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WO2015062348A1 - 一种再生纤维素膜、功能膜及其制备方法 - Google Patents

一种再生纤维素膜、功能膜及其制备方法 Download PDF

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Publication number
WO2015062348A1
WO2015062348A1 PCT/CN2014/084986 CN2014084986W WO2015062348A1 WO 2015062348 A1 WO2015062348 A1 WO 2015062348A1 CN 2014084986 W CN2014084986 W CN 2014084986W WO 2015062348 A1 WO2015062348 A1 WO 2015062348A1
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Prior art keywords
cellulose
film
ionic liquid
solvent
transverse
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PCT/CN2014/084986
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English (en)
French (fr)
Inventor
张军
张晓煜
余坚
李瑞丰
武进
高玉刚
张金明
邱金江
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中国科学院化学研究所
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Application filed by 中国科学院化学研究所 filed Critical 中国科学院化学研究所
Priority to US15/033,382 priority Critical patent/US9834652B2/en
Priority to EP14859132.4A priority patent/EP3064534B1/en
Priority to JP2016527282A priority patent/JP6427183B2/ja
Publication of WO2015062348A1 publication Critical patent/WO2015062348A1/zh

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    • 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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • 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 invention relates to a regenerated cellulose film (also called cellophane, cellulose film), a functional film and a preparation method thereof, in particular to a biaxially stretched regenerated cellulose film, a functional film and a preparation method thereof, belonging to an organic polymer field.
  • a regenerated cellulose film also called cellophane, cellulose film
  • a functional film and a preparation method thereof in particular to a biaxially stretched regenerated cellulose film, a functional film and a preparation method thereof, belonging to an organic polymer field.
  • Cellulose is the most widely distributed natural polymer in nature, and it is an inexhaustible renewable resource. Compared with synthetic polymers, cellulose has the advantages of being completely biodegradable, non-toxic, non-polluting, and biocompatible. With the depletion of fossil resources such as petroleum and coal, the research and development of cellulose-based materials is of great significance for promoting the sustainable development of civilization.
  • Regenerated cellulose membrane (also known as cellophane and cellulose membrane) prepared from cellulose is an important membrane material, which is non-toxic, transparent, non-electrostatic, high temperature resistant, good barrier property and degradable. Widely used in the packaging of food, medicine, cosmetics, high-end garments, precision instruments and other products. Since natural cellulose has high crystallinity and a large amount of intermolecular and intramolecular hydrogen bonds, it does not melt, is difficult to dissolve, and has poor processability. Industrially, the existing regenerated cellulose film production mainly uses viscose technology. After derivatization of natural cellulose, a cellulose solution is obtained, and then cellulose is regenerated, which not only has high pollution and high energy consumption in the production process. Moreover, the degradation of cellulose in production is severe, and the performance of the product is difficult to improve.
  • Biaxial stretching technology is widely used to improve the physical and mechanical properties of polymer membranes. After nearly three to four decades of rapid development, it has formed a large production capacity, including polypropylene, polyester, polystyrene and polychlorinated chlorine. A variety of synthetic polymers such as ethylene and polyamine. Compared with the unstretched film, the mechanical strength of the biaxially stretched polymer film is remarkably improved; the transparency and surface gloss are improved; the thickness is uniform, the thickness deviation is small; and the barrier property is improved.
  • the two-way stretching technology also has certain requirements on the properties of the polymer raw material itself, such as the high strength of the polymer (see the trial production of BOPP special materials, Li Yisen, Synthetic Resin and Plastics, 1991, 8(4): 25) .
  • the film In the production of regenerated cellulose membranes by viscose technology, by adjusting the speed ratio between different rolls, the film can be made to have a higher strength in the longitudinal direction, in contrast to the strength of the cellulose film in the transverse direction. ⁇ ⁇ poor, severe contraction. Since the molecular weight of cellulose is seriously degraded during the derivatization process, the cellulose film obtained by the viscose technique cannot increase its transverse tensile strength by means of transverse stretching.
  • the molecular weight of cellulose is reduced during dissolution and regeneration, and the obtained film may be transversely stretched. It makes it possible to prepare a biaxially stretched cellulose film.
  • PCT Application W097/24215 provides a method of preparing a biaxially stretched regenerated cellulose film from a cerium solution of cellulose.
  • the method extrudes the cellulose solution onto the film of the elastomer, and stretches the elastomer film before removing the hydrazine solvent to achieve biaxial stretching of the cellulose solution.
  • the strength of the cellulose solution is low, and the liquid film is easily broken during stretching, resulting in instability of the process.
  • the molecular chain stretched and oriented in the solution is easy to recover, and the washing and drying process causes the formed regenerated cellulose film to further shrink, affecting the performance of the cellulose film.
  • PCT application W098/49224 extrudes the NMMO solution of cellulose from the extrusion die into the coagulation bath, and after the solvent is washed away, the formed film is transversely stretched, and finally dried and shaped; or the dried film is moistened. After wet, it is stretched in the transverse direction. However, the transversely stretched film still shrinks to some extent when dried, resulting in a decrease in the size of the film in the transverse direction and a decrease in tensile strength.
  • PCT application WO02/100925 will form a cellulose film which has been subjected to a coagulation bath and is washed away from NMMO in two steps for transverse stretching, and the first step is to excessively stretch the film. The two steps are allowed to relax the stretched film to the desired degree of stretching.
  • PCT application WO 02/100926 reduces the shrinkage of the film in the transverse direction by continuing to maintain a certain tension in the transverse direction for the transversely stretched film.
  • the obtained stretched film maintains good dimensional stability when it is in contact with water or an alkali solution, the tensile strength of the stretched film in the transverse direction is not increased much, and is less than 60% of the strength in the longitudinal direction, transverse and longitudinal. Performance is still uneven.
  • ionic liquids have emerged as a green solvent for emerging natural celluloses because of their high solubility, non-volatility, chemical stability and thermal stability, and ease of recycling.
  • ionic liquids for dissolving cellulose see Chinese Invention Patent: ZL 02147004.9, ZL 02155945.7, ZL 02823875.3, ZL 200680012598.x, CN 200710085298.0.
  • the process for preparing a regenerated cellulose functional film using an ionic liquid as a solvent has also been reported (see ZL 200410101800.9): The ionic liquid solution of cellulose is shaped and then solidified into a solidification, further washed, and dried to obtain a cellulose film.
  • the object of the present invention is to overcome the disadvantages of the prior art that the regenerated cellulose film has poor transverse and longitudinal tensile strength and large difference, and provides a biaxially stretched regenerated cellulose film having excellent tensile strength in both transverse and longitudinal directions. And its functional film.
  • Another object of the present invention is to provide a process for producing the above-described regenerated cellulose film and its functional film.
  • the above method provided by the present invention can be used in the preparation of a regenerated cellulose film having an ionic liquid as a cellulose solvent and a functional film thereof.
  • a biaxially stretched regenerated cellulose film characterized in that the ratio of the transverse stretching and the longitudinal stretching of the cellulose film is at most 400%, and the ratio of the longitudinal tensile strength to the transverse tensile strength is less than 1.8.
  • the ratio of the longitudinal tensile strength to the transverse tensile strength of the present invention is less than 1.8, preferably less than 1.5, more preferably less than 1.4.
  • the cellulose film has a transverse stretching ratio of 101 to 400%, preferably 150 to 300%; and a longitudinal stretching ratio of 110 to 400%, preferably 150 to 300%.
  • the transverse and longitudinal stretching ratios of the cellulose film are the same or different.
  • the transverse stretching and the longitudinal stretching can be carried out simultaneously or in stages. It is possible to perform transverse stretching first and then longitudinal stretching; it is also possible to perform longitudinal stretching first and then transverse stretching.
  • the cellulose film is stretched at least once in the transverse direction, preferably from 2 to 4 times, more preferably from 1 to 3 times.
  • the cellulose film is longitudinally stretched at least once, preferably 2 to 4 times, more preferably 1 to 3 times.
  • the film is easily stretched in the longitudinal direction; while the transverse stretching requires an increase in equipment, so the less the number of lateral stretching, the more economical, However, the number of stretching is more favorable to the film properties. Taken together, it can be 2-4 times, preferably 1 ⁇ 3 times.
  • each draw ratio can be the same or different in the same direction. Taking 3 times of stretching as an example, when the stretching multiple is the same, the stretching ratio is 120% in each lateral direction; when the stretching multiple is different, the transverse direction can be stretched 130% for the first time and 120% for the second time, the third time. Stretching 110%, or horizontally stretching 125% for the first time, 125% for the second stretch, and 105% for the third stretch.
  • the total draw ratio is as described above.
  • the cellulose is natural cellulose, and preferably, the degree of polymerization of the natural cellulose raw material is in the range of 200 to 2,000.
  • the cellulose of the present invention is selected from at least one of the following cellulose raw materials: microcrystalline cellulose, cotton pulp, wood pulp, bamboo pulp, cotton wool, bagasse, wood, and straw produced from straw. Prime.
  • the regenerated cellulose film is obtained by stretching a cellulose/ionic liquid solution and then stretching it.
  • the cellulose/ionic liquid solution is extruded through a die and then shaped by a known casting or calendering method, and then passed through an air gap into a coagulation bath to form a cellulose gel film.
  • the cellulose film is referred to as ⁇ because it contains a solvent before drying. When the film is completely removed by solvent drying, it is called a cellulose film.
  • the coagulation bath is a mixture of an ionic liquid and a cellulose non-solvent such as water, decyl alcohol, ethanol or acetone.
  • a cellulose non-solvent such as water, decyl alcohol, ethanol or acetone.
  • the temperature of the coagulation bath can be adjusted within the range of 10 ⁇ 80'C, thereby adjusting the solidification rate of cellulose.
  • the cellulose/ionic liquid solution enters the coagulation bath, the cellulose is solidified into a film shape in the presence of a non-solvent to obtain a gel film.
  • the present invention also provides a biaxially stretched regenerated cellulose functional film, characterized in that the functional film comprises the above-mentioned cellulose film and an organic and/or inorganic functional additive.
  • the invention also provides a preparation method of a biaxially stretched regenerated cellulose film, characterized in that the method comprises the following steps:
  • transverse and longitudinal tension is applied to the stretched film during the drying process, and finally, a regenerated cellulose film is obtained by winding.
  • the preparation method of the present invention combines cellulose ionic liquid solvent technology and biaxial stretching technology to prepare a regenerated cellulose membrane and a functional membrane thereof.
  • an ionic liquid is used as a solvent to form, solidify, wash, stretch, and dry from a cellulose/ionic liquid solution.
  • the vegan film, and the process can impart properties to the biaxially stretched cellulose film over existing commercial regenerated cellulose films.
  • the cellulose solution or the cellulose gel film after the extrusion die is longitudinally stretched by the difference in speed between rolls.
  • the weight ratio of the ionic liquid solvent to the cellulose non-solvent in the film is less than 4:1, and the cellulose ⁇ JM is once performed by a stretching device (biaxial stretching machine, tenter or stenter) Or multiple times of transverse stretching, the use of fractional stretching can reduce the extent of each stretching, thereby reducing the possibility of breakage of the film during stretching.
  • the thickness of the film is lowered by the transverse stretching, which facilitates the washing of the residual ionic liquid in the cellulose gel film, and the removal of water or other non-solvent when the film is dried.
  • the film When the cellulose gel film is dried, the film is transversely stretched or a certain lateral tension is applied by a stretching device, which can prevent shrinkage of the film during drying, and further improve the performance of the cellulose film in the transverse direction and the longitudinal direction. Balance.
  • the transverse stretching and the longitudinal stretching may be carried out simultaneously or in stages. It is possible to carry out the transverse stretching first and then the longitudinal stretching; it is also possible to perform the longitudinal stretching first and then the transverse stretching.
  • the present invention preferably has a lateral stretching of 2-4 times, and the final transverse stretching ratio is 101 to 400%.
  • the invention preferably has 2-4 longitudinal stretching, and the longitudinal stretching ratio is 110-400%.
  • the coagulation bath is a mixture of an ionic liquid and a cellulose non-solvent such as water, methanol, ethanol or acetone.
  • the coagulation bath is a mixture of an ionic liquid solvent and water or other cellulose nonsolvent in a weight ratio of from 0 to 150:100, preferably from 0 to 120:100, more preferably from 0 to 80:100.
  • the temperature of the coagulation bath can be adjusted within a range of 10 to 80 ° C, thereby adjusting the fiber The rate of solidification of the vitamin.
  • the cellulose/ionic liquid solution enters the coagulation bath, the cellulose is solidified into a film shape in the presence of a non-solvent to obtain ⁇ jg.
  • step (3) during the solidification and washing of the cellulose gel film, when the weight ratio of the ionic liquid solvent to the cellulose non-solvent in the film is smaller than
  • the cellulose is coagulated in both transverse and longitudinal directions.
  • the cellulose is condensed away from the coagulation bath and then washed, and washed to remove the ionic liquid in the film.
  • the wash bath can be water or other cellulosic non-solvent that is miscible with the ionic liquid.
  • the washing bath temperature is 10 ⁇ 80'C, preferably 20 ⁇ 60' (:.
  • the present invention can also employ a known method of reverse washing.
  • the water or solvent in the gel film after the ionic liquid is washed may be removed by a known drying method, for example, heating under reduced pressure, drying by hot air, hot roll drying, infrared temperature drying, microwave drying, etc., but not limited thereto. These methods.
  • the cellulose gel film in the step (3), in the solidification and washing process of the cellulose gel film, when the weight ratio of the ionic liquid solvent in the MJI ⁇ to the cellulose non-solvent in the film is less than 4:1, preferably 3 At least 1, the cellulose is coagulated at least once in the transverse direction, preferably in the transverse stretching of 1 to 3 times.
  • the residual ionic liquid is further removed by washing.
  • the washing bath is water or another cellulose non-solvent.
  • transverse and longitudinal tension is applied to the film during drying of the cellulose gel film.
  • the film is stretched in the transverse direction and the longitudinal direction during the drying of the cellulose gel film.
  • the total stretching ratio of the cellulose film in the transverse direction and the longitudinal direction is up to 400%.
  • the cellulose/ionic liquid solution is obtained by dissolving the natural cellulose raw material in an ionic liquid solvent.
  • the ionic liquid solvent is a mixed solvent of an ionic liquid capable of dissolving cellulose, an ionic liquid in which cellulose is dissolved, or an ionic liquid in which cellulose is dissolved and other cosolvents.
  • Mixed solvent is a mixed solvent of an ionic liquid capable of dissolving cellulose, an ionic liquid in which cellulose is dissolved, or an ionic liquid in which cellulose is dissolved and other cosolvents.
  • the ionic liquid is formed of an imidazole or a pyridine type cation and an anion having a melting point of less than 100.
  • the organic molten salt of C is preferably an organic molten salt which can dissolve cellulose.
  • the present invention may use a mixed ionic liquid to dissolve cellulose, wherein the mixed ionic liquid may be an ionic liquid capable of dissolving cellulose, or an ionic liquid capable of dissolving cellulose and an ion not dissolving cellulose. a mixture of liquids.
  • the cation is preferably any one of the following: 1-ethyl-3-methylimidazolium cation, 1-propyl-3-methylimidazolium cation, 1-allyl-3-methylimidazolium cation, 1- Butyl-3-methylimidazolium cation, N-ethylpyridinium cation, N-butylpyridinium cation, N-n-hexylpyridinium cation.
  • the cation is particularly preferably any one of the following: 1-ethyl-3-methylimidazolium cation, 1-allyl-3-methylimidazolium cation, and 1-butyl-3-methylimidazolium cation.
  • the anion is preferably any one of the following: chloride ion, bromide ion, formate ion, acetate ion, propionate ion, butyrate ion and methyl phosphate ion; the anion is particularly preferably any of the following: Chloride, citrate, acetate and yttrium phosphate Child.
  • the ionic liquid is used singly or in combination, or with N,N-dimethyl sulfoxide, N,N-dimercaptopurine, N,N-dimercaptoacetamide or N - Mixtures such as methylpyrrolidone and other cosolvents.
  • the cosolvent is N,N-dimethyl sulfoxide, N,N-dimercaptophthalamide, N,N-dimercaptoethyl StJfe or N-decylpyrrolidone.
  • the cellulose is natural cellulose, and preferably, the degree of polymerization of the natural cellulose raw material is in the range of 200 to 2,000.
  • the cellulose of the present invention is selected from at least one of the following cellulose raw materials: microcrystalline cellulose, cotton pulp, wood pulp, bamboo pulp, cotton wool, bagasse, wood, and from plant straw.
  • Cellulose the degree of polymerization of the cellulose is preferably between 200 and 2,000.
  • the cellulose ionic liquid solution of the present invention is a transparent and uniform solution having a cellulose content of 3 to 20% (relative to the weight of the ionic liquid solvent).
  • the dissolution temperature of cellulose is 50-150. C, the dispersion and dissolution of the cellulose can be accelerated by means of a known method of stirring, microwave, ultrasonic or screw extrusion.
  • the present invention also provides a method for preparing a biaxially stretched regenerated cellulose functional film, characterized in that the method comprises the following steps:
  • a biaxially stretched cellulose functional film which is enhanced, toughened and otherwise functionalized can be prepared.
  • the method for preparing a functional film according to the present invention is characterized in that the organic and/or inorganic functional additive of the present invention is chitin, chitosan, alginic acid, layered nano-soil, graphene, carbon nanotube, angstrom One or more of aragonite nanotube, nano carbon fiber, carbon black, nano titanium dioxide, nano zinc oxide or nano silicon dioxide.
  • the content of the organic and/or inorganic functional additive is from 0.1 to 20% (relative to the weight of cellulose in the film).
  • the present invention also provides a biaxially oriented regenerated cellulose film or functional film prepared by the above method.
  • the present invention also provides the use of the above cellulose film or functional film.
  • the application fields of the conventional cellulose film or functional film in the prior art are applicable, for example, in the packaging of products such as foods, medicines, cosmetics, high-grade garments, precision instruments, and the like.
  • the technical effect of the invention is:
  • Ionic liquids have excellent solubility for cellulose, and cellulose is less degraded during ionic liquid dissolution.
  • the biaxial stretching technology of the regenerated cellulose film and the functional film thereof according to the present invention makes full use of the characteristics of high gel strength and large elongation at break of the cellulose gel film obtained by using the ionic liquid as a solvent. Condensation of cellulose in the transverse and longitudinal directions Stretching, while reducing the thickness of the cellulose film, improving the tensile strength and thickness uniformity in the transverse and longitudinal directions, obtaining a high-performance regenerated cellulose film and its functional film, can significantly expand the application field of cellulose . detailed description
  • the conventional conventional process produces a uniaxial stretching of the film in the longitudinal direction, which may be referred to as a "uniaxially stretched film", with the result that the film has a large difference in longitudinal and transverse properties.
  • This patent improves the prior art process by allowing the film to stretch in the transverse direction as well as improving the film properties in the transverse direction, plus the original longitudinal stretch, hence the term biaxial stretching.
  • the longitudinally stretched portion is similar to the conventional process, the present invention does not specifically emphasize how to perform longitudinal stretching in the examples, and only the total draw ratio in the longitudinal direction is given in the examples.
  • Example 1 Example 1
  • the wood pulp (degree of polymerization 650) was dissolved at 90 ° C with 1-allyl-3-methylchloroimidazolium salt ionic liquid (AMIMC1) to obtain a 10% by weight cellulose solution.
  • AMIMC1 1-allyl-3-methylchloroimidazolium salt ionic liquid
  • the ionic liquid solvent was stretched 1.5 times in the transverse direction at a weight ratio of cellulose to solvent in the film of 1.6:1. Condensation after stretching! ⁇ Further washing in 30'C water to remove ionic liquid.
  • Use a biaxial stretching device to keep the film horizontal when drying Size.
  • the final obtained stretched regenerated cellulose film had a total draw ratio of 2.5 times in the machine direction, 1.3 times the total draw ratio in the transverse direction, a longitudinal tensile strength of 175 MPa, and a transverse tensile strength of 139 MPa. Comparative Example 1
  • the pulp pulp (degree of polymerization 650) was dissolved at 90 ° C with 1-allyl-3-methylimidazolium chloride salt ionic liquid (AMIMC1) to obtain a cellulose solution having a concentration of 10% by weight.
  • AMIMC1 1-allyl-3-methylimidazolium chloride salt ionic liquid
  • the port was extruded into a 50 ° C water-soluble 3 ⁇ 4 a-containing coagulation bath containing 5% by weight of an ionic liquid to obtain an unstretched cellulose gel film.
  • the C water is a washing bath, and the ionic liquid is further removed by washing.
  • the regenerated cellulose film obtained after drying had a total draw ratio of 2.5 times in the machine direction, transverse unstretched, longitudinal tensile strength of 168.6 MPa, and transverse tensile strength of 74.8 MPa.
  • Example 2 Example 2
  • the cotton pulp (degree of polymerization 750) was dissolved at 90 ° C with 1-allyl-3-methylimidazolium chloride ionic liquid (AMIMC1) to obtain a cellulose solution having a concentration of 8% by weight.
  • AMIMC1 1-allyl-3-methylimidazolium chloride ionic liquid
  • the port was extruded into a coagulation bath of 50 ⁇ of an aqueous solution containing 60% by weight of an ionic liquid to obtain unstretched cellulose mj ⁇ .
  • the weight ratio of the ionic liquid solvent to the cellulose non-solvent in the film was 1.25 times in the transverse direction at a weight ratio of 4:1.
  • the condensed after stretching was further washed in 50' C water to remove the ionic liquid.
  • the biaxially stretched regenerated cellulose film obtained after drying has a draw ratio of 1.2 times in the longitudinal direction and a draw ratio of 1.1 times in the transverse direction, and longitudinal stretching The strength was 170.1 MPa, and the transverse tensile strength was 126.2 MPa.
  • the wood pulp (degree of polymerization 650) was dissolved at 100 Torr with 1-ethyl-3-mercaptoimidazolium chloride ionic liquid (EMIMC1) to obtain a cellulose solution having a concentration of 10% by weight.
  • EMIMC1 1-ethyl-3-mercaptoimidazolium chloride ionic liquid
  • the undrawn cellulose is passed through the coagulation bath, and ions are ionized in the film.
  • the liquid solvent was first stretched in the transverse direction at a weight ratio of cellulose nonsolvent of 2.6:1 in the film, and stretched 1.25 times.
  • the wood pulp (degree of polymerization 650) was dissolved at 80 ° C with 1-butyl-3-mercaptoimidazole acetate ionic liquid (BMIMAc) to obtain a cellulose solution having a concentration of 10% by weight.
  • BMIMAc 1-butyl-3-mercaptoimidazole acetate ionic liquid
  • the port was extruded into a 50 ° C water-soluble 3 ⁇ 4 a solidification bath containing 5% by weight of an ionic liquid to obtain an unstretched cellulose.
  • the first transverse stretching is performed at a weight ratio of the ionic liquid solvent to the cellulose non-solvent in the film of 1.5:1 in the film, and the stretching is 1.7 times; in the film, the ionic liquid solvent is relative to the cellulose non-solvent in the film.
  • the second transverse stretching was performed 1.4 times; the third transverse stretching was performed at an ionic liquid content of 0, and the stretching was 1.4 times.
  • the stretched gel was further washed in 50'C water to remove the ionic liquid.
  • the fourth transverse stretching was carried out while drying, and the stretching was 1.3 times.
  • the resulting biaxially oriented regenerated cellulose film had a total draw ratio of 4.0 times in the machine direction, a total draw ratio of 3.3 times in the transverse direction, a longitudinal tensile strength of 180.3 MPa, and a transverse tensile strength of 148.6 MPa.
  • the pulp pulp (degree of polymerization 650) was dissolved at 70 ° C with 1-butyl-3-mercaptoimidazolium acetate ionic liquid (BMIMAc) to obtain a cellulose solution having a concentration of 8% by weight. After defoaming, filtering and extruding through the i3 ⁇ 4 port to 20. An unstretched cellulose gel film was obtained by coagulating a C of 20% by weight of an ionic liquid in ethanol.
  • BMIMAc 1-butyl-3-mercaptoimidazolium acetate ionic liquid
  • the first transverse stretching is carried out in the film at a weight ratio of ionic liquid solvent to the cellulose non-solvent in the film of 1.9:1, and the stretching is 1.3 times; after washing with one of the above coagulation baths, the ionic liquid solvent in the film is relatively
  • the second transverse stretching was carried out at a weight ratio of cellulose non-solvent of 0.8:1 in the film, and the stretching was 1.2 times.
  • the condensed after stretching is further at 20.
  • the ionic liquid is removed by washing in C ethanol. Use a biaxial stretching device to maintain the film in a lateral dimension when dry.
  • the resulting biaxially oriented regenerated cellulose film had a total draw ratio of 2.0 times in the longitudinal direction, a total draw ratio of 1.3 times in the transverse direction, a longitudinal tensile strength of 169.0 MPa, and a transverse tensile strength of 125.7 MPa.
  • the wood pulp (degree of polymerization 650) was dissolved at 100 ° C with 1-allyl-3-methylchloroimidazolium salt ionic liquid (AMIMC1) to obtain a cellulose solution having a concentration of 10% by weight.
  • AMIMC1 1-allyl-3-methylchloroimidazolium salt ionic liquid
  • Defoaming After filtration, it was extruded through a die into a coagulation bath consisting of a 60 ° C aqueous solution containing 5% by weight of an ionic liquid to obtain unstretched cellulose 3 ⁇ 4J ⁇ .
  • the weight ratio of the ionic liquid solvent to the cellulose non-solvent in the film is 0.7:1, and the first transverse stretching is performed, and the stretching is 1.4 times; after washing with one of the above coagulation baths, the ionic liquid solvent in the film is relatively
  • the second transverse stretching was carried out at a weight ratio of cellulose non-solvent of 0.3:1 in the film, and the stretching was 1.3 times.
  • the condensation after stretching is further at 30.
  • the ionic liquid is removed by washing in C water.
  • the third transverse stretching was carried out while drying, and the stretching was 1.2 times.
  • the resulting biaxially oriented regenerated cellulose film had a total draw ratio of 2.5 times in the machine direction, a total draw ratio of 1.8 times in the transverse direction, a longitudinal tensile strength of 191.4 MPa, and a transverse tensile strength of 143.2 MPa.
  • the cotton pulp (degree of polymerization 750) was dissolved at 80 ° C with 1-butyl-3-methylchloroimidazolium salt ionic liquid (BMIMC1) to obtain a cellulose solution having a concentration of 8% by weight. Acidified carbon nanotubes were added at 3% (relative to the weight of cellulose in the film). After mixing, defoaming, and filtering, it was extruded through a die into a coagulation bath composed of an aqueous solution containing 10% by weight of an ionic liquid of 30 e C to obtain an unstretched cellulose gel film.
  • BMIMC1 1-butyl-3-methylchloroimidazolium salt ionic liquid
  • the first transverse stretching was carried out at a weight ratio of the ionic liquid solvent to the cellulose non-solvent in the film of 0.5:1 in the film, and the stretching was 1.4 times.
  • the condensed after stretching was further washed in 30 'C water to remove the ionic liquid.
  • the second transverse stretching was carried out while drying, and the stretching was 1.1 times.
  • the resulting biaxially oriented regenerated cellulose film had a total draw ratio of 2.0 times in the longitudinal direction, a total draw ratio of 1.4 times in the transverse direction, a longitudinal tensile strength of 192.2 MPa, and a transverse tensile strength of 144.1 MPa.
  • a mixed solvent of 1-allyl-3-indolyl chloride imidazolium salt ionic liquid (AMIMC1) and N,N-dimethylsulfoxide (90:10 by weight) was used at 80.
  • the wood pulp (polymerization degree 650) was dissolved under C to obtain a cellulose solution having a concentration of 8% by weight.
  • the weight ratio of the ionic liquid solvent to the cellulose non-solvent in the film was 1.6 times in the transverse direction at 0.4:1.
  • the condensation after stretching is further at 20.
  • the C water was washed to remove the ionic liquid and N,N-dimercaptosulfoxide.
  • the resulting biaxially oriented regenerated cellulose film had a total draw ratio of 1.5 times in the machine direction and the transverse direction, a longitudinal tensile strength of 183.0 MPa, and a transverse tensile strength of 146.4 MPa.
  • a mixed solvent of 1-butyl-3-methylimidazolium acetate ionic liquid (BMIMAc) and N,N-dimethylformamide (80:20 by weight) was used at 80.
  • the wood pulp degree of polymerization 650
  • a layered nanoclay of 2% (relative to the weight of cellulose in the film) was added. After mixing, defoaming, and filtering, it was extruded through a die into a coagulation bath of 40 ° C water to obtain an unstretched cellulose gel film.
  • the weight ratio of the ionic liquid solvent to the cellulose non-solvent in the film is 0.7:1 for the first transverse stretching, and the stretching is 1.5 times; and the second transverse stretching is performed at the ionic liquid content of 0%. , stretched 1.2 times. Condensation after stretching! ⁇ Further washing in 20 Torr of water to remove ionic liquid and N,N-dimethyl decylamine. Use a biaxial stretching device to keep the film in a lateral dimension when dry.
  • microcrystalline cellulose degree of polymerization 230
  • AMIMC1 1-allyl-3-indolyl chloride imidazolium salt ionic liquid
  • 1% relative to the weight of cellulose in the membrane
  • the port was extruded into a coagulation bath of 60 ° C water to obtain unstretched cellulose 3 ⁇ 4 ⁇ .
  • the weight ratio of the ionic liquid solvent to the cellulose non-solvent in the film was 1.2 times in the transverse stretch at 0.3:1.
  • the wood pulp (degree of polymerization 650) was dissolved at 80 ° C with 1-allyl-3-methylchloroimidazolium salt ionic liquid (AMIMC1) to obtain a 8% by weight cellulose solution.
  • AMIMC1 1-allyl-3-methylchloroimidazolium salt ionic liquid
  • the first transverse stretching was carried out at a weight ratio of the ionic liquid solvent to the cellulose non-solvent in the film of 0.3:1 in the film, and the stretching was 1.2 times.
  • the condensed after stretching is further washed in water at 20 ° C Deionized liquid and acetone.
  • the second transverse stretching was carried out while drying, and the stretching was 1.2 times.
  • the resulting biaxially oriented regenerated cellulose film had a total draw ratio of 1.8 times in the longitudinal direction, a total draw ratio of 1.3 times in the transverse direction, a longitudinal tensile strength of 178.9 MPa, and a transverse tensile strength of 135.5 MPa.
  • the wood pulp (degree of polymerization 650) was dissolved at 70 ° C with 1-butyl-3-methylimidazolium acetate ionic liquid (BMIMAc) to obtain a 5% by weight cellulose solution.
  • BMIMAc 1-butyl-3-methylimidazolium acetate ionic liquid
  • 2% (relative to the weight of cellulose in the membrane) of alginic acid and 2% (relative to the weight of cellulose in the membrane) of nanosilica were added.
  • the first transverse stretching is performed at a weight ratio of ionic liquid solvent to the cellulose non-solvent in the film at a ratio of 1.1:1 in the film, and the stretching is 1.4 times; after washing with one of the above coagulation baths, the ionic liquid solvent in the film is relatively
  • the second transverse stretching was carried out at a weight ratio of cellulose nonsolvent of 0.2:1 in the film, and the stretching was 1.3 times.
  • the condensation after stretching is further at 20.
  • the ionic liquid is removed by washing in C ethanol. Use a biaxial stretching device to keep the film in a lateral dimension when dry.
  • the resulting biaxially oriented regenerated cellulose film had a total draw ratio of 2.0 times in the longitudinal direction, a total draw ratio of 1.7 times in the transverse direction, a longitudinal tensile strength of 190.9 MPa, and a transverse tensile strength of 152.1 MPa.
  • the cellulose film shrinks during washing and drying, and is more severe in the transverse direction. Therefore, the total draw ratio of the final cellulose film is less than the product of each draw ratio.
  • the film was not stretched in the transverse direction, and the obtained film width was smaller than the original film width. The application of transverse stretching reduces the extent of film shrinkage, which increases the film width and increases the transverse tensile strength.

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Abstract

本发明涉及一种再生纤维素膜、功能膜及其制备方法，所述方法主要包括如下步骤：（1）纤维素/离子液体溶液使用模头挤出、压延或流延的方法赋形；（2）赋形的溶液进入凝固浴形成纤维素凝胶膜；（3）在凝固和洗涤的过程中，对纤维素凝胶膜进行至少一次的横向和纵向拉伸；（4）在干燥过程中，进一步对拉伸膜施加横向和纵向张力，最后经收卷得到再生纤维素膜。在纤维素/离子液体溶液中可加入有机和/或无机的功能型添加剂，通过上述方法得到再生纤维素功能膜。通过上述方法得到的再生纤维素膜及其功能膜具有均衡的和较高的纵、横向拉伸强度，同时具有好的平整度。

Description

说 明 书 一种再生纤维素膜、 功能膜及其制备方法 技术领域
本发明涉及一种再生纤维素膜（又称玻璃纸、 纤维素膜）、 功能膜及 其制备方法， 尤其涉及一种双向拉伸的再生纤维素膜、 功能膜及其制备 方法， 属于有机高分子领域。 背景技术
纤维素是自然界分布最广、储量最大的天然高分子，是一种取之不尽、 用之不竭的可再生资源。 与合成高分子相比， 纤维素具有完全可生物降 解、 无毒、 无污染、 生物相容性好等优点。 随着石油、 煤炭等化石资源 的日益枯竭， 纤维素基材料的研究和开发对促进人类的可持续发展具有 重要的意义。
以纤维素为原料制备的再生纤维素膜（又称玻璃纸、 纤维素膜）是一 类重要的膜材料， 具有无毒、 透明、 不产生静电、 耐高温、 阻隔性好、 可降解的特性， 广泛用于食品、 药品、 化妆品、 高档成衣、 精密仪器等 产品的包装。 由于天然纤维素具有高的结晶度和大量的分子间和分子内 氢键， 使其不熔融， 难以溶解， 加工性能差。 工业上， 现有的再生纤维 素膜生产主要采用黏胶技术， 对天然纤维素进行衍生化后， 得到纤维素 溶液， 再进行纤维素的再生， 不仅生产过程存在高污染、 高能耗的问题, 而且生产中纤维素降解严重， 产品的性能难以提高。
双向拉伸技术被广泛用于提高聚合物膜的物理力学性能， 经过近三、 四十年的快速发展， 已经形成艮大的生产能力， 产品涉及聚丙烯、 聚酯、 聚苯乙烯、 聚氯乙烯、 聚酜胺等多种合成高分子。 与未拉伸膜相比， 双 向拉伸聚合物膜的力学强度显著提高； 透明度和表面光泽度提高； 厚度 均匀、 厚度偏差小； 阻隔性能改善。 但双向拉伸技术对聚合物原料本身 的性质也有一定的要求， 如聚合物要有较高的强度（参见 BOPP专用料 的试制， 李怡森， 合成树脂及塑料， 1991，8(4):25 )。
在黏胶技术制备再生纤维素膜的生产中， 通过调节不同辊筒间的速 比， 可以使膜在纵向方向上产生较高的强度， 相比之下， 纤维素膜在横 向方向上的强度 ί艮差， 收缩严重。 由于纤维素的分子量在衍生化过程中 降解严重， 黏胶技术得到的纤维素膜无法借助横向拉伸提高其横向拉伸 强度。
而在纤维素的非衍生化溶剂体系中， 如 Ν-甲基吗啉 -Ν-氧化物 ( ΝΜΜΟ ), 纤维素的分子量在溶解、 再生时的降解减轻， 得到的膜有 可能进行横向拉伸， 使制备双向拉伸的纤维素膜成为可能。
PCT申请 W097/24215提供了从纤维素的 ΝΜΜΟ溶液制备双向拉伸 再生纤维素膜的方法。 该方法将纤维素溶液挤出附着到弹性体的膜上， 在除去 ΝΜΜΟ溶剂之前拉伸弹性体膜以达到对纤维素溶液双向拉伸的 目的。 但纤维素溶液强度低， 液体膜在拉伸中容易破裂， 造成工艺过程 的不稳定。 另外， 在溶液中被拉伸取向的分子链容易回复， 而且洗涤和 干燥过程会导致成型的再生纤维素膜进一步收缩， 影响纤维素膜性能的 提高。 PCT申请 W098/49224将纤维素的 NMMO溶液从挤出模口挤出 到凝固浴中， 在醒 MO溶剂洗净后将成型的膜进行横向拉伸， 最后干 燥定型； 或是将干燥的膜润湿后进行横向拉伸。 但横向拉伸膜在干燥时 仍会有一定程度的收缩，导致膜在横向方向的尺寸减小，拉伸强度降低。 因此， 在 PCT申请 W098/49224的基础上， PCT申请 WO02/100925将 经过凝固浴成型并洗去 NMMO后的纤维素膜分两步进行横向拉伸， 第 一步将膜超量拉伸， 第二步让拉伸的膜松弛到所需的拉伸程度。 PCT申 请 WO02/100926则通过对横向拉伸膜继续在横向方向上保持一定的张 力， 来减小膜在横向上的收缩。 虽然得到的拉伸膜与水或碱溶液接触时 能保持较好的尺寸稳定性， 但拉伸膜在橫向方向的拉伸强度提高不大， 低于纵向方向的强度的 60%， 横向与纵向性能仍然不均衡。
最近， 离子液体作为一类新兴的天然纤维素的绿色溶剂， 因为其溶解 能力强、 不挥发、 化学稳定性和热稳定性好、 容易回收而倍受关注。 已 有用于溶解纤维素的离子液体的专利 （参见中国发明专利： ZL 02147004.9, ZL 02155945.7, ZL 02823875.3, ZL 200680012598.x, CN 200710085298.0 )。 以离子液体为溶剂制备再生纤维素功能膜的工艺也有 专利报道（参见 ZL 200410101800.9 ): 纤维素的离子液体溶液赋形后进 入凝固^：固再生， 进一步洗涤、 干^得到纤维素膜。
目前，还没有在纤维素凝固成凝 «后在其洗涤阶段进行横向拉伸进 而制备欢向拉伸膜的报道。 我们的研究发现， 纤维素的离子液体溶液在 凝固后， 形成的纤维素凝胶膜具有优异的凝胶强度。 同时， 由于纤维素 膜中适量离子液体的存在又比纤维素溶剂完全除去的纤维素凝^^ 具有更好的可变形性， 因此更适合进行双向拉伸加工； 而且经横向拉伸 后凝胶膜的幅宽增加、 厚度降低， 有利于膜中残余离子液体溶剂的洗出 以及膜在干燥时水分的脱除。 另外， 经双向拉伸法制备纤维素功能膜的 技术也未见报道。 发明内容
本发明的目的在于克服现有技术得到的再生纤维素膜横向和纵向拉 伸强度较差、 差别较大的缺点， 提供一种横向和纵向均有优异拉伸强度 的双向拉伸再生纤维素膜及其功能膜。
本发明的另一个目的在于提供上述再生纤维素膜及其功能膜的制备 方法。
本发明提供的上述方法可用于以离子液体为纤维素溶剂的再生纤维 素膜及其功能膜的制备中。
本发明通过如下技术方案实现：
一种双向拉伸再生纤维素膜， 其特征在于， 纤维素膜横向拉伸和纵 向拉伸的倍数至多为 400% ,纵向拉伸强度与横向拉伸强度之比小于 1.8。 的差别。本发明的纵向拉伸强度与横向拉伸强度的比例小于 1.8，优选小 于 1.5, 更优选小于 1.4。
根据本发明， 所述纤维素膜的横向拉伸倍数为 101~400%， 优选 150-300%; 纵向拉伸倍数为 110~400%， 优选 150-300%。
根据本发明， 所述纤维素膜的横向和纵向拉伸倍率相同或者不同。 根据本发明，横向拉伸和纵向拉伸可以同步进行，也可以分步进行。 可以先进行横向拉伸， 然后进行纵向拉伸； 也可以先进行纵向拉伸， 然 后进行横向拉伸。
根据本发明， 所述纤维素膜的横向拉伸至少 1次， 优选进行 2到 4 次拉伸， 更优选进行 1到 3次拉伸。
根据本发明， 所述纤维素膜的纵向拉伸至少 1次， 优选 2~4次， 更 优选进行 1到 3次拉伸。
本领域了解，从生产角度，传统工艺中通过调节不同辊筒间的速比， 容易使膜在纵向方向上实现拉伸； 而橫向拉伸需要增加设备， 因此橫向 拉伸次数越少越经济， 但拉伸次数多对膜性能更为有利。 综合来看， 2-4 次均可， 优选 1~3次。
根据本发明， 每次拉伸倍数在同一个方向上可以相同或不同。 以 3 次拉伸为例，拉伸倍数相同时，横向每一次拉伸倍数 120%;拉伸倍数不 同时，横向可以第一次拉伸 130% ,第二次拉伸 120% ,第三次拉伸 110% , 或者横向可以第一次拉伸 125% ,第二次拉伸 125% ,第三次拉伸 105%。 总的拉伸倍数如前所述。
根据本发明， 所述纤维素为天然纤维素， 优选地， 所述天然纤维素 原料的聚合度在 200-2000范围。本发明所述纤维素选自下述纤维素原料 中的至少一种： 微晶纤维素、 棉浆粕、 木浆粕、 竹浆粕、 脱脂棉、 甘蔗 渣、 木材以及 物秸秆中制得的纤维素。
根据本发明， 所述再生纤维素膜是通过将纤维素 /离子液体溶液成型 后进行拉伸得到。 根据本发明， 所述纤维素 /离子液体溶液经模口挤出后可采用公知的 流延或压延方法赋形， 然后通过气隙进入凝固浴形成纤维素凝胶膜。
本发明中， 纤维素膜在干燥前因含有溶剂， 因而称之为^ ^。 而 膜干燥完全脱除溶剂后， 即称为纤维素膜。
根据本发明， 所述凝固浴为离子液体与水、 曱醇、 乙醇或丙酮等纤 维素非溶剂的混合物。 凝固浴中离子液体溶剂与纤维素非溶剂重量比在
0~150:100范围内调节， 凝固浴温度可在 10~80'C范围内调节， 借此调节 纤维素的凝固速率。 纤维素 /离子液体溶液进入凝固浴后， 在非溶剂的存 在下纤维素凝固成膜的形状， 得到凝胶膜。
本发明还提供一种双向拉伸再生纤维素功能膜，其特征在于，所述功 能膜包括上述的纤维素膜以及有机和 /或无机的功能型添加剂。
本发明还提供一种双向拉伸再生纤维素膜的制备方法， 其特征在于， 所述方法包括如下步骤：
(1)将纤维素 /离子液体溶液使用模头挤出、压延或¾½的方法赋形；
(2)赋形的溶液进入凝固浴形成纤维素凝^ I；
(3)在凝固和洗涤的过程中，对纤维素凝 进行至少一次的横向拉 伸和至少一次的纵向拉伸；
(4)在干燥过程中，进一步对拉伸膜施加横向和纵向张力，最后经收 卷得到再生纤维素膜。
本发明的制备方法结合了纤维素的离子液体溶剂技术和双向拉伸技 术进行再生纤维素膜及其功能膜的制备。 综合而言， 本发明发现以离子 液体为溶剂， 从纤维素 /离子液体溶液通过赋形、 凝固、 洗涤、 拉伸、 干 维素膜， 而且该工艺可以赋予双向拉伸纤维素膜优于现有商品化的再生 纤维素膜的性能。
利用辊筒间速度差对挤出模口后的纤维素溶液或纤维素凝胶膜进行 纵向拉伸。 在纤维素凝胶膜中离子液体溶剂相对于膜中纤维素非溶剂的 重量比小于 4:1用拉伸设备（双向拉伸机、 拉幅机或展幅机）对纤维素 ^JM进行一次或多次的横向拉伸， 采用分次拉伸可以减小每次拉伸的 程度， 从而降低膜在拉伸时破损的可能。 膜的厚度因横向拉伸而降低， 有利于纤维素凝胶膜中残余离子液体的洗涤， 以及膜在干燥时水或其它 非溶剂的脱除。 在纤维素凝胶膜干燥时， 用拉伸设备对膜进行横向拉伸 或施加一定的横向张力， 能够防止膜在干燥时的收缩， 进一步提高纤维 素膜在横向方向和纵向方向上的性能的均衡性。
本发明中， 横向拉伸和纵向拉伸可以同步进行， 也可以分步进行。 可以先进行横向拉伸， 然后进行纵向拉伸； 也可以先进行纵向拉伸， 然 后进行横向拉伸。 本发明优选 2-4次的横向拉伸， 最终的横向拉伸倍数 为 101~400%。 本发明优选 2-4 次的纵向拉伸， 纵向拉伸倍数为 110-400%.
根据本发明的方法， 步骤（2 )中， 所述凝固浴为离子液体与水、 甲 醇、 乙醇或丙酮等纤维素非溶剂的混合物。 所述凝固浴为离子液体溶剂 与水或其它纤维素非溶剂重量比为 0~150:100， 优选 0~120:100， 更优选 0-80:100的混合物。
根据本发明， 所述凝固浴温度可在 10~80'C范围内调节， 借此调节纤 维素的凝固速率。 纤维素 /离子液体溶液进入凝固浴后， 在非溶剂的存在 下纤维素凝固成膜的形状， 得到^ jg 。
根据本发明的方法， 步骤（3 )中， 在纤维素凝胶膜的凝固和洗涤过 程中， 当^^ I中离子液体溶剂相对于膜中纤维素非溶剂的重量比小于
4:1， 优选 3:1， 时对纤维素凝 进行横向和纵向拉伸。
步猓（3 )中， 纤维素凝 离开凝固浴后 i ^洗涤浴， 进行洗涤， 以洗涤除去膜中的离子液体。 所述洗涤浴可以是水或其它与离子液体混 溶的纤维素非溶剂。 所述洗涤浴温度为 10~80'C， 优选为 20~60' (：。
步骤（3 )中， 本发明还可以采用公知的逆向洗涤的方法。 离子液体 洗净后凝胶膜中的水或溶剂可以通过公知的干燥方法除去， 例如， 减压 条件下升温干燥、 鼓热风干燥、 热辊干燥、 红外升温干燥、微波干燥等， 但并不限于这些方法。
根据本发明的方法， 步骤（3 )中， 在纤维素凝胶膜的凝固和洗涤过 程中， 当 MJI^中离子液体溶剂相对于膜中纤维素非溶剂的重量比小于 4:1，优选 3:1, 时对纤维素凝 进行至少一次的横向拉伸，优选进行 1 到 3次的横向拉伸。
根据本发明的方法， 步骤（3 )中， 在纤维素凝^ I拉伸后， 进一步 洗涤除去残余的离子液体。
根据本发明的方法， 步骤（3 )中， 洗涤浴为水或其它的纤维素非溶 剂。
根据本发明的方法， 步骤（4 )中， 在纤维素凝胶膜干燥过程中， 对 膜施加横向和纵向张力。 根据本发明的方法， 步骤（4 )中， 在纤维素凝胶膜干燥过程中， 对 膜进行横向和纵向拉伸。
根据本发明的方法， 步骤（4 )中， 纤维素膜横向、 纵向方向总的拉 伸倍数最高可达 400%。
根据本发明的方法， 步骤（1 ) 中， 纤维素 /离子液体溶液是将天然 纤维素原料溶于离子液体溶剂中获得的。
根据本发明的方法， 步骤（1 )中， 所述离子液体溶剂为可以溶解纤 维素的离子液体、 溶解纤维素的离子液体组成的混合溶剂、 或溶解纤维 素的离子液体与其它共溶剂组成的混合溶剂。
根据本发明，所述离子液体是由咪唑或吡啶型阳离子与阴离子所形成 的、 熔点低于 100。C的有机熔融盐， 优选可以溶解纤维素的有机熔融盐。 还优选地， 本发明可以使用混合的离子液体溶解纤维素其中所述混合的 离子液体可以均是能溶解纤维素的离子液体， 也可以是能溶解纤维素的 离子液体与不溶解纤维素的离子液体的混合物。
优选地， 阳离子优选下述任意一种： 1-乙基 -3-甲基咪唑阳离子、 1-丙 基 -3-甲基咪唑阳离子、 1-烯丙基 -3-甲基咪唑阳离子、 1-丁基 -3-甲基咪唑 阳离子、 N-乙基吡啶阳离子、 N-丁基吡啶阳离子、 N-正己基吡啶阳离子。 所述阳离子尤其优选下述任意一种： 1-乙基 -3-甲基咪唑阳离子、 1-烯丙 基 -3-甲基咪唑阳离子和 1-丁基 -3-甲基咪唑阳离子。
优选地， 阴离子优选下述任意一种： 氯离子、 溴离子、 甲酸根离子、 醋酸根离子、 丙酸根离子、 丁酸根离子和磷酸甲酯离子； 所述阴离子尤 其优选下述任意一种： 氯离子、 曱酸根离子、 醋酸根离子和磷酸曱酯离 子。
根据本发明， 所述离子液体单独或混^吏用， 或是与 N，N-二甲基亚 砜、 N，N-二曱基曱醜胺、 N，N-二曱基乙酰胺或 N-甲基吡咯烷酮等共溶剂 混^^吏用 .
根据本发明， 所述共溶剂为 N，N-二甲基亚砜、 N，N-二曱基曱酰胺、 N，N-二曱基乙 StJfe或 N-曱基吡咯烷酮。
根据本发明， 纤维素为天然纤维素， 优选地， 所述天然纤维素原料 的聚合度在 200~2000范围。
本发明所述纤维素选自下述纤维素原料中的至少一种： 微晶纤维素、 棉浆粕、 木浆粕、 竹浆粕、 脱脂棉、 甘蔗渣、 木材以及从植物秸秆中制 得的纤维素； 所述纤维素的聚合度优选在 200至 2000之间。
本发明所述的纤维素离子液体溶液为纤维素含量在 3~20% (相对于 离子液体溶剂的重量） 的透明均匀的溶液。 纤维素的溶解温度为 50~150。C， 可借助公知的^ 0¾搅拌、 微波、 超声或螺杆挤出的方法加速 纤维素的分散和溶解。
本发明还提供一种双向拉伸再生纤维素功能膜的制备方法， 其特征 在于， 所述方法包括如下步骤：
(1)在纤维素 /离子液体溶液中加入有机和 /或无机的功能型添加剂；
(2)将上述添加了有机和 /或无机添加剂的纤维素 /离子液体溶液使用 模头挤出、 压延或流延的方法赋形；
(3)赋形的溶液进入凝固浴形成纤维素凝胶膜；
(4)在凝固和洗涤的过程中，对纤维素凝！ ^进行至少一次的横向拉 伸和至少一次的纵向拉伸；
(5)在干燥过程中，进一步对拉伸膜施加横向和纵向张力，最后经收 卷得到再生纤维素膜。
把特定的有机和 /或无机功能添加剂加入到纤维素溶液中， 可以制备 增强、 增韧和其它功能化的双向拉伸纤维素功能膜。
根据本发明功能膜的制备方法， 其特征在于， 本发明所述有机和 /或 无机的功能添加剂为曱壳素、 壳聚糖、 海藻酸、层状纳米 土、石墨烯、 碳纳米管、 埃洛石纳米管、 纳米碳纤维、 炭黑、 纳米二氧化钛、 纳米氧 化锌或纳米二氧化硅中的一种或几种。
根据功能膜的制备方法， 其特征在于： 有机和 /或无机的功能型添加 剂的含量在 0.1~20% (相对于膜中纤维素的重量)。
本发明还提供通过上述方法制备得到的一种双向拉伸再生纤维素膜 或功能膜。
本发明还提供上述纤维素膜或功能膜的应用。 现有技术中的常规纤 维素膜或者功能膜的应用领域都适用， 例如应用于食品、 药品、化妆品、 高档成衣、 精密仪器等产品的包装。 本发明技术效果：
离子液体对纤维素具有优异的溶解能力， 并且纤维素在离子液体溶 解过程中降解程度较低。 本发明所涉及的再生纤维素膜及其功能膜的双 向拉伸技术， 充分利用以离子液体为溶剂得到的纤维素凝胶膜具有较高 凝胶强度和较大断裂伸长率的特点， 在横向和纵向上对纤维素凝 进 行拉伸， 在降低纤维素膜厚度的同时， 提高其在横向和纵向上的拉伸强 度及厚度均匀性， 获得高性能的再生纤维素膜及其功能膜， 可显著扩大 纤维素的应用领域。 具体实施方式
下面给出的实施例对本发明进行详细描述。 但是本领域技术人员理 解， 下述实施例不是对本发明保护范围的限制， 任何在本发明基础上做 出的改进和变化， 都在本发明的保护范围之内。
需要说明的是，现有的传统工艺都会对膜在纵向方向上产生单方向的 拉伸， 可称为 "单向拉伸膜"， 结果是导致膜在纵向、横向性能上的巨大 差异。 本专利改进现有工艺， 让膜在横向方向上也产生拉伸， 提高横向 方向上膜的性能， 加上原有的纵向拉伸， 因此称为双向拉伸。 考虑到纵 向拉伸部分与传统工艺相似， 本发明在实施例中没有具体强调如何进行 纵向拉伸， 只在实施例中给出了纵向方向上总的拉伸倍数。 实施例 1
用 1-烯丙基 -3-甲基氯咪唑盐离子液体 ( AMIMC1 )在 90'C下溶解木 浆粕（聚合度 650 )， 得到 10% (重量）的纤维素溶液。 经脱泡、 过滤后 通 i«口挤出到 50Ό的含 5% (重量） 离子液体的水溶液组成的凝固浴 中， 得到未拉伸的纤维素凝胶膜。 在膜中离子液体溶剂相对于膜中纤维 素非溶剂的重量比为 1.6:1处在横向上拉伸 1.5倍。 拉伸后的凝! ^进一 步在 30'C水中洗涤除去离子液体。 干燥时用双向拉伸设备让膜保持横向 尺寸。 最后得到的欢向拉伸再生纤维素膜在纵向上的总拉伸倍数为 2.5 倍， 横向上的总拉伸倍数为 1.3倍， 纵向拉伸强度为 175 MPa, 横向拉 伸强度为 139 MPa。 对照例 1
用 1-烯丙基 -3-甲基咪唑氯盐离子液体 ( AMIMC1 )在 90'C下溶解木 浆粕（聚合度 650 )， 得到浓度为 10% (重量）的纤维素溶液。 经脱泡、 过滤后通 口挤出到 50'C的含 5% (重量）的离子液体的水溶 ¾ a成 的凝固浴中， 得到未拉伸的纤维素凝胶膜。 以 30。C水为洗涤浴， 进一步 洗涤除去离子液体。 干燥后得到的再生纤维素膜在纵向上的总拉伸倍数 为 2.5倍， 横向未拉伸， 纵向拉伸强度为 168.6 MPa, 横向拉伸强度为 74.8 MPa. 实施例 2
用 1-烯丙基 -3-甲基咪唑氯盐离子液体 ( AMIMC1 )在 90'C下溶解棉 浆粕（聚合度 750 ), 得到浓度为 8% (重量）的纤维素溶液。 经脱泡、 过滤后通 口挤出到 50Ό的含 60% (重量）的离子液体的水溶液组成 的凝固浴中， 得到未拉伸的纤维素 mj^。 经过上述凝固浴， 在膜中离 子液体溶剂相对于膜中纤维素非溶剂的重量比为 4:1 处在横向上拉伸 1.25倍。 拉伸后的凝 进一步在 50'C水中洗涤除去离子液体。 干燥时 用双向拉伸设备让膜保持横向尺寸。 干燥后得到的双向拉伸再生纤维素 膜在纵向上的拉伸倍数为 1.2倍，横向上的拉伸倍数为 1.1倍， 纵向拉伸 强度为 170.1MPa， 横向拉伸强度为 126.2MPa。 实施例 3
用 1-乙基 -3-曱基咪唑氯盐离子液体（EMIMC1 )在 100Ό下溶解木浆 粕（聚合度 650 )， 得到浓度为 10% (重量）的纤维素溶液。 经脱泡、 过 滤后通 i«口挤出到 50'C的含 15% (重量）的离子液体的水溶液组成的 凝固浴中， 得到未拉伸的纤维素 经过上述凝固浴， 在膜中离子 液体溶剂相对于膜中纤维素非溶剂的重量比为 2.6:1处进行第一次横向 拉伸， 拉伸 1.25倍。 在膜中离子液体溶剂相对于膜中纤维素非溶剂的重 量比为 0.7:1处时进行第二次横向拉伸， 拉伸 1.25倍。 拉伸后的凝^ 进一步在 30'C水中洗涤除去离子液体。 干燥时用双向拉伸设备让膜保持 横向尺寸。 最后得到的双向拉伸再生纤维素膜在纵向上的总拉伸倍数为 2.0倍， 横向上的总拉伸倍数为 1.4倍， 纵向拉伸强度为 185.3MPa, 横 向拉伸强度为 130.2MPa。 实施例 4
用 1-丁基 -3-曱基咪唑醋酸盐离子液体 ( BMIMAc )在 80'C下溶解木 浆粕（聚合度 650 )， 得到浓度为 10% (重量）的纤维素溶液。 经脱泡、 过滤后通 口挤出到 50'C的含 5% (重量）的离子液体的水溶 ¾ a成 的凝固浴中， 得到未拉伸的纤维素^^。 在膜中离子液体溶剂相对于 膜中纤维素非溶剂的重量比为 1.5:1处进行第一次横向拉伸，拉伸 1.7倍; 在膜中离子液体溶剂相对于膜中纤维素非溶剂的重量比为 0.6:1处进行 第二次横向拉伸，拉伸 1.4倍；在离子液体含量为 0处进行第三次横向拉 伸，拉伸 1.4倍。拉伸后的凝^ ^进一步在 50'C水中洗涤除去离子液体。 干燥时进行第四次横向拉伸，拉伸 1.3倍。最后得到的双向拉伸再生纤维 素膜在纵向上的总拉伸倍数为 4.0倍，横向上的总拉伸倍数为 3.3倍， 纵 向拉伸强度为 180.3MPa， 横向拉伸强度为 148.6MPa。 实施例 5
用 1-丁基 -3-曱基咪唑醋酸盐离子液体 ( BMIMAc )在 70'C下溶解木 浆粕（聚合度 650 ), 得到浓度为 8% (重量）的纤维素溶液。 经脱泡、 过滤后通 i¾口挤出到 20。C的含 20% (重量）的离子液体的乙醇溶 ¾ a 成的凝固浴中， 得到未拉伸的纤维素凝胶膜。 在膜中离子液体溶剂相对 于膜中纤维素非溶剂的重量比为 1.9:1处进行第一次横向拉伸， 拉伸 1.3 倍； 经过一道上述凝固浴的洗涤， 在膜中离子液体溶剂相对于膜中纤维 素非溶剂的重量比为 0.8:1处进行第二次横向拉伸， 拉伸 1.2倍。 拉伸后 的凝 进一步在 20。C乙醇中洗涤除去离子液体。 干燥时用双向拉伸设 备让膜保持横向尺寸。 最后得到的双向拉伸再生纤维素膜纵向上的总拉 伸倍数为 2.0倍， 横向上的总拉伸倍数为 1.3 倍， 纵向拉伸强度为 169.0MPa, 横向拉伸强度为 125.7MPa。 实施例 6
用 1-烯丙基 -3-甲基氯咪唑盐离子液体 ( AMIMC1 )在 100'C下溶解木 浆粕（聚合度 650 ), 得到浓度为 10% (重量）的纤维素溶液。 经脱泡、 过滤后通过模口挤出到 60'C的含 5% (重量）的离子液体的水溶液组成 的凝固浴中， 得到未拉伸的纤维素 ¾J^。 在膜中离子液体溶剂相对于 膜中纤维素非溶剂的重量比为 0.7:1处进行第一次横向拉伸，拉伸 1.4倍; 经过一道上述凝固浴的洗涤， 在膜中离子液体溶剂相对于膜中纤维素非 溶剂的重量比为 0.3:1处进行第二次横向拉伸， 拉伸 1.3倍。 拉伸后的凝 进一步在 30。C水中洗涤除去离子液体。干燥时进行第三次横向拉伸， 拉伸 1.2倍。最后得到的双向拉伸再生纤维素膜在纵向上的总拉伸倍数为 2.5倍， 横向上的总拉伸倍数为 1.8倍， 纵向拉伸强度为 191.4MPa, 横 向拉伸强度为 143.2MPa。 实施例 7
用 1-丁基 -3-甲基氯咪唑盐离子液体 ( BMIMC1 )在 80'C下溶解棉浆 粕（聚合度 750 )， 得到浓度为 8% (重量）的纤维素溶液。 加入 3% (相 对于膜中纤维素的重量）的酸化碳纳米管。 经混合、 脱泡、 过滤后通过 模口挤出到 30eC的含 10% (重量）的离子液体的水溶液组成的凝固浴中， 得到未拉伸的纤维素凝胶膜。 在膜中离子液体溶剂相对于膜中纤维素非 溶剂的重量比为 0.5:1处进行第一次横向拉伸， 拉伸 1.4倍。 拉伸后的凝 进一步在 30'C水中洗涤除去离子液体。干燥时进行第二次横向拉伸， 拉伸 1.1倍。 最后得到的双向拉伸再生纤维素膜纵向上的总拉伸倍数为 2.0倍， 横向上的总拉伸倍数为 1.4倍， 纵向拉伸强度为 192.2MPa, 横 向拉伸强度为 144.1MPa。 实施例 8
用 1-烯丙基 -3-曱基氯咪唑盐离子液体 ( AMIMC1 )和 N，N-二甲基亚 砜（ 90:10重量比）的混合溶剂在 80。C下溶解木浆粕（聚合度 650 )， 得 到浓度为 8% (重量）的纤维素溶液。 加入 5% (相对于膜中纤维素的重 量）的壳聚糖。 经混合、 脱泡、 过滤后通过模口挤出到 30'C的水的凝固 浴中， 得到未拉伸的纤维素凝胶膜。 在膜中离子液体溶剂相对于膜中纤 维素非溶剂的重量比为 0.4:1处横向拉伸 1.6倍。 拉伸后的凝^进一步 在 20。C水中洗涤除去离子液体和 N，N-二曱基亚砜。干燥时用双向拉伸设 备让膜保持横向尺寸。 最后得到的双向拉伸再生纤维素膜在纵向、 横向 上的总拉伸倍数均为 1.5倍， 纵向拉伸强度为 183.0MPa， 横向拉伸强度 为 146.4MPa。 实施例 9
用 1-丁基 -3-甲基咪唑醋酸盐离子液体 ( BMIMAc )和 N，N-二甲基甲 酰胺 ( 80:20重量比）的混合溶剂在 80。C下溶解木浆粕（聚合度 650 ), 得到浓度为 10% (重量）的纤维素溶液。 加入 2% (相对于膜中纤维素 的重量）的层状纳米黏土。 经混合、 脱泡、 过滤后通过模口挤出到 40'C 的水的凝固浴中， 得到未拉伸的纤维素凝胶膜。 在膜中离子液体溶剂相 对于膜中纤维素非溶剂的重量比为 0.7:1处进行第一次横向拉伸， 拉伸 1.5倍； 在离子液体含量为 0%处进行第二次横向拉伸， 拉伸 1.2倍。 拉 伸后的凝! ^进一步在 20Ό水中洗涤除去离子液体和 N，N-二甲基曱跣 胺。 干燥时用双向拉伸设备让膜保持横向尺寸。 最后得到的双向拉伸再 生纤维素膜纵向上的总拉伸倍数为 1.8倍,横向上的总拉伸倍数为 1.6倍， 纵向拉伸强度为 205.3MPa， 横向拉伸强度为 160.1MPa。 实施例 10
用 1-烯丙基 -3-曱基氯咪唑盐离子液体 ( AMIMC1 )在 70'C下溶解微 晶纤维素（聚合度 230 )， 得到浓度为 15% (重量）的纤维素溶液。 加入 1% (相对于膜中纤维素的重量）的埃洛石纳米管。 经混合、 脱泡、 过滤 后通 口挤出到 60'C的水的凝固浴中， 得到未拉伸的纤维素¾^ 。 在膜中离子液体溶剂相对于膜中纤维素非溶剂的重量比为 0.3:1处横向 拉伸拉伸 1.2倍。拉伸后的凝 进一步在 20'C水中洗涤除去离子液体。 干燥时用双向拉伸设备让膜保持横向尺寸。 最后得到的双向拉伸再生纤 维素膜在纵向、 横向上的总拉伸倍数均为 1.1 倍， 纵向拉伸强度为 89.0MPa， 横向拉伸强度为 85.2MPa。 实施例 11
用 1-烯丙基 -3-甲基氯咪唑盐离子液体 ( AMIMC1 )在 80'C下溶解木 浆粕（聚合度 650 )， 得到 8% (重量）的纤维素溶液。加入 2% (相对于 膜中纤维素的重量）的纳米碳纤维和 2% (相对于膜中纤维素的重量）的 炭黑。 经混合、 脱泡、 过滤后通过模口挤出到 15'C的含 10% (重量）的 离子液体的丙酮溶液组成的凝固浴中， 得到未拉伸的纤维素凝胶膜。 在 膜中离子液体溶剂相对于膜中纤维素非溶剂的重量比为 0.3:1处进行第 一次横向拉伸， 拉伸 1.2倍。 拉伸后的凝 进一步在 20°C水中洗涤除 去离子液体和丙酮。干燥时进行第二次横向拉伸，拉伸 1.2倍。最后得到 的双向拉伸再生纤维素膜纵向上的总拉伸倍数为 1.8倍,横向上的总拉伸 倍数为 1.3倍， 纵向拉伸强度为 178.9MPa, 横向拉伸强度为 135.5MPa。
实施例 12
用 1-丁基 -3-甲基咪唑醋酸盐离子液体 ( BMIMAc )在 70'C下溶解木 浆粕（聚合度 650 ), 得到 5% (重量）的纤维素溶液。加入 2% (相对于 膜中纤维素的重量）的海藻酸和 2% (相对于膜中纤维素的重量）的纳米 二氧化硅。 经脱泡、 过滤后通过模口挤出到 40eC的含 10% (重量）的 BMIMAc离子液体的水溶液组成的凝固浴中， 得到未拉伸的纤维素 膜。在膜中离子液体溶剂相对于膜中纤维素非溶剂的重量比为 1.1:1处进 行第一次横向拉伸，拉伸 1.4倍； 经过一道上述凝固浴的洗涤，在膜中离 子液体溶剂相对于膜中纤维素非溶剂的重量比为 0.2:1处进行第二次横 向拉伸， 拉伸 1.3倍。 拉伸后的凝 进一步在 20。C乙醇中洗涤除去离 子液体。 干燥时用双向拉伸设备让膜保持横向尺寸。 最后得到的双向拉 伸再生纤维素膜纵向上的总拉伸倍数为 2.0倍， 横向上的总拉伸倍数为 1.7倍， 纵向拉伸强度为 190.9MPa, 横向拉伸强度为 152.1MPa。
通过上述实施例我们可以看出， 纤维素膜在洗涤、 干燥过程中都会 有收缩， 横向上更为严重。 因此最终的纤维素膜的总拉伸倍数要小于每 次拉伸倍数的乘积。 而对照例中， 膜未进行横向拉伸， 得到的膜宽小于 原始的膜宽。 施加横向拉伸会减小膜收缩的程度， 会让膜宽增加， 而横 向拉伸强度增大。

Claims

权利 要求
1.一种双向拉伸再生纤维素膜，其特征在于，纤维素膜横向拉伸和纵 向拉伸的倍数至多为 400% ,纵向拉伸强度与横向拉伸强度之比小于 1.8。
2.根据权利要求 1的纤维素膜，其特征在于，所述纤维素膜的纵向拉 伸强度与横向拉伸强度的比例小于 1.8， 优选小于 1.5， 更优选小于 1.4。
所述纤维素膜的横向拉伸倍数为 101~400%， 纵向拉伸倍数为 110-400%»
优选地， 所述纤维素膜的横向和仲向拉伸倍率相同或者不同。
优选地， 所述纤维素膜的横向拉伸至少 1次， 优选进行 2到 4次拉 伸， 更优选进行 1到 3次拉伸。
优选地， 所述纤维素膜的纵向拉伸至少 1次， 优选 2-4次， 更优选 进行 1到 3次拉伸。
3.根据权利要求 1或 2的纤维素膜， 其特征在于， 所述纤维素为天 然纤维素，优选地，所述天然纤维素原料的聚合度在 200~2000范围。所 述纤维素选自下述纤维素原料中的至少一种： 微晶纤维素、 棉浆粕、 木 浆粕、 竹浆粕、脱脂棉、甘蔗渣、木材以及从植物秸秆中制得的纤维素。
4.根据权利要求 1-3任一项的纤维素膜， 其特征在于， 所述再生纤 维素膜是通过将纤维素 /离子液体溶液成型后进行拉伸得到。
优选地， 所述纤维素 /离子液体溶液经模口挤出后可采用 的 或压延方法赋形， 然后通过气隙进入凝固浴形成纤维素凝胶膜。
优选地， 纤维素凝胶膜干燥完全脱除溶剂后， 成为纤维素膜。 优选地， 所述凝固浴为离子液体与水、 曱醇、 乙醇或丙酮等纤维素 非溶剂的混合物。 凝固浴中离子液体溶剂与纤维素非溶剂重量比在
0-150:100范围内调节， 凝固浴温度可在 10~80°C范围内调节。 纤维素 / 离子液体溶液进入凝固浴后，在非溶剂的存在下纤维素凝固成膜的形状， 得到凝胶膜。
5. —种双向拉伸再生纤维素功能膜， 其特征在于， 所述功能膜包括 权利要求 1-4任一项的纤维素膜以及有机和 /或无机的功能型添加剂。
6.—种权利要求 1-4任一项的双向拉伸再生纤维素膜的制备方法，其 特征在于， 所述方法包括如下步骤：
(1)将纤维素 /离子液体溶液使用模头挤出、压延或«的方法赋形；
(2)赋形的溶液进入凝固浴形成纤维素凝
(3)在凝固和洗涤的过程中，对纤维素凝 进行至少一次的横向拉 伸和至少一次的纵向拉伸；
(4)在干燥过程中，进一步对拉伸膜施加横向和纵向张力，最后经收 卷得到再生纤维素膜。
7.根据权利要求 6的方法， 其特征在于， 步骤（2 ) 中， 所述凝固浴 为离子液体与水、 曱醇、 乙醇或丙酮等纤维素非溶剂的混合物。 所述凝 固浴为离子液体溶剂与水或其它纤维素非溶剂重量比为 0~150:100，优选 0-120:100, 更优选 0~80:100的混合物。
优选地，所述凝固浴温度可在 10~80'C范围内调节。纤维素 /离子液体 溶液进入凝固浴后， 在非溶剂的存在下纤维素凝固成膜的形状， 得到凝 。 优选地， 步骤（3 )中， 在纤维素^^的凝固和洗涤过程中， 当凝 胶膜中离子液体溶剂相对于膜中纤维素非溶剂的重量比小于 4:1, 优选
3:1, 时对纤维素凝 进行横向和纵向拉伸。
优选地， 步骤（3 )中， 纤维素凝^!离开凝固浴后 i^v洗涤浴， 进 行洗涤， 以洗涤除去膜中的离子液体。 所述洗涤浴可以是水或其它与离 子液体混溶的纤维素非溶剂。 所述洗涤浴温度为 10~80Ό， 优选为 20~60oC。
优选地， 步驟（4 )中， 离子液体洗净后凝^ I中的水或溶剂可以通 过公知的干燥方法除去， 例如， 减压条件下升温干燥、 鼓热风干燥、 热 辊干燥、 红外升温干燥、 微波干燥等， 但并不限于这些方法。
优选地， 步骤（3 )中， 在纤维素 的凝固和洗涤½中， 当凝 胶膜中离子液体溶剂相对于膜中纤维素非溶剂的重量比小于 4:1， 优选 3:1, 时对纤维素凝 进行至少一次的横向拉伸， 优选进行 1到 3次的 横向拉伸。
优选地， 步骤（3 )中， 在纤维素凝 拉伸后， 进一步洗涤除去残 余的离子液体。
优选地， 步骤（3 )中， 洗涤浴为水或其它的纤维素非溶剂。
优选地， 步骤（4 )中， 在纤维素凝胶膜干燥过程中， 对膜施加横向 和纵向张力。
优选地， 步骤（4 )中， 在纤维素凝胶膜干燥过程中， 对膜进行横向 和纵向拉伸。
优选地， 步骤（3 )、 （4 ) 中， 纤维素膜横向、 纵向方向总的拉伸程 度最高可达 400%。
8.根据权利要求 6或 7的方法， 其特征在于， 步骤（1 )中， 纤维素 / 离子液体溶液是将天然纤维素原料溶于离子液体溶剂中获得的。
优选地， 步骤（1 )中， 所述离子液体溶剂为可以溶解纤维素的离子 液体、 溶解纤维素的离子液体组成的混合溶剂、 或溶解纤维素的离子液 体与其它共溶剂组成的混合溶剂。
优选地，所述离子液体是由咪唑或吡啶型阳离子与阴离子所形成的、 熔点低于 100。C的有机熔融盐，优选可以溶解纤维素的有机熔融盐。还优 选地， 本发明可以使用混合的离子液体溶解纤维素， 其中所述混合的离 子液体可以均是能溶解纤维素的离子液体， 也可以是能溶解纤维素的离 子液体与不溶解纤维素的离子液体的混合物。
优选地， 阳离子优选下述任意一种： 1-乙基 -3-甲基咪唑阳离子、 1- 丙基 -3-甲基咪峻阳离子、 1-烯丙基 -3-甲基咪唑阳离子、 1-丁基 -3-甲基咪 唑阳离子、 N-乙基吡啶阳离子、 N-丁基吡啶阳离子、 N-正己基吡啶阳离 子。 所述阳离子尤其优选下述任意一种： 1-乙基 -3-甲基咪峻阳离子、 1- 烯丙基 -3-甲基咪唑阳离子和 1-丁基 -3-甲基咪唑阳离子。
优选地， 阴离子优选下述任意一种： 氯离子、 溴离子、 甲酸根离子、 醋酸根离子、 丙酸根离子、 丁酸根离子和磷酸甲酯离子； 所述阴离子尤 其优选下述任意一种： 氯离子、 甲酸根离子、 醋酸根离子和磷酸甲酯离 子。
优选地， 所述离子液体单独或混合使用， 或是与 N，N-二甲基亚砜、 N，N-二曱基曱 StJ &、 N，N-二曱基乙酰胺或 N-曱基吡咯烷酮等共溶剂混合 使用。
优选地， 所述共溶剂为 N，N-二曱基亚砜、 N，N-二曱基曱跣胺、 Ν,Ν- 二曱基乙酰胺或 Ν-曱基吡咯垅酮。
9.一种权利要求 5所述的默向拉伸再生纤维素功能膜的制备方法，其 特征在于， 所述方法包括如下步骤：
(1)在纤维素 /离子液体溶液中加入有机和 /或无机的功能型添加剂；
(2)将上述添加了有机和 /或无机添加剂的纤维素 /离子液体溶液使用 模头挤出、 压延或流延的方法赋形；
(3)赋形的溶液进入凝固浴形成纤维素凝胶膜；
(4)在凝固和洗涤的过程中，对纤维素凝 进行至少一次的横向拉 伸和至少一次的纵向拉伸；
(5)在干燥过程中，进一步对拉伸膜施加横向和纵向张力，最后经收 卷得到再生纤维素膜。
优选地， 所述有机和 /或无机的功能添加剂为甲壳素、 壳聚糖、 海藻 酸、 层状纳米黏土、 石墨烯、 碳纳米管、 埃洛石纳米管、 纳米碳纤维、 炭黑、 纳米二氧化钛、 纳米氧化锌或纳米二氧化硅中的一种或几种。
优选地， 所述有机和 /或无机的功能型添加剂的含量在 0.1~20% (相 对于膜中纤维素的重量)。
10.权利要求 1-4任一项的纤维素膜或权利要求 5的功能膜的应用。 优选应用于食品、 药品、 化妆品、 高档成衣、 精密仪器等产品的包装。
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