Rheology of 1‐butyl‐3‐methylimidazolium chloride cellulose solutions. I. Shear rheology

In this article, shear rheology of solutions of different concentrations obtained by dissolution of cellulose in the ionic liquid (IL) solvent 1‐butyl‐3‐methylimidazolium chloride ([Bmim]Cl) was studied by measuring the complex viscosity and dynamic moduli at different temperatures. The obtained viscosity curves were compared with those of lyocell solutions and melt blowing grade polypropylene melts of different melt flow rates (MFR). Master curves were generated for complex viscosity and dynamic moduli by using Carreau and Cross viscosity models to fit experimental data. From the Arrhenius plots of the shift factors with respect to temperature, the activation energies for shear flow were determined. These varied between 18.99 and 24.09 kCal/mol, and were compared with values for lyocell solutions and different polymeric melts, such as polyolefins, polystyrene, and polycarbonate. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Rheology of 1‐butyl‐3‐methylimidazolium chloride cellulose solutions. III. Elongational rheology

The elongational rheology of solutions of cellulose in the ionic liquid solvent 1‐butyl‐3‐methylimidazolium chloride ([Bmim]Cl) was measured at 80, 90, and 100°C; 8, 10, and 12 wt% cellulose; Hencky strains 5, 6, 7; and strain rates from 1 to 100 s^?1. Master curves were generated by shifting the elongational viscosity curves with respect to temperature and Hencky strain. Also, general master curves were generated by simultaneously shifting with respect to both temperatures and Hencky strain. From the Arrhenius plots of the temperature shift factors, the activation energy for elongational flow was determined. The elongational rheology of these solutions was elongational strain rate thinning similar to that of their shear behavior and polymer melts and they were also strain hardening. Both effects and the viscosity increased with cellulose concentration. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

浆粕性质对纤维素/[Bmim]Cl纺丝原液性能的影响

选用棉浆和木浆3种纤维素浆粕为原料,以离子液体1-丁基-3-甲基咪唑氯盐([Bmim] Cl)为溶剂,探讨了浆粕的聚合度(DP)和α-纤维素含量对其在[Bmim] Cl中的溶解情况、纺丝液的流变行为及其纤维性能的影响.结果表明:浆粕的DP和α-纤维素含量越高,其在[Bmim] Cl中完全溶解所需时间就越长;相对于α-纤...     

Rheological properties of cotton pulp cellulose dissolved in 1‐butyl‐3‐methylimidazolium chloride solutions

Rheological properties of cotton pulp dissolved in 1‐butyl‐3‐methylimidazolium chloride ([Bmim]Cl) solutions were characterized using an advanced rheometer. The complex viscosity, dynamic modulus, and shear viscosity at different temperature were studied. In the steady shear measurements, all the solutions show a shear‐thinning behavior at high shear rates. The complex viscosity as a function of frequency was fitted by extended Carreau–Yasuda model. In all cotton pulp/[Bmim]Cl solutions, the complex dynamic viscosity (η*) and steady shear viscosity (η_a) followed the Cox–Merz rule only at lower frequency. The effects of tested temperature on viscosity and viscoelastic behavior of the solutions were also investigated. The value of activation energy for the dissolution of cotton pulp in ionic liquids was 65.28 kJ/mol at the concentration of 10 wt% and was comparable with the ones for the dissolution of cellulose in NMMO. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers     

Fabrication of cellulose membrane with “imprinted morphology” and low crystallinity from spherulitic [Bmim]Cl

In the present study, regenerated cellulose membrane with “imprinted morphology” and low crystallinity was fabricated from the crystal cellulose/[Bmim]Cl solution. Spherulites of 1‐butyl‐3‐methilimidazolium chloride ([Bmim]Cl) and cellulose/[Bmim]Cl solution were observed using polarized optical microscopy under certain condition. The fabricated cellulose membranes presented some particular characteristics compared with the membrane prepared from traditional cellulose/[Bmim]Cl solution. All the fabricated membranes were characterized by optical microscope, Wide‐angle X‐ray diffraction (WAXD), thermo‐gravimetric analysis, and mechanical testing. The images showed that the resulting membranes prepared from crystal cellulose/[Bmim]Cl solution were “imprinted” with patterns which originated from the crystalline structure of [Bmim]Cl. The results of WAXD showed that the obtained cellulose membrane exhibited low diffraction peaks and crystallinity of approximately 24.57%. Furthermore, the low crystallinity led to the low mechanical property (27.5 MPa), thermal stability (315.4 °C), and high moisture regain (9.5%). © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43798.     

Rheological characterization of concentrated cellulose solutions in 1‐allyl‐3‐methylimidazolium chloride

The rheological properties of high concentrated wood pulp cellulose 1‐allyl‐3‐methy‐limidazolium Chloride ([Amim]Cl) solutions were investigated by using steady shear and dynamic viscoelastic measurement in a large range of concentrations (10–25 wt %). The measurement reveals that cellulose may slightly degrade at 110°C in [Amim]Cl and the Cox–Merz rule is valid for 10 wt % cellulose solution. All of the cellulose solutions showed a shear thinning behavior over the shear rate at temperature from 80 to 120°C. The zero shear viscosity (η_o) was obtained by using the simplified Cross model to fit experimental data. The η_o values were used for detailed viscosity‐concentration and activation energy analysis. The exponent in the viscosity‐concentration power law was found to be 3.63 at 80°C, which is comparable with cellulose dissolved in other solvents, and to be 5.14 at 120°C. The activation energy of the cellulose solution dropped from 70.41 to 30.54 kJ/mol with an increase of concentration from 10 to 25 wt %. The effects of temperature and concentration on the storage modulus (G′), the loss modulus (G″) and the first normal stress difference (N₁) were also analyzed in this study. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Regenerated cellulose membrane prepared with ionic liquid 1‐butyl‐3‐methylimidazolium chloride as solvent using wheat straw

BACKGROUND: Currently, cellulose membranes are prepared by cellulose acetate hydrolysis or chemical derivatization dissolution and regeneration using cotton pulp or wood pulp. In this study, the concept ‘lignocelluloses biorefinery’ was used, and good quality long fiber was fractionated from wheat straw using clean technologies. The objective of this study is to develop wheat straw cellulose to prepare regenerated cellulose membrane with ionic liquid 1‐butyl‐3‐methylimidazolium chloride ([BMIM]Cl) as solvent. RESULTS: Wheat straw cellulose (WSC) fractionated from wheat straw contained 93.6% α‐cellulose and the degree of polymerization (DP) was 580. WSC was dissolved directly without derivatization in [BMIM]Cl. With increase in dissolving temperature, the DP of the regenerated cellulose dropped, which resulted in a decrease in the intensity of regenerated cellulose membrane. After regeneration in [BMIM]Cl, the WSC transformed from cellulose I to cellulose II, and the crystallinity of the regenerated cellulose was lower than the original cellulose. The regenerated WSC membrane had good mechanical performance and permeability, the tensile strength and breaking elongation were 170 MPa and 6.4%, respectively, the pure water flux was 238.9 L m^?2 h^?1 at 0.3 MPa pressure, and the rejection of BSA was stabilized at about 97%. CONCLUSION: Wheat straw cellulose fractionated from wheat straw satisfied the requirement to prepare regenerated cellulose membrane using ionic liquid [BMIM]Cl as solvent. Copyright © 2012 Society of Chemical Industry     

The viscoelastic behavior of concentrated polyacrylonitrile/1‐butyl‐3‐methylimidazolium chloride from solution to gel

The viscoelastic behavior of concentrated polyacrylonitrile (PAN) /1‐butyl‐3‐methylimidazolium chloride ([BMIM]Cl) solutions at different concentrations and temperatures has been investigated by rheology. For concentrated polymer solutions at low temperature (40°C), the shear viscosity was found to show a raid decrease from the ending of Newtonian plateau. At relatively high shear rate or frequency for the concentrated PAN/[BMIM]Cl solutions, the deviation from the empirical Cox–Merz rule was quite evident, which suggested the formation of heterogeneous structures within these solutions. However, the dependence of G′ and G″ on angular frequency presented approximate linearity with similar slope at some temperatures between 100°C and 20°C. All the results lead us to the fact that the gelation has occurred within the concentrated solutions during cooling and the process was found to be thermoreversible. The gelation temperatures of the solutions have exhibited strong concentration dependence. It may be suggested that the microphase separation may be the major reason for the gelation of the concentrated PAN/[BMIM]Cl solutions during cooling process. POLYM. ENG. SCI., 54:598–606, 2014. © 2013 Society of Plastics Engineers     

Recycling Chiral Imidazolidin‐4‐one Catalyst for Asymmetric Diels–Alder Reactions: Screening of Various Ionic Liquids

Various imidazolium ionic liquids such as [Bmim]PF₆, [Bmim]SbF₆, [Bmim]OTf and [Bmim]BF₄ were screened for recycling an organic catalyst [(5S)‐5‐benzyl‐2,2,3‐trimethylimidazolidin‐4‐one ( 1 )] for asymmetric Diels–Alder reactions. Good yields and enantioselectivies (up to 85% yield and 93% ee) were obtained from reactions in [Bmim]PF₆ or [Bmim]SbF₆. However, reactions in [Bmim]OTf or [Bmim]BF₄ gave racemic products in low yields. Isolation of the products by simple extraction using diethyl ether allowed recycling of the ionic liquid containing the immobilized catalyst in subsequent reactions without significant decrease of yields and enantioselectivities.     

聚苯并咪唑在离子液体中流变行为的研究

采用氯化1-丁基-3-甲基咪唑([Bmin]Cl)离子液体作为溶剂制各聚苯并咪唑离子(PBI/[Bmin]Cl)溶液,对不同浓度及温度下的PBI/[Bmin]Cl溶液进行流变性能的测试,并探讨了这些因素对溶液流变性能的影响。结果表明:聚苯并咪唑溶液的零切粘度随溶液浓度的增加而增加,PBI/[Bmin]Cl溶液存在切力变稀现象,当溶液浓度高达5%时,这一现象明显化。同时,数据表明PBI/[Bmin]Cl溶液流变性能对于温度的变化尤为敏感,随温度的升高溶液的零切粘度显著下降,而溶液的非牛顿指数却随之升高,切力变稀现象变得越来越不明显。     

Preparation of high‐molecular‐weight poly(N‐vinylcarbazole) by the photoinduced low‐temperature solution polymerization of N‐vinylcarbazole in 1,1,2,2‐tetrachloroethane

For the preparation of high‐molecular‐weight (HMW) poly(N‐vinylcarbazole) (PVCZ) with a narrow molecular weight distribution, N‐vinylcarbazole (VCZ) was solution‐polymerized in 1,1,2,2‐tetrachloroethane (TCE) at ?20, 0, and 20°C with photoinitiation. The effects of the polymerization temperature and the concentrations of the polymerization solvent and photoinitiator on the polymerization behavior and molecular parameters of PVCZ were investigated. A low polymerization temperature with photoirradiation was successful in obtaining HMW PVCZ with a smaller temperature rise during polymerization than that for thermal free‐radical polymerization by azobisisobutyronitrile (AIBN). The photo‐solution‐polymerization rate of VCZ in TCE was proportional to [AIBN]^0.45. The molecular weight was higher and the molecular weight distribution was narrower for PVCZ made at lower temperatures. For PVCZ prepared in TCE at ?20°C with a photoinitiator concentration of 0.00003 mol/mol of VCZ, a weight‐average molecular weight of 920,000 was obtained, with a polydispersity index of 1.46, and the degree of transparency converged to about 99%. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2391–2396, 2003     

[Bmim]Cl中CrCl3-AlCl3催化纤维素降解制取5-羟甲基糠醛

5-羟甲基糠醛是一种具有很高利用价值的化学平台化合物。以离子液体1-丁基-3-甲基咪唑氯盐（[Bmim]Cl）为溶剂,以CrCl₃和AlCl₃为复合催化剂,在油浴加热条件下催化纤维素降解制取5-羟甲基糠醛,研究了催化剂种类、催化剂量、温度、纤维素浓度、气氛、纤维素聚合度、反应规模等不同因素对纤维素降解制取5-羟甲基糠醛的影响。结果表明,[Bmim]Cl用量为10 g,棉花添加量为0.5 g,x（CrCl₃）=25%（mol）,x（AlCl₃）=2.5%（mol）,反应温度为120℃,反应气氛为N₂（dry）气氛,反应时间为4 h时,HMF产率最高,达到59%。此外,反应过程中水的作用机理也被给予了相应解释。     

Facile preparation for robust and freestanding silk fibroin films in a 1‐butyl‐3‐methyl imidazolium acetate ionic liquid system

Silk fibroin film (SFF) with excellent mechanical properties was prepared for the first time with Bombyx mori silk fibroin as the material and 1‐butyl‐3‐methyl imidazolium acetate ([Bmim]OAc) ionic liquid (IL) as the solvent. The aim was to understand whether the microstructure of SFF could be modified and whether the mechanical properties were improved when [Bmim]OAc IL was used as a solution. With this new system, the obtained SFF was easily peeled off of the substrate, and the silk fibroin proteins retained the α‐helix secondary structure (silk I). Further test results show that the tensile strength (126.8–129.7 MPa) and anti‐UV performance were stronger than the silk fibroin regenerated by traditional ways. Therefore, this study provided and identified a new method with [Bmim]OAc to obtain SFF with strong mechanical properties. This facile preparation and related SFF with excellent mechanical strength could have potential applications in biocompatible implants, synthetic coatings for artificial skin, and many other areas. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42822.     

Rheology of cellulosic N‐methylmorpholine oxide monohydrate solutions of different degrees of polymerization

Preparation and shear and elongational rheology of cellulose solutions of different degrees of polymerization (DP) in N‐methylmorpholine oxide monohydrate (lyocell) were investigated. The dissolution process takes place in two stages, depending on the content of low and high DP fractions from the dissolving pulp blends. The influence of the DP of cellulosic chains on elongational and shear viscosity is greater at low deformation rates. Low DP solutions behave more like viscous fluids and the increase of the chain length brings about an increase of the elastic component. Orientation induced by the convergence flow is enhanced by the higher DP cellulosic chains. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 396–405, 2001     

Partitioning Behavior of Penicillin G in Aqueous Two Phase System Formed by Ionic Liquids and Phosphate

Abstract

An aqueous two‐phase system (ATPS) was presented with hydrophilic ionic liquid 1‐butyl‐3‐methylimidazolium chloride ([Bmim]Cl) and NaH₂PO₄ aqueous solution in this paper. The partitioning behavior of penicillin G in the ATPS was investigated. Concentrations of NaH₂PO₄, penicillin G, and [Bmim]Cl were evaluated to determine their effects on the partition coefficient and extraction yield of penicillin G. It was found that both of partition coefficient and extraction yield strongly depended on the concentration of [Bmim]Cl, penicillin and NaH₂PO₄. A high extraction yield of 93% was achieved with the following parameters: NaH₂PO₄ · 2H₂O 40% (wt%), penicillin 45000～50000 u/ml, [Bmim]Cl 20～21% (wt%). The [Bmim]Cl/NaH₂PO₄ system was also applied in a real filtration of penicillin G fermentation broth and the extraction yield was averaged at 91.5%. It is worthy noting that the working pH value of ATPS was at the range of 5～6, no emulsification and protein denaturation could be observed.     

Selective Production of Diacylglycerols Through Glycerolysis by Ionic Liquid: 1‐Butyl‐3‐Methylimidazolium Imidazolide as Catalyst and Reaction Medium

In this study, 1‐butyl‐3‐methylimidazolium imidazolide ([Bmim]Im) was found effective to catalyze the glycerolysis of triacylglycerols (TAG) for selective production of diacylglycerols (DAG). About 60 % content of DAG and 80 % conversion of TAG were achieved with [Bmim]Im at 15 % (wt% based on TAG), without requirement of any other catalyst and reaction medium. In addition, the weight ratio of DAG to monoacylglycerols (MAG) was at 0.9 when the glycerol/TAG mole ratio was 5:1, indicating [Bmim]Im was selective for DAG generation.     

Measurement,Correlation and Thermodynamics of Solubility of 2,6‐Diamino‐3,5‐Dinitropyrazine‐1‐Oxide (LLM‐105) in Eight Solvents

The solubility of insensitive explosive 2,6‐diamino‐3,5‐dinitropyrazine‐1‐oxide (LLM‐105) in dimethyl sulphoxide (DMSO), N,N‐dimethylformamide (DMF), N‐methyl‐2‐pyrrolidone (NMP), N,N‐diethylformamide (DEF), 1,4‐dioxane, 1,4‐butyrolactone, ethyl acetate and 1‐butyl‐3‐methylimidazolium trifluoromethanesulfonate ([Bmim]CF₃SO₃), were measured by a polythermal method in the temperature range of 293.15 K to 375.15 K at the atmospheric pressure. The solubility of LLM‐105 decreased in the order of DMSO, NMP, DMF, DEF, 1,4‐butyrolactone, [Bmim]CF₃SO₃, 1,4‐dioxane, ethyl acetate. With higher temperature, the solubility of LLM‐105 increased in all solvents. The solubility data was correlated against temperature with the modified Apelblat equation and Ideal solution model. In addition, the dissolution enthalpy, entropy, and mole Gibbs free energy of LLM‐105 in each solvent were also calculated from the experimental solubility data by using van′t Hoff equation with the temperature dependence. The results show that the dissolution process of LLM‐105 in these solvents is endothermic and the mechanism is the entropy‐driving. DMSO is suggested as the appropriate solvent for the cooling crystallization or drowning‐out crystallization of LLM‐105.     

Synthesis and characterization of α‐butyl‐omega‐{3‐[2‐hydroxy‐3‐(N‐methyl‐N‐hydroxy‐ ethylamino)propoxy]propyl}polydimethylsiloxane

A novel synthesis path for the monotelechelic polydimethylsiloxane with a diol‐end group, α‐butyl‐omega‐{3‐[2‐hydroxy‐3‐(N‐methyl‐N‐hydroxyethylamino)propoxy]propyl}polydimethylsiloxane, is described in this article. The preparation included three steps, which were anionic ring‐opening polymerization, hydrosilylation, and epoxy addition. The structure and polydispersity index of the products were analyzed and confirmed by FTIR, ¹H NMR, ¹³C NMR, H? H, and C? H. Correlated Spectroscopy and gel permeation chromatography. The results demonstrated that each step was successfully carried out and the targeted products were accessed in all cases. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Influence of acetated‐based and bromo‐based ionic liquids treatment on wool dyeing with acid blue 7

Bromo‐based and acetated‐based ionic liquids (ILs), 1‐butyle‐3‐methylimidazolium bromo ([Bmim]Br), 1‐ethyl‐3‐mthylimidazolium bromo ([Emim]Br), 1‐butyle‐3‐methylimidazolium acetate ([Bmim]Ac), and 1‐ethyl‐3‐mthylimidazolium acetate ([Emim]Ac), were synthesized and employed for wool surface treatment. Scanning electron microscope results indicated that the wool surfaces treated with acetated‐based ILs were eroded more than those treated with bromo‐based ILs. Comparable studies showed that the wool samples treated with acetate‐based ILs, especially [Emim]Ac, had higher initial dyeing rate and equilibrium exhaustion than those with bromo‐based ILs. Along with treatment temperature and time increasing, acetate‐based ILs had more remarkable effects on mechanical and dyeing properties of the wool samples than bromo‐based ILs. The wool samples treated with [Emim]Ac at 60°C for 10 min had excellent low‐temperature dyeing properties. The color depth (K/S) investigations showed that the wool samples treated with acetate‐based ILs possessed darker color depth than those treated with the bromo‐based ILs. Color fastnesses of the wool samples treated with [Bmim]Br, [Emim]Br and [Bmim]Ac exhibited the same grades as the untreated sample, while wet color fastnesses of [Emim]Ac treated sample were slightly decreased. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012