Preparation method of fluorescent waterborne polyurethane emulsion based on chromophore in diisocyanate

A technology of diisocyanate and water-based polyurethane, applied in luminescent materials, chemical instruments and methods, organic chemistry, etc., can solve the problems of color variety, fluorescent function, vividness, migration resistance and weather resistance, and insufficient content of fluorescent conjugated groups control, complex reaction and other issues, to achieve the effect of good fluorescence intensity persistence, not easy to migrate, and uniform distribution

Active Publication Date: 2013-06-26

UNIV OF SCI & TECH OF CHINA +1

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Problems solved by technology

Due to the limitation of the solubility of small molecule fluorescent pigments or dyes in water, the compatibility of fluorescent pigments or dye particles with water-based polyurethane, the migration of fluorescent pigments or dye particles during the use of materials, etc., the obtained products have fluorescent functions. Current water-based polyurethane materials are deficient in color variety, fluorescent function, vividness, migration resistance and weather resistance, and some small molecule fluorescent pigments or heavy metals in dyes will also bring certain environmental problems

[0004] Chinese...

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Abstract

The invention discloses a preparation method of a fluorescent waterborne polyurethane emulsion based on chromophore in diisocyanate. The preparation method is characterized by comprising the following steps of: enabling monoamine or monohydric alcohol containing fluorescent chromophore to be reacted with isocyanate, or enabling diamine or dihydric alcohol containing the fluorescent chromophore to be reacted with diisocyanate with a symmetric structure to synthesize diisocyanate containing the fluorescent chromophore, and then combining the diisocyanate containing the fluorescent chromophore with common diisocyanate to partially or completely substitute for the common diisocyanate to prepare the fluorescent waterborne polyurethane. According to the preparation method disclosed by the invention, the hard segment content and type of the prepared fluorescent waterborne polyurethane and the content (2-40wt%) of the fluorescent chromophore are controllable by adjusting the types and proportions of the diisocyanate and a chain extender, and the prepared fluorescent waterborne polyurethane has the advantages that the fluorescent chromophore is uniformly distributed and difficult to migrate, the fluorescent intensity is good in durability, and improvement in terms of optical, thermal and certain functional characteristics can be achieved while the fluorescent property is achieved.

Application Domain

Organic chemistryLuminescent compositions

Technology Topic

DiamineIsocyanate +7

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Examples

Experimental program(4)

Example Embodiment

[0046] Example 1:

[0047] Put 10.00g HDI and 9.88g FL into a three-necked flask, add 60ml N,N-dimethylformamide as solvent, and then add 0.01g DBTDL as catalyst, react at 60℃ for 5 hours under mechanical stirring, and cool to 30 The solvent was distilled off under reduced pressure at °C, and then the product was washed 3 times with acetone, and the washed product was dried in a vacuum drying oven to a constant weight to obtain a fluorescent diisocyanate FLDI.

[0048] 36.00 grams of PTMG (M n =2000) Put it into a 500ml three-necked flask, dehydrate at 115°C for 1 hour and then cool to 50°C. Take 7.95 g of fluorescent diisocyanate FLDI and 15.60 g of IPDI into a three-necked flask, stir and react at 85°C for 3 hours, then add 3.70 g of hydrophilic chain extender DMPA, 2.80 g of BDO, 0.02 g of DBTDL and 45.00 g of methyl ethyl ketone, constant temperature After stirring at 75°C for 3 hours, the temperature was lowered to 30°C, and the reaction product was transferred to a high-speed shearing disperser. 2.80 g TEA was added at 3000 rpm. After reacting for 5 minutes, 140 g water was added and stirred for 1 minute. Then it was transferred to a rotary evaporator, and methyl ethyl ketone was removed under vacuum conditions of 50°C and 0.01MPa to obtain a yellow fluorescent water-based polyurethane (FLDI-WPU) emulsion with a fluorescent group content of 12.04%.

[0049] If the other conditions of this embodiment remain unchanged and the addition amount of FLDI and IPDI is changed, a stable fluorescent waterborne polyurethane emulsion with a controllable fluorophore content in the range of 2-40 wt% can be obtained.

[0050] Attached figure 1 Infrared spectra of FLDI and FLDI-WPU synthesized in this example. It can be seen from the FLDI-WPU spectrum that the characteristic absorption peaks of polyurethane are located at 3325cm. -1 (ν N-H ), 2858-2932cm -1 (ν CH2 andν CH3 ), 1706cm -1 (ν C=O ), 1535cm -1 (δ N-H ) And 1110cm -1 (ν C-O-C ); the FLDI spectra are located at 1601cm -1 (δ C=C ),1110cm -1 (δ Ph-O ) And 772cm -1 (γ C-H ) FLDI characteristic absorption peak can also be seen in the FLDI-WPU spectrum, and the representative isocyanate group NCO is located at 2271cm -1 (ν C=O The characteristic absorption peak of) is clearly visible in the FLDI spectrum, but disappears in the FLDI-WPU spectrum, indicating that FLDI has completely participated in the reaction during the synthesis and preparation of polyurethane.

[0051] Attached figure 2 The concentration of the fluorescent chromophore is 1×10 -5 Comparison of the fluorescence spectra of mol/L FL aqueous solution and FLDI-WPU, the maximum fluorescence emission peak of both is located at 515nm, and the peak shape is similar. figure 2 It shows that when the fluorescent group is chemically keyed into the molecular chain of the waterborne polyurethane, the fluorescence intensity is greatly enhanced, showing a typical fluorescence enhancement effect.

Example Embodiment

[0052] Example 2:

[0053] Add 6.00 g of p-phenylene diisocyanate and 20 ml of N,N-dimethylformamide into a three-necked flask, raise the temperature to 30°C, add ST6.60 g and 30 ml of N,N-dimethylformamide dropwise with mechanical stirring The solution is controlled for half an hour and the dripping is completed. After reacting at 30°C for 2 hours, the solvent was distilled off under reduced pressure, and the product was washed once with dichloromethane. The washed product was placed in a vacuum drying oven and dried to a constant weight to obtain a fluorescent diisocyanate STDI.

[0054] Add 10.00 g of HDI trimer and 20 ml of N,N-dimethylformamide into a three-necked flask, raise the temperature to 30℃, and add dropwise 2.84 g of AN and 6 ml of N,N-dimethylformamide under mechanical stirring. Solution, control for half an hour to finish dripping. After reacting at 30°C for 2 hours, the solvent was distilled off under reduced pressure, and the product was washed once with dichloromethane. The washed product was dried in a vacuum drying oven to a constant weight to obtain the fluorescent diisocyanate ANDI.

[0055] Add 20 grams of PCL (M n =1000) Put it into a 500mL three-necked flask, dehydrate at 110°C for 1 hour and then cool to 50°C. Take 3.60 g of fluorescent diisocyanate STDI, 3.40 g of ANDI, 21.30 g of IPDI and 0.03 g of DBTDL into a three-necked flask, stir and react at 85°C for 2 hours, then add 3.36 g of hydrophilic chain extender TA and 5.10 g of BDO And 55.00 g of butanone, stirred at 75°C for 4 hours and then cooled to 20°C. The reaction product was transferred to a high-speed shear disperser, and 4.52 g of TEA was added at 3000 rpm. After 5 minutes of reaction, 140 was added. After stirring for 1 minute, add 0.30 g of EDA to react for 30 minutes. The reaction product is transferred to a rotary evaporator, and methyl ethyl ketone is removed under vacuum conditions of 50°C and 0.01MPa to obtain a fluorescent water-based with a fluorophore content of 12.27% Polyurethane emulsion.

[0056] If the other conditions of this embodiment remain unchanged, and ST is replaced with phenosafranine, disperse violet 26 or 2,3-diaminonaphthalene, respectively, stable fluorescent waterborne polyurethane emulsions with controllable fluorescent group content can be obtained.

Example Embodiment

[0057] Example 3:

[0058] Add 25.00 g of HDI trimer and 30 ml of N,N-dimethylformamide into a 250 mL three-necked flask, raise the temperature to 30°C, pass nitrogen protection, and add 14.50 g of Azure A and 30 ml of N under mechanical stirring. ,N-Dimethylformamide solution, control the dripping for half an hour. After the reaction was maintained at 30°C for 2 hours, the solvent was distilled off under reduced pressure, and the product was washed once with acetone. The washed product was dried in a vacuum drying oven to a constant weight to obtain the fluorescent diisocyanate AADI.

[0059] Add 60.00 grams of PPG (M n =1000) Put it into a 500mL three-necked flask, dehydrate at 120℃ for 1 hour and then cool to 50℃. Take 18.00 grams of fluorescent diisocyanate AADI, 35.00 grams of TDI and 0.03 grams of DBTDL and add them to a three-necked flask. After stirring at 80°C for 3 hours, add 7.20 grams of hydrophilic chain extender DMPA, 8.60 grams of DEG and 90.00 grams of acetone. , Stir the reaction at 65°C for 4 hours and then lower the temperature to 5°C. The reaction product was transferred to a high-speed shearing disperser, 5.50 g of TEA was added at 3000 rpm, 240 g of water was added after 5 minutes of reaction, and then 0.80 g of EDA was added to react for 30 minutes after stirring for 1 minute. The reaction product was transferred to a rotary evaporator, and acetone was removed under vacuum conditions of 40° C. and 0.01 MPa to obtain a blue fluorescent water-based polyurethane emulsion with a fluorescent group content of 13.89%.

[0060] If the other conditions of this example remain unchanged, and PPG is replaced with PBA, PCL, PCDL or PTMG, or any combination of two or three of them, a stable fluorescent water-based with controllable fluorophore content can be obtained. Polyurethane emulsion.

[0061] If the other conditions of this example remain unchanged, and the Azure A is replaced with 1-naphthylamine, 2-AF, 9-phenanthramine or APTS, a stable fluorescent waterborne polyurethane with controllable fluorescent group content can be obtained. Lotion.

[0062] If the other conditions of this embodiment remain unchanged, and DEG is replaced with EG or HDO, or any combination of two or three of them, a stable fluorescent waterborne polyurethane emulsion with a controllable fluorescent group content can be obtained.

[0063] When other conditions in this embodiment remain unchanged, replacing EDA with IPDA can also obtain a stable fluorescent waterborne polyurethane emulsion with a controllable fluorescent group content.

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Classification and recommendation of technical efficacy words

Evenly distributed
Not easy to migrate

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Preparation method of fluorescent waterborne polyurethane emulsion based on chromophore in diisocyanate

AI-Extracted Technical Summary

Problems solved by technology

Abstract

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Example Embodiment

Example Embodiment

Example Embodiment

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Description & Claims & Application Information

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