CN103741507B - Be applicable to the covalent bond colorize method of silk - Google Patents
Be applicable to the covalent bond colorize method of silk Download PDFInfo
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- CN103741507B CN103741507B CN201310737395.9A CN201310737395A CN103741507B CN 103741507 B CN103741507 B CN 103741507B CN 201310737395 A CN201310737395 A CN 201310737395A CN 103741507 B CN103741507 B CN 103741507B
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Abstract
The invention discloses a kind of covalent bond colorize method being applicable to silk: the dyestuff containing aryl primary amine group with the tyrosine residue in silk, Mannich occurs and reacts 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, described contain aryl primary amine group dyestuff and aldehyde material mole be 1:1 ~ 2; Dye bath ratio is 1:20 ~ 100; Value in Dyeing Process remains on 4.0 ~ 6.5, and dyeing temperature is 30 ~ 70 DEG C, temperature retention time 0.5 ~ 24 hour; After dyeing terminates, through superheated water and cold water washing, thus remove the impurity be adsorbed on silk, dry.The method dyeing condition is gentle, energy-conserving and environment-protective, and the moisture resistant fastness problem that fundamentally can solve silk fiber.
Description
Technical field
The present invention relates to a kind of covalent bond colorize method being 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 at present for dyeing silk mainly contain ACID DYES, premetallized dye and REACTIVE DYES.Although ACID DYES is bright in colour, chromatogram is complete, dye-uptake is high, it is combined with silk fiber by ionic forces, and be vulnerable to the solvation impact of water, usual moisture resistant fastness is not good.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 metal ion is residual can cause negative effect to health and environment.With reactive group in REACTIVE DYES structure, can react with the phenolic hydroxyl group in the amino of silk fiber macromolecular chain end and tyrosine residue during dyeing and generate covalent bond and stained with on fiber, but the covalent bond formed between REACTIVE DYES and protein fibre mostly is ester group and amide groups, in stronger acid, alkaline media, hydrolysis scission of link easily occurs, REACTIVE DYES also thoroughly cannot solve the moisture resistant fastness problem of silk fiber thus; In addition, there is serious hydrolysis problem in reactive dye color fixing process, produce a large amount of colorful wastewater, sewage disposal difficulty is large.Therefore, design one can form firm covalent bonds with silk fiber, makes it have excellent moisture resistant fastness, and reduces blowdown flow rate, is dyeing and finishing industry problem in the urgent need to address.
Silk fiber dyeing is usual is medium with water, 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 is made up of fibroin and silk gum two parts, and the fibroin fiber degree of crystallinity after natural silk degumming is high, and amino dye seat is few, and depth is poor.In the amino acid forming silk fiber, only have tyrosine to contain phenolic structure, not only content is high, and is mainly distributed in fiber amorphous region that the aqueous solution easily infiltrates.Such as, the tyrosine residue molar content of Bombyx mori Silk Fibroin, tussah silk peptide is respectively 0.65 and
0.48mmol/1g fiber, far exceedes the dye seat demand of dye to dark heavy colour pool fiber.
The chemical modification of protein side base is a kind of important method 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, this kind of reaction is called that Mannich reacts under mild conditions.
This seminar once applied for " a kind of colouring method of protein material " (201010039595.3), the method utilizes tyrosine residue in protein fibre material as coupling component, and the method using for reference ice dyeing dyeing makes the tyrosine residue generation coupling reaction in different diazols and protein fibre develop the color.The method is equally also applicable to the painted of silk fiber, and moisture resistant fastness is excellent.But the method is single due to coupling component, obtain dark difficulty, be only applicable to Huang, orange, the light silk fiber such as red painted.
Summary of the invention
The technical problem to be solved in the present invention is to provide and a kind ofly can forms dye coloring method----a kind of covalent bond colorize method being applicable to silk of firm covalent bonds with silk.
In order to solve the problems of the technologies described above, the invention provides a kind of covalent bond colorize method being applicable to silk: the dyestuff containing aryl primary amine group with the tyrosine residue in silk, Mannich occurs and reacts under the effect of aldehyde material, thus 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, 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 in 4.0 ~ 6.5 scopes, dyeing temperature is 30 ~ 70 DEG C, temperature retention time 0.5 ~ 24 hour, after dyeing terminates, then through superheated water and cold water washing (being such as the deionized water washing through 60 DEG C and 15 DEG C), thus removing is adsorbed on impurity on silk (by dyestuff loose colour and aldehyde material from washes clean silk), dries (drying in the air to constant weight under the room temperature of 10 ~ 25 DEG C).
Remarks illustrate:
Regulate above-mentioned pH value with the cushioning liquid of Acetic acid-sodium acetate, this is routine techniques.
The above-mentioned dyestuff containing aryl primary amine group, at least needs existence aryl primary amine in namely described dye structure.
As the improvement being 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 being applicable to the covalent bond colorize method of silk of the present invention: the described dyestuff containing aryl primary amine group is any one dyestuff following:
Weld:
At ColorationTechnology, inform in 129,144-149;
Orchil:
In AsianJournalofChemistry (2009), inform in 21 (6), 4812-4820;
Blue dyes 3:
In RevistadeChimie (Bucharest, Romania) (1969), inform in 20 (12), 717-27.
In the present invention, to silk without particular/special requirement, mulberry silk and squeezing silk.
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 according to Mannich reaction mechanism, provide a kind of can by the dyestuff containing aryl primary amine base and the silk fiber method by C-N abutment strong bonded.The method dyeing condition is gentle, energy-conserving and environment-protective, and the moisture resistant fastness problem that fundamentally can solve silk fiber.
The present invention utilizes the reactivity of tyrosine residue, adopt Mannich reaction to be utilized by the dyestuff (can whole chromatogram be contained) containing aryl primary amine group aldehyde material to build bridge and the tyrosine residue covalent bonds in silk fiber, the moisture resistant fastness of silk can be promoted equally; In addition, compared with " a kind of colouring method of protein material " of informing in background technology, method of the present invention by changing the method for dyestuff chromogen, can obtain the shades of colour containing whole chromatogram.
Of the present invention utilize Mannich react by the dyestuff containing aryl primary amine base and silk fiber as follows by the reaction equation of the colouring method of C-N abutment strong bonded:
The beneficial effect that the present invention has is:
Carry out upper dye tool with upper dyeing method provided by the present invention to silk fiber or fabric to have the following advantages: (1) can select the existing acid dyeing containing aryl primary amine base, and such dye chromatography is complete, and development cost is low; (2) dye stabilizer, is not hydrolyzed; (3) can dye under close to the condition of room temperature, energy consumption is low; (4) in this decoration method, dyestuff and silk fiber react fixation under mildly acidic conditions, compared 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.
Detailed description of the invention:
Embodiment 1, a kind of covalent bond colorize method being applicable to silk, select the dyestuff containing aryl primary amine group to be weld, its structural formula is as follows:
Aldehyde material specifically selects 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 be the cushioning liquid of 6.5(Acetic acid-sodium acetate to regulate above-mentioned pH value, this is routine techniques), dyeing temperature is 40 DEG C, temperature retention time 20 hours.
After dyeing terminates, then through 60 DEG C and the washing of 15 DEG C of deionized waters, thus remove and be adsorbed on impurity on silk (by dyestuff loose colour and formaldehyde from washes clean silk), dry (drying in the air to constant weight under room temperature).
Recording dyestuff (water-soluble solution) maximum absorption wavelength is 448nm, after upper dyeing and weaving thing, maximum absorption wavelength is 400nm, by the silk after method process described in embodiment 1 according to national standard " color fastness to washing GB/T3921-2008 " and national standard " colour fastness to rubbing experiment GB/T3920-2008 ".DYED FABRICS wet rubbing fastness is 4 grades, and it is 4 grades that washing fastness is stained with cotton, and being stained with silk is 4-5 level, and former state variable color is 3-4 level, and known employing the method stained with fabric and has excellent COLOR FASTNESS.
Embodiment 2, a kind of covalent bond colorize method being applicable to silk, select the dyestuff containing aryl primary amine group to be orchil, its structural formula is as follows:
Aldehyde material specifically selects 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 DEG C, temperature retention time 24 hours.
After dyeing terminates, then through 60 DEG C and 15 DEG C of deionized water washings, thus remove the impurity be 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, by the silk after method process described in embodiment 2 according to national standard " color fastness to washing GB/T3921-2008 " and national standard " colour fastness to rubbing experiment GB/T3920-2008 ".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 stained with fabric and has excellent COLOR FASTNESS.
Embodiment 3, a kind of covalent bond colorize method being applicable to silk, select the dyestuff containing aryl primary amine group to be blue dyes, its structural formula is as follows:
Aldehyde material specifically selects propionic aldehyde.
Colorize method is specific as follows:
Squeeze in silk fabric at 1000g and 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 DEG C, temperature retention time 0.5 hour.
After dyeing terminates, then through 60 DEG C and 15 DEG C of deionized water washings, thus remove the impurity be 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, by the silk after method process described in embodiment 3 according to national standard " color fastness to washing GB/T3921-2008 " and national standard " colour fastness to rubbing experiment GB/T3920-2008 ".Resistance to dry fastness is 4-5 level, and resistance to wet 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 stained with fabric and has excellent COLOR FASTNESS.
Comparative example 1,
Blue dyes in embodiment 3 dyes (being equivalent to acid dyeing) to silk fabric when 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 DEG C, under bath raio 1:50, pH8-10 dyeing condition, silk degree of fixation only reaches about 85%, and silk ultimate strength loses about 10%(data 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, aldehyde material is utilized by dyestuff containing arylamine group to build bridge and the tyrosine residue covalent bonds in silk fiber, wherein dye structure used is stablized, dyeing only needs to dye under weak acid acidity (pH6.5) condition, there is not hydrolysis problem.In addition, decoration method of the present invention is compared with alkaline high temperature fixation reactive dyeing, and the loss of silk ultimate strength is less than 1%; And solve the hydrolysis problem of silk at alkali condition, in addition method weld of the present invention dyes under close to the condition of room temperature, decreases the consumption of energy, reach the object of energy-saving and emission-reduction.
Finally, it is also to be noted that what enumerate above is only several specific embodiments of the present invention.Obviously, the invention is not restricted to above embodiment, many distortion can also be had.All distortion that those of ordinary skill in the art can directly derive from content disclosed by the invention or associate, all should think protection scope of the present invention.
Claims (2)
1. be applicable to the covalent bond colorize method of silk, it is characterized in that: the dyestuff containing aryl primary amine group with the tyrosine residue in silk, Mannich occurs and reacts 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 DEG C, temperature retention time 0.5 ~ 24 hour; Described aldehyde material is formaldehyde, acetaldehyde, propionic aldehyde, butyraldehyde or benzaldehyde;
After dyeing terminates, through superheated water and cold water washing, thus remove the impurity be adsorbed on silk, dry.
2. the covalent bond colorize method being applicable to silk according to claim 1, is characterized in that:
The described dyestuff containing aryl primary amine group is any one dyestuff following:
Weld, structural formula is:
Orchil, structural formula is:
Blue dyes, structural formula is
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103741507B (en) * | 2013-12-27 | 2015-11-11 | 浙江理工大学 | Be applicable to the covalent bond colorize method of silk |
| CN106083625B (en) * | 2016-05-31 | 2018-07-03 | 安徽工程大学 | A kind of chemical modification method of tyrosine |
| 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 |
| CN108505366B (en) * | 2018-04-13 | 2022-04-29 | 江南大学 | Method for dyeing real silk through 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 |
| 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 |
| 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 |
| 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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