CN101982508B - Carboxylic ester type disperse dye capable of being washed by alkali and preparation method thereof - Google Patents
Carboxylic ester type disperse dye capable of being washed by alkali and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a carboxylic ester type disperse dye capable of being washed by alkali. The molecular structure of the disperse dye contains a carboxylic ester group, and the structural general formula of the disperse dye is shown in the specifications, wherein D is a color body containing an azo structure, m is equal to 1 or 2, X is CnH(2n+1) or groups shown in the specifications, n in the CnH(2n+1) meets the following conditions: n is greater than or equal to 2 and is less than or equal to 18, and n is an integer. The invention also discloses a preparation method of the carboxylic ester type disperse dye capable of being washed by alkali. The dye can improve the dyeing rate and the color fastness on PLA, PET and PTT fibers.
Description
Technical field
The present invention relates to a kind of carboxylic ester type disperse dye capable of being washed by alkali and preparation method thereof.
Background technology
Trevira mainly comprises polyethylene terephthalate (PET), Poly(Trimethylene Terephthalate) (PTT), polybutylene terephthalate (PBT) and emerging poly(lactic acid) (PLA) fiber, this fibrid has high-crystallinity usually, without the strongly hydrophilic group, therefore present hydrophobicity in molecular backbone chain.The trevira spin-drawing and pre-thermally-stabilised after, the molecular layer that the surface has one deck to align, be difficult for penetrating, and lack the active group of being combined with dyestuff in molecular structure, therefore dyeing is more 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 dispersed dye molecule of trevira dyeing, it is the nonionic dye that a class is insoluble in water, in need to being scattered in water with insoluble minuteness particle under the dispersion agent effect, usually the aggregate form with a plurality of dye molecules exists, and dye granule is larger.When dyeing in water medium, trevira can not resemble cotton fibre and by violent swelling, the space be increased, dye granule is difficult to be penetrated at short notice fibrous inside, needs to realize dying by the kinetic energy that improves dye molecule and the method that fortifying fibre macromolecular chain segment mobility enlarges the fiber hole in the trevira dyeing course.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 have the dye uptake over 90% on PET.
As a kind of emerging environment-friendly type polyester fiber, acid fiber by polylactic has good biocompatibility, 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 polyster fibre are not good, cause the scarcity of acid fiber by polylactic suitable dyes.Qian Hong flies to wait and has studied the impact of dispersed dye molecular structure on the polylactic acid fiber dyeing performance, and contrasts with coloration result on polyster fibre.Because all there are larger difference in acid fiber by polylactic and polyster fibre aspect molecular structure and dyeing, most of terylene with dispersed dye on acid fiber by polylactic dye uptake and colour fastness on the low side, be difficult to satisfy and take requirement.After dying fiber on dispersed dye, dyestuff and fiber are to combine by weak Van der Waals force.Van der Waals force is large, 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.Without aromatic ring and there are relatively many ester groups, give the certain polarity of acid fiber by polylactic molecular chain and kindliness preferably on the polylactic acid molecule chain.If introduce polar group in dye molecule, these polar groups can and acid fiber by polylactic macromole generation dipolar forces, hydrogen bonded improve Van der Waals force between dyestuff and fiber molecule, be conducive to improve dye uptake and the colour fastness of dyestuff.Studies show that the dye uptake of azoic dyestuff and the substituent kind in molecule have dependency, have the dyestuff of carboxylic acid ester groups in molecular structure, dye uptake is generally higher.Dyestuff similar to the molecular structure of fiber (all having the such polarity dots of ester group) is described, is conducive to dye on dyestuff.
Zhang Shufen etc. had once developed a class hydrophobic fibre slightly water-soluble sulfonamide type dye, and this dyestuff gives dyestuff different avidity by the chain length of the straight chained alkyl that the adjusting sulfoamido connects, 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 tinting strength and the colour fastness of dyestuff; Introduce the sulphonamide polar group in dye structure, not only can give the dyestuff slightly water-soluble, thereby the molecular polarity that has also increased dyestuff is conducive to improve the fastness to sublimation of dyestuff.This class dyestuff synthesis technique is simple, can synthesize by sulfonating chlorinating, aminolysis reaction or diazotization, coupled reaction the slightly water-soluble sulfonamide type dye that contains straight chained alkyl, 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 better colour fastness.
In sum, poly(lactic acid) (PLA) fiber belongs to a kind of more emerging trevira, and much dye uptake and the colour fastness on the PLA fiber is not good at the good dispersed dye of coloration result on the PET fiber.How to design and a kind ofly can present the dyestuff of better coloration result on the PLA fiber, become the industry and urgently wish the problem that solves.
In please number be that 200810162925.0 patent of invention " azo structure carboxylic amide type dyes for polylactic acid fiber dyeing and preparation method thereof " provides a kind of can present the dyestuff of better coloration result on the PLA fiber, it has advantages of that dye uptake is high, colour fastness good, but also have the following disadvantages: must adopt reduction clearing technique to remove the loose colour of fiber surface, therefore also need to use reductive agent in the arrangement process after DYED FABRICS, thereby cause complicated component in sewage, the pollution treatment cost is high.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of carboxylic ester type disperse dye capable of being washed by alkali and preparation method thereof, uses this kind dyestuff can improve dye uptake and colour fastness on PLA, PET, ptt fiber.
In order to solve the problems of the technologies described above, the invention provides a kind of carboxylic ester type disperse dye capable of being washed by alkali, contain the carboxylate group in its molecular structure, its general structure is as follows:
In formula: D is azo structure contained color bodies, m be 1 or 2, X be C
nH
2n+1,
Or
, C
nH
2n+1In n meet the following conditions: 2≤n≤18, and n is integer.
As a kind of improvement of carboxylic ester type disperse dye capable of being washed by alkali of the present invention, the structural formula of D is as follows:
In 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 COOX; 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 COOX, and contain 1～2-COOX in the structure of described dyestuff.
Another kind as carboxylic ester type disperse dye capable of being washed by alkali of the present invention improves, and the structural formula of D is as follows:
In formula: R
6Be H or OH; R
7Be H, Cl, OH, CN, COOX or NHCOC
2H
5R
8Be H, OH, OCH
3, OC
2H
5, COOX or NHCOC
2H
5R
9Be H, OH, OCH
3, OC
2H
5, COOX 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 COOX; And contain 1～2-COOX in the structure of described dyestuff, and can not have simultaneously 2-COOX in same aromatic ring.
Another kind as carboxylic ester type disperse dye capable of being washed by alkali of the present invention improves, and the structural formula of D is as follows:
In formula: R
12Be H or OH; R
13Be H, Cl, OH, CN, COOX or NHCOC
2H
5R
14Be H, OH, OCH
3, OC
2H
5, COOX or NHCOC
2H
5R
15Be H, OH, OCH
3, OC
2H
5, COOX or NHCOC
2H
5R
16Be H, Cl, CH
3, C
2H
5, OH, OCH
3, OC
2H
5, CN, NO
2Or COOX; R
17Be H, CH
3, C
2H
5, OH, OCH
3, OC
2H
5, Cl, CN, NO
2Or COOX; R
18Be H, CH
3, C
2H
5, OH, OCH
3, OC
2H
5, Cl, CN or NHCOCH
3And contain 1～2-COOX in the structure of this dyestuff, and can not have simultaneously 2-COOX in same aromatic ring.
The present invention also provides a kind of preparation method of above-mentioned carboxylic ester type disperse dye capable of being washed by alkali simultaneously, and it adopts sulfur oxychloride chloride, esterification process, specifically comprises the following steps:
1) N that, adds 1.4～3.0ml sulfur oxychloride, 10～30ml solvent and 0.1～0.4ml by every 0.01mol carboxy-containing acid group's dyestuff, the ratio of dinethylformamide (DMF), add in reactor above-mentioned 4, be warming up to 55～75 ℃, reaction 0.5～6hr;
2), reaction is complete, after 90 ℃ of decompressions steamed excessive sulfur oxychloride and solvent, frozen water washing and filtering repeatedly until be washed till neutrality, obtained the carboxyl acyl chloride intermediate after vacuum-drying;
3), first add the carboxyl acyl chloride intermediate and prevent the zeolite of bumping in reactor, then add pyridine and reactant, back flow reaction 1～2 hour; Described carboxyl acyl chloride intermediate: reactant: the mol ratio of pyridine is 1: 2: 20, and described reactant is Fatty Alcohol(C12-C14 and C12-C18), hexalin or phenol, and described pyridine is as solvent and acid binding agent;
4), with step 3) distillation of the reaction product of gained removes pyridine and remaining reactant (Fatty Alcohol(C12-C14 and C12-C18), hexalin or phenol), gets resistates; Described resistates is carried out pickling, washing and drying successively, get carboxylic ester type disperse dye capable of being washed by alkali.
Improvement as above-mentioned preparation method of the present invention: step 4): it is that 3% dilute hydrochloric acid solution carries out pickling that resistates is first utilized mass concentration, then filter, then the filter cake that will filter gained with clear water be washed till raffinate be neutral and colourless till; Filter cake after then washing at room temperature dries, and gets carboxylic ester type disperse dye capable of being washed by alkali.
Further improvement as above-mentioned preparation method of the present invention: step 1): solvent is benzene or toluene.
The present invention also provides the another kind of preparation method of above-mentioned carboxylic ester type disperse dye capable of being washed by alkali simultaneously, and the method is to adopt diazonium, coupling process, specifically comprises the following steps:
1), coupling component and the water that will contain the carboxylate group adds in reactor, with mass concentration 10% sodium hydroxide solution adjust pH to 8～12; Then being cooled to 0～10 ℃, dripping the hydrochloric acid soln of arylamine diazonium salt under agitation condition, is that 10% sodium carbonate solution is controlled the pH value of mixture in reactor 8～10 with mass concentration in the dropping process; After dropwising, at 0～10 ℃ of reaction 5～10hr; The described carboxylate group's of containing coupling component and the mol ratio of arylamine diazonium salt are 1.05: 1.0;
Perhaps coupling component intermediate and water are added in reactor, with mass concentration 10% sodium hydroxide solution adjust pH to 8～12; Then being cooled to 0～10 ℃, dripping the hydrochloric acid soln of the arylamine diazonium salt that contains carboxylic acid ester groups under agitation condition, is that 10% sodium carbonate solution is controlled the pH value of mixture in reactor 8～10 with mass concentration in the dropping process; After dropwising, at 0～10 ℃ of reaction 5～10hr; Described coupling component intermediate is 1.05: 1.0 with the mol ratio that contains the arylamine diazonium salt of carboxylic acid ester groups;
Coupling component and the water that perhaps will contain the carboxylate group add in reactor, with mass concentration 10% sodium hydroxide solution adjust pH to 8～12; Then being cooled to 0～10 ℃, dripping the hydrochloric acid soln of the arylamine diazonium salt that contains carboxylic acid ester groups under agitation condition, is that 10% sodium carbonate solution is controlled the pH value of mixture in reactor 8～10 with mass concentration in the dropping process; After dropwising, at 0～10 ℃ of reaction 5～10hr; The described carboxylate group's of containing coupling component is 1.05: 1.0 with the mol ratio that contains the arylamine diazonium salt of carboxylic acid ester groups;
2), reaction is complete, filters, and utilizes frozen water to be washed till filtrate and is neutrality, after drying, obtains carboxylic ester type disperse dye capable of being washed by alkali.
Therefore, the preparation method of carboxylic ester type disperse dye capable of being washed by alkali of the present invention by introduce carboxylate group's method in dye structure, is divided into following several preparation technology:
(1) when take carboxy-containing acid group's dyestuff during as starting raw material, the preparation of carboxylic ester type disperse dye capable of being washed by alkali can be adopted chloride-esterification process.
(2) when diazonium or coupling component contain the carboxylate group, the preparation of azo structure carboxylicesters type dye is divided into arylamine diazonium salt and the coupling process that contains the coupling process of the coupling component of carboxylic acid ester groups, the arylamine diazonium salt that contains carboxylic acid ester groups and coupling component, contain the arylamine diazonium salt of carboxylic acid ester groups and contain three kinds of techniques of coupling process of the coupling component of carboxylic acid ester groups.
The present invention has developed a class carboxylic ester type disperse dye capable of being washed by alkali, and kind, the length that this class dyestuff can connect by changing the carboxylate group end group is regulated the avidity between dyestuff and different trevira; The introducing of carboxylic acid ester groups polar group in dye structure has simultaneously increased the dipolar forces between dyestuff and fiber, is conducive to the raising of dye uptake and colour fastness.This class dyestuff synthesis technique is simple, by chloride, esterification or diazotization, the synthetic azo structure carboxylicesters type dye 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 better colour fastness.Need to prove especially: use carboxylic ester type disperse dye capable of being washed by alkali of the present invention, the dye uptake that can solve on the PLA fiber hangs down and the poor problem of colour fastness.In addition, when PET and ptt fiber dyeing aftertreatment, can directly adopt alkali wash to remove removal floating color, compare with traditional reduction clearing method, have advantages of the reductive agent of release.
Carboxylic ester type disperse dye capable of being washed by alkali is used for the dyeing of the hydrophobicity trevira such as PET, PTT, PLA, its dyeing is: (particle diameter 1～2mm) 200g, water 50～100g added in sand mill sand milling 2～10 hours to get carboxylic ester type disperse dye capable of being washed by alkali 5～10g of the present invention, dispersion agent NNO 5～10g, quartz sand, filter with Büchner funnel, filter screen is 120 purpose woven wires, gets dye paste; Colourity requirement by 0.5～2% pipettes dye paste, be transferred in Dyeing pipe after adding entry by bath raio 1: 15～30, add PET, PTT or the PLA of wish dyeing to put into the high-temperature pressure dyeing instrument, heat-up rate by 2 ℃/min rises to 110～130 ℃, is incubated and is down 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.
Carboxylic ester type disperse dye capable of being washed by alkali of the present invention, introduce the strong carboxylate group of polarity in dye structure, can improve avidity and the fastness to sublimation of dyestuff on trevira, and by changing type and the length of the end group that carboxylic acid ester groups connects, avidity and the colour fastness of adjustable product to fiber, improve the dye uptake of dyestuff, reduce the discharging of pollutant effluents, improve its application performance.Because the carboxylic ester type disperse dye capable of being washed by alkali of developing has avidity controllability and good colour fastness concurrently, has application prospect widely.
Embodiment
The preparation method of embodiment 1, a kind of carboxylic ester type disperse dye capable of being washed by alkali, carry out following steps successively:
1), in the there-necked flask that thermometer, reflux condensing tube and mechanical stirring device are housed, add 3.2g (0.01mol) 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 is complete, and reaction solution is warming up to 90 ℃, decompression is after (0.01MPa) distill out excessive sulfur oxychloride and solvent (benzene), be chilled to room temperature, be transferred in frozen water, filter, utilize frozen water to be washed till filtrate and be neutrality, obtain the carboxyl acyl chloride intermediate after vacuum-drying;
3), in the there-necked flask that agitator, thermometer, prolong are housed, first add 3.4g (0.01mol) carboxyl acyl chloride intermediate and 16.1ml (0.2mol) pyridine, add again 1.2ml (0.02mol) ethanol and several zeolites, back flow reaction 1.5 hours;
The effect of zeolite is to prevent bumping, generally puts into 2～5 and all can.
4), with step 3) distillation of the reaction product of gained removes pyridine and remaining ethanol, gets resistates; Pouring described resistates into the 100ml mass concentration is in 3% dilute hydrochloric acid solution, fully filters after washing, and it is colourless that filter cake is washed till raffinate neutrality with clear water; At room temperature dry, get the carboxylic acid, ethyl ester type dye.
The structural formula of this carboxylic acid, ethyl ester type dye is as follows:
The preparation method of embodiment 2, a kind of carboxylic ester type disperse dye capable of being washed by alkali, carry out following steps successively:
1), in the there-necked flask that thermometer, 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), be equal to embodiment 1;
3), in the there-necked flask that agitator, thermometer, prolong are housed, first add 3.4g (0.01mol) carboxyl acyl chloride intermediate and 16.1ml (0.2mol) pyridine, add again 1.5ml (0.02mol) n-propyl alcohol and several zeolites, back flow reaction 1.5 hours;
4), be equal to embodiment 1, get carboxylic acid n-propyl type dye.
The structural formula of this carboxylic acid n-propyl type dye is as follows:
The preparation method of embodiment 3, a kind of carboxylic ester type disperse dye capable of being washed by alkali, carry out following steps successively:
1), in the there-necked flask that thermometer, 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), be equal to embodiment 1;
3), in the there-necked flask that agitator, thermometer, prolong are housed, first add 3.4g (0.01mol) carboxyl acyl chloride intermediate and 16.1ml (0.2mol) pyridine, add again 1.8ml (0.02mol) propyl carbinol and several zeolites, back flow reaction 1.5 hours;
4), be equal to embodiment 1, get the synthesis type dye.
The structural formula of this synthesis type dye is as follows:
Embodiment 4～24,
Replace the ethanol in embodiment 1 with Pentyl alcohol, n-hexyl alcohol, n-Heptyl alcohol, n-Octanol, nonanol-, nonylcarbinol, positive undecyl alcohol, n-dodecanol, positive tridecanol, tetradecanol, pentadecanol, positive hexadecanol, positive heptadecyl alcohol, positive stearyl alcohol, hexalin, phenol, Virahol, sec-butyl alcohol, the trimethyl carbinol, 2-amylalcohol, 3-amylalcohol respectively, all the other are with embodiment 1; Obtain respectively corresponding carboxylic acid n-pentyl ester, the just own ester of carboxylic acid, the positive heptyl ester of carboxylic acid, carboxylic acid n-octyl, carboxylic acid ester in the positive ninth of the ten Heavenly Stems, carboxylic acid ester in the positive last of the ten Heavenly stems, carboxylic acid undecyl ester, positive ten diester of carboxylic acid, positive 13 esters of carboxylic acid, positive 14 esters of carboxylic acid, positive ten five-esters of carboxylic acid, the positive hexadecyl ester of carboxylic acid, positive 17 esters of carboxylic acid, the positive octadecyl ester of carboxylic acid, cyclohexyl carboxylate, carboxylic acid phenyl ester, carboxylic acid isopropyl, sec-butyl carboxylate, carboxylic acid tert-butyl ester, carboxylic acid 2-pentyl ester, carboxylic acid 3-pentyl ester type dye.
Embodiment 25,
Make the phenyl of the 1-in 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 the carboxylic acid, ethyl ester type dye.
Embodiment 26,
Make the phenyl of the 1-in 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 the carboxylic acid, ethyl ester type dye.
Embodiment 27,
Make the phenyl of the 1-in embodiment 1-3-methyl-4-(4 '-carboxylic acid benzhydrazon)-5-pyrazolone into 4-[(2-hydroxyl naphthyl) azo]-phenylformic acid, all the other are with embodiment 1; Get the carboxylic acid, ethyl ester type dye.
Embodiment 28,
Make the phenyl of the 1-in 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 the carboxylic acid, ethyl ester type dye.
Embodiment 29,
Make the phenyl of the 1-in 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 the carboxylic acid, ethyl ester type dye.
Embodiment 30,
Make the phenyl of the 1-in embodiment 1-3-methyl-4-(4 '-carboxylic acid benzhydrazon)-5-pyrazolone into 4-[(2-hydroxyl naphthyl) azo]-naphthoic acid, all the other are with embodiment 1; Get the carboxylic acid, ethyl ester type dye.
Embodiment 31,
Make the phenyl of the 1-in 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 the carboxylic acid, ethyl ester type dye.
Embodiment 32,
Make the phenyl of the 1-in 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 the carboxylic acid, ethyl ester type dye.
The preparation method of embodiment 33, a kind of carboxylic ester type disperse dye capable of being washed by alkali, carry out following steps successively:
1), in churned mechanically beaker, add 3.66g (0.021mol) 1-phenyl-3-methyl-5-pyrazolones ketone intermediate, 20ml water, with 10% sodium hydroxide solution adjust pH to 8～12, be cooled to 0～10 ℃, stir the lower hydrochloric acid soln (making for 3.3g (0.02mol) p-aminophenyl carboxylic acid, ethyl ester mixes with the hydrochloric acid soln of 1.45g Sodium Nitrite) that drips p-aminophenyl carboxylic acid, ethyl ester diazonium salt, 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 is complete, filters, and utilizes frozen water to be washed till filtrate and is neutrality, after drying, obtains the carboxylic acid, ethyl ester type dye.
The structural formula of this carboxylic acid, ethyl ester type dye is as follows:
Embodiment 34～56,
p-aminophenyl carboxylic acid, ethyl ester diazonium salt in embodiment 33 is made respectively into the p-aminophenyl carboxylic acid n-propyl diazonium salt of same molar, p-aminophenyl synthesis diazonium salt, p-aminophenyl carboxylic acid n-pentyl ester diazonium salt, the just own ester diazonium salt of p-aminophenyl carboxylic acid, the positive heptyl ester diazonium salt of p-aminophenyl carboxylic acid, p-aminophenyl carboxylic acid n-octyl diazonium salt, p-aminophenyl carboxylic acid ester diazonium salt in the positive ninth of the ten Heavenly Stems, p-aminophenyl carboxylic acid ester diazonium salt in the positive last of the ten Heavenly stems, p-aminophenyl carboxylic acid undecyl ester diazonium salt, the positive ten diester diazonium salts of p-aminophenyl carboxylic acid, the positive 13 ester diazonium salts of p-aminophenyl carboxylic acid, the positive 14 ester diazonium salts of p-aminophenyl carboxylic acid, the positive ten five-ester diazonium salts of p-aminophenyl carboxylic acid, the positive hexadecyl ester diazonium salt of p-aminophenyl carboxylic acid, the positive 17 ester diazonium salts of p-aminophenyl carboxylic acid, the positive octadecyl ester diazonium salt of p-aminophenyl carboxylic acid, p-aminophenyl cyclohexyl carboxylate diazonium salt, p-aminophenyl carboxylic acid phenyl ester diazonium salt, p-aminophenyl carboxylic acid isopropyl diazonium salt, p-aminophenyl sec-butyl carboxylate diazonium salt, p-aminophenyl carboxylic acid tert-butyl ester diazonium salt, p-aminophenyl carboxylic acid 2-pentyl ester diazonium salt, p-aminophenyl carboxylic acid 3-pentyl ester diazonium salt, all the other are with embodiment 33, the corresponding carboxylic acid n-propyl that obtains respectively, synthesis, the carboxylic acid n-pentyl ester, the just own ester of carboxylic acid, the positive heptyl ester of carboxylic acid, the carboxylic acid n-octyl, carboxylic acid ester in the positive ninth of the ten Heavenly Stems, carboxylic acid ester in the positive last of the ten Heavenly stems, the carboxylic acid undecyl ester, positive ten diester of carboxylic acid, positive 13 esters of carboxylic acid, positive 14 esters of carboxylic acid, positive ten five-esters of carboxylic acid, the positive hexadecyl ester of carboxylic acid, positive 17 esters of carboxylic acid, the positive octadecyl ester of carboxylic acid, cyclohexyl carboxylate, the carboxylic acid phenyl ester, the carboxylic acid isopropyl, sec-butyl carboxylate, carboxylic acid tert-butyl ester, carboxylic acid 2-pentyl ester, carboxylic acid 3-pentyl ester type dye.
The preparation method of embodiment 57, a kind of carboxylic ester type disperse dye capable of being washed by alkali, carry out following steps successively:
1), in churned mechanically beaker, add 5.2g (0.021mol) 1-(4-carboxylic acid, ethyl ester base phenyl)-3-methyl-5-pyrazolone intermediate, 20ml water, with 10% sodium hydroxide solution adjust pH to 8～12, be cooled to 0～10 ℃, stir the lower hydrochloric acid soln (making for 1.86g (0.02mol) aniline mixes with the hydrochloric acid soln of 1.45g Sodium Nitrite) that drips diazonium salt of aniline, 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 is complete, filters, and utilizes frozen water to be washed till filtrate and is neutrality, obtains the carboxylic acid, ethyl ester type dye after drying.
Embodiment 58～80,
make the 1-in embodiment 57 (4-carboxylic acid, ethyl ester base phenyl)-3-methyl-5-pyrazolone intermediate into the 1-(4-carboxylic acid n-propyl base phenyl) of same molar-3-methyl-5-pyrazolone, 1-(4-synthesis base phenyl)-3-methyl-5-pyrazolone, 1-(4-carboxylic acid n-pentyl ester base phenyl)-3-methyl-5-pyrazolone, 1-(the just own ester group phenyl of 4-carboxylic acid)-3-methyl-5-pyrazolone, 1-(the positive heptyl ester base of 4-carboxylic acid phenyl)-3-methyl-5-pyrazolone, 1-(4-carboxylic acid n-octyl base phenyl)-3-methyl-5-pyrazolone, 1-(4-carboxylic acid ester group phenyl in the positive ninth of the ten Heavenly Stems)-3-methyl-5-pyrazolone, 1-(4-carboxylic acid ester group phenyl in the positive last of the ten Heavenly stems)-3-methyl-5-pyrazolone, 1-(4-carboxylic acid undecyl ester base phenyl)-3-methyl-5-pyrazolone, 1-(the positive 12 ester group phenyl of 4-carboxylic acid)-3-methyl-5-pyrazolone, 1-(the positive 13 ester group phenyl of 4-carboxylic acid)-3-methyl-5-pyrazolone, 1-(the positive 14 ester group phenyl of 4-carboxylic acid)-3-methyl-5-pyrazolone, 1-(the positive ten five-ester base phenyl of 4-carboxylic acid)-3-methyl-5-pyrazolone, 1-(the positive hexadecyl ester base of 4-carboxylic acid phenyl)-3-methyl-5-pyrazolone, 1-(the positive 17 ester group phenyl of 4-carboxylic acid)-3-methyl-5-pyrazolone, 1-(the positive octadecyl ester base of 4-carboxylic acid phenyl)-3-methyl-5-pyrazolone, 1-(4-cyclohexyl carboxylate base phenyl)-3-methyl-5-pyrazolone, 1-(4-carboxylic acid carbobenzoxy phenyl)-3-methyl-5-pyrazolone, 1-(4-carboxylic acid isopropyl base phenyl)-3-methyl-5-pyrazolone, 1-(4 sec-butyl carboxylate base phenyl)-3-methyl-5-pyrazolone, 1-(4-carboxylic acid tert-butyl ester base phenyl)-3-methyl-5-pyrazolone, 1-(4-carboxylic acid 2-pentyl ester base phenyl)-3-methyl-5-pyrazolone, 1-(4-carboxylic acid 3-pentyl ester base phenyl)-3-methyl-5-pyrazolone, all the other are with embodiment 57, the corresponding carboxylic acid n-propyl that obtains respectively, synthesis, the carboxylic acid n-pentyl ester, the just own ester of carboxylic acid, the positive heptyl ester of carboxylic acid, the carboxylic acid n-octyl, carboxylic acid ester in the positive ninth of the ten Heavenly Stems, carboxylic acid ester in the positive last of the ten Heavenly stems, the carboxylic acid undecyl ester, positive ten diester of carboxylic acid, positive 13 esters of carboxylic acid, positive 14 esters of carboxylic acid, positive ten five-esters of carboxylic acid, the positive hexadecyl ester of carboxylic acid, positive 17 esters of carboxylic acid, the positive octadecyl ester of carboxylic acid, cyclohexyl carboxylate, the carboxylic acid phenyl ester, the carboxylic acid isopropyl, sec-butyl carboxylate, carboxylic acid tert-butyl ester, carboxylic acid 2-pentyl ester, carboxylic acid 3-pentyl ester type dye.
Embodiment 81,
1), in churned mechanically beaker, add 5.2g (0.021mol) 1-(4-carboxylic acid, ethyl ester base phenyl)-3-methyl-5-pyrazolone intermediate, 20ml water, with 10% sodium hydroxide solution adjust pH to 8～12, be cooled to 0～10 ℃, stir the lower hydrochloric acid soln (making for 3.3g (0.02mol) p-aminophenyl carboxylic acid, ethyl ester mixes with the hydrochloric acid soln of 1.45g Sodium Nitrite) that drips p-aminophenyl carboxylic acid, ethyl ester diazonium salt, and control the pH value 8～10 with 10% sodium carbonate solution, 600 droplets/hour, after dropwising, then at 7 ℃ of reaction 3hr,
2), reaction is complete, filters, and utilizes frozen water to be washed till filtrate and is neutrality, obtains the carboxylic acid, ethyl ester type dye after drying.
Below by experiment, the application of carboxylic ester type disperse dye capable of being washed by alkali of the present invention in PET, PTT, PLA dyeing keratin-fiber is described.
Experiment 1,
(particle diameter 1～2mm) 200g, water 50～100g added in sand mill sand milling 2～10 hours to get in embodiment 1 synthetic carboxylic acid, ethyl ester type dye 5～10g, dispersion agent NNO 5～10g, quartz sand, filter with Büchner funnel, filter screen is 120 purpose woven wires, gets dye paste; Colourity requirement by 0.5～2% pipettes the dispersed dye mill base, be transferred in Dyeing pipe after adding entry by bath raio 1: 15～30, add the PET fabric of wish dyeing to put into the high-temperature pressure dyeing instrument, heat-up rate by 2 ℃/min rises to 110～130 ℃, is incubated and is down to room temperature after 1 hour, takes out the dyeing cloth specimen, washing, merge dyeing residual liquid and washings, constant volume is surveyed the device absorbancy, and the dye uptake that utilizes Law of Lambert-Beer to find the solution dyestuff is 96.5%; After above-mentioned dyeing cloth specimen is adopted national standard " measuring method of disperse dyeing coloured light and intensity " (GB/T 2394-1980) post-treating method reduction clearing, its color fastness to water is 5 grades, anti-dry fastness is 5 grades, and wet rubbing fastness is 5 grades, 4 grades of color fastness to sublimations.
In addition, can also adopt alkali wash to remove the loose colour of PET fabric face, concrete grammar is as follows: after dying good sample process 20min under 90 ℃ in the 0.4g/L NaOH aqueous solution, then through hot water and repeatedly rinsing of cold water; After alkali wash was processed, the color fastness to water of above-mentioned sample was 5 grades, and anti-dry fastness is 5 grades, and wet rubbing fastness is 5 grades, 4 grades of color fastness to sublimations.Every colour fastness of the sample that obtains after every colour fastness and reduction clearing is suitable.
Experiment 2,
Make the PET fabric in experiment 1 into the PTT fabric, all the other are with experiment 1.Result is as follows: the dye uptake of dyestuff is 94.8%.After alkali cleaning after every colour fastness of sample and reduction clearing every colour fastness of sample suitable, its color fastness to water is 5 grades, anti-dry fastness is 5 grades, wet rubbing fastness is 4 grades, 4 grades of color fastness to sublimations.
Experiment 3,
Make the PET fabric in experiment 1 into the PLA fabric, all the other are with experiment 1.Result is as follows: the dye uptake of dyestuff on poly(lactic acid) (PLA) fabric is 94.2%.
Experiment 4,
Make the carboxylic acid, ethyl ester type dye in experiment 1 into carboxylic acid n-propyl dyestuff (embodiment 2 gained), all the other are with experiment 1.Result is as follows: the dye uptake of dyestuff on PET is 98.7%.After alkali wash was processed, every colour fastness of the sample that obtains after every colour fastness of sample and reduction clearing was suitable, and color fastness to water is 5 grades, and anti-dry fastness is 5 grades, and wet rubbing fastness is 5 grades, 4 grades of color fastness to sublimations.
Experiment 5,
Make the PET fabric in experiment 4 into the PTT fabric, all the other are with experiment 4.Result is as follows: the dye uptake of dyestuff on PTT is 96.0%, and after alkali wash was processed, every colour fastness of the sample that obtains after every colour fastness of sample and reduction clearing was suitable, color fastness to water is 5 grades, anti-dry fastness is 5 grades, and wet rubbing fastness is 4 grades, 4 grades of color fastness to sublimations.
Experiment 6,
Make the PET fabric in experiment 4 into the PLA fabric, all the other are with experiment 3.Result is as follows: the dye uptake of dyestuff on PLA is 93.1%.
Experiment 7,
Make the carboxylic acid, ethyl ester dyestuff in experiment 1 into other carboxylic acid, ethyl ester type dyes (embodiment 33 gained), all the other are with experiment 1.Result is as follows: the dye uptake of dyestuff on PET is 94.3%.After alkali wash was processed, every colour fastness of the sample that obtains after every colour fastness of sample and reduction clearing was suitable, and color fastness to water is 5 grades, and anti-dry fastness is 5 grades, and wet rubbing fastness is 5 grades, 4 grades of color fastness to sublimations.
Experiment 8,
Make the PET fabric in experiment 7 into the PTT fabric, all the other are with experiment 7.Result is as follows: the dye uptake of dyestuff on PTT is 95.3%, and after alkali wash was processed, every colour fastness of the sample that obtains after every colour fastness of sample and reduction clearing was suitable, color fastness to water is 5 grades, anti-dry fastness is 5 grades, and wet rubbing fastness is 4 grades, 4 grades of color fastness to sublimations.
Experiment 9,
Make the PET fabric in experiment 7 into the PLA fabric, all the other are with experiment 7.Result is as follows: the dye uptake of dyestuff on PLA is 90.3%.
The contrast experiment 1:
Make the carboxylic acid, ethyl ester dyestuff in experiment 1 and 2 into existing disperse yellow brown 2RCW, all the other are with experiment 1 and 2.Result is as follows:
The dye uptake of dyestuff on PET is respectively 91.7%, and after reduction clearing, its color fastness to water is 5 grades, and anti-dry fastness is 5 grades, and wet rubbing fastness is 5 grades, 4 grades of color fastness to sublimations; After alkali wash is processed, every colour fastness of the sample that every colour fastness of sample obtains after a little less than reduction clearing, its color fastness to water is 4 grades, and anti-dry fastness is 4 grades, and wet rubbing fastness is 4 grades, 3 grades of color fastness to sublimations.
The dye uptake of dyestuff on poly(lactic acid) (PLA) fiber is 47.1%.
The contrast experiment 2: with 3 kinds of dyestuffs (carboxylic acyl ethamine dyestuff, carboxylic acyl n-Butyl Amine 99 dyestuff, carboxylic acyl Isopropylamine dyestuff) of gained in 200810162925.0 patents of invention, then it is respectively used to the dyeing of PET, PTT fabric.
1), the dye uptake of carboxylic acyl ethamine dyestuff on PET be 93.4%, after reduction clearing, the color fastness to water of sample is 5 grades, anti-dry fastness is 5 grades, wet rubbing fastness is 4 grades, 4 grades of color fastness to sublimations.
And after the alkali wash processing, every colour fastness of sample is relatively poor, and color fastness to water is 4 grades, and anti-dry fastness is 4 grades, and wet rubbing fastness is 4 grades, 3 grades of color fastness to sublimations.
2), the dye uptake of carboxylic acyl ethamine dyestuff on PTT be 92.1%, after reduction clearing, the color fastness to water of sample is 5 grades, anti-dry fastness is 4 grades, wet rubbing fastness is 4 grades, 4 grades of color fastness to sublimations.
And after the alkali wash processing, every colour fastness of sample is relatively poor, and color fastness to water is 4 grades, and anti-dry fastness is 4 grades, and wet rubbing fastness is 3 grades, 3 grades of color fastness to sublimations.
3), the dye uptake of carboxylic acyl n-Butyl Amine 99 dyestuff on PET be 96%, after reduction clearing, the color fastness to water of sample is 5 grades, anti-dry fastness is 5 grades, wet rubbing fastness is 5 grades, 4 grades of color fastness to sublimations.
And after the alkali wash processing, every colour fastness of sample is relatively poor, and color fastness to water is 4 grades, and anti-dry fastness is 4 grades, and wet rubbing fastness is 4 grades, 3 grades of color fastness to sublimations.
4), the dye uptake of carboxylic acyl n-Butyl Amine 99 dyestuff on PTT is 94.5%; After reduction clearing, the color fastness to water of sample is 5 grades, and anti-dry fastness is 5 grades, and wet rubbing fastness is 5 grades, 4 grades of color fastness to sublimations.
And after the alkali wash processing, every colour fastness of sample is relatively poor, and color fastness to water is 4 grades, and anti-dry fastness is 4 grades, and wet rubbing fastness is 4 grades, 3 grades of color fastness to sublimations.
5), the dye uptake of carboxylic acyl Di-n-Butyl Amine dyestuff on PET is 94.3%; After reduction clearing, the color fastness to water of sample is 5 grades, and anti-dry fastness is 5 grades, and wet rubbing fastness is 5 grades, 4 grades of color fastness to sublimations.
And after the alkali wash processing, every colour fastness of sample is relatively poor, and color fastness to water is 4 grades, and anti-dry fastness is 4 grades, and wet rubbing fastness is 4 grades, 3 grades of color fastness to sublimations.
6), the dye uptake of carboxylic acyl Di-n-Butyl Amine dyestuff on PTT is 92.5%; After reduction clearing, the color fastness to water of sample is 5 grades, and anti-dry fastness is 5 grades, and wet rubbing fastness is 5 grades, 4 grades of color fastness to sublimations.
And after the alkali wash processing, every colour fastness of sample is relatively poor, and color fastness to water is 4 grades, and anti-dry fastness is 4 grades, and wet rubbing fastness is 4 grades, 3 grades of color fastness to sublimations.
At last, 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, 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 (2)
1. general structure is
The purposes of compound, it is characterized in that: as carboxylic ester type disperse dye capable of being washed by alkali;
M be 1 or 2, X be C
nH
2n+1,
C
nH
2n+1In n meet the following conditions: 2≤n≤18, and n is integer;
D is azo structure contained color bodies, and the structural formula of described D is as follows:
In 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 COOX; 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 COOX; And contain 1～2-COOX in the structure of described dyestuff.
2. general structure according to claim 1 is
The purposes of compound, it is characterized in that:
Described D is
For
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