CN111635301A - Novel photoinitiator and preparation method thereof - Google Patents
Novel photoinitiator and preparation method thereof Download PDFInfo
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- CN111635301A CN111635301A CN202010385779.9A CN202010385779A CN111635301A CN 111635301 A CN111635301 A CN 111635301A CN 202010385779 A CN202010385779 A CN 202010385779A CN 111635301 A CN111635301 A CN 111635301A
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- novel photoinitiator
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- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000006482 condensation reaction Methods 0.000 claims abstract description 15
- SHJXSYJQBXYBGA-UHFFFAOYSA-N 2-cyclohexyl-2-hydroxy-1-phenylethanone Chemical compound C=1C=CC=CC=1C(=O)C(O)C1CCCCC1 SHJXSYJQBXYBGA-UHFFFAOYSA-N 0.000 claims abstract description 13
- -1 aldehyde compounds Chemical class 0.000 claims abstract description 12
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims description 62
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 32
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 13
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 12
- 239000012265 solid product Substances 0.000 claims description 10
- 125000003342 alkenyl group Chemical group 0.000 claims description 8
- 125000000304 alkynyl group Chemical group 0.000 claims description 8
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 125000003545 alkoxy group Chemical group 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 6
- 150000002367 halogens Chemical class 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- ZCSHNCUQKCANBX-UHFFFAOYSA-N lithium diisopropylamide Chemical compound [Li+].CC(C)[N-]C(C)C ZCSHNCUQKCANBX-UHFFFAOYSA-N 0.000 claims description 6
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 6
- IZALUMVGBVKPJD-UHFFFAOYSA-N benzene-1,3-dicarbaldehyde Chemical compound O=CC1=CC=CC(C=O)=C1 IZALUMVGBVKPJD-UHFFFAOYSA-N 0.000 claims description 5
- OUKQTRFCDKSEPL-UHFFFAOYSA-N 1-Methyl-2-pyrrolecarboxaldehyde Chemical compound CN1C=CC=C1C=O OUKQTRFCDKSEPL-UHFFFAOYSA-N 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 4
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 claims description 4
- HMGXRGDTHQEUAO-UHFFFAOYSA-N 1-methylpyrrole-2,5-dicarbaldehyde Chemical compound CN1C(C=O)=CC=C1C=O HMGXRGDTHQEUAO-UHFFFAOYSA-N 0.000 claims description 3
- YNESATAKKCNGOF-UHFFFAOYSA-N lithium bis(trimethylsilyl)amide Chemical compound [Li+].C[Si](C)(C)[N-][Si](C)(C)C YNESATAKKCNGOF-UHFFFAOYSA-N 0.000 claims description 3
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 3
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- 125000003277 amino group Chemical group 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 229940043279 diisopropylamine Drugs 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 238000010521 absorption reaction Methods 0.000 abstract description 17
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 abstract 1
- 239000013078 crystal Substances 0.000 description 12
- 238000006116 polymerization reaction Methods 0.000 description 12
- 238000005160 1H NMR spectroscopy Methods 0.000 description 11
- 239000000178 monomer Substances 0.000 description 11
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 10
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 10
- 238000001914 filtration Methods 0.000 description 10
- 238000001291 vacuum drying Methods 0.000 description 10
- 238000005406 washing Methods 0.000 description 10
- 238000000862 absorption spectrum Methods 0.000 description 9
- 238000001816 cooling Methods 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 6
- 230000001376 precipitating effect Effects 0.000 description 6
- 239000007795 chemical reaction product Substances 0.000 description 4
- 238000002390 rotary evaporation Methods 0.000 description 4
- 125000001246 bromo group Chemical group Br* 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229910021576 Iron(III) bromide Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- CVEDVJRENZAPPJ-UHFFFAOYSA-N potassium;ethanol;2-methylpropan-2-olate Chemical compound [K+].CCO.CC(C)(C)[O-] CVEDVJRENZAPPJ-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium chloride Substances Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012663 cationic photopolymerization Methods 0.000 description 1
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- KVFDZFBHBWTVID-UHFFFAOYSA-N cyclohexanecarbaldehyde Chemical compound O=CC1CCCCC1 KVFDZFBHBWTVID-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000007336 electrophilic substitution reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- MNWBNISUBARLIT-UHFFFAOYSA-N sodium cyanide Chemical compound [Na+].N#[C-] MNWBNISUBARLIT-UHFFFAOYSA-N 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
- C07C45/72—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups
- C07C45/74—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups combined with dehydration
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
- C07C255/49—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
- C07C255/56—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing cyano groups and doubly-bound oxygen atoms bound to the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/76—Ketones containing a keto group bound to a six-membered aromatic ring
- C07C49/82—Ketones containing a keto group bound to a six-membered aromatic ring containing hydroxy groups
- C07C49/835—Ketones containing a keto group bound to a six-membered aromatic ring containing hydroxy groups having unsaturation outside an aromatic ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
- C07D207/32—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
- C07D207/33—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms with substituted hydrocarbon radicals, directly attached to ring carbon atoms
- C07D207/333—Radicals substituted by oxygen or sulfur atoms
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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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
Abstract
The invention relates to the technical field of organic synthesis, in particular to a novel photoinitiator and a preparation method thereof. The emission wavelength range of the LED light source used in the market at present is more than 365nm, the maximum absorption wavelength of the traditional photoinitiator 184 is 333nm and is not matched with the emission wavelength of the LED light source, in order to ensure that the maximum absorption wavelength of the traditional 184 photoinitiator is matched with the emission wavelength of the LED light source, the invention provides a novel photoinitiator which is obtained by the condensation reaction of hydroxycyclohexylacetophenone containing double alpha H carbonyl and aldehyde compounds, the main absorption wavelength of the novel photoinitiator can reach more than 365nm and is matched with the LED light source used in the market, and the novel photoinitiator has good application prospect.
Description
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a novel photoinitiator and a preparation method thereof.
Background
Photopolymerization technology is a new green technology and has been receiving attention in recent decades. Photopolymerization is mainly divided into two forms of radical photopolymerization and cationic photopolymerization, wherein radical photopolymerization is widely used in industry due to advantages of high polymerization efficiency, high conversion rate and the like.
The photoinitiator plays an important role as a photopolymerization system, in recent years, LED light sources are generally used in the field of photopolymerization, the wavelength range of the LED light sources used in the market at present is more than 365nm (365nm-770nm), the maximum absorption wavelength of the traditional 184 photoinitiator is 333nm and is lower than the emission wavelength of the LED light source, and if the traditional 184 photoinitiator is used for initiating photopolymerization under the irradiation of the LED light source, the efficiency of double bond conversion in the photopolymerization reaction is inevitably reduced.
Disclosure of Invention
Aiming at the problems in the prior art, the technical problems to be solved by the invention are as follows: how to improve the maximum absorption wavelength of the traditional 184 photoinitiator, the maximum absorption wavelength is matched with the emission wavelength of an LED light source, and the double bond conversion rate of the polymerization monomer under the irradiation of the LED light source is improved.
The technical scheme adopted by the invention for solving the technical problems is as follows:
the invention provides a novel photoinitiator, which is obtained by condensation reaction of hydroxycyclohexylacetophenone containing double alpha H carbonyl and aldehyde compounds, and the reaction equation is as follows:
wherein n is 1-2, formula I wherein: 4R2Represents a substituent on 4 arbitrary vacant positions on a benzene ring; r1And R2Is one of hydrogen atom, alkyl, alkenyl, alkoxy, alkynyl, hydroxyl, nitro, halogen, sulfonic group and alkyl, alkenyl, alkoxy and alkynyl which are substituted by hydroxyl, halogen, nitro, sulfonic group, cyano and amino; r3Is one of alkyl, alkenyl, alkynyl, aryl and heterocyclic aryl.
Specifically, the R is3Is one of hydroxyl, halogen, nitro, sulfonic group, cyano, amino-substituted alkyl, alkenyl, alkoxy and alkynyl.
Specifically, the novel photoinitiator comprises the following chemical formula:
a preparation method of a novel photoinitiator comprises the following steps:
(1) firstly, preparing hydroxyl cyclohexyl acetophenone containing double alpha H carbonyl;
(2) and (2) carrying out condensation reaction on the hydroxycyclohexylacetophenone containing the double alpha H carbonyl group obtained in the step (1) and an aldehyde compound, and after the reaction is finished, purifying a solid product to obtain the novel photoinitiator.
Specifically, the molar ratio of the hydroxycyclohexylacetophenone containing the bis-alpha H carbonyl group in the condensation reaction to the aldehyde compound is 1: 1-2.
Specifically, the temperature of the condensation reaction is 20-80 ℃, the reaction time is 1-6h, and the pH of the condensation reaction is 8-12.
Specifically, the solvent of the condensation reaction is methanol, ethanol, isopropanol, tert-butanol, tetrahydrofuran, dimethylformamide or dimethyl sulfoxide.
Specifically, the catalyst for the condensation reaction is sodium hydroxide, potassium hydroxide, sodium tert-butoxide, potassium tert-butoxide, sodium bicarbonate, diisopropylamine, pyridine, lithium diisopropylamide, triethanolamine, methyldiethanolamine or lithium hexamethyldisilazide.
Specifically, the aldehyde compound is benzaldehyde, m-phthalaldehyde, 1-methyl-1H-pyrrole-2, 5-dicarbaldehyde or 1-methyl-1H-pyrrole-2-formaldehyde.
The invention has the beneficial effects that:
(1) the main absorption wavelength of the novel photoinitiator prepared by the invention is more than 356nm, and the novel photoinitiator is matched with the emission wavelength of an LED light source commonly used in the field of photopolymerization, so that the novel photoinitiator has more excellent performance and stronger marketability.
(2) The method for preparing the novel photoinitiator is simple, the product can be obtained by one-step condensation reaction, the preparation cost is low, and the industrial production is easy to carry out.
Drawings
FIG. 1: uv absorption spectrum of the novel photoinitiator prepared in example 1.
FIG. 2: double bond conversion of the novel photoinitiator prepared in example 1.
FIG. 3: ultraviolet absorption spectrum of the novel photoinitiator prepared in example 2.
FIG. 4: example 2 conversion of double bonds of the novel photoinitiator prepared.
FIG. 5: ultraviolet absorption spectrum of the novel photoinitiator prepared in example 3.
FIG. 6: example 3 the conversion of double bonds of the novel photoinitiator prepared.
FIG. 7: ultraviolet absorption spectrum of the novel photoinitiator prepared in example 4.
FIG. 8: example 4 conversion of double bonds of the novel photoinitiator prepared.
FIG. 9: ultraviolet absorption spectrum of the novel photoinitiator prepared in example 5.
FIG. 10: example 5 preparation of a novel photoinitiator with double bond conversion.
FIG. 11: ultraviolet absorption spectrum of the novel photoinitiator prepared in example 6.
FIG. 12: example 6 shows the conversion of double bonds of the novel photoinitiator.
FIG. 13: ultraviolet absorption spectrum of the novel photoinitiator prepared in example 7.
FIG. 14: example 7 shows the conversion of double bonds of the novel photoinitiator.
FIG. 15: ultraviolet absorption spectrum of the novel photoinitiator prepared in example 8.
FIG. 16: example 8 preparation of a novel photoinitiator with double bond conversion.
FIG. 17: ultraviolet absorption spectrum of the novel photoinitiator prepared in example 9.
FIG. 18: example 9 preparation of a novel photoinitiator with double bond conversion.
FIG. 19: double bond conversion of conventional commercial 184 photoinitiators.
Detailed Description
The present invention will now be described in further detail with reference to the accompanying drawings.
Preparation example of 4- (1-hydroxycyclohexane-1-carbonyl) acetophenone:
dissolving 0.1mol of hydroxycyclohexylacetophenone in 100mL of ethanol, introducing 0.2mol of methyl chloride, and adding 3g of anhydrous AlCl3The methylated hydroxycyclohexylacetophenone is obtained by vacuum filtration, and 1g MnO is added220mL of H with the mass fraction of 65 percent is dripped2SO4The methyl group is oxidized to an aldehyde group. 0.15mol of CH is added dropwise3MgBr undergoes addition reaction and is finally oxidized into methyl ketone, and the reaction equation is as follows:
example 1
Dissolving 0.1mol of 4- (1-hydroxycyclohexane-1-carbonyl) acetophenone and 0.1mol of benzaldehyde in 50mL of ethanol, adjusting the pH of the solution to 10 by using 1 wt% of NaOH aqueous solution as a catalyst, and carrying out N reaction at 60 DEG C2After reacting for 2 hours under the atmosphere, continuously precipitating crystals in the cooling process of the reaction system, filtering, washing and recrystallizing the crystals for vacuum drying to finally obtain the novel photoinitiator, wherein the reaction equation is as follows:
the prepared novel photoinitiator initiates 1, 6-hexanediol diacrylate (HDDA) monomer reaction polymerization reaction with the mass concentration of 1 wt% under the irradiation of a 365nm wavelength LED light source, as shown in the attached figure 2 of the specification, the double bond conversion rate within 150s is 80%; description accompanying figure 1 shows that the maximum absorption wavelength of the novel photoinitiator prepared in example 1 is 385 nm.
Novel photoinitiators are prepared by1The HNMR and MS were confirmed by the structure,1H-NMR(D-DMSO,400MHz):1.43-1.61(10H,m),4.59(1H,s),7.33(1H,t),7.38(2H,t),7.54(2H,d),7.61(1H,d),7.93(2H,d),8.06(1H,d),8.12(2H,d);MS(m/z):334(M+1)+。
example 2
Dissolving 0.1mol of 4- (1-hydroxycyclohexane-1-carbonyl) acetophenone and 0.05mol of isophthalaldehyde in 40mL of ethanol, adjusting the pH to 11 with 1.5 wt% of NaOH aqueous solution as a catalyst, and keeping the temperature at 60 ℃ under N2After reacting for 2.5h under the atmosphere, continuously precipitating crystals in the cooling process of the reaction system, filtering, washing and recrystallizing the crystals for vacuum drying to finally obtain the novel photoinitiator, wherein the reaction equation is as follows:
the prepared novel photoinitiator initiates 1, 6-hexanediol diacrylate (HDDA) monomer reaction polymerization reaction with the mass concentration of 1 wt% under the irradiation of a 365nm wavelength LED light source, as shown in the attached figure 4 of the specification, the double bond conversion rate within 100s is 90%; description figure 3 shows that the maximum absorption wavelength of the novel photoinitiator prepared in example 2 is 435 nm.
Novel photoinitiators are prepared by1The HNMR and MS were confirmed by the structure,1H-NMR(D-DMSO,400MHz):1.43-1.89(20H,m),4.57(2H,s),6.67(1H,s),7.24(1H,t),7.48(2H,d),7.61(2H,d),7.91(4H,d),8.06(2H,d),8.11(4H,d);MS(m/z):590(M+1)+。
example 3
Dissolving 0.5mol of 4- (1-hydroxycyclohexane-1-carbonyl) propiophenone and 0.05mol of benzaldehyde in 45mL of ethanol, adjusting the pH to 11 with 2 wt% of KOH aqueous solution as a catalyst, and keeping the temperature at 60 ℃ under N2After reaction for 1.5h under the atmosphere, the reaction product is extracted repeatedly with dichloromethane, andand (2) carrying out vacuum rotary evaporation on the reaction liquid at 45 ℃ to obtain a solid product, filtering, washing and recrystallizing the solid product, and then carrying out vacuum drying to finally obtain the novel photoinitiator, wherein the reaction equation is as follows:
the prepared novel photoinitiator initiates 1, 6-hexanediol diacrylate (HDDA) monomer reaction polymerization reaction with the mass concentration of 1 wt% under the irradiation of an LED light source with the wavelength of 405nm, as shown in the attached figure 6 of the specification, the double bond conversion rate within 300s is 80%; FIG. 5 shows that the maximum absorption wavelength of the novel photoinitiator prepared in example 3 is 400 nm.
Novel photoinitiators are prepared by1The HNMR and MS were confirmed by the structure,1H-NMR(D-DMSO,400MHz):1.44-1.87(10H,m),2.24(3H,s),4.57(1H,s),7.33(1H,t),7.39(2H,t),7.45(2H,d),7.61(1H,s),7.93(2H,d),8.11(2H,d);MS(m/z):348(M+1)+。
example 4
Dissolving 0.15mol of 4- (1-hydroxycyclohexane-1-carbonyl) propiophenone and 0.15mol of isophthalaldehyde in 60mL of methanol, adjusting the pH to 11 with 2 wt% of potassium tert-butoxide in methanol as a catalyst, and adjusting the temperature to 60 ℃ under N2After reacting for 2 hours under the atmosphere, continuously precipitating crystals in the cooling process of the reaction system, filtering, washing and recrystallizing the crystals for vacuum drying to finally obtain the novel photoinitiator, wherein the reaction equation is as follows:
the prepared novel photoinitiator initiates 1, 6-hexanediol diacrylate (HDDA) monomer reaction polymerization reaction with the mass concentration of 1 wt% under the irradiation of an LED light source with the wavelength of 405nm, as shown in the attached figure 8 of the specification, the double bond conversion rate within 300s is 90%; FIG. 7 shows that the maximum absorption wavelength of the novel photoinitiator prepared in example 4 is 450 nm;
novel photoinitiators are prepared by1HNMR and MSBy the time of the confirmation of the structure,1H-NMR(D-DMSO,400MHz):1.44-1.87(20H,m),2.24(6H,s),4.58(2H,s),6.66(1H,s),7.25(1H,t),7.48(2H,d),7.61(2H,s),7.93(4H,d),8.13(4H,d);MS(m/z):618(M+1)+。
example 5
Adding 0.1mol of 4- (1-hydroxycyclohexane-1-carbonyl) propiophenone and 0.5mol of 1-methyl-1H-pyrrole-2, 5-diformaldehyde into 40mL of methanol for dissolving, using 1.5 wt% of potassium tert-butoxide ethanol solution as a catalyst, adjusting the pH to 11, and adjusting the temperature to 60 ℃ to N2After reacting for 3 hours under the atmosphere, continuously precipitating crystals in the cooling process of the reaction system, filtering, washing and recrystallizing the crystals for vacuum drying to finally obtain the novel photoinitiator, wherein the reaction equation is as follows:
the prepared novel photoinitiator initiates 1, 6-hexanediol diacrylate (HDDA) monomer reaction polymerization reaction with the mass concentration of 1 wt% under the irradiation of an LED light source with the wavelength of 405nm, as shown in the attached figure 10 of the specification, the double bond conversion rate within 200s is 83%; the specification and the attached figure 9 show that the maximum absorption wavelength of the prepared novel photoinitiator is 410 nm;
novel photoinitiators are prepared by1The HNMR and MS were confirmed by the structure,1H-NMR(D-DMSO,400MHz):1.44-1.85(20H,m),2.31(6H,s),3.58(3H,s),4.65(2H,s),6.49(2H,d),7.65(2H,s),7.93(4H,d),8.13(4H,d);MS(m/z):621(M+1)+。
example 6
0.2mol of 4- (1-hydroxycyclohexane-1-carbonyl) acetophenone and 0.2mol of 1-methyl-1H-pyrrole-2-formaldehyde are added into 40mL of ethanol for dissolution, 2 wt% of potassium hydroxide aqueous solution is used as a catalyst, the pH is adjusted to 10, and the temperature is 60 ℃ N2After reacting for 1h in the atmosphere, repeatedly extracting a reaction product by methylene dichloride through a cooling reaction system, carrying out vacuum rotary evaporation at 45 ℃ to obtain a solid product, filtering, washing and recrystallizing the solid product, and carrying out vacuum drying to finally obtain the novel photoinitiator, wherein the reaction equation is as follows:
the prepared novel photoinitiator initiates 1, 6-hexanediol diacrylate (HDDA) monomer reaction polymerization reaction with the mass concentration of 1 wt% under the irradiation of an LED light source with the wavelength of 405nm, as shown in the attached figure 12 of the specification, the double bond conversion rate within 300s is 65%; FIG. 11 shows that the maximum absorption wavelength of the novel photoinitiator prepared in example 6 is 450 nm;
novel photoinitiators are prepared by1The HNMR and MS were confirmed by the structure,1H-NMR(D-DMSO,400MHz):1.39-1.85(10H,m),3.91(3H,s),4.64(1H,s),6.09(1H,t),6.69(1H,d),7.59(1H,d),7.90(1H,d),7.93(2H,d),8.09(2H,d);MS(m/z):337(M+1)+。
example 7
(1) Dissolving 0.2mol of 4- (1-hydroxycyclohexane-1-carbonyl) acetophenone in 100mL of mixed solution of ethanol and water (the volume ratio of ethanol to water is 1:1), dropwise adding 20mL of 65% concentrated sulfuric acid, mixing and stirring for reaction for 0.5h in an ice bath, adding 0.2mol of sodium hydroxide, dropwise adding 50mL of 10% HCl, acidifying to obtain phenolic hydroxyl, and finally adding 0.2mol of CH3I, electrophilic substitution is carried out to form methoxy;
(2) adding 0.2mol of methoxy-substituted 4- (1-hydroxycyclohexane-1-carbonyl) acetophenone and 0.2mol of 1-methyl-1H-pyrrole-2-formaldehyde into 40mL of ethanol for dissolving, taking 1 wt% of lithium hexamethyldisilazide as a catalyst, adjusting the pH to 11, and adjusting the temperature to 80 ℃ to N2After reacting for 1h in the atmosphere, repeatedly extracting a reaction product by methylene dichloride through a cooling reaction system, carrying out vacuum rotary evaporation at 45 ℃ to obtain a solid product, filtering, washing and recrystallizing the solid product, and carrying out vacuum drying to finally obtain the novel photoinitiator, wherein the reaction equation is as follows:
the prepared novel photoinitiator initiates 1, 6-hexanediol diacrylate (HDDA) monomer reaction polymerization reaction with the mass concentration of 1 wt% under the irradiation of an LED light source with the wavelength of 405nm, as shown in the attached figure 14 of the specification, the double bond conversion rate within 200s is 90%; the specification and the attached figure 13 show that the maximum absorption wavelength of the prepared novel photoinitiator is 450 nm;
novel photoinitiators are prepared by1The HNMR and MS were confirmed by the structure,1H-NMR(D-DMSO,400MHz):1.39-1.85(10H,m),3.85(3H,s),3.91(3H,s),4.64(1H,s),6.09(1H,t),6.64(1H,d),7.15(1H,d),7.43(1H,d),7.61(1H,d),7.90(1H,d),7.93(2H,d),8.06(1H,d);MS(m/z):367(M+1)+。
example 8
(1) Dissolving 0.05mol of 4- (1-hydroxycyclohexane-1-carbonyl) propiophenone in 50mL of ethanol, and introducing 0.1mol of Br2At 1g of FeBr3The substitution reaction is carried out under the catalysis of (2) to introduce bromine atoms on a benzene ring, and the reaction equation is as follows.
(2) Adding bromo-0.05 mol of 4- (1-hydroxycyclohexane-1-carbonyl) propiophenone and 0.02mol of 1-methyl-1H-pyrrole-2, 5-dimethyl aldehyde into 40mL of methanol for dissolving, using 1.5 wt% of potassium tert-butoxide ethanol solution as a catalyst, adjusting pH to 11, and adjusting temperature to 60 ℃ to obtain N2After reacting for 6 hours under the atmosphere, continuously precipitating crystals in the cooling process of the reaction system, filtering, washing and recrystallizing the crystals for vacuum drying to finally obtain the novel photoinitiator, wherein the reaction equation is as follows:
the prepared novel photoinitiator initiates 1, 6-hexanediol diacrylate (HDDA) monomer reaction polymerization reaction with the mass concentration of 1 wt% under the irradiation of an LED light source with the wavelength of 405nm, as shown in the attached figure 16 of the specification, the double bond conversion rate within 300s is 90%; the specification and the attached figure 15 show that the maximum absorption wavelength of the prepared novel photoinitiator is 420 nm;
novel photoinitiators are prepared by1The HNMR and MS were confirmed by the structure,1H-NMR(D-DMSO,400MHz):1.41-1.85(20H,m),2.36(6H,s),3.61(3H,s),4.64(2H,s),6.49(2H,d),7.62(2H,s),7.87(2H,d),8.01(2H,d),8.11(2H,d);MS(m/z):779(M+1)+。
example 9
(1) Dissolving 0.2mol of 4- (1-hydroxycyclohexane-1-carbonyl) acetophenone in 100mL of ethanol aqueous solution (the volume ratio of ethanol to water is 1:1), and introducing 0.3mol of Br2At 1g of FeBr3Under the catalysis of (1), bromine atoms are introduced to a benzene ring through a substitution reaction, 0.2mol of NaCN is added to substitute the bromine atoms to obtain a cyanated product, and the reaction formula is as follows:
(2) dissolving 0.2mol of 4- (1-hydroxycyclohexane-1-carbonyl) acetophenone and 0.1mol of isophthalaldehyde in 40mL of ethanol, adjusting the pH to 8 with 1.5 wt% of lithium diisopropylamide as a catalyst, and carrying out N reaction at 20 DEG C2After reacting for 1h in the atmosphere, continuously precipitating crystals in the cooling process of the reaction system, filtering, washing, recrystallizing and carrying out vacuum drying on the crystals to finally obtain the novel photoinitiator, wherein the reaction equation is as follows:
the prepared novel photoinitiator initiates 1, 6-hexanediol diacrylate (HDDA) monomer reaction polymerization reaction with the mass concentration of 1 wt% under the irradiation of an LED light source with the wavelength of 405nm, as shown in the attached figure 18 of the specification, the double bond conversion rate within 200s is 60%; the specification and the attached figure 17 show that the maximum absorption wavelength of the prepared novel photoinitiator is 450 nm;
prepared novel lightInitiator through1The HNMR and MS were confirmed by the structure,1H-NMR(D-DMSO,400MHz):1.46-1.91(20H,m),4.62(2H,s),6.67(1H,s),7.24(1H,t),7.48(2H,d),7.61(2H,d),8.06(2H,d),8.21(2H,d),8.42(2H,s);MS(m/z):640(M+1)+。
comparative example 1
A traditional commercial 184 photoinitiator initiates a 1, 6-hexanediol diacrylate (HDDA) monomer reaction polymerization reaction with a mass concentration of 1 wt% under the irradiation of a 365nm wavelength LED light source, and the double bond conversion rate within 100s is 10%.
Comparative example 2
Adding 0.2mol of 4- (1-hydroxycyclohexane-1-carbonyl) acetophenone and 0.2mol of cyclohexane formaldehyde into 20mL of ethanol for dissolving, using 1.5 wt% of sodium hydroxide aqueous solution as a catalyst, adjusting the pH value to 8, reacting at 0 ℃ for 0.5h, repeatedly extracting a reaction product with dichloromethane, carrying out vacuum rotary evaporation on the reaction liquid at 45 ℃ to obtain a solid product, and carrying out vacuum drying on the solid product obtained after filtering, washing and recrystallizing to finally obtain a hydroxycyclohexylacetophenone photoinitiator, wherein the reaction equation is as follows:
the hydroxycyclohexylacetophenone photoinitiator prepared in comparative example 2 has a structure of1The HNMR and the mass spectrum are confirmed,1H-NMR(D-DMSO,400MHz):1.24-1.89(20H,m),2.48(1H,m),4.68(1H,s),6.9(1H,d),7.06(1H,m),7.93(2H,d),8.12(2H,d);MS(m/z):340(M+1)+(ii) a The maximum absorption wavelength is 310 nm.
In light of the foregoing description of the preferred embodiment of the present invention, many modifications and variations will be apparent to those skilled in the art without departing from the spirit and scope of the invention. The technical scope of the present invention is not limited to the content of the specification, and must be determined according to the scope of the claims.
Claims (10)
1. A novel photoinitiator is characterized by having a structure shown in a general formula I:
wherein n is 1-2, formula I wherein: 4R2Represents a substituent on 4 arbitrary vacant positions on a benzene ring; r1And R2Is one of hydrogen atom, alkyl, alkenyl, alkoxy, alkynyl, hydroxyl, nitro, halogen, sulfonic group and alkyl, alkenyl, alkoxy and alkynyl which are substituted by hydroxyl, halogen, nitro, sulfonic group, cyano and amino; r3Is one of alkyl, alkenyl, alkynyl, aryl and heterocyclic aryl.
2. A novel photoinitiator according to claim 1, characterised in that: the R is3Is one of hydroxyl, halogen, nitro, sulfonic group, cyano, amino-substituted alkyl, alkenyl, alkoxy and alkynyl.
4. the preparation method of the novel photoinitiator is characterized by comprising the following steps:
(1) firstly, the hydroxyl cyclohexyl acetophenone containing double alpha H carbonyl is prepared
(2) And (2) carrying out condensation reaction on the hydroxycyclohexylacetophenone containing the double alpha H carbonyl group obtained in the step (1) and an aldehyde compound, and after the reaction is finished, purifying a solid product to obtain the novel photoinitiator.
5. The method for preparing a novel photoinitiator according to claim 3, characterized in that: the molar ratio of the hydroxycyclohexylacetophenone containing double alpha H carbonyl groups in the condensation reaction to the aldehyde compound is 1: 1-2.
6. The method for preparing a novel photoinitiator according to claim 3, characterized in that: the temperature of the condensation reaction is 20-80 ℃, the reaction time is 1-6h, and the pH value of the condensation reaction is 8-12.
7. The method for preparing a novel photoinitiator according to claim 3, characterized in that: the solvent of the condensation reaction is methanol, ethanol, isopropanol, tert-butanol, tetrahydrofuran, dimethylformamide or dimethyl sulfoxide.
8. The method for preparing a novel photoinitiator according to claim 3, characterized in that: the catalyst for the condensation reaction is sodium hydroxide, potassium hydroxide, sodium tert-butoxide, potassium tert-butoxide, sodium bicarbonate, diisopropylamine, pyridine, lithium diisopropylamide, triethanolamine, methyldiethanolamine or lithium hexamethyldisilazide.
10. the method for preparing a novel photoinitiator according to claim 3, characterized in that: the aldehyde compound is benzaldehyde, m-phthalaldehyde, 1-methyl-1H-pyrrole-2, 5-dicarboxaldehyde or 1-methyl-1H-pyrrole-2-formaldehyde.
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WO2023169520A1 (en) * | 2022-03-09 | 2023-09-14 | 湖北固润科技股份有限公司 | Use of arylvinyl a-carbonyl acid ester compound as photoinitiator in led photopolymerization and preparation method therefor |
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