CN113024691A - Low-migration carbazolyl acylphosphine photoinitiator and synthesis method thereof - Google Patents
Low-migration carbazolyl acylphosphine photoinitiator and synthesis method thereof Download PDFInfo
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- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 title claims abstract description 32
- 238000013508 migration Methods 0.000 title claims abstract description 25
- 238000001308 synthesis method Methods 0.000 title abstract description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims abstract description 78
- -1 N-substituted carbazole Chemical class 0.000 claims abstract description 19
- YFPJFKYCVYXDJK-UHFFFAOYSA-N Diphenylphosphine oxide Chemical compound C=1C=CC=CC=1[P+](=O)C1=CC=CC=C1 YFPJFKYCVYXDJK-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000006170 formylation reaction Methods 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims description 34
- 150000001875 compounds Chemical class 0.000 claims description 33
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims description 26
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 239000007800 oxidant agent Substances 0.000 claims description 15
- 230000001590 oxidative effect Effects 0.000 claims description 15
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 claims description 10
- JRNVZBWKYDBUCA-UHFFFAOYSA-N N-chlorosuccinimide Chemical compound ClN1C(=O)CCC1=O JRNVZBWKYDBUCA-UHFFFAOYSA-N 0.000 claims description 10
- 230000002194 synthesizing effect Effects 0.000 claims description 9
- 229910052801 chlorine Inorganic materials 0.000 claims description 8
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 8
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 8
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 7
- 239000000460 chlorine Substances 0.000 claims description 7
- NKLCNNUWBJBICK-UHFFFAOYSA-N dess–martin periodinane Chemical compound C1=CC=C2I(OC(=O)C)(OC(C)=O)(OC(C)=O)OC(=O)C2=C1 NKLCNNUWBJBICK-UHFFFAOYSA-N 0.000 claims description 7
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 5
- 238000006646 Dess-Martin oxidation reaction Methods 0.000 claims description 5
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 5
- 229910052794 bromium Inorganic materials 0.000 claims description 5
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 4
- 239000003999 initiator Substances 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- 230000000977 initiatory effect Effects 0.000 abstract description 5
- 238000005935 nucleophilic addition reaction Methods 0.000 abstract description 5
- 230000003647 oxidation Effects 0.000 abstract description 5
- 238000007254 oxidation reaction Methods 0.000 abstract description 5
- 230000026030 halogenation Effects 0.000 abstract description 4
- 238000005658 halogenation reaction Methods 0.000 abstract description 4
- 125000003172 aldehyde group Chemical group 0.000 abstract description 2
- 230000022244 formylation Effects 0.000 abstract description 2
- 239000013067 intermediate product Substances 0.000 abstract description 2
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 21
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 21
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 18
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 18
- 238000005160 1H NMR spectroscopy Methods 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 description 7
- 238000004679 31P NMR spectroscopy Methods 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000012074 organic phase Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- QGJXVBICNCIWEL-UHFFFAOYSA-N 9-ethylcarbazole-3-carbaldehyde Chemical compound O=CC1=CC=C2N(CC)C3=CC=CC=C3C2=C1 QGJXVBICNCIWEL-UHFFFAOYSA-N 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 4
- 229910052753 mercury Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000002835 absorbance Methods 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 239000012065 filter cake Substances 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 238000000016 photochemical curing Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- AHDFNBLZEFXYOG-UHFFFAOYSA-N 6-bromo-9-ethylcarbazole-3-carbaldehyde Chemical compound O=CC1=CC=C2N(CC)C3=CC=C(Br)C=C3C2=C1 AHDFNBLZEFXYOG-UHFFFAOYSA-N 0.000 description 2
- NREGAMUYOIJUQQ-UHFFFAOYSA-N 6-chloro-9-ethylcarbazole-3-carbaldehyde Chemical compound O=CC1=CC=C2N(CC)C3=CC=C(Cl)C=C3C2=C1 NREGAMUYOIJUQQ-UHFFFAOYSA-N 0.000 description 2
- PLAZXGNBGZYJSA-UHFFFAOYSA-N 9-ethylcarbazole Chemical compound C1=CC=C2N(CC)C3=CC=CC=C3C2=C1 PLAZXGNBGZYJSA-UHFFFAOYSA-N 0.000 description 2
- 230000005526 G1 to G0 transition Effects 0.000 description 2
- 238000005654 Michaelis-Arbuzov synthesis reaction Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 2
- 230000008033 biological extinction Effects 0.000 description 2
- 125000001246 bromo group Chemical group Br* 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 238000001723 curing Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000005911 haloform reaction Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- OQVOIJIQWMJKJY-UHFFFAOYSA-N 1,2-dichloroethane;n,n-dimethylformamide Chemical compound ClCCCl.CN(C)C=O OQVOIJIQWMJKJY-UHFFFAOYSA-N 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 1
- 230000000397 acetylating effect Effects 0.000 description 1
- 230000021736 acetylation Effects 0.000 description 1
- 238000006640 acetylation reaction Methods 0.000 description 1
- 150000001263 acyl chlorides Chemical class 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- VMUAFIWZWXGPGP-UHFFFAOYSA-N butoxy(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(OCCCC)C1=CC=CC=C1 VMUAFIWZWXGPGP-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- RLOWWWKZYUNIDI-UHFFFAOYSA-N phosphinic chloride Chemical compound ClP=O RLOWWWKZYUNIDI-UHFFFAOYSA-N 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
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Classifications
-
- 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
-
- 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
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom
- C07F9/572—Five-membered rings
- C07F9/5728—Five-membered rings condensed with carbocyclic rings or carbocyclic ring systems
Abstract
The invention discloses a low-migration carbazolyl acylphosphine photoinitiator and a synthesis method thereof. The structure of the photoinitiator is as shown in the formula (I)]As shown. According to the method, an aldehyde group is introduced into an N-substituted carbazole molecule through Vilsmeier formylation, and after halogenation, nucleophilic addition is carried out on diphenyl phosphine oxide in ethyl acetate to directly filter to obtain an intermediate product, and finally oxidation is carried out to obtain the photoinitiator with high yield. The photoinitiator disclosed by the invention has the advantages of high initiation efficiency, low mobility and the like, is suitable for a UV-LED light source, and has good industrial application value.
Description
Technical Field
The invention belongs to the field of UV-LED photocuring, and particularly relates to a low-migration carbazolyl acylphosphine photoinitiator and a synthesis method thereof.
Background
Most photoinitiators have high initiation efficiency only in a proper wavelength range, while high-pressure mercury lamps which are traditionally used in the field of photocuring have dispersed emission spectral distribution, and some wavelengths cannot initiate the photoinitiators, so that the utilization efficiency is low. And the high-pressure mercury lamp has the defects of high power consumption, large heat productivity, mercury pollution and the like, and is not in accordance with environmental protection and green economy. Therefore, the UV-LED light source with concentrated emission spectrum, high luminous efficiency and low energy consumption replaces a high-pressure mercury lamp, which is the future development direction of the industry. Acylphosphine-type photoinitiators may be well-suited for use in UV-LED light sources, but commercial acylphosphine photoinitiators (e.g., "TPO") have high mobility, which may limit the use of acylphosphine photoinitiators in dentistry, food, and the like. And carbazolyl is introduced into the molecule as a chromophore, so that the molecule not only can bring an absorption peak with a proper wavelength but also can have a higher molar extinction coefficient under a normal condition, and therefore, higher absorbance is obtained. Finally, a higher initiation efficiency can be obtained. In addition, the introduction of carbazolyl in the molecule can greatly improve the molecular weight of the photoinitiator, and is greatly helpful for reducing the mobility.
The prior art methods for partially synthesizing acylphosphorus compounds are exemplified by: CN 102863559A is prepared by acetylating aromatic ring, introducing acetyl, then performing haloform reaction to convert acetyl into carboxyl, converting carboxyl into acyl chloride by thionyl chloride, and finally performing Arbuzov reaction with diphenyl butoxy phosphine to generate acyl phosphine. The steps are complicated. The conditions of the steps of acetylation and acyl chlorination are strict and strict without water; haloform reaction and Arbuzov reaction can generate a large amount of harmful halogenated substances, and the pollution is serious and the atom utilization rate is low.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide a low-migration carbazolyl acylphosphine photoinitiator and a synthesis method thereof.
The purpose of the invention is realized by at least one of the following technical solutions.
The structure of the low-migration carbazolyl acylphosphine photoinitiator provided by the invention is shown as the following formula (I):
wherein R is1One selected from C1-18 alkyl, benzyl, and p-methoxybenzyl; r2Is selected from one of hydrogen, chlorine and bromine.
The invention provides a low-migration carbazolyl acylphosphine photoinitiator, which has a structural formula as follows:
the synthesis method of the low-migration carbazolyl acylphosphine photoinitiator provided by the invention is characterized in that when R is2When selected from hydrogen, the reaction equation is as follows:
the invention provides a synthesis method of a low-migration carbazolyl acylphosphine photoinitiator, which comprises the following steps:
(1) adding a compound [ II ], N-Dimethylformamide (DMF) and phosphorus oxychloride into a solvent to perform Vilsmeier formylation reaction to generate N-substituted carbazole formaldehyde shown as a structural formula [ III ];
(2) under the condition of taking ethyl acetate as a solvent, reacting N-substituted carbazole formaldehyde shown as a structural formula [ III ] with diphenylphosphine oxide to generate a compound [ V ];
(3) oxidizing the compound [ V ] with an oxidizing agent to produce a photoinitiator represented by the formula [ I ].
Further, the solvent in the step (1) is one of 1, 2-dichloroethane and chlorobenzene; the molar ratio of the compound [ II ] to the N, N-dimethylformamide is 1: 1.0-1.1;
further, the mol ratio of the compound [ II ] in the step (1) to the phosphorus oxychloride is 1:1.0-1.1
Further, the molar volume ratio of the compound [ II ] in the step (1) to the solvent is 0.59-0.6 mol/L;
further, in the step (1), when the phosphorus oxychloride is added into the solvent, the temperature of the solvent is 0-5 ℃;
further, the temperature of Vilsmeier formylation reaction is 80-90 ℃, and the time of Vilsmeier formylation reaction is 10-12 h.
Preferably, the reaction temperature is controlled to be 0 ℃ when the phosphorus oxychloride is dripped in the step (1), and the temperature is increased and controlled to be 80-90 ℃ after the dripping is finished.
Further, the molar ratio of the N-substituted carbazole formaldehyde to the diphenylphosphine oxide in the step (2) is 1: 1.2-1.4.
Further, the concentration of the diphenylphosphine oxide in the ethyl acetate in the step (2) is 0.18-0.2 mol/L.
Further, the reaction time of the step (2) is 10-12h, and the reaction temperature is room temperature.
Further, the oxidant in the step (3) is one of dess-Martin oxidant (CAS:87413-09-0) and active manganese dioxide.
The synthesis method of the low-migration carbazolyl acylphosphine photoinitiator provided by the invention is characterized in that when R is2When chlorine or bromine is selected, the reaction equation is as follows:
the invention provides a synthesis method of a low-migration carbazolyl acylphosphine photoinitiator, which comprises the following steps:
(1) adding a compound [ II ], N-dimethylformamide and phosphorus oxychloride into a solvent to perform Vilsmeier formylation reaction to generate N-substituted carbazole formaldehyde shown as a structural formula [ III ];
(2) reacting the N-substituted carbazole formaldehyde in the step (1) with N-bromosuccinimide or N-chlorosuccinimide to generate a compound [ IV ];
(3) under the condition of taking ethyl acetate as a solvent, reacting the compound [ IV ] with diphenylphosphine oxide to generate a compound [ V ];
(4) oxidizing the compound [ V ] with an oxidizing agent to produce a photoinitiator represented by the formula [ I ].
Further, the solvent in the step (1) is one of 1, 2-dichloroethane and chlorobenzene; the molar ratio of the compound [ II ] to the N, N-dimethylformamide is 1: 1.0-1.1;
further, the molar ratio of the compound [ II ] in the step (1) to the phosphorus oxychloride is 1: 1.0-1.1;
further, the molar volume ratio of the compound [ II ] in the step (1) to the solvent is 0.59-0.6 mol/L;
further, in the step (1), when the phosphorus oxychloride is added into the solvent, the temperature of the solvent is 0-5 ℃;
further, the temperature of Vilsmeier formylation reaction is 80-90 ℃, and the time of Vilsmeier formylation reaction is 10-12 h.
Further, the molar ratio of the N-substituted carbazole formaldehyde to the N-bromosuccinimide in the step (2) is 1: 1.0-1.2;
further, the molar ratio of the N-substituted carbazole formaldehyde to the N-chlorosuccinimide in the step (2) is 1: 1.0-1.2;
further, the reaction temperature in the step (2) is room temperature, and the reaction time is 12-18 h;
further, the molar ratio of the compound [ IV ] in the step (3) to the diphenylphosphine oxide is 1: 1.1-1.2;
further, the temperature of the reaction in the step (3) is room temperature;
further, the reaction time of the step (3) is 10-12 h;
further, the concentration of the compound [ IV ] in the ethyl acetate in the step (3) is 0.19-0.21 mol/L;
further, the oxidant in the step (4) is one of dess-Martin oxidant (CAS:87413-09-0) and active manganese dioxide.
Preferably, the reaction of step (2) is carried out in a solvent which is DMF or acetonitrile.
In the step (3), ethyl acetate is used as a solvent, so that the generated product can be precipitated and purified by filtering and washing with ethyl acetate.
The invention introduces chlorine or bromine atoms into molecules, can improve the initiation efficiency, increase the solubility of the initiator in the monomer and reduce the mobility.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the synthesis method provided by the invention introduces aldehyde group into N-substituted carbazole molecule by Vilsmeier formylation, after halogenation, nucleophilic addition is carried out on diphenyl phosphine oxide in ethyl acetate to directly filter to obtain intermediate product, and finally oxidation is carried out to obtain the photoinitiator with high yield.
(2) The photoinitiator provided by the invention has the advantages of high initiation efficiency, low mobility and the like, is suitable for a UV-LED light source, and has good industrial application value.
Drawings
FIG. 1 is a UV-VIS absorption spectrum of a photoinitiator prepared according to examples 1,2 and 3 of the present invention and TPO in acetonitrile;
FIG. 2 is a graph of the photocuring conversion of the photoinitiator prepared in examples 1,2 and 3 of the present invention and TPO in trimethylolpropane triacrylate (TMPTA) versus time.
Detailed Description
The following examples are presented to further illustrate the practice of the invention, but the practice and protection of the invention is not limited thereto. It is noted that the processes described below, if not specifically described in detail, are all realizable or understandable by those skilled in the art with reference to the prior art. The reagents or apparatus used are not indicated to the manufacturer, and are considered to be conventional products available by commercial purchase.
Example 1: preparation of low-migration carbazolyl acylphosphine photoinitiator P1
a. Vilsmeier formylation reaction of N-ethyl carbazole
N-Ethylcarbazole (10.5g,0.054mol) was dissolved in 32mL of 1, 2-dichloroethaneDMF (4.13mL, 0.054mol) was added and stirred, cooled to 0 ℃ and POCl was added dropwise3(5.0mL,0.054mol), stirring for 5min after the dropwise addition is finished, heating the oil bath to 85 ℃ for reflux, adding 15 wt% sodium hydroxide aqueous solution under the ice bath after 12h until the pH value is 7-8, extracting with ethyl acetate for 3 times, combining organic phases, washing with saturated salt solution once, drying with anhydrous sodium sulfate, removing a large amount of solvent by reduced pressure distillation, and recrystallizing with petroleum ether to obtain 11.1g of white solid 9-ethyl carbazole-3-formaldehyde with the yield of 92.5%.1H NMR(500MHz,CDCl3)δ10.09(s,1H),8.61(s,1H),8.16(d,J＝7.8Hz,1H),8.01(d,J＝8.5Hz,1H),7.54(t,J＝7.7Hz,1H),7.47(dd,J＝7.8,6.5Hz,2H),7.33(t,J＝7.4Hz,1H),4.41(q,J＝7.2Hz,2H),1.47(t,J＝7.3Hz,3H).
b. Nucleophilic addition
9-Ethylcarbazole-3-carbaldehyde (11.1g,50mmol) and diphenylphosphine oxide (13.1g,65mmol) were dissolved in 250mL of ethyl acetate, stirred for 12h, filtered, the filter cake was washed 3 times with ethyl acetate and dried to give 14.88g of a white solid (intermediate), yield: 70 percent.1H NMR(500MHz,DMSO)δ8.00(s,1H),7.95(d,J＝7.7Hz,1H),7.87(dd,J＝18.0,9.7Hz,4H),7.59–7.39(m,9H),7.35(d,J＝8.5Hz,1H),7.17(t,J＝7.4Hz,1H),6.52(dd,J＝18.3,5.6Hz,1H),5.78(dd,J＝12.4,6.9Hz,1H),4.37(q,J＝6.8Hz,2H),1.26(t,J＝7.0Hz,3H).31PNMR(202MHz,DMSO)δ27.57(s).HRMS(m/z):(APCI)calcd.for C27H25NO2P[M+H]+:426.1623，found 426.1617.
c. Oxidation by oxygen
Dissolving the intermediate (10.59g,25mmol) obtained in the step b in 250mL of dichloromethane, adding Daisy-Martin oxidant (11.67g, 27.5mmol), stirring for 1h, adding saturated sodium bicarbonate aqueous solution until the pH value is 7-8, extracting the water phase for 3 times by dichloromethane, combining the organic phases, washing once by saturated saline solution, drying by anhydrous sodium sulfate, distilling under reduced pressure to remove the solvent, recrystallizing by ethyl acetate to obtain the low-migration carbazolyl acylphosphine photoinitiator P110.36g with the yield of 98%, wherein the low-migration carbazolyl acylphosphine photoinitiator P1 is a yellow solid.1H NMR(500MHz,CDCl3)δ9.50(d,J＝1.1Hz,1H),8.69(dd,J＝8.8,1.3Hz,1H),8.19(d,J＝7.7Hz,1H),8.02–7.88(m,4H),7.59–7.45(m,7H),7.44–7.39(m,2H),7.31(t,J＝7.4Hz,1H),4.36(q,J＝7.2Hz,2H),1.43(t,J＝7.2Hz,3H).31P NMR(202MHz,CDCl3)δ22.59,22.54,22.48.HRMS(m/z):(APCI)calcd.for C27H23NO2P[M+H]+:424.1466，found 424.1460.
Example 2: preparation of low-migration carbazolyl acylphosphine photoinitiator P2
a. Halogenation
9-Ethylcarbazole-3-carbaldehyde (11.1g,50mmol) was dissolved in 170mL acetonitrile, N-chlorosuccinimide (7.34g,55mmol) was added, the reaction was monitored by TLC, after 18h the reaction was complete, and the bulk of the solvent was removed by distillation under reduced pressure, as a mixture of petroleum ether: taking ethyl acetate as a mobile phase and 200-mesh 300-mesh silica gel as a stationary phase to perform column chromatography to obtain 10.3g of white solid 6-chloro-9-ethylcarbazole-3-formaldehyde with the yield of 80 percent.1HNMR(500MHz,CDCl3)δ10.07(s,1H),8.50(d,J＝1.2Hz,1H),8.06(d,J＝2.0Hz,1H),8.01(dd,J＝8.5,1.5Hz,1H),7.49–7.41(m,2H),7.35(d,J＝8.7Hz,1H),4.35(q,J＝7.3Hz,2H),1.44(t,J＝7.3Hz,3H).HRMS(m/z):(APCI)calcd.for C15H13ClNO[M+H]+:258.0686，found 258.0680.
b. Nucleophilic addition
6-chloro-9-ethylcarbazole-3-carbaldehyde (9.9g,38.4mmol) and diphenylphosphine oxide (8.54g,42.3mmol) were dissolved in 200mL of ethyl acetate, stirred for 12h, filtered, the filter cake was washed 3 times with ethyl acetate, dried to give 13.5g of a white solid (intermediate), yield: 76 percent.1H NMR(500MHz,DMSO)δ8.06–8.00(m,1H),7.91–7.81(m,2H),7.66–7.34(m,5H),6.53(dd,J＝18.4,5.6Hz,1H),5.78–5.73(m,1H),4.39(q,J＝7.0Hz,1H),1.26(t,J＝7.1Hz,2H).31P NMR(202MHz,DMSO)δ27.46(s).HRMS(m/z):(APCI)calcd.forC27H24ClNO2P[M+H]+:460.1233，found 460.1229.
c. Oxidation by oxygen
Dissolving the intermediate (10.0g,21.74mmol) obtained in b in 400mL dichloromethane, adding dess-Martin oxidant (10.1g, 23.92mmol), stirring for 1h, adding saturated aqueous sodium bicarbonate solution until pH is 7-8, extracting the aqueous phase with dichloromethane 3 times, combining the organic phasesWashing the obtained product once by using saturated saline solution, drying the obtained product by using anhydrous sodium sulfate, removing the solvent by reduced pressure distillation, and recrystallizing the obtained product by using ethyl acetate to obtain the low-migration carbazolyl acylphosphine photoinitiator P29.02g with the yield of 90%, wherein the low-migration carbazolyl acylphosphine photoinitiator P2 is a light yellow solid.1H NMR(500MHz,CDCl3)δ9.50(d,J＝1.2Hz,1H),8.61(dd,J＝8.8,1.3Hz,1H),8.12(d,J＝2.0Hz,1H),8.00–7.92(m,4H),7.58–7.46(m,6H),7.40(dd,J＝8.6,2.0Hz,1H),7.35(d,J＝8.8Hz,1H),7.26(d,J＝4.2Hz,1H),4.27(q,J＝7.2Hz,2H),1.37(t,J＝7.2Hz,3H).31P NMR(202MHz,CDCl3)δ22.44(s).HRMS(m/z):(APCI)calcd.forC27H22ClNO2P[M+H]+:458.1077，found 458.1071.
Example 3: preparation of low-migration carbazolyl acylphosphine photoinitiator P3
a. Halogenation
Dissolving 9-ethylcarbazole-3-carbaldehyde (10.0g,43.8mmol) in 270mL of acetonitrile, adding N-bromosuccinimide (8.58g,48.2mmol), monitoring the reaction by TLC, after 12 hours the reaction is complete, adding saturated common salt solution 200mL, extracting 3 times with ethyl acetate, combining the organic phases, washing the organic phase 3 times with saturated common salt solution, drying with anhydrous sodium sulfate, distilling under reduced pressure to remove a large amount of solvent, and removing the solvent with petroleum ether: and (3) performing column chromatography by taking ethyl acetate as a mobile phase and 200-mesh 300-mesh silica gel as a stationary phase, wherein the ethyl acetate is 10:1-5:1(V/V), so as to obtain 12.66g of white solid 6-bromo-9-ethylcarbazole-3-formaldehyde with the yield of 96%.1H NMR(500MHz,CDCl3)δ10.09(s,1H),8.55(s,1H),8.27(s,1H),8.04(d,J＝8.5Hz,1H),7.62(d,J＝8.6Hz,1H),7.49(d,J＝8.5Hz,1H),7.34(d,J＝8.6Hz,1H),4.39(q,J＝7.3Hz,2H),1.46(t,J＝7.3Hz,3H).HRMS(m/z):(APCI)calcd.forC15H13BrNO[M+H]+:302.0181，found 302.0175.
b. Nucleophilic addition
6-bromo-9-ethylcarbazole-3-carbaldehyde (4.86g,16.1mmol) and diphenylphosphine oxide (3.58g,17.7mmol) were dissolved in 80mL of ethyl acetate, stirred for 12h, filtered, the filter cake was washed 3 times with ethyl acetate, dried to give 6.52g of a white solid (intermediate), yield: 72 percent.1H NMR(500MHz,DMSO)δ8.16(s,1H),8.05(s,1H),7.87(dd,J＝17.3,7.1Hz,4H),7.59–7.43(m,9H),7.38(d,J＝8.5Hz,1H),6.56(dd,J＝18.4,5.6Hz,1H),5.76(t,J＝5.8Hz,1H),4.37(q,J＝7.0Hz,2H),1.24(t,J＝7.1Hz,3H).31P NMR(202MHz,DMSO)δ27.44(s).HRMS(m/z):(APCI)calcd.forC27H24BrNO2P[M+H]+:504.0728，found 504.0723.
c. Oxidation by oxygen
Dissolving the intermediate (6.48g,12.85mmol) obtained in the step b in 260mL of dichloromethane, adding Daisy-Martin oxidant (6.00g, 14.1mmol), stirring for 1h, adding saturated sodium bicarbonate aqueous solution until the pH value is 7-8, extracting the water phase with dichloromethane for 3 times, combining organic phases, washing with saturated saline solution once, drying with anhydrous sodium sulfate, distilling under reduced pressure to remove the solvent, recrystallizing with ethyl acetate, namely dichloromethane 1:1(V/V), to obtain the low-migration carbazolyl acylphosphine photoinitiator P35.91g, the yield is 91%, and the low-migration carbazolyl acylphosphine photoinitiator P3 is a yellow solid.1H NMR(500MHz,CDCl3)δ9.52(s,1H),8.64(dd,J＝8.8,1.2Hz,1H),8.32(d,J＝1.8Hz,1H),8.02–7.89(m,4H),7.62–7.54(m,3H),7.50(ddd,J＝7.2,5.4,2.4Hz,4H),7.42(d,J＝8.8Hz,1H),7.31(d,J＝8.6Hz,1H),4.35(q,J＝7.2Hz,2H),1.43(t,J＝7.2Hz,3H).31P NMR(202MHz,CDCl3)δ22.49(s).HRMS(m/z):(APCI)calcd.forC27H22BrNO2P[M+H]+:502.0572，found 502.0566.
Example 4: test for light absorption Properties
The absorbance test was carried out on 0.07mM of photoinitiators P1, P2, P3 and 1.5mM of TPO (2,4, 6-trimethylbenzoyldiphenylphosphine oxide) using acetonitrile as a solvent using an ultraviolet-visible spectrophotometer to obtain FIG. 1, in which the maximum absorption wavelengths of photoinitiators P1, P2 and P3 are 366nm, 363nm and 364nm, respectively, as shown in FIG. 1.
Example 5: test of photocurability
Respectively adding 1 wt% of photoinitiators P1, P2, P3 and TPO into TMPTA (trimethylolpropane triacrylate), respectively dripping onto dry potassium bromide salt sheet, attaching a layer of polyvinyl chloride film to prevent oxygen inhibition, testing real-time infrared, turning on an LED lamp with a wavelength of 395nm at 10s, and controlling the light intensity to be 30mW/cm2. Can be used for1635cm-1The conversion was calculated from the data of the peak area of the double bond with time using the following formula:
wherein A isc＝c,tIs t s time 1635cm-1Area of double bond peak, Ac＝c,0Is initially 1635cm-1Peak area of double bond.
As shown in FIG. 2, when the lamp was turned on for 3 seconds, the curing proceeded rapidly, and the photoinitiators P1, P2, and P3 reached high conversions of 59%, 54%, and 43%, respectively, which were higher than 40% conversion of commercially available TPO. As shown in FIG. 2, the introduction of chlorine and bromine atoms into the molecule can lead to a significant increase in conversion.
Example 6: migration test
The TMPTA solution of example 5 was irradiated with an LED light source having a wavelength of 395nm for 5min under a nitrogen atmosphere to ensure complete curing, 100mg of the cured film was weighed and ground, and then put into 2mL of acetonitrile to be stirred for 96h, insoluble substances were removed by filtration, the volume was adjusted to 10mL with acetonitrile, and the absorbance A was measured. Migration mass was calculated using the formula:
wherein M isrIs the molar mass of the photoinitiator,. epsilon.is the molar extinction coefficient of the photoinitiator, l is the cuvette length (1cm), m0Is the cured film quality.
The mobility of each photoinitiator is shown in table 1. As shown in table 1, the introduction of chlorine and bromine into the molecule can reduce the mobility of the initiator, and particularly, the introduction of chlorine atom can significantly reduce the mobility.
TABLE 1
The above examples are only preferred embodiments of the present invention, which are intended to be illustrative and not limiting, and those skilled in the art should understand that they can make various changes, substitutions and alterations without departing from the spirit and scope of the invention.
Claims (10)
1. A low-migration carbazolyl acylphosphine photoinitiator is characterized in that the structure is shown as the following formula [ I ]:
wherein R is1One selected from C1-18 alkyl, benzyl, and p-methoxybenzyl; r2Is selected from one of hydrogen, chlorine and bromine.
2. The low-mobility carbazolyl acylphosphine photoinitiator according to claim 1, wherein the initiator has the formula of one of the following structures:
3. a method for synthesizing the low-migration carbazolyl acylphosphine photoinitiator according to any one of claims 1 to 2, wherein R is2When selected from hydrogen, the reaction equation is as follows:
4. the method for synthesizing the low-mobility carbazolyl acylphosphine photoinitiator according to claim 3, comprising the steps of:
(1) adding a compound [ II ], N-dimethylformamide and phosphorus oxychloride into a solvent to perform Vilsmeier formylation reaction to generate N-substituted carbazole formaldehyde shown as a structural formula [ III ];
(2) under the condition of taking ethyl acetate as a solvent, reacting N-substituted carbazole formaldehyde shown as a structural formula [ III ] with diphenylphosphine oxide to generate a compound [ V ];
(3) oxidizing the compound [ V ] with an oxidizing agent to produce a photoinitiator represented by the formula [ I ].
5. The method for synthesizing the low-mobility carbazolyl acylphosphine photoinitiator according to claim 4, wherein the solvent in the step (1) is one of 1, 2-dichloroethane and chlorobenzene; the molar ratio of the compound [ II ] to the N, N-dimethylformamide is 1: 1.0-1.1; the molar ratio of the compound [ II ] to the phosphorus oxychloride is 1: 1.0-1.1; the molar volume ratio of the compound [ II ] to the solvent is 0.59-0.6 mol/L; in the step (1), when the phosphorus oxychloride is added into the solvent, the temperature of the solvent is 0-5 ℃; the temperature of the Vilsmeier formylation reaction is 80-90 ℃, and the Vilsmeier formylation reaction time is 10-12 h.
6. The method for synthesizing the low-mobility carbazolyl acylphosphine photoinitiator according to claim 4, wherein the molar ratio of the N-substituted carbazolyl formaldehyde to the diphenylphosphine oxide in the step (2) is 1: 1.2-1.4; the concentration of the diphenylphosphine oxide in the ethyl acetate in the step (2) is 0.18-0.2 mol/L; the reaction time in the step (2) is 10-12 h; and (3) the oxidant is one of dess-martin oxidant and active manganese dioxide.
7. A method for synthesizing the low-migration carbazolyl acylphosphine photoinitiator according to any one of claims 1 to 2, wherein R is2When chlorine or bromine is selected, the reaction equation is as follows:
8. the method for synthesizing the low-mobility carbazolyl acylphosphine photoinitiator according to claim 7, comprising the steps of:
(1) adding a compound [ II ], N-dimethylformamide and phosphorus oxychloride into a solvent to perform Vilsmeier formylation reaction to generate N-substituted carbazole formaldehyde shown as a structural formula [ III ];
(2) reacting the N-substituted carbazole formaldehyde in the step (1) with N-bromosuccinimide or N-chlorosuccinimide to generate a compound [ IV ];
(3) under the condition of taking ethyl acetate as a solvent, reacting the compound [ IV ] with diphenylphosphine oxide to generate a compound [ V ];
(4) oxidizing the compound [ V ] with an oxidizing agent to produce a photoinitiator represented by the formula [ I ].
9. The method for synthesizing the low-mobility carbazolyl acylphosphine photoinitiator according to claim 8, wherein the solvent in the step (1) is one of 1, 2-dichloroethane and chlorobenzene; the molar ratio of the compound [ II ] to the N, N-dimethylformamide is 1: 1.0-1.1; the molar ratio of the compound [ II ] to the phosphorus oxychloride is 1: 1.0-1.1; the molar volume ratio of the compound [ II ] to the solvent is 0.59-0.6: 1 mol/L; in the step (1), when the phosphorus oxychloride is added into the solvent, the temperature of the solvent is 0-5 ℃; the temperature of the Vilsmeier formylation reaction is 80-90 ℃, and the Vilsmeier formylation reaction time is 10-12 h.
10. The method for synthesizing the low-mobility carbazolyl acylphosphine photoinitiator according to claim 8, wherein the molar ratio of the N-substituted carbazole formaldehyde to the N-bromosuccinimide in the step (2) is 1: 1.0-1.2; the molar ratio of the N-substituted carbazole formaldehyde to the N-chlorosuccinimide in the step (2) is 1:1.0-1.2, and the reaction time in the step (2) is 12-18 h; the molar ratio of the compound [ IV ] in the step (3) to diphenylphosphine oxide is 1: 1.1-1.2; the reaction time in the step (3) is 10-12 h; the concentration of the compound [ IV ] in the ethyl acetate in the step (3) is 0.19-0.21 mol/L; and (4) the oxidant is one of dess-martin oxidant and active manganese dioxide.
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