CN110407682A - A kind of polypropylene luminescent material of europium complex, its ligand and europium complex doping - Google Patents
A kind of polypropylene luminescent material of europium complex, its ligand and europium complex doping Download PDFInfo
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- CN110407682A CN110407682A CN201910690772.5A CN201910690772A CN110407682A CN 110407682 A CN110407682 A CN 110407682A CN 201910690772 A CN201910690772 A CN 201910690772A CN 110407682 A CN110407682 A CN 110407682A
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- europium complex
- europium
- complex
- polypropylene
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- 229910052693 Europium Inorganic materials 0.000 title claims abstract description 82
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 title claims abstract description 81
- -1 polypropylene Polymers 0.000 title claims abstract description 35
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 34
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 34
- 239000000463 material Substances 0.000 title claims abstract description 31
- 239000003446 ligand Substances 0.000 title claims abstract description 27
- YNPNZTXNASCQKK-UHFFFAOYSA-N Phenanthrene Natural products C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 claims abstract description 16
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000002360 preparation method Methods 0.000 claims abstract description 13
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 claims abstract description 12
- GAGGCOKRLXYWIV-UHFFFAOYSA-N europium(3+);trinitrate Chemical compound [Eu+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GAGGCOKRLXYWIV-UHFFFAOYSA-N 0.000 claims abstract description 9
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 claims abstract description 8
- WBYWAXJHAXSJNI-SREVYHEPSA-N Cinnamic acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1 WBYWAXJHAXSJNI-SREVYHEPSA-N 0.000 claims abstract description 8
- 229930016911 cinnamic acid Natural products 0.000 claims abstract description 8
- 235000013985 cinnamic acid Nutrition 0.000 claims abstract description 8
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 claims abstract description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 239000003960 organic solvent Substances 0.000 claims abstract description 7
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000011261 inert gas Substances 0.000 claims abstract description 4
- 238000004090 dissolution Methods 0.000 claims abstract description 3
- 238000010992 reflux Methods 0.000 claims abstract description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 18
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 6
- 229960000583 acetic acid Drugs 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 239000012044 organic layer Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 235000019441 ethanol Nutrition 0.000 claims description 3
- 239000012362 glacial acetic acid Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000000284 extract Substances 0.000 claims description 2
- 239000010410 layer Substances 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims 1
- 230000021615 conjugation Effects 0.000 claims 1
- 239000007789 gas Substances 0.000 claims 1
- 239000012264 purified product Substances 0.000 claims 1
- 239000000741 silica gel Substances 0.000 claims 1
- 229910002027 silica gel Inorganic materials 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 150000003384 small molecules Chemical class 0.000 abstract description 4
- 238000004020 luminiscence type Methods 0.000 abstract description 3
- 238000003756 stirring Methods 0.000 abstract description 3
- 229910052761 rare earth metal Inorganic materials 0.000 description 12
- 150000002910 rare earth metals Chemical class 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000007787 solid Substances 0.000 description 5
- 239000004305 biphenyl Substances 0.000 description 4
- 235000010290 biphenyl Nutrition 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- 239000003480 eluent Substances 0.000 description 3
- 238000010898 silica gel chromatography Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000010146 3D printing Methods 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- NZZIMKJIVMHWJC-UHFFFAOYSA-N dibenzoylmethane Chemical compound C=1C=CC=CC=1C(=O)CC(=O)C1=CC=CC=C1 NZZIMKJIVMHWJC-UHFFFAOYSA-N 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 239000012769 display material Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000012259 ether extract Substances 0.000 description 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N ethyl acetate Substances CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 1
- 229910001940 europium oxide Inorganic materials 0.000 description 1
- AEBZCFFCDTZXHP-UHFFFAOYSA-N europium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Eu+3].[Eu+3] AEBZCFFCDTZXHP-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 230000003760 hair shine Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
- C07C45/72—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups
- C07C45/74—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups combined with dehydration
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
- C07C45/79—Separation; Purification; Stabilisation; Use of additives by solid-liquid treatment; by chemisorption
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
- C07C45/80—Separation; Purification; Stabilisation; Use of additives by liquid-liquid treatment
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/76—Ketones containing a keto group bound to a six-membered aromatic ring
- C07C49/794—Ketones containing a keto group bound to a six-membered aromatic ring having unsaturation outside an aromatic ring
- C07C49/796—Ketones containing a keto group bound to a six-membered aromatic ring having unsaturation outside an aromatic ring polycyclic
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/003—Compounds containing elements of Groups 3 or 13 of the Periodic Table without C-Metal linkages
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0091—Complexes with metal-heteroatom-bonds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/18—Metal complexes
- C09K2211/182—Metal complexes of the rare earth metals, i.e. Sc, Y or lanthanide
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Abstract
The invention discloses the polypropylene luminescent materials that a kind of europium complex and europium complex adulterate.The structure of the europium complex and its ligand is as shown in formula II and formula I.The long conjugated ligand of the europium complex the preparation method comprises the following steps: by sodium ethoxide, tetrahydrofuran, acetophenone and cinnamic acid mix after carry out back flow reaction under inert gas protection, isolate and purify product after completion of the reaction up to the long conjugated ligand of europium complex.The europium complex carries out heating stirring dissolution the preparation method comprises the following steps: the long conjugated ligand and europium nitrate of europium complex are added in organic solvent, then Phen solution is added dropwise, heating reflux reaction is carried out after being added dropwise, and isolates and purifies product after reaction up to europium complex.The polypropylene luminescent material of the doping of europium complex obtained in polypropylene is doped to using above-mentioned europium complex, both with the characteristics of luminescence of small molecule europium complex, it may have the good mechanical property of polypropylene high molecular material.
Description
Technical field
The present invention relates to red light material preparation technical fields, and in particular to a kind of europium complex, its ligand and europium complex
The polypropylene luminescent material of doping.
Background technique
Organic electroluminescence device will realize that full color flat panel is shown, need the red, green, blue three coloured light of high color purity.However,
The electroluminescent spectrum of most of organic materials is wider, is unfavorable for the realization of total colouring.Wherein, the transition energy gap of emitting red light
It is small, it is difficult the energy match with carrier blocking layers, cannot effectively makes electrons and holes compound in luminous zone.Therefore organic
In red, green, blue three primary colours display material, red illuminating material is considered as a most weak ring.
The emission peak of Rare Earth Europium Complex mostlys come from Eu3+'s5D0——7F2Characteristic emission, not with the difference of ligand
And change, emission peak is located at 617nm or so.Emission spectra is almost line spectrum, and half-peak breadth only has several nanometers, has saturation
Red emission；It shines moreover, europium complex belongs to triplet, the luminous efficiency theory upper limit is up to 100%.
Rare earth compounding/polymer composites are a kind of inorganic/polymer materials with wide application prospect.Due to
Rare earth itself have unique chemical property and physical property, and optical field obtain achievement, it is more next by people
More concerns.But current research is concentrated mainly on polyvinyl acetate, polyurethane, polystyrene isopolarity polymer with
On metal complex.
Summary of the invention
Primary technical problem to be solved by this invention is to provide a kind of long conjugated ligand of europium complex.
Another technical problem to be solved by this invention is to provide a kind of europium complex.
Another technical problem to be solved by this invention is to provide a kind of polypropylene luminescent material of europium complex doping.
Above-mentioned technical problem to be solved by this invention is achieved by the following technical programs:
A kind of long conjugated ligand of europium complex, which is characterized in that there is structure shown in formula I:
The chemical name of the long conjugated ligand of the europium complex of structure shown in formula I is 1,5- diphenyl -4- alkene -1,3- penta 2
Ketone (abbreviation DPPD).
A kind of europium complex has structure shown in formula II:
The europium complex of structure shown in formula II is named as again based on rare-earth europium-DPPD- Phen ternary in the present invention
Complex.
The preparation method of the long conjugated ligand of above-mentioned europium complex, includes the following steps:
Back flow reaction is carried out under inert gas protection after sodium ethoxide, tetrahydrofuran, acetophenone and cinnamic acid are mixed
16~for 24 hours, isolate and purify product after completion of the reaction up to the long conjugated ligand of the europium complex；
The sodium ethoxide, tetrahydrofuran, acetophenone and cinnamic acid amount ratio be 4~6g:60~100mL:10~
15mL:12~18g.
Most preferably, the amount ratio of the sodium ethoxide, tetrahydrofuran, acetophenone and cinnamic acid is 5g:80mL:
11mL:15g。
Preferably, the inert gas is nitrogen.
Preferably, product is isolated and purified after completion of the reaction method particularly includes: is acidified, then used with glacial acetic acid after completion of the reaction
Ether extracts organic layer, and uses NaHCO respectively3, deionized water washing, then rotation boils off ether, obtains sticky faint yellow
Oily liquids is finally purified with silica gel column chromatography up to the long conjugated ligand of the europium complex.
It is further preferred that being acidified after completion of the reaction with 30% glacial acetic acid, then organic layer is extracted with ether, and use respectively
5%NaHCO3, deionized water wash 2 times, then rotation boil off ether, obtain sticky pale yellow oily liquid, finally use silicon
The gel column chromatography eluting long conjugated ligand up to the europium complex.
It is further preferred that petroleum ether and acetic acid second that it is 4:1 by volume ratio that the eluent of the silica gel column chromatography, which is selected,
The eluent of ester composition.
The preparation method of above-mentioned europium complex, comprises the following steps:
The long conjugated ligand and europium nitrate of above-mentioned europium complex are added to progress heating stirring dissolution in organic solvent,
Then Phen solution is added dropwise, 0.5~2h of heating reflux reaction is carried out after being added dropwise, isolates and purifies product after reaction
Up to the europium complex；
The long conjugated ligand of the europium complex, europium nitrate, organic solvent and Phen solution amount ratio be
0.005~0.015mol:0.05~0.15mol:300~600mL:50~150mL；
The concentration of the Phen solution is 0.03~0.06mol/L.
Most preferably, the long conjugated ligand of the europium complex, europium nitrate, organic solvent and Phen solution
Amount ratio is 0.01mol:0.1mol:400mL:100mL；
The concentration of the Phen solution is 0.05mol/L.
Preferably, product is isolated and purified after reaction method particularly includes: it cools down after reaction, solid is precipitated, it is quiet
Set overnight, filtering, filter cake washed, dried after through re crystallization from toluene, obtain light yellow solid up to the europium complex.
The present invention also provides a kind of polypropylene luminescent materials of europium complex doping, which is characterized in that matches comprising above-mentioned europium
Close object.
Preferably, the polypropylene luminescent material of europium complex doping, the material composition comprising following parts by weight: poly-
98~100 parts of propylene；0.1~2 part of europium complex.
It is further preferred that the polypropylene luminescent material that the europium complex adulterates, the raw material comprising following parts by weight
Ingredient: 99~100 parts of polypropylene；0.1~1 part of europium complex.
The polypropylene luminescent material of the most described europium complex doping, the material composition comprising following parts by weight: polypropylene
99.5 parts；0.5 part of europium complex.
The preparation method of the polypropylene luminescent material of above-mentioned europium complex doping, comprises the following steps: weigh polypropylene and
Europium complex, using Haake mixer mixing, the polypropylene luminescent material of obtained europium complex doping after being plasticized completely.
The utility model has the advantages that (1) 1,5- diphenyl -4- alkene -1,3- pentanedione (DPPD) of the present invention is than classical β-two
Ketone compound dibenzoyl methane (DBM) has longer conjugated chain and lesser steric hindrance, therefore the complex ratio formed
Existing europium complex has more preferable conjugacy and coplanarity；(2) europium complex of structure shown in formula II has hair well
Optical property, while the europium complex can be good at compatible with polypropylene, the present invention according to polyacrylic characteristic, develops for the first time
One kind can be suitable for polyacrylic luminescent material；(3) it is doped in polypropylene and is obtained using europium complex of the present invention
Europium complex doping polypropylene luminescent material, both with the characteristics of luminescence of small molecule europium complex, it may have polypropylene is high
The good mechanical property of molecular material, therefore, the polypropylene luminescent material of the europium complex doping not only impart small
The good mechanical property of molecule europium complex also gives the good luminescent properties of polypropylene and can improve polyacrylic mechanical property
Can, to make it possible that polypropylene becomes 3D printing material.
Detailed description of the invention
Fig. 1 is that the present invention is based on the fluorescence spectras of rare-earth europium-DPPD- Phen ternary complex.
Fig. 2 is that the present invention is based on the TG of rare-earth europium-DPPD- Phen ternary complex figures.
Specific embodiment
The present invention is explained further below in conjunction with specific embodiment, but embodiment does not do any type of limit to the present invention
It is fixed.
The synthesis of 1 1,5- diphenyl -4- alkene -1,3- pentanedione (DPPD) of embodiment
Sequentially added in the three-neck flask of a 250mL the freshly prepd sodium ethoxide of 5g, the tetrahydrofuran that 80mL steams again,
11mL acetophenone and 15g cinnamic acid, under nitrogen protection electromagnetic agitation, back flow reaction 20h.After completion of the reaction with 30% ice vinegar
Acid acidification extracts organic layer with ether, and uses 5%NaHCO respectively3, deionization wash 2 times, then rotation boil off ether, obtain
Sticky pale yellow oily liquid.Purified with silica gel column chromatography, is made with petroleum ether (60~90 DEG C)-ethyl acetate (V: V=4: 1)
Eluent obtains 2.92g1,5- diphenyl -4- alkene -1,3- pentanedione (DPPD), yield 20%.
Synthesis of the embodiment 2 based on rare-earth europium-DPPD- Phen ternary complex
Europium oxide is dissolved in dust technology, moisture content is boiled off, is precipitated crystal, europium nitrate Eu (NO3) is obtained3.It is burnt at tri- mouthfuls of 100mL
In bottle, it is added DPPD 2.36g (0.01mol), europium nitrate Eu (NO3)333.8g (0.1mol), 95% ethyl alcohol (400mL), heating
Stirring to solid dissolves, and the ethanol solution (100mL) of Phen 1g (0.005mol) is added dropwise, finishes and is heated to flowing back, after 1h
Stop heating.After cooling, be precipitated solid, stand overnight, filter, filter cake washed, dried after through re crystallization from toluene, obtain light yellow
Solid 3g (0.027mol) i.e. speed search based on rare-earth europium-DPPD- Phen ternary complex, yield 80%, fusing point is
278-280℃。
It will be seen from figure 1 that being existed based on rare-earth europium-DPPD- Phen ternary complex of being prepared of the present embodiment
The characteristic spectrum of bright europium ion is issued at 612nm；Compared with existing europium complex, the present embodiment be prepared based on
Rare-earth europium-DPPD- Phen ternary complex has the fluorescence of more pure color.
Figure it is seen that through TG test it is found that the present embodiment be prepared based on rare-earth europium-DPPD- Phen
The initial decomposition temperature of ternary complex is greater than 300 DEG C, has better hot property than existing europium complex.
The preparation of the polypropylene luminescent material of 3 europium complex of embodiment doping
Weigh polypropylene 45g, the conjunction based on rare-earth europium-DPPD- Phen ternary complex that embodiment 2 is prepared
At 0.5g, using Haake mixer mixing, the polypropylene luminescent material of obtained europium complex doping after being plasticized completely.
The polypropylene luminescent material for the europium complex doping that the present embodiment is prepared, both with small molecule europium complex
The characteristics of luminescence, it may have the good mechanical property of polypropylene high molecular material, therefore, poly- the third of the europium complex doping
Alkene luminescent material not only imparts the good mechanical property of small molecule europium complex, also gives the good luminescent properties of polypropylene
And polyacrylic mechanical property can be improved, to make it possible that polypropylene becomes 3D printing material.
Claims (10)
1. a kind of long conjugated ligand of europium complex, which is characterized in that have structure shown in formula I:
2. a kind of europium complex, which is characterized in that have structure shown in formula II:
3. the preparation method of the long conjugated ligand of europium complex described in claim 1, which comprises the steps of:
Will sodium ethoxide, tetrahydrofuran, acetophenone and cinnamic acid mix after carry out under inert gas protection back flow reaction 16~
For 24 hours, product is isolated and purified after completion of the reaction up to the long conjugated ligand of the europium complex；
The sodium ethoxide, tetrahydrofuran, acetophenone and cinnamic acid amount ratio be 4~6g:60~100mL:10~15mL:
12~18g.
4. the preparation method of the long conjugated ligand of europium complex according to claim 3, which is characterized in that the ethyl alcohol
Sodium, tetrahydrofuran, acetophenone and cinnamic acid amount ratio be 5g:80mL:11mL:15g.
5. the preparation method of the long conjugated ligand of europium complex according to claim 3, which is characterized in that the inertia
Gas is nitrogen.
6. the preparation method of the long conjugated ligand of europium complex according to claim 3, which is characterized in that after completion of the reaction
Isolate and purify product method particularly includes: be acidified after completion of the reaction with glacial acetic acid, then extract organic layer with ether, and use respectively
NaHCO3, deionized water washing, then rotation boil off ether, obtain sticky pale yellow oily liquid, finally use silica gel column layer
The long conjugated ligand that analysis purifies up to the europium complex.
7. the preparation method of europium complex as claimed in claim 2, which is characterized in that comprise the following steps:
The long conjugated ligand and europium nitrate of europium complex described in claim 1 are added in organic solvent heat and stirred
Dissolution is mixed, Phen solution is then added dropwise, 0.5~2h of heating reflux reaction is carried out after being added dropwise, is separated after reaction
Purified product is up to the europium complex；
The long conjugated ligand of the europium complex, europium nitrate, organic solvent and Phen solution amount ratio be 0.005
~0.015mol:0.05~0.15mol:300~600mL:50~150mL；
The concentration of the Phen solution is 0.03~0.06mol/L.
8. the preparation method of europium complex as claimed in claim 7, which is characterized in that the long conjugation of the europium complex is matched
Body, europium nitrate, organic solvent and Phen solution amount ratio be 0.01mol:0.1mol:400mL:100mL；
The concentration of the Phen solution is 0.05mol/L.
9. a kind of polypropylene luminescent material of europium complex doping, which is characterized in that cooperate comprising europium as claimed in claim 2
Object.
10. the polypropylene luminescent material of europium complex doping according to claim 9, which is characterized in that include following weight
The material composition of amount part: 98~100 parts of polypropylene；0.1~2 part of europium complex.
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