Water-enhanced room-temperature phosphorescence emission polymers and methods of synthesis and use thereof

Abstract

The application belongs to the field of polymer synthesis and material science, and specifically discloses a water-enhanced room-temperature phosphorescence-emitting polymer, a synthesis method and application thereof, wherein a linear polymer is synthesized from a polyisocyanate, an amide monomer and a silane coupling agent under the catalysis of self-catalysis or dibutyltin dilaurate, the polymer is coated on a base material, and can be cured and formed into an organic room-temperature phosphorescence coating at room temperature, and realizes room-temperature phosphorescence-enhanced emission after hydrolysis and curing. The required time for hydrolysis and curing can be effectively changed by adjusting the monomer ratio, and the method has the advantages of adjustable structure, low toxicity, wide monomer adaptability, simple operation, low monomer cost and the like. The prepared organic room-temperature phosphorescence polymer has excellent water-phase afterglow stability, and simultaneously has excellent adhesion and long-life afterglow, and can be applied to the fields of coating, biological imaging and anti-counterfeiting.

Description

Technical Field

[0001] The invention belongs to the fields of polymer synthesis and materials science, and specifically discloses a water-enhanced room-temperature phosphorescence emission polymer and a synthesis method and application thereof. Background Art

[0002] Traditional methods for preparing room-temperature phosphorescent materials rely primarily on metal complexes. Metal complexes enable metal-ligand charge transfer, and their strong orbital-spin coupling significantly enhances the intersystem crossing rate, enabling long-lived room-temperature phosphorescence emission. However, the high cost and biological toxicity of noble metals have, to a certain extent, limited their application and development.

[0003] Compared with phosphors containing metal complexes, metal-free pure organic phosphors have the advantages of easy structural adjustment, low toxicity and low cost. Therefore, organic room temperature phosphorescent materials are widely used in fields such as anti-counterfeiting encryption, bioimaging, light-emitting devices and functional sensing as a new type of afterglow material. However, the triplet excitons of pure organic phosphors are easily quenched by oxygen, or inactivated by dissipation through non-radiative transition pathways at room temperature, resulting in energy loss, and the luminescence efficiency of organic room temperature phosphorescent materials is often very low. In addition, due to the enhanced non-radiative transition caused by the intensified intermolecular motion in the aqueous environment, the effects of dissolved oxygen and solvent relaxation in the aqueous environment lead to phosphorescence quenching. Therefore, the construction of afterglow coating materials with stable and efficient room temperature phosphorescence emission in an aqueous environment has broad application prospects. Summary of the Invention

[0004] In order to solve the defects of organic room temperature phosphorescent materials, the present invention synthesizes an organic room temperature phosphorescent polymer by a polycondensation method by amide monomer, isocyanate monomer and silane coupling agent monomer under the conditions of self-catalysis or dibutyltin dilaurate catalysis, and constructs a cross-linked network structure after curing by hydrolysis of the silane segment, builds a rigid environment for the luminophore, and realizes enhanced room temperature phosphorescence emission effect. Moreover, due to the dense network structure, the entry of water is hindered, and the quenching effect of solution oxygen on the luminophore in the aqueous environment is avoided. Stable room temperature phosphorescence emission in an aqueous environment can be achieved. Its product can be directly cured into a film and combined with a substrate to form a novel organic room temperature phosphorescent coating with blue and long-life afterglow characteristics, and can achieve enhanced room temperature phosphorescence emission after encountering water. This method has the advantages of using pure organic compound monomers, mild reaction conditions, wide monomer adaptability, simple operation and low monomer cost.

[0005] In order to achieve the above objectives, the present invention is implemented through the following technical solutions:

[0006] The organic room temperature phosphorescent polymer comprises the following components in terms of mass percentage: 35-44 wt% of isocyanate monomer, 25-34 wt% of amide monomer, and 30-38 wt% of silane coupling agent monomer.

[0007] The isocyanate monomer is one or more of dicyclohexylmethane diisocyanate (HMDI), hexamethylene diisocyanate (HDI), toluene diisocyanate (MDI), and isophorone diisocyanate (IPDI).

[0008] The amide monomer is one or more of azodicarbonamide (ADA), oxalyl diamide (ODM), malonamide (MAA), succinamide (BAD) or adipic diamide (ADM).

[0009] The silane coupling agent monomer is one or more of methacryloxypropyltrimethoxysilane (MPS), 3-aminopropyltrimethoxysilane (APTMS) or 3-aminopropyltriethoxysilane (APTES).

[0010] The present invention also provides a method for synthesizing an organic room temperature phosphorescent polymer. The organic room temperature phosphorescent polymer is prepared by a polycondensation method. Specifically, isocyanate monomers, amide monomers, and silane coupling agent monomers are subjected to a polycondensation reaction under autocatalytic or catalyst-catalyzed conditions in a dry environment protected by an inert gas to obtain a polymer. The polymer is then hydrolyzed and cured to obtain an organic room temperature phosphorescent coating.

[0011] The mass ratio of polyisocyanate to catalyst is 100-5000:1; the polycondensation reaction environment is a dry environment protected by inert gas; the polycondensation reaction temperature is 80-120° C.; and the polycondensation reaction time is 12-48 hours.

[0012] The organic room temperature phosphorescent polymer is used to prepare afterglow coatings, thin film interlayers and anti-counterfeiting coatings. The specific preparation method of the coating is: casting the organic room temperature phosphorescent polymer on a substrate material and then curing it through hydrolysis, cross-linking and curing.

[0013] The base material is stainless steel, metal material, general plastic or glass; the curing conditions are: cross-linking and curing at room temperature for 8-24 hours.

[0014] Beneficial effects:

[0015] The present invention provides a one-step method for synthesizing organic room-temperature phosphorescent polymers under mild reaction conditions. It achieves enhanced room-temperature phosphorescence emission in an aqueous environment and maintains long-term stability in the aqueous environment, significantly reducing the operational difficulty, time, and economic costs of polymer synthesis. Furthermore, the method utilizes a wide range of selectable monomers, and any functionalized isocyanate can be used as a reactive monomer for polycondensation.

[0016] The organic room temperature phosphorescent coating prepared by the invention has long-life afterglow performance, water-enhanced RTP emission performance, adhesion performance and good water-phase room temperature phosphorescent emission stability. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Figure 1 Schematic diagram of adhesion performance test.

[0018] Figure 2 These are afterglow photographs of the organic room temperature phosphorescent polymer coating prepared in Example 2 after being immersed in water for 30 days and irradiated with 365nm ultraviolet light and after the irradiation was stopped. The exposure time is 1 s.

[0019] Figure 3 This is the HNHR test of the organic room temperature phosphorescent polymer prepared in Example 2.

[0020] Figure 4 This is the FT-IR spectrum of the organic room temperature phosphorescent polymer prepared in Example 2.

[0021] Figure 5 The organic room temperature phosphorescent polymer prepared in Example 3 and the fluorescence emission spectra at 0 min, 10 min and 30 min after coating.

[0022] Figure 6 The organic room temperature phosphorescent polymer prepared in Example 3 and the phosphorescence emission spectra at 0 min, 10 min and 30 min after coating.

[0023] Figure 7 This is the lifetime decay spectrum of the organic room temperature phosphorescent polymer prepared in Example 3. DETAILED DESCRIPTION

[0024] The following will clearly and completely describe the technical solutions in the embodiments of the present invention in conjunction with the embodiments of the present invention and the accompanying drawings. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention.

[0025] Example 1

[0026] Weigh 0.204 g of azodicarbonamide, 0.154 g of hexamethylene diisocyanate, 0.1 g of toluene diisocyanate and 0.4 g of methacryloyloxypropyltrimethoxysilane into a 10 mL flask, mix and stir at 80 ° C under inert gas protection for 48 hours. After the reaction, an organic room temperature phosphorescent polymer is obtained with a yield of 99%. The polymer is cast on a substrate (316L stainless steel) and cured at room temperature for 24 hours to obtain a coating.

[0027] Performance tests were performed at room temperature.

[0028] According to the ASTM D1002 test standard, an organic room temperature phosphorescent polymer was applied to the surface of two 2cm×2cm substrates (316L stainless steel) and then bonded together. After curing, an adhesion test was performed. Figure 1 , the performance is shown in Table 1.

[0029] Example 2

[0030] 0.204 g malonamide, 0.171 g isophorone diisocyanate and 0.234 g methacryloxypropyltrimethoxysilane were weighed into a 10 mL flask and stirred at 80 ° C under inert gas protection for 48 h. After the reaction, an organic room temperature phosphorescent polymer was obtained with a yield of 99%. 1 mg of the sample was tested for H NMR and FTIR. Figure 3 and Figure 4 .

[0031] Example 3

[0032] Weigh 1g of adipic acid diamide, 1.01g of hexamethylene diisocyanate, and 0.8g of 3-aminopropyltrimethoxysilane in a 10mL flask. Mix and stir at 80°C under inert gas for 24h. After the reaction, an organic room temperature phosphorescent polymer is obtained with a yield of 99%. The polymer is cast on a substrate (316L stainless steel) and cured at room temperature for 12h to obtain a coating. The fluorescence spectrum, phosphorescence spectrum, and phosphorescence lifetime are tested. Figure 5 、 Figure 6 and Figure 7 .

[0033] Example 4

[0034] Weigh 1 g of succinamide, 1.95 g of toluene diisocyanate, and 0.25 g of 3-aminopropyltrimethoxysilane into a 10 mL flask, mix and stir at 80°C under inert gas protection for 24 hours. After the reaction, an organic room temperature phosphorescent polymer is obtained with a yield of 85%. The polymer is cast on a substrate (316L stainless steel) and cured at room temperature for 24 hours to obtain a coating.

[0035] Example 5

[0036] Weigh 1 g of adipic acid diamide, 0.51 g of isophorone diisocyanate, 0.5 g of toluene diisocyanate, and 0.6 g of 3-aminopropyltriethoxysilane into a 10 mL flask, mix and stir at 80°C under inert gas protection for 48 hours. After the reaction, an organic room temperature phosphorescent polymer is obtained with a yield of 80%. The polymer is cast on a substrate (316L stainless steel) and cured at room temperature for 24 hours to obtain a coating.

[0037] Example 6

[0038] Take 1 g of azodicarbonamide, 1.48 g of dicyclohexyl methane diisocyanate, 2.46 g of methacryloyloxypropyl trimethoxysilane in a 10 mL flask, under inert gas protection, 100 ℃ mixing stirring reaction 12 h, after the reaction, the organic room temperature phosphorescent polymer is obtained, the yield is 80%, the polymer is cast on the substrate (316L type stainless steel), and is cured at room temperature for 24 h to obtain a coating.

[0039] Example 7

[0040] Take 0.204 g of malonamide, 0.341 g of isofluroketone diisocyanate, 0.834 g of methacryloyloxypropyl trimethoxysilane in a 10 mL flask, under inert gas protection, 100 ℃ mixing stirring reaction 12 h, after the reaction, the organic room temperature phosphorescent polymer is obtained, the yield is 80%, the polymer is cast on the substrate, and is cured at room temperature for 24 h to obtain a coating.

[0041] Example 8

[0042] Take 0.204 g of malonamide, 0.141 g of toluene diisocyanate, 0.26 g of dicyclohexyl methane diisocyanate and 0.1404 g of 3-aminopropyl trimethoxysilane (APTMS) in a 10 mL flask, under inert gas protection, 120 ℃ mixing stirring reaction 24 h, after the reaction, the organic room temperature phosphorescent polymer is obtained, the yield is 89%, the polymer is cast on the substrate (316L type stainless steel), and is cured at room temperature for 24 h to obtain a coating.

[0043] Example 9

[0044] Take 1 g of adipamide, 1.01 g of hexamethylene diisocyanate and 2.8 g of 3-aminopropyl trimethoxysilane in a 10 mL flask, under inert gas protection, 80 ℃ mixing stirring reaction 24 h, after the reaction, the organic room temperature phosphorescent polymer is obtained, the yield is 99%, the polymer is cast on the substrate (316L type stainless steel), and is cured at room temperature for 12 h to obtain a coating.

[0045] Example 10

[0046] Take 1 g of adipamide, 2.01 g of hexamethylene diisocyanate and 4.8 g of 3-aminopropyl trimethoxysilane in a 10 mL flask, under inert gas protection, 80 ℃ mixing stirring reaction 24 h, after the reaction, the organic room temperature phosphorescent polymer is obtained, the yield is 99%, the polymer is cast on the substrate (316L type stainless steel), and is cured at room temperature for 12 h to obtain a coating.

[0047] Example 11

[0048] Weigh 1 g of adipic acid diamide, 3.01 g of hexamethylene diisocyanate and 8.8 g of 3-aminopropyltrimethoxysilane into a 10 mL flask, mix and stir at 80 ° C under inert gas protection for 24 hours. After the reaction, an organic room temperature phosphorescent polymer is obtained with a yield of 99%. The polymer is cast on a substrate (316L stainless steel) and cured at room temperature for 12 hours to obtain a coating.

[0049] Table 1 Stretch and adhesion of the examples

[0050] Example Tensile strength (MPa) Elongation at break (%) Adhesion force (MPa) 1 10.2±1.82 95.84±6.05 1.17±0.12 2 12.53±2.78 95.76±5.09 1.08±0.10 3 11.56±2.28 105.23±7.34 0.91±0.13 4 9.15±1.38 118.23±5.05 0.93±0.31 5 8.96±2.71 113.89±6.05 1.19±0.20 6 50.21±3.48 7.78±0.25 0.54±0.09 7 40.89±2.32 6.98±1.31 0.61±0.08 8 12.61±0.16 103.83±3.68 1.08±0.17 9 13.41±0.27 85.76±3.04 1.28±0.14 10 30.77±2.26 8.99±2.77 0.63±0.11 11 55.41±3.67 6.98±1.15 0.45±0.12

[0051] The above description is only a preferred specific embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any technician familiar with the technical field, within the technical scope disclosed by the present invention, who makes equivalent replacements or changes based on the technical solutions and inventive concepts of the present invention, should be covered by the scope of protection of the present invention.

Claims

1. A polymer that emits water-enhanced room temperature phosphorescence, characterized in that: The water-enhanced room temperature phosphorescent emission polymer is composed of: 35-44 wt% of isocyanate monomer, 25-34 wt% of amide monomer, and 30-38 wt% of silane coupling agent monomer in terms of mass percentage; The amide monomer is one or more of azodicarbonamide ADA, oxalyl diamide ODM, malonamide MAA, succinamide BAD or adipic acid diamide ADM; The silane coupling agent monomer is one or more of methacryloxypropyltrimethoxysilane MPS, 3-aminopropyltrimethoxysilane APTMS or 3-aminopropyltriethoxysilane APTES.

2. The water-enhanced room temperature phosphorescence emitting polymer according to claim 1, characterized in that The isocyanate monomer is one or more of dicyclohexylmethane diisocyanate HMDI, hexamethylene diisocyanate HDI, toluene diisocyanate TDI, and isophorone diisocyanate IPDI.

3. A method for synthesizing a polymer having water-enhanced room temperature phosphorescence emission according to claim 1, characterized in that: The synthesis method comprises the following steps: preparing an organic room temperature phosphorescent polymer by combining an isocyanate monomer, an amide monomer and a silane coupling agent monomer in a dry environment protected by an inert gas under autocatalytic or catalyst catalytic conditions.

4. The method for synthesizing a polymer having water-enhanced room temperature phosphorescence emission according to claim 3, wherein: The catalyst is dibutyltin dilaurate, and the mass ratio of polyisocyanate to the catalyst is 100-5000:

1.

5. Use of the polymer for water-enhanced room temperature phosphorescence emission according to claim 1, characterized in that: The water-enhanced room temperature phosphorescent emission polymer is used for preparing afterglow coating, thin film interlayer or anti-counterfeiting coating.

6. The use of the polymer for water-enhanced room temperature phosphorescence emission according to claim 5, characterized in that: The preparation method of the coating comprises the following steps: casting a water-enhanced room temperature phosphorescent emitting polymer on a base material, and then allowing the polymer to stand at room temperature to undergo hydrolysis, cross-linking, and solidification to form a film.

7. The use of the polymer for water-enhanced room temperature phosphorescence emission according to claim 6, characterized in that: The base material is stainless steel, metal material, general plastic or glass.

8. The use of the polymer for water-enhanced room temperature phosphorescence emission according to claim 6, characterized in that: The cross-linking and curing time is 8-24 hours.

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