CN102558909B - Hydroxy-terminated polyether type macromolecular fluorescent dye and synthesis method thereof - Google Patents
Hydroxy-terminated polyether type macromolecular fluorescent dye and synthesis method thereof Download PDFInfo
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- CN102558909B CN102558909B CN 201110419107 CN201110419107A CN102558909B CN 102558909 B CN102558909 B CN 102558909B CN 201110419107 CN201110419107 CN 201110419107 CN 201110419107 A CN201110419107 A CN 201110419107A CN 102558909 B CN102558909 B CN 102558909B
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Abstract
The invention discloses a hydroxy-terminated polyether type macromolecular fluorescent dye and a synthesis method thereof. The structural formula of the macromolecular fluorescent dye is shown in the specification, wherein n represents the degree of polymerization and is 13, 22 or 45. The solvent extraction resistance and anti-ultraviolet stability of the macromolecular fluorescent dye are good; and the dye has the hydroxy-terminated structure and can be used in the synthesis of materials such as colorful fluorescent polyester and polyurethane.
Description
One, technical field
The present invention relates to a kind of fluorescence dye and preparation method thereof, specifically a kind of end hydroxy polyether type polymeric fluorescent dye and synthetic method thereof.
Two, background technology
High molecular dye is by certain chemical reaction dye molecule to be introduced high molecular main chain or hung on the coloured macromolecule polymkeric substance that forms on the side chain.It has characteristics such as the high strength of macromolecular material, anti-solvent, heat-resisting, anti-migration, easy film forming and workability, and has strong absorbent and the chromophoric characteristic of organic molecule dyestuff to light.In recent years, along with progressively going deep into of novel material developments such as colour polyurethane, polyester, for overcoming the small molecules organic dye migration and defective such as anti-solvent extraction difference taking place easily, makes the structure that the formation chemical bond links to each other between dyestuff and the urethane become important research direction.Therefore, prepare research and cause that gradually people pay close attention to terminal hydroxy group structuring polymer fluorescence dye.Having synthesized by series reaction as U.S. patent of invention US6794420B2 is the end hydroxy polyether type high molecular dye of chromophore with the anthraquinone.This high molecular dye is used for the production of colour polyurethane foam materials, obtains satisfied effect.(Chen Liusheng such as Chen Liusheng, Du Jinhuan, Wang Yanqiao. a kind of polyether-type fragrance azo high molecular dye. photographic science and photochemistry .1985, (3): 6-12) to N, accelerine sets out, through diazotization and linked reaction, again with epoxy chloropropane condensation prepared monomer, high molecular dye-it is (right-N to gather to obtain suspended side chain polyether-type fragrance azo with cationic polymerization at last, N-dimethyl amino-azo-benzene base) glycidyl ether. (Pang Xiaoyi such as Pang Xiaoyi, Xin Zhong, Dai Gance. the synthetic and workability of the research .XI. anthraquinone type polyester pigment of polymeric pigments. functional polymer journal, 1998,11 (3): 335-360) synthesize 1 respectively, 5-two (beta-hydroxyethyl) aminoanthraquinone, 1,4-two (beta-hydroxyethyl) aminoanthraquinone carries out copolycondensation with BHET and has synthesized corresponding anthraquinone type polyester pigment.But above high molecular dye does not all have fluorescence property, only can satisfy the painted requirement of material.
Three, summary of the invention
The present invention aims to provide a kind of end hydroxy polyether type polymeric fluorescent dye and synthetic method thereof, and technical problem to be solved is to make it have fluorescence property when giving the high molecular dye tinctorial property, and has good ultraviolet resistance stability.
Scattered fluorescent yellow 8GFF (C.1. DISPERSE YELLOW 82) is a kind of important coumarins fluorescence dye, and chemical name is 3-(2-benzimidazolyl-)-7-(diethylin) tonka bean camphor.Owing to have substituting groups such as benzimidazolyl-and amino simultaneously in its molecular structure,, give its intensive yellow-green fluorescence with lactonic ring formation " pushing away-La " electron system of tonka bean camphor.
The present invention is basic dyestuff with scattered fluorescent yellow 8GFF, and warp and pyromellitic acid anhydride (PMDA) condensation prepared intermediate carry out esterification with polyoxyethylene glycol (PEG) again and prepare end hydroxy polyether type polymeric fluorescent dye.
Technical solution problem of the present invention adopts following technical scheme:
End hydroxy polyether type polymeric fluorescent dye of the present invention, its chemical structural formula is as follows:
Wherein n represents the polymerization degree, is the mean polymerisation degree of the polyoxyethylene glycol of use among the present invention, and n is 13,22 or 45.
The synthetic method of end hydroxy polyether type polymeric fluorescent dye of the present invention is to be basic dyestuff with scattered fluorescent yellow 8GFF, comprises condensation, esterification, separation, washing and dry each unit process, it is characterized in that:
Described condensation is to be solvent with DMF, and scattered fluorescent yellow 8GFF and pyromellitic acid anhydride are pressed 1: the mixed in molar ratio of 4-6, stir down and obtained 8GFF-PMDA condensation intermediate in 1.5-2.5 hour in 70-90 ℃ of reaction;
Described esterification is to be solvent with DMF, is catalyzer with the vitriol oil, with the 8GFF-PMDA condensation intermediate of step a preparation and PEG by 1: under agitation reacted 4-6 hour after the mass ratio of 0.08-0.30 mixes in 130-150 ℃; The mol ratio of described catalyzer and 8GFF-PMDA condensation intermediate is 3-5: 1.
Described PEG is PEG600, PEG1000 or PEG2000.
The concrete operations step is as follows:
A, be solvent with DMF, with scattered fluorescent yellow 8GFF and pyromellitic acid anhydride by 1: the mixed in molar ratio of 4-6, stir down in 70-90 ℃ of reaction 1.5-2.5 hour, reaction is finished after DMF washing, filtration and drying obtain 8GFF-PMDA condensation intermediate;
B, be solvent with DMF, with the vitriol oil is catalyzer, with the PEG of the 8GFF-PMDA condensation intermediate of step a preparation and different molecular weight by 1: under agitation reacted 4-6 hour after the mass ratio of 0.08-0.30 mixes in 130-150 ℃, reaction is cooled to 45-55 ℃ after finishing, pH value with saturated solution of sodium carbonate conditioned reaction liquid is 7, adds methyl alcohol and separates out product; The mol ratio of described catalyzer and 8GFF-PMDA condensation intermediate is 3-5: 1;
C, products therefrom obtain end hydroxy polyether type 8GFF-PMDA-PEG polymeric fluorescent dye successively after deionized water wash, filtration and drying.
The end hydroxy polyether type 8GFF polymeric fluorescent dye that the method that proposes according to the present invention prepares has advantages such as fluorescence intensity height, ultraviolet resistance good stability, when being used to produce colored polyester and polyurethane material, is difficult for by solvent extraction.
Four, description of drawings
Fig. 1 is the infrared spectrogram of the present invention 8GFF, the PMDA that use and the 8GFF-PMDA intermediate for preparing.Wherein, curve (a) is 8GFF, and curve (b) is PMDA, and curve (c) is the 8GFF-PMDA intermediate.In Fig. 1 curve (a), 3343cm
-1The place is the stretching vibration absorption peak of N-H among the 8GFF; 1689cm
-1The place is for the stretching vibration absorption peak of C=O in the lactone, because of moving to the lower wave number direction with the C=C conjugation; In the curve (b), 1770cm
-1The place is the stretching vibration absorption peak of C=O in the acid anhydrides.In the curve (c), 3343cm
-1Locate no N-H stretching vibration absorption peak; 3243cm
-1The place is the stretching vibration absorption peak of O-H; 1708cm
-1The place is the overlapping peaks of the stretching vibration absorption peak of C=O in carboxylic acid and the acid amides.Show that 8GFF forms amido linkage by N-H key and anhydride reaction.
Fig. 2 is the infrared spectrogram of end hydroxy polyether type polymeric fluorescent dye of the present invention.Wherein, curve (a) is the product of embodiment 2 preparations, and curve (b) is the product of embodiment 3 preparations, and curve (c) is the product of embodiment 4 preparations.Among Fig. 2,3238cm
-1The place is the stretching vibration absorption peak of O-H base, 1705cm
-1The place is the overlapping peaks of the stretching vibration absorption peak of C=O base in ester and the amido linkage, 1253cm
-1The place is aromatic oxide stretching vibration absorption peak, 1133cm
-1The place is for aliphatic ether stretching vibration absorption peak, illustrate that reaction has formed the 8GFF dyestuff of end carboxyl to 8GFF with PMDA, and reacts with PEG and to have formed end hydroxy polyether type 8GFF polymeric fluorescent dye.
Five, embodiment
Below in conjunction with embodiment the present invention is done to describe further.
Embodiment 1:
End hydroxy polyether type polymeric fluorescent dye is to prepare by the following method in the present embodiment:
In the 250mL four-hole boiling flask, add 1.2g pyromellitic acid anhydride (PMDA), 3.3g fluorescent yellow 8GFF and 140mL exsiccant DMF solvent, stirring and dissolving to system is clear solution, warming-in-water to 80 ℃ isothermal reaction, system has product to separate out behind the reaction 0.5h, continue to stop behind the isothermal reaction 2h, after the DMF washing, filtering three times, 80 ℃ of dry 8GFF-PMDA condensation intermediate 3.9g, yields 86.7% of getting of convection oven.
Embodiment 2:
In 50mL single port flask, adding 0.88g 8GFF-PMDA condensation intermediate (0.001mol) and 3.00g vacuum-drying constant weight molecular-weight average are 600 PEG600, add the dry DMF solvent of the 10mL that contains the 0.004mol concentrated sulfuric acid catalyst again, the magnetic agitation dissolving, oil bath is warming up to 140 ℃ of isothermal reaction 5h.Reaction finish the back with in the saturated solution of sodium carbonate and system to pH value be 7, separate out product to system adding methyl alcohol; Products therefrom is filtered, and filter residue is with distilled water repetitive scrubbing, filtration, and to remove unreacted PEG, 60 ℃ of vacuum-dryings get end hydroxy polyether type 8GFF-PMDA-PEG polymeric fluorescent dye 0.87g to constant weight then.The molecular-weight average of the polymeric fluorescent dye of present embodiment preparation is 2050.
Embodiment 3:
With molecular weight be 1000 PEG in the single port flask 80 ℃ to vacuumize dry 3h standby.Adding 0.88g 8GFF-PMDA condensation intermediate (0.001mol) and 5.00g molecular-weight average are 1000 PEG1000 in 50mL single port flask, add the dry DMF solvent of the 10mL that contains the 0.005mol concentrated sulfuric acid catalyst again, the magnetic agitation dissolving, oil bath is warming up to 140 ℃ of isothermal reaction 5h.Reaction finish the back with in the saturated solution of sodium carbonate and system to pH value be 7, separate out product to system adding methyl alcohol; Products therefrom is filtered, and filter residue is with distilled water repetitive scrubbing, filtration, to remove unreacted PEG; 60 ℃ of vacuum-dryings get end hydroxy polyether type 8GFF-PMDA-PEG polymeric fluorescent dye 1.45g to constant weight.The molecular-weight average of the polymeric fluorescent dye of present embodiment preparation is 2850.
Embodiment 4:
Adding 0.88g 8GFF-PMDA condensation intermediate (0.001mol) and 10.00g vacuum-drying constant weight molecular-weight average are 2000 PEG2000 in 50mL single port flask, add the dry DMF solvent of the 10mL that contains the 0.005mol concentrated sulfuric acid catalyst again, the magnetic agitation dissolving, oil bath is warming up to 140 ℃ of isothermal reaction 5h.Reaction finish the back with in the saturated solution of sodium carbonate and system to pH value be 7, separate out product to system adding methyl alcohol; Products therefrom is filtered, and filter residue is with distilled water repetitive scrubbing, filtration, to remove unreacted PEG; 60 ℃ of vacuum-dryings get end hydroxy polyether type 8GFF-PMDA-PEG polymeric fluorescent dye 3.16g to constant weight.The molecular-weight average of the polymeric fluorescent dye of present embodiment preparation is 4850.
The performance comparison of the end hydroxy polyether type polymeric fluorescent dye of embodiment 2-4 preparation is as follows:
The performance of table 1 8GFF and end hydroxy polyether type polymeric fluorescent dye
*Annotate: the excitation wavelength of fluorescence spectrometry is 400nm.
From table 1 data as can be seen, through with PMDA and polyether reactant after, the fusing point of product and ultraviolet resistance stability are improved; And with the increase of pfpe molecule amount in synthetic, the fusing point of polymeric fluorescent dye and ultraviolet resistance stability progressively improve.Embodiment 5: the preparation of the synthetic color fluorescence polyurethane foamed material of polymeric fluorescent dye original position
In the 250mL there-necked flask, add 10mL the polymeric fluorescent dye 8GFF-PMDA-PEG600 and the 2.5g tolylene diisocyanate of exsiccant DMF, 3gPEG600,2g the present invention preparation, it is transparent to be stirred to solution, oil bath is warming up to 130 ℃, stirs reaction 4h down, gets yellow thickness performed polymer.Get the 4g performed polymer and place beaker, add distilled water 0.1g, dibutyl tin dilaurate 0.02g, trolamine 0.14g and triethylene diamine 0.02g then, put into after stirring and smoke 20min under 110 ℃ in the baking oven and get the xanchromatic polyurethane foam.
The preparation of the painted color fluorescence polyurethane foamed material of comparative example 1:8GFF
Add 10mL exsiccant DMF, 3.gPEG600,0.333g8GFF and 2.5g tolylene diisocyanate in the 250mL there-necked flask, it is transparent to be stirred to solution, and oil bath is warming up to 130 ℃, stirs reaction 4h down, gets yellow thickness performed polymer.Get the 4g performed polymer and place beaker, add distilled water 0.1g, dibutyl tin dilaurate 0.02g, trolamine 0.14g and triethylene diamine 0.02g then, put into after stirring and smoke 20min under 110 ℃ in the baking oven and get the xanchromatic polyurethane foam.
Get embodiment 5 and comparative example 1 gained polyurethane foam samples 1g respectively, place 20mL ethanol, soak after 5 hours and to take out oven dry, and the DMF solution that is configured to same concentrations is surveyed its fluorescence intensity respectively.
The solvent resistance of table 2 foam materials
*Annotate: the excitation wavelength of fluorescence spectrometry is 400nm.
Data adopt method synthetic polymeric fluorescent dye original position synthetic color fluorescence polyurethane foamed material of the present invention as can be seen from table 2, carry out painted polyurethane foamed material than direct use 8GFF and have better anti-solvent extraction performance.
Claims (4)
1. end hydroxy polyether type polymeric fluorescent dye is characterized in that its chemical structural formula is as follows:
Wherein n represents the polymerization degree, and n is 13,22 or 45.
2. the synthetic method of the described end hydroxy polyether type of claim 1 polymeric fluorescent dye is characterized in that operating according to the following steps:
In the 250mL four-hole boiling flask, add 1.2g pyromellitic acid anhydride, 3.3g fluorescent yellow 8GFF and 140mL exsiccant DMF solvent, stirring and dissolving to system is clear solution, warming-in-water to 80 ℃ isothermal reaction, system has product to separate out behind the reaction 0.5h, continue to stop behind the isothermal reaction 2h, after the DMF washing, filtering three times, 80 ℃ of dry 8GFF-PMDA condensation intermediate 3.9g that get of convection oven; In 50mL single port flask, adding 0.88g8GFF-PMDA condensation intermediate and 3.00g vacuum-drying constant weight molecular-weight average are 600 PEG600, add the dry DMF solvent of the 10mL that contains the 0.004mol concentrated sulfuric acid catalyst again, the magnetic agitation dissolving, oil bath is warming up to 140 ℃ of isothermal reaction 5h, reaction finish the back with in the saturated solution of sodium carbonate and system to pH value be 7, separate out product to system adding methyl alcohol; Products therefrom is filtered, and filter residue is with distilled water repetitive scrubbing, filtration, and to remove unreacted PEG, 60 ℃ of vacuum-dryings get end hydroxy polyether type 8GFF-PMDA-PEG polymeric fluorescent dye 0.87g to constant weight then.
3. the synthetic method of the described end hydroxy polyether type of claim 1 polymeric fluorescent dye is characterized in that operating according to the following steps:
In the 250mL four-hole boiling flask, add 1.2g pyromellitic acid anhydride, 3.3g fluorescent yellow 8GFF and 140mL exsiccant DMF solvent, stirring and dissolving to system is clear solution, warming-in-water to 80 ℃ isothermal reaction, system has product to separate out behind the reaction 0.5h, continue to stop behind the isothermal reaction 2h, after the DMF washing, filtering three times, 80 ℃ of dry 8GFF-PMDA condensation intermediate 3.9g that get of convection oven; With molecular weight be 1000 PEG in the single port flask 80 ℃ to vacuumize dry 3h standby, adding 0.88g8GFF-PMDA condensation intermediate and 5.00g molecular-weight average are 1000 PEG1000 in 50mL single port flask, add the dry DMF solvent of the 10mL that contains the 0.005mol concentrated sulfuric acid catalyst again, the magnetic agitation dissolving, oil bath is warming up to 140 ℃ of isothermal reaction 5h, reaction finish the back with in the saturated solution of sodium carbonate and system to pH value be 7, separate out product to system adding methyl alcohol; Products therefrom is filtered, and filter residue is with distilled water repetitive scrubbing, filtration, to remove unreacted PEG; 60 ℃ of vacuum-dryings get end hydroxy polyether type 8GFF-PMDA-PEG polymeric fluorescent dye 1.45g to constant weight.
4. the synthetic method of the described end hydroxy polyether type of claim 1 polymeric fluorescent dye is characterized in that operating according to the following steps:
In the 250mL four-hole boiling flask, add 1.2g pyromellitic acid anhydride, 3.3g fluorescent yellow 8GFF and 140mL exsiccant DMF solvent, stirring and dissolving to system is clear solution, warming-in-water to 80 ℃ isothermal reaction, system has product to separate out behind the reaction 0.5h, continue to stop behind the isothermal reaction 2h, after the DMF washing, filtering three times, 80 ℃ of dry 8GFF-PMDA condensation intermediate 3.9g that get of convection oven; Adding 0.88g8GFF-PMDA condensation intermediate and 10.00g vacuum-drying constant weight molecular-weight average are 2000 PEG2000 in 50mL single port flask, add the dry DMF solvent of the 10mL that contains the 0.005mol concentrated sulfuric acid catalyst again, the magnetic agitation dissolving, oil bath is warming up to 140 ℃ of isothermal reaction 5h.Reaction finish the back with in the saturated solution of sodium carbonate and system to pH value be 7, separate out product to system adding methyl alcohol; Products therefrom is filtered, and filter residue is with distilled water repetitive scrubbing, filtration, to remove unreacted PEG; 60 ℃ of vacuum-dryings get end hydroxy polyether type 8GFF-PMDA-PEG polymeric fluorescent dye 3.16g to constant weight.
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