CN103275334B - Preparation method of waterborne polyurethane containing fluorescent dye - Google Patents
Preparation method of waterborne polyurethane containing fluorescent dye Download PDFInfo
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Abstract
The invention discloses a preparation method of waterborne polyurethane containing a fluorescent dye, comprising the following steps: carrying out a reaction between the fluorescent dye containing reactive hydrogen and isocyanate and grafting parent dyes on polyurethane molecular chains, carrying out methods such as chain extension, crosslinking, side suspension of active groups and introduction of a hydrophilc agent, introducing crosslinking points, active groups and hydrophilic groups on the polyurethane chains, making molecular weight large enough, neutralizing and emulsifying to prepare the waterborne polyurethane fluorescent dye. The fluorescent polyurethane prepared by the preparation method still has strong two-photon effect and photoluminescence effect in an aqueous phase and an adhesive film. Thus, the waterborne polyurethane containing the fluorescent dye can be applied in aspects of anti-counterfeiting mark, traffic sign, biological development, biological detection, medicine tracing, chemical detection, fluorescent ink, fluorescent paint and the like.
Description
Technical field
The invention belongs to fluorescence aqueous polyurethane technical field, be specifically related to a kind of preparation method of the aqueous polyurethane containing fluorescence dye.
Background technology
Fluorescence dye is a class material of develop rapidly in recent years.It can pass through molecular designing, thus realizes wavelength of fluorescence, fluorescence intensity, the control of two-photon effect.So fluorescence dye can be applied in anti-counterfeiting mark, traffic sign, biological developing, biological detection, chemical detection, fluorescent ink, the aspects such as fluorescent coating.
But fluorescence dye also has its defect.Such as, synthesis step is complicated, and synthesis cost is high, harsher to environmental requirement, easily aging when applying.Even some fluorescence dye can not be dispersed in water well, meets water and occurs fluorescent weakening, quenching of fluorescence or the phenomenon be directly hydrolyzed.These defects not only limit the Application Areas of fluorescence dye, and limit the popularization of fluorescence dye.
In order to solve the above defect of fluorescence dye, in Chinese patent Authorization Notice No. CN1159387C " coating fluorescent powder, method for making and the long-afterglow fluorescent water-borne coatings containing coating fluorescent powder ", disclose the method for the coated fluorescent material of a kind of high molecular polymer.Fluorescent material is mixed into high molecular polymer by it, then containing fluorescent material polymer cure, will be mixed in aqueous high molecular and make fluorescent aqueous paint after pulverizing.The method is simple to operate, but the dispersion of fluorescent material in aqueous high molecular is subject to the restriction of pulverized particles, cannot reach other dispersion of molecular level.
Announcing one of knowing clearly in Chinese patent notification number CN1990613B " silk screen printing fluorescent paint for color conversion and preparation method thereof " is mixed into from polyacrylic ester or epoxy acrylate prepolymer by fluorescence dye, adopts the mode of thermofixation to solidify after coating.Because fluorescence dye is directly mixed into, degree of scatter is limited, and add-on is more, and fluorescence dye add-on is 10 ~ 50%.The method is not economical especially.
Chinese patent application notification number CN101921507A " aqueous anti-counterfeiting stamp ink " discloses a kind of method fluorescent material being mixed into aqueous polyurethane.Because degree of scatter is limited, the method fluorescent material add-on is 15% ~ 25%, and this add-on is uneconomical for synthetic fluorescent material costly.
Aqueous polyurethane application surface is relatively wider, and its molecular weight and soft durometer can free adjustment.The most important thing is that aqueous polyurethane is a kind of segmented copolymer, it contains oleophylic segment and hydrophilic segment.Synthetic fluorescence dye is received on urethane segment, can be very high by the degree of scatter of fluorescence dye, be other dispersion of molecular level.Under the protection of polyurethane molecular chain, fluorescence molecule can at aqueous phase stable existence, and fluorescence molecule add-on still can have stronger fluorescence and two-photon effect when 0.01%.Application cost and viable cell context of detection that this is reducing senior fluorescence dye are significant.
Fluorescence molecule is received on polyurethane molecular chain and can solve the protection of fluorescence molecule and the problem of dispersion, reduce fluorescence dye application cost simultaneously.This fluorescence aqueous polyurethane can be applied in anti-counterfeiting mark, traffic sign, biological developing, biological detection, chemical detection, fluorescent ink, the aspects such as fluorescent coating.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of the aqueous polyurethane containing fluorescence dye.The present invention adopts graft reaction processing method, selects the fluorescence dye containing hydroxyl or amino, vulcabond, macromolecular polyol, small molecule chain extender, hydrophilic chain extender to be Material synthesis fluorescence aqueous polyurethane.Dye matrix is accessed on polyurethane molecular chain by the fluorescence dye containing reactive hydrogen and isocyanate reaction, again by chain extension, crosslinked, side hangs active group, draw the method for hydrophilizing agent, polyurethane chain is introduced cross-linking set, active group and hydrophilic radical, and after making molecular weight enough large, neutralization, emulsification is with obtained aqueous polyurethane fluorescence dye.By to the design of urethane and the selection of fluorescence molecule, fluorescence aqueous polyurethane can have different purposes.
For achieving the above object, the present invention is by the following technical solutions:
Containing a preparation method for the aqueous polyurethane of fluorescence dye, it is characterized in that comprising following operation steps:
(1) fluorescence dye 5 ~ 2000mg 5 ~ 30g aprotic solvent is dissolved, obtain fluorescent dye solution;
(2) under drying nitrogen protection; macromolecular polyol by after vacuum hydro-extraction: 20 ~ 40g adds in 250ml there-necked flask; by being metered into polyisocyanates 10 ~ 60g, adding after fluorescent dye solution mixes and being warming up to 70 ~ 90 DEG C of reactions 2 hours, obtaining fluorescence polyurethane prepolymer
a 1 ;
(3) to fluorescence polyurethane prepolymer
a 1 in add hydrophilic chain extender 1 ~ 20g, small molecules dibasic alcohol 0 ~ 15g, small molecule polyol 0 ~ 10g, catalyzer 0 ~ 0.12g, aprotic solvent 20 ~ 100g, and 50 ~ 70 DEG C of reactions after 4 ~ 6 hours, be cooled to 20 ~ 40 DEG C of dischargings, obtain fluorescence Waterborne Polyurethane Prepolymer
a 2 ;
(4) by fluorescence Waterborne Polyurethane Prepolymer
a 2 pour in Emulsion cask, with in neutralizing agent 0 ~ 10g and after, add water: 150 ~ 300g emulsify at a high speed, add the fluorescence aqueous polyurethane emulsion obtaining solid content 10 ~ 45%.
Step of the present invention (1) and the aprotic solvent described in (3) are acetone, N-Methyl pyrrolidone, butanone, N, one or both solvents in dinethylformamide, N,N-dimethylacetamide, METHYLPYRROLIDONE, ethyl acetate.
Fluorescence dye described in step of the present invention (1) has phenyl ring conjugated structure, has fluorescence or two-photon fluorescence effect, containing hydroxyl or amino in molecule.Such as:
And the mixture of one or more in its homologue, derivative and isomer.Add-on is 0.01-1% by weight.
Macromolecular polyol described in step of the present invention (2) is polyoxypropyleneglycol, polyoxytrimethylene triol, polyethylene glycol adipate glycol, poly-hexanodioic acid-1,4-butanediol ester glycol, polytetrahydrofuran diol, polypropylene adipate (PPA) glycol, polyneopentyl glycol adipate glycol, poly-hexanodioic acid neopentyl glycol-1, one or both mixture in 6-hexylene glycol esterdiol, poly-carbonic acid 1,6-hexylene glycol esterdiol, polyhexamethylene adipate glycol, polycarbonate polyol, polycaprolactone polyol and its homologue, derivative and isomer.Add-on is 20 ~ 40g.
Described in step of the present invention (2) vulcabond be tolylene diisocyanate (TDI), 4, one or both mixture in 4 '-diphenylmethanediisocyanate (MDI), HMDI (HMDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI) and its homologue, isomer.Add-on is 10 ~ 60g.
Hydrophilic chain extender described in step of the present invention (3) is one or both the mixture in dimethylol propionic acid (DMPA), dimethylolpropionic acid (DMBA), N methyldiethanol amine, trolamine, polyoxyethylene glycol, dihydroxyl half ester and its homologue, derivative and isomer.Add-on is 1 ~ 20g.
Small molecules dibasic alcohol described in step of the present invention (3) is ethylene glycol, glycol ether, dipropylene glycol, 1,4-butyleneglycol, decanediol, 1,6-hexylene glycol, neopentyl glycol, one or both the mixture in propylene glycol and its homologue, derivative and isomer.Add-on is 0.5 ~ 8g.
Small molecule polyol (functionality is greater than 2) described in step of the present invention (3) is TriMethylolPropane(TMP), one in glycerine, tetramethylolmethane, trolamine.
Catalyzer described in step of the present invention (3) is one or both in dibutyl tin laurate, stannous octoate.
Neutralizing agent described in step of the present invention (4) is the one in triethylamine, acetic acid.
Fluorescence polyurethane material is by infrared spectra, and photoluminescence spectrum, Z-scanning spectra obtains the confirmation of photoluminescence and two-photon effect aspect.
Fluorescence urethane prepared in accordance with the present invention still has stronger two-photon effect and photoluminescence effect in aqueous phase and glued membrane, therefore this invention can at anti-counterfeiting mark, traffic sign, biological developing, biological detection, pharmaceutical indications, chemical detection, fluorescent ink, the aspects such as fluorescent coating are applied.
Accompanying drawing explanation
Fig. 1 is fluorescence aqueous polyurethane infrared spectrum prepared by embodiment 1.
Fig. 2 is fluorescence aqueous polyurethane glued membrane photoluminescence spectrum prepared by embodiment 1.
Fig. 3 is fluorescence aqueous polyurethane glued membrane Z scan-data (700nm wavelength) prepared by embodiment 1.
Fig. 4 is fluorescence aqueous polyurethane glued membrane Z scan-data (800nm wavelength) prepared by embodiment 1.
Embodiment
Being further described the present invention below in conjunction with embodiment, is not restriction the present invention.
Luminescent dye molecule structure in embodiment is:
Luminescent dye molecule A
Luminescent dye molecule B.
embodiment 1:17mg hydroxyl fluorescence dye A 5g DMF is dissolved, obtains the DMF solution of fluorescence dye A.At N
2protection under, by the polyoxytrimethylene triol 40g of 110 DEG C of vacuum hydro-extractions after 2 hours, 4, the N of 4 '-dicyclohexyl methane diisocyanate (HMDI) 13.76g and fluorescence dye A, dinethylformamide solution is placed in the there-necked flask of 250ml, in 80 DEG C of reactions 2 hours, then dimethylol propionic acid 2.18g and 1 is added, 4-butyleneglycol 1.26g, add dibutyl tin laurate 0.06g, stannous octoate 0.06g, acetone 60g, be cooled to 20 DEG C of dischargings in 60 DEG C of reactions after 6 hours, obtain fluorescence Waterborne Polyurethane Prepolymer; Pour in Emulsion cask by this performed polymer, under the rotating speed of 3000r/min, add triethylamine 2.26g and neutralize, add water 150g, emulsification, obtains the translucent fluorescence aqueous polyurethane emulsion of pistac.
Infrared spectrogram after the emulsion film forming of Fig. 1 obtained by example 1.Can find out that 3000 ~ 3800cm-1 is NH vibration absorption peak by Fig. 1,2814 ~ 3015cm-1 is the vibration absorption peak of CH2,1618 ~ 1770cm-1 is the vibration absorption peak of C=O, and 1500 ~ 1600cm-1 is that acid amides II is with, and 1045 ~ 1177cm-1 is the vibration absorption peak of O-C=O.By infrared data analyze known we synthesized water-base polyurethane material.Because fluorescence dye add-on is too little, the infrared signature peak of dyestuff is not obvious.
Fig. 2 is fluorescence aqueous polyurethane glued membrane photoluminescence spectrum prepared by embodiment 1.By Fig. 2 our fluorescence aqueous polyurethane of synthesis known, there is under the rayed of 400 ~ 550nm wavelength comparatively high light photoluminescence effect.Fig. 3 and Fig. 4 is fluorescence aqueous polyurethane glued membrane Z scan-data under 700nm wavelength and 800nm wavelength illumination respectively prepared by embodiment 1.
Sheik-Bahae etc. proposed in 1989 to adopt single beam to measure the symbol of nonlinear refractive index n2 and the Z-scan method of size.For two-photon absorbing material, its focus place transmitance reaches minimum.The Z-scanning spectra of Fig. 3 and Fig. 4 shows this fluorescence aqueous polyurethane glued membrane and all possess excellent two-photon absorption performance under 700nm and 800nm wavelength Gaussian beam.
embodiment 2:622mg hydroxyl fluorescence dye A 30g N-Methyl pyrrolidone is dissolved, obtains the N-Methyl pyrrolidone solution of fluorescence dye A.At N
2protection under; by the polyethylene glycol adipate glycol 40g of 110 DEG C of vacuum hydro-extractions after 2 hours; 4; 4 '-dicyclohexyl methane diisocyanate (HMDI) 13.76g; the N-Methyl pyrrolidone solution of hexamethylene diisocyanate (HDI) 5g and fluorescence dye A is placed in the there-necked flask of 250ml; in 90 DEG C of reactions 2 hours; then dimethylol propionic acid 2.18g and ethylene glycol 1.26g is added; add dibutyl tin laurate 0.06g; stannous octoate 0.06g; acetone 60g, in 60 DEG C of reactions 6 hours.Be cooled to 20 DEG C of dischargings, obtain fluorescence Waterborne Polyurethane Prepolymer; Pour in Emulsion cask by this performed polymer, under the rotating speed of 3000r/min, add triethylamine 2.26 grams neutralization, add water 245g emulsification, obtains the translucent fluorescence aqueous polyurethane emulsion of yellow-green colour.
embodiment 3:7mg hydroxyl fluorescence dye A 5g N,N-dimethylacetamide is dissolved, obtains the N,N-dimethylacetamide solution of fluorescence dye A.At N
2protection under, by the polyoxypropyleneglycol 30g of 110 DEG C of vacuum hydro-extractions after 2 hours, the N of tolylene diisocyanate (TDI) 30.45g and fluorescence dye A, N-dimethylacetamide solution is placed in the there-necked flask of 250ml, in 80 DEG C of reactions 2 hours, then dihydroxyl half ester 5.59g and glycol ether 1.26g is added, add 1,4-butyleneglycol 0.5g, add dibutyl tin laurate 0.06g, stannous octoate 0.06g, acetone 60g, be cooled to 20 DEG C in 60 DEG C of reactions after 6 hours, obtain fluorescence Waterborne Polyurethane Prepolymer; Pour in Emulsion cask by this performed polymer, under the rotating speed of 3000r/min, add triethylamine 2.7g and neutralize, add water 225g emulsification, obtains the translucent fluorescence aqueous polyurethane emulsion of pistac.
embodiment 4:20mg is dissolved containing amino fluorescein dyestuff B 5g METHYLPYRROLIDONE, obtains the METHYLPYRROLIDONE solution of fluorescence dye B.At N
2protection under, by the poly-hexanodioic acid neopentyl glycol-1 of 110 DEG C of vacuum hydro-extractions after 2 hours, 6-hexylene glycol esterdiol 20g, polyoxytrimethylene triol 20g, isophorone diisocyanate (IPDI) 17.76g, hexamethylene diisocyanate (HDI) 8.45g and and the METHYLPYRROLIDONE solution of fluorescence dye B be placed in the there-necked flask of 250ml, stirring reaction 2 hours at 80 DEG C of temperature, be cooled to 40 DEG C and add dimethylolpropionic acid 3.49g and dipropylene glycol 5.41g, glycerine 0.67g, add dibutyl tin laurate 0.06g, stannous octoate 0.06g, acetone 20g, 20 DEG C are cooled to after 6 hours in 60 DEG C of reactions, add 40g acetone, obtain fluorescence Waterborne Polyurethane Prepolymer, pour in Emulsion cask by this performed polymer, under the rotating speed of 3000r/min, add triethylamine 2.63g and neutralize, add water 150g emulsification, obtains the translucent fluorescence aqueous polyurethane emulsion of pistac.
embodiment 5:by 13mg hydroxyl fluorescence dye A, use 5g acetic acid ethyl dissolution, obtain the ethyl acetate solution of fluorescence dye.At N
2protection under, by the polypropylene adipate (PPA) glycol 40g of 110 DEG C of vacuum hydro-extractions after 2 hours, the ethyl acetate solution of isophorone diisocyanate (IPDI) 17.76g and fluorescence dye A, be placed in 250ml there-necked flask, in 90 DEG C of reactions 2 hours, then N methyldiethanol amine 6.6g is added, ethyl acetate 60g, in 65 DEG C of reactions 1 hour, finally add 1, 6-hexylene glycol 1.68g, tetramethylolmethane 0.7g, add dibutyl tin laurate 0.06g, stannous octoate 0.06g, in 60 DEG C of reactions after 4.5 hours, be cooled to 25 DEG C of dischargings, namely fluorescence base polyurethane prepolymer for use as is obtained, this performed polymer is poured in Emulsion cask, under the rotating speed of 2000r/min, adds the neutralization of 3.3g acetic acid, add 220g emulsifying water, obtain yellow-green colour aqueous polyurethane fluorescent emulsion.
embodiment 6:by 2000mg hydroxyl fluorescence dye A, dissolve with 30g N-Methyl pyrrolidone, obtain the N-Methyl pyrrolidone solution of fluorescence dye A.At N
2protection under, by the polycarbonate diol 40g of 110 DEG C of vacuum hydro-extractions after 2 hours, 4, the N-Methyl pyrrolidone solution of 4 '-diphenylmethanediisocyanate (MDI) 54g and fluorescence dye A is placed in 250ml there-necked flask, in 70 DEG C of reactions 2 hours, then N methyldiethanol amine 7.2g is added, acetone 60g, in 65 DEG C of reactions 1 hour, finally add glycol ether 8.6g, TriMethylolPropane(TMP) (TMP) 0.41g, the each 0.06g of stannous octoate, after 4.5 hours in 60 DEG C of reactions, be cooled to 25 DEG C of dischargings, namely obtain fluorescence base polyurethane prepolymer for use as; This performed polymer is poured in Emulsion cask, under the rotating speed of 2000r/min, adds the neutralization of 3.68g acetic acid, add 220g emulsifying water, obtain green aqueous polyurethane fluorescent emulsion.
embodiment 7:by 6mg hydroxyl fluorescence dye A, dissolve with 5g N-Methyl pyrrolidone, obtain the N-Methyl pyrrolidone solution of fluorescence dye A.At N
2protection under, by the polytetrahydrofuran diol 30g of 110 DEG C of vacuum hydro-extractions after 2 hours, the N-Methyl pyrrolidone solution of tolylene diisocyanate (TDI) 13.05g and fluorescence dye A, be placed in 250ml there-necked flask, react 2 hours at 90 DEG C of temperature, then trolamine 3.5g is added, acetone 70g, in 65 DEG C of reactions 1 hour, finally add decanediol 3.42g, TriMethylolPropane(TMP) (TMP) 0.31g, catalyst dibutyltin dilaurylate 0.06g, after 4.5 hours in 60 DEG C of reactions, be cooled to 25 DEG C of dischargings, namely obtain fluorescence base polyurethane prepolymer for use as; This performed polymer is poured in Emulsion cask, under the rotating speed of 2000r/min, adds the neutralization of 1.45g acetic acid, add 200g emulsifying water, obtain yellow-green colour aqueous polyurethane fluorescent emulsion.
embodiment 8:by 80mg hydroxyl fluorescence dye A, dissolve with 5g N-Methyl pyrrolidone, obtain the N-Methyl pyrrolidone solution of fluorescence dye A.Under the protection of N2, by the polyhexamethylene adipate glycol 40g of 110 DEG C of vacuum hydro-extractions after 2 hours, 4, the N-Methyl pyrrolidone solution of 4 '-diphenylmethanediisocyanate (MDI) 50g and fluorescence dye A, be placed in 250ml there-necked flask, in 70 DEG C of reactions 2 hours, then N methyldiethanol amine 7.2g is added, acetone 30g, in 65 DEG C of reactions 1 hour, finally adds glycol ether 8.6g, catalyst dibutyltin dilaurylate 0.03g, after 4.5 hours in 60 DEG C of reactions, be cooled to 25 DEG C of dischargings, namely obtain fluorescence base polyurethane prepolymer for use as; This performed polymer is poured in Emulsion cask, under the rotating speed of 2000r/min, adds the neutralization of 3.68g acetic acid, add 150g emulsifying water, obtain yellow-green colour aqueous polyurethane fluorescent emulsion.
embodiment 9:by 1000mg hydroxyl fluorescence dye A, dissolve with 30g N-Methyl pyrrolidone, obtain the N-Methyl pyrrolidone solution of fluorescence dye A.At N
2protection under, by the polycaprolactone polyol 25g of 110 DEG C of vacuum hydro-extractions after 2 hours, 4, the N-Methyl pyrrolidone solution of 4 '-dicyclohexyl methane diisocyanate (HMDI) 35g and fluorescence dye A, be placed in 250ml there-necked flask, in 90 DEG C of reactions 2 hours, then add N methyldiethanol amine 3.41g, acetone 30g, in 65 DEG C of reactions 1 hour, finally add 1,6-hexylene glycol 3.95g, catalyst dibutyltin dilaurylate 0.06g, stannous octoate 0.06g, after 4.5 hours in 60 DEG C of reactions, be cooled to 25 DEG C of dischargings, namely obtain fluorescence base polyurethane prepolymer for use as; This performed polymer is poured in Emulsion cask, under the rotating speed of 2000r/min, adds the neutralization of 1.72g acetic acid, add 200g emulsifying water, obtain green aqueous polyurethane fluorescent emulsion.
embodiment 10:by 5mg hydroxyl fluorescence dye A, use 10g acetone solution, obtain the acetone soln of fluorescence dye A.Under the protection of N2, by the polyneopentyl glycol adipate glycol 20g of 110 DEG C of vacuum hydro-extractions after 2 hours, 4, the acetone soln of 4 '-dicyclohexyl methane diisocyanate (HMDI) 10g and fluorescence dye A, be placed in 250ml there-necked flask, in 90 DEG C of reactions 2 hours, then N methyldiethanol amine 10g is added, acetone 100g, in 65 DEG C of reactions 1 hour, finally add neopentyl glycol 10g, trolamine 10g, catalyst dibutyltin dilaurylate 0.12g, in 70 DEG C of reactions after 4 hours, be cooled to 40 DEG C of dischargings, namely obtain fluorescence base polyurethane prepolymer for use as; This performed polymer is poured in Emulsion cask, under the rotating speed of 2000r/min, adds the neutralization of 4g acetic acid, add 100g emulsifying water, obtain yellow-green colour aqueous polyurethane fluorescent emulsion.
embodiment 11:by 20mg hydroxyl fluorescence dye A, dissolve with 10g butanone, obtain the butanone solution of fluorescence dye A.Under the protection of N2, by the polycarbonate polyol 40g of 110 DEG C of vacuum hydro-extractions after 2 hours, 4, the butanone solution of 4 '-dicyclohexyl methane diisocyanate (HMDI) 60g and fluorescence dye A, be placed in 250ml there-necked flask, in 90 DEG C of reactions 2 hours, then polyoxyethylene glycol 20g is added, butanone 20g, in 65 DEG C of reactions 1 hour, finally add dimethylol propionic acid 1g, neopentyl glycol 15g, the sub-tin 0.12g of octoate catalyst, in 50 DEG C of reactions after 6 hours, be cooled to 20 DEG C of dischargings, namely obtain fluorescence base polyurethane prepolymer for use as; This performed polymer is poured in Emulsion cask, under the rotating speed of 2000r/min, adds the neutralization of 1g triethylamine, add 140g emulsifying water, obtain yellow-green colour aqueous polyurethane fluorescent emulsion.
embodiment 12:by 20mg hydroxyl fluorescence dye A, use 10g acetic acid ethyl dissolution, obtain the ethyl acetate solution of fluorescence dye A.Under the protection of N2, by the polycarbonate polyol 40g of 110 DEG C of vacuum hydro-extractions after 2 hours, 110 DEG C of vacuum hydro-extraction polyoxyethylene glycol 20g after 2 hours, ethyl acetate 20g, the ethyl acetate solution of HMDI (HMDI) 60g and fluorescence dye A, is placed in 250ml there-necked flask, in 90 DEG C of reactions 2 hours, then propylene glycol 8g is added, ethyl acetate 60g, in 65 DEG C of reactions 2 hours, finally add the sub-tin 0.12g of octoate catalyst, after 5 hours in 65 DEG C of reactions, be cooled to 20 DEG C of dischargings, namely obtain fluorescence base polyurethane prepolymer for use as; This performed polymer is poured in Emulsion cask, under the rotating speed of 2000r/min, adds 300g emulsifying water, obtain yellow-green colour aqueous polyurethane fluorescent emulsion.
embodiment 13:by 10mg hydroxyl fluorescence dye A, use 10g acetone solution, obtain the acetone soln of fluorescence dye A.Under the protection of N2, by the polycarbonate polyol 40g of 110 DEG C of vacuum hydro-extractions after 2 hours, 4, the acetone soln of 4 '-dicyclohexyl methane diisocyanate (HMDI) 20g and fluorescence dye A, be placed in 250ml there-necked flask, in 90 DEG C of reactions 2 hours, then N methyldiethanol amine 2g is added, trolamine 0.8g, acetone 100g, in 65 DEG C of reactions 1 hour, finally add neopentyl glycol 0.5g, catalyst dibutyltin dilaurylate 0.12g, in 70 DEG C of reactions after 4 hours, be cooled to 40 DEG C of dischargings, namely obtain fluorescence base polyurethane prepolymer for use as; This performed polymer is poured in Emulsion cask, under the rotating speed of 2000r/min, to add in 2.5g acetic acid and after, add 300g emulsifying water, obtain yellow-green colour aqueous polyurethane fluorescent emulsion.
embodiment 14:by 1200mg hydroxyl fluorescence dye A, dissolve with 5gN-methyl-2-pyrrolidone, obtain the N-Methyl pyrrolidone solution of fluorescence dye A.Under the protection of N2, by the polycaprolactone polyol 25g of 110 DEG C of vacuum hydro-extractions after 2 hours, 4, the N-Methyl pyrrolidone solution of 4 '-dicyclohexyl methane diisocyanate (HMDI) 55g and fluorescence dye A, be placed in 250ml there-necked flask, in 90 DEG C of reactions 2 hours, then add N methyldiethanol amine 8g, acetone 30g, in 65 DEG C of reactions 1 hour, finally add 1,6-hexylene glycol 8g, catalyst dibutyltin dilaurylate 0.06g, stannous octoate 0.06g, after 4.5 hours in 60 DEG C of reactions, be cooled to 25 DEG C of dischargings, namely obtain fluorescence base polyurethane prepolymer for use as; This performed polymer is poured in Emulsion cask, under the rotating speed of 2000r/min, with in 3.72g acetic acid and after, add 400g emulsifying water, obtain yellow-green colour aqueous polyurethane fluorescent emulsion.
embodiment 15:by 20mg containing amino fluorescein dyestuff B, dissolve by 10g N,N-dimethylacetamide, obtain the N,N-dimethylacetamide solution of fluorescence dye B.Under the protection of N2, by the polycaprolactone polyol 20g of 110 DEG C of vacuum hydro-extractions after 2 hours, polyoxypropyleneglycol 20g, tolylene diisocyanate (TDI) 10g, 4, the N of 4 '-dicyclohexyl methane diisocyanate (HMDI) 55g and fluorescence dye B, N-dimethylacetamide solution, be placed in 250ml there-necked flask, in 90 DEG C of reactions 2 hours, then polyoxyethylene glycol 8g is added, N methyldiethanol amine 8g, N, N-N,N-DIMETHYLACETAMIDE 20g, in 65 DEG C of reactions 1 hour, finally add 1, 6-hexylene glycol 8g, TriMethylolPropane(TMP) 1g, catalyst dibutyltin dilaurylate 0.06g, stannous octoate 0.06g, in 70 DEG C of reactions after 6 hours, be cooled to 25 DEG C of dischargings, namely fluorescence base polyurethane prepolymer for use as is obtained, this performed polymer is poured in Emulsion cask, under the rotating speed of 2000r/min, with in 3.7g acetic acid and after, add 300g emulsifying water, obtain yellow-green colour aqueous polyurethane fluorescent emulsion.
What finally illustrate is, above embodiment is only in order to illustrate technical scheme of the present invention and unrestricted, although by referring to the preferred embodiments of the present invention, invention has been described, but those of ordinary skill in the art is to be understood that, various change can be made to it in the form and details, and not depart from the spirit and scope of the present invention that appended claims limits.
Claims (3)
1., containing a preparation method for the aqueous polyurethane of fluorescence dye, it is characterized in that comprising following operation steps:
(1), by fluorescence dye 5 ~ 2000mg 5 ~ 10g aprotic solvent dissolve, obtain fluorescent dye solution;
(2), under drying nitrogen protection; macromolecular polyol 20 ~ 40g after vacuum hydro-extraction is added in 250ml there-necked flask; by being metered into vulcabond 10 ~ 60g; add after fluorescent dye solution mixes and be warming up to 70 ~ 90 DEG C of reactions 2 hours, obtain fluorescence polyurethane prepolymer a
1;
(3), to fluorescence polyurethane prepolymer a
1in add hydrophilic chain extender 1 ~ 20g, small molecules dibasic alcohol 0 ~ 15g, small molecule polyol 0 ~ 10g, catalyzer 0 ~ 0.12g, aprotic solvent 20 ~ 100g, and 50 ~ 70 DEG C of reactions after 4 ~ 6 hours, be cooled to 20 ~ 40 DEG C of dischargings, obtain fluorescence Waterborne Polyurethane Prepolymer a2;
(4), fluorescence Waterborne Polyurethane Prepolymer a2 is poured in Emulsion cask, with in neutralizing agent 2 ~ 10g and after, add water 150 ~ 300g emulsify at a high speed, obtains the fluorescence aqueous polyurethane emulsion of solid content 15 ~ 45%;
Wherein, step (1) and the aprotic solvent described in step (3) are acetone, N-Methyl pyrrolidone, butanone, N, one or both in dinethylformamide, N,N-dimethylacetamide, METHYLPYRROLIDONE, ethyl acetate;
Fluorescence dye described in step (1) has phenyl ring conjugated structure, has fluorescence or two-photon fluorescence effect, containing hydroxyl or amino in molecule;
Macromolecular polyol described in step (2) is polyoxypropyleneglycol, polyoxytrimethylene triol, polyethylene glycol adipate glycol, poly-hexanodioic acid-1,4-butanediol ester glycol, polytetrahydrofuran diol, polypropylene adipate (PPA) glycol, polyneopentyl glycol adipate glycol, poly-hexanodioic acid neopentyl glycol-1, one or both in 6-hexylene glycol esterdiol, poly-carbonic acid 1,6-hexylene glycol esterdiol, polyhexamethylene adipate glycol, polycarbonate polyol, polycaprolactone polyol and its homologue and isomer; Vulcabond described in step (2) is tolylene diisocyanate (TDI), 4, one or both in 4 '-diphenylmethanediisocyanate (MDI), HMDI (HMDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI) and its homologue and isomer;
Hydrophilic chain extender described in step (3) is one or both in dimethylol propionic acid (DMPA), dimethylolpropionic acid (DMBA), N methyldiethanol amine, trolamine, polyoxyethylene glycol, dihydroxyl half ester and its homologue, derivative and isomer;
Small molecules dibasic alcohol described in step (3) is ethylene glycol, glycol ether, dipropylene glycol, propylene glycol, 1, one or both in 4-butyleneglycol, decanediol, 1,6-hexylene glycol, neopentyl glycol and its homologue, derivative and isomer;
Small molecule polyol described in step (3) is the one in TriMethylolPropane(TMP), glycerine, tetramethylolmethane, trolamine;
Catalyzer described in step (3) is one or both in dibutyl tin laurate, stannous octoate;
Neutralizing agent described in step (4) is the one in triethylamine, acetic acid.
2. the preparation method of a kind of aqueous polyurethane containing fluorescence dye according to claim 1, is characterized in that: the fluorescence dye described in step (1) is 0.01 ~ 2% by urethane solid weight ratio add-on.
3. the preparation method of a kind of aqueous polyurethane containing fluorescence dye according to claim 1, is characterized in that: the small molecules dibasic alcohol add-on described in step (3) is 0.5 ~ 8g.
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| EP3243857A1 (en) * | 2016-05-13 | 2017-11-15 | Centre National de la Recherche Scientifique - CNRS - | Uniform sequence-defined polyurethanes and uses thereof as molecular labels |
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| US6001936A (en) * | 1997-10-24 | 1999-12-14 | 3M Innovative Properties Company | Dye enhanced durability through controlled dye environment |
| CN101967255A (en) * | 2010-09-21 | 2011-02-09 | 大连市轻化工研究所 | Waterborne resin for plastic film coating and preparation method thereof |
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| EP3243857A1 (en) * | 2016-05-13 | 2017-11-15 | Centre National de la Recherche Scientifique - CNRS - | Uniform sequence-defined polyurethanes and uses thereof as molecular labels |
| WO2017194694A1 (en) * | 2016-05-13 | 2017-11-16 | Centre National De La Recherche | Uniform sequence-defined polyurethanes and uses thereof as molecular labels |
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