CN102618084B - Heterocyclic ring blue disperse dye and synthesizing method and application thereof - Google Patents
Heterocyclic ring blue disperse dye and synthesizing method and application thereof Download PDFInfo
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- CN102618084B CN102618084B CN201210045264XA CN201210045264A CN102618084B CN 102618084 B CN102618084 B CN 102618084B CN 201210045264X A CN201210045264X A CN 201210045264XA CN 201210045264 A CN201210045264 A CN 201210045264A CN 102618084 B CN102618084 B CN 102618084B
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- dicyanoethyl
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Abstract
The invention discloses a heterocyclic ring blue disperse dye and a synthesizing method and application thereof. A structural formula of the heterocyclic ring blue disperse dye is shown. In the formula, R=H, C1and CH3. The synthesizing method comprises the steps of dissolving 2-amino-3, 5-binitro thiophene in a sulfuric acid-phosphoric acid solution, diazotizing at the low temperature, respectively coupling the solution with N,N-dicyanoethylaniline, N,N-dicyanoethyl-m-chloroaniline and N,N-dicyanoethyl-m-methylaniline, performing cooling, crystallization and reduced-pressure filtration, and washing the solution to be neutral to obtain the blue disperse dye. The dye can be a single structure or can be prepared into a mixed structure, can be used for dyeing polyester fiber, cellulose acetate fiber and other synthetic fiber, also can be used for dyeing acetylated modified wood and cyanoethylated modified wood, have dark dyeing and good dyeing performance, embodies excellent color fastness, and dyeing color is bright-colored blue.
Description
Technical field
The present invention relates to fine chemical product synthesizes and Application Areas.Be specifically related to the heterocycle blue disperse dye, relate to their synthetic method, also relate to their dyeing on the dyeing on polyester piece good and acetylize, cyanoethylation modified wood.
Background technology
The mono-cyanoethylation product of aromatic amine is widely used in dispersed dye synthetic.For example, N-cyanoethyl aniline, N-ethyl-N-cyanoethyl aniline, N hydroxyethyl N cyanoethyl aniline, N-cyanoethyl Ortho-Chloro aniline, N-butyl-N-cyanoethyl aniline, N-second propyloic-N-cyanoethyl aniline etc. all have been used to the synthetic of azo dispersion dyes.But the double fluoride ethyl purification product of aromatic amine is few as the synthetic middle report that coupling component is applied to dispersed dye, product the earliest mainly contains DISPERSE YELLOW 163, disperses tangerine 44 and disperse tangerine 45, but their diazo component is the aromatic amine with benzene ring structure.Over nearly 20 years, with heterocyclic aromatic amine, as thiazole or benzothiazole aromatic amine derivant as diazo component, aromatic amine double fluoride ethyl purification product is that the synthetic heterocycle/bis-cyanoethyl that has of coupling component is that azo dispersion dyes is in continuous appearance, but its coloured light be take yellow, orange and orange basically as main, its maximum absorption wavelength basically, below 550nm, is shown in that seldom coloring intensity is high, beautiful in colour and washes sticky colour fastness and the high blue azo dispersion dyes of light fastness.
Dispersed dye are used widely to the dyeing on dacron fabric, cellulose acetate fabric and mixed fiber fabric thereof, timber also adopts the dyestuff such as acid, alkaline, direct, active to dye basically, dispersed dye have larger difference because of the polarity with timber, dye uptake is low, fastness is poor, coloured light light is dark, so generally be not used in stained wood.
Summary of the invention
The present invention is to provide heterocycle blue disperse dye and its synthetic method; and with they dyeing to trevira, cellulose acetate and BLENDED FABRIC thereof; and, to the dyeing of acetylize modified wood, cyanoethylation modified wood, obtain having blue fabric or the blue water-fast timber of outstanding every colour fastness.
Dyestuff of the present invention is the azo dispersion dyes that a class has heterocycle/bis-cyanoethyl structure; can in slightly acidic or weakly alkaline dye liquor, dye to trevira, cellulose acetate and BLENDED FABRIC thereof; also can be for the dyeing to acetylize modified wood, cyanoethylation modified wood; the coloured light of coloring matter is blueness, has beautiful in colour, high Chromaticity intensity, the sticky colour fastness of high washing and high light fastness.
Technical scheme of the present invention is: amino-3 with 2-, the 5-dinitro thiophene is as diazo component, N, and the N-dicyanoethyl-aniline, N, N-dicyanoethyl meta-aminotoluene or N, N-dicyanoethyl m-chloro aniline are that the coupling component obtains corresponding Heterocylic azo-dyes; The chemical structure of general formula of described compound is:
General formula I, wherein R=H or R=Cl or R=CH
3.
In dyestuff of the present invention, contain one or more in the compound of the structure shown in general formula I.
The preparation method of such blue heterocycle azo dispersed dye is: by 2-amino-3, the 5-dinitro thiophene is dissolved in H
3PO
4-H
2SO
4Mixing solutions in, under-5～20 ℃, carry out diazotization with Sodium Nitrite-sulfuric acid or nitrosyl sulfuric acid.Join again N, N-dicyanoethyl-aniline, N, N-dicyanoethyl meta-aminotoluene or N, the H of N-dicyanoethyl m-chloro aniline
3PO
4-H
2SO
4Coupling solution in, at low temperatures-5～25 ℃ are carried out coupling, after coupling completes, are warmed up to 50～80 ℃, insulation 2～12h turns brilliant, by filtration under diminished pressure, wash, drain, drying, obtain solid dye.
Described H
3PO
4-H
2SO
4Mixing solutions in H
3PO
4Mass percent concentration at 30～70%, H
2SO
4Mass percent concentration 20～40%.Described H
3PO
4-H
2SO
4Coupling solution in H
3PO
4Mass percentage concentration at 20～40%, H
2SO
4Mass percent concentration 30～60%.
The structure of blue heterocycle azo dispersed dye of the present invention determines that method is: synthetic drying solid dyestuff is carried out to recrystallization, then dry with acetone, by ultraviolet, infrared, nuclear-magnetism, mass spectrum and ultimate analysis etc., analyze detection means, determine its chemical structure and composition.Dyestuff maximum absorption wavelength of the present invention, at 575～599nm, is the blueness series azo dispersion dyes that a class contains heterocycle and two cyanoethyl constitutional featuress; Its molar extinction coefficient of such dyestuff is 4.2 * 10
4～4.6 * 10
4, embody the feature of high Chromaticity intensity.
Dyestuff of the present invention to the dyeing process of textile fibres is: synthetic drying solid dyestuff is carried out to sand milling together with a certain amount of Dispersant MF, water, granulated glass sphere, then carry out spraying drying, obtain corresponding commercial dye.Take given commodity dyestuff, synthetic fabrics and water, add emulsifier op-10, PH conditioning agent, under 60～140 ℃, with high temperature-pressure dyeing machine, polyester textile or cellulose acetate were dyeed after for some time, sample is dyed in taking-up, after soaping, washing, the fabric of dyeing is blue, the be correlated with mensuration of fastness of the national standard of then measuring according to relevant textiles fastness.
Heterocyclic blue azo dispersion dyes synthetic in the present invention expands to the dyeing to acetylize timber, cyanoethylation timber, the purposes that can open up undoubtedly dispersed dye, the assortment of increase timber, the water resistance of the coloured timber of raising.
Dyestuff of the present invention to the dyeing process of chemical modification timber is: with acetylize modified wood, cyanoethylation modified wood, replace synthetic fabrics, carry out according to the dyeing process of above-mentioned heterocycle azo dispersed dye to textile fibres.
The heterocycle azo dispersed dye of blueness of the present invention have that lovely luster, high, the every colour fastness of coloring intensity are outstanding, the dye uptake advantages of higher.These heterocycle azo dispersed dye can be used for dyed polyester fiber, cellulose acetate and BLENDED FABRIC thereof in the scope of PH=3～9, the coloured light of DYED FABRICS is blue, its washing (sticky look) fastness reaches 4～5 grades, and light fastness reaches 6～7 grades, and the dyeing dye uptake reaches 85～95%.These heterocycle azo dispersed dye also can be used for the dyeing of acetylize modified wood and cyanoethylation modified wood, and the coloured light of stained specimens is blue, and its washing (sticky look) fastness reaches 4～5 grades, and light fastness reaches 6～7 grades.It the results are shown in subordinate list 1 and accompanying drawing 1.
Simultaneously; also can be by above any two kinds; or the composition of three kinds of heterocyclic blue dispersion dyes formations is for the dyeing of trevira, cellulose acetate and BLENDED FABRIC thereof; and be applicable to the dyeing of acetylize modified wood and cyanoethylation modified wood; it is blue that the coloured light of its product dyed thereby is similarly, and have beautiful in colour, high Chromaticity intensity, the sticky colour fastness of high washing and high light fastness.
The accompanying drawing explanation
Accompanying drawing 1: heterocyclic blue dispersion dyes dyed polyester textiles, acetylize fir powder and cyanoethylation fir powder figure.
Embodiment
Following examples are intended to illustrate the present invention rather than limitation of the invention further.
Embodiment 1
Target product (A
1) synthesis technique and tint applications
In the 250mL there-necked flask with agitator, add 28mL 85%H
3PO
4With 12mL 98%H
2SO
4, 10mL water, add 4.73g 2-amino-3 under stirring, and the 5-dinitro thiophene, slowly drip nitrosyl sulfuric acid under stirring, complete to diazotization reaction.Meanwhile, in the 500mL beaker with agitator, add 30mL water, 20mL 85%H
3PO
4, 32mL98%H
2SO
4, 4.98g N, the N-dicyanoethyl-aniline, be cooled to 5 ℃.Under stirring, slowly splash into diazonium salt, drip off, continue to react to the diazo component disappearance, suction filtration, be washed to neutrality, drains, and drying, obtain the brown solid dyestuff, λ
max=575nm (acetone), ε=4.5 * 10
4C 48.05, and H 3.12, and N 24.64; IR (cm
-1, KBr), v:2925,2853,2248,1597,1547,1506,1455,841,756,685;
1H NMR (CDCl
3, 400MHz) δ: 2.71 (t, 4H, CH
2), 3.91 (t, 4H, CH
2), 6.77～7.53 (m, 4H, C
6H
3), 8.41 (s, 1H, C
4H); MS (m/z): 382,341,295,288,241,122.The dyestuff of synthesized is target product (A
1).
Dry product dyestuff obtained above is mixed with diffusant, and its ratio is dyestuff (dry product): dispersing agent MF: sodium lignosulfonate: water=1: 1: 1: 6.0, and sand milling to particle diameter is less than 1U, and spraying drying obtains commercial dye.In the dye vat that fills 200g water, add the above-mentioned dyestuff of 0.020g, add emulsifier op-10,1mL HAc-NaAc (2.OM), 2.000 polyester piece good, airtight dye vat is put into dyeing machinery, slowly heat up, about 30min rises to 120 ℃ of insulation 40min, takes out and dyes sample after cooling, after soaping, washing, is dark bright blue.Then according to textiles GB/T 3921-2008 standard testing, evaluate its washing fastness and its weathering color fastness is evaluated in the GB/T8427-1998 standard testing, the sticky colour fastness of its washing is 5 grades, and light fastness is 7 grades.With spectrophotometry, recording the dyestuff dye uptake is 86.8%.
With the acetylize fir powder, replace polyester piece good to dye, dying sample is mazarine, and the sticky colour fastness of washing is 5 grades, and the dyestuff dye uptake is 96.3%.With the cyanoethylation fir powder, replace polyester piece good to dye, dying sample is mazarine, and the sticky colour fastness of washing is 4～5 grades, and dye uptake is 95.0%.
Embodiment 2
Target product (A
2) synthesis technique and tint applications
Press embodiment 1, use 5.43g N, N-dicyanoethyl meta-aminotoluene replaces N, and the N-dicyanoethyl-aniline, obtain the blue solid dyestuff, λ
max=599nm (acetone), ε=4.6 * 10
4C 49.35, and H 3.79, and N 23.64; IR (cm
-1, KBr), v:2928,2854,2250,1602,1541,1496,1457,829,756,728,690;
1H NMR (CDCl
3, 400MHz) δ: 2.54 (t, 3H, CH
3), 2.73 (t, 4H, CH
2), 3.72 (t, 4H, CH
2), 6.60～7.53 (m, 3H, C
6H
3), 7.71 (s, 1H, C
4H); MS (m/z): 382,341,295,288,241,122.The dyestuff of synthesized is target product (A
2).
Press embodiment 1, adopt this dyestuff Dichlorodiphenyl Acetate fabric to dye, fabric is bright blue, and the sticky colour fastness of washing is 5 grades, and light fastness is 7 grades, and dye uptake is 96.2%.
With the acetylize fir powder, replace Acetate Fabrics to dye, dying sample is bright blue, and the sticky colour fastness of washing is 5 grades, and dye uptake is 99.2%.With the cyanoethylation fir powder, replace polyester piece good to dye, dying sample is bright blue, and the sticky colour fastness of washing is 4～5 grades, and dye uptake is 98.1%.
Embodiment 3
Target product (A
3) synthesis technique and tint applications
Press embodiment 1, use 5.84g N, N-dicyanoethyl m-chloro aniline replaces N, and the N-dicyanoethyl-aniline, obtain the blue solid dyestuff, λ
max=578nm (ethanol), ε=42 * 10
4C 44.21, and H 2.93, and N 22.47; IR (cm
-1, KBr), v:2924,2853,2252,1598,1543,1515,1498,1469,821,785,775,728;
1H NMR (CDCl
3, 400MHz) δ: 2.65 (t, 4H, CH
2), 3.79 (t, 4H, CH
2), 6.65～7.21 (m, 3H, C
6H
3), 7.52 (s, 1H, C
4H); MS (m/z): 382,341,295,288,241,122.The dyestuff of synthesized is target product (A
3).
Press embodiment 1, with this dyestuff of 0.010g, replace the dyestuff of embodiment 1, to polyester piece good dyeing, fabric is light blue, and the sticky colour fastness of washing is 4～5 grades, and light fastness is 7 grades, and dye uptake is 86.9%.
Subordinate list 1, the result of heterocyclic blue dispersion dyes dyeing synthetic fabrics of the present invention and chemical modification timber
Claims (5)
1. the preparation method of heterocycle blue disperse dye, contain one or more in the compound of structure shown in formula I in described dyestuff, this compound consists of diazo component and coupling component; Its diazo component is 2-amino-3, the 5-dinitro thiophene; Coupling component is N, N-dicyanoethyl-aniline, or N, N-dicyanoethyl m-chloro aniline or N, N-dicyanoethyl m-toluidine;
Formula I, wherein: R=H, Cl or CH
3
Described preparation of dyestuff method is: by 2-amino-3, the 5-dinitro thiophene is dissolved in H
3PO
4-H
2SO
4Mixing solutions in, under-5～20 ℃, carry out diazotization with Sodium Nitrite-sulfuric acid or nitrosyl sulfuric acid; Join again and contain N, N-dicyanoethyl-aniline, N, N-dicyanoethyl meta-aminotoluene or N, the H of N-dicyanoethyl m-chloro aniline
3PO
4-H
2SO
4Coupling solution in, at low temperatures-5～25 ℃ are carried out coupling, after coupling completes, are warmed up to 50～80 ℃, insulation 2～12h turns brilliant, by filtration under diminished pressure, wash, drain, drying, obtain solid dye.
2. method according to claim 1, is characterized in that, described H
3PO
4-H
2SO
4Mixing solutions in H
3PO
4Mass percent concentration at 30～70%, H
2SO
4Mass percent concentration 20～40%; Described H
3PO
4-H
2SO
4H in coupling solution
3PO
4Mass percentage concentration at 20～40%, H
2SO
4Mass percent concentration 30～60%.
3. the application of heterocyclic blue dispersion dyes claimed in claim 1, be applicable to the dyeing of acetylize modified wood or cyanoethylation modified wood, and the coloured light that obtains stained wood is blue.
4. according to application claimed in claim 3, the dyeing of acetylize modified wood or cyanoethylation modified wood, its timber is wood powder, wood chip, sheet material or round log.
5. according to the described application of claim 3 or 4, in dyeing course, dyeing temperature carries out under 60～140 ℃, and dyeing time is 0.5～10h.
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| CN103602095B (en) * | 2013-09-10 | 2016-04-20 | 江苏亚邦染料股份有限公司 | One class Monoazo type dispersed dye, preparation method and application |
| US10293515B2 (en) | 2016-12-08 | 2019-05-21 | Electronic For Imaging, Inc. | Coloration of acetylated wood |
| US10315332B2 (en) | 2016-12-08 | 2019-06-11 | Electronics For Imaging, Inc. | Coloration of acetylated wood |
| CN115521636B (en) * | 2022-10-24 | 2023-06-30 | 浙江博澳新材料股份有限公司 | Sun-proof anthraquinone disperse dye containing dicyano and preparation method thereof |
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Effective date of registration: 20160728 Address after: 312369 Shangyu, Shaoxing, Hangzhou Bay Industrial Park, No. East Road, No. seven, No. 1 Patentee after: Zhejiang Dibang Chemical Co., Ltd. Address before: 410004 Shaoshan South Road, Hunan, No. 498, No. Patentee before: Central South University of Forestry and Technology |