CN101787222A - Method for preparing water-soluble vinyl sulfone epoxy resin-matrix macromolecule reactive dye by diazo coupling - Google Patents
Method for preparing water-soluble vinyl sulfone epoxy resin-matrix macromolecule reactive dye by diazo coupling Download PDFInfo
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Abstract
The invention relates to a method for preparing water-soluble vinyl sulfone epoxy resin-matrix macromolecule reactive dye by diazo coupling. The method adopts epoxy resin precursor with functional group capable of performing diazo coupling as the macromolecule main chain, and prepares the aromatic amino compounds of hydroxyethyl sulfone sulfate into diazonium salt, and finally conducts the diazo coupling reaction of diazonium salt and epoxy resin precursor to prepare the water-soluble vinyl sulfone epoxy resin-matrix macromolecule reactive dye. The macromolecule reactive dye has good water solubility, ensures the vinyl sulfone matrix to react with materials containing certain hydroxyl and amino to finish the color fixation, and also solves the dye fastness problem. The method has simple synthesis course, easy functionality control and high diazo coupling rate. The reactive dye is applicable to cotton, linen, silk, woolen, leather and paper, and can be used as the colorant for plastics, rubber, paint and adhesive and also can be used as the colorant component of digital jet printing ink.
Description
Technical field
The present invention relates to the method that a kind of diazo coupling legal system is equipped with water-soluble vinyl sulfone epoxy resin-matrix macromolecule reactive dye, belong to the high molecular dye field.
Background technology
At dye field, azoic dyestuff is with its simple synthetic method, and compound structure changes various, molar extinction coefficient is higher, by the time advantage such as the fast light and moisture resistant fastness of high-grade in having considerably beyond other class dyestuffs, is the dye that kind is maximum, output is maximum on kind and output.When azoic dyestuff obtains widespread use, also find the shortcoming of aspects such as its tack, water-wash resistance, poor stability and environmental pollution be serious.In processes such as washing, the small molecules azoic dyestuff easily migrates to material surface, causes decolouring and variable color.Particularly the azo small molecules with the long-term contact process of human body in, easily diffuse and penetrate into human body, people's health is had very big influence.Along with many azo small molecules dyestuff potential carinogenicity are found in succession; the instruction and the rules of various greenisms are formulated again in succession; make people that sight is turned to the synthetic and exploitation that substitutes dyestuff, wherein the high molecular of low molecular dye is one of approach that can address the above problem.
The study on the synthesis of high molecular dye arises from the beginning of the sixties, and 1973, Marechal etc. realized colourless macromolecular material and the chemical bonding that dichroic dye molecule is arranged.After this, the researchdevelopment of high molecular dye is very rapid, has become a frontier of functional high-polymer and dyestuff chemistry research.In the prior art, Ching-Tzer Huang etc. are at Journal of Applied PolymerScience, Vol.100, report among the 1919-1931 (2006), adopt Resins, epoxy and Succinic anhydried to carry out the half ester reaction, behind the purifying with in the triethylamine and salify obtain the epoxy resin latex of Water-borne modification, then with the water-soluble dye reaction that contains amino, make the Resins, epoxy high molecular dye of water and milk, its weak point is preparation method's complexity, needs to use a kind of homemade polymine to finish fixation.Chinese patent publication number CN 1284524A, open day February 21 calendar year 2001, the patent of invention name is called " method of polymkeric substance diazo coupling method synthetic epoxy resin family macromolecule dyestuff ", it is macromolecular scaffold that this application case discloses with the epoxy resin primary polymer, prepare diazonium salt with aromatic amino compound, adopt the diazo coupling legal system to be equipped with the method for epoxy resin high molecular dye, this method is improved the anti-infiltration and the resistance to migration of dyestuff, its weak point is that the high molecular dye of preparation do not have can be further and the active group of dyeing substrate reactions, degree of fixation is not high, part high molecular dye poorly water-soluble.Chinese patent publication number CN 1205350A, open day on January 20th, 1999, the patent of invention name is called " protein high molecular dye ", this application case discloses to contain amino protein high molecular and has done macromolecular scaffold, but by make in the protein high molecular amino with have the reactive group dye matrix and carry out chemical reaction, make a kind of protein high molecular dye, reaction principle is equivalent to dyestuff protein high molecular is dyeed, its weak point be protein high molecular dye do not have can with dyeing substrate reactions group, in its use, need to add the crosslinked fixation of finishing of linking agent.
Although high molecular dye earns widespread respect, it is actually rare to can be used for actual high molecular dye product.Up to the present, also do not have to find about adopting the diazo coupling legal system to be equipped with the report of water-soluble vinyl sulfone epoxy resin-matrix macromolecule reactive dye aspect.
Summary of the invention
Problem at above-mentioned existence, the purpose of this invention is to provide a kind of method that adopts the diazo coupling legal system to be equipped with water-soluble vinyl sulfone epoxy resin-matrix macromolecule reactive dye, start with from Molecular Structure Design, having proposed with the Resins, epoxy precursor that has the functional group that can carry out diazo coupling reaction is high polymer main chain, hydroxyethyl sulfone sulfate class arylamine is prepared into diazonium salt, coupled reaction by Resins, epoxy precursor and diazonium salt, can directly prepare water-soluble vinyl sulfone epoxy resin-matrix macromolecule reactive dye, its technical solution is carried out according to the following steps:
(1) preparation of epoxy resin precursor
The epoxy resin precursor is the Resins, epoxy family macromolecule that has functional group's (aniline residue) that can carry out diazo coupling reaction, and its general structural formula is shown in (c).At 110～130 ℃, reaction obtains the Resins, epoxy precursor under the nitrogen protection condition by Resins, epoxy and aniline.
Wherein (a) is Resins, epoxy, and any in bisphenol-A diglycidylether, bisphenol-f diglycidylether or bis-phenol-H diglycidylether, the R in the following formula are a kind of in the following structure:
Wherein (b) is aniline,
The preparation method of Resins, epoxy precursor is as follows: at N
2Protection down, by molar weight than being Resins, epoxy: aniline=1: 1 slowly is warming up to 110～130 ℃ with above-mentioned any one Resins, epoxy and aniline uniform mixing, and insulation reaction made the Resins, epoxy precursor more than 72 hours.
(2) adopt following any method to obtain ethyl sulfonyl sulfate class arylamine diazonium salt solution, reaction formula is as follows:
Y=HSO wherein
4Or Cl
Being used for carrying out diazotizing hydroxyethyl sulfone sulfate class arylamine has: P-aminoazobenzene-β hydroxyethyl sulfone sulfate, a beta-sulfuric ester ethyl sulfonyl base aniline, 2-anisidine-4-β hydroxyethyl sulfone sulfate, 2-benzaminic acid-4-β hydroxyethyl sulfone sulfate, 4-β hydroxyethyl sulfone sulfate ester aniline-2-sulfonic acid, 2-[2-(3-aminobenzoyl amido) ethyl sulfuryl] ethanol sulfuric ester, 6-β hydroxyethyl sulfone sulfate-2-naphthylamines-1-sulfonic acid etc., wherein Ar is a kind of in the following structure
Diazonium salt solution preparation method 1: under 0 ℃ of condition, compare Ar-NH by molar weight
2: H
2SO
4=1: 2.5～3, get massfraction and be 30% sulphuric acid soln; Hydroxyethyl sulfone sulfate class arylamine is added water mix, add 10%Na
2CO
3Solution, regulation system pH is 6～7, is stirred to arylamine and dissolves fully, compares Ar-NH by molar weight
2: NaNO
2Add Sodium Nitrite solid at=1: 1～1.2, is stirred to fully slowly to be added drop-wise in the above-mentioned sulphuric acid soln after the dissolving, is terminal point when being stirred to no unhindered amina, standby;
Diazonium salt solution preparation method 2: under 0 ℃ of condition, compare Ar-NH by molar weight
2: HCl=1: 2.5～3 to get volume ratio be 1: 10 hydrochloric acid soln; Hydroxyethyl sulfone sulfate class arylamine is added water mix, add 10%Na
2CO
3Solution, regulation system pH is 6～7, is stirred to arylamine and dissolves fully, compares Ar-NH by molar weight
2: NaNO
2Add Sodium Nitrite solid at=1: 1～1.2, is stirred to fully slowly to be added drop-wise in the above-mentioned hydrochloric acid soln after the dissolving, is terminal point when being stirred to no unhindered amina, standby;
(3) diazo coupling reaction of Resins, epoxy precursor and ethyl sulfonyl sulfate class arylamine diazonium salt:
In ice-water bath, with above-mentioned Resins, epoxy precursor N, dinethylformamide (DMF) solvent dissolves fully, under high-speed stirring, by molar weight than ethyl sulfonyl sulfate class arylamine diazonium salt: Resins, epoxy precursor=0.4～1.2: 1, above-mentioned ethyl sulfonyl sulfate class arylamine diazonium salt solution is slowly joined in the above-mentioned Resins, epoxy precursor solution, 0 ℃ of left and right sides insulation reaction more than 12 hours, after reaction is finished, after precipitation, filtration, washing and drying, get water-soluble vinyl sulfone epoxy resin-matrix macromolecule reactive dye, its general reaction formula is as follows
Owing to adopted above technical scheme, diazo coupling legal system of the present invention is equipped with the method for water-soluble vinyl sulfone epoxy resin-matrix macromolecule reactive dye, this method synthetic route is simple, functionality is easy to control, the coupled reaction transformation efficiency can be up to more than 90%, through simple purification process, can directly obtain the water-soluble how active epoxy resin-matrix macromolecule dyestuff of various lovely lusters.
Water-soluble vinyl sulfone epoxy resin-matrix macromolecule reactive dye of the present invention, contain water-soluble sulfate group on the molecular chain, the good water solubility of high molecular dye is dissolvable in water in the water, reduce the use of organic solvent, can be used as the tinting material component of digital ink-jet printed ink.
Water-soluble vinyl sulfone epoxy resin-matrix macromolecule reactive dye of the present invention, the ethyl sulfone group that contains a plurality of lateral reactivities on the molecular chain, under alkaline condition, the vinyl sulfone(Remzaol active group that forms can form by covalent linkage with the dyeing substrate that contains reactive groups such as hydroxyl and amino finishes fixation, solve problems such as painted fastness and colourity, the dyeing of materials such as cotton, fiber crops, silk, hair, leather, paper can be widely used in, colour fastness to rubbing and the water-fast high product dyed thereby of colour fastness grade of washing can be obtained.Have neither part nor lot in the high molecular dye of reaction, can become not water-soluble hydroxyethyl sulfone type high molecular dye in hydrolysis under the alkaline condition, through staticly settling, filter, wash, dry, recyclable hydroxyethyl sulfone type high molecular dye, reduce coloured liquid discharging, reduced environmental pollution.
Water-soluble vinyl sulfone epoxy resin-matrix macromolecule reactive dye of the present invention, with Resins, epoxy is the high molecular dye skeleton, good with the consistency of superpolymer, dye coloring power is strong, Dry Sack is bright-coloured, solvent resistance, resistance to migration is good and the less molecular dye of thermotolerance improves greatly, can be used as the tinting material and the weighting agent of materials such as plastics, rubber, coating, binding agent.
Water-soluble vinyl sulfone epoxy resin-matrix macromolecule dyestuff of the present invention, the molecular weight height can not be seen through by cytolemma, so be difficult for being absorbed by organism, has reduced the harm to organism.
Patent of the present invention is compared with " method of polymkeric substance diazo coupling method synthetic epoxy resin family macromolecule dyestuff " with Chinese patent " protein high molecular dye ", high molecular dye of the present invention is water-soluble how active high molecular dye, the high molecular dye good water solubility of preparation, to textile dyeing fastness height such as cotton, fiber crops, silk, hairs, and the discharging of coloured liquid is low.
Embodiment
Below in conjunction with specific embodiment the present invention is done and to describe in further detail.
Embodiment 1
Get 196.0 gram (0.5mol) dihydroxyphenyl propane-diglycidylethers (epoxy equivalent (weight)=196) and 46.5 gram aniline (0.5mol), after mixing, at N
2Slowly be warming up under the condition about 110 ℃, insulation reaction got white transparent epoxy resin class precursor solid after 72 hours.
Get the 1.65mL vitriol oil, join in the 10mL water, mix, it is standby to make temperature be reduced to 0 ℃ of left and right sides.Getting 3.51 gram (0.012mol) P-aminoazobenzene-β hydroxyethyl sulfone sulfates (para-ester) joins in the 30mL water, add 10% sodium carbonate solution then, regulation system pH is 6～7, being stirred to para-ester dissolves fully, add 0.836 gram 99% (0.012mol) Sodium Nitrite solid, stirring slowly is added drop-wise in the above-mentioned sulphuric acid soln after it is dissolved fully, is terminal point when being stirred to no unhindered amina.
Get 4.85 gram (0.01mol) above-mentioned Resins, epoxy precursor, add 400mLN, N '-dimethyl formamide, stirring places ice-water bath after it is dissolved fully, and temperature is reduced to about 0 ℃, slowly drip above-mentioned para-ester diazonium salt solution, about 12 hours,, get water-soluble vinyl sulfone epoxy resin-matrix macromolecule reactive dye 0 ℃ of following insulation reaction through precipitation, filtration, washing and drying treatment.
Embodiment 2
Adopt identical Resins, epoxy precursor among the embodiment 1.Get epoxy resin precursor identical among the embodiment 1 4.85 grams (0.01mol), add 400mLN, N '-dimethyl formamide, stirring is reduced to about 0 ℃ with the temperature of ice-water bath with solution after making its dissolving fully.
Get the 3mL36.5% concentrated hydrochloric acid, join in the 30mL water, mix, it is standby to make temperature be reduced to 0 ℃ of left and right sides.Getting 3.51 gram (0.012mol) para-esters joins in the 30mL water, add 10% sodium carbonate solution then, regulation system pH is 6～7, being stirred to para-ester dissolves fully, add 0.836 gram 99% (0.012mol) Sodium Nitrite solid, stirring slowly is added drop-wise in the above-mentioned hydrochloric acid soln after it is dissolved fully, is terminal point when being stirred to no unhindered amina.
Above-mentioned diazonium salt solution slowly is added drop-wise in the above-mentioned Resins, epoxy precursor solution, about 12 hours,, gets water-soluble vinyl sulfone epoxy resin-matrix macromolecule reactive dye through precipitation, filtration, washing and drying treatment 0 ℃ of following insulation reaction.
Embodiment 3
Adopt identical Resins, epoxy precursor among the embodiment 1.Get epoxy resin precursor identical among the embodiment 1 4.85 grams (0.01mol), add 400mLN, N '-dimethyl formamide, stirring is reduced to about 0 ℃ with the temperature of ice-water bath with solution after making its dissolving fully.
Get the 0.40mL vitriol oil, join in the 10mL water, mix, it is standby to make temperature be reduced to 0 ℃ of left and right sides.Getting 0.732 gram (2.5mmol) 96% (para-ester) joins in the 30mL water, add 10% sodium carbonate solution then, regulation system pH is 6～7, being stirred to para-ester dissolves fully, add 0.174 gram 99% (2.5mmol) Sodium Nitrite solid, slowly be added drop-wise to above-mentioned sulphuric acid soln after being stirred to fully dissolving, be terminal point when being stirred to no unhindered amina.
Above-mentioned diazonium salt solution slowly is added drop-wise in the above-mentioned Resins, epoxy precursor solution, about 12 hours,, gets water-soluble vinyl sulfone epoxy resin-matrix macromolecule reactive dye through precipitation, filtration, washing and drying treatment 0 ℃ of following insulation reaction.
Embodiment 4
Adopt identical Resins, epoxy precursor among the embodiment 1.Get epoxy resin precursor identical among the embodiment 1 4.85 grams (0.01mol), add 400mLN, N '-dimethyl formamide, stirring is reduced to about 0 ℃ with the temperature of ice-water bath with solution after making its dissolving fully.
Get the 1.60mL vitriol oil, join in the 10mL water, mix, it is standby to make temperature be reduced to 0 ℃ of left and right sides.Getting 2.92 gram (0.01mol) para-esters joins in the 30mL water, add 10% sodium carbonate solution then, regulation system pH is 6～7, being stirred to para-ester dissolves fully, add 0.697 gram 99% (0.01mol) Sodium Nitrite solid, slowly be added drop-wise in the above-mentioned sulphuric acid soln after being stirred to fully dissolving, be terminal point when being stirred to no unhindered amina.
Above-mentioned diazonium salt solution slowly is added drop-wise in the above-mentioned Resins, epoxy precursor solution, about 12 hours,, gets water soluble vinyl-sulfone polyurethane class high molecular reactive dye through precipitation, filtration, washing and drying treatment 0 ℃ of following insulation reaction.
Embodiment 5
Adopt identical Resins, epoxy precursor among the embodiment 1.Get epoxy resin precursor identical among the embodiment 1 4.85 grams (0.01mol), add 400mLN, N '-dimethyl formamide, stirring is reduced to about 0 ℃ with the temperature of ice-water bath with solution after making its dissolving fully.
Get the 1.65mL vitriol oil, join in the 10mL water, mix, it is back standby that temperature is reduced to about 0 ℃.Join in the 30mL water by beta-sulfuric ester ethyl sulfonyl base aniline (a position ester) between 3.51 grams (0.012mol), add 10% sodium carbonate solution then, regulation system pH is 6～7, being stirred to it dissolves fully, add 0.836 gram 99% (0.012mol) Sodium Nitrite solid, slowly be added drop-wise in the above-mentioned sulphuric acid soln after being stirred to fully dissolving, be terminal point when being stirred to no unhindered amina.
Above-mentioned diazonium salt solution slowly is added drop-wise in the above-mentioned Resins, epoxy precursor solution, about 12 hours,, gets water-soluble vinyl sulfone epoxy resin-matrix macromolecule reactive dye through precipitation, filtration, washing and drying treatment 0 ℃ of following insulation reaction.
Embodiment 6
Adopt identical Resins, epoxy precursor among the embodiment 1.Get epoxy resin precursor identical among the embodiment 1 4.85 grams (0.01mol), add 400mLN, N '-dimethyl formamide, stirring is reduced to about 0 ℃ with the temperature of ice-water bath with solution after making its dissolving fully.
Get the 1.65mL vitriol oil, join in the 10mL water, mix, it is back standby that temperature is reduced to about 0 ℃.Join in the 30mL water by 3.732 gram (0.012mol) 2-anisidine-4-β hydroxyethyl sulfone sulfates, add 10% sodium carbonate solution then, regulation system pH is 6～7, being stirred to it dissolves fully, add 0.836 gram 99% (0.012mol) Sodium Nitrite solid, slowly be added drop-wise in the above-mentioned sulphuric acid soln after being stirred to fully dissolving, be terminal point when being stirred to no unhindered amina.
Above-mentioned diazonium salt solution slowly is added drop-wise in the above-mentioned Resins, epoxy precursor solution, about 12 hours,, gets water-soluble vinyl sulfone epoxy resin-matrix macromolecule reactive dye through precipitation, filtration, washing and drying treatment 0 ℃ of following insulation reaction.
Embodiment 7
Adopt identical Resins, epoxy precursor among the embodiment 1.Get epoxy resin precursor identical among the embodiment 1 4.85 grams (0.01mol), add 400mLN, N '-dimethyl formamide, stirring is reduced to about 0 ℃ with the temperature of ice-water bath with solution after making its dissolving fully.
Get the 1.65mL vitriol oil, join in the 10mL water, mix, it is back standby that temperature is reduced to about 0 ℃.Join in the 30mL water by 3.732 gram (0.012mol) 2-benzaminic acid-4-β hydroxyethyl sulfone sulfates, add 10% sodium carbonate solution then, regulation system pH is 6～7, being stirred to it dissolves fully, add 0.836 gram 99% (0.012mol) Sodium Nitrite solid, slowly be added drop-wise in the above-mentioned sulphuric acid soln after being stirred to fully dissolving, be terminal point when being stirred to no unhindered amina.
Above-mentioned diazonium salt solution slowly is added drop-wise in the above-mentioned Resins, epoxy precursor solution, about 12 hours,, gets water-soluble vinyl sulfone epoxy resin-matrix macromolecule reactive dye through precipitation, filtration, washing and drying treatment 0 ℃ of following insulation reaction.
Embodiment 8
Adopt identical Resins, epoxy precursor among the embodiment 1.Get epoxy resin precursor identical among the embodiment 1 4.85 grams (0.01mol), add 400mLN, N '-dimethyl formamide, stirring is reduced to about 0 ℃ with the temperature of ice-water bath with solution after making its dissolving fully.
Get the 1.65mL vitriol oil, join in the 10mL water, mix, it is back standby that temperature is reduced to about 0 ℃.Join in the 30mL water by 4.332 gram (0.012mol) 4-β hydroxyethyl sulfone sulfate ester aniline-2-sulfonic acid (sulfonation para-ester), add 10% sodium carbonate solution then, regulation system pH is 6～7, being stirred to it dissolves fully, add 0.836 gram 99% (0.012mol) Sodium Nitrite solid, slowly be added drop-wise in the above-mentioned sulphuric acid soln after being stirred to fully dissolving, be terminal point when being stirred to no unhindered amina.
Above-mentioned diazonium salt solution slowly is added drop-wise in the above-mentioned Resins, epoxy precursor solution, about 12 hours,, gets water-soluble vinyl sulfone epoxy resin-matrix macromolecule reactive dye through precipitation, filtration, washing and drying treatment 0 ℃ of following insulation reaction.
Embodiment 9
Adopt identical Resins, epoxy precursor among the embodiment 1.Get epoxy resin precursor identical among the embodiment 1 4.85 grams (0.01mol), add 400mLN, N '-dimethyl formamide, stirring is reduced to about 0 ℃ with the temperature of ice-water bath with solution after making its dissolving fully.
Get the 1.65mL vitriol oil, join in the 10mL water, mix, it is back standby that temperature is reduced to about 0 ℃.Get 4.229 gram (0.012mol) 2-[2-(3-aminobenzoyl amido) ethyl sulfuryls] the ethanol sulfuric ester joins in the 30mL water, add 10% sodium carbonate solution then, regulation system pH is 6～7, being stirred to it dissolves fully, add 0.836 gram 99% (0.012mol) Sodium Nitrite solid again, slowly be added drop-wise in the above-mentioned sulphuric acid soln after being stirred to fully dissolving, be terminal point when being stirred to no unhindered amina.
Above-mentioned diazonium salt solution slowly is added drop-wise in the above-mentioned Resins, epoxy precursor solution, about 12 hours,, gets water-soluble vinyl sulfone epoxy resin-matrix macromolecule reactive dye through precipitation, filtration, washing and drying treatment 0 ℃ of following insulation reaction.
Embodiment 10
Adopt identical Resins, epoxy precursor among the embodiment 1.Get epoxy resin precursor identical among the embodiment 1 4.85 grams (0.01mol), add 400mLN, N '-dimethyl formamide, stirring is reduced to about 0 ℃ with the temperature of ice-water bath with solution after making its dissolving fully.
Get the 1.65mL vitriol oil, join in the 10mL water, mix, it is back standby that temperature is reduced to about 0 ℃.Getting 3.016 gram (0.012mol) 6-β hydroxyethyl sulfone sulfate-2-naphthylamines-1-sulfonic acid joins in the 30mL water, add 10% sodium carbonate solution then, regulation system pH is 6～7, being stirred to it dissolves fully, add 0.836 gram 99% (0.012mol) Sodium Nitrite solid again, slowly be added drop-wise in the above-mentioned sulphuric acid soln after being stirred to fully dissolving, be terminal point when being stirred to no unhindered amina.
Above-mentioned diazonium salt solution slowly is added drop-wise in the above-mentioned Resins, epoxy precursor solution, about 12 hours,, gets water-soluble vinyl sulfone epoxy resin-matrix macromolecule reactive dye through precipitation, filtration, washing and drying treatment 0 ℃ of following insulation reaction.
Embodiment 11
Get 180.0 gram (0.5mol) bisphenol-f diglycidylethers (epoxy equivalent (weight)=180) and 46.5 gram aniline (0.5mo1), after mixing, at N
2Slowly be warming up under the condition about 110 ℃, insulation reaction got white transparent epoxy resin class precursor solid after 72 hours.
Get the 1.65mL vitriol oil, join in the 10mL water, mix, it is back standby that temperature is reduced to about 0 ℃.Getting 3.51 gram (0.012mol) para-esters joins in the 30mL water, add 10% sodium carbonate solution then, regulation system pH is 6～7, being stirred to para-ester dissolves fully, add 0.836 gram 99% (0.012mol) Sodium Nitrite solid again, slowly be added drop-wise in the above-mentioned sulphuric acid soln after being stirred to fully dissolving, be terminal point when being stirred to no unhindered amina.
Get above-mentioned epoxy resin precursor 4.53 grams (0.01mol), use 300mL N, N '-dimethyl formamide dissolving is reduced to about 0 ℃ with the temperature of ice-water bath with solution the back fully.Slowly drip above-mentioned diazonium salt solution, about 12 hours,, get water-soluble vinyl sulfone epoxy resin family macromolecule reactive dyestuffs through precipitation, filtration, washing and drying treatment 0 ℃ of following insulation reaction.
Embodiment 12
Adopt identical Resins, epoxy precursor among the embodiment 11.Get epoxy resin precursor identical among the embodiment 11 4.53 grams (0.01mol), use 300mLN, N '-dimethyl formamide dissolving is reduced to about 0 ℃ with the temperature of ice-water bath with solution the back fully.
Get the 3mL36.5% concentrated hydrochloric acid, join in the 30mL water, mix, it is back standby that temperature is reduced to about 0 ℃.Getting 3.51 gram (0.012mol) para-esters joins in the 30mL water, add 10% sodium carbonate solution then, regulation system pH is 6～7, being stirred to para-ester dissolves fully, add 0.836 gram 99% (0.012mol) Sodium Nitrite solid again, slowly be added drop-wise in the above-mentioned hydrochloric acid soln after being stirred to fully dissolving, be terminal point when being stirred to no unhindered amina.
Above-mentioned diazonium salt solution slowly is added drop-wise in the above-mentioned Resins, epoxy precursor solution, about 12 hours,, gets water-soluble vinyl sulfone epoxy resin-matrix macromolecule reactive dye through precipitation, filtration, washing and drying treatment 0 ℃ of following insulation reaction.
Embodiment 13
Adopt identical Resins, epoxy precursor among the embodiment 11.Get epoxy resin precursor identical among the embodiment 11 4.53 grams (0.01mol), use 300mLN, N '-dimethyl formamide dissolving is reduced to about 0 ℃ with the temperature of ice-water bath with solution the back fully.
Get the 0.40mL vitriol oil, join in the 10mL water, mix, it is back standby that temperature is reduced to about 0 ℃.Getting 0.732 gram (2.5mmol) para-ester joins in the 30mL water, add 10% sodium carbonate solution then, regulation system pH is 6～7, being stirred to para-ester dissolves fully, add 0.174 gram 99% (2.5mmol) Sodium Nitrite solid again, be stirred to fully the dissolving back and slowly drip above-mentioned solution, be terminal point when being stirred to no unhindered amina.
Above-mentioned diazonium salt solution slowly is added drop-wise in the above-mentioned Resins, epoxy precursor solution, about 12 hours,, gets water-soluble vinyl sulfone epoxy resin-matrix macromolecule reactive dye through precipitation, filtration, washing and drying treatment 0 ℃ of following insulation reaction.
Embodiment 14
Adopt identical Resins, epoxy precursor among the embodiment 11.Get epoxy resin precursor identical among the embodiment 11 4.53 grams (0.01mol), use 300mLN, N '-dimethyl formamide dissolving is reduced to about 0 ℃ with the temperature of ice-water bath with solution the back fully.
Get the 1.60mL vitriol oil, join in the 10mL water, mix, it is back standby that temperature is reduced to about 0 ℃.Getting 2.92 gram (0.01mol) para-esters joins in the 30mL water, add 10% sodium carbonate solution then, regulation system pH is 6～7, being stirred to para-ester dissolves fully, add 0.697 gram 99% (0.01mol) Sodium Nitrite solid again, slowly be added drop-wise in the above-mentioned sulphuric acid soln after being stirred to fully dissolving, be terminal point when being stirred to no unhindered amina.
Above-mentioned diazonium salt solution slowly is added drop-wise in the above-mentioned Resins, epoxy precursor solution, about 12 hours,, gets water-soluble vinyl sulfone epoxy resin-matrix macromolecule reactive dye through precipitation, filtration, washing and drying treatment 0 ℃ of following insulation reaction.
Embodiment 15
Adopt identical Resins, epoxy precursor among the embodiment 11.Get epoxy resin precursor identical among the embodiment 11 4.53 grams (0.01mol), use 300mLN, N '-dimethyl formamide dissolving is reduced to about 0 ℃ with the temperature of ice-water bath with solution the back fully.
Get the 1.65mL vitriol oil, join in the 10mL water, mix, it is back standby that temperature is reduced to about 0 ℃.Get 3.51 the gram (0.012mol) between the position ester join in the 30mL water, add 10% sodium carbonate solution then, regulation system pH is 6～7, being stirred to it dissolves fully, add 0.836 gram 99% (0.012mol) Sodium Nitrite solid again, be stirred to fully the dissolving back and slowly drip in the above-mentioned sulphuric acid soln, be terminal point when being stirred to no unhindered amina.
Above-mentioned diazonium salt solution slowly is added drop-wise in the above-mentioned Resins, epoxy precursor solution, about 12 hours,, gets water-soluble vinyl sulfone epoxy resin-matrix macromolecule reactive dye through precipitation, filtration, washing and drying treatment 0 ℃ of following insulation reaction.
Embodiment 16
Adopt identical Resins, epoxy precursor among the embodiment 11.Get epoxy resin precursor identical among the embodiment 11 4.53 grams (0.01mol), use 300mLN, N '-dimethyl formamide dissolving is reduced to about 0 ℃ with the temperature of ice-water bath with solution the back fully.
Get the 1.65mL vitriol oil, join in the 10mL water, mix, it is back standby that temperature is reduced to about 0 ℃.Getting 3.732 gram (0.012mol) 2-anisidine-4-β hydroxyethyl sulfone sulfates joins in the 30mL water, add 10% sodium carbonate solution then, regulation system pH is 6～7, being stirred to it dissolves fully, add 0.836 gram 99% (0.012mol) Sodium Nitrite solid again, slowly be added drop-wise in the above-mentioned sulphuric acid soln after being stirred to fully dissolving, be terminal point when being stirred to no unhindered amina.
Above-mentioned diazonium salt solution slowly is added drop-wise in the above-mentioned Resins, epoxy precursor solution, about 12 hours,, gets water-soluble vinyl sulfone epoxy resin-matrix macromolecule reactive dye through precipitation, filtration, washing and drying treatment 0 ℃ of following insulation reaction.
Embodiment 17
Adopt identical Resins, epoxy precursor among the embodiment 11.Get epoxy resin precursor identical among the embodiment 11 4.53 grams (0.01mol), use 300mL N, N '-dimethyl formamide dissolving is reduced to about 0 ℃ with the temperature of ice-water bath with solution the back fully.
Get the 1.65mL vitriol oil, join in the 10mL water, mix, it is back standby that temperature is reduced to about 0 ℃.Getting 3.732 gram (0.012mol) 2-benzaminic acid-4-β hydroxyethyl sulfone sulfates joins in the 30mL water, add 10% sodium carbonate solution then, regulation system pH is 6～7, being stirred to it dissolves fully, add 0.836 gram 99% (0.012mol) Sodium Nitrite solid again, slowly be added drop-wise in the above-mentioned sulphuric acid soln after being stirred to fully dissolving, be terminal point when being stirred to no unhindered amina.
Above-mentioned diazonium salt solution slowly is added drop-wise in the above-mentioned Resins, epoxy precursor solution, about 12 hours,, gets water-soluble vinyl sulfone epoxy resin-matrix macromolecule reactive dye through precipitation, filtration, washing and drying treatment 0 ℃ of following insulation reaction.
Embodiment 18
Adopt identical Resins, epoxy precursor among the embodiment 11.Get epoxy resin precursor identical among the embodiment 11 4.53 grams (0.01mol), use 300mL N, N '-dimethyl formamide dissolving is reduced to about 0 ℃ with the temperature of ice-water bath with solution the back fully.
Get the 1.65mL vitriol oil, join in the 10mL water, mix, it is back standby that temperature is reduced to about 0 ℃.Getting 4.332 gram (0.012mol) 4-β hydroxyethyl sulfone sulfate ester aniline-2-sulfonic acid (sulfonation para-ester) joins in the 30mL water, add 10% sodium carbonate solution then, regulation system pH is 6～7, being stirred to it dissolves fully, add 0.836 gram 99% (0.012mol) Sodium Nitrite solid again, be stirred to fully the dissolving back and slowly drip above-mentioned solution, be terminal point when being stirred to no unhindered amina.
Above-mentioned diazonium salt solution slowly is added drop-wise in the above-mentioned Resins, epoxy precursor solution, about 12 hours,, gets water-soluble vinyl sulfone epoxy resin-matrix macromolecule reactive dye through precipitation, filtration, washing and drying treatment 0 ℃ of following insulation reaction.
Embodiment 19
Adopt identical Resins, epoxy precursor among the embodiment 11.Get epoxy resin precursor identical among the embodiment 11 4.53 grams (0.01mol), use 300mLN, N '-dimethyl formamide dissolving is reduced to about 0 ℃ with the temperature of ice-water bath with solution the back fully.
Get the 1.65mL vitriol oil, join in the 10mL water, mix, it is back standby that temperature is reduced to about 0 ℃.Get 4.229 gram (0.012mol) 2-[2-(3-aminobenzoyl amido) ethyl sulfuryls] the ethanol sulfuric ester joins in the 30mL water, add 10% sodium carbonate solution then, regulation system pH is 6～7, being stirred to it dissolves fully, add 0.836 gram 99% (0.012mol) Sodium Nitrite solid again, slowly be added drop-wise in the above-mentioned sulphuric acid soln after being stirred to fully dissolving, be terminal point when being stirred to no unhindered amina.
Above-mentioned diazonium salt solution slowly is added drop-wise in the above-mentioned Resins, epoxy precursor solution, about 12 hours,, gets water-soluble vinyl sulfone epoxy resin-matrix macromolecule reactive dye through precipitation, filtration, washing and drying treatment 0 ℃ of following insulation reaction.
Embodiment 20
Adopt identical Resins, epoxy precursor among the embodiment 11.Get epoxy resin precursor identical among the embodiment 11 4.53 grams (0.01mol), use 300mLN, N '-dimethyl formamide dissolving is reduced to about 0 ℃ with the temperature of ice-water bath with solution the back fully.
Get the 1.65mL vitriol oil, join in the 10mL water, mix, it is back standby that temperature is reduced to about 0 ℃.Join in the 30mL water by 3.016 gram (0.012mol) 6-β hydroxyethyl sulfone sulfate-2-naphthylamines-1-sulfonic acid, add 10% sodium carbonate solution then, regulation system pH is 6～7, being stirred to it dissolves fully, add 0.836 gram 99% (0.012mol) Sodium Nitrite solid again, slowly be added drop-wise in the above-mentioned sulphuric acid soln after being stirred to fully dissolving, be terminal point when being stirred to no unhindered amina.
Above-mentioned diazonium salt solution slowly is added drop-wise in the above-mentioned Resins, epoxy precursor solution, about 12 hours,, gets water-soluble vinyl sulfone epoxy resin-matrix macromolecule reactive dye through precipitation, filtration, washing and drying treatment 0 ℃ of following insulation reaction.
Embodiment 21
Get 240.0 gram (0.5mol) bis-phenol-H diglycidylethers (epoxy equivalent (weight)=240) and 46.5 gram aniline (0.5mol), after mixing, at N
2Slowly be warming up under the condition about 110 ℃, insulation reaction got white transparent epoxy resin class precursor solid after 72 hours.
Get the 1.65mL vitriol oil, join in the 10mL water, mix, it is back standby that temperature is reduced to about 0 ℃.Getting 3.51 gram (0.012mol) para-esters joins in the 30mL water, add 10% sodium carbonate solution then, regulation system pH is 6～7, being stirred to para-ester dissolves fully, add 0.836 gram 99% (0.012mol) Sodium Nitrite solid again, slowly be added drop-wise in the above-mentioned sulphuric acid soln after being stirred to fully dissolving, be terminal point when being stirred to no unhindered amina.
Get above-mentioned epoxy resin precursor 5.73 grams (0.01mol), use 400mL N, N '-dimethyl formamide dissolving is reduced to about 0 ℃ with the temperature of ice-water bath with solution the back fully.Slowly drip above-mentioned diazonium salt solution, about 12 hours,, get water-soluble vinyl sulfone epoxy resin family macromolecule reactive dyestuffs through precipitation, filtration, washing and drying treatment 0 ℃ of following insulation reaction.
Embodiment 22
Adopt identical Resins, epoxy precursor among the embodiment 21.Get epoxy resin precursor identical among the embodiment 21 5.73 grams (0.01mol), use 300mLN, N '-dimethyl formamide dissolving is reduced to about 0 ℃ with the temperature of ice-water bath with solution the back fully.
Get the 3mL36.5% concentrated hydrochloric acid, join in the 30mL water, mix, it is back standby that temperature is reduced to about 0 ℃.Getting 3.51 gram (0.012mol) para-esters joins in the 30mL water, add 10% sodium carbonate solution then, regulation system pH is 6～7, being stirred to para-ester dissolves fully, add 0.836 gram 99% (0.012mol) Sodium Nitrite solid again, slowly be added drop-wise in the above-mentioned hydrochloric acid soln after being stirred to fully dissolving, be terminal point when being stirred to no unhindered amina.
Above-mentioned diazonium salt solution slowly is added drop-wise in the above-mentioned Resins, epoxy precursor solution, about 12 hours,, gets water-soluble vinyl sulfone epoxy resin-matrix macromolecule reactive dye through precipitation, filtration, washing and drying treatment 0 ℃ of following insulation reaction.
Embodiment 23
Adopt identical Resins, epoxy precursor among the embodiment 21.Get epoxy resin precursor identical among the embodiment 21 5.73 grams (0.01mol), use 300mLN, N '-dimethyl formamide dissolving is reduced to about 0 ℃ with the temperature of ice-water bath with solution the back fully.
Get the 0.40mL vitriol oil, join in the 10mL water, mix, it is back standby that temperature is reduced to about 0 ℃.Getting 0.732 gram (2.5mmol) para-ester joins in the 30mL water, add 10% sodium carbonate solution then, regulation system pH is 6～7, being stirred to para-ester dissolves fully, add 0.174 gram 99% (2.5mmol) Sodium Nitrite solid again, slowly be added drop-wise in the above-mentioned sulphuric acid soln after being stirred to fully dissolving, be terminal point when being stirred to no unhindered amina.
Above-mentioned diazonium salt solution slowly is added drop-wise in the above-mentioned Resins, epoxy precursor solution, about 12 hours,, gets water-soluble vinyl sulfone epoxy resin-matrix macromolecule reactive dye through precipitation, filtration, washing and drying treatment 0 ℃ of following insulation reaction.
Embodiment 24
Adopt identical Resins, epoxy precursor among the embodiment 21.Get epoxy resin precursor identical among the embodiment 21 5.73 grams (0.01mol), use 300mLN, N '-dimethyl formamide dissolving is reduced to about 0 ℃ with the temperature of ice-water bath with solution the back fully.
Get the 1.60mL vitriol oil, join in the 10mL water, mix, it is back standby that temperature is reduced to about 0 ℃.Getting 2.92 gram (0.01mol) para-esters joins in the 30mL water, add 10% sodium carbonate solution then, regulation system pH is 6～7, being stirred to para-ester dissolves fully, add 0.697 gram 99% (0.01mol) Sodium Nitrite solid again, slowly be added drop-wise in the above-mentioned sulphuric acid soln after being stirred to fully dissolving, be terminal point when being stirred to no unhindered amina.
Above-mentioned diazonium salt solution slowly is added drop-wise in the above-mentioned Resins, epoxy precursor solution, about 12 hours,, gets water-soluble vinyl sulfone epoxy resin-matrix macromolecule reactive dye through precipitation, filtration, washing and drying treatment 0 ℃ of following insulation reaction.
Embodiment 25
Adopt identical Resins, epoxy precursor among the embodiment 21.Get epoxy resin precursor identical among the embodiment 21 5.73 grams (0.01mol), use 300mLN, N '-dimethyl formamide dissolving is reduced to about 0 ℃ with the temperature of ice-water bath with solution the back fully.
Get the 1.65mL vitriol oil, join in the 10mL water, mix, it is back standby that temperature is reduced to about 0 ℃.Join in the 30mL water by position ester between 3.51 grams (0.012mol), add 10% sodium carbonate solution then, regulation system pH is 6～7, being stirred to it dissolves fully, add 0.836 gram 99% (0.012mol) Sodium Nitrite solid again, slowly be added drop-wise in the above-mentioned sulphuric acid soln after being stirred to fully dissolving, be terminal point when being stirred to no unhindered amina.
Above-mentioned diazonium salt solution slowly is added drop-wise in the above-mentioned Resins, epoxy precursor solution, about 12 hours,, gets water-soluble vinyl sulfone epoxy resin-matrix macromolecule reactive dye through precipitation, filtration, washing and drying treatment 0 ℃ of following insulation reaction.
Embodiment 26
Adopt identical Resins, epoxy precursor among the embodiment 21.Get epoxy resin precursor identical among the embodiment 21 5.73 grams (0.01mol), use 300mL N, N '-dimethyl formamide dissolving is reduced to about 0 ℃ with the temperature of ice-water bath with solution the back fully.
Get the 1.65mL vitriol oil, join in the 10mL water, mix, it is back standby that temperature is reduced to about 0 ℃.Getting 3.732 gram (0.012mol) 2-anisidine-4-β hydroxyethyl sulfone sulfates joins in the 30mL water, add 10% sodium carbonate solution then, regulation system pH is 6～7, being stirred to it dissolves fully, add 0.836 gram 99% (0.012mol) Sodium Nitrite solid again, slowly be added drop-wise in the above-mentioned sulphuric acid soln after being stirred to fully dissolving, be terminal point when being stirred to no unhindered amina.
Above-mentioned diazonium salt solution slowly is added drop-wise in the above-mentioned Resins, epoxy precursor solution, about 12 hours,, gets water-soluble vinyl sulfone epoxy resin-matrix macromolecule reactive dye through precipitation, filtration, washing and drying treatment 0 ℃ of following insulation reaction.
Embodiment 27
Adopt identical Resins, epoxy precursor among the embodiment 21.Get epoxy resin precursor identical among the embodiment 21 5.73 grams (0.01mol), use 300mLN, N '-dimethyl formamide dissolving is reduced to about 0 ℃ with the temperature of ice-water bath with solution the back fully.
Get the 1.65mL vitriol oil, join in the 10mL water, mix, it is back standby that temperature is reduced to about 0 ℃.Getting 3.732 gram (0.012mol) 2-benzaminic acid-4-β hydroxyethyl sulfone sulfates joins in the 30mL water, add 10% sodium carbonate solution then, regulation system pH is 6～7, being stirred to it dissolves fully, add 0.836 gram 99% (0.012mol) Sodium Nitrite solid again, slowly be added drop-wise in the above-mentioned sulphuric acid soln after being stirred to fully dissolving, be terminal point when being stirred to no unhindered amina.
Above-mentioned diazonium salt solution slowly is added drop-wise in the above-mentioned Resins, epoxy precursor solution, about 12 hours,, gets water-soluble vinyl sulfone epoxy resin-matrix macromolecule reactive dye through precipitation, filtration, washing and drying treatment 0 ℃ of following insulation reaction.
Embodiment 28
Adopt identical Resins, epoxy precursor among the embodiment 21.Get epoxy resin precursor identical among the embodiment 21 5.73 grams (0.01mol), use 300mL N, N '-dimethyl formamide dissolving is reduced to about 0 ℃ with the temperature of ice-water bath with solution the back fully.
Get the 1.65mL vitriol oil, join in the 10mL water, mix, it is back standby that temperature is reduced to about 0 ℃.Getting 4.332 gram (0.012mol) 4-β hydroxyethyl sulfone sulfate ester aniline-2-sulfonic acid (sulfonation para-ester) joins in the 30mL water, add 10% sodium carbonate solution then, regulation system pH is 6～7, being stirred to it dissolves fully, add 0.836 gram 99% (0.012mol) Sodium Nitrite solid again, slowly be added drop-wise in the above-mentioned sulphuric acid soln after being stirred to fully dissolving, be terminal point when being stirred to no unhindered amina.
Above-mentioned diazonium salt solution slowly is added drop-wise in the above-mentioned Resins, epoxy precursor solution, about 12 hours,, gets water-soluble vinyl sulfone epoxy resin-matrix macromolecule reactive dye through precipitation, filtration, washing and drying treatment 0 ℃ of following insulation reaction.
Embodiment 29
Adopt identical Resins, epoxy precursor among the embodiment 21.Get epoxy resin precursor identical among the embodiment 21 5.73 grams (0.01mol), use 300mLN, N '-dimethyl formamide dissolving is reduced to about 0 ℃ with the temperature of ice-water bath with solution the back fully.
Get the 1.65mL vitriol oil, join in the 10mL water, mix, it is back standby that temperature is reduced to about 0 ℃.Get 4.229 gram (0.012mol) 2-[2-(3-aminobenzoyl amido) ethyl sulfuryls] the ethanol sulfuric ester joins in the 30mL water, add 10% sodium carbonate solution then, regulation system pH is 6～7, being stirred to it dissolves fully, add 0.836 gram 99% (0.012mol) Sodium Nitrite solid again, slowly be added drop-wise in the above-mentioned sulphuric acid soln after being stirred to fully dissolving, be terminal point when being stirred to no unhindered amina.
Above-mentioned diazonium salt solution slowly is added drop-wise in the above-mentioned Resins, epoxy precursor solution, about 12 hours,, gets water-soluble vinyl sulfone epoxy resin-matrix macromolecule reactive dye through precipitation, filtration, washing and drying treatment 0 ℃ of following insulation reaction.
Embodiment 30
Adopt identical Resins, epoxy precursor among the embodiment 21.Get epoxy resin precursor identical among the embodiment 21 5.73 grams (0.01mol), use 300mL N, N '-dimethyl formamide dissolving is reduced to about 0 ℃ with the temperature of ice-water bath with solution the back fully.
Get the 1.65mL vitriol oil, join in the 10mL water, mix, it is back standby that temperature is reduced to about 0 ℃.Getting 3.016 gram (0.012mol) 6-β hydroxyethyl sulfone sulfate-2-naphthylamines-1-sulfonic acid joins in the 30mL water, add 10% sodium carbonate solution then, regulation system pH is 6～7, being stirred to it dissolves fully, add 0.836 gram 99% (0.012mol) Sodium Nitrite solid again, slowly be added drop-wise in the above-mentioned sulphuric acid soln after being stirred to fully dissolving, be terminal point when being stirred to no unhindered amina.
Above-mentioned diazonium salt solution slowly is added drop-wise in the above-mentioned Resins, epoxy precursor solution, about 12 hours,, gets water-soluble vinyl sulfone epoxy resin-matrix macromolecule reactive dye through precipitation, filtration, washing and drying treatment 0 ℃ of following insulation reaction.
Embodiment 31
Get 227.3 gram (0.5mol) dihydroxyphenyl propane-diglycidylethers (epoxy equivalent (weight)=227) and 46.5 gram aniline (0.5mol), after mixing, at N
2Slowly be warming up under the condition about 110 ℃, insulation reaction got white transparent epoxy resin class precursor solid after 72 hours.
Get the 1.65mL vitriol oil, join in the 10mL water, mix, it is back standby that temperature is reduced to about 0 ℃.Getting 3.51 gram (0.012mol) para-esters joins in the 30mL water, add 10% sodium carbonate solution then, regulation system pH is 6～7, being stirred to para-ester dissolves fully, add 0.836 gram 99% (0.012mol) Sodium Nitrite solid again, slowly be added drop-wise in the above-mentioned sulphuric acid soln after being stirred to fully dissolving, be terminal point when being stirred to no unhindered amina.
Get 5.476 gram (0.01mol) above-mentioned Resins, epoxy precursor, add 400mLN, N '-dimethyl formamide, stirring places ice-water bath after it is dissolved fully, and temperature is reduced to about 0 ℃, slowly drip above-mentioned diazonium salt solution, about 12 hours,, get water-soluble vinyl sulfone epoxy resin-matrix macromolecule reactive dye 0 ℃ of following insulation reaction through precipitation, filtration, washing and drying treatment.
Embodiment 32
Get 164.0 gram (0.5mol) bisphenol-f diglycidylethers (epoxy equivalent (weight)=164) and 46.5 gram aniline (0.5mol), after mixing, at N
2Slowly be warming up under the condition about 110 ℃, insulation reaction got white transparent epoxy resin class precursor solid after 72 hours.
Get the 1.65mL vitriol oil, join in the 10mL water, mix, it is back standby that temperature is reduced to about 0 ℃.Getting 3.51 gram (0.012mol) para-esters joins in the 30mL water, add 10% sodium carbonate solution then, regulation system pH is 6～7, being stirred to para-ester dissolves fully, add 0.836 gram 99% (0.012mol) Sodium Nitrite solid again, slowly be added drop-wise in the above-mentioned sulphuric acid soln after being stirred to fully dissolving, be terminal point when being stirred to no unhindered amina.
Get above-mentioned epoxy resin precursor 4.21 grams (0.01mol), use 300mL N, N '-dimethyl formamide dissolving is reduced to about 0 ℃ with the temperature of ice-water bath with solution the back fully.Slowly drip above-mentioned diazonium salt solution, about 12 hours,, get water-soluble vinyl sulfone epoxy resin family macromolecule reactive dyestuffs through precipitation, filtration, washing and drying treatment 0 ℃ of following insulation reaction.
Claims (1)
1. a diazo coupling legal system is equipped with the method for water-soluble vinyl sulfone epoxy resin-matrix macromolecule reactive dye, it is characterized in that: with the Resins, epoxy precursor is high polymer main chain, prepare diazonium salt with hydroxyethyl sulfone sulfate class arylamine, be equipped with water-soluble vinyl sulfone epoxy resin-matrix macromolecule reactive dye by the diazo coupling legal system, this method comprises following step:
(1) preparation of epoxy resin precursor
The Resins, epoxy precursor is the epoxy-based polymer that has functional group's (aniline residue) that can carry out diazo coupling reaction; its general structure is shown in (c); at 110～130 ℃, reaction obtains the Resins, epoxy precursor under the nitrogen protection condition by Resins, epoxy and aniline, and its general reaction formula is as follows
Wherein (a) is Resins, epoxy, and any in bisphenol-A diglycidylether, bisphenol-f diglycidylether or bis-phenol-H diglycidylether, the R in the following formula are a kind of in the following structure,
Wherein (b) is aniline,
The preparation method of Resins, epoxy precursor is as follows: at N
2Protection down, by molar weight than being Resins, epoxy: aniline=1: 1 slowly is warming up to 110～130 ℃ with above-mentioned any one Resins, epoxy and aniline uniform mixing, and insulation reaction made the Resins, epoxy precursor more than 72 hours.
(2) adopt following any method to obtain ethyl sulfonyl sulfate class arylamine diazonium salt solution, reaction equation is as follows:
Y=HSO wherein
4Or Cl,
Being used for carrying out diazotizing hydroxyethyl sulfone sulfate class arylamine has: P-aminoazobenzene-β hydroxyethyl sulfone sulfate, a beta-sulfuric ester ethyl sulfonyl base aniline, 2-anisidine-4-β hydroxyethyl sulfone sulfate, 2-benzaminic acid-4-β hydroxyethyl sulfone sulfate, 4-β hydroxyethyl sulfone sulfate ester aniline-2-sulfonic acid, 2-[2-(3-aminobenzoyl amido) ethyl sulfuryl] ethanol sulfuric ester, 6-β hydroxyethyl sulfone sulfate-2-naphthylamines-1-sulfonic acid etc., wherein Ar is a kind of in the following structure
Diazonium salt solution preparation method 1: under 0 ℃ of condition, compare Ar-NH by molar weight
2: H
2SO
4=1: 2.5～3, it is standby to get massfraction and be 30% sulphuric acid soln, hydroxyethyl sulfone sulfate class arylamine is added water mix, and adds 10%Na
2CO
3Solution, regulation system pH is 6～7, is stirred to arylamine and dissolves fully, compares Ar-NH by molar weight
2: NaNO
2Add Sodium Nitrite solid at=1: 1～1.2, is stirred to fully slowly to be added drop-wise in the above-mentioned sulphuric acid soln after the dissolving, is terminal point when being stirred to no unhindered amina;
Diazonium salt solution preparation method 2: under 0 ℃ of condition, compare Ar-NH by molar weight
2: HCl=1: 2.5～3 to get volume ratio be that 1: 10 hydrochloric acid soln is standby, hydroxyethyl sulfone sulfate class arylamine added water mix, and adds 10%Na
2CO
3Solution, regulation system pH is 6～7, is stirred to arylamine and dissolves fully, compares Ar-NH by molar weight
2: NaNO
2Add Sodium Nitrite solid at=1: 1～1.2, is stirred to fully slowly to be added drop-wise in the above-mentioned hydrochloric acid soln after the dissolving, is terminal point when being stirred to no unhindered amina;
(3) diazo coupling reaction of Resins, epoxy precursor and ethyl sulfone class arylamine diazonium salt:
In ice-water bath, with above-mentioned Resins, epoxy precursor N, the dinethylformamide solvent dissolves fully, under high-speed stirring, by molar weight than ethyl sulfonyl sulfate class arylamine diazonium salt: Resins, epoxy precursor=0.4～1.2: 1, above-mentioned ethyl sulfonyl sulfate class arylamine diazonium salt solution is slowly joined in the above-mentioned Resins, epoxy precursor solution, and more than 12 hours, its general reaction formula is as follows 0 ℃ of left and right sides insulation reaction
After reaction is finished, after precipitation, filtration, washing and drying, get water-soluble vinyl sulfone epoxy resin-matrix macromolecule reactive dye.
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| CN104693385A (en) * | 2015-02-12 | 2015-06-10 | 浙江理工大学 | Trithio ester compounds containing quantitative sulfate ethyl sulfone group, and synthesis method and application 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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| CN104693385A (en) * | 2015-02-12 | 2015-06-10 | 浙江理工大学 | Trithio ester compounds containing quantitative sulfate ethyl sulfone group, and synthesis method and application thereof |
| CN104693385B (en) * | 2015-02-12 | 2017-03-01 | 浙江理工大学 | Trithio ester compounds containing quantitative sulfuric acid ester ethyl sulfone group and its synthetic method and application |
| 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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