阅读说明：本技术 含氟改性室温磷光生物基水性聚氨酯的制备方法和用途 (Preparation method and application of fluorine-containing modified room-temperature phosphorescent bio-based waterborne polyurethane ) 是由 李维虎 王启东 黄星 赵曦 戴家兵 朱保凌 于 2020-06-16 设计创作，主要内容包括：本发明提供一种含氟改性室温磷光生物基水性聚氨酯的制备方法和用途,属于水性聚氨酯技术领域。本发明利用含氟聚醚二元醇、生物基多元醇、异氰酸酯、小分子扩链剂、亲水物质及小分子后扩链剂合成制备含氟改性生物基水性聚氨酯,该含氟改性生物基水性聚氨酯具有优异耐折性能、耐磨性能、耐热性能、力学性能、存储性能、生物降解性及恒温恒湿性能,且该含氟改性生物基水性成膜后在在室温下用365nm紫外灯照射下表现为蓝色磷光,其磷光寿命能够达到40ms左右,该含氟改性室温磷光生物基水性聚氨酯可以用于防伪标识、显示仪器、光学成像及OLED等领域。(The invention provides a preparation method and application of fluorine-containing modified room-temperature phosphorescent bio-based waterborne polyurethane, belonging to the technical field of waterborne polyurethane. The fluorine-containing modified bio-based waterborne polyurethane is synthesized by utilizing fluorine-containing polyether diol, bio-based polyol, isocyanate, a micromolecule chain extender, a hydrophilic substance and a micromolecule post-chain extender to prepare the fluorine-containing modified bio-based waterborne polyurethane, the fluorine-containing modified bio-based waterborne polyurethane has excellent folding resistance, wear resistance, heat resistance, mechanical property, storage performance, biodegradability and constant temperature and humidity performance, blue phosphorescence is shown under the irradiation of a 365nm ultraviolet lamp at room temperature after the fluorine-containing modified bio-based waterborne polyurethane is formed into a film, the phosphorescence service life can reach about 40ms, and the fluorine-containing modified room temperature phosphorescence bio-based waterborne polyurethane can be used in the fields of anti-counterfeiting marks, display instruments, optical imaging, OLEDs and the like.)

1. The preparation method of the fluorine-containing modified room temperature phosphorescent bio-based waterborne polyurethane is characterized by comprising the following steps of:

s1, stirring the bio-based macromolecular polyol, the fluorine-containing polyether glycol, the bio-based isocyanate and the aliphatic isocyanate at 80-100 ℃ for 1-3h, then adding the carboxylic acid type hydrophilic chain extender, stirring at 80-100 ℃ for 2-3h, continuously adding the micromolecular polyol chain extender, and stirring at 80-100 ℃ for 2-4h to obtain the waterborne polyurethane prepolymer;

s2, cooling the aqueous polyurethane prepolymer prepared in the step S1 to 1-20 ℃, adding a neutralizing agent, transferring the aqueous polyurethane prepolymer into a high-speed dispersion machine, adding deionized water with the mass 2-3 times of the total solid mass under the high-speed stirring of 1400-1600 r/min, and adding a small-molecular polyamine chain extender after 1-3min to prepare the fluorine-containing modified room-temperature phosphorescent bio-based aqueous polyurethane.

2. The preparation method of the fluorine-containing modified room temperature phosphorescent bio-based waterborne polyurethane as claimed in claim 1, wherein the preparation raw materials comprise the following components in parts by weight:

3. the method for preparing fluorine-containing modified room temperature phosphorescent bio-based waterborne polyurethane as claimed in claim 1 or 2, wherein the bio-based macromolecular polyol in step S1 is one or two or more selected from castor oil, castor oil-modified polyol, dimer acid polyol, 1, 3-propylene glycol polyether polyol, soybean oil, palm oil polyol and rosin ester polyol.

4. The method for preparing fluorine-containing modified room temperature phosphorescent bio-based waterborne polyurethane as claimed in claim 1 or 2, wherein the fluorine-containing polyether diol of step S1 is one or two or more of perfluoropolyether diol, semifluoropolyether diol, and side chain fluorine-containing polyether diol.

5. The method for preparing fluorine-containing modified room temperature phosphorescent bio-based waterborne polyurethane as claimed in claim 1 or 2, wherein the bio-based isocyanate in step S1 is one or two or more of dimer acid diisocyanate, bio-matrix 1, 4-butylene diisocyanate and bio-matrix 1, 5-pentylene diisocyanate.

6. The method for preparing fluorine-containing modified room temperature phosphorescent bio-based waterborne polyurethane as claimed in claim 1 or 2, wherein the carboxylic acid type hydrophilic chain extender in step S1 is dimethylolpropionic acid or dihydroxybutyric acid.

7. The method for preparing fluorine-containing modified room temperature phosphorescent bio-based waterborne polyurethane as claimed in claim 1 or 2, wherein the small molecule polyol chain extender in step S1 is one or two or more of trimethylolpropane, glycerol, butanediol, 1, 3-propanediol, ethylene glycol and cyclohexanedimethanol.

8. The method for preparing fluorine-containing modified room temperature phosphorescent bio-based waterborne polyurethane as claimed in claim 1 or 2, wherein the neutralizing agent in step S2 is one or two or more of triethylamine, diethanolamine and triethanolamine.

9. The method for preparing fluorine-containing modified room temperature phosphorescent bio-based waterborne polyurethane as claimed in claim 1 or 2, wherein the small molecule polyamine chain extender in step S2 is one or two or more of ethylenediamine, hexamethylenediamine and isophoronediamine.

10. The application of the fluorine-containing modified room temperature phosphorescent bio-based waterborne polyurethane prepared by the preparation method of any one of claims 1 to 9 in the fields of anti-counterfeiting marks, display instruments, optical imaging and OLEDs.

Technical Field

The invention provides a preparation method and application of fluorine-containing modified room-temperature phosphorescent bio-based waterborne polyurethane, belonging to the technical field of waterborne polyurethane.

Background

The bio-based macromolecular polyol and the bio-based isocyanate are prepared from vegetable oil, so that the raw material resources are rich, the price is low, and the acquisition ways are more; the bio-based waterborne polyurethane resin has the advantages of better degradability, environmental friendliness and the like, and accords with the current concept of green environmental protection; the development of bio-based waterborne polyurethane resin can reduce or even eliminate the use of petroleum polyols, and the use of vegetable oil polyols can not only save energy and excessively utilize, but also promote the development of agriculture, so the development of bio-based waterborne polyurethane resin has very important significance.

Phosphorescence is a long-lived emission phenomenon, and room temperature phosphorescence is commonly observed in inorganic compounds (e.g., nightmares). Conventional wisdom holds that phosphorescence can only be achieved at low temperatures for organic compounds. This is due to: on the one hand, excitons are highly localized in organic compounds and are very easily recombined, which is very disadvantageous for long-life processes such as phosphorescence; on the other hand, generation of phosphorescence requires overcoming the limitations of spin-forbidden and non-radiative transitions of the molecules themselves. The common room temperature phosphorescent materials need to introduce metal elements such as Pt and Ir, and the metal elements are expensive and have inherent instability in the case of high-energy blue emitters. For pure organic compounds, phosphorescence of pure organic compounds is limited to cryogenic and inert environments for a long period of time, since triplet excited states are easily deactivated by non-radiative processes such as vibration and oxygen quenching.

Disclosure of Invention

The invention aims to overcome the defects in the prior art and provides a preparation method of fluorine-containing modified room temperature phosphorescent bio-based waterborne polyurethane.

The invention aims to solve another technical problem of providing the application of the fluorine-containing modified room temperature phosphorescent bio-based waterborne polyurethane.

In order to solve the technical problem, the technical scheme is that the preparation method of the fluorine-containing modified room temperature phosphorescent bio-based waterborne polyurethane comprises the following steps:

s1, stirring the bio-based macromolecular polyol, the fluorine-containing polyether glycol, the bio-based isocyanate and the aliphatic isocyanate at 80-100 ℃ for 1-3h, then adding the carboxylic acid type hydrophilic chain extender, stirring at 80-100 ℃ for 2-3h, continuously adding the micromolecular polyol chain extender, and stirring at 80-100 ℃ for 2-4h to obtain the waterborne polyurethane prepolymer;

s2, cooling the aqueous polyurethane prepolymer prepared in the step S1 to 1-20 ℃, adding a neutralizing agent, transferring the aqueous polyurethane prepolymer into a high-speed dispersion machine, adding deionized water with the mass 2-3 times of the total solid mass under the high-speed stirring of 1400-1600 r/min, and adding a small-molecular polyamine chain extender after 1-3min to prepare the fluorine-containing modified room-temperature phosphorescent bio-based aqueous polyurethane.

The preparation method of the fluorine-containing modified room temperature phosphorescent bio-based waterborne polyurethane is further improved as follows:

preferably, the preparation raw materials comprise the following components in parts by weight:

preferably, the bio-based macromolecular polyol in step S1 is one or two or more selected from castor oil, castor oil-modified polyol, dimer acid polyol, 1, 3-propylene glycol polyether polyol, soybean oil, palm oil polyol, and rosin ester polyol.

Preferably, the fluoropolyether diol in step S1 is one or two or more of perfluoropolyether diol, semifluoropolyether diol, and side chain fluoropolyether diol.

Preferably, the bio-based isocyanate in step S1 is one or two or more of dimer acid diisocyanate, bio-matrix 1, 4-butylene diisocyanate and bio-matrix 1, 5-pentylene diisocyanate.

Preferably, the carboxylic acid type hydrophilic chain extender of step S1 is dimethylolpropionic acid or dihydroxybutyric acid.

Preferably, the small-molecule polyol chain extender in step S1 is one or two or more selected from trimethylolpropane, glycerol, butanediol, 1, 3-propanediol, ethylene glycol and cyclohexanedimethanol.

Preferably, the neutralizing agent in step S2 is one or two or more of triethylamine, diethanolamine, and triethanolamine.

Preferably, the small molecule polyamine chain extender in step S2 is one or two or more of ethylenediamine, hexamethylenediamine and isophoronediamine.

In order to solve another technical problem, the invention adopts the technical scheme that the fluorine-containing modified room temperature phosphorescent bio-based waterborne polyurethane is applied to the fields of anti-counterfeiting marks, display instruments, optical imaging and OLEDs.

Compared with the prior art, the invention has the beneficial effects that:

1) the fluorine-containing modified bio-based waterborne polyurethane has excellent folding resistance, wear resistance, heat resistance, mechanical property, storage property, biodegradability and constant temperature and humidity performance, and after the fluorine-containing modified bio-based waterborne polyurethane is formed into a film, the film is shown to be blue phosphorescence under the irradiation of a 365nm ultraviolet lamp at room temperature, and the phosphorescence service life can reach about 40 ms.

2) In the prior art, micromolecules containing heavy atoms (halogens and the like) are introduced into waterborne polyurethane, room-temperature phosphorescent waterborne polyurethane is prepared by blending, the blended product is easy to cause micromolecules to migrate, so that the phosphorescent property of the blended product is weakened or even disappears, the room-temperature phosphorescent service life is 16-24ms, and the used waterborne polyurethane is conventional waterborne polyurethane and has unobvious biodegradation performance;

the invention provides a preparation method of fluorine-containing modified room temperature phosphorescent bio-based waterborne polyurethane, which is characterized in that raw materials of bio-based macromolecular polyol and bio-based isocyanate are rich in source and good in biodegradability to prepare bio-based waterborne polyurethane resin; the perfluorinated polyether polyol is directly synthesized into a bio-based waterborne polyurethane structure through chemical modification, so that the room-temperature phosphorescence of a pure organic compound luminous body is realized, the harsh conditions that a common phosphorescent substance needs to be excited in a freezing low-temperature and inert environment are overcome, the plasticity is strong, and the application range is wide; the prepared fluorine-containing modified room temperature phosphorescent bio-based waterborne polyurethane has strong phosphorescent intensity and the room temperature phosphorescent service life of 35-50 ms.

3) The fluorine-containing modified room temperature phosphorescent bio-based waterborne polyurethane has excellent physical and biological properties, and can be used in the fields of anti-counterfeiting marks, display instruments, optical imaging, OLEDs and the like.

Detailed Description

In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail below with reference to embodiments, and all other embodiments obtained by a person of ordinary skill in the art without any creative effort based on the embodiments of the present invention belong to the protection scope of the present invention.

Note that "%" and "part(s)" shown in the description herein mean "% by mass" and "part(s) by mass", respectively, unless otherwise specified.