CN101328626A - Method for continuously preparing regenerated cellulose fibre - Google Patents

Method for continuously preparing regenerated cellulose fibre Download PDF

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CN101328626A
CN101328626A CN 200710117683 CN200710117683A CN101328626A CN 101328626 A CN101328626 A CN 101328626A CN 200710117683 CN200710117683 CN 200710117683 CN 200710117683 A CN200710117683 A CN 200710117683A CN 101328626 A CN101328626 A CN 101328626A
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China
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cellulose
spinning
methylimidazolium
radical
ionic liquid
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CN 200710117683
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Chinese (zh)
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何嘉松
军 张
进 武
王三元
王东兴
魏广信
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中国科学院化学研究所;保定天鹅股份有限公司
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Priority to CN 200710117683 priority Critical patent/CN101328626A/en
Publication of CN101328626A publication Critical patent/CN101328626A/en

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    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50Manufacturing or production processes characterised by the final manufactured product
    • Y02P70/62Manufacturing or production processes characterised by the final manufactured product related technologies for production or treatment of textile or flexible materials or products thereof, including footwear
    • Y02P70/621Production or treatment of artificial filaments or the like
    • Y02P70/625Recovery of starting material, waste material or solvents during the manufacturing process
    • Y02P70/627Recovery of starting material, waste material or solvents during the manufacturing process of cellulose, cellulose derivatives or proteins

Abstract

The invention discloses a method for continuously preparing regenerated cellulose fibers through the solvent method, comprising the following steps that: a cellulose raw material is dissolved into an ion liquid to prepare a spinning liquid; gel type regenerated cellulose fibers are obtained through spinning; and the regenerated cellulose fibers are obtained through cleaning, rear draft and drying, wherein, the ion liquid is selected from one or a plurality among the following ion liquids: a). an ion liquid with 1, 3-dialkyl imidazole as a cation and formiate radical, radical vinegar or propionate radical as an anion; and b). an ion liquid with 1-R1-3-R2- dialkyl imidazole as the cation and chlorine, bromine, iodine, formiate radical, radical vinegar, sulfate radical, nitrate radical, tetrafluoroborate radical, thiocyanate radical, hexafluorophosphate radical, p-toluenesulfonate radical or trifluoromethanesulfonic acid radical as the anion. The method has the advantages of wide technological range, mild temperature condition, adequate pressure, quick spinning speed and so on, can prepare the regenerated cellulose fibers with superior performance and complete specifications, and has low production cost, high production efficiency and wide application prospect.

Description

一种连续制备再生纤维素纤维的方法技术领域本发明涉及一种溶剂法连续制备再生纤维素纤维的方法,具体地说,涉及一种以低黏度离子液体为溶剂连续制备再生纤维素纤维的方法。 TECHNICAL FIELD The continuous preparation of regenerated cellulose fibers of the present invention relates to a process for the continuous preparation solvent regenerated cellulose fibers, in particular, relates to a method for low viscosity ionic liquid and the continuous preparation of regenerated cellulose fiber . 背景技术随着工业生产能力的增加,石油等矿产资源日益难以满足人类未来的需求,因此可再生的天然资源具有越来越重要的地位。 BACKGROUND With the increase in industrial production capacity, oil and other mineral resources are increasingly difficult to meet the needs of the future of mankind, and therefore renewable natural resources have an increasingly important role. 纤维素是地球上最为丰富的天然高分子, 充分利用纤维素资源对于人类的可持续发展具有重要意义。 Cellulose is the most abundant natural polymer on earth, make full use of cellulose resources for sustainable human development is important. 目前,在化纤制造领域,利用纤维素的方式主要是所谓的粘胶工艺,即将纤维素制备成碱纤维素,经老化后与二硫化碳进行化学反应,生成纤维素黄原酸酯,纤维素黄原酸酯溶解在碱性溶液中,熟成后经脱泡、过滤,在酸浴中喷丝,凝固成形,同时纤维素黄原酸酯又分解成纤维素,然后再进行拉伸、水洗,最后进行上油、巻取或切断等后处理,制备出再生纤维素长纤或短纤。 Currently, in the field of chemical manufacturing using cellulose viscose way the so-called primary process, i.e. cellulose into alkali cellulose prepared, after chemical reaction with carbon disulfide aging generates cellulose xanthate, cellulose xanthate ester is dissolved in an alkaline solution, after aging by deaeration, filtration, spinning in an acid bath, solid molding, while the cellulose xanthate to cellulose decomposition and then stretched, washed with water, and finally after oil and the like, or the cutting process takes Volume prepared regenerated cellulose filament or staple. 粘胶工艺技术成熟,但是污染大,废水多,能耗高。 Viscose process technology is mature, but pollution, waste water, high energy consumption. 为了寻找更好的纤维素纤维制造方法,纤维素直接溶剂法纺丝受到越来越广泛的重视。 In order to find better methods for producing cellulosic fibers, solvent-spun cellulose by direct more and more attention. 所谓纤维素的直接溶剂, 就是在溶解过程中不与纤维素发生化学反应的溶剂。 Direct solvents for cellulose, the cellulose solvent is a chemical reaction does not occur during dissolution. 纤维素在这种溶剂中仍保持原来的分子结构,即溶解只给纤维素造成物理变化,没有造成化学变化。 In this cellulose solvent remains original molecular structure, i.e. only cause physical changes to dissolve cellulose, does not cause chemical changes. 纤维素的直接溶剂现在己经发现了很多种,但是由于毒性、腐蚀性、回收等方面的问题,许多纤维素直接溶剂不适合工业生产,真正己经得到工业利用的纤维素直接溶剂只有NMMO(N 一甲基吗啉N—氧化物)体系,但目前这一技术仍不成熟。 Direct solvent for cellulose have now found a very wide range, but due to issues of toxic, corrosive, recycling, the solvent does not directly suitable for many industrial cellulose production, cellulose really has obtained directly using only industrial solvent NMMO ( N-methylmorpholine N- oxide) system, but the technology is still not mature. 专利WO 2006/000197 Al公开了以1,3-二垸基咪唑卤素盐离子液体为溶剂制备再生纤维素纤维和再生纤维素膜的方法。 Patent WO 2006/000197 Al discloses a 1,3-halo alkyl with imidazole ionic liquid regenerated cellulose fiber and method of preparing regenerated cellulose membrane solvent. 但是,1,3-二烷基咪唑卤素盐离子液体的熔点和黏度很高,其熔点在100'C左右,这样使得在制备过程中,需要较高的温度以及较低的纤维素浓度,生产成本高,生产效率低。 However, the melting point and viscosity of the 1,3-dialkyl-imidazol-halo high ionic liquid having a melting point of about 100'C, so that during the manufacturing process, require higher temperatures and lower concentrations of cellulose, production the high cost and low productivity. 发明内容本发明的目的是提供离子液体制备再生纤维素纤维的方法。 Object of the present invention to provide a method of preparing ionic liquid regenerated cellulose fiber. 本发明所提供的利用离子液体制备再生纤维素纤维的方法,是将纤维素原料溶解在离子液体中,得到纺丝液,纺丝得到凝胶态的再生纤维素纤维,再经过洗涤、后牵伸和烘干,得到再生纤维素纤维,其中,离子液体选自以下如下离子液体中的一种或几种:a) 阳离子为1,3-二烷基咪唑,阴离子为甲酸根、醋酸根或丙酸根的离子液体;其中,烷基为含有1一8个碳原子的烷基;b) 阳离子为lR^-R2-二烃基咪唑,阴离子选自氯、溴、碘、甲酸根、醋酸根、丙酸根、硫酸根、硝酸根、四氟硼酸根、硫氰酸根、六氟磷酸根、对甲苯磺酸根和三氟甲磺酸根的离子液体;其中,A为符合以下规则的烃基:①至少含有2个碳原子, ②不多于20个碳原子,③至少含有一个双键;R2为含有l〜4个碳原子的饱和或不饱和的烃基。 Regenerated cellulose fibers according to the present invention, the method of preparing the liquid provided by the ion, the cellulosic raw material is dissolved in the ionic liquid, to obtain a spinning solution, regenerated cellulosic fibers obtained by spinning in a gel state, and then after washing, the retractor stretch and drying, regenerated cellulose fibers, wherein the ionic liquid is selected from one or more of the following ionic liquids: a) a 1,3-dialkyl imidazolium cation, the anion is formate, acetate or propionate and phosphate ionic liquid; wherein alkyl is an alkyl group containing 1 to 8 carbon atoms; b) a cation lR ^ -R2- dialkyl imidazole, anion selected from chloride, bromide, iodide, formate, acetate, propionate phosphonate, sulfate, nitrate, tetrafluoroborate, thiocyanate, hexafluorophosphate, p-toluenesulfonate ion liquid and trifluoromethane sulfonate; wherein, a is a hydrocarbon group subject to the following rules: ① the at least 2 carbon atoms, ② not more than 20 carbon atoms, ③ containing at least one double bond; R2 is a saturated or unsaturated hydrocarbon group l~4 carbon atoms. 优选的,离子液体选自以下离子液体或其混合物:l-乙基-3-甲基咪唑甲酸盐,1-乙基-3-甲基咪唑醋酸盐,l-乙基-3-甲基咪唑丙酸盐,l-丙基-3-甲基咪唑甲酸盐,1-丙基-3-甲基咪唑醋酸盐,l-丙基-3-甲基咪唑丙酸盐,l-丁基-3-甲基咪唑甲酸盐,1-丁基-3-甲基咪唑醋酸盐,l-丁基-3-甲基咪唑丙酸盐,l-烯丙基-3-甲基咪唑氯盐,1-烯丙基-3-甲基咪唑甲酸盐,l-烯丙基-3-甲基咪唑醋酸盐,l-烯丙基-3-甲基咪唑丙酸盐,1-烯丙基-3-甲基咪唑硫酸盐,l-甲基烯丙基-3-甲基咪唑氯盐,l-甲基烯丙基-3-甲基咪唑甲酸盐,l-甲基烯丙基-3-甲基咪唑醋酸盐,l-甲基烯丙基-3-甲基咪唑丙酸盐,1-甲基烯丙基-3-甲基咪唑硫酸盐。 Preferably, the ionic liquid is selected from the ionic liquids or mixtures thereof: l- ethyl-3- methylimidazolium formate, 1-ethyl-3-methylimidazolium acetate, l- ethyl-3-carboxylic imidazole propionate, l- propyl-3-methylimidazolium formate, 1-propyl-3-methylimidazolium acetate, l- propyl-3-methylimidazolium propionate, l- butyl-3- methylimidazolium formate, 1-butyl-3-methylimidazolium acetate, l- butyl-3-methylimidazolium propionate, l- allyl-3-methyl imidazolium chloride, 1-allyl-3-methylimidazolium formate, l- allyl-3-methylimidazolium acetate, l- allyl-3-methylimidazolium propionate, 1 - allyl-3-methylimidazolium sulfate, l- methyl-allyl-3-methylimidazolium chloride, l- methyl-allyl-3-methylimidazolium formate, l- methyl allyl-3-methylimidazolium acetate, l- methallyl 3-methylimidazolium propionate, 1-methyl-allyl-3-methylimidazolium sulfate. 为了能降低纺丝液的粘度,离子液体中还可加有复配溶剂,复配溶剂为离子液体重量的5〜40%;所述复配溶剂选自二甲基亚砜、二甲基甲酰胺、二甲基乙酰胺中的一种或几种。 In order to reduce the viscosity of the spinning solution, it may also be added in the ionic liquid solvent mixtures, solvent mixtures of 5 ~ 40% by weight of an ionic liquid; the solvent is selected from dimethyl sulfoxide complex, dimethylformamide amide, dimethylacetamide one or several. 在本发明中,纺丝液中纤维素的平均聚合度为200〜3000,质量浓度为3〜30%; 优选的,纺丝液中纤维素的平均聚合度为250〜1500,质量浓度为5〜25%。 In the present invention, the average degree of polymerization of the cellulose in the spinning solution is 200~3000, the concentration of 3~30%; preferably, the average degree of polymerization of the cellulose in the spinning solution is 250~1500, the concentration of 5 ~ 25%. 纺丝液的温度为40〜18(TC,粘度为50〜10000Pa*s;优选的,纺丝液的温度为60〜160°C, 粘度为100〜5000Pa*s。应用本发明方法,纺丝得到凝胶态的再生纤维素纤维是采用干喷湿纺工艺进行的,是将纺丝液挤压通过开有若干喷丝孔的喷丝装置进入空气,在空气中经历拉伸, 然后进入凝固浴固化,得到凝胶态的再生纤维素纤维。其中,喷丝孔直径为0.05〜lmm,喷丝压力为0.5〜4MPa,喷丝速度为10〜200 米/分钟,从喷丝孔到凝固浴的距离为0.005〜0.5米,牵伸比为1〜200;优选的,喷丝孔直径为0.05〜0.5mm,喷丝速度为20〜100米/分钟,从喷丝孔到凝固浴的距离为0.05〜0.3米,牵伸比为5〜100。凝固浴为含0〜70%重量离子液体的水溶液,凝固浴的温度为10〜50°C。在对纺丝得到凝胶态的再生纤维素纤维进行洗涤、后牵伸和烘干时,洗涤以水为洗涤剂即可;后牵伸的倍数为1〜5倍,后 The temperature of the spinning solution is 40~18 (TC, viscosity 50~10000Pa * s; Preferably, the temperature of the spinning solution is 60~160 ° C, a viscosity of 100~5000Pa * s method of the invention, the spinning. obtained regenerated cellulose fiber in the gel state dry-jet wet spinning process is performed, the spinning solution is extruded through the opening with a plurality of spinning orifice means into the air, subjected to stretching in the air, and then into a coagulating curing bath, regenerated cellulose fibers in a gel state. wherein the nozzle hole diameter 0.05~lmm, nozzle pressure 0.5~4MPa, spinning speed of 10~200 m / min into a coagulation bath from a nozzle hole distance of 0.005~0.5 m, draft ratio 1~200; preferably, the nozzle hole diameter 0.05~0.5mm, spinning speed of 20-100 m / min, the distance from the nozzle orifice to the coagulating bath is 0.05~0.3 m, draft ratio 5~100. solidifying bath of an aqueous solution containing 0~70% by weight of the ionic liquid, the coagulation bath temperature of 10~50 ° C. of regenerated cellulose spun in the gel state washing the fiber after drawing and drying, the detergent can be washed with water; the draft multiples ~ 5 times, after 伸次数为0〜3次;烘干温度为80〜200 。C。本发明通过筛选具有低熔点、低粘度的离子液体作为纤维素的直接溶剂进行纺丝,能够降低纤维素溶解、纺丝时的温度,并能够提高纺丝液的浓度,使得纺丝工艺条件更加温和,并且,工艺参数范围宽,增加了纺丝工艺的方便性和可调节性。本发明方法具有工艺范围宽、温度条件温和、压力适中、纺丝速度快等优点,能够制备性能优良、规格齐全的再生纤维素纤维,生产成本低,生产效率高,应用前景广阔。具体实施方式本发明利用离子液体制备再生纤维素纤维的方法,是将纤维素溶解于低黏度、低熔点的离子液体中,形成纤维素/离子液体溶液作为纺丝液,然后,将纺丝液纺丝,即可得到再生纤维素纤维。纺丝工艺有多种, 一般可选用干喷湿纺工艺:将受到挤压的纺丝液从开有一定数目小孔的喷丝装置中 Extending the number of times of 0~3; drying temperature of 80~200 .C present invention is an ionic liquid having a low melting point, low viscosity, as directly by screening for solvent spinning of cellulose, cellulose dissolution can be reduced, spinning. temperature, and concentration of the spinning solution can be increased, so that the spinning process conditions are more moderate, and wide range of process parameters, and increase the convenience of adjustability of the spinning process. the method of the present invention have a wide range of process, temperature conditions regenerated cellulose fibers mild, moderate pressure, fast spinning speed, etc., can be prepared in excellent performance, complete specifications, low production costs, high production efficiency, wide application prospect. DETAILED embodiment of the present invention was prepared using the ionic liquid regenerated cellulose fiber the method, cellulose is dissolved in a low viscosity, a low melting point ionic liquids to form a cellulose / ionic liquid solution as a spinning solution and then spinning the spinning solution, to obtain regenerated cellulosic fibers. spinning there are a variety of processes, generally use dry-jet wet spinning process: spinning means a spinning liquid will be squeezed from a certain number of small holes are opened in 入空气,在空气中经历拉伸,然后进入凝固浴,在凝固浴中固化,得到凝胶态的再生纤维素纤维,再经过洗涤、后牵伸和烘干, 即可得到再生纤维素纤维。在本发明中,纺丝液主要由离子液体和纤维素组成。纤维素的种类包括细菌纤维素、棉花、脱脂棉、棉短绒、棉浆粕、木浆粕、竹浆粕、微晶纤维素以及麻、稻草、 小麦秸秆、棉花秸秆、玉米秸秆、甘蔗渣和各种草中等提取的纯度达到90%以上纤维素。这些纤维素的聚合度依来源而不同,如微晶纤维素的聚合度为180〜250,竹浆粕的聚合度为450〜550,木桨粕的聚合度为550〜650,棉浆粕的聚合度为800〜1000, 脱脂棉的聚合度为1500~3000,细菌纤维素的聚合度为10万〜100万。 Air, subjected to stretching in the air, and then into a coagulating bath, solidified in a coagulation bath, regenerated cellulose fiber in the gel state, and then after washing, drawing and drying, to obtain regenerated cellulosic fibers. In in the present invention, the spinning solution mainly composed of an ionic liquid and cellulose. kind of bacterial cellulose include cellulose, cotton, cotton linters, cotton pulp, wood pulp, bamboo pulp, microcrystalline cellulose, and hemp, rice straw, wheat straw, cotton stalks, corn stover, bagasse, grasses and the extracted medium purity more than 90% cellulose. the polymerization degree of the cellulose differ by source, such as the degree of polymerization of the microcrystalline cellulose is 180~250, the degree of polymerization of 450~550 bamboo pulp, wood pulp degree of polymerization of 550~650 meal, cotton pulp is 800~1000 polymerization degree, polymerization degree of 1500 to 3000 cotton, bacterial cellulose a polymerization degree of 100,000 ~ 100 million. 用不同分子量的纤维素原料进行搭配,可以使纤维素的平均聚合度为180〜3000之间的任意值。 To match with different molecular weights of the cellulose raw material, average degree of polymerization of the cellulose can be an arbitrary value between 180~3000. 所使用的离子液体选自如下种类的离子液体-a) 阳离子为1,3-二烷基咪唑,阴离子为甲酸根、醋酸根或丙酸根的离子液体;其中,烷基为含有1一8个碳原子的垸基;b) 阳离子为l-Rr3-R2-二烃基咪唑,阴离子选自氯、溴、碘、甲酸根、醋酸根、 丙酸根、硫酸根、硝酸根、四氟硼酸根、硫氰酸根、六氟磷酸根、对甲苯磺酸根和三氟甲磺酸根的离子液体;其中,Ri为符合以下规则的烃基:①至少含有2个碳原子, ②不多于20个碳原子,③至少含有一个双键;R2为含有l〜4个碳原子的饱和或不饱和的烃基。 The ionic liquid used is selected from the species of the ionic liquid -a) is 1,3-dialkyl imidazolium cation, the anion is formate, acetate or propionate ionic liquid; wherein an alkyl group containing 1 8 alkyl with a carbon atom; b) a cation is l-Rr3-R2- dialkyl imidazole, anion selected from chloride, bromide, iodide, formate, acetate, propionate, sulfate, nitrate, tetrafluoroborate, sulfur cyanate, hexafluorophosphate, p-toluenesulfonate ion liquid and triflate; wherein, Ri of a hydrocarbon group following rules: ① the containing at least two carbon atoms, ② not more than 20 carbon atoms, ③ containing at least one double bond; R2 is a saturated or unsaturated hydrocarbon group l~4 carbon atoms. 这些离子液体具有较低的熔点, 一般在2(TC以下;优选的,离子液体为AMIMC1 (l-烯丙基-3-甲基咪唑氯盐),其熔点为约17。C; EMIMAc (l-乙基-3-甲基咪唑醋酸盐),AMIMAc (l-烯丙基-3-甲基咪唑醋酸盐),和BMIMAc (l-丁基-3-甲基咪唑醋酸盐),它们的熔点远低于0'C;其他离子液体在0"C以上一直保持液态。采用干喷湿纺工艺进行纺丝时,纺丝液的可纺性与纺丝液的黏度和温度有关。在实验中发现,4(TC下,黏度低至lOPa's的溶液,如4%的微晶纤维素溶液就可以纺丝, 但是纤维强度较差。黏度增加至100P&s (40°C),如8%的微晶纤维素溶液,就能够得到强度较好的纤维。实际操作允许的最高黏度与所用喷丝板的孔径有关,孔径越大, 可纺的溶液黏度越大。在我们的研究中,使用的喷丝板孔径最大为lmm,能够用黏度高达10万Pa.s的溶液纺丝。 一般可根据纺丝液的黏度选择喷丝板 These ionic liquids having a low melting point, typically 2 (TC or less; preferably, the ionic liquid is AMIMC1 (l- allyl-3-methylimidazolium chloride) having a melting point of about 17.C; EMIMAc (l - ethyl-3- methylimidazolium acetate), AMIMAc (l- allyl-3-methylimidazolium acetate), and BMIMAc (l- butyl-3- methylimidazolium acetate), far below their melting points 0'C; other ionic liquids remain liquid at above 0 "C while the dry-jet wet spinning process using spinning, viscosity and temperature of the dope may be spun of the relevant spinning solution. found in the experiment, (at 4 TC, lOPa's low viscosity solution such as 4% of the microcrystalline cellulose solution can be spun, but the fiber strength is poor. viscosity increased to 100P & s (40 ° C), such as 8% microcrystalline cellulose solution, it is possible to obtain better strength fibers allows practical maximum viscosity and the pore size of the spinneret, the greater pore size, the greater the viscosity of the solution can be spun. in our study, the maximum pore diameter spinneret lmm, can be up to 100,000 Pa.s spinning solution with a viscosity generally be selected according to the viscosity of the spinneret of the spinning solution 的孔径,推荐的喷丝板孔径与纺丝液黏度关系见表1。表1.喷丝板孔径与纺丝液黏度<table>table see original document page 7</column></row> <table>纺丝液的黏度(本文中所有的黏度数据均指零切黏度)由纤维素的聚合度、纺丝液浓度和温度共同决定,典型数值见表2。随着浓度增大,纤维素/AMIMCl溶液的黏度迅速增加,如聚合度为1500的脱脂棉溶液,溶液浓度从1%逐步增加至16%时, 黏度从190 Pa's逐步增加到大于30万Pa's。纤维素聚合度的高低对黏度也有重大影响, 如聚合度为1500,浓度为8%的纤维素溶液,8(TC时黏度大于40000 Pa's;而相同温度下,聚合度为600的8%的溶液,黏度约为2500Pa's。温度对溶液的黏度影响也很大,如聚合度为600的8%的纤维素溶液,40。C时黏度约为23000 Pa's,温度升至100 'C时,黏度降低至约500Pa's。根据黏度的这种变化规律,可以在比较大的范围内调节纺丝 Pore ​​size, spinneret aperture and recommended spinning liquid are shown in Table 1. Table 1. Viscosity spinneret aperture and dope viscosity <table> table see original document page 7 </ column> </ row> <table > the viscosity of the spinning solution (all viscosity data refer to herein as the zero shear viscosity), solution concentration and temperature determined by the degree of polymerization of cellulose, typical values ​​are shown in Table 2. as the concentration increases, the cellulose / viscosity AMIMCl solution rapidly increases, such as when a polymerization degree of pledget solution 1500, solution concentration from 1% increased gradually to 16% and a viscosity from 190 Pa's gradually increased to more than 300,000 Pa's. low cellulose degree of polymerization on the viscosity also has a significant , such as the degree of polymerization of 1500, at a concentration of 8% of the cellulose solution, 8 (viscosity greater than 40000 Pa's TC time; and at the same temperature, the degree of polymerization of 8% 600 a solution viscosity of about 2500Pa's temperature to the solution. viscosity of a great impact, such as a polymerization degree of 600 8% cellulose solution, 40.C when the viscosity of about 23000 Pa's, the temperature was raised to 100 'C, the viscosity is reduced to about 500Pa's. the viscosity of this variation , the spinning may be adjusted within a relatively large range 的配方和喷丝温度。较理想的纺丝液黏度为50〜10000 Pa's (喷丝温度下), 更好地,为100〜5000 Pa's (喷丝温度下)。表2.纺丝液黏度与聚合度、浓度、温度的关系(离子液体为AMIMC1)聚合度" 浓度6 (wt%) 温度rc) 黏度e (Pa-s)<table>table see original document page 8</column></row> <table> Formulation and nozzle temperature. The ideal viscosity of the spinning solution 50~10000 Pa's (at spinning temperature), better, of 100~5000 Pa's (the spinning temperature). Table 2. The viscosity of the spinning liquid relationship between the degree of polymerization, concentration, temperature (ionic liquids AMIMC1) degree of polymerization "concentration 6 (wt%) temperature RC) viscosity e (Pa-s) <table> table see original document page 8 </ column> </ row> <table>

l占均聚合度.6纤维素在纺丝溶液中的百分数.e零切黏度 为了配制黏度合适的纺丝液,关键的选择条件是纺丝液中纤维素浓度和纤维素聚合度。 l representing average degree of polymerization of cellulose .6 percent .e zero shear viscosity of the spinning solution in order to formulate an appropriate dope viscosity, critical choices that the cellulose concentration in the spinning solution and the degree of polymerization of cellulose. 浓度低至1%的脱脂棉溶液可以在60°(:下顺利纺丝,浓度高达30%的微晶纤维素溶液在160〜180。C下也能纺丝。浓度越高,生产效率越高;聚合度越大,对提高产品品质越有利。因此较好的纺丝液浓度应该在5%以上,但以不超过25%为宜。根据原料的不同组合,纤维素的聚合度可以在180〜3000之间任意变化。由于纺丝温度不能任意提高,聚合度越高,适宜的浓度就越低。综合考虑各方面的因素,优选的纺丝液配方为:纤维素浓度5%〜25%,聚合度250〜1500。为了能降低纺丝液的粘度,离子液体中还可加有复配溶剂,复配溶剂为离子液体重量的5〜40%;复配溶剂选自二甲基亚砜、二甲基甲酰胺、二甲基乙酰胺。纺丝液中还可添加有功能材料,功能材料选自抗紫外剂、抗菌剂、阻燃剂、蒙脱土、碳纳米管、 壳聚糖和麦饭石;功能材料的添加量为纤维素重量的0.01〜10%。将 Concentrations as low as 1% solution of cotton may be 60 ° (: smooth spinning at a concentration of up to 30% microcrystalline cellulose solution can be spun at 160~180.C higher the concentration, the higher the efficiency;. the larger the degree of polymerization, more advantageous to improve product quality. Therefore, a better solution concentration should be at least 5%, but preferably not more than 25%. depending on the composition of the raw material, the degree of polymerization of cellulose may 180~ any of a spinning temperature can change due to any increase, the higher the degree of polymerization between 3000, the lower the appropriate concentration considering various factors, it is preferable to dope formulation: cellulose concentration of 5% ~ 25%, the polymerization degree of 250~1500 order to reduce the viscosity of the spinning solution, may also be added in the ionic liquid solvent mixtures, solvent mixtures of 5 ~ 40% by weight of an ionic liquid; the solvent is selected from dimethyl sulfoxide complex, dimethyl formamide, dimethyl acetamide. spinning solution may be added with a functional material, the functional material is selected from UV, antimicrobial agents, flame retardants, montmorillonite, carbon nanotubes, and chitosan Maifanshi;. 0.01~10% by weight of the added amount of cellulose material will function 纺丝液进行喷丝是一个多参数的过程,主要的参数有:喷丝温度、喷丝压力、 喷丝板孔径、气隙长度(从喷丝孔到凝固浴的距离)和牵伸比(即凝固浴后第一个牵伸辊的线速度与喷丝孔处喷丝速度的比值)。喷丝温度影响纺丝液的黏度, 一般用升高温度的办法降低黏度。可是纺丝液温度不能无限制提高。为避免在高温下导致的纤维素明显降解,纺丝液温度不宜超过200°C。在我们的实验中,常用的纺丝温度为60、 80、 100、 120、 140°C。对于高浓度、 高聚合度的纤维素溶液纺丝,可以考虑使用150〜18(TC的高温。在选择喷丝板孔径时,要考虑喷丝压力的限制和纤维纤度的要求。虽然孔径在0.05〜lmm的喷丝板均可以使用,但是比较理想的孔径范围在0.05〜0.5mm之间。选定纺丝液组成、喷丝温度、喷丝板孔径后,喷丝压力决定了喷丝速度。当纺丝液黏度较低、喷丝 Was subjected to spinning nozzle is a multi-parameter, the main parameters are: temperature of the nozzle, pressure nozzle, spinneret aperture, gap length (the distance from the spinneret holes into a coagulation bath) and a draft ratio ( i.e., the ratio of the linear velocity of the first coagulation bath with a drawing roller speed spinning nozzle hole). spinneret temperature on the viscosity of the spinning solution, the general approach used to reduce the viscosity rise in temperature. However, the temperature of the spinning liquid can not be unlimited increased. in order to avoid the cellulose at high temperatures due to significant degradation of the spinning liquid temperature should not exceed 200 ° C. in our experiments, the spinning temperature is commonly 60, 80, 100, 120, 140 ° C for high concentrations, the cellulose solution spun high polymerization degree, consider using 150~18 (TC high temperature. in selecting spinneret pore, and to consider the requirement limits denier fiber spinning pressure. while the pore size 0.05~lmm spinneret can be used, but the ideal pore size range between 0.05~0.5mm. selected spinning solution composition, spinning temperature, spinneret aperture, nozzle pressure determines the spinning speed when low viscosity spinning solution, spinning 板孔径较大时,0.2MPa的压力就能喷出丝来。最慢的喷丝速度可以低至0.5米/分钟。在优选的纺丝条件下,通常喷丝压力在0.5MPa〜4MPa之间,此时喷丝速度可以在10〜200米/分钟之间变动。为便于牵伸,通过调节喷丝温度和压力, 通常把喷丝速度控制在20〜100米/分钟之间。气隙长度的上下限决定于操作因素。为避免凝固浴的波动触及喷丝板,气隙最小值为5mm,气隙最大值为0.5米,更大时操作就不很方便。在使用多孔喷丝板时,气隙越大,纤维越容易粘在一起。比较实用的气隙范围是5〜30厘米,使用多孔喷丝板时气隙长度最好不超过20厘米。 When the aperture plate is large, the discharge pressure of 0.2MPa the wire can be slowest speed spinning can be as low as 0.5 m / min. In a preferred spinning conditions, generally between nozzle pressure 0.5MPa~4MPa in this case the spinning speed may vary between 10~200 m / min. For ease of drawing, by adjusting the nozzle pressure and temperature, usually between 20-100 spinning speed control m / min. air gap length the upper and lower limits determined by operational factors. in order to avoid fluctuations in the coagulation bath touch spinneret minimum gap of 5mm, the maximum gap of 0.5 m, is not more convenient operation. when a porous spinneret , the greater the gap, the more easily the fibers to stick together. more practical range of 5~30 cm air gap, when using a porous spinneret gap length is preferably not more than 20 centimeters. 纤维素/离子液体纺丝体系的牵伸比可以小于l,由于挤出胀大现象,最小的牵伸比可以是Ol,但是小于l的牵伸比没有应用意义,而较大的牵伸比,有利于提高纤维的强度。 Draft ratio cellulose / ionic liquid spinning system may be less than l, since the extrudate swell phenomenon, the minimum draft ratio may be Ol, l but less than the draw ratio meaning not applied, while the larger draft ratio , help to improve the strength of the fiber. 合理选择纺丝条件,可以获得很大的牵伸比。 Reasonable choice of spinning conditions, you can get a great draft ratio. 如使用10X的浆粕溶液、0.5mm 喷丝板和50cm气隙,在10(TC下,以0.3MPa的压力纺丝,喷丝速度为0.5米/分钟, 牵伸速度可以达到100m/分钟,牵伸比高达200。大牵伸比虽然有利于增加喷丝孔径、 降低喷丝速度和喷丝压力,但是要求有大的气隙,在使用多孔喷丝板时容易造成纤维粘连。因此牵伸比最好控制在1〜100之间,较好地为3〜30,更好地为5〜20。在干喷湿纺工艺中,可以在气隙段采用侧吹风的办法以加快纤维冷却。在喷丝板孔数小于20的时候,风冷对改善纺丝工艺无明显效果。当孔数很高的时候,风冷才对提高工艺的稳定性有一定作用。从喷丝孔喷出的纺丝液细流在气隙中拉伸后,在凝固浴中凝固成凝胶态的初生纤维。凝固浴应是能够溶解离子液体,使纤维素再生的溶剂,比如水、乙醇、甲醇、二氯甲烷、氯仿等。从经济性和环保性考虑,优选为水。随 As used in the pulp solution 10X, 0.5mm and 50cm spinneret air gap 10 (the TC, a pressure of 0.3MPa spinning, spinning speed of 0.5 m / min, drawing speeds of up to 100m / min, large draft ratio as high as 200. the draft ratio may help increase spinneret hole diameter, spinning speed and spinning stress reduction, but requires a large air gap, when using a porous likely to cause spinneret fibronectin Accordingly drafting ratio is preferably controlled between 1~100, preferably of 3~30, 5~20 is better. in the dry-jet wet spinning process, the air blow may be employed in the air gap section approach to speed up the cooling of the fiber. when the number of holes in the spinneret of less than 20, the spinning process to improve the air-cooled significant effect when a high number of pores when air fishes have a role to improve the stability of the process. ejected from the orifice after the dope stream in the air gap of fine stretch, coagulation in the coagulation bath the nascent fiber into a gel state. coagulation bath should be capable of dissolving the ionic liquid, the solvent is regenerated cellulose, such as water, ethanol, methanol, dimethyl methylene chloride, chloroform and the like. economic and environmental considerations, preferably water. with 纺丝时间的延长,凝固浴中的离子液体含量逐渐增加。当离子液体在凝固浴中的重量比达到70%时,纤维仍然能够迅速固化。当离子液体在凝固浴中的重量比达到80%时,纤维固化速度变慢,此时牵伸速度不能超过20米/秒。因此,可以选择含0〜70%重量离子液体的水溶液为凝固浴。凝固浴的温度可以有很大的调整范围,可以在凝固点到沸点之间变化。但是从实用角度考虑,凝固浴的温度应该在室温附近。考虑到废热的利用,凝固浴温度在15〜5(TC之间应该较为有利, 一般可以在10〜30°C。对初步固化的纤维进行后牵伸处理是提高纤维强度、改善纤维品质的重要方法。 通过研究发现中,本发明纺丝体系所能达到的后牵伸倍数与在气隙中进行的一次牵伸的倍数有关。 一次牵伸倍数越高,后牵伸所能达到的倍数越低。如一次牵伸的倍数为0.1时,后牵伸的能达到 Spinning extended time, the ionic liquid content in the coagulation bath is gradually increased. When the ionic liquid in a coagulation bath ratio by weight of 70%, the fibers are still able to cure rapidly. As the ionic liquid in a coagulation bath ratio by weight of 80% when the fibers slow curing, drawing speed at this time can not exceed 20 m / sec. Thus, it is possible to select an aqueous solution containing 0~70% by weight of ionic liquid coagulation bath. the coagulation bath temperature may have great adjustment range, can vary between the freezing point to the boiling point. from the practical point of view, however, the coagulation bath temperature should be consideration of the use of waste heat in the vicinity of room temperature, the coagulation bath temperature in 15~5 (should be more favorable between TC, can generally 10~ 30 ° C. preliminary cured fiber after drawing process is to increase fiber strength, an important method of improving fiber quality. study found, the spinning system of the present invention can be achieved with the draw ratio in the air gap the lower drawing of a multiple of about. a higher draw ratio, the draw can be achieved in multiples as a multiple of 0.1 of the draft, the draft can reach 倍数为2.2,最大不超过2.5; —次牵伸为10时,后牵伸能达到的倍数为1.3,最大不超过1.5; —次牵伸大于30的时候,后牵伸的倍数为1-1.1, 即基本上不能进行后牵伸。基于以上事实,应用本发明的纺丝液体系进行干喷湿纺时,可行的工艺条件范围是:纺丝液温度为40〜180°C ,纺丝液黏度为50〜10000Pa's,喷丝孔直径为0.05〜lmm, 喷丝速度为10〜200米/分钟,从喷丝孔到凝固浴(即气隙)的长度为0.005〜0.5米, 牵伸比为1〜200。较好的工艺范围是:纺丝液温度为60〜16(TC,纺丝液黏度为100〜 5000Pa's,喷丝孔直径为0.05〜0.5mm,喷丝速度为20〜100米/分钟,从喷丝孔到凝固浴(即气隙)的长度为0.05〜0.3米,牵伸比为5〜100。 A factor of 2.2, the maximum is not more than 2.5; - 10 times of drawing, post-drawing to achieve a multiple of 1.3, the maximum is not more than 1.5; - 30 times greater than when the drawing, post-drawing multiples 1-1.1 , i.e., after the draft is not substantially based on the above facts, the application of the present invention is spinning solution was dry-jet wet spinning, feasible range of process conditions are: temperature of the spinning solution is 40~180 ° C, the spinning liquid viscosity of 50~10000Pa's, the nozzle hole diameter 0.05~lmm, spinning speed of 10~200 m / min, the length of the nozzle hole into a coagulation bath (i.e., air gap) is 0.005~0.5 m, draft ratio . 1~200 preferred processes are: a temperature of spinning solution 60~16 (TC, spinning solution viscosity of 100~ 5000Pa's, the nozzle hole diameter 0.05~0.5mm, spinning speed of 20-100 m / minutes, the length of the nozzle hole into a coagulation bath (i.e., air gap) is 0.05~0.3 m, draft ratio 5~100. 以上工艺中使用的纺丝液中纤维素浓度一般为3%〜30% (重量),所用纤维素原料的平均聚合度为一般200〜3000。 Cellulose concentration of the spinning solution used in the above processes is generally 3% ~ 30% (by weight), the average degree of polymerization of the cellulose raw material used is generally 200~3000. 较好地,纺丝液浓度为5%〜25%,制备纺丝液的纤维素原料的平均聚合度为250〜1500。 Preferably, the solution concentration of 5% ~ 25%, average polymerization degree of the cellulose raw material for preparing the spinning solution is 250~1500. 在本发明纺丝液体系——纤维素/离子液体溶液中还可以加入某些溶剂,起到进一步降低溶液黏度的作用,但又不引起纤维素沉淀。 In the spinning solution according to the present invention - the cellulose / ionic liquid solution may be added to certain solvents, functions to further reduce the solution viscosity effect, but without causing precipitation of the cellulose. 例如,加入溶液重量15%的二甲基亚砜、二甲基甲酰胺、二甲基乙酰胺等,能使溶液黏度下降约40%,但是溶液仍然澄清透明。 For example, addition of a solution of 15% by weight of dimethyl sulfoxide, dimethylformamide, dimethylacetamide, etc., to make the solution viscosity decreased to about 40%, but the solution was still clear and transparent. 而且,所用离子液体不仅可以为单一种类的离子液体,也可以是几种离子液体的混合液。 Furthermore, the ionic liquid used may be not only a single kind of ionic liquid may be a mixture of several ionic liquids. 例如,在AMIMC1中加入约40X的BMIMC1,溶液黏度不但不增加, 反而略微下降。 For example, adding BMIMC1 about 40X in AMIMC1, the viscosity of the solution not only did not increase, but decreased slightly. 该复配离子液体溶解纤维素的能力仍然很好,而且黏度与纤维素/AMIMC1溶液相当,纺丝工艺也相近。 The ability to dissolve cellulose ionic liquid compound remains good, and viscosity of the cellulose / AMIMC1 quite solution, the spinning process is also similar. 利用纤维素/离子液体纺丝体系,除了能够制造本色丝外,通过添加染料、颜料、 消光剂或各种功能性添加剂,还能够制造染色的、消光的或功能性的再生纤维素丝。 Using cellulose / ionic liquid spinning system, in addition to wire external character can be produced by the addition of dyes, pigments, matting agents, or a variety of functional additives can also be dyed with extinction or regenerated cellulose filaments functionality. 在制造染色或消光的纤维素丝,纺丝工艺基本不用改变,因为颜料、染料或消光剂的添加量本身就很少,纺丝体系的黏度基本不变。 Producing a dyed yarn or cellulose extinction, substantially without changing the spinning process, because the amount of added pigments, dyes or flatting agents itself is small, the viscosity of the spinning system substantially unchanged. 在纤维素/离子液体溶液中添加各种功能型添加剂,如抗紫外剂、抗菌剂、蒙脱土、碳纳米管、壳聚糖、或麦饭石等,就可以制造具有特殊功能的再生纤维素丝。 Add various functional additives cellulose / ionic liquid solution, such as UV, antimicrobial agents, montmorillonite, carbon nanotubes, chitosan, or other stone, recycled fibers can be produced with special functions. Su silk. 为了不对纺丝工艺造成太大的影响,功能添加剂的添加量一般为纤维素干重的0.01〜10%。 In order not to significantly affect the spinning process, the amount of the functional additive is generally added to cellulose by dry weight of 0.01~10%. 应用本发明纺丝体系和方法可以得到再生纤维素长丝和短丝:制备长丝的工艺包括以下步骤:原料准备、混合、溶解、过滤、脱泡、纺丝、洗涤和后牵伸、烘干、上油、巻绕等。 Spinning systems and methods of the present invention is applied can be obtained regenerated cellulose staple fiber and filament: filament preparation process comprises the steps of: preparing a raw material, mixing, dissolving, filtration, degassing, spinning, washing and drawing, drying dry, oil, and the like around the Volume. 制备短丝的工艺包括以下步骤:原料准备、混合、溶解、过滤、脱泡、纺丝、洗涤和后牵伸、烘干、上油、巻曲、切断、打包等。 The process for producing a short fiber comprising the steps of: preparing a raw material, mixing, dissolving, filtration, degassing, spinning, washing and stretching, drying, oiling, Volume curved, cutting and baling. 在原料准备步骤中,纤维素被粉碎成粉末,或开松成蓬松状态。 In the raw material preparation step, the cellulose is pulverized into a powder, or opening into a bulky state. 粉碎或开松纤维素的目的在于增加离子液体浸透纤维素的速度,使纤维素更容易被溶解。 Purpose opening or pulverized cellulose is to increase the ionic liquid permeation speed of the cellulose, the cellulose is more easily dissolved. 使用低温冷却粉碎的办法能够把纤维素粉碎成粉末,或者使用开松机能够J巴纤维素开成需要的蓬松状态。 Using cryogenic cooling can be pulverized to approach the cellulose crushed into a powder, or the use of bulky state opener J bar can be opened to the desired cellulose. 混合步骤使纤维素和离子液体混合均匀。 Mixing step of cellulose and an ionic liquid mixed. 把纤维素投入到离子液体中,然后搅拌捏合至均匀。 The ionic liquid into the cellulose, and then kneaded with stirring until homogeneous. 溶解时,温度越高,溶解速度越快。 When dissolved, the higher the temperature, the faster the dissolution. 但是使用过高的溶解温度不仅能耗高,而且易造成纤维素降解和离子液体变色,因此最高溶解温度不超过20(TC,较适宜的溶解温度为80〜15(TC。由于高分子量、高浓度纤维素溶液的黏度一般很大, 而且离子液体不挥发,因此,脱泡最好在真空下进行,真空度最高可以使用-0.1MPa。如前所述,纺丝采用干喷湿纺法,具体参数一般为:喷丝温度40〜18(TC,黏度100〜10000Pa.s,喷丝板孔径O.O5〜0.5mm,喷丝速度为20〜100米/分钟,气隙长度0.005〜0.5米,牵伸比1〜200。凝固浴的组成可以为含0〜80%重量离子液体的水溶液,温度在0〜9(TC之间;优选为,浓度为0〜70%重量离子液体的水溶液,温度为10〜50°C。从凝固浴中出来的初生纤维经历3〜16次水洗,以彻底洗脱纤维中的离子液体。在洗涤过程中及洗涤后, 对纤维进行0〜3次后牵伸,后牵伸的总牵伸比为1〜5。纤维的干燥温 However, the use of high temperature not only high energy consumption was dissolved, and easily lead to color degradation of cellulose and an ionic liquid, thus dissolving the maximum temperature did not exceed 20 (TC, more appropriate dissolution temperature of 80~15 (TC. Due to the high molecular weight, high the concentration of cellulose solution viscosity is generally large, and the ionic liquid does not volatilize, and therefore, degassing is preferably carried out under vacuum, up to a degree of vacuum may be used -0.1MPa. As described above, the spinning by a dry jet wet spinning method, typically specific parameters: nozzle temperature 40~18 (TC, viscosity 100~10000Pa.s, spinneret aperture O.O5~0.5mm, spinning speed of 20-100 m / min, the air gap length 0.005~0.5 m ., draft ratio 1~200 composition of the coagulation bath may be an aqueous solution of 0~80% by weight of ion-containing liquid, the temperature (between 0~9 TC; preferably, 0~70% by weight aqueous solution at a concentration of ionic liquid, after the temperature is 10~50 ° C. out from the coagulation bath the nascent fiber experiences 3~16 washes, elution ionic liquid to thoroughly fibers after washing and during the washing process, the fibers are led 0~3 times extension, the total draw ratio of the drawing 1 ~ 5. drying temperature fibers 度为80〜200 °C,可以采取热辊干燥,也可以采取蒸汽烘干。根据需要,总纺丝速度可以在50〜1000米/分钟之间调整。这样可以得到产品规格为0.5〜2000dtex之间各种长丝和短丝。在生产过程中,对从凝固、洗涤工序回收的离子液体水溶液进行常规过滤、超滤处理,以除去其中可能残留的纤维素或其它不溶物颗粒,过滤液经脱色处理。再结合常压蒸发、多级闪蒸、多效蒸发、薄膜蒸发、反渗透、离子交换等手段,或者这些手段的组合运用对过滤液中的离子液体进行回收。通过回收,使大于99Q/^的离子液体实现循环利用,而且使大部分水实现循环利用。以下以具体实施例来说明本发明工艺。 Degree of 80~200 ° C, hot roll drying may take, may also take the steam drying. If necessary, the total spinning speed can be adjusted between 50~1000 m / min. Thus obtained product specifications for the 0.5~2000dtex various inter-filament and staple fiber. in the production process, solidification of the washing step of the recovered ionic liquid aqueous solution subjected to conventional filtration, ultrafiltration, to remove the residual cellulose which may, or other insoluble particles, was filtered through bleaching treatment. recombined evaporation pressure, multi-stage flash, multiple effect evaporation, thin film evaporation, reverse osmosis, ion exchange means, or a combination of these measures the use of an ionic liquid filtrate is recovered by recycling, making greater than 99Q / ^ achieve recycling ionic liquid, but also to achieve recycling most of the water. the following specific examples will be described in the process of the present invention.

实施例1〜17 Example 1~17

使用微晶纤维素、木桨粕、脱脂棉三种原料,配制了平均分子量为300〜800,浓度在8〜18X的纤维素/AMIMC1溶液,经过滤、脱泡处理后在各种条件下进行干喷湿纺,凝固浴为浓度为0〜20% (重量)的AMIMC1水溶液。 Microcrystalline cellulose, wood pulp meal, cotton three materials, the average molecular weight of 300~800 formulated, the concentration of the cellulose / AMIMC1 8~18X the solution, was filtered, defoamed and subjected to dry treatment under various conditions jet wet spinning, solidifying bath of a concentration of 0~20% (by weight) aqueous solution of AMIMC1. 初生纤维经6次去离子水洗涤,80〜150。 Spun fiber was washed six times with deionized water, 80~150. C烘干。 C drying. 产品纤维恒温房间内放置48小时后测拉伸性能,每个样品测10次,取平均值。 After 48 hours the product measured room temperature tensile properties of fibers, each sample was measured 10 times and averaged. 具体的喷丝条件和产品纤度、拉伸强度见表3。 Specific spinning conditions and product fineness, tensile strength in Table 3.

实验证明,纤维素/低黏度离子液体体系适合于用干喷湿纺技术进行纺丝,具有工艺范围宽、温度条件温和、压力适中、纺丝速度快等优点,能够制备性能优良、规格齐全的再生纤维素纤维。 Experiments show that the cellulose / ionic liquid system is suitable for low viscosity spun by dry jet wet spinning technique, with a wide range of technology, mild temperature conditions, moderate pressure, fast spinning speed, etc., excellent properties can be produced, the complete specifications Regenerated Cellulose Fiber.

同时,实验表明,通过简单的减压蒸发就能够实现离子液体的循环利用,离子液体的回收率能够达到99%以上。 Meanwhile, experiments show that, by simple evaporation under reduced pressure can be realized recycling the ionic liquid, the ionic liquid recovery can reach more than 99%.

实施例18〜35 Example 18~35

按照与AMIMC1基本相同的工艺,使用l-乙基-3-甲基咪唑醋酸盐等其它低黏度离子液体进行了纤维素纺丝实验,典型的实验数据与结果列于表4中。 Following AMIMC1 substantially the same process, other low-viscosity ionic liquids l- ethyl-3- methylimidazolium acetate, etc. cellulose spinning experiment, typical experimental data and results are shown in Table 4.

从这些实施例可以看出,与使用AMIMC1做纤维素溶剂一样,使用这些低黏度离子液体在比较低的温度下也可以纺制出再生纤维素纤维,所得纤维性能良好。 As can be seen from these examples, using the same solvent as cellulose AMIMC1, ionic liquids using these low viscosity at a relatively low temperature may be a spun regenerated cellulose fibers, the resultant fibers good performance.

实施例36〜40 Example 36~40

按照与实施例1〜5基本相同的工艺,使用l-烯丙基-3-甲基咪唑氯盐离子液体为溶剂,在纤维素溶液中加入不同含量碳纳米管进行了纤维素纺丝实验,典型的实验数 Example 1 ~ 5 according to substantially the same process, using l- allyl-3-methyl-imidazolium chloride ionic liquid as solvent, was added varying amounts of carbon nanotubes are spun cellulose experiments cellulose solution, a typical experiment number

据与结果列于表5中,其中,纤维素浓度:8%,纤维素聚合度:550,喷丝温度:80 According to the results shown in Table 5, wherein the cellulose concentration: 8%, cellulose polymerization degree: 550, nozzle temperature: 80

. C,气隙长度:5cm,喷丝压力:2MPa; 喷丝速度:40m/s, 牵伸速度:160m/s, 喷丝板孔数:1,喷丝板孔径:0. lmm。 C, gap length: 5cm, nozzle pressure: 2MPa; spinning speed:. 40m / s, drawing speed: 160m / s, the number of spinneret holes: 1, spinneret aperture: 0 lmm.

从这些实施例可以看出,与使用AMIMC1做纤维素溶剂一样,在纤维素/离子液体中加入碳纳米管可以纺制出具有抗静电性能的再生纤维素纤维,所得纤维力学性能良好。 As can be seen from these examples, using the same solvent as cellulose AMIMC1, carbon nanotubes are added to the cellulose / ionic liquid can be a spun regenerated cellulose fiber having antistatic properties, good mechanical properties of the resulting fibers.

表5含碳纳米管的纤维素/AMIMCl溶液干喷湿纺的实施例 Table 5 Cellulose containing carbon nanotube / AMIMCl embodiment of dry-jet wet spinning a solution of

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实施例39〜41 Example 39~41

按照与实施例1〜5基本相同的工艺,使用l-烯丙基-3-甲基咪唑氯盐离子液体为溶剂,在纤维素溶液中加入复配溶剂DMSO进行了纤维素纺丝实验,典型的实验数据与结果列于表6中,其中,纤维素浓度:8%,纤维素聚合度:550,喷丝温度:80 °C, 气隙长度:5 cm, 喷丝速度:40 m/s,牵伸速度:200 m/s,喷丝板孔数:1,喷丝板孔径:0. 05mm。 Example 1 ~ 5 according to substantially the same process, using l- allyl-3-methyl-imidazolium chloride ionic liquid as solvent, the solvent added DMSO complex in the cellulose solution was spun cellulose experiment, typical the experimental data and results are shown in table 6, wherein the cellulose concentration: 8%, cellulose polymerization degree: 550, nozzle temperature: 80 ° C, gap length: 5 cm, the spinning speed: 40 m / s , drawing speed: 200 m / s, the number of spinneret holes: 1, spinneret aperture:. 0 05mm.

从这些实施例可以看出,与单独使用AMIMC1做纤维素溶剂一样,在纤维素/离子液体中加入复配溶剂DMSO同样可以纺制出再生纤维素纤维,所得纤维力学性能良好。 From these examples it can be seen that, as cellulose AMIMC1 used alone as a solvent, the solvent added DMSO complex in the cellulose / ionic liquid can also be a spun regenerated cellulose fibers, the resultant fiber good mechanical properties. 使用其他的复配溶剂如二甲基甲酰胺、二甲基乙酰胺等也具有同样的效果,并且, 这些复配溶剂也可以混合使用,这也不影响纺丝效果。 Other complex using a solvent such as dimethyl formamide, dimethyl acetamide and the like have the same effect, and these solvent mixtures may also be used in combination, which does not affect spinning effect.

表6含复配溶剂二甲基亚砜(DMSO)的纤维素/AMIMCl溶液干喷湿纺的实施例 Table 6 Cellulose-containing compound dimethyl sulfoxide (DMSO) is / AMIMCl embodiment of dry-jet wet spinning a solution of

实施例<table>table see original document page 13</column></row> <table>表3纤维素/AMIMCl溶液干喷湿纺的实施例<table>table see original document page 14</column></row> <table>表4使用其他离子液体进行纤维素溶液干喷湿纺的实施例 EXAMPLES Example <table> table see original document page 13 </ column> </ row> <table> Table 3 Cellulose / AMIMCl dry-jet wet spinning a solution of <table> table see original document page 14 </ column> < / row> <table> table 4 using other ionic liquid solution of cellulose dry-jet wet spinning in Example

<table>table see original document page 15</column></row> <table> <Table> table see original document page 15 </ column> </ row> <table>

Claims (11)

1、一种利用离子液体制备再生纤维素纤维的方法,是将纤维素原料溶解在离子液体中形成纺丝液,纺丝得到凝胶态的再生纤维素纤维,再经过洗涤、后牵伸和烘干,得到再生纤维素纤维,其特征在于:所述离子液体选自以下如下离子液体中的一种或几种: a)阳离子为1,3-二烷基咪唑,阴离子为甲酸根、醋酸根或丙酸根的离子液体;其中,烷基为含有1-8个碳原子的烷基; b)阳离子为1-R1-3-R2-二烃基咪唑,阴离子选自氯、溴、碘、甲酸根、醋酸根、丙酸根、硫酸根、硝酸根、四氟硼酸根、硫氰酸根、六氟磷酸根、对甲苯磺酸根和三氟甲磺酸根的离子液体;其中,R1为符合以下规则的烃基:①至少含有2个碳原子,②不多于20个碳原子,③至少含有一个双键;R2为含有1~4个碳原子的饱和或不饱和的烃基。 1. A method of preparing ionic liquid by using regenerated cellulose fibers, the cellulose starting material is dissolved to form a spinning solution in an ionic liquid, regenerated cellulosic fibers obtained by spinning in a gel state, and then after washing, drawing and drying dried, regenerated cellulose fibers, characterized in that: the ionic liquid is selected from one or more of the following ionic liquids are as follows: a) a 1,3-dialkyl imidazolium cation, the anion is formate, acetate ionic liquids or propionate; wherein alkyl is an alkyl group having 1 to 8 carbon atoms; b) the cation is 1-R1-3-R2- dialkyl imidazole, anion selected from chloride, bromide, iodide, formate , acetate, propionate, sulfate, nitrate, tetrafluoroborate, thiocyanate, hexafluorophosphate, p-toluenesulfonate ion liquid and triflate; wherein, Rl is a hydrocarbon group subject to the following rules : ① containing at least 2 carbon atoms, ② not more than 20 carbon atoms, ③ containing at least one double bond; R2 is a saturated or unsaturated hydrocarbon group having 1 to 4 carbon atoms.
2、 根据权利要求1所述的方法,其特征在于:所述离子液体选自以下离子液体或其混合物:l-乙基-3-甲基咪唑甲酸盐,l-乙基-3-甲基咪唑醋酸盐,l-乙基-3-甲基咪唑丙酸盐,l-丙基-3-甲基咪唑甲酸盐,l-丙基-3-甲基咪唑醋酸盐,l-丙基-3-甲基咪唑丙酸盐,l-丁基-3-甲基咪唑甲酸盐,l-丁基-3-甲基咪唑醋酸盐,l-丁基-3-甲基咪唑丙酸盐,l-烯丙基-3-甲基咪唑氯盐,l-烯丙基-3-甲基咪唑甲酸盐,l-烯丙基-3-甲基咪唑醋酸盐,l-烯丙基-3-甲基咪唑丙酸盐,l-烯丙基-3-甲基咪唑硫酸盐,1-甲基烯丙基-3-甲基咪唑氯盐,l-甲基烯丙基-3-甲基咪唑甲酸盐,l-甲基烯丙基-3-甲基咪唑醋酸盐, l-甲基烯丙基-3-甲基咪唑丙酸盐,l-甲基烯丙基-3-甲基咪唑硫酸盐。 2. The method according to claim 1, wherein: the ionic liquid selected from the ionic liquids or mixtures thereof: L-ethyl-3- methylimidazolium formate, l- ethyl-3-carboxylic imidazole acetate, l- ethyl-3-methylimidazolium propionate, l- propyl-3-methylimidazolium formate, l- propyl-3-methylimidazolium acetate, l- propyl-3-methylimidazolium propionate, l- butyl-3-methylimidazolium formate, l- butyl-3-methylimidazolium acetate, l- butyl-3-methylimidazolium propionate, l- allyl-3-methylimidazolium chloride, l- allyl-3-methylimidazolium formate, l- allyl-3-methylimidazolium acetate, l- allyl-3-methylimidazolium propionate, l- allyl-3-methylimidazolium sulfate, 1-methyl-allyl-3-methylimidazolium chloride, l- methallyl 3-methylimidazolium formate, l- methyl-allyl-3-methylimidazolium acetate, l- methyl-allyl-3-methylimidazolium propionate, l- methallyl -3-methylimidazolium sulfate.
3、 根据权利要求1所述的方法,其特征在于:所述离子液体中还可加有复配溶齐U,复配溶剂为离子液体重量的5〜40%;所述复配溶剂选自二甲基亚砜、二甲基甲酰胺、二甲基乙酰胺中的一种或几种。 3. The method according to claim 1, wherein: the ionic liquid compound may also be added together dissolved U, complex ionic liquid solvent is 5 ~ 40% by weight; the solvent is selected from compound dimethyl sulfoxide, dimethyl formamide, dimethyl acetamide or a few.
4、 根据权利要求1所述的方法,其特征在于:所述纺丝液中纤维素的平均聚合度为200〜3000,质量浓度为3〜30%;优选的,纺丝液中纤维素的平均聚合度为250 一1500,质量浓度为5〜25%。 4. The method of claim 1, wherein: the average degree of polymerization of the cellulose in the spinning solution is 200~3000, the concentration of 3~30%; preferably, the spinning solution of cellulose The average degree of polymerization of 250 to 1500, the concentration of 5~25%.
5、 根据权利要求1所述的方法,其特征在于:所述纤维素为从细菌纤维素、棉花、脱脂棉、棉短绒、棉浆粕、木浆粕、竹浆粕、微晶纤维素以及麻、稻草、小麦秸秆、棉花秸秆、玉米秸秆、甘蔗渣和各种草中提取的纯度达到90%以上的纤维素,或者这些纤维素原料的混合物。 5. The method according to claim 1, wherein: said bacterial cellulose from cellulose, cotton, cotton linters, cotton pulp, wood pulp, bamboo pulp, microcrystalline cellulose, and hemp, rice straw, wheat straw, cotton stalks, corn stover, bagasse, grasses and extracted purity of more than 90% of cellulose, or a mixture of these cellulosic feedstocks.
6、 根据权利要求1所述的方法,其特征在于:所述纺丝液中还添加有功能材料,功能材料选自抗紫外剂、抗菌剂、阻燃剂、蒙脱土、碳纳米管、壳聚糖和麦饭石;功能材料的添加量为纤维素重量的0.01〜10%。 6. The method of claim 1, wherein: said spinning solution added with further functional materials, functional materials selected from ultraviolet, antimicrobial agents, flame retardants, montmorillonite, carbon nanotubes, chitosan and Maifanshi; 0.01~10% by weight of the functional additive amount of cellulose material.
7、 根据权利要求1所述的方法,其特征在于:纺丝液的温度为40〜18(TC,粘度为50〜10000 Pa*s;优选的,纺丝液的温度为60〜160°C,粘度为100〜5000 Pa.s。 7. The method of claim 1, wherein: the temperature of the spinning solution is 40~18 (TC, viscosity 50~10000 Pa * s; Preferably, the temperature of the spinning solution is 60~160 ° C and a viscosity of 100~5000 Pa.s.
8、 根据权利要求1一7任一所述的方法,其特征在于:纺丝得到凝胶态的再生纤维素纤维是采用干喷湿纺工艺进行的,是将纺丝液挤压通过开有若干喷丝孔的喷丝装置进入空气,在空气中经历拉伸,然后进入凝固浴固化,得到凝胶态的再生纤维素纤维。 8. A method as claimed in any one of claims 1 a 7, wherein: regenerated cellulosic fibers obtained by spinning the gel state dry-jet wet spinning process is performed, the spinning solution is extruded through the opened a plurality of spinner orifice into the air, subjected to stretching in the air, and then cured into a coagulating bath, to obtain regenerated cellulose fiber in the gel state.
9、 根据权利要求8所述的方法,其特征在于:喷丝孔直径为0.05〜lmm,喷丝压力为0.5—4MPa,喷丝速度为10〜200米/分钟,从喷丝孔到凝固浴的距离为0.005〜 0.5米,牵伸比为1〜200;优选的,喷丝孔直径为0.05〜0.5mm,喷丝速度为20〜100 米/分钟,从喷丝孔到凝固浴的距离为0.05〜0.3米,牵伸比为5〜100。 9. The method of claim 8, wherein: the nozzle hole diameter 0.05~lmm, nozzle pressure is 0.5-4MPa, spinning speed of 10~200 m / min into a coagulation bath from a nozzle hole 0.005~ distance of 0.5 m, draw ratio of 1~200; preferably, the nozzle hole diameter 0.05~0.5mm, spinning speed of 20-100 m / min, the distance from the nozzle orifice to the coagulating bath is 0.05~0.3 m, draft ratio 5~100.
10、 根据权利要求8所述的方法,其特征在于:所述凝固浴为含0〜70%重量离子液体的水溶液,凝固浴的温度为10〜50°C。 10. The method of claim 8, wherein: 0~70% by weight of a bath containing an aqueous solution of the ionic liquid coagulation, the coagulation bath temperature of 10~50 ° C.
11、 根据权利要求1一7任一所述的方法,其特征在于:所述洗涤以水为洗涤剂; 所述后牵伸的倍数为1〜5倍,后牵伸次数为0〜3次;烘干温度为80〜20(TC。 11. The method according to any of claims 1 a 7, wherein: said wash water to the detergent; the draft multiples after 1 ~ 5 times, the number of post-drawing 0~3 times ; drying temperature is 80~20 (TC.
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CN107675491A (en) * 2017-11-14 2018-02-09 河南工程学院 A kind of high ultraviolet reflection rate film based on bacteria cellulose and preparation method thereof
CN107675491B (en) * 2017-11-14 2019-10-11 河南工程学院 A kind of high ultraviolet reflection rate film and preparation method thereof based on bacteria cellulose
CN108130608A (en) * 2018-01-31 2018-06-08 中原工学院 A kind of method that waste pure cotton dress object recycling prepares regenerated celulose fibre
CN109468688A (en) * 2018-11-22 2019-03-15 绍兴美标纺织品检验有限公司 The spinning process of cellulose fibre

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