CN103952927A - Linen fiber biologic dyeing process based on laccase catalysis polymerization color generation reaction - Google Patents
Linen fiber biologic dyeing process based on laccase catalysis polymerization color generation reaction Download PDFInfo
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- CN103952927A CN103952927A CN201410184009.2A CN201410184009A CN103952927A CN 103952927 A CN103952927 A CN 103952927A CN 201410184009 A CN201410184009 A CN 201410184009A CN 103952927 A CN103952927 A CN 103952927A
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- linen
- flax fibre
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- laccase
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Abstract
The invention discloses a linen fiber biologic dyeing process based on laccase catalysis polymerization color generation reaction, which belongs to the technical field of application of linen fiber dyeing and finishing processing in the linen spinning industry. The process organically combines laccase catalysis colorless micromolecule phenol monomer polymerization color generation and linen fiber dyeing, and aims at reducing the energy consumption in dyeing linen fibers, shorting the procedures of the dyeing process, solving the technical problems that a conventional dyeing method is high in dyeing condition requirement, the dyeing process is complex, the water and energy consumption is high and the like, and achieving the biologic method dyeing of the linen fibers by utilizing the efficiency and the cleanliness of the laccase catalysis polymerization color generation reaction. The process comprises the following steps: treating the linen fibers in sodium hydroxide solution and sodium silicate solution with certain concentrations for a period of time, washing in water, neutralizing by acetic acid, drying, subsequently adding into a buffer solution with phenol monomers and laccase, reacting for a period of time at certain temperature to polymerize the phenol monomers to form a colored high-molecular polymer which is combined with the linen fibers, performing high temperature color fixation and enzyme inactivation treatment, washing in water and drying. The process can replace the conventional dyeing method to realize biologic method dyeing of the linen fibers.
Description
Technical field
A flax fibre biological stain technique based on Laccase Catalyzed polymerization color producing reaction, belongs to the applied technical field that in ramie textile industry, flax fibre dyeing and finishing is processed.
Background technology
In recent years, along with the increasingly stringent of domestic and international environmental regulation, the dyeing processing that cleans of each fibrid was shown great attention to.Traditional dyeing method and theory based on little molecule synthesis dyestuff face lot of challenges, are mainly reflected in: synthetic dyestuffs preparation section complexity, environmental pollution are large; Dyeing condition requires that high (often needing harsh pH value and high temperature), dyeing complexity, water consumption energy consumption are high, dyeing waste-water difficult treatment.Common dyes molecular weight is low, and dyeing product crock fastness is not good enough, tinting strength, tinting power is low, and dye utilization rate is low, also existing problems in various degree of fast light, heat resistance, and fiber is poor for applicability etc.The natural dye of rising in recent years is because of deficiencies such as chromatogram are incomplete, use heavy metal mordant contaminated environment, dyefastness is poor, and practical application is extremely restricted.
High molecular dye can overcome a series of deficiencies that above-mentioned low molecular dye exists.In general, high molecular dye is, through series of chemical, chromophoric group is implanted to high molecular main chain or side chain, thereby the new class coloured macromolecule compound forming, they had both had the characteristics such as the gorgeous color of little molecular dye and stronger colorability, there is again the advantages such as macromolecular material solvent resistance, resistance to migration and heat resistance, be widely used in the field such as plastic processing, photosensitive material.Although high molecular dye development in recent years is rapid, on polymer macromolecule skeleton, the chromophoric group of combination is few, synthetic method exists activated monomer to prepare difficulty and aggregate rate is low, product is difficult to the problems such as purifying, has restricted the practical application of high molecular dye.Therefore, exploring novel high molecular dye synthetic method is of great practical significance undoubtedly.
Along with the development of biotechnology, utilize the research of biology enzyme synthetic polymer to receive original more concerns.With compare by chemical catalysis technology synthetic high polymer, biological enzyme catalyst is synthetic have combined coefficient high, select the plurality of advantages such as the good and polymerizing condition milder of selectivity.In this respect, the organic synthesis process based on Laccase Catalyzed is simple, reaction condition is gentle and basic nonhazardous (unique accessory substance is water), replaces the synthetic method of conventional chemical to obtain day by day deep research thereby be therefore taken as.
Since finding laccase composition from the eighties in 19th century and propose laccase (laccase) concept in lacquer tree secretion (paint liquid), laccase and catalytic reaction thereof are just the focuses that people study always.Particularly in recent years, along with the commercialization of good stability, industrial microorganism laccase preparation that commercial Application cost is low, oxidation reaction occurs the substrates such as Laccase Catalyzed phenols, aromatic amine and fatty amines (under small molecular mediator exists, the oxidable substrate scope of laccase can further expand non-zymolyte to) research and application have made great progress.Research both at home and abroad shows, laccase can the colourless aromatic of the little molecule of catalysis (as phenol, arylamine etc.) oxidation generate living radical intermediate, the active particle that these reactivities are stronger both can cause the exogenous molecules glycerol polymerization (heterologous molecule polymerization) with special construction, also can cause himself polymerization and generate macromolecular compound (homolgous molecule polymerization), make new material or there is the material of novel capabilities.Meanwhile, aldehydes matter can present different color and lusters after oxidation, has been widely used in coloring hairs.
Fiber crops are one of textile raw materials of using the earliest of the mankind, and there is abundant flax fibre resource in China.Abundant lignin is contained on flax fibre surface, and its content of lignin is as shown in table 1.
The chemical composition of table 1 flax fibre
Research both at home and abroad shows, lignin is the suitable substrates of laccase, phenolic hydroxyl group in its molecular structure is after Laccase Catalyzed, can form Phenoxy radical, the active particle that these reactivities are stronger can cause the exogenous molecules with special construction as the monomer polymerization such as phenols, aromatic amine formation colored polymeric.
The present invention utilizes the catalytic polymerization characteristic of laccase, the polymerization of colourless little molecular phenolics compound for catalysis is formed to coloured high molecular polymer, and this process is combined with the dyeing of flax fibre, realize the bioanalysis dyeing of flax fibre high-efficiency cleaning, for new method and route are opened up in the dyeing of fibrous material.
Summary of the invention
The present invention is taking the flax fibre that is rich in lignin as representative fibers, colourless Laccase Catalyzed little molecular phenolics monomer polymerization is added lustre to and combined with flax fibre dyeing, be intended to utilize the high efficiency of Laccase Catalyzed polymerization color producing reaction and spatter property to realize the bioanalysis dyeing of flax fibre.Use the present invention can reduce the dyeing energy consumption of flax fibre, shorten dyeing flow process, the requirement of solution traditional dyeing method dyeing condition is high, dyeing is complicated, water consumption energy consumption high-technology problem, realizes the object of green dyeing and finishing processing.
Technical scheme of the present invention: a kind of flax fibre biological stain technique based on Laccase Catalyzed polymerization color producing reaction, flax fibre or fabric are processed certain hour in certain density NaOH and sodium silicate solution, part is removed the remaining slurry on pectin and the linen on flax fibre surface, and the lignin on flax fibre surface is fully exposed.Then water cleaning, dilute acetic acid solution neutralization, low temperature drying.Again flax fibre or linen through alkali treatment are immersed in the hac buffer that contains certain density phenolic monomers and laccase, under uniform temperature and certain pH value, process certain hour, make phenolic monomers polymerization form coloured high molecular polymer and be combined with flax fibre surface lignin, realizing the biological stain of flax fibre linen alive.Then carry out high temperature fixation and the enzyme processing of going out, more fully washing, the various unreacted phenolic monomers on removal flax fibre or linen and the enzyme of deactivation, finally dry.
Its technological process is:
(1) alkali treatment of flax fibre or linen
Flax fibre or the processing of linen → soda bath (NaOH5-30g/L, Na
2siO
42g/L, JFC2g/L, bath raio 1: 10-100,90-100 DEG C, 0.5-2h) → 50 DEG C of washing (2-3 time) → dilute acetic acid solution washings (1-10g/L acetic acid, 10-30min) → washing → dry (50 DEG C-80 DEG C).
The object of flax fibre or linen alkali treatment is to remove remaining slurry on pectic substance on flax fibre and linen, and the lignin on flax fibre can more be come out, and increases the grafting site of phenolic monomers, improves graft effect.But the concentration of NaOH can not be too high because the phenolic hydroxyl group on lignin can with caustic soda effect, make its solubility in alkali lye increase and be removed, grafting site is reduced, thereby causes graft effect to decline.
(2) flax fibre or the linen biological stain based on Laccase Catalyzed polymerization color producing reaction
The flax fibre of process alkali treatment or fabric → join and contain phenolic monomers and laccase, in the NaAc_HAc buffer solution of pH5.0, at 50 DEG C of isothermal reaction 5h, (laccase consumption is 100U/L, the consumption 25mmol/L of phenolic monomers; bath raio 1: 50) → high temperature fixation and the fully clean → 50-90 DEG C oven dry of enzyme (90 DEG C, 30min) → clear water of going out.
A kind of flax fibre biological stain technique based on Laccase Catalyzed polymerization color producing reaction, the gunny products that this method is suitable for processing is the fiber that is rich in lignin, as linen fibre, hemp, ramee, sisal fiber, tossa, can be to be also rich in other fiber of lignin as bamboo fibre, lumber fibre etc.The flax fibre using can be both flax fibre itself, can be also woven, knitted fabric or the supatex fabric of being made up of these flax fibres.
A flax fibre biological stain technique based on Laccase Catalyzed polymerization color producing reaction, is characterized in that by the phenolic monomers of Laccase Catalyzed polymerization can be catechol, resorcinol, hydroquinones, can be also catechol, caffeic acid etc.
Beneficial effect of the present invention: a kind of flax fibre biological stain technique based on Laccase Catalyzed polymerization color producing reaction of the present invention, cause colourless little molecular phenolics monomer polymerization by Laccase Catalyzed and form coloured high polymer, and be combined with flax fibre surface lignin, bioanalysis dyeing and the dyeing flax fibre of having realized flax fibre clean and effective have compared with high color fastness.Laccase Catalyzed polymerization color producing reaction also has selective height, treatment conditions gentleness, advantages of environment protection.
Detailed description of the invention
Embodiment 1
Sample kind: sodolin.
Preparation NaOH20g/L, Na
2siO
4the alkali lye of 2g/L and JFC2g/L, drops into sodolin, and bath raio 1: 30 is processed 1.5h in 95 DEG C of waters bath with thermostatic control, and taking-up is rear with 50 DEG C of hot washes 2-3 time, then processes 30min with the dilute acetic acid solution of 3g/L, finally fully washes 60 DEG C of dry for standby with clear water.
The learnt from else's experience sodolin of above-mentioned alkali treatment, join that in the NaAc_HAc buffer solution that contains catechol monomer and laccase, pH5.0, (laccase consumption is 100U/L, the consumption of catechol monomer is 25mmol/L); bath raio 1: 50; at 50 DEG C of isothermal reaction 5h; 90 DEG C of high temperature fixation 30min, clear water is fully clean, 70 DEG C of oven dry.
After above-mentioned PROCESS FOR TREATMENT, sodolin obtains dark brown cloth cover Color, and K/S value increases by 6.64,3 grades of washing variable color fastness, 4 grades of washing staining fastnesses, dry fastness 4-5 level, fastness to wet rubbing 4-5 level.
Embodiment 2
Sample kind: megila
Preparation NaOH20g/L, Na
2siO
4the alkali lye of 2g/L and JFC2g/L, drops into sodolin, and bath raio 1: 30 is processed 2.0h in 90 DEG C of waters bath with thermostatic control, and taking-up is rear with 60 DEG C of hot washes 2-3 time, then processes 20min with the dilute acetic acid solution of 2g/L, finally fully washes 50 DEG C of dry for standby with clear water.
The learnt from else's experience megila of above-mentioned alkali treatment, join that in the NaAc_HAc buffer solution that contains hydroquinones monomer and laccase, pH5.0, (laccase consumption is 100U/L, the consumption of hydroquinones monomer is 25mmol/L); bath raio 1: 50; at 50 DEG C of isothermal reaction 5h; 90 DEG C of high temperature fixation 30min, clear water is fully clean, 70 DEG C of oven dry.
After above-mentioned PROCESS FOR TREATMENT, megila obtains burgundy painting cloth face Color, and K/S value increases by 7.15, washing variable color fastness 3-4 level, 4 grades of washing staining fastnesses, 5 grades of dry fastnesses, fastness to wet rubbing 4-5 level.
Claims (3)
1. the flax fibre biological stain technique based on Laccase Catalyzed polymerization color producing reaction, it is characterized in that flax fibre or fabric to process certain hour in certain density NaOH and sodium silicate solution, part is removed the remaining slurry on pectin and the linen on flax fibre surface, and the lignin on flax fibre surface is fully exposed; Then water cleaning, dilute acetic acid solution neutralization, low temperature drying; Again flax fibre or linen through alkali treatment are immersed in the hac buffer that contains certain density phenolic monomers and laccase, under uniform temperature and certain pH value, process certain hour, make phenolic monomers polymerization form coloured high molecular polymer and be combined with flax fibre surface lignin, realizing the biological stain of flax fibre linen alive; Then carry out high temperature fixation and the enzyme processing of going out, more fully washing, the various unreacted phenolic monomers on removal flax fibre or linen and the enzyme of deactivation, finally dry;
Its technological process is:
(1) alkali treatment of flax fibre or linen
Flax fibre or the processing of linen → soda bath (NaOH5-30g/L, Na
2siO
42g/L, JFC2g/L, bath raio 1: 10-100,90-100 DEG C, 0.5-2h) → 50 DEG C of washing (2-3 time) → dilute acetic acid solution washings (1-10g/L acetic acid, 10-30min) → washing → dry (50-80 DEG C);
(2) flax fibre or the linen biological stain based on Laccase Catalyzed polymerization color producing reaction
The flax fibre of process alkali treatment or fabric → join and contain phenolic monomers and laccase, in the NaAc_HAc buffer solution of pH5.0, at 50 DEG C of isothermal reaction 5h, (laccase consumption is 100U/L, the consumption 25mmol/L of phenolic monomers; bath raio 1: 50) → high temperature fixation and the fully clean → 50-90 DEG C oven dry of enzyme (90 DEG C, 30min) → clear water of going out.
2. a kind of flax fibre biological stain technique based on Laccase Catalyzed polymerization color producing reaction according to claim 1, it is characterized in that the gunny products that is suitable for processing is the fiber that is rich in lignin, as linen fibre, hemp, ramee, sisal fiber, tossa, can be to be also rich in other fiber of lignin as bamboo fibre, lumber fibre etc.; The flax fibre using can be both flax fibre itself, can be also woven, knitted fabric or the supatex fabric of being made up of these flax fibres.
3. a kind of flax fibre biological stain technique based on Laccase Catalyzed polymerization color producing reaction according to claim 1, it is characterized in that by the phenolic monomers of Laccase Catalyzed polymerization can be catechol, resorcinol, hydroquinones, can be also catechol, caffeic acid etc.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9718944B2 (en) | 2015-04-02 | 2017-08-01 | Cnh Industrial Canada, Ltd. | Method of coloring biocomposite materials |
| CN108478465A (en) * | 2018-04-03 | 2018-09-04 | 南通大学 | A kind of biological health black hair dyeing technique |
| CN108978270A (en) * | 2018-07-27 | 2018-12-11 | 南通霆川电子科技有限公司 | A kind of flaxen fiber biological stain technique based on Laccase Catalyzed polymerization reaction |
| CN109183446A (en) * | 2018-08-22 | 2019-01-11 | 胡超 | Jute fabric plus material producing method |
| CN110725141A (en) * | 2019-11-18 | 2020-01-24 | 武汉纺织大学 | Enzyme-dyed lyocell fiber fabric and preparation method thereof |
| CN112593425A (en) * | 2020-12-05 | 2021-04-02 | 浙江灏宇科技有限公司 | Finishing method for improving color fastness of cotton fabric dyed by laccase-catalyzed plant dye |
| CN112813707A (en) * | 2021-01-22 | 2021-05-18 | 南通大学 | Ecological cotton fabric dyeing method based on laccase/polyacid synergistic reaction |
| CN113026389A (en) * | 2021-03-18 | 2021-06-25 | 南通大学 | Method for enzymatic dyeing of cashmere by using tea polyphenol low-temperature paint |
| CN113047062A (en) * | 2021-03-26 | 2021-06-29 | 南通大学 | Cotton fabric dyeing method based on polyacid catalysis |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9718944B2 (en) | 2015-04-02 | 2017-08-01 | Cnh Industrial Canada, Ltd. | Method of coloring biocomposite materials |
| CN108478465A (en) * | 2018-04-03 | 2018-09-04 | 南通大学 | A kind of biological health black hair dyeing technique |
| CN108978270A (en) * | 2018-07-27 | 2018-12-11 | 南通霆川电子科技有限公司 | A kind of flaxen fiber biological stain technique based on Laccase Catalyzed polymerization reaction |
| CN109183446A (en) * | 2018-08-22 | 2019-01-11 | 胡超 | Jute fabric plus material producing method |
| CN110725141A (en) * | 2019-11-18 | 2020-01-24 | 武汉纺织大学 | Enzyme-dyed lyocell fiber fabric and preparation method thereof |
| CN110725141B (en) * | 2019-11-18 | 2022-04-22 | 武汉纺织大学 | Enzyme-dyed lyocell fiber fabric and preparation method thereof |
| CN112593425A (en) * | 2020-12-05 | 2021-04-02 | 浙江灏宇科技有限公司 | Finishing method for improving color fastness of cotton fabric dyed by laccase-catalyzed plant dye |
| CN112813707A (en) * | 2021-01-22 | 2021-05-18 | 南通大学 | Ecological cotton fabric dyeing method based on laccase/polyacid synergistic reaction |
| CN112813707B (en) * | 2021-01-22 | 2021-09-07 | 南通大学 | Ecological cotton fabric dyeing method based on laccase/polyacid synergistic reaction |
| CN113026389A (en) * | 2021-03-18 | 2021-06-25 | 南通大学 | Method for enzymatic dyeing of cashmere by using tea polyphenol low-temperature paint |
| CN113047062A (en) * | 2021-03-26 | 2021-06-29 | 南通大学 | Cotton fabric dyeing method based on polyacid catalysis |
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Application publication date: 20140730 |