CN101768373A - Method for preparing water soluble vinyl-sulfone polyurethane class high molecular reactive dye with diazo coupling method - Google Patents

Method for preparing water soluble vinyl-sulfone polyurethane class high molecular reactive dye with diazo coupling method Download PDF

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CN101768373A
CN101768373A CN201010028937A CN201010028937A CN101768373A CN 101768373 A CN101768373 A CN 101768373A CN 201010028937 A CN201010028937 A CN 201010028937A CN 201010028937 A CN201010028937 A CN 201010028937A CN 101768373 A CN101768373 A CN 101768373A
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易长海
甘厚磊
金雪
王罗新
邹汉涛
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Wuhan University of Science and Engineering WUSE
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Wuhan University of Science and Engineering WUSE
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Abstract

The present invention relates to a method for preparing water soluble vinyl-sulfone polyurethane class high molecular reactive dye with a diazo coupling method. A polyurethane precursor is used as a high molecular skeleton, diazo salt is then prepared from hydroxyethyl sulfone sulfate class arylamine, the diazo salt finally has diazo coupling reaction with the polyurethane precursor, and the water soluble vinyl-sulfone polyurethane class high molecular reactive dye is prepared. The dye having good water solubility can react with materials containing hydroxy or amino groups under alkaline conditions to complete color fixation. The problems about dyeing fastness, etc are solved. The method has the advantages of simple synthesis thought, easy functionality control, high diazo coupling rate, etc. The dye can be used for dyeing materials containing cotton, hemp, silk, fur, leather, paper, etc, can be used in the spinning processing of spandex stock solution for preparing colored spandex, can be used as the coloring agent and the filler of plastics, rubber, paint and adhesives, and can be used as the coloring agent ingredient of digital jet printing ink.

Description

A kind of diazo coupling legal system is equipped with the method for water soluble vinyl-sulfone polyurethane class high molecular reactive dye
Technical field
The present invention relates to the method that a kind of diazo coupling legal system is equipped with water soluble vinyl-sulfone polyurethane class high molecular reactive dye, belong to the high molecular dye field.
Background technology
At dye field, general dyestuff (except the reactive dyestuffs) is to be fixed on by ionic linkage, hydrogen bond, hydrophobic interaction etc. to be dyed on the material, bonding force is not strong, in placement, washing, dry-cleaning process, easily migrate to material surface, causing constantly comes off fades, and defective such as the small molecule active dyestuff exists dye utilization rate low, and environmental pollution is serious.Along with the attention of people to green, environmental protection, all there is special requirement in many fields to the performance of dyestuff, and this makes people that sight is turned in the synthetic and exploitation that substitutes dyestuff, and the high molecular of low molecular dye just can address the above problem effectively.
High molecular dye is 20th century new dyes that grow up of the mid-1970s, it is by certain chemical reaction dye molecule to be introduced the main chain of macromolecular chain or hung on the coloured macromolecule polymkeric substance that forms on the side chain, it is with high molecular easy film-forming properties, high strength, anti-solvent, thermotolerance and organic dye are to excellent performance such as the strong absorbent of light and colorful property.Wherein the azo high molecular dye is that azo-functional group is grafted on the polymer macromolecule, obtain having the polymer macromolecule of azo side group, up to now, a large amount of side chain type azobenzene polymers have been synthesized, press polymeric main chain structure difference, mainly can be divided into several big classes such as poly-(methyl) acrylate type, polyester type, polysiloxane type, polystyrene type and polyurethane-type.Urethane (PU) is a class very important polymkeric substance in polymeric material field, from drawing attention very soon once occurring, has obtained fast development.Urethane is a class multi-block polymer, and general urethane is obtained by binary or polynary organic isocyanate and polyol reaction.Contain similar amide group in its structure (NHCO-) and ester group (structure COO-), so its character is between between the two.Since the good toughness of urethane, the intensity height, the performance that wear resistance, lower temperature resistance, resistance to tearing and good biocompatibility etc. are outstanding, it is wide to make it use, and occupies first of the various synthetic materialss.At present, the synthetic method of urethane azoic dyestuff mainly contains following two kinds:
But a. synthetic earlier urethane that contains diazo coupling reaction carries out diazo coupling reaction with diazonium salt again.As Bai Xuduo etc., in Chinese periodical " applied chemistry ", volume the 7th interim the report was called " the synthetic and sign of azo chromophore side group urethane " in 2000 the 1st, the document discloses with N-phenyldiethanol-amine and Toluene-2,4-diisocyanate, 4-vulcabond elder generation synthesis of polyurethane polymer, carry out diazo coupling reaction again, form urethane azo high molecular dye.
Figure G2010100289371D00021
Its weak point is that synthetic polyurethane high molecule dyestuff do not have can be further and the active group of dyeing substrate reactions, and high molecular dye is not water-soluble.
But the b. synthetic earlier azo small molecules that has reactive group is again with monomer that contains isocyanate group or prepolymer reaction.As Tinca Buruiana, E.C.Buruiana is at Journal of Applied Polymer Science.2005,96 have reported Poly-by name (etherurethane) Anionomers with Azobenzene Carboxylate Groups:Synthesis and Properties, the document discloses first diazo coupling and has prepared hydroxyl azo small molecules, with di-isocyanate reaction, form urethane azo high molecular dye again.
Figure G2010100289371D00022
Its weak point is that the polyurethane high molecule dyestuff of preparation do not have can be further and the active group of dyeing substrate reactions, and a little less than high molecular dye is water-soluble, and the affinity between the pole filter is bad.
Because azo class urethane high molecular dye all is solvent type basically, its cost height pollutes greatly, and the application aspect textile printing and dyeing is few.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 polyurethane class high molecular reactive dye aspect.
Summary of the invention
Problem at above-mentioned existence, the purpose of this invention is to provide the method that a kind of diazo coupling legal system is equipped with water soluble vinyl-sulfone polyurethane class high molecular reactive dye, start with from Molecular Structure Design, proposition is a macromolecular scaffold to have the polyurethanes precursor that can carry out diazo coupling reaction functional group, to have hydroxyethyl sulfone sulfate class arylamine and be prepared into diazonium salt, coupled reaction by polyurethanes precursor and diazonium salt, directly prepare water soluble vinyl-sulfone polyurethane class high molecular reactive dye, its technical solution is carried out according to the following steps:
(1) polyurethanes precursor preparation
The polyurethanes precursor is the polyurethane polymer that contains functional group's (N-phenyldiethanol-amine residue) that can carry out diazo coupling reaction; its general molecular structural formula is shown in (e); the polyurethanes precursor by vulcabond and N-phenyldiethanol-amine at N; in N '-dimethyl formamide solution; polyreaction obtains under the nitrogen protection, and its general reaction formula is as follows:
Figure G2010100289371D00031
Wherein (c) is diisocyanate monomer, be Toluene-2,4-diisocyanate, 4-vulcabond, ditan-4,4 '-vulcabond, 1, hexamethylene-diisocyanate, isophorone diisocyanate, xylylene diisocyanate, naphthalene-1, any in the 5-vulcabond, the R in the following formula are a kind of in the following structure:
Figure G2010100289371D00032
Wherein (d) is the N-phenyldiethanol-amine,
The preparation method of polyurethanes precursor is as follows: at N 2Protection down, be vulcabond by the molar weight ratio: N-phenyldiethanol-amine=1: 1, with above-mentioned any one vulcabond and N-phenyldiethanol-amine N, the dinethylformamide solvent dissolves fully, mixing stirs, drip a small amount of dibutyl tin, slowly be warming up to 80～85 ℃, insulation reaction 12 hours, through precipitation, filter washing, the dry polyurethanes precursor that gets;
(2) adopt following any method to obtain ethyl sulfonyl sulfate class arylamine diazonium salt solution, its general 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 the Ar of following formula 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; Get hydroxyethyl sulfone sulfate class arylamine and add the water mixing, 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;
Diazonium salt solution preparation method 2: under 0 ℃ of condition, compare Ar-NH by molar weight 2: HCl=1: 2.5～3, get volume ratio and 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;
(3) coupled reaction of polyurethanes precursor and hydroxyethyl sulfone sulfate class arylamine diazonium salt:
In ice-water bath, with above-mentioned polyurethanes precursor N, dinethylformamide (DMF) solvent dissolves fully, under evenly stirring, by molar weight than ethyl sulfonyl sulfate class arylamine diazonium salt: polyurethanes precursor=0.4～1.2: 1, above-mentioned hydroxyethyl sulfone sulfate class arylamine diazonium salt solution is slowly joined in the above-mentioned polyurethanes precursor solution, insulation reaction is 12 hours under 0 ℃ of condition, after reaction is finished, after precipitation, filtration, washing and drying, get water soluble vinyl-sulfone polyurethane class high molecular reactive dye, its general reaction formula is as follows
Figure G2010100289371D00051
Owing to adopted above technical scheme, diazo coupling legal system of the present invention is equipped with the method for water soluble vinyl-sulfone polyurethane class high molecular reactive dye, this method synthetic route is simple, functionality is easy to control, and be easy to preparation and contain the chromophoric urethane dyestuff of different content, the coupled reaction transformation efficiency can through simple purification process, can directly obtain the water-soluble how active polyurethane class high molecular dyestuff of various lovely lusters up to more than 90%.
Water soluble vinyl-sulfone polyurethane class high molecular dyestuff of the present invention is a kind of water-soluble polymer dyestuff, contain water-soluble sulfate group on the molecular chain, the good water solubility of high molecular dye, be 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 polyurethane class high molecular dyestuff of the present invention is a kind of active high molecular dye, owing to contain the ethyl sulfone group of a plurality of lateral reactivities on the molecular chain, under alkaline condition, the vinyl sulfone(Remzaol active group that forms can be finished fixation by the formation of covalent linkage with the dyeing substrate that contains reactive groups such as hydroxyl and amino, 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.And have neither part nor lot in the high molecular dye of reaction, can become not water-soluble hydroxyethyl sulfone type polyurethane family macromolecule dyestuff in hydrolysis under the alkaline condition, through staticly settle, filter, washing, drying treatment, recyclable hydroxyethyl sulfone type polyurethane family macromolecule dyestuff, reduce coloured liquid discharging, reduced environmental pollution.
Water soluble vinyl-sulfone polyurethane class high molecular dyestuff of the present invention, molecular backbone chain contains carbamate, with spandex good consistency is arranged, and can be applicable in the spandex fibre stoste spinning processing, prepares coloured spandex fibre.
Water-soluble vinyl sulfone type polyurethane based high molecular dyestuff of the present invention, with the polymkeric substance is the high molecular dye skeleton, good with the consistency of superpolymer, Dry Sack is bright-coloured, strong coloring force, solvent resistance, resistance to migration, the less molecular dye of thermotolerance improve greatly, can be used as the tinting material and the weighting agent of materials such as plastics, rubber, coating, binding agent.
Embodiment
Below in conjunction with specific embodiment the present invention is done and to describe in further detail.
Embodiment 1
Get 9.05 gram (0.05mol) N-phenyldiethanol-amines; add 150mL DMF, after the magnetic agitation dissolving, be added dropwise to 8.807 gram (0.05mol) Toluene-2,4-diisocyanates; 4-vulcabond (TDI) and a spot of dibutyl tin are warming up to 85 ℃ of reactions 12 hours under nitrogen protection.Through precipitation, filtration, washing and dry, get white polyurethane precursor solid.
Get the 1.65mL vitriol oil, join in the 10mL water, mix, treat that temperature is standby after being reduced to 0 ℃.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 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 polyurethanes precursor 3.571 grams (0.01mol), use 100mL N, N '-dimethyl formamide dissolving fully afterwards is reduced to 0 ℃ with ice-water bath with the temperature of solution.The above-mentioned diazonium salt solution of slow dropping evenly stirred insulation reaction 12 hours down at 0 ℃, through precipitation, filtration, washing and drying treatment, got water soluble vinyl-sulfone polyurethane class high molecular reactive dye.
Embodiment 2
Adopt identical urethane precursor among the embodiment 1.Get urethane precursor identical among the embodiment 1 3.571 gram (0.01mol), use 100mL N, N '-dimethyl formamide dissolving fully afterwards is reduced to 0 ℃ with ice-water bath with the temperature of solution.
Get 3mL 36.5% concentrated hydrochloric acid, join in the 30mL water, mix, treat that temperature is standby after being reduced to 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 urethane precursor solution, evenly stirred insulation reaction 12 hours down,, get water soluble vinyl-sulfone polyurethane class high molecular reactive dye through precipitation, filtration, washing and drying treatment at 0 ℃.
Embodiment 3
Adopt identical urethane precursor among the embodiment 1.Get urethane precursor identical among the embodiment 1 3.571 gram (0.01mol), use 100mLN, N '-dimethyl formamide dissolving fully afterwards is reduced to 0 ℃ with ice-water bath with the temperature of solution.
Get the 0.40mL vitriol oil, join in the 10mL water, mix, treat that temperature is standby after being reduced to 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 slowly to be added drop-wise to after the dissolving fully and be terminal point when being stirred to no unhindered amina behind the above-mentioned sulphuric acid soln.
Above-mentioned diazonium salt solution slowly is added drop-wise in the above-mentioned urethane precursor solution, evenly stirred insulation reaction 12 hours down,, get water soluble vinyl-sulfone polyurethane class high molecular reactive dye through precipitation, filtration, washing and drying treatment at 0 ℃.
Embodiment 4
Adopt identical urethane precursor among the embodiment 1.Get urethane precursor identical among the embodiment 1 3.571 gram (0.01mol), use 100mLN, N '-dimethyl formamide dissolving fully afterwards is reduced to 0 ℃ with ice-water bath with the temperature of solution.
Get the 1.60mL vitriol oil, join in the 10mL water, mix, treat that temperature is standby after being reduced to 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 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 urethane precursor solution, evenly stirred insulation reaction 12 hours down,, get water soluble vinyl-sulfone polyurethane class high molecular reactive dye through precipitation, filtration, washing and drying treatment at 0 ℃.
Embodiment 5
Adopt identical urethane precursor among the embodiment 1.Get urethane precursor identical among the embodiment 1 3.571 gram (0.01mol), use 100mLN, N '-dimethyl formamide dissolving fully afterwards is reduced to 0 ℃ with ice-water bath with the temperature of solution.
Get the 1.65mL vitriol oil, join in the 10mL water, mix, treat that temperature is standby after being reduced to 0 ℃.Get 3.51 the gram (0.012mol) between beta-sulfuric ester ethyl sulfonyl base aniline (a 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, by 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 urethane precursor solution, evenly stirred insulation reaction 12 hours down,, get water soluble vinyl-sulfone polyurethane class high molecular reactive dye through precipitation, filtration, washing and drying treatment at 0 ℃.
Embodiment 6
Adopt identical urethane precursor among the embodiment 1.Get urethane precursor identical among the embodiment 1 3.571 gram (0.01mol), use 100mL N, N '-dimethyl formamide dissolving fully afterwards is reduced to 0 ℃ with ice-water bath with the temperature of solution.
Get the 1.65mL vitriol oil, join in the 10mL water, mix, treat that temperature is standby after being reduced to 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 urethane precursor solution, evenly stirred insulation reaction 12 hours down,, get water soluble vinyl-sulfone polyurethane class high molecular reactive dye through precipitation, filtration, washing and drying treatment at 0 ℃.
Embodiment 7
Adopt identical urethane precursor among the embodiment 1.Get urethane precursor identical among the embodiment 1 3.571 gram (0.01mol), use 100mLN, N '-dimethyl formamide dissolving fully afterwards is reduced to 0 ℃ with ice-water bath with the temperature of solution.
Get the 1.65mL vitriol oil, join in the 10mL water, mix, treat that temperature is standby after being reduced to 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 urethane precursor solution, evenly stirred insulation reaction 12 hours down,, get water soluble vinyl-sulfone polyurethane class high molecular reactive dye through precipitation, filtration, washing and drying treatment at 0 ℃.
Embodiment 8
Adopt identical urethane precursor among the embodiment 1.Get urethane precursor identical among the embodiment 1 3.571 gram (0.01mol), use 100mLN, after N '-dimethyl formamide dissolving is complete, the temperature of solution is reduced to 0 ℃ with ice-water bath.
Get the 1.65mL vitriol oil, join in the 10mL water, mix, treat that temperature is standby after being reduced to 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 urethane precursor solution, evenly stirred insulation reaction 12 hours down,, get water soluble vinyl-sulfone polyurethane class high molecular reactive dye through precipitation, filtration, washing and drying treatment at 0 ℃.
Embodiment 9
Adopt identical urethane precursor among the embodiment 1.Get urethane precursor identical among the embodiment 1 3.571 gram (0.01mol), use 100mL N, N '-dimethyl formamide dissolving fully afterwards is reduced to 0 ℃ with ice-water bath with the temperature of solution.
Get the 1.65mL vitriol oil, join in the 10mL water, mix, treat that temperature is standby after being reduced to 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 urethane precursor solution, evenly stirred insulation reaction 12 hours down,, get water soluble vinyl-sulfone polyurethane class high molecular reactive dye through precipitation, filtration, washing and drying treatment at 0 ℃.
Embodiment 10
Adopt identical urethane precursor among the embodiment 1.Get urethane precursor identical among the embodiment 1 3.571 gram (0.01mol), use 100mLN, N '-dimethyl formamide dissolving fully afterwards is reduced to 0 ℃ with ice-water bath with the temperature of solution.
Get the 1.65mL vitriol oil, join in the 10mL water, mix, treat that temperature is standby after being reduced to 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 urethane precursor solution, evenly stirred insulation reaction 12 hours down,, get water soluble vinyl-sulfone polyurethane class high molecular reactive dye through precipitation, filtration, washing and drying treatment at 0 ℃.
Embodiment 11
Get 9.05 gram (0.05mol) N-phenyldiethanol-amines and 12.513 gram (0.05mol) ditans-4; 4 '-vulcabond (MDI), add 150mL DMF, be stirred to dissolving fully after; drip a spot of dibutyl tin, 80 ℃ of nitrogen protections were reacted 12 hours down.Through precipitation, filter washing, the dry white polyurethane class precursor solid that gets.
Get the 1.65mL vitriol oil, join in the 10mL water, mix, treat that temperature is standby after being reduced to 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 urethane precursor 4.313 grams (0.01mol), use 100ml N, after N '-dimethyl formamide dissolving is complete, the temperature of solution is reduced to 0 ℃ with ice-water bath.Above-mentioned diazonium salt solution slowly is added drop-wise in the above-mentioned urethane precursor solution, evenly stirred insulation reaction 12 hours down,, get water soluble vinyl-sulfone polyurethane class high molecular reactive dye through precipitation, filtration, washing and drying treatment at 0 ℃.
Embodiment 12
Adopt identical urethane precursor among the embodiment 11.Get urethane precursor identical among the embodiment 11 4.313 gram (0.01mol), use 100mL N, N '-dimethyl formamide dissolving fully afterwards is reduced to 0 ℃ with ice-water bath with the temperature of solution.
Get the 3mL36.5% concentrated hydrochloric acid, join in the 30mL water, mix, treat that temperature is standby after being reduced to 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, 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 urethane precursor solution, evenly stirred insulation reaction 12 hours down,, get water soluble vinyl-sulfone polyurethane class high molecular reactive dye through precipitation, filtration, washing and drying treatment at 0 ℃.
Embodiment 13
Adopt identical urethane precursor among the embodiment 11.Get urethane precursor identical among the embodiment 11 4.313 gram (0.01mol), use 100mLN, N '-dimethyl formamide dissolving fully afterwards is reduced to 0 ℃ with ice-water bath with the temperature of solution.
Get the 0.40mL vitriol oil, join in the 10mL water, mix, treat that temperature is standby after being reduced to 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 urethane precursor solution, evenly stirred insulation reaction 12 hours down,, get water soluble vinyl-sulfone polyurethane class high molecular reactive dye through precipitation, filtration, washing and drying treatment at 0 ℃.
Embodiment 14
Adopt identical urethane precursor among the embodiment 11.Get urethane precursor identical among the embodiment 11 4.313 gram (0.01mol), use 100mLN, N '-dimethyl formamide dissolving fully afterwards is reduced to 0 ℃ with ice-water bath with the temperature of solution.
Get the 1.60mL vitriol oil, join in the 10mL water, mix, treat that temperature is standby after being reduced to 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 urethane precursor solution, evenly stirred insulation reaction 12 hours down,, get water soluble vinyl-sulfone polyurethane class high molecular reactive dye through precipitation, filtration, washing and drying treatment at 0 ℃.
Embodiment 15
Adopt identical urethane precursor among the embodiment 11.Get urethane precursor identical among the embodiment 11 4.313 gram (0.01mol), use 100mL N, N '-dimethyl formamide dissolving fully afterwards is reduced to 0 ℃ with ice-water bath with the temperature of solution.
Get the 1.65mL vitriol oil, join in the 10mL water, mix, treat that temperature is standby after being reduced to 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, 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 urethane precursor solution, evenly stirred insulation reaction 12 hours down,, get water soluble vinyl-sulfone polyurethane class high molecular reactive dye through precipitation, filtration, washing and drying treatment at 0 ℃.
Embodiment 16
Adopt identical urethane precursor among the embodiment 11.Get urethane precursor identical among the embodiment 11 4.313 gram (0.01mol), use 100mLN, N '-dimethyl formamide dissolving fully afterwards is reduced to 0 ℃ with ice-water bath with the temperature of solution.
Get the 1.65mL vitriol oil, join in the 10mL water, mix, treat that temperature is standby after being reduced to 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 urethane precursor solution, evenly stirred insulation reaction 12 hours down,, get water soluble vinyl-sulfone polyurethane class high molecular reactive dye through precipitation, filtration, washing and drying treatment at 0 ℃.
Embodiment 17
Adopt identical urethane precursor among the embodiment 11.Get urethane precursor identical among the embodiment 11 4.313 gram (0.01mol), use 100mL N, N '-dimethyl formamide dissolving fully afterwards is reduced to 0 ℃ with ice-water bath with the temperature of solution.
Get the 1.65mL vitriol oil, join in the 10mL water, mix, treat that temperature is standby after being reduced to 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 urethane precursor solution, evenly stirred insulation reaction 12 hours down,, get water soluble vinyl-sulfone polyurethane class high molecular reactive dye through precipitation, filtration, washing and drying treatment at 0 ℃.
Embodiment 18
Adopt identical urethane precursor among the embodiment 11.Get urethane precursor identical among the embodiment 11 4.313 gram (0.01mol), use 100mL N, N '-dimethyl formamide dissolving fully afterwards is reduced to 0 ℃ with ice-water bath with the temperature of solution.
Get the 1.65mL vitriol oil, join in the 10mL water, mix, treat that temperature is standby after being reduced to 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 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 urethane precursor solution, evenly stirred insulation reaction 12 hours down,, get water soluble vinyl-sulfone polyurethane class high molecular reactive dye through precipitation, filtration, washing and drying treatment at 0 ℃.
Embodiment 19
Adopt identical urethane precursor among the embodiment 11.Get urethane precursor identical among the embodiment 11 4.313 gram (0.01mol), use 100mL N, N '-dimethyl formamide dissolving fully afterwards is reduced to 0 ℃ with ice-water bath with the temperature of solution.
Get the 1.65mL vitriol oil, join in the 10mL water, mix, treat that temperature is standby after being reduced to 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 urethane precursor solution, evenly stirred insulation reaction 12 hours down,, get water soluble vinyl-sulfone polyurethane class high molecular reactive dye through precipitation, filtration, washing and drying treatment at 0 ℃.
Embodiment 20
Adopt identical urethane precursor among the embodiment 11.Get urethane precursor identical among the embodiment 11 4.313 gram (0.01mol), use 100mLN, N '-dimethyl formamide dissolving fully afterwards is reduced to 0 ℃ with ice-water bath with the temperature of solution.
Get the 1.65mL vitriol oil, join in the 10mL water, mix, treat that temperature is standby after being reduced to 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 urethane precursor solution, evenly stirred insulation reaction 12 hours down,, get water soluble vinyl-sulfone polyurethane class high molecular reactive dye through precipitation, filtration, washing and drying treatment at 0 ℃.
Embodiment 21
Get 9.05 gram (0.05mol) N-phenyldiethanol-amines, add 150mL DMF, after being stirred to it and dissolving fully, drip 8.41 gram (0.05mol) hexamethylene diisocyanate (HDI) and a spot of dibutyl tins, 80 ℃ of nitrogen protections were reacted 12 hours down.Through precipitation, filter washing, the dry polyurethanes precursor that gets.
Get the 1.65mL vitriol oil, join in the 10mL water, mix, treat that temperature is standby after being reduced to 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 urethane precursor 3.49 grams (0.01mol), use 100mL N, N '-dimethyl formamide dissolving fully afterwards is reduced to 0 ℃ with ice-water bath with the temperature of solution.The above-mentioned diazonium salt solution of slow dropping evenly stirred insulation reaction 12 hours down at 0 ℃, through precipitation, filtration, washing and drying treatment, got water soluble vinyl-sulfone polyurethane class high molecular reactive dye.
Embodiment 22
Adopt identical urethane precursor among the embodiment 21.Get urethane precursor identical among the embodiment 21 3.49 gram (0.01mol), use 100mL N, N '-dimethyl formamide dissolving fully afterwards is reduced to 0 ℃ with ice-water bath with the temperature of solution.
Get 3mL 36.5% concentrated hydrochloric acid, join in the 30mL water, mix, treat that temperature is standby after being reduced to 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 urethane precursor solution, evenly stirred insulation reaction 12 hours down,, get water soluble vinyl-sulfone polyurethane class high molecular reactive dye through precipitation, filtration, washing and drying treatment at 0 ℃.
Embodiment 23
Adopt identical urethane precursor among the embodiment 21.Get urethane precursor identical among the embodiment 21 3.49 gram (0.01mol), use 100mL N, N '-dimethyl formamide dissolving fully afterwards is reduced to 0 ℃ with ice-water bath with the temperature of solution.
Get the 0.40mL vitriol oil, join in the 10mL water, mix, treat that temperature is standby after being reduced to 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 urethane precursor solution, evenly stirred insulation reaction 12 hours down,, get water soluble vinyl-sulfone polyurethane class high molecular reactive dye through precipitation, filtration, washing and drying treatment at 0 ℃.
Embodiment 24
Adopt identical urethane precursor among the embodiment 21.Get urethane precursor identical among the embodiment 21 3.49 gram (0.01mol), use 100mL N, N '-dimethyl formamide dissolving fully afterwards is reduced to 0 ℃ with ice-water bath with the temperature of solution.
Get the 1.60mL vitriol oil, join in the 10mL water, mix, treat that temperature is standby after being reduced to 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 urethane precursor solution, evenly stirred insulation reaction 12 hours down,, get water soluble vinyl-sulfone polyurethane class high molecular reactive dye through precipitation, filtration, washing and drying treatment at 0 ℃.
Embodiment 25
Adopt identical urethane precursor among the embodiment 21.Get urethane precursor identical among the embodiment 21 3.49 gram (0.01mol), use 100mL N, N '-dimethyl formamide dissolving fully afterwards is reduced to 0 ℃ with ice-water bath with the temperature of solution.
Get the 1.65mL vitriol oil, join in the 10mL water, mix, treat that temperature is standby after being reduced to 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, 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 urethane precursor solution, evenly stirred insulation reaction 12 hours down,, get water soluble vinyl-sulfone polyurethane class high molecular reactive dye through precipitation, filtration, washing and drying treatment at 0 ℃.
Embodiment 26
Adopt identical urethane precursor among the embodiment 21.Get urethane precursor identical among the embodiment 21 3.49 gram (0.01mol), use 100mL N, N '-dimethyl formamide dissolving fully afterwards is reduced to 0 ℃ with ice-water bath with the temperature of solution.
Get the 1.65mL vitriol oil, join in the 10mL water, mix, treat that temperature is standby after being reduced to 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 urethane precursor solution, evenly stirred insulation reaction 12 hours down,, get water soluble vinyl-sulfone polyurethane class high molecular reactive dye through precipitation, filtration, washing and drying treatment at 0 ℃.
Embodiment 27
Adopt identical urethane precursor among the embodiment 21.Get urethane precursor identical among the embodiment 21 3.49 gram (0.01mol), use 100mL N, N '-dimethyl formamide dissolving fully afterwards is reduced to 0 ℃ with ice-water bath with the temperature of solution.
Get the 1.65mL vitriol oil, join in the 10mL water, mix, treat that temperature is standby after being reduced to 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 urethane precursor solution, evenly stirred insulation reaction 12 hours down,, get water soluble vinyl-sulfone polyurethane class high molecular reactive dye through precipitation, filtration, washing and drying treatment at 0 ℃.
Embodiment 28
Adopt identical urethane precursor among the embodiment 21.Get urethane precursor identical among the embodiment 21 3.49 gram (0.01mol), use 100mL N, N '-dimethyl formamide dissolving fully afterwards is reduced to 0 ℃ with ice-water bath with the temperature of solution.
Get the 1.65mL vitriol oil, join in the 10mL water, mix, treat that temperature is standby after being reduced to 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 urethane precursor solution, evenly stirred insulation reaction 12 hours down,, get water soluble vinyl-sulfone polyurethane class high molecular reactive dye through precipitation, filtration, washing and drying treatment at 0 ℃.
Embodiment 29
Adopt identical urethane precursor among the embodiment 21.Get urethane precursor identical among the embodiment 21 3.49 gram (0.01mol), use 100mL N, N '-dimethyl formamide dissolving fully afterwards is reduced to 0 ℃ with ice-water bath with the temperature of solution.
Get the 1.65mL vitriol oil, join in the 10mL water, mix, treat that temperature is standby after being reduced to 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 urethane precursor solution, evenly stirred insulation reaction 12 hours down,, get water soluble vinyl-sulfone polyurethane class high molecular reactive dye through precipitation, filtration, washing and drying treatment at 0 ℃.
Embodiment 30
Adopt identical urethane precursor among the embodiment 21.Get urethane precursor identical among the embodiment 21 3.49 gram (0.01mol), use 100mL N, N '-dimethyl formamide dissolving fully afterwards is reduced to 0 ℃ with ice-water bath with the temperature of solution.
Get the 1.65mL vitriol oil, join in the 10mL water, mix, treat that temperature is standby after being reduced to 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 urethane precursor solution, evenly stirred insulation reaction 12 hours down,, get water soluble vinyl-sulfone polyurethane class high molecular reactive dye through precipitation, filtration, washing and drying treatment at 0 ℃.
Embodiment 31
Get 9.05 gram (0.05mol) N-phenyldiethanol-amines, add 150mLDMF, after being stirred to it and dissolving fully, drip 11.115 gram (0.05mol) isophorone diisocyanate (IPDI) and a spot of dibutyl tins, 85 ℃ of nitrogen protections were reacted 12 hours.Through precipitation, filter washing, the dry polyurethanes precursor that gets.
Get the 1.65mL vitriol oil, join in the 10mL water, mix, treat that temperature is standby after being reduced to 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 urethane precursor 4.033 grams (0.01mol), use 100mL N, N '-dimethyl formamide dissolving fully afterwards is reduced to 0 ℃ with ice-water bath with the temperature of solution.The above-mentioned diazonium salt solution of slow dropping evenly stirred insulation reaction 12 hours down at 0 ℃, through precipitation, filtration, washing and drying treatment, got water soluble vinyl-sulfone polyurethane class high molecular reactive dye.
Embodiment 32
Adopt identical urethane precursor among the embodiment 31.Get urethane precursor identical among the embodiment 31 4.033 gram (0.01mol), use 100mL N, N '-dimethyl formamide dissolving fully afterwards is reduced to 0 ℃ with ice-water bath with the temperature of solution.
Get the 3mL36.5% concentrated hydrochloric acid, join in the 30mL water, mix, treat that temperature is standby after being reduced to 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 urethane precursor solution, evenly stirred insulation reaction 12 hours down,, get water soluble vinyl-sulfone polyurethane class high molecular reactive dye through precipitation, filtration, washing and drying treatment at 0 ℃.
Embodiment 33
Adopt identical urethane precursor among the embodiment 31.Get urethane precursor identical among the embodiment 31 4.033 gram (0.01mol), use 100mL N, N '-dimethyl formamide dissolving fully afterwards is reduced to 0 ℃ with ice-water bath with the temperature of solution.
Get the 0.40mL vitriol oil, join in the 10mL water, mix, treat that temperature is standby after being reduced to 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 urethane precursor solution, evenly stirred insulation reaction 12 hours down,, get water soluble vinyl-sulfone polyurethane class high molecular reactive dye through precipitation, filtration, washing and drying treatment at 0 ℃.
Embodiment 34
Adopt identical urethane precursor among the embodiment 31.Get urethane precursor identical among the embodiment 31 4.033 gram (0.01mol), use 100mLN, N '-dimethyl formamide dissolving fully afterwards is reduced to 0 ℃ with ice-water bath with the temperature of solution.
Get the 1.60mL vitriol oil, join in the 10mL water, mix, treat that temperature is standby after being reduced to 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 urethane precursor solution, evenly stirred insulation reaction 12 hours down,, get water soluble vinyl-sulfone polyurethane class high molecular reactive dye through precipitation, filtration, washing and drying treatment at 0 ℃.
Embodiment 35
Adopt identical urethane precursor among the embodiment 31.Get urethane precursor identical among the embodiment 31 4.033 gram (0.01mol), use 100mL N, N '-dimethyl formamide dissolving fully afterwards is reduced to 0 ℃ with ice-water bath with the temperature of solution.
Get the 1.65mL vitriol oil, join in the 10mL water, mix, treat that temperature is standby after being reduced to 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, 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 urethane precursor solution, evenly stirred insulation reaction 12 hours down,, get water soluble vinyl-sulfone polyurethane class high molecular reactive dye through precipitation, filtration, washing and drying treatment at 0 ℃.
Embodiment 36
Adopt identical urethane precursor among the embodiment 31.Get urethane precursor identical among the embodiment 31 4.033 gram (0.01mol), use 100mL N, N '-dimethyl formamide dissolving fully afterwards is reduced to 0 ℃ with ice-water bath with the temperature of solution.
Get the 1.65mL vitriol oil, join in the 10mL water, mix, treat that temperature is standby after being reduced to 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 urethane precursor solution, evenly stirs insulation reaction down about 12 hours,, get water soluble vinyl-sulfone polyurethane class high molecular reactive dye through precipitation, filtration, washing and drying treatment at 0 ℃.
Embodiment 37
Adopt identical urethane precursor among the embodiment 31.Get urethane precursor identical among the embodiment 31 4.033 gram (0.01mol), use 100mL N, N '-dimethyl formamide dissolving fully afterwards is reduced to 0 ℃ with ice-water bath with the temperature of solution.
Get the 1.65mL vitriol oil, join in the 10mL water, mix, treat that temperature is standby after being reduced to 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 urethane precursor solution, evenly stirred insulation reaction 12 hours down,, get water soluble vinyl-sulfone polyurethane class high molecular reactive dye through precipitation, filtration, washing and drying treatment at 0 ℃.
Embodiment 38
Adopt identical urethane precursor among the embodiment 31.Get urethane precursor identical among the embodiment 31 4.033 gram (0.01mol), use 100mL N, N '-dimethyl formamide dissolving fully afterwards is reduced to 0 ℃ with ice-water bath with the temperature of solution.
Get the 1.65mL vitriol oil, join in the 10mL water, mix, treat that temperature is standby after being reduced to 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 urethane precursor solution, evenly stirred insulation reaction 12 hours down,, get water soluble vinyl-sulfone polyurethane class high molecular reactive dye through precipitation, filtration, washing and drying treatment at 0 ℃.
Embodiment 39
Adopt identical urethane precursor among the embodiment 31.Get urethane precursor identical among the embodiment 31 4.033 gram (0.01mol), use 100mL N, N '-dimethyl formamide dissolving fully afterwards is reduced to 0 ℃ with ice-water bath with the temperature of solution.
Get the 1.65mL vitriol oil, join in the 10mL water, mix, treat that temperature is standby after being reduced to 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 urethane precursor solution, evenly stirred insulation reaction 12 hours down,, get water soluble vinyl-sulfone polyurethane class high molecular reactive dye through precipitation, filtration, washing and drying treatment at 0 ℃.
Embodiment 40
Adopt identical urethane precursor among the embodiment 31.Get urethane precursor identical among the embodiment 31 4.033 gram (0.01mol), use 100mL N, N '-dimethyl formamide dissolving fully afterwards is reduced to 0 ℃ with ice-water bath with the temperature of solution.
Get the 1.65mL vitriol oil, join in the 10mL water, mix, treat that temperature is standby after being reduced to 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 urethane precursor solution, evenly stirred insulation reaction 12 hours down,, get water soluble vinyl-sulfone polyurethane class high molecular reactive dye through precipitation, filtration, washing and drying treatment at 0 ℃.
Embodiment 41
Get 9.05 gram (0.05mol) N-phenyldiethanol-amines, add 150mLDMF, after being stirred to it and dissolving fully, drip 9.41 gram (0.05mol) xylylene diisocyanate (XDI) and a spot of dibutyl tins, 85 ℃ of nitrogen protections were reacted 12 hours down.Through precipitation, filter washing, the dry polyurethanes precursor that gets.
Get the 1.65mL vitriol oil, join in the 10mL water, mix, treat that temperature is standby after being reduced to 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 urethane precursor 3.692 grams (0.01mol), use 100mLN, N '-dimethyl formamide dissolving fully afterwards is reduced to 0 ℃ with ice-water bath with the temperature of solution.The above-mentioned diazonium salt solution of slow dropping evenly stirred insulation reaction 12 hours down at 0 ℃, through precipitation, filtration, washing and drying treatment, got water soluble vinyl-sulfone polyurethane class high molecular reactive dye.
Embodiment 42
Adopt identical urethane precursor among the embodiment 41.Get urethane precursor identical among the embodiment 41 3.692 gram (0.01mol), use 100mL N, N '-dimethyl formamide dissolving fully afterwards is reduced to 0 ℃ with ice-water bath with the temperature of solution.
Get 3mL 36.5% concentrated hydrochloric acid, join in the 30mL water, mix, treat that temperature is standby after being reduced to 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 urethane precursor solution, evenly stirred insulation reaction 12 hours down,, get water soluble vinyl-sulfone polyurethane class high molecular reactive dye through precipitation, filtration, washing and drying treatment at 0 ℃.
Embodiment 43
Adopt identical urethane precursor among the embodiment 41.Get urethane precursor identical among the embodiment 41 3.692 gram (0.01mol), use 100mL N, N '-dimethyl formamide dissolving fully afterwards is reduced to 0 ℃ with ice-water bath with the temperature of solution.
Get the 0.40mL vitriol oil, join in the 10mL water, mix, treat that temperature is standby after being reduced to 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 urethane precursor solution, evenly stirred insulation reaction 12 hours down,, get water soluble vinyl-sulfone polyurethane class high molecular reactive dye through precipitation, filtration, washing and drying treatment at 0 ℃.
Embodiment 44
Adopt identical urethane precursor among the embodiment 41.Get urethane precursor identical among the embodiment 41 3.692 gram (0.01mol), use 100mL N, N '-dimethyl formamide dissolving fully afterwards is reduced to 0 ℃ with ice-water bath with the temperature of solution.
Get the 1.60mL vitriol oil, join in the 10mL water, mix, treat that temperature is standby after being reduced to 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 urethane precursor solution, evenly stirred insulation reaction 12 hours down,, get water soluble vinyl-sulfone polyurethane class high molecular reactive dye through precipitation, filtration, washing and drying treatment at 0 ℃.
Embodiment 45
Adopt identical urethane precursor among the embodiment 41.Get urethane precursor identical among the embodiment 41 3.692 gram (0.01mol), use 100mL N, N '-dimethyl formamide dissolving fully afterwards is reduced to 0 ℃ with ice-water bath with the temperature of solution.
Get the 1.65mL vitriol oil, join in the 10mL water, mix, treat that temperature is standby after being reduced to 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, 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 urethane precursor solution, evenly stirred insulation reaction 12 hours down,, get water soluble vinyl-sulfone polyurethane class high molecular reactive dye through precipitation, filtration, washing and drying treatment at 0 ℃.
Embodiment 46
Adopt identical urethane precursor among the embodiment 41.Get urethane precursor identical among the embodiment 41 3.692 gram (0.01mol), use 100mL N, N '-dimethyl formamide dissolving fully afterwards is reduced to 0 ℃ with ice-water bath with the temperature of solution.
Get the 1.65mL vitriol oil, join in the 10mL water, mix, treat that temperature is standby after being reduced to 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 urethane precursor solution, evenly stirred insulation reaction 12 hours down,, get water soluble vinyl-sulfone polyurethane class high molecular reactive dye through precipitation, filtration, washing and drying treatment at 0 ℃.
Embodiment 47
Adopt identical urethane precursor among the embodiment 41.Get urethane precursor identical among the embodiment 41 3.692 gram (0.01mol), use 100mL N, N '-dimethyl formamide dissolving fully afterwards is reduced to 0 ℃ with ice-water bath with the temperature of solution.
Get the 1.65mL vitriol oil, join in the 10mL water, mix, treat that temperature is standby after being reduced to 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 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 urethane precursor solution, evenly stirred insulation reaction 12 hours down,, get water soluble vinyl-sulfone polyurethane class high molecular reactive dye through precipitation, filtration, washing and drying treatment at 0 ℃.
Embodiment 48
Adopt identical urethane precursor among the embodiment 41.Get urethane precursor identical among the embodiment 41 3.692 gram (0.01mol), use 100mL N, N '-dimethyl formamide dissolving fully afterwards is reduced to 0 ℃ with ice-water bath with the temperature of solution.
Get the 1.65mL vitriol oil, join in the 10mL water, mix, treat that temperature is standby after being reduced to 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 urethane precursor solution, evenly stirred insulation reaction 12 hours down,, get water soluble vinyl-sulfone polyurethane class high molecular reactive dye through precipitation, filtration, washing and drying treatment at 0 ℃.
Embodiment 49
Adopt identical urethane precursor among the embodiment 41.Get urethane precursor identical among the embodiment 41 3.692 gram (0.01mol), use 100mL N, N '-dimethyl formamide dissolving fully afterwards is reduced to 0 ℃ with ice-water bath with the temperature of solution.
Get the 1.65mL vitriol oil, join in the 10mL water, mix, treat that temperature is standby after being reduced to 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 urethane precursor solution, evenly stirred insulation reaction 12 hours down,, get water soluble vinyl-sulfone polyurethane class high molecular reactive dye through precipitation, filtration, washing and drying treatment at 0 ℃.
Embodiment 50
Adopt identical urethane precursor among the embodiment 41.Get urethane precursor identical among the embodiment 41 3.692 gram (0.01mol), use 100mL N, N '-dimethyl formamide dissolving fully afterwards is reduced to 0 ℃ with ice-water bath with the temperature of solution.
Get the 1.65mL vitriol oil, join in the 10mL water, mix, treat that temperature is standby after being reduced to 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 urethane precursor solution, evenly stirred insulation reaction 12 hours down,, get water soluble vinyl-sulfone polyurethane class high molecular reactive dye through precipitation, filtration, washing and drying treatment at 0 ℃.
Embodiment 51
Get 9.05 gram (0.05mol) N-phenyldiethanol-amines, add 150mL DMF, after being stirred to it and dissolving fully, drip 10.50 gram (0.05mol) naphthalenes-1,5-vulcabond (NDI) and a spot of dibutyl tin, 85 ℃ of nitrogen protections were reacted 12 hours down.Through precipitation, filter washing, the dry white polyurethane class precursor solid that gets.
Get the 1.65mL vitriol oil, join in the 10mL water, mix, treat that temperature is standby after being reduced to 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, be stirred to and slowly be added drop-wise in the above-mentioned sulphuric acid soln after it dissolves fully, be terminal point when being stirred to no unhindered amina.
Get above-mentioned urethane precursor 3.91 grams (0.01mol), use 100mL N, N '-dimethyl formamide dissolving fully afterwards is reduced to 0 ℃ with ice-water bath with the temperature of solution.The above-mentioned diazonium salt solution of slow dropping evenly stirred insulation reaction 12 hours down at 0 ℃, through precipitation, filtration, washing and drying treatment, got water soluble vinyl-sulfone polyurethane class high molecular reactive dye.
Embodiment 52
Adopt identical urethane precursor among the embodiment 51.Get urethane precursor identical among the embodiment 51 3.91 gram (0.01mol), use 100mL N, N '-dimethyl formamide dissolving fully afterwards is reduced to 0 ℃ with ice-water bath with the temperature of solution.
Get 3mL 36.5% concentrated hydrochloric acid, join in the 30mL water, mix, treat that temperature is standby after being reduced to 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 urethane precursor solution, evenly stirred insulation reaction 12 hours down,, get water soluble vinyl-sulfone polyurethane class high molecular reactive dye through precipitation, filtration, washing and drying treatment at 0 ℃.
Embodiment 53
Adopt identical urethane precursor among the embodiment 51.Get urethane precursor identical among the embodiment 51 3.91 gram (0.01mol), use 100mL N, N '-dimethyl formamide dissolving fully afterwards is reduced to 0 ℃ with ice-water bath with the temperature of solution.
Get the 0.40mL vitriol oil, join in the 10mL water, mix, treat that temperature is standby after being reduced to 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 urethane precursor solution, evenly stirred insulation reaction 12 hours down,, get water soluble vinyl-sulfone polyurethane class high molecular reactive dye through precipitation, filtration, washing and drying treatment at 0 ℃.
Embodiment 54
Adopt identical urethane precursor among the embodiment 51.Get urethane precursor identical among the embodiment 51 3.91 gram (0.01mol), use 100mL N, N '-dimethyl formamide dissolving fully afterwards is reduced to 0 ℃ with ice-water bath with the temperature of solution.
Get the 1.60mL vitriol oil, join in the 10mL water, mix, treat that temperature is standby after being reduced to 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 urethane precursor solution, evenly stirred insulation reaction 12 hours down,, get water soluble vinyl-sulfone polyurethane class high molecular reactive dye through precipitation, filtration, washing and drying treatment at 0 ℃.
Embodiment 55
Adopt identical urethane precursor among the embodiment 51.Get urethane precursor identical among the embodiment 51 3.91 gram (0.01mol), use 100mL N, N '-dimethyl formamide dissolving fully afterwards is reduced to 0 ℃ with ice-water bath with the temperature of solution.
Get the 1.65mL vitriol oil, join in the 10mL water, mix, treat that temperature is standby after being reduced to 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, 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 urethane precursor solution, evenly stirred insulation reaction 12 hours down,, get water soluble vinyl-sulfone polyurethane class high molecular reactive dye through precipitation, filtration, washing and drying treatment at 0 ℃.
Embodiment 56
Adopt identical urethane precursor among the embodiment 51.Get urethane precursor identical among the embodiment 51 3.91 gram (0.01mol), use 100mL N, N '-dimethyl formamide dissolving fully afterwards is reduced to 0 ℃ with ice-water bath with the temperature of solution.
Get the 1.65mL vitriol oil, join in the 10mL water, mix, treat that temperature is standby after being reduced to 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 urethane precursor solution, evenly stirred insulation reaction 12 hours down,, get water soluble vinyl-sulfone polyurethane class high molecular reactive dye through precipitation, filtration, washing and drying treatment at 0 ℃.
Embodiment 57
Adopt identical urethane precursor among the embodiment 51.Get urethane precursor identical among the embodiment 51 3.91 gram (0.01mol), use 100mL N, N '-dimethyl formamide dissolving fully afterwards is reduced to 0 ℃ with ice-water bath with the temperature of solution.
Get the 1.65mL vitriol oil, join in the 10mL water, mix, treat that temperature is standby after being reduced to 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 urethane precursor solution, evenly stirred insulation reaction 12 hours down,, get water soluble vinyl-sulfone polyurethane class high molecular reactive dye through precipitation, filtration, washing and drying treatment at 0 ℃.
Embodiment 58
Adopt identical urethane precursor among the embodiment 51.Get urethane precursor identical among the embodiment 51 3.91 gram (0.01mol), use 100mL N, N '-dimethyl formamide dissolving fully afterwards is reduced to 0 ℃ with ice-water bath with the temperature of solution.
Get the 1.65mL vitriol oil, join in the 10mL water, mix, treat that temperature is standby after being reduced to 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 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 urethane precursor solution, evenly stirred insulation reaction 12 hours down,, get water soluble vinyl-sulfone polyurethane class high molecular reactive dye through precipitation, filtration, washing and drying treatment at 0 ℃.
Embodiment 59
Adopt identical urethane precursor among the embodiment 51.Get urethane precursor identical among the embodiment 51 3.91 gram (0.01mol), use 100mL N, N '-dimethyl formamide dissolving fully afterwards is reduced to 0 ℃ with ice-water bath with the temperature of solution.
Get the 1.65mL vitriol oil, join in the 10mL water, mix, treat that temperature is standby after being reduced to 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 urethane precursor solution, evenly stirred insulation reaction 12 hours down,, get water soluble vinyl-sulfone polyurethane class high molecular reactive dye through precipitation, filtration, washing and drying treatment at 0 ℃.
Embodiment 60
Adopt identical urethane precursor among the embodiment 51.Get urethane precursor identical among the embodiment 51 3.91 gram (0.01mol), use 100mL N, N '-dimethyl formamide dissolving fully afterwards is reduced to 0 ℃ with ice-water bath with the temperature of solution.
Get the 1.65mL vitriol oil, join in the 10mL water, mix, treat that temperature is standby after being reduced to 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 urethane precursor solution, evenly stirred insulation reaction 12 hours down,, get water soluble vinyl-sulfone polyurethane class high molecular reactive dye through precipitation, filtration, washing and drying treatment at 0 ℃.

Claims (1)

1. a diazo coupling legal system is equipped with the method for water soluble vinyl-sulfone polyurethane class high molecular reactive dye, it is characterized in that: with the polyurethanes precursor is high polymer main chain, prepare diazonium salt with hydroxyethyl sulfone sulfate class arylamine, be equipped with water soluble vinyl-sulfone polyurethane class high molecular reactive dye by the diazo coupling legal system, this method comprises following step:
(1) preparation of polyurethanes precursor
The polyurethanes precursor is the polyurethane polymer that has functional group's (N-phenyldiethanol-amine residue) that can carry out diazo coupling reaction; its general molecular structural formula is shown in (c); the polyurethanes precursor by vulcabond and N-phenyldiethanol-amine at N; in N '-dimethyl formamide solution; polyreaction obtains under the nitrogen protection, and its general reaction formula is as follows
Wherein (a) is diisocyanate monomer, be Toluene-2,4-diisocyanate, 4-vulcabond, ditan-4,4 '-vulcabond, 1, hexamethylene-diisocyanate, isophorone diisocyanate, xylylene diisocyanate, naphthalene-1, any in the 5-vulcabond, the R in the following formula are a kind of in the following structure
Wherein (b) is the N-phenyldiethanol-amine,
The preparation method of polyurethanes precursor is as follows: at N 2Protection down, be vulcabond by the molar weight ratio: N-phenyldiethanol-amine=1: 1, with above-mentioned any one vulcabond and N-phenyldiethanol-amine N, the dinethylformamide solvent dissolves fully, mixing stirs, drip a small amount of dibutyl tin, slowly be warming up to 80～85 ℃, insulation reaction 12 hours, through precipitation, filter washing, the dry polyurethanes precursor that gets;
(2) adopt following any method to obtain ethyl sulfonyl sulfate class arylamine diazonium salt solution, its general 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, between 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] the ethanol sulfuric ester, 6-β hydroxyethyl sulfone sulfate-2-naphthylamines-1-sulfonic acid etc., wherein the Ar of following formula is a kind of in the following structure
Figure F2010100289371C00022
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; Get hydroxyethyl sulfone sulfate class arylamine and add the water mixing, 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;
Diazonium salt solution preparation method 2: under 0 ℃ of condition, compare Ar-NH by molar weight 2: HCl=1: 2.5～3, the hydrochloric acid soln of getting volume ratio and be 1: 10 is standby; 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;
(3) coupled reaction of polyurethanes precursor and hydroxyethyl sulfone sulfate class arylamine diazonium salt:
In ice-water bath, with above-mentioned polyurethanes precursor N, dinethylformamide (DMF) solvent dissolves fully, evenly stir down, by molar weight than ethyl sulfonyl sulfate class arylamine diazonium salt: polyurethanes precursor=0.4～1.2: 1, above-mentioned ethyl sulfonyl sulfate class arylamine diazonium salt solution is slowly joined in the above-mentioned polyurethanes precursor solution, and insulation reaction is 12 hours under 0 ℃ of condition, and its general reaction formula is as follows
Figure F2010100289371C00031
After reaction is finished, after precipitation, filtration, washing and drying, get water soluble vinyl-sulfone polyurethane class high molecular reactive dye.
CN201010028937A 2010-01-08 2010-01-08 Method for preparing water soluble vinyl-sulfone polyurethane class high molecular reactive dye with diazo coupling method Pending CN101768373A (en)

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