CN112279940B - Acylphosphine photoinitiator and preparation method thereof - Google Patents
Acylphosphine photoinitiator and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 72
- -1 aryl phosphine dichloride Chemical compound 0.000 claims abstract description 49
- 238000000034 method Methods 0.000 claims abstract description 28
- 239000003054 catalyst Substances 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000012044 organic layer Substances 0.000 claims abstract description 14
- 239000000126 substance Substances 0.000 claims abstract description 14
- 239000007800 oxidant agent Substances 0.000 claims abstract description 9
- 230000001590 oxidative effect Effects 0.000 claims abstract description 8
- 150000003934 aromatic aldehydes Chemical class 0.000 claims abstract description 7
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 7
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 4
- 238000000605 extraction Methods 0.000 claims abstract description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 65
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 16
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 15
- 229910052720 vanadium Inorganic materials 0.000 claims description 12
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 4
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 4
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 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
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 4
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 2
- FAPDDOBMIUGHIN-UHFFFAOYSA-K antimony trichloride Chemical compound Cl[Sb](Cl)Cl FAPDDOBMIUGHIN-UHFFFAOYSA-K 0.000 claims description 2
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 2
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 claims description 2
- UPWPDUACHOATKO-UHFFFAOYSA-K gallium trichloride Chemical compound Cl[Ga](Cl)Cl UPWPDUACHOATKO-UHFFFAOYSA-K 0.000 claims description 2
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- ZFJMTDFOGDGPTF-UHFFFAOYSA-N phosphanium;chloride;hydrochloride Chemical compound P.Cl.Cl ZFJMTDFOGDGPTF-UHFFFAOYSA-N 0.000 claims description 2
- 239000012286 potassium permanganate Substances 0.000 claims description 2
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 8
- 239000000463 material Substances 0.000 claims 1
- 125000003944 tolyl group Chemical group 0.000 claims 1
- 239000003999 initiator Substances 0.000 abstract description 17
- 238000012986 modification Methods 0.000 abstract description 5
- 230000004048 modification Effects 0.000 abstract description 5
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 4
- 229910000073 phosphorus hydride Inorganic materials 0.000 abstract description 4
- 125000001476 phosphono group Chemical group [H]OP(*)(=O)O[H] 0.000 abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 32
- 229910001873 dinitrogen Inorganic materials 0.000 description 32
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 16
- 230000007062 hydrolysis Effects 0.000 description 16
- 238000006460 hydrolysis reaction Methods 0.000 description 16
- 238000003760 magnetic stirring Methods 0.000 description 16
- 238000010992 reflux Methods 0.000 description 16
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 16
- 238000005406 washing Methods 0.000 description 16
- 238000001723 curing Methods 0.000 description 14
- 229910052736 halogen Inorganic materials 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 238000001816 cooling Methods 0.000 description 8
- 238000001704 evaporation Methods 0.000 description 8
- 238000004128 high performance liquid chromatography Methods 0.000 description 8
- 239000005457 ice water Substances 0.000 description 8
- 239000003208 petroleum Substances 0.000 description 8
- 238000001953 recrystallisation Methods 0.000 description 8
- 235000010265 sodium sulphite Nutrition 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 239000003513 alkali Substances 0.000 description 7
- XGRJZXREYAXTGV-UHFFFAOYSA-N chlorodiphenylphosphine Chemical compound C=1C=CC=CC=1P(Cl)C1=CC=CC=C1 XGRJZXREYAXTGV-UHFFFAOYSA-N 0.000 description 7
- 125000000217 alkyl group Chemical group 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- IMDXZWRLUZPMDH-UHFFFAOYSA-N dichlorophenylphosphine Chemical compound ClP(Cl)C1=CC=CC=C1 IMDXZWRLUZPMDH-UHFFFAOYSA-N 0.000 description 6
- 230000000977 initiatory effect Effects 0.000 description 6
- 238000004321 preservation Methods 0.000 description 6
- YFPJFKYCVYXDJK-UHFFFAOYSA-N Diphenylphosphine oxide Chemical compound C=1C=CC=CC=1[P+](=O)C1=CC=CC=C1 YFPJFKYCVYXDJK-UHFFFAOYSA-N 0.000 description 5
- AYKIQGZBMKNWKZ-UHFFFAOYSA-N [(2,4-dimethylphenyl)-phenylphosphoryl]-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(=C(C=C1)P(=O)(C2=CC=CC=C2)C(=O)C3=C(C=C(C=C3C)C)C)C AYKIQGZBMKNWKZ-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 150000002367 halogens Chemical class 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- BTCBJVLJLQFVSC-UHFFFAOYSA-N C(C1=CC=CC=C1)=O.C1(=CC(=CC(=C1)C)C)C Chemical compound C(C1=CC=CC=C1)=O.C1(=CC(=CC(=C1)C)C)C BTCBJVLJLQFVSC-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 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 3
- NXHPIYRSMIFFBV-UHFFFAOYSA-N formaldehyde;1,3,5-trimethylbenzene Chemical compound O=C.CC1=CC(C)=CC(C)=C1 NXHPIYRSMIFFBV-UHFFFAOYSA-N 0.000 description 3
- 230000031700 light absorption Effects 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- GSXOXKQHZXJLCC-UHFFFAOYSA-N 1-methyl-4-phenylphosphonoylbenzene Chemical compound C1=CC(C)=CC=C1P(=O)C1=CC=CC=C1 GSXOXKQHZXJLCC-UHFFFAOYSA-N 0.000 description 2
- ROJKOPZQZIPZCV-UHFFFAOYSA-N 2-(2,4,6-trimethylphenyl)benzaldehyde Chemical compound CC1=CC(C)=CC(C)=C1C1=CC=CC=C1C=O ROJKOPZQZIPZCV-UHFFFAOYSA-N 0.000 description 2
- MJWYGDXXIKYCEQ-UHFFFAOYSA-N CC(C=C1)=CC(C)=C1P(C1=CC=CC=C1)=O Chemical compound CC(C=C1)=CC(C)=C1P(C1=CC=CC=C1)=O MJWYGDXXIKYCEQ-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000006757 chemical reactions by type Methods 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 2
- 238000000016 photochemical curing Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- MDWXPVQYOHGGFU-UHFFFAOYSA-N C1(=CC=CC=C1)[PH2]=O.C1(=CC=CC=C1)C1=CC=CC=C1 Chemical compound C1(=CC=CC=C1)[PH2]=O.C1(=CC=CC=C1)C1=CC=CC=C1 MDWXPVQYOHGGFU-UHFFFAOYSA-N 0.000 description 1
- DEBBGGOZVNVPPJ-UHFFFAOYSA-N C1=CC(F)=CC=C1P(=O)C1=CC=CC=C1 Chemical compound C1=CC(F)=CC=C1P(=O)C1=CC=CC=C1 DEBBGGOZVNVPPJ-UHFFFAOYSA-N 0.000 description 1
- LNIMHMMIOURCHD-UHFFFAOYSA-N CC=1C(=C(C=CC1)P(C1=CC=CC=C1)=O)C Chemical compound CC=1C(=C(C=CC1)P(C1=CC=CC=C1)=O)C LNIMHMMIOURCHD-UHFFFAOYSA-N 0.000 description 1
- JCYCMEXSPMJRCT-UHFFFAOYSA-N FC1=CC=C(C=C1)[PH2]=O Chemical compound FC1=CC=C(C=C1)[PH2]=O JCYCMEXSPMJRCT-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 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 1
- ITTMQMRZPLTPKA-UHFFFAOYSA-N [(4-methylphenyl)-phenylphosphoryl]-(2,4,6-trimethylphenyl)methanone Chemical compound C1=CC(C)=CC=C1P(=O)(C=1C=CC=CC=1)C(=O)C1=C(C)C=C(C)C=C1C ITTMQMRZPLTPKA-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 150000001263 acyl chlorides Chemical class 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- UWCPYKQBIPYOLX-UHFFFAOYSA-N benzene-1,3,5-tricarbonyl chloride Chemical compound ClC(=O)C1=CC(C(Cl)=O)=CC(C(Cl)=O)=C1 UWCPYKQBIPYOLX-UHFFFAOYSA-N 0.000 description 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- WKGDNXBDNLZSKC-UHFFFAOYSA-N oxido(phenyl)phosphanium Chemical compound O=[PH2]c1ccccc1 WKGDNXBDNLZSKC-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920002397 thermoplastic olefin Polymers 0.000 description 1
- IEDVJHCEMCRBQM-UHFFFAOYSA-N trimethoprim Chemical compound COC1=C(OC)C(OC)=CC(CC=2C(=NC(N)=NC=2)N)=C1 IEDVJHCEMCRBQM-UHFFFAOYSA-N 0.000 description 1
- 229960001082 trimethoprim Drugs 0.000 description 1
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- 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 Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/53—Organo-phosphine oxides; Organo-phosphine thioxides
- C07F9/5337—Phosphine oxides or thioxides containing the structure -C(=X)-P(=X) or NC-P(=X) (X = O, S, Se)
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- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Crystallography & Structural Chemistry (AREA)
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- General Health & Medical Sciences (AREA)
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Abstract
The invention provides an acylphosphine photoinitiator, which has a chemical structural formula shown as a formula (I), and also provides a preparation method thereof: (1) By reacting aryl phosphine dichloride or derivatives thereof, aromatic hydrocarbons or derivatives thereofPutting the organism and the catalyst into a reaction bottle to obtain a complex of diaryl phosphine chloride and the catalyst; (2) Slowly dripping the solution obtained in the step 1 into water, continuing to react, adding an extractant for extraction, and separating an organic layer for later use; (3) Putting the obtained organic layer into a reaction bottle, and putting aromatic aldehyde or derivatives thereof into the reaction bottle for reaction at the temperature of-10-25 ℃; (4) And (3) adding a catalyst and an oxidant into the reaction liquid obtained in the step (3) at a certain temperature to prepare the acylphosphine photoinitiator. The invention carries out structural modification on the benzene ring at the side of the phosphono in the structure of the acyl phosphine initiator for the first time, and has mild reaction conditions, simple treatment process and environmental protection.
Description
Technical Field
The invention belongs to the technical field of organic synthesis and application, and particularly relates to an acylphosphine photoinitiator and a preparation method thereof.
Background
Compared with the traditional curing technology, the photo-curing technology has the characteristics of high efficiency, energy conservation, environmental protection, economy, wide applicability and the like, and is increasingly applied to curing of paint, printing ink and adhesives. The photocurable system generally comprises: light source, monomer and initiator, wherein the matching of light source and initiator wavelength determines the quality of the curing formulation. Near UV light and visible light initiation are safer and more energy efficient than UV light initiation, while long wavelength light can be suitable for curing thick coatings, so developing long wavelength initiators that match near UV light and visible light is one of the research hotspots in the field of photo curing.
2,4, 6-trimethylbenzoyl-diphenylphosphine oxide (TPO, formula V) is a commercial photoinitiator suitable for deep curing of coatings and is prepared by two conventional methods: (1) acid chloride method. The preparation process is that phenyl phosphorus dichloride (BPD) is subjected to high-temperature disproportionation to prepare Diphenyl Phosphorus Chloride (DPC), and after esterification, the diphenyl phosphorus chloride is reacted with trimesic chloride to obtain a product, as shown in a reaction formula 1; (2) aldehyde method. DPC is prepared by high BPD Wen Qihua, DPC is hydrolyzed to obtain Diphenyl Phosphine Oxide (DPO), DPO reacts with trimethoprim and is oxidized to obtain a product, as shown in a reaction formula 2; both methods for preparing TPO comprise the DPC preparation process of BPD with high Wen Qihua, and a large amount of catalyst solid waste is generated in the DPC preparation process, so that the environment is seriously polluted, and therefore, the development of a synthetic route for TPO green and environment-friendly is one of research hotspots.
TPO (thermoplastic olefin) preparation method by reaction type 1 acyl chloride method
In order to improve the initiation efficiency of TPO, a great deal of literature reports on structural modification of TPO, but so far, studies on structural modification of TPO have been mainly focused on modification of benzene ring structure in benzoyl (right side in formula V), and studies on modification of benzene ring structure in phosphono (left side in formula V) have not been reported. Furthermore, when fluorine atoms with smaller surface energy are introduced into the structure of TPO, the initiator can be promoted to float up in the curing system, the initiator is distributed in a gradient manner in the curing system, the initiator is enriched on the surface of the curing system, the surface layer curing effect can be greatly enhanced, and the oxygen resistance problem is reduced.
Disclosure of Invention
The invention aims to provide an acylphosphine photoinitiator, and a preparation method and application of the compound.
The technical scheme adopted by the invention is as follows:
an acylphosphine photoinitiator, characterized in that: the chemical structural formula of the acylphosphine photoinitiator is shown as (I):
wherein R is 1 -R 15 Independently selected from the group consisting of H, alkyl, halogen substituted alkyl, aryl, wherein halogen comprises: F. cl, br, I, preferably F.
Further, the alkyl group and the halogen-substituted alkyl group are preferably carbon chain structures having 1 to 6 carbon atoms.
The preparation method of the acylphosphine photoinitiator comprises the following steps:
(1) Adding aryl phosphine dichloride or a derivative thereof, aromatic hydrocarbon or a derivative thereof and a catalyst into a reaction bottle, heating to a certain temperature, reacting for a certain time, and decompressing and distilling unreacted raw materials after the reaction is finished to obtain a complex of the diaryl phosphine dichloride and the catalyst;
(2) Slowly dripping the complex of the diaryl phosphine chloride and the catalyst into water at a certain temperature, continuing to react for a certain time after dripping, adding an extractant for extraction, and separating an organic layer for later use;
(3) Adding the obtained organic layer into a reaction bottle, adding aromatic aldehyde or its derivative at-10-25 ℃ for reaction for 0.5-5 h, and keeping the reaction liquid for later use;
(4) At a certain temperature, adding a catalyst and an oxidant into the reaction liquid obtained in the step (3), and reacting for a certain time to obtain an acylphosphine photoinitiator;
the chemical structural formula of the aryl phosphine dichloride or the derivative thereof used in the first step in the process is shown as (II):
wherein R is 1 -R 5 Independently selected from the group consisting of H, alkyl, halogen substituted alkyl, aryl, wherein halogen comprises: F. cl, br, I, preferably F.
The alkyl and halogen substituted alkyl are preferably carbon chain structures with 1-6 carbon atoms.
The chemical structural formula of the arene or the derivative thereof used in the first step in the process is shown as (III):
wherein R is 6 -R 10 Independently selected from the group consisting of H, alkyl, halogen substituted alkyl, wherein halogen comprises: F. cl, br, I, preferably F.
The chemical structural formula of the aromatic aldehyde or the derivative thereof used in the third step is shown as (IV):
wherein R is 11 -R 15 Independently selected from the group consisting of H, alkyl, halogen substituted alkyl, wherein halogen comprises: F. cl, br, I, preferably F.
The catalyst used in the first step in the process is as follows: one or more of anhydrous aluminum chloride, anhydrous gallium chloride, anhydrous indium chloride, anhydrous bismuth chloride, anhydrous antimony chloride, anhydrous tin chloride, anhydrous magnesium chloride and anhydrous ferric chloride, preferably: anhydrous aluminum chloride;
the certain temperature in the first step of the process is 50-150 ℃, preferably 90 ℃; the certain time is 2-48 hours, preferably 12 hours;
the ratio of the amount of the aryl phosphine dichloride or the derivative thereof to the amount of the aromatic hydrocarbon or the derivative substance used in the first step of the process is 1:0.5-1: 5, preferably 1:1.3; the ratio of the amounts of the substances of the aryl phosphine dichloride or the derivative catalyst is 1:0.8-1:3, preferably 1:1.4;
in the second step of the above process, the temperature is 0 to 50 ℃, preferably: 0 ℃; the certain time is 0 to 20 hours, preferably 4 hours; the extractant is one or more selected from benzene, toluene, dichloromethane, dichloroethane, chloroform, carbon tetrachloride, chlorobenzene and nitrobenzene;
in the third step of the above process, the temperature is-10 to 25 ℃, preferably: 15-25 ℃; the certain time is 0.5 to 5 hours, preferably 1 hour; the ratio of the amount of the aromatic aldehyde or derivative thereof to the amount of the substance of the aromatic phosphine dichloride or derivative thereof used is 1:0.6 to 1:1.5, preferably 1:1;
in the fourth step of the process, the certain temperature is 0-20 ℃, preferably 6-10 ℃; the certain time is 1 to 20 hours, preferably 8 hours;
the catalyst in the fourth step of the process is as follows: one or more of vanadium pentoxide, vanadium diacetylacetonate, manganese dioxide and ammonium metavanadate, preferably vanadium diacetylacetonate; the catalyst is 0.1% -5%, preferably 1% of the amount of aryl phosphine dichloride or derivative substances;
the oxidant in the fourth step of the process is as follows: one or more of potassium permanganate, hydrogen peroxide and tert-butyl peroxide, preferably tert-butyl peroxide; the ratio of the amount of oxidant used to the amount of aryl phosphine dichloride or derivative thereof is 1:1 to 5:1, preferably 1.3:1;
preparation of aryl phosphine dichloride reference P-heteroatom-substituted arylphosphines, alajorin, M.et al Science of Synthesis,31b,2105-2153; other reagents and medicines are all commercially available.
The beneficial technical effects of the invention are as follows:
(1) The structure of the benzene ring at the side of the phosphono in the structure of the acyl phosphine initiator is modified for the first time, and the prepared acyl phosphine initiator belongs to a photoinitiator with a new structure;
(2) The invention provides a preparation method of an acyl phosphine photoinitiator, which has the advantages of mild reaction conditions, simple treatment process, green environmental protection and the like, and belongs to a green environmental protection process;
(3) The photoinitiator containing F prepared by the invention is in gradient distribution in a curing system, so that the oxygen resistance effect existing on the surface of the curing system in the curing process can be effectively reduced; the prepared initiator with the new structure containing the power supply group has strong light absorption capacity and red shift of light absorption wavelength, greatly enhances the matching property with near UV light and visible light, and has huge application potential as a new initiator.
Detailed Description
The invention will be further described with reference to the drawings and specific examples.
FIG. 1 is a schematic diagram showing 2,4, 6-trimethylbenzoyl-2, 4-xylylphenylphosphine oxide (2, 4-DMTPO) obtained in example 3 of the present invention 1 HNMR spectrogram; 1 H NMR(500MHz,CDCl 3 )δ7.85–7.79(m,2H),7.68(dd,J＝12.7,7.9Hz,1H),7.56–7.51(m,1H),7.46(td,J＝7.5,3.0Hz,2H),7.09(dd,J＝11.7,6.0Hz,2H),6.81(s,2H),2.35(d,J＝4.5Hz,6H),2.26(s,3H),2.06(s,6H)；
FIG. 2 is a schematic diagram showing 2,4, 6-trimethylbenzoyl-2, 4-xylylphenylphosphine oxide (2, 4-DMTPO) obtained in example 3 of the present invention 13 CNMR spectrogram; 13 C NMR(126MHz,CDCl 3 )δ219.28(d,J＝71.8Hz),143.44–142.93(m),140.63,136.50(d,J＝40.4Hz),135.34,133.42–131.74(m),130.81(d,J＝92.5Hz),129.27–128.41(m),126.29(d,J＝12.7Hz),124.63(d,J＝95.8Hz),21.61–21.18(m),19.85.
FIG. 3 is a diagram of 2,4, 6-trimethyl prepared in example 3 of the inventionBenzoyl-2, 4-xylylphenylphosphine oxide (2, 4-DMTPO) 31 PNMR spectrogram; 31 P NMR(202MHz,CDCl3)δ19.67；
FIG. 4 is a schematic diagram of 2,4, 6-trimethylbenzoyl-4-fluorophenyl phosphine oxide (4-FTPO) obtained in example 4 of the present invention 1 HNMR spectrogram; 1 H NMR(400MHz,CDCl 3 )δ8.04–7.95(d,J＝5.5Hz,4H),7.62–7.47(m,3H),7.20(td,J＝8.8,2.3Hz,2H),6.82(s,2H),2.26(s,3H),2.03(s,6H).
FIG. 5 is a schematic diagram of 2,4, 6-trimethylbenzoyl-4-fluorophenyl phosphine oxide (4-FTPO) obtained in example 4 of the present invention 13 CNMR spectrogram; 2,4, 6-trimethylbenzoyl-4-fluorophenyl phenylphosphine oxide (4-FTPO) 13 C NMR spectrum (101 MHz, CDCl) 3 )δ168.81–162.17(m),138.33–126.77(m),125.68(dd,J＝96.0,3.5Hz),116.22(dd,J＝21.3,12.6Hz),20.49(d,J＝152.5Hz)；
FIG. 6 is a schematic diagram of 2,4, 6-trimethylbenzoyl-4-fluorophenyl phosphine oxide (4-FTPO) obtained in example 4 of the present invention 31 PNMR spectrogram; 31 P NMR(162MHz,CDCl 3 )δ12.21.；
FIG. 7 is a graph showing UV absorbance profile of 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide (TPO), 2,4, 6-trimethylbenzoyl-2, 4-xylylphenylphosphine oxide (2, 4-DMTPO) and 2,4, 6-trimethylbenzoyl-4-fluorophenyl phenylphosphine oxide (4-FTPO)
Example 1
The structural formula of the 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide (TPO) is shown as follows
Into a dry three-necked flask (50 ml) equipped with magnetic stirring, a thermometer, a reflux condenser, and a nitrogen gas conduit, dry nitrogen gas was introduced, and air in the flask was purged. 17.4g of aluminum trichloride, 17.9g of phenyl phosphine dichloride and 11g of benzene are sequentially put into a three-mouth bottle, the temperature of the oil bath is slowly raised to the set temperature of 90 ℃, and the heat preservation reaction is carried out for 12 hours. Evaporating unreacted raw materials under reduced pressure, and cooling to room temperature; the reaction solution is slowly added into 100g of ice-water mixture for hydrolysis, and the reaction is continued for 4 hours after the hydrolysis is completed. 120g of toluene was added to the reaction solution, and the organic layer was subjected to alkaline washing and water washing to obtain a toluene solution of diphenyl phosphine oxide.
Into a dry three-necked flask (250 ml) equipped with magnetic stirring, a thermometer, a reflux condenser, and a nitrogen gas conduit, dry nitrogen gas was introduced, and air in the flask was purged. Adding 14.9g of diphenyl phosphine oxide and mesitylene formaldehyde obtained in the process to react for 1h at 15-25 ℃; the temperature of the reaction solution is reduced to 6-10 ℃, 0.27g of vanadium diacetylacetonate is added, 16.7g of 70% tertiary butyl alcohol peroxide is slowly dripped, the reaction is carried out for 8 hours after the dripping is finished, the solvent is distilled off after the reaction solution is washed by sodium sulfite solution and water, and 20ml of petroleum ether is added for recrystallization, thus obtaining TPO. The product yield was 65% and the HPLC content was 99.1%.
Example 2
2,4, 6-trimethylbenzoyl-4-tolylphenylphosphine oxide (4-MTPO) has the following structural formula:
into a dry three-necked flask (50 ml) equipped with magnetic stirring, a thermometer, a reflux condenser, and a nitrogen gas conduit, dry nitrogen gas was introduced, and air in the flask was purged. 17.4g of aluminum trichloride, 17.9g of phenyl phosphine dichloride and 12.9g of toluene are sequentially put into a three-mouth bottle, the temperature of the oil bath is slowly raised to the set temperature of 90 ℃, and the reaction is carried out for 12 hours under the heat preservation. Evaporating unreacted raw materials under reduced pressure, and cooling to room temperature; the reaction solution is slowly added into 100g of ice-water mixture for hydrolysis, and the reaction is continued for 4 hours after the hydrolysis is completed. 120g of toluene was added to the reaction solution, and the organic layer was subjected to alkali washing and water washing to obtain a toluene solution of 4-tolylphenylphosphine oxide.
Into a dry three-necked flask (250 ml) equipped with magnetic stirring, a thermometer, a reflux condenser, and a nitrogen gas conduit, dry nitrogen gas was introduced, and air in the flask was purged. Adding 14.9g of 4-tolylphenylphosphine oxide and mesitylene benzaldehyde obtained in the process, and reacting for 1h at 15-25 ℃; the temperature of the reaction solution is reduced to 6-10 ℃, 0.27g of vanadium diacetylacetonate is added, 16.7g of 70% tertiary butyl alcohol peroxide is slowly dripped, the reaction is carried out for 8 hours after the dripping is finished, the solvent is distilled off after the reaction solution is washed by sodium sulfite solution and water, and 20ml of petroleum ether is added for recrystallization, thus obtaining 4-MTPO. The product yield was 68% and the HPLC content was 99.1%.
Example 3
2,4, 6-trimethylbenzoyl-2, 4-xylylphenylphosphine oxide (2, 4-DMTPO) has the following structural formula:
into a dry three-necked flask (50 ml) equipped with magnetic stirring, a thermometer, a reflux condenser, and a nitrogen gas conduit, dry nitrogen gas was introduced, and air in the flask was purged. 17.4g of aluminum trichloride, 17.9g of phenyl phosphine dichloride and 14.9g of m-xylene are sequentially put into a three-mouth bottle, the temperature of an oil bath is slowly raised to the set temperature of 90 ℃, and the reaction is carried out for 12 hours under the heat preservation. Evaporating unreacted raw materials under reduced pressure, and cooling to room temperature; the reaction solution is slowly added into 100g of ice-water mixture for hydrolysis, and the reaction is continued for 4 hours after the hydrolysis is completed. 120g of toluene was added to the reaction solution, and the organic layer was subjected to alkali washing and water washing to obtain a toluene solution of 2, 4-xylylphenylphosphine oxide.
Into a dry three-necked flask (250 ml) equipped with magnetic stirring, a thermometer, a reflux condenser, and a nitrogen gas conduit, dry nitrogen gas was introduced, and air in the flask was purged. Adding 14.9g of 2, 4-xylyl phenyl phosphine oxide and mesityl benzaldehyde obtained in the process to react for 1h at 15-25 ℃; the temperature of the reaction solution is reduced to 6-10 ℃, 0.27g of vanadium diacetylacetonate is added, 16.7g of 70% tertiary butyl alcohol peroxide is slowly dripped, the reaction is carried out for 8 hours after the dripping is finished, the solvent is distilled off after the reaction solution is washed by sodium sulfite solution and water, and 20ml of petroleum ether is added for recrystallization, thus obtaining 2,4-DMTPO. The product yield was 71% and the HPLC content was 99.1%.
Example 4
2,4, 6-trimethylbenzoyl-4-fluorophenyl phosphine oxide (4-FTPO) has the following structural formula:
into a dry three-necked flask (50 ml) equipped with magnetic stirring, a thermometer, a reflux condenser, and a nitrogen gas conduit, dry nitrogen gas was introduced, and air in the flask was purged. 17.4g of aluminum trichloride, 17.9g of fluorophenyl phosphine dichloride and 11g of benzene are sequentially put into a three-mouth bottle, the temperature of the oil bath is slowly increased to the set temperature of 90 ℃, and the heat preservation reaction is carried out for 12 hours. Evaporating unreacted raw materials under reduced pressure, and cooling to room temperature; the reaction solution is slowly added into 100g of ice-water mixture for hydrolysis, and the reaction is continued for 4 hours after the hydrolysis is completed. 120g of toluene was added to the reaction solution, and the organic layer was subjected to alkali washing and water washing to obtain a toluene solution of 4-fluorophenyl phosphine oxide.
Into a dry three-necked flask (250 ml) equipped with magnetic stirring, a thermometer, a reflux condenser, and a nitrogen gas conduit, dry nitrogen gas was introduced, and air in the flask was purged. Adding 14.9g of 4-fluorophenyl phenylphosphine oxide and mesitylene benzaldehyde obtained in the process, and reacting for 1h at 15-25 ℃; the temperature of the reaction solution is reduced to 6-10 ℃, 0.27g of vanadium diacetylacetonate is added, 16.7g of 70% tertiary butyl alcohol peroxide is slowly dripped, the reaction is carried out for 8 hours after the dripping is finished, the solvent is distilled off after the reaction solution is washed by sodium sulfite solution and water, and 20ml of petroleum ether is added for recrystallization, thus obtaining 4-FTPO. The product yield was 62% and the HPLC content was 98.5%.
Example 5
2,4, 6-trimethylbenzoyl-4-trifluoromethylphenylphosphine oxide (4-TFTPO) has the following structural formula:
into a dry three-necked flask (50 ml) equipped with magnetic stirring, a thermometer, a reflux condenser, and a nitrogen gas conduit, dry nitrogen gas was introduced, and air in the flask was purged. 17.4g of aluminum trichloride, 24.7g of 4-trifluorophenyl phosphine dichloride and 11g of benzene are sequentially put into a three-mouth bottle, the temperature of the oil bath is slowly raised to the set temperature of 90 ℃, and the heat preservation reaction is carried out for 12 hours. Evaporating unreacted raw materials under reduced pressure, and cooling to room temperature; the reaction solution is slowly added into 100g of ice-water mixture for hydrolysis, and the reaction is continued for 4 hours after the hydrolysis is completed. 120g of toluene was added to the reaction solution, and the organic layer was subjected to alkali washing and water washing to obtain a toluene solution of 4-trifluorotolyl phenylphosphine oxide.
Into a dry three-necked flask (250 ml) equipped with magnetic stirring, a thermometer, a reflux condenser, and a nitrogen gas conduit, dry nitrogen gas was introduced, and air in the flask was purged. Adding 14.9g of 4-trifluoro-tolyl phenylphosphine oxide and mesityl benzaldehyde obtained in the process, and reacting for 1h at 15-25 ℃; the temperature of the reaction solution is reduced to 6-10 ℃, 0.27g of vanadium diacetylacetonate is added, 16.7g of 70% tertiary butyl alcohol peroxide is slowly dripped, the reaction is carried out for 8 hours after the dripping is finished, the solvent is distilled off after the reaction solution is washed by sodium sulfite solution and water, and 20ml of petroleum ether is added for recrystallization, thus obtaining 4-TFTPO. The product yield was 70% and the HPLC content was 98.5%.
Example 6
2,4, 6-trimethylbenzoyl-4-fluorophenyl-4-tolylphosphine oxide (4-F-4-MTPO) has the following structural formula:
into a dry three-necked flask (50 ml) equipped with magnetic stirring, a thermometer, a reflux condenser, and a nitrogen gas conduit, dry nitrogen gas was introduced, and air in the flask was purged. 17.4g of aluminum trichloride, 19.7g of 4-trifluorophenyl phosphine dichloride and 13g of toluene are sequentially put into a three-mouth bottle, the temperature of the oil bath is slowly raised to the set temperature of 90 ℃, and the reaction is carried out for 12 hours under the heat preservation. Evaporating unreacted raw materials under reduced pressure, and cooling to room temperature; the reaction solution is slowly added into 100g of ice-water mixture for hydrolysis, and the reaction is continued for 4 hours after the hydrolysis is completed. 120g of toluene was added to the reaction solution, and the organic layer was subjected to alkali washing and water washing to obtain a toluene solution of 4-fluorophenyl-4-tolylphosphine oxide.
Into a dry three-necked flask (250 ml) equipped with magnetic stirring, a thermometer, a reflux condenser, and a nitrogen gas conduit, dry nitrogen gas was introduced, and air in the flask was purged. Adding 14.9g of 4-fluorophenyl-4-tolyl phosphine oxide and mesitylene formaldehyde obtained in the process to react for 1h at 15-25 ℃; the temperature of the reaction solution is reduced to 6-10 ℃, 0.27g of vanadium diacetylacetonate is added, 16.7g of 70% tertiary butyl alcohol peroxide is slowly dripped, the reaction is carried out for 8 hours after the dripping is finished, the solvent is distilled off after the reaction solution is washed by sodium sulfite solution and water, and 20ml of petroleum ether is added for recrystallization, thus obtaining 4-F-4-MTPO. The product yield was 67% and the HPLC content was 97.5%.
Example 7
2,4, 6-trimethylbenzoyl-4-trifluorophenyl-4-tolylphosphine oxide (4-TF-4-MTPO) has the following structural formula:
into a dry three-necked flask (50 ml) equipped with magnetic stirring, a thermometer, a reflux condenser, and a nitrogen gas conduit, dry nitrogen gas was introduced, and air in the flask was purged. 17.4g of aluminum trichloride, 24.7g of 4-trifluoromethylphenyl phosphine dichloride and 13g of toluene are sequentially put into a three-necked flask, and the temperature of the oil bath is slowly raised to the set temperature of 90 ℃ for reaction for 12 hours. Evaporating unreacted raw materials under reduced pressure, and cooling to room temperature; the reaction solution is slowly added into 100g of ice-water mixture for hydrolysis, and the reaction is continued for 4 hours after the hydrolysis is completed. 120g of toluene was added to the reaction solution, and the organic layer was subjected to alkali washing and water washing to obtain a toluene solution of 4-trifluoromethylphenyl-4-tolylphosphine oxide.
Into a dry three-necked flask (250 ml) equipped with magnetic stirring, a thermometer, a reflux condenser, and a nitrogen gas conduit, dry nitrogen gas was introduced, and air in the flask was purged. Adding 14.9g of 4-trifluoromethylphenyl-4-tolyl phosphine oxide and mesitylene formaldehyde obtained in the process to react for 1h at 15-25 ℃; the temperature of the reaction solution is reduced to 6-10 ℃, 0.27g of vanadium diacetylacetonate is added, 16.7g of 70% tertiary butyl alcohol peroxide is slowly added dropwise, the reaction is carried out for 8 hours after the completion of the dropwise addition, the solvent is distilled off after the reaction solution is washed by sodium sulfite solution and water, and 20ml of petroleum ether is added for recrystallization, thus obtaining 4-TF-4-MTPO. The product yield was 71% and the HPLC content was 98.3%.
Example 8
2,4, 6-trimethylbenzoyl-biphenylphenylphosphine oxide (DPTPO) has the structural formula:
into a dry three-necked flask (50 ml) equipped with magnetic stirring, a thermometer, a reflux condenser, and a nitrogen gas conduit, dry nitrogen gas was introduced, and air in the flask was purged. 17.4g of aluminum trichloride, 17.9g of phenyl phosphine dichloride and 21.7g of biphenyl are sequentially put into a three-mouth bottle, the temperature of the oil bath is slowly raised to the set temperature of 90 ℃, and the reaction is carried out for 12 hours. Evaporating unreacted raw materials under reduced pressure, and cooling to room temperature; the reaction solution is slowly added into 100g of ice-water mixture for hydrolysis, and the reaction is continued for 4 hours after the hydrolysis is completed. 120g of toluene was added to the reaction solution, and the organic layer was subjected to alkali washing and water washing to obtain a toluene solution of biphenylphenylphosphine oxide.
Into a dry three-necked flask (250 ml) equipped with magnetic stirring, a thermometer, a reflux condenser, and a nitrogen gas conduit, dry nitrogen gas was introduced, and air in the flask was purged. Adding 14.9g of biphenyl phenylphosphine oxide and mesitylene benzaldehyde obtained in the process, and reacting for 1h at 15-25 ℃; the temperature of the reaction solution is reduced to 6-10 ℃, 0.27g of vanadium diacetylacetonate is added, 16.7g of 70% tertiary butyl alcohol peroxide is slowly dripped, the reaction is carried out for 8 hours after the dripping is finished, the solvent is distilled off after the reaction solution is washed by sodium sulfite solution and water, and 20ml of petroleum ether is added for recrystallization, thus obtaining DPTPO. The product yield was 71% and the HPLC content was 98.1%.
The products obtained in examples 3 and 4 above were tested and the results are given in the following table:
TABLE 1 absorption characterization data for photoinitiators TPO,2,4-DMTPO and 4-FTPO
TABLE 2 4-FTPO curing TMPTA upper and lower surface fluorine EDX test results for photoinitiators
Description:
(1) Compared with a commercial photo-initiator TPO, the maximum absorption wavelength of the 2,4-DMDPO initiator prepared by the invention is red shifted, and the initiator can be matched with an LED initiation light source; meanwhile, the light absorption coefficient is increased, and the stronger initiation effect is preliminarily verified;
(2) Compared with the commercialized photo-initiator TPO, the maximum absorption wavelength of the 4-FTPO prepared in the invention is unchanged, but the absorption coefficient is increased, which indicates that the 4-FTPO has stronger initiating effect; meanwhile, because of the introduction of F atoms, the initiator can migrate in a curing system, so that gradient distribution is generated, and the property can solve the problem of surface oxygen resistance of the initiator.
Claims (11)
1. An acylphosphine photoinitiator, characterized in that: the chemical structural formula is shown as follows:
2. the process for preparing an acylphosphine photoinitiator according to claim 1, comprising the steps of:
(1) Adding aryl phosphine dichloride or a derivative thereof, aromatic hydrocarbon or a derivative thereof in a formula (III) and a catalyst in a reaction bottle, reacting at a certain temperature for a certain time, and decompressing and distilling unreacted raw materials after the reaction is finished to obtain a complex of the diaryl phosphine dichloride and the catalyst, wherein the certain temperature is 50-150 ℃; the certain time is 2-48 hours;
(2) Slowly dripping the complex of the diaryl phosphine chloride and the catalyst into water at a certain temperature, continuing to react for a certain time after dripping, adding an extractant for extraction, and separating an organic layer for later use; the certain temperature is 0-50 ℃; the certain time is 0-20 hours;
(3) Adding the obtained organic layer into a reaction bottle, adding the aromatic aldehyde or the derivative thereof in the formula (IV) at a certain temperature, and reacting for a certain time to obtain a reaction solution for later use; the certain temperature is-10-25 ℃; the certain time is 0.5-5 h;
(4) Putting a catalyst and an oxidant into the reaction liquid obtained in the step (3) at a certain temperature, and reacting for a certain time to obtain an acylphosphine photoinitiator, wherein the certain temperature is 0-20 ℃; the certain time is 1-20 hours.
3. The process for preparing an acylphosphine photoinitiator according to claim 2, wherein: in the step (1), the ratio of the amount of the aryl phosphine dichloride or the derivative thereof in the formula (II) to the amount of the aromatic hydrocarbon or the derivative thereof in the formula (III) is 1:0.5-1: 5, a step of; the ratio of the aryl phosphine dichloride or the derivative thereof in the formula (II) to the catalyst is 1:0.8-1:3; the catalyst is at least one of anhydrous aluminum chloride, anhydrous gallium chloride, anhydrous indium chloride, anhydrous bismuth chloride, anhydrous antimony chloride, anhydrous tin chloride, anhydrous magnesium chloride and anhydrous ferric chloride.
4. A process for the preparation of an acylphosphine photoinitiator according to claim 3, characterised in that: the temperature in the step (1) is 90 ℃; the time is 12h; the ratio of the amount of aryl phosphine dichloride or derivative thereof of formula (II) to the amount of aromatic hydrocarbon or derivative thereof of formula (III) is 1:1.3; the ratio of aryl phosphine dichloride or derivative thereof of formula (II) to the amount of material of the catalyst is 1:1.4; the catalyst used was anhydrous aluminum chloride.
5. The process for preparing an acylphosphine photoinitiator according to claim 2, wherein: the extractant used in the step (2) is at least one selected from benzene, toluene, methylene dichloride, dichloroethane, chloroform, carbon tetrachloride, chlorobenzene and nitrobenzene.
6. The process for preparing an acylphosphine photoinitiator according to claim 5, wherein: in the step (2), the temperature is 0 ℃ and the time is 4 hours, and the extractant is toluene.
7. The process for preparing an acylphosphine photoinitiator according to claim 2, wherein: the ratio of the amount of the aromatic aldehyde or derivative thereof of formula (IV) to the amount of the aromatic phosphine dichloride or derivative thereof used in step (3) is 1:0.6 to 1:1.5.
8. The process for preparing an acylphosphine photoinitiator according to claim 7, wherein: the temperature in the step (3) is 15-25 ℃; the time is 1h; the ratio of the amount of the substance of the formula (IV) of the aromatic aldehyde or derivative thereof to the amount of the substance of the aryl phosphine dichloride or derivative thereof used is 1:1.
9. The process for preparing an acylphosphine photoinitiator according to claim 2, wherein: in the step (4), the catalyst used is: one or more of vanadium pentoxide, vanadium diacetylacetonate, manganese dioxide and ammonium metavanadate; the catalyst is 0.1% -5% of the amount of aryl phosphine dichloride or derivative substances thereof; the used oxidizing agent is as follows: one or more of potassium permanganate, hydrogen peroxide and tert-butyl peroxide; the ratio of the amount of the oxidant to the aryl phosphine dichloride or the derivative thereof is 1:1-5:1.
10. The process for preparing an acylphosphine photoinitiator according to claim 9, wherein: in the step (4), the temperature is 6-10 ℃; the time is 8 hours; the catalyst is vanadium diacetylacetonate; the catalyst used was 1% of the amount of the substance of aryl phosphine dichloride or its derivative; the oxidant is tert-butyl peroxide; the ratio of the amount of oxidant used to the amount of aryl phosphine dichloride or derivative thereof is 1.3:1.
11. Use of an acylphosphine photoinitiator according to claim 1 as a long wavelength photoinitiator.
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