CN101787222B - 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 a kind of method that diazotization and coupling prepares water-soluble vinyl sulfone epoxy resin-matrix macromolecule reactive dye, belong to high molecular dye field.
Background technology
At dye field, azoic dyestuff is with its simple synthetic method, and compound structure change is various, molar extinction coefficient is higher, the advantages such as fast light and moisture resistant fastness by the time senior in having, considerably beyond other class dyestuffs in kind and output, are the dyes that kind is maximum, output is maximum.Obtain while widespread use at azoic dyestuff, also find the shortcoming of the aspects such as its tack, water-wash resistance, poor stability and environmental pollution be serious.In the processes such as washing, small molecules azoic dyestuff easily migrates to material surface, causes and decolours and variable color.Particularly azo small molecules is with human body Long Term Contact process, easily diffuses and penetrate into human body, has a great impact the health of people.The carinogenicity potential along with many azo small molecule dyes is found in succession; instruction and the regulation of various greenism are formulated again in succession; make people sight be turned to synthesis and the exploitation of substitute dyestuff, wherein the high molecular of low molecule dyestuff is one of approach that can solve the problem.
The study on the synthesis of high molecular dye arises from the beginning of the sixties, 1973, and Marechal etc. achieve the chemical bonding of colourless macromolecular material and colored dyes molecule.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 in 1919-1931 (2006), epoxy resin and Succinic anhydried is adopted to carry out half-esterification reaction, with the epoxy resin latex obtaining Water-borne modification in triethylamine with salify after purifying, then with containing amino water-soluble dye react, the epoxy resin high molecular dye of obtained aqueous emulsion, its weak point is that preparation method is complicated, needs to use a kind of homemade polymine to complete fixation.China Patent Publication No. CN 1284524A, 21 days February calendar year 2001 of publication date, patent of invention name is called " method of polymkeric substance diazotization and coupling synthetic epoxy resin family macromolecule dyestuff ", this application case discloses with epoxy resin primary polymer as macromolecular scaffold, diazonium salt is prepared with aromatic amino compound, diazotization and coupling is adopted to prepare the method for epoxy resin high molecular dye, the method makes the resistance to infiltration of dyestuff and resistance to migration be improved, its weak point is the active group that the high molecular dye of preparation does not have to react with dyed substrate further, degree of fixation is not high, part high molecular dye poorly water-soluble.China Patent Publication No. CN 1205350A, publication date on January 20th, 1999, patent of invention name is called " protein high molecular dye ", this application case discloses to do macromolecular scaffold containing amino protein high molecular, by making amino in protein high molecular and having and can carry out chemical reaction by reactive group dye matrix, obtained a kind of protein high molecular dye, reaction principle is equivalent to dyestuff and dyes to protein high molecular, its weak point is the group that protein high molecular dye does not have to react with dyed substrate, in its use procedure, need to add cross-linking agents to complete fixation.
Although high molecular dye earns widespread respect, can be used for actual high molecular dye product actually rare.Up to the present, also do not find about adopting diazotization and coupling to prepare report in water-soluble vinyl sulfone epoxy resin-matrix macromolecule reactive dye.
Summary of the invention
For above-mentioned Problems existing, the object of this invention is to provide a kind of method adopting diazotization and coupling to prepare water-soluble vinyl sulfone epoxy resin-matrix macromolecule reactive dye, start with from Molecular Structure Design, propose with carrying out the epoxy resin precursor of the functional group of diazo coupling reaction for high polymer main chain, hydroxyethyl sulfone sulfate class arylamine is prepared into diazonium salt, by the coupled reaction of epoxy resin precursor and diazonium salt, directly can 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
Epoxy resin precursor is the epoxy resin family macromolecule with functional group's (anilino residue) that can carry out diazo coupling reaction, and its general structural formula is as shown in (c).Epoxy resin precursor, is obtained by reacting under nitrogen protection condition at 110 ~ 130 DEG C by epoxy resin and aniline.
Wherein (a) is epoxy resin, and be any one in bisphenol-A diglycidylether, bisphenol-f diglycidylether or bis-phenol-H diglycidylether, the R in above formula is the one in following structure:
Wherein (b) is aniline,
The preparation method of epoxy resin precursor is as follows: at N
2under protection, be epoxy resin by molar weight ratio: aniline=1: 1 by any one epoxy resin above-mentioned and aniline Homogeneous phase mixing, is slowly warming up to 110 ~ 130 DEG C, insulation reaction more than 72 hours, obtained epoxy resin precursor.
(2) adopt following any one method to obtain ethyl sulfonyl sulfate class arylamine diazonium salt solution, reaction formula is as follows:
Wherein Y=HSO
4or Cl
Be used for carrying out diazotizing hydroxyethyl sulfone sulfate class arylamine to have: 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-AB base) ethyl sulfuryl] ethanol sulfuric acid ester, 6-β hydroxyethyl sulfone sulfate-2-naphthylamines-1-sulfonic acid etc., wherein Ar is the one in following structure
Diazonium salt solution preparation method 1: under 0 DEG C of condition, compares Ar-NH by molar weight
2: H
2sO
4=1: 2.5 ~ 3, get the sulphuric acid soln that massfraction is 30%; Add water hydroxyethyl sulfone sulfate class arylamine mixing, adds 10%Na
2cO
3solution, regulation system pH is 6 ~ 7, is stirred to arylamine and dissolves completely, compares Ar-NH by molar weight
2: NaNO
2=1: 1 ~ 1.2 add Sodium Nitrite solid, are stirred to after dissolving completely and are slowly added drop-wise in above-mentioned sulphuric acid soln, be stirred to and be terminal without during unhindered amina, for subsequent use;
Diazonium salt solution preparation method 2: under 0 DEG C of condition, compares Ar-NH by molar weight
2: HCl=1: 2.5 ~ 3 get the hydrochloric acid soln that volume ratio is 1: 10; Add water hydroxyethyl sulfone sulfate class arylamine mixing, adds 10%Na
2cO
3solution, regulation system pH is 6 ~ 7, is stirred to arylamine and dissolves completely, compares Ar-NH by molar weight
2: NaNO
2=1: 1 ~ 1.2 add Sodium Nitrite solid, are stirred to after dissolving completely and are slowly added drop-wise in above-mentioned hydrochloric acid soln, be stirred to and be terminal without during unhindered amina, for subsequent use;
(3) diazo coupling reaction of epoxy resin precursor and ethyl sulfonyl sulfate class arylamine diazonium salt:
In ice-water bath, by above-mentioned epoxy resin precursor N, dinethylformamide (DMF) solvent dissolves completely, under high velocity agitation, by molar weight than ethyl sulfonyl sulfate class arylamine diazonium salt: epoxy resin precursor=0.4 ~ 1.2: 1, above-mentioned ethyl sulfonyl sulfate class arylamine diazonium salt solution is slowly joined in above-mentioned epoxy resin precursor solution, about 0 DEG C insulation reaction more than 12 hours, after reaction completes, through precipitation, filter, washing and drying after, obtain water-soluble vinyl sulfone epoxy resin-matrix macromolecule reactive dye, its general reaction formula is as follows
Owing to have employed above technical scheme, diazotization and coupling of the present invention prepares the method for water-soluble vinyl sulfone epoxy resin-matrix macromolecule reactive dye, the method synthetic route is simple, functionality is easy to control, coupled reaction transformation efficiency can up to more than 90%, through simple purification process, water-soluble many active epoxy resin-matrix macromolecule dyestuffs of various lovely luster directly can be obtained.
Water-soluble vinyl sulfone epoxy resin-matrix macromolecule reactive dye of the present invention, containing water-soluble sulphate esters group on molecular chain, the good water solubility of high molecular dye, is dissolvable in water in water, decrease 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, ethyl sulfone group containing multiple lateral reactivity on molecular chain, in the basic conditions, the vinyl sulfone(RemzaolHuo Xingranliaohuoxingjituan) active group formed can form fixation with containing hydroxyl and the amino dyed substrate of reactive group that waits by covalent linkage, the problems such as the fastness of solution dyeing and colourity, the dyeing of the materials such as cotton, fiber crops, silk, hair, leather, paper can be widely used in, colour fastness to rubbing and the high product dyed thereby of water-fastness colour fastness grade can be obtained.Have neither part nor lot in the high molecular dye of reaction, the hydroxyethyl sulfone type high molecular dye becoming not water-soluble can be hydrolyzed in the basic conditions, through staticly settling, filtering, wash, dry, recyclable hydroxyethyl sulfone type high molecular dye, decrease the discharge of coloured liquid, reduce environmental pollution.
Water-soluble vinyl sulfone epoxy resin-matrix macromolecule reactive dye of the present invention, take epoxy resin as high molecular dye skeleton, good with the consistency of superpolymer, dye coloring power is strong, Dry Sack is bright-coloured, good and the thermotolerance of solvent resistance, resistance to migration comparatively small molecule dyes improves greatly, can be used as tinting material and the weighting agent of the materials such as plastics, rubber, coating, binding agent.
Water-soluble vinyl sulfone epoxy resin-matrix macromolecule dyestuff of the present invention, molecular weight is high, can not for cytolemma institute through, therefore not easily absorb by organism, decrease the harm to organism.
Patent of the present invention is compared with " method of polymkeric substance diazotization and coupling synthetic epoxy resin family macromolecule dyestuff " with Chinese patent " protein high molecular dye ", high molecular dye of the present invention is water-soluble many active high molecular dyes, the high molecular dye good water solubility of preparation, high to textile dyeing fastness such as cotton, fiber crops, silk, hairs, and the discharge of coloured liquid is low.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in further detail.
Embodiment 1
Get 196.0 grams of (0.5mol) dihydroxyphenyl propane-diglycidylethers (epoxy equivalent (weight)=196) and 46.5 grams of aniline (0.5mol), after being uniformly mixed, at N
2slowly be warming up to about 110 DEG C under condition, insulation reaction, after 72 hours, obtains white clear epoxy resin precursor solid.
Get the 1.65mL vitriol oil, join in 10mL water, mix, make temperature be reduced to about 0 DEG C for subsequent use.Getting 3.51 grams of (0.012mol) P-aminoazobenzene-β hydroxyethyl sulfone sulfate (para-ester) joins in 30mL water, then 10% sodium carbonate solution is added, regulation system pH is 6 ~ 7, be stirred to para-ester to dissolve completely, add 0.836 gram of 99% (0.012mol) Sodium Nitrite solid, stirring is slowly added drop-wise in above-mentioned sulphuric acid soln after making it dissolve completely, is stirred to and is terminal without during unhindered amina.
Get 4.85 grams (0.01mol) above-mentioned epoxy resin precursor, add 400mLN, N '-dimethyl formamide, stirring is placed in ice-water bath after making it dissolve completely, makes temperature be reduced to about 0 DEG C, slow dropping is to above-mentioned para-ester diazonium salt solution, insulation reaction 12 hours at 0 DEG C, through precipitation, filtration, washing and drying treatment, obtains water-soluble vinyl sulfone epoxy resin-matrix macromolecule reactive dye.
Embodiment 2
Adopt epoxy resin precursor identical in embodiment 1.Epoxy resin precursor identical in Example 1 4.85 grams (0.01mol), adds 400mLN, N '-dimethyl formamide, stirs and makes it dissolve completely, with ice-water bath, the temperature of solution is reduced to about 0 DEG C.
Get 3mL36.5% concentrated hydrochloric acid, join in 30mL water, mix, make temperature be reduced to about 0 DEG C for subsequent use.Getting 3.51 grams of (0.012mol) para-esters joins in 30mL water, then 10% sodium carbonate solution is added, regulation system pH is 6 ~ 7, be stirred to para-ester to dissolve completely, add 0.836 gram of 99% (0.012mol) Sodium Nitrite solid, stirring is slowly added drop-wise in above-mentioned hydrochloric acid soln after making it dissolve completely, is stirred to and is terminal without during unhindered amina.
Above-mentioned diazonium salt solution is slowly added drop-wise in above-mentioned epoxy resin precursor solution, insulation reaction 12 hours at 0 DEG C, through precipitation, filtration, washing and drying treatment, obtains water-soluble vinyl sulfone epoxy resin-matrix macromolecule reactive dye.
Embodiment 3
Adopt epoxy resin precursor identical in embodiment 1.Epoxy resin precursor identical in Example 1 4.85 grams (0.01mol), adds 400mLN, N '-dimethyl formamide, stirs and makes it dissolve completely, with ice-water bath, the temperature of solution is reduced to about 0 DEG C.
Get the 0.40mL vitriol oil, join in 10mL water, mix, make temperature be reduced to about 0 DEG C for subsequent use.Getting 0.732 gram (2.5mmol) 96% (para-ester) joins in 30mL water, then 10% sodium carbonate solution is added, regulation system pH is 6 ~ 7, be stirred to para-ester to dissolve completely, add 0.174 gram of 99% (2.5mmol) Sodium Nitrite solid, be stirred to after dissolving completely and be slowly added drop-wise to above-mentioned sulphuric acid soln, be stirred to and be terminal without during unhindered amina.
Above-mentioned diazonium salt solution is slowly added drop-wise in above-mentioned epoxy resin precursor solution, insulation reaction 12 hours at 0 DEG C, through precipitation, filtration, washing and drying treatment, obtains water-soluble vinyl sulfone epoxy resin-matrix macromolecule reactive dye.
Embodiment 4
Adopt epoxy resin precursor identical in embodiment 1.Epoxy resin precursor identical in Example 1 4.85 grams (0.01mol), adds 400mLN, N '-dimethyl formamide, stirs and makes it dissolve completely, with ice-water bath, the temperature of solution is reduced to about 0 DEG C.
Get the 1.60mL vitriol oil, join in 10mL water, mix, make temperature be reduced to about 0 DEG C for subsequent use.Getting 2.92 grams of (0.01mol) para-esters joins in 30mL water, then 10% sodium carbonate solution is added, regulation system pH is 6 ~ 7, be stirred to para-ester to dissolve completely, add 0.697 gram of 99% (0.01mol) Sodium Nitrite solid, be stirred to after dissolving completely and be slowly added drop-wise in above-mentioned sulphuric acid soln, be stirred to and be terminal without during unhindered amina.
Above-mentioned diazonium salt solution is slowly added drop-wise in above-mentioned epoxy resin precursor solution, insulation reaction 12 hours at 0 DEG C, through precipitation, filtration, washing and drying treatment, obtains water soluble vinyl-sulfone polyurethane class high molecular reactive dye.
Embodiment 5
Adopt epoxy resin precursor identical in embodiment 1.Epoxy resin precursor identical in Example 1 4.85 grams (0.01mol), adds 400mLN, N '-dimethyl formamide, stirs and makes it dissolve completely, with ice-water bath, the temperature of solution is reduced to about 0 DEG C.
Get the 1.65mL vitriol oil, join in 10mL water, mix, for subsequent use after making temperature be reduced to about 0 DEG C.Join in 30mL water by beta-sulfuric ester ethyl sulfonyl base aniline between 3.51 grams (0.012mol) (a position ester), then 10% sodium carbonate solution is added, regulation system pH is 6 ~ 7, be stirred to it to dissolve completely, add 0.836 gram of 99% (0.012mol) Sodium Nitrite solid, be stirred to after dissolving completely and be slowly added drop-wise in above-mentioned sulphuric acid soln, be stirred to and be terminal without during unhindered amina.
Above-mentioned diazonium salt solution is slowly added drop-wise in above-mentioned epoxy resin precursor solution, insulation reaction 12 hours at 0 DEG C, through precipitation, filtration, washing and drying treatment, obtains water-soluble vinyl sulfone epoxy resin-matrix macromolecule reactive dye.
Embodiment 6
Adopt epoxy resin precursor identical in embodiment 1.Epoxy resin precursor identical in Example 1 4.85 grams (0.01mol), adds 400mLN, N '-dimethyl formamide, stirs and makes it dissolve completely, with ice-water bath, the temperature of solution is reduced to about 0 DEG C.
Get the 1.65mL vitriol oil, join in 10mL water, mix, for subsequent use after making temperature be reduced to about 0 DEG C.Join in 30mL water by 3.732 grams of (0.012mol) 2-anisidine-4-β hydroxyethyl sulfone sulfates, then 10% sodium carbonate solution is added, regulation system pH is 6 ~ 7, be stirred to it to dissolve completely, add 0.836 gram of 99% (0.012mol) Sodium Nitrite solid, be stirred to after dissolving completely and be slowly added drop-wise in above-mentioned sulphuric acid soln, be stirred to and be terminal without during unhindered amina.
Above-mentioned diazonium salt solution is slowly added drop-wise in above-mentioned epoxy resin precursor solution, insulation reaction 12 hours at 0 DEG C, through precipitation, filtration, washing and drying treatment, obtains water-soluble vinyl sulfone epoxy resin-matrix macromolecule reactive dye.
Embodiment 7
Adopt epoxy resin precursor identical in embodiment 1.Epoxy resin precursor identical in Example 1 4.85 grams (0.01mol), adds 400mLN, N '-dimethyl formamide, stirs and makes it dissolve completely, with ice-water bath, the temperature of solution is reduced to about 0 DEG C.
Get the 1.65mL vitriol oil, join in 10mL water, mix, for subsequent use after making temperature be reduced to about 0 DEG C.Join in 30mL water by 3.732 grams of (0.012mol) 2-benzaminic acid-4-β hydroxyethyl sulfone sulfates, then 10% sodium carbonate solution is added, regulation system pH is 6 ~ 7, be stirred to it to dissolve completely, add 0.836 gram of 99% (0.012mol) Sodium Nitrite solid, be stirred to after dissolving completely and be slowly added drop-wise in above-mentioned sulphuric acid soln, be stirred to and be terminal without during unhindered amina.
Above-mentioned diazonium salt solution is slowly added drop-wise in above-mentioned epoxy resin precursor solution, insulation reaction 12 hours at 0 DEG C, through precipitation, filtration, washing and drying treatment, obtains water-soluble vinyl sulfone epoxy resin-matrix macromolecule reactive dye.
Embodiment 8
Adopt epoxy resin precursor identical in embodiment 1.Epoxy resin precursor identical in Example 1 4.85 grams (0.01mol), adds 400mLN, N '-dimethyl formamide, stirs and makes it dissolve completely, with ice-water bath, the temperature of solution is reduced to about 0 DEG C.
Get the 1.65mL vitriol oil, join in 10mL water, mix, for subsequent use after making temperature be reduced to about 0 DEG C.Join in 30mL water by 4.332 grams of (0.012mol) 4-β hydroxyethyl sulfone sulfate ester aniline-2-sulfonic acid (sulfonation para-ester), then 10% sodium carbonate solution is added, regulation system pH is 6 ~ 7, be stirred to it to dissolve completely, add 0.836 gram of 99% (0.012mol) Sodium Nitrite solid, be stirred to after dissolving completely and be slowly added drop-wise in above-mentioned sulphuric acid soln, be stirred to and be terminal without during unhindered amina.
Above-mentioned diazonium salt solution is slowly added drop-wise in above-mentioned epoxy resin precursor solution, insulation reaction 12 hours at 0 DEG C, through precipitation, filtration, washing and drying treatment, obtains water-soluble vinyl sulfone epoxy resin-matrix macromolecule reactive dye.
Embodiment 9
Adopt epoxy resin precursor identical in embodiment 1.Epoxy resin precursor identical in Example 1 4.85 grams (0.01mol), adds 400mLN, N '-dimethyl formamide, stirs and makes it dissolve completely, with ice-water bath, the temperature of solution is reduced to about 0 DEG C.
Get the 1.65mL vitriol oil, join in 10mL water, mix, for subsequent use after making temperature be reduced to about 0 DEG C.Getting 4.229 grams of (0.012mol) 2-[2-(3-AB base) ethyl sulfuryl] ethanol sulfuric acid ester joins in 30mL water, then 10% sodium carbonate solution is added, regulation system pH is 6 ~ 7, be stirred to it to dissolve completely, add 0.836 gram of 99% (0.012mol) Sodium Nitrite solid again, be stirred to after dissolving completely and be slowly added drop-wise in above-mentioned sulphuric acid soln, be stirred to and be terminal without during unhindered amina.
Above-mentioned diazonium salt solution is slowly added drop-wise in above-mentioned epoxy resin precursor solution, insulation reaction 12 hours at 0 DEG C, through precipitation, filtration, washing and drying treatment, obtains water-soluble vinyl sulfone epoxy resin-matrix macromolecule reactive dye.
Embodiment 10
Adopt epoxy resin precursor identical in embodiment 1.Epoxy resin precursor identical in Example 1 4.85 grams (0.01mol), adds 400mLN, N '-dimethyl formamide, stirs and makes it dissolve completely, with ice-water bath, the temperature of solution is reduced to about 0 DEG C.
Get the 1.65mL vitriol oil, join in 10mL water, mix, for subsequent use after making temperature be reduced to about 0 DEG C.Getting 3.016 grams of (0.012mol) 6-β hydroxyethyl sulfone sulfate-2-naphthylamines-1-sulfonic acid joins in 30mL water, then 10% sodium carbonate solution is added, regulation system pH is 6 ~ 7, be stirred to it to dissolve completely, add 0.836 gram of 99% (0.012mol) Sodium Nitrite solid again, be stirred to after dissolving completely and be slowly added drop-wise in above-mentioned sulphuric acid soln, be stirred to and be terminal without during unhindered amina.
Above-mentioned diazonium salt solution is slowly added drop-wise in above-mentioned epoxy resin precursor solution, insulation reaction 12 hours at 0 DEG C, through precipitation, filtration, washing and drying treatment, obtains water-soluble vinyl sulfone epoxy resin-matrix macromolecule reactive dye.
Embodiment 11
Get 180.0 grams of (0.5mol) bisphenol-fs diglycidylether (epoxy equivalent (weight)=180) and 46.5 grams of aniline (0.5mo1), after being uniformly mixed, at N
2slowly be warming up to about 110 DEG C under condition, insulation reaction, after 72 hours, obtains white clear epoxy resin precursor solid.
Get the 1.65mL vitriol oil, join in 10mL water, mix, for subsequent use after making temperature be reduced to about 0 DEG C.Getting 3.51 grams of (0.012mol) para-esters joins in 30mL water, then 10% sodium carbonate solution is added, regulation system pH is 6 ~ 7, be stirred to para-ester to dissolve completely, add 0.836 gram of 99% (0.012mol) Sodium Nitrite solid again, be stirred to after dissolving completely and be slowly added drop-wise in above-mentioned sulphuric acid soln, be stirred to and be terminal without during unhindered amina.
Get above-mentioned epoxy resin precursor 4.53 grams (0.01mol), use 300mL N, N '-dimethyl formamide dissolves completely, with ice-water bath, the temperature of solution is reduced to about 0 DEG C.The above-mentioned diazonium salt solution of slow dropping, insulation reaction 12 hours at 0 DEG C, through precipitation, filtration, washing and drying treatment, obtains water-soluble vinyl sulfone epoxy resin family macromolecule reactive dyestuffs.
Embodiment 12
Adopt epoxy resin precursor identical in embodiment 11.Epoxy resin precursor identical in Example 11 4.53 grams (0.01mol), dissolves completely with 300mLN, N '-dimethyl formamide, with ice-water bath, the temperature of solution is reduced to about 0 DEG C.
Get 3mL36.5% concentrated hydrochloric acid, join in 30mL water, mix, for subsequent use after making temperature be reduced to about 0 DEG C.Getting 3.51 grams of (0.012mol) para-esters joins in 30mL water, then 10% sodium carbonate solution is added, regulation system pH is 6 ~ 7, be stirred to para-ester to dissolve completely, add 0.836 gram of 99% (0.012mol) Sodium Nitrite solid again, be stirred to after dissolving completely and be slowly added drop-wise in above-mentioned hydrochloric acid soln, be stirred to and be terminal without during unhindered amina.
Above-mentioned diazonium salt solution is slowly added drop-wise in above-mentioned epoxy resin precursor solution, insulation reaction 12 hours at 0 DEG C, through precipitation, filtration, washing and drying treatment, obtains water-soluble vinyl sulfone epoxy resin-matrix macromolecule reactive dye.
Embodiment 13
Adopt epoxy resin precursor identical in embodiment 11.Epoxy resin precursor identical in Example 11 4.53 grams (0.01mol), dissolves completely with 300mLN, N '-dimethyl formamide, with ice-water bath, the temperature of solution is reduced to about 0 DEG C.
Get the 0.40mL vitriol oil, join in 10mL water, mix, for subsequent use after making temperature be reduced to about 0 DEG C.Getting 0.732 gram of (2.5mmol) para-ester joins in 30mL water, then 10% sodium carbonate solution is added, regulation system pH is 6 ~ 7, be stirred to para-ester to dissolve completely, add 0.174 gram of 99% (2.5mmol) Sodium Nitrite solid again, be stirred to after dissolving completely and slowly drip above-mentioned solution, be stirred to and be terminal without during unhindered amina.
Above-mentioned diazonium salt solution is slowly added drop-wise in above-mentioned epoxy resin precursor solution, insulation reaction 12 hours at 0 DEG C, through precipitation, filtration, washing and drying treatment, obtains water-soluble vinyl sulfone epoxy resin-matrix macromolecule reactive dye.
Embodiment 14
Adopt epoxy resin precursor identical in embodiment 11.Epoxy resin precursor identical in Example 11 4.53 grams (0.01mol), dissolves completely with 300mLN, N '-dimethyl formamide, with ice-water bath, the temperature of solution is reduced to about 0 DEG C.
Get the 1.60mL vitriol oil, join in 10mL water, mix, for subsequent use after making temperature be reduced to about 0 DEG C.Getting 2.92 grams of (0.01mol) para-esters joins in 30mL water, then 10% sodium carbonate solution is added, regulation system pH is 6 ~ 7, be stirred to para-ester to dissolve completely, add 0.697 gram of 99% (0.01mol) Sodium Nitrite solid again, be stirred to after dissolving completely and be slowly added drop-wise in above-mentioned sulphuric acid soln, be stirred to and be terminal without during unhindered amina.
Above-mentioned diazonium salt solution is slowly added drop-wise in above-mentioned epoxy resin precursor solution, insulation reaction 12 hours at 0 DEG C, through precipitation, filtration, washing and drying treatment, obtains water-soluble vinyl sulfone epoxy resin-matrix macromolecule reactive dye.
Embodiment 15
Adopt epoxy resin precursor identical in embodiment 11.Epoxy resin precursor identical in Example 11 4.53 grams (0.01mol), dissolves completely with 300mLN, N '-dimethyl formamide, with ice-water bath, the temperature of solution is reduced to about 0 DEG C.
Get the 1.65mL vitriol oil, join in 10mL water, mix, for subsequent use after making temperature be reduced to about 0 DEG C.Getting position ester between 3.51 grams (0.012mol) joins in 30mL water, then 10% sodium carbonate solution is added, regulation system pH is 6 ~ 7, be stirred to it to dissolve completely, add 0.836 gram of 99% (0.012mol) Sodium Nitrite solid again, be stirred to after dissolving completely and slowly drip in above-mentioned sulphuric acid soln, be stirred to and be terminal without during unhindered amina.
Above-mentioned diazonium salt solution is slowly added drop-wise in above-mentioned epoxy resin precursor solution, insulation reaction 12 hours at 0 DEG C, through precipitation, filtration, washing and drying treatment, obtains water-soluble vinyl sulfone epoxy resin-matrix macromolecule reactive dye.
Embodiment 16
Adopt epoxy resin precursor identical in embodiment 11.Epoxy resin precursor identical in Example 11 4.53 grams (0.01mol), dissolves completely with 300mLN, N '-dimethyl formamide, with ice-water bath, the temperature of solution is reduced to about 0 DEG C.
Get the 1.65mL vitriol oil, join in 10mL water, mix, for subsequent use after making temperature be reduced to about 0 DEG C.Getting 3.732 grams of (0.012mol) 2-anisidine-4-β hydroxyethyl sulfone sulfates joins in 30mL water, then 10% sodium carbonate solution is added, regulation system pH is 6 ~ 7, be stirred to it to dissolve completely, add 0.836 gram of 99% (0.012mol) Sodium Nitrite solid again, be stirred to after dissolving completely and be slowly added drop-wise in above-mentioned sulphuric acid soln, be stirred to and be terminal without during unhindered amina.
Above-mentioned diazonium salt solution is slowly added drop-wise in above-mentioned epoxy resin precursor solution, insulation reaction 12 hours at 0 DEG C, through precipitation, filtration, washing and drying treatment, obtains water-soluble vinyl sulfone epoxy resin-matrix macromolecule reactive dye.
Embodiment 17
Adopt epoxy resin precursor identical in embodiment 11.Epoxy resin precursor identical in Example 11 4.53 grams (0.01mol), uses 300mL N, and N '-dimethyl formamide dissolves completely, with ice-water bath, the temperature of solution is reduced to about 0 DEG C.
Get the 1.65mL vitriol oil, join in 10mL water, mix, for subsequent use after making temperature be reduced to about 0 DEG C.Getting 3.732 grams of (0.012mol) 2-benzaminic acid-4-β hydroxyethyl sulfone sulfates joins in 30mL water, then 10% sodium carbonate solution is added, regulation system pH is 6 ~ 7, be stirred to it to dissolve completely, add 0.836 gram of 99% (0.012mol) Sodium Nitrite solid again, be stirred to after dissolving completely and be slowly added drop-wise in above-mentioned sulphuric acid soln, be stirred to and be terminal without during unhindered amina.
Above-mentioned diazonium salt solution is slowly added drop-wise in above-mentioned epoxy resin precursor solution, insulation reaction 12 hours at 0 DEG C, through precipitation, filtration, washing and drying treatment, obtains water-soluble vinyl sulfone epoxy resin-matrix macromolecule reactive dye.
Embodiment 18
Adopt epoxy resin precursor identical in embodiment 11.Epoxy resin precursor identical in Example 11 4.53 grams (0.01mol), uses 300mL N, and N '-dimethyl formamide dissolves completely, with ice-water bath, the temperature of solution is reduced to about 0 DEG C.
Get the 1.65mL vitriol oil, join in 10mL water, mix, for subsequent use after making temperature be reduced to about 0 DEG C.Getting 4.332 grams of (0.012mol) 4-β hydroxyethyl sulfone sulfate ester aniline-2-sulfonic acid (sulfonation para-ester) joins in 30mL water, then 10% sodium carbonate solution is added, regulation system pH is 6 ~ 7, be stirred to it to dissolve completely, add 0.836 gram of 99% (0.012mol) Sodium Nitrite solid again, be stirred to after dissolving completely and slowly drip above-mentioned solution, be stirred to and be terminal without during unhindered amina.
Above-mentioned diazonium salt solution is slowly added drop-wise in above-mentioned epoxy resin precursor solution, insulation reaction 12 hours at 0 DEG C, through precipitation, filtration, washing and drying treatment, obtains water-soluble vinyl sulfone epoxy resin-matrix macromolecule reactive dye.
Embodiment 19
Adopt epoxy resin precursor identical in embodiment 11.Epoxy resin precursor identical in Example 11 4.53 grams (0.01mol), dissolves completely with 300mLN, N '-dimethyl formamide, with ice-water bath, the temperature of solution is reduced to about 0 DEG C.
Get the 1.65mL vitriol oil, join in 10mL water, mix, for subsequent use after making temperature be reduced to about 0 DEG C.Getting 4.229 grams of (0.012mol) 2-[2-(3-AB base) ethyl sulfuryl] ethanol sulfuric acid ester joins in 30mL water, then 10% sodium carbonate solution is added, regulation system pH is 6 ~ 7, be stirred to it to dissolve completely, add 0.836 gram of 99% (0.012mol) Sodium Nitrite solid again, be stirred to after dissolving completely and be slowly added drop-wise in above-mentioned sulphuric acid soln, be stirred to and be terminal without during unhindered amina.
Above-mentioned diazonium salt solution is slowly added drop-wise in above-mentioned epoxy resin precursor solution, insulation reaction 12 hours at 0 DEG C, through precipitation, filtration, washing and drying treatment, obtains water-soluble vinyl sulfone epoxy resin-matrix macromolecule reactive dye.
Embodiment 20
Adopt epoxy resin precursor identical in embodiment 11.Epoxy resin precursor identical in Example 11 4.53 grams (0.01mol), dissolves completely with 300mLN, N '-dimethyl formamide, with ice-water bath, the temperature of solution is reduced to about 0 DEG C.
Get the 1.65mL vitriol oil, join in 10mL water, mix, for subsequent use after making temperature be reduced to about 0 DEG C.Join in 30mL water by 3.016 grams of (0.012mol) 6-β hydroxyethyl sulfone sulfate-2-naphthylamines-1-sulfonic acid, then 10% sodium carbonate solution is added, regulation system pH is 6 ~ 7, be stirred to it to dissolve completely, add 0.836 gram of 99% (0.012mol) Sodium Nitrite solid again, be stirred to after dissolving completely and be slowly added drop-wise in above-mentioned sulphuric acid soln, be stirred to and be terminal without during unhindered amina.
Above-mentioned diazonium salt solution is slowly added drop-wise in above-mentioned epoxy resin precursor solution, insulation reaction 12 hours at 0 DEG C, through precipitation, filtration, washing and drying treatment, obtains water-soluble vinyl sulfone epoxy resin-matrix macromolecule reactive dye.
Embodiment 21
Get 240.0 grams of (0.5mol) bis-phenols-H diglycidylether (epoxy equivalent (weight)=240) and 46.5 grams of aniline (0.5mol), after being uniformly mixed, at N
2slowly be warming up to about 110 DEG C under condition, insulation reaction, after 72 hours, obtains white clear epoxy resin precursor solid.
Get the 1.65mL vitriol oil, join in 10mL water, mix, for subsequent use after making temperature be reduced to about 0 DEG C.Getting 3.51 grams of (0.012mol) para-esters joins in 30mL water, then 10% sodium carbonate solution is added, regulation system pH is 6 ~ 7, be stirred to para-ester to dissolve completely, add 0.836 gram of 99% (0.012mol) Sodium Nitrite solid again, be stirred to after dissolving completely and be slowly added drop-wise in above-mentioned sulphuric acid soln, be stirred to and be terminal without during unhindered amina.
Get above-mentioned epoxy resin precursor 5.73 grams (0.01mol), use 400mL N, N '-dimethyl formamide dissolves completely, with ice-water bath, the temperature of solution is reduced to about 0 DEG C.The above-mentioned diazonium salt solution of slow dropping, insulation reaction 12 hours at 0 DEG C, through precipitation, filtration, washing and drying treatment, obtains water-soluble vinyl sulfone epoxy resin family macromolecule reactive dyestuffs.
Embodiment 22
Adopt epoxy resin precursor identical in embodiment 21.Epoxy resin precursor identical in Example 21 5.73 grams (0.01mol), dissolves completely with 300mLN, N '-dimethyl formamide, with ice-water bath, the temperature of solution is reduced to about 0 DEG C.
Get 3mL36.5% concentrated hydrochloric acid, join in 30mL water, mix, for subsequent use after making temperature be reduced to about 0 DEG C.Getting 3.51 grams of (0.012mol) para-esters joins in 30mL water, then 10% sodium carbonate solution is added, regulation system pH is 6 ~ 7, be stirred to para-ester to dissolve completely, add 0.836 gram of 99% (0.012mol) Sodium Nitrite solid again, be stirred to after dissolving completely and be slowly added drop-wise in above-mentioned hydrochloric acid soln, be stirred to and be terminal without during unhindered amina.
Above-mentioned diazonium salt solution is slowly added drop-wise in above-mentioned epoxy resin precursor solution, insulation reaction 12 hours at 0 DEG C, through precipitation, filtration, washing and drying treatment, obtains water-soluble vinyl sulfone epoxy resin-matrix macromolecule reactive dye.
Embodiment 23
Adopt epoxy resin precursor identical in embodiment 21.Epoxy resin precursor identical in Example 21 5.73 grams (0.01mol), dissolves completely with 300mLN, N '-dimethyl formamide, with ice-water bath, the temperature of solution is reduced to about 0 DEG C.
Get the 0.40mL vitriol oil, join in 10mL water, mix, for subsequent use after making temperature be reduced to about 0 DEG C.Getting 0.732 gram of (2.5mmol) para-ester joins in 30mL water, then 10% sodium carbonate solution is added, regulation system pH is 6 ~ 7, be stirred to para-ester to dissolve completely, add 0.174 gram of 99% (2.5mmol) Sodium Nitrite solid again, be stirred to after dissolving completely and be slowly added drop-wise in above-mentioned sulphuric acid soln, be stirred to and be terminal without during unhindered amina.
Above-mentioned diazonium salt solution is slowly added drop-wise in above-mentioned epoxy resin precursor solution, insulation reaction 12 hours at 0 DEG C, through precipitation, filtration, washing and drying treatment, obtains water-soluble vinyl sulfone epoxy resin-matrix macromolecule reactive dye.
Embodiment 24
Adopt epoxy resin precursor identical in embodiment 21.Epoxy resin precursor identical in Example 21 5.73 grams (0.01mol), dissolves completely with 300mLN, N '-dimethyl formamide, with ice-water bath, the temperature of solution is reduced to about 0 DEG C.
Get the 1.60mL vitriol oil, join in 10mL water, mix, for subsequent use after making temperature be reduced to about 0 DEG C.Getting 2.92 grams of (0.01mol) para-esters joins in 30mL water, then 10% sodium carbonate solution is added, regulation system pH is 6 ~ 7, be stirred to para-ester to dissolve completely, add 0.697 gram of 99% (0.01mol) Sodium Nitrite solid again, be stirred to after dissolving completely and be slowly added drop-wise in above-mentioned sulphuric acid soln, be stirred to and be terminal without during unhindered amina.
Above-mentioned diazonium salt solution is slowly added drop-wise in above-mentioned epoxy resin precursor solution, insulation reaction 12 hours at 0 DEG C, through precipitation, filtration, washing and drying treatment, obtains water-soluble vinyl sulfone epoxy resin-matrix macromolecule reactive dye.
Embodiment 25
Adopt epoxy resin precursor identical in embodiment 21.Epoxy resin precursor identical in Example 21 5.73 grams (0.01mol), dissolves completely with 300mLN, N '-dimethyl formamide, with ice-water bath, the temperature of solution is reduced to about 0 DEG C.
Get the 1.65mL vitriol oil, join in 10mL water, mix, for subsequent use after making temperature be reduced to about 0 DEG C.Join in 30mL water by position ester between 3.51 grams (0.012mol), then 10% sodium carbonate solution is added, regulation system pH is 6 ~ 7, be stirred to it to dissolve completely, add 0.836 gram of 99% (0.012mol) Sodium Nitrite solid again, be stirred to after dissolving completely and be slowly added drop-wise in above-mentioned sulphuric acid soln, be stirred to and be terminal without during unhindered amina.
Above-mentioned diazonium salt solution is slowly added drop-wise in above-mentioned epoxy resin precursor solution, insulation reaction 12 hours at 0 DEG C, through precipitation, filtration, washing and drying treatment, obtains water-soluble vinyl sulfone epoxy resin-matrix macromolecule reactive dye.
Embodiment 26
Adopt epoxy resin precursor identical in embodiment 21.Epoxy resin precursor identical in Example 21 5.73 grams (0.01mol), uses 300mL N, and N '-dimethyl formamide dissolves completely, with ice-water bath, the temperature of solution is reduced to about 0 DEG C.
Get the 1.65mL vitriol oil, join in 10mL water, mix, for subsequent use after making temperature be reduced to about 0 DEG C.Getting 3.732 grams of (0.012mol) 2-anisidine-4-β hydroxyethyl sulfone sulfates joins in 30mL water, then 10% sodium carbonate solution is added, regulation system pH is 6 ~ 7, be stirred to it to dissolve completely, add 0.836 gram of 99% (0.012mol) Sodium Nitrite solid again, be stirred to after dissolving completely and be slowly added drop-wise in above-mentioned sulphuric acid soln, be stirred to and be terminal without during unhindered amina.
Above-mentioned diazonium salt solution is slowly added drop-wise in above-mentioned epoxy resin precursor solution, insulation reaction 12 hours at 0 DEG C, through precipitation, filtration, washing and drying treatment, obtains water-soluble vinyl sulfone epoxy resin-matrix macromolecule reactive dye.
Embodiment 27
Adopt epoxy resin precursor identical in embodiment 21.Epoxy resin precursor identical in Example 21 5.73 grams (0.01mol), dissolves completely with 300mLN, N '-dimethyl formamide, with ice-water bath, the temperature of solution is reduced to about 0 DEG C.
Get the 1.65mL vitriol oil, join in 10mL water, mix, for subsequent use after making temperature be reduced to about 0 DEG C.Getting 3.732 grams of (0.012mol) 2-benzaminic acid-4-β hydroxyethyl sulfone sulfates joins in 30mL water, then 10% sodium carbonate solution is added, regulation system pH is 6 ~ 7, be stirred to it to dissolve completely, add 0.836 gram of 99% (0.012mol) Sodium Nitrite solid again, be stirred to after dissolving completely and be slowly added drop-wise in above-mentioned sulphuric acid soln, be stirred to and be terminal without during unhindered amina.
Above-mentioned diazonium salt solution is slowly added drop-wise in above-mentioned epoxy resin precursor solution, insulation reaction 12 hours at 0 DEG C, through precipitation, filtration, washing and drying treatment, obtains water-soluble vinyl sulfone epoxy resin-matrix macromolecule reactive dye.
Embodiment 28
Adopt epoxy resin precursor identical in embodiment 21.Epoxy resin precursor identical in Example 21 5.73 grams (0.01mol), uses 300mL N, and N '-dimethyl formamide dissolves completely, with ice-water bath, the temperature of solution is reduced to about 0 DEG C.
Get the 1.65mL vitriol oil, join in 10mL water, mix, for subsequent use after making temperature be reduced to about 0 DEG C.Getting 4.332 grams of (0.012mol) 4-β hydroxyethyl sulfone sulfate ester aniline-2-sulfonic acid (sulfonation para-ester) joins in 30mL water, then 10% sodium carbonate solution is added, regulation system pH is 6 ~ 7, be stirred to it to dissolve completely, add 0.836 gram of 99% (0.012mol) Sodium Nitrite solid again, be stirred to after dissolving completely and be slowly added drop-wise in above-mentioned sulphuric acid soln, be stirred to and be terminal without during unhindered amina.
Above-mentioned diazonium salt solution is slowly added drop-wise in above-mentioned epoxy resin precursor solution, insulation reaction 12 hours at 0 DEG C, through precipitation, filtration, washing and drying treatment, obtains water-soluble vinyl sulfone epoxy resin-matrix macromolecule reactive dye.
Embodiment 29
Adopt epoxy resin precursor identical in embodiment 21.Epoxy resin precursor identical in Example 21 5.73 grams (0.01mol), dissolves completely with 300mLN, N '-dimethyl formamide, with ice-water bath, the temperature of solution is reduced to about 0 DEG C.
Get the 1.65mL vitriol oil, join in 10mL water, mix, for subsequent use after making temperature be reduced to about 0 DEG C.Getting 4.229 grams of (0.012mol) 2-[2-(3-AB base) ethyl sulfuryl] ethanol sulfuric acid ester joins in 30mL water, then 10% sodium carbonate solution is added, regulation system pH is 6 ~ 7, be stirred to it to dissolve completely, add 0.836 gram of 99% (0.012mol) Sodium Nitrite solid again, be stirred to after dissolving completely and be slowly added drop-wise in above-mentioned sulphuric acid soln, be stirred to and be terminal without during unhindered amina.
Above-mentioned diazonium salt solution is slowly added drop-wise in above-mentioned epoxy resin precursor solution, insulation reaction 12 hours at 0 DEG C, through precipitation, filtration, washing and drying treatment, obtains water-soluble vinyl sulfone epoxy resin-matrix macromolecule reactive dye.
Embodiment 30
Adopt epoxy resin precursor identical in embodiment 21.Epoxy resin precursor identical in Example 21 5.73 grams (0.01mol), uses 300mL N, and N '-dimethyl formamide dissolves completely, with ice-water bath, the temperature of solution is reduced to about 0 DEG C.
Get the 1.65mL vitriol oil, join in 10mL water, mix, for subsequent use after making temperature be reduced to about 0 DEG C.Getting 3.016 grams of (0.012mol) 6-β hydroxyethyl sulfone sulfate-2-naphthylamines-1-sulfonic acid joins in 30mL water, then 10% sodium carbonate solution is added, regulation system pH is 6 ~ 7, be stirred to it to dissolve completely, add 0.836 gram of 99% (0.012mol) Sodium Nitrite solid again, be stirred to after dissolving completely and be slowly added drop-wise in above-mentioned sulphuric acid soln, be stirred to and be terminal without during unhindered amina.
Above-mentioned diazonium salt solution is slowly added drop-wise in above-mentioned epoxy resin precursor solution, insulation reaction 12 hours at 0 DEG C, through precipitation, filtration, washing and drying treatment, obtains water-soluble vinyl sulfone epoxy resin-matrix macromolecule reactive dye.
Embodiment 31
Get 227.3 grams of (0.5mol) dihydroxyphenyl propane-diglycidylethers (epoxy equivalent (weight)=227) and 46.5 grams of aniline (0.5mol), after being uniformly mixed, at N
2slowly be warming up to about 110 DEG C under condition, insulation reaction, after 72 hours, obtains white clear epoxy resin precursor solid.
Get the 1.65mL vitriol oil, join in 10mL water, mix, for subsequent use after making temperature be reduced to about 0 DEG C.Getting 3.51 grams of (0.012mol) para-esters joins in 30mL water, then 10% sodium carbonate solution is added, regulation system pH is 6 ~ 7, be stirred to para-ester to dissolve completely, add 0.836 gram of 99% (0.012mol) Sodium Nitrite solid again, be stirred to after dissolving completely and be slowly added drop-wise in above-mentioned sulphuric acid soln, be stirred to and be terminal without during unhindered amina.
Get 5.476 grams (0.01mol) above-mentioned epoxy resin precursor, add 400mLN, N '-dimethyl formamide, stirring is placed in ice-water bath after making it dissolve completely, makes temperature be reduced to about 0 DEG C, slow dropping is to above-mentioned diazonium salt solution, insulation reaction 12 hours at 0 DEG C, through precipitation, filtration, washing and drying treatment, obtains water-soluble vinyl sulfone epoxy resin-matrix macromolecule reactive dye.
Embodiment 32
Get 164.0 grams of (0.5mol) bisphenol-fs diglycidylether (epoxy equivalent (weight)=164) and 46.5 grams of aniline (0.5mol), after being uniformly mixed, at N
2slowly be warming up to about 110 DEG C under condition, insulation reaction, after 72 hours, obtains white clear epoxy resin precursor solid.
Get the 1.65mL vitriol oil, join in 10mL water, mix, for subsequent use after making temperature be reduced to about 0 DEG C.Getting 3.51 grams of (0.012mol) para-esters joins in 30mL water, then 10% sodium carbonate solution is added, regulation system pH is 6 ~ 7, be stirred to para-ester to dissolve completely, add 0.836 gram of 99% (0.012mol) Sodium Nitrite solid again, be stirred to after dissolving completely and be slowly added drop-wise in above-mentioned sulphuric acid soln, be stirred to and be terminal without during unhindered amina.
Get above-mentioned epoxy resin precursor 4.21 grams (0.01mol), use 300mL N, N '-dimethyl formamide dissolves completely, with ice-water bath, the temperature of solution is reduced to about 0 DEG C.The above-mentioned diazonium salt solution of slow dropping, insulation reaction 12 hours at 0 DEG C, through precipitation, filtration, washing and drying treatment, obtains water-soluble vinyl sulfone epoxy resin family macromolecule reactive dyestuffs.
Claims (1)
1. a diazotization and coupling prepares the method for water-soluble vinyl sulfone epoxy resin-matrix macromolecule reactive dye, it is characterized in that: with epoxy resin precursor for high polymer main chain, diazonium salt is prepared with hydroxyethyl sulfone sulfate arylamine, prepare water-soluble vinyl sulfone epoxy resin-matrix macromolecule reactive dye by diazotization and coupling, the method comprises following step:
(1) preparation of epoxy resin precursor
Epoxy resin precursor is the epoxy-based polymer with the anilino residue functional group that can carry out diazo coupling reaction; its general structure is as shown in (c); epoxy resin precursor by epoxy resin and aniline at 110 ~ 130 DEG C; be obtained by reacting under nitrogen protection condition, its general reaction formula is as follows
Wherein (a) is epoxy resin, and be any one in bisphenol-A diglycidylether, bisphenol-f diglycidylether or bis-phenol-H diglycidylether, the R in above formula is the one in following structure,
Wherein (b) is aniline,
The preparation method of epoxy resin precursor is as follows: at N
2under protection, be epoxy resin by molar weight ratio: aniline=1: 1 by any one epoxy resin above-mentioned and aniline Homogeneous phase mixing, is slowly warming up to 110 ~ 130 DEG C, insulation reaction more than 72 hours, obtained epoxy resin precursor;
(2) adopt following any one method to obtain ethyl sulfonyl sulfate arylamine diazonium salt solution, reaction equation is as follows:
Wherein Y=HSO
4or Cl,
Be used for carrying out diazotizing hydroxyethyl sulfone sulfate arylamine to have: p-aminophenyl-β hydroxyethyl sulfone sulfate, a beta-sulfuric ester ethyl sulfonyl base aniline, 2-anisidine-5-β hydroxyethyl sulfone sulfate, 2-benzaminic acid-5-β hydroxyethyl sulfone sulfate, 4-β hydroxyethyl sulfone sulfate ester aniline-2-sulfonic acid, 2-[2-(3-aminobenzamidoyl) ethyl sulfuryl] ethanol sulfuric acid ester, 6-β hydroxyethyl sulfone sulfate-2-naphthylamines-1-sulfonic acid, wherein Ar is the one in following structure
Diazonium salt solution preparation method 1: under 0 DEG C of condition, compares Ar-NH by molar weight
2: H
2sO
4=1: 2.5 ~ 3, get massfraction be 30% sulphuric acid soln for subsequent use, add water hydroxyethyl sulfone sulfate arylamine mixing, adds 10%Na
2cO
3solution, regulation system pH is 6 ~ 7, is stirred to arylamine and dissolves completely, compares Ar-NH by molar weight
2: NaNO
2=1: 1 ~ 1.2 add Sodium Nitrite solid, are stirred to after dissolving completely and are slowly added drop-wise in above-mentioned sulphuric acid soln, be stirred to and be terminal without during unhindered amina;
Diazonium salt solution preparation method 2: under 0 DEG C of condition, compares Ar-NH by molar weight
2: HCl=1: 2.5 ~ 3 get volume ratio be 1: 10 hydrochloric acid soln for subsequent use, add water hydroxyethyl sulfone sulfate arylamine mixing, adds 10%Na
2cO
3solution, regulation system pH is 6 ~ 7, is stirred to arylamine and dissolves completely, compares Ar-NH by molar weight
2: NaNO
2=1: 1 ~ 1.2 add Sodium Nitrite solid, are stirred to after dissolving completely and are slowly added drop-wise in above-mentioned hydrochloric acid soln, be stirred to and be terminal without during unhindered amina;
(3) diazo coupling reaction of epoxy resin precursor and ethyl sulfonyl sulfate arylamine diazonium salt:
In ice-water bath, by above-mentioned epoxy resin precursor N, dinethylformamide solvent dissolves completely, under high velocity agitation, by molar weight than ethyl sulfonyl sulfate arylamine diazonium salt: epoxy resin precursor=0.4 ~ 1.2: 1, slowly join in above-mentioned epoxy resin precursor solution by above-mentioned ethyl sulfonyl sulfate arylamine diazonium salt solution, insulation reaction more than 12 hours under 0 DEG C of condition, its general reaction formula is as follows
After reaction completes, after precipitation, filtration, washing and drying, obtain water-soluble vinyl sulfone epoxy resin-matrix macromolecule reactive dye.
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| 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 |
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