CN117624235A - Preparation method of photoinitiator bis (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide - Google Patents
Preparation method of photoinitiator bis (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide Download PDFInfo
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- CN117624235A CN117624235A CN202311548097.5A CN202311548097A CN117624235A CN 117624235 A CN117624235 A CN 117624235A CN 202311548097 A CN202311548097 A CN 202311548097A CN 117624235 A CN117624235 A CN 117624235A
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- trimethylbenzoyl
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- phenylphosphine
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- phenylphosphine oxide
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- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- GUCYFKSBFREPBC-UHFFFAOYSA-N [phenyl-(2,4,6-trimethylbenzoyl)phosphoryl]-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C(=O)C1=C(C)C=C(C)C=C1C GUCYFKSBFREPBC-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 111
- -1 aldehyde compounds Chemical class 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 19
- WVVPZQNKNLCVCJ-UHFFFAOYSA-N phenyl-bis[(2,4,6-trimethylphenyl)methyl]phosphane Chemical compound CC1=CC(C)=CC(C)=C1CP(C=1C=CC=CC=1)CC1=C(C)C=C(C)C=C1C WVVPZQNKNLCVCJ-UHFFFAOYSA-N 0.000 claims abstract description 17
- RPGWZZNNEUHDAQ-UHFFFAOYSA-N phenylphosphine Chemical compound PC1=CC=CC=C1 RPGWZZNNEUHDAQ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 150000001875 compounds Chemical class 0.000 claims abstract description 13
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 claims abstract description 13
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 9
- 239000007810 chemical reaction solvent Substances 0.000 claims abstract description 8
- 229910052751 metal Inorganic materials 0.000 claims abstract description 8
- 239000002184 metal Substances 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 230000009471 action Effects 0.000 claims abstract description 6
- 230000008569 process Effects 0.000 claims abstract description 6
- 230000002378 acidificating effect Effects 0.000 claims abstract description 5
- 239000007800 oxidant agent Substances 0.000 claims abstract description 5
- 230000001590 oxidative effect Effects 0.000 claims abstract description 4
- 239000011261 inert gas Substances 0.000 claims abstract description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 21
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 14
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 10
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 7
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 claims description 6
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 6
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 claims description 6
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 6
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims description 6
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 5
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 5
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 5
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 5
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 4
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 4
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 4
- 229940078916 carbamide peroxide Drugs 0.000 claims description 4
- 229940078494 nickel acetate Drugs 0.000 claims description 4
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 claims description 4
- 229920002866 paraformaldehyde Polymers 0.000 claims description 4
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 claims description 4
- AQLJVWUFPCUVLO-UHFFFAOYSA-N urea hydrogen peroxide Chemical compound OO.NC(N)=O AQLJVWUFPCUVLO-UHFFFAOYSA-N 0.000 claims description 4
- SPXOTSHWBDUUMT-UHFFFAOYSA-N 138-42-1 Chemical compound OS(=O)(=O)C1=CC=C([N+]([O-])=O)C=C1 SPXOTSHWBDUUMT-UHFFFAOYSA-N 0.000 claims description 3
- HWTDMFJYBAURQR-UHFFFAOYSA-N 80-82-0 Chemical compound OS(=O)(=O)C1=CC=CC=C1[N+]([O-])=O HWTDMFJYBAURQR-UHFFFAOYSA-N 0.000 claims description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 3
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 3
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 claims description 3
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 claims description 3
- 235000011285 magnesium acetate Nutrition 0.000 claims description 3
- 239000011654 magnesium acetate Substances 0.000 claims description 3
- 229940069446 magnesium acetate Drugs 0.000 claims description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 3
- 235000011056 potassium acetate Nutrition 0.000 claims description 3
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 3
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 3
- 235000011151 potassium sulphates Nutrition 0.000 claims description 3
- 235000019260 propionic acid Nutrition 0.000 claims description 3
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 3
- 239000001632 sodium acetate Substances 0.000 claims description 3
- 235000017281 sodium acetate Nutrition 0.000 claims description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 3
- 235000011152 sodium sulphate Nutrition 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 3
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 claims description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 claims description 2
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 claims description 2
- GPWHDDKQSYOYBF-UHFFFAOYSA-N ac1l2u0q Chemical compound Br[Br-]Br GPWHDDKQSYOYBF-UHFFFAOYSA-N 0.000 claims description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- OTCKOJUMXQWKQG-UHFFFAOYSA-L magnesium bromide Chemical compound [Mg+2].[Br-].[Br-] OTCKOJUMXQWKQG-UHFFFAOYSA-L 0.000 claims description 2
- 229910001623 magnesium bromide Inorganic materials 0.000 claims description 2
- 239000002699 waste material Substances 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 2
- IFBMOBFQBJZBMV-UHFFFAOYSA-N [phenyl-(2,4,6-trimethylbenzoyl)phosphanyl]-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(C=1C=CC=CC=1)C(=O)C1=C(C)C=C(C)C=C1C IFBMOBFQBJZBMV-UHFFFAOYSA-N 0.000 abstract 1
- 239000007787 solid Substances 0.000 description 28
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- 239000000047 product Substances 0.000 description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 14
- 239000012265 solid product Substances 0.000 description 14
- 238000004128 high performance liquid chromatography Methods 0.000 description 11
- 239000012065 filter cake Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 7
- 238000002844 melting Methods 0.000 description 7
- 230000008018 melting Effects 0.000 description 7
- 239000003208 petroleum Substances 0.000 description 7
- 229910052783 alkali metal Inorganic materials 0.000 description 6
- 150000001340 alkali metals Chemical class 0.000 description 6
- 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 5
- 239000000203 mixture Substances 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical group C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 description 4
- 239000000543 intermediate Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001723 curing Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- YCWSUKQGVSGXJO-NTUHNPAUSA-N nifuroxazide Chemical group C1=CC(O)=CC=C1C(=O)N\N=C\C1=CC=C([N+]([O-])=O)O1 YCWSUKQGVSGXJO-NTUHNPAUSA-N 0.000 description 2
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 238000010146 3D printing Methods 0.000 description 1
- UQRONKZLYKUEMO-UHFFFAOYSA-N 4-methyl-1-(2,4,6-trimethylphenyl)pent-4-en-2-one Chemical group CC(=C)CC(=O)Cc1c(C)cc(C)cc1C UQRONKZLYKUEMO-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical compound [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000011350 dental composite resin Substances 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 229910000358 iron sulfate Inorganic materials 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000012048 reactive intermediate Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Abstract
The invention discloses a preparation method of photoinitiator bis (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide, which comprises the following steps: (1) In the inert gas environment, in a first reaction solvent, phenylphosphine, aldehyde compounds and mesitylene are used as raw materials, under the action of an acidic substance and a metal catalyst, the reaction temperature is 20-200 ℃, the intermediate compound of formula 1 bis (2, 4, 6-trimethylbenzyl) phenylphosphine is obtained after the reaction is completed, and (2) the compound of formula I and an oxidant are reacted in a second reaction solvent under the action of a main catalyst and a cocatalyst, the reaction temperature is-20-100 ℃, and the target compound photoinitiator bis (2, 4, 6-trimethylbenzoyl) phenylphosphine is obtained after the reaction is completed. The invention is a preparation method of photoinitiator with simple process flow, high yield, less three wastes and low cost, and has good industrial production prospect.
Description
Technical Field
The invention relates to the technical field of photoinitiator synthesis, in particular to a preparation method of a photoinitiator bis (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide compound.
Background
A photoinitiator is a substance that absorbs radiation energy and undergoes a photochemical change upon excitation to produce a reactive intermediate (radical or cation) having the ability to initiate polymerization. Photoinitiators are key components of the photocurable materials and play a decisive role in the speed of photocuring of the photocurable materials. The diaryl formyl aryl phosphine oxide compound is used as a novel photoinitiator and is widely applied to industries such as coating, printing ink, adhesive and the like by virtue of excellent performance. The most excellent performance is photoinitiator 819 (CAS 162881-26-7, the chemical structure is shown in the following figure, the chemical name is all called bis (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide, BAPO for short), the maximum absorption wavelength can reach 450nm, 3 high-activity free radicals (2 mesityl free radicals and 1 diphenyl phosphono free radical) can be generated after photolysis, and the curing can be efficiently initiated, so that the method has wide application in the field of 3D printing with high requirements on the curing speed, in particular in the field of dental composite material preparation.
The number of synthetic routes with practical value reported at present is mainly 2: strip 1 is the following route reported by basf in patent CN 100436461:
the method adopts a 3-step synthesis method, takes aryl phosphine dichloride as a starting material, and reacts with alkali metal sodium or potassium to generate corresponding aryl phosphine dialkali metal salt under the promotion of chlorobenzene or n-butyl alcohol serving as an activating agent, then reacts with aryl formyl chloride to obtain a diaryl formyl phenylphosphine intermediate, and finally the corresponding diaryl formyl aryl phosphine oxide is obtained through oxidation.
When the method is used for amplifying the materials with the kilogram level or more, 3 more serious problems exist: firstly, the main material aryl phosphine dichloride is a dangerous article, is very difficult to purchase and transport, has very high potential safety risk to operators, and belongs to raw materials which need to be avoided as much as possible in chemical reaction; secondly, the alkali metal adopted in the first step needs to be melted at high temperature in the reaction process and then scattered into alkali metal small particles with the particle size smaller than 50 mu m, so that the operation is very dangerous, fire is very easy to cause in the reaction process, the operation is very unfriendly to operators, and the principle of green production is not met; thirdly, after the second step of reaction is completed, a large amount of water is needed to quench excessive sodium and residual aryl phosphine dialkali metal salt, and the amount of high-salt wastewater generated is very high and does not meet the requirements of green production.
Strip 2 is the following route reported in patent CN 103012478:
the route adopts a 5-step synthesis method, and step 1 takes aryl phosphine dichloride as a starting material to react with alkali metal sodium to generate corresponding aryl phosphine disodium salt; step 2, aromatic hydrocarbon is taken as a raw material, and reacts with paraformaldehyde and hydrochloric acid to obtain corresponding arylmethyl chloride; the arylmethyl chloride reacts with the disodium arylphosphine salt obtained in the step 1 to obtain a diarylmethyl phenylphosphine intermediate, the diarylmethyl arylphosphine oxide intermediate is obtained through oxidation, and the corresponding diarylmethyl arylphosphine oxide is obtained through catalytic oxidation.
When the method is used for amplifying the materials with the kilogram level or more, 4 more serious problems exist: firstly, the main material aryl phosphine dichloride is a dangerous article, is very difficult to purchase and transport, has very high potential safety risk to operators, and belongs to raw materials which need to be avoided as much as possible in chemical reaction; secondly, the alkali metal adopted in the first step needs to be melted at high temperature in the reaction process and then is scattered into small alkali metal particles (commonly called sodium sand) with the particle size smaller than 50 mu m, the operation is very dangerous, fire is easily caused in the reaction process, the operation is extremely unfriendly to operators, and the principle of green production is not met; thirdly, after the second step of reaction is completed, a large amount of water is needed to quench excessive sodium and residual aryl phosphine dialkali metal salt, and the amount of high-salt wastewater generated is very high and does not meet the requirements of green production; fourth, the steps are long, 5 steps of reactions are performed, the operation complexity is high, the production cost is high, and the reaction economy is poor.
The 2 routes have various problems, which severely limit the further application of the process. The method has the advantages of reasonable route design, safe and easily obtained raw materials, high process safety, less three wastes, high product purity and very important significance for the operator-friendly method for synthesizing the diaryl formyl aryl phosphine oxide.
Disclosure of Invention
In view of the problems in the prior art, the invention develops a preparation method of a photoinitiator bis (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide compound, which has high yield and purity, is environment-friendly, has low cost, is more suitable for industrial mass production, and has wide application prospect.
One of the technical problems to be solved by the invention is to provide a preparation method of a photoinitiator bis (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide, which comprises the following steps:
(1) In an inert gas environment, taking phenylphosphine, aldehyde compounds and mesitylene as raw materials, reacting at a reaction temperature of 20-200 ℃ under the action of an acidic substance and a metal catalyst, and obtaining an intermediate compound of a formula 1 bis (2, 4, 6-trimethylbenzyl) phenylphosphine after the reaction is completed, wherein the first reaction solvent is one or more selected from acetonitrile, ethylene glycol diethyl ether, ethylene glycol dimethyl ether, DMF, DMSO, ethyl acetate, tetrahydrofuran, 2-methyltetrahydrofuran, dioxane, chlorobenzene, nitrobenzene and o-dichlorobenzene;
(2) Dropwise adding a compound of the formula I into a second reaction solvent under the action of an oxidant, a main catalyst and a cocatalyst, reacting at the reaction temperature of-20-100 ℃, and obtaining a target compound photoinitiator bis (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide after the reaction is completed, wherein the second reaction solvent is one or more selected from water, ethanol, methanol, isopropanol, tertiary butanol, acetic acid, propionic acid and acetonitrile;
in a preferred embodiment of the present invention, the aldehyde compound is selected from one or more of formaldehyde, trioxymethylene and paraformaldehyde.
In a preferred embodiment of the present invention, the acidic material is selected from one or more of methanesulfonic acid, p-nitrobenzenesulfonic acid, o-nitrobenzenesulfonic acid, and trifluoromethanesulfonic acid.
In a preferred embodiment of the present invention, the metal catalyst is selected from one or more of potassium bromide, sodium bromide, bromine, lithium bromide, ferric trichloride, and ferric tribromide.
In a preferred embodiment of the present invention, the oxidizing agent is selected from one or more of hydrogen peroxide and carbamide peroxide.
In a preferred embodiment of the present invention, the main catalyst is selected from one or more of magnesium sulfate, sodium sulfate, potassium sulfate, iron sulfate and nickel sulfate.
In a preferred embodiment of the present invention, the promoter is selected from one or more of nickel acetate, sodium acetate, potassium acetate, iron acetate and magnesium acetate.
In a preferred embodiment of the present invention, the mass ratio of the phenylphosphine, the aldehyde compound and the mesitylene is 1:0.5 to 20:2 to 10.
In a preferred embodiment of the present invention, the mass ratio of the phenylphosphine, the aldehyde compound and the mesitylene is 1:0.5 to 20:2 to 10.
In a preferred embodiment of the present invention, the mass ratio of the procatalyst to the compound of formula I is from 0.001 to 0.1:1.
in a preferred embodiment of the invention, the ratio of the amounts of the abovementioned cocatalysts to the substances of the compounds of the formula I is from 0.0001 to 0.002:1.
advantageous effects
The preparation method of the photoinitiator bis (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide compound provided by the invention is a preparation method of the photoinitiator with simple process flow, high yield, less three wastes and low cost, and has good industrial production prospect.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Materials, reagents and the like used in the examples described below are commercially available unless otherwise specified.
Example 1
Step S1: preparation of bis (2, 4, 6-trimethylbenzyl) phenylphosphine
2L of acetonitrile, 110.10 g (1.0 mol) of phenylphosphine, 240.40 g (2.0 mol) of mesitylene, 45.04 g (0.5 mol) of trioxymethylene, 9.61 g (0.1 mol) of methanesulfonic acid, and 1.62 g (0.01 mol) of ferric trichloride are sequentially added to a 5L reaction flask while keeping a slight positive pressure of nitrogen. After the addition, stirring evenly, and heating the reaction solution to 20 ℃ for reaction. The reaction was incubated for 24 hours and completed.
The reaction solution was cooled to room temperature, 2L of petroleum ether was added thereto, cooled to 0℃and kept at a temperature overnight, a large amount of solids were precipitated, and the cake was collected by filtration to give 335.19 g (0.895 mol) as a yellow solid product. Yield 89.5%, purity of product: 99.13% (HPLC); 1H NMR (400 MHz, CDCl 3): delta 7.61-7.66 (m, 2H), 7.36-7.47 (m, 3H), 6.78 (s, 4H), 3.40 (s, 4H), 2.24 (s, 6H), 2.13 (s, 12H).
Step S2: preparation of phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide
680.2 g (6.0 mol) 30 percent hydrogen peroxide, 200 mL water, 0.108g (0.000895 mol) magnesium sulfate and 0.316 g (0.0018 mol) nickel acetate are added into a 5L reaction bottle in sequence, and after the addition is finished, the mixture is stirred uniformly; a solution of 335.19 g (0.895 mol) bis (2, 4, 6-trimethylbenzyl) phenylphosphine in 300 ml ethanol was added dropwise to the reaction solution, and a pale yellow solid was continuously precipitated in the reaction solution during the addition. After the completion of the dropping, the reaction solution was stirred continuously for 1 hour, and the reaction was completed, at which time a large amount of pale yellow solid was precipitated in the reaction solution. The reaction solution is cooled to 0 ℃, kept warm and crystallized for 3 hours, a large amount of solids are continuously precipitated, filtered, and a filter cake is collected to obtain 337.827g (0.807 mol) pale yellow solid product, the melting point is 130-131 ℃, and the yield is 90.2%.
2-step reaction total yield 80.7%, product purity: 99.25%.1H NMR (400 MHz, CDCl 3): delta 7.84-7.92 (m, 2H), 7.51-7.57 (m, 1H), 7.37-7.45 (m, 2H), 6.79 (s, 4H), 2.25 (s, 6H), 2.14 (s, 12H).
Example 2
Step S1: preparation of bis (2, 4, 6-trimethylbenzyl) phenylphosphine
2L of ethylene glycol dimethyl ether, 110.10 g (1.0 mol) of phenylphosphine, 480.8 g (4.0 mol) of mesitylene, 90.08g (1 mol) of trioxymethylene, 16.26 g (0.08 mol) of p-nitrobenzenesulfonic acid and 1.03 g (0.01 mol) of sodium bromide are sequentially added into a 5L reaction flask while keeping a slight positive pressure of nitrogen. After the addition, stirring evenly, and heating the reaction solution to 40 ℃ for reaction. The reaction was incubated for 20 hours and completed.
The reaction solution was cooled to room temperature, a proper amount of petroleum ether was added thereto, cooled to 0 ℃, kept at a temperature overnight, a large amount of solids were precipitated, filtered, and the filter cake was collected to obtain 345.67 g (0.923 mol) as a yellow solid product. Yield 92.3%, purity of product: 98.89% (HPLC); the nuclear magnetic data are consistent with step S1 of example 1.
Step S2: preparation of phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide
680.2 g (6.0 mol) 30 percent hydrogen peroxide, 200 mL methanol, 1.31g (0.00923 mol) sodium sulfate and 0.076g (0.000923 mol) sodium acetate are added into a 5L reaction bottle in sequence, and after the addition is finished, the mixture is stirred uniformly; a solution of 345.67 g (0.923 mol) bis (2, 4, 6-trimethylbenzyl) phenylphosphine in 300 ml isopropanol was added dropwise to the reaction solution, and a pale yellow solid was continuously precipitated in the reaction solution during the addition. After the completion of the dropping, the reaction solution was stirred continuously for 2 hours, and the reaction was completed, at this time, a large amount of pale yellow solid was precipitated in the reaction solution. The reaction solution is cooled to 0 ℃, kept warm and crystallized for 3 hours, a large amount of solids are continuously precipitated, filtered, and a filter cake is collected to obtain a pale yellow solid product 360.76 g (0.862 mol), the melting point is 130-131 ℃, and the yield is 93.4%.
2-step reaction total yield 86.2%, product purity: 98.75% (HPLC). The nuclear magnetic data are consistent with step S2 of example 1.
Example 3
Step S1: preparation of bis (2, 4, 6-trimethylbenzyl) phenylphosphine
To a 5L flask, 2L DMSO,110.10 g (1.0 mol) phenylphosphine, 721.2 g (6.0 mol) mesitylene, 324.65 g (4 mol) 37% formaldehyde, 20.32 g (0.1 mol) o-nitrobenzenesulfonic acid, and 3.68 g (0.02 mol) magnesium bromide were added sequentially while maintaining a slight positive pressure of nitrogen. After the addition, stirring evenly, and heating the reaction liquid to 60 ℃ for reaction. The reaction was incubated for 18 hours and completed.
The reaction solution was cooled to room temperature, a proper amount of petroleum ether was added thereto, cooled to 0 ℃, kept at a temperature overnight, a large amount of solids were precipitated, filtered, and the cake was collected to obtain 350.54g (0.936 mol) of a yellow solid product. Yield 93.6%, purity of product: 98.65% (HPLC); the nuclear magnetic data are consistent with step S1 of example 1.
Step S2: preparation of phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide
680.2 g (6.0 mol) carbamide peroxide, 2000 mL tertiary butanol, 8.16g (0.0468 mol) potassium sulfate and 0.0735 g (0.000749 mol) potassium acetate are added into a 5L reaction bottle in sequence, and after the addition is finished, the mixture is stirred uniformly; to the reaction solution, 350.54g (0.936 mol) of a solution of bis (2, 4, 6-trimethylbenzyl) phenylphosphine in 300 ml t-butanol was added dropwise, and a pale yellow solid was continuously precipitated in the reaction solution during the addition. After the completion of the dropping, the reaction solution was stirred continuously for 1.5 hours, and the reaction was completed, at this time, a large amount of pale yellow solid was precipitated in the reaction solution. The reaction solution is cooled to 0 ℃, kept warm and crystallized for 3 hours, a large amount of solids are continuously precipitated, filtered, and a filter cake is collected to obtain a 366.62 g (0.876 mol) pale yellow solid product, the melting point is 130-131 ℃, and the yield is 90.5%.
2-step reaction total yield 87.6%, product purity: 99.17%. The nuclear magnetic data are consistent with step S2 of example 1.
Example 4
Step S1: preparation of bis (2, 4, 6-trimethylbenzyl) phenylphosphine
To a 5L reaction flask, 2L of tetrahydrofuran, 110.10 g (1.0 mol) of phenylphosphine, 961.6g (8.0 mol) of mesitylene, 811.62 g (10 mol) of 37% formaldehyde, 15.01 g (0.1 mol) of trifluoromethanesulfonic acid, and 2.61 g (0.03 mol) of lithium bromide were sequentially added while maintaining a slight positive pressure of nitrogen. After the addition, stirring evenly, and heating the reaction solution to 82 ℃ for reaction. The reaction was incubated for 16 hours and completed.
The reaction solution was cooled to room temperature, a proper amount of petroleum ether was added thereto, cooled to 0 ℃, kept at a temperature overnight, a large amount of solids were precipitated, filtered, and the cake was collected to obtain 342.68g (0.915 mol) of a yellow solid product. Yield 91.5%, purity of product: 99.32% (HPLC). The nuclear magnetic data are consistent with step S1 of example 1.
Step S2: preparation of phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide
680.2 g (6.0 mol) carbamide peroxide, 2000 mL acetic acid, 29.27g (0.07 mol) ferric sulfate and 0.0699g (0.0004 mol) ferric acetate are added into a 5L reaction bottle in sequence, and after the addition is finished, the mixture is stirred uniformly; to the reaction solution was added dropwise a solution of 342.68g (0.915 mol) of bis (2, 4, 6-trimethylbenzyl) phenylphosphine in 300 ml propionic acid, and a pale yellow solid was continuously precipitated in the reaction solution during the addition. After the completion of the dropping, the reaction solution was stirred continuously for 2.5 hours, and the reaction was completed, at this time, a large amount of pale yellow solid was precipitated in the reaction solution. The reaction solution is cooled to 0 ℃, kept warm and crystallized for 3 hours, a large amount of solids are continuously precipitated, filtered, and a filter cake is collected to obtain 342.31g (0.818 mol) pale yellow solid product, the melting point is 130-131 ℃, and the yield is 89.4%.
2-step reaction total yield 81.8%, product purity: 98.75%. The nuclear magnetic data are consistent with step S2 of example 1.
Example 5
Step S1: preparation of bis (2, 4, 6-trimethylbenzyl) phenylphosphine
To a 5L reaction flask, 2L of o-dichlorobenzene, 110.10 g (1.0 mol) of phenylphosphine, 1202 g (10.0 mol) of mesitylene, 1801.6 g (20 mol) of paraformaldehyde, 9.61 g (0.1 mol) of methanesulfonic acid, and 1.62 g (0.01 mol) of ferric trichloride were sequentially added while maintaining a slight positive pressure of nitrogen. After the addition, stirring evenly, and heating the reaction solution to 150 ℃ for reaction. The reaction was incubated for 12 hours and completed.
The reaction solution was cooled to room temperature, a proper amount of petroleum ether was added thereto, cooled to 0 ℃, kept at a temperature overnight, a large amount of solids were precipitated, filtered, and the filter cake was collected to obtain 330.32 g (0.882 mol) as a yellow solid product. Yield 88.2%, purity of product: 99.43% (HPLC); the nuclear magnetic data are consistent with step S1 of example 1.
Step S2: preparation of phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide
680.2 g (6.0 mol) 30 percent hydrogen peroxide, 200 mL acetonitrile, 8.49g (0.071 mol) magnesium sulfate, 2.73 g (0.0177 mol) nickel sulfate and 0.013 g (0.000088 mol) magnesium acetate are sequentially added into a 5L reaction bottle, and after the addition is finished, the mixture is stirred uniformly; a solution of 330.32 g (0.882 mol) bis (2, 4, 6-trimethylbenzyl) phenylphosphine in 300 ml acetonitrile was added dropwise to the reaction solution, and a pale yellow solid was continuously precipitated in the reaction solution during the addition. After the completion of the dropping, the reaction solution was stirred continuously for 3 hours, and the reaction was completed, at this time, a large amount of pale yellow solid was precipitated in the reaction solution. The reaction solution is cooled to 0 ℃, kept warm and crystallized for 3 hours, a large amount of solids are continuously precipitated, filtered, and a filter cake is collected to obtain 329.97g (0.789 mol) of pale yellow solid product, the melting point is 130-131 ℃, and the yield is 89.4%.
2-step reaction total yield 78.9%, product purity: 99.35% (HPLC). The nuclear magnetic data are consistent with step S2 of example 1.
Comparative example 1:
step S1: preparation of bis (2, 4, 6-trimethylbenzyl) phenylphosphine
To a 5L reaction flask, 2L of acetonitrile, 110.10 g (1.0 mol) of phenylphosphine, 240.40 g (2.0 mol) of mesitylene, 60.35 g (0.67 mol) of trioxymethylene, and 9.61 g (0.1 mol) of methanesulfonic acid were sequentially added while maintaining a slight positive pressure of nitrogen. After the addition, stirring evenly, and heating the reaction solution to 82 ℃ for reaction. The reaction was incubated for 24 hours and completed.
The reaction solution was cooled to room temperature, 2L of petroleum ether was added thereto, cooled to 0℃and kept at a temperature overnight, a large amount of solids were precipitated, and the cake was collected by filtration to give 120.218g (0.321 mol) of a yellow solid product. Yield 32.1%, purity of product: 98.35% (HPLC); the nuclear magnetic data are consistent with step S1 of example 1.
Step S2: preparation of phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide
Maintaining nitrogen slight positive pressure, sequentially adding 680.2 g (6.0 mol) 30% hydrogen peroxide, 200 mL ethanol and 1.21g (0.01 mol) magnesium sulfate into a 5L reaction bottle, and stirring after adding; a solution of 120.218g (0.321 mol) of bis (2, 4, 6-trimethylbenzyl) phenylphosphine in 300 ml ethanol was added dropwise to the reaction solution, and a pale yellow solid was continuously precipitated in the reaction solution during the addition. After the completion of the dropping, the reaction solution was stirred continuously for 1 hour, and the reaction was completed, at which time a large amount of pale yellow solid was precipitated in the reaction solution. The reaction solution is cooled to 0 ℃, kept warm and crystallized for 3 hours, a large amount of solids are continuously precipitated, filtered, and a filter cake is collected to obtain 48.96g (0.117 mol) pale yellow solid product, the melting point is 130-131 ℃, and the yield is 36.4%.
2-step reaction total yield 11.7%, product purity: 97.66% (HPLC). The nuclear magnetic data are consistent with step S2 of example 1.
Comparative example 2:
step S1: preparation of bis (2, 4, 6-trimethylbenzyl) phenylphosphine
2L of acetonitrile, 110.10 g (1.0 mol) of phenylphosphine, 240.40 g (2.0 mol) of mesitylene, 60.35 g (0.67 mol) of trioxymethylene, and 1.62 g (0.01 mol) of ferric trichloride are sequentially added into a 5L reaction flask while keeping a slight positive pressure of nitrogen. After the addition, stirring evenly, and heating the reaction solution to 82 ℃ for reaction. The reaction was incubated for 24 hours and completed.
The reaction solution was cooled to room temperature, 2L of petroleum ether was added thereto, cooled to 0℃and kept at a temperature overnight, a large amount of solids were precipitated, and the cake was collected by filtration to give 155.42g (0.415 mol) of a yellow solid product. Yield 41.5%, purity of product: 98.73% (HPLC). The nuclear magnetic data are consistent with step S1 of example 1.
Step S2: preparation of phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide
Maintaining nitrogen slight positive pressure, sequentially adding 680.2 g (6.0 mol) 30% hydrogen peroxide, 200 mL ethanol and 0.89 g (0.001 mol) nickel acetate into a 5L reaction bottle, and stirring after adding; a solution of 155.42g (0.415 mol) of bis (2, 4, 6-trimethylbenzyl) phenylphosphine in 300 ml ethanol was added dropwise to the reaction solution, and a pale yellow solid was continuously precipitated in the reaction solution during the addition. After the completion of the dropping, the reaction solution was stirred continuously for 1 hour, and the reaction was completed, at which time a large amount of pale yellow solid was precipitated in the reaction solution. The reaction solution is cooled to 0 ℃, kept warm and crystallized for 3 hours, a large amount of solids are continuously precipitated, filtered, and a filter cake is collected to obtain 39.42g (0.0942 mol) of pale yellow solid product, the melting point is 130-131 ℃, and the yield is 22.7%.
2-step reaction total yield 9.42%, product purity: 98.39% (HPLC). The nuclear magnetic data are consistent with step S2 of example 1.
The above examples are provided for illustrating the technical concept and features of the present invention and are intended to enable those skilled in the art to understand the contents of the present invention and implement the same, and are not intended to limit the scope of the present invention; all equivalent changes or modifications made according to the spirit of the present invention should be included in the scope of the present invention.
Claims (10)
1. A method for preparing a photoinitiator bis (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide, comprising:
(1) In an inert gas environment, taking phenylphosphine, aldehyde compounds and mesitylene as raw materials, reacting at a reaction temperature of 20-200 ℃ under the action of an acidic substance and a metal catalyst, and obtaining an intermediate compound of a formula 1 bis (2, 4, 6-trimethylbenzyl) phenylphosphine after the reaction is completed, wherein the first reaction solvent is one or more selected from acetonitrile, ethylene glycol diethyl ether, ethylene glycol dimethyl ether, DMF, DMSO, ethyl acetate, tetrahydrofuran, 2-methyltetrahydrofuran, dioxane, chlorobenzene, nitrobenzene and o-dichlorobenzene;
(2) Dropwise adding a compound of the formula I into a second reaction solvent under the action of an oxidant, a main catalyst and a cocatalyst, reacting at the reaction temperature of-20-100 ℃, and obtaining a target compound photoinitiator bis (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide after the reaction is completed, wherein the second reaction solvent is one or more selected from water, ethanol, methanol, isopropanol, tertiary butanol, acetic acid, propionic acid and acetonitrile;
。
2. the method for preparing the photoinitiator bis (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide according to claim 1, wherein the aldehyde compound is selected from one or more of formaldehyde, trioxymethylene and paraformaldehyde.
3. The method for preparing the photoinitiator bis (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide according to claim 1, wherein the acidic substance is one or more selected from methane sulfonic acid, p-nitrobenzenesulfonic acid, o-nitrobenzenesulfonic acid and trifluoromethane sulfonic acid.
4. The method for preparing the photoinitiator bis (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide according to claim 1, wherein the metal catalyst is selected from one or more of potassium bromide, sodium bromide, magnesium bromide, lithium bromide, ferric trichloride and ferric tribromide.
5. The method for preparing the photoinitiator bis (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide according to claim 1, wherein the oxidant is one or more selected from hydrogen peroxide and carbamide peroxide.
6. The method for preparing the photoinitiator bis (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide according to claim 1, wherein the main catalyst is one or more selected from magnesium sulfate, sodium sulfate, potassium sulfate, ferric sulfate and nickel sulfate.
7. The method for preparing the photoinitiator bis (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide according to claim 1, wherein the cocatalyst is one or more selected from nickel acetate, sodium acetate, potassium acetate, iron acetate and magnesium acetate.
8. The method for producing a photoinitiator bis (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide according to claim 1, wherein the mass ratio of the phenylphosphine, the aldehyde compound and the mesitylene is 1:0.5 to 20:2 to 10.
9. The process for the preparation of the photoinitiator bis (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide according to claim 1, characterized in that the mass ratio of procatalyst to the substance of the compound of formula I is between 0.001 and 0.1:1.
10. the process for the preparation of the photoinitiator bis (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide according to claim 1, characterized in that the ratio of the amount of the cocatalyst to the compound of formula I is between 0.0001 and 0.002:1.
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