CN1112412C - Diazo coupling process of polymer to synthesize high molecular epoxy resin dye - Google Patents
Diazo coupling process of polymer to synthesize high molecular epoxy resin dye Download PDFInfo
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Abstract
The present invention relates to a diazo coupling method for a polymer for synthesizing high molecular epoxy resin dye. Firstly, an epoxy resin primary polymer is prepared. Then, an aromatic amino compound is prepared into diazonium salt. Finally, the diazo coupling reaction of the polymer is implemented to obtain the product of the present invention. A reaction yield and a conversion rate are generally greater than 90%. The present invention can be used for preparing various kinds of cationic, anionic and dispersive macromolecule azo dye and pigment, is suitable for dyeing cotton, hemp, silk, wool, leather, polymers, etc., can be used as main components for painting, paint and colored writing ink and has the advantages of high adhesiveness, high water resistance, high stability, etc.
Description
The present invention relates to a kind of method of polymkeric substance diazo coupling method synthetic epoxy resin family macromolecule dyestuff, belong to high molecular dye
Technical field.
Dyestuff all has important use at every aspect and a lot of industrial sector of daily life.Azoic dyestuff has been widely used in the dyeing of cotton, fiber crops, wool, silk, polymeric amide, polyester, leather, paper and food etc.Azoic dyestuff (N=N-) is made of with the aromatic carbon ring or the heterocycle that are attached thereto azo group.Because there is the infinite selection possibility of being close to number and aspects such as position, substituting group at raw material, azo group, and have synthesized miscellaneous various azoic dyestuff.Its major advantage has: synthetic relatively simply, easily realize large-scale commercial production, have shades of colour and in the strong tinting strength of various substrate surfaces etc.No matter from the kind or the consumption of existing dyestuff, azoic dyestuff has all occupied the maximum market share.
Azoic dyestuff is also found aspect shortcomings such as its tack, water-wash resistance and poor stability when obtaining widespread use.In processes such as washing, the small molecules azoic dyestuff is easily from the substrate desorption and be diffused into the water.In some processes, also there is the micromolecular side reaction of azo, cause problem such as obviously fade.Particularly when the azo small molecules infiltrates people's skin by diffusion, serious health problem will be caused.Simultaneously, azoic dyestuff is very poor to the tinting strength of nonpolar hydrophobic surface such as polyethylene, polypropylene etc., can not get using widely aspect the dyeing of these polymkeric substance.Designing and synthesizing various polymeric dyes is the effective ways that address the above problem.At present, the main synthetic method of polymeric azo dyestuff has following three major types:
A. report at Prog.Polym.Sci. (Jpn) 1971,7,1 as H.Kamogawa, but first anamorphic zone reactive group
The azo small molecules is again with itself and polymer reaction
B. as R.Benson, J.T.Guthrie, R.B.Lartey etc. are at Polymer 1975,16, and 903 report that first synthetic macromolecule diazonium salt is again with small molecule coupled
C. as N.S.Batty and J.T.Guthrie at Polymer 1975,16, report in 43, synthetic polymerisable azo small molecules carries out polyreaction with it
The objective of the invention is to propose a kind of method of polymkeric substance diazo coupling method synthetic epoxy resin family macromolecule dyestuff, by the specific molecule design, the synthetic earlier various epoxy resin primary polymers that diazo coupling reaction group (as aniline, methyl substituted aniline or naphthylamines compound residue) can take place that have.By the diazo coupling reaction of primary polymer, directly prepare various high molecular dyes.Condition of the present invention is suitable for the direct diazo coupling of above-mentioned various polymkeric substance.Under condition of the present invention, the transformation efficiency of diazo coupling reaction can be up to more than 95%.Handle through simple, can directly obtain the high molecular dye of various lovely lusters.
The method of the polymkeric substance diazo coupling method synthetic epoxy resin family macromolecule dyestuff that the present invention proposes comprises following each step:
1, the preparation of epoxy resin primary polymer
Primary polymer is the Resins, epoxy family macromolecule that has functional group's (as residues such as aniline, methyl substituted aniline or naphthylamines) that can carry out diazo coupling reaction.Its general structural formula is shown in (7).The epoxy resin primary polymer is reacted under melting condition by epoxy monomer and aniline or naphthylamines and obtains.General reaction formula is as follows:
Wherein, (5) are commercial epoxy monomer, and as bisphenol-A diglycidylether, 1,4 cyclohexane dimethanol diglycidylether, Resorcinol diglycidylether, the R in the following formula is:
Wherein, (6) are aniline, methyl substituted aniline or naphthalene etc., and X is:
The preparation method is as follows for the epoxy resin primary polymer: under nitrogen protection, with etc. above-mentioned any one epoxy monomer and above-mentioned any one aromatic amine uniform mixing of amount, and slowly heating.When temperature reaches 100-130 ℃, keep homo(io)thermism.Under this temperature, polyreaction 24-48 hour, obtain primary polymer white transparent solid.
2, diazonium salt solution preparation
Aromatic amino compound is prepared into diazonium salt, and general reaction formula is as follows
Wherein, Y=HSO
4Or Cl
Be used for carrying out diazotizing aromatic amine Ar-NH
2Have: a. aniline or substituted aniline (substituting group can be methyl, chlorine, nitro, methoxyl group, oxyethyl group, phenoxy group, carboxyl, hydroxyl, ester group, amide group and sulfonic group etc.), b. naphthylamines or napthylamine sulfonic acid, c. amino-heterocyclic compounds etc.
Diazonium salt solution preparation method 1: with above-mentioned aromatic amine uniform mixing in the mixing solutions of the vitriol oil and Glacial acetic acid, Ar-NH
2: H
2SO
4=1: 2-3 (amount ratio), the volume ratio of the vitriol oil and Glacial acetic acid is 1: 12.5-20.Under 5 ℃, slowly add 30-40% (weight/volume) sodium nitrite in aqueous solution, Ar-NH
2: NaNO
2=1: 1-1.2 (amount ratio).Obtain transparent aromatic amine diazonium salt solution behind the stirring reaction.
Diazonium salt solution preparation method 2: with above-mentioned aromatic amine uniform mixing in the 10M concentrated hydrochloric acid solution, Ar-NH
2: HCl=1: 2.5-3 (amount ratio).Under 5 ℃, slowly add 30-40% (weight/volume) sodium nitrite in aqueous solution, Ar-NH
2: NaNO
2=1: 1-1.2 (amount ratio).Obtain transparent aromatic amine diazonium salt solution behind the stirring reaction.
Diazonium salt solution preparation method 3: under 70 ℃, solid sodium nitrite is progressively joined in the vitriol oil NaNO
2: H
2SO
4=1: 2 (weight/volume).In adition process, control adding speed makes temperature be no more than 75 ℃.To obtain nitrosyl-sulfuric acid solution and in ice-water bath, cool off, be incorporated as vitriol oil volume 10-12.5 Glacial acetic acid dilution doubly simultaneously.Amino-heterocyclic compounds is added in the above-mentioned nitrosyl-sulfuric acid solution Ar-NH
2: NaNO
2=1: 1-1.2 (amount ratio).Obtain the diazonium salt solution of homogeneous transparent.
3. polymkeric substance diazo coupling reaction
Above-mentioned primary polymer is dissolved in dimethyl formamide, N,N-DIMETHYLACETAMIDE or the N-Methyl pyrrolidone isopolarity organic solvent, and concentration is the 0.01-0.1 mol.In ice-water bath, solution temperature is dropped to 0 ℃, and remain on this temperature.Above-mentioned diazonium salt solution is slowly added above-mentioned polymers soln.The ratio of diazonium salt and primary polymer is determined according to the requirement of using, diazonium salt: the unit=0.2-1.25 of the taken place diazo coupling reaction in the primary polymer: 1 (amount ratio).Diazonium salt and primary polymer reacted 8-12 hour under the situation of vigorous stirring.General reaction formula is as follows
Wherein, X is the above-mentioned various group that carries out diazo coupling reaction, and Ar is above-mentioned various aromatic group.After reaction is finished, in above-mentioned reaction system, add excessive water, obtain polymer precipitation.After filtration, after washing and the drying, promptly obtain product.Reaction yield and transformation efficiency are generally all greater than 90%.
The present invention can be used for preparing various positively charged ions, negatively charged ion and decentralized polymeric azo dyestuff and pigment.These dyestuffs and pigment are applicable to dyeing such as cotton, fiber crops, silk, hair, leather, polymkeric substance and paper, and can be used as the main component of lacquer, coating and color inks.Have advantages such as tack, water-wash resistance and good stability, can replace existing various positively charged ion, negatively charged ion and decentralized small molecules dyestuff.Compare with the preparation method of existing various high molecular dyes, have advantages such as the obviously simple and suitability of technology is strong.Can prepare and variously be suitable for painted new dyes such as cotton, fiber crops, silk, hair, leather, polymkeric substance and paper, and be easy to large-scale commercial production.
Introduce embodiments of the invention below.
Embodiment 1: under nitrogen protection, and with 76 gram (0.2mol) bisphenol-A diglycidylethers (molecular weight=381) and 18.6 gram (0.2mol) aniline uniform mixing, and slowly heating.When temperature reaches 110 ℃, keep homo(io)thermism.Under this temperature, polyreaction 24 hours obtains primary polymer white transparent solid.With vinylbenzene is standard specimen, is 57000 with the molecular weight of this polymkeric substance of gel permeation chromatography.
1.892 gram (4mmol) above-mentioned primary polymers are dissolved in 250 milliliters of dimethyl formamides, solution temperature are reduced to 0 ℃ with ice-water bath.With 0.6906 gram (5mmol) p-Nitroaniline uniform mixing in the glacial acetic acid solution of 0.5 milliliter of vitriol oil and 10 milliliters, under 5 ℃, slowly add 0.85 milliliter of 40% (w/v) sodium nitrite in aqueous solution, obtain transparent p-Nitroaniline diazonium salt solution behind the stirring reaction.This diazonium salt solution is slowly joined in the primary polymer solution, and reaction is 12 hours under 0 ℃ of nitrogen protection.The water post precipitation obtains the scarlet polymeric dye.The wavelength of polymkeric substance maximum absorption is 496 nanometers.The transformation efficiency of measuring with the hydrogen nuclear magnetic resonance method is greater than 95%.
Embodiment 2: adopt the identical primary polymer of embodiment 1.1.892 gram (4mmol) above-mentioned primary polymers are dissolved in 300 milliliters of dimethyl formamides, solution temperature are reduced to 0 ℃ with ice-water bath.
Under 70 ℃, 0.4 gram Sodium Nitrite is progressively joined in 0.8 milliliter the vitriol oil, in adition process, control adding speed makes temperature be no more than 75 ℃.To obtain nitrosyl-sulfuric acid solution and in ice-water bath, cool off, simultaneously with 10 milliliters of Glacial acetic acid dilutions.1.426 gram (5mmol) 2-amino-5-(4-nitrophenyl sulphonyl) thiazoles are added in the above-mentioned nitrosyl-sulfuric acid solution.Obtain the diazonium salt solution of homogeneous transparent.This diazonium salt solution is slowly joined in the primary polymer solution, and reaction is 12 hours under 0 ℃ of nitrogen protection.The water post precipitation obtains the polymeric dye of purple.The wavelength of polymkeric substance maximum absorption is 545 nanometers.The transformation efficiency of measuring with the hydrogen nuclear magnetic resonance method is 70%.
Embodiment 3: adopt the identical primary polymer of embodiment 1.18.92 gram (40mmol) above-mentioned primary polymers are dissolved in 2 liters of dimethyl formamides, solution temperature are reduced to 0 ℃ with ice-water bath.
Under 70 ℃, 3.5 gram Sodium Nitrites are progressively joined in 7 milliliters the vitriol oil, in adition process, controlled temperature is no more than 75 ℃.To obtain nitrosyl-sulfuric acid solution and in ice-water bath, cool off, simultaneously with 70 milliliters of Glacial acetic acid dilutions.7.26 gram (50mmol) 2-amino-5-nitrothiazoles are added above-mentioned nitrosyl-sulfuric acid solution.Obtain the diazonium salt solution of homogeneous transparent.This diazonium salt solution is slowly joined in the primary polymer solution, and reaction is 12 hours under 0 ℃ of nitrogen protection.The water post precipitation obtains the polymeric dye of avy blue.The wavelength of polymkeric substance maximum absorption is 571 nanometers.The transformation efficiency of measuring with the hydrogen nuclear magnetic resonance method is 77%.
Embodiment 4: adopt the identical primary polymer of embodiment 1.1.892 gram (4mmol) above-mentioned primary polymers are dissolved in 80 milliliters of dimethyl formamides, solution temperature are reduced to 0 ℃ with ice-water bath.
With 1.381 gram (5mmol) two hydration 2-amino-5-nitrobenzene sodium sulfonate uniform mixing in the glacial acetic acid solution of 0.6 milliliter of vitriol oil and 10 milliliters, under 5 ℃, slowly add 0.9 milliliter of 40% (w/v) sodium nitrite in aqueous solution, obtain transparent 2-amino-5-nitrobenzene sodium sulfonate diazonium salt solution behind the stirring reaction.This diazonium salt solution is slowly joined in the primary polymer solution, and reaction is 12 hours under 0 ℃ of nitrogen protection.The water post precipitation obtains the bright red polymeric dye.The wavelength of polymkeric substance maximum absorption is 483 nanometers.The transformation efficiency of measuring with the hydrogen nuclear magnetic resonance method is greater than 95%.
Embodiment 5: under nitrogen protection, and with 51.27 gram (0.2mol) 1,4 cyclohexane dimethanol diglycidylethers and 18.63 gram (0.2mol) aniline uniform mixing, and slowly heating.When temperature reaches 110 ℃, keep homo(io)thermism.Under this temperature, polyreaction 36 hours obtains primary polymer white transparent solid.Molecular weight with this polymkeric substance of gel permeation chromatography is 3500.1.4 gram (4mmol) above-mentioned primary polymers are dissolved in 40 milliliters of dimethyl formamides, solution temperature are reduced to 0 ℃ with ice-water bath.
With 1.381 gram (5mmol) two hydration 2-amino-5-nitrobenzene sodium sulfonate uniform mixing in the glacial acetic acid solution of 0.7 milliliter of vitriol oil and 10 milliliters, under 5 ℃, slowly add 1 milliliter of 40% (w/v) sodium nitrite in aqueous solution, obtain transparent 2-amino-5-nitrobenzene sodium sulfonate diazonium salt solution behind the stirring reaction.This diazonium salt solution is slowly joined in the above-mentioned primary polymer solution, and reaction is 12 hours under 0 ℃ of nitrogen protection.The water post precipitation obtains the bright red polymeric dye.The wavelength of polymkeric substance maximum absorption is 482 nanometers.The transformation efficiency of measuring with the hydrogen nuclear magnetic resonance method is greater than 95%.This polymkeric substance has well water-soluble.Embodiment 6: under nitrogen protection, and with 39.2 gram (0.1mol) bisphenol-A diglycidylethers (molecular weight=392) and 9.3 gram (0.1mol) aniline uniform mixing, and slowly heating.When temperature reaches 110 ℃, keep homo(io)thermism.Under this temperature, polyreaction 48 hours obtains primary polymer white transparent solid.With vinylbenzene is standard specimen, is 32000 with the molecular weight of this polymkeric substance of gel permeation chromatography.
0.9704 gram (2mmol) above-mentioned primary polymer is dissolved in 66 milliliters of dimethyl formamides, solution temperature is reduced to 0 ℃ with ice-water bath.With 0.0552 gram (0.4mmol) p-Nitroaniline uniform mixing in the glacial acetic acid solution of 0.05 milliliter of vitriol oil and 1 milliliter, under 5 ℃, slowly add 0.1 milliliter of 33% (w/v) sodium nitrite in aqueous solution, obtain transparent p-Nitroaniline diazonium salt solution behind the stirring reaction.This diazonium salt solution is slowly joined in the primary polymer solution, and reaction is 12 hours under 0 ℃ of nitrogen protection.The water post precipitation obtains the scarlet polymeric dye.The wavelength of polymkeric substance maximum absorption is 496 nanometers.The azo functionality of measuring with the hydrogen nuclear magnetic resonance method is 15.3%.
Embodiment 7: adopt the identical primary polymer of embodiment 6.0.9704 gram (2mmol) above-mentioned primary polymer is dissolved in 66 milliliters of dimethyl formamides, solution temperature is reduced to 0 ℃ with ice-water bath.
With 0.1104 gram (0.8mmol) p-Nitroaniline uniform mixing in the glacial acetic acid solution of 0.1 milliliter of vitriol oil and 2 milliliters, under 5 ℃, slowly add 0.2 milliliter of 33% (w/v) sodium nitrite in aqueous solution, obtain transparent p-Nitroaniline diazonium salt solution behind the stirring reaction.This diazonium salt solution is slowly joined in the primary polymer solution, and reaction is 12 hours under 0 ℃ of nitrogen protection.The water post precipitation obtains the scarlet polymeric dye.The wavelength of polymkeric substance maximum absorption is 496 nanometers.The azo functionality of measuring with the hydrogen nuclear magnetic resonance method is 32.9%.
Embodiment 8: adopt the identical primary polymer of embodiment 6.0.9704 gram (2mmol) above-mentioned primary polymer is dissolved in 66 milliliters of dimethyl formamides, solution temperature is reduced to 0 ℃ with ice-water bath.
With 0.1380 gram (1mmol) p-Nitroaniline uniform mixing in the glacial acetic acid solution of 0.125 milliliter of vitriol oil and 2.5 milliliters, under 5 ℃, slowly add 0.25 milliliter of 33% (w/v) sodium nitrite in aqueous solution, obtain transparent p-Nitroaniline diazonium salt solution behind the stirring reaction.This diazonium salt solution is slowly joined in the primary polymer solution, and reaction is 12 hours under 0 ℃ of nitrogen protection.The water post precipitation obtains the scarlet polymeric dye.The wavelength of polymkeric substance maximum absorption is 496 nanometers.The azo functionality of measuring with the hydrogen nuclear magnetic resonance method is 41.3%.
Embodiment 9: adopt the identical primary polymer of embodiment 6.0.9704 gram (2mmol) above-mentioned primary polymer is dissolved in 66 milliliters of dimethyl formamides, solution temperature is reduced to 0 ℃ with ice-water bath.
With 0.1656 gram (1.2mmol) p-Nitroaniline uniform mixing in the glacial acetic acid solution of 0.15 milliliter of vitriol oil and 3 milliliters, under 5 ℃, slowly add 0.3 milliliter of 33% (w/v) sodium nitrite in aqueous solution, obtain transparent p-Nitroaniline diazonium salt solution behind the stirring reaction.This diazonium salt solution is slowly joined in the primary polymer solution, and reaction is 12 hours under 0 ℃ of nitrogen protection.The water post precipitation obtains the scarlet polymeric dye.The wavelength of polymkeric substance maximum absorption is 496 nanometers.The azo functionality of measuring with the hydrogen nuclear magnetic resonance method is 50.2%.
Embodiment 10: adopt the identical primary polymer of embodiment 6.0.9704 gram (2mmol) above-mentioned primary polymer is dissolved in 66 milliliters of dimethyl formamides, solution temperature is reduced to 0 ℃ with ice-water bath.
With 0.1932 gram (1.4mmol) p-Nitroaniline uniform mixing in the glacial acetic acid solution of 0.175 milliliter of vitriol oil and 3.5 milliliters, under 5 ℃, slowly add 0.35 milliliter of 33% (w/v) sodium nitrite in aqueous solution, obtain transparent p-Nitroaniline diazonium salt solution behind the stirring reaction.This diazonium salt solution is slowly joined in the primary polymer solution, and reaction is 12 hours under 0 ℃ of nitrogen protection.The water post precipitation obtains the scarlet polymeric dye.The wavelength of polymkeric substance maximum absorption is 496 nanometers.The azo functionality of measuring with the hydrogen nuclear magnetic resonance method is 58.4%.
Embodiment 11: adopt the identical primary polymer of embodiment 6.0.9704 gram (2mmol) above-mentioned primary polymer is dissolved in 66 milliliters of dimethyl formamides, solution temperature is reduced to 0 ℃ with ice-water bath.
With 0.2208 gram (1.6mmol) p-Nitroaniline uniform mixing in the glacial acetic acid solution of 0.2 milliliter of vitriol oil and 4 milliliters, under 5 ℃, slowly add 0.4 milliliter of 33% (w/v) sodium nitrite in aqueous solution, obtain transparent p-Nitroaniline diazonium salt solution behind the stirring reaction.This diazonium salt solution is slowly joined in the primary polymer solution, and reaction is 12 hours under 0 ℃ of nitrogen protection.The water post precipitation obtains the scarlet polymeric dye.The wavelength of polymkeric substance maximum absorption is 496 nanometers.The azo functionality of measuring with the hydrogen nuclear magnetic resonance method is 67.1%.
Embodiment 12: adopt the identical primary polymer of embodiment 6.0.9704 gram (2mmol) above-mentioned primary polymer is dissolved in 66 milliliters of dimethyl formamides, solution temperature is reduced to 0 ℃ with ice-water bath.
With 0.2484 gram (1.8mmol) p-Nitroaniline uniform mixing in the glacial acetic acid solution of 0.225 milliliter of vitriol oil and 4.5 milliliters, under 5 ℃, slowly add 0.45 milliliter of 33% (w/v) sodium nitrite in aqueous solution, obtain transparent p-Nitroaniline diazonium salt solution behind the stirring reaction.This diazonium salt solution is slowly joined in the primary polymer solution, and reaction is 12 hours under 0 ℃ of nitrogen protection.The water post precipitation obtains the scarlet polymeric dye.The wavelength of polymkeric substance maximum absorption is 496 nanometers.The azo functionality of measuring with the hydrogen nuclear magnetic resonance method is 71.8%.
Embodiment 13: adopt the identical primary polymer of embodiment 6.0.9704 gram (2mmol) above-mentioned primary polymer is dissolved in 66 milliliters of dimethyl formamides, solution temperature is reduced to 0 ℃ with ice-water bath.
With 0.2764 gram (2mmol) p-Nitroaniline uniform mixing in the glacial acetic acid solution of 0.25 milliliter of vitriol oil and 5 milliliters, under 5 ℃, slowly add 0.5 milliliter of 33% (w/v) sodium nitrite in aqueous solution, obtain transparent p-Nitroaniline diazonium salt solution behind the stirring reaction.This diazonium salt solution is slowly joined in the primary polymer solution, and reaction is 12 hours under 0 ℃ of nitrogen protection.The water post precipitation obtains the scarlet polymeric dye.The wavelength of polymkeric substance maximum absorption is 496 nanometers.The azo functionality of measuring with the hydrogen nuclear magnetic resonance method is 76.2%.
Embodiment 14: adopt the identical primary polymer of embodiment 1.1.892 gram (4mmol) above-mentioned primary polymers are dissolved in 250 milliliters of dimethyl formamides, solution temperature are reduced to 0 ℃ with ice-water bath.
0.6909 gram (5mmol) p-Nitroaniline uniform mixing in 1.5 milliliters of 10M concentrated hydrochloric acid solutions, under 5 ℃, is slowly added 1 milliliter of 40% (w/v) sodium nitrite in aqueous solution, obtain transparent p-Nitroaniline diazonium salt solution behind the stirring reaction.This diazonium salt solution is slowly joined in the primary polymer solution, and reaction is 12 hours under 0 ℃ of nitrogen protection.The water post precipitation obtains the scarlet polymeric dye.The wavelength of polymkeric substance maximum absorption is 496 nanometers.The transformation efficiency of measuring with the hydrogen nuclear magnetic resonance method is greater than 95%.
Embodiment 15: adopt the identical primary polymer of embodiment 1.1.892 gram (4mmol) above-mentioned primary polymers are dissolved in 250 milliliters of dimethyl formamides, solution temperature are reduced to 0 ℃ with ice-water bath.
0.6909 gram (5mmol) p-Nitroaniline uniform mixing in 1.25 milliliters of 10M concentrated hydrochloric acid solutions, under 5 ℃, is slowly added 0.85 milliliter of 40% (w/v) sodium nitrite in aqueous solution, obtain transparent p-Nitroaniline diazonium salt solution behind the stirring reaction.This diazonium salt solution is slowly joined in the primary polymer solution, and reaction is 12 hours under 0 ℃ of nitrogen protection.The water post precipitation obtains the scarlet polymeric dye.The wavelength of polymkeric substance maximum absorption is 496 nanometers.The transformation efficiency of measuring with the hydrogen nuclear magnetic resonance method is greater than 95%.
Embodiment 16: under nitrogen protection, and with 7.6 gram (0.02mol) bisphenol-A diglycidylethers (molecular weight=381) and 2.143 gram (0.02mol) 2-aminotoluene uniform mixing, and slowly heating.When temperature reaches 120 ℃, keep homo(io)thermism.Under this temperature, polyreaction 48 hours obtains primary polymer white transparent solid.
1.953 gram (4mmol) above-mentioned primary polymers are dissolved in 250 milliliters of N,N-DIMETHYLACETAMIDEs, solution temperature are reduced to 0 ℃ with ice-water bath.With 0.6909 gram (5mmol) p-Nitroaniline uniform mixing in the glacial acetic acid solution of 0.8 milliliter of vitriol oil and 10 milliliters, under 5 ℃, slowly add 1.15 milliliter of 30% (w/v) sodium nitrite in aqueous solution, obtain transparent p-Nitroaniline diazonium salt solution behind the stirring reaction.This diazonium salt solution is slowly joined in the primary polymer solution, and reaction is 8 hours under 0 ℃ of nitrogen protection.The water post precipitation obtains the scarlet polymeric dye.The wavelength of polymkeric substance maximum absorption is 496 nanometers.The transformation efficiency of measuring with the hydrogen nuclear magnetic resonance method is greater than 95%.
Embodiment 17: under nitrogen protection, and with 7.6 gram (0.02mol) bisphenol-A diglycidylethers (molecular weight=381) and 2.143 gram (0.02mol) 3-monomethylaniline uniform mixing, and slowly heating.When temperature reaches 120 ℃, keep homo(io)thermism.Under this temperature, polyreaction 48 hours obtains primary polymer white transparent solid.
1.953 gram (4mmol) above-mentioned primary polymers are dissolved in 250 milliliters of N,N-DIMETHYLACETAMIDEs, solution temperature are reduced to 0 ℃ with ice-water bath.With 0.6909 gram (5mmol) p-Nitroaniline uniform mixing in the glacial acetic acid solution of 0.8 milliliter of vitriol oil and 10 milliliters, under 5 ℃, slowly add 1.4 milliliter of 30% (w/v) sodium nitrite in aqueous solution, obtain transparent p-Nitroaniline diazonium salt solution behind the stirring reaction.This diazonium salt solution is slowly joined in the primary polymer solution, and reaction is 8 hours under 0 ℃ of nitrogen protection.The water post precipitation obtains the scarlet polymeric dye.
Embodiment 18: under nitrogen protection, with 7.6 gram (0.02mol) bisphenol-A diglycidylethers (molecular weight=381) and 2.424 gram (0.02mol) 2,5-xylidine uniform mixing, and slowly heating.When temperature reaches 130 ℃, keep homo(io)thermism.Under this temperature, polyreaction 48 hours obtains primary polymer white transparent solid.
2.009 gram (4mmol) above-mentioned primary polymers are dissolved in 250 milliliters of N,N-DIMETHYLACETAMIDEs, solution temperature are reduced to 0 ℃ with ice-water bath.With 0.6909 gram (5mmol) p-Nitroaniline uniform mixing in the glacial acetic acid solution of 0.8 milliliter of vitriol oil and 10 milliliters, under 5 ℃, slowly add 0.9 milliliter of 40% (w/v) sodium nitrite in aqueous solution, obtain transparent p-Nitroaniline diazonium salt solution behind the stirring reaction.This diazonium salt solution is slowly joined in the primary polymer solution, and reaction is 10 hours under 0 ℃ of nitrogen protection.The water post precipitation obtains the scarlet polymeric dye.
Embodiment 19: under nitrogen protection, with 7.6 gram (0.02mol) bisphenol-A diglycidylethers (molecular weight=381) and 2.424 gram (0.02mol) 2,6-xylidine uniform mixing, and slowly heating.When temperature reaches 130 ℃, keep homo(io)thermism.Under this temperature, polyreaction 48 hours obtains primary polymer white transparent solid.
2.009 gram (4mmol) above-mentioned primary polymers are dissolved in 250 milliliters of N,N-DIMETHYLACETAMIDEs, solution temperature are reduced to 0 ℃ with ice-water bath.With 0.6909 gram (5mmol) p-Nitroaniline uniform mixing in the glacial acetic acid solution of 0.8 milliliter of vitriol oil and 10 milliliters, under 5 ℃, slowly add 0.85 milliliter of 40% (w/v) sodium nitrite in aqueous solution, obtain transparent p-Nitroaniline diazonium salt solution behind the stirring reaction.This diazonium salt solution is slowly joined in the primary polymer solution, and reaction is 10 hours under 0 ℃ of nitrogen protection.The water post precipitation obtains the scarlet polymeric dye.
Embodiment 20: under nitrogen protection, and with 7.6 gram (0.02mol) bisphenol-A diglycidylethers (molecular weight=381) and 2.8636 gram (0.02mol) naphthalidine uniform mixing, and slowly heating.When temperature reaches 100 ℃, keep homo(io)thermism.Under this temperature, polyreaction 48 hours obtains primary polymer white transparent solid.
2.097 gram (4mmol) above-mentioned primary polymers are dissolved in 250 milliliters of N-Methyl pyrrolidone, solution temperature are reduced to 0 ℃ with ice-water bath.With 0.6909 gram (5mmol) p-Nitroaniline uniform mixing in the glacial acetic acid solution of 0.7 milliliter of vitriol oil and 10 milliliters, under 5 ℃, slowly add 1.2 milliliter of 33% (w/v) sodium nitrite in aqueous solution, obtain transparent p-Nitroaniline diazonium salt solution behind the stirring reaction.This diazonium salt solution is slowly joined in the primary polymer solution, and reaction is 12 hours under 0 ℃ of nitrogen protection.The water post precipitation obtains the scarlet polymeric dye.
Embodiment 21: adopt the identical primary polymer of embodiment 1.1.892 gram (4mmol) above-mentioned primary polymers are dissolved in 250 milliliters of dimethyl formamides, solution temperature are reduced to 0 ℃ with ice-water bath.
With 0.9409 gram (5mmol) to 4-nitro-naphthalidine uniform mixing in the glacial acetic acid solution of 0.7 milliliter of vitriol oil and 10 milliliters, under 5 ℃, slowly add 1.2 milliliter of 33% (w/v) sodium nitrite in aqueous solution, obtain transparent 4-nitro-naphthalidine diazonium salt solution behind the stirring reaction.This diazonium salt solution is slowly joined in the primary polymer solution, and reaction is 12 hours under 0 ℃ of nitrogen protection.The water post precipitation obtains the scarlet polymeric dye.The wavelength of polymkeric substance maximum absorption is 499 nanometers.The transformation efficiency of measuring with the hydrogen nuclear magnetic resonance method is greater than 95%.
Embodiment 22: under nitrogen protection, and with 44.5 gram (0.2mol) Resorcinol diglycidylethers (molecular weight=222.24) and 18.6 gram (0.2mol) aniline uniform mixing, and slowly heating.When temperature reaches 110 ℃, keep homo(io)thermism.Under this temperature, polyreaction 24 hours obtains primary polymer white transparent solid.
1.261 gram (4mmol) above-mentioned primary polymers are dissolved in 250 milliliters of dimethyl formamides, solution temperature are reduced to 0 ℃ with ice-water bath.With 0.6906 gram (5mmol) p-Nitroaniline uniform mixing in the glacial acetic acid solution of 0.6 milliliter of vitriol oil and 10 milliliters, under 5 ℃, slowly add 1.2 milliliter of 30% (w/v) sodium nitrite in aqueous solution, obtain transparent p-Nitroaniline diazonium salt solution behind the stirring reaction.This diazonium salt solution is slowly joined in the primary polymer solution, and reaction is 12 hours under 0 ℃ of nitrogen protection.The water post precipitation obtains the scarlet polymeric dye.The wavelength of polymkeric substance maximum absorption is 496 nanometers.
Embodiment 23: adopt the identical primary polymer of embodiment 5.1.4 gram (4mmol) above-mentioned primary polymers are dissolved in 60 milliliters of dimethyl formamides, solution temperature are reduced to 0 ℃ with ice-water bath.
With 0.886 gram (5mmol) 4-amino-Phenylsulfonic acid uniform mixing in the glacial acetic acid solution of 0.7 milliliter of vitriol oil and 10 milliliters, under 5 ℃, slowly add 1.3 milliliter of 30% (w/v) sodium nitrite in aqueous solution, obtain transparent 4-amino-Phenylsulfonic acid diazonium salt solution behind the stirring reaction.This diazonium salt solution is slowly joined in the above-mentioned primary polymer solution, and reaction is 12 hours under 0 ℃ of nitrogen protection.The water post precipitation obtains the scarlet polymeric dye.The wavelength of polymkeric substance maximum absorption is 514 nanometers.The transformation efficiency of measuring with the hydrogen nuclear magnetic resonance method is 69%.This polymkeric substance has well water-soluble.
Embodiment 24: adopt the identical primary polymer of embodiment 5.1.4 gram (4mmol) above-mentioned primary polymers are dissolved in 50 milliliters of dimethyl formamides, solution temperature are reduced to 0 ℃ with ice-water bath.
With 0.886 gram (5mmol) 3-amino-Phenylsulfonic acid uniform mixing in the glacial acetic acid solution of 0.7 milliliter of vitriol oil and 10 milliliters, under 5 ℃, slowly add 1.4 milliliter of 30% (w/v) sodium nitrite in aqueous solution, obtain transparent 4-amino-Phenylsulfonic acid diazonium salt solution behind the stirring reaction.This diazonium salt solution is slowly joined in the above-mentioned primary polymer solution, and reaction is 12 hours under 0 ℃ of nitrogen protection.The water post precipitation obtains the light red polymeric dye.The wavelength of polymkeric substance maximum absorption is 464 nanometers.The transformation efficiency of measuring with the hydrogen nuclear magnetic resonance method is 54%.This polymkeric substance has well water-soluble.
Embodiment 25: adopt the identical primary polymer of embodiment 5.1.4 gram (4mmol) above-mentioned primary polymers are dissolved in 250 milliliters of dimethyl formamides, solution temperature are reduced to 0 ℃ with ice-water bath.
With 1.1162 gram (5mmol) 4-amino-1-naphthalene sulfonic aicd uniform mixing in the glacial acetic acid solution of 0.7 milliliter of vitriol oil and 10 milliliters, under 5 ℃, slowly add 1 milliliter of 33% (w/v) sodium nitrite in aqueous solution, obtain transparent 4-amino-1-naphthalene sulfonic aicd diazonium salt solution behind the stirring reaction.This diazonium salt solution is slowly joined in the above-mentioned primary polymer solution, and reaction is 12 hours under 0 ℃ of nitrogen protection.The water post precipitation obtains the scarlet polymeric dye.This polymkeric substance has well water-soluble.
Embodiment 26: adopt the identical primary polymer of embodiment 5.1.4 gram (4mmol) above-mentioned primary polymers are dissolved in 250 milliliters of dimethyl formamides, solution temperature are reduced to 0 ℃ with ice-water bath.
With 1.1162 gram (5mmol) 5-amino-1-naphthalene sulfonic aicd uniform mixing in the glacial acetic acid solution of 0.7 milliliter of vitriol oil and 10 milliliters, under 5 ℃, slowly add 1.1 milliliter of 33% (w/v) sodium nitrite in aqueous solution, obtain transparent 5-amino-1-naphthalene sulfonic aicd diazonium salt solution behind the stirring reaction.This diazonium salt solution is slowly joined in the above-mentioned primary polymer solution, and reaction is 12 hours under 0 ℃ of nitrogen protection.The water post precipitation obtains the scarlet polymeric dye.This polymkeric substance has well water-soluble.
Embodiment 27: adopt the identical primary polymer of embodiment 5.1.4 gram (4mmol) above-mentioned primary polymers are dissolved in 70 milliliters of dimethyl formamides, solution temperature are reduced to 0 ℃ with ice-water bath.
With 0.686 gram (5mmol) 4-amino-phenylformic acid uniform mixing in the glacial acetic acid solution of 0.7 milliliter of vitriol oil and 10 milliliters, under 5 ℃, slowly add 1 milliliter of 40% (w/v) sodium nitrite in aqueous solution, obtain transparent 4-amino-phenylformic acid diazonium salt solution behind the stirring reaction.This diazonium salt solution is slowly joined in the above-mentioned primary polymer solution, and reaction is 12 hours under 0 ℃ of nitrogen protection.The water post precipitation obtains the yellow polymer dyestuff.This polymkeric substance has well water-soluble.
Embodiment 28: adopt the identical primary polymer of embodiment 5.1.4 gram (4mmol) above-mentioned primary polymers are dissolved in 250 milliliters of dimethyl formamides, solution temperature are reduced to 0 ℃ with ice-water bath.
Under 70 ℃, 0.37 gram Sodium Nitrite is progressively joined in 0.74 milliliter the vitriol oil, in adition process, control adding speed makes temperature be no more than 75 ℃.To obtain nitrosyl-sulfuric acid solution and in ice-water bath, cool off, simultaneously with 8 milliliters of Glacial acetic acid dilutions.0.471 gram (5mmol) 4-aminopyridine is added in the above-mentioned nitrosyl-sulfuric acid solution.Obtain the diazonium salt solution of homogeneous transparent.This diazonium salt solution is slowly joined in the primary polymer solution, and reaction is 12 hours under 0 ℃ of nitrogen protection.The water post precipitation obtains red polymeric dye.The wavelength of polymkeric substance maximum absorption is 440 nanometers.The transformation efficiency of measuring with the hydrogen nuclear magnetic resonance method is greater than 95%.
Embodiment 29: adopt the identical primary polymer of embodiment 1.1.892 gram (4mmol) above-mentioned primary polymers are dissolved in 400 milliliters of dimethyl formamides, solution temperature are reduced to 0 ℃ with ice-water bath.
Under 70 ℃, 0.39 gram Sodium Nitrite is progressively joined in 0.78 milliliter the vitriol oil, in adition process, control adding speed makes temperature be no more than 75 ℃.To obtain nitrosyl-sulfuric acid solution and in ice-water bath, cool off, simultaneously with 9 milliliters of Glacial acetic acid dilutions.With 0.666 gram (5mmol) 2-amino-4,5-dinitrile imidazoles adds in the above-mentioned nitrosyl-sulfuric acid solution.Obtain the diazonium salt solution of homogeneous transparent.This diazonium salt solution is slowly joined in the primary polymer solution, and reaction is 12 hours under 0 ℃ of nitrogen protection.The water post precipitation obtains red polymeric dye.The wavelength of polymkeric substance maximum absorption is 489 nanometers.The transformation efficiency of measuring with the hydrogen nuclear magnetic resonance method is 72%.
Embodiment 30: adopt the identical primary polymer of embodiment 1.1.892 gram (4mmol) above-mentioned primary polymers are dissolved in 250 milliliters of dimethyl formamides, solution temperature are reduced to 0 ℃ with ice-water bath.
With 1.146 gram (5mmol) 7-amino-4-trifluoromethyl coumarin uniform mixing in the glacial acetic acid solution of 0.5 milliliter of vitriol oil and 10 milliliters, under 5 ℃, slowly add 1.3 milliliter of 33% (w/v) sodium nitrite in aqueous solution, obtain transparent 7-amino-4-trifluoromethyl coumarin diazonium salt solution behind the stirring reaction.This diazonium salt solution is slowly joined in the above-mentioned primary polymer solution, and reaction is 12 hours under 0 ℃ of nitrogen protection.The water post precipitation obtains the scarlet polymeric dye.The wavelength of polymkeric substance maximum absorption is 471 nanometers, and the transformation efficiency of measuring with the hydrogen nuclear magnetic resonance method is 85%.
Claims (1)
1, a kind of method of polymkeric substance diazo coupling method synthetic epoxy resin family macromolecule dyestuff is characterized in that this method comprises following each step:
(1) preparation of epoxy resin primary polymer:
Primary polymer is the Resins, epoxy family macromolecule that has the functional group that can carry out diazo coupling reaction, its general structural formula is shown in (3), the epoxy resin primary polymer is reacted under melting condition by epoxy monomer and aniline or naphthylamines and obtains, and general reaction formula is as follows:
Wherein, (1) is epoxy monomer, any in bisphenol-A diglycidylether, 1,4 cyclohexane dimethanol diglycidylether or the Resorcinol diglycidylether, and the R in the following formula is any of following structural formula:
Wherein, (2) are any in aniline, methyl substituted aniline or the naphthalene, and X is any of following structural formula:
The preparation method is as follows for the epoxy resin primary polymer: under nitrogen protection, with etc. above-mentioned any one epoxy monomer and above-mentioned any one aromatic amine uniform mixing of amount, and slowly heating, when temperature reaches 100-130 ℃, keep homo(io)thermism, under this temperature, polyreaction 24-48 hour, obtain primary polymer white transparent solid;
(2) with a kind of preparation diazonium salt solution in following three kinds of methods:
Aromatic amino compound is prepared into diazonium salt, and general reaction formula is as follows
Wherein, Y=HSO
4Or Cl
Be used for carrying out diazotizing aromatic amine Ar-NH
2Have: a. aniline or substituted aniline, substituting group in the substituted benzene is any in methyl, chlorine, nitro, methoxyl group, oxyethyl group, phenoxy group, carboxyl, hydroxyl, ester group, amide group or the sulfonic group, b. naphthylamines or napthylamine sulfonic acid, or any in the c. amino-heterocyclic compounds;
Diazonium salt solution preparation method 1: in the mixing solutions of the vitriol oil and Glacial acetic acid, its mol ratio is Ar-NH with above-mentioned aromatic amine uniform mixing
2: H
2SO
4=1: 2-3, the volume ratio of the vitriol oil and Glacial acetic acid is 1: 12.5-20, under 5 ℃, slowly adding weight/volume is the 30-40% sodium nitrite in aqueous solution, its molar weight is than being Ar-NH
2: NaNO
2=1: 1-1.2 obtains transparent aromatic amine diazonium salt solution behind the stirring reaction;
Diazonium salt solution preparation method 2: in the 10M concentrated hydrochloric acid solution, its mol ratio is Ar-NH with above-mentioned aromatic amine uniform mixing
2: HCl=1: 2.5-3, under 5 ℃, slowly adding by weight/volume is the 30-40% sodium nitrite in aqueous solution, its amount is than being Ar-NH
2: NaNO
2=1: 1-1.2 obtains transparent aromatic amine diazonium salt solution behind the stirring reaction;
Diazonium salt solution preparation method 3: under 70 ℃, solid sodium nitrite is progressively joined in the vitriol oil, its by weight/volume is NaNO
2: H
2SO
4=1: 2, in adition process, control adding speed makes temperature be no more than 75 ℃, to obtain nitrosyl-sulfuric acid solution cools off in ice-water bath, be incorporated as vitriol oil volume 10-12.5 Glacial acetic acid dilution doubly simultaneously, amino-heterocyclic compounds is added in the above-mentioned nitrosyl-sulfuric acid solution, and the spring amount is than being Ar-NH
2: NaNO
2=1: 1-1.2 obtains the diazonium salt solution of homogeneous transparent;
(3). the polymkeric substance diazo coupling reaction:
Above-mentioned primary polymer is dissolved in dimethyl formamide, in N,N-DIMETHYLACETAMIDE or the N-Methyl pyrrolidone polar organic solvent, concentration is the 0.01-0.1 mol, in ice-water bath, solution temperature is dropped to 0 ℃, and remain on this temperature, above-mentioned diazonium salt solution is slowly added above-mentioned polymers soln, the ratio of diazonium salt and primary polymer is, diazonium salt: the unitary amount of the taken place diazo coupling reaction in the primary polymer is than being 0.2-1.25: 1, diazonium salt and primary polymer are under the situation of vigorous stirring, reaction 8-12 hour, general reaction formula is as follows
Wherein, X is the above-mentioned various group that carries out diazo coupling reaction, Ar is above-mentioned various aromatic group, after reaction is finished, in above-mentioned reaction system, add excessive water, obtain polymer precipitation, after filtration, after washing and the drying, promptly obtain polymkeric substance diazo coupling method synthetic epoxy resin family macromolecule dyestuff.
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| CN101768373A (en) * | 2010-01-08 | 2010-07-07 | 武汉科技学院 | Method for preparing water soluble vinyl-sulfone polyurethane class high molecular reactive dye with diazo coupling method |
| CN101787222B (en) * | 2010-01-08 | 2015-06-03 | 武汉科技学院 | Method for preparing water-soluble vinyl sulfone epoxy resin-matrix macromolecule reactive dye by diazo coupling |
| CN103275014B (en) * | 2013-06-13 | 2015-09-23 | 盐城工学院 | Containing compound, the Preparation Method And The Use of five yuan of azoles ring tetrazo structures |
| CN105061773B (en) * | 2015-09-08 | 2018-05-08 | 东莞市冠尊实业有限公司 | A kind of chitin modified epoxy resin-matrix macromolecule dyestuff and preparation method thereof |
| CN105219124A (en) * | 2015-10-20 | 2016-01-06 | 湖州博仁纺织品有限公司 | A kind of novel active thickening agent for digit printing and preparation method thereof |
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| CN86106149A (en) * | 1985-09-13 | 1987-06-03 | 米利肯研究有限公司 | Colored thermoplastic resin article |
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