Ultra-long room-temperature phosphorescent polyurethane elastomer material as well as preparation method and application thereof
By integrating phosphorescent molecules into a polyurethane matrix with soft and hard segments, the developed elastomer addresses efficiency and stability issues, offering long-lasting phosphorescence and improved mechanical properties for flexible lighting and security applications.
Patent Information
- Application Number
- CN202510636935.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-05-18
- Publication Date
- 2025-07-15
AI Technical Summary
The prior art is difficult to prepare high-performance room temperature phosphorescent materials that are stretchable and tolerant of humid and heat environments, and the material is not flexible and stable, which limits its application in the fields of flexible light emitting devices and information encryption.
By covalently connecting the phosphorescent molecules to the polyurethane material, using the soft and hard segment microphase separation structure of the polyurethane material, an ultra-long room temperature phosphorescent polyurethane elastomer material with stretchable and adjustable afterglow colors is prepared, and the efficient preparation of the material is achieved by combining the organotin catalyst and specific reaction conditions.
The obtained materials have excellent mechanical properties and environmental stability, achieving the adjustability and long-life phosphorescence effect of the afterglow color, and are suitable for flexible light emitting devices and information encryption materials.
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Figure CN120309875A_ABST
Abstract
Description
Technical Field
[0001] The invention relates to a stretchable, afterglow color-tunable, ultra-long room-temperature phosphorescent polyurethane elastomer material resistant to wet and hot environments, its preparation method and application, belonging to the technical field of polymer materials. Background Art
[0002] Organic room-temperature phosphorescent materials have attracted much attention in advanced application fields such as anti-counterfeiting technology, organic light-emitting diodes, data encryption, bioimaging, and molecular sensing. However, there are still many difficulties in realizing high-performance organic room-temperature phosphorescent materials, which are attributed to the low intersystem crossing efficiency between the singlet and triplet excited states, and the easy non-radiative deactivation of triplet excitons under environmental conditions. Preparing polymer room-temperature phosphorescent materials is one of the feasible strategies to overcome these problems. Most polymer room-temperature phosphorescent materials are obtained by directly copolymerizing with phosphorescent monomers or introducing phosphorescent dopants into rigid polymer matrices such as polymethyl methacrylate and polyvinyl alcohol. The thermal motion of phosphorescent groups is restricted by covalent bonds, hydrogen bonds, rigid structures, etc., thereby inhibiting the non-radiative decay of the excited triplet state and achieving an efficient room-temperature phosphorescent effect. However, the resulting structural rigidity and smaller free volume not only inhibit the thermal motion of phosphorescent groups, but also severely limit the movement and arrangement of polymer chains, resulting in poor stretchability and flexibility; and most room-temperature phosphorescent polymers are sensitive to water and heat, resulting in limited use scenarios.
[0003] At present, there are still great challenges in preparing stretchable, ultra-long room-temperature phosphorescent materials resistant to wet and hot environments through simple and efficient preparation methods. Summary of the Invention
[0004] In view of this, the purpose of the present invention is to provide a stretchable, afterglow color-tunable, ultra-long room-temperature phosphorescent polyurethane elastomer material resistant to wet and hot environments and its preparation method to meet the application in flexible light-emitting devices, information encryption, or advanced anti-counterfeiting.
[0005] The implementation process of the present invention is as follows: A room-temperature phosphorescent polyurethane elastomer material, the structural formula of the polyurethane elastomer material is shown as follows:
[0006] Among them, A is selected from substituted or unsubstituted isophorone group, phenyl group, biphenyl group, diphenylmethane group, dicyclohexylmethane group, xylene group, naphthyl group, cyclohexyl group, C3-C6 alkyl group, and the substituents are C1-C4 alkyl group, C1-C4 alkoxy group, halogenomethyl group; B is a polyether polyol; P is a phosphorescent group; x is a positive integer from 0 to 60, y is a positive integer from 1 to 4, and z is a positive integer from 10 to 80.
[0007] Preferably, x is a positive integer from 1 to 50, y is a positive integer from 1 to 4, and z is a positive integer from 20 to 70.
[0008] More preferably, x is a positive integer from 5 to 40, y is a positive integer from 1 to 4, and z is a positive integer from 20 to 60.
[0009] The above polyether polyol is selected from at least one of polyethylene glycol 200 - 1000, polytetrahydrofuran 1000 - 2000, polycaprolactone 1000 - 2000, and polyetheramine 1000 - 2000.
[0010] The preparation method of the above room-temperature phosphorescent polyurethane elastomer material includes the following steps: (1) React a diisocyanate and a dried polyether polyol under the action of an organotin catalyst to obtain a prepolymer; The structural formula of the diisocyanate is OCN-A-NCO, where A is selected from a substituted or unsubstituted isophorone group, phenyl group, biphenyl group, diphenylmethane group, dicyclohexylmethane group, xylene group, naphthyl group, cyclohexyl group, and C3 - C6 alkyl group, and the substituents are C1 - C4 alkyl groups, C1 - C4 alkoxy groups, and halomethyl groups; (2) React the prepolymer with a phosphorescent molecule to obtain a copolymerized polymer of the phosphorescent molecule; (3) React the copolymerized polymer of the phosphorescent molecule with adipic dihydrazide to obtain a crude product of the room-temperature phosphorescent polyurethane elastomer material.
[0011] In the above step (1), the organotin catalyst used is selected from at least one of dibutyltin dilaurate, dimethyltin dineodecanoate, methyltin mercaptide, dibutyltin dilaurate, and dioctyltin dilaurate.
[0012] In the above step (1), the diisocyanate is preferably: .
[0013] In the above step (1), the molar ratio of the diisocyanate to the polyether polyol is 8:(1 - 4), and the reaction temperature is 30 - 100 °C.
[0014] In the above step (2), the structural formula of the phosphorescent molecule is .
[0015] In the above step (2), the molar ratio of the diisocyanate to the phosphorescent molecule is 60:(1 - 4), and the reaction temperature is 30 - 100 °C.
[0016] In the above step (3), the molar ratio of the diisocyanate to adipic dihydrazide is 2:(1 - 2), and the reaction temperature is 30 - 100 °C.
[0017] In step (3) above, methanol is added to the crude product of the room-temperature phosphorescent polyurethane elastomer material to remove the unreacted isocyanate, thereby obtaining the room-temperature phosphorescent polyurethane elastomer material.
[0018] Application of the stretchable, afterglow color-tunable, and humidity- and heat-resistant ultra-long room-temperature phosphorescent polyurethane elastomer material prepared by the present invention in the fields of flexible light-emitting devices, information encryption, or advanced anti-counterfeiting materials.
[0019] The inventors found that polyurethane materials are composed of thermodynamically incompatible soft segments and hard segments, with a unique microphase separation structure, providing an ideal platform for integrating multiple functions into a single polymer. Generally, the soft segments are composed of polyether or polyester polyols, having high molecular chain mobility, which is beneficial to improving the stretchability and flexibility of the polymer. The hard segments contain rigid and polar groups, such as urethane groups or urea groups, which can form hydrogen bonds within and between polymer chains, causing the polymer chains to fold and entangle, forming a dense polymer network structure and enhancing the structural rigidity of the polymer. This structure is not only beneficial to preventing the intrusion of water in the environment, but also beneficial to suppressing the thermal motion of phosphorescent groups, stabilizing triplet excitons, and thus obtaining ultra-long room-temperature phosphorescence. In addition, polyurethane has tunability, and room-temperature phosphorescent materials with specific properties can be customized by adjusting factors such as the synthesis conditions, monomer types, and ratios of polyurethane.
[0020] Compared with the prior art, in the present invention, a phosphorescent molecule is covalently linked to a polyurethane material to obtain a polyurethane material with room-temperature phosphorescence. By changing the structure of the phosphorescent molecule, color-tunable room-temperature phosphorescence is achieved, and the material also exhibits excellent mechanical properties and environmental stability, giving it broad application prospects in the fields of flexible light-emitting devices, information encryption, and advanced anti-counterfeiting materials; in addition, the preparation process of the material in the present invention is simple and easy to implement, and the obtained material has advantages such as uniform structure and high repeatability, and is worthy of being vigorously promoted and used. Description of the Drawings
[0021] Figure 1 Infrared spectrum of the room-temperature phosphorescent polyurethane elastomer material prepared in Example 1; Figure 2 Afterglow picture of the room-temperature phosphorescent polyurethane elastomer material prepared in Example 1 excited by a 365 nm ultraviolet lamp; Figure 3 Fluorescence spectrum and phosphorescence spectrum of the room-temperature phosphorescent polyurethane elastomer material prepared in Example 1; Figure 4 Phosphorescence decay curve and phosphorescence lifetime of the room-temperature phosphorescent polyurethane elastomer material prepared in Example 1; Figure 5The stress-strain curve of the room-temperature phosphorescent polyurethane elastomer material prepared in Example 1; Figure 6 The afterglow picture of the room-temperature phosphorescent polyurethane elastomer material prepared in Example 1 after being immersed in water and excited by a 365 nm ultraviolet lamp; Figure 7 The afterglow picture of the room-temperature phosphorescent polyurethane elastomer material prepared in Example 1 after being excited by a 365 nm ultraviolet lamp under heating conditions. Detailed implementation manners
[0022] In order to make the objectives, technical solutions and advantages of the present invention clearer and more understandable, the present invention will be further described in detail below in conjunction with specific embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not used to limit the present invention.
[0023] The raw materials or auxiliaries used in the embodiments of the present invention can all be obtained by purchase and self-preparation.
[0024] A preparation method of a stretchable, afterglow color-tunable, and humidity- and heat-resistant ultra-long room-temperature phosphorescent polyurethane elastomer material provided by an embodiment of the present invention specifically includes the following steps:
[0025] (1) React a diisocyanate and a dried polyether polyol under an organotin catalyst to obtain a prepolymer I; wherein the molar ratio of the diisocyanate to the polyether polyol is 8:(1-4), and the reaction temperature is 30-100 °C; The structural formula of the diisocyanate is OCN-A-NCO, and A is selected from a substituted or unsubstituted isophorone group, phenyl group, biphenyl group, diphenylmethane group, dicyclohexylmethane group, xylene group, naphthyl group, cyclohexyl group, C3-C6 alkyl group; .
[0026] (2) React the prepolymer I with a phosphorescent molecule to obtain a copolymerized phosphorescent molecule polymer II; wherein the molar ratio of the diisocyanate to the phosphorescent molecule is 60:(1-4), and the reaction temperature is 30-100 °C; .
[0027] (3) React the copolymerized phosphorescent molecule polymer II with adipic dihydrazide to obtain a crude material product; wherein the molar ratio of the diisocyanate to adipic dihydrazide is 2:(1-2), and the reaction temperature is 30-100 °C.
[0028] (4) Methanol was added to the crude product of the material to remove the unreacted diisocyanate in the reaction. Then the reaction solution was poured on a glass plate and dried to obtain an ultra-long room-temperature phosphorescent polyurethane elastomer material that is stretchable, has an adjustable afterglow color, and is resistant to wet and hot environments.
[0029] In the specific implementation process of the embodiment of the present invention: in the above step (1), the structural formula of the diisocyanate is:
[0030] In the specific implementation process of the embodiment of the present invention: in the above step (2), the structural formula of the phosphorescent molecule is:
[0031] The following are specific examples: Example 1
[0032] (1) Poly(tetramethylene ether) glycol 2000 was dried under reduced pressure at 100 °C for 3 hours to remove moisture. 200.0 mg of poly(tetramethylene ether) glycol 2000 (0.1 mmol), 106.8 mg of 4,4'-dicyclohexylmethane diisocyanate (0.407 mmol), 10.0 mg of dibutyltin dilaurate, and 3.0 mL of N,N-dimethylacetamide were added to a 10.0 mL round-bottom flask. Under the protection of nitrogen, the reaction was carried out at 75 °C for 3 hours; (2) 3.5 mg of the phosphorescent molecule oICZ-diol (0.007 mmol) was dissolved in 1 mL of N,N-dimethylacetamide and added to the flask to continue the reaction for 1 hour; (3) The reaction temperature was lowered to 40 °C, 52.3 mg of adipic dihydrazide (0.3 mmol) was dissolved in N,N-dimethylacetamide and added to the reaction solution. Under the protection of nitrogen, the reaction was carried out at 40 °C for 15 hours.
[0033] (4) After the reaction was complete, 1.0 mL of anhydrous methanol was added and stirred for 0.5 hours to remove the unreacted diisocyanate in the reaction. Then the reaction solution was poured on a glass plate and placed in a vacuum drying oven for 12 hours to obtain a polyurethane material with a number-average molecular weight of 12607 g / mol and a weight-average molecular weight of 28426 g / mol.
[0034] Figure 1 The infrared spectrum of the room-temperature phosphorescent polyurethane elastomer material obtained for Example 1; by analysis Figure 1 It can be seen that the characteristic vibration peaks of -NCO and -OH disappeared at 2245 cm -1 and 3462 cm -1 respectively; the characteristic vibration peaks of -N-H and -C=O attributed to the amide part after the conversion of isocyanate appeared at 3294 cm-1 and 1644 cm -1 。This phenomenon clearly indicates that all the raw materials participating in the reaction have achieved complete conversion.
[0035] Figure 2 Figure showing the afterglow of the room-temperature phosphorescent polyurethane elastomer material prepared in Example 1 after excitation by 365 nm ultraviolet light; by analyzing Figure 2 it can be seen that: the room-temperature phosphorescent polyurethane elastomer material obtained in Example 1 can emit a blue afterglow lasting up to 17 seconds after excitation by a 365 nm ultraviolet lamp.
[0036] Figure 3 Fluorescence spectrum and phosphorescence spectrum of the room-temperature phosphorescent polyurethane elastomer material prepared in Example 1; by analyzing Figure 3 it can be seen that: the fluorescence emission peak of the room-temperature phosphorescent polyurethane elastomer material obtained in Example 1 is located at 395 nm, and the phosphorescence emission peaks are located at 446 nm and 477 nm.
[0037] Figure 4 Phosphorescence decay curve of the room-temperature phosphorescent polyurethane elastomer material prepared in Example 1; by analyzing Figure 4 it can be seen that: the phosphorescence lifetime of the room-temperature phosphorescent polyurethane elastomer material obtained in Example 1 is 1846 ms.
[0038] Figure 5 Stress-strain curve of the room-temperature phosphorescent polyurethane elastomer material prepared in Example 1; by analyzing Figure 5 it can be seen that: the fracture stress of the room-temperature phosphorescent polyurethane elastomer material obtained in Example 1 is 22.4 MPa, and the elongation at break is 789%.
[0039] Figure 6 Figure showing the afterglow of the room-temperature phosphorescent polyurethane elastomer material prepared in Example 1 after being immersed in water and excited by a 365 nm ultraviolet lamp; by analyzing Figure 6 it can be seen that: when the room-temperature phosphorescent polyurethane elastomer material obtained in Example 1 is immersed in water for 48 hours, the duration of the afterglow remains basically unchanged; Figure 7 Figure showing the afterglow of the room-temperature phosphorescent polyurethane elastomer material prepared in Example 1 under heating conditions after excitation by a 365 nm ultraviolet lamp; by analyzing Figure 7 it can be seen that: after the room-temperature phosphorescent polyurethane elastomer material obtained in Example 1 is heated to 100 °C, it can still emit a blue afterglow lasting for 1 second. Example 2
[0040] This example provides a room-temperature phosphorescent polyurethane elastomer material, which is only different from Example 1 in that the molar ratio of polytetrahydrofuran 2000 to adipic dihydrazide is 4:4. The types, dosages, and preparation methods of the remaining components are the same as those in Example 1. The number-average molecular weight is 14258 g / mol, and the weight-average molecular weight is 35811 g / mol. Example 3
[0041] This example provides a room-temperature phosphorescent polyurethane elastomer material, which is only different from Example 1 in that the molar ratio of polytetrahydrofuran 2000 to adipic dihydrazide is 3:5. The types, dosages, and preparation methods of the remaining components are the same as those in Example 1. The number-average molecular weight is 13369 g / mol, and the weight-average molecular weight is 32838 g / mol. Example 4
[0042] This example provides a room-temperature phosphorescent polyurethane elastomer material, which is only different from Example 1 in that the molar ratio of polytetrahydrofuran 2000 to adipic dihydrazide is 1:7. The types, dosages, and preparation methods of the remaining components are the same as those in Example 1. The number-average molecular weight is 16598 g / mol, and the weight-average molecular weight is 36501 g / mol. Example 5
[0043] This example provides a room-temperature phosphorescent polyurethane elastomer material, which is only different from Example 1 in that the molar ratio of polytetrahydrofuran 2000 to adipic dihydrazide is 0:8. The types, dosages, and preparation methods of the remaining components are the same as those in Example 1. The number-average molecular weight is 10137 g / mol, and the weight-average molecular weight is 13594 g / mol. Example 6
[0044] This example provides a room-temperature phosphorescent polyurethane elastomer material, which is only different from Example 1 in that polytetrahydrofuran 2000 is replaced with polycaprolactone 2000. The types, dosages, and preparation methods of the remaining components are the same as those in Example 1. The number-average molecular weight is 13649 g / mol, and the weight-average molecular weight is 29127 g / mol. Example 7
[0045] This example provides a room-temperature phosphorescent polyurethane elastomer material, which is only different from Example 1 in that polytetrahydrofuran 2000 is replaced with polyetheramine 2000. The types, dosages, and preparation methods of the remaining components are the same as those in Example 1. The number-average molecular weight is 15285 g / mol, and the weight-average molecular weight is 31934 g / mol. Example 8
[0046] This example provides a room-temperature phosphorescent polyurethane elastomer material, which is different from Example 1 only in that 4,4'-dicyclohexylmethane diisocyanate is replaced with an equal amount of isophorone diisocyanate, and the types, dosages, and preparation methods of the other components are the same as those in Example 1. The number-average molecular weight is 12825 g / mol, and the weight-average molecular weight is 26741 g / mol. Example 9
[0047] This example provides a room-temperature phosphorescent polyurethane elastomer material, which is different from Example 1 only in that oICZ-diol is replaced with mICZ-diol, and the types, dosages, and preparation methods of the other components are the same as those in Example 1. The number-average molecular weight is 28360 g / mol, and the weight-average molecular weight is 38585 g / mol. The phosphorescent color of the material is cyan. Example 10
[0048] This example provides a room-temperature phosphorescent polyurethane elastomer material, which is different from Example 1 only in that oICZ-diol is replaced with NpICZ-diol, and the types, dosages, and preparation methods of the other components are the same as those in Example 1. The number-average molecular weight is 19596 g / mol, and the weight-average molecular weight is 27037 g / mol. The phosphorescent color of the material is light green. The performance test data of Examples 1-10 are shown in Table 1.
[0049] Table 1 Comparison of the phosphorescent and mechanical properties of the materials in the examples Phosphorescence lifetime (ms) Mechanical strength (MPa) Tensile strain (%) Example 1 1846 22.4 789 Example 2 1568 12.8 1400 Example 3 1628 18.0 1305 Example 4 1888 26.1 200 Example 5 1185 16.8 14 Example 6 1989 15.4 480 Example 7 2051 13.6 650 Example 8 1127 8.1 1323 Example 9 1719 23.5 868 Example 10 764 24.6 845 In summary, by covalently connecting phosphorescent molecules to the polyurethane material, the present invention significantly endows the obtained materials with phosphorescent properties, realizes color-tunable room-temperature phosphorescence by changing the structure of the phosphorescent molecules, and also exhibits excellent mechanical properties and environmental stability, making it have broad application prospects in the fields of flexible light-emitting devices, information encryption, and advanced anti-counterfeiting materials.
[0050] The above are only the preferred specific embodiments of the present invention, but the protection scope of the present invention is not limited thereto. Any changes or substitutions that can be easily thought of by those skilled in the art within the technical scope disclosed by the present invention should be covered by the protection scope of the present invention. Therefore, the protection scope of the present invention should be subject to the protection scope of the claims.
Claims
1. A room-temperature phosphorescent polyurethane elastomer material, characterized in that: The structural formula of the polyurethane elastomer material is as follows: ， Among them, A is selected from a substituted or unsubstituted isophorone group, phenyl group, biphenyl group, diphenylmethane group, dicyclohexylmethane group, xylene group, naphthyl group, cyclohexyl group, C3-C6 alkyl group, and the substituent is C1-C4 alkyl group, C1-C4 alkoxy group, halogenomethyl group; B is a polyether polyol; P is a phosphorescent group; x is a positive integer from 0 to 60, y is a positive integer from 1 to 4, and z is a positive integer from 10 to 80.
2. The room-temperature phosphorescent polyurethane elastomer material according to claim 1, wherein: The polyether polyol is selected from at least one of polyethylene glycol 200-1000, polytetrahydrofuran 1000-2000, polycaprolactone 1000-2000, and polyetheramine 1000-2000.
3. The preparation method of the room temperature phosphorescent polyurethane elastomer material according to claim 1, characterized in that The method includes the following steps: (1) React a diisocyanate and a dried polyether polyol under the action of an organotin catalyst to obtain a prepolymer; The structural formula of the diisocyanate is OCN-A-NCO, and A is selected from a substituted or unsubstituted isophorone group, phenyl group, biphenyl group, diphenylmethane group, dicyclohexylmethane group, xylene group, naphthyl group, cyclohexyl group, C3-C6 alkyl group, and the substituent is C1-C4 alkyl group, C1-C4 alkoxy group, halogenomethyl group; (2) React the prepolymer with a phosphorescent molecule to obtain a polymer copolymerized with a phosphorescent molecule; (3) React the polymer copolymerized with a phosphorescent molecule with adipic dihydrazide to obtain a crude product of a room temperature phosphorescent polyurethane elastomer material.
4. The preparation method of the room temperature phosphorescent polyurethane elastomer material according to claim 3, characterized in that: In the above step (1), the organotin catalyst is selected from at least one of dibutyltin di-neodecanoate, dimethyltin di-neodecanoate, methyltin mercaptide, dibutyltin dilaurate, and dioctyltin dilaurate.
5. The preparation method of the room temperature phosphorescent polyurethane elastomer material according to claim 3, wherein: In the above step (1), the molar ratio of the diisocyanate to the polyether polyol is 8:(1-4), and the reaction temperature is 30-100 °C.
6. The preparation method of the room-temperature phosphorescent polyurethane elastomer material according to claim 3, characterized in that: In the above step (2), the molar ratio of the diisocyanate to the phosphorescent molecule is 60:(1-4), and the reaction temperature is 30-100 °C.
7. The preparation method of the room-temperature phosphorescent polyurethane elastomer material according to claim 3, wherein: In the above step (3), the molar ratio of the diisocyanate to adipic dihydrazide is 2:(1-2), and the reaction temperature is 30-100 °C.
8. The preparation method of the room-temperature phosphorescent polyurethane elastomer material according to claim 3, wherein: In the above step (1), the diisocyanate is selected from 。 9. The room-temperature phosphorescent polyurethane elastomer material according to claim 3, wherein: In the above step (2), the structural formula of the phosphorescent molecule is:
10. Application of the room temperature phosphorescent polyurethane elastomer material described in claim 1 in flexible light-emitting devices, information encryption, or advanced anti-counterfeiting materials.