WO2018227894A1 - Procédé de coloration profonde et à haute concentration pour nanocellulose - Google Patents

Procédé de coloration profonde et à haute concentration pour nanocellulose Download PDF

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WO2018227894A1
WO2018227894A1 PCT/CN2017/113756 CN2017113756W WO2018227894A1 WO 2018227894 A1 WO2018227894 A1 WO 2018227894A1 CN 2017113756 W CN2017113756 W CN 2017113756W WO 2018227894 A1 WO2018227894 A1 WO 2018227894A1
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nanocellulose
solution
reaction
electrolyte salt
dye
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PCT/CN2017/113756
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English (en)
Chinese (zh)
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付时雨
王文波
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华南理工大学
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Publication of WO2018227894A1 publication Critical patent/WO2018227894A1/fr

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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/58—Material containing hydroxyl groups
    • D06P3/60—Natural or regenerated cellulose
    • D06P3/66—Natural or regenerated cellulose using reactive dyes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
    • C08J3/07—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media from polymer solutions
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/38—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using reactive dyes
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/81—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using dyes dissolved in inorganic solvents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
    • C08J2301/02—Cellulose; Modified cellulose

Definitions

  • the invention belongs to the field of nanofiber materials, and particularly relates to a high-concentration dyeing method for nanocellulose.
  • the concentration of the nanocellulose and the reactive dye in the ordinary aqueous solution is generally 0.5%-2% It is difficult to achieve deep dyeing of nanocellulose and full utilization of dyes. Since both nanocellulose and reactive dyes have strong electronegativity, a large amount of strong electrolyte salts must be added during the reaction to counteract the negative electrical influence. The addition of a large amount of salt also increases the difficulty of wastewater treatment.
  • the method of the invention can increase the concentration of nanocellulose during the reaction to 5%-10% To achieve high-concentration, nano-cellulose-free salt-free dyeing. The amount of grafting of the reactive dye on the nanocellulose and the dye uptake rate are greatly improved.
  • the prepared nanocellulose is promising for use in the field of anti-counterfeiting of paper or inkjet printing of nanocellulose, and has strong practical value.
  • the present invention provides a high-concentration depth dyeing method of nanocellulose.
  • the dyed nanocellulose prepared by the invention has small size and high dyeing degree, and is highly expected to be applied to the fields of inkjet printing of nanocellulose and anti-counterfeiting of paper, and has strong practical value.
  • the present invention is achieved by the following technical solutions.
  • a high-concentration depth dyeing method for nanocellulose comprising the following steps:
  • step (1) Adding a reactive dye to the obtained nanocellulose mixed solution, adding a base or a strong base weak acid salt, stirring uniformly, heating up, condensing and refluxing reaction, so that the dye is sufficiently dyed onto the nanocellulose;
  • the reaction vessel is rapidly cooled with cold water, and the reaction solution is centrifuged in a high-speed refrigerated centrifuge to remove the unreacted dye and the surface of the fiber, and the obtained precipitate is dispersed in an aqueous solution of a strong electrolyte salt, and the centrifugation is repeated. Until the supernatant is colorless, the precipitate obtained is the deeply dyed nanocellulose.
  • the strong electrolyte salt of the step (1) is one or more of NaCl, KCl, Na 2 SO 4 and K 2 SO 4 ; the strong electrolyte salt is used in an amount of 0.5 wt% of the aqueous nanocellulose solution. -3wt%.
  • the mass ratio of nanocellulose to water in the nanocellulose mixture in step (1) is 5:95-10:90
  • the volume ratio of ethanol to water is 50:50-95:5.
  • the reactive dye is one or more of reactive red, active orange, active yellow, active green, reactive blue, reactive violet, reactive brown, reactive ash and reactive black; the amount of reactive dye is nanocellulose 0.2 wt% -30 Wt%.
  • the reaction liquid of the step (2) is added with or without a strong electrolyte salt;
  • the strong electrolyte salt is one or more of NaCl, KCl, Na 2 SO 4 and K 2 SO 4 ;
  • the amount of the strong electrolyte salt in the reaction liquid is 0-40 g/L.
  • the base or strong base weak acid salt of step (2) is one or more of ammonia water, NaOH, KOH, Na 2 CO 3 , K 2 CO 3 and pH buffer.
  • the medium-strong electrolyte salt, the reactive dye, the alkali or the strong base weak acid salt may be added before the temperature rise or may be added after the temperature rise, or may be added after the temperature is added before the temperature is added.
  • the pH of the reaction solution is 9-13
  • the reaction time is 30-240 min
  • the reaction temperature is 60 °C -80 °C.
  • the pH of the reaction solution can be adjusted to neutral by acid, or the pH can be adjusted without acid, and the mixture is centrifuged several times until the pH of the solution is neutral; the pH value is adjusted.
  • the acid used in the case of the sex is one or more of a HCl solution, a H 2 SO 4 solution, a HNO 3 solution, an H 3 PO 4 solution, and a CH 3 COOH solution.
  • the strong electrolyte salt of the step (3) is one or more of NaCl, KCl, Na 2 SO 4 and K 2 SO 4 ; the concentration of the strong electrolyte salt in the aqueous solution is 0.5 wt% -3 Wt%.
  • a high-concentration depth dyeing method of nanocellulose comprises the following steps:
  • aqueous nanocellulose solution 0.5 wt% to 3 wt% of a strong electrolyte salt was added to the aqueous nanocellulose solution, and the nanocellulose was precipitated by high speed centrifugation.
  • a mixture of nanocellulose, ethanol and water is prepared in a certain ratio.
  • To the prepared mixture was added 0-40 g/L NaCl, 0.2 wt%-30 wt% reactive dye, 5-40 g/L Na 2 CO 3 . After stirring uniformly, the temperature was raised to 80-90 ° C, and it was condensed and refluxed for 30-240 min. After completion of the reaction, the reaction vessel was rapidly cooled with cold water, and the reaction liquid was centrifuged by a high-speed refrigerated centrifuge.
  • the obtained precipitate was sufficiently dispersed in an ethanol water mixture or a 0.5 wt% to 3 wt% strong electrolyte salt solution, and the centrifugation was repeated until the supernatant was colorless, and the precipitate obtained was a deeply dyed nanocellulose.
  • nanocellulose is reacted with a reactive dye in a mixture of ethanol and water. Since the nanocellulose and the reactive dye are insoluble in ethanol, the nanocellulose and the reactive dye are only grafted in a small amount of water in the mixed solution during the actual reaction.
  • the present invention has the following advantages and benefits:
  • the invention can realize the graft reaction of the high-concentration nano cellulose with the high-concentration dye.
  • concentration of nanocellulose during the reaction can be increased from 0.5 wt% to 2 wt% in the normal aqueous solution of nanocellulose.
  • Wt%-10 wt% can greatly improve the dyeing depth of nanocellulose.
  • the dye uptake rate can be increased from 20%-40% in the normal aqueous solution of nanocellulose to 50%-70%. It can greatly improve the dye utilization rate and reduce the inefficient hydrolysis of the dye.
  • the grafting reaction of the invention is carried out at a high concentration, and the grafting reaction between the nanocellulose and the reactive dye can be realized without adding a strong electrolyte salt, thereby reducing the amount of washing water and the salt content of the water after washing, which is beneficial to Treatment of reaction wastewater.
  • the nanocellulose and the reactive dye are covalently bonded, have very good stability, are not easy to fade, and no toxic substances participate or are formed in the whole dyeing process, and the prepared nanocellulose is promising for paper. In the field of anti-counterfeiting or nano-cellulose printing, it has high practical value.
  • the grafting amount and dyeing rate described below are determined according to the following methods: UV-visible full-wavelength scanning is performed on different dyes to determine the maximum absorption peak corresponding wavelength (for example, Reactive Red 120 513nm The maximum absorption peak is at the wavelength; the standard curve of the dye is made at this wavelength; the centrifugation solution is centrifuged several times after the completion of the reaction, and the volume and absorbance are measured; the dye content in the centrate is calculated according to the standard curve, and the dye is on the nanocellulose.
  • the graft amount and the dye uptake rate is as follows:
  • graft amount (m dye - Abs * V / a) / m NFC
  • Abs Absorbance of total supernatant obtained after centrifugation after completion of reaction
  • 1 wt% of NaCl was added to 500 ml of a 0.5 wt% aqueous nanocellulose solution, and centrifuged at a high speed refrigerated centrifuge (9000 rpm). The obtained precipitate was dispersed in absolute ethanol, and the centrifugation was repeated a plurality of times.
  • Deionized water was added to the prepared nanocellulose ethanol mixture to prepare a nanocellulose mixture (the mass ratio of nanocellulose to water was 5:95, and the volume ratio of absolute ethanol to water was 80:20).
  • 10 wt% of Reactive Red 120 reactive dye, 10 g/L of NaCl, and 10 g/L of Na 2 CO 3 were added to the prepared nanocellulose mixture, and the mixture was uniformly stirred.
  • the mixture was heated to reflux and refluxed for 120 min. After completion of the reaction, the reaction vessel was rapidly cooled with cold water, and the reaction liquid was centrifuged by a high-speed refrigerated centrifuge (9000 rpm). The obtained precipitate was dispersed in a NaCl solution having a concentration of 1 wt%, and the centrifugation was repeated until the supernatant was colorless, and the precipitate obtained was a deeply dyed nanocellulose.
  • the grafting amount of Reactive Red 120 in the dyed nanocellulose prepared in this example was 30.1 mg/g. Nanocellulose, the dye uptake rate was 47.3%, and the dyed nanocellulose did not produce obvious physical changes such as size change and curl.
  • 1 wt% of NaCl was added to 500 ml of a 0.5 wt% aqueous nanocellulose solution, and centrifuged at a high speed refrigerated centrifuge (9000 rpm). The obtained precipitate was dispersed in absolute ethanol, and the centrifugation was repeated a plurality of times.
  • Deionized water was added to the prepared nanocellulose ethanol mixture to prepare a nanocellulose mixture (the mass ratio of nanocellulose to water was 10:90, and the volume ratio of absolute ethanol to water was 95:5).
  • 10 wt% of Reactive Red 120 reactive dye, 10 g/L of NaCl, and 10 g/L of Na 2 CO 3 were added and stirred well.
  • the mixture was heated to reflux and refluxed for 120 min. After completion of the reaction, the reaction vessel was rapidly cooled with cold water, and the reaction liquid was centrifuged by a high-speed refrigerated centrifuge (9000 rpm). The obtained precipitate was dispersed in a 1 wt% NaCl solution, and the centrifugation was repeated until the supernatant was colorless, and the precipitate obtained was a deeply dyed nanocellulose.
  • the grafting amount of Reactive Red 120 in the dyed nanocellulose prepared in this example was 65.5 mg/g. Nanocellulose, the dye uptake rate was 56.6%, and the dyed nanocellulose did not produce obvious physical changes such as size change and curl.
  • 1 wt% of NaCl was added to 500 ml of a 0.5 wt% aqueous nanocellulose solution, and centrifuged at a high speed refrigerated centrifuge (9000 rpm). The obtained precipitate was dispersed in absolute ethanol, and the centrifugation was repeated a plurality of times.
  • Deionized water was added to the prepared nanocellulose ethanol mixture to prepare a nanocellulose mixture (the mass ratio of nanocellulose to water was 7.5:92.5, and the volume ratio of absolute ethanol to water was 50:50).
  • 10 wt% of Reactive Red 120 reactive dye, 10 g/L of NaCl, and 10 g/L of Na 2 CO 3 were added and stirred well.
  • the mixture was heated to reflux and refluxed for 120 min. After completion of the reaction, the reaction vessel was rapidly cooled with cold water, and the reaction liquid was centrifuged by a high-speed refrigerated centrifuge (9000 rpm). The obtained precipitate was dispersed in a 1 wt% NaCl solution, and the centrifugation was repeated until the supernatant was colorless, and the precipitate obtained was a deeply dyed nanocellulose.
  • the grafting amount of Reactive Red 120 in the dyed nanocellulose prepared in this example was 50.1 mg/g. Nanocellulose, the dye uptake rate was 51.3%, and the dyed nanocellulose did not produce obvious physical changes such as size change and curl.
  • 1 wt% of NaCl was added to 500 ml of a 0.5 wt% aqueous nanocellulose solution, and centrifuged at a high speed refrigerated centrifuge (9000 rpm). The obtained precipitate was dispersed in absolute ethanol, and the centrifugation was repeated a plurality of times.
  • Deionized water was added to the prepared nanocellulose ethanol mixture to prepare a nanocellulose mixture (the mass ratio of nanocellulose to water was 5:95, and the volume ratio of absolute ethanol to water was 80:20).
  • 2 wt% of Reactive Red 120 reactive dye, 10 g/L of Na 2 CO 3 was added to the prepared mixture, and the mixture was stirred well. The mixture was heated to reflux and refluxed for 120 min.
  • the reaction vessel was rapidly cooled with cold water, and the reaction liquid was centrifuged by a high-speed refrigerated centrifuge (9000 rpm). The obtained precipitate was dispersed in a 50% aqueous solution of ethanol, and the centrifugation was repeated until the supernatant was colorless, and the precipitate obtained was a deeply dyed nanocellulose.
  • the grafting amount of Reactive Red 120 in the dyed nanocellulose prepared in this example was 55.3 mg/g. Nanocellulose, the dye uptake rate was 61.8%, and the dyed nanocellulose did not produce obvious physical changes such as size change and curl.
  • 1 wt% of NaCl was added to 500 ml of a 0.5 wt% aqueous nanocellulose solution, and centrifuged at a high speed refrigerated centrifuge (9000 rpm). The obtained precipitate was dispersed in absolute ethanol, and the centrifugation was repeated a plurality of times.
  • Deionized water was added to the prepared nanocellulose ethanol mixture to prepare a nanocellulose mixture (the mass ratio of nanocellulose to water was 5:95, and the volume ratio of absolute ethanol to water was 80:20).
  • 0.2 wt% of Reactive Red 120 reactive dye, 10 g/L of NaCl, and 10 g/L of Na 2 CO 3 were added to the prepared mixture, and the mixture was stirred well.
  • the mixture was heated to reflux and refluxed for 240 min. After completion of the reaction, the reaction vessel was rapidly cooled with cold water, and the reaction liquid was centrifuged by a high-speed refrigerated centrifuge (9000 rpm). The obtained precipitate was dispersed in a 1 wt% NaCl solution, and the centrifugation was repeated until the supernatant was colorless, and the precipitate obtained was a deeply dyed nanocellulose.
  • the grafting amount of Reactive Red 120 in the dyed nanocellulose prepared in this example was 6.3 mg/g.
  • Nanocellulose, dye dyeing rate was 70.3%, and the dyed nanocellulose did not produce obvious physical changes such as size change and curl.
  • 1 wt% of NaCl was added to 500 ml of a 0.5 wt% aqueous nanocellulose solution, and centrifuged at a high speed refrigerated centrifuge (9000 rpm). The obtained precipitate was dispersed in absolute ethanol, and the centrifugation was repeated a plurality of times.
  • Deionized water was added to the prepared nanocellulose ethanol mixture to prepare a nanocellulose mixture (the mass ratio of nanocellulose to water was 5:95, and the volume ratio of absolute ethanol to water was 80:20).
  • 30 wt% of Reactive Red 120 reactive dye, 10 g/L of NaCl, and 10 g/L of Na 2 CO 3 were added and stirred well.
  • the mixture was heated to reflux and refluxed for 30 min. After completion of the reaction, the reaction vessel was rapidly cooled with cold water, and the reaction liquid was centrifuged by a high-speed refrigerated centrifuge (9000 rpm). The obtained precipitate was dispersed in a 1 wt% NaCl solution, and the centrifugation was repeated until the supernatant was colorless, and the precipitate obtained was a deeply dyed nanocellulose.
  • the grafting amount of Reactive Red 120 in the dyed nanocellulose prepared in this example was 70.3 mg/g.
  • Nanocellulose, dye dyeing rate was 30.7%, and the dyed nanocellulose did not produce obvious physical changes such as size change and curl.
  • 1 wt% of NaCl was added to 500 ml of a 0.5 wt% aqueous nanocellulose solution, and centrifuged at a high speed refrigerated centrifuge (9000 rpm). The obtained precipitate was dispersed in absolute ethanol, and the centrifugation was repeated a plurality of times.
  • Deionized water was added to the prepared nanocellulose ethanol mixture to prepare a nanocellulose mixture (the mass ratio of nanocellulose to water was 5:95, and the volume ratio of absolute ethanol to water was 80:20).
  • 15.1 wt% of Reactive Red 120 reactive dye, 10 g/L of NaCl, and 10 g/L of Na 2 CO 3 were added and stirred well.
  • the mixture was heated to reflux and refluxed for 135 min. After completion of the reaction, the reaction vessel was rapidly cooled with cold water, and the reaction liquid was centrifuged by a high-speed refrigerated centrifuge (9000 rpm). The obtained precipitate was dispersed in a 1 wt% NaCl solution, and the centrifugation was repeated until the supernatant was colorless, and the precipitate obtained was a deeply dyed nanocellulose.
  • the grafting amount of Reactive Red 120 in the dyed nanocellulose prepared in this example was 66.7 mg/g.
  • Nanocellulose, dye dyeing rate was 58.9%, and the dyed nanocellulose did not produce obvious physical changes such as size change and curl.
  • 1 wt% of NaCl was added to 500 ml of a 0.5 wt% aqueous nanocellulose solution, and centrifuged at a high speed refrigerated centrifuge (9000 rpm). The obtained precipitate was dispersed in absolute ethanol, and the centrifugation was repeated a plurality of times.
  • Deionized water was added to the prepared nanocellulose ethanol mixture to prepare a nanocellulose mixture (the mass ratio of nanocellulose to water was 10:90, and the volume ratio of absolute ethanol to water was 95:5).
  • 2 wt% of Reactive Red 120 reactive dye, 10 g/L of NaCl, and 10 g/L of Na 2 CO 3 were added to the prepared mixture, and the mixture was stirred well.
  • the mixture was heated to reflux and refluxed for 120 min. After completion of the reaction, the reaction vessel was rapidly cooled with cold water, and the reaction liquid was centrifuged by a high-speed refrigerated centrifuge (9000 rpm). The obtained precipitate was dispersed in a 1 wt% NaCl solution, and the centrifugation was repeated until the supernatant was colorless, and the precipitate obtained was a deeply dyed nanocellulose.
  • the grafting amount of Reactive Red 120 in the dyed nanocellulose prepared in this example was 61.4 mg/g.
  • Nanocellulose, dye dyeing rate was 71.2%, and the dyed nanocellulose did not produce obvious physical changes such as size change and curl.
  • 1 wt% of NaCl was added to 500 ml of a 0.5 wt% aqueous nanocellulose solution, and centrifuged at a high speed refrigerated centrifuge (9000 rpm). The obtained precipitate was dispersed in absolute ethanol, and the centrifugation was repeated a plurality of times.
  • Deionized water was added to the prepared nanocellulose ethanol mixture to prepare a nanocellulose mixture (the mass ratio of nanocellulose to water was 5:95, and the volume ratio of absolute ethanol to water was 80:20).
  • 10 wt% of Reactive Yellow 84 reactive dye, 10 g/L of NaCl, and 10 g/L of Na 2 CO 3 were added and stirred well.
  • the mixture was heated to reflux and refluxed for 120 min. After completion of the reaction, the reaction vessel was rapidly cooled with cold water, and the reaction liquid was centrifuged by a high-speed refrigerated centrifuge (9000 rpm). The obtained precipitate was dispersed in a 1 wt% NaCl solution, and the centrifugation was repeated until the supernatant was colorless, and the precipitate obtained was a deeply dyed nanocellulose.
  • the grafting amount of Reactive Red 120 in the dyed nanocellulose prepared in this example was 28.4 mg/g.
  • Nanocellulose dye dyeing rate was 44.0%, and the dyed nanocellulose did not produce obvious physical changes such as size change and curl.
  • 1 wt% of NaCl was added to 500 ml of a 0.5 wt% aqueous nanocellulose solution, and centrifuged at a high speed refrigerated centrifuge (9000 rpm). The obtained precipitate was dispersed in absolute ethanol, and the centrifugation was repeated a plurality of times.
  • Deionized water was added to the prepared nanocellulose ethanol mixture to prepare a nanocellulose mixture (the mass ratio of nanocellulose to water was 5:95, and the volume ratio of absolute ethanol to water was 80:20).
  • 10 wt% of M-3RE Yellow reactive dye, 10 g/L of NaCl, and 10 g/L of Na 2 CO 3 were added and stirred well.
  • the mixture was heated to reflux and refluxed for 30 min. After completion of the reaction, the reaction vessel was rapidly cooled with cold water, and the reaction liquid was centrifuged by a high-speed refrigerated centrifuge (9000 rpm). The obtained precipitate was dispersed in a 1 wt% NaCl solution, and the centrifugation was repeated until the supernatant was colorless, and the precipitate obtained was a deeply dyed nanocellulose.
  • the grafting amount of Reactive Red 120 in the dyed nanocellulose prepared in this example was 25.3 mg/g. Nanocellulose, the dye uptake rate was 41.8%, and the dyed nanocellulose did not produce obvious physical changes such as size change and curl.
  • 1 wt% of NaCl was added to 500 ml of a 0.5 wt% aqueous nanocellulose solution, and centrifuged at a high speed refrigerated centrifuge (9000 rpm). The obtained precipitate was dispersed in absolute ethanol, and the centrifugation was repeated a plurality of times.
  • Deionized water was added to the prepared nanocellulose ethanol mixture to prepare a nanocellulose mixture (the mass ratio of nanocellulose to water was 5:95, and the volume ratio of absolute ethanol to water was 80:20).
  • 10 wt% of Reactive Blue 71 reactive dye, 10 g/L of NaCl, and 10 g/L of Na 2 CO 3 were added and stirred well.
  • the mixture was heated to reflux and refluxed for 30 min. After completion of the reaction, the reaction vessel was rapidly cooled with cold water, and the reaction liquid was centrifuged by a high-speed refrigerated centrifuge (9000 rpm). The obtained precipitate was dispersed in a 1 wt% NaCl solution, and the centrifugation was repeated until the supernatant was colorless, and the precipitate obtained was a deeply dyed nanocellulose.
  • the grafting amount of Reactive Red 120 in the dyed nanocellulose prepared in this example was 32.7 mg/g nanocellulose, and the dye uptake rate was 49.0%.
  • the dyed nanocellulose did not produce significant dimensional change, curl, etc. Physical form changes.

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Abstract

La présente invention concerne un procédé de coloration profonde et à haute concentration pour nanocellulose. Ledit procédé comprend les étapes consistant à: ajouter un sel d'électrolyte fort à une solution aqueuse de nanocellulose, effectuer une centrifugation, puis ajouter de l'éthanol et de l'eau pour formuler une solution mélangée de nanocellulose; ajouter un colorant actif, un alcali ou un sel d'acide faible fortement alcalin dans la solution mélangée, puis chauffer, condenser et refluer la solution; et après l'achèvement de la réaction, réaliser une centrifugation, et collecter le précipité, de façon à obtenir une nanocellulose colorée profonde. La concentration de la nanocellulose dans la présente invention peut être augmentée à 5% - 10% de 0,5% - 2% de nanocellulose commune dans une réaction de coloration, ce qui permet d'augmenter le taux de greffage. L'absorption de colorant d'un colorant peut être augmentée à 50% - 70% de 20% - 40% de nanocellulose commune, ce qui permet d'augmenter le taux d'utilisation du colorant. La présente invention est avantageuse pour le traitement des eaux usées de réaction. En outre, la nanocellulose colorée préparée par la présente invention présente une très bonne stabilité, ne se décolore pas facilement, est de petite taille et présente une aptitude à la coloration élevée, étant souhaitable pour être appliquée dans des domaines tels que l'impression à jet d'encre de nanocellulose et l'anti-contrefaçon de papier, ayant une grande valeur pratique.
PCT/CN2017/113756 2017-06-15 2017-11-30 Procédé de coloration profonde et à haute concentration pour nanocellulose WO2018227894A1 (fr)

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CN107201678B (zh) * 2017-06-15 2020-07-28 华南理工大学 一种纳米纤维素的高浓深度染色方法
CN108165094B (zh) * 2017-12-15 2021-07-16 华南理工大学 一种纳米纤维素基笔芯水性墨及其制备方法
CN110656526B (zh) * 2019-10-08 2021-10-01 齐鲁工业大学 一种纤维浆料制备纳米纤维素的方法
CN115612312B (zh) * 2022-11-08 2024-01-09 浙江天浩新材料股份有限公司 一种稳定性高的纳米纤维素染料分散液及其制备方法

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