CN112143253A - Cationic fluorescent dye based on benzyl naphthalimide structure and preparation and application thereof - Google Patents
Cationic fluorescent dye based on benzyl naphthalimide structure and preparation and application thereof Download PDFInfo
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- CN112143253A CN112143253A CN202011014623.6A CN202011014623A CN112143253A CN 112143253 A CN112143253 A CN 112143253A CN 202011014623 A CN202011014623 A CN 202011014623A CN 112143253 A CN112143253 A CN 112143253A
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- fluorescent dye
- cationic fluorescent
- naphthamide
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- 239000007850 fluorescent dye Substances 0.000 title claims abstract description 97
- 125000002091 cationic group Chemical group 0.000 title claims abstract description 88
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000004744 fabric Substances 0.000 claims abstract description 56
- 229920000728 polyester Polymers 0.000 claims abstract description 42
- RMHJJUOPOWPRBP-UHFFFAOYSA-N naphthalene-1-carboxamide Chemical compound C1=CC=C2C(C(=O)N)=CC=CC2=C1 RMHJJUOPOWPRBP-UHFFFAOYSA-N 0.000 claims description 31
- 238000006243 chemical reaction Methods 0.000 claims description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 25
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 21
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- IUNMPGNGSSIWFP-UHFFFAOYSA-N dimethylaminopropylamine Chemical compound CN(C)CCCN IUNMPGNGSSIWFP-UHFFFAOYSA-N 0.000 claims description 17
- 238000005406 washing Methods 0.000 claims description 17
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 13
- DTUOTSLAFJCQHN-UHFFFAOYSA-N 4-bromo-1,8-naphthalic anhydride Chemical compound O=C1OC(=O)C2=CC=CC3=C2C1=CC=C3Br DTUOTSLAFJCQHN-UHFFFAOYSA-N 0.000 claims description 11
- 239000012065 filter cake Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- 239000012074 organic phase Substances 0.000 claims description 9
- NTZMSBAAHBICLE-UHFFFAOYSA-N 4-nitrobenzene-1,2-dicarbonitrile Chemical compound [O-][N+](=O)C1=CC=C(C#N)C(C#N)=C1 NTZMSBAAHBICLE-UHFFFAOYSA-N 0.000 claims description 8
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 claims description 8
- 229940073608 benzyl chloride Drugs 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 238000012544 monitoring process Methods 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 8
- 238000004809 thin layer chromatography Methods 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 7
- 238000000967 suction filtration Methods 0.000 claims description 7
- OOFAEFCMEHZNGP-UHFFFAOYSA-N 1-n',1-n'-dimethylpropane-1,1-diamine Chemical compound CCC(N)N(C)C OOFAEFCMEHZNGP-UHFFFAOYSA-N 0.000 claims description 6
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 6
- 239000000706 filtrate Substances 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 5
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000002243 precursor Substances 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 238000004043 dyeing Methods 0.000 abstract description 38
- 239000000975 dye Substances 0.000 abstract description 19
- XJHABGPPCLHLLV-UHFFFAOYSA-N benzo[de]isoquinoline-1,3-dione Chemical group C1=CC(C(=O)NC2=O)=C3C2=CC=CC3=C1 XJHABGPPCLHLLV-UHFFFAOYSA-N 0.000 abstract description 5
- 239000000523 sample Substances 0.000 description 11
- 239000000835 fiber Substances 0.000 description 10
- 239000000843 powder Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 229920004933 Terylene® Polymers 0.000 description 8
- 239000005020 polyethylene terephthalate Substances 0.000 description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 238000002284 excitation--emission spectrum Methods 0.000 description 4
- 238000002189 fluorescence spectrum Methods 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 3
- 238000002835 absorbance Methods 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- -1 benzyl naphthalimide Chemical compound 0.000 description 2
- 150000001768 cations Chemical group 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical compound CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 2
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- 229920002972 Acrylic fiber Polymers 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 210000004243 sweat Anatomy 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B57/00—Other synthetic dyes of known constitution
- C09B57/08—Naphthalimide dyes; Phthalimide dyes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D221/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00
- C07D221/02—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00 condensed with carbocyclic rings or ring systems
- C07D221/04—Ortho- or peri-condensed ring systems
- C07D221/06—Ring systems of three rings
- C07D221/14—Aza-phenalenes, e.g. 1,8-naphthalimide
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/41—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using basic dyes
- D06P1/42—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using basic dyes using basic dyes without azo groups
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
- D06P3/34—Material containing ester groups
- D06P3/52—Polyesters
- D06P3/522—Polyesters using basic dyes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Materials Engineering (AREA)
- Coloring (AREA)
Abstract
The invention relates to a cationic fluorescent dye based on a benzyl naphthalimide structure, and a preparation method and application thereof, wherein the structure is shown as a general formula I. The fluorescent cationic dye is used for dyeing modified polyester fabrics, has high dye uptake and color yield, uniform dyeing and strong fluorescence, and fills the application blank of the fluorescent dye with the naphthalimide structure in the modified polyester fabrics.
Description
Technical Field
The invention belongs to the field of organic fluorescent dyes and preparation and application thereof, and particularly relates to a cationic fluorescent dye based on a benzyl naphthalimide structure and preparation and application thereof.
Background
The polyester fiber structure is free of hydrophilic groups, sweat and air permeability are poor, wearing experience is affected, static electricity is easily generated on the surface, fine dust is adsorbed to cause fiber contamination, fluffing and pilling are easy to occur, and researchers can prepare modified polyester fibers by adding a third monomer and even a fourth monomer during molecular polymerization for overcoming the defects. The modified terylene has soft hand feeling and good anti-pilling performance. As a novel fiber, researchers develop some cationic fluorescent dyes suitable for dyeing the novel fiber, and the development and application of the cationic fluorescent dyes suitable for modified polyester fibers are blank. In order to widen the application range and improve the application performance of the modified polyester fabric, the development of the cationic fluorescent dye suitable for the modified polyester fabric is also an urgent problem to be solved.
CN103382313A discloses a benzyl naphthalimide fluorescent dye and preparation and application thereof, the benzyl naphthalimide fluorescent dye in the invention can not be used as a cationic fluorescent dye to be applied to printing and dyeing of modified polyester fibers, and the naphthalimide fluorescent dye in the invention is used as a fluorescent probe molecule and is only applied to the fields of biology and environment.
Disclosure of Invention
The invention aims to solve the technical problem of providing a cationic fluorescent dye based on a benzyl naphthalimide structure, and preparation and application thereof, and overcoming the defect that the existing naphthalimide fluorescent dye cannot be applied to printing and dyeing of modified polyester fibers.
The invention relates to a cationic fluorescent dye shown in a general formula I,
R＝-CH2CH2OH or
The method specifically comprises the following steps:
the invention discloses a preparation method of a cationic fluorescent dye, which comprises the following steps:
refluxing 4-bromo-1, 8-naphthalic anhydride and ethanolamine serving as raw materials in ethanol to obtain N-hydroxyethyl-4-bromo-1, 8-naphthamide, refluxing N-hydroxyethyl-4-bromo-1, 8-naphthamide and N, N-dimethylpropylenediamine in ethylene glycol monomethyl ether to obtain N-hydroxyethyl-4- (N, N-dimethylpropylenediamine) -1, 8-naphthamide, and reacting N-hydroxyethyl-4- (N, N-dimethylpropylenediamine) -1, 8-naphthamide and benzyl chloride in acetone to obtain a cationic fluorescent dye I;
or reacting the obtained cationic fluorescent dye I with 4-nitrophthalonitrile to obtain the cationic fluorescent dye II.
Further, the cationic fluorescent dye preparation equation is as follows:
the preparation method comprises the following specific steps:
(1) sequentially adding ethanol and 4-bromo-1, 8-naphthalic anhydride into a reactor (a three-neck flask), stirring and heating to 40 ℃, dropwise adding ethanolamine, slowly heating to ethanol reflux, monitoring the reaction by using TLC (thin layer chromatography) until the 4-bromo-1, 8-naphthalic anhydride is completely reacted, stopping the reaction, cooling the system, performing suction filtration, washing with water until the filtrate is neutral (removing redundant ethanolamine), collecting a filter cake, drying, and recrystallizing with ethanol to obtain white powder which is N-hydroxyethyl-4-bromo-1, 8-naphthamide;
(2) sequentially adding ethylene glycol monomethyl ether and N-hydroxyethyl-4-bromo-1, 8-naphthamide into a reactor (a three-neck flask), stirring and heating, slowly adding N, N-dimethyl propane diamine, monitoring the reaction by using TLC (thin layer chromatography) until the N-hydroxyethyl-4-bromo-1, 8-naphthamide completely reacts, stopping the reaction, cooling the system, adding water into the system, extracting the mixture for three times by using dichloromethane, collecting an organic phase, washing the organic phase twice by using pure water, removing water from the obtained organic phase by using anhydrous sodium sulfate, performing suction filtration, collecting filtrate, removing a solvent dichloromethane, and purifying to obtain yellow crystal powder which is N-hydroxyethyl-4- (N, N-dimethyl propane diamine) -1, 8-naphthamide;
(3) sequentially adding acetone, N-hydroxyethyl-4- (N, N-dimethyl propylene diamine) -1, 8-naphthamide and benzyl chloride into a reactor (a three-neck flask), stirring and heating, monitoring the reaction by using TLC (thin layer chromatography) until the N-hydroxyethyl-4- (N, N-dimethyl propylene diamine) -1, 8-naphthamide is completely reacted, stopping the reaction, cooling the system, directly performing suction filtration, washing a filter cake with acetone and ethanol, and drying to obtain yellow powder which is cationic fluorescent dye I (namely cationic fluorescent dye (1) in a chemical equation);
(4) sequentially adding a cationic fluorescent dye I, 4-nitrophthalonitrile and DMF (dimethyl formamide) into a reactor (three-neck flask), stirring and heating under the protection of nitrogen, and adding K2CO3Adding the mixture five times in two hours, monitoring the reaction by using TLC until the cationic fluorescent dye I completely reacts, directly filtering the mixture after the system is cooled, washing a filter cake by using a small amount of water, and drying the filter cake to obtain yellow powder which is the cationic fluorescent dye II (namely the cationic fluorescent dye (2) in the chemical equation).
The preferred mode of the above preparation method is as follows:
the molar ratio of the 4-bromo-1, 8-naphthalic anhydride to the ethanolamine in the step (1) is 1: 1.1-1.2; the reaction temperature is 70-85 ℃, and the reaction time is 3-5 h.
In the step (2), the molar ratio of the N-hydroxyethyl-4-bromo-1, 8-naphthamide to the N, N-dimethylpropylenediamine is 1: 1.1-1.5;
the reaction temperature is 110-130 ℃, and the reaction time is 3-6 h.
The post-treatment method used in the step (2) is to remove the solvent by reduced pressure distillation and purify by ethyl acetate recrystallization.
In the step (3), the molar ratio of the precursor compound N-hydroxyethyl-4- (N, N-dimethyl propylene diamine) -1, 8-naphthamide to benzyl chloride is 1: 1.1-2; the reaction temperature is 40-70 ℃, and the reaction time is 10-14 h.
The molar ratio of the cationic fluorescent dye I to the 4-nitrophthalonitrile in the step (4) is 1: 0.90-0.98; cationic fluorescent dyes I and K2CO3The molar ratio of (A) to (B) is 1: 1.5-2.5.
In the step (4), the reaction temperature is 45-55 ℃, and the reaction time is 40-50 h.
The application of the cationic fluorescent dye in the modified polyester fabric is characterized in that the modified polyester fabric dyed by the cationic fluorescent dye (1) shows strong yellow-green fluorescence under an ultraviolet lamp, the modified polyester fabric dyed by the cationic fluorescent dye (2) shows strong green fluorescence under the ultraviolet lamp, and the dyed fabric has excellent color fastness.
The modified terylene is cation dyeable terylene (CDP) obtained by adding a third monomer 3, 5-dimethyl benzene dicarboxylate sodium Sulfonate (SIPM) into terylene fiber, and the density/10 cm is 570 (warp) multiplied by 290 (weft); gram weight 157g m-2。
Advantageous effects
(1) The cationic fluorescent dye provided by the invention has a novel structure, and fills the blank of the cationic fluorescent dye suitable for dyeing modified polyester fabrics at present;
(2) the cationic fluorescent dye based on the benzyl naphthalimide structure is used for modifying dyeing dye uptake of polyester, and has the advantages of high color yield, full hue, uniform color and high fluorescence intensity;
(3) the cationic fluorescent dye based on the benzyl naphthalimide structure is used for dyeing modified terylene uniformly and has excellent color fastness.
Drawings
FIG. 1 is an FTIR spectrum of the cationic fluorescent dye (1) obtained in example 1;
FIG. 2 shows the cationic fluorescent dye (1) obtained in example 11H NMR spectrum chart;
FIG. 3 is an FTIR spectrum of the cationic fluorescent dye (2) obtained in example 2;
FIG. 4 shows the cationic fluorescence obtained in example 1Of the optical dyes (2)1H NMR spectrum chart;
FIG. 5 shows the UV-visible absorption of the cationic fluorescent dye (1) obtained in example 1;
FIG. 6 fluorescence excitation-emission spectrum of the cationic fluorescent dye (1) obtained in example 1;
FIG. 7 ultraviolet-visible absorption light of the cationic fluorescent dye (2) obtained in example 2;
FIG. 8 fluorescence excitation-emission spectrum of the cationic fluorescent dye (2) obtained in example 2;
FIG. 9 is a graph of a dyeing process for modified polyester fabric;
FIG. 10 is a photograph of a cationic fluorescent dye (1) dyeing a cloth sample of a modified polyester fabric under different light sources;
FIG. 11 is a photograph of a sample cloth of a modified polyester fabric dyed by a cationic fluorescent dye (2) under different light sources;
FIG. 12 fluorescence spectra of example 5 stained swatches;
FIG. 13 fluorescence spectrum of example 6 dyed cloth sample.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
The drugs and materials used in the examples were: the modified terylene is cation dyeable terylene (CDP) obtained by adding a third monomer of 3, 5-dimethyl benzene dicarboxylate sodium Sulfonate (SIPM) into terylene fiber, and the density/10 cm:570 (warp) × 290 (weft), grammage: 157g/m2Supplied by Zhejiang Shengfa textile printing and dyeing Co., Ltd; 4-bromo-1, 8-naphthalic anhydride (98%), dichloromethane (99.5%), benzyl chloride (99%), 4-nitrophthalonitrile (98%) was purchased from Shanghai Tanta Tech, Inc.; anhydrous ethanol (99.5%), ethylene glycol monomethyl ether (99%), ethanolamine (99%), and N, N-dimethylpropylenediamine (99%) were tested by the national pharmaceutical groupPurchased by agent limited.
Example 1
(1) Adding 80mL of ethanol and 5.54g of 4-bromo-1, 8-naphthalic anhydride into a 100mL three-neck flask in sequence, stirring and heating to 40 ℃, dropwise adding 1.4mL of ethanolamine, slowly heating to 80 ℃, carrying out reflux reaction for 3h, and completely reacting the 4-bromo-1, 8-naphthalic anhydride. Stopping reaction, cooling the system, filtering, washing with water until the filtrate is neutral, collecting a filter cake, drying, and recrystallizing with ethanol to obtain 5.28g of white powder which is N-hydroxyethyl-4-bromo-1, 8-naphthamide with the yield of 82.80%.
(2) 60mL of ethylene glycol monomethyl ether and 3.20g N-hydroxyethyl-4-bromo-1, 8-naphthamide are sequentially added into a 100mL three-neck flask, the mixture is stirred and heated, 6.4mLN, N-dimethyl propane diamine is slowly added, the reaction lasts for 4 hours at 125 ℃, and the N-hydroxyethyl-4-bromo-1, 8-naphthamide is completely reacted. The reaction was stopped and the system was cooled. Adding water into the system, extracting with dichloromethane for three times, collecting an organic phase, washing the organic phase with pure water for two times, removing water from the finally obtained organic phase with anhydrous sodium sulfate, performing suction filtration, collecting filtrate, distilling under reduced pressure to remove a solvent of dichloromethane, and recrystallizing with ethyl acetate to obtain 2.80g of yellow crystalline powder which is N-hydroxyethyl-4- (N, N-dimethylpropylenediamine) -1, 8-naphthamide with the yield of 82.17%.
(3) 40mL of acetone, 2.00 mL of 2.00g N-hydroxyethyl-4- (N, N-dimethylpropylenediamine) -1, 8-naphthamide and 3.40mL of benzyl chloride are sequentially added into a 100mL three-neck flask, the temperature is raised to 56 ℃ by stirring, the reaction is carried out for 12h at the temperature, and the N-hydroxyethyl-4- (N, N-dimethylpropylenediamine) -1, 8-naphthamide is completely reacted. The reaction was stopped, the system was cooled, filtered directly, the filter cake was washed with acetone, ethanol and dried to give 1.52g of yellow powder as the cationic fluorescent dye (1) in 55.56% yield.
(4) Infrared (FTIR) spectrum and nuclear magnetic resonance hydrogen spectrum (FTIR) of the cationic fluorescent dye (1) obtained in the test (3)1H NMR), the results are shown in fig. 1 and fig. 2, respectively.1H NMR(DMSO)：8.75(d，1H，Ar-H),8.45(d，1H，Ar-H),8.28(d,1H,Ar-H),8.03(t,1H,NH),7.71(t,1H,Ar-H),7.48-7.52(m,3H,Ar-H),7.39-7.42(t,2H,Ar-H),6.86(d,1H,Ar-H),4.81(t,1H,OH),4.56(s,2H,CH2),4.13(t,2H,CH2),3.56-3.60(m,2H,CH2),3.50-3.54(m,2H,CH2),3.42-3.46(t,2H,CH2),2.99(s,6H,CH3),2.21-2.29(m,2H,CH2)。
Example 2
(1) 0.80g of the cationic fluorescent dye (1) obtained in example 1, 0.30g of 4-nitrophthalonitrile and 15mL of DMF were sequentially added to a 100mL three-necked flask, and the mixture was stirred under nitrogen atmosphere and heated to 48 ℃ to 0.48g of K2CO3Five times of adding the cationic fluorescent dye into the mixture within two hours, and continuing the reaction for 46 hours after the addition is finished, so that the cationic fluorescent dye (1) completely reacts. After the system is cooled, the direct suction filtration is carried out, a small amount of water is used for washing a filter cake, and the drying is carried out, so that 0.55g of yellow powder which is the cationic fluorescent dye (2) can be obtained, and the yield is 54.45%.
(2) FTIR spectrum of cationic fluorescent dye (2) obtained in test (1) and1the results of H NMR are shown in FIGS. 3 and 4, respectively.1H NMR(DMSO)：8.71(d，1H，Ar-H),8.48(d，1H，Ar-H),8.31(d,1H,Ar-H),8.03(s,1H,Ar-H),8.01(t,1H,NH),7.77(d,1H,Ar-H),7.74(t,1H,Ar-H),7.47-7.51(m,3H,Ar-H),7.45(d,1H,Ar-H),7.39-7.42(t,2H,Ar-H),6.88(d,1H,Ar-H),4.54(s,2H,CH2),4.45(m,4H,CH2),3.51-3.55(m,2H,CH2),3.40-3.44(t,2H,CH2),2.98(s,6H,CH3),2.19-2.27(m,2H,CH2)。
Example 3
The cationic fluorescent dye (1) prepared in example 1 was dissolved in pure water at a concentration of 0.01mM, and its ultraviolet-visible absorption spectrum and fluorescence excitation-emission spectrum were measured using an ultraviolet spectrophotometer and fluorescence spectrometer, respectively, as shown in fig. 5 and 6. From FIGS. 5 and 6, it is clear that the maximum absorption wavelength of the cationic fluorescent dye (1) is 442nm, the maximum excitation wavelength is 442nm, and the maximum emission wavelength is 546 nm.
Example 4
The cationic fluorescent dye (2) prepared in example 2 was dissolved in pure water at a concentration of 0.01mM, and its ultraviolet-visible absorption spectrum and fluorescence excitation-emission spectrum were measured using an ultraviolet spectrophotometer and fluorescence spectrometer, respectively, as shown in fig. 7 and 8. From FIGS. 7 and 8, it is understood that the maximum absorption wavelength of the cationic fluorescent dye (2) is 448nm, the maximum excitation wavelength is 448nm, and the maximum emission wavelength is 549 nm.
Example 5
The cationic fluorescent dye (1) obtained in example 1 was used to dye a modified polyester fabric according to the dyeing process graph shown in fig. 9. Specifically, dyeing the cloth sample at 30 ℃, heating to 120 ℃ at the speed of 1 ℃/min, carrying out heat preservation dyeing at 120 ℃ for 50min, and then naturally cooling to 60 ℃. And (3) soaping the dyed fabric for 15min at 85 ℃, washing with water, and drying, wherein the soaping agent is 1.0g/L washing powder, and the soaping bath ratio is 1: 20. The dosage of the ionic fluorescent dye (1) during dyeing is 2.0 (o.w.f%), and the bath ratio is 1: 20. And (5) testing the dye-uptake rate and the color yield of the dye after dyeing.
The dye uptake test method comprises the following steps: and (3) soaping and washing the dyed cloth sample, collecting the dyeing residual liquid and the colored cleaning liquid, reasonably diluting the dyeing residual liquid and the colored cleaning liquid to a certain multiple, testing the absorbance of the dyeing residual liquid and the colored cleaning liquid by an ultraviolet spectrophotometer, and calculating the dyeing uptake rate according to the ratio of the absorbance to the absorbance of the dyeing stock solution. In the experiment, Integ value is selected to represent the color yield of the dyed fabric, a Datacolor D-650 computer color measuring and matching instrument is adopted, and the color measuring light source is D65Light source, 10 ° viewing angle, 5 measurements per sample were averaged. The cationic fluorescent dye (1) of this example was found to have a dye uptake of 94.17% and an integer value of cloth-like color yield of 24.96. The result shows that the cationic fluorescent dye (1) is used for dyeing modified polyester fabrics, and has high dye uptake and high color yield.
The photo of the dyed fabric sample under the fluorescent lamp and the ultraviolet lamp is shown in figure 10, and the photo shows that the dyed fabric with the cationic fluorescent dye (1) is bright yellow under the fluorescent lamp and bright yellow-green fluorescence under the irradiation of the 365nm ultraviolet lamp, and the dyed fabric has full hue, bright color and no color spots or defects under the fluorescent lamp or the ultraviolet lamp, so that the level-dyeing property of the dyed modified polyester fabric with the cationic fluorescent dye (1) is good.
Reference is made to GB/T3920-: xenon arc test Standard the dyed fabric was tested for various colorfastness properties (same as the test standards for other examples), and the test results are shown in Table 1. The results in table 1 show that the dry and wet rubbing color fastness of the modified polyester fabric dyed by the cationic fluorescent dye (1) and the washing color fastness of the cellulose acetate, cotton, nylon, polyester and acrylic fibers reach 4-5 grades, the washing color fastness of the wool fabric is 4 grades, and the light color fastness is 4-5 grades, which indicates that the cationic fluorescent dye (1) has excellent color fastness for dyeing the modified polyester fabric.
TABLE 1 color fastness of modified polyester fabrics dyed with cationic fluorescent dyes (1)
Example 6
The cationic fluorescent dye (2) obtained in example 2 was used to dye a modified polyester fabric according to the dyeing process graph shown in fig. 9, wherein the amount of the cationic fluorescent dye (2) was 2.0 (o.w.f%), the bath ratio was 1:20, the dye uptake of the test dye after dyeing was 98.76%, and the cloth sample dye yield Integ value was 27.56. The result shows that the cationic fluorescent dye (2) is used for dyeing modified polyester fabrics, and has high dye uptake and high color yield.
The photos of the dyed cloth sample under the fluorescent lamp and the ultraviolet lamp are shown in fig. 11, and the photos show that the dyed fabric with the cationic fluorescent dye (2) is bright yellow under the fluorescent lamp and bright green fluorescence under the irradiation of the 365nm ultraviolet lamp, and the dyed fabric is full in hue, bright in color, free of color spots and defects under the fluorescent lamp and the ultraviolet lamp, so that the level-dyeing property of the cationic fluorescent dye (2) dyed modified polyester fabric is good. The results of the various color fastness tests are shown in table 2. The results in Table 2 show that the dry and wet rubbing color fastness, the washing color fastness and the light color fastness of the modified polyester fabric dyed by the cationic fluorescent dye (2) reach 4-5 levels, which shows that the cationic fluorescent dye (2) has excellent color fastness on the dyeing of the modified polyester fabric.
TABLE 2 color fastness of modified polyester fabrics dyed with cationic fluorescent dye (2)
Example 7
The fluorescence spectrum of the dyed cloth obtained in example 5 was measured by a fluorescence spectrometer, and the result is shown in FIG. 12. As can be seen from the figure, the maximum emission wavelength of the modified polyester fabric dyed by the cationic fluorescent dye (1) is 548nm, and the fluorescence intensity is as high as 1.71 multiplied by 107Showing intense fluorescence.
Example 8
The fluorescence spectrum of the dyed cloth obtained in example 6 was measured by a fluorescence spectrometer, and the result is shown in FIG. 13. As can be seen from the figure, the maximum emission wavelength of the modified polyester fabric dyed by the cationic fluorescent dye (2) is 529nm, and the fluorescence intensity is as high as 1.23 multiplied by 107Showing intense fluorescence.
Comparative example 1
Taking the N-hydroxyethyl-4- (N, N-dimethylpropylenediamine) -1, 8-naphthamide obtained in the step (2) in the example 1 as naphthalimide fluorescent dye A, wherein the structure is as follows:
the modified polyester fabric is dyed by the same dyeing and post-treatment process as the example 5, the dyeing rate of the modified polyester fabric is 48.32% after the dyeing is finished, and the dye yield Integ value of a cloth sample is 15.63. Compared with the dye-uptake of 94.17% and the color yield Integ value of 24.96 of the modified polyester fabric dyed by the cationic fluorescent dye (1) in the example 5, the dye-uptake is obviously reduced. The cationic fluorescent dye is used for dyeing modified polyester fabrics, the dye uptake and the color yield are obviously increased, and the cationic fluorescent dye is more suitable for dyeing the modified polyester fabrics.
Comparative example 2
The dye with the following structure is taken and marked as naphthalimide fluorescent dye B, the modified polyester fabric is dyed by adopting the dyeing and post-treatment process which is the same as that of the example 6, the dyeing rate is 56.21 percent when the dyeing is finished, and the dye yield Integ value of a cloth sample is 17.35. Compared with the dye-uptake of 98.76% and the color yield Integ value of 27.56 of the modified polyester fabric dyed by the cationic fluorescent dye (2) in the example 6, the dye-uptake is obviously reduced. The cationic fluorescent dye is used for dyeing modified polyester fabrics, the dye uptake and the color yield are obviously increased, and the cationic fluorescent dye is more suitable for dyeing the modified polyester fabrics.
Claims (10)
1. A cationic fluorescent dye with a benzyl naphthalimide structure shown in a general formula I,
R＝-CH2CH2OH or
2. The cationic fluorescent dye according to claim 1, wherein the structure is specifically:
3. a method of preparing a cationic fluorescent dye comprising:
refluxing 4-bromo-1, 8-naphthalic anhydride and ethanolamine serving as raw materials in ethanol to obtain N-hydroxyethyl-4-bromo-1, 8-naphthamide, refluxing N-hydroxyethyl-4-bromo-1, 8-naphthamide and N, N-dimethylpropylenediamine in ethylene glycol monomethyl ether to obtain N-hydroxyethyl-4- (N, N-dimethylpropylenediamine) -1, 8-naphthamide, and reacting N-hydroxyethyl-4- (N, N-dimethylpropylenediamine) -1, 8-naphthamide and benzyl chloride in acetone to obtain a cationic fluorescent dye I;
or reacting the obtained cationic fluorescent dye I with 4-nitrophthalonitrile to obtain the cationic fluorescent dye II.
4. The preparation method according to claim 3, wherein the preparation method specifically comprises:
(1) adding ethanol and 4-bromo-1, 8-naphthalic anhydride into a reactor in sequence, stirring and heating to 40 ℃, dropwise adding ethanolamine, slowly heating to ethanol reflux, monitoring the reaction by using TLC (thin layer chromatography), stopping the reaction until the 4-bromo-1, 8-naphthalic anhydride is completely reacted, cooling the system, performing suction filtration, washing with water until the filtrate is neutral, collecting a filter cake, drying, and recrystallizing to obtain N-hydroxyethyl-4-bromo-1, 8-naphthamide;
(2) sequentially adding ethylene glycol monomethyl ether and N-hydroxyethyl-4-bromo-1, 8-naphthamide into a reactor, stirring and heating, slowly adding N, N-dimethyl propane diamine, monitoring the reaction by using TLC (thin layer chromatography) until the N-hydroxyethyl-4-bromo-1, 8-naphthamide is completely reacted, stopping the reaction, cooling the system, adding water into the system, extracting by using dichloromethane, collecting an organic phase, washing the organic phase by using pure water, removing water from the obtained organic phase by using anhydrous sodium sulfate, performing suction filtration, collecting filtrate, removing a solvent dichloromethane, and purifying to obtain the N-hydroxyethyl-4- (N, N-dimethyl propane diamine) -1, 8-naphthamide;
(3) sequentially adding acetone, N-hydroxyethyl-4- (N, N-dimethyl propane diamine) -1, 8-naphthamide and benzyl chloride into a reactor, stirring and heating, monitoring the reaction by using TLC (thin layer chromatography) until the N-hydroxyethyl-4- (N, N-dimethyl propane diamine) -1, 8-naphthamide is completely reacted, stopping the reaction, cooling the system, directly filtering, washing a filter cake by using acetone and ethanol, and drying to obtain a cationic fluorescent dye I;
(4) sequentially adding a cationic fluorescent dye I, 4-nitrophthalonitrile and DMF (dimethyl formamide) into a reactor, stirring and heating under the protection of nitrogen, and adding K2CO3Adding the mixture five times within two hours, monitoring the reaction by using TLC (thin layer chromatography) until the cationic fluorescent dye I completely reacts, directly filtering the mixture after the system is cooled, washing a filter cake by using a small amount of water, and drying to obtain the cationAnd (3) a daughter fluorescent dye II.
5. The preparation method according to claim 4, wherein the molar ratio of 4-bromo-1, 8-naphthalic anhydride to ethanolamine in step (1) is 1: 1.1-1.2; the reaction temperature is 70-85 ℃, and the reaction time is 3-5 h.
6. The preparation method according to claim 4, wherein the molar ratio of N-hydroxyethyl-4-bromo-1, 8-naphthamide to N, N-dimethylpropylenediamine in the step (2) is 1:1.1 to 1.5; the reaction temperature is 110-130 ℃, and the reaction time is 3-6 h.
7. The preparation method according to claim 4, wherein the molar ratio of the precursor compound N-hydroxyethyl-4- (N, N-dimethylpropylenediamine) -1, 8-naphthamide to benzyl chloride in the step (3) is 1: 1.1-2; the reaction temperature is 40-70 ℃, and the reaction time is 10-14 h.
8. The preparation method according to claim 4, wherein the molar ratio of the cationic fluorescent dye I to the 4-nitrophthalonitrile in the step (4) is 1: 0.90-0.98; cationic fluorescent dyes I and K2CO3The molar ratio of (A) to (B) is 1: 1.5-2.5.
9. The preparation method according to claim 4, wherein the reaction temperature in the step (4) is 45-55 ℃ and the reaction time is 40-50 h.
10. Use of the cationic fluorescent dye according to claim 1 in modifying polyester fabrics.
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