CN106866874B - Solid red-to-yellow conversion copolymer system and preparation method and application thereof - Google Patents
Solid red-to-yellow conversion copolymer system and preparation method and application thereof Download PDFInfo
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- 229920001577 copolymer Polymers 0.000 title claims abstract description 41
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000007787 solid Substances 0.000 title abstract description 25
- -1 rhodamine series compound Chemical class 0.000 claims abstract description 29
- 239000000178 monomer Substances 0.000 claims abstract description 21
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 7
- 238000011065 in-situ storage Methods 0.000 claims abstract description 6
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 3
- 239000010703 silicon Substances 0.000 claims abstract description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 60
- 239000000470 constituent Substances 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 8
- 150000002148 esters Chemical class 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 4
- 150000005846 sugar alcohols Polymers 0.000 claims description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N alpha-methacrylic acid Natural products CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 3
- 239000012046 mixed solvent Substances 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000001259 photo etching Methods 0.000 claims 1
- 229920001296 polysiloxane Polymers 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 21
- 102100026735 Coagulation factor VIII Human genes 0.000 abstract description 7
- 101000911390 Homo sapiens Coagulation factor VIII Proteins 0.000 abstract description 7
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 abstract description 7
- 238000006392 deoxygenation reaction Methods 0.000 abstract description 4
- 239000012298 atmosphere Substances 0.000 abstract description 2
- 230000000977 initiatory effect Effects 0.000 abstract description 2
- MCTALTNNXRUUBZ-UHFFFAOYSA-N molport-000-691-724 Chemical compound [Pd+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 MCTALTNNXRUUBZ-UHFFFAOYSA-N 0.000 abstract description 2
- 239000004065 semiconductor Substances 0.000 abstract description 2
- IISHLYLZTYTIJJ-UHFFFAOYSA-N 1-hydroxyethyl 2-methylprop-2-enoate Chemical compound CC(O)OC(=O)C(C)=C IISHLYLZTYTIJJ-UHFFFAOYSA-N 0.000 abstract 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 abstract 1
- 230000002238 attenuated effect Effects 0.000 abstract 1
- 239000000891 luminescent agent Substances 0.000 abstract 1
- 238000012546 transfer Methods 0.000 description 63
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 29
- 229940043267 rhodamine b Drugs 0.000 description 26
- 230000005284 excitation Effects 0.000 description 16
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 15
- 239000011347 resin Substances 0.000 description 11
- 229920005989 resin Polymers 0.000 description 11
- VYXSBFYARXAAKO-UHFFFAOYSA-N ethyl 2-[3-(ethylamino)-6-ethylimino-2,7-dimethylxanthen-9-yl]benzoate;hydron;chloride Chemical compound [Cl-].C1=2C=C(C)C(NCC)=CC=2OC2=CC(=[NH+]CC)C(C)=CC2=C1C1=CC=CC=C1C(=O)OCC VYXSBFYARXAAKO-UHFFFAOYSA-N 0.000 description 10
- 238000002156 mixing Methods 0.000 description 7
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 239000003999 initiator Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 206010070834 Sensitisation Diseases 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000012452 mother liquor Substances 0.000 description 3
- 238000010672 photosynthesis Methods 0.000 description 3
- 230000029553 photosynthesis Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000013558 reference substance Substances 0.000 description 3
- 230000008313 sensitization Effects 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005281 excited state Effects 0.000 description 2
- 230000003760 hair shine Effects 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 230000000717 retained effect Effects 0.000 description 2
- HMFOYSVOOQLCHV-UHFFFAOYSA-N 2-(2-methylphenyl)ethenol Chemical compound CC1=CC=CC=C1C=CO HMFOYSVOOQLCHV-UHFFFAOYSA-N 0.000 description 1
- NQTADLQHYWFPDB-UHFFFAOYSA-N N-Hydroxysuccinimide Chemical compound ON1C(=O)CCC1=O NQTADLQHYWFPDB-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 230000005283 ground state Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 235000003642 hunger Nutrition 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- YYMBJDOZVAITBP-UHFFFAOYSA-N rubrene Chemical compound C1=CC=CC=C1C(C1=C(C=2C=CC=CC=2)C2=CC=CC=C2C(C=2C=CC=CC=2)=C11)=C(C=CC=C2)C2=C1C1=CC=CC=C1 YYMBJDOZVAITBP-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000037351 starvation Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/054—Optical elements directly associated or integrated with the PV cell, e.g. light-reflecting means or light-concentrating means
- H01L31/055—Optical elements directly associated or integrated with the PV cell, e.g. light-reflecting means or light-concentrating means where light is absorbed and re-emitted at a different wavelength by the optical element directly associated or integrated with the PV cell, e.g. by using luminescent material, fluorescent concentrators or up-conversion arrangements
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
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- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
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- C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
- C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
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- C08K5/00—Use of organic ingredients
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- C08K5/17—Amines; Quaternary ammonium compounds
- C08K5/19—Quaternary ammonium compounds
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- C08F220/281—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing only one oxygen, e.g. furfuryl (meth)acrylate or 2-methoxyethyl (meth)acrylate
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Abstract
The invention discloses a solid red-to-yellow up-conversion copolymer system and a preparation method and application thereof, wherein α -hydroxyethyl methacrylate (HEMA) and 3- (methacryloyloxy) propyl trimethoxy silane (TMSPMA) are used as monomers, and a sensitizer (sandwich type palladium phthalocyanine) and a luminescent agent (rhodamine series compound) with a certain ratio are uniformly coated by in-situ polymerization under the initiation of azoisobutyronitrile to obtain the solid red-to-yellow up-conversion copolymer systemSolid red-to-yellow upconverting silicon copolymers; not only solves the problem that deoxygenation is needed in a solution state, but also more importantly solves the bottleneck problem that the conversion efficiency on the existing solid polymer is low. Excited by a 655nm semiconductor laser (laser power density 1W cm)‑2) Up-conversion efficiency (F) of the solid copolymer obtained by the present inventionUC) Up to 12.75%; and in the air atmosphere, the conversion efficiency value on the solid can be kept more than 4 days to be almost not attenuated; has application value in the field of solar energy utilization.
Description
The invention belongs to triplet states to bury in oblivion upper conversion art, and in particular to a kind of solid-state is red-turn-Huang on conversion be copolymerized object
System and the preparation method and application thereof.
Background technique
It is usually dissolved in by sensitizer with luminous agent based on conversion (TTA-UC) material in triplet state-triplet state annihilation organic
Solvent constitutes bicomponent system, mechanism are as follows: (1) irradiation of low energy exciting light, sensitizer absorb the energy of exciting light by
Its ground state (S0) transit to singlet excitation state (1S*), swashing for triplet state is transitted to by intersystem crossing process (ISC) later
Hair state (3S*)；(2) sensitizer passes through triplet state-triplet state energy transfer (TTT) mechanism, by the energy of its triplet excited states
(3S*) be transferred to luminous agent (3A*)；(3) when the acceptor molecule concentration of Triplet Excited State reaches a certain level, two are in three
Line state (3A* luminous agent molecule), which mutually collides, occurs triplet state-triplet state annihilation (triplet-triplet
Annihilation, TTA), obtained on certain probability one in singlet luminous agent molecule (1) and a base A*
Luminous agent molecule (the A of state0)；At this point, the luminous agent molecule of singlet issues the upper conversion light of short wavelength due to attenuation.
Currently, the TTA-UC material of solution state can get higher upper conversion quantum efficiency under exciting light irradiation, it is such as green
The upper transfer efficiency of light-turn-blue light reaches as high as (36 %), the upper transfer efficiency of feux rouges-turn-yellow light reaches as high as 6-7%；It is aobvious
Show photovoltaic, photocatalysis and in terms of potential application value.However, since the oxygen in air can quench sensitization
The triplet of agent and luminous agent will be obtained on TTA- and be converted, and must be carried out in anaerobic state, this makes conversion in reality
It is severely limited in.The research for thereby promoting solid-state up-conversion technology of preparing becomes hot subject.2008
Year, Tanya N. Singh-Rachford and Felix N. Castellano was reported sensitizer PdPc (OBu)8With receptor
Rubrene is supported on thin slice, and the feux rouges-of preparation turns-yellow light solid-state up-conversion, though it can oxygen effectively in shroud air
Quenching to triplet state, however transfer efficiency is very low on the solid polymer obtained.(referring to: (1) G. Chen, J. Seo, C.
Yang, P. N. Prasad,Chem. Soc. Rev.,2013,42:8304-8338；(2) Bao Wang, Bin Sun,
Xiaomei Wang et al,J. Phys. Chem. C,2014, 118, 1417-1425; (3)Tanya N. Singh-
Rachford, Felix N. Castellano, Coordination Chemistry Reviews., 2010, 254,
2560-2573；(4) Yuen Yap Cheng, Burkhard Fuckel, Tony Khoury, Raphael G. C. R.
Clady, Murad J. Y. Tayebjee, N. J. Ekins-Daukes, Maxwell J. Crossley, and
Timothy W. Schmidt,J. Phys. Chem. L,2010, 1, 1795-1799;(5) Tanya N. Singh-
Rachford, Felix N. Castellano, J. Phys. Chem. C,2008,112,3550-3556).
As it can be seen that though the solid-state up-conversion of existing preparation can solve the problems, such as solution state starvation, solid-state material
Upper transfer efficiency greatly reduces compared with solution state, this makes being restricted in for solid-state up-conversion.
Summary of the invention
The invention discloses a kind of solid-state it is red-turn-Huang on convert copolymer systems, solve solution state and need asking for deoxygenation
Topic, while solving the bottleneck problem that transfer efficiency is low on current solid polymer；Exposure transfer efficiency thereon in air
(12.75%) it is almost unattenuated to be positively retained at 4 days or more efficiency, there is application value in field of solar energy utilization.
The present invention adopts the following technical scheme that, a kind of solid-state is red-turn-Huang on convert copolymer systems, coated for copolymer
Sensitizer and luminous agent system；The copolymer contains hydroxyl and silicon.
In above-mentioned technical proposal, the chemical structural formula of the copolymer are as follows:
Wherein, n is 2500~3000；
Sensitizer (the PdPc2) chemical structural formula are as follows:
The chemical structural formula of the luminous agent is the one kind of (RhB, RhBS, Rh6G) in following chemical structural formula:
The invention also discloses above-mentioned solid-state it is red-turn-Huang on conversion copolymer systems preparation method, including following step
Suddenly, under nitrogen atmosphere, by silyl acrylate ester monomer and hydroxy acryl acid ester monomer, azo-compound and sensitizer/shine
Agent two-constituent solution mixing, then vacuumize, then carry out home position polymerization reaction, obtain solid-state it is red-turn-Huang on convert copolymer
System.Specially under nitrogen atmosphere, by silyl acrylate ester monomer and hydroxy acryl acid ester monomer, azo-compound and sensitization
Agent/luminous agent two-constituent solution mixing, then vacuumizes, home position polymerization reaction 4 h~8 h is then carried out at 60 DEG C~90 DEG C
, preferably 78 DEG C 5 h of reaction, obtain solid-state it is red-turn-Huang on convert copolymer systems.
In above-mentioned technical proposal, the mass ratio of silyl acrylate ester monomer and hydroxy acryl acid ester monomer is (1~10):
1；The molar ratio of sensitizer and luminous agent is 1: (300~3000).
In above-mentioned technical proposal, the silyl acrylate ester monomer is 3- (methacryloxypropyl) propyl trimethoxy silicon
Alkane；The hydroxy acryl acid ester monomer is α-methacrylic acid hydroxyl ethyl ester；
Sensitizer (the PdPc2) chemical structural formula are as follows:
The chemical structural formula of the luminous agent is the one kind of (RhB, RhBS, Rh6G) in following chemical structural formula:
In above-mentioned technical proposal, in sensitizer/luminous agent two-constituent solution, solvent is polyalcohol mixed solvent, preferably
Volume ratio is 1: the normal propyl alcohol of (1~10)/ethylene glycol mixed solvent.
The present invention is with α-methacrylic acid hydroxyl ethyl ester (HEMA) and 3- (methacryloxypropyl) propyl trimethoxy silicane
(TMSPMA) it is monomer, under azo isobutyronitrile initiation, the sensitizer (sandwich centainly matched is uniformly coated by in-situ polymerization
Type palladium phthalocyanine) with luminous agent (rhodamine series compound), obtain a kind of solid-state it is red-turn-Huang on convert siliceous copolymer.It solves
Converting system (Triplet Sensitizers and luminous agent) is easy the problem of being quenched by oxygen in existing solution state；Importantly, this
The solid-state up-conversion of invention obtains efficiently upper the transfer efficiency, (excitation light wave a length of 655 under semiconductor laser irradiation
Nm, power density 1W/cm2), the upper transfer efficiency of acquisition is up to 12.75%.And under identical shooting condition, it is corresponding on
The upper transfer efficiency for converting solution significantly reduces (8.84%)；Meanwhile upper in the lower air atmosphere of polymer exposure turn is converted in the solid-state
Changing efficiency can keep 4 days, and under the same conditions, converting system can only be kept 2~3 hours in solution state.Therefore the present invention is gone back
Disclose above-mentioned solid-state it is red-turn-Huang on convert copolymer systems preparing the application in dim light up-conversion.
Polymeric system is converted in the solid-state that the present invention obtains not only had solved that transfer efficiency is low in current solid-state but also solves
Solution state needs oxygen-impermeable using bottleneck problem at present, has potential application valence in photovoltaic solar cell and photosynthesis field
Value.Therefore invention additionally discloses above-mentioned solid-state it is red-turn-Huang on convert copolymer systems in photovoltaic solar cell or photosynthesis
Application in field.
The synthetic route of above-mentioned copolymer structure is as follows:
The luminous agent is rhodamine derivative, and structure is as follows:
Wherein, luminous agent Rhodamine Derivatives RhBS synthesis can be exemplified below:
By the dicyclohexylcarbodiimide of the rhodamine B (RhB) of 0.479g (1mmol) and 0.206g (1mmol)
(DCC) it is dissolved in the methylene chloride of 20mL.Then the N- hydroxysuccinimide of 0.115g (1mmol) is added, stirs at room temperature
Mix reaction for 24 hours.After filtering, column chromatography separation obtains pure purple product.It is derivative that X-5 micro-meldometer measures rhodamine B
142.5 DEG C of the fusing point of object.
Solid-state triplet state of the present invention is buried in oblivion in upper conversion two-component system, and three lines between sensitizer and luminous agent molecule are passed through
The light of long wavelength, is converted to the light of short wavelength by state transfer, this process is known as frequency upooaversion, and (also known as triplet state buries in oblivion upper turn
Change), this process, which need to only lead to 655nm excitation, can realize and be converted into high-frequency yellow light by low frequency feux rouges.
Due to the above technical solutions, the present invention has the following advantages over the prior art:
1. copolymer disclosed by the invention is from siliceous and hydroxyl two kinds of acrylate monomers, the effect of the former monomer
Polymer material excellent light penetrability and thermal stability, the latter's monomer are assigned since hydroxyl effect is conducive to Triplet Sensitizers
Efficiently upper transfer efficiency occurs with luminous agent, thus coat obtain after sensitizer and luminous agent it is efficient it is red-turn-yellow dim light on
Polymer is converted, there is application value in field of solar energy utilization.
2. upper conversion copolymer systems disclosed by the invention are due to being coated upper conversion two-component system using in-situ polymerization
In the polymer, have the function of oxygen in excellent isolation air, efficiently solve converting system in solution state and need to completely cut off
The problem of oxygen, can realize up-conversion luminescence in air, and can stablize 4 days or more, will greatly facilitate its practical application.
3. converting copolymer systems on solid-state dim light disclosed by the invention in excitation light intensity in 1W/cm2Under, upper transfer efficiency
It has been more than transfer efficiency in liquid (8.84%) up to 12.75%, has solved transfer efficiency in current solid-state and be lower than corresponding solution state
Upper transfer efficiency；With great practical value.
4. it is cheap and easy to get to convert copolymer systems raw material on solid-state dim light disclosed by the invention, nontoxic and high transparency, no dirt
Contaminate object discharge, solve the prior art due in liquid converting system use it is very inconvenient, and solvent often toxic and volatile
It is inflammable and explosive, the problem of endangering human health or safety；Meet requirement and the direction of contemporary green chemistry, it is prior
It is that the preparation process for converting resin in the present invention is simple, is suitable for industrial production.
5. the present invention is using siliceous and hydroxyl two kinds of acrylate monomers, quick by in-situ copolymerization cladding triplet state
The polyhydric alcohol solutions of agent and luminous agent, obtain it is a kind of it is efficient it is red-turn-yellow dim light on convert polymer, solve solution
State needs the problem of deoxygenation, while solving the bottleneck problem that transfer efficiency is low on current solid polymer；Exposure is in air
It is almost unattenuated to be positively retained at 4 days or more efficiency for transfer efficiency (12.75%) thereon, has the valence of applying in field of solar energy utilization
Value.
Detailed description of the invention
Red turn of yellow pictorial diagram in copolymer different vessels is converted in Fig. 1 embodiment one in solid-state；
Sensitizer PdPc in Fig. 2 embodiment one2In the polymer in solution absorption and fluorogram；
In Fig. 3 embodiment one luminous agent RhB in the polymer in solution absorption and fluorogram；
PdPc in Fig. 4 embodiment one2With the upconversion emission of RhB in the solution with excitation light power variable density figure；
PdPc in Fig. 5 embodiment one2With the logarithmic chart of RhB upper shift strength in the solution and exciting power；
PdPc in Fig. 6 embodiment one2Become with upconversion emission of the RhB in solid polymer with excitation light power density
Change figure；
PdPc in Fig. 7 embodiment one2With the logarithmic chart of the RhB upper shift strength in solid polymer and exciting power；
PdPc in Fig. 8 embodiment one2With the upconversion emission of RhBS in the solution with excitation light power variable density figure；
PdPc in Fig. 9 embodiment one2With the logarithmic chart of RhBS upper shift strength in the solution and exciting power；
PdPc in Figure 10 embodiment one2With upconversion emission of the RhBS in solid polymer with excitation light power density
Variation diagram；
PdPc in Figure 11 embodiment one2With the logarithm of the RhBS upper shift strength in solid polymer and exciting power
Figure；
Resin (PdPc is converted in Figure 12 embodiment one in solid-state2With (the i.e. upper conversion of the aerial curve of stability of RhB)
Efficiency and time relationship) figure；
The solar battery schematic diagram of resin is converted in Figure 13 embodiment one in solid-state；
Resin up-conversion solar cell I-V curve figure is converted in Figure 14 embodiment one in solid-state.
Specific embodiment
With reference to the accompanying drawing and embodiment the invention will be further described:
Embodiment one
(1) solution (PdPc is converted in bi-component2/ luminous agent) configuration: by sensitizer (PdPc2) (concentration is 4 × 10 to mother liquor-5Mol/L) and luminous agent mother liquor (concentration be 1 × 10-2Mol/L it after) being mixed according to certain molar weight proportion and deaerates, obtains
Sensitizer/luminous agent two-constituent solution, solvent involved in above-mentioned all solution be spectroscopic pure normal propyl alcohol/ethylene glycol (v/v,
1/2).
Any one of following rhodamine derivative can be selected in luminous agent type:
(2) copolymer systems preparation is converted in solid-state: in nitrogen atmosphere, by 2- hydroxy vinyl methylbenzene e pioic acid methyl ester
(HEMA) and 3- (methacryloxypropyl) propyl trimethoxy silicane (TMSPMA) presses 1: 1(mass ratio) mixing, 0.5%(matter is added
Measure ratio) azodiisobutyronitrile be used as initiator, add two-constituent solution (sensitizer and luminous agent mol ratio are 1:
3000) (30 min) is vacuumized after, being sufficiently stirred, then in 78 DEG C of 5 h of heat preservation；It is total to take out conversion in natural cooling formation solid-state
Polymeric systems.
According to step (2), two-constituent solution is changed to sensitizer (PdPc respectively2) mother liquor, luminous agent mother liquor, it can obtain
Obtain single-component solid copolymer.
Copolymer systems are converted in solid-state, in red laser (655 nm, 1 W/cm of power density2) excitation under, test
Its upconversion emission.Attached drawing 1 is to excite down (1 W/cm with laser2) obtain the pictorial diagram converted on red turn of Huang, left and right figure point
Not in different vessels, bi-component PdPc2/RhB。
Attached drawing 2, attached drawing 3 are respectively the absorption and fluorogram of the sensitizer and luminous agent of one pack system in solution state and solid-state
Spectrum.As it can be seen that solid state substrate is conducive to the raising of the absorbability and luminous intensity of sensitizer, is also beneficial to compared with solution state
The raising of the absorbability and luminous intensity of luminous agent.
Attached drawing 4 is PdPc2Red laser (655nm) the device spoke of/RhB bi-component (solution state) system in different capacity density
According under, the upconversion emission figure measured, attached drawing 5 is the logarithmic relationship of 4 obtained upper shift strengths and exciting power with reference to the accompanying drawings
Figure.
As it can be seen that when excitation light source power density is by 0.1mW/cm2Increase to 1 mW/cm2When, upper shift strength maximum can increase
To 5X10-3, peak position is converted thereon at 604nm.Middle PdPc is calculated according to formula (1)2/ RhB(solution state) on transfer efficiency
It is 6.8%.
Wherein, ArAnd AsIt is the absorbance of reference substance and sensitizer at 655nm, F respectivelysBe respectively with Fr luminous agent and
The integral area of up-conversion fluorescence intensity of the reference substance under the excitation of 655nm,WithFor luminous agent system and reference object
It is refractive index,For fluorescence quantum yield of the reference substance under the excitation of 655nm.
Under above-mentioned identical shooting condition (655nm), corresponding solid-state PdPc is obtained2The upconversion emission of/RhB polymer
As shown in attached drawing 6.Attached drawing 6 and attached drawing 7 are red laser under the exciting light irradiation of different capacity density, and copolymerization is converted in solid-state
The intensity variation curve of objects system.As it can be seen that when excitation light source power density is by 0.1mW/cm2Increase to 1 mW/cm2When, upper conversion
Intensity is improved to 0.01, and shift strength and the logarithmic relationship figure of exciting power are as shown in attached drawing 7 in corresponding solid-state.According to formula
(1) solid-state PdPc is calculated2The upper transfer efficiency of/RhB bi-component is 10.2%.
By 4 ~ attached drawing of attached drawing 7 as it can be seen that under identical testing conditions (sensitizer/luminous agent concentration), solid-state PdPc2/RhB
The upper transfer efficiency of polymer is 10.2%, is higher than solution state PdPc2The upper transfer efficiency (6.8%) of/RhBS.
It can thus be seen that upper transfer efficiency when solid upper transfer efficiency is higher than solution state.
Attached drawing 8 is PdPc2/ RhBS(solution state) system different capacity density red laser (655nm) device irradiation under,
The upconversion emission figure measured, attached drawing 9 are the logarithmic relationship figures of corresponding upper shift strength and exciting power.As it can be seen that when excitation
Light source power density is by 0.1mW/cm2Increase to 1 mW/cm2When, upper shift strength maximum can increase to 0.006, convert peak position thereon
At 616nm.Middle PdPc is calculated according to formula (1)2/ RhBS(solution state) on transfer efficiency be 8.7%.
Attached drawing 10 is the solid-state PdPc under the exciting light irradiation of red laser (655nm) different capacity density2/ RhBS is poly-
Shift strength change curve on object is closed, attached drawing 11 is the logarithmic chart of corresponding upper shift strength and exciting power.As it can be seen that when excitation
Light source power density is by 0.1mW/cm2Increase to 1 mW/cm2When, upper shift strength maximum can increase to 0.015, according to formula (1)
Calculate middle PdPc2/ RhBS(solution state) on transfer efficiency be 8.7%.
By 8~attached drawing of attached drawing 11 as it can be seen that under the same test conditions, solid-state PdPc2The upper transfer efficiency of/RhBS polymer
It is 12.8%, is higher than solution state PdPc2The upper transfer efficiency (8.7%) of/RhBS.
Attached drawing 12 is sensitizer/luminous agent (PdPc2/ RhB) under same concentrations, polymer and solution in air, thereon
Transfer efficiency versus time curve.After visible solid state resin places 4 days in air, upper transfer efficiency still can achieve original
90% come, under above-mentioned identical shooting condition, the upper transfer efficiency stability for obtaining corresponding solution state is then 2~3 hours.
The stability that resin is converted in obvious solid-state is far superior to solution state, has actual use value.
Application of the resin in terms of solar battery is converted in solid-state:
According to Figure 13 shown device, solid state laser (excitation wavelength: 655 nm, 1 Wcm of power density-2) turn in irradiation
Copolymer is changed, through optical filter, upper conversion yellow light direct irradiation on the solar cell, passes through keithley 2400
SourceMeter measures I-V curve as shown in figure 14.It is (glimmering to avoid the lower conversion of sensitizer using 655 short pass filters
Light) it is absorbed by battery.
Table 1 is the upper transfer efficiency of above-mentioned upper converting system in different media, it can be clearly seen that solid polymer
Upper transfer efficiency is higher than transfer efficiency in solution state, is higher by 40% to 50% or more.
The upper transfer efficiency of the above-mentioned upper converting system of table 1 in different media
Embodiment two
According to the preparation method of embodiment one, wherein HEMA, TMSPMA press 1: 2(mass ratio) mixing, 0.5%(mass is added
Than) azodiisobutyronitrile as initiator, add two-constituent solution (sensitizer and luminous agent mol ratio be 1: 3000),
Convert copolymer systems in preparation solid-state, when luminous agent RhB, RhBS, Rh6G, upper transfer efficiency is respectively 9.6%, 12.3%,
2.9%.Correspondingly, in other conditions situation all the same, the upper transfer efficiency of luminous agent RhB, RhBS, Rh6G in solution state
It is respectively as follows: 6.8%, 8.7% and 2.2%.Comparative example one and embodiment two can be seen that the ratio pair of two kinds of polymer monomer
The influence of the upper transfer efficiency of converting system is smaller in solid-state；Meanwhile under the same conditions, in solid-state converting system upper conversion
Efficiency is greater than upper transfer efficiency when solution state.After solid resin places 4 days in air, upper transfer efficiency still can achieve original
90% come, under above-mentioned identical shooting condition, the upper transfer efficiency stability for obtaining corresponding solution state is then 2~3 hours.
Embodiment three
According to the preparation method of embodiment one, wherein sensitizer, the solvent involved in agent solution that shines are that spectrum is pure
Propyl alcohol/ethylene glycol (v/v, 1/6)；HEMA, TMSPMA press 1: 4(mass ratio) mixing, be added 0.5%(mass ratio) azo two it is different
Butyronitrile adds two-constituent solution (sensitizer and luminous agent mol ratio be 1: 3000), prepares and turn in solid-state as initiator
Change copolymer systems, when luminous agent RhB, RhBS, Rh6G, upper transfer efficiency is respectively 9.4%, 11.8%, 2.6%.Correspondingly,
In other conditions situation all the same, the upper transfer efficiency of luminous agent RhB, RhBS, Rh6G in solution state is respectively as follows: 6.4%,
8.3% and 1.9%.Comparative example one and embodiment three can be seen that as solvent normal propyl alcohol/ethylene glycol ratio changes, molten
The upper transfer efficiency of liquid is also with reduction；Meanwhile under the same conditions, in solid-state converting system upper transfer efficiency be greater than it is molten
Upper transfer efficiency when liquid.After solid resin places 4 days in air, upper transfer efficiency still can achieve original 90%,
Under above-mentioned identical shooting condition, the upper transfer efficiency stability for obtaining corresponding solution state is then 2~3 hours.
Example IV
According to the preparation method of embodiment one, wherein HEMA, TMSPMA press 1: 4(mass ratio) mixing, 0.5%(mass is added
Than) azodiisobutyronitrile as initiator, add two-constituent solution (sensitizer and luminous agent mol ratio be 1: 2000),
Convert copolymer systems in preparation solid-state, when luminous agent RhB, RhBS, Rh6G, upper transfer efficiency is respectively 4.5%, 7.2%,
1.7%.Correspondingly, in other conditions situation all the same, the upper transfer efficiency of luminous agent RhB, RhBS, Rh6G in solution state
It is respectively as follows: 3.8%, 5.3% and 1.3%.Comparative example one can be seen that with example IV as sensitizer/luminous agent mole is matched
Than becoming smaller, either solution state and solid upper transfer efficiency is also with reduction, still.The upper conversion of converting system in solid-state
Efficiency is all larger than upper transfer efficiency when solution state.After solid resin places 4 days in air, upper transfer efficiency still be can achieve
Originally 90%, under above-mentioned identical shooting condition, the upper transfer efficiency stability for obtaining corresponding solution state is then 2~3 small
When.
Embodiment five
According to the preparation method of embodiment one, wherein sensitizer, the solvent involved in agent solution that shines are that spectrum is pure
Propyl alcohol/ethylene glycol (v/v, 1/10)；HEMA, TMSPMA press 1: 6(mass ratio) mixing, be added 0.5%(mass ratio) azo two it is different
Butyronitrile adds two-constituent solution (sensitizer and luminous agent mol ratio be 1: 2000), prepares and turn in solid-state as initiator
Change copolymer systems, when luminous agent RhB, RhBS, Rh6G, upper transfer efficiency is respectively 4.3%, 6.9%, 1.5%.Correspondingly, exist
In other conditions situation all the same, the upper transfer efficiency of luminous agent RhB, RhBS, Rh6G in solution state is respectively as follows: 3.5%,
5.1% and 1.1%.Comparative example one can be seen that with embodiment five as sensitizer/luminous agent mol ratio becomes smaller no matter
Solution state and solid upper transfer efficiency also with reduction, but in solid-state the upper transfer efficiency of converting system be all larger than it is molten
Upper transfer efficiency when liquid.After solid resin places 4 days in air, upper transfer efficiency still can achieve original 90%,
Under above-mentioned identical shooting condition, the upper transfer efficiency stability for obtaining corresponding solution state is then 2~3 hours.
The present invention with siliceous and hydroxyl two kinds of acrylate monomers, coats triplet sensitization by in-situ copolymerization for the first time
Agent and luminous agent polyhydric alcohol solutions, obtain it is a kind of it is efficient it is red-turn-yellow dim light on convert polymer, excited in power 655nm
Device (power density 1W/cm2) under irradiation, measure transfer efficiency and reach as high as 12.75%；And in air may be used without deoxygenation
Holding 4 days or more almost unattenuated, shows the potential application value in terms of photovoltaic solar cell and photosynthesis.
Claims (6)
1. a kind of solid-state is red-turn-Huang on convert copolymer systems, which is characterized in that the solid-state is red-turn-Huang on conversion be copolymerized
Objects system is that copolymer coats sensitizer and luminous agent system；The copolymer contains hydroxyl and silicon；
The chemical structural formula of the sensitizer are as follows:
The chemical structural formula of the luminous agent is one of following chemical structural formula:
；
The solid-state is red-turn-Huang on the preparation methods of conversion copolymer systems include the following steps, will be siliceous under nitrogen atmosphere
Acrylate monomer and hydroxy acryl acid ester monomer, azo-compound are mixed with sensitizer/luminous agent two-constituent solution, are taken out true
Then sky carries out home position polymerization reaction, obtain solid-state it is red-turn-Huang on convert copolymer systems.
2. according to claim 1 solid-state it is red-turn-Huang on convert copolymer systems, which is characterized in that acrylate containing silicone list
Body and the mass ratio of hydroxy acryl acid ester monomer are (1~10): 1；The molar ratio of sensitizer and luminous agent is 1: (300~
3000).
3. according to claim 1 solid-state it is red-turn-Huang on convert copolymer systems, which is characterized in that the silyl acrylate
Ester monomer is 3- (methacryloxypropyl) propyl trimethoxy silicane；The hydroxy acryl acid ester monomer is α-methacrylic acid
Hydroxyl ethyl ester.
4. according to claim 1 solid-state it is red-turn-Huang on convert copolymer systems, which is characterized in that the sensitizer/hair
In photo etching two-constituent solution, solvent is polyalcohol mixed solvent.
5. according to claim 1 solid-state it is red-turn-Huang on convert copolymer systems, which is characterized in that the in-situ polymerization
The condition of reaction is to react the h of 4 h~8 at 60 DEG C~90 DEG C.
6. solid-state described in claim 1 is red-turn-Huang on convert copolymer systems and preparing the application in dim light up-conversion.
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