流变规律进行了研究。测试结果显示:纤维素-[Amim]Cl浓溶液属于假塑性流体。运用Cross和Carreau两种黏度模型对实验数据进行拟合,得到了表观黏度的主曲线,通过Arrhenius方程确定了移位活化能(ΔEa)为91.86~164.97 kJ/mol。与纤维素-氯代1-丁基-3-甲基咪唑([Bmim]Cl)溶液、纤维素-N-甲基吗啉-N-氧化物(NMMO)溶液、熔融聚合物(如聚丙烯、聚乙烯等)的活化能以及流变规律进行了对比。结果表明,纤维素-[Amim]Cl浓溶液的ΔEa较高,温度对体系黏度影响较大。     

壳聚糖在4种咪唑型离子液体中溶解性的研究

研究、比较了壳聚糖在4种咪唑型离子液体氯化1-丁基-3-甲基咪唑([BMIM]Cl)、1-丁基-3-甲基咪唑醋酸盐([ BMIM] Ac)、1-乙基-3-甲基咪唑醋酸盐([EMIM] Ac)和氯化1-烯丙基-3-甲基咪唑([AMIM] Cl)中的溶解性,提出了可能的溶解机理,并利用红外光谱(FTIR)、热重分析(TGA...     

纤维素-三(4-甲基苯甲酸酯)手性固定相的制备及对映异构体拆分

以微晶纤维素和对甲基苯甲酰氯为原料,合成了纤维素-三(4-甲基苯甲酸酯),并以3-氨丙基-三乙氧基硅烷修饰的硅胶为载体,制备了涂敷型纤维素-三(4-甲基苯甲酸酯)液相色谱固定相,对该固定相进行了表征,并在正相条件下对13种对映异构体进行了拆分,其中9种得到了分离,该柱表现出良好的手性分离性能.     

293.15K时咪唑醋酸盐-乙醇二元体系的体积性质及分子间相互作用

用比重瓶法测定了293.15 K时1-甲基咪唑醋酸盐([Mim]Ac)/1,3-二甲基咪唑醋酸盐([Mmim]Ac)/1-乙基-3-甲基咪唑醋酸盐([Emim]Ac)-乙醇(EtOH)二元体系在全组成范围内的密度.计算出[Mim]Ac/[Mmim]Ac/[Emim]Ac和EtOH的表观摩尔体积和体系的超额摩尔体积.用三参数多项式关联拟合了表观摩尔体积与摩尔分数的关系,外推出组分的极限偏摩尔体积和摩尔体积.[Mim]Ac/[Mmim]Ac/[Emim]Ac和EtOH的摩尔体积的外推值与实验值分别在±0.07和±0.04 cm3/mol范围内相一致.计算出了[Mim]Ac/[Mmim]Ac/[Emim]Ac和EtOH分别在无限稀溶液中的溶剂化系数.用Redlich-Kister方程关联拟合了超额摩尔体积与摩尔分数的关系.分别根据极限偏摩尔体积、摩尔体积与极限偏摩尔体积的差值、溶剂化系数和超额摩尔体积对照讨论了分子间相互作用的强弱.结果显示,在[Mim]Ac/[Mmim]Ac/[Emim]Ac的浓度无限稀溶液中,[Mim]Ac/[Mmim]Ac/[Emim]Ac-EtOH分子对间相互作用的强弱顺序为[Mim]Ac-EtOH[Mmim]Ac-EtOH[Emim]Ac-EtOH;在EtOH的浓度无限稀溶液中,以及体系中[Mim]Ac/[Mmim]Ac/[Emim]Ac的摩尔分数在0.15~0.95间时,[Mim]Ac/[Mmim]Ac/[Emim]Ac-EtOH分子对间相互作用的强弱顺序都为[Emim]Ac-EtOH[Mmim]Ac-EtOH[Mim]Ac-EtOH.     

键合纤维素(4-甲基苯甲酸酯)手性固定相的制备及其手性拆分

采用包夹聚合法,将硅小球同硅烷化试剂反应制得乙烯基硅胶,然后将该乙烯基硅胶同经十一烯酰氯、4-甲基苯甲酰氯衍生的纤维素共聚,制备出含不同官能团的聚合物包夹硅基的键合型纤维素(4-甲基苯甲酸酯)类手性固定相。分别以正己烷异丙醇、正己烷四氢呋喃为流动相,对此键合型手性固定相的手性识别能力进行了评价。为了与同类型的涂敷型纤维素(4-甲基苯甲酸酯)手性固定相作比较,合成了涂敷型纤维素(4-甲基苯甲酸酯)手性固定相。结果表明,键合型纤维素(4-甲基苯甲酸酯)手性固定相具有一定的手性识别能力,可以拆分所研究的6种手性化合物中的4种。     

纤维素丙酸酯-g-二乙二醇正十六烷基醚固-固相变材料的制备及性能

以二月桂酸二丁基锡(DBTDL)为催化剂,微晶纤维素为骨架材料,二乙二醇正十六烷基醚(E2C16)为相变材料,采用化学接枝法制备了系列纤维素丙酸酯-g-二乙二醇正十六烷基醚(CP-g-E2C16)固-固相变材料.利用傅里叶变换红外光谱(FTIR)、核磁共振氢谱(1H NMR)、差示扫描量热仪(DSC)、热重分析(TG)和X射线衍射(XRD)对CP-g-E2C16相变材料的结构和热性能进行了表征.结果表明,得到了E2C16的取代度和接枝含量分别为0.12~0.37和17.1%~33.4%的CP-g-E2C16固-固相变材料.CP-g-E2C16接枝共聚物的相变温度和相变焓分别为25~34℃和40~62 J/g,符合人的体感舒适温度范围.CP-g-E2C16固-固相变材料的耐热温度高于237℃,与E2C16相比提高21~40℃,有望应用于熔融纺丝法制备纤维素基储热调温纤维领域.     

咪唑类高铼酸盐催化微晶纤维素降解反应研究

以咪唑类高铼酸盐为催化剂,以离子液体1-烯丙基-3-甲基咪唑氯盐([Amim]Cl)为溶剂降解微晶纤维素(MCC)。分别考察反应温度、反应时间、反应物浓度、催化剂用量和结构对纤维素降解反应的影响。结果表明,以5%1-(3-磺酸)丙基-3-甲基咪唑高铼酸盐([mim-(CH_2)_3SO_3H]ReO_4)为催化剂,在微波辅助加热条件下,0.1 g纤维素在2.0 g离子液体[Amim]Cl中于160℃降解30 min,还原糖收率(TRS)和葡萄糖收率最高可达89.6%和46.7%。研究还对咪唑类高铼酸催化纤维素降解反应的催化机理进行讨论,认为催化剂芳环阳离子、ReO-4中Re=O与纤维素分子中羟基的相互作用是促进纤维素降解的关键     

293.15K时咪唑醋酸盐-乙醇二元体系的体积性质及分子间相互作用简

用比重瓶法测定了293.15 K时1-甲基咪唑醋酸盐([Mim]Ac)/1,3-二甲基咪唑醋酸盐([Mmim]Ac)/1-乙基-3-甲基咪唑醋酸盐([Emim]Ac)-乙醇(EtOH)二元体系在全组成范围内的密度. 计算出[Mim]Ac/[Mmim]Ac/[Emim]Ac和EtOH的表观摩尔体积和体系的超额摩尔体积. 用三参数多项式关联拟合了表观摩尔体积与摩尔分数的关系,外推出组分的极限偏摩尔体积和摩尔体积. [Mim]Ac/[Mmim]Ac/[Emim]Ac和EtOH的摩尔体积的外推值与实验值分别在±0.07和±0.04 cm3/mol范围内相一致. 计算出了[Mim]Ac/[Mmim]Ac/[Emim]Ac和EtOH分别在无限稀溶液中的溶剂化系数. 用Redlich-Kister 方程关联拟合了超额摩尔体积与摩尔分数的关系. 分别根据极限偏摩尔体积、摩尔体积与极限偏摩尔体积的差值、溶剂化系数和超额摩尔体积对照讨论了分子间相互作用的强弱. 结果显示,在[Mim]Ac/[Mmim]Ac/[Emim]Ac的浓度无限稀溶液中,[Mim]Ac/[Mmim]Ac/[Emim]Ac-EtOH分子对间相互作用的强弱顺序为[Mim]Ac-EtOH>[Mmim]Ac-EtOH >[Emim]Ac-EtOH;在EtOH的浓度无限稀溶液中,以及体系中[Mim]Ac/[Mmim]Ac/[Emim]Ac的摩尔分数在0.15～0.95间时,[Mim]Ac/[Mmim]Ac/[Emim]Ac-EtOH分子对间相互作用的强弱顺序都为[Emim]Ac-EtOH>[Mmim]Ac-EtOH>[Mim]Ac-EtOH.     

催化剂用量对醋酸纤维素接枝聚乙二醇单甲醚相变材料接枝率和性能的影响

以二月桂酸二丁基锡(DBTDL)作为催化剂,以醋酸纤维素(CDA)为基体材料、以聚乙二醇单甲醚(MPEG)为工作物质,利用溶液聚合法合成了纤维素接枝聚乙二醇单甲醚相变材料,研究了催化剂用量对MPEG接枝产物接枝率和性能的影响.结果表明,当催化剂用量为0.15%(质量分数,下同)时,MPEG1000和MPEG1500接枝产物的接枝率均达到最大值,分别为224.03%和189.30%;当催化剂用量为0.1%时,MPEG2000接枝产物的接枝率最大,达129.99%.此外,由不同分子量MPEG制备的接枝产物的相变温度和相变焓不同,不同产物在升温过程中均呈现较好的固-固相变调温性能.     

壳聚糖苯甲酰化衍生物固定相的制备及其手性识别

为制备新型手性分离材料,用含不同取代基的苯甲酰氯修饰壳聚糖,合成了壳聚糖-二(4-甲基苯甲酸酯)-(4-甲基苯甲酰胺)、壳聚糖-二(苯甲酸酯)-(苯甲酰胺)、壳聚糖-二(3,5-二甲基苯甲酸酯)-(3,5-二甲基苯甲酰胺)和壳聚糖-二(4-氯苯甲酸酯)-(4-氯苯甲酰胺)4种新的衍生物,以N,N-二甲基甲酰胺为溶剂,将壳聚糖衍生物涂敷于大孔的3-氨丙基硅胶上,制得相应的手性固定相.测试了固定相的手性识别性能,结果表明这些固定相均有较好的对映体选择性.涂覆量为16%的固定相比涂覆量为20%的固定相有更好的手性分离性能,以壳聚糖-二(3,5-二甲基苯基甲酸酯)-(3,5-二甲基苯基甲酰胺)制备的固定相有最强的手性识别性能,以壳聚糖-二(4-甲基苯甲酸酯)-(4-甲基苯甲酰胺)制备的固定相对手性化合物有最大的分离度.     

Effects of Cationic Structure on Cellulose Dissolution in Ionic Liquids: A Molecular Dynamics Study

In recent years, great progress has been made in the dissolution of cellulose with ionic liquids (ILs). However, the mechanism of cellulose dissolution, especially the role the IL cation played in the dissolution process, has not been clearly understood. Herein, the mixtures of cellulose with a series of imidazolium‐based chloride ionic liquids and 1‐butyl‐3‐methyl pyridinium chloride ([C₄mpy]Cl) were simulated to study the effect that varying the heterocyclic structure and alkyl chain length of the IL cation has on the dissolution of cellulose. It was shown that the dissolution of cellulose in [C₄mpy]Cl is better than that in [C₄mim]Cl. For imidazolium‐based ILs, the shorter the alkyl chain is, the higher the solubility will be. In addition, an all‐atom force field for 1‐allyl‐3‐methyl imidazolium cation ([Amim]⁺) was developed, for the first time, to investigate the effect the electron‐withdrawing group within the alkyl chain of the IL cation has on the dissolution of cellulose. It was found that the interaction energy between [Amim]⁺ and cellulose was greater than that between [C₃mim]⁺ and cellulose, indicating that the presence of electron‐withdrawing group in alkyl chain of the cation enhanced the interaction between the cation and cellulose due to the increase of electronegativity of the cations. These findings are used to assess the cationic effect on the dissolution of cellulose in ILs. They are also expected to be important for rational design of novel ILs for efficient dissolution of cellulose.     

致孔剂聚乙二醇对纤维素中空纤维膜结构与性能的影响

以离子液体氯代1-烯丙基-3-甲基咪唑（[AMI M]Cl）为溶剂纺制纤维素中空纤维膜,考察了聚乙二醇（PEG）分子量及其质量分数对中空纤维膜结构与性能的影响。采用场发射扫描电子显微镜（FESEM）对膜内、外表面形态结构进行了观察,测试了中空纤维膜的水通量、截留率等渗透性能以及最大拉伸强度、断裂伸长率等力学性能。结果表...     

Separation of ternary systems of hydrophilic ionic liquid with miscible organic compounds by RPLC with refractive index detection

A rapid and simple analytical method was developed for the simultaneous and quantitative determination and separation of hydrophilic imidazolium ionic liquids (ILs) (1-butyl-3-methylimidazolium chloride, [C(4)mim]Cl; 1-hexyl-3-methylimidazolium chloride, [C(6)mim]Cl; 1-octyl-3-methylimidazolium chloride, [C(8)mim]Cl; 1-allyl-3-methylimidazolium chloride, [Amim]Cl; or 1-allyl-3-methylimidazolium bromide, [Amim]Br) with miscible ethyl acetate and EtOH and their mixtures using reverse phase liquid chromatography coupled with refractive index detection (RPLC-RI). The influence of 60 to 100% (volume percentage) methanol in the mobile phase on the IL systems ([C(4)mim]Cl, [C(6)mim]Cl, [C(8)mim]Cl, [Amim]Br, or [Amim]Cl)-ethyl acetate-EtOH was investigated. The optimum mobile phase for the system [C(8)mim]Cl-ethyl acetate-EtOH, [C(4)mim]Cl-ethyl acetate-EtOH, [Amim]Br-ethyl acetate-EtOH and [Amim]Cl-ethyl acetate-EtOH was methanol/water (60:40, v/v), and methanol/water (70:30, v/v) for [C(6)mim]Cl-ethyl acetate-EtOH. Under optimum mobile phase conditions for each system, the RSD of the retention time ranged from 0.02 to 0.04%, and the RSDs of the peak area percent ranged from 0.23 to 1.85%, which showed good reproducibility of the RPLC-RI method. The RPLC-RI method can determine IL, ethyl acetate, and EtOH simultaneously in 5 min, and the analytes, especially IL, can be eluted completely. The results show that the RPLC-RI method can be used to separate and determine ILs in mixtures with organic compounds simultaneously and quantitatively.     

纤维素在离子液体[AMMor]Cl/[AMIm]Cl混合溶剂中的均相乙酰化反应研究

利用混配离子液体N-烯丙基-N-甲基吗啉氯盐(N-allyl-N-methylmorpholinium chloride,[AMMor]Cl)和1-烯丙基-3-甲基咪唑氯盐(1-allyl-3-methylimidazolium chloride,[AMIm]Cl)作为溶剂,乙酰氯为乙酰化试剂,研究了在没有催化剂条件下的纤维素的均相乙酰化反应.生成的醋酸纤维素(CA)的取代度由2.58到3.00.用FT-IR,1HNMR和13CNMR进行表征.结果表明,[AMMor]Cl/[AMIm]Cl混配的离子液体是一种良好的均相乙酰化介质,纤维素C-6,C-3和C-2三个位置上的羟基均发生了乙酰化反应,且得到纯的纤维素醋酸酯.此反应方便可控,简单高效,不仅降低了成本,离子液体比较容易回收,可以再次利用.     

Employment of [Amim] Cl in the effort to upgrade the properties of cellulose acetate based polymer electrolytes

Transparent thin film polymer electrolytes were prepared by solvent casting technique with the doping of environmental-friendly ionic liquid, 1-allyl-3-methylimidazolium chloride ([Amim] Cl) into the matrix formed by cellulose acetate (CA) and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI). The ionic conducting nature of this system improves significantly from the order of 10^?7–10^?2 S cm^?1 upon increasing doping of [Amim] Cl content till a maximum of 4.68 × 10^?2 S cm^?1 is attained for the composition CA:LiTFSI:[Amim] Cl (14:6:80 wt%). The improving trend in ionic conductivity results from the bond weakening between the connecting atoms in the crystalline region that induces to the increase in amorphous counterpart fractions in the CA matrix. This observation was proved via the accountancies in the reduction of relative viscosity, root mean square value and increase in void as increase in [Amim] Cl doping. The resultant phase conversion hence permits immense lithium ion (Li⁺) fluidity along the polymer backbone and assisting the improvement in ionic conductivity. The thin film polymer electrolyte is found to be elastic in the presence of crystalline fraction and radically deforms upon the chains diffusion into the amorphous fraction. The linear curvatures of the Arrhenius plot justify the conductivity improvement as via the increasing frequency of Li⁺ ions hopping as the temperature increases. The increasing addition of [Amim] Cl diminishes both the heat-resistivity and thermal stability of CA:LiTFSI:[Amim] Cl matrix.     

Theoretical study on cation-anion interaction and vibrational spectra of 1-allyl-3-methylimidazolium-based ionic liquids

In order to deepen the understanding of the cation-anion interaction in ionic liquids, the structures of cation, anions, and cation-anion ion-pairs of 1-allyl-3-methylimidazolium-based ionic liquids are optimized using density functional theory (DFT), and their most stable geometries are discussed. The structural parameters, hydrogen bonds and interaction energies of 1-allyl-3-methylimidazolium dicyanamide ([Amim]DCA), 1-allyl-3-methylimidazolium chloride ([Amim]Cl), 1-allyl-3-methylimidazolium formate ([Amim]FmO) and 1-allyl-3-methylimidazolium acetate ([Amim]AcO) ion pairs are studied. The vibrational frequencies of [Amim]DCA and [Amim]Cl have been calculated and scaled values have been compared with experimental FT-IR and FT-Raman spectra. The complete assignments were performed on the basis of the potential energy distribution (PED) of the vibrational modes.     

Studies on the thermal behavior of CS:LiTFSI:[Amim] Cl polymer electrolytes exerted by different [Amim] Cl content

The principle motivation of this research work is to develop environmental-friendly polymer electrolytes utilizing corn starch (CS), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) and 1-allyl-3-methylimidazolium chloride ([Amim] Cl) by solution casting technique. The highest ionic conductivity value was achieved for the composition CS:LiTFSI:[Amim] Cl (14 wt. %:6 wt. %:80 wt. %) which exhibits the ionic conductivity value of 5.68 × 10⁻² S cm⁻¹ at 40 °C with the activation energy of 4.86 kJ mol⁻¹. This sample possess high concentration of amorphous phase coupled with greater presence of conducting cations (lithium, Li⁺ and imidazolium, [Amim]⁺) as depicted by the dielectric loss tangent plot. The conductivity-temperature plots were found to obey Arrhenius rule in which the conductivity mechanism is thermally assisted. The melting temperature of polymer electrolyte decreases with increase in [Amim] Cl content. This is attributed to the good miscibility of [Amim] Cl in CS:LiTFSI matrix inducing structural disorderliness. Reference to the TGA results it is found that the addition of [Amim] Cl diminishes the heat-resistivity whereas enhancement in the thermal stability occurred at the initial addition and declines with further doping of [Amim] Cl.     

三种离子液体的合成及其对棉纤维素溶解性能的比较研究

合成了三种含有羧基或醚基的离子液体, 1-羧甲基-3-乙基咪唑氯化物([CmEIM]Cl)、1-甲氧乙基-3-乙基咪唑氯化物([C2OC1-EIM]Cl)和1-[2-(2-氯乙氧基)乙基]-3-乙基咪唑氯化物([Cl-C2OC2-EIM]Cl), 用FT-IR和1H NMR对它们的化学结构进行了表征. 测定并比较了这三种离子液体对棉纤维素的溶解能力, 并用FT-IR, SEM和XRD研究了溶解前和再生后纤维素的化学结构、形貌及晶体结构的变化. 结果表明, 在三种离子液体中, [C2OC1-EIM]Cl对棉纤维素的溶解性最好. 在溶解过程中, 随着温度的升高, 纤维素在离子液体中的溶解度增加, 但聚合度下降, 特别是在[Cl-C2OC2-EIM]Cl中溶解时, 纤维素的聚合度下降最严重. 研究结果表明, 含羧基的离子液体会由于分子间氢键的缔合作用降低其对纤维素的溶解性. 侧基较大的离子液体对纤维素的溶解性也较差.     

Binding cellulose and chitosan via click chemistry: Synthesis,characterization, and formation of some hollow tubes

A novel cellulose‐click‐chitosan polymer was prepared successfully in three steps: (1) propargyl cellulose with degrees of substitution (DS) from 0.25 to 1.24 was synthesized by etherification of bamboo Phyllostachys bambusoide cellulose with propargyl chloride in DMA/LiCl in the presence of NaH. The regioselectivity of propargylation on anhydrous glucose unit determined by GC‐MS was in the order of 2 >> 6 > 3; (2) the functional azide groups were introduced onto the chitosan chains by reacting chitosan with 4‐azidobenzoic acid in [Amim]Cl/DMF and the DS ranged from 0.02 to 0.46; (3) thus, the cellulose‐click‐chitosan polymer was obtained via click reaction, that is, the Cu(I)‐catalyzed Huisgen 1,3‐dipolar cycloaddition reaction, between the terminal alkyne groups of cellulose and the azide groups on the chitosan backbone at room temperature. The successful binding of cellulose and chitosan was confirmed and characterized by FTIR and CP/MAS ¹³C NMR spectroscopy. TGA analyses indicated that the cellulose‐click‐chitosan polymer had a higher thermal stability than that of cellulose and chitosan as well as cellulose–chitosan complex. More interestingly, some hollow tubes with near millimeter length were also observed by SEM. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012