CN103741507A - Covalent bond tinting method applicable to silks - Google Patents
Covalent bond tinting method applicable to silks Download PDFInfo
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- CN103741507A CN103741507A CN201310737395.9A CN201310737395A CN103741507A CN 103741507 A CN103741507 A CN 103741507A CN 201310737395 A CN201310737395 A CN 201310737395A CN 103741507 A CN103741507 A CN 103741507A
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Abstract
The invention discloses a covalent bond tinting method applicable to silks. The covalent bond tinting method comprises the following steps: carrying out a Mannich reaction on tyrosine residues in the silks by a dye containing aromatic primary amine radicals in the presence of aldehydes materials, wherein a mass ratio of the dye containing the aromatic primary amine radicals to the silks is (0.005-0.03) to 1; a mol ratio of the dye containing the aromatic primary amine radicals to the aldehydes materials is 1 to (1-2); a dye bath ratio of the dye containing the aromatic primary amine radicals to the aldehydes materials is 1 to (20-100); a dye bath pH (Potential of Hydrogen) value keeps within a range of 4.0-6.5; a dyeing temperature is 30-70 DEG C; the heat preservation time is 0.5-24h; after dyeing, washing a product with hot water and cool water, so as to remove impurities adsorbed on the silks; and finally, drying. The method has the advantages of moderate dyeing conditions, energy conversation and environmental friendliness; the problem of fastness in wet-resistant treatment of the fibers of the silks can be foundationally solved.
Description
Technical field
The present invention relates to a kind of covalent bond colorize method that is applicable to silk.
Background technology
There is the not good problem of dyefastness in silk fiber, the existing silk fiber colouring method that is applicable to respectively has deficiency.Synthetic dyestuffs for dyeing silk mainly contain ACID DYES, premetallized dye and REACTIVE DYES at present.Although ACID DYES is bright in colour, chromatogram is complete, dye-uptake is high, it is combined with silk fiber by ion bonding force, is vulnerable to the solvation impact of water, and moisture resistant fastness is not good conventionally.Premetallized dye forms complex compound by acting on fiber of metal (chromium, cobalt) ion, has good moisture resistant fastness, but in fiber and dye liquor, a large amount of residual meetings of metal ion cause negative effect to health and environment.In REACTIVE DYES structure with reactive group, during dyeing, can react with the amino of silk fiber macromolecular chain end and the phenolic hydroxyl group in tyrosine residue and generate covalent bond and dying on fiber, yet the covalent bond forming between REACTIVE DYES and protein fibre mostly is ester group and amide groups, hydrolysis scission of link easily occurs in stronger acid, alkaline media, and REACTIVE DYES also cannot thoroughly solve the moisture resistant fastness problem of silk fiber thus; In addition, exist serious hydrolysis problem in reactive dye color fixing process, produce a large amount of colorful wastewaters, sewage disposal difficulty is large.Therefore, designing and a kind ofly can form firm covalent bonds with silk fiber, make it have excellent moisture resistant fastness, and reduce blowdown flow rate, is dyeing and finishing industry problem in the urgent need to address.
Silk fiber dyeing be take water conventionally as medium, and dye molecule enters fiber amorphous region and amino acid forms physics or chemically combined process, and the morphosis of its dyeability and fiber, aggregated structure, amino acid form closely related.Silk consists of fibroin and silk gum two parts, and the fibroin fiber degree of crystallinity after natural silk degumming is high, and it is few that amino dyes seat, and depth is poor.In forming the amino acid of silk fiber, only have tyrosine to contain phenol formula structure, not only content is high, and is mainly distributed in the easy fiber amorphous region of infiltrating of the aqueous solution.For example, the tyrosine residue molar content of Bombyx mori Silk Fibroin, tussah silk peptide is respectively 0.65 and
0.48m mol/1g fiber, the seat demand of dying of dying to dark heavy colour pool fiber that surpasses far away.
The chemical modification of protein side group is a kind of important method of improving Sporal Protein Chemical Properties.Can there are three components with aldehyde material, aryl primary amine and derivative thereof and react in the tyrosine residue in protein or polypeptide, make three kinds of materials by covalent bond strong bonded under gentle condition, and this class reaction is called Mannich reaction.
This seminar once applied for " a kind of colouring method of protein material " (201010039595.3), the method is to utilize tyrosine residue in protein fibre material as coupling component, and the method for using for reference ice dyeing dyeing develops the color different diazols and the tyrosine residue generation coupling reaction in protein fibre.The method is equally also applicable to the painted of silk fiber, and moisture resistant fastness is excellent.But the method is because coupling component is single, obtain dark difficulty, be only applicable to the painted of Huang, orange, the light silk fiber such as red.
Summary of the invention
The technical problem to be solved in the present invention is to provide and a kind ofly can forms with silk the dye coloring method of firm covalent bonds----a kind of covalent bond colorize method that is applicable to silk.
In order to solve the problems of the technologies described above, the invention provides a kind of covalent bond colorize method that is applicable to silk: the dyestuff containing aryl primary amine group reacts with the tyrosine residue generation Mannich in silk under the effect of aldehyde material, thereby dye molecule is firmly connected in the large molecule of silk;
Described is 0.005～0.03:1 containing the dyestuff of aryl primary amine group and the mass ratio of silk, containing the dyestuff of aryl primary amine group and the mol ratio of aldehyde material, is 1:1～2; Dye bath ratio is 1:20～100; Value in Dyeing Process remains in 4.0～6.5 scopes, dyeing temperature is 30～70 ℃, temperature retention time 0.5～24 hour, after dyeing finishes, then for example, through superheated water and cold water washing (being the deionized water washing through 60 ℃ and 15 ℃), thereby remove the impurity (washes clean from silk by dyestuff loose colour and aldehyde material) being adsorbed on silk, dry (under the room temperature of 10～25 ℃, drying in the air to constant weight).
Remarks explanation:
With the cushioning liquid of acetic acid-sodium acetate, regulate above-mentioned pH value, this is routine techniques.
The above-mentioned dyestuff containing aryl primary amine group, at least needs to exist an aryl primary amine in described dye structure.
As the improvement that is applicable to the covalent bond colorize method of silk of the present invention: aldehyde material is formaldehyde, acetaldehyde, propionic aldehyde, butyraldehyde or benzaldehyde.
As the further improvement that is applicable to the covalent bond colorize method of silk of the present invention: the described dyestuff containing aryl primary amine group is following any one dyestuff:
Weld:
At Coloration Technology, in 129,144-149, inform;
Orchil:
At Asian Journal of Chemistry (2009), 21 (6), in 4812-4820, inform;
Blue dyes 3:
In Revistade Chimie (Bucharest, Romania) (1969), 20 (12), in 717-27, inform.
In the present invention, to silk, without specific (special) requirements, mulberry silk and squeezing silk all can.
Consider that in silk fiber, tyrosine residue content is higher, and be mainly distributed in the fiber amorphous region that the aqueous solution easily infiltrates, the present invention is according to Mannich reaction mechanism, and providing a kind of can pass through the method for C-N abutment strong bonded by the dyestuff that contains aryl primary amine base and silk fiber.The method dyeing condition is gentle, energy-conserving and environment-protective, and can fundamentally solve the moisture resistant fastness problem of silk fiber.
The present invention utilizes the reactivity of tyrosine residue, adopt Mannich reaction that the dyestuff that contains aryl primary amine group (can contain whole chromatogram) is utilized to the tyrosine residue covalent bonds in aldehyde material bridge formation and silk fiber, can promote equally the moisture resistant fastness of silk; In addition, compare with " a kind of colouring method of protein material " of informing in background technology, method of the present invention can, by changing the method for dyestuff chromogen, obtain the shades of colour of containing whole chromatogram.
The Mannich of utilization reaction of the present invention is as follows by the reaction equation of the colouring method of C-N abutment strong bonded by the dyestuff that contains aryl primary amine base and silk fiber:
The beneficial effect that the present invention has is:
On silk fiber or fabric being carried out with upper dyeing method provided by the present invention, dying tool has the following advantages: (1) can select the existing acid dyeing containing aryl primary amine base, and such dyestuff chromatogram is complete, and development cost is low; (2) dyestuff is stable, is not hydrolyzed; (3) can dye approaching under the condition of room temperature, energy consumption is low; (4) in this decoration method, dyestuff reacts fixation with silk fiber under solutions of weak acidity, compares with alkaline high temperature fixation reactive dyeing, little to the damage of silk fiber; (5) institute's dyeing and weaving thing wet colour fastness is high.
The specific embodiment:
Embodiment 1, a kind of covalent bond colorize method that is applicable to silk, selecting the dyestuff containing aryl primary amine group is weld, its structural formula is as follows:
Aldehyde material is specifically selected formaldehyde.
Colorize method is specific as follows:
In 1000g Light of Mulberry Silk Fabrics, add 5g(0.0134mol) dyestuff and the formaldehyde of 0.0134mol; Dye bath ratio is 1:50; Value in Dyeing Process is that 6.5(regulates above-mentioned pH value with the cushioning liquid of acetic acid-sodium acetate, and this is routine techniques), dyeing temperature is 40 ℃, temperature retention time 20 hours.
After dyeing finishes, then through 60 ℃ and 15 ℃ of deionized water washings, thereby remove the impurity (washes clean from silk by dyestuff loose colour and formaldehyde) being adsorbed on silk, dry (under room temperature, drying in the air to constant weight).
Recording dyestuff (water-soluble solution) maximum absorption wavelength is 448nm, after upper dyeing and weaving thing, maximum absorption wavelength is 400nm, and the silk after method described in embodiment 1 is processed is tested to GB/T3920-2008 > > according to national standard < < color fastness to washing GB/T3921-2008 > > and national standard < < colour fastness to rubbing.DYED FABRICS wet rubbing fastness is 4 grades, and it is 4 grades that washing fastness is stained with cotton, is stained with silk for 4-5 level, and former state variable color is 3-4 level, and known employing the method is being dyed fabric and had excellent COLOR FASTNESS.
Embodiment 2, a kind of covalent bond colorize method that is applicable to silk, selecting the dyestuff containing aryl primary amine group is orchil, its structural formula is as follows:
Aldehyde material is specifically selected acetaldehyde.
Colorize method is specific as follows:
In 1000g Light of Mulberry Silk Fabrics, add 30g(0.07mol) dyestuff and the acetaldehyde of 0.14mol; Dye bath ratio is 1:100; Value in Dyeing Process is 4.0, and dyeing temperature is 30 ℃, temperature retention time 24 hours.
After dyeing finishes, then through 60 ℃ and 15 ℃ of deionized water washings, thereby remove the impurity being adsorbed on silk, dry.
Recording dyestuff (water-soluble solution) maximum absorption wavelength is 530nm, after upper dyeing and weaving thing, maximum absorption wavelength is 540nm, and the silk after method described in embodiment 2 is processed is tested to GB/T3920-2008 > > according to national standard < < color fastness to washing GB/T3921-2008 > > and national standard < < colour fastness to rubbing.DYED FABRICS wet rubbing fastness is 3-4 level, and it is 4-5 level that washing fastness is stained with cotton, and being stained with silk is 4 grades, and former state variable color is 3-4 level, and known this method is being dyed fabric and had excellent COLOR FASTNESS.
Embodiment 3, a kind of covalent bond colorize method that is applicable to silk, selecting the dyestuff containing aryl primary amine group is blue dyes, its structural formula is as follows:
Aldehyde material is specifically selected propionic aldehyde.
Colorize method is specific as follows:
In 1000g squeezes silk fabric, add 20g(0.049mol) dyestuff and the propionic aldehyde of 0.07mol; Dye bath ratio is 1:20; Value in Dyeing Process is 6.0, and dyeing temperature is 70 ℃, temperature retention time 0.5 hour.
After dyeing finishes, then through 60 ℃ and 15 ℃ of deionized water washings, thereby remove the impurity being adsorbed on silk, dry.
Recording dyestuff (water-soluble solution) maximum absorption wavelength is 628nm, after upper dyeing and weaving thing, maximum absorption wavelength is 630nm, and the silk after method described in embodiment 3 is processed is tested to GB/T3920-2008 > > according to national standard < < color fastness to washing GB/T3921-2008 > > and national standard < < colour fastness to rubbing.Resistance to dry fastness is 4-5 level, and moisture-proof friction is 4-5 level, and washing fastness is stained with a 4-5 level, and sticky cotton is 4-5 level, and former state variable color is 4 grades, and known this method is being dyed fabric and had excellent COLOR FASTNESS.
Comparative example 1,
Blue dyes in embodiment 3 dyes (being equivalent to acid dyeing) to silk fabric in the situation that not adding propionic aldehyde, recording the resistance to dry fastness of DYED FABRICS is 4 grades, and fastness to wet rubbing is 3-4 level, and it is 4 grades that washing fastness is stained with silk, sticky cotton is 4-5 level, and former state variable color is 4 grades.
Its moisture resistant fastness is obviously not as the present invention.
Comparative example 2,
The yellow SD of REACTIVE DYES Remazol is at 2%owf, 90 ℃, bath raio 1:50, under pH8-10 dyeing condition, silk degree of fixation only reaches 85% left and right, and silk ultimate strength loses about 10%(data and comes from University Of Suzhou's Master's thesis: Guo Changqing, silk fabric chromaticity of reactive dye research .2007.).By comparison, weld in embodiment 1 utilizes the reactivity of tyrosine residue, the dyestuff that contains arylamine group is utilized to the tyrosine residue covalent bonds in aldehyde material bridge formation and silk fiber, wherein dye structure used is stable, dyeing only need to be dyeed under acid (pH6.5) condition of weak acid, does not have hydrolysis problem.In addition, decoration method of the present invention is compared with alkaline high temperature fixation reactive dyeing, and silk ultimate strength loses less than 1%; And solved the hydrolysis problem of silk at alkali condition, in addition method weld of the present invention is to dye approaching under the condition of room temperature, has reduced the consumption of energy, reaches the object of energy-saving and emission-reduction.
Finally, it is also to be noted that, what more than enumerate is only several specific embodiments of the present invention.Obviously, the invention is not restricted to above embodiment, can also have many distortion.All distortion that those of ordinary skill in the art can directly derive or associate from content disclosed by the invention, all should think protection scope of the present invention.
Claims (3)
1. the covalent bond colorize method that is applicable to silk, is characterized in that: the dyestuff containing aryl primary amine group reacts with the tyrosine residue generation Mannich in silk under the effect of aldehyde material;
Described is 0.005～0.03:1 containing the dyestuff of aryl primary amine group and the mass ratio of silk, and described is 1:1～2 containing the dyestuff of aryl primary amine group and the mol ratio of aldehyde material; Dye bath ratio is 1:20～100; Value in Dyeing Process remains on 4.0～6.5, and dyeing temperature is 30～70 ℃, temperature retention time 0.5～24 hour;
After dyeing finishes, through superheated water and cold water washing, thereby remove the impurity being adsorbed on silk, dry.
2. the covalent bond colorize method that is applicable to silk according to claim 1, is characterized in that:
Described aldehyde material is formaldehyde, acetaldehyde, propionic aldehyde, butyraldehyde or benzaldehyde.
3. the covalent bond colorize method that is applicable to silk according to claim 2, is characterized in that:
The described dyestuff containing aryl primary amine group is following any one dyestuff:
Weld, structural formula is:
Orchil, structural formula is:
Blue dyes, structural formula is:
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103741507B (en) * | 2013-12-27 | 2015-11-11 | 浙江理工大学 | Be applicable to the covalent bond colorize method of silk |
| CN106083625A (en) * | 2016-05-31 | 2016-11-09 | 安徽工程大学 | A kind of chemical modification method of tyrosine |
| CN108130759A (en) * | 2017-12-22 | 2018-06-08 | 浙江理工大学 | Realize the method that aryl primary amine dyestuff dyes protein fibre fabric covalent bond |
| CN108505366A (en) * | 2018-04-13 | 2018-09-07 | 江南大学 | A method of carrying out silk dyeing by being grafted polypeptide and coupling reaction |
| CN109535095A (en) * | 2018-12-10 | 2019-03-29 | 浙江理工大学上虞工业技术研究院有限公司 | Aryl primary amine fluorescent whitening agent and preparation method thereof suitable for silk |
| CN110592977A (en) * | 2019-08-20 | 2019-12-20 | 浙江理工大学上虞工业技术研究院有限公司 | Rapid reactive dyeing method suitable for silk |
| CN111205670A (en) * | 2020-02-29 | 2020-05-29 | 浙江理工大学上虞工业技术研究院有限公司 | Double-aromatic primary amine acid dye containing H acid structure and preparation method thereof |
| CN111303654A (en) * | 2020-02-29 | 2020-06-19 | 浙江理工大学上虞工业技术研究院有限公司 | Diarylamine acid dye containing β -naphthylamine structure and preparation method thereof |
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103741507B (en) * | 2013-12-27 | 2015-11-11 | 浙江理工大学 | Be applicable to the covalent bond colorize method of silk |
| CN106083625A (en) * | 2016-05-31 | 2016-11-09 | 安徽工程大学 | A kind of chemical modification method of tyrosine |
| CN106083625B (en) * | 2016-05-31 | 2018-07-03 | 安徽工程大学 | A kind of chemical modification method of tyrosine |
| CN108130759A (en) * | 2017-12-22 | 2018-06-08 | 浙江理工大学 | Realize the method that aryl primary amine dyestuff dyes protein fibre fabric covalent bond |
| CN108130759B (en) * | 2017-12-22 | 2020-03-31 | 浙江理工大学 | Method for realizing covalent binding dyeing of protein fiber fabric by aromatic primary amine dye |
| CN108505366A (en) * | 2018-04-13 | 2018-09-07 | 江南大学 | A method of carrying out silk dyeing by being grafted polypeptide and coupling reaction |
| CN109535095B (en) * | 2018-12-10 | 2021-08-27 | 浙江理工大学上虞工业技术研究院有限公司 | Aromatic primary amine fluorescent whitening agent suitable for silk and preparation method thereof |
| CN109535095A (en) * | 2018-12-10 | 2019-03-29 | 浙江理工大学上虞工业技术研究院有限公司 | Aryl primary amine fluorescent whitening agent and preparation method thereof suitable for silk |
| CN110592977A (en) * | 2019-08-20 | 2019-12-20 | 浙江理工大学上虞工业技术研究院有限公司 | Rapid reactive dyeing method suitable for silk |
| CN110592977B (en) * | 2019-08-20 | 2021-10-26 | 浙江理工大学上虞工业技术研究院有限公司 | Rapid reactive dyeing method suitable for silk |
| CN111303654A (en) * | 2020-02-29 | 2020-06-19 | 浙江理工大学上虞工业技术研究院有限公司 | Diarylamine acid dye containing β -naphthylamine structure and preparation method thereof |
| CN111205670B (en) * | 2020-02-29 | 2021-03-02 | 浙江理工大学上虞工业技术研究院有限公司 | Double-aromatic primary amine acid dye containing H acid structure and preparation method thereof |
| CN111205670A (en) * | 2020-02-29 | 2020-05-29 | 浙江理工大学上虞工业技术研究院有限公司 | Double-aromatic primary amine acid dye containing H acid structure and preparation method thereof |
| CN111303654B (en) * | 2020-02-29 | 2021-09-03 | 浙江理工大学上虞工业技术研究院有限公司 | Biaryl primary amine acid dye containing beta-naphthylamine structure and preparation method thereof |
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Application publication date: 20140423 Assignee: Zhejiang Sci-Tech University Shangyu Industrial Technology Research Institute Co., Ltd. Assignor: Zhejiang University of Technology Contract record no.: X2019330000038 Denomination of invention: Covalent bond tinting method applicable to silks Granted publication date: 20151111 License type: Common License Record date: 20191108 |
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