CN101423671B - Azo structure carboxylic amide type dyes for polylactic acid fiber dyeing and preparation method thereof - Google Patents
Azo structure carboxylic amide type dyes for polylactic acid fiber dyeing and preparation method thereof Download PDFInfo
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- CN101423671B CN101423671B CN2008101629250A CN200810162925A CN101423671B CN 101423671 B CN101423671 B CN 101423671B CN 2008101629250 A CN2008101629250 A CN 2008101629250A CN 200810162925 A CN200810162925 A CN 200810162925A CN 101423671 B CN101423671 B CN 101423671B
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Abstract
The invention discloses a carboxamide type dye which has an azo structure and is used for dyeing polylactic acid fibre. The molecular structure contains a carboxamide group; the general structural formula of the dye is shown above. In the formula, D is a chromogen with the azo structure; m is 1 or 2; X is H or n-CnH2n+1; Y is H, n-CnH2n+1, C6H12 or C6H6; and in the n-CnH2n+1, n meets the following condition: n is more than or equal to 1 and less than or equal to 18, and n is an integer. The invention simultaneously discloses a method for preparing the dye. The dye is used to improve the rate of dye-uptake and color fastness on the PLA fibre.
Description
Technical field
The present invention relates to a kind of azo structure carboxylic amide type dyes for polylactic acid fiber dyeing and preparation method thereof that is applicable to.
Background technology
Trevira mainly comprises polyethylene terephthalate (PET), PTT (PTT), polybutylene terephthalate (PBT) and emerging POLYACTIC ACID (PLA) fiber; This fibrid has high-crystallinity usually; Therefore no strongly hydrophilic group in the molecular backbone chain presents hydrophobicity.After trevira spin-drawing and preheating are stable, the molecular layer that the surface has one deck to align, be difficult for penetrating, and lack in the molecular structure and dyestuff generation bonded reactive group, therefore dyeing is difficult.The trevira molecular arrangement is neat, and when temperature was low, the macromolecular chain segment motion was inactive, and the space is less; In addition; Be suitable for not having water miscible sulfonic acid group, hydroxy-acid group plasma group in the painted dispersed dye molecule of trevira; It is one type of nonionic dye that is insoluble in water; Need under the dispersion agent effect, be scattered in the water with insoluble minuteness particle, the aggregate form with a plurality of dye molecules exists usually, and dye granule is bigger.When in water medium, dyeing; Trevira can not resemble the cotton fibre and through violent swelling the space increased; Dye granule is difficult to be penetrated at short notice fibrous inside, in the trevira dyeing course, need realize dying through kinetic energy that improves dye molecule and the method that fortifying fibre macromolecular chain segment mobility enlarges the fiber hole.Therefore dispersed dye main high temperature and high pressure method, thermosoling, support methods of adopting on trevira dyes.The PET dyeing temperature is 130 ℃; Most of dispersed dye all have the dye uptake above 90% on PET.
As a kind of emerging environment-friendly type polyester fiber, acid fiber by polylactic has excellent biological compatibility, absorbability, degradability, heat impedance and anti-ultraviolet function.Along with the exploitation of low-cost novel process, acid fiber by polylactic is applied in fields such as textiles, biomedicine and packings.But many dispersed dye dyeing behavioies on acid fiber by polylactic at excellent performance on the polyster fibre are not good, cause the scarcity of acid fiber by polylactic suitable dyes.Since acid fiber by polylactic was realized suitability for industrialized production, Chinese scholars had been carried out big quantity research to the physicochemical property of acid fiber by polylactic.Aspect dyeing, generally believe that dispersed dye are more suitable for the painted of acid fiber by polylactic.Yang etc. once studied the dyeing condition and the dyeing behavior of dispersed dye on acid fiber by polylactic commonly used; For avoiding the acid fiber by polylactic hydrolysis to influence its intensity and Color; Suggestion POLYACTIC ACID fabric dyes in acidulous dye bath (pH 5～6); Temperature is no more than 110 ℃, and dyeing time is no more than 45min.
Qian Hong flies to wait and has studied the dispersed dye molecular structure to the polylactic acid fiber dyeing Effect on Performance, and contrasts with coloration result on the polyster fibre.Because acid fiber by polylactic and polyster fibre all exist aspect molecular structure and the dyeing than big-difference, most of terylene are on the low side with dispersed dye dye uptake and colour fastness on acid fiber by polylactic, are difficult to the satisfied requirement of taking.After dying fiber on the dispersed dye, dyestuff and fiber are to combine through more weak Van der Waals force.Van der Waals force is big, and dyestuff avidity on fiber is high, and colour fastness is good, shows as high dye uptake; Otherwise colour fastness is poor, and dye uptake is low.No aromatic ring and have more relatively ester group on the polylactic acid molecule chain is given certain polarity of acid fiber by polylactic molecular chain and kindliness preferably.If in dye molecule, introduce polar group, these polar groups can and acid fiber by polylactic macromole generation dipolar forces, hydrogen bonded improve the Van der Waals force between dyestuff and fiber molecule, help improving the dye uptake and the colour fastness of dyestuff.Research shows that the dye uptake of azoic dye and the substituent kind in the molecule have dependency, has the dyestuff of carboxylic acid ester groups in the molecular structure, and dye uptake is generally higher.The similar molecular (all having the such polarity dots of ester group) of dyestuff and fiber is described, is helped dying on the dyestuff.
Zhang Shufen etc. had once developed one type of hydrophobic fibre and had used slightly water-soluble sulfonamide type dye, and this dyestuff gives dyestuff different avidity through the chain length of regulating the straight chained alkyl that sulfoamido connected, thereby is applicable to the dyeing of different hydrophobic fibres; Increase the linearity of dyestuff by means of the linear structure of straight chained alkyl, thereby improve the affinity of dyestuff and fiber, improve the tinting strength and the colour fastness of dyestuff; In dye structure, introduce the sulphonamide polar group, not only can give the dyestuff slightly water-soluble, thereby the molecular polarity that has also increased dyestuff helps improving the fastness to sublimation of dyestuff.This type dyestuff synthesis technique is simple; Can synthesize the slightly water-soluble sulfonamide type dye that contains straight chained alkyl through sulfonating chlorinating, aminolysis reaction or diazotization, coupled reaction; And it is used for the dyeing of hydrophobic fibre terylene, polypropylene fibre and acid fiber by polylactic; When improving dye utilization rate, also can give coloured fibre preferable colour fastness.
In sum, POLYACTIC ACID (PLA) fiber belongs to a kind of more emerging trevira, and is a lot of not good at dye uptake and the colour fastness of the good dispersed dye of coloration result on the PET fiber on the PLA fiber.How to design a kind of dyestuff that can on the PLA fiber, present preferable coloration result, become the industry and urgently hope the problem that solves.
Summary of the invention
The technical problem that the present invention will solve provides a kind of azo structure carboxylic amide type dyes for polylactic acid fiber dyeing and preparation method thereof that is applicable to, uses this kind dyestuff can improve dye uptake and colour fastness on the PLA fiber.
In order to solve the problems of the technologies described above, the present invention provides a kind of azo structure carboxylic amide type dyes for polylactic acid fiber dyeing, contains carboxylacyl amine group in its molecular structure, and its general structure is following:
In the formula: D is azo structure contained color bodies, and m is 1 or 2, and X is H or n-C
nH
2n+1, Y is H, n-C
nH
2n+1,
Or
, n-C
nH
2n+1In n meet the following conditions: 1≤n≤18, and n is an integer.
As a kind of improvement of azo structure carboxylic amide type dyes of the present invention, the structural formula of D is following:
In the formula: R
1Be H, CH
3, C
2H
5, OH, OCH
3, OC
2H
5, Cl, Br, CN or NO
2R
2Be H, CH
3, C
2H
5, OH, OCH
3, OC
2H
5, Cl, Br, CN, NO
2Or CONXY; R
3Be H, CH
3, CN or C
6H
5R
4Be H, CH
3, C
2H
5, OH, OCH
3, OC
2H
5, Cl, CN or NHCOCH
3R
5Be H, CH
3, C
2H
5, OH, OCH
3, OC
2H
5, Cl, CN, NO
2Or CONXY and said; Contain 1～2-CONXY in the structure of dyestuff.
Another kind as azo structure carboxylic amide type dyes of the present invention improves, and the structural formula of D is following:
In the formula: R
6Be H or OH; R
7Be H, Cl, OH, CN, CONXY or NHCOC
2H
5R
8Be H, OH, OCH
3, OC
2H
5, CONXY or NHCOC
2H
5R
9Be H, OH, OCH
3, OC
2H
5, CONXY or NHCOC
2H
5R
10Be H, CH
3, C
2H
5, OH, OCH
3, OC
2H
5, Cl, CN or NHCOCH
3R
11Be H, CH
3, C
2H
5, OH, OCH
3, OC
2H
5, Cl, CN, NO
2Or CONXY; And contain 1～2-CONXY in the structure of said dyestuff, and can not have 2-CONXY simultaneously in the same aromatic ring.
Another kind as azo structure carboxylic amide type dyes of the present invention improves, and the structural formula of D is following:
In the formula: R
12Be H or OH; R
13Be H, Cl, OH, CN, CONXY or NHCOC
2H
5R
14Be H, OH, OCH
3, OC
2H
5, CONXY or NHCOC
2H
5R
15Be H, OH, OCH
3, OC
2H
5, CONXY or NHCOC
2H
5R
16Be H, Cl, CH
3, C
2H
5, OH, OCH
3, OC
2H
5, CN, NO
2Or CONXY; R
17Be H, CH
3, C
2H
5, OH, OCH
3, OC
2H
5, Cl, CN, NO
2Or CONXY; R
18Be H, CH
3, C
2H
5, OH, OCH
3, OC
2H
5, Cl, CN or NHCOCH
3And contain 1～2-CONXY in the structure of this dyestuff, and can not have 2-CONXY simultaneously in the same aromatic ring.
The present invention also provides a kind of preparation method of above-mentioned azo structure carboxylic amide type dyes for polylactic acid fiber dyeing simultaneously, and it adopts sulfur oxychloride chloride, amination method, specifically may further comprise the steps:
1), add 1.4～3.0ml sulfur oxychloride, 10～30ml solvent and 0.1～0.4mlN by every 3.2g carboxy-containing acid group's dyestuff, the ratio of dinethylformamide (DMF) will above-mentioned 4 adds in the reactor drum, is warming up to 55～75 ℃, reacts 0.5～6hr;
2), reaction finishes, after 90 ℃ down decompression steamed excessive sulfur oxychloride and solvent, frozen water washing and filtration until being washed till neutrality, obtained the carboxyl acyl chloride midbody after the vacuum-drying repeatedly;
3), in reactor drum, add earlier the carboxyl acyl chloride midbody and as the acetone of solvent, wait the dissolving of carboxyl acyl chloride midbody after, add fat primary amine, hexahydroaniline, aniline or fatty primary secondary amine again and add Powdered K
2CO
3, under room temperature, mixed stirring reaction 1 hour, said fat primary amine, hexahydroaniline, aniline or fatty primary secondary amine: carboxyl acyl chloride midbody: K
2CO
3Mol ratio=1:1:0.5～2;
4), the reactant of step 3) gained is boiled off acetone, resistates; Said resistates is carried out pickling, washing and drying successively, get azo structure carboxylic amide type dyes for polylactic acid fiber dyeing.
Improvement as above-mentioned preparation method of the present invention: in the step 4): it is that 3% dilute hydrochloric acid solution carries out pickling that resistates is utilized concentration earlier, filters then, and the filter cake that will filter gained again uses clear water to be washed till raffinate for till neutral and colourless; Filter cake after then will washing at room temperature dries, and gets azo structure carboxylic amide type dyes for polylactic acid fiber dyeing.
Further improvement as above-mentioned preparation method of the present invention: in the step 1): solvent is benzene or toluene.
The present invention also provides the another kind of preparation method of above-mentioned azo structure carboxylic amide type dyes for polylactic acid fiber dyeing simultaneously, and this method is to adopt diazonium, coupling process, specifically may further comprise the steps:
1), will contain in the coupling component and water adding reactor drum of carboxylacyl amine group, with mass concentration 10% sodium hydroxide solution adjust pH to 8～12; Be cooled to 0～10 ℃ then, drip down the hydrochloric acid soln of arylamine diazonium salt in agitation condition, using mass concentration in the dropping process is that the pH value of mixture in the 10% sodium carbonate solution controlling reactor is 8～10; After dropwising, at 0～10 ℃ of reaction 5～10hr; Saidly contain the coupling component of carboxylacyl amine group and the mol ratio of arylamine diazonium salt is 1.05:1.0;
Perhaps coupling component midbody and water are added in the reactor drum, with mass concentration 10% sodium hydroxide solution adjust pH to 8～12; Be cooled to 0～10 ℃ then, drip down the hydrochloric acid soln of the arylamine diazonium salt that contains carboxamide groups in agitation condition, using mass concentration in the dropping process is that the pH value of mixture in the 10% sodium carbonate solution controlling reactor is 8～10; After dropwising, at 0～10 ℃ of reaction 5～10hr; Said coupling component midbody is 1.05:1.0 with the mol ratio that contains the arylamine diazonium salt of carboxamide groups;
The coupling component and the water that perhaps will contain carboxylacyl amine group add in the reactor drum, with mass concentration 10% sodium hydroxide solution adjust pH to 8～12; Be cooled to 0～10 ℃ then, drip down the hydrochloric acid soln of the arylamine diazonium salt that contains carboxamide groups in agitation condition, using mass concentration in the dropping process is that the pH value of mixture in the 10% sodium carbonate solution controlling reactor is 8～10; After dropwising, at 0～10 ℃ of reaction 5～10hr; The said coupling component that contains carboxylacyl amine group is 1.05:1.0 with the mol ratio that contains the arylamine diazonium salt of carboxamide groups;
2), reaction finishes, and filters, and utilizes frozen water to be washed till filtrating and is neutrality, after the drying, obtains azo structure carboxylic amide type dyes for polylactic acid fiber dyeing.
Therefore, the preparation method of azo structure carboxylic amide type dyes for polylactic acid fiber dyeing of the present invention, the method by in dye structure, introducing carboxylacyl amine group is divided into following several kinds of preparation technologies:
(1) when being starting raw material with the azoic dyestuff that contains the carboxylic acid group, the preparation of azo structure carboxylic amide type dyes can be adopted solvent method.
(2) when diazonium or coupling component contain carboxylacyl amine group, the preparation of azo structure carboxylic amide type dyes is divided into the coupling process and the two kinds of technologies of coupling process that contain the arylamine diazonium salt and the coupling component of carboxamide groups of arylamine diazonium salt and the coupling component that contains carboxamide groups.
The present invention has developed a kind polyester dyeing keratin-fiber and has used azo structure carboxylic amide type dyes, and this type dyestuff can be regulated the avidity between dyestuff and different trevira through changing kind, length that carboxylacyl amine group connects end group; The introducing of carboxamide groups polar group in the dye structure has simultaneously increased the dipolar forces between dyestuff and the fiber, helps the raising of dye uptake and colour fastness.This type dyestuff synthesis technique is simple; Through chloride, aminolysis reaction or diazotization, the synthetic azo structure carboxylic amide type dyes that contains different end group of coupled reaction; And it is used for the dyeing of trevira PET, PTT and PLA fiber; Not only improve dye utilization rate, but also can give coloured fibre preferable colour fastness.Need to prove especially: use azo structure carboxylic amide type dyes of the present invention, can solve the low problem with the colour fastness difference of dye uptake on the PLA fiber.
Azo structure carboxylic amide type dyes for polylactic acid fiber dyeing of the present invention is used for the dyeing of hydrophobicity trevira such as PET, PTT, PLA; Its dyeing is: (particle diameter 1～2mm) 200g, water 50～100g added in the sand mill sand milling 2～10 hours to get synthetic azo structure carboxylic amide type dyes 5～10g of the present invention, dispersion agent NNO5～10g, silica sand; Filter with B; Filter screen is 120 purpose woven wires, gets dye paste; Colourity requirement by 0.5～2% pipettes dye paste, is transferred in the Dyeing pipe after adding entry by bath raio 1:15～30, adds the painted PET of desire, PTT or PLA and puts into the high-temperature pressure dyeing appearance; Heat-up rate by 2 ℃/min rises to 110～130 ℃, is incubated and reduces to room temperature after 0.5～1 hour, takes out the dyeing cloth specimen; Washing; Merge dyeing residual liquid and washings, constant volume is surveyed its absorbancy, utilizes working curve to calculate the dye uptake of dyestuff.
Azo structure carboxylic amide type dyes for polylactic acid fiber dyeing of the present invention; In dye structure, introduce the strong carboxylacyl amine group of polarity, can improve avidity and the fastness to sublimation of dyestuff on trevira, and pass through the type and the length of the end group of change carboxamide groups connection; Adjustable product is to the avidity and the colour fastness of fiber; Improve the dye uptake of dyestuff, reduce the discharging of pollutant effluents, improve its application performance.Because the azo structure carboxylic amide type dispersed dye of developing have avidity controllability and good colour fastness concurrently, have application prospect widely.
Embodiment
Embodiment 1, a kind of trevira dye with the preparation method of azo structure carboxylic amide type dyes, carry out following steps successively:
1), in the there-necked flask that TM, reflux condensing tube and mechanical stirring device are housed, add 3.2g 1-phenyl-3-methyl-4-(4 '-carboxylic acid benzhydrazon)-5-pyrazolone, 20ml benzene, 0.2ml DMF, 2.2ml sulfur oxychloride, be warming up to 60 ℃, reaction 2h;
2), reaction finishes, and reaction solution is warming up to 90 ℃, after decompression steams excessive sulfur oxychloride and solvent, is chilled to room temperature, is transferred in the frozen water, filters, and utilizes frozen water to be washed till filtrating and is neutrality, obtains the carboxyl acyl chloride midbody after the vacuum-drying;
3), in the there-necked flask that whisking appliance, TM, prolong are housed, add earlier 3.4g carboxyl acyl chloride midbody and 25ml acetone as solvent, wait the carboxyl acyl chloride midbody to be dissolved in acetone after, add the Powdered K of 0.73g n-Butyl Amine 99 and 0.83g again
2CO
3, under room temperature, mixed stirring reaction 1 hour;
4), the reactant of step 3) gained is boiled off acetone, resistates; Pouring said resistates into the 100ml mass concentration is in 3% dilute hydrochloric acid solution, the thorough washing after-filtration, and it is colourless that filter cake is washed till raffinate neutrality with clear water; At room temperature dry, get carboxylic acyl n-Butyl Amine 99 type dye.
Embodiment 2, a kind of trevira dye with the preparation method of azo structure carboxylic amide type dyes, carry out following steps successively:
1), in the there-necked flask that TM, reflux condensing tube and mechanical stirring device are housed, add 6.4g 1-phenyl-3-methyl-4-(4 '-carboxylic acid benzhydrazon)-5-pyrazolone, 60ml benzene, 0.6ml DMF, 6ml sulfur oxychloride, be warming up to 55 ℃, reaction 6h;
2), with embodiment 1;
3), in the there-necked flask that whisking appliance, TM, prolong are housed, add earlier 3.4g carboxyl acyl chloride midbody and 25ml acetone as solvent, wait the carboxyl acyl chloride midbody to be dissolved in acetone after, add the Powdered K of 0.87g n-amylamine and 1.38g again
2CO3 mixed stirring reaction 1 hour under room temperature;
4), with embodiment 1, carboxylic acyl n-amylamine type dye.
Embodiment 3, a kind of trevira dye with the preparation method of azo structure carboxylic amide type dyes, carry out following steps successively:
1), in the there-necked flask that TM, reflux condensing tube and mechanical stirring device are housed, add 6.4g 1-phenyl-3-methyl-4-(4 '-carboxylic acid benzhydrazon)-5-pyrazolone, 50ml benzene, 0.8ml DMF, 5.5ml sulfur oxychloride, be warming up to 55 ℃, reaction 3h;
2), with embodiment 1;
3), in the there-necked flask that whisking appliance, TM, prolong are housed, add earlier 3.4g carboxyl acyl chloride midbody and 25ml acetone as solvent, wait the carboxyl acyl chloride midbody to be dissolved in acetone after, add the Powdered K of 1.0g normal hexyl Amine and 2.5g again
2CO
3, under room temperature, mixed stirring reaction 1 hour,
4), with embodiment 1, carboxylic acyl normal hexyl Amine type dye.
Embodiment 4～22,
Replace the n-Butyl Amine 99 among the embodiment 1 with positive heptyl amice, NSC 9824, positive nonyl amine, n-Decylamine, positive undecylamine, positive amino dodecane, positive tridecyl amine, positive tetradecy lamine, positive pentadecyl amine, positive cetylamine, positive heptadecyl-amine, positive stearylamine, hexahydroaniline, aniline, n n dimetylaniline, diethylamine, Di-n-Butyl Amine, two normal hexyl Amines, two NSC 9824s respectively, all the other are with embodiment 1; Obtain the positive heptyl amice of corresponding carboxylic acyl, NSC 9824, positive nonyl amine, n-Decylamine, positive undecylamine, positive amino dodecane, positive tridecyl amine, positive tetradecy lamine, positive pentadecyl amine, positive cetylamine, positive heptadecyl-amine, positive stearylamine, hexahydroaniline, aniline, n n dimetylaniline, diethylamine, Di-n-Butyl Amine, two normal hexyl Amines, two NSC 9824 type dyes respectively.
Embodiment 23,
Make the phenyl of the 1-among the embodiment 1-3-methyl-4-(4 '-carboxylic acid benzhydrazon)-5-pyrazolone into 1-(4 '-carboxylic acid phenyl)-3-methyl-4-benzhydrazon-5-pyrazolone, all the other are with embodiment 1; Get carboxylic acyl n-Butyl Amine 99 type dye.
Embodiment 24,
Make the phenyl of the 1-among the embodiment 1-3-methyl-4-(4 '-carboxylic acid benzhydrazon)-5-pyrazolone into 1-(p-carboxylic acid phenyl)-3-methyl-4-(p-carboxylic acid phenyl hydrazone group)-5-pyrazolone, all the other are with embodiment 1; Get carboxylic acyl n-Butyl Amine 99 type dye.
Embodiment 25,
Make the phenyl of the 1-among the embodiment 1-3-methyl-4-(4 '-carboxylic acid benzhydrazon)-5-pyrazolone into 4-[(2 hydroxy naphthalene base) azo]-phenylformic acid, all the other are with embodiment 1; Get carboxylic acyl n-Butyl Amine 99 type dye.
Embodiment 26,
Make the phenyl of the 1-among the embodiment 1-3-methyl-4-(4 '-carboxylic acid benzhydrazon)-5-pyrazolone into 2-hydroxyl-1-phenylazo-6-naphthoic acid, all the other are with embodiment 1; Get carboxylic acyl n-Butyl Amine 99 type dye.
Embodiment 27,
Make the phenyl of the 1-among the embodiment 1-3-methyl-4-(4 '-carboxylic acid benzhydrazon)-5-pyrazolone into 2-hydroxyl-1-(p-carboxylic acid phenyl azo)-6-naphthoic acid, all the other are with embodiment 1; Get carboxylic acyl n-Butyl Amine 99 type dye.
Embodiment 28,
Make the phenyl of the 1-among the embodiment 1-3-methyl-4-(4 '-carboxylic acid benzhydrazon)-5-pyrazolone into 4-[(2 hydroxy naphthalene base) azo]-naphthoic acid, all the other are with embodiment 1; Get carboxylic acyl n-Butyl Amine 99 type dye.
Embodiment 29,
Make the phenyl of the 1-among the embodiment 1-3-methyl-4-(4 '-carboxylic acid benzhydrazon)-5-pyrazolone into 2-hydroxyl-1-(1-naphthyl) azo-6-naphthoic acid, all the other are with embodiment 1; Get carboxylic acyl n-Butyl Amine 99 type dye.
Embodiment 30,
Make the phenyl of the 1-among the embodiment 1-3-methyl-4-(4 '-carboxylic acid benzhydrazon)-5-pyrazolone into 2-hydroxyl-1-(4-carboxylic acid naphthyl azo)-6-naphthoic acid, all the other are with embodiment 1; Get carboxylic acyl n-Butyl Amine 99 type dye.
Embodiment 31, a kind of trevira dye with the preparation method of azo structure carboxylic amide type dyes, carry out following steps successively:
1), in churned mechanically beaker, add 3.7g 1-phenyl-3-methyl-5-pyrazolones ketone midbody, 20ml water, with 10% sodium hydroxide solution adjust pH to 8～12; Be cooled to 0～10 ℃; Stir the hydrochloric acid soln (be mixed the getting of hydrochloric acid soln of 3.8g p-aminophenyl carboxylic acyl n-Butyl Amine 99 and 1.4g Sodium Nitrite) that drips p-aminophenyl carboxylic acyl n-Butyl Amine 99 diazonium salt down, 600 droplets/hour, and control the pH value 8～10 with 10% sodium carbonate solution; After dropwising, then at 0 ℃ of reaction 10hr;
2), reaction finishes, and filters, and utilizes frozen water to be washed till filtrating and is neutrality, after the drying, obtains carboxylic acyl n-Butyl Amine 99 type dye.
Embodiment 32～52,
Make the p-aminophenyl carboxylic acyl n-Butyl Amine 99 diazonium salt among the embodiment 31 p-aminophenyl carboxylic acyl n-amylamine diazonium salt, p-aminophenyl carboxylic acyl normal hexyl Amine diazonium salt, the positive heptyl amice diazonium salt of p-aminophenyl carboxylic acyl, p-aminophenyl carboxylic acyl NSC 9824 diazonium salt, the positive nonyl amine diazonium salt of p-aminophenyl carboxylic acyl, p-aminophenyl carboxylic acyl n-Decylamine diazonium salt, the positive undecylamine diazonium salt of p-aminophenyl carboxylic acyl, the positive amino dodecane diazonium salt of p-aminophenyl carboxylic acyl, the positive tridecyl amine diazonium salt of p-aminophenyl carboxylic acyl, the positive tetradecy lamine diazonium salt of p-aminophenyl carboxylic acyl, the positive pentadecyl amine diazonium salt of p-aminophenyl carboxylic acyl, the positive cetylamine diazonium salt of p-aminophenyl carboxylic acyl, the positive heptadecyl-amine diazonium salt of p-aminophenyl carboxylic acyl, the positive stearylamine diazonium salt of p-aminophenyl carboxylic acyl, p-aminophenyl carboxylic acyl hexahydroaniline diazonium salt, p-aminophenyl carboxylic acylaniline diazonium salt, p-aminophenyl carboxylic acyl n n dimetylaniline diazonium salt, p-aminophenyl carboxylic acyl diethylamine diazonium salt, p-aminophenyl carboxylic acyl Di-n-Butyl Amine diazonium salt, p-aminophenyl carboxylic acyl two normal hexyl Amine diazonium salts, the p-aminophenyl carboxylic acyl two NSC 9824 diazonium salts of same molar into respectively, all the other are with embodiment 61; Corresponding respectively carboxylic acyl n-amylamine, carboxylic acyl normal hexyl Amine, the positive heptyl amice of carboxylic acyl, NSC 9824, positive nonyl amine, n-Decylamine, positive undecylamine, positive amino dodecane, positive tridecyl amine, positive tetradecy lamine, positive pentadecyl amine, positive cetylamine, positive heptadecyl-amine, positive stearylamine, hexahydroaniline, aniline, n n dimetylaniline, diethylamine, Di-n-Butyl Amine, two normal hexyl Amines, the two NSC 9824 type dyes of obtaining.
Embodiment 53, a kind of trevira dye with the preparation method of azo structure carboxylic amide type dyes, carry out following steps successively:
1), in churned mechanically beaker, add 5.7g 1-(4-carboxylic acyl n-butylamine-based phenyl)-3-methyl-5-pyrazolone midbody, 20ml water, with 10% sodium hydroxide solution adjust pH to 8～12; Be cooled to 0～10 ℃; Stir the hydrochloric acid soln (be mixed the getting of hydrochloric acid soln of 1.6g aniline and 1.4g Sodium Nitrite) that drips diazonium salt of aniline down, 600 droplets/hour, and control the pH value 8～10 with 10% sodium carbonate solution; After dropwising, then at 5 ℃ of reaction 6hr;
2), reaction finishes, and filters, and utilizes frozen water to be washed till filtrating and is neutrality, obtains carboxylic acyl n-Butyl Amine 99 type dye after the drying.
Embodiment 54～74,
Make the 1-among the embodiment 53 (4-carboxylic acyl n-butylamine-based phenyl)-3-methyl-5-pyrazolone midbody 1-(4-carboxylic acyl n-amylamine base phenyl)-3-methyl-5-pyrazolone, 1-(4-carboxylic acyl normal hexyl Amine base phenyl)-3-methyl-5-pyrazolone, 1-(the positive heptyl amice base of 4-carboxylic acyl phenyl)-3-methyl-5-pyrazolone, 1-(4-carboxylic acyl NSC 9824 base phenyl)-3-methyl-5-pyrazolone, 1-(the positive nonyl amine base of 4-carboxylic acyl phenyl)-3-methyl-5-pyrazolone, 1-(4-carboxylic acyl n-Decylamine base phenyl)-3-methyl-5-pyrazolone, 1-(the positive undecylamine base of 4-carboxylic acyl phenyl)-3-methyl-5-pyrazolone, 1-(the positive amino dodecane base of 4-carboxylic acyl phenyl)-3-methyl-5-pyrazolone, 1-(the positive tridecyl amine base of 4-carboxylic acyl phenyl)-3-methyl-5-pyrazolone, 1-(the positive tetradecy lamine base of 4-carboxylic acyl phenyl)-3-methyl-5-pyrazolone, 1-(the positive pentadecyl amine base of 4-carboxylic acyl phenyl)-3-methyl-5-pyrazolone, 1-(the positive cetylamine base of 4-carboxylic acyl phenyl)-3-methyl-5-pyrazolone, 1-(the positive heptadecyl-amine base of 4-carboxylic acyl phenyl)-3-methyl-5-pyrazolone, 1-(the positive stearylamine base of 4-carboxylic acyl phenyl)-3-methyl-5-pyrazolone, 1-(4-carboxylic acyl cyclohexylamino phenyl)-3-methyl-5-pyrazolone, 1-(4-carboxylic acylaniline base phenyl)-3-methyl-5-pyrazolone, 1-(4-carboxylic acyl dimethylaminophenyl)-3-methyl-5-pyrazolone, 1-(4-carboxylic acyl diethylin phenyl)-3-methyl-5-pyrazolone, 1-(4-carboxylic acyl Di-n-Butyl Amine base phenyl)-3-methyl-5-pyrazolone, 1-(4-carboxylic acyl two normal hexyl Amine base phenyl)-3-methyl-5-pyrazolone, the 1-(4-carboxylic acyl two NSC 9824 base phenyl)-3-methyl-5-pyrazolone of same molar into, all the other are with embodiment 83; Corresponding respectively carboxylic acyl n-amylamine, normal hexyl Amine, positive heptyl amice, NSC 9824, positive nonyl amine, n-Decylamine, positive undecylamine, positive amino dodecane, positive tridecyl amine, positive tetradecy lamine, positive pentadecyl amine, positive cetylamine, positive heptadecyl-amine, positive stearylamine, hexahydroaniline, aniline, n n dimetylaniline, diethylamine, Di-n-Butyl Amine, two normal hexyl Amines, the two NSC 9824 type dyes of obtaining.
Embodiment 75,
1), in churned mechanically beaker; Add 5.7g 1-(4-carboxylic acyl n-butylamine-based phenyl)-3-methyl-5-pyrazolone midbody, 20ml water; With 10% sodium hydroxide solution adjust pH to 8～12, be cooled to 0～10 ℃, stir the hydrochloric acid soln (being mixed the getting of hydrochloric acid soln of 3.8g p-aminophenyl carboxylic acyl n-Butyl Amine 99 and 1.4g Sodium Nitrite) that drips p-aminophenyl carboxylic acyl n-Butyl Amine 99 diazonium salt down; And with 10% sodium carbonate solution control pH value 8～10; 600 droplets/hour, after dropwising, then at 7 ℃ of reaction 3hr;
2), reaction finishes, and filters, and utilizes frozen water to be washed till filtrating and is neutrality, obtains carboxylic acyl n-Butyl Amine 99 type dye after the drying.
Explain that through experiment trevira dyeing of the present invention is with the application of azo structure carboxylic amide type dyes in PET, PTT, PLA dyeing keratin-fiber below.
Experiment 1,
(particle diameter 1～2mm) 200g, water 50～100g added in the sand mill sand milling 2～10 hours to get synthetic carboxylic acyl n-Butyl Amine 99 dyestuff 5～10g among the embodiment 1, dispersion agent NNO5～10g, silica sand; Filter with B; Filter screen is 120 purpose woven wires, gets dye paste; Colourity requirement by 0.5～2% pipettes the dispersed dye mill base, is transferred in the Dyeing pipe after adding entry by bath raio 1:15～30, adds the painted PET fabric of desire and puts into the high-temperature pressure dyeing appearance; Heat-up rate by 2 ℃/min rises to 110～130 ℃, is incubated and reduces to room temperature after 1 hour, takes out the dyeing cloth specimen; Washing merges dyeing residual liquid and washings, and constant volume is surveyed the device absorbancy; The dye uptake that utilizes Law of Lambert-Beer to find the solution dyestuff is 96%, and color fastness to water is 4～5 grades, and anti-dry fastness is 4～5 grades; The moisture-proof crockfastness is 4～5 grades, 4 grades of color fastness to sublimations.
Experiment 2,
Make the PET fabric in the experiment 1 into PTT, PLA fabric respectively, all the other are with experiment 1.The result is following: the dye uptake of dyestuff on PTT is respectively 94.5%, and the color fastness to water on the PTT fabric is 4～5 grades, and anti-dry fastness is the 4-5 level, and the moisture-proof crockfastness is the 4-5 level, 4 grades of color fastness to sublimations; Dye uptake on POLYACTIC ACID (PLA) fiber is 95.0%, and color fastness to water is 4 grades, and anti-dry fastness is 4 grades, and the moisture-proof crockfastness is 4 grades, 3～4 grades of color fastness to sublimations.
Experiment 3,
Make the carboxylic acyl n-Butyl Amine 99 dyestuff in the experiment 1 into carboxylic acyl Di-n-Butyl Amine dyestuff, all the other are with experiment 1.The result is following: the dye uptake of dyestuff is 94.3%, and color fastness to water is 4～5 grades, and anti-dry fastness is 4～5 grades, and the moisture-proof crockfastness is 4～5 grades, 4 grades of color fastness to sublimations.
Experiment 4,
Make the PET fabric in the experiment 3 into PTT, PLA fabric respectively, all the other are with experiment 3.The result is following: the dye uptake of dyestuff on PTT is respectively 92.5%, and the color fastness to water on the PTT fabric is 4～5 grades, and anti-dry fastness is the 4-5 level, and the moisture-proof crockfastness is the 4-5 level, 4 grades of color fastness to sublimations; Dye uptake on acid fiber by polylactic is 97.0%, and color fastness to water is 4～5 grades, and anti-dry fastness is 4～5 grades, and the moisture-proof crockfastness is 4 grades, 3～4 grades of color fastness to sublimations.
Experiment 5,
Make the carboxylic acyl n-Butyl Amine 99 dyestuff in the experiment 1 into carboxylic acyl positive amino dodecane dyestuff, all the other are with experiment 1.The result is following: the dye uptake of dyestuff is 94.3%, and color fastness to water is 4～5 grades, and anti-dry fastness is 4～5 grades, and the moisture-proof crockfastness is 4～5 grades, 4 grades of color fastness to sublimations.
Experiment 6,
Make the PET fabric in the experiment 5 into PTT, PLA fabric respectively, all the other are with experiment 5.The result is following: the dye uptake of dyestuff on PTT is respectively 92.5%, and the color fastness to water on the PTT fabric is 4～5 grades, and anti-dry fastness is the 4-5 level, and the moisture-proof crockfastness is the 4-5 level, 4 grades of color fastness to sublimations; Dye uptake on acid fiber by polylactic is 94.2%, and color fastness to water is 4～5 grades, and anti-dry fastness is 4～5 grades, and the moisture-proof crockfastness is 4 grades, 3～4 grades of color fastness to sublimations.
Experiment 7,
Make the carboxylic acyl n-Butyl Amine 99 dyestuff in the experiment 1 into the carboxylic acylaniline dyestuff, all the other are with experiment 1.The result is following: the dye uptake of dyestuff is 94.3%, and color fastness to water is 4～5 grades, and anti-dry fastness is 4～5 grades, and the moisture-proof crockfastness is 4～5 grades, 4 grades of color fastness to sublimations.
Experiment 8,
Make the PET fabric in the experiment 7 into PTT, PLA fabric respectively, all the other are with experiment 7.The result is following: the dye uptake of dyestuff on PTT is respectively 92.5%, and the color fastness to water on the PTT fabric is 4～5 grades, and anti-dry fastness is the 4-5 level, and the moisture-proof crockfastness is the 4-5 level, 4 grades of color fastness to sublimations; Dye uptake on acid fiber by polylactic is 88%, and color fastness to water is 4～5 grades, and anti-dry fastness is 4～5 grades, and the moisture-proof crockfastness is 4 grades, 3～4 grades of color fastness to sublimations.
The contrast experiment 1:
Make the carboxylic acyl n-Butyl Amine 99 dyestuff in the experiment 1 and 2 into existing disperse yellow brown 2RCW, all the other are with experiment 1 and 2.The result is following:
The dye uptake of dyestuff on PET is respectively 91.7%, and the color fastness to water on the PET fabric is the 4-5 level, and anti-dry fastness is the 4-5 level, and the moisture-proof crockfastness is the 4-5 level, 4 grades of color fastness to sublimations;
The dye uptake of dyestuff on PTT is respectively 90.5%, and the color fastness to water on the PTT fabric is the 4-5 level, and anti-dry fastness is the 4-5 level, and the moisture-proof crockfastness is the 4-5 level, 4 grades of color fastness to sublimations;
The dye uptake of dyestuff on POLYACTIC ACID (PLA) fiber is 47.1%, and color fastness to water is 3 grades, and anti-dry fastness is 3 grades, and the moisture-proof crockfastness is the 3-4 level, color fastness to sublimation 3-4 level.
At last, it is also to be noted that what more than enumerate only is several specific embodiments of the present invention.Obviously, the invention is not restricted to above embodiment, many distortion can also be arranged.All distortion that those of ordinary skill in the art can directly derive or associate from content disclosed by the invention all should be thought protection scope of the present invention.
Claims (8)
1. an azo structure carboxylic amide type dyes for polylactic acid fiber dyeing is characterized in that, contains carboxylacyl amine group in its molecular structure, and its general structure is following:
In the formula: D is azo structure contained color bodies, and m is 2, and X is n-C
nH
2n+1, Y is H, n-C
nH
2n+1Or
N-C
nH
2n+1In n meet the following conditions: 1≤n≤18, and n is an integer.
2. azo structure carboxylic amide type dyes for polylactic acid fiber dyeing according to claim 1 is characterized in that, the structural formula of said D is following:
In the formula: R
1Be H, CH
3, C
2H
5, OH, OCH
3, OC
2H
5, Cl, Br, CN or NO
2R
2Be H, CH
3, C
2H
5, OH, OCH
3, OC
2H
5, Cl, Br, CN, NO
2Or CONXY; R
3Be H, CH
3, CN or C
6H
5R
4Be H, CH
3, C
2H
5, OH, OCH
3, OC
2H
5, Cl, CN or NHCOCH
3R
5Be H, CH
3, C
2H
5, OH, OCH
3, OC
2H
5, Cl, CN, NO
2Or CONXY; And contain 1～2-CONXY in the structure of said dyestuff.
3. azo structure carboxylic amide type dyes for polylactic acid fiber dyeing according to claim 1 is characterized in that, the structural formula of said D is following:
In the formula: R
6Be H or OH; R
7Be H, Cl, OH, CN, CONXY or NHCOC
2H
5R
8Be H, OH, OCH
3, OC
2H
5, CONXY or NHCOC
2H
5R
9Be H, OH, OCH
3, OC
2H
5, CONXY or NHCOC
2H
5R
10Be H, CH
3, C
2H
5, OH, OCH
3, OC
2H
5, Cl, CN or NHCOCH
3R
11Be H, CH
3, C
2H
5, OH, OCH
3, OC
2H
5, Cl, CN, NO
2Or CONXY; And contain 1～2-CONXY in the structure of said dyestuff, and can not have 2-CONXY simultaneously in the same aromatic ring.
4. azo structure carboxylic amide type dyes for polylactic acid fiber dyeing according to claim 1 is characterized in that, the structural formula of said D is following:
In the formula: R
12Be H or OH; R
13Be H, Cl, OH, CN, CONXY or NHCOC
2H
5R
14Be H, OH, OCH
3, OC
2H
5, CONXY or NHCOC
2H
5R
15Be H, OH, OCH
3, OC
2H
5, CONXY or NHCOC
2H
5R
16Be H, Cl, CH
3, C
2H
5, OH, OCH
3, OC
2H
5, CN, NO
2Or CONXY; R
17Be H, CH
3, C
2H
5, OH, OCH
3, OC
2H
5, Cl, CN, NO
2Or CONXY; R
18Be H, CH
3, C
2H
5, OH, OCH
3, OC
2H
5, Cl, CN or NHCOCH
3And contain 1～2-CONXY in the structure of said dyestuff, and can not have 2-CONXY simultaneously in the same aromatic ring.
5. like the preparation method of any one azo structure carboxylic amide type dyes for polylactic acid fiber dyeing in the claim 1～4, it is characterized in that may further comprise the steps:
1), add 1.4～3.0ml sulfur oxychloride, 10～30ml solvent and 0.1～0.4mlN according to the carboxy-containing acid group's of per 3. 2g dyestuff, the ratio of dinethylformamide will above-mentioned 4 adds in the reactor drum, is warming up to 55～75 ℃, reacts 0.5～6hr;
2), reaction finishes, after 90 ℃ down decompression steamed excessive sulfur oxychloride and solvent, frozen water washing and filtration until being washed till neutrality, obtained the carboxyl acyl chloride midbody after the vacuum-drying repeatedly;
3), in reactor drum, add earlier the carboxyl acyl chloride midbody and as the acetone of solvent, wait the dissolving of carboxyl acyl chloride midbody after, add fat primary amine, hexahydroaniline, aniline or fatty primary secondary amine again and add Powdered K
2CO
3, under room temperature, mixed stirring reaction 1 hour, said fat primary amine, hexahydroaniline, aniline or fatty primary secondary amine: carboxyl acyl chloride midbody: K
2CO
3Mol ratio=1:1:0.5～2;
4), the reactant of step 3) gained is boiled off acetone, resistates; Said resistates is carried out pickling, washing and drying successively, get azo structure carboxylic amide type dyes for polylactic acid fiber dyeing.
6. the preparation method of azo structure carboxylic amide type dyes for polylactic acid fiber dyeing according to claim 5; It is characterized in that: in the said step 4): it is that 3% dilute hydrochloric acid solution carries out pickling that resistates is utilized concentration earlier; Filter then, the filter cake that will filter gained again uses clear water to be washed till raffinate for till neutral and colourless; Filter cake after then will washing at room temperature dries, and gets azo structure carboxylic amide type dyes for polylactic acid fiber dyeing.
7. the preparation method of azo structure carboxylic amide type dyes for polylactic acid fiber dyeing according to claim 6, it is characterized in that: in the said step 1): solvent is benzene or toluene.
8. like the preparation method of any one azo structure carboxylic amide type dyes for polylactic acid fiber dyeing in the claim 1～4, it is characterized in that may further comprise the steps:
1), will contain in the coupling component and water adding reactor drum of carboxylacyl amine group, with mass concentration 10% sodium hydroxide solution adjust pH to 8～12; Be cooled to 0～10 ℃ then, drip down the hydrochloric acid soln of arylamine diazonium salt in agitation condition, using mass concentration in the dropping process is that the pH value of mixture in the 10% sodium carbonate solution controlling reactor is 8～10; After dropwising, at 0～10 ℃ of reaction 5～10hr; Saidly contain the coupling component of carboxylacyl amine group and the mol ratio of arylamine diazonium salt is 1.05:1.0;
Perhaps coupling component midbody and water are added in the reactor drum, with mass concentration 10% sodium hydroxide solution adjust pH to 8～12; Be cooled to 0～10 ℃ then, drip down the arylamine diazonium salt hydrochloric acid soln that contains carboxamide groups in agitation condition, using mass concentration in the dropping process is that the pH value of mixture in the 10% sodium carbonate solution controlling reactor is 8～10; After dropwising, at 0～10 ℃ of reaction 5～10hr; Said coupling component midbody is 1.05:1.0 with the mol ratio that contains the arylamine diazonium salt of carboxamide groups;
The coupling component and the water that perhaps will contain carboxylacyl amine group add in the reactor drum, with mass concentration 10% sodium hydroxide solution adjust pH to 8～12; Be cooled to 0～10 ℃ then, drip down the arylamine diazonium salt hydrochloric acid soln that contains carboxamide groups in agitation condition, using mass concentration in the dropping process is that the pH value of mixture in the 10% sodium carbonate solution controlling reactor is 8～10; After dropwising, at 0～10 ℃ of reaction 5～10hr; The said coupling component that contains carboxylacyl amine group is 1.05:1.0 with the mol ratio that contains the arylamine diazonium salt of carboxamide groups;
2), reaction finishes, and filters, and utilizes frozen water to be washed till filtrating and is neutrality, after the drying, obtains azo structure carboxylic amide type dyes for polylactic acid fiber dyeing.
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|---|---|---|---|---|
| CN1227583A (en) * | 1996-08-06 | 1999-09-01 | 恩格尔哈德公司 | Lake of azoie color |
| CN1251121A (en) * | 1997-12-26 | 2000-04-19 | 株式会社上野制药应用研究所 | Water soluble azo compound and process for prepn. of |
| CN1995150A (en) * | 2006-12-21 | 2007-07-11 | 大连理工大学 | Slightly water-soluble sulfonamide type dye for dying hydrophobic fiber and its preparation |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1227583A (en) * | 1996-08-06 | 1999-09-01 | 恩格尔哈德公司 | Lake of azoie color |
| CN1251121A (en) * | 1997-12-26 | 2000-04-19 | 株式会社上野制药应用研究所 | Water soluble azo compound and process for prepn. of |
| CN1995150A (en) * | 2006-12-21 | 2007-07-11 | 大连理工大学 | Slightly water-soluble sulfonamide type dye for dying hydrophobic fiber and its preparation |
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