CN104829471B - A kind of anthracene derivative and its preparation method and application and obtained UV photocuring light-emittings material and preparation method thereof - Google Patents
A kind of anthracene derivative and its preparation method and application and obtained UV photocuring light-emittings material and preparation method thereof Download PDFInfo
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- CN104829471B CN104829471B CN201510254679.1A CN201510254679A CN104829471B CN 104829471 B CN104829471 B CN 104829471B CN 201510254679 A CN201510254679 A CN 201510254679A CN 104829471 B CN104829471 B CN 104829471B
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- 239000000463 material Substances 0.000 title claims abstract description 71
- 238000000016 photochemical curing Methods 0.000 title claims abstract description 49
- 150000001454 anthracenes Chemical class 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 36
- 239000000178 monomer Substances 0.000 claims abstract description 27
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 24
- 230000000694 effects Effects 0.000 claims abstract description 12
- 229920002554 vinyl polymer Polymers 0.000 claims description 19
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 claims description 16
- 239000007789 gas Substances 0.000 claims description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- -1 aldehyde radical Chemical class 0.000 claims description 9
- 238000005859 coupling reaction Methods 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 238000006069 Suzuki reaction reaction Methods 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 5
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 5
- 239000004327 boric acid Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 238000006467 substitution reaction Methods 0.000 claims description 4
- 238000013019 agitation Methods 0.000 claims description 3
- 125000003368 amide group Chemical group 0.000 claims description 3
- 239000011737 fluorine Substances 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 3
- 238000006443 Buchwald-Hartwig cross coupling reaction Methods 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 2
- 125000004104 aryloxy group Chemical group 0.000 claims description 2
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 2
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 2
- 125000004446 heteroarylalkyl group Chemical group 0.000 claims description 2
- 125000005553 heteroaryloxy group Chemical group 0.000 claims description 2
- 125000004415 heterocyclylalkyl group Chemical group 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 10
- 238000003786 synthesis reaction Methods 0.000 abstract description 10
- 238000007639 printing Methods 0.000 abstract description 9
- 239000003086 colorant Substances 0.000 abstract description 8
- 239000011248 coating agent Substances 0.000 abstract description 7
- 238000000576 coating method Methods 0.000 abstract description 7
- 125000001424 substituent group Chemical group 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 5
- 239000000976 ink Substances 0.000 description 21
- 239000000203 mixture Substances 0.000 description 20
- 239000000126 substance Substances 0.000 description 15
- 238000004519 manufacturing process Methods 0.000 description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- FTALTLPZDVFJSS-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl prop-2-enoate Chemical compound CCOCCOCCOC(=O)C=C FTALTLPZDVFJSS-UHFFFAOYSA-N 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 238000004440 column chromatography Methods 0.000 description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 6
- 238000001953 recrystallisation Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 238000003760 magnetic stirring Methods 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 4
- 238000005286 illumination Methods 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 description 3
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 2
- 229910000024 caesium carbonate Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- MLNKXLRYCLKJSS-RMKNXTFCSA-N (2e)-2-hydroxyimino-1-phenylethanone Chemical compound O\N=C\C(=O)C1=CC=CC=C1 MLNKXLRYCLKJSS-RMKNXTFCSA-N 0.000 description 1
- YIKSHDNOAYSSPX-UHFFFAOYSA-N 1-propan-2-ylthioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C=CC=C2C(C)C YIKSHDNOAYSSPX-UHFFFAOYSA-N 0.000 description 1
- SODQFLRLAOALCF-UHFFFAOYSA-N 1lambda3-bromacyclohexa-1,3,5-triene Chemical compound Br1=CC=CC=C1 SODQFLRLAOALCF-UHFFFAOYSA-N 0.000 description 1
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 description 1
- ZHQNDEHZACHHTA-UHFFFAOYSA-N 9,9-dimethylfluorene Chemical compound C1=CC=C2C(C)(C)C3=CC=CC=C3C2=C1 ZHQNDEHZACHHTA-UHFFFAOYSA-N 0.000 description 1
- ZBSRRYSIUJREEE-UHFFFAOYSA-N COc(cc1)ccc1-c1c(cccc2)c2c(C=C)c2ccccc12 Chemical compound COc(cc1)ccc1-c1c(cccc2)c2c(C=C)c2ccccc12 ZBSRRYSIUJREEE-UHFFFAOYSA-N 0.000 description 1
- CHLICZRVGGXEOD-UHFFFAOYSA-N Cc(cc1)ccc1OC Chemical compound Cc(cc1)ccc1OC CHLICZRVGGXEOD-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-N Formic acid Chemical class OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical class CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001638 boron Chemical class 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000012952 cationic photoinitiator Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006880 cross-coupling reaction Methods 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical class C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 125000001072 heteroaryl group Chemical group 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- WQDGUYZIAJKLAB-UHFFFAOYSA-N octan-2-yl nitrite Chemical class CCCCCCC(C)ON=O WQDGUYZIAJKLAB-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- 150000002940 palladium Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 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
- 230000001681 protective effect Effects 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000012258 stirred mixture Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000007039 two-step reaction Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Indole Compounds (AREA)
Abstract
The present invention relates to UV photocuring light-emitting Material Fields, more particularly to a kind of anthracene derivative and its preparation method and application.Anthracene derivative has following structure：
Description
Technical field
The present invention relates to UV photocuring light-emitting Material Fields, in particular to a kind of anthracene derivative and its preparation side
Method and application and obtained UV photocuring light-emittings material and preparation method thereof.
Background technology
Luminescence generated by light is a kind of quite important and universal phenomenon, and the luminous research of inorganic matter and application have had longer
History, but phosphor haves the shortcomings that some are difficult to overcome：Species is few, controllability is small, use condition is harsh, energy
Amount efficiency is not high, it is difficult to obtain blue light etc., therefore the new luminescent material of exploration will be particularly significant.With the organic of big conjugated system
Molecule easily produces the transition of electron energy level under the exciting of electric laser etc., by adjusting substitution functional group, can inspire not
The light of co-wavelength comes, and then obtains the luminescent material of different colours.Because the species of organic compound is various, structure is a variety of more
Sample, can meet a variety of purposes, and the research of organic material is increasingly subject to the attention of people in recent years in illumination field.
Embedded photoluminescent material is widely used in Display Technique, (such as Organic Light Emitting Diode, Plasma Display Technology)
Lighting field, luminous printing ink, anti-fake material etc..Wherein luminous printing ink is applied to illumination field and obtains extensive interest, because of its tool
The features such as having transparent height, good film-forming property, thin coating, can draw in the materials such as all kinds of embossments, circular engravure, macromolecule picture, lamp decoration；Separately
On the one hand, in ink, embedded photoluminescent material is added, fluorescent ink is prepared into, be plotted in the bag such as bill, Zheng Juan, product brand
Fill on product, original decorations are color not influenceing, the variable novel information of printing can be obtained, its antifalse effect is enhanced, also improve
Artistic aesthetic property.
Anthracene is the polycyclic aromatic compounds that a class has conjugatedπbond, and it possesses good heat endurance, strong electronics is passed
Lead, navy blue photoluminescent property and high quantum yield, be widely used in the research field of Organic Light Emitting Diode, probe.But
It is applied to the fewer of anti-fake material.Anthryl class UV photocuring light-emittings material is used for the researches of anti-fake material.
UV photocuring light-emitting materials be it is a kind of can be in film forming under ultraviolet light, the material of drying, typically by resin, Dan Ju
Thing, additive and light trigger composition.Resin tool reactivity worth wherein in UV luminescent materials, can occur light with luminescent material and gather
Reaction is closed, polymer is formed.UV technologies are combined with luminescent material, and it is less applied to the report of anti-fake material.And show
There is the particle of the UV photocuring light-emitting materials of technology big, poorly soluble, it is impossible to utilize special mode of printing (such as ink jet printing
Deng) obtain security pattern the shortcomings of.
In view of this, it is special to propose the present invention.
The content of the invention
The first object of the present invention is to provide a kind of anthracene derivative, and described anthracene derivative has good stability,
Soluble good the advantages of, it is possible to the R substituent group different by introducing, the fluorescent material of different colours is obtained, can be well
Applied in anti-counterfeit printing.
The second object of the present invention is to provide a kind of preparation method of described anthracene derivative, the material of this method synthesis
Expect that yield is high, raw material used are easy to purchase, prepare easy.
The third object of the present invention is application of the anthracene derivative in UV photocuring light-emitting materials described in offer, institute
The anthracene derivative stated can dissolve each other with activated monomer, light trigger and auxiliary agent etc., and the ink being made can be solid under the irradiation of UV lamp
Change, form film, film can send fluorescence, reach false proof effect.The UV photocuring light-emitting films of preparation have it is transparent it is high, into
The features such as film is good, coating is thin.
The fourth object of the present invention is to provide a kind of UV photocuring light-emittings material, anthracene derivative and activated monomer, light
There is double bond in the UV photocuring light-emittings material i.e. ink that initiator and auxiliary agent are made, anthracene compound, can be with light under UV illumination
Initiator etc. reacts, and then solidifies, and the ink being made can be solidified into film under the irradiation of UV lamp.It is thin under common uv lamp
Film can send fluorescence, reach false proof effect.The UV photocuring light-emitting films of preparation have transparent height, good film-forming property, coating thin
The features such as.
The fifth object of the present invention is the preparation method of the UV photocuring light-emitting materials described in offer, and preparation method is simple
Easy, the ink performance being made is excellent.
In order to realize the above-mentioned purpose of the present invention, spy uses following technical scheme：
A kind of anthracene derivative, with following structure：
Wherein, R is
Any of；
R1 is end-capping group, selected from hydrogen, fluorine, alkyl, alkoxy, aldehyde radical, amido, cyano group, C6-C30 aryl, C2-C30
Heteroaryl, C6-C30 aralkyl, C2-C30 heteroarylalkyl, C5-C30 aryloxy group, C2-C30 heteroaryloxy, C3-
Any of C30 cycloalkyl or C2-C30 Heterocyclylalkyl.
The anthracene derivative that the present invention is provided is as main body luminescent material, and property stable in the air is good, soluble good, and can
By introducing different R substituent groups, to obtain the fluorescent material of different colours, it can be applied well in anti-counterfeit printing.Such as：
R is general in navy blue for the anthracene derivative of phenyl, and R is general in green for the anthracene derivative of hexichol amido.
Present invention also offers the preparation method of described anthracene derivative, comprise the following steps：
(a) the bromo- 10- anthracenes boric acid of 9- is subjected to Suzuki reactions, obtains 9- vinyl -10- bromine anthracenes；
(b) the 9- vinyl -10- bromines anthracene is subjected to coupling reaction, obtains 9- vinyl -10- aryl substitution anthracene.
The preparation method first passes through Suzuki reactions i.e. suzuki reaction, in palladium salt using the bromo- 10- anthracenes boric acid of 9- as raw material
Under catalysis, cross-coupling occurs for boric acid and the alkene of aryl, obtains 9- vinyl -10- bromine anthracenes；Again by being crosslinked coupling reaction,
The bromo of 10- is replaced, target product 9- vinyl -10- aryl substitution anthracene is obtained, two-step reaction is to obtain target product.
Preparation method is simple and easy to apply, and the anthracene derivative yield of synthesis is high, and raw material used are easy to purchase, prepares easy.
Preferably, in step (b), the coupling reaction is Suzuki reactions, Buchwald-Hartwig or other Pd-
Any of catalyzed coupling reaction.The crosslinking coupling reaction is classical crosslinking coupling reaction, technology maturation, it is easy to apply,
Product is stable.
Preferably, the reaction is carried out under the protection of rare gas.Rare gas includes nitrogen, helium, argon gas etc..
Rare gas is stable in properties, is reacted under the protection of rare gas, prevents other generations reacted, enters quick and high efficient reaction
OK, and obtained products collection efficiency is high.
Present invention also offers application of the described anthracene derivative in UV photocuring light-emitting materials.Described anthracene class is spread out
The biological main body luminescent material as UV photocuring light-emitting materials, it is soluble good, the features such as air-stable, it is soluble in common
Solvent such as methanol, ethanol, in acetone；The ink being made can solidify under the irradiation of UV lamp, form film, and film can be sent
Fluorescence, reaches false proof effect.
Specifically, it is mainly single by described anthracene derivative, activity the invention provides a kind of UV photocuring light-emittings material
Body, light trigger and auxiliary agent are made.The UV photocuring light-emitting materials that anthracene derivative is made with activated monomer, light trigger and auxiliary agent
Material is to have double bond in ink, anthracene compound, under UV illumination, can be reacted with light trigger etc., and then is solidified, and therefore, is made
Ink film can be solidified under the irradiation of UV lamp.Under common uv lamp, film can send fluorescence, reach false proof effect
Really.The features such as UV photocuring light-emitting films of preparation have transparent height, good film-forming property, thin coating.
In order to further enhance the synergy of each composition, the UV photocuring light-emitting material more superior to obtain performance is excellent
Selection of land, by weight, 1~5 part of anthracene derivative, 88~95 parts of activated monomer, 3~6 parts of light trigger, 1~3 part of auxiliary agent.
It is highly preferred that by weight, 2~4 parts of anthracene derivative, 85~90 parts of activated monomer, 4~5 parts of light trigger,
2~3 parts of auxiliary agent.
Preferably, the activated monomer includes ethoxyethoxyethyl acrylate (EOEOEA), 3,4- epoxy hexamethylenes
Ylmethyl -3,4 epoxycyclohexyl formic acid esters (TTA21), hexamethylene -1,2- dicarboxylic acids 2-glycidyl ester (TTA26) and 1,6-
One or more in hexanediyl ester (EM221).
Preferably, the light trigger include mixed type triaryl sulphur hexafluorophosphate TR-PAG-201 (JR-184),
1- hydroxy cyclohexylphenyls benzoylformaldoxime (JR-907), thio-phenyl-to oxygen azo-cycle acetone (JR-910), isopropyl thioxanthone and propylene
One or more in sour 2- Octyl Nitrites (PAG201).
Wherein, activated monomer can be TTA21, TTA26, EOEOEA or EM221, wherein, TTA21, TTA26 can be from Jiangsu
Tai Teer Chemical Co., Ltd.s are bought, and EOEOEA can be bought from Tianjin Tianjin proud son of heaven chemical plant factory, and EM221 can be from the chemical work in Changxing
Industry limited company buys；Light trigger can be JR-184, JR-907, JR-910 or PAG201, wherein, JR-184, JR-
907th, JR-910 can be bought from Tianjin Jiuri Chemical Co., Ltd., and cationic photoinitiator PAG201 can be from Changzhou strongly
Electronics new material Co., Ltd buys.
Preferably, the auxiliary agent is the high auxiliary agent Rad 2700 of enlightening.
The model Rad 2700 of German enlightening height production is applied to the Cross-linkable granule surface contral auxiliary agent of photocuring system, can
Improve flatness, resistance to marring, mobility, levelability and non-stick, also acted on froth breaking.
Present invention also offers the preparation method of described UV photocuring light-emitting materials, in the environment of lucifuge, by anthracene class
Derivative, activated monomer, light trigger and auxiliary agent ultrasonic agitation are mixed.Preparation method is simple and easy to apply, the ink being made
Can be excellent.
In order that preferably merged between each composition, mixing it is more homogeneous, with more excellent performance, it is preferable that
The mixing is：25-35min is stirred with rotating speed 150-250r/min.
Compared with prior art, beneficial effects of the present invention are：
(1) a kind of anthracene derivative main body luminescent material for providing of the present invention, with good stability, it is excellent that solubility is good etc.
Point, it is possible to the R substituent group different by introducing, obtains the fluorescent material of different colours, can be extensive in anti-counterfeit printing
Using.
(2) preparation method for the anthracene derivative that the present invention is provided, the material yield height of this method synthesis, former material used
Material is easy to purchase, prepares easy.
(3) application present invention also offers anthracene derivative in UV photocuring light-emitting materials, the ink being made is in UV
Film can be solidified under the irradiation of lamp, under common uv lamp, film can send fluorescence, reach false proof effect.
(4) the invention provides a kind of UV photocuring light-emittings material, mainly by described anthracene derivative, activated monomer,
Light trigger and auxiliary agent are made.The UV photocuring light-emitting materials that anthracene derivative is made with activated monomer, light trigger and auxiliary agent
That is ink, the ink being made can solidify under the irradiation of UV lamp, form film, and film can send fluorescence, reach false proof effect.
The features such as UV photocuring light-emitting films of preparation have transparent height, good film-forming property, thin coating.
(5) it is more superior to obtain performance in order to further enhance the synergy of each composition of UV photocuring light-emitting materials
UV photocuring light-emitting materials, present invention also defines the parts by weight of each composition.
(6) simple and easy to apply present invention also offers the preparation method of UV photocuring light-emitting materials, the ink performance being made is excellent
It is different.
Embodiment
Embodiment of the present invention is described in detail below in conjunction with embodiment, but those skilled in the art will
Understand, the following example is merely to illustrate the present invention, and is not construed as limiting the scope of the present invention.It is unreceipted specific in embodiment
Condition person, the condition advised according to normal condition or manufacturer is carried out.Agents useful for same or the unreceipted production firm person of instrument, are
Can be by the conventional products of commercially available acquisition.
Embodiment 1
Route of synthesis is：
Preparation process is as follows：
The first step：Under conditions of argon gas protection, with the bromo- 10- anthracenes boric acid 500mg (1.66mmoL) of 9-, 1- bromine ethene
200mg (1.87mmoL) is raw material, and tetrakis triphenylphosphine palladium 70mg (0.06mmoL) is catalyst, helps to lift reaction rate
With target compound yield；Potassium carbonate 300mg (2.2mmoL) provides alkaline environment；Add in single neck bottle；Then toluene is added
(10mL) and ethanol (4mL), toluene and ethanol provide liquid reaction system.Stir and be warming up to 90 DEG C, backflow 24 hours, filtering
Go out product, through column chromatography chromatogram or recrystallization, obtain the 9- vinyl -10- bromine anthracenes of high-purity, yield about 60%.
Second step：Under conditions of argon gas protection, by 9- vinyl -10- bromine anthracene 500mg (1.75mmoL), 4- methoxyl groups
Phenyl boric acid 301mg (2.0mmoL), tetrakis triphenylphosphine palladium 70mg (0.06mmoL), potassium carbonate 300mg (2.2mmoL) add single
In neck bottle, toluene (10mL) and ethanol (4mL), strong stirring are then added, keeping temperature is 90 DEG C, is flowed back 24 hours, filtering
Go out product, through column chromatography chromatogram or recrystallization, obtain 9- vinyl -10- (4- methoxyphenyls) anthracene (384mg) of high-purity,
Yield about 70%.
Mass spectrogram：m/z:310.14 (100.0%), 311.14 (25.1%), 312.14 (3.2%).
Embodiment 2
Route of synthesis is：
Preparation process is：
9- vinyl -10- bromine anthracenes are prepared by the method in embodiment 1；
Under conditions of argon gas protection, by 9- vinyl -10- bromine anthracene 500mg (1.75mmol), the fluorine-based diphenylamines of 4,4- bis-
415mg (2mmoL), tert-butyl group phosphine 90mg (3mmoL), palladium 90mg (0.36mmoL), cesium carbonate 400mg (1.22mmoL) add
Enter in single neck bottle, then add ortho-xylene (15mL), strong stirring, keeping temperature is 120 DEG C, flows back 48 hours, filters out
Product, through column chromatography chromatogram or recrystallization, obtains the target product (373mg) of high-purity, yield about 49%.
In mass spectrogram, m/z:431.19 (100.0%), 432.19 (33.2%), 433.20 (5.2%).
Embodiment 3
Route of synthesis is：
Preparation process is：
9- vinyl -10- bromine anthracenes are prepared by the method in embodiment 1；
Under conditions of nitrogen protection, 9- vinyl -10- bromine anthracene 500mg (1.75mmoL) are dissolved in THF (40mL) molten
Liquid, then adds n- butyl lithiums 1.4ml (2.4mmoL), and mixing is stirred 30 minutes at -78 DEG C, two (4- tolyls) are fluorinated
Boron 950mg (2mmoL) is dissolved in n- pentanes (30ml) and instilled in above-mentioned reactant, and room temperature in heating, keeping temperature is reacted 24 hours.
Reactant is poured into 100mL water, is extracted with dichloromethane, isolates product, through column chromatography chromatogram or recrystallization, obtains high-purity
Target product (365mg), yield about 52%.
In mass spectrogram, m/z:396.20 (100.0%), 397.21 (32.7%), 395.21 (24.8%), 396.21
(8.1%), 398.21 (5.2%), 397.22 (1.3%).
Embodiment 4
Route of synthesis is：
Preparation process is：
9- vinyl -10- bromine anthracenes are prepared by the method in embodiment 1；
Under nitrogen protective condition, by 9- vinyl -10- bromine anthracene 500mg (1.75mmoL), 9,9- dimethyl fluorene -2- boron
Sour 476mg (2.0mmoL), tetrakis triphenylphosphine palladium 70mg (0.06mmoL), potassium carbonate 500mg (3.6mmoL) add single neck bottle
In, toluene (15mL) and ethanol (4mL), strong stirring are then added, keeping temperature is 90 DEG C, is flowed back 24 hours, filtering is produced
Thing, through column chromatography chromatogram or recrystallization, obtains the target product (477mg) of high-purity, yield about 68%.
In mass spectrogram, m/z:396.19 (100.0%), 397.19 (33.8%), 398.19 (5.4%)
Embodiment 5
Route of synthesis is：
Preparation process is：
9- vinyl -10- bromine anthracenes are prepared by the method in embodiment 1；
Under conditions of nitrogen protection, by 9- vinyl -10- bromine anthracene 500mg (1.75mmoL), carbazole 334mg
(2mmoL), tert-butyl group phosphine 90mg (3mmoL), palladium 90mg (0.36mmoL), cesium carbonate 400mg (1.22mmoL) add list
In neck bottle, ortho-xylene (15ml), strong stirring are then added, keeping temperature is 120 DEG C, flows back 48 hours, filters out product,
Through column chromatography chromatogram or recrystallization, the target product (392mg) of high-purity, yield about 60% are obtained.
In mass spectrogram, m/z:369.15 (100.0%), 370.16 (30.5%), 371.16 (4.5%).
In addition, the anthracene class that the present invention is also prepared for other different R and R1 using the method similar from embodiment 1-4 derives
Thing, obtained anthracene derivative purity is high, and yield is also higher.Anthracene derivative prepared by embodiment 1 and embodiment 2 carries out light
Spectrum is determined, and specific data are as shown in table 1.
The spectroscopic data of table 1
As it can be seen from table 1 anthracene derivative decomposition temperature prepared by the present invention is all higher than 200 DEG C, fusing point is higher, says
It is bright that there is good heat endurance；Excitation wavelength can be seen that by adjusting different R substituent groups, can obtain different face
The fluorescent material of color, and then be conducive to preparing the false proof fluorescent ink of different colours.
Test example 1
3 parts of the anthracene derivative (75mg) that embodiment 1 is synthesized and 90 parts of monomer (2.25g), 5 parts of light trigger
2 parts of (125mg) and auxiliary agent (50mg) are mixed, EOEOEA (0.9g) that activated monomer produces for commercially available Tianjin proud son of heaven chemical plant,
The EM221 (1.35g) of Changxing Chemical Industry Co Ltd's production mixture, ratio is=2:3 (weight ratios), it is light-initiated
The JR-910 (125mg) that Tianjin Jiuri Chemical Co., Ltd. produces is selected in agent, using magnetic stirring apparatus by mixture to turn
Speed is carried out after disperseing for 30 minutes for 200r/min stirrings, obtains UV photocuring light-emitting materials.
Test example 2
By embodiment it is 2-in-1 into 2 parts of anthracene derivative (50mg) and 90 parts of monomer (2.25g), 6 parts of light trigger
27002 parts of high auxiliary agent Rad of (150mg) and enlightening (50mg) is mixed, the EOEOEA that monomer produces for commercially available Tianjin proud son of heaven chemical plant
The EM221 (1.35g) of (0.9g), Changxing Chemical Industry Co Ltd production mixture, ratio is=2:3 (weight
Than), light trigger select Tianjin Jiuri Chemical Co., Ltd. produce JR-907 (150mg), using magnetic stirring apparatus with
Rotating speed is stirred the mixture for after carrying out within 30 minutes disperseing for 200r/min, obtains UV photocuring light-emitting materials.
Test example 3
2 parts of the anthracene derivative (50mg) that embodiment 3 is synthesized and 90 parts of monomer (2.25g), 6 parts of light trigger
27002 parts of high auxiliary agent Rad of (150mg) and enlightening (50mg) is mixed, and monomer is the TTA21 of commercially available Jiangsu Tai Teer Chemical Manufactures
The EM221 (1.35g) of (0.9g), Changxing Chemical Industry Co Ltd production mixture, ratio is=2:3 (weight
Than), light trigger select Tianjin Jiuri Chemical Co., Ltd. produce JR-184 (150mg), using magnetic stirring apparatus with
Rotating speed is stirred the mixture for after carrying out within 25 minutes disperseing for 250r/min, obtains UV photocuring light-emitting materials.
Test example 4
1 part of the anthracene derivative (25mg) that embodiment 4 is synthesized and 95 parts of monomer (2.375g), 3 parts of light trigger
27001 parts of high auxiliary agent Rad of (75mg) and enlightening (25mg) is mixed, and activated monomer produces for commercially available Tianjin proud son of heaven chemical plant
EOEOEA (0.95g), the EM221 (1.425g) of Changxing Chemical Industry Co Ltd's production mixture, ratio are=2:3
(weight ratio), light trigger selects the JR-907 (37.5mg) of Tianjin Jiuri Chemical Co., Ltd.'s production, Changzhou strength electricity
The PAG201 (37.5mg) of sub- new material Co., Ltd production mixture, ratio is=1:1 (weight ratio), uses magnetic agitation
Device is stirred the mixture for by 150r/min of rotating speed after carrying out within 35 minutes disperseing, and obtains UV photocuring light-emitting materials.
Test example 5
1 part of the anthracene derivative (25mg) that embodiment 5 is synthesized and 92 parts of monomer (2.3g), 5 parts of light trigger (125mg)
With 27002 parts of high auxiliary agent Rad of enlightening (50mg) mixing, the EOEOEA that monomer produces for commercially available Tianjin proud son of heaven chemical plant
The EM221 (1.38g) of (0.92g), Changxing Chemical Industry Co Ltd production mixture, light trigger is long from Tianjin
JR-907 (62.5mg), the PAG201 of Changzhou Tronly New Electronic Materials Co., Ltd.'s production of day chemical limited company's production
The mixture of (62.5mg), ratio is=1:1 (weight ratio), is stirred mixture by 200r/min of rotating speed using magnetic stirring apparatus
Mix after carrying out within 30 minutes disperseing, obtain UV photocuring light-emitting materials.
Test example 6
5 parts of the anthracene derivative (125mg) that embodiment 5 is synthesized and 88 parts of monomer (2.2g), 6 parts of light trigger
27001 parts of high auxiliary agent Rad of (150mg) and enlightening (25mg) is mixed, the EOEOEA that monomer produces for commercially available Tianjin proud son of heaven chemical plant
The EM221 (1.32g) of (0.88g), Changxing Chemical Industry Co Ltd production mixture, ratio is=2:3 (weight
Than), JR-907 (75mg) that initiator is produced from Tianjin Jiuri Chemical Co., Ltd., Changzhou electronic strong new material has
The PAG201 (75mg) of limit company production mixture, ratio is=1:1 (weight ratio), using magnetic stirring apparatus using rotating speed as
220r/min is stirred the mixture for after carrying out within 28 minutes disperseing, and obtains UV photocuring light-emitting materials.
Test example 1-6 is produced to obtained UV photocuring light-emittings anti-fake material and carries out performance test, its performance and flexographic plate
Printing quality index is shown in Table 2.
The testing result of table 2
From table 2 it can be seen that the UV photocuring light-emittings anti-fake material i.e. UV fluorescent ink jet inks that the present invention is provided, synthesis life
Production. art is simple, and surface tension is appropriate, modest viscosity, and curing rate is very fast, excellent performance.Empirical tests, the ink being made is in UV
It can solidify under the irradiation of lamp, form film, film can send fluorescence, reach false proof effect.The UV photocuring light-emittings of preparation are thin
The features such as film has transparent height, good film-forming property, thin coating.
In addition, UV photocuring light-emitting anti-fake materials are made in other anthracene derivatives, it may have consistent effect.
Anthracene derivative yield prepared by the present invention is high, and performance is stable in atmosphere；The different R substituent by adjusting
Group, can obtain the fluorescent material of different colours, and then be conducive to preparing the false proof fluorescent ink of different colours, can apply to prevent
Pseudo- print field.In addition, the film that UV photocurings anti-fake material is prepared using the mode of UV ink-jets, in the purple that wavelength is 365nm
Under outer light irradiation, it is fully cured, the film of preparation under uviol lamp (λ=298nm) sends navy blue fluorescence.
Although illustrate and describing the present invention with specific embodiment, but it will be appreciated that without departing substantially from the present invention's
Many other changes and modification can be made in the case of spirit and scope.It is, therefore, intended that in the following claims
Including belonging to all such changes and modifications in the scope of the invention.
Claims (12)
1. for a kind of anthracene derivative in UV photocuring light-emitting materials, it is characterised in that with following structure：
Wherein, R is
Any of；
R1 is end-capping group, selected from hydrogen, fluorine, alkyl, alkoxy, aldehyde radical, amido, cyano group, C6-C30 aryl, C2-C30 it is miscellaneous
Aryl, C6-C30 aralkyl, C2-C30 heteroarylalkyl, C5-C30 aryloxy group, C2-C30 heteroaryloxy, C3-C30
Any of cycloalkyl or C2-C30 Heterocyclylalkyl；
When R isWhen, R1 is not hydrogen.
2. the preparation method of the anthracene derivative described in claim 1, it is characterised in that comprise the following steps：
(a) the bromo- 10- anthracenes boric acid of 9- is subjected to Suzuki reactions, obtains 9- vinyl -10- bromine anthracenes；
(b) the 9- vinyl -10- bromines anthracene is subjected to coupling reaction, obtains 9- vinyl -10- aryl substitution anthracene.
3. preparation method according to claim 2, it is characterised in that in step (b), the coupling reaction is Suzuki
Any of reaction, Buchwald-Hartwig or other Pd- catalyzed coupling reactions.
4. preparation method according to claim 2, it is characterised in that the reaction is entered under the protection of rare gas
OK.
5. preparation method according to claim 4, it is characterised in that the rare gas is any in argon gas, nitrogen
Kind.
6. a kind of UV photocuring light-emittings material, it is characterised in that mainly by the anthracene derivative described in claim 1, activity
Monomer, light trigger and auxiliary agent are made.
7. UV photocuring light-emittings material according to claim 6, it is characterised in that by weight, anthracene derivative 1~
5 parts, 88~95 parts of activated monomer, 3~6 parts of light trigger, 1~3 part of auxiliary agent.
8. UV photocuring light-emittings material according to claim 6, it is characterised in that the activated monomer include EOEOEA,
One or more in TTA21, TTA26 and EM221.
9. UV photocuring light-emittings material according to claim 6, it is characterised in that the light trigger include JR-184,
One or more in JR-907, JR-910 and PAG201.
10. UV photocuring light-emittings material according to claim 6, it is characterised in that the auxiliary agent is the high auxiliary agent Rad of enlightening
2700。
11. the preparation method of the UV photocuring light-emitting materials described in claim any one of 6-10, it is characterised in that in lucifuge
Under environment, anthracene derivative, activated monomer, light trigger and auxiliary agent ultrasonic agitation are mixed.
12. the preparation method of UV photocuring light-emittings material according to claim 11, it is characterised in that the mixing is：
25-35min is stirred with rotating speed 150-250r/min.
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| On the neophyl-like rearrangement of 2-(9-anthryl)ethyl radicals;Leardini, Rino 等;《Journal of the American Chemical Society》;19891231;第111卷(第20期);第7723-7732页 * |
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