CN113979834A - Photocuring initiator, preparation method thereof and photocuring composition containing photocuring initiator - Google Patents
Photocuring initiator, preparation method thereof and photocuring composition containing photocuring initiator Download PDFInfo
- Publication number
- CN113979834A CN113979834A CN202111336692.3A CN202111336692A CN113979834A CN 113979834 A CN113979834 A CN 113979834A CN 202111336692 A CN202111336692 A CN 202111336692A CN 113979834 A CN113979834 A CN 113979834A
- Authority
- CN
- China
- Prior art keywords
- photo
- reaction
- preparing
- acid
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000000016 photochemical curing Methods 0.000 title claims abstract description 40
- 239000003999 initiator Substances 0.000 title claims abstract description 35
- 239000000203 mixture Substances 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 36
- -1 saturated potassium hexafluorophosphate Chemical class 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 239000007787 solid Substances 0.000 claims abstract description 20
- 125000005520 diaryliodonium group Chemical group 0.000 claims abstract description 16
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 14
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 13
- 239000011630 iodine Substances 0.000 claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 12
- 239000007800 oxidant agent Substances 0.000 claims abstract description 11
- 230000001590 oxidative effect Effects 0.000 claims abstract description 9
- 238000000967 suction filtration Methods 0.000 claims abstract description 8
- 239000002253 acid Substances 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 5
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 4
- 239000000460 chlorine Substances 0.000 claims abstract description 4
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims abstract description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims abstract description 4
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims abstract description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 4
- 125000001424 substituent group Chemical group 0.000 claims abstract description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 20
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 claims description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-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
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 6
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims description 6
- 150000001555 benzenes Chemical class 0.000 claims description 6
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-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
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 claims description 6
- YTZKOQUCBOVLHL-UHFFFAOYSA-N tert-butylbenzene Chemical compound CC(C)(C)C1=CC=CC=C1 YTZKOQUCBOVLHL-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 4
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims description 4
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 4
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 3
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 2
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 2
- 239000012425 OXONE® Substances 0.000 claims description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 2
- HJKYXKSLRZKNSI-UHFFFAOYSA-I pentapotassium;hydrogen sulfate;oxido sulfate;sulfuric acid Chemical compound [K+].[K+].[K+].[K+].[K+].OS([O-])(=O)=O.[O-]S([O-])(=O)=O.OS(=O)(=O)O[O-].OS(=O)(=O)O[O-] HJKYXKSLRZKNSI-UHFFFAOYSA-I 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 229960001922 sodium perborate Drugs 0.000 claims description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 2
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 13
- 238000003786 synthesis reaction Methods 0.000 abstract description 13
- 239000006227 byproduct Substances 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 125000001997 phenyl group Chemical class [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 32
- 239000000047 product Substances 0.000 description 32
- 238000003756 stirring Methods 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 8
- 238000005160 1H NMR spectroscopy Methods 0.000 description 8
- HZNVUJQVZSTENZ-UHFFFAOYSA-N 2,3-dichloro-5,6-dicyano-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(C#N)=C(C#N)C1=O HZNVUJQVZSTENZ-UHFFFAOYSA-N 0.000 description 8
- 239000000706 filtrate Substances 0.000 description 8
- 238000001914 filtration Methods 0.000 description 8
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 230000002194 synthesizing effect Effects 0.000 description 5
- NHQDETIJWKXCTC-UHFFFAOYSA-N 3-chloroperbenzoic acid Chemical compound OOC(=O)C1=CC=CC(Cl)=C1 NHQDETIJWKXCTC-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- HJAMWVFQXYTJBE-UHFFFAOYSA-M bis(4-bromophenyl)iodanium;trifluoromethanesulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)F.C1=CC(Br)=CC=C1[I+]C1=CC=C(Br)C=C1 HJAMWVFQXYTJBE-UHFFFAOYSA-M 0.000 description 2
- FWNJUSYYKZFUQB-UHFFFAOYSA-M bis(4-chlorophenyl)iodanium;trifluoromethanesulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)F.C1=CC(Cl)=CC=C1[I+]C1=CC=C(Cl)C=C1 FWNJUSYYKZFUQB-UHFFFAOYSA-M 0.000 description 2
- DSALILVWXNPMMK-UHFFFAOYSA-M bis(4-methoxyphenyl)iodanium;4-methylbenzenesulfonate Chemical compound CC1=CC=C(S([O-])(=O)=O)C=C1.C1=CC(OC)=CC=C1[I+]C1=CC=C(OC)C=C1 DSALILVWXNPMMK-UHFFFAOYSA-M 0.000 description 2
- JMTCFPYKCIJFQZ-UHFFFAOYSA-M bis(4-methylphenyl)iodanium;4-methylbenzenesulfonate Chemical compound CC1=CC=C(S([O-])(=O)=O)C=C1.C1=CC(C)=CC=C1[I+]C1=CC=C(C)C=C1 JMTCFPYKCIJFQZ-UHFFFAOYSA-M 0.000 description 2
- UEJFJTOGXLEPIV-UHFFFAOYSA-M bis(4-tert-butylphenyl)iodanium;4-methylbenzenesulfonate Chemical compound CC1=CC=C(S([O-])(=O)=O)C=C1.C1=CC(C(C)(C)C)=CC=C1[I+]C1=CC=C(C(C)(C)C)C=C1 UEJFJTOGXLEPIV-UHFFFAOYSA-M 0.000 description 2
- 238000001723 curing Methods 0.000 description 2
- 239000012955 diaryliodonium Substances 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- FODCFYIWOJIZQL-UHFFFAOYSA-N 1-methylsulfanyl-3,5-bis(trifluoromethyl)benzene Chemical compound CSC1=CC(C(F)(F)F)=CC(C(F)(F)F)=C1 FODCFYIWOJIZQL-UHFFFAOYSA-N 0.000 description 1
- 206010034972 Photosensitivity reaction Diseases 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive 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
- YCOXTKKNXUZSKD-UHFFFAOYSA-N as-o-xylenol Natural products CC1=CC=C(O)C=C1C YCOXTKKNXUZSKD-UHFFFAOYSA-N 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 239000012952 cationic photoinitiator Substances 0.000 description 1
- 238000010538 cationic polymerization reaction Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- SNHMUERNLJLMHN-UHFFFAOYSA-N iodobenzene Chemical compound IC1=CC=CC=C1 SNHMUERNLJLMHN-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 230000036211 photosensitivity Effects 0.000 description 1
- 239000003211 polymerization photoinitiator Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C25/00—Compounds containing at least one halogen atom bound to a six-membered aromatic ring
- C07C25/18—Polycyclic aromatic halogenated hydrocarbons
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a photocuring initiator which is polysubstituted diaryl iodonium hexafluorophosphate and has a structure shown in a formula I, wherein a substituent group R is selected from any one of methyl, ethyl, isopropyl, tert-butyl, methoxy, p-dimethyl, chlorine and bromine. The invention also provides a preparation method of the photocuring initiator, which comprises the following steps: (1) taking substituted benzene and elemental iodine as reaction raw materials, adding acid, then adding a first solvent, and then adding an oxidant for reaction to obtain an intermediate; (2) and (2) dissolving the intermediate obtained in the step (1) in a second solvent to form a solution, dropwise adding a saturated potassium hexafluorophosphate solution for reaction, and performing suction filtration to obtain the polysubstituted diaryl iodonium hexafluorophosphate after solids are precipitated from the solution. The invention also provides a photocuring composition comprising the photocuringAnd (4) reacting the initiator. The method can reduce the process cost, and byproducts generated in the synthesis process are easy to treat and easy to realize industrial mass production.
Description
Technical Field
The invention relates to the technical field of photocuring materials, in particular to a photocuring initiator, a preparation method thereof and a photocuring composition containing the photocuring initiator.
Background
The ultraviolet curing technology is a process for rapidly converting a liquid substance with chemical reaction activity into a solid substance by utilizing ultraviolet initiation. The technology has the characteristics of high curing speed, high efficiency, wide adaptability, economy, energy conservation, less pollution, low toxicity and environmental friendliness, and is widely applied to the fields of printing plate making, photoresists, printing inks, coatings, adhesives, rapid forming, food packaging and medical biomaterials.
The light-cured system generally comprises four parts of a prepolymer, a photoinitiator, a reactive diluent and an additive. The photoinitiator which is the most core photoinitiator in the photocuring technology naturally has high research and application values, and the existing photoinitiators are mainly divided into two types, namely a free radical type photoinitiator and a cationic photoinitiator according to the initiation mechanism. Among them, diaryliodonium salts have been the most widely used cationic polymerization photoinitiators so far because of their advantages such as good photosensitivity, thermal stability and photoinitiation activity.
In 2007, the Olofsson topic group developed a method for synthesizing diaryliodonium trifluoromethanesulfonate using iodobenzene and aromatic hydrocarbon as raw materials and m-chloroperoxybenzoic acid as an oxidizing agent. (adv. Synth. Catal.2007,349, 2610-2618.)
In 2008, the Olofsson subject group developed a new method for synthesizing diaryl iodonium p-toluenesulfonate by using anisole and iodine as raw materials and m-chloroperoxybenzoic acid as an oxidizing agent. (Synlett 2008,4,592 and 596.)
However, in the prior art for synthesizing diaryl iodonium salts, m-chloroperoxybenzoic acid is used as an oxidant in the methods, so the method is very expensive, and the m-chloroperoxybenzoic acid which is a byproduct generated in the reaction is very complicated in treatment process and difficult to recycle. In addition, the above method is difficult to realize a large amount of industrial production requirements. Therefore, it is of great significance to develop a new method for synthesizing diaryl iodonium salt with lower cost and easy processing of byproducts.
Disclosure of Invention
The invention aims to solve the technical problems that the synthesis process of diaryl iodonium salt in the prior art is high in cost, byproducts generated in the process are not easy to treat, and industrial mass production is difficult to realize. The invention provides a photocuring initiator, a preparation method thereof and a photocuring composition containing the photocuring initiator, which can reduce the preparation cost of the photocuring initiator, and by-products generated in the synthesis process are easy to treat and easy to realize industrial mass production.
In order to solve the above technical problems, an embodiment of the present invention discloses a photocuring initiator, which is a polysubstituted diaryliodonium hexafluorophosphate and has a structure shown in formula I:
wherein, the substituent group R is selected from any one of methyl, ethyl, isopropyl, tert-butyl, methoxy, p-dimethyl, chlorine and bromine.
According to another specific embodiment, the present invention discloses a photo-curing initiator, and the substituent group R is selected from any one or more of methyl, ethyl, isopropyl, tert-butyl, methoxy, p-dimethyl, chlorine and bromine.
The embodiment of the invention also discloses a preparation method of the photocuring initiator, which comprises the following steps:
(1) taking substituted benzene and elemental iodine as reaction raw materials, adding acid, then adding a first solvent, and then adding an oxidant for reaction to obtain an intermediate;
(2) and (2) dissolving the intermediate obtained in the step (1) in a second solvent to form a solution, dropwise adding a saturated potassium hexafluorophosphate solution, and performing suction filtration to obtain the polysubstituted diaryl iodonium hexafluorophosphate after solids are precipitated from the solution.
According to another specific embodiment of the invention, the embodiment of the invention discloses a preparation method of the photocuring initiator, in the step (1), the substituted benzene is any one of toluene, ethylbenzene, cumene, tert-butylbenzene, anisole, p-xylene, chlorobenzene and bromobenzene.
According to another specific embodiment of the invention, in step (1), the molar ratio of the substituted benzene to the elemental iodine is 4:1-8:1, the molar ratio of the acid addition amount to the elemental iodine is 2:1-4:1, the molar ratio of the first solvent addition amount to the elemental iodine is 30:1-60:1, and the molar ratio of the oxidant addition amount to the elemental iodine is 4:1-8: 1.
According to another embodiment of the present invention, there is disclosed a method for preparing a photo-curing initiator, wherein in the step (2), the molar ratio of the saturated potassium hexafluorophosphate solution to the intermediate is 1:1 to 3: 1.
According to another specific embodiment of the invention, the embodiment of the invention discloses a preparation method of a photocuring initiator, wherein the acid is any one of p-toluenesulfonic acid, trifluoromethanesulfonic acid, hydrochloric acid, sulfuric acid and acetic acid;
the first solvent is any one of dichloromethane, dichloroethane, methanol, ethyl acetate, acetone and methyl tert-butyl ether.
According to another specific embodiment of the invention, the embodiment of the invention discloses a preparation method of a photocuring initiator, and the oxidant is any one of 50% hydrogen peroxide, sodium perborate, sodium persulfate, potassium monopersulfate, ammonium persulfate, benzoyl peroxide and 55% tert-butyl hydroperoxide.
According to another specific embodiment, the embodiment of the invention discloses a preparation method of the photo-curing initiator, and the second solvent is any one of acetonitrile, methanol, ethanol and isopropanol.
According to another embodiment of the present invention, the embodiment of the present invention discloses a method for preparing a photo-curing initiator, wherein in the step (1), the reaction temperature is controlled to be 30-80 ℃, and the reaction time is controlled to be 48 hours.
The embodiment of the invention also discloses a photocuring composition which comprises the photocuring initiator.
Compared with the prior art, the invention has the following effects:
the photocuring initiator and the preparation method can reduce the preparation cost of the photocuring initiator, and byproducts generated in the synthesis process are easy to treat, so that the industrial mass production is easy to realize.
Detailed Description
The following description of the embodiments of the present invention is provided for illustrative purposes, and other advantages and effects of the present invention will become apparent to those skilled in the art from the present disclosure. While the invention will be described in conjunction with the preferred embodiments, it is not intended that features of the invention be limited to these embodiments. On the contrary, the invention is described in connection with the embodiments for the purpose of covering alternatives or modifications that may be extended based on the claims of the present invention. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. The invention may be practiced without these particulars. Moreover, some of the specific details have been left out of the description in order to avoid obscuring or obscuring the focus of the present invention. It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict.
The invention relates to a specific synthesis process as shown in the formula, wherein the polysubstituted diaryl iodonium hexafluorophosphate is prepared by a method comprising the following steps:
example 1
The related synthesis process comprises the following steps:
adding 11.1g of toluene, 5.1g of elemental iodine, 10.3g of p-toluenesulfonic acid and 50mL of dichloroethane into a 250mL round-bottom flask in sequence, slowly dropwise adding 10.3g of 50% hydrogen peroxide under stirring, heating to 60 ℃ for reaction for 48 hours, filtering to remove solids after the reaction is finished, washing the filtrate with water, and desolventizing to obtain 16.3g of intermediate bis (4-methylphenyl) iodonium p-toluenesulfonic acid salt; 16.3g of the intermediate bis (4-methylphenyl) iodonium p-toluenesulfonate thus obtained was dissolved in 10mL of ethanol, and then a saturated potassium hexafluorophosphate solution (14.7g of potassium hexafluorophosphate dissolved in 200mL of water) was added dropwise thereto with stirring, and the mixture was stirred at room temperature for 2 hours, after a solid precipitated from the solution, it was filtered by suction to obtain 15.2g of the product bis (4-methylphenyl) iodonium hexafluorophosphate in a yield of 84%. Of the resulting product1H NMR(500MHz,CDCl3)δ8.02(d,J＝8.5Hz,4H),7.28(d,J＝7.8Hz,4H),2.38(s,6H)；13C NMR(125MHz,CDCl3) δ 141.8,136.0,132.3,111.2, 21.3. The above results confirmed that the obtained product was the objective product.
Example 2
The related synthesis process comprises the following steps:
adding 12.7g of ethylbenzene, 5.1g of elemental iodine, 10.3g of p-toluenesulfonic acid and 50mL of dichloroethane into a 250mL round-bottom flask in sequence, slowly dropwise adding 10.3g of 50% hydrogen peroxide under stirring, heating to 60 ℃ for reaction for 48 hours, filtering to remove solids after the reaction is finished, washing the filtrate with water, and desolventizing to obtain 15.3g of an intermediate bis (4-ethylphenyl) iodonium p-toluenesulfonic acidSalt; 15.3g of the intermediate bis (4-ethylphenyl) iodonium p-toluenesulfonate thus obtained was dissolved in 10mL of ethanol, and then a saturated potassium hexafluorophosphate solution (14.7g of potassium hexafluorophosphate dissolved in 200mL of water) was added dropwise thereto with stirring, and the mixture was stirred at room temperature for 2 hours, after a solid precipitated from the solution, the product bis (4-ethylphenyl) iodonium hexafluorophosphate was obtained in an amount of 14.5g with a yield of 75% by suction filtration. Of the resulting product1H NMR(500MHz,CDCl3)δ8.07(d,J＝8.5Hz,4H),7.38(d,J＝8.4Hz,4H),2.70(q,J＝7.3Hz,4H),1.26(t,J＝7.2Hz,6H)；13C NMR(125MHz,CDCl3) δ 147.0,135.6,130.9,112.4,28.7, 15.4. The above results confirmed that the obtained product was the objective product.
Example 3
The related synthesis process comprises the following steps:
adding 14.4g of cumene, 5.1g of elementary iodine, 10.3g of p-toluenesulfonic acid and 50mL of dichloroethane into a 250mL round-bottom flask in sequence, then slowly dropwise adding 10.3g of 50% hydrogen peroxide under the stirring condition, heating to 60 ℃ for reaction for 48 hours, filtering to remove solids after the reaction is finished, and washing and desolventizing filtrate to obtain 16.5g of intermediate bis (4-isopropylphenyl) iodonium p-toluenesulfonic acid salt; 16.5g of the intermediate bis (4-isopropylphenyl) iodonium p-toluenesulfonate thus obtained was dissolved in 10mL of ethanol, and then a saturated potassium hexafluorophosphate solution (14.7g of potassium hexafluorophosphate dissolved in 200mL of water) was added dropwise thereto with stirring, and the mixture was stirred at room temperature for 2 hours, after solids were precipitated from the solution, the product bis (4-isopropylphenyl) iodonium hexafluorophosphate was obtained in an amount of 15.5g with a yield of 76% by suction filtration. 1H NMR (500MHz, CDCl3) δ 8.06(d, J ═ 8.4Hz,4H),7.28(d, J ═ 7.5Hz,4H),2.89-2.73(m,2H),1.26(d, J ═ 6.6Hz,12H) of the resulting product; 13C NMR (125MHz, CDCl3) delta 150.6,135.6,129.3,113.2,33.9, 23.9. The above results confirmed that the obtained product was the objective product.
Example 4
The related synthesis process comprises the following steps:
adding 16.1g of tert-butylbenzene, 5.1g of elemental iodine, 10.3g of p-toluenesulfonic acid and 50mL of dichloroethane into a 250mL round-bottom flask in sequence, slowly dropwise adding 10.3g of 50% hydrogen peroxide under stirring, heating to 60 ℃ for reaction for 48 hours, filtering to remove solids after the reaction is finished, washing the filtrate with water, and desolventizing to obtain 15.8g of intermediate bis (4-tert-butylphenyl) iodonium p-toluenesulfonic acid salt; 15.8g of the intermediate bis (4-tert-butylphenyl) iodonium p-toluenesulfonate thus obtained was dissolved in 10mL of ethanol, and then a saturated potassium hexafluorophosphate solution (14.7g of potassium hexafluorophosphate dissolved in 200mL of water) was added dropwise thereto with stirring, and the mixture was stirred at room temperature for 2 hours, after a solid precipitated from the solution, the product bis (4-tert-butylphenyl) iodonium hexafluorophosphate was obtained in an amount of 14.9g with a yield of 69%. Of the resulting product1H NMR(500MHz,CDCl3)δ8.05(d,J＝8.5Hz,4H),7.50(d,J＝8.5Hz,4H),1.36(s,18H)；13C NMR(125MHz,CDCl3) δ 154.9,135.7,128.2,113.4,34.6, 31.2. The above results confirmed that the obtained product was the objective product.
Example 5
The related synthesis process comprises the following steps:
13.0g of anisole, 5.1g of iodine simple substance, 10.3g of p-toluenesulfonic acid and 50mL of dichloroethane are sequentially added into a 250mL round-bottom flask, 10.3g of 50% hydrogen peroxide is slowly and dropwise added under the condition of stirring, and then the mixture is heated to 60 ℃ to react for 48 hours. After the reaction, the solid was removed by filtration, and the filtrate was washed with water and desolventized to obtain 16.8g of intermediate bis (4-methoxyphenyl) iodonium p-toluenesulfonate. The intermediate bis (4-methoxyphenyl) iodonium p-toluenesulfonate, which was obtained in 16.8g, was dissolved in 10mL of ethanol, and then a saturated potassium hexafluorophosphate solution (14.7g of potassium hexafluorophosphate dissolved in 200mL of water) was added dropwise thereto with stirring, and stirred at room temperature for 2 hours, after a solid precipitated from the solution, it was filtered by suction to obtain 15.8g of bis (4-methoxyphenyl) iodonium hexafluorophosphate as a product in a yield of 81%. 1H NMR (500MHz, CDCl3) δ 8.05(d, J ═ 8.5Hz,4H),7.03(d, J ═ 8.4Hz,4H),3.79(s,6H) of the resulting product; 13C NMR (125MHz in CDCl3) delta 162.9,137.4,117.5,107.1, 55.4. The above results confirmed that the obtained product was the objective product.
Example 6
The related synthesis process comprises the following steps:
adding 12.7g of p-xylene, 5.1g of elemental iodine, 10.3g of p-toluenesulfonic acid and 50mL of dichloroethane into a 250mL round-bottom flask in sequence, then slowly dropwise adding 10.3g of 50% hydrogen peroxide under the stirring condition, heating to 60 ℃ for reaction for 48 hours, filtering to remove solids after the reaction is finished, and washing and desolventizing filtrate to obtain 13.2g of intermediate bis (2, 5-dimethylphenyl) iodonium p-toluenesulfonic acid salt; 13.2g of the obtained intermediate bis (2, 5-dimethylphenyl) iodonium p-toluenesulfonate was dissolved in 10mL of ethanol, and then a saturated potassium hexafluorophosphate solution (14.7g of potassium hexafluorophosphate dissolved in 200mL of water) was added dropwise thereto with stirring, and stirred at room temperature for 2 hours, and after a solid precipitated from the solution, 12.3g of the product bis (2, 5-dimethylphenyl) iodonium hexafluorophosphate was obtained by suction filtration at a yield of 64%. Of the resulting product1H NMR(500MHz,CDCl3)δ7.97(s,2H),7.14(s,4H),2.41(s,6H),2.36(s,6H)；13C NMR(125MHz,CDCl3) δ 139.8,137.2,134.8,132.1,131.2,110.8,27.3, 21.0. The above results confirmed that the obtained product was the objective product.
Example 7
The related synthesis process comprises the following steps:
13.5g of chlorobenzene, 5.1g of elemental iodine, 9g of trifluoromethanesulfonic acid and 50mL of dichloroethane are sequentially added into a 250mL round-bottom flask, then 10.3g of 50% hydrogen peroxide is slowly dripped under the stirring condition, then the mixture is heated to 60 ℃ to react for 48 hours, after the reaction is finished, the solid is removed by filtration, and after washing and desolventizing are carried out on the filtrate, 16.4g of intermediate bis (4-chlorophenyl) iodonium trifluoromethanesulfonate is obtained; the obtained 16.4g of intermediate bis (4-chlorophenyl) iodonium trifluoromethanesulfonate was dissolved in 10mL of ethanol, and then a saturated potassium hexafluorophosphate solution (14.7g of potassium hexafluorophosphate dissolved in 200mL of water) was added dropwise thereto with stirring, and stirred at room temperature for 2 hours, and after a solid precipitated from the solution, 16.7g of the product bis (4-chlorophenyl) iodonium hexafluorophosphate was obtained by suction filtration at a yield of 82%. 1H NMR (500MHz, CDCl3) δ 8.09(d, J ═ 8.4Hz,4H),7.55(d, J ═ 8.5Hz,4H) of the resulting product; 13C NMR (125MHz in CDCl3) delta 137.4,137.3,131.9,112.3. The above results confirmed that the obtained product was the objective product.
Example 8
The related synthesis process comprises the following steps:
adding 18.8g of bromobenzene, 5.1g of elemental iodine, 9g of trifluoromethanesulfonic acid and 50mL of dichloroethane into a 250mL round-bottom flask in sequence, then slowly dropwise adding 10.3g of 50% hydrogen peroxide under the stirring condition, heating to 60 ℃ for reacting for 48 hours, filtering to remove solids after the reaction is finished, and washing and desolventizing the filtrate to obtain 19.3g of intermediate bis (4-bromophenyl) iodonium trifluoromethanesulfonate; 19.3g of the intermediate bis (4-bromophenyl) iodonium trifluoromethanesulfonate thus obtained was dissolved in 10mL of ethanol, and then a saturated potassium hexafluorophosphate solution (14.7g of potassium hexafluorophosphate dissolved in 200mL of water) was added dropwise thereto with stirring, and the mixture was stirred at room temperature for 2 hours, and after a solid precipitated from the solution, 19.6g of the product bis (4-bromophenyl) iodonium hexafluorophosphate was obtained by suction filtration at a yield of 82%. Of the resulting product1H NMR(500MHz,CDCl3)δ8.08(d,J＝8.5Hz,4H),7.65(d,J＝8.5Hz,4H)；13C NMR(125MHz,CDCl3) δ 137.5,134.5,125.4,113.2. The above results confirmed that the obtained product was the objective product.
The invention provides a new way for synthesizing polysubstituted diaryl iodonium hexafluorophosphate, and the polysubstituted diaryl iodonium hexafluorophosphate obtained by the invention has high photoinitiation activity; the oxidant used in the method is cheap and easy to obtain, and meanwhile, the generated by-product is easy to treat, the reaction condition is mild, and the industrial production requirement can be met.
While the invention has been described with reference to certain preferred embodiments thereof, it will be understood by those skilled in the art that the foregoing is a more particular description of the invention than is possible with reference to the specific embodiments, which are not to be construed as limiting the invention. Various changes in form and detail, including simple deductions or substitutions, may be made by those skilled in the art without departing from the spirit and scope of the invention.
Claims (10)
1. A photo-curing initiator, wherein the initiator is a polysubstituted diaryliodonium hexafluorophosphate, the polysubstituted diaryliodonium hexafluorophosphate having the structure shown in formula I:
wherein, the substituent group R is selected from any one of methyl, ethyl, isopropyl, tert-butyl, methoxy, p-dimethyl, chlorine and bromine.
2. A method for preparing the photo-curing initiator according to claim 1, comprising the steps of:
(1) taking substituted benzene and elemental iodine as reaction raw materials, adding acid, then adding a first solvent, and then adding an oxidant for reaction to obtain an intermediate;
(2) and (2) dissolving the intermediate obtained in the step (1) in a second solvent to form a solution, dropwise adding a saturated potassium hexafluorophosphate solution for reaction, and performing suction filtration to obtain the polysubstituted diaryl iodonium hexafluorophosphate after a solid is precipitated from the solution.
3. The method of preparing the photo-curing initiator according to claim 2, wherein in the step (1), the substituted benzene is any one of toluene, ethylbenzene, cumene, tert-butylbenzene, anisole, p-xylene, chlorobenzene, and bromobenzene.
4. The method of preparing the photo-curing initiator according to claim 2, wherein in the step (1), the molar ratio of the substituted benzene to the elemental iodine is 4:1 to 8:1, the molar ratio of the acid addition amount to the elemental iodine is 2:1 to 4:1, the molar ratio of the first solvent addition amount to the elemental iodine is 30:1 to 60:1, and the molar ratio of the oxidant addition amount to the elemental iodine is 4:1 to 8: 1.
5. The method for preparing the photo-curing initiator according to claim 2, wherein in the step (2), the saturated potassium hexafluorophosphate solution is added in a molar ratio of 1:1 to 3:1 to the intermediate.
6. The method for preparing the photo-curing initiator according to claim 2, wherein the acid is any one of p-toluenesulfonic acid, trifluoromethanesulfonic acid, hydrochloric acid, sulfuric acid, and acetic acid;
the first solvent is any one of dichloromethane, dichloroethane, methanol, ethyl acetate, acetone and methyl tert-butyl ether.
7. The method for preparing the photo-curing initiator according to claim 2, wherein the oxidant is any one of 50% hydrogen peroxide, sodium perborate, sodium persulfate, potassium monopersulfate, ammonium persulfate, benzoyl peroxide, and 55% t-butyl hydroperoxide.
8. The method of preparing the photo-curing initiator according to claim 2, wherein the second solvent is any one of acetonitrile, methanol, ethanol, and isopropanol.
9. The method for preparing the photo-curing initiator according to claim 2, wherein in the step (1), the reaction temperature is controlled to be 30 to 80 ℃ and the reaction time is controlled to be 48 hours.
10. A photocurable composition comprising the photocurable initiator according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111336692.3A CN113979834B (en) | 2021-11-11 | 2021-11-11 | Photocuring initiator, preparation method thereof and photocuring composition containing photocuring initiator |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111336692.3A CN113979834B (en) | 2021-11-11 | 2021-11-11 | Photocuring initiator, preparation method thereof and photocuring composition containing photocuring initiator |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113979834A true CN113979834A (en) | 2022-01-28 |
| CN113979834B CN113979834B (en) | 2023-01-17 |
Family
ID=79748116
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111336692.3A Active CN113979834B (en) | 2021-11-11 | 2021-11-11 | Photocuring initiator, preparation method thereof and photocuring composition containing photocuring initiator |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113979834B (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104628516A (en) * | 2013-11-08 | 2015-05-20 | 上海予利化学科技有限公司 | Cation photoinitiator 4-isobutylphenyl-4'-methylphenyl iodonium hexafluorophosphate preparation method |
-
2021
- 2021-11-11 CN CN202111336692.3A patent/CN113979834B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104628516A (en) * | 2013-11-08 | 2015-05-20 | 上海予利化学科技有限公司 | Cation photoinitiator 4-isobutylphenyl-4'-methylphenyl iodonium hexafluorophosphate preparation method |
Non-Patent Citations (2)
| Title |
|---|
| 刘安昌等: "阳离子光引发剂的研究进展", 《中国感光学会辐射固化专业委员会2020第二十一届辐射固化年会 论文报告集》 * |
| 肖志超等: "二芳基碘鎓盐在有机反应中的研究新进展", 《有机化学》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113979834B (en) | 2023-01-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP2992517B1 (en) | Method for producing sulfonium salt | |
| CN102212150B (en) | Polymerizable thioxanthone photoinitiator containing auxiliary initiator amine and preparation method thereof | |
| CN107814694B (en) | Fluorene initiator, preparation method thereof, photocuring composition with fluorene initiator and application of composition in photocuring field | |
| CN113454095A (en) | Acylphosphinoxide compound and preparation method thereof | |
| CN109232668B (en) | Ferrocene derivative used as photo-oxidation-reduction catalyst in photopolymerization and composition thereof | |
| EP0463862B1 (en) | Aromatic vinyl ether compounds and compositions, and method of making the same | |
| JP2002523529A (en) | Thermal and photo-initiated radical polymerization in the presence of an additional fragmentation agent | |
| CN113979834B (en) | Photocuring initiator, preparation method thereof and photocuring composition containing photocuring initiator | |
| CN113248636B (en) | Thioxanthone visible light initiator, preparation method and application | |
| CN112694548B (en) | Acylphosphine oxide photoinitiator and preparation method and application thereof | |
| CN112279940B (en) | Acylphosphine photoinitiator and preparation method thereof | |
| KR100293266B1 (en) | Method of synthesis sulfonium salts | |
| CN112538093B (en) | Preparation method of photoinitiator | |
| CN110804076A (en) | Method for preparing 1-ferrocenyl-3-aryl-3- (ethyl dicarboxylate group methine) -acetone | |
| CN113527138A (en) | P-fluorobenzoyl oxime ester photoinitiator for preparing photochromic material and preparation method and application thereof | |
| JPS63215720A (en) | Production of functional group-terminated lactone polymer | |
| CN112409295B (en) | Fluorene initiator, photocuring composition containing same and application thereof | |
| JP2962805B2 (en) | Curable resin composition | |
| CN116854552A (en) | Polysubstituted olefin and preparation method thereof | |
| Zawadiak et al. | Synthesis of New Primary-Tertiary Alkyl Bisperoxides by Reaction of Tertiary Hydroperoxides with Bromoalkanesin a PTC System | |
| WO2023042894A1 (en) | Furanacrylic acid ester polymer, production method therefor, and polymerizable monomer for use in producing said polymer and production method therefor | |
| CN116135865A (en) | Preparation method of photoinitiator TPO | |
| JP2002088007A (en) | O-substituted calix arenes and technique associated therewith | |
| JP2007112788A (en) | Oxetane compound | |
| JP2004528440A (en) | Composition of acid macromonomer and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |