阅读说明：本技术 一种纯纺再生纤维素纤维生条的制备方法 (Preparation method of pure-spinning regenerated cellulose fiber raw sliver ) 是由 郭志清 陈立 王晴 牛春霞 文小兵 于 2021-10-26 设计创作，主要内容包括：本申请涉及纺织纤维领域,具体公开了一种纯纺再生纤维素纤维生条的制备方法,制备方法为：制备碳纳米材料；制备玉米皮再生纤维素纤维纺丝液：将玉米皮清洗后粉碎,制成玉米皮浆粕,加入到氯化1-烯丙基-3-甲基咪唑中,混合均匀,在温度为70-90℃和真空条件下,均质、过滤,将滤液脱泡,制得玉米皮再生纤维素纤维纺丝液；制备纺丝原液；纺丝；制备生条。本申请的再生纤维素纤维具有原料来源丰富,成本低廉,制备工艺简单,抗菌、吸附和防臭效果好,且抗菌性持久,芳香味持久,附加值高的优点。(The application relates to the field of textile fibers, and particularly discloses a preparation method of a pure-spinning regenerated cellulose fiber raw sliver, which comprises the following steps: preparing a carbon nano material; preparing a corn bran regenerated cellulose fiber spinning solution: cleaning and crushing corn husks to prepare corn husk pulp, adding the corn husk pulp into 1-allyl-3-methylimidazole chloride, uniformly mixing, homogenizing and filtering under the vacuum condition at the temperature of 70-90 ℃, and defoaming filtrate to prepare a corn husk regenerated cellulose fiber spinning solution; preparing a spinning solution; spinning; and (4) preparing the raw strips. The regenerated cellulose fiber has the advantages of rich raw material sources, low cost, simple preparation process, good antibacterial, adsorption and deodorization effects, lasting antibacterial property, lasting fragrance and high added value.)

1. The preparation method of the pure-spun regenerated cellulose fiber raw sliver is characterized by comprising the following steps:

preparing a carbon nano material: respectively cleaning sesame stalks and enteromorpha, then crushing, mixing, freeze-drying, heating to 300-600 ℃ in an inert atmosphere, calcining for 30-50min to prepare carbide, adding an oxidant, uniformly stirring, drying at 60-80 ℃, soaking with an acid solution, washing to neutrality, and vacuum-drying to prepare a carbon nano material, wherein the mass ratio of the sesame stalks, the enteromorpha and the oxidant is 1:0.5-1: 1-5;

preparing a corn bran regenerated cellulose fiber spinning solution: cleaning and crushing corn husks to prepare corn husk pulp, adding the corn husk pulp into chlorinated 1-allyl-3-methylimidazole, uniformly mixing, homogenizing and filtering at the temperature of 70-90 ℃ under a vacuum condition, and defoaming filtrate to prepare a corn husk regenerated cellulose fiber spinning solution, wherein the mass ratio of the corn husk pulp to the chlorinated 1-allyl-3-methylimidazole is 0.3-0.5: 1;

preparing a spinning solution: dispersing carbon nano materials in water or absolute ethyl alcohol, forming carbon nano material dispersion liquid with the mass percentage concentration of 10-15% after ultrasonic dispersion, adding the carbon nano material dispersion liquid into the corn bran regenerated cellulose fiber spinning solution, shearing and blending to prepare spinning stock solution, wherein the mass ratio of the carbon nano material dispersion liquid to the corn bran regenerated cellulose fiber spinning solution is 3: 7-12;

spinning: carrying out wet spinning on the spinning stock solution, and forming pure spinning regenerated cellulose fibers through a coagulating bath;

preparing raw strips: and opening and carding the pure-spun regenerated cellulose fibers to prepare the pure-spun regenerated cellulose fiber raw sliver.

2. The method of producing a spun-laid regenerated cellulose fiber sliver of claim 1, characterized in that: the carbide is also added with an antibacterial agent, and the mass ratio of the antibacterial agent to the carbide is 0.1-0.3: 1.

3. The method of producing a spun-laid regenerated cellulose fiber sliver of claim 2, wherein the antimicrobial agent is produced by:

(1) soaking 2-4 parts by weight of spirulina powder in 4-5 parts by weight of silver nitrate solution with the mass percent concentration of 35-40%, centrifuging, washing with deionized water until the pH value is 6-8, drying at 60-80 ℃, uniformly mixing with 3-5 parts by weight of sodium alginate solution with the mass percent concentration of 1-3% and 3-5 parts by weight of glutaraldehyde, and stirring at the constant temperature of 50-60 ℃ for 1-2 hours;

(2) uniformly stirring 10-30 parts by weight of 2-4% chitosan acetic acid solution, 0.05-0.15 part by weight of ammonium acetate and 10-15 parts by weight of n-amyl alcohol, then dropwise adding the product obtained in the step (1), stirring while dropwise adding, freeze-drying, drying at 98-100 ℃ for 30-40min, and soaking with absolute ethyl alcohol for 20-24 h.

4. The method for preparing the pure-spun regenerated cellulose fiber raw sliver according to claim 1, wherein in the spinning step, before wet spinning is carried out, essence microcapsules are added into a spinning solution, the mixture is uniformly mixed, and then the wet spinning is carried out, wherein the mass ratio of the essence microcapsules to the spinning solution is 0.05-0.1: 1.

5. The method for preparing the pure woven regenerated cellulose fiber raw sliver according to claim 4, wherein the essence microcapsule is prepared by the following method: emulsifying 1-3 parts by weight of essence, 2-4 parts by weight of styrene-maleic anhydride copolymer solution with the mass percentage concentration of 10-15%, 0.1-0.5 part by weight of emulsifier and 10-20 parts by weight of deionized water for 10-20min, adjusting the pH value to 3-5, adding 6-10 parts by weight of melamine resin and 0.5-1 part by weight of polyvinyl alcohol, heating to 70-80 ℃, adjusting the pH value to 6-7, performing suction filtration, and drying to constant weight.

6. The method for preparing the pure-spun regenerated cellulose fiber raw sliver according to claim 5, wherein the essence microcapsules are pretreated by the following steps before being added into the spinning solution:

mixing 3-5 parts by weight of nano silicon dioxide, 0.1-0.5 part by weight of sodium dodecyl sulfate, 1-1.5 parts by weight of silane coupling agent aqueous solution with the mass percent concentration of 1-1.5% and 1-2 parts by weight of polydimethylsiloxane, ultrasonically dispersing for 1-2h, adding 3-5 parts by weight of essence microcapsules, adjusting the pH value to 5-7, stirring for 1-2h, centrifuging, washing and drying.

7. The method for preparing the spun-laid regenerated cellulose fiber raw sliver according to claim 1, wherein in the spinning step, the coagulation bath is distilled water, the temperature is 60 to 80 ℃, and the length of the coagulation bath is 1 to 3 m.

8. The method for preparing the pure-spun regenerated cellulose fiber raw sliver according to claim 1, wherein in the step of preparing the corn bran regenerated cellulose fiber spinning solution, the homogenization time is 3-5 times, and the rotation speed of each homogenization is 14000-16000 r/min.

9. The method for preparing the pure-spun regenerated cellulose fiber raw sliver according to claim 1, wherein in the step of preparing the carbon nanomaterial, the oxidizing agent is one of potassium permanganate or phosphorus pentoxide.

10. The method for preparing the spun regenerated cellulose fiber raw sliver according to claim 1, wherein in the step of preparing the carbon nanomaterial, the acid solution is 10-30% of hydrochloric acid or 30-50% of sulfuric acid by mass percent.

Technical Field

The application relates to the technical field of textile fibers, in particular to a preparation method of a pure-spinning regenerated cellulose fiber raw sliver.

Background

The regenerated cellulose fiber is cellulose fiber prepared by regenerating natural cellulose serving as a raw material. The regenerated cellulose fiber has good hygroscopicity, drapability, easy dyeing property and biodegradability, is widely used for weaving, yarn making, wool making, knitting and the like, is particularly suitable for making underwear due to comfortable wearing, and can be blended or interwoven with cellulose such as wool, hemp, silk and the like. At present, the regenerated cellulose fiber is mainly prepared by taking wood pulp, bamboo pulp, cotton meal and the like as raw materials through a viscose method or a solvent method.

In the prior art, chinese patent application No. CN201610424631.5 discloses a method for preparing regenerated cellulose fibers, (1) pulp is added into an aqueous solution of N-methylmorpholine-N-oxide, then an antioxidant is added to the solution, and the solution is stirred and premixed to obtain a premixed solution, wherein the pulp comprises the following raw materials in parts by weight: 20-30 parts of cotton pulp, 10-20 parts of wood pulp and 50-70 parts of bamboo pulp; (2) placing the premixed solution in a vacuum environment at the temperature of 80-90 ℃ to obtain a spinning stock solution; (3) spinning the spinning solution to obtain the regenerated cellulose fiber, wherein the spinning bath is an aqueous solution of N-methylmorpholine-N-oxide during spinning.

The existing regenerated cellulose fiber adopts cotton pulp, wood pulp and bamboo pulp as raw materials, but with the enhancement of environmental awareness of people, people pay attention to the living environment, and the country puts forward to improve the national forest coverage rate, limits the deforestation, and influences the source of the regenerated cellulose, so that the method actively develops a new cellulose source and is extremely important.

Disclosure of Invention

In order to make up the shortage of the existing regenerated cellulose fiber pulp raw material supply and add a new raw material source for the regenerated cellulose fiber, the application provides a preparation method of a pure-spinning regenerated cellulose fiber raw sliver.

In a first aspect, the present application provides a method for preparing a pure-spun regenerated cellulose fiber raw sliver, which adopts the following technical scheme:

a method for preparing pure spinning regenerated cellulose fiber raw strips comprises the following steps:

preparing a carbon nano material: respectively cleaning sesame stalks and enteromorpha, then crushing, mixing, freeze-drying, heating to 300-600 ℃ in an inert atmosphere, calcining for 30-50min to prepare carbide, adding an oxidant, uniformly stirring, drying at 60-80 ℃, soaking with an acid solution, washing to neutrality, and vacuum-drying to prepare a carbon nano material, wherein the mass ratio of the sesame stalks, the enteromorpha and the oxidant is 1:0.5-1: 1-5;

preparing a corn bran regenerated cellulose fiber spinning solution: cleaning and crushing corn husks to prepare corn husk pulp, adding the corn husk pulp into chlorinated 1-allyl-3-methylimidazole, uniformly mixing, homogenizing and filtering at the temperature of 70-90 ℃ under a vacuum condition, and defoaming filtrate to prepare a corn husk regenerated cellulose fiber spinning solution, wherein the mass ratio of the corn husk pulp to the chlorinated 1-allyl-3-methylimidazole is 0.3-0.5: 1;

preparing a spinning solution: dispersing carbon nano materials in water or absolute ethyl alcohol, forming carbon nano material dispersion liquid with the mass percentage concentration of 10-15% after ultrasonic dispersion, adding the carbon nano material dispersion liquid into the corn bran regenerated cellulose fiber spinning solution, shearing and blending to prepare spinning stock solution, wherein the mass ratio of the carbon nano material dispersion liquid to the corn bran regenerated cellulose fiber spinning solution is 3: 7-12;

spinning: carrying out wet spinning on the spinning stock solution, and forming pure spinning regenerated cellulose fibers through a coagulating bath;

preparing raw strips: and opening and carding the pure-spun regenerated cellulose fibers to prepare the pure-spun regenerated cellulose fiber raw sliver.

By adopting the technical scheme, the enteromorpha prolifera grows fast, resources are rich, but the enteromorpha prolifera is often attached to other cultured organisms and has certain harm to culture, in the recent years, large-scale enteromorpha prolifera flooding occurs near the sea of Qingdao, how to change waste into valuable is realized, and the application value of the enteromorpha prolifera is widely concerned and researched. After salt, sand and other impurities of the enteromorpha are removed after the enteromorpha is washed, the water is removed by freeze drying, and the enteromorpha is oxidized after carbonization, so that the adsorption performance is improved; sesame stalks are rich in cellulose sources, and have porous structures after carbonization and oxidation, so that the adsorption effect of cellulose fibers can be improved.

The corn bran is burnt along with the straws in a large amount, so that the waste and the environment pollution are realized, the corn bran pulp is dissolved by ionic liquid chlorinated 1-allyl-3-methylimidazole for spinning, the development direction of future green production is met, the wet spinning is adopted, the forming is sufficient in a coagulating bath, the formed fiber is relatively uniform, and the physical and mechanical properties are good. The enteromorpha, the sesame stalk and the corn bran are used as raw materials for preparing the regenerated cellulose fiber, the defect of insufficient raw materials of the regenerated cellulose fiber is overcome, a textile raw material with sufficient resources, high quality and low price is provided for the textile industry, and the prepared regenerated cellulose fiber has the advantages of good mechanical property and excellent adsorbability.

Preferably, the carbide is also added with an antibacterial agent, and the mass ratio of the antibacterial agent to the carbide is 0.1-0.3: 1.

By adopting the technical scheme, since various microorganisms such as bacteria and fungi are inevitably contacted in life and diseases are transmitted by means of contact and the like, the antibacterial agent is added into the carbide, and the antibacterial agent is loaded in the regenerated cellulose fiber along with wet spinning of the spinning solution, so that the regenerated cellulose fiber has antibacterial effect.

Preferably, the antibacterial agent is prepared by the following method:

(1) soaking 2-4 parts by weight of spirulina powder in 4-5 parts by weight of silver nitrate solution with the mass percent concentration of 35-40%, centrifuging, washing with deionized water until the pH value is 6-8, drying at 60-80 ℃, uniformly mixing with 3-5 parts by weight of sodium alginate solution with the mass percent concentration of 1-3% and 3-5 parts by weight of glutaraldehyde, and stirring at the constant temperature of 50-60 ℃ for 1-2 hours;

(2) uniformly stirring 10-30 parts by weight of 2-4% chitosan acetic acid solution, 0.05-0.15 part by weight of ammonium acetate and 10-15 parts by weight of n-amyl alcohol, then dropwise adding the product obtained in the step (1), stirring while dropwise adding, freeze-drying, drying at 98-100 ℃ for 30-40min, and soaking with absolute ethyl alcohol for 20-24 h.

By adopting the technical scheme, the spirulina is a macroporous mesoporous solid with the pore diameter of more than 50nm, has large adsorption capacity and high adsorption speed, and can be used as a carrier for loading nano silver particles, thereby changing waste into valuable, reducing the cost of the antibacterial agent on one hand, and being beneficial to environmental protection on the other hand. After nano silver particles are loaded in a cavity of the spirulina powder, chitosan and sodium alginate are used as wall materials, the silver-loaded spirulina is coated in a composite film formed by the chitosan and the sodium alginate, ammonium acetate and n-amyl alcohol are used as pore-forming agents, uniform and communicated pores are formed on the composite film, the coated silver-loaded spirulina powder is conveniently released, and therefore the slow-release antibacterial agent is prepared, and the antibacterial durability of regenerated cellulose fibers is prolonged; in addition, the enteromorpha contains rich enteromorpha polysaccharide, the activity of the enteromorpha polysaccharide is strong, and the enteromorpha polysaccharide serving as a catalyst of the spirulina powder can enable the spirulina powder to better exert the algae activity and further improve the sterilization effect; in addition, the addition of the glutaraldehyde can increase the crosslinking between the chitosan and the spirulina, and the hydroxyl on the surface of the chitosan can generate hydrogen bond action with the glutaraldehyde, so that the surface free energy of the coated spirulina is reduced, thereby improving the dispersibility of the antibacterial agent in the spinning solution and preventing the aggregation of the antibacterial agent.

Preferably, in the spinning step, before wet spinning, essence microcapsules are added into the spinning solution, the mixture is uniformly mixed, and then wet spinning is performed, wherein the mass ratio of the essence microcapsules to the spinning solution is 0.05-0.1: 1.

By adopting the technical scheme, the fragrance has special functions of optimizing the environment and optimizing the personal image, can influence the emotion of people, eliminate fatigue, delight the body and mind and improve the working efficiency, and in order to improve the added value of the regenerated cellulose fiber, the essence microcapsules are added into the regenerated cellulose fiber, so that the monotonous fragrance is diversified and humanized, and the high-quality living needs pursued by people can be met.

Preferably, the essence microcapsule is prepared by the following method: emulsifying 1-3 parts by weight of essence, 2-4 parts by weight of styrene-maleic anhydride copolymer solution with the mass percentage concentration of 10-15%, 0.1-0.5 part by weight of emulsifier and 10-20 parts by weight of deionized water for 10-20min, adjusting the pH value to 3-5, adding 6-10 parts by weight of melamine resin and 0.5-1 part by weight of polyvinyl alcohol, heating to 70-80 ℃, adjusting the pH value to 6-7, performing suction filtration, and drying to constant weight.

By adopting the technical scheme, the melamine resin is used as the wall material and is coated on the surface of the essence under the action of components such as styrene-maleic anhydride copolymer, and the like, and the polyvinyl alcohol is added to improve the coating rate of the melamine resin, has a dispersing and emulsifying effect, can be partially adsorbed on the surface of the wall material, contributes to improving the stability of the wall material and the binding force of the melamine resin and the essence, and improves the stability of the microcapsule.

Preferably, the essence microcapsule is pretreated by the following steps before being added into the spinning solution:

mixing 3-5 parts by weight of nano silicon dioxide, 0.1-0.5 part by weight of sodium dodecyl sulfate, 1-1.5 parts by weight of silane coupling agent aqueous solution with the mass percent concentration of 1-1.5% and 1-2 parts by weight of polydimethylsiloxane, ultrasonically dispersing for 1-2h, adding 3-5 parts by weight of essence microcapsules, adjusting the pH value to 5-7, stirring for 1-2h, centrifuging, washing and drying.

By adopting the technical scheme, the particles of the nano-silica are dispersed in the aqueous solution of the silane coupling agent, and a network-like structure is formed due to the interaction and the restraint among the particles in the solution, so that the viscosity of a solution system is increased, the silane coupling agent can introduce active groups to the surface of the nano-silica, and the silica is loaded on the surface of the essence microcapsule to improve the roughness of the essence microcapsule, and the hydroxyl on the surface of the nano-silica loaded on the surface of the essence microcapsule can react with the hydroxyl in the spinning solution to increase the binding force between the essence microcapsule and the spinning solution, prevent the essence microcapsule from being separated from regenerated cellulose fibers, and further improve the fragrance durability of the essence microcapsule; and the polydimethylsiloxane improves the hydrophobicity of the nano silicon dioxide, so that the water washing resistance of the essence microcapsule is improved, and the fragrance durability of the essence microcapsule is further improved.

Preferably, in the spinning step, the coagulation bath is distilled water, the temperature is 60-80 ℃, and the length of the coagulation bath is 1-3 m.

Through adopting above-mentioned technical scheme, the coagulating bath enables the fibre to form fast, and the temperature that makes the coagulating bath is 60-80 ℃, can prevent the high temperature, the going on of the surperficial layer of too fast solidification prevention double diffusion for the loudness and the crystallinity of removing of amorphous region reduce in the cellulose, thereby lead to the fibre intensity to reduce, prevent in addition that the temperature is too low, the temperature of double diffusion is slower, the solidification speed of spinning trickle is slower, under certain tensile stretch, solidification insufficient strand silk takes place the slip and fracture between the molecule easily, lead to the fibre intensity to reduce.

Preferably, in the step of preparing the corn bran regenerated cellulose fiber spinning solution, the homogenizing time is 3-5 times, and the rotating speed of each homogenizing is 14000-.

By adopting the technical scheme, during homogenization, if the rotating speed is too large, the shearing stress is larger, so that the corn bran fiber pulp is easier to break, the dissolution of the corn bran fiber pulp in the ionic liquid is promoted, the dissolution is more sufficient at a higher speed, but when the rotating speed exceeds 16000r/min, the molecular long chains of the cellulose in the corn bran are sheared, a large amount of degradation is generated, and the mechanical property of the regenerated cellulose fiber is reduced.

Preferably, in the step of preparing the carbon nanomaterial, the oxidant is one of potassium permanganate or phosphorus pentoxide.

By adopting the technical scheme, potassium permanganate or phosphorus pentoxide can oxidize carbides formed by calcining enteromorpha and sesame stalks, so that the adsorption capacity of the carbides is enhanced, and the adsorption and deodorization effects of regenerated cellulose fibers are improved.

Preferably, in the step of preparing the carbon nano-material, the acid solution is 10-30% of hydrochloric acid or 30-50% of sulfuric acid by mass percent.

By adopting the technical scheme, the carbide is soaked in the acid solution, impurities in the carbide are removed, and the porosity of the surface of the carbide is increased.

In summary, the present application has the following beneficial effects:

1. the enteromorpha, the sesame stalk and the corn bran are preferably adopted as the raw materials of the regenerated cellulose fiber, so that the method is favorable for environmental protection, improves the utilization rate of the enteromorpha, the sesame stalk and the corn bran, realizes the reutilization of waste, changes waste into valuable, reduces the production cost, meets the requirement of the state for vigorously developing new regenerated biological materials, and provides a textile raw material with sufficient resources, high quality and low price for the regenerated cellulose fiber.

2. The preferred adoption spirulina carries nanometer silver granule in this application to the antibacterial agent is made to the wall material that cladding sodium alginate and chitosan formed, wherein use ammonium acetate and n-amyl alcohol as the pore-forming agent, the release of the spirulina powder of carrying silver of being convenient for, spirulina powder and waterside tongue mutually support, can improve the antibiotic effect of regenerated cellulose fibre, and glutaraldehyde can increase the cross-linking of spirulina and chitosan, reinforcing adsorptivity, thereby make regenerated cellulose fibre have antibiotic and adsorptivity strong, advantage that deodorization effect is good.

3. In the application, the essence microcapsules are preferably added into the spinning solution, so that the regenerated cellulose fiber has the advantages of air permeability, comfort, moisture absorption and softness of common cellulose fiber, the defects of natural cellulose fiber and traditional regenerated cellulose fiber are overcome, the excellent aromatic performance is improved, and the good development prospect is realized.

Detailed Description

Preparation examples 1 to 5 of antibacterial agent

The spirulina powder of preparation examples 1-5 is selected from Qingdao Haiweisen Biotech Co., Ltd, cat # 1011; the chitosan is selected from Shanxi Munsen Biotech, Inc. with model number of 34.

Preparation example 1: (1) crushing 2kg of spirulina powder to 20nm, soaking in 4kg of silver nitrate solution with the mass percentage concentration of 35%, centrifuging at the rotating speed of 4500r/min for 10min, washing with deionized water until the pH value is 6, drying at 60 ℃, uniformly mixing with 3kg of sodium alginate solution with the mass percentage concentration of 3% and 3kg of glutaraldehyde, and stirring at the constant temperature of 60 ℃ for 2 h; (2) uniformly stirring 10kg of chitosan acetic acid solution with the mass percentage concentration of 2%, 0.05kg of ammonium acetate and 10kg of n-amyl alcohol, then dropwise adding the product obtained in the step (1), stirring while dropwise adding, freeze-drying, drying at 98 ℃ for 40min, soaking for 20h at room temperature by using absolute ethyl alcohol, wherein the pre-freezing temperature during freeze-drying is-60 ℃, the pre-freezing time is 1h, and then freezing for 20h at-20 ℃.

Preparation example 2: (1) crushing 4kg of spirulina powder to 20nm, soaking in 5kg of silver nitrate solution with the mass percentage concentration of 40%, centrifuging at the rotating speed of 4500r/min for 10min, washing with deionized water until the pH value is 8, drying at 80 ℃, uniformly mixing with 5kg of sodium alginate solution with the mass percentage concentration of 1% and 5kg of glutaraldehyde, and stirring at the constant temperature of 50 ℃ for 1 h; (2) uniformly stirring 30kg of chitosan acetic acid solution with the mass percentage concentration of 4%, 0.15kg of ammonium acetate and 15kg of n-amyl alcohol, then dropwise adding the product obtained in the step (1) while stirring, freeze-drying, drying at 100 ℃ for 30min, soaking with absolute ethyl alcohol at room temperature for 24h, wherein the pre-freezing temperature during freeze-drying is-60 ℃, the pre-freezing time is 1h, and then freezing at-20 ℃ for 20 h.

Preparation example 3: the difference from preparation example 1 is that no spirulina powder was added.

Preparation example 4: the difference from preparation example 1 is that ammonium acetate and n-pentanol are not added.

Preparation example 5: the difference from preparation example 1 is that glutaraldehyde was not added.

Preparation examples 6 to 8 of essence microcapsules

The melamine resin in preparation examples 6-8 is selected from Luo Yang Ye square New Material Co., Ltd, model number TF-780; the polyvinyl alcohol is selected from Guangzhou Qigsheng chemical company, model number 1788; OP-10 is selected from Zheng Tianen chemical products, Inc.; the lavender essence is selected from Shandong blue eagle chemical science and technology company, and has a model of LDY 1126; the styrene-maleic anhydride copolymer is selected from Luo-yang light-coupled New materials Co., Ltd, and is YF 652.

Preparation example 6: emulsifying 1kg essence, 2kg water solution of styrene-maleic anhydride copolymer with mass percent concentration of 10%, 0.1kg emulsifier and 10kg deionized water for 10min, adjusting pH to 3, adding 6kg melamine resin and 0.5kg polyvinyl alcohol, heating to 70 deg.C, adjusting pH to 6, vacuum filtering, drying to constant weight, wherein the essence is lavender essence and the emulsifier is OP-10.

Preparation example 7: emulsifying 3kg of essence, 4kg of styrene-maleic anhydride copolymer solution with the mass percentage concentration of 15%, 0.5kg of emulsifier and 20kg of deionized water for 20min, adjusting the pH to 5, adding 10kg of melamine resin and 1kg of polyvinyl alcohol, heating to 80 ℃, adjusting the pH to 7, performing suction filtration, and drying to constant weight, wherein the essence is lavender essence and the emulsifier is OP-10.

Preparation example 8: the difference from preparation example 6 is that polyvinyl alcohol was not added.

Examples

Tianshi Landun-ZW 48 is selected from Nanjing Tianshi Landun Biotech Co., Ltd; RX-xj type essence microcapsule is selected from Hefeizxue New Material Co; the Enteromorpha is selected from offshore islands, and the sesame stalk is selected from the region of Staumph.

Example 1: a method for preparing pure spinning regenerated cellulose fiber raw strips comprises the following steps:

s1, preparing the carbon nano material: respectively cleaning sesame stalks and enteromorpha, then crushing to 100 meshes, mixing, freeze-drying, heating to 300 ℃ in a nitrogen atmosphere, calcining for 50min to prepare carbide, adding an oxidant, uniformly stirring, drying at 60 ℃, soaking with an acid solution, washing to neutrality, and vacuum-drying to prepare a carbon nano material, wherein the mass ratio of the sesame stalks, the enteromorpha and the oxidant is 1:0.5:5, the freeze-drying temperature is-20 ℃, the time is 10h, the acid solution is hydrochloric acid with the mass percentage concentration of 10%, and the oxidant is potassium permanganate;

s2, preparing a corn bran regenerated cellulose fiber spinning solution: cleaning and crushing corn husks to prepare corn husk pulp, adding the corn husk pulp into chlorinated 1-allyl-3-methylimidazole which is dried in vacuum at 90 ℃ for 12 hours, uniformly mixing, homogenizing for 3 times at 70 ℃ and under vacuum conditions, wherein the rotating speed of each homogenization is 16000r/min, filtering, defoaming the filtrate under-0.0.1 MPa for 12 hours to prepare a corn husk regenerated cellulose fiber spinning solution, wherein the mass ratio of the corn husk pulp to the chlorinated 1-allyl-3-methylimidazole is 0.3: 1;

s3, preparing a spinning solution: dispersing carbon nano materials in water or absolute ethyl alcohol, performing ultrasonic dispersion to form carbon nano material dispersion liquid with the mass percentage concentration of 10%, adding the carbon nano material dispersion liquid into the corn bran regenerated cellulose fiber spinning solution, shearing and blending to prepare spinning stock solution, wherein the mass ratio of the carbon nano material dispersion liquid to the corn bran regenerated cellulose fiber spinning solution is 3: 7;

s4, spinning: carrying out wet spinning on the spinning solution, forming pure spinning regenerated cellulose fibers by a coagulating bath, wherein the temperature of the spinning solution is 70 ℃, the spinning speed is 300m/min, the air gap is 10mm, the coagulating bath is distilled water, the temperature of the coagulating bath is 60 ℃, the length is 3m, and the drafting multiple is 1.1 times;

s5, preparing raw strips: and opening and carding the pure-spun regenerated cellulose fibers to prepare the pure-spun regenerated cellulose fiber raw sliver.

Example 2: a method for preparing a pure-spun regenerated cellulose fiber raw sliver, which is different from the method in example 1 in that:

s1, preparing the carbon nano material: respectively cleaning sesame stalks and enteromorpha, then crushing the cleaned sesame stalks and enteromorpha into 100 meshes, mixing, freeze-drying, heating to 600 ℃ in a nitrogen atmosphere, calcining for 30min to prepare carbides, adding an oxidant, uniformly stirring, drying at 80 ℃, soaking in an acid solution, washing to neutrality, and vacuum-drying to prepare a carbon nano material, wherein the mass ratio of the sesame stalks, the enteromorpha and the oxidant is 1:1:1, the freeze-drying temperature is-20 ℃, the time is 10h, the acid solution is sulfuric acid with the mass percentage concentration of 10%, and the oxidant is phosphorus pentoxide;

s2, preparing a corn bran regenerated cellulose fiber spinning solution: cleaning and crushing corn husks to prepare corn husk pulp, adding the corn husk pulp into chlorinated 1-allyl-3-methylimidazole which is dried for 10 hours in vacuum at the temperature of 70 ℃, uniformly mixing, homogenizing for 5 times under the conditions of 90 ℃ and vacuum, wherein the rotating speed of each homogenization is 14000r/min, filtering, defoaming the filtrate for 12 hours at the pressure of-0.0.1 MPa to prepare a corn husk regenerated cellulose fiber spinning solution, wherein the mass ratio of the corn husk pulp to the chlorinated 1-allyl-3-methylimidazole is 0.5: 1;

s3, preparing a spinning solution: dispersing carbon nano materials in water or absolute ethyl alcohol, performing ultrasonic dispersion to form carbon nano material dispersion liquid with the mass percentage concentration of 10%, adding the carbon nano material dispersion liquid into the corn bran regenerated cellulose fiber spinning solution, shearing and blending to prepare spinning stock solution, wherein the mass ratio of the carbon nano material dispersion liquid to the corn bran regenerated cellulose fiber spinning solution is 3: 12;

s4, spinning: carrying out wet spinning on the spinning solution, forming pure spinning regenerated cellulose fibers by a coagulating bath, wherein the temperature of the spinning solution is 70 ℃, the air gap is 10mm, the spinning speed is 300m/min, the coagulating bath is distilled water, the temperature of the coagulating bath is 80 ℃, the length of the coagulating bath is 3m, and the drafting multiple is 1.1 times;

s5, preparing raw strips: and opening and carding the pure-spun regenerated cellulose fibers to prepare the pure-spun regenerated cellulose fiber raw sliver.

Example 3: a method for preparing pure spinning regenerated cellulose fiber raw strips is different from the method in the embodiment 1 in that in the step S2, the homogenizing times are 9 times, and the homogenizing rotating speed is 20000r/min each time.

Example 4: a method for preparing a pure-spun regenerated cellulose fiber raw sliver is different from the method in example 1 in that in step S1, an antibacterial agent is added into carbide, the mass ratio of the antibacterial agent to the carbide is 0.3:1, and the antibacterial agent is selected from Shilangen-ZW 48.

Example 5: a method for preparing a pure-spun regenerated cellulose fiber sliver is different from the method in the example 1 in that in the step S1, an antibacterial agent is added into carbide, the mass ratio of the antibacterial agent to the carbide is 0.3:1, and the antibacterial agent is selected from the preparation example 1 of the antibacterial agent.

Examples 6 to 9: a method of producing a pure spun regenerated cellulose fiber sliver, which differs from example 5 in that the antimicrobial agent is selected as shown in table 1.

TABLE 1 selection of antibacterial agents in examples 5-9

Example 10: the difference between the preparation method of the pure-spinning regenerated cellulose fiber raw sliver and the embodiment 5 is that in the step S4, essence microcapsules are added into spinning solution, the mixture is uniformly mixed and then wet spinning is carried out, the mass ratio of the essence microcapsules to the spinning solution is 0.1:1, and the type of the essence microcapsules is RX-xj.

Example 11: a method for preparing pure spinning regenerated cellulose fiber raw strips, which is different from the embodiment 10 in that essence microcapsules are prepared from the preparation 6.

Example 12: a method for preparing pure spinning regenerated cellulose fiber raw strips, which is different from the embodiment 10 in that essence microcapsules are prepared from the preparation 7.

Example 13: a method for preparing pure spinning regenerated cellulose fiber raw strips, which is different from the embodiment 10 in that essence microcapsules are prepared from the preparation 8.

Example 14: a method for preparing pure spinning regenerated cellulose fiber raw sliver, which is different from the embodiment 11 in that the essence microcapsule is pretreated by the following steps before being added into spinning solution: mixing 3kg of nano silicon dioxide, 0.1kg of sodium dodecyl sulfate, 1kg of silane coupling agent aqueous solution with the mass percent concentration of 1.5% and 1kg of polydimethylsiloxane, ultrasonically dispersing for 1h, adding 3kg of essence microcapsules, adjusting the pH value to 5, stirring for 2h, centrifuging, washing and drying, wherein the silane coupling agent is gamma-aminopropyltrimethoxysilane.

Example 15: a method for preparing a pure-spun regenerated cellulose fiber sliver, which is different from the method in example 14 in that no silane coupling agent is added.

Example 16: a method of making a pure spun regenerated cellulose fiber sliver, which differs from example 14 in that no polydimethylsiloxane is added.

Example 17: the preparation method of the pure-spun regenerated cellulose fiber raw sliver is different from the embodiment 11 in that the pure-spun regenerated cellulose fiber raw sliver is subjected to post-treatment by using essence microcapsules, and the post-treatment method comprises the following steps: mixing the essence microcapsule with water to obtain 50% treating solution, and padding the raw strips in the treating solution to obtain 60% residue.

Comparative example

Comparative example 1: the difference between the preparation method of the pure-spinning regenerated cellulose fiber raw strip and the embodiment 1 is that enteromorpha is not added when the carbon nano material is prepared.

Comparative example 2: a method for preparing a pure-spun regenerated cellulose fiber raw sliver, which is different from the method of example 1 in that sesame stalks are not added in the preparation of the carbon nanomaterial.

Comparative example 3: a method of preparing regenerated cellulose fibers comprising the steps of:

(1) adding 20 parts by weight of cotton pulp, 10 parts by weight of wood pulp and 70 parts by weight of bamboo pulp into an aqueous solution of N-methylmorpholine-N-oxide, then adding antioxidant propyl gallate, stirring for 60 minutes at 90 ℃, fully soaking the raw materials to obtain a premixed solution, wherein in the cotton pulp, the wood pulp and the bamboo pulp, the content of methyl cellulose is respectively: 95.1%, 95.3%, 95.4%, the total content of heavy metals being less than 0.07%, the average degree of polymerization being 540, 535, 500, respectively, the mass fraction of N-methylmorpholine-N-oxide in the aqueous solution being 68.0%, the ratio of the total weight of the individual pulps to the total weight of the aqueous solution of N-methylmorpholine-N-oxide being 1: 20, the addition amount of the propyl gallate is 0.2 percent of the total weight of the methylcellulose;

(2) adding the premixed solution obtained in the step (1) into a film evaporation vacuumizing device at 90 ℃, vacuumizing to enable the vacuum degree to be-0.08 MPa, standing for 10min, finally completely dissolving each pulp to obtain spinning stock solution, wherein the content of alpha fibers in the obtained spinning stock solution is 12.1%, the viscosity is 14000Pa & s, and filtering the obtained spinning stock solution to remove impurities;

(3) and (3) adding the spinning solution obtained in the step (2) into a spinning machine for spinning at 98 ℃, enabling the spinning solution to enter an air bath after being sprayed out, then enabling the spinning solution to be in contact with an aqueous solution of N-methylmorpholine-N-oxide with the mass percent of 20%, enabling the temperature of the spinning bath to be 20 ℃, obtaining regenerated cellulose fibers after re-precipitation, then collecting the obtained regenerated cellulose fibers, putting the regenerated cellulose fibers into a washing machine for washing, bleaching and oiling in sequence, and finally drying for 12 minutes at 125 ℃ by using a chain plate type dryer.

Performance test

Regenerated cellulose fibers were prepared according to the methods in the respective examples and comparative examples, and the properties of the regenerated cellulose fibers were measured according to the following methods, and the results of the measurements are recorded in table 2.

1. Dry and wet breaking strength and elongation at break: testing according to GB/T14463 and 2008 viscose staple fiber; 2. the bacteriostasis rate is as follows: soaping according to GB/T8629-2001 family washing and drying degree for textile test, wherein the soaping temperature is 40 ℃, and after 100 soaping, according to GB/T20944.3-2008 evaluation part 3 of antibacterial performance of textiles: detecting by an oscillation method;

3. adsorption rate: taking 25g of the regenerated cellulose fibers prepared in each example or comparative example, respectively adding 1.25mL of volatile liquid into a glass container (the regenerated cellulose fibers are in contact with the liquid), sealing and storing in a dark place, detecting the change of the concentration of volatile substances in the glass container by using a gas chromatography-mass spectrometer after 24 hours, and recording the change rate;

4. fragrance durability: the regenerated cellulose fibers prepared in each example or comparative example were soaped according to the method of GB/T8629-2001, Home Wash and drying for textile test, the soaping temperature was 50 ℃, the soaped regenerated cellulose fibers were evaluated for the presence of fragrance by 5 judges within 24 hours, the evaluation time of the judges did not exceed 15min until the regenerated cellulose fibers were odorless, and the number of fiber washes was tested.

TABLE 2 detection of properties of regenerated cellulose fibers

It can be seen from the data in table 2 that the carbon nanomaterial prepared from sesame straw and enteromorpha in examples 1 and 2 is then doped into the spinning solution prepared from corn bran as pulp, and the regenerated cellulose fiber prepared by wet spinning has the characteristics of good fiber performance, high strength and softness, and also has good adsorption and deodorization effects.

In example 3, the number of times of homogenizing the dope was increased and the rotation speed was increased, and the strength of the produced regenerated cellulose fiber was lowered, which means that the number of times of homogenizing was increased and the rotation speed was increased during homogenizing, and the pulp could not be dissolved more sufficiently, and the cellulose crystallinity was rather lowered.

In example 4, a commercially available antibacterial agent was added to the carbide as compared with example 1, and the data in table 2 shows that the antibacterial rate of the regenerated cellulose fiber against escherichia coli and staphylococcus aureus was significantly increased after 100 soapings.

Example 5 and example 6 use the antibacterial agents prepared in preparation examples 1 and 2, respectively, and compared with example 4, the regenerated cellulose fibers prepared in examples 5 and 6 still have an antibacterial rate of more than 90% after 100 soaping, the antibacterial durability is further enhanced, and the adsorbability and the deodorization effect are further improved.

In example 7, the antibacterial ratio of the regenerated cellulose fibers was lower than in examples 5 and 6 because no spirulina powder was added during the preparation of the antibacterial agent, as compared with example 5.

Example 8 with the antibacterial agent prepared in preparation example 4, the antibacterial rate of the regenerated cellulose fiber was decreased after 100 soaping and the adsorption effect of formaldehyde and ammonia gas was reduced compared to example 5.

In example 9, the antimicrobial agent prepared in preparation example 5 was used, and it can be seen from the data in table 2 that the antimicrobial agent prepared without glutaraldehyde had little effect on the bacteriostatic ratio of the regenerated cellulose fibers, but decreased the adsorbability of the regenerated cellulose fibers.

Example 10 compared with example 5, the perfume microcapsule is added into the spinning solution, and as can be seen from the data in table 2, the perfume of the regenerated cellulose fiber prepared in example 10 is completely lost after 18 times of soaping, and the perfume persistence of the regenerated cellulose fiber is improved compared with example 5.

In examples 11 and 12, compared with example 10, the regenerated cellulose fiber is soaped more than 25 times, and the fragrance is completely lost, which shows that the fragrance microcapsules prepared in preparation examples 6 and 7 of the present application can effectively improve the retention of the fragrance.

The regenerated cellulose fiber prepared in example 13 is safe in fragrance loss after being soaped 21 times, and compared with example 10, the fragrance durability of the regenerated cellulose fiber is reduced, which shows that the polyvinyl alcohol can improve the fragrance durability of the essence microcapsule.

Compared with example 11, in example 14, the essence microcapsules are pretreated by using nano-silica, a silane coupling agent and the like, and table 2 shows that the fragrance of the regenerated cellulose fiber prepared in example 14 is completely lost after being soaped for 38 times, which indicates that the pretreatment of the essence microcapsules can increase the adhesion between the essence microcapsules and the regenerated cellulose fiber and increase the durability.

Example 15 compared with example 14, when the essence microcapsule is pretreated, the silane coupling agent is not added, the silicon dioxide can not be loaded on the surface of the essence microcapsule, and after 33 times of washing, the fragrance of the essence microcapsule is lost.

Example 16 compared to example 14, when the perfume micro-capsule was pre-treated, without using polydimethylsiloxane, the hydrophobicity of the silica surface was reduced and the binding force with the surface of regenerated cellulose fiber was weakened, so that there was no perfume at all in 34 soapings.

Example 17 post-treatment of the regenerated cellulose fiber with perfume microcapsules, which adhere to the surface of the fiber and are easily removed from the fiber after washing and stirring, resulted in loss of flavor.

Comparative examples 1 and 2 compared with example 1, when preparing the carbon nanomaterial, the enteromorpha and the sesame stalk are not added respectively, and it can be seen from the data in table 2 that the regenerated cellulose fibers prepared in comparative examples 1 and 2 have reduced adsorbability and reduced deodorization effect.

Comparative example 3 is a regenerated cellulose fiber prepared in the prior art using cotton pulp, bamboo pulp and wood pulp as raw materials, which has dry and wet breaking strengths and dry and wet elongation at break not much different from those of example 1, but the regenerated cellulose fiber prepared in example 1 has more excellent adsorbability and deodorizing effect.

The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.