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CN118667351A - Method for improving dispersion performance of cellulase on organic pigment - Google Patents

Method for improving dispersion performance of cellulase on organic pigment Download PDF

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Publication number
CN118667351A
CN118667351A CN202410613274.1A CN202410613274A CN118667351A CN 118667351 A CN118667351 A CN 118667351A CN 202410613274 A CN202410613274 A CN 202410613274A CN 118667351 A CN118667351 A CN 118667351A
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cellulase
deionized water
pigment
organic pigment
mass ratio
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CN202410613274.1A
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CN118667351B (en
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郝龙云
宋佳丽
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Qingdao University
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Qingdao University
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    • CCHEMISTRY; METALLURGY
    • C12BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12NMICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
    • C12N9/00Enzymes; Proenzymes; Compositions thereof; Processes for preparing, activating, inhibiting, separating or purifying enzymes
    • C12N9/14Hydrolases (3)
    • C12N9/24Hydrolases (3) acting on glycosyl compounds (3.2)
    • C12N9/2402Hydrolases (3) acting on glycosyl compounds (3.2) hydrolysing O- and S- glycosyl compounds (3.2.1)
    • C12N9/2405Glucanases
    • C12N9/2434Glucanases acting on beta-1,4-glucosidic bonds
    • C12N9/2437Cellulases (3.2.1.4; 3.2.1.74; 3.2.1.91; 3.2.1.150)
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09BORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/006Preparation of organic pigments
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09BORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0071Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
    • C09B67/008Preparations of disperse dyes or solvent dyes
    • C09B67/0082Preparations of disperse dyes or solvent dyes in liquid form
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09BORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0071Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
    • C09B67/0084Dispersions of dyes
    • C09B67/0085Non common dispersing agents
    • CCHEMISTRY; METALLURGY
    • C12BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12YENZYMES
    • C12Y302/00Hydrolases acting on glycosyl compounds, i.e. glycosylases (3.2)
    • C12Y302/01Glycosidases, i.e. enzymes hydrolysing O- and S-glycosyl compounds (3.2.1)
    • C12Y302/01004Cellulase (3.2.1.4), i.e. endo-1,4-beta-glucanase

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Zoology (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Bioinformatics & Cheminformatics (AREA)
  • Genetics & Genomics (AREA)
  • General Health & Medical Sciences (AREA)
  • General Engineering & Computer Science (AREA)
  • Biochemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Medicinal Chemistry (AREA)
  • Molecular Biology (AREA)
  • Biomedical Technology (AREA)
  • Biotechnology (AREA)
  • Microbiology (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)

Abstract

一种提高纤维素酶对有机颜料分散性能的方法,其特征在于采用以下工艺:(1)将质量比为5:1的纤维素酶和NaOH加入去离子水中充分溶解,40℃下缓慢加入占纤维酶质量60%的油酰氯,并用NaOH溶液保持体系pH值在9~10之间,滴加完毕后升温至50℃继续反应2 h,随后加入盐酸调节pH值至1~2,析出反应物沉淀并用去离子水洗涤至中性,真空干燥得到改性纤维素酶;(2)将质量比为10:1:0.2的有机颜料、改性纤维素酶和氢氧化钠加入去离子水中,超声处理30 min,得到颜料分散体。利用本发明所述方法对纤维素酶进行改性,得到改性纤维素酶,能够进一步提升对有机颜料的分散能力。A method for improving the dispersibility of cellulase on organic pigments, characterized by the following process: (1) adding cellulase and NaOH in a mass ratio of 5:1 to deionized water to fully dissolve, slowly adding oleyl chloride accounting for 60% of the mass of the cellulase at 40°C, and using NaOH solution to keep the pH value of the system between 9 and 10, heating to 50°C after the addition is completed and continuing the reaction for 2 hours, then adding hydrochloric acid to adjust the pH value to 1-2, precipitating the reactant precipitate and washing it with deionized water to neutrality, and vacuum drying to obtain modified cellulase; (2) adding organic pigment, modified cellulase and sodium hydroxide in a mass ratio of 10:1:0.2 to deionized water, and ultrasonically treating for 30 minutes to obtain a pigment dispersion. Modifying cellulase using the method of the present invention to obtain modified cellulase can further improve the dispersibility of organic pigments.

Description

Method for improving dispersion performance of cellulase on organic pigment
Technical Field
The invention relates to a method for improving the dispersion performance of cellulase on organic pigment, belonging to the technical field of textile printing and dyeing.
Background
The aqueous organic pigment can be used for printing and dyeing of various textiles, has the advantages of short process flow, low water consumption and the like, and is one of important technologies for promoting sustainable development of textile printing and dyeing industry. The organic pigment has strong hydrophobicity and is difficult to uniformly and stably disperse in an aqueous medium. In general, the organic pigments need to be physically or chemically dispersed to form stable dispersions of primary particles for successful use. Physical dispersion utilizes high-strength shearing or impact force to break up and uniformly disperse pigment particles, and mainly comprises grinding, ultrasonic and gas (liquid) flow grinding modes and the like. Chemical dispersion is mainly treated by methods such as chemical modification, grafting, coating and the like according to the properties of pigment particles, so that the pigment has surface properties different from the original ones. In comparison, the physical dispersion method is simpler to operate and is more widely applied.
In the physical dispersion process of the organic pigment, a certain amount of dispersing agent is required to be added. The dispersing agent can be adsorbed to the surface of the pigment, and generates charge repulsive force and steric hindrance effect to prevent pigment particles from being aggregated again, so that a stable suspension state is maintained. The dispersing agent for the water-based pigment system mainly comprises three types of inorganic, organic small molecule and high molecule dispersing agents. The inorganic dispersant mainly comprises polyphosphate, silicate, carbonate and the like; the organic small molecule dispersant is mainly an anionic surfactant, a cationic surfactant and a nonionic surfactant; the polymer dispersant mainly comprises polyelectrolyte, natural polymer, etc. In recent years, the application of natural polymer dispersants has been focused, and natural polymer substances such as casein, gelatin, lecithin, chitosan, sodium alginate, cellulose and the like, and modified derivatives thereof have been used by researchers for dispersing organic pigments to obtain a certain effect.
Cellulase is a generic term for enzymes that catalyze the hydrolysis of cellulose and is mainly composed of endoglucanases, exoglucanases and beta-glucosidase. The chemical nature of cellulases is protein, which exhibits certain colloidal properties in aqueous solutions. In the physical crushing process such as ultrasonic, cellulase can be combined to the surface of the organic pigment, and the enzyme protein has typical amphoteric property, so that the electrical property of the organic pigment dispersion can be regulated and controlled, and the application range of the organic pigment dispersion is widened.
Disclosure of Invention
The invention aims to provide a method for improving the dispersion performance of cellulase on organic pigment, which takes oleoyl chloride as an acylating agent to carry out graft modification on the cellulase to obtain modified cellulase, so that the dispersion capability of the cellulase on the organic pigment can be further improved.
The invention comprises the following processes:
(1) Adding cellulase and NaOH with the mass ratio of 5:1 into deionized water for full dissolution, slowly adding oleoyl chloride accounting for 60% of the mass of the cellulase at 40 ℃, keeping the pH value of the system between 9 and 10 by using NaOH solution, heating to 50 ℃ after the dripping is finished, continuing to react for 2h, then adding hydrochloric acid to adjust the pH value to 1-2, separating out reactant precipitate, washing with deionized water to be neutral, and carrying out vacuum drying to obtain modified cellulase;
(2) Adding the organic pigment, the modified cellulase and the sodium hydroxide into deionized water according to the mass ratio of 10:1:0.2, and carrying out ultrasonic treatment on the mixture for 30 min to obtain a pigment dispersion.
Adding cellulase and NaOH with the mass ratio of 5:1 into deionized water for full dissolution, wherein the cellulase is commercially available cellulase for textile printing and dyeing. Slowly adding oleoyl chloride accounting for 60% of the mass of the cellulose at 40 ℃, keeping the pH value of the system between 9 and 10 by using NaOH solution, heating to 50 ℃ after the dripping is finished, and continuing to react for 2h, wherein the oleoyl chloride introduces a carbon chain through acylation reaction with amino groups on cellulose molecules in the process, so that the performance of enzyme protein is changed. And then adding hydrochloric acid to adjust the pH value to 1-2, precipitating a reactant precipitate, washing with deionized water to be neutral, and drying in vacuum to obtain the modified cellulase. With the modified cellulase obtained, an organic pigment can be dispersed in water. Adding the organic pigment, the modified cellulase and the sodium hydroxide into deionized water according to the mass ratio of 10:1:0.2, and carrying out ultrasonic treatment on the mixture for 30min to obtain a pigment dispersion. Because the structure is optimized, the modified cellulase can better disperse the organic pigment into the aqueous medium.
Detailed Description
The invention is further illustrated by the following examples.
Example 1
(1) Adding cellulase and NaOH with the mass ratio of 5:1 into deionized water for full dissolution, slowly adding oleoyl chloride accounting for 60% of the mass of the cellulase at 40 ℃, keeping the pH value of the system between 9 and 10 by using NaOH solution, heating to 50 ℃ after the dripping is finished, continuing to react for 2h, then adding hydrochloric acid to adjust the pH value to 1-2, separating out reactant precipitate, washing with deionized water to be neutral, and carrying out vacuum drying to obtain modified cellulase;
(2) Adding organic pigment yellow, modified cellulase and sodium hydroxide in a mass ratio of 10:1:0.2 into deionized water, and carrying out ultrasonic treatment on the mixture for 30 min to obtain a pigment dispersion.
Comparative example 1
Organic pigment yellow, cellulase and sodium hydroxide in a mass ratio of 10:1:0.2 were added to deionized water, and treated under the same conditions as in example 1 to obtain a pigment dispersion.
The test shows that the average particle size of the pigment yellow dispersion obtained in example 1 is 408 nm, and the average particle size of the pigment yellow dispersion obtained in comparative example 1 is 2674 nm, and the modified cellulase has stronger dispersing capability; the dynamic instability index TSI value of the pigment yellow dispersion obtained via example 1 was 4.24, while the dynamic instability index TSI value of the pigment yellow dispersion obtained via comparative example 1 was 86, indicating that the modified cellulase can significantly improve the stability of the pigment dispersion.
Example 2
(1) Adding cellulase and NaOH with the mass ratio of 5:1 into deionized water for full dissolution, slowly adding oleoyl chloride accounting for 60% of the mass of the cellulase at 40 ℃, keeping the pH value of the system between 9 and 10 by using NaOH solution, heating to 50 ℃ after the dripping is finished, continuing to react for 2h, then adding hydrochloric acid to adjust the pH value to 1-2, separating out reactant precipitate, washing with deionized water to be neutral, and carrying out vacuum drying to obtain modified cellulase;
(2) Adding organic pigment blue, modified cellulose and sodium hydroxide in a mass ratio of 10:1:0.2 into deionized water, and performing ultrasonic treatment for 30 min to obtain pigment dispersion.
Comparative example 2
The organic pigment blue, cellulase and sodium hydroxide in a mass ratio of 10:1:0.2 were added to deionized water and treated under the same conditions as in example 2.
The test shows that the pigment blue dispersion obtained in the example 2 has the average particle size of 166 nm, and the pigment blue dispersion obtained in the comparative example 2 has the average particle size of 1071 nm, and the modified cellulase has stronger dispersing capability; the pigment dispersion obtained via example 2 has a dynamic instability index TSI value of 6.94, whereas the pigment dispersion obtained via comparative example 2 has a dynamic instability index TSI value of 38.93, indicating that the modified cellulase can significantly improve the stability of the pigment dispersion.

Claims (1)

1. A method for improving the dispersion performance of cellulase on organic pigment is characterized by adopting the following process:
(1) Adding cellulase and NaOH with the mass ratio of 5:1 into deionized water for full dissolution, slowly adding oleoyl chloride accounting for 60% of the mass of the cellulase at 40 ℃, keeping the pH value of the system between 9 and 10 by using NaOH solution, heating to 50 ℃ after the dripping is finished, continuing to react for 2h, then adding hydrochloric acid to adjust the pH value to 1-2, separating out reactant precipitate, washing with deionized water to be neutral, and carrying out vacuum drying to obtain modified cellulase;
(2) Adding the organic pigment, the modified cellulase and the sodium hydroxide into deionized water according to the mass ratio of 10:1:0.2, and carrying out ultrasonic treatment on the mixture for 30 min to obtain a pigment dispersion.
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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB809221A (en) * 1954-06-10 1959-02-18 Hoechst Ag A process for dyeing shaped structures of aromatic polyesters
FR1356864A (en) * 1963-05-22 1964-03-27 Hoechst Ag Process for dyeing and printing textile materials, in particular vegetable fiber materials
US4428750A (en) * 1979-06-01 1984-01-31 Hoechst Aktiengesellschaft Process for the localized lightening, white discharging or colored discharging of dyeings on textile sheet-like structures using dye dissolving agent
CN104923122A (en) * 2015-05-16 2015-09-23 山东全杰皮革研究所有限公司 Method for preparing collagen polypeptide based surfactant
CN107129533A (en) * 2017-05-05 2017-09-05 王全杰 A kind of preparation method of albumen based surfactants
CN107353672A (en) * 2017-07-08 2017-11-17 青岛大学 It is a kind of to improve method of the non-ionic dispersing agent to organic pigment dispersive property
CN108864754A (en) * 2018-06-19 2018-11-23 青岛大学 A method of cellulase is improved to organic pigment dispersion efficiency
CN116655902A (en) * 2023-04-17 2023-08-29 广东丽臣奥威实业有限公司 Non-liquid surfactant composition and preparation process thereof

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB809221A (en) * 1954-06-10 1959-02-18 Hoechst Ag A process for dyeing shaped structures of aromatic polyesters
FR1356864A (en) * 1963-05-22 1964-03-27 Hoechst Ag Process for dyeing and printing textile materials, in particular vegetable fiber materials
US4428750A (en) * 1979-06-01 1984-01-31 Hoechst Aktiengesellschaft Process for the localized lightening, white discharging or colored discharging of dyeings on textile sheet-like structures using dye dissolving agent
CN104923122A (en) * 2015-05-16 2015-09-23 山东全杰皮革研究所有限公司 Method for preparing collagen polypeptide based surfactant
CN107129533A (en) * 2017-05-05 2017-09-05 王全杰 A kind of preparation method of albumen based surfactants
CN107353672A (en) * 2017-07-08 2017-11-17 青岛大学 It is a kind of to improve method of the non-ionic dispersing agent to organic pigment dispersive property
CN108864754A (en) * 2018-06-19 2018-11-23 青岛大学 A method of cellulase is improved to organic pigment dispersion efficiency
CN116655902A (en) * 2023-04-17 2023-08-29 广东丽臣奥威实业有限公司 Non-liquid surfactant composition and preparation process thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
杨超;王蕊;蔡玉青;房宽峻;郝龙云;: "Tween 20/Span 20和纤维素酶协同分散酞菁铜颜料", 印染助剂, no. 04, 20 April 2018 (2018-04-20), pages 35 - 41 *

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