CN113832561B - Preparation method of pure spinning regenerated cellulose fiber raw strip - Google Patents
Preparation method of pure spinning regenerated cellulose fiber raw strip Download PDFInfo
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- CN113832561B CN113832561B CN202111244135.9A CN202111244135A CN113832561B CN 113832561 B CN113832561 B CN 113832561B CN 202111244135 A CN202111244135 A CN 202111244135A CN 113832561 B CN113832561 B CN 113832561B
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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
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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
- 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
- D01F1/10—Other agents for modifying properties
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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
- 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
- D01F1/10—Other agents for modifying properties
- D01F1/103—Agents inhibiting growth of microorganisms
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01G—PRELIMINARY TREATMENT OF FIBRES, e.g. FOR SPINNING
- D01G15/00—Carding machines or accessories; Card clothing; Burr-crushing or removing arrangements associated with carding or other preliminary-treatment machines
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01G—PRELIMINARY TREATMENT OF FIBRES, e.g. FOR SPINNING
- D01G9/00—Opening or cleaning fibres, e.g. scutching cotton
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Abstract
The application relates to the field of textile fibers, and particularly discloses a preparation method of a pure spinning regenerated cellulose fiber raw strip, which comprises the following steps: preparing a carbon nanomaterial; preparing corn husk regenerated cellulose fiber spinning solution: cleaning corn husk, pulverizing to obtain corn husk pulp, adding into 1-allyl-3-methylimidazole chloride, mixing, homogenizing at 70-90deg.C under vacuum, filtering, and defoaming the filtrate to obtain corn husk regenerated cellulose fiber spinning solution; preparing spinning solution; spinning; preparing 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 aromatic flavor and high added value.
Description
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 strip.
Background
The regenerated cellulose fiber is prepared by taking natural cellulose as a raw material and regenerating. The regenerated cellulose fiber has good hygroscopicity, drapability, easy dyeing and biodegradability, is widely used for weaving, thread 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 from wood pulp, bamboo pulp, cotton pulp and the like serving as raw materials by a viscose method or a solvent method.
In the prior art, a preparation method of regenerated cellulose fibers is disclosed in Chinese patent application No. CN201610424631.5, wherein (1) pulp is added into an aqueous solution of N-methylmorpholine-N-oxide, and then an antioxidant is added for stirring and premixing to obtain a premix, and 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 premix in a vacuum environment at 80-90 ℃ to obtain spinning stock solution; (3) Spinning the spinning solution to obtain 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, people attach importance to living environment, and the nationality is proposing to improve the national forest coverage rate, limit the deforestation of forests, influence the source of regenerated cellulose, thus actively developing a new cellulose source, and being very important.
Disclosure of Invention
In order to make up for the deficiency of the supply of the existing regenerated cellulose fiber pulp raw materials and add a new raw material source for regenerated cellulose fibers, the application provides a preparation method of pure spinning regenerated cellulose fiber raw strips.
In a first aspect, the present application provides a method for preparing a pure spun regenerated cellulose fiber raw strip, which adopts the following technical scheme:
the preparation method of the pure spinning regenerated cellulose fiber raw strip comprises the following steps:
preparing a carbon nanomaterial: respectively cleaning sesame stems and enteromorpha, pulverizing, mixing, freeze-drying, heating to 300-600 ℃ in an inert atmosphere, calcining for 30-50min to obtain carbide, adding an oxidant, uniformly stirring, drying at 60-80 ℃, soaking in an acid solution, washing to neutrality, and vacuum-drying to obtain a carbon nanomaterial, wherein the mass ratio of the sesame stems to the enteromorpha to the oxidant is 1:0.5-1:1-5;
preparing corn husk regenerated cellulose fiber spinning solution: cleaning corn husks, crushing to prepare corn husks pulp, adding the corn husks pulp into chlorinated 1-allyl-3-methylimidazole, uniformly mixing, homogenizing and filtering at the temperature of 70-90 ℃ under the vacuum condition, and defoaming filtrate to prepare a corn husks regenerated cellulose fiber spinning solution, wherein the mass ratio of the corn husks pulp to the chlorinated 1-allyl-3-methylimidazole is 0.3-0.5:1;
preparing a spinning solution: dispersing a carbon nano material in water or absolute ethyl alcohol, performing ultrasonic dispersion to form a carbon nano material dispersion liquid with the mass percentage concentration of 10-15%, adding the carbon nano material dispersion liquid into corn husk regenerated cellulose fiber spinning liquid, and performing shearing blending to prepare spinning stock solution, wherein the mass ratio of the carbon nano material dispersion liquid to the corn husk regenerated cellulose fiber spinning liquid is 3:7-12;
spinning: wet spinning is carried out on the spinning solution, and pure spinning regenerated cellulose fibers are formed through coagulating bath;
preparing raw strips: the pure spinning regenerated cellulose fiber is subjected to opening and carding to prepare the pure spinning regenerated cellulose fiber raw strip.
By adopting the technical scheme, the enteromorpha grows faster, the resources are rich, but the enteromorpha is often attached to other breeding organisms, so that the breeding is endangered to a certain extent, the island is in offshore mass enteromorpha flooding in the present year, how to change waste into valuable is realized, and the application value of the enteromorpha is widely focused and studied. The enteromorpha is washed to remove salt, sand and other impurities, then freeze-dried to remove water, carbonized and oxidized, and the adsorption performance is improved; sesame seed stems are rich cellulose sources, and have porous structures after carbonization and oxidation, so that the adsorption effect of cellulose fibers can be improved.
The corn husks are burnt in a large amount along with the straws, waste and pollute the environment, the ionic liquid chloridized 1-allyl-3-methylimidazole is adopted to dissolve corn husks pulp for spinning, the development direction of future green production is met, the wet spinning is adopted, the forming is sufficient in a coagulating bath, and the formed fibers are uniform and have good physical and mechanical properties. The enteromorpha, the sesame seed stems and the corn husks are used as raw materials for preparing the regenerated cellulose fibers, so that the defect of insufficient raw materials of the regenerated cellulose fibers is overcome, a textile raw material with sufficient resources, high quality and low cost is provided for textile industry, and the prepared regenerated cellulose fibers have the advantages of good mechanical properties and excellent adsorptivity.
Preferably, an antibacterial agent is also added into the carbide, and the mass ratio of the antibacterial agent to the carbide is 0.1-0.3:1.
By adopting the technical scheme, various microorganisms such as bacteria and fungi are inevitably contacted in life, diseases are transmitted through the modes of contact and the like, an antibacterial agent is added into carbide, and along with wet spinning of spinning stock solution, the antibacterial agent is loaded into regenerated cellulose fibers, so that the regenerated cellulose fibers have antibacterial effect.
Preferably, the antimicrobial agent is made by the following method:
(1) Soaking 2-4 parts by weight of spirulina powder in 4-5 parts by weight of 35-40% silver nitrate solution, centrifuging, washing with deionized water to pH 6-8, drying at 60-80 ℃, uniformly mixing with 3-5 parts by weight of 1-3% sodium alginate solution and 3-5 parts by weight of glutaraldehyde, and stirring at 50-60 ℃ for 1-2h at constant temperature;
(2) Uniformly stirring 10-30 parts by weight of chitosan acetic acid solution with the mass percentage concentration of 2-4%, 0.05-0.15 part by weight of ammonium acetate and 10-15 parts by weight of n-amyl alcohol, dropwise adding the product obtained in the step (1), stirring while dropwise adding, freeze-drying, drying at 98-100 ℃ for 30-40min, and soaking in absolute ethyl alcohol for 20-24 h.
By adopting the technical scheme, the spirulina is a macroporous mesoporous solid with the pore diameter larger than 50nm, has large adsorption capacity and high adsorption speed, and can be used as a carrier for loading nano silver particles, so that waste is changed into valuables, the cost of the antibacterial agent is reduced, and the environment is protected. After nano silver particles are loaded in a cavity of spirulina powder, chitosan and sodium alginate are adopted as wall materials, silver-loaded spirulina is coated in a composite film formed by the chitosan and the sodium alginate, ammonium acetate and n-amyl alcohol are adopted as pore-forming agents, uniform and internally communicated pores are formed on the composite film, and the coated silver-loaded spirulina powder is released conveniently, so that a slow-release antibacterial agent is prepared, and the antibacterial durability of regenerated cellulose fibers is prolonged; in addition, the enteromorpha contains rich enteromorpha polysaccharide, has strong activity, and can be used as a catalyst of the spirulina powder, so that the spirulina powder can better exert the activity of the algae, and the sterilization effect is further improved; in addition, the addition of glutaraldehyde can increase the cross-linking between chitosan and spirulina, and the hydroxyl on the surface of chitosan can generate hydrogen bond action with glutaraldehyde, so that the free energy on the surface of the coated spirulina is reduced, the dispersibility of the antibacterial agent in the spinning solution is improved, and the agglomeration of the antibacterial agent is prevented.
Preferably, in the spinning step, before wet spinning, essence microcapsules are added into the spinning solution, and after uniform mixing, 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 the special functions of optimizing the environment and optimizing the personal image, can influence the emotion of people, eliminate fatigue, pleasure body and mind and improve the working efficiency, and the essence microcapsules are added into the regenerated cellulose fibers to improve the added value of the regenerated cellulose fibers, so that the monotonous fragrance becomes diversified and humanized, and can meet the pursued high-quality living needs of people.
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, carrying out suction filtration, and drying to constant weight.
By adopting the technical scheme, melamine resin is used as the wall material, the wall material is coated on the surface of the essence under the action of components such as styrene-maleic anhydride copolymer, and the polyvinyl alcohol is added to improve the coating rate of the melamine resin, and has the dispersion and emulsification effects, so that the wall material can be partially adsorbed on the surface of the wall material, the stability of the wall material and the binding force of the melamine resin and the essence are improved, and the stability of the microcapsule is improved.
Preferably, the essence microcapsules are subjected to the following pretreatment before being added into the spinning solution:
mixing 3-5 parts by weight of nano silicon dioxide with 0.1-0.5 part by weight of sodium dodecyl sulfate, 1-1.5 parts by weight of 1-1.5% by weight of silane coupling agent aqueous solution and 1-2 parts by weight of polydimethylsiloxane, performing ultrasonic dispersion for 1-2 hours, adding 3-5 parts by weight of essence microcapsule, adjusting the pH value to 5-7, stirring for 1-2 hours, centrifuging, washing and drying.
By adopting the technical scheme, the particles of the nano silicon dioxide are dispersed in the aqueous solution of the silane coupling agent, and because the interaction among the particles in the solution is restricted to form a network-like structure, the viscosity of a solution system is increased, the silane coupling agent can introduce active groups to the surface of the nano silicon dioxide, so that the silicon dioxide is loaded on the surface of the essence microcapsule, the roughness of the essence microcapsule is improved, hydroxyl groups on the surface of the nano silicon dioxide loaded on the surface of the essence microcapsule can react with hydroxyl groups in the spinning stock solution, the binding force of the essence microcapsule and the spinning stock solution is increased, the essence microcapsule is prevented from being separated from regenerated cellulose fibers, and the fragrance durability of the essence microcapsule is improved; and the polydimethylsiloxane improves the hydrophobicity of the nano silicon dioxide, so that the 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 coagulating bath is distilled water, the temperature is 60-80 ℃, and the length of the coagulating bath is 1-3m.
By adopting the technical scheme, the coagulating bath can enable the fiber to be formed rapidly, the temperature of the coagulating bath is 60-80 ℃, the excessively high temperature and the excessively fast coagulating surface layer can be prevented from preventing double diffusion, the loudness and crystallinity of an amorphous region in cellulose are reduced, so that the fiber strength is reduced, in addition, the excessively low temperature and the double diffusion temperature are prevented, the coagulating speed of spinning trickle is slower, and under a certain tension stretching condition, the insufficiently coagulated silk is easy to slip among molecules and break, so that the fiber strength is reduced.
Preferably, in the step of preparing the corn husk regenerated cellulose fiber spinning solution, the homogenization times are 3-5 times, and the rotation speed of each homogenization is 14000-16000r/min.
By adopting the technical scheme, when homogenizing, if the rotating speed is too large, the shearing stress is large, so that the corn husk pulp is more easily crushed, the dissolving of the corn husk pulp in the ionic liquid is promoted, the higher the speed is, the more sufficient the dissolving is, and when the rotating speed exceeds 16000r/min, the long chain of the cellulose molecules in the corn husk is 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 and phosphorus pentoxide.
By adopting the technical scheme, the potassium permanganate or the phosphorus pentoxide can oxidize the carbide formed by calcining the enteromorpha and the sesame stalks, so that the adsorption capacity of the carbide is enhanced, and the adsorption and deodorization effects of the regenerated cellulose fiber are improved.
Preferably, in the step of preparing the carbon nanomaterial, the acid solution is 10-30% hydrochloric acid or 30-50% sulfuric acid by mass percent.
By adopting the technical scheme, the acid solution is used for soaking the carbide, so that impurities in the carbide are removed, and the porosity of the carbide surface is increased.
In summary, the present application has the following beneficial effects:
1. as the enteromorpha, the sesame seed stems and the corn husks are preferably adopted as the raw materials of the regenerated cellulose fibers, the environment is protected, the utilization rate of the enteromorpha, the sesame seed stems and the corn husks is improved, the waste is recycled, the waste is changed into valuable, the production cost is reduced, the requirements of the state on the development of regenerated biological new materials are met, and the textile raw materials with sufficient resources, high quality and low price are provided for the regenerated cellulose fibers.
2. According to the method, the spirulina is preferably used for loading nano silver particles, and the wall material formed by the sodium alginate and the chitosan is coated to prepare the antibacterial agent, wherein ammonium acetate and n-amyl alcohol are used as pore-forming agents, so that silver-loaded spirulina powder is released conveniently, the spirulina powder and enteromorpha are matched with each other, the antibacterial effect of regenerated cellulose fibers can be improved, and glutaraldehyde can increase the crosslinking of the spirulina and the chitosan, so that the adsorptivity is enhanced, and the regenerated cellulose fibers have the advantages of strong antibacterial property and adsorptivity and good deodorizing effect.
3. In the application, essence microcapsules are preferably added into the spinning solution, so that the regenerated cellulose fiber has the advantages of ventilation, comfort, moisture absorption and softness of common cellulose fiber, overcomes the defects of natural cellulose fiber and traditional regenerated cellulose fiber, increases the excellent aromatic performance and has good development prospect.
Detailed Description
Preparation examples 1 to 5 of antibacterial agents
The spirulina powder in preparation examples 1-5 is selected from Qingdao Haifenesin biotechnology Co., ltd, and has product number of 1011; the chitosan is selected from Shanxi Yun Sen Biotechnology Co., ltd, model 34.
Preparation example 1: (1) Crushing 2kg of spirulina powder to 20nm, soaking in 4kg of 35% silver nitrate solution by mass percent, centrifuging at a rotating speed of 4500r/min for 10min, washing with deionized water to pH value of 6, drying at 60 ℃, uniformly mixing with 3kg of 3% sodium alginate solution by mass percent and 3kg of glutaraldehyde, and stirring at a constant temperature of 60 ℃ for 2h; (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, dropwise adding the product obtained in the step (1), stirring while dropwise adding, freeze-drying, drying at 98 ℃ for 40min, soaking in absolute ethyl alcohol at room temperature for 20h, pre-freezing at-60 ℃ for 1h during freeze-drying, and then freezing at-20 ℃ for 20h.
Preparation example 2: (1) Crushing 4kg of spirulina powder to 20nm, soaking in 5kg of 40% silver nitrate solution by mass percent, centrifuging at a rotating speed of 4500r/min for 10min, washing with deionized water to pH value of 8, drying at 80 ℃, uniformly mixing with 5kg of 1% sodium alginate solution by mass percent and 5kg of glutaraldehyde, and stirring at a constant temperature of 50 ℃ for 1h; (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, dropwise adding the product obtained in the step (1), stirring while dropwise adding, freeze-drying, drying for 30min at 100 ℃, soaking in absolute ethyl alcohol at room temperature for 24h, pre-freezing at-60 ℃ for 1h during freeze-drying, and then freezing at-20 ℃ for 20h.
Preparation example 3: the difference from preparation example 1 is that spirulina powder was not added.
Preparation example 4: the difference from preparation 1 is that no ammonium acetate and no n-pentanol are added.
Preparation example 5: the difference from preparation example 1 is that glutaraldehyde was not added.
Preparation examples 6-8 of essence microcapsules
The melamine resin in preparation examples 6-8 was selected from Luoyang-side New Material Co., ltd, model TF-780; the polyvinyl alcohol is selected from Guangzhou Qiqi chemical industry Co., ltd, and the model is 1788; OP-10 is selected from Zhengzhou Tianen chemical products Co., ltd; the lavender essence is selected from Shandong blue eagle chemical technology Co., ltd, and the model is LDY1126; the styrene-maleic anhydride copolymer is selected from Luoyang-light-side New Material Co., ltd, model YF652.
Preparation example 6: emulsifying 1kg essence, 2kg of a 10% styrene-maleic anhydride copolymer aqueous solution, 0.1kg of an emulsifier and 10kg of deionized water for 10min, adjusting the pH to 3, adding 6kg of melamine resin and 0.5kg of polyvinyl alcohol, heating to 70 ℃, adjusting the pH to 6, carrying out suction filtration, and drying to constant weight, wherein the essence is lavender essence, and the emulsifier is OP-10.
Preparation example 7: 3kg of essence, 4kg of styrene-maleic anhydride copolymer solution with the mass percentage concentration of 15%, 0.5kg of emulsifying agent and 20kg of deionized water are emulsified for 20min, the pH is regulated to 5, 10kg of melamine resin and 1kg of polyvinyl alcohol are added, the temperature is raised to 80 ℃, the pH is regulated to 7, the suction filtration is carried out, the constant weight is reached, the essence is lavender essence, and the emulsifying agent is OP-10.
Preparation example 8: the difference from preparation example 6 is that no polyvinyl alcohol was added.
Examples
The Tianshi blue shield-ZW 48 is selected from Nanjing Tianshi blue shield biotechnology Co., ltd; RX-xj type essence microcapsule is selected from Hefei Ruixue New Material Co., ltd; the Enteromorpha prolifera is selected from the offshore of Qingdao, and the sesame seed stalk is selected from the region of a standing-horse shop.
Example 1: the preparation method of the pure spinning regenerated cellulose fiber raw strip comprises the following steps:
s1, preparing a carbon nanomaterial: respectively cleaning sesame stems and enteromorpha, pulverizing to 100 meshes, mixing, freeze-drying, heating to 300 ℃ in nitrogen atmosphere, calcining for 50min to obtain carbide, adding an oxidant, uniformly stirring, drying at 60 ℃, soaking in an acid solution, washing to neutrality, and vacuum-drying to obtain a carbon nanomaterial, wherein the mass ratio of the sesame stems to the enteromorpha to 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 percent concentration of 10%, and the oxidant is potassium permanganate;
s2, preparing corn husk regenerated cellulose fiber spinning solution: washing corn husks, crushing to prepare corn husks pulp, adding the corn husks pulp into chlorinated 1-allyl-3-methylimidazole which is dried in vacuum at 90 ℃ for 12 hours, uniformly mixing, homogenizing for 3 times at the temperature of 70 ℃ and under the vacuum condition, wherein the homogenizing rotating speed is 16000r/min each time, filtering, defoaming filtrate for 12 hours at-0.0.1 MPa, and preparing corn husks regenerated cellulose fiber spinning solution, wherein the mass ratio of the corn husks pulp to the chlorinated 1-allyl-3-methylimidazole is 0.3:1;
s3, preparing a spinning solution: dispersing a carbon nano material in water or absolute ethyl alcohol, performing ultrasonic dispersion to form a carbon nano material dispersion liquid with the mass percent concentration of 10%, adding the carbon nano material dispersion liquid into corn husk regenerated cellulose fiber spinning liquid, and performing shearing blending to prepare a spinning solution, wherein the mass ratio of the carbon nano material dispersion liquid to the corn husk regenerated cellulose fiber spinning liquid is 3:7;
s4, spinning: wet spinning is carried out on the spinning solution, pure spinning regenerated cellulose fibers are formed through a coagulating bath, 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 draft multiple is 1.1 times;
s5, preparing raw strips: the pure spinning regenerated cellulose fiber is subjected to opening and carding to prepare the pure spinning regenerated cellulose fiber raw strip.
Example 2: the preparation method of the pure spinning regenerated cellulose fiber raw strip is different from the embodiment 1 in that:
s1, preparing a carbon nanomaterial: respectively cleaning sesame stems and enteromorpha, pulverizing to 100 meshes, mixing, freeze-drying, heating to 600 ℃ in nitrogen atmosphere, calcining for 30min to obtain carbide, adding an oxidant, uniformly stirring, drying at 80 ℃, soaking in an acid solution, washing to neutrality, and vacuum-drying to obtain a carbon nanomaterial, wherein the mass ratio of the sesame stems to the enteromorpha to the oxidant is 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 corn husk regenerated cellulose fiber spinning solution: washing corn husks, crushing to prepare corn husks pulp, adding the corn husks pulp into chlorinated 1-allyl-3-methylimidazole which is dried in vacuum for 10 hours at 70 ℃, uniformly mixing, homogenizing for 5 times at the temperature of 90 ℃ and under the vacuum condition, wherein the homogenizing rotating speed is 14000r/min each time, filtering, defoaming filtrate for 12 hours at the pressure of minus 0.0.1MPa, and preparing corn husks regenerated cellulose fiber spinning solution, wherein the mass ratio of the corn husks pulp to the chlorinated 1-allyl-3-methylimidazole is 0.5:1;
s3, preparing a spinning solution: dispersing a carbon nano material in water or absolute ethyl alcohol, performing ultrasonic dispersion to form a carbon nano material dispersion liquid with the mass percent concentration of 10%, adding the carbon nano material dispersion liquid into corn husk regenerated cellulose fiber spinning liquid, and performing shearing blending to prepare a spinning solution, wherein the mass ratio of the carbon nano material dispersion liquid to the corn husk regenerated cellulose fiber spinning liquid is 3:12;
s4, spinning: wet spinning is carried out on the spinning solution, pure spinning regenerated cellulose fibers are formed through a coagulating bath, the temperature of the spinning solution is 70 ℃, an 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 is 3m, and the draft multiple is 1.1 times;
s5, preparing raw strips: the pure spinning regenerated cellulose fiber is subjected to opening and carding to prepare the pure spinning regenerated cellulose fiber raw strip.
Example 3: a method for preparing a pure spun regenerated cellulose fiber raw strip is different from the embodiment 1 in that in the step S2, the homogenization frequency is 9 times, and the homogenization rotating speed is 20000r/min each time.
Example 4: a method for preparing a pure spinning regenerated cellulose fiber raw bar is different from the embodiment 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 Shi blue shield-ZW 48.
Example 5: a method for preparing a pure spun regenerated cellulose fiber raw bar is different from example 1 in that in step S1, an antibacterial agent is added into carbide, the mass ratio of the antibacterial agent to carbide is 0.3:1, and the antibacterial agent is selected from preparation example 1 of the antibacterial agent.
Examples 6 to 9: a process for preparing a pure spun regenerated cellulose fiber raw sliver differs from example 5 in that the antimicrobial agent is selected as shown in Table 1.
Table 1 selection of antimicrobial agents in examples 5-9
Example 10: a preparation method of pure spinning regenerated cellulose fiber raw strips is different from example 5 in that in step S4, essence microcapsules are added into spinning stock solution, wet spinning is carried out after uniform mixing, the mass ratio of the essence microcapsules to the spinning stock solution is 0.1:1, and the model of the essence microcapsules is RX-xj.
Example 11: a method for preparing a pure spun regenerated cellulose fiber raw bar is different from example 10 in that essence microcapsules are prepared from preparation example 6.
Example 12: a process for preparing a pure spun regenerated cellulose fiber raw bar differs from example 10 in that essence microcapsules are prepared from preparation example 7.
Example 13: a process for preparing a pure spun regenerated cellulose fiber raw bar differs from example 10 in that essence microcapsules are prepared from preparation 8.
Example 14: the process for the preparation of pure spun regenerated cellulose fiber raw sliver differs from example 11 in that the essence microcapsules are subjected to the following pretreatment before being added to the spinning solution: 3kg of nano silicon dioxide is mixed with 0.1kg of sodium dodecyl sulfate, 1kg of a silane coupling agent aqueous solution with the mass percentage concentration of 1.5% and 1kg of polydimethylsiloxane, the mixture is subjected to ultrasonic dispersion for 1h, 3kg of essence microcapsules are added, the pH value is regulated to be 5, and after stirring for 2h, the mixture is centrifuged, washed and dried, wherein the silane coupling agent is gamma-aminopropyl trimethoxy silane.
Example 15: a method for producing a pure spun regenerated cellulose fiber raw sliver is different from example 14 in that a silane coupling agent is not added.
Example 16: a process for producing a pure spun regenerated cellulose fiber raw sliver differs from example 14 in that polydimethylsiloxane is not added.
Example 17: the preparation method of the pure spinning regenerated cellulose fiber raw strip is different from the embodiment 11 in that essence microcapsules are used for carrying out post-treatment on the pure spinning regenerated cellulose fiber raw strip, and the post-treatment method is as follows: mixing essence microcapsule with water to obtain 50% treating liquid, padding raw strips in the treating liquid with rolling residue ratio of 60%.
Comparative example
Comparative example 1: the preparation method of the pure spinning regenerated cellulose fiber raw strip is different from the embodiment 1 in that enteromorpha is not added when preparing the carbon nanomaterial.
Comparative example 2: a method for preparing a pure spun regenerated cellulose fiber raw bar is different from example 1 in that no sesame seed rod is added when preparing the carbon nanomaterial.
Comparative example 3: a method for 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 an antioxidant propyl gallate, and stirring at 90 ℃ for 60 minutes to fully impregnate each raw material to obtain a premix, wherein the content of alpha-fibers in the cotton pulp, the wood pulp and the bamboo pulp is respectively as follows: 95.1%, 95.3%, 95.4%, the total content of heavy metals is less than 0.07%, the average value of polymerization degree is 540, 535, 500, the mass fraction of N-methylmorpholine-N-oxide in the aqueous solution is 68.0%, the ratio of the total weight of each pulp to the total weight of the aqueous solution of N-methylmorpholine-N-oxide is 1:20, the addition amount of propyl gallate is 0.2% of the total weight of the alpha-fiber;
(2) Adding the premix liquid obtained in the step (1) into a thin film evaporation vacuumizing device at 90 ℃, vacuumizing to enable the vacuum degree to be-0.08 MPa, standing for 10min, and finally completely dissolving each pulp to obtain a spinning solution, wherein the content of alpha-fiber in the obtained spinning solution is 12.1%, the viscosity is 14000Pa & s, and filtering the obtained spinning solution to remove impurities;
(3) And (3) adding the spinning solution obtained in the step (2) into a spinning machine at 98 ℃ for spinning, entering an air bath after the spinning solution is sprayed out, then contacting with an aqueous solution of 20 mass percent of N-methylmorpholine-N-oxide, obtaining regenerated cellulose fibers after the spinning bath is re-precipitated at 20 ℃, then bundling the obtained regenerated cellulose fibers, placing the bundled regenerated cellulose fibers into a washing machine for washing, sequentially bleaching and oiling, and finally drying for 12 minutes at 125 ℃ by using a chain plate dryer.
Performance test
Regenerated cellulose fibers were prepared according to the methods in each of examples and comparative examples, and the properties of the regenerated cellulose fibers were measured according to the following methods, and the measurement results are recorded in table 2.
1. Dry and wet break strength and elongation at break: testing according to GB/T14463-2008 viscose staple fiber; 2. antibacterial rate: soaping is carried out according to GB/T8629-2001 household washing and drying degree for textile test, the soaping temperature is 40 ℃, after soaping for 100 times, the part 3 of the evaluation of the antibacterial property of textiles according to GB/T20944.3-2008: detecting by an oscillation method;
3. adsorption rate: taking 25g of regenerated cellulose fibers prepared in each example or comparative example, respectively adding the regenerated cellulose fibers and 1.25mL of volatile liquid into a glass container (the regenerated cellulose fibers are contacted with the liquid), sealing, preserving in a dark place, detecting the change of the concentration of volatile substances in the glass container by adopting a gas chromatography-mass spectrometer after 24 hours, and recording the change rate;
4. fragrance duration: the regenerated cellulose fiber prepared in each example or comparative example is soaped according to the method in GB/T8629-2001 household washing and drying degree for textile test, the soaping temperature is 50 ℃, the soaped regenerated cellulose fiber is evaluated whether fragrance exists or not by 5 judges within 24 hours, the evaluating time of the judges is not more than 15 minutes until the regenerated cellulose fiber is not fragrant, and the washing times of the fiber are tested.
TABLE 2 Performance detection of regenerated cellulose fibers
As can be seen from the data in table 2, in the embodiment 1 and the embodiment 2, the carbon nanomaterial is prepared by adopting the sesame stalk and the enteromorpha, and then the carbon nanomaterial is mixed into the spinning solution prepared by taking corn husks as pulp, and the regenerated cellulose fiber prepared by wet spinning has the characteristics of good fiber performance, high strength and softness, and in addition, the regenerated cellulose fiber has better adsorption and deodorization effects.
In example 3, the number of homogenization of the spinning dope was increased, the rotational speed was increased, and the strength of the regenerated cellulose fiber produced was decreased, which means that the number of homogenization was increased, and the rotational speed was increased during homogenization, which did not dissolve the pulp sufficiently, but rather decreased the crystallinity of the cellulose.
Example 4 compared to example 1, the carbide with the addition of a commercial antimicrobial agent, the data in Table 2 shows that the regenerated cellulose fiber has a significantly increased antimicrobial rate against E.coli and Staphylococcus aureus after 100 soaks.
In example 5 and example 6, the antibacterial agents prepared in preparation example 1 and preparation example 2 were used, respectively, and compared with example 4, the regenerated cellulose fibers prepared in example 5 and example 6 could still achieve an antibacterial rate of 90% or more after 100 soaping, the antibacterial durability was further enhanced, and the adsorptivity and deodorizing effect were further improved.
Example 7 shows that the antibacterial agent is prepared without adding spirulina powder, and the antibacterial rate of the regenerated cellulose fiber is reduced compared with example 5 and example 6.
Example 8 the antibacterial agent prepared in preparation example 4 was used, and the antibacterial rate was lowered and the adsorption effect on formaldehyde and ammonia gas was reduced after 100 soaping of the regenerated cellulose fiber compared with example 5.
As can be seen from the data in Table 2, the antibacterial agent prepared in preparation example 5 was used in example 9, and the antibacterial agent prepared without glutaraldehyde had little effect on the antibacterial rate of regenerated cellulose fibers, but the adsorptivity of regenerated cellulose fibers was lowered.
Example 10 also included essence microcapsules in the dope compared to example 5, and it can be seen from the data in table 2 that the regenerated cellulose fiber prepared in example 10 was completely released after washing with soap 18 times, and the durability of the flavor of the regenerated cellulose fiber was improved compared to example 5.
In examples 11 and 12, the flavor was completely lost after washing with soap for 25 times or more, compared with example 10, indicating that the flavor microcapsules prepared in preparation examples 6 and 7 of the present application are effective in improving the flavor retention.
The regenerated cellulose fiber produced in example 13 was found to have a reduced fragrance duration compared to example 10, due to the safe loss of fragrance upon washing with soap for 21 times, indicating that polyvinyl alcohol can improve fragrance duration of the perfume microcapsules.
In example 14, compared with example 11, the essence microcapsules were pretreated with nano silica, silane coupling agent, etc., and as shown in table 2, the regenerated cellulose fibers prepared in example 14 were completely released after 38 soaping, which means that the pretreatment of the essence microcapsules can increase the adhesion between the essence microcapsules and the regenerated cellulose fibers and increase the durability.
In example 15, compared with example 14, when the essence microcapsule is pretreated, the silane coupling agent is not added, the silicon dioxide cannot be loaded on the surface of the essence microcapsule, and after 33 times of water washing, the fragrance of the essence microcapsule is lost.
In example 16, compared with example 14, in the case of pretreatment of the essence microcapsules, the hydrophobicity of the silica surface was lowered and the binding force with the regenerated cellulose fiber surface was weakened without using polydimethylsiloxane, so that the soap washing was completely free from fragrance for 34 times.
Example 17 the regenerated cellulose fibers produced were post-treated with perfume microcapsules, which were attached to the fiber surface and, after washing with water and stirring, were easily removed from the fibers, resulting in loss of perfume.
Comparative examples 1 and 2 compared with example 1, when preparing the carbon nanomaterial, enteromorpha and sesame seed stems were not added, respectively, and as can be seen from the data in table 2, the adsorptivity of the regenerated cellulose fibers prepared in comparative examples 1 and 2 was reduced, and the deodorizing effect was reduced.
Comparative example 3 is a regenerated cellulose fiber prepared using cotton pulp, bamboo pulp and wood pulp as raw materials in the prior art, which has a dry and wet breaking strength and a dry and wet breaking elongation that are not much different from those of example 1, but the regenerated cellulose fiber prepared in example 1 has more excellent adsorptivity and deodorizing effect.
The present embodiment is merely illustrative of the present application and is not intended to be limiting, and those skilled in the art, after having read the present specification, may make modifications to the present embodiment without creative contribution as required, but is protected by patent laws within the scope of the claims of the present application.
Claims (7)
1. The preparation method of the pure spinning regenerated cellulose fiber raw strip is characterized by comprising the following steps of:
preparing a carbon nanomaterial: respectively cleaning sesame stems and enteromorpha, pulverizing, mixing, freeze-drying, heating to 300-600 ℃ in an inert atmosphere, calcining for 30-50min to obtain carbide, adding an oxidant, uniformly stirring, drying at 60-80 ℃, soaking in an acid solution, washing to neutrality, and vacuum-drying to obtain a carbon nanomaterial, wherein the mass ratio of the sesame stems to the enteromorpha to the oxidant is 1:0.5-1:1-5;
preparing corn husk regenerated cellulose fiber spinning solution: cleaning corn husks, crushing to prepare corn husks pulp, adding the corn husks pulp into chlorinated 1-allyl-3-methylimidazole, uniformly mixing, homogenizing and filtering at the temperature of 70-90 ℃ under the vacuum condition, and defoaming filtrate to prepare a corn husks regenerated cellulose fiber spinning solution, wherein the mass ratio of the corn husks pulp to the chlorinated 1-allyl-3-methylimidazole is 0.3-0.5:1;
preparing a spinning solution: dispersing a carbon nano material in water or absolute ethyl alcohol, performing ultrasonic dispersion to form a carbon nano material dispersion liquid with the mass percentage concentration of 10-15%, adding the carbon nano material dispersion liquid into corn husk regenerated cellulose fiber spinning liquid, and performing shearing blending to prepare spinning stock solution, wherein the mass ratio of the carbon nano material dispersion liquid to the corn husk regenerated cellulose fiber spinning liquid is 3:7-12;
spinning: wet spinning is carried out on the spinning solution, and pure spinning regenerated cellulose fibers are formed through coagulating bath;
preparing raw strips: opening and carding the pure spinning regenerated cellulose fibers to prepare pure spinning regenerated cellulose fiber raw strips;
in the spinning step, before wet spinning, essence microcapsules are added into the spinning solution, wet spinning is carried out after uniform mixing, and the mass ratio of the essence microcapsules to the spinning solution is 0.05-0.1:1;
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, regulating 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 ℃, regulating the pH value to 6-7, carrying out suction filtration, and drying to constant weight;
before the essence microcapsule is added into the spinning solution, the essence microcapsule is pretreated by the following steps:
mixing 3-5 parts by weight of nano silicon dioxide with 0.1-0.5 part by weight of sodium dodecyl sulfate, 1-1.5 parts by weight of 1-1.5% by weight of silane coupling agent aqueous solution and 1-2 parts by weight of polydimethylsiloxane, performing ultrasonic dispersion for 1-2 hours, adding 3-5 parts by weight of essence microcapsule, adjusting the pH value to 5-7, stirring for 1-2 hours, centrifuging, washing and drying.
2. The method for producing a pure spun regenerated cellulose fiber raw sliver according to claim 1, wherein: an antibacterial agent is also added into the carbide, and the mass ratio of the antibacterial agent to the carbide is 0.1-0.3:1.
3. The method of producing a pure spun regenerated cellulose fiber raw sliver according to claim 2, wherein the antibacterial agent is produced by the following method:
(1) Soaking 2-4 parts by weight of spirulina powder in 4-5 parts by weight of 35-40% silver nitrate solution, centrifuging, washing with deionized water to pH 6-8, drying at 60-80 ℃, uniformly mixing with 3-5 parts by weight of 1-3% sodium alginate solution and 3-5 parts by weight of glutaraldehyde, and stirring at 50-60 ℃ for 1-2h at constant temperature;
(2) Uniformly stirring 10-30 parts by weight of chitosan acetic acid solution with the mass percentage concentration of 2-4%, 0.05-0.15 part by weight of ammonium acetate and 10-15 parts by weight of n-amyl alcohol, dropwise adding the product obtained in the step (1), stirring while dropwise adding, freeze-drying, drying at 98-100 ℃ for 30-40min, and soaking in absolute ethyl alcohol for 20-24 h.
4. The method for producing a pure spun regenerated cellulose fiber raw sliver according to claim 1, wherein in the spinning step, the coagulation bath is distilled water at a temperature of 60-80 ℃ and a coagulation bath length of 1-3m.
5. The method for producing a raw bar of pure-spun regenerated cellulose fiber according to claim 1, wherein in the step of producing a spinning solution of regenerated cellulose fiber from corn husk, the number of homogenization is 3 to 5, and the number of revolution per homogenization is 14000 to 16000r/min.
6. The method for producing a raw bar of pure spun regenerated cellulose fiber according to claim 1, wherein in the step of producing a carbon nanomaterial, the oxidizing agent is one of potassium permanganate and phosphorus pentoxide.
7. The method for producing a raw bar of pure spun regenerated cellulose fiber according to claim 1, wherein in the step of producing a carbon nanomaterial, the acid solution is 10 to 30% by mass of hydrochloric acid or 30 to 50% by mass of sulfuric acid.
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