CN101423671A - 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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- CN101423671A CN101423671A CNA2008101629250A CN200810162925A CN101423671A CN 101423671 A CN101423671 A CN 101423671A CN A2008101629250 A CNA2008101629250 A CN A2008101629250A CN 200810162925 A CN200810162925 A CN 200810162925A CN 101423671 A CN101423671 A CN 101423671A
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- amide type
- polylactic acid
- type dyes
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- 239000000835 fiber Substances 0.000 title claims abstract description 76
- 238000004043 dyeing Methods 0.000 title claims abstract description 57
- 229920000747 poly(lactic acid) Polymers 0.000 title claims abstract description 48
- 239000004626 polylactic acid Substances 0.000 title claims abstract description 28
- 239000000975 dye Substances 0.000 title claims description 172
- 150000001408 amides Chemical class 0.000 title claims description 40
- 238000002360 preparation method Methods 0.000 title claims description 21
- 238000000034 method Methods 0.000 claims abstract description 17
- 125000005392 carboxamide group Chemical class NC(=O)* 0.000 claims abstract description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 13
- -1 carboxyl acyl chloride Chemical class 0.000 claims description 88
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 42
- 239000012954 diazonium Substances 0.000 claims description 39
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 27
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- 238000006243 chemical reaction Methods 0.000 claims description 26
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 22
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 20
- 239000002253 acid Substances 0.000 claims description 19
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 18
- 238000010168 coupling process Methods 0.000 claims description 18
- 238000005859 coupling reaction Methods 0.000 claims description 17
- 230000008878 coupling Effects 0.000 claims description 15
- 125000003277 amino group Chemical group 0.000 claims description 14
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 11
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 10
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 9
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 claims description 8
- 150000001989 diazonium salts Chemical class 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 238000013019 agitation Methods 0.000 claims description 6
- 239000000706 filtrate Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 238000010792 warming Methods 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 239000012065 filter cake Substances 0.000 claims description 5
- 238000005554 pickling Methods 0.000 claims description 4
- 150000003141 primary amines Chemical class 0.000 claims description 4
- 230000006837 decompression Effects 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 239000000376 reactant Substances 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- 150000004982 aromatic amines Chemical class 0.000 claims 2
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 claims 2
- 125000000217 alkyl group Chemical group 0.000 abstract description 6
- 238000002474 experimental method Methods 0.000 description 26
- 229920002215 polytrimethylene terephthalate Polymers 0.000 description 20
- 229920004935 Trevira® Polymers 0.000 description 18
- 239000004744 fabric Substances 0.000 description 18
- 239000005020 polyethylene terephthalate Substances 0.000 description 18
- 238000000859 sublimation Methods 0.000 description 17
- 230000008022 sublimation Effects 0.000 description 17
- 229920000139 polyethylene terephthalate Polymers 0.000 description 16
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 11
- 125000001589 carboacyl group Chemical group 0.000 description 10
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 9
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 9
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 7
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- UKJLNMAFNRKWGR-UHFFFAOYSA-N cyclohexatrienamine Chemical group NC1=CC=C=C[CH]1 UKJLNMAFNRKWGR-UHFFFAOYSA-N 0.000 description 6
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 6
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 6
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 6
- FJLUATLTXUNBOT-UHFFFAOYSA-N 1-Hexadecylamine Chemical compound CCCCCCCCCCCCCCCCN FJLUATLTXUNBOT-UHFFFAOYSA-N 0.000 description 5
- JPZYXGPCHFZBHO-UHFFFAOYSA-N 1-aminopentadecane Chemical compound CCCCCCCCCCCCCCCN JPZYXGPCHFZBHO-UHFFFAOYSA-N 0.000 description 5
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 5
- PLZVEHJLHYMBBY-UHFFFAOYSA-N Tetradecylamine Chemical compound CCCCCCCCCCCCCCN PLZVEHJLHYMBBY-UHFFFAOYSA-N 0.000 description 5
- KAJZYANLDWUIES-UHFFFAOYSA-N heptadecan-1-amine Chemical compound CCCCCCCCCCCCCCCCCN KAJZYANLDWUIES-UHFFFAOYSA-N 0.000 description 5
- FJDUDHYHRVPMJZ-UHFFFAOYSA-N nonan-1-amine Chemical compound CCCCCCCCCN FJDUDHYHRVPMJZ-UHFFFAOYSA-N 0.000 description 5
- ABVVEAHYODGCLZ-UHFFFAOYSA-N tridecan-1-amine Chemical compound CCCCCCCCCCCCCN ABVVEAHYODGCLZ-UHFFFAOYSA-N 0.000 description 5
- QFKMMXYLAPZKIB-UHFFFAOYSA-N undecan-1-amine Chemical compound CCCCCCCCCCCN QFKMMXYLAPZKIB-UHFFFAOYSA-N 0.000 description 5
- MHZGKXUYDGKKIU-UHFFFAOYSA-N Decylamine Chemical compound CCCCCCCCCCN MHZGKXUYDGKKIU-UHFFFAOYSA-N 0.000 description 4
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000004576 sand Substances 0.000 description 4
- 238000005411 Van der Waals force Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 238000010907 mechanical stirring Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 235000010288 sodium nitrite Nutrition 0.000 description 3
- 229940124530 sulfonamide Drugs 0.000 description 3
- 239000006004 Quartz sand Substances 0.000 description 2
- 229920004933 Terylene® Polymers 0.000 description 2
- 238000007098 aminolysis reaction Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006193 diazotization reaction Methods 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-O diazynium Chemical compound [NH+]#N IJGRMHOSHXDMSA-UHFFFAOYSA-O 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000003801 milling Methods 0.000 description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 150000003335 secondary amines Chemical class 0.000 description 2
- 150000003456 sulfonamides Chemical class 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- VGKYEIFFSOPYEW-UHFFFAOYSA-N 2-methyl-4-[(4-phenyldiazenylphenyl)diazenyl]phenol Chemical compound Cc1cc(ccc1O)N=Nc1ccc(cc1)N=Nc1ccccc1 VGKYEIFFSOPYEW-UHFFFAOYSA-N 0.000 description 1
- DELDCGTZFVPZIJ-UHFFFAOYSA-N 6-hydroxy-5-phenyldiazenylnaphthalene-2-carboxylic acid Chemical compound OC=1C=CC2=CC(C(=O)O)=CC=C2C=1N=NC1=CC=CC=C1 DELDCGTZFVPZIJ-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- PIZUBEYJOBWWNF-UHFFFAOYSA-N NC(CCCCCCCCCCC)[N+]#N Chemical class NC(CCCCCCCCCCC)[N+]#N PIZUBEYJOBWWNF-UHFFFAOYSA-N 0.000 description 1
- 208000034530 PLAA-associated neurodevelopmental disease Diseases 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- WXIUBYCJAAEOFL-UHFFFAOYSA-N [S].ClOCl Chemical compound [S].ClOCl WXIUBYCJAAEOFL-UHFFFAOYSA-N 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
- 125000003262 carboxylic acid ester group Chemical group [H]C([H])([*:2])OC(=O)C([H])([H])[*:1] 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000001261 hydroxy acids Chemical group 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002052 molecular layer Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- DPBLXKKOBLCELK-UHFFFAOYSA-N pentan-1-amine Chemical compound CCCCCN DPBLXKKOBLCELK-UHFFFAOYSA-N 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- FDDDEECHVMSUSB-UHFFFAOYSA-N sulfanilamide Chemical compound NC1=CC=C(S(N)(=O)=O)C=C1 FDDDEECHVMSUSB-UHFFFAOYSA-N 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
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- Coloring (AREA)
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), Poly(Trimethylene Terephthalate) (PTT), polybutylene terephthalate (PBT) and emerging poly(lactic acid) (PLA) fiber, this fibrid has high-crystallinity usually, therefore no strongly hydrophilic group in the molecular backbone chain presents hydrophobicity.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 lacking in the molecular structure and dyestuff generation bonded active group, therefore dyeing difficulty.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 the nonionic dye that a class is insoluble in water, need under the dispersion agent effect, be scattered in the water with insoluble minuteness particle, usually the aggregate form with a plurality of dye molecules exists, and dye granule is bigger.When in water medium, dyeing, trevira can not resemble the 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 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 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 poly(lactic acid) fabric dyes in acidulous dye bath (pH5～6), 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 satisfy and take requirement.After dying fiber on the dispersed dye, dyestuff and fiber are to combine by more weak Van der Waals force.Van der Waals force is big, and dyestuff is the avidity height on fiber, 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 Van der Waals force between dyestuff and fiber molecule, help improving the dye uptake and the colour fastness of dyestuff.Studies show that the dye uptake of azoic dye and the substituent kind in the molecule have dependency, have the dyestuff of carboxylic acid ester groups in the 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, helps dying on the 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 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 class dyestuff synthesis technique is simple, can synthesize the slightly water-soluble sulfonamide type dye that contains straight chained alkyl by 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, poly(lactic 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 wish the problem that solves.
Summary of the invention
The technical problem to be solved in the present invention 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 invention provides a kind of azo structure carboxylic amide type dyes for polylactic acid fiber dyeing, contain carboxylacyl amine group in its molecular structure, its general structure is as follows:
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 as follows:
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 described; 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 as follows:
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 described 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 as follows:
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, 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 filtering repeatedly until being washed till neutrality, obtained the carboxyl acyl chloride intermediate after the vacuum-drying;
3), in reactor, add earlier the carboxyl acyl chloride intermediate and as the acetone of solvent, wait the dissolving of carboxyl acyl chloride intermediate 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, described fat primary amine, hexahydroaniline, aniline or fatty primary secondary amine: carboxyl acyl chloride intermediate: K
2CO
3Mol ratio=1:1:0.5～2;
4), the reactant of step 3) gained is boiled off acetone, resistates; Described 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, the filter cake that will filter gained again with clear water be washed till raffinate be neutral and colourless till; 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 of carboxylacyl amine group, with mass concentration 10% sodium hydroxide solution adjust pH to 8～12; Being cooled to 0～10 ℃ then, dripping down the hydrochloric acid soln of arylamine diazonium salt in agitation condition, is that the pH value of the interior mixture of 10% sodium carbonate solution controlling reactor is 8～10 with mass concentration in the dropping process; After dropwising, at 0～10 ℃ of reaction 5～10hr; Describedly contain the coupling component of carboxylacyl amine group and the mol ratio of arylamine diazonium salt is 1.05:1.0;
Perhaps coupling component intermediate and water are added in the reactor, with mass concentration 10% sodium hydroxide solution adjust pH to 8～12; Being cooled to 0～10 ℃ then, dripping down the hydrochloric acid soln of the arylamine diazonium salt that contains carboxamide groups in agitation condition, is that the pH value of the interior mixture of 10% sodium carbonate solution controlling reactor is 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 carboxamide groups;
The coupling component and the water that perhaps will contain carboxylacyl amine group add in the reactor, with mass concentration 10% sodium hydroxide solution adjust pH to 8～12; Being cooled to 0～10 ℃ then, dripping down the hydrochloric acid soln of the arylamine diazonium salt that contains carboxamide groups in agitation condition, is that the pH value of the interior mixture of 10% sodium carbonate solution controlling reactor is 8～10 with mass concentration in the dropping process; After dropwising, at 0～10 ℃ of reaction 5～10hr; The described 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 filtrate 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 introduce carboxylacyl amine group in dye structure is divided into following several preparation technology:
(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 azo structure carboxylic amide type dyes, and this class dyestuff can be regulated avidity between dyestuff and different trevira by 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 class dyestuff synthesis technique is simple, by 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 problem of the low and 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, quartz sand, filter with B, filter screen is 120 purpose woven wires, gets dye paste; Colourity requirement by 0.5～2% pipettes dye paste, be transferred in the Dyeing pipe after adding entry by bath raio 1:15～30, add the painted PET of desire, PTT or PLA and put into the high-temperature pressure dyeing instrument, 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 by changing the type and the length of the end group that carboxamide groups connects, 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
The preparation method that azo structure carboxylic amide type dyes is used in embodiment 1, the dyeing of a kind of trevira, 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 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 filtrate and is neutrality, obtains the carboxyl acyl chloride intermediate after the vacuum-drying;
3), in the there-necked flask that agitator, thermometer, prolong are housed, add earlier 3.4g carboxyl acyl chloride intermediate and 25ml acetone as solvent, wait the carboxyl acyl chloride intermediate 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 described 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.
The preparation method that azo structure carboxylic amide type dyes is used in embodiment 2, the dyeing of a kind of trevira, 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), with embodiment 1;
3), in the there-necked flask that agitator, thermometer, prolong are housed, add earlier 3.4g carboxyl acyl chloride intermediate and 25ml acetone as solvent, wait the carboxyl acyl chloride intermediate to be dissolved in acetone after, add the Powdered K of 0.87g n-amylamine and 1.38g again
2CO
3, under room temperature, mixed stirring reaction 1 hour;
4), with embodiment 1, carboxylic acyl n-amylamine type dye.
The preparation method that azo structure carboxylic amide type dyes is used in embodiment 3, the dyeing of a kind of trevira, 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), with embodiment 1;
3), in the there-necked flask that agitator, thermometer, prolong are housed, add earlier 3.4g carboxyl acyl chloride intermediate and 25ml acetone as solvent, wait the carboxyl acyl chloride intermediate 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, n-octyl amine, 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, dimethylamine, diethylamine, Di-n-Butyl Amine, two normal hexyl Amines, two n-octyl amine respectively, all the other are with embodiment 1; Obtain the positive heptyl amice of corresponding carboxylic acyl, n-octyl amine, 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, dimethylamine, diethylamine, Di-n-Butyl Amine, two normal hexyl Amines, two n-octyl amine 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-hydroxyl naphthyl) 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-hydroxyl naphthyl) 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.
The preparation method that azo structure carboxylic amide type dyes is used in embodiment 31, the dyeing of a kind of trevira, carry out following steps successively:
1), in churned mechanically beaker, add 3.7g 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 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 filtrate and is neutrality, after the drying, obtains carboxylic acyl n-Butyl Amine 99 type dye.
Embodiment 32～52,
P-aminophenyl carboxylic acyl n-Butyl Amine 99 diazonium salt among the embodiment 31 is made into the p-aminophenyl carboxylic acyl n-amylamine diazonium salt of same molar respectively, p-aminophenyl carboxylic acyl normal hexyl Amine diazonium salt, the positive heptyl amice diazonium salt of p-aminophenyl carboxylic acyl, p-aminophenyl carboxylic acyl n-octyl amine 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 dimethylamine 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, p-aminophenyl carboxylic acyl two n-octyl amine diazonium salts, 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, n-octyl amine, 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, dimethylamine, diethylamine, Di-n-Butyl Amine, two normal hexyl Amines, the two n-octyl amine type dyes of obtaining.
The preparation method that azo structure carboxylic amide type dyes is used in embodiment 53, the dyeing of a kind of trevira, 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 intermediate, 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 filtrate and is neutrality, obtains carboxylic acyl n-Butyl Amine 99 type dye after the drying.
Embodiment 54～74,
1-among the embodiment 53 (4-carboxylic acyl n-butylamine-based phenyl)-3-methyl-5-pyrazolone intermediate is made into 1-(4-carboxylic acyl n-amylamine base the phenyl)-3-methyl-5-pyrazolone of same molar, 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 n-octyl amine 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, 1-(4-carboxylic acyl two n-octyl amine base phenyl)-3-methyl-5-pyrazolone, all the other are with embodiment 83; Corresponding respectively carboxylic acyl n-amylamine, normal hexyl Amine, positive heptyl amice, n-octyl amine, 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, dimethylamine, diethylamine, Di-n-Butyl Amine, two normal hexyl Amines, the two n-octyl amine 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 intermediate, 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 filtrate and is neutrality, obtains carboxylic acyl n-Butyl Amine 99 type dye after the drying.Below by experiment the trevira dyeing application of azo structure carboxylic amide type dyes in PET, PTT, PLA dyeing keratin-fiber of the present invention is described.
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, dispersion agent NNO5～10g among the embodiment 1, quartz 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, be transferred in the Dyeing pipe after adding entry by bath raio 1:15～30, add the painted PET fabric of desire and put into the high-temperature pressure dyeing instrument, heat-up rate by 2 ℃/min rises to 110～130 ℃, be incubated and reduce to room temperature after 1 hour, take 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%, color fastness to water is 4～5 grades, anti-dry fastness is 4～5 grades, and the moisture-proof crock fastness 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 as follows: 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 crock fastness is the 4-5 level, 4 grades of color fastness to sublimations; Dye uptake on poly(lactic 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 crock fastness 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 as follows: 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 crock fastness 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 as follows: 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 crock fastness 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 crock fastness 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 as follows: 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 crock fastness 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 as follows: 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 crock fastness 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 crock fastness 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 as follows: 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 crock fastness 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 as follows: 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 crock fastness 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 crock fastness 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 as follows:
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 crock fastness 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 crock fastness is the 4-5 level, 4 grades of color fastness to sublimations;
The dye uptake of dyestuff on poly(lactic 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 crock fastness 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, a kind of 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 as follows:
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.
2, azo structure carboxylic amide type dyes for polylactic acid fiber dyeing according to claim 1 is characterized in that, the structural formula of described D is as follows:
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 described 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 described D is as follows:
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 described 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 described D is as follows:
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 described dyestuff, and can not have 2-CONXY simultaneously in the same aromatic ring.
5,, it is characterized in that may further comprise the steps as the preparation method of any one azo structure carboxylic amide type dyes for polylactic acid fiber dyeing in the claim 1～4:
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 every 3.2g dyestuff, the ratio of dinethylformamide will above-mentioned 4 adds in the reactor, 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 filtering repeatedly until being washed till neutrality, obtained the carboxyl acyl chloride intermediate after the vacuum-drying;
3), in reactor, add earlier the carboxyl acyl chloride intermediate and as the acetone of solvent, wait the dissolving of carboxyl acyl chloride intermediate 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, described fat primary amine, hexahydroaniline, aniline or fatty primary secondary amine: carboxyl acyl chloride intermediate: K
2CO
3Mol ratio=1:1:0.5～2;
4), the reactant of step 3) gained is boiled off acetone, resistates; Described 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 described 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 with clear water be washed till raffinate be neutral and colourless till; 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 is characterized in that: in the described step 1): solvent is benzene or toluene.
8,, it is characterized in that may further comprise the steps as the preparation method of any one azo structure carboxylic amide type dyes for polylactic acid fiber dyeing in the claim 1～4:
1), will contain in the coupling component and water adding reactor of carboxylacyl amine group, with mass concentration 10% sodium hydroxide solution adjust pH to 8～12; Being cooled to 0～10 ℃ then, dripping down the hydrochloric acid soln of arylamine diazonium salt in agitation condition, is that the pH value of the interior mixture of 10% sodium carbonate solution controlling reactor is 8～10 with mass concentration in the dropping process; After dropwising, at 0～10 ℃ of reaction 5～10hr; Describedly contain the coupling component of carboxylacyl amine group and the mol ratio of arylamine diazonium salt is 1.05:1.0;
Perhaps coupling component intermediate and water are added in the reactor, with mass concentration 10% sodium hydroxide solution adjust pH to 8～12; Being cooled to 0～10 ℃ then, dripping down the arylamine diazonium salt hydrochloric acid soln that contains carboxamide groups in agitation condition, is that the pH value of the interior mixture of 10% sodium carbonate solution controlling reactor is 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 carboxamide groups;
The coupling component and the water that perhaps will contain carboxylacyl amine group add in the reactor, with mass concentration 10% sodium hydroxide solution adjust pH to 8～12; Being cooled to 0～10 ℃ then, dripping down the arylamine diazonium salt hydrochloric acid soln that contains carboxamide groups in agitation condition, is that the pH value of the interior mixture of 10% sodium carbonate solution controlling reactor is 8～10 with mass concentration in the dropping process; After dropwising, at 0～10 ℃ of reaction 5～10hr; The described 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 filtrate and is neutrality, after the drying, obtains azo structure carboxylic amide type dyes for polylactic acid fiber dyeing.
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Cited By (3)
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| CN101953802A (en) * | 2010-09-14 | 2011-01-26 | 陈敏伟 | Lansoprazole enteric preparation and preparation method thereof |
| CN101982508A (en) * | 2010-08-24 | 2011-03-02 | 浙江理工大学 | Carboxylic ester type disperse dye capable of being washed by alkali and preparation method thereof |
| CN109440490A (en) * | 2018-10-12 | 2019-03-08 | 山东理工大学 | Polylactic acid fiber dyeing azo structure lactic acid ester type disperse dyes and preparation method thereof and dyeing |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US6001167A (en) * | 1996-08-06 | 1999-12-14 | Engelhard Corporation | Pigment compositions |
| TW527402B (en) * | 1997-12-26 | 2003-04-11 | Ueno Seiyaku Oyo Kenkyujo Kk | Water soluble azo compound and a process for preparing the same |
| 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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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101982508A (en) * | 2010-08-24 | 2011-03-02 | 浙江理工大学 | Carboxylic ester type disperse dye capable of being washed by alkali and preparation method thereof |
| CN101982508B (en) * | 2010-08-24 | 2013-06-12 | 浙江理工大学 | Carboxylic ester type disperse dye capable of being washed by alkali and preparation method thereof |
| CN101953802A (en) * | 2010-09-14 | 2011-01-26 | 陈敏伟 | Lansoprazole enteric preparation and preparation method thereof |
| CN101953802B (en) * | 2010-09-14 | 2012-05-09 | 陈敏伟 | Lansoprazole enteric preparation and preparation method thereof |
| CN109440490A (en) * | 2018-10-12 | 2019-03-08 | 山东理工大学 | Polylactic acid fiber dyeing azo structure lactic acid ester type disperse dyes and preparation method thereof and dyeing |
| CN109440490B (en) * | 2018-10-12 | 2021-01-01 | 山东理工大学 | Lactic acid ester type disperse dye with azo structure for dyeing polylactic acid fiber, and preparation method and dyeing process thereof |
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