WO2016078523A1 - 包含石墨烯的粘胶纤维及其制备方法 - Google Patents

包含石墨烯的粘胶纤维及其制备方法 Download PDF

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WO2016078523A1
WO2016078523A1 PCT/CN2015/094290 CN2015094290W WO2016078523A1 WO 2016078523 A1 WO2016078523 A1 WO 2016078523A1 CN 2015094290 W CN2015094290 W CN 2015094290W WO 2016078523 A1 WO2016078523 A1 WO 2016078523A1
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graphene
viscose
cellulose
sulfite
sulfate
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PCT/CN2015/094290
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English (en)
French (fr)
Inventor
唐一林
江成真
高绍丰
田文智
孙智华
许日鹏
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济南圣泉集团股份有限公司
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Application filed by 济南圣泉集团股份有限公司 filed Critical 济南圣泉集团股份有限公司
Priority to KR1020167031603A priority Critical patent/KR101783951B1/ko
Priority to DK15860957.8T priority patent/DK3192902T3/da
Priority to US15/307,713 priority patent/US10196460B2/en
Priority to RU2017117327A priority patent/RU2689580C2/ru
Priority to EP15860957.8A priority patent/EP3192902B1/en
Priority to JP2017513309A priority patent/JP6253044B2/ja
Priority to AU2015349249A priority patent/AU2015349249B2/en
Priority to BR112017010591-8A priority patent/BR112017010591A2/zh
Priority to CA2966805A priority patent/CA2966805C/en
Priority to ES15860957T priority patent/ES2732874T3/es
Priority to MX2017006630A priority patent/MX2017006630A/es
Publication of WO2016078523A1 publication Critical patent/WO2016078523A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B9/00—Cellulose xanthate; Viscose
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/184—Preparation
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/194—After-treatment
    • 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
    • D01F2/06—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from viscose
    • D01F2/08—Composition of the spinning solution or the bath

Definitions

  • the invention relates to a viscose fiber and a preparation process thereof, in particular to a graphene viscose fiber and a preparation process thereof.
  • Viscose fiber is mainly made up of natural cellulose such as cotton linters, corn cob, wood and a small amount of bamboo. After a series of treatment processes such as cooking and bleaching, it is made into a pulp slurry with high purity of cellulose. It is prepared by impregnation, pressing, crushing, ageing, yellowing, dissolving, mixing, filtering, defoaming, filtration, spinning, post-treatment, drying, packing, etc. Currently, it is used as textile fiber.
  • CN103046151A discloses a graphene blended regenerated cellulose fiber which is prepared by mixing a graphene oxide solution with a regenerated cellulose solution, molding by a viscose wet spinning process, and then reducing.
  • the viscose fiber obtained by the method has a slight improvement in strength, and the dry breaking strength is up to 2.62 cN/dtex, and the wet breaking strength is 1.54 cN/dtex.
  • these publications demonstrate the efficacy of graphene to increase fiber strength.
  • CN103556275A discloses a far-infrared bamboo charcoal viscose fiber and a preparation method thereof, and the invention provides a far-infrared bamboo charcoal adhesive in order to make up for the blank of the far-infrared bamboo charcoal viscose fiber and solve the problem that the bamboo charcoal viscose fiber has poor spinnability.
  • Fiber and its preparation method The utility model is characterized in that: the far infrared ceramic powder content in the fiber is 1 to 10%, the bamboo charcoal content is 0.1 to 10%, the far infrared emissivity is >80%, the ammonia absorption rate is ⁇ 50%, the gas permeability is ⁇ 500 mm/s, and the water is washable. Color fastness is 4 to 5 grades.
  • the far-infrared bamboo charcoal viscose fiber of the invention not only has the heat-insulating effect, but also the far-infrared rays radiated have the health-care function of activating cell tissue and promoting blood circulation.
  • the invention provides a new viscose fiber and a preparation method thereof to further increase the far red of the viscose fiber External function and antibacterial and antibacterial properties.
  • a method for preparing a viscose fiber comprises introducing a graphene having a layer number of not more than 10 layers into a viscose liquid or a viscose liquid semi-finished product.
  • the amount of the graphene is 0.05 to 1.0%, more preferably 0.2 to 0.8%, of the ⁇ -cellulose in the viscose solution.
  • the raw material for preparing graphene used in the present invention is derived from biomass, and the biomass resource is selected from any one or at least two combinations of plants and/or agricultural and forestry waste; preferably softwood, hardwood, forestwood, agricultural and forestry waste Any one or a combination of at least two; the agricultural and forestry waste is preferably selected from the group consisting of cornstalks, corn cobs, sorghum, beet pulp, bagasse, furfural residue, xylose residue, wood chips, cotton stalks, husks, and Any one or a combination of at least two of the reeds, preferably a corn cob, is currently commercially available.
  • the preparation of the viscose solution includes pulp impregnation, pressing, pulverizing, aging, yellowing, dissolving, ripening, filtering, defoaming steps, and the graphene is introduced prior to filtration.
  • the graphene is first made into a dispersion system, and the dispersion solvent is water.
  • the dispersion has a solids content of 10 to 40%.
  • the preparation of the viscose solution includes pulp impregnation, pressing, pulverizing, aging, yellowing, dissolving, aging, filtering, defoaming steps, and the graphene is introduced during the dissolving step.
  • the graphene is pre-dispersed in a dilute alkali solution for dissolving the cellulose flavonate.
  • the invention further relates to a viscose fiber comprising graphene which is not graphene oxide.
  • the non-oxidized graphene specifically means that it is not prepared by a redox method, or that an oxidation step is not performed in the process of preparing graphene.
  • the graphene may be a combination of any one or at least two of a warped, curled, and folded conformation microscopically exhibited in a six-membered ring-shaped honeycomb sheet structure.
  • the microscopic morphology of the sheet structure of graphene is typically obtained by observation with an electron microscope, and may be a transmission electron microscope or a scanning electron microscope.
  • the present invention uses specific graphene in viscose fibers, and the above-described optimization of the preparation method, the far-infrared detection normal viscogenicity of the viscose fiber obtained is greater than 0.80, preferably greater than 0.85, such as 0.87, 0.89, 0.91. , 0.92, 0.93, etc., more preferably greater than 0.88.
  • the number of graphene layers used in the present invention is not more than 15 layers of graphene, preferably not more than 10 layers.
  • the graphene used in the examples of the present invention is produced by the applicant, and the number of layers is between 3 and 10 layers, which is obtained by heat-treating cellulose, and belongs to non-oxidized graphene.
  • the graphene is obtained by using corn cob as a starting material to obtain porous cellulose, and then subjecting the porous cellulose to a gradient heating treatment.
  • a specific preparation method is disclosed in CN104016341A, the disclosure of which is incorporated herein by reference.
  • the method for preparing the graphene includes the following steps:
  • the treating agent used is acid, acid-Asia Sulfate, or alkali-sulfite, wherein the acid is preferably sulfuric acid, the base is preferably calcium hydroxide, sodium hydroxide, ammonium hydroxide or magnesium hydroxide, and the sulfite is preferably calcium sulfite, magnesium sulfite, sodium sulfite. Or ammonium sulfite;
  • the treatment temperature is from 50 ° C to 150 ° C, preferably from 80 ° C to 120 ° C;
  • the porous cellulose obtained in the previous step is sequentially placed in an anaerobic environment at 300 ° C to 400 ° C, 800 ° C to 900 ° C, 1100 ° C to 1300 ° C, 300 ° C to 400 ° C, and 900 ° C to 1000 ° C. Insulation to obtain a graphene precursor;
  • graphene is added to the viscose.
  • the amount of graphene is not more than 1%, preferably 0.05 to 0.99%, more preferably 0.1 to 0.8%, still more preferably 0.3 to 0.5%, of the ⁇ -cellulose content in the viscose.
  • the viscose liquid used in the present invention is a viscose liquid well known in the prior art, and is prepared by using pulp as a raw material for impregnation, pressing, pulverizing, aging, yellowing, dissolving, ripening, filtering, defoaming, etc. Process.
  • the pulp is impregnated with an aqueous solution of sodium hydroxide having a concentration of about 18% to convert the cellulose into alkali cellulose, the hemicellulose is eluted, and the degree of polymerization is partially lowered; and the excess alkali solution is removed by pressing.
  • the bulky alkali cellulose is pulverized on a pulverizer and becomes a loose floc, and the uniformity of chemical reaction is improved by the increase in surface area.
  • Alkali cellulose undergoes oxidative cleavage under the action of oxygen to lower the average degree of polymerization, a process called aging. After aging, the alkali cellulose is reacted with carbon disulfide to form a cellulose xanthate, which is yellowed, further weakening the hydrogen bond between the macromolecules, and the cellulose xanthate in the dilute alkali solution due to the hydrophilicity of the xanthate group The solubility performance is greatly improved.
  • the solid cellulose xanthate is dissolved in a dilute lye, which is a viscose.
  • the newly formed viscose is not easy to be formed due to its high viscosity and salt value. It must be placed at a certain temperature for a certain period of time, which is called ripening, so that the sodium cellulose sodium silicate in the viscose is gradually hydrolyzed and saponified, the degree of esterification is lowered, the viscosity and the The stability of the electrolyte action also changes. Defoaming and filtration should be carried out after ripening to remove bubbles and impurities.
  • graphene can be introduced in various steps of preparing the viscose solution described above, for example, prior to comminution, or prior to aging, or prior to germination, or prior to ripening. It is usually not introduced after the filtration or defoaming step.
  • the present invention preferably introduces graphene after aging, prior to filtration, and the inventors have found that the efficiency of mixing graphene at this time is higher, and the mixing time can be reduced to more than half, and can usually be reduced to one-third.
  • the graphene it is preferred to first form the graphene into a dispersion system, and then uniformly mix the dispersion solution with the viscose solution.
  • a preferred dispersion solvent is water.
  • the graphene is made into a dispersion having a solid content of 0.1 to 1%.
  • the graphene is first dispersed in a dilute alkali solution for dissolving the cellulose xanthate, and then the yellowed cellulose, that is, the cellulose flavanate, is added.
  • the advantage of this method is that it is not necessary to additionally introduce water due to the introduction of graphene, and the cellulose is combined with graphene after dissolution, and the mixing is more uniform.
  • the graphene when the graphene is dispersed in the dilute alkali solution and after the addition of the cellulose xanthate, it is not necessary to stir for a long time, but after a short time of stirring after the aging, the dispersion of the graphene can be greatly improved. effectiveness.
  • the corn cob was hydrolyzed in sulfuric acid for 10 min at 90 ° C to obtain lignocellulose.
  • the quality of the sulfuric acid was 3% of the mass of the corn cob; at 70-180 ° C, it was mixed with 2:1 sulfuric acid and magnesium sulfite.
  • the treatment agent treats the lignocellulose to obtain porous cellulose, and the quality of the sulfuric acid is 4% by mass of the lignocellulose.
  • the porous cellulose was bleached with hydrogen peroxide, the mass of the hydrogen peroxide was 5% by mass of the porous cellulose, the bleaching temperature of the hydrogen peroxide bleaching was 100 ° C, and the bleaching time was 5 h.
  • porous cellulose and manganese chloride obtained above were subjected to catalytic treatment by stirring at 20 ° C for 2 hours, and the mass ratio of manganese chloride to porous cellulose was 0.01 :1; the obtained catalytically treated product was at 70 ° C Drying gives a first intermediate product having a water content of less than 10% by weight.
  • the first intermediate product was placed in a carbonization furnace, and nitrogen gas was introduced into the carbonization furnace as a shielding gas at a gas permeation amount of 200 mL/min, and the first intermediate product was heated from 25 ° C to 300 ° C at a rate of 5 ° C/min.
  • the second intermediate product was heated from 300 ° C to 800 ° C at a rate of 20 ° C / min, and kept for 3.5 hours to obtain a third intermediate product; the third intermediate product was 50 ° C / The rate of min is raised from 800 ° C to 1100 ° C, and kept for 6 hours to obtain a fourth intermediate product; the fourth intermediate product is cooled from 1100 ° C to 900 ° C at a rate of 30 ° C / min, and kept for 2 hours; The four intermediates were cooled to 60 °C.
  • the cooled fourth intermediate product was washed in an aqueous solution of sodium hydroxide having a mass concentration of 3% at 60 ° C for 4 hours to obtain a first washed product; at 70 ° C, the first washed product was at a mass concentration of The mixture was washed in 4% aqueous hydrochloric acid for 4 hours to obtain a second washed product; the second washed product was washed with distilled water until neutral and dried to obtain graphene.
  • Example 1 is obtained by using graphene as 5 times of water. After dispersion, the graphene dispersion was blended with the viscose solution, and stirred at a high speed mixer for 1 hour to form a blend solution, and the amount of graphene was 0.1% by mass of the cellulose. Filtration, defoaming, and then spinning, desulfurization, water washing, drying, and Graphene viscose fiber.
  • the composition of the coagulation bath sulfuric acid 105g / l, sodium sulfate 200g / l, zinc sulfate 12g / l.
  • the far-infrared normal emissivity of the obtained graphene viscose fiber was 0.85, and the antibacterial inhibition rate against Staphylococcus aureus was 85%.
  • the yellowed lint cellulose after yellowing was dissolved in a dilute sodium hydroxide addition solution, and the graphene obtained in Example 1 was previously added to the dilute sodium hydroxide solution. After the aging, a viscose liquid having a solid content of 8% was prepared, and stirred at a high speed mixer for half an hour, and the amount of graphene was 0.6% of the mass of the cellulose. Filtration, defoaming, and then spinning, desulfurization, water washing, and drying to obtain graphene viscose fibers.
  • the composition of the coagulation bath sulfuric acid 105g / l, sodium sulfate 200g / l, zinc sulfate 12g / l.
  • the far-infrared normal emissivity of the obtained graphene viscose fiber was 0.88, and the antibacterial inhibition rate against Staphylococcus aureus was 95%.
  • the corn cob cellulose was used as a raw material, and the yellowed corn cob cellulose was dissolved in a dilute sodium hydroxide addition solution, and the graphene obtained in Example 1 was previously added to the dilute sodium hydroxide solution. After the ripening, a viscose liquid having a solid content of 10% was prepared, and stirred at a high speed mixer for half an hour, and the amount of graphene was 1% of the mass of the cellulose. Filtration, defoaming, and then spinning, desulfurization, water washing, drying, to obtain corncob viscose fiber.
  • the composition of the coagulation bath sulfuric acid 105g / l, sodium sulfate 200g / l, zinc sulfate 12g / l.
  • the far-infrared normal emissivity of the obtained graphene viscose fiber was 0.90, and the antibacterial inhibition rate against Staphylococcus aureus was 97%.
  • the corn cob is used as a raw material, and after being alkalized, pressed, pulverized, aged, yellowed, dissolved, and matured, a viscose liquid having a solid content of 8% is obtained, and stirred at a high speed mixer for half an hour. Filtration, defoaming, and then spinning, desulfurization, water washing, and drying to obtain graphene viscose fibers.
  • the composition of the coagulation bath sulfuric acid 105g / l, sodium sulfate 200g / l, zinc sulfate 12g / l.
  • the far-infrared normal emissivity of the obtained graphene viscose fiber was 0.70, and the antibacterial inhibition rate against Staphylococcus aureus was 20%.
  • the yellowed corn cob cellulose is dissolved in a dilute sodium hydroxide addition solution, and the graphene prepared by the above redox method is previously added to the dilute sodium hydroxide solution.
  • a viscose liquid having a solid content of 10% was prepared, and stirred at a high speed mixer for half an hour, and the amount of graphene was 1% of the mass of the cellulose. Filtration, defoaming, and then spinning, desulfurization, water washing, and drying to obtain graphene viscose fibers.
  • the composition of the coagulation bath sulfuric acid 105g / l, sodium sulfate 200g / l, zinc sulfate 12g / l.
  • the far-infrared normal emissivity of the obtained graphene viscose fiber was 0.80, and the antibacterial inhibition rate against Staphylococcus aureus was 50%.
  • the infrared detection data is based on: the National Textile Products Quality Supervision and Inspection Center, in accordance with the FZ/T64010-2000 inspection method for inspection;
  • Antibacterial test data based on: National Textile Products Quality Supervision and Inspection Center, in accordance with GB/T20944.3-2008 test method.
  • the invention uses the graphene self-made by the applicant for the preparation of the viscose fiber, and obviously improves the far-infrared performance and the antibacterial property of the conventional viscose fiber, and similar effects are not found in the prior art.

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Abstract

本发明涉及一种包含石墨烯的粘胶纤维及其制备方法，其中的石墨烯是层数不高于10的非氧化石墨烯。制备方法是，在纺丝之前，向粘胶液中引入石墨烯。根据本发明获得的粘胶纤维具有显著的远红外和抗菌性能。

Description

包含石墨烯的粘胶纤维及其制备方法 技术领域
本发明涉及一种粘胶纤维及其制备工艺，尤其涉及一种石墨烯粘胶纤维及其制备工艺。
背景技术
粘胶纤维主要是以棉短绒、玉米芯、木材和少量的竹材等天然纤维素为原料，经过蒸煮、漂白等一系列处理过程而制成纤维素纯度很高的溶解浆浆粕，再经浸渍、压榨、粉碎、老成、黄化、溶解、混合、过滤、脱泡、过滤、纺丝、后处理、干燥、打包等工段制备而成，目前，用作纺织纤维的较多。
CN103046151A公开一种石墨烯共混再生纤维素纤维，其利用氧化石墨烯溶液与再生纤维素溶液混合、通过粘胶湿法纺丝工艺成型后，再经还原制备而成。该方法获得的粘胶纤维在强度方面略有提高，其干断裂强度最高达到2.62cN/dtex，湿断裂强度达到1.54cN/dtex。但是这些公开中体现出了石墨烯能够增加纤维强度的功效。
CN103556275A公开了一种远红外竹炭粘胶纤维及其制备方法，本发明为了弥补目前远红外竹炭粘胶纤维的空白，解决竹炭粘胶纤维可纺性差的问题，提供了一种远红外竹炭粘胶纤维及其制备方法。其特征在于：按重量计，纤维中远红外陶瓷粉含量1～10％，竹炭含量0.1～10％，远红外发射率＞80％，氨吸收率≥50％，透气性≥500mm/s，耐水洗色牢度4～5级。本发明的远红外竹炭粘胶纤维不仅具有保温功效，辐射的远红外线还具有活化细胞组织、促进血液循环的保健功能。
但是这些公开中体现了远红外功效是通过引入陶瓷粉来获得的。
发明内容
本发明提出一种新的粘胶纤维及其制备方法，以进一步增加粘胶纤维的远红 外功能和抗菌抑菌性能。
根据本发明，用于制备粘胶纤维的方法包括：向粘胶液或者粘胶液半成品中引入层数不高于10层的石墨烯。
优选地，所述石墨烯的用量为粘胶液中α-纤维素的0.05～1.0％，更优选为0.2～0.8％。
本发明使用的石墨烯的制备原料来自生物质，生物质资源选自植物和/或农林废弃物中的任意1种或至少2种的组合；优选针叶木、阔叶木、林叶木、农林废弃物中的任意1种或至少2种的组合；所述农林废弃物优选自玉米杆、玉米芯、高粱杆、甜菜渣、甘蔗渣、糠醛渣、木糖渣、木屑、棉秆、果壳、和芦苇中的任意1种或至少2种的组合，优选玉米芯，目前已经公开销售。
采用生物质原料尤其是玉米芯制备的石墨烯微观上表现出多孔，使得比表面积更大，尤其是申请人自制的石墨烯。
在一种优选实施方式中，粘胶液的制备包括浆粕浸渍、压榨、粉碎、老化、黄化、溶解、熟成、过滤、脱泡步骤，所述石墨烯是过滤之前引入。
进一步地，将石墨烯先制成分散体系，分散溶剂是水。该分散体系的固含量为10～40％。
在另一种优选实施方式中，粘胶液的制备包括浆粕浸渍、压榨、粉碎、老化、黄化、溶解、熟成、过滤、脱泡步骤，所述石墨烯是在溶解步骤之中引入，将石墨烯预先分散在用于溶解纤维素黄酸酯的稀碱溶液中。
本发明还涉及一种粘胶纤维，其中包含石墨烯，该石墨烯不是氧化石墨烯。
所述的非氧化石墨烯具体是指不是通过氧化还原法制备得到，或者说在制备石墨烯过程中没有经过氧化步骤。
所述石墨烯可以是六元环蜂窝状片层结构微观上呈现翘曲、卷曲、折叠构象中的任意1种或至少2种的组合。
关于石墨烯的片层结构的微观形貌典型的可以通过电子显微镜观察获得，可以是透射电镜或扫描电镜。
本发明将特定的石墨烯用于粘胶纤维中，并且对制备方法进行了上述优化，所获得的粘胶纤维的远红外检测法向发射率大于0.80，优选大于0.85，例如0.87、0.89、0.91、0.92、0.93等，更优选大于0.88。
具体实施方式
本发明使用的石墨烯层数不超过15层的石墨烯，优选不超过10层。本发明实施例中使用的石墨烯是由本申请人生产，其层数在3-10层之间，是通过对纤维素进行热处理获得，属于非氧化石墨烯。
该石墨烯是以玉米芯为起始原料，制得多孔纤维素，再将该多孔纤维素进行梯度升温处理而获得的。CN104016341A公开了具体的制备方法，其披露的内容以引用形式并入本文。
在具体实施例中，具体而言，该石墨烯的制备方法包括如下步骤：
1)、将玉米芯在酸中进行水解，得到木质纤维素；
2)、用处理剂在70℃～180℃，优选为90℃～150℃，最优选为100℃～120℃处理该木质纤维素，得到多孔纤维素，使用的处理剂为酸、酸-亚硫酸盐、或者碱-亚硫酸盐，其中的酸优选为硫酸，碱优选为氢氧化钙、氢氧化钠、氢氧化铵或氢氧化镁，亚硫酸盐优选为亚硫酸钙、亚硫酸镁、亚硫酸钠或亚硫酸铵；
3)用选自氯化铁、氯化亚铁、硝酸铁、硝酸亚铁、硫酸铁、硫酸亚铁、铁氰化钾、亚铁氰化钾、三草酸合铁酸钾、氯化钴、硝酸钴、硫酸钴、乙酸钴、氯化镍、硝酸镍、硫酸镍和乙酸镍的催化剂处理多孔纤维素，处理温度为50℃～150℃，优选80℃～120℃；
4)在无氧环境下，依次将上一步获得的多孔纤维素置于300℃～400℃、800℃～900℃、1100℃～1300℃、300℃～400℃、和900℃～1000℃下保温，获得石墨烯前体；
5)分别用碱、酸和水洗涤该石墨烯前体，得到终产物石墨烯。
上述方法虽然使用的是玉米芯，但是，从理论上可以合理推知，利用其它植物资源也是可行的，因此本发明不排除其它植物资源。
根据本发明，为了获得远红外和抗菌功能的粘胶纤维，将石墨烯加入粘胶液中。石墨烯的用量不超过粘胶液中α-纤维素含量的1％，优选0.05～0.99％，更优选0.1～0.8％，更优选0.3～0.5％。
本发明中使用的粘胶液是现有技术熟知的粘胶液，其制备方法是，以浆粕为原料，进行浸渍、压榨、粉碎、老化、黄化、溶解、熟成、过滤、脱泡等工序。浆粕经浓度为18％左右的氢氧化钠水溶液浸渍，使纤维素转化成碱纤维素，半纤维素溶出，聚合度部分下降；再经压榨除去多余的碱液。块状的碱纤维素在粉碎机上粉碎后变为疏松的絮状体，由于表面积增大使以后的化学反应均匀性提高。碱纤维素在氧的作用下发生氧化裂解使平均聚合度下降，这个过程称为老化。老化后将碱纤维素与二硫化碳反应生成纤维素黄酸酯称黄化，使大分子间的氢键进一步削弱，由于黄酸基团的亲水性，使纤维素黄酸酯在稀碱液中的溶解性能大为提高。把固体纤维素黄酸酯溶解在稀碱液中，即是粘胶。刚制成的粘胶因粘度和盐值较高不易成形，必须在一定温度下放置一定时间称为熟成，使粘胶中纤维素黄酸钠逐渐水解和皂化，酯化度降低，粘度和对电解质作用的稳定性也随着改变。在熟成之后应进行脱泡和过滤，以除去气泡和杂质。
一般而言，可以在上述制备粘胶液的多个环节中引入石墨烯，例如在粉碎之前、或者老化之前，或者黄化之前，或者熟成之前。通常不会在过滤或者脱泡步骤之后引入。本发明优选在熟成之后、过滤之前引入石墨烯，发明人发现，在这时加入石墨烯的混合效率更高，可以将混合时间缩减至一半以上，通常可以缩减至三分之一。
本发明中，优选将石墨烯先制成分散体系，然后将该分散溶液与粘胶液混合均匀。优选的分散溶剂是水。优选将石墨烯制成固含量为0.1～1％的分散体系。
一个更优选的方式是先将石墨烯分散在用于溶解纤维素黄酸酯的稀碱溶液中，分散好后再加入黄化过的纤维素即纤维素黄酸酯。这种方法的优势是：不必因为引入石墨烯的缘故而另外引入水，纤维素在溶解后即与石墨烯结合，混合更加均匀。在这种实施方式中，将石墨烯分散于稀碱溶液时以及在加入纤维素黄酸酯之后，不必长时间搅拌，而在经过熟化之后进行短时间搅拌即可，可以大大提高石墨烯的分散效率。
接下来，在过滤和脱泡之后进行纺丝、脱硫、水洗、上油以及烘干，即得到最终的粘胶纤维。这些属于传统方法，本文不做详细描述。
实施例1——石墨烯制备
在90℃下，将玉米芯在硫酸中进行10min的水解，得到木质纤维素，硫酸的质量为玉米芯质量的3％；在70～180℃下，用2:1的硫酸和亚硫酸镁混合处理剂处理木质纤维素，得到多孔纤维素，硫酸的质量为木质纤维素质量的4％。用双氧水漂白多孔纤维素，双氧水的质量为多孔纤维素质量的5％，双氧水漂白的漂白温度为100℃，漂白时间为5h。
将上述得到的多孔纤维素和氯化锰，在20℃下搅拌2小时进行催化处理，氯化锰和多孔纤维素的质量比为0.01：1；将得到的催化处理后的产物在70℃下干燥，得到含水量低于10wt％的第一中间产物。
将第一中间产物置于炭化炉中，以200mL/min的气体通入量向碳化炉中通入氮气作为保护气，将第一中间产物以5℃/min的速率从25℃升温至300℃，保温4小时，得到第二中间产物；将第二中间产物以20℃/min的速率从300℃升温至800℃，保温3.5小时，得到第三中间产物；将第三中间产物以50℃/min的速率从800℃升温至1100℃，保温6小时，得到第四中间产物；将第四中间产物以30℃/min的速率从1100℃降温至900℃，保温2小时；将降温后的第四中间产物冷却至60℃。
在60℃下，将上述冷却后的第四中间产物在质量浓度为3％的氢氧化钠水溶液中洗涤4小时，得到第一洗涤产物；在70℃下，将第一洗涤产物在质量浓度为4％的盐酸水溶液中洗涤4小时，得到第二洗涤产物；将第二洗涤产物用蒸馏水洗涤至中性后干燥，得到石墨烯。
实施例2——粘胶纤维制备
以棉短绒为原料，经浸渍碱化、压榨、粉碎、老化、黄化、溶解、熟成后制得固含为8％的粘胶液；将实施例1获得石墨烯以5倍质量的水分散，然后石墨烯分散液与粘胶液共混，以高速搅拌机搅拌1小时，形成共混溶液，石墨烯用量是纤维素质量的0.1％。过滤、脱泡，然后经过纺丝、脱硫、水洗、干燥，制得 石墨烯粘胶纤维。其中，凝固浴的组成：硫酸105g/l，硫酸钠200g/l，硫酸锌12g/l。所获得石墨烯粘胶纤维的远红外法向发射率0.85，对金黄色葡萄球菌抗菌抑菌率为85％。
实施例3——粘胶纤维制备
将黄化后的短棉绒纤维素溶解在稀氢氧化钠添溶液中，稀氢氧化钠溶液中预先加入实施例1得到的石墨烯。熟成后制得固含为8％的粘胶液，以高速搅拌机搅拌半小时，石墨烯用量是纤维素质量的0.6％。过滤、脱泡，然后经过纺丝、脱硫、水洗、干燥，制得石墨烯粘胶纤维。其中，凝固浴的组成：硫酸105g/l，硫酸钠200g/l，硫酸锌12g/l。所获得石墨烯粘胶纤维的远红外法向发射率0.88，对金黄色葡萄球菌抗菌抑菌率为95％。
实施例4——粘胶纤维制备
以玉米芯为原料，将黄化后的玉米芯纤维素溶解在稀氢氧化钠添溶液中，稀氢氧化钠溶液中预先加入实施例1得到的石墨烯。熟成后制得固含为10％的粘胶液，以高速搅拌机搅拌半小时，石墨烯用量是纤维素质量的1％。过滤、脱泡，然后经过纺丝、脱硫、水洗、干燥，制得玉米芯粘胶纤维。其中，凝固浴的组成：硫酸105g/l，硫酸钠200g/l，硫酸锌12g/l。所获得石墨烯粘胶纤维的远红外法向发射率0.90，对金黄色葡萄球菌抗菌抑菌率为97％。
对比例1
以玉米芯为原料，经浸渍碱化、压榨、粉碎、老化、黄化、溶解、熟成后制得固含为8％的粘胶液，以高速搅拌机搅拌半小时。过滤、脱泡，然后经过纺丝、脱硫、水洗、干燥，制得石墨烯粘胶纤维。其中，凝固浴的组成：硫酸105g/l，硫酸钠200g/l，硫酸锌12g/l。所获得石墨烯粘胶纤维的远红外法向发射率0.70，对金黄色葡萄球菌抗菌抑菌率为20％。
对比例2
以石墨为原料制备石墨烯的方法：
(1)向5g鳞片石墨和150ml浓硫酸的混合溶液中加入50ml的浓硝酸， 常温下搅拌24h，用去离子水清洗3次，60℃中烘干，得到石墨层间化合物；
(2)将上述得到的石墨层间化合物在1050℃中迅速膨胀30s，得到膨胀石墨；
(3)将3g高锰酸钾缓慢加入0.3g上述所得的膨胀石墨和60ml浓硫酸的混合物中，在60℃的条件下搅拌24h，在冰浴条件下加入60ml去离子水和15ml过氧化氢，将混合物水洗至中性，获得氧化石墨烯；
(4)将上述所得的氧化石墨烯在水中分散，用离心法将氧化石墨烯分离；用转速、时间分别为8000rmp和40min进行离心，得到上层清液1和沉淀物1，所得的上层清液1即为小尺寸氧化石墨烯；将上层清液1分散，用转移印花法将氧化石墨烯转移到聚对苯二甲酸塑料(PET)基体上，用HI酸在50℃下还原60min，即得到石墨烯。
将黄化后的玉米芯纤维素溶解在稀氢氧化钠添溶液中，稀氢氧化钠溶液中预先加入上述氧化还原法制备得到的石墨烯。熟成后制得固含为10％的粘胶液，以高速搅拌机搅拌半小时，石墨烯用量是纤维素质量的1％。过滤、脱泡，然后经过纺丝、脱硫、水洗、干燥，制得石墨烯粘胶纤维。其中，凝固浴的组成：硫酸105g/l，硫酸钠200g/l，硫酸锌12g/l。所获得石墨烯粘胶纤维的远红外法向发射率0.80，对金黄色葡萄球菌抗菌抑菌率为50％。
其中，红外检测数据依据：经国家纺织制品质量监督检验中心，按照FZ/T64010-2000检验方法进行检验；
抑菌检测数据依据：经国家纺织制品质量监督检验中心，按照GB/T20944.3-2008检验方法。
本发明将申请人自制的石墨烯用于粘胶纤维的制备，明显提高了现有普通粘胶纤维的远红外性能和抗菌性能，现有技术中没有出现类似的效果。

Claims (10)

  1. 用于制备粘胶纤维的方法，其特征在于包括：
    向粘胶液或者粘胶液半成品中引入层数不高于10层的石墨烯，并且为非氧化石墨烯。
  2. 权利要求1所述的方法，其中，所述石墨烯的用量为粘胶液中α-纤维素的0.05～1.0％。
  3. 权利要求2所述的方法，其中，所述石墨烯的用量为粘胶液中α-纤维素的0.2～0.8％。
  4. 权利要求1所述的方法，其中，所述石墨烯通过以下方法制得：
    1)、将玉米芯在无机水溶液酸中进行水解，得到木质纤维素；
    2)、用处理剂在70℃～180℃，优选为90℃～150℃，最优选为100℃～120℃处理该木质纤维素，得到多孔纤维素，使用的处理剂为酸、酸-亚硫酸盐、或者碱-亚硫酸盐，其中的酸优选为硫酸，碱优选为氢氧化钙、氢氧化钠、氢氧化铵或氢氧化镁，亚硫酸盐优选为亚硫酸钙、亚硫酸镁、亚硫酸钠或亚硫酸铵；
    3)用选自氯化铁、氯化亚铁、硝酸铁、硝酸亚铁、硫酸铁、硫酸亚铁、铁氰化钾、亚铁氰化钾、三草酸合铁酸钾、氯化钴、硝酸钴、硫酸钴、乙酸钴、氯化镍、硝酸镍、硫酸镍和乙酸镍的催化剂处理多孔纤维素，处理温度为50℃～150℃，优选80℃～120℃；
    4)在无氧环境下，依次将上一步获得的多孔纤维素置于300℃～400℃、800℃～900℃、1100℃～1300℃、300℃～400℃、和900℃～1000℃下保温，获得石墨烯前体；
    5)分别用碱、酸和水洗涤该石墨烯前体，得到终产物石墨烯。
  5. 权利要求1所述的方法，其中，粘胶液的制备包括浆粕浸渍、压榨、粉碎、老化、黄化、溶解、熟成、过滤、脱泡步骤，所述石墨烯是在过滤之前引入。
  6. 权利要求5所述的方法，其中，将石墨烯先制成分散体系，分散溶剂是水。该分散体系的固含量为0.1～1％。
  7. 权利要求1所述的方法，其中粘胶液的制备包括浆粕浸渍、压榨、粉碎、老 化、黄化、溶解、熟成、过滤、脱泡步骤，所述石墨烯是在溶解步骤之中引入，将石墨烯预先分散在用于溶解纤维素黄酸酯的稀碱溶液中。
  8. 权利要求7所述的方法，其中，在熟成步骤后将包含石墨烯的粘胶液高速搅拌半小时。
  9. 一种粘胶纤维，其中包含石墨烯，并且该石墨烯不是氧化石墨烯。
  10. 权利要求9所述的粘胶纤维，其中，所述石墨烯的层数在10层以内。
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