Solid red-to-yellow upconversion copolymer system, and preparation method and application thereof

Abstract

The invention discloses a solid red-to-yellow upconversion copolymer system, and a preparation method and application thereof. Alpha-hydroxyethyl methylacrylate (HEMA) and 3-(methacryloxypropyl)trimethoxy silane (TMSPMA) are taken as monomers. Under the trigger of azoisobutyronitrile, a sensitizer (sandwiched palladium phthalocyanine) and a luminescence agent (rhodamine-series compound) in a certain proportion are uniformly coated through in-situ polymerization to obtain a solid red-to-yellow upconversion silicon copolymer. The problem of deoxygenization needed for a solution state is solved, and more importantly, the bottleneck problem of low upconversion efficiency of a solid polymer at present is solved. Under the excitation of a 655nm semiconductor laser (laser power density 1W*cm-2), the upconversion efficiency (FUC) of the obtained solid copolymer is up to 12.75 percent; moreover, in an air atmosphere, the solid upconversion efficiency value can be maintained to be almost non-attenuated within over four days, and the solid red-to-yellow upconversion copolymer system has an application value in the field of solar energy utilization.

Description

[0001] The invention belongs to the field of triplet annihilation upconversion, and specifically relates to a solid red-transition-yellow upconversion copolymer system and its preparation method and application. Background technique

[0002] Materials based on triplet-triplet annihilation upconversion (TTA-UC) usually consist of a sensitizer and a luminescent agent dissolved in an organic solvent to form a two-component system. The mechanism is: (1) irradiation of low-energy excitation light, the sensitizer The energy absorbed by the excitation light is converted from its ground state (S 0 ) to the singlet excited state ( 1 S*), and then transition to the triplet excited state ( 3 S*); (2) The sensitizer transfers the energy of its triplet excited state ( 3 S*) transferred to the luminescent agent ( 3 A*); (3) When the concentration of acceptor molecules in the triplet excited state reaches a certain level, two are in the triplet state ( 3 A*) The luminescent agent molecul...

Examples

Embodiment 1

[0054] (1) Two-component upconversion solution (PdPc 2 / luminescent agent) configuration: the sensitizer (PdPc 2 ) Mother liquor (concentration is 4×10 -5 mol / L) and luminescent agent mother solution (concentration is 1×10 -2 mol / L) are mixed according to a certain molar ratio and degassed to obtain a two-component solution of sensitizer / luminescent agent. The solvents involved in all the above solutions are spectrally pure n-propanol / ethylene glycol (v / v, 1 / 2).

[0055] The luminescent agent can be any one of the following rhodamine derivatives:

[0056]

[0057] (2) Preparation of solid-state up-conversion copolymer system: In a nitrogen atmosphere, 2-hydroxyethylene methyl acrylate (HEMA) and 3-(methacryloyloxy)propyltrimethoxysilane (TMSPMA) Mix according to 1:1 (mass ratio), add 0.5% (mass ratio) of azobisisobutyronitrile as an initiator, and then add a two-component solution (the molar ratio of sensitizer and luminescent agent is 1:3000), Vacuumize (30 min) afte...

Embodiment 2

[0078] According to the preparation method of Example 1, wherein HEMA and TMSPMA are mixed at 1:2 (mass ratio), 0.5% (mass ratio) of azobisisobutyronitrile is added as an initiator, and then a two-component solution (sensitizer The molar ratio of the luminescent agent and the luminescent agent is 1:3000) to prepare a solid-state up-conversion copolymer system. When the luminescent agent is RhB, RhBS, and Rh6G, the up-conversion efficiencies are 9.6%, 12.3%, and 2.9%, respectively. Correspondingly, under other conditions being the same, the upconversion efficiencies of the luminescent agents RhB, RhBS and Rh6G in the solution state are: 6.8%, 8.7% and 2.2%, respectively. Comparing Example 1 with Example 2, it can be seen that the ratio of the two polymer monomers has little influence on the up-conversion efficiency of the solid-state up-conversion system; meanwhile, under the same conditions, the up-conversion efficiency of the solid-state up-conversion system is greater than U...

Embodiment 3

[0080] According to the preparation method of Example 1, the solvents involved in the sensitizer and luminescent agent solutions are both spectroscopically pure propanol / ethylene glycol (v / v, 1 / 6); HEMA and TMSPMA are 1:4 (mass ratio ) mixed, adding 0.5% (mass ratio) of azobisisobutyronitrile as an initiator, and then adding a two-component solution (the molar ratio of sensitizer and luminescent agent is 1:3000) to prepare a solid-state up-conversion copolymer system , when the luminescent agent is RhB, RhBS, and Rh6G, the up-conversion efficiency is 9.4%, 11.8%, and 2.6%, respectively. Correspondingly, under other conditions being the same, the upconversion efficiencies of the luminescent agents RhB, RhBS, and Rh6G in the solution state were: 6.4%, 8.3%, and 1.9%, respectively. Comparing Example 1 with Example 3, it can be seen that as the ratio of solvent n-propanol / ethylene glycol changes, the up-conversion efficiency of the solution state also decreases; meanwhile, under t...

[0001] The invention belongs to the field of triplet annihilation upconversion, and specifically relates to a solid red-transition-yellow upconversion copolymer system and its preparation method and application. Background technique

[0002] Materials based on triplet-triplet annihilation upconversion (TTA-UC) usually consist of a sensitizer and a luminescent agent dissolved in an organic solvent to form a two-component system. The mechanism is: (1) irradiation of low-energy excitation light, the sensitizer The energy absorbed by the excitation light is converted from its ground state (S 0 ) to the singlet excited state ( 1 S*), and then transition to the triplet excited state ( 3 S*); (2) The sensitizer transfers the energy of its triplet excited state ( 3 S*) transferred to the luminescent agent ( 3 A*); (3) When the concentration of acceptor molecules in the triplet excited state reaches a certain level, two are in the triplet state ( 3 A*) The luminescent agent molecul...

Examples

Embodiment 1

[0054] (1) Two-component upconversion solution (PdPc 2 / luminescent agent) configuration: the sensitizer (PdPc 2 ) Mother liquor (concentration is 4×10 -5 mol / L) and luminescent agent mother solution (concentration is 1×10 -2 mol / L) are mixed according to a certain molar ratio and degassed to obtain a two-component solution of sensitizer / luminescent agent. The solvents involved in all the above solutions are spectrally pure n-propanol / ethylene glycol (v / v, 1 / 2).

[0055] The luminescent agent can be any one of the following rhodamine derivatives:

[0056]

[0057] (2) Preparation of solid-state up-conversion copolymer system: In a nitrogen atmosphere, 2-hydroxyethylene methyl acrylate (HEMA) and 3-(methacryloyloxy)propyltrimethoxysilane (TMSPMA) Mix according to 1:1 (mass ratio), add 0.5% (mass ratio) of azobisisobutyronitrile as an initiator, and then add a two-component solution (the molar ratio of sensitizer and luminescent agent is 1:3000), Vacuumize (30 min) afte...

Embodiment 2

[0078] According to the preparation method of Example 1, wherein HEMA and TMSPMA are mixed at 1:2 (mass ratio), 0.5% (mass ratio) of azobisisobutyronitrile is added as an initiator, and then a two-component solution (sensitizer The molar ratio of the luminescent agent and the luminescent agent is 1:3000) to prepare a solid-state up-conversion copolymer system. When the luminescent agent is RhB, RhBS, and Rh6G, the up-conversion efficiencies are 9.6%, 12.3%, and 2.9%, respectively. Correspondingly, under other conditions being the same, the upconversion efficiencies of the luminescent agents RhB, RhBS and Rh6G in the solution state are: 6.8%, 8.7% and 2.2%, respectively. Comparing Example 1 with Example 2, it can be seen that the ratio of the two polymer monomers has little influence on the up-conversion efficiency of the solid-state up-conversion system; meanwhile, under the same conditions, the up-conversion efficiency of the solid-state up-conversion system is greater than U...

Embodiment 3

[0080] According to the preparation method of Example 1, the solvents involved in the sensitizer and luminescent agent solutions are both spectroscopically pure propanol / ethylene glycol (v / v, 1 / 6); HEMA and TMSPMA are 1:4 (mass ratio ) mixed, adding 0.5% (mass ratio) of azobisisobutyronitrile as an initiator, and then adding a two-component solution (the molar ratio of sensitizer and luminescent agent is 1:3000) to prepare a solid-state up-conversion copolymer system , when the luminescent agent is RhB, RhBS, and Rh6G, the up-conversion efficiency is 9.4%, 11.8%, and 2.6%, respectively. Correspondingly, under other conditions being the same, the upconversion efficiencies of the luminescent agents RhB, RhBS, and Rh6G in the solution state were: 6.4%, 8.3%, and 1.9%, respectively. Comparing Example 1 with Example 3, it can be seen that as the ratio of solvent n-propanol / ethylene glycol changes, the up-conversion efficiency of the solution state also decreases; meanwhile, under t...

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