凝固条件对纤维素/丝素蛋白纤维相形态及性能的影响

蛋白质纤维具有光滑柔顺、透气吸湿等优点,然而天然蛋白纤维产量有限。再生蛋白纤维的制备通常采用与其它成纤高分子接枝或共混的方法,有利于提高再生蛋白纤维的断裂强度。选用同为天然高分子的纤维素为基体,以共溶剂溶解纤维素与蛋白质,进而纺丝成形制得力学性能满足要求的纤维素/丝素蛋白共混纤维。为了探究凝固剂组成对纤维素/丝素蛋白共混纤维相形态及性能的影响,选用水、乙醇、乙醇/1-丁基-3-甲基咪唑氯盐([BMIM]Cl)等作为凝固剂。研究发现:乙醇作为凝固剂时,纤维素与丝素蛋白能很好地同时凝固;而当在乙醇凝固浴中加入适量的[BMIM]Cl径向均匀分散。通过对凝固剂组成的调控能有效提升纤维的力学强度。     

New class of cellulose fiber spun from the novel solution of cellulose by wet spinning method

A novel cellulose solution, prepared by dissolving an alkali-soluble cellulose, which was obtained by the steam explosion treatment on almost pure natural cellulose (soft wood pulp), into the aqueous sodium hydroxide solution with specific concentration (9.1 wt %) was employed for the first time to prepare a new class of multifilament-type cellulose fiber. For this purpose a wet spinning system with acid coagulation bath was applied. The mechanical properties and structural characteristics of the resulting cellulose fibers were compared with those of regenerated cellulose fibers such as viscose rayon and cuprammonium rayon commercially available. X-ray analysis shows that the new cellulose fiber is crystallographically cellulose II, and its crystallinity is higher but its crystalline orientation is slightly lower than those of other commercial regenerated fibers. The degree of breakdown of intramolecular hydrogen bond at C₃[X_am(C₃)] of the cellulose fiber, as determined by solid-state cross-polarization magic-angle sample spinning (CP/MAS) ¹³C NMR, is much lower than other, and the NMR spectra of its dry and wet state were significantly different from each other, indicating that cellulose molecules in the new cellulose fiber are quite mobile when wet. This phenomenon has not been reported for so-called regenerated cellulose fibers.     

蔗渣纤维素在离子液体中的溶解与再生

以蔗渣纤维素为原料,在1-烯丙基-3-甲基咪唑氯盐([Amim]Cl)离子液体中,制备出蔗渣纤维素再生膜。通过偏光显微镜观察了蔗渣纤维素的溶解过程,采用红外光谱、扫描电镜、X射线衍射、热重及力学性能等分析测试手段,对蔗渣纤维素及再生膜进行表征,结果表明:未经活化的蔗渣纤维素可快速、直接溶解在离子液体中,再生前后蔗渣纤维素发生了从纤维素Ⅰ到纤维素Ⅱ的晶型转变,蔗渣纤维素再生膜具有致密的结构,热力学稳定性达到292℃,拉伸强度高达144MPa。     

Diffusion dynamics of ionic liquids during the coagulation of solution spinning for acrylic fibers

The coagulation dynamics of acrylic polymer (PAN) with 1‐butyl‐3‐methylimidazolium chloride [BMIM]Cl as solvent for PAN and H₂O as nonsolvent was investigated in detail. On the basis of Fick's second law of diffusion, a mass‐transfer model of [BMIM]Cl from concentrated PAN/[BMIM]Cl solution was established as verified with the experimental data. The established model has a good fit with the experimental data and the diffusion coefficient D of [BMIM]Cl was calculated according to the model. The diffusion coefficient D decreased a little when the concentration of solution increased. As increasing the coagulation bath concentration, the diffusion coefficient D initially increased and then decreased, reaching a maximum of 5 wt% in the coagulation bath. The diffusion coefficient D decreased with the coagulation bath temperature. From the diffusion coefficient and the structure of the coagulated filament, it can be concluded that the diffusion rate of [BMIM]Cl from PAN concentrate solutions is relatively slow, which is prospective to prepare uniform‐structure fibers. POLYM. ENG. SCI., 48:184–190, 2008. © 2007 Society of Plastics Engineers     

废旧涤棉面料组分溶解分离研究

采用离子液体[Amim]Cl对废旧涤棉混纺面料中含棉成分进行溶解回收。通过正交试验法,研究了温度、[Amim]Cl质量分数、时间、溶质与溶剂比例等因素对溶解过程的影响,得到优化的溶解工艺条件,同时研究了溶剂对涤纶的影响。结果表明:处理后的面料中接近99.2%的棉纤维被溶解,而涤纶没有明显损伤。影响棉纤维溶解效果因素的主次关系依次为:溶解温度,溶解时间,[Amim]Cl质量分数,溶质与溶剂质量比。优化的溶解工艺参数为:溶解温度95℃,溶解时间5 h,[Amim]Cl质量分数99%,溶质与溶剂质量比0.2∶3.5。红外分析表明:溶解处理的样品中棉的特征峰基本消失。     

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     

凝固浴浓度对离子液体法纤维素纤维结构以及性能的影响

探讨了以离子液体1-丁基-3-甲基咪唑氯盐([BMIM]Cl)为溶剂制备的纤维素纤维纺丝工艺条件中凝固浴浓度对纤维结晶结构以及力学性能的影响。实验表明:在相同拉伸比和气隙条件下,凝固浴浓度对再生纤维素纤维的结构以及性能影响较大。随着凝固浴浓度的增加,纤维的结晶度和无定形取向都呈现先增大后减小的趋势,纤维的横向晶粒变小,拉伸强度、初始模量也呈先增大后减小的趋势。     

凝固浴温度对再生细菌纤维素纤维结构与性能的影响

以细菌纤维素为原料,N-甲基吗啉-N-氧化物为溶剂制得纺丝原液,在不同的凝固浴温度条件下,制备再生细菌纤维素纤维,对其形貌、结晶度、取向度、力学性能、吸湿保湿性等进行了研究.结果表明:随着凝固浴温度的提高,再生细菌纤维素纤维表面逐渐趋于光滑,且结晶度提高、取向度和断裂强度降低;凝固浴温度为0～45℃,再生细菌纤维素纤维...     

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 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     

A new process for dissolution of cellulose in ionic liquids

A new dissolving process (two‐step dissolving process), that is, cellulose was first swelled to the maximum in aqueous 1‐butyl‐3‐methylimidazolium chloride ([BMIM]Cl) solution, and then dissolved by stirring under vacuum to remove excessive water, was developed to prepare the cellulose/[BMIM]Cl spinning dope with high quality. The results showed that the initial water contents in [BMIM]Cl have great influence on the swelling and dissolution of cellulose, and the suitable swelling range of aqueous [BMIM]Cl solution, in which cellulose can be swollen but not dissolved, was 2–5% water content. In this range, the higher water content in aqueous [BMIM]Cl solution, the more swelling time would be taken for cellulose to reach the maximal swelling ratio. Based on these results, cellulose/[BMIM]Cl spinning dopes were prepared by using two‐step dissolving process. In the range of our experiments, cellulose spinning dopes prepared by the two‐step dissolving process had better properties, such as fewer particles, lower apparent viscosity, and higher uniformity, compared with the direct dissolving process. By using this new dissolving process, the spinning performance of cellulose/[BMIM]Cl dopes was improved, and the mechanical properties of regenerated cellulose fibers were better than those prepared by the direct dissolving process. Therefore, it is a good way to prepare cellulose/[BMIM]Cl spinning dopes by using the new dissolving process. POLYM. ENG. SCI., 2012. © 2012 Society of Plastics Engineers     

MWCNTs含量对纤维素/[BMIM]Cl溶液及其纤维性能和形态结构的影响

分析了经表面功能化的MWCNTs(多壁碳纳米管)在纤维素/[BMIM]Cl(1-丁基-3-甲基咪唑氯盐)体系中的分散稳定性,探讨了MWCNTs/纤维素/[BMIM]Cl溶液的流变行为,并通过干湿法制备了不同MWCNTs含量的离子液体法纤维素纤维,对其力学性能和表面形态结构进行了研究。结果表明:MWCNTs/纤维素/[BMIM]Cl溶液为切力变稀流体。随着溶液中MWCNTs添加量的增加,溶液表观黏度先增大后减小;适量的MWCNTs可以均匀分散在纤维素/[BMIM]Cl溶液体系中并具有良好的可纺性,所制得的MWCNTs/纤维素纤维表面较光滑且力学性能明显改善。其中,含1%MWCNTs的纤维素纤维的初始模量和断裂强度较高,分别比未添加MWCNTs的纤维提高66.7%和22.7%。     

Hydrolysis of cellulose in 1-allyl-3-methylimidazolium chloride catalyzed by methyltrioxorhenium

Methyltrioxorhenium (MTO) has been applied as catalyst to promote cellulose hydrolysis by using the ionic liquid 1-allyl-3-methylimidazolium chloride ([Amim]Cl) as solvent. When using 7 mol% of MTO, 70 μL of water, ca. 0.6 mmol of microcrystalline cellulose and 2.0 g of [Amim]Cl under microwave irradiation for 30 min at 150 °C, 51.2% of total reducing sugar (TRS) and 24.7% of glucose yield can be obtained. The nucleophilic attack of electron-rich O atom of β-1,4-glycosidic bond to electron-poor Re atom of MTO, leading to the broken of β-1,4-glycosidic bond, is assumed to be crucial for cellulose degradation.     

Dry-jet wet electrospinning of native cellulose microfibers with macroporous structures from ionic liquids

In this study, we have provided a review of electrospun cellulose micro/nanofibers from ionic liquids (ILs) and cosolvents from which we identify a lack of previous studies focusing on the structural morphology of the dry-jet wet electrospun native cellulose fibers from ILs. We have therefore aimed to investigate factors influencing the structural morphology of cellulose/IL electrospun fibers and investigate the coagulation parameters on this morphology. The electrospinning of 10% w/v cellulose/([C2MIM][OAc]/MIM) (1/1, v/v) solution was shown to produce macroporous fibers with average diameters of 2.8 ± 1.4 μm with pore sizes from 100 to 200 nm. We have found that coagulation bath type and immersion time affect the morphological structure of the electrospun fibers. The fiber spinnability, formation, and morphological structure are mainly dependent on the method used to collect and coagulate/solidify the fibers. The physical properties of the dissolved cellulose were measured and these are discussed in terms of the solution spinnability. The structural morphology of the electrospun cellulose fibers was characterized by scanning electron microscopy, and finally the extraction of IL from the fiber body was confirmed by nuclear magnetic resonance. The electrospun cellulose fibers morphology shows the formation of both micron and nanometer sized fibers with different morphological “macroporous” structures. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47153.     

以离子液体为溶剂的纤维素纤维的结构与性能

以离子液体氯化1-丁基-3-甲基咪唑([BMIM]Cl)为溶剂,制备了纤维素/[BMIM]Cl溶液,探讨了该体系的流变性能,并对所纺得的纤维素纤维的结构与性能进行了分析。结果表明:纤维素/[BMIM]Cl溶液为切力变稀流体,当剪切速率较大时,温度对体系黏度几乎没有影响,因此可以在较高剪切速率下降低纺丝温度;由该体系纺制的纤维具有纤维素II晶型的结构;随着拉伸比的提高,纤维的取向程度及结晶度增大,从而使纤维力学性能提高,所得纤维的表面光滑、结构致密,其染色性能及抗原纤化性能与Lyocell纤维基本相近。从而证明了用离子液体[BMIM]Cl所纺制的纤维素纤维性能良好,可望成为继Lyocell纤维之后的又一新型绿色纤维素纤维。     

Structure and properties of cellulose fibers from ionic liquids

1‐Butyl‐3‐methylimidazolium chloride ([BMIM]Cl) was used as a solvent for cellulose, the rheological behavior of the cellulose/[BMIM]Cl solution was studied, and the fibers were spun with a dry‐jet–wet‐spinning process. In addition, the structure and properties of the prepared cellulose fibers were investigated and compared with those of lyocell fibers. The results showed that the cellulose/[BMIM]Cl solution was a typical shear‐thinning fluid, and the temperature had little influence on the apparent viscosity of the solution when the shear rate was higher than 100 s^?1. In addition, the prepared fibers had a cellulose II crystal structure just like that of lyocell fibers, and the orientation and crystallinity of the fibers increased with the draw ratio increasing, so the mechanical properties of the fibers improved. Fibers with a tenacity of 4.28cN/dtex and a modulus of 56.8 cN/dtex were prepared. Moreover, the fibers had a smooth surface as well as a round and compact structure, and the dyeing and antifibrillation properties of the fibers were similar to those of lyocell fibers; however, the color of these dyed fibers was brighter than that of lyocell fibers. Therefore, these fibers could be a new kind of environmentally friendly cellulose fiber following lyocell fibers. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

All-cellulose films with excellent strength and toughness via a facile approach of dissolution–regeneration

This study describes a green method for preparing all-cellulose nanocomposites through a dissolution and regeneration process. Cotton linter pulp was dissolved in 7 wt % NaOH/12 wt % urea aqueous solution precooled to −12°C. Self-assembly of cellulose molecules into nanostructured cellulose fiber is achieved by using water addition and controlling the temperature to regenerate cellulose. By changing the microenvironment of the cellulose solution, the morphology of the nanostructured cellulose fibers and the mechanical properties of the regenerated cellulose films can be tuned. Then, a series of regenerated cellulose films have been prepared and characterized from various aspects. Compared with other all-cellulose films in the literature, the regenerated all-cellulose nanocomposite films prepared in this work exhibited good optical transparency, thermal stability, and excellent tensile strength (up to 135 MPa) when the regeneration temperature was adjusted to 50°C. This work provided a green and promising approach to prepare high-performance and environmentally friendly all-cellulose nanocomposites. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 46925.     

X-ray studies of regenerated cellulose fibers wet spun from cotton linter pulp in NaOH/thiourea aqueous solutions

Regenerated cellulose fibers were fabricated by dissolution of cotton linter pulp in NaOH (9.5 wt%) and thiourea (4.5 wt%) aqueous solution followed by wet-spinning and multi-roller drawing. The multi-roller drawing process involved three stages: coagulation (I), coagulation (II) and post-treatment (III). The crystalline structure and morphology of regenerated cellulose fiber was investigated by synchrotron wide-angle X-ray diffraction (WAXD) and small-angle X-ray scattering (SAXS) techniques. Results indicated that only the cellulose II crystal structure was found in regenerated cellulose fibers, proving that the cellulose crystals were completely transformed from cellulose I to II structure during spinning from NaOH/thiourea aqueous solution. The crystallinity, orientation and crystal size at each stage were determined from the WAXD analysis. Drawing of cellulose fibers in the coagulation (II) bath (H₂SO₄/H₂O) was found to generate higher orientation and crystallinity than drawing in the post-treatment (III). Although the post-treatment process also increased crystal orientation, it led to a decrease in crystallinity with notable reduction in the anisotropic fraction. Compared with commercial rayon fibers fabricated by the viscose process, the regenerated cellulose fibers exhibited higher crystallinity but lower crystal orientation. SAXS results revealed a clear scattering maximum along the meridian direction in all regenerated cellulose fibers, indicating the formation of lamellar structure during spinning.     

Mesoporous Carbon Fibers Prepared from Regenerated Rice Straw Fibers

Regenerated cellulose fibers from rice straws with a diameter of 10 to 25 μm and initial modulus of 11 to 13 GPa were prepared by wet spinning in rice straw/N‐methylmorpholine‐N‐oxide (MMO) solution. X‐ray diffraction analysis indicates that the rice straw regenerated fibers are classified as cellulose (II). From the regenerated cellulose fiber based on rice straw, mesoporous carbon fiber was prepared by carbonization. This observation indicates that a potential utility of rice straw as a new mesoporous materials.     

High‐strength regenerated cellulose fibers spun from 1‐butyl‐3‐methylimidazolium chloride solutions

High‐performance regenerated cellulose fibers were prepared from cellulose/1‐butyl‐3‐methylimidazolium chloride (BMIMCl) solutions via dry‐jet wet spinning. The spinnability of the solution was initially evaluated using the maximum winding speed of the solution spinning line under various ambient temperatures and relative humidities in the air gap. The subsequent spinning trials were conducted under various air gap conditions in a water coagulation bath. It was found that low temperature and low relative humidity in the air gap were important to obtain fibers with high tensile strength at a high draw ratio. From a 10 wt % cellulose/BMIMCl solution, regenerated fibers with tensile strength up to 886 MPa were prepared below 22 °C and relative humidity of 50%. High strengthening was also strongly linked with the fixation effect on fibers during washing and drying processes. Furthermore, an effective attempt to prepare higher performance fibers was conducted from a higher polymer concentration solution using a high molecular weight dissolving pulp. Eventually, fibers with a tensile strength of ～1 GPa and Young's modulus over 35 GPa were prepared. These tensile properties were ranked at the highest level for regenerated cellulose fibers prepared by an ionic liquid–based process. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45551.