WO2014056383A1 - 一种溶解纤维素的方法 - Google Patents

一种溶解纤维素的方法 Download PDF

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WO2014056383A1
WO2014056383A1 PCT/CN2013/083373 CN2013083373W WO2014056383A1 WO 2014056383 A1 WO2014056383 A1 WO 2014056383A1 CN 2013083373 W CN2013083373 W CN 2013083373W WO 2014056383 A1 WO2014056383 A1 WO 2014056383A1
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cellulose
solvent
solution
hours
dissolving
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PCT/CN2013/083373
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English (en)
French (fr)
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汤炼
周金平
王云波
李道喜
李雅明
郑志强
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湖北天思科技股份有限公司
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Priority to JP2014555936A priority Critical patent/JP5913638B2/ja
Priority to EP13845708.0A priority patent/EP2845874B1/en
Publication of WO2014056383A1 publication Critical patent/WO2014056383A1/zh
Priority to US14/540,696 priority patent/US20150135991A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/02—Cellulose; Modified cellulose
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B1/00—Preparatory treatment of cellulose for making derivatives thereof, e.g. pre-treatment, pre-soaking, activation
    • C08B1/003—Preparation of cellulose solutions, i.e. dopes, with different possible solvents, e.g. ionic liquids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
    • C08J3/05—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media from solid polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
    • C08J2301/02—Cellulose; Modified cellulose

Definitions

  • the present invention relates to a method of dissolving cellulose.
  • cellulosic resources are closely related to the textile, light industry, chemical, defense, petroleum, pharmaceutical, biotechnology, environmental protection and energy sectors, and are widely used in the production of cellulose materials such as paper, fiber membranes, polymers and coatings.
  • natural cellulose molecules have a high degree of crystallinity, and a large number of hydrogen bonds exist between molecules and molecules, which makes them difficult to dissolve and difficult to melt process.
  • viscose fiber has always occupied a major position in the field of textile regenerated cellulose fibers.
  • the cellulose solvent is divided into a non-derivatized solvent and a derivatization solvent, and a derivatization solvent (CS 2 /NaOH/H 2 O, N 2 O 4 / dimethyl group) in which the cellulose undergoes a derivatization reaction during the dissolution process
  • a derivatization solvent CS 2 /NaOH/H 2 O, N 2 O 4 / dimethyl group
  • An amide or the like which does not form a derivative during the dissolution process, is called a non-derivatized solvent (amine oxide system, LiOH/dimethylacetamide, ionic liquid, NaOH/urea, etc.). Since the insoluble solvent dissolves cellulose as a physical process, its dissolution process is not easy to affect the chemical structure of cellulose, and the process of producing cellulose products is relatively simple.
  • Celanese company in GB patent t263810 proposed that cellulose is soluble in the phosphoric acid system, the system is a complex solution of phosphoric acid and polyphosphoric acid, the temperature control is strict when dissolving cellulose, and the solubility of the system must be improved to improve the quality of P 2 O 5 The fraction, its long dissolution time also limits the development of industrialization.
  • Graenacher discovered that molten N-ethylpyridine chloride can dissolve cellulose, but it has not been developed due to its high melting point.
  • Swatloski et al. found that cellulose can be directly dissolved in room temperature ionic liquid without activation.
  • the ionic liquid 1-butyl-3-methylimidazole was reported as a cellulose solvent.
  • Patent JP 1777283 discloses the dissolution of cellulose in a 2.5 mol/L NaOH aqueous solution, but only a steam blasting treatment of wood pulp cellulose having a degree of polymerization of less than 250, which is dissolved in the aqueous NaOH solution at about 4 ° C. Among them, the fiber and film produced by the method have extremely low strength and are not suitable for industrial production.
  • Wuhan University patents CN00114486.3, CN00114485.5, CN03128386.1, CN200310111566.3, CN200410013389.X and WO 2006/128346A1 use aqueous solutions of sodium hydroxide and urea, aqueous solutions of sodium hydroxide and thiourea directly under low temperature conditions. Dissolving natural cellulose, the solution can be stable for a long time in the range of 0-5 ° C. Fibers and membranes are obtained in the laboratory using this solvent system, but the properties of the cellulose solution in the system are greatly affected by temperature. Industrialization has not been achieved so far.
  • Cellulose non-derivatized solvent does not chemically change cellulose in the production process of cellulose products, and the process flow is simple, so it has been greatly developed. However, in general, the non-derivatized solvent dissolves cellulose first. Activation, the simplicity of the activation process, the environmental friendliness of the solvent, the stability of the prepared cellulose solution, and the economics of the raw materials all constrain the industrialization process.
  • the cellulose is heated and activated by a heating device, and then dissolved by using a solvent.
  • the solvent dissolves cellulose by a freeze-thaw method to prepare a cellulose solution having a high concentration and high stability, and the obtained cellulose solution can be used for the production of other cellulose products such as fibers, films, sponges, and the like.
  • the technical solution of the present invention is a method for dissolving cellulose, characterized in that the cellulose is first heated and activated by a heating device, and then dissolved by using a solvent.
  • the cellulose is heated and activated, and the activation heating temperature is 130-270 ° C, and the heating time is 0.1-100 hours.
  • One such solvent is an aqueous solution containing 6 w% t-12 wt% sodium hydroxide and 0.1 wt%-6 wt% zinc oxide.
  • a preferred solvent for dissolving cellulose is 7.0 wt% to 9.0 wt% sodium hydroxide and 0.5 wt% to 2.0.
  • a method of dissolving cellulose of the present invention, wherein the solvent dissolves cellulose is carried out as follows:
  • step 2) The material subjected to the step 1) freezing treatment is thawed at a temperature not higher than 32 ° C, and the thawing process is allowed to stand or mechanically stirred to obtain a concentration of 3 wt% -12 Wt% cellulose solution.
  • the freezing temperature is -12 ⁇ -18 ° C
  • the freezing time is 0.1-50 hours
  • the degree of polymerization DP of the cellulose ranges from 350 to 550;
  • the thawing temperature is 10 to 22 ° C
  • the concentration of the cellulose solution obtained by the dissolution is 5.0 wt% to 8.5. Wt%.
  • the cellulose solution obtained by the invention has good solubility and high stability, and can be in -8 ⁇ Maintaining good stability after standing for several days at 32 °C.
  • the cellulose solution can be used for the preparation of fibers, films or sponges, and is particularly suitable for industrial production.
  • the invention has the following advantages:
  • the solubility of the cellulose solution is good, there is no colloidal particles with a diameter larger than 5 microns in the solution; the stability of the solution is good, and there is no significant change after standing at room temperature for 24 to 120 hours; the concentration of the solution is relatively high, in the present invention Solution concentration can reach wt%3-12 Wt%, which is close to the cellulose concentration in the current viscose production, suitable for industrial production;
  • the activation equipment is simple and easy to implement, the solvent is simple to prepare, the solvent components are only NaOH, zinc oxide and water, and the components are cheap and have good economy. Since the solvent component is simple, in the process of preparing the cellulose product, solvent recovery is easy, the recovery cost is low, and the recycled product can be recycled, which is advantageous for large-scale industrial production.
  • Figure 1 is a microscopic morphology of a cellulose solution prepared in Example 1 of the present invention.
  • Example 2 is a microscopic morphology of a cellulose solution prepared in Example 2 of the present invention.
  • Figure 3 is a microscopic morphology of a cellulose solution prepared in Example 3 of the present invention.
  • Figure 4 is a microscopic morphology of a cellulose solution prepared in Example 4 of the present invention.
  • Figure 5 is a microscopic morphology of a cellulose solution prepared in Example 5 of the present invention.
  • Figure 6 is a microscopic morphology of a cellulose solution prepared in Example 6 of the present invention.
  • Figure 7 is a graph showing the change in stability of cellulose in the cellulose solution prepared in Example 1, Example 2, Example 3, Example 4, Example 5, and Example 6 of the present invention as a function of time.
  • Figures 1 - 6 show a 100x magnification photograph using a fiber projector CYG-055DI.
  • a certain mass of cotton pulp cellulose having a polymerization degree of 350 was weighed and placed in an oven at 138 ° C for 3 hours, and taken out for use.
  • an aqueous solution of sodium hydroxide having a mass concentration of 12% and zinc oxide having a mass concentration of 5% is used as a cellulose solvent, and the heat-activated cellulose is weighed according to a ratio of a mass concentration of 8.5%.
  • the cellulose is placed in a well-prepared cellulose solvent and stirred evenly so that all of the cellulose is below the liquid level.
  • the mixture was then frozen in a freezer at -15 ° C for 5 hours, taken out and thawed at room temperature, and the room temperature was 22 ° C.
  • the temperature of the mixture was raised to 22 ° C and stirred with a glass rod to obtain a clear cellulose solution.
  • a small amount of this solution was placed in a fiber projector CYG-055DI, observed and photographed at 100 times magnification.
  • the micrograph is shown in Figure 1.
  • the cellulose is completely dissolved, and the colloidal particles are less than 5 microns in diameter.
  • the solution was stored at room temperature of 22 ° C for 100 hours.
  • the upper layer of liquid was taken at different time periods to dry and weigh the solid content of the cellulose.
  • the relationship between the solid content of the cellulose in the initial 0 hour solution is shown in Figure 7, and the sedimentation amount after 100 hours. It was 5.5 wt%, and the unsettled weight ratio was 94.5 wt%.
  • the cellulose solution has good solubility and stability.
  • a certain mass of cotton pulp cellulose having a polymerization degree of 550 was weighed and placed in an oven at 230 ° C for 0.3 hours, and taken out for use.
  • an aqueous solution of sodium hydroxide having a mass concentration of 7% and zinc oxide having a mass concentration of 1.0% is used as a cellulose solvent, and the heat-activated cellulose is weighed according to a ratio of a concentration of 4.5%.
  • the cellulose is placed in a well-prepared cellulose solvent and stirred evenly so that all of the cellulose is below the liquid level.
  • the mixture was then frozen in a freezer at -13 ° C for 12 hours, taken out and thawed at room temperature, and the room temperature was 23 ° C.
  • the temperature of the mixture was raised to 23 ° C and stirred with a glass rod to obtain a clear cellulose solution.
  • a small amount of this solution was placed in a fiber projector CYG-055DI, and observed and photographed at 100 times magnification.
  • the micrograph is shown in Figure 2.
  • the cellulose is completely dissolved, and the colloidal particles are less than 5 microns in diameter.
  • the solution was stored at room temperature of 23 ° C for 120 hours.
  • the solid content of the cellulose was measured by taking the upper layer of liquid at different time intervals.
  • the relationship between the solid content of the cellulose and the solid content of the solution in the initial 0 hour is shown in Figure 7, and the sedimentation amount after 120 hours. It was 4.8 wt%, and the unsettled weight ratio was 95.2% by weight.
  • a certain mass of cotton pulp cellulose having a polymerization degree of 380 was weighed and placed in an oven at 190 ° C for 0.8 hours, and taken out for use.
  • an aqueous solution of sodium hydroxide having a mass concentration of 6% and zinc oxide having a mass concentration of 0.5% is used as a cellulose solvent, and the heat-activated cellulose is weighed according to a ratio of a mass concentration of 5%.
  • the cellulose is placed in a well-prepared cellulose solvent and stirred evenly so that all of the cellulose is below the liquid level.
  • the mixture was frozen in a freezer at -16 ° C for 1 hour, taken out and thawed at a rate of 150 r / min at room temperature, and the room temperature was 22 ° C.
  • the temperature of the mixture was raised to 22 ° C to obtain a clear cellulose solution.
  • a small amount of this solution was placed in a fiber projector CYG-055DI, and observed and photographed at 100 times magnification.
  • the micrographs shown in Fig. 3 were all dissolved, and the colloidal particles were less than 5 ⁇ m in diameter.
  • the solution was stored at room temperature of 22 ° C for 120 hours.
  • the upper layer of liquid was taken at different time intervals to dry and weigh the solid content of the cellulose.
  • the relationship between the solid content of the cellulose in the initial 0 hour solution is shown in Figure 7, and the sedimentation amount after 120 hours. It was 5.9 wt%, and the unsettled weight ratio was 94.1% by weight.
  • a certain mass of cotton pulp cellulose having a polymerization degree of 450 was weighed and placed in an oven at 175 ° C for 1 hour, and taken out for use.
  • an aqueous solution of sodium hydroxide having a mass concentration of 10% and zinc oxide having a mass concentration of 1.5% is used as a cellulose solvent, and the heat-activated cellulose is weighed according to a ratio of a concentration of 7.0%.
  • the cellulose is placed in a well-prepared cellulose solvent and stirred evenly so that all of the cellulose is below the liquid level.
  • the mixture was then frozen in a freezer at -25 ° C for 10 hours, taken out and thawed at room temperature, and the room temperature was 24 ° C.
  • the temperature of the mixture was raised to 24 ° C and stirred with a glass rod to obtain a clear cellulose solution.
  • a small amount of this solution was placed on a fiber projector CYG-055DI, observed and photographed at 100 times magnification.
  • the micrograph is shown in Figure 4.
  • the cellulose is completely dissolved, and the colloidal particles are less than 5 microns in diameter.
  • the solution was stored at room temperature of 24 ° C for 120 hours.
  • the upper layer of liquid was taken at different time periods to dry and weigh the solid content of cellulose.
  • the relationship between the solid content of the cellulose in the initial 0 hour solution is shown in Figure 7, and the sedimentation amount after 120 hours. It was 4.7 wt%, and the unsettled weight ratio was 95.3 wt%.
  • a certain mass of cotton pulp cellulose having a polymerization degree of 420 was weighed and placed in an oven at 210 ° C for 1.5 hours, and taken out for use.
  • an aqueous solution of sodium hydroxide having a mass concentration of 11% and zinc oxide having a mass concentration of 2.5% is disposed as a cellulose solvent, and the heat-activated cellulose is weighed according to a ratio of a concentration of 6.5%.
  • the cellulose is placed in a well-prepared cellulose solvent and stirred evenly so that all of the cellulose is below the liquid level.
  • the mixture was then frozen in a freezer at -20 ° C for 3 hours, taken out and thawed at room temperature, and the room temperature was 22 ° C.
  • the temperature of the mixture was raised to 22 ° C and stirred with a glass rod to obtain a clear cellulose solution.
  • a small amount of this solution was placed in a fiber projector CYG-055DI, and observed and photographed at 100 times magnification.
  • the micrograph is shown in Fig. 5.
  • the cellulose is completely dissolved, and the colloidal particles have a diameter of less than 5 ⁇ m.
  • the solution was stored at room temperature of 22 ° C for 120 hours.
  • the upper layer of liquid was taken at different time intervals to dry and weigh the solid content of the cellulose.
  • the relationship between the solid content of the cellulose in the initial 0 hour solution is shown in Figure 7, and the sedimentation amount after 120 hours. It was 5.7 wt%, and the unsettled weight ratio was 94.3 wt%.
  • a certain mass of cotton pulp cellulose having a polymerization degree of 500 was weighed and placed in an oven at 200 ° C for 1 hour, and taken out for use.
  • an aqueous solution of sodium hydroxide having a mass concentration of 8% and zinc oxide having a mass concentration of 0.7% is used as a cellulose solvent, and the heat-activated cellulose is weighed according to a mass concentration of 7.5%.
  • Put in the prepared cellulose solvent stir evenly, let the cellulose all immersed below the liquid surface. Then, the mixture was frozen in a freezer at -28 ° C for 10 hours, taken out and thawed slowly at room temperature, and the room temperature was 21 ° C.
  • the temperature of the mixture was raised to 21 ° C to obtain a clear cellulose solution.
  • a small amount of this solution was placed in a fiber projector CYG-055DI, and observed and photographed at 100 times magnification.
  • the micrographs of the cellulose shown in Fig. 6 were all dissolved, and the colloidal particles were less than 5 ⁇ m in diameter.
  • the solution was stored at 21 ° C for 120 hours at room temperature.
  • the upper layer of liquid was taken at different time intervals to dry and weigh the solid content of the cellulose.
  • the relationship between the solid content of the cellulose in the initial 0 hour solution is shown in Figure 7, and the sedimentation amount after 100 hours. It was 5.6 wt%, and the unsettled weight ratio was 94.4% by weight.

Abstract

一种溶解纤维素的方法，先釆用加热设备对纤维素进行加热活化，再釆用溶剂溶解。加热活化温度为130-270℃，加热时间为0.1-100小时，其溶剂为6wt%-12wt%氢氧化钠和0.1wt%-6wt%氧化锌的水溶液。溶解方法：把聚合度DP=300—700的纤维素加热活化，然后将纤维素分散于溶剂中，在-10~-30℃下冷冻0.1-50小时；再在不高于32℃条件下解冻，解冻过程静置或者机械搅拌，得到浓度3wt%-12wt%的纤维素溶液。所得纤维素溶液溶解性和稳定性良好，在-8~32℃下静置数天仍保持较好的稳定性。该纤维素溶液可用于纤维、膜或海绵的制备，适合工业化生产。

Description

一种溶解纤维素的方法 技术领域
本发明涉及一种溶解纤维素的方法。
背景技术
纤维素( Cellulose) 是自然界中广泛存在的可再生资源，由于其独特的反应功能和分子特性可望成为未来主要的化工原料之一。目前，纤维素资源与纺织、轻工、化工、国防、石油、医药、生物技术、环境保护和能源等部门息息相关，被广泛应用于造纸、纤维膜、聚合物和涂料等纤维素材料的生产。然而，天然纤维素分子有较高的结晶度，分子间和分子内存在大量的氢键，这使其难溶解也难熔融加工。长期以来，在纺织再生纤维素纤维领域中，粘胶纤维一直占据着主要地位。粘胶工艺虽然可以生产出理想的再生纤维素纤维，但生产过程复杂，工艺难以控制，占地面积及消耗大，产生大量有毒气体和废水，污染极其严重，因此面临被淘汰的局面。目前，新型无毒无害的溶剂及溶解纤维素的方法已经成为纤维素产业发展的重要方向。
纤维素溶剂分为非衍生化溶剂和衍生化溶剂，纤维素在溶解过程中发生了衍生化反应的称为衍生化溶剂（CS2/NaOH/H2O、N2O4/二甲基甲酰胺等），在溶解过程中没有形成衍生物的称为非衍生化溶剂（胺氧化物体系、LiOH/二甲基乙酰胺、离子液体、NaOH/尿素等）。由于非衍生化溶剂溶解纤维素是一个物理过程，其溶解过程对纤维素化学结构不易产生影响，其生产纤维素产品的过程相对也较为简单。
在纤维素产品发展的历史中，非衍生化溶剂得到了大量的研究。1939年US专利2179181报道了三甲基氧化胺、三乙基氧化胺和二甲基环己基氧化胺等叔胺氧化物可以溶解纤维素。后来，英国专利1144048进一步发现NMMO（4-甲基吗啉-N-氧化物，N-甲基吗啉水溶液，氧化甲基吗啉，分子式：C5H11NO2）更适合作纤维素的溶剂，NMMO溶解纤维素简化了工艺流程，降低了化学原料的使用量和能耗，生产过程完全是物理变化，所用溶剂NMMO无毒性，环境友好，其制得的纤维产品称为Lyocell(国内称为天丝)。但是，其存在溶剂价格高、溶解条件苛刻以及回收系统复杂等问题。US4302252提出，LiCL/DMAc（二甲基乙酰胺）体系能与纤维素形成溶剂化配合物，对纤维素有溶解作用，其溶解性能好，溶液稳定性好，但是该体系溶解范围较窄，价格昂贵，且DMAc具有强刺激性及一定毒性。Celanese 公司在GB专利t263810提出纤维素在磷酸体系中可溶，该体系为磷酸与多聚磷酸复合溶液，溶解纤维素时对温度控制严格，而且提高体系的溶解性能必须提高P2O5的质量分数，其溶解时间也较长也限制了产业化的发展。1934年Graenacher发现了熔融的N-乙基吡啶氯化物可以溶解纤维素，但因熔点较高，没有得到应用发展。2002年Swatloski等发现纤维素无需活化就可以直接溶解在室温离子液体中，同年，报道了离子液体1-丁基-3-甲基氯化咪唑可作为纤维素溶剂。2003年任强等合成了一种新的室温离子液体—1-烯丙基-3-甲基咪唑氯化物，同样对纤维素有很好的溶解性能。2005年罗慧谋等合成了氯化1-（2-羟乙基）-3-甲基咪唑离子液体，发现70℃时活化后的微晶纤维素在其中溶解度达到5%-7%，但是，此种液体温度超过80℃就开始分解，没有实用价值。专利JP1777283中公开了纤维素在2.5mol/L NaOH水溶液中的溶解，但是只能是经蒸汽爆破处理过的聚合度低于250的木浆纤维素，它在4℃左右溶解于这种NaOH水溶液中，该方法制得的纤维及膜的强度极低，不适合工业化生产。文献《浙江化工》1006-4184（2007）12-0001-03提到采用亚硫酸盐木浆板为原料、氢氧化钠溶液为溶剂研究纤维素在强碱中的溶解情况，在2℃条件下研究了浓度约为6wt%混合物的粘度，但是其没有对更低温度下的溶解行为进行研究，也没有对溶液的溶解性、稳定性作详细探讨，不具备实用价值。武汉大学专利CN00114486.3、CN00114485.5、CN03128386.1、CN200310111566.3、CN200410013389.X及WO 2006/128346A1中采用氢氧化钠与尿素的水溶液、氢氧化钠与硫脲的水溶液在低温条件下直接溶解天然纤维素，该溶液在0-5℃的范围内能长时间保持稳定，采用这种溶剂体系在实验室中得到了纤维和膜，但是该体系中纤维素溶液性质受温度影响较大，至今未能实现工业化。
纤维素非衍生化溶剂在纤维素产品生产过程中不会对纤维素产生化学变化，其工艺流程简单，因而得到了长足发展，但是，一般非衍生化溶剂溶解纤维素时先要对纤维素进行活化，活化工艺的简洁性、溶剂的环境友好性、制备的纤维素溶液的稳定性、原材料的经济性都制约了其工业化进程。
 技术问题
本发明的目的是提供一种溶解纤维素的方法。本方法先采用加热设备对纤维素进行加热活化，再采用一种溶剂进行溶解。该溶剂通过冷冻-解冻的方法溶解纤维素，制备出具有高浓度、高稳定性的纤维素溶液，所得纤维素溶液可用于纤维、膜、海绵等其它纤维素产品的制造。
 技术解决方案
为实现上述目的，本发明的技术方案是：一种溶解纤维素的方法，其特征在于，先采用加热设备对纤维素进行加热活化，再采用一种溶剂进行溶解。
其中，所述的对纤维素进行加热活化，其活化加热温度为130-270℃，加热时间为0.1-100小时。
所述的一种溶剂为含6 w%t-12 wt%氢氧化钠和0.1wt%-6 wt%氧化锌的水溶液。
优选的一种溶解纤维素的溶剂为含7.0wt%~9.0 wt%氢氧化钠和0.5wt%~2.0 wt%氧化锌的水溶液。
本发明的一种溶解纤维素的方法，其溶剂溶解纤维素按如下步骤进行：
1）把聚合度DP=300~700的纤维素加热活化后分散于该溶剂中，在-10~-30℃下冷冻0.1~50小时；
2）将经步骤1）冷冻处理过的物料在不高于32℃的条件下解冻，解冻过程静置或采用机械搅拌，溶解得到浓度3wt%-12 wt%纤维素溶液。
所述的一种溶解纤维素的方法，其优选方案是：
所述的步骤1）中，冷冻温度为-12~-18℃，冷冻时间为0.1~50小时，纤维素的聚合度DP范围为350~550；
所述的步骤2）中，解冻温度为10~22℃，溶解得到的纤维素溶液的浓度为5.0 wt%~8.5 wt%。
本发明所得纤维素溶液溶解性良好，稳定性较高，可在-8~ 32℃条件下静置数天仍保持较好的稳定性。该纤维素溶液可用于纤维、膜或海绵的制备，特别适合工业化生产。
 有益效果
本发明与现有技术相比，具有如下优点：
1）纤维素溶液的溶解性良好，溶液中没有直径大于5微米的胶体粒子；溶液的稳定性较好，常温下静置24~120小时都没有明显变化；溶液浓度较高，本发明中的溶液浓度可达到wt%3-12 wt%，与目前粘胶生产中纤维素浓度接近，适合进行工业化生产；
2）活化及溶解过程简单易于操作，溶解过程只要冷冻过程要求低温环境，其他可以在室温条件下进行，克服了以往技术的复杂和条件的苛刻等缺点；
3）活化设备简单易于实现，溶剂配制简单，溶剂组分只有NaOH、氧化锌和水，组分价格便宜，具有良好的经济性。由于溶剂组分简单，因而在制备纤维素产品过程中，溶剂回收容易，回收成本低，且回收物能循环利用，有利于大规模工业化生产。
 附图说明
图1是本发明实施例1所制备的纤维素溶液的微观形态。
图2是本发明实施例2所制备的纤维素溶液的微观形态。
图3是本发明实施例3所制备的纤维素溶液的微观形态。
图4是本发明实施例4所制备的纤维素溶液的微观形态。
图5是本发明实施例5所制备的纤维素溶液的微观形态。
图6是本发明实施例6所制备的纤维素溶液的微观形态。
图7是本发明实例1、例2、例3、例4、例5、例6所制备的纤维素溶液中纤维素的稳定性随时间的变化图。
图1-图6为使用纤维投影仪CYG-055DI，100倍放大照片。
 本发明的实施方式
为了更好地理解本发明，下面结合实施例进一步阐明本发明的内容，但本发明的内容不仅仅局限于下面的实施例。
实施例1
称量一定质量的聚合度为350的棉浆纤维素，置于烘箱中138℃加热3小时，取出备用。以水为溶剂，配置质量浓度为12%的氢氧化钠和质量浓度为5%的氧化锌的水溶液作纤维素溶剂，按照配置质量浓度为8.5%的比例称量加热活化后的纤维素，将纤维素放入配好的纤维素溶剂中，搅拌均匀，让纤维素全部没入液面以下。然后将此混合物放入-15℃的冻库中冷冻5小时，取出静置于室温下解冻，室温为22℃，待混合物温度升至22℃，用玻璃棒搅拌即得透明纤维素溶液。取少量此溶液置于纤维投影仪CYG-055DI，100倍放大下观察并拍照，其显微图片如图1所示，纤维素全部溶解，胶体颗粒直径小于5微米。此溶液在22℃室温环境存放100小时，在不同时间段取上层液体干燥称量纤维素固含量，与初始0小时溶液中纤维素固含量对比关系如附图7所示，100小时后沉降量为5.5wt%，未沉降重量比例为94.5wt%。本纤维素溶液溶解性及稳定性良好。
 本发明的实施方式
实施例2
称量一定质量的聚合度为550的棉浆纤维素，置于烘箱中230℃加热0.3小时，取出备用。以水为溶剂，配置质量浓度为7%的氢氧化钠和质量浓度为1.0%的氧化锌的水溶液作纤维素溶剂，按照配置质量浓度为4.5%的比例称量加热活化后的纤维素，将纤维素放入配好的纤维素溶剂中，搅拌均匀，让纤维素全部没入液面以下。然后将此混合物放入-13℃的冻库中冷冻12小时，取出静置于室温下解冻，室温为23℃，待混合物温度升至23℃，用玻璃棒搅拌即得透明纤维素溶液。取少量此溶液置于纤维投影仪CYG-055DI，100倍放大下观察并拍照，其显微图片如图2所示，纤维素全部溶解，胶体颗粒直径小于5微米。此溶液在23℃室温环境存放120小时，在不同时间段取上层液体干燥称量纤维素固含量，与初始0小时溶液中纤维素固含量对比关系如附图7所示，120小时后沉降量为4.8wt%，未沉降重量比例为95.2wt%。
 本发明的实施方式
实施例3
称量一定质量的聚合度为380的棉浆纤维素，置于烘箱中190℃加热0.8小时，取出备用。以水为溶剂，配置质量浓度为6%的氢氧化钠和质量浓度为0.5%的氧化锌的水溶液作纤维素溶剂，按照配置质量浓度为5%的比例称量加热活化后的纤维素，将纤维素放入配好的纤维素溶剂中，搅拌均匀，让纤维素全部没入液面以下。然后将此混合物放入-16℃的冻库中冷冻1小时，取出于室温下以150r/min的速度搅拌解冻，室温为22℃，待混合物温度升至22℃，即得透明纤维素溶液。取少量此溶液置于纤维投影仪CYG-055DI，100倍放大下观察并拍照，其显微图片如图3所示纤维素全部溶解，胶体颗粒直径小于5微米。此溶液在22℃室温环境存放120小时，在不同时间段取上层液体干燥称量纤维素固含量，与初始0小时溶液中纤维素固含量对比关系如附图7所示，120小时后沉降量为5.9wt%，未沉降重量比例为94.1wt%。
 本发明的实施方式
实施例4
称量一定质量的聚合度为450的棉浆纤维素，置于烘箱中175℃加热1小时，取出备用。以水为溶剂，配置质量浓度为10%的氢氧化钠和质量浓度为1.5%的氧化锌的水溶液作纤维素溶剂，按照配置质量浓度为7.0%的比例称量加热活化后的纤维素，将纤维素放入配好的纤维素溶剂中，搅拌均匀，让纤维素全部没入液面以下。然后将此混合物放入-25℃的冻库中冷冻10小时，取出静置于室温下解冻，室温为24℃，待混合物温度升至24℃，用玻璃棒搅拌即得透明纤维素溶液。取少量此溶液置于纤维投影仪CYG-055DI，100倍放大下观察并拍照，其显微图片如图4所示,纤维素全部溶解，胶体颗粒直径小于5微米。此溶液在24℃室温环境存放120小时，在不同时间段取上层液体干燥称量纤维素固含量，与初始0小时溶液中纤维素固含量对比关系如附图7所示，120小时后沉降量为4.7wt%，未沉降重量比例为95.3wt%。
 本发明的实施方式
实施例5
称量一定质量的聚合度为420的棉浆纤维素，置于烘箱中210℃加热1.5小时，取出备用。以水为溶剂，配置质量浓度为11%的氢氧化钠和质量浓度为2.5%的氧化锌的水溶液作纤维素溶剂，按照配置质量浓度为6.5%的比例称量加热活化后的纤维素，将纤维素放入配好的纤维素溶剂中，搅拌均匀，让纤维素全部没入液面以下。然后将此混合物放入-20℃的冻库中冷冻3小时，取出静置于室温下解冻，室温为22℃，待混合物温度升至22℃，用玻璃棒搅拌即得透明纤维素溶液。取少量此溶液置于纤维投影仪CYG-055DI，100倍放大下观察并拍照，其显微图片如图5所示,纤维素全部溶解，胶体颗粒直径小于5微米。此溶液在22℃室温环境存放120小时，在不同时间段取上层液体干燥称量纤维素固含量，与初始0小时溶液中纤维素固含量对比关系如附图7所示，120小时后沉降量为5.7wt%，未沉降重量比例为94.3wt%。
 本发明的实施方式
实施例6
称量一定质量的聚合度为500的棉浆纤维素，置于烘箱中200℃加热1小时，取出备用。以水为溶剂，配置质量浓度为8%的氢氧化钠和质量浓度为0.7%的氧化锌的水溶液作纤维素溶剂，按照质量浓度为7.5%的比例称量加热活化后的纤维素，将纤维素放入配好的纤维素溶剂中，搅拌均匀，让纤维素全部没入液面以下。然后将此混合物放入-28℃的冻库中冷冻10小时，取出于室温下缓慢搅拌解冻，室温为21℃，待混合物温度升至21℃，即得透明纤维素溶液。取少量此溶液置于纤维投影仪CYG-055DI，100倍放大下观察并拍照，其显微图片如图6所示纤维素全部溶解，胶体颗粒直径小于5微米。此溶液在21℃室温环境存放120小时，在不同时间段取上层液体干燥称量纤维素固含量，与初始0小时溶液中纤维素固含量对比关系如附图7所示，100小时后沉降量为5.6wt%，未沉降重量比例为94.4wt%。

Claims (9)

1. 一种溶解纤维素的方法，其特征在于，先采用加热设备对纤维素进行加热活化，再采用一种溶剂进行溶解。
2. 根据权利要求1所述的溶解纤维素的方法，其特征在于，对纤维素进行加热活化的加热温度为130-270℃，加热时间为0.1-100小时。
3. 根据权利要求1所述的溶解纤维素的方法，其特征在于，所述的溶剂为含6 w%t-12 wt%氢氧化钠和0.1wt%-6wt%氧化锌的水溶液。
4. 根据权利要求1所述的溶解纤维素的方法，其特征在于，所述的溶剂为含7.0wt%~9.0 wt%氢氧化钠和0.5wt%~2.0 wt%氧化锌的水溶液。
5. 如权利要求1或3或4所述的一种溶解纤维素的方法，其特征在于，所述的溶剂溶解纤维素按如下步骤进行：
1）把聚合度DP=300~700的纤维素加热活化后分散于所述的溶剂中，在-10~-30℃下冷冻0.1~50小时；
2）将经步骤1) 冷冻后纤维素在不高于32℃的条件下解冻，解冻过程静置或采用机械搅拌，溶解得到浓度3wt%-12 wt%纤维素溶液。
6. 根据权利要求5所述的一种溶解纤维素的方法，其特征在于：所述的步骤1）中，冷冻温度为-12~-18℃；冷冻时间为0.1~50小时。
7. 根据权利要求5所述的一种溶解纤维素的方法，其特征在于：所述的步骤1）中，纤维素的聚合度DP范围为350~550。
8. 根据权利要求5所述的一种溶解纤维素的方法，其特征在于：所述的步骤2）中，解冻温度为10~22℃。
9. 根据权利要求5所述的一种溶解纤维素的方法，其特征在于：所述的步骤2）中，溶解得到的纤维素溶液的浓度为5.0 wt%~8.5 wt%。
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CN102875821B (zh) 2014-05-07
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CN102875821A (zh) 2013-01-16
EP2845874A4 (en) 2015-09-16
US20150135991A1 (en) 2015-05-21
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EP2845874B1 (en) 2017-03-22

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