CN107868034A - One kind is applied to the light trigger of UV LED lights solidification - Google Patents
One kind is applied to the light trigger of UV LED lights solidification Download PDFInfo
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- CN107868034A CN107868034A CN201610860726.1A CN201610860726A CN107868034A CN 107868034 A CN107868034 A CN 107868034A CN 201610860726 A CN201610860726 A CN 201610860726A CN 107868034 A CN107868034 A CN 107868034A
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- light trigger
- acetone
- led
- hydroxy
- methyls
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- 238000007711 solidification Methods 0.000 title description 2
- 230000008023 solidification Effects 0.000 title description 2
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 claims abstract description 12
- ZWVHTXAYIKBMEE-UHFFFAOYSA-N 2-hydroxyacetophenone Chemical class OCC(=O)C1=CC=CC=C1 ZWVHTXAYIKBMEE-UHFFFAOYSA-N 0.000 claims abstract description 6
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000002360 preparation method Methods 0.000 claims abstract description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 25
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 18
- SIMFZBAGLIDEPJ-UHFFFAOYSA-N C1(=CC=CC=C1)CC(C)=O.C(C)OOOCC Chemical compound C1(=CC=CC=C1)CC(C)=O.C(C)OOOCC SIMFZBAGLIDEPJ-UHFFFAOYSA-N 0.000 claims description 7
- 238000000016 photochemical curing Methods 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 6
- -1 Hydrogen Chemical class 0.000 claims description 4
- 239000003999 initiator Substances 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 125000002252 acyl group Chemical group 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 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 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 239000005457 ice water Substances 0.000 claims 2
- KAESVJOAVNADME-UHFFFAOYSA-N 1H-pyrrole Natural products C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 239000011230 binding agent Substances 0.000 claims 1
- 238000005516 engineering process Methods 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- 238000006243 chemical reaction Methods 0.000 description 14
- 239000002904 solvent Substances 0.000 description 14
- CSCPPACGZOOCGX-WFGJKAKNSA-N acetone d6 Chemical compound [2H]C([2H])([2H])C(=O)C([2H])([2H])[2H] CSCPPACGZOOCGX-WFGJKAKNSA-N 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- 239000012043 crude product Substances 0.000 description 10
- 238000013019 agitation Methods 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 238000001914 filtration Methods 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N hydrochloric acid Substances Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- UIIMBOGNXHQVGW-UHFFFAOYSA-M sodium bicarbonate Substances [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- 239000013067 intermediate product Substances 0.000 description 6
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 6
- 238000004587 chromatography analysis Methods 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 239000012044 organic layer Substances 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000012965 benzophenone Substances 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000001723 curing Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- MDKVPSJRUXOFFV-UHFFFAOYSA-N 2-methoxy-9h-carbazole Chemical class C1=CC=C2C3=CC=C(OC)C=C3NC2=C1 MDKVPSJRUXOFFV-UHFFFAOYSA-N 0.000 description 1
- PHKYYUQQYARDIU-UHFFFAOYSA-N 3-methyl-9h-carbazole Chemical class C1=CC=C2C3=CC(C)=CC=C3NC2=C1 PHKYYUQQYARDIU-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 239000007832 Na2SO4 Substances 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 238000003848 UV Light-Curing Methods 0.000 description 1
- SSOONFBDIYMPEU-UHFFFAOYSA-N [3-hydroxy-2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propyl] prop-2-enoate Chemical compound OCC(CO)(CO)COCC(CO)(CO)COC(=O)C=C SSOONFBDIYMPEU-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- AEVNDWITFKNVRU-UHFFFAOYSA-N anthra[2,3-b]carbazole Chemical compound C1=CC=C2C=C(C=C3C(C=C4NC=5C(C4=C3)=CC=CC=5)=C3)C3=CC2=C1 AEVNDWITFKNVRU-UHFFFAOYSA-N 0.000 description 1
- 150000003851 azoles Chemical class 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 150000001716 carbazoles Chemical class 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 229940126214 compound 3 Drugs 0.000 description 1
- 229940125898 compound 5 Drugs 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/56—Ring systems containing three or more rings
- C07D209/80—[b, c]- or [b, d]-condensed
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/56—Ring systems containing three or more rings
- C07D209/80—[b, c]- or [b, d]-condensed
- C07D209/82—Carbazoles; Hydrogenated carbazoles
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/56—Ring systems containing three or more rings
- C07D209/80—[b, c]- or [b, d]-condensed
- C07D209/82—Carbazoles; Hydrogenated carbazoles
- C07D209/86—Carbazoles; Hydrogenated carbazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/56—Ring systems containing three or more rings
- C07D209/80—[b, c]- or [b, d]-condensed
- C07D209/82—Carbazoles; Hydrogenated carbazoles
- C07D209/88—Carbazoles; Hydrogenated carbazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to carbon atoms of the ring system
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- 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
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polymerisation Methods In General (AREA)
Abstract
The invention belongs to field of light-sensitive high molecular materials.The present invention is prepared for a kind of light trigger that can be applied to UV LED light curing systems based on α hydroxy acetophenones photoinitiator, acryloyl chloride and carbazole derivates.The synthesis step of the present invention is simple, and preparation cost is low, and product has higher curing efficiency under the irradiation of UV LED light sources, contributes to the popularization and development of UV LED light curing technologies.
Description
Technical field
The invention belongs to field of light-sensitive high molecular materials, and in particular to one kind is applied to UV LED (UV-LED)
The light trigger of photocuring system and its application in curing field.
Background technology
It using the ultraviolet light-initiated liquid fast transition with chemical reactivity is solid that UV-curing technology, which is,
The process of state material.The technology has the characteristics of efficient, wide adaptability, economy, energy-conservation, environment-friendly, and it is widely used in
Plate making, stereolithography, ink, coating, adhesive, packaging for foodstuff and biomaterial for medical purpose field.
Conventional UV light sources are high-pressure sodium lamp, but the spectrum model of light that traditional uv equipment as mercury lamp is launched
Enclose wider, light source utilization rate is not high；And the service life of mercury lamp is limited and energy consumption is big；It is in addition, easy using mercury lamp for a long time
Substantial amounts of ozone is produced, is detrimental to health and ecological safety.In view of this, UV-LED be considered as it is a kind of have good prospects replace
For light source, it has the characteristics of unimodal Wavelength distribution (such as 365nm, 395nm, 405nm), can reduced caused by short UV light
Infringement, power consumption is saved, while also contribute to improve production efficiency.However, LED light source of the traditional photoinitiator in long wavelength
The lower initiation performance of irradiation is not that very well, much all can not smoothly solidify or solidification effect is bad, the reason for causing the phenomenon
It is that energy can not realize transmission well, and this also seriously limits the development and popularization of UV-LED photocuring technologies.Therefore, it is
Development of the LED light polymerization technique in photopolymerization field is preferably promoted, is efficiently drawn to having in LED light polymerization system
The research for sending out the light trigger of efficiency is very significant.
The content of the invention
The purpose of the application is to provide a kind of light trigger for being applied to UV-LED photocurings, it is characterised in that this kind of initiation
The molecular structure of agent is as follows：
Wherein, R is selected from alpha-hydroxyacetophenone structure, preferably 2- hydroxy-2-methyls-phenylacetone -1 (
1173), 1- hydroxy-cyciohexyls Benzophenone (184), 2- hydroxy-2-methyls-to ethoxy ether phenylacetone (2959)；R1Hydrogen, alkoxy, hydroxyl, halogen atom, phenyl, acyl group, carbazyl, anthryl etc. are independently chosen from respectively；
Present invention also offers the preparation method of the initiator, its general synthesis technique are as shown below：
In the preparation process of the initiator：
(a) by alpha-hydroxyacetophenone, triethylamine, by 1:1.07 mol ratio is added in reactor, and is added in right amount
Dichloromethane makees solvent, and 10min is stirred at room temperature；Then will be dissolved with acryloyl chloride under condition of ice bath (with triethylamine equimolar)
Dichloromethane solution is added dropwise in three-necked flask, and 2h is added dropwise recession and removes ice bath, continues stirring reaction 6h at room temperature.
Reaction terminates rear filtration product, respectively with deionized water, 1molL-1Hydrochloric acid and 1molL-1Sodium bicarbonate aqueous solution washs
Twice, organic layer is through anhydrous Na for filtrate2SO4After drying, filtering, it is evaporated under reduced pressure removing solvent and obtains crude product, then with ethanol weight
Crystallization, obtains intermediate product A；
(b) product A and appropriate acetone are added in reactor, 10min is stirred at room temperature, will be molten under condition of ice bath
The acetone for having carbazole derivates is added dropwise in three-necked flask, is reacted 5h, removal of solvent under reduced pressure, is obtained product；
In above-mentioned preparation process, the preferred 2- hydroxy-2-methyls-phenylacetone -1 of alpha-hydroxyacetophenone described in step a (1173), 1- hydroxy-cyciohexyls Benzophenone (184), 2- hydroxy-2-methyls-to ethoxy ether phenyl
Acetone (2959)；
In above-mentioned preparation process, the preferably following compound of carbazole derivates described in step b, but it is not limited only to followingization
Compound：
Compared with prior art, the advantage of the invention is that：
(1) synthesis step of the invention is simple, and it is low to prepare cost.
(2) compared with traditional photoinitiator, UV absorption of the invention is obviously prolonged, under the effect of UV-LED light sources, tool
There is a higher Light-Curing Efficiency, application performance is excellent.
Embodiment
The following example describes the present invention in detail, but does not limit the scope of the invention.
Synthetic example 1：
The structural formula of compound 1
(a) by 1- hydroxy-cyciohexyls Benzophenone (184) (15.33g, 0.075mol), triethylamine (8.10g,
0.08mol) and 100mL dichloromethane solutions are added to the tri- mouthfuls of burnings of 250ml for being equipped with mechanical agitation and constant pressure funnel
In bottle, 10min is stirred at room temperature.Then will be dissolved with the 60mL dichloromethanes of acryloyl chloride (7.24g, 0.08mol) under condition of ice bath
Alkane solution is added dropwise in three-necked flask, and 2h is added dropwise recession and removes ice bath, continues stirring reaction 6h at room temperature.Reaction knot
Filtration product after beam, respectively with deionized water, 1molL-1Hydrochloric acid and 1molL-1Sodium bicarbonate aqueous solution washs filtrate two
Secondary, organic layer is through anhydrous Na2SO4After drying, filtering, it is evaporated under reduced pressure and removes solvent and obtain crude product, then by the use of ethanol as molten
Agent, it is recrystallized, finally give intermediate product 184Ac.
(b) 184Ac (3.10g, 0.012mol) and 20mL acetone are added to and are equipped with magnetic agitation and constant pressure addition leakage
In the 100ml three-necked flasks of bucket, 10min is stirred at room temperature.Then will be dissolved with carbazole (2.01g, 0.012mol) under condition of ice bath
10mL acetone solns be added dropwise in three-necked flask, after about 5h, reaction reach balance, removal of solvent under reduced pressure, utilize post color
Spectrum purification crude product, obtains product 1, and carry out Structural Identification by NMR spectrum.
1HNMR(400MHz,Acetone-d6)δ(ppm):8.16-7.22(13H,aromatics),4.26-4.23
(2H,-N-CH2),2.52-2.50(2H,-CH2- C=O), 1.97-1.44 (10H, cyclohexane)
13CNMR(400MHz,Acetone-d6)δ(ppm):198.61,173.28,135.14,134.11,133.11,
128.81,128.60,122.82,121.76,121.46,119.83,109.63,88.89,55.10,35.25,32.83,
21.34,21.12,
Synthetic example 2：
The structural formula of compound 2
The 184Ac (3.10g, 0.012mol) and 20mL acetone that are synthesized in embodiment 1 are added to and are equipped with magnetic agitation
In the 100ml three-necked flasks of constant pressure funnel, 10min is stirred at room temperature.Then will be dissolved with 2- phenyl clicks under condition of ice bath
The 15mL acetone solns of azoles (2.92g, 0.012mol) are added dropwise in three-necked flask, and after about 5h, reaction reaches balance, depressurizes
Solvent is removed, using chromatography over CC crude product, obtains product 2, and Structural Identification is carried out by NMR spectrum.
1HNMR(400MHz,Acetone-d6)δ(ppm):8.40-7.14(17H,aromatics),4.25-4.23
(2H,-N-CH2),2.51-2.49(2H,-CH2- C=O), 1.97-1.43 (10H, cyclohexane)
13CNMR(400MHz,Acetone-d6)δ(ppm):198.60,173.25,141.62,140.83,137.08,
135.13,133.15,129.23,128.81,128.60,128.46,127.94,127.63,124.02,121.76,121.45,
119.83,119.34,118.94,110.17,109.93,109.61,88.89,55.10,35.25,32.83,21.34,21.12
Synthetic example 3：
The structural formula of compound 3
(a) by 2- hydroxy-2-methyls-phenylacetone -1 (1173) (16.42g, 0.10mol), triethylamine
(10.81g0.11mol) and 150mL dichloromethane solutions are added to the 500ml for being equipped with mechanical agitation and constant pressure funnel
In three-necked flask, 10min is stirred at room temperature.Then will be dissolved with acryloyl chloride (9.96g, 0.12mol) 100mL under condition of ice bath
Dichloromethane solution is added dropwise in three-necked flask, and 2h is added dropwise recession and removes ice bath, continues stirring reaction 6h at room temperature.
Reaction terminates rear filtration product, respectively with deionized water, 1molL-1Hydrochloric acid and 1molL-1Sodium bicarbonate aqueous solution washs
Twice, organic layer is through anhydrous Na for filtrate2SO4After drying, filtering, it is evaporated under reduced pressure removing solvent and obtains crude product, then made with ethanol
For solvent, it is recrystallized, finally gives intermediate product 1173Ac.
(b) 1173Ac (5.24g, 0.024mol) and 35mL acetone are added to and are equipped with magnetic agitation and constant pressure addition leakage
In the 100ml three-necked flasks of bucket, 10min is stirred at room temperature.Then under condition of ice bath will dissolved with 2- methoxyl carbazoles (4.73g,
20mL acetone 0.024mol) is added dropwise in three-necked flask, and after about 5h, reaction reaches balance, removal of solvent under reduced pressure, utilizes
Chromatography over CC crude product, product 3 is obtained, and Structural Identification is carried out by NMR spectrum.
1HNMR(400MHz,Acetone-d6)δ(ppm):8.34-6.79(12H,aromatics),4.24-4.22
(2H,-N-CH2),3.88(3H,O-CH3),2.51-2.48(2H,-CH2- C=O), 1.54 (6H ,-CH3)
13CNMR(400MHz,Acetone-d6)δ(ppm):198.60,173.15,156.53,137.58,135.13,
133.15,128.83,128.60,128.43,121.82,121.72,121.44,119.83,117.44,110.17,109.63,
109.15,99.64,55.89,55.10,35.25,21.94
Synthetic example 4：
The structural formula of compound 4
The intermediate product 1173Ac (5.24g, 0.024mol) and 35mL acetone that are synthesized in embodiment 3 are added to and be equipped with
In the 100ml three-necked flasks of magnetic agitation and constant pressure funnel, 10min is stirred at room temperature.Then under condition of ice bath by molten 3,
The 20mL acetone of 3'- connection carbazoles (3.99g, 0.012mol) is added dropwise in three-necked flask, and after about 5h, reaction reaches balance,
Removal of solvent under reduced pressure, using chromatography over CC crude product, product 4 is obtained, and Structural Identification is carried out by NMR spectrum.
1HNMR(400MHz,Acetone-d6)δ(ppm):8.18-7.32(24H,aromatics),4.24-4.23
(4H,-N-CH2),2.52-2.50(4H,-CH2- C=O), 1.53 (12H ,-CH3)
13CNMR(400MHz,Acetone-d6)δ(ppm):198.60,173.15,143.73,139.88,135.12,
133.13,128.81,128.65,128.43,125.15,121.72,121.44,119.83,119.44,116.84,111.64,
109.63,103.35,90.74,55.10,35.25,21.91
Synthetic example 5：
The structural formula of compound 5
(a) by 2- hydroxy-2-methyls-to ethoxy ether phenylacetone (2959)(22.43g,
0.10mol), triethylamine (10.81g 0.11mol) and 150mL dichloromethane solutions are added to and are equipped with mechanical agitation and perseverance
In the 500ml three-necked flasks for pressing dropping funel, 10min is stirred at room temperature.Then will be dissolved with acryloyl chloride under condition of ice bath
The 100mL dichloromethane solutions of (9.96g, 0.12mol) are added dropwise in three-necked flask, and 2h is added dropwise recession and removes ice bath,
Continue stirring reaction 6h at room temperature.Reaction terminates rear filtration product, respectively with deionized water, 1molL-1Hydrochloric acid and
1mol·L-1Twice, organic layer is through anhydrous Na for sodium bicarbonate aqueous solution washing filtrate2SO4After drying, filtering, it is evaporated under reduced pressure and removes
Solvent obtains crude product, then by the use of ethanol as solvent, it is recrystallized, finally gives intermediate product 2959Ac.
(b) 2959Ac (6.68g, 0.024mol) and 40mL acetone are added to and are equipped with magnetic agitation and constant pressure addition leakage
In the 100ml three-necked flasks of bucket, 10min is stirred at room temperature.Then under condition of ice bath will dissolved with 3- methyl carbazoles (4.34g,
20mL acetone 0.024mol) is added dropwise in three-necked flask, and after about 5h, reaction reaches balance, removal of solvent under reduced pressure, utilizes
Chromatography over CC crude product, product 5 is obtained, and Structural Identification is carried out by NMR spectrum.
1HNMR(400MHz,Acetone-d6)δ(ppm):8.35-6.98(11H,aromatics),4.45-4.41
(4H,-O-CH2-CH2-O),4.23-4.22(2H,-N-CH2-),2.52-2.50(2H,-CH2- C=O), 2.46-2.45 (3H,
Ph-CH3),1.35(6H,-CH3)
13CNMR(400MHz,Acetone-d6)δ(ppm):198.58,170.45,166.82,136.88,129.72,
129.41,128.91,128.75,128.43,128.15,126.72,123.73,121.74,121.42,119.83,109.64,
108.03,99.65,81.30,66.41,62.34,55.12,34.90,27.91,21.63
Synthetic example 6：
The structural formula of compound 6
The intermediate product 2959Ac (6.68g, 0.024mol) and 35mL acetone that are synthesized in embodiment 5 are added to and be equipped with
In the 250ml three-necked flasks of magnetic agitation and constant pressure funnel, 10min is stirred at room temperature.Then will be dissolved with condition of ice bath
The 40mL acetone of anthra [2,3-b] carbazole (7.62g, 0.024mol) is added dropwise in three-necked flask, and after about 5h, reaction reaches
Balance, removal of solvent under reduced pressure, using chromatography over CC crude product, product 6 is obtained, and structure mirror is carried out by NMR spectrum
It is fixed.
1HNMR(400MHz,Acetone-d6)δ(ppm):8.47-6.99(18H,aromatics),4.45-4.42
(4H,-O-CH2-CH2-O),4.24-4.22(2H,-N-CH2-),2.53-2.52(2H,-CH2- C=O), 1.35 (6H ,-CH3)
13CNMR(400MHz,Acetone-d6)δ(ppm):198.59,170.45,166.81,131.78,129.72,
129.41,128.41,128.15,126.71,126.55,125.61,125.23,125.35,121.74,121.42,119.83,
109.64,99.65,81.30,66.41,62.34,55.12,34.92,27.91
Comparative example 7
1st, photosensitive polymer combination is prepared
According to the specific formula in following ratio and table 1, Photosensitve resin composition is configured：
A：Acrylate copolymer (200 mass parts)
B：Dipentaerythritol acrylate (100 mass parts)
C：Light trigger (5 mass parts)
Table 1:
2nd, filming performance is tested
After above-mentioned composition lucifuge is uniformly mixed, feeding, using bar film, forms thickness in PET templates
About 15 μm of film, then irradiate (Shenzhen Lamplic Science Co., Ltd., model UVEL-ET, light intensity with UV-LED light sources
100mW/cm2) film is exposed under 395nm wavelength, time for exposure 120s, whether observe it being capable of film-forming.
Test result is as shown in table 2.
Table 2
From table 2 it can be seen that the photosensitive polymer combination containing the light trigger prepared by the present invention is in UV-LED light
It can smoothly solidify (embodiment 1-3) under the irradiation of source, this shows that the initiator of the present invention has under UV-LED photocuring systems
There is good applicability.
Claims (4)
1. one kind is applied to the light trigger of UV-LED photocurings, it is characterised in that the molecular structure of this kind of initiator is as follows：
Wherein, R is selected from alpha-hydroxyacetophenone structure, preferably 2- hydroxy-2-methyls-phenylacetone -1 (1173), 1- hydroxyls
Base-phenylcyclohexyl ketone (184), 2- hydroxy-2-methyls-to ethoxy ether phenylacetone (
2959)；R1Hydrogen, alkoxy, hydroxyl, halogen atom, phenyl, acyl group, carbazyl, anthryl etc. are independently chosen from respectively.
2. according to claim 1, a kind of light trigger for being applied to UV-LED photocurings, it is characterised in that its general conjunction
It is as shown below into technique.
3. according to claim 2, it is characterised in that the preparation process of the light trigger comprises the following steps：
(1) in step a, under ice-water bath, the dichloromethane that acryloyl chloride is added drop-wise to alpha-hydroxyacetophenone photoinitiator is molten
In liquid, wherein doing acid binding agent using triethylamine；
(2) in step b, the product prepared by step a and carbazole derivates are mixed under ice-water bath, react 5~12h.
4. according to claim 2,3, it is characterised in that it is characterized in that the carbazole derivates described in step b are preferably following
Compound, but it is not limited only to following compound.
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