聚乙烯醇/再生纤维素纳米纤维膜的制备

采用N-甲基吗啉-N-氧化物(NMMO)对废旧涤棉织物中的棉纤维进行溶解回收,通过正交试验优化溶解工艺条件,并利用静电纺丝技术制备聚乙烯醇(PVA)/再生纤维素纳米纤维膜。试验发现影响棉纤维溶解效果的主次因素关系为:溶解温度NMMO的质量分数二甲基亚砜(DMSO)溶胀时间溶质(棉纤维)与溶剂(NMMO水溶液)质量比。溶解的最优条件是:反应温度95℃,NMMO的质量分数为87%,DMSO溶胀90 min,溶质与溶剂质量比为3∶100。此时用扫描电镜观察到PVA/再生纤维素纳米纤维膜中纳米的直径比较均匀。     

木浆纤维素/NMMO·H_2O溶液的流变性能研究

以含水率13.7%的N-甲基吗啉-N-氧化物(NMMO)为溶剂溶解木浆纤维素形成溶液,采用红外光谱分析仪对木浆纤维素的溶解过程进行表征,并采用黏度计研究了木浆纤维素/NMMO·H2O溶液的流变性能。结果表明:木浆纤维素在NMMO中先溶胀后溶解,且可完全溶解;木浆纤维素/NMMO·H2O溶液的流动呈现切力变稀的假塑性流体特征;木浆纤维素质量分数为6%时,溶液的非牛顿流动特征明显,溶液的表观黏度(ηa)随木浆纤维素浓度的增加明显增加,随剪切速率(γ)及温度的上升而下降,当γ高于一定值即logγ大于1.3时,溶液的ηa不受温度的影响,只随γ的上升而下降,且剪切应力不随γ变化而变化,为恒定值。     

纤维素在NMMO水溶液中的溶胀过程及影响因素分析

采用显微镜观察和离心表征的方法,通过控制单一因素变量探讨溶胀时间、溶胀温度、N-甲基吗啉-N-氧化物(NMMO)溶液质量分数等对纤维素在NMMO水溶液中溶胀行为的影响。显微镜观察的结果表明:在溶胀初期,溶剂迅速渗透到纤维素中使单纤维直径变大,20 min后纤维素溶胀接近饱和,纤维直径基本不再变化;随着NMMO质量分数的增加、溶胀温度的升高,纤维素纤维的溶胀率以及吸液率增加,表明纤维素溶胀效果更好。     

纤维素浆粕性质对其在NMMO溶液中的溶胀性能的影响

将4种聚合度及α-纤维素含量不同的纤维素浆粕在85℃下分别溶解于质量分数为74%,78%,80%的N-甲基吗啉-N-氧化物(NMMO)溶液中,研究了纤维素浆粕性质对其在NMMO溶液中的溶胀性能的影响。结果表明:纤维素浆粕的结晶度越高、聚合度越大、α-纤维素含量越高,溶胀效果越差;在相同实验条件下,浆粕的疏松性对其溶胀效果影响很大,浆粕越疏松,其溶胀效果越好;溶胀过程不会改变纤维素的晶型,但会使纤维素结晶度有所下降;聚合度适中、结晶度较低,疏松的纤维素浆粕适宜作为Lyocell纤维的原料。     

纤维素/NMMO溶液及其薄膜的制备与性能研究

以水质量分数为13.3%的N-甲基吗啉-N-氧化物(NMMO)为溶剂溶解棉浆粕,制备质量分数为5%～11%的纤维素/NMMO溶液。将所得溶液制备纤维素薄膜,考察了纤维素/NMMO溶液的稳定性,研究了凝固浴温度和组成对纤维素薄膜的成膜性、断面形态及力学性能的影响。结果表明:纤维素/NMMO溶液随着浓度增大,其粘度先增大后减小,再急剧上升;纤维素/NMMO溶液在玻璃介质中稳定性较好,微量Cu~(2+),Fe~(3+)等杂质存在时,其稳定性显著下降;纤维素薄膜随凝固浴温度升高,其透明性、拉伸强度和断裂伸长率均下降;相对于水,含有乙醇和NMMO的凝固浴能减缓双扩散的速度,使纤维素薄膜的拉伸强度略有提高,断裂伸长率出现不同程度下降。     

棉纤维在LiCl/DMAc极性溶液中的溶解性能研究

采用不同方法将棉纤维活化并溶解在LiCl/DMAc极性溶液中,研究了活化方法、溶解温度、时间及LiCl浓度对棉纤维素溶解性的影响。结果表明:DMAc热活化法为较好的活化方法;提高溶解温度,延长溶解时间及提高LiCl浓度均有利于棉纤维溶解;棉纤维在LiCl质量分数为12%的LiCl/DMAc溶液中,150℃下搅拌4h,溶解度可达3%。碱活化法使棉纤维素聚合度大幅度降低,可提高棉纤维溶解度至8%。通过扫描电镜和X射线衍射方法研究了棉纤维在前处理和溶解过程中的形态和结构变化,初步揭示了纤维素高温处理后在低温下发生溶解的机理。     

纤维素在NMMO水溶液中的溶胀行为研究

通过离心分离法表征纤维素在N-甲基吗啉-N-氧化物水溶液中的溶胀行为,研究了NMMO浓度、温度对纤维素浆粕溶胀的影响;用显微镜追踪拍摄纤维素的溶胀过程,测定纤维的溶胀率,验证了离心分离法的可行性。结果表明:随着NMMO浓度、溶胀温度的升高,纤维素溶胀率增大,溶胀效果变好;纤维素在NMMO水溶液中的最佳溶胀条件为NMMO质量分数78%、温度75℃,溶胀时间40 min。     

TiO_2对棉浆粕/NMMO·H_2O溶液流变性能的影响

以N-甲基吗啉-N-氧化物水溶液(NMMO·H_2O)为溶剂,溶解棉浆粕制成棉浆粕/NMMO·H_2O溶液,在此溶液中加入一定量的二氧化钛(TiO_2),制得TiO_2/棉浆粕/NMMO·H_2O溶液;研究了TiO_2质量分数0~4.0%、棉浆粕质量分数5%~7%的TiO_2/棉浆粕/NMMO·H_2O溶液在80~100℃的流变性能。结果表明:少量TiO_2使棉浆粕/NMMO·H_2O溶液体系零剪切黏度(η0)增大,随着TiO_2含量增加,溶液的η0下降,TiO_2质量分数为4.0%时,溶液的η0低于未添加TiO_2的溶液的η0;TiO_2/棉浆粕/NMMO·H_2O溶液在80~100℃的非牛顿指数(n)小于1,溶液n随着TiO_2含量增加而增大,随着棉浆粕浓度增加而减小;溶液的黏流活化能(Eη)随着TiO_2含量增加先增大后减小,随着棉浆粕浓度增加而减小,在TiO_2质量分数为2.0%时,Eη较大。     

纤维素在N-甲基吗啉-N-氧化物/水溶液中的溶胀与溶解性能

研究了纤维素在N-甲基吗啉-N-氧化物(NMMO)/水体系中的溶胀、溶解过程对纤维素溶液性能的影响,为纤维素在NMMO/水体系中纺丝成形提供理论依据.利用X-射线衍射(XRD)探索了纤维素溶胀后的结晶结构变化,利用旋转流变仪探讨了纤维素浓度、聚合度等对纤维素溶液流变性能的影响.结果表明:经溶胀后的纤维素,非晶区被部分破坏,使其结晶度下降,从而更易被均匀、快速地溶解;纤维素的聚合度越大,含量越高,其大分子链的解缠及伸展越困难,分子间作用越大,纤维素溶液的流动性越差,越不利于纤维素的纺丝成形.     

棉浆粕/NMMO·H_2O溶液的流变性能研究

以N-甲基吗啉-N-氧化物的水溶液(NMMO·H_2O)为溶剂溶解棉浆粕制成棉浆粕/NMMO·H_2O溶液,研究了棉浆粕质量分数为4%~8%的棉浆粕/NMMO·H_2O溶液在85~100℃的流变性能。结果表明:在低剪切速率(γ)下,棉浆粕/NMMO·H_2O溶液的表观黏度(ηa)随温度上升而下降,一定温度时γ达到一定值后,ηa出现转折点呈急速下降趋势,且随着温度的升高,ηa出现转折点的γ增大;棉浆粕/NMMO·H_2O溶液体系为切力变稀的假塑性流体,一定γ下,棉浆粕浓度越高,体系黏度越大,但γ达到一定值后,体系黏度出现转折点呈急剧下降趋势,且随着浓度的增大,ηa出现转折点的γ减小;溶液体系在85~100℃内,其非牛顿指数小于1,且随温度升高而减小,随着棉浆粕浓度的增加,溶液体系的黏流活化能减小,溶液体系的黏-温敏感性减小。     

新型碳纤维用原丝——高强高模Lyocell纤维纺丝工艺研究

采用天然高相对分子质量纤维素脱脂棉为原料 ,制备了高强高模纤维素纤维 ( L yocell纤维 ) ,并用此作为碳纤维原丝 ,成功制得了强度优于粘胶基碳纤维的 L yocell基碳纤维。考察了高相对分子质量纤维素的溶解特点 ,纺丝工艺对 L yocell纤维聚集态及性能的影响 ,比较了 L yocell纤维和粘胶原丝的表面及截面形态。实验表明 :高相对分子质量纤维素溶解的静溶胀时间和温度对其溶解有明显的影响 ;纺丝过程中 ,大的气隙长度对提高纤维的性能有利 ;随着凝固浴中 N -甲基吗啉 N -氧化物( NMMO )的浓度增加 ,纤维的强度和模量增加 ,当其在凝固浴中的质量分数达到 10 %时 ,强度模量最大 ,浓度继续增加 ,纤维的力学性能开始下降 ;拉伸比增加 ,L yocell纤维的强度模量增加 ,当拉伸比大于 3.0时 ,纤维的性能略有下降     

Physical agglomeration behavior in preparation of cellulose‐N‐methyl morpholine N‐oxide hydrate solutions by simple mixing

The different melting temperatures of N‐methyl morpholine N‐oxide (NMMO) hydrates in the cellulose–NMMO hydrate solution may be explained by the rather different crystal structures of NMMO hydrates, which are determined by the amount of the hydrates. The preparative process of cellulose–NMMO hydrate solution may result in cellulose structural change from cellulose I to cellulose II, depending on the amount of the hydrate. Mixtures of cellulose and NMMO hydrate in a blender was changed from the granules to slurry with increasing mixing time at 60–70°C, which is below the melting point of the NMMO hydrate. In the case of 15 wt % cellulose–NMMO hydrate granules, which were made by mixing for 20 min, the melting points of various NMMO hydrates were obtained as 77.8°C (n = 0.83), 70.2°C (n = 0.97), and 69.7°C (n = 1.23), respectively, depending on the hydrate number. However, the melting points of cellulose–NMMO hydrate slurry and solution were shifted lower than those of cellulose granules, while the mixing time of slurry and solution are 25 and 35 min, respectively. These melting behaviors indicate instantaneous liquefaction of the NMMO hydrate and the diffusion of the NMMO hydrate into cellulose during mixing in a blender. When cellulose was completely dissolved in NMMO hydrate, the crystal structure of cellulose showed only cellulose II structure. In the cellulose–NMMO products of granules or slurry obtained by high‐speed mixing, which is a new preparation method, they still retained the original cellulose I structure. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1687–1697, 2004     

高半纤维素浆粕制备Lyocell纤维的研究

采用半纤维素质量分数21%的高半纤维素浆粕在N-甲基吗琳-N-氧化物(NMMO)水溶液中制备Lyocell纤维,并与半纤维素质量分数为10%的高α-纤维素浆粕的可纺性进行了对比。结果表明:高半纤维素浆粕在溶剂NMMO·H_2O中更易溶解,其过滤性能和可纺性能好,可在较高浆粕浓度下纺丝,制备成Lyo- cell纤维的产率高,且能提高Lyocell纤维的力学性能。高半纤维素浆液的稳定性能略低,在溶剂回收中需要消耗较多的双氧水进行氧化回收溶剂NMMO。     

Physical properties of lyocell fibers spun from different solution‐dope phases

The hydration number (n) of NMMO hydrates has a significant effect on the rheological properties and phase of the cellulose solutions in the hydrates. The physical properties of the lyocell fibers spun from the cellulose solutions in NMMO hydrates with different values of n were investigated relative to the phase of the solution dope. NMMO hydrate with n = 1.1 could not fully dissolve cellulose, resulting in a heterogeneous solution. NMMO hydrate with n = 0.72 produced a mesophase solution that exhibited a good spinnability. When NMMO hydrates with n = 0.72 and 1.0 were used, the lyocell fiber spun from 15 wt % solution dope gave higher tensile strength than that spun from 12 wt % solution dope. NMMO hydrate with n = 1.0 produced a lyocell fiber whose tensile strength was slightly affected by spin–draw ratio but the tensile strength of the lyocell fiber prepared from NMMO hydrate with n = 0.72 was monotonically increased with increasing spin–draw ratio. Further, the latter gave higher birefringence. The lyocell fiber spun from 15 wt % solution in NMMO hydrate with n = 0.72 produced finely fibrillated structures. When treated with sonic wave the lyocell fiber prepared from 15 wt % cellulose (DP_w 940) solution in NMMO hydrate with n = 0.72 yielded the most serious fibrillation on the fiber surface. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 981–989, 2002     

Lyocell纤维生产过程中NMMO浓度测定方法研究

采用电位滴定法对Lyocell纤维生产过程中NMMO质量分数进行了测定,探讨了超声时间、溶剂体积比等测试条件对测试结果的影响,并对测试方法的准确性及精密度进行了分析,证实该方法稳定、便捷,适用于生产过程中NMMO/水/纤维素三相体系中NMMO质量分数的快速测定。     

Dry jet‐wet spinning of bagasse/N‐methylmorpholine‐N‐oxide hydrate solution and physical properties of lyocell fibres

Sugarcane bagasse, a cheap cellulosic waste material, was investigated as a raw material for producing lyocell fibers at a reduced cost. In this study, bagasse was dissolved in N‐methylmorpholine‐N‐oxide (NMMO) 0.9 hydrate, and fibers were prepared by the dry jet‐wet spinning method with coagulation in an aqueous NMMO solution. The effects of NMMO in 0 to 50% concentrations on the physical properties of fibers were investigated. The coagulating bath contained water/NMMO (10%) solution produced fiber with the highest drawability and highest physical properties. The cross‐section morphology of these fibers reveals fibrillation due to the high degree of crystallinity and high molecular orientation. In the higher NMMO concentrated baths (30 to 50%), the prepared fibers were hollow inside, which could be useful to make highly absorbent materials. The lyocell fibers prepared from bagasse have a tensile strength of 510 MPa, initial modulus of 30 GPa, and dynamic modulus of approximately 41 GPa. These properties are very comparable with those of commercial lyocell fibers. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Manufacture and performance of ethylamine hydroxyethyl chitosan/cellulose fiber in N-methylmorpholine-N-oxide system

Ethylamine hydroxyethyl chitosan (EHC), a novel chitosan derivative which is soluble in aqueous N-methylmorpholine-N-oxide (NMMO) and antibacterial to Escherichia coli (E. coli) was synthesized. The structure, solubility and antibacterial capability of EHC were investigated. Results demonstrated the potential application for EHC in manufacture of antibacterial EHC/cellulose Lyocell fiber. Through environment-friendly Lyocell process in aqueous NMMO, the EHC/cellulose fiber was successfully fabricated and the various properties of EHC/cellulose fiber were studied. Results showed the EHC/cellulose fiber exhibited favorable consistency, antibacterial activity, mechanical properties and water retention compared with the fiber without EHC.     

Effects of a pretreatment with N‐methylmorpholine‐N‐oxide on the structures and properties of ramie

To improve the dyeing properties of ramie, the ecofriendly organic solvent N‐methylmorpholine‐N‐oxide (NMMO) was used to substitute sodium hydroxide as a ramie‐fiber swelling solvent. Through padding and baking pretreatment, ramie fabric was modified by an NMMO aqueous solution. Ultraviolet–visible spectrophotometry, Fourier transform infrared spectroscopy, X‐ray diffraction, and differential scanning calorimetry were used to investigate the effects of NMMO pretreatment on the structure of the ramie, whereas the color strength (K/S, where K is the light absorption coefficient and S is the scattering coefficient), adsorption isotherm, and dye uptake rate curve were measured to investigate the effects of NMMO pretreatment on the dyeing properties of the ramie. The results show that the ramie fiber experienced a limited and irreversible swelling because of the partial breakage of interhydrogen and intrahydrogen bonds of cellulose molecules in the amorphous area, but the crystal and chemical structure of the ramie fiber did not change obviously under the experimental conditions. The K/S value of the NMMO‐modified ramie fabrics dyed with reactive dyes increased by about 100%, and the dye uptake increased by 27.88% compared to that of the raw sample, whereas the standard affinity and diffusion coefficient value of the reactive dyes on the NMMO‐modified ramie fabric were higher than those of the raw ramie fabric. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010