Water-enhanced room-temperature phosphorescence emission polymer as well as synthesis method and application thereof

Abstract

The invention belongs to the field of polymer synthesis and material science, and particularly discloses a water-enhanced room-temperature phosphorescence emission polymer and a synthesis method and application thereof.The water-enhanced room-temperature phosphorescence emission polymer is synthesized from polyisocyanate, an amide monomer and a silane coupling agent under autocatalysis or catalysis of dibutyltin dilaurate to form a linear polymer; when the polymer is coated on a matrix material, the polymer can be cured and molded at room temperature to obtain an organic room-temperature phosphorescent coating, and room-temperature phosphorescent enhanced emission is realized after hydrolysis and curing. The time required for hydrolytic curing can be effectively changed by regulating and controlling the proportion of the monomers, and the method has the advantages of adjustable structure, low toxicity, wide adaptability of the monomers, simplicity in operation, low cost of the monomers and the like. The prepared organic room-temperature phosphorescent polymer has the characteristics of excellent water-phase afterglow stability, excellent adhesive power, long-life afterglow and the like, and can be applied to the fields of coatings, biological imaging and anti-counterfeiting.

Description

Technical Field

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

[0002] Traditional methods for preparing room temperature phosphorescent materials mainly rely on metal complexes, which can undergo metal-ligand charge transfer, and their strong orbital spin coupling can greatly increase the intersystem crossing rate, thus achieving long-life room temperature phosphorescent emission. However, the high cost and biological toxicity of precious metals have limited their application and development to a certain extent.

[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 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 dissipated and inactivated 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 intensified intermolecular motion in the aqueous environment, the non-radiative transition is enhanced, and the effects of dissolved oxygen and solvent relaxation in the aqueous environment lead to phosphorescence quenching. Therefore, the afterglow coating material with stable and efficient room temperature phosphorescence emission in the 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 organic room temperature phosphorescent polymers by a one-step method by condensation polymerization of amide monomers, isocyanate monomers and silane coupling agent monomers under the conditions of self-catalysis or dibutyltin dilaurate catalysis, and constructs a cross-linked network structure after hydrolysis and curing of the silane segment, constructs a rigid environment for the luminophore, and realizes the enhancement of room temperature phosphorescent emission effect, and due to the dense network structure, hinders the entry of water, avoids the quenching effect of solution oxygen on the luminophore in the aqueous environment. Stable room temperature phosphorescent 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 new type of organic room temperature phosphorescent coating with blue and long-life afterglow characteristics, and the enhancement of room temperature phosphorescent emission can be achieved after encountering water. The 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 composition of the organic room temperature phosphorescent polymer according to mass percentage is: 35-44wt% of isocyanate monomer, 25-34wt% of amide monomer, and 30-38wt% 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, which 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, and then the organic room temperature phosphorescent coating is obtained by hydrolysis and curing.

[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 12-48h.

[0012] The organic room temperature phosphorescent polymer is used to prepare afterglow coating, thin film interlayer and anti-counterfeiting coating. The specific preparation method of the coating is: cast the organic room temperature phosphorescent polymer on the base material and then solidify it into a film 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 method for synthesizing an organic room temperature phosphorescent polymer provided by the present invention is a one-step synthesis with mild reaction conditions, and realizes room temperature phosphorescent enhanced emission in an aqueous environment and maintains the stability of the aqueous environment for a long time, which greatly reduces the operational difficulty, time and economic cost of polymer synthesis. Moreover, the range of monomers that can be selected is wide, and functionalized isocyanates can be used as reactive monomers 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 under 365 nm ultraviolet irradiation and after irradiation is stopped, with an exposure time of 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 technical solutions in the embodiments of the present invention will be described clearly and completely below in combination 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 creative work are within the scope of protection of the present invention.

[0025] Example 1

[0026] Weigh 0.204g of azodicarbonamide, 0.154g of hexamethylene diisocyanate, 0.1g of toluene diisocyanate and 0.4g of methacryloxypropyltrimethoxysilane into a 10mL flask, and stir and react at 80°C under inert gas protection for 48h. 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 24h to obtain a coating.

[0027] Performance tests were conducted at room temperature.

[0028] According to the ASTM D1002 test standard, an organic room temperature phosphorescent polymer was applied to the surface of two substrates (316L stainless steel) of 2 cm×2 cm and 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 of malonamide, 0.171 g of isophorone diisocyanate and 0.234 g of methacryloxypropyltrimethoxysilane were weighed into a 10 mL flask, and stirred at 80 ° C for 48 h under the protection of inert gas. After the reaction, an organic room temperature phosphorescent polymer was obtained with a yield of 99%. 1 mg of the sample was taken for testing of H NMR and FTIR. Figure 3 and Figure 4 .

[0031] Example 3

[0032] Weigh 1g of hexamethylenediamine, 1.01g of hexamethylene diisocyanate and 0.8g of 3-aminopropyltrimethoxysilane in a 10mL flask, stir and react at 80°C for 24h under inert gas protection. 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. Test the fluorescence spectrum, phosphorescence spectrum and phosphorescence lifetime. 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, and stir and react 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 in a 10 mL flask, and stir and react 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] Weigh 1g of azodicarbonamide, 1.48g of dicyclohexylmethane diisocyanate, and 2.46g of methacryloxypropyltrimethoxysilane into a 10mL flask, and stir and react at 100°C under inert gas protection for 12h. 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 24h to obtain a coating.

[0039] Example 7

[0040] Weigh 0.204 g of malonamide, 0.341 g of isophorone diisocyanate, and 0.834 g of methacryloxypropyltrimethoxysilane into a 10 mL flask, and stir and react at 100 °C under inert gas protection for 12 h. After the reaction, an organic room temperature phosphorescent polymer is obtained with a yield of 80%. The polymer is cast on a substrate and cured at room temperature for 24 h to obtain a coating.

[0041] Example 8

[0042] Weigh 0.204 g of succinamide, 0.141 g of toluene diisocyanate, 0.26 g of dicyclohexylmethane diisocyanate and 0.1404 g of 3-aminopropyltrimethoxysilane (APTMS) into a 10 mL flask, and stir and react at 120° C. under inert gas protection for 24 hours. After the reaction, an organic room temperature phosphorescent polymer is obtained with a yield of 89%. The polymer is cast on a substrate (316L stainless steel) and cured at room temperature for 24 hours to obtain a coating.

[0043] Example 9

[0044] Weigh 1g of hexamethylene diamine, 1.01g of hexamethylene diisocyanate and 2.8g of 3-aminopropyltrimethoxysilane into a 10mL flask, and stir and react at 80°C under inert gas protection 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.

[0045] Example 10

[0046] Weigh 1g of hexamethylene diisocyanate, 2.01g of hexamethylene diisocyanate and 4.8g of 3-aminopropyltrimethoxysilane into a 10mL flask, and stir and react at 80°C under inert gas protection 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.

[0047] Embodiment 11

[0048] Weigh 1g of hexamethylene diamine, 3.01g of hexamethylene diisocyanate and 8.8g of 3-aminopropyltrimethoxysilane into a 10mL flask, and stir and react at 80°C under inert gas protection 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.

[0049] Table 1 Stretching 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 implementation manner of the present invention, but the protection scope of the present invention is not limited thereto. Any technician familiar with the technical field can make equivalent replacements or changes according to the technical scheme and inventive concept of the present invention within the technical scope disclosed by the present invention, which should be covered by the protection scope 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 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.

2. The water-enhanced room temperature phosphorescent 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 MDI, and isophorone diisocyanate IPDI.

3. The water-enhanced room temperature phosphorescent emitting polymer according to claim 1, characterized in that: The amide monomer is one or more of azodicarbonamide ADA, oxalyl diamide ODM, malonamide MAA, succinamide BAD or adipic diamide ADM.

4. The water-enhanced room temperature phosphorescent emitting polymer according to claim 1, characterized in that: The silane coupling agent monomer is one or more of methacryloxypropyltrimethoxysilane MPS, 3-aminopropyltrimethoxysilane APTMS or 3-aminopropyltriethoxysilane APTES.

5. 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 under the conditions of self-catalysis or catalyst catalysis by placing isocyanate monomers, amide monomers and silane coupling agent monomers in a dry environment protected by an inert gas.

6. The method for synthesizing a polymer having water-enhanced room temperature phosphorescence emission according to claim 5, characterized in that: The catalyst is dibutyltin dilaurate, and the mass ratio of polyisocyanate to the catalyst is 100-5000:

1.

7. An application 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.

8. The use of the polymer for water-enhanced room temperature phosphorescence emission according to claim 7, characterized in that: The preparation method of the coating is: casting a water-enhanced room temperature phosphorescent emitting polymer on a base material, and after standing at room temperature, the silane chain segments are hydrolyzed, cross-linked and cured to form a film.

9. The use of the polymer for water-enhanced room temperature phosphorescence emission according to claim 8, characterized in that: The base material is stainless steel, metal material, general plastic or glass.

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

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