WO2024066728A1 - 一种纤维素纺丝液的制备方法及其制备的产品与应用 - Google Patents

一种纤维素纺丝液的制备方法及其制备的产品与应用 Download PDF

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Publication number
WO2024066728A1
WO2024066728A1 PCT/CN2023/110496 CN2023110496W WO2024066728A1 WO 2024066728 A1 WO2024066728 A1 WO 2024066728A1 CN 2023110496 W CN2023110496 W CN 2023110496W WO 2024066728 A1 WO2024066728 A1 WO 2024066728A1
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Prior art keywords
cellulose
solvent
spinning solution
preparing
regenerated cellulose
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PCT/CN2023/110496
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English (en)
French (fr)
Inventor
谢跃亭
杨军杰
邵长金
姚永鑫
郭反修
苏海霞
闫国祥
张钧恒
李一博
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新乡化纤股份有限公司
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Publication of WO2024066728A1 publication Critical patent/WO2024066728A1/zh

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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
    • D01F2/02—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from solutions of cellulose in acids, bases or salts
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D1/00—Treatment of filament-forming or like material
    • D01D1/02—Preparation of spinning solutions
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D10/00—Physical treatment of artificial filaments or the like during manufacture, i.e. during a continuous production process before the filaments have been collected
    • D01D10/06—Washing or drying
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/06—Wet spinning methods
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/08—Melt spinning methods
    • D01D5/096—Humidity control, or oiling, of filaments, threads or the like, leaving the spinnerettes
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/12—Stretch-spinning methods
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt

Definitions

  • the invention belongs to the technical field of new textile materials, and particularly relates to a method for preparing regenerated cellulose fibers.
  • Regenerated cellulose fiber is a high-quality fiber variety, which is loved by the public for its unique touch and comfortable body feel.
  • Regenerated cellulose fiber is generally made of cotton pulp or wood pulp, and is dissolved and spun through the traditional viscose process.
  • Plant Juncao has the advantages of windbreak and sand fixation, drought resistance and waterlogging resistance, water storage, and strong resistance to adversity.
  • the growth cycle of Juncao is much lower than that of forest resources such as trees. After being cut down and harvested, it continues to reproduce and grow from the root system. It is a rare green renewable resource in nature.
  • the current Juncao industry has the advantages of huge storage capacity and rich resources. However, the overall utilization rate of Juncao is extremely low, and only a small amount is used in the edible and medicinal mushroom industry.
  • Juncao is rich in cellulose and is an excellent raw material for replacing cotton pulp and wood pulp to prepare regenerated cellulose fiber. Therefore, how to use Juncao in the processing of regenerated cellulose fiber is a problem worth exploring, and it is also a hot spot and difficulty in the current research and development of the textile field.
  • the traditional carbon disulfide viscose system uses carbon disulfide in the process of making glue, and the production process is prone to produce sulfur-containing toxic gases, accompanied by a large amount of energy consumption and pollution.
  • the spinning of the new solvent system meets the requirements of green environmental protection, and compared with other solvent systems, the preparation and production process is particularly simple.
  • the new solvent system In the process of developing a new solvent system to dissolve the mushroom grass pulp to manufacture mushroom grass regenerated cellulose fiber, it was found that compared with the traditional carbon disulfide viscose system, the new solvent system has a faster dissolution rate for the mushroom grass pulp, and the dissolution of the mushroom grass pulp cellulose can be completed in a very short time. After dissolution, cellulose spinning solution is obtained.
  • the faster dissolution rate is conducive to shortening the preparation time of the spinning solution and reducing energy consumption.
  • the new solvent system has a strong ability to continuously act on cellulose macromolecules after the cellulose is dissolved.
  • the residual new solvent system in the cellulose spinning solution can further destroy the cellulose macromolecules in the spinning solution, resulting in the breakage of the cellulose macromolecule molecular chain; especially in the industrial production process, the spinning solution needs to be processed before spinning.
  • the present invention aims to provide a method for preparing regenerated cellulose fibers.
  • the first aspect of the present invention provides a method for preparing a cellulose spinning solution, which specifically comprises: dissolving a cellulose raw material with a cellulose solvent system to obtain a dissolved solution; adding a stabilizer to the dissolved solution, mixing evenly, filtering, and obtaining a cellulose spinning solution; the stabilizer is a metal sulfate; the cellulose solvent system includes a cellulose solvent, the cellulose solvent is composed of a solvent A and a solvent B, and the solvent A is an alkylammonium hydroxide or an alkylammonium hydroxide aqueous solution.
  • the metal sulfate is at least one of ferric sulfate, ferrous sulfate, magnesium sulfate and barium sulfate. More preferably, the metal sulfate is ferric sulfate.
  • the content of the stabilizer in the cellulose spinning solution is 50 to 3000 ppm. More preferably, the content of the stabilizer in the cellulose spinning solution is 100 to 3000 ppm. Most preferably, the content of the stabilizer in the cellulose spinning solution is 1000 ppm.
  • the solvent B is an aprotic solvent or an aqueous solution of an aprotic solvent.
  • the alkylammonium hydroxide is at least one of tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide and tetrabutylammonium hydroxide. More preferably, the alkylammonium hydroxide is tetrabutylammonium hydroxide.
  • the aprotic solvent is at least one of N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethylpropionamide, N,N-dimethylbutyramide, N,N-dimethylhexanamide, dimethyl sulfoxide, dibutyl sulfoxide, urea and thiourea. More preferably, the aprotic solvent is dimethyl sulfoxide.
  • the cosolvent is at least one of aromatic polyoxyethylene ether, tetramethylammonium chloride, tetraethylammonium chloride, tetrapropylammonium chloride and tetrabutylammonium chloride. More preferably, the cosolvent is aromatic polyoxyethylene ether; most preferably, the cosolvent is viscose additive HB-3803L.
  • the mass ratio of the cellulose raw material to the cellulose solvent is (1-20):(80-99). More preferably, the mass ratio of the cellulose raw material to the cellulose solvent is 1:9.
  • the cellulose solvent system further comprises a cosolvent, and the amount of the cosolvent is 0-5% of the total weight of the cellulose raw material and the cellulose solvent. More preferably, the amount of the cosolvent is 1% of the total weight of the cellulose raw material and the cellulose solvent.
  • the volume fraction of solvent A in the cellulose solvent is 10% to 100%, and the volume fraction of solvent B is 0 to 90%. More preferably, the volume fraction of solvent A in the cellulose solvent is 50%, and the volume fraction of solvent B is 50%.
  • the mass fraction of alkylammonium hydroxide in the solvent A is 30% to 70%;
  • the solvent B is a dimethyl sulfoxide aqueous solution, and the mass fraction of dimethyl sulfoxide in the dimethyl sulfoxide aqueous solution is 95%.
  • the dissolution temperature is 20-40° C., and the dissolution time is 0.5-2 h. More preferably, the dissolution temperature is 30° C., and the dissolution time is 1 h.
  • the cellulose raw material is at least one of Juncao pulp, cotton pulp, wood pulp and bamboo pulp. More preferably, the cellulose raw material is Juncao pulp.
  • the second aspect of the present invention provides a cellulose spinning solution product prepared by the method for preparing cellulose spinning solution described in the first aspect.
  • the third aspect of the present invention provides the use of the cellulose spinning solution product described in the second aspect in the preparation of regenerated cellulose fibers.
  • the fourth aspect of the present invention provides a method for preparing regenerated cellulose fiber, wherein the preparation method uses the cellulose spinning solution product described in the second aspect as a raw material, degassing and spinning to obtain to regenerated cellulose fibers.
  • the specific operation of the spinning treatment is: the cellulose spinning solution is subjected to a coagulation bath to form primary silk, and then the regenerated cellulose fiber is obtained through drawing, drying and oiling; preferably, after the spinning treatment, it also includes: directly winding the regenerated cellulose fiber to form regenerated cellulose filaments, or cutting, opening and packaging to form grass regenerated cellulose staple fibers; the spinning equipment can adopt traditional viscose filament or staple spinning equipment; preferably, the coagulation bath is a mixed aqueous solution of sulfuric acid and tetrabutylammonium sulfate, the concentration of sulfuric acid in the coagulation bath is 120 ⁇ 2g/L, and the concentration of tetrabutylammonium sulfate is 120g/L; the temperature of the coagulation bath is 45°C.
  • the fifth aspect of the present invention provides a regenerated cellulose fiber product prepared by the preparation method of regenerated cellulose fiber described in the fourth aspect above, wherein the regenerated cellulose fiber product is regenerated cellulose fiber filament or regenerated cellulose fiber staple; preferably, the dry breaking strength of the regenerated cellulose fiber filament is 1.3-2.02 cN/dtex, the dry breaking elongation is 6%-15%, and the fineness is 120D; preferably, the dry breaking strength of the regenerated cellulose fiber staple is 1.5-2.2 cN/dtex, the dry breaking elongation is 6%-15%, and the fineness is 1.5D.
  • the present invention has the following beneficial effects:
  • the present invention adopts a cellulose solvent system to dissolve the cellulose raw material, and then adds a stabilizer metal sulfate to the dissolved solution after the dissolution.
  • the metal sulfate can reduce the activity of alkylammonium hydroxide in the solvent system, effectively slowing down the degradation effect of the cellulose solvent system on cellulose macromolecules, avoiding excessive degradation of cellulose macromolecules in the cellulose spinning solution during the degassing and spinning process, effectively protecting the cellulose macromolecules in the spinning solution, and further improving the strength and toughness of the regenerated cellulose fiber prepared using the cellulose spinning solution; at the same time, the addition of the stabilizer can greatly improve the stability of the prepared cellulose spinning solution, prolong the storage time of the cellulose spinning solution, and gain sufficient time for production spinning.
  • the cellulose spinning solution prepared by the present invention is used for spinning, and the regenerated cellulose fiber filaments prepared have high strength and good toughness, and their dry breaking strength is 1.3-2.02 cN/dtex, and their dry breaking elongation is 6%-15%; the regenerated cellulose fiber staples prepared have high strength and good toughness, and their dry breaking strength is 1.5-2.2 cN/dtex, and their dry breaking elongation is 6%-15%.
  • the cellulose spinning solution of the present invention is prepared by using Juncao pulp as raw material.
  • Juncao raw material has the characteristics of wide planting area, extremely rich yield, low price, etc., which can effectively reduce the production cost of cellulose spinning solution and alleviate the problem of insufficient raw materials for existing cellulose fiber production; moreover, by The high-value utilization of biomass mushroom grass and the reduction of forest tree felling by “replacing wood with grass” can further protect the ecological environment.
  • a method for preparing a cellulose spinning solution comprising the following specific steps:
  • cellulose raw material cellulose raw material, cellulose solvent and co-solvent into a dissolving device, stir and dissolve at 30°C for 1 hour to obtain a dissolving solution.
  • the mass ratio of the cellulose raw material to the cellulose solvent is 1:9; the amount of the co-solvent is 1% of the total weight of the cellulose raw material and the cellulose solvent.
  • the cellulose raw material is Juncao pulp, which is prepared by pulping process using Juncao as raw material.
  • the cellulose solvent consists of solvent A and solvent B, and the volume ratio of solvent A to solvent B is 1:1; the solvent A is tetrabutylammonium hydroxide aqueous solution, and the mass fraction of tetrabutylammonium hydroxide in the tetrabutylammonium hydroxide aqueous solution is 55%; the solvent B is dimethyl sulfoxide aqueous solution, and the mass fraction of dimethyl sulfoxide in the dimethyl sulfoxide aqueous solution is 95%.
  • the co-solvent is viscose additive HB-3803L (purchased from Shenyang Haobo Industrial Co., Ltd.).
  • step (2) adding a stabilizer to the solution prepared in step (1), stirring and mixing for 1 hour, filtering to remove undissolved impurities and some large cellulose particles, and obtaining a cellulose spinning solution; the content of the stabilizer in the cellulose spinning solution is 500 ppm, and the stabilizer is ferric sulfate.
  • Embodiment 1-2
  • Example 1-2 The contents of Example 1-2 are substantially the same as those of Example 1-1, except that: in step (2) The stabilizer is ferrous sulfate.
  • Embodiment 1-3
  • Example 1-3 The content of Example 1-3 is basically the same as that of Example 1-1, except that the stabilizer in step (2) is magnesium sulfate.
  • Embodiment 1-4
  • Example 1-4 The content of Example 1-4 is basically the same as that of Example 1-1, except that the stabilizer in step (2) is barium sulfate.
  • Embodiment 1-5 are identical to Embodiment 1-5:
  • Example 1-5 The content of Example 1-5 is basically the same as that of Example 1-1, except that no stabilizer is added in step (2).
  • step (2) continue to stir and mix the solution prepared in step (1) for 1 hour, filter, and obtain cellulose spinning solution.
  • the present invention uses the cellulose spinning solutions prepared in Example 1-1 to Example 1-5 as raw materials for spinning to prepare regenerated cellulose fiber filaments, and performs performance index tests on the prepared fiber filaments.
  • the test results are shown in Table 1.
  • the preparation method of regenerated cellulose fiber filament is as follows: vacuum degassing the cellulose spinning solution for 10 hours to remove bubbles in the cellulose spinning solution, spinning using a spinning device (spinning speed is 110 m/min), and the cellulose spinning solution is passed through a coagulation bath (the coagulation bath is a mixed aqueous solution of sulfuric acid and tetrabutylammonium sulfate, the sulfuric acid concentration in the coagulation bath is 120 ⁇ 2 g/L, the concentration of tetrabutylammonium sulfate is 120 g/L; the temperature of the coagulation bath is 45°C) to form primary silk, and then through drawing, drying, oiling, to make regenerated cellulose fiber fibers, finally directly wound into shape to make Juncao regenerated cellulose filaments (the product specifications of Juncao regenerated cellulose filaments are: 120D/30F).
  • the prepared fiber filaments have low strength and poor toughness; the strength and toughness of the fiber filaments prepared after spinning with the spinning solution with added stabilizer are significantly improved.
  • the strengthening effect is particularly prominent, and the dry breaking strength and dry breaking elongation of the prepared fiber filaments are both increased by more than 1 times.
  • a method for preparing a cellulose spinning solution comprising the following specific steps:
  • cellulose raw material cellulose raw material, cellulose solvent and co-solvent into a dissolving device, stir and dissolve at 30°C for 1 hour to obtain a dissolving solution.
  • the mass ratio of the cellulose raw material to the cellulose solvent is 1:9; the amount of the co-solvent is 1% of the total weight of the cellulose raw material and the cellulose solvent.
  • the cellulose raw material is Juncao pulp, which is prepared by pulping process using Juncao as raw material.
  • the cellulose solvent consists of solvent A and solvent B, and the volume ratio of solvent A to solvent B is 1:1; the solvent A is tetrabutylammonium hydroxide aqueous solution, and the mass fraction of tetrabutylammonium hydroxide in the tetrabutylammonium hydroxide aqueous solution is 55%; the solvent B is dimethyl sulfoxide aqueous solution, and the mass fraction of dimethyl sulfoxide in the dimethyl sulfoxide aqueous solution is 95%.
  • the co-solvent is viscose additive HB-3803L (purchased from Shenyang Haobo Industrial Co., Ltd.).
  • step (2) adding a stabilizer to the solution prepared in step (1), stirring and mixing for 1 hour, filtering to remove undissolved impurities and some large cellulose particles, and obtaining a cellulose spinning solution; the content of the stabilizer in the cellulose spinning solution is 50 ppm, and the stabilizer is ferric sulfate.
  • Example 2-2 The content of Example 2-2 is basically the same as that of Example 2-1, except that the content of the stabilizer in the cellulose spinning solution in step (2) is 100 ppm.
  • Embodiment 2-3 is a diagrammatic representation of Embodiment 2-3.
  • Example 2-3 The content of Example 2-3 is basically the same as that of Example 2-1, except that: in step (2) The content of the stabilizer in the cellulose spinning solution is 1000 ppm.
  • Embodiment 2-4
  • Example 2-4 The content of Example 2-4 is basically the same as that of Example 2-1, except that the content of the stabilizer in the cellulose spinning solution in step (2) is 1500 ppm.
  • Embodiment 2-5 is a diagrammatic representation of Embodiment 2-5:
  • Example 2-5 is basically the same as that of Example 2-1, except that the content of the stabilizer in the cellulose spinning solution in step (2) is 2000 ppm.
  • Embodiment 2-6 is a diagrammatic representation of Embodiment 2-6.
  • Example 2-6 The content of Example 2-6 is basically the same as that of Example 2-1, except that the content of the stabilizer in the cellulose spinning solution in step (2) is 3000 ppm.
  • the present invention uses the cellulose spinning solutions prepared in Examples 2-1 to 2-6 as raw materials for spinning to prepare regenerated cellulose fiber filaments (the preparation method of the regenerated cellulose fiber filaments is the same as that in Example 1), and the prepared regenerated fiber filaments are tested for performance indicators, and the test results are shown in Table 2.
  • adding ferric sulfate as a stabilizer to the spinning solution is beneficial to improving the spinning strength and toughness, and the amount of ferric sulfate added is very important.
  • the amount of ferric sulfate added is 50ppm, the strength and toughness of the prepared regenerated cellulose fiber filaments are improved very little; with the increase of the amount of ferric sulfate, the dry breaking strength and dry breaking elongation of the regenerated cellulose fiber filaments are significantly improved.
  • the dosage of ferric sulfate is 1000ppm.
  • the dry breaking strength and dry breaking elongation of the regenerated cellulose fiber filaments reach the highest, which are 2.02cN/dtex and 15.1% respectively, and the prepared regenerated cellulose filaments have high strength and toughness; when the dosage of ferric sulfate is further increased, the dry breaking strength and dry breaking elongation of the regenerated cellulose fiber filaments gradually decrease. Therefore, the dosage of the stabilizer ferric sulfate is preferably 1000ppm.
  • the present invention uses the cellulose spinning solutions prepared in Example 1-1, Example 1-5 and Example 2-3 as raw materials for spinning, and produces on a staple spinning machine, and forms primary fibers through a coagulation bath (the coagulation bath is a mixed aqueous solution of sulfuric acid and tetrabutylammonium sulfate, the sulfuric acid concentration in the coagulation bath is 120 ⁇ 2g/L, the concentration of tetrabutylammonium sulfate is 120g/L; the temperature of the coagulation bath is 45°C), and then through drawing, washing, oiling, dehydration and drying, cutting, opening, and packaging to form Juncao regenerated cellulose staples (product specifications: 1.5D ⁇ 38mm).
  • the prepared regenerated cellulose fiber staples were tested for performance indicators, and the test results are shown in Table 3.
  • the prepared fiber staple has low strength and poor toughness; the strength and toughness of the fiber filaments prepared after spinning with the spinning solution with added stabilizer iron sulfate are significantly improved, and when the addition amount of iron sulfate is 1000ppm, the dry breaking strength and dry breaking elongation of the regenerated cellulose fiber staple both reach the highest, which are 2.2cN/dtex and 15.0% respectively, and the prepared regenerated cellulose has higher strength and toughness.
  • Embodiment 3 is a diagrammatic representation of Embodiment 3
  • Example 3 The content of Example 3 is the same as that of Example 1-1, except that the cellulose raw material is a mixture of Juncao pulp and cotton pulp in a mass ratio of 1:1, wherein the Juncao pulp is prepared using Juncao as raw material through a pulping process.
  • the cellulose raw material is a mixture of Juncao pulp and cotton pulp in a mass ratio of 1:1, wherein the Juncao pulp is prepared using Juncao as raw material through a pulping process.
  • the cellulose spinning solution prepared in Example 3 was used as a raw material for spinning to prepare regenerated cellulose fiber filaments (the preparation method of the regenerated cellulose fiber filaments is the same as that in Example 1) with a dry breaking strength of 1.95 cN/dtex, a dry breaking elongation of 14.8%, and a fineness of 120D.
  • Embodiment 4 is a diagrammatic representation of Embodiment 4:
  • Example 4 The content of Example 4 is the same as that of Example 1-1, except that the cellulose raw material is a mixture of Juncao pulp and wood pulp in a mass ratio of 1:1, wherein Juncao pulp is prepared using Juncao as raw material through a pulping process.
  • the cellulose raw material is a mixture of Juncao pulp and wood pulp in a mass ratio of 1:1, wherein Juncao pulp is prepared using Juncao as raw material through a pulping process.
  • Embodiment 5 is a diagrammatic representation of Embodiment 5:
  • Example 5 The content of Example 5 is the same as that of Example 1-1, except that the cellulose raw material is a mixture of Juncao pulp and bamboo pulp in a mass ratio of 1:1, wherein the Juncao pulp is prepared using Juncao as raw material through a pulping process.
  • the cellulose raw material is a mixture of Juncao pulp and bamboo pulp in a mass ratio of 1:1, wherein the Juncao pulp is prepared using Juncao as raw material through a pulping process.
  • Embodiment 6 is a diagrammatic representation of Embodiment 6
  • Example 6 The content of Example 6 is the same as that of Example 1-1, except that the mass ratio of the cellulose raw material to the cellulose solvent is 5:95.
  • the cellulose spinning solution prepared in Example 6 was used as a raw material for spinning to prepare regenerated cellulose fiber filaments (the preparation method of the regenerated cellulose fiber filaments was the same as that in Example 1) with a dry breaking strength of 1.65 cN/dtex, a dry breaking elongation of 8.4%, and a fineness of 120D.
  • Embodiment 7 is a diagrammatic representation of Embodiment 7:
  • Example 7 The content of Example 7 is the same as that of Example 1-1, except that the cellulose solvent consists of solvent A and solvent B, and the volume ratio of solvent A to solvent B is 7:3.
  • the cellulose spinning solution prepared in Example 7 was used as a raw material for spinning to prepare regenerated cellulose fiber filaments (the preparation method of the regenerated cellulose fiber filaments was the same as that in Example 1) with a dry breaking strength of 1.71 cN/dtex, a dry breaking elongation of 9.2%, and a fineness of 120D.

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Abstract

一种再生纤维素纤维的制备方法，该制备方法具体为：采用纤维素溶剂体系对纤维素原料进行溶解，得到溶解液；向溶解液中加入稳定剂，混合均匀后，过滤，得到纤维素纺丝液，所述稳定剂为金属硫酸盐；纤维素纺丝液经脱泡、纺丝处理，得到再生纤维素纤维。该制备方法中稳定剂的添加能避免纤维素纺丝液中的纤维素大分子被过度降解，有效保护了纺丝液中纤维素大分子，提高了利用该纤维素纺丝液制备的再生纤维素纤维的强度和韧性，制备得到的再生纤维素纤维长丝强度高，韧性好，品质高。

Description

一种纤维素纺丝液的制备方法及其制备的产品与应用
本申请要求于2022年09月26日提交中国专利局、申请号为CN202211174734.2、发明名称为“一种纤维素纺丝液的制备方法及其制备的产品与应用”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本发明属于纺织新材料技术领域，具体涉及一种再生纤维素纤维的制备方法。
背景技术
再生纤维素纤维是一种优质的纤维品种，因其独特的触感和舒适的体感被大众所喜爱。再生纤维素纤维一般是以棉浆浆粕或木浆浆粕为原料，通过传统粘胶工艺溶解纺丝而成。植物菌草具有防风固沙、抗旱耐涝、储存水分、抗逆性强等优势。菌草生长周期远低于树木等森林资源，其经砍伐收割后由根系继续繁衍生长，是自然界不可多得的绿色可再生资源，当前菌草产业已具备储存量巨大，资源丰富等优势。但菌草的总体利用率极低，仅少量用于食药用菌产业，高附加值的应用仍处于待开发状态。据了解菌草中富含纤维素，是替代棉浆、木浆制备再生纤维素纤维的绝佳原料，因此如何把菌草使用于再生纤维素纤维加工是一个值得探索的问题，也是当前纺织领域研发的热点和攻关的难点。
传统的二硫化碳粘胶体系在制胶过程中使用二硫化碳，生产过程易产生含硫毒气，伴随形成大量的能耗和污染。新型溶剂体系纺丝符合绿色环保要求，且与其他溶剂体系相比，制备生产工艺尤为简单。在研发新型溶剂体系溶解菌草桨粕制造菌草再生纤维素纤维的过程中发现，相比于传统二硫化碳粘胶体系，新型溶剂体系对菌草桨粕的溶解速度更快，在极短时间内即可完成菌草桨粕纤维素的溶解，溶解后得到纤维素纺丝液，更快的溶解速度有利于缩短纺丝液制备时间，减少能耗。但在实际生产过程中还发现，纤维素溶解后该新型溶剂体系对纤维素大分子的持续作用能力强，纤维素纺丝液中的残留的新型溶剂体系能够进一步破坏纺丝液中的纤维素大分，导致纤维素大分子分子链断裂；特别是在工业生产过程中纺丝液进行纺丝前需要进行过 滤、脱泡等预处理操作，在过滤、脱泡的过程中，新型溶剂体系对纤维素大分子的持续溶解作用会导致纤维素纺丝液中的纤维大分子被破坏，导致纺丝液经纺丝工艺制备的再生纤维素纤维强度低、韧性差，甚至导致纺丝后无法正常形成连续纤维，严重影响菌草再生纤维素纤维的使用。因此如何解决此问题，成为制备新溶剂法菌草再生纤维素纤维的关键。
发明内容
针对现有技术中存在的问题和不足，本发明的目的旨在提供一种再生纤维素纤维的制备方法。
为实现发明目的，本发明采用的技术方案如下：
本发明第一方面提供了一种纤维素纺丝液的制备方法，该制备方法具体为：采用纤维素溶剂体系对纤维素原料进行溶解，得到溶解液；向溶解液中加入稳定剂，混合均匀，过滤，得到纤维素纺丝液；所述稳定剂为金属硫酸盐；所述纤维素溶剂体系包括纤维素溶剂，所述纤维素溶剂由溶剂A和溶剂B组成，所述溶剂A为烷基氢氧化铵或烷基氢氧化铵水溶液。
根据上述的纤维素纺丝液的制备方法，优选地，所述金属硫酸盐为硫酸铁、硫酸亚铁、硫酸镁、硫酸钡中的至少一种。更加优选地，所述金属硫酸盐为硫酸铁。
根据上述的纤维素纺丝液的制备方法，优选地，所述纤维素纺丝液中稳定剂的含量为50～3000ppm。更加优选地，所述纤维素纺丝液中稳定剂的含量为100～3000ppm。最优选地，所述纤维素纺丝液中稳定剂的含量为1000ppm。
根据上述的纤维素纺丝液的制备方法，优选地，所述溶剂B为非质子溶剂或非质子溶剂的水溶液。
根据上述的纤维素纺丝液的制备方法，优选地，所述烷基氢氧化铵为四甲基氢氧化铵、四乙基氢氧化铵、四丙基氢氧化铵、四丁基氢氧化铵中的至少一种。更加优选地，所述烷基氢氧化铵为四丁基氢氧化铵。
根据上述的纤维素纺丝液的制备方法，优选地，所述非质子溶剂为N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、N,N-二甲基丙酰胺、N,N-二甲基丁酰胺、N,N-二甲基己酰胺、二甲亚砜、二丁基亚砜、尿素、硫脲中的至少一种。 更加优选地，所述非质子溶剂为二甲亚砜。
根据上述的纤维素纺丝液的制备方法，优选地，所述助溶剂为芳香基聚氧乙烯醚、四甲基氯化铵、四乙基氯化铵、四丙基氯化铵、四丁基氯化铵之中的至少一种。更加优选地，所述助溶剂为芳香基聚氧乙烯醚；最优选地，所述助溶剂为粘胶助剂HB-3803L。
根据上述的纤维素纺丝液的制备方法，优选地，所述纤维素原料与纤维素溶剂的质量比为(1～20)：(80～99)。更加优选地，纤维素原料与纤维素溶剂的质量比为1：9。
根据上述的纤维素纺丝液的制备方法，优选地，所述纤维素溶剂体系还包括助溶剂；所述助溶剂用量为纤维素原料和纤维素溶剂总重的0～5％。更加优选地，所述助溶剂用量为纤维素原料和纤维素溶剂总重的1％。
根据上述的纤维素纺丝液的制备方法，优选地，所述纤维素溶剂中溶剂A的体积分数为10％～100％，溶剂B的体积分数为0～90％。更加优选地，纤维素溶剂中溶剂A的体积分数为50％，溶剂B的体积分数为50％。
根据上述的纤维素纺丝液的制备方法，优选地，所述溶剂A中烷基氢氧化铵的质量分数为30％～70％；所述溶剂B为二甲基亚砜水溶液，所述二甲基亚砜水溶液中二甲基亚砜的质量分数为95％。
根据上述的纤维素纺丝液的制备方法，优选地，所述溶解的温度为20～40℃，所述溶解的时间为0.5～2h。更加优选地，所述溶解的温度为30℃，所述溶解的时间为1h。
根据上述的纤维素纺丝液的制备方法，优选地，所述纤维素原料为菌草浆、棉浆、木浆、竹浆中的至少一种。更加优选地，所述纤维素原料为菌草浆。
本发明第二方面提供了一种利用上述第一方面所述纤维素纺丝液的制备方法制备的纤维素纺丝液产品。
本发明第三方面提供了上述第二方面所述纤维素纺丝液产品在制备再生纤维素纤维中的应用。
本发明第四方面提供了一种再生纤维素纤维的制备方法，该制备方法是采用上述第二方面所述的纤维素纺丝液产品为原料，经脱泡、纺丝处理，得 到再生纤维素纤维。
根据上述的再生纤维素纤维的制备方法，所述纺丝处理的具体操作为：纤维素纺丝液经凝固浴形成初生丝，再经过牵伸、烘干、上油得到再生纤维素纤维；优选地，所述纺丝处理后，还包括：将所述再生纤维素纤维直接卷绕成型制成再生纤维素长丝，或者经过切断、开松、打包制成菌草再生纤维素短丝；纺丝设备可采用传统的粘胶长丝或短丝纺丝设备；优选地，所述凝固浴为硫酸和四丁基硫酸铵的混合水溶液，所述凝固浴中硫酸浓度为120±2g/L，四丁基硫酸铵的浓度为120g/L；所述凝固浴的温度为45℃。
本发明第五方面提供了一种利用上述第四方面所述再生纤维素纤维的制备方法制备的再生纤维素纤维产品，所述再生纤维素纤维产品为再生纤维素纤维长丝或再生纤维素纤维短丝；优选地，所述再生纤维素纤维长丝的干断裂强度为1.3～2.02cN/dtex，干断裂伸长率为6％～15％，纤度为120D；优选地，所述再生纤维素纤维短丝的干断裂强度为1.5～2.2cN/dtex，干断裂伸长率为6％～15％，纤度为1.5D。
与现有技术相比，本发明的有益效果如下：
(1)本发明在采用纤维素溶剂体系对纤维素原料进行溶解，溶解后向溶解液中加入稳定剂金属硫酸盐，金属硫酸盐能够降低溶剂体系中烷基氢氧化铵的活性，有效减缓纤维素溶剂体系对纤维素大分子的降解作用，避免了纤维素纺丝液中的纤维素大分子在脱泡、纺丝过程中被过度降解，有效保护了纺丝液中纤维素大分子，进而提高了利用该纤维素纺丝液制备的再生纤维素纤维的强度和韧性；同时，稳定剂的添加能够极大提高制备的纤维素纺丝液的稳定性，延长了纤维素纺丝液的存放时间，为生产纺丝争取了充足的时间。
(2)采用本发明制备的纤维素纺丝液进行纺丝，制备得到的再生纤维素纤维长丝的强度高，韧性好，其干断裂强度为1.3～2.02cN/dtex，干断裂伸长率为6％～15％；制备得到的再生纤维素纤维短丝的强度高，韧性好，其干断裂强度为1.5～2.2cN/dtex，干断裂伸长率为6％～15％。
(3)本发明纤维素纺丝液采用菌草浆为原料制备而成，菌草原料具有种植区域广、产量极为丰富、价格低廉等特点，可有效降低纤维素纺丝液的生产成本，同时缓解了现有纤维素纤维生产原料不足的问题；而且，同时，通过 生物质菌草的高值化利用，“以草代木”减少森林树木砍伐，能够进一步保护生态环境。
具体实施方式
以下实施例仅适用于对本发明进行进一步阐述。应该说明的是，本发明所使用的所有技术以及科学术语除另有说明外具有与本发明所属技术领域相同的含义。下列实施例中未注明具体条件的实验方法，均采用本技术领域常规技术，或按照生产厂商所建议的条件；所用试剂或仪器未注明生产厂商者，均为可以通过市购获得的常规产品。
为了使得本领域技术人员能够更加清楚地了解本发明的技术方案，以下将结合具体的实施例详细说明本发明的技术方案。
实施例1：稳定剂种类探讨：
为了探讨稳定剂种类对制备的纤维素液纺丝性能的影响，本发明进行了实施例1-1～实施例1-5。
实施例1-1：
一种纤维素纺丝液的制备方法，具体步骤为：
(1)将纤维素原料、纤维素溶剂、助溶剂加入到溶解设备中，在30℃搅拌溶解1h，得到溶解液。所述纤维素原料与纤维素溶剂的质量比为1:9；所述助溶剂的用量为纤维素原料和纤维素溶剂总重量的1％。所述纤维素原料为菌草浆，该菌草浆是以菌草为原料经过制浆工序制备而成。所述纤维素溶剂由溶剂A和溶剂B组成，溶剂A和溶剂B的体积比为1:1；所述溶剂A为四丁基氢氧化铵水溶液，四丁基氢氧化铵水溶液中四丁基氢氧化铵的质量分数为55％；所述溶剂B为二甲基亚砜水溶液，二甲基亚砜水溶液中二甲基亚砜的质量分数为95％。所述助溶剂为粘胶助剂HB-3803L(购自沈阳浩博实业有限公司)。
(2)向步骤(1)制备的溶解液中加入稳定剂，搅拌混合1h，过滤除去未溶解的杂质和部分纤维素大颗粒，得到纤维素纺丝液；纤维素纺丝液中稳定剂的含量为500ppm，所述稳定剂为硫酸铁。
实施例1-2：
实施例1-2的内容与实施例1-1基本相同，其不同之处在于：步骤(2)中 所述稳定剂为硫酸亚铁。
实施例1-3：
实施例1-3的内容与实施例1-1基本相同，其不同之处在于：步骤(2)中所述稳定剂为硫酸镁。
实施例1-4：
实施例1-4的内容与实施例1-1基本相同，其不同之处在于：步骤(2)中所述稳定剂为硫酸钡。
实施例1-5：
实施例1-5的内容与实施例1-1基本相同，其不同之处在于：步骤(2)中不添加稳定剂。
步骤(2)的具体操作为：将步骤(1)制备的溶解液继续搅拌混合1h，过滤，得到纤维素纺丝液。
为了比较不同稳定剂种类对制备的纤维素液纺丝性能的影响，本发明分别采用实施例1-1～实施例1-5制备的纤维素纺丝液为原料进行纺丝，制备再生纤维素纤维长丝，并对制备的纤维长丝进行性能指标检测，其检测结果如表1所示。
再生纤维素纤维长丝的制备方法为：将纤维素纺丝液真空脱泡处理10h，脱除纤维素纺丝液中的气泡，使用纺丝设备进行纺丝(纺丝速度为110米/分)，纤维素纺丝液经凝固浴(凝固浴为硫酸和四丁基硫酸铵的混合水溶液，凝固浴中硫酸浓度为120±2g/L，四丁基硫酸铵的浓度为120g/L；凝固浴的温度为45℃)形成初生丝，再经过牵伸、烘干、上油、制成再生纤维素纤维纤维，最后直接卷绕成型制成菌草再生纤维素长丝(菌草再生纤维素长丝的产品规格为：120D/30F)。
表1稳定剂种类对制备的再生纤维素纤维长丝性能的影响

由表1可知，使用未添加稳定剂的纺丝液进行纺丝时，制备的纤维长丝强度低，韧性差；添加稳定剂的纺丝液纺丝后制备的纤维长丝的强度和韧性均有明显提高，其中，以硫酸铁作为稳定剂时，增强效果尤为突出，制备的纤维长丝干断裂强度和干断裂伸长率均提升1倍以上。
实施例2：稳定剂用量探讨
为了探讨稳定剂用量对制备的纤维素液纺丝性能的影响，本发明进行了实施例2-1～实施例2-6。
实施例2-1：
一种纤维素纺丝液的制备方法，具体步骤为：
(1)将纤维素原料、纤维素溶剂、助溶剂加入到溶解设备中，在30℃搅拌溶解1h，得到溶解液。所述纤维素原料与纤维素溶剂的质量比为1:9；所述助溶剂的用量为纤维素原料和纤维素溶剂总重量的1％。所述纤维素原料为菌草浆，该菌草浆是以菌草为原料经过制浆工序制备而成。所述纤维素溶剂由溶剂A和溶剂B组成，溶剂A和溶剂B的体积比为1:1；所述溶剂A为四丁基氢氧化铵水溶液，四丁基氢氧化铵水溶液中四丁基氢氧化铵的质量分数为55％；所述溶剂B为二甲基亚砜水溶液，二甲基亚砜水溶液中二甲基亚砜的质量分数为95％。所述助溶剂为粘胶助剂HB-3803L(购自沈阳浩博实业有限公司)。
(2)向步骤(1)制备的溶解液中加入稳定剂，搅拌混合1h，过滤除去未溶解的杂质和部分纤维素大颗粒，得到纤维素纺丝液；纤维素纺丝液中稳定剂的含量为50ppm，所述稳定剂为硫酸铁。
实施例2-2：
实施例2-2的内容与实施例2-1基本相同，其不同之处在于：步骤(2)中纤维素纺丝液中稳定剂的含量为100ppm。
实施例2-3：
实施例2-3的内容与实施例2-1基本相同，其不同之处在于：步骤(2)中 纤维素纺丝液中稳定剂的含量为1000ppm。
实施例2-4：
实施例2-4的内容与实施例2-1基本相同，其不同之处在于：步骤(2)中纤维素纺丝液中稳定剂的含量为1500ppm。
实施例2-5：
实施例2-5的内容与实施例2-1基本相同，其不同之处在于：步骤(2)中纤维素纺丝液中稳定剂的含量为2000ppm。
实施例2-6：
实施例2-6的内容与实施例2-1基本相同，其不同之处在于：步骤(2)中纤维素纺丝液中稳定剂的含量为3000ppm。
为了比较不同稳定剂用量对制备的纤维素液纺丝性能的影响，本发明分别采用实施例2-1～实施例2-6制备的纤维素纺丝液为原料进行纺丝，制备再生纤维素纤维长丝(再生纤维素纤维长丝的制备方法与实施例1相同)，并对制备的再纤维长丝进行性能指标检测，其检测结果如表2所示。
表2稳定剂用量对制备的再生纤维素纤维长丝性能的影响
由表2可知，在纺丝液中添加稳定剂硫酸铁有利于提高纺丝强度和韧性，且硫酸铁的添加量很重要。当硫酸铁的添加量为50ppm时，制备的再生纤维素纤维长丝强度和韧性提升效果很小；随着硫酸铁用量的增加，再生纤维素纤维长丝的干断裂强度和干断裂伸长率均有明显的提高，当硫酸铁添加 量为1000ppm时，再生纤维素纤维长丝的干断裂强度和干断裂伸长率均达到了最高，分别为2.02cN/dtex和15.1％，制备的再生纤维素长丝具有较高的强度和韧性；再进一步增大硫酸铁的用量时，再生纤维素纤维长丝的干断裂强度和干断裂伸长率反而逐步下降。因此，稳定剂硫酸铁的用量优选为1000ppm。
为了进一步研究稳定剂硫酸铁对制备的再生纤维素纤维短丝性能的影响，本发明分别采用实施例1-1、实施例1-5和实施例2-3制备的纤维素纺丝液为原料进行纺丝，在短丝纺丝机上生产，经凝固浴(凝固浴为硫酸和四丁基硫酸铵的混合水溶液，凝固浴中硫酸浓度为120±2g/L，四丁基硫酸铵的浓度为120g/L；凝固浴的温度为45℃)形成初生纤维，再经牵伸、水洗、上油、脱水烘干、切断、开松、打包制成菌草再生纤维素短丝(产品规格为：1.5D×38mm)。对制备的再生纤维素纤维短丝进行性能指标检测，其检测结果如表3所示。
表3稳定剂对制备的再生纤维素纤维短丝性能的影响
由表3可知，使用未添加稳定剂的纺丝液进行纺丝时，制备的纤维短丝强度低，韧性差；添加稳定剂硫酸铁的纺丝液纺丝后制备的纤维长丝的强度和韧性均有明显提高，而且，当硫酸铁的添加量为1000ppm时，再生纤维素纤维短丝的干断裂强度和干断裂伸长率均达到了最高，分别为2.2cN/dtex和15.0％，制备的再生纤维素具有较高的强度和韧性。
实施例3：
实施例3的内容与实施例1-1相同，其不同之处在于，所述纤维素原料为菌草浆和棉浆按质量比1:1混合得到的混合物，其中，菌草浆是以菌草为原料经过制浆工序制备而成。
以实施例3制备的纤维素纺丝液为原料进行纺丝，制备再生纤维素纤维长丝(再生纤维素纤维长丝的制备方法与实施例1相同)干断裂强度为1.95cN/dtex，干断裂伸长率为14.8％，纤度为120D。
实施例4：
实施例4的内容与实施例1-1相同，其不同之处在于，所述纤维素原料为菌草浆和木浆按质量比1:1混合得到的混合物，其中，菌草浆是以菌草为原料经过制浆工序制备而成。
实施例5：
实施例5的内容与实施例1-1相同，其不同之处在于，所述纤维素原料为菌草浆和竹浆按质量比1:1混合得到的混合物，其中，菌草浆是以菌草为原料经过制浆工序制备而成。
实施例6：
实施例6的内容与实施例1-1相同，其不同之处在于，所述纤维素原料与纤维素溶剂的质量比为5:95。
以实施例6制备的纤维素纺丝液为原料进行纺丝，制备再生纤维素纤维长丝(再生纤维素纤维长丝的制备方法与实施例1相同)干断裂强度为1.65cN/dtex，干断裂伸长率为8.4％，纤度为120D。
实施例7：
实施例7的内容与实施例1-1相同，其不同之处在于，所述纤维素溶剂由溶剂A和溶剂B组成，溶剂A和溶剂B的体积比为7:3。
以实施例7制备的纤维素纺丝液为原料进行纺丝，制备再生纤维素纤维长丝(再生纤维素纤维长丝的制备方法与实施例1相同)干断裂强度为1.71cN/dtex，干断裂伸长率为9.2％，纤度为120D。
上述实施例为本发明的具体实施方式，但本发明的实施方式并不受上述实施例的限制，其它任何不超出本发明设计思路组合、改变、修饰、替代、简化，均落入本发明的保护范围之内。

Claims (15)

  1. 一种纤维素纺丝液的制备方法，其特征在于，采用纤维素溶剂体系对纤维素原料进行溶解，得到溶解液；向溶解液中加入稳定剂，混合均匀，过滤，得到纤维素纺丝液；所述稳定剂为金属硫酸盐；所述纤维素溶剂体系包括纤维素溶剂，所述纤维素溶剂由溶剂A和溶剂B组成，所述溶剂A为烷基氢氧化铵或烷基氢氧化铵水溶液。
  2. 根据权利要求1所述的纤维素纺丝液的制备方法，其特征在于，所述金属硫酸盐为硫酸铁、硫酸亚铁、硫酸镁、硫酸钡中的至少一种。
  3. 根据权利要求1或2所述的纤维素纺丝液的制备方法，其特征在于，所述纤维素纺丝液中稳定剂的含量为50～3000ppm。
  4. 根据权利要求1述的纤维素纺丝液的制备方法，其特征在于，所述溶剂B为非质子溶剂或非质子溶剂的水溶液。
  5. 根据权利要求4所述的纤维素纺丝液的制备方法，其特征在于，所述烷基氢氧化铵为四甲基氢氧化铵、四乙基氢氧化铵、四丙基氢氧化铵、四丁基氢氧化铵中的至少一种；所述非质子溶剂为N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、N,N-二甲基丙酰胺、N,N-二甲基丁酰胺、N,N-二甲基己酰胺、二甲亚砜、二丁基亚砜、尿素、硫脲中的至少一种；所述助溶剂为芳香基聚氧乙烯醚、四甲基氯化铵、四乙基氯化铵、四丙基氯化铵、四丁基氯化铵之中的至少一种。
  6. 根据权利要求1所述的纤维素纺丝液的制备方法，其特征在于，所述纤维素原料为菌草浆、棉浆、木浆、竹浆中的至少一种。
  7. 根据权利要求4或5或6所述的纤维素纺丝液的制备方法，其特征在于，所述纤维素原料与纤维素溶剂的质量比为(1～20)：(80～99)；所述纤维素溶剂体系还包括助溶剂；所述助溶剂用量为纤维素原料和纤维素溶剂总重的0～5％；所述纤维素溶剂中溶剂A的体积分数为10％～100％，溶剂B的体积分数为0～90％。
  8. 根据权利要求1所述的纤维素纺丝液的制备方法，其特征在于，所述溶解的温度为20～40℃，所述溶解的时间为0.5～2h。
  9. 一种利用权利要求1～8任一所述纤维素纺丝液的制备方法制备的纤维素纺丝液产品。
  10. 权利要求9所述纤维素纺丝液产品在制备再生纤维素纤维中的应用。
  11. 一种再生纤维素纤维的制备方法，其特征在于，采用权利要求9所述的纤维素纺丝液产品为原料，经脱泡、纺丝处理，得到再生纤维素纤维。
  12. 根据权利要求11所述的再生纤维素纤维的制备方法，其特征在于，所述纺丝处理的具体操作为：纤维素纺丝液经凝固浴形成初生丝，再经过牵伸、烘干、上油得到再生纤维素纤维。
  13. 根据权利要求11或12所述的再生纤维素纤维的制备方法，其特征在于，所述纺丝处理后，还包括：将所述再生纤维素纤维直接卷绕成型制成再生纤维素长丝，或者经过切断、开松、打包制成菌草再生纤维素短丝。
  14. 一种利用权利要求11～13任一项所述再生纤维素纤维的制备方法制备的再生纤维素纤维产品。
  15. 根据权利要求14所述的再生纤维素纤维产品，其特征在于，所述再生纤维素纤维产品为再生纤维素纤维长丝或再生纤维素纤维短丝。
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