CN111574350A - Novel hydroxycyclohexyl acetophenone photoinitiator and preparation method thereof - Google Patents

Novel hydroxycyclohexyl acetophenone photoinitiator and preparation method thereof Download PDF

Info

Publication number
CN111574350A
CN111574350A CN202010386051.8A CN202010386051A CN111574350A CN 111574350 A CN111574350 A CN 111574350A CN 202010386051 A CN202010386051 A CN 202010386051A CN 111574350 A CN111574350 A CN 111574350A
Authority
CN
China
Prior art keywords
group
alkyl
novel
alkoxy
alkenyl
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
Application number
CN202010386051.8A
Other languages
Chinese (zh)
Other versions
CN111574350B (en
Inventor
朱晓群
杨帆
聂俊
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Changzhou Institute for Advanced Materials Beijing University of Chemical Technology
Original Assignee
Changzhou Institute for Advanced Materials Beijing University of Chemical Technology
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Changzhou Institute for Advanced Materials Beijing University of Chemical Technology filed Critical Changzhou Institute for Advanced Materials Beijing University of Chemical Technology
Priority to CN202010386051.8A priority Critical patent/CN111574350B/en
Publication of CN111574350A publication Critical patent/CN111574350A/en
Application granted granted Critical
Publication of CN111574350B publication Critical patent/CN111574350B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • 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
    • 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
    • C07D207/34—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 hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D207/36—Oxygen or sulfur atoms
    • C07D207/38—2-Pyrrolones
    • 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
    • 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
    • C08F22/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides or nitriles thereof
    • C08F22/10—Esters
    • C08F22/1006—Esters of polyhydric alcohols or polyhydric phenols, e.g. ethylene glycol dimethacrylate
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

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 relates to the technical field of organic synthesis, in particular to a novel hydroxycyclohexyl acetophenone 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 main absorption wavelength of the traditional photoinitiator 184 is less than 365nm and is not matched with the emission wavelength of the LED light source, in order to ensure that the main absorption wavelength of the traditional photoinitiator is matched with the emission wavelength of the LED light source, the invention provides the novel hydroxycyclohexyl acetophenone photoinitiator which is obtained by one-step condensation reaction of an aldehyde group functionalized hydroxycyclohexyl acetophenone compound and a ketone compound containing an alpha H atom, the main absorption wavelength of the novel hydroxycyclohexyl acetophenone photoinitiator can reach more than 365nm and is matched with the LED light source used in the market, and the novel hydroxycyclohexyl acetophenone photoinitiator has good application prospect.

Description

Novel hydroxycyclohexyl acetophenone photoinitiator and preparation method thereof
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a novel hydroxycyclohexyl acetophenone 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 double bond conversion rate of a polymerization monomer in the photopolymerization reaction is inevitably reduced.
Therefore, how to increase the maximum absorption wavelength of the conventional 184 photoinitiator to match the emission wavelength of the LED light source is a major technical problem to be solved in the field of photoinitiators.
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 increase the maximum absorption wavelength of the conventional photoinitiator 184 is matched with the emission wavelength of the LED light source, and the double bond conversion rate of the polymerized monomer under the irradiation of the LED light source is increased.
The reaction equation involved in the invention is as follows:
Figure BDA0002483871900000011
reaction equation a
Figure BDA0002483871900000021
Reaction equation b
Figure BDA0002483871900000022
Reaction equation c
Figure BDA0002483871900000023
Reaction equation d
The technical scheme adopted by the invention for solving the technical problems is as follows:
the invention provides a novel hydroxycyclohexyl acetophenone photoinitiator, which comprises the following chemical general formula:
Figure BDA0002483871900000024
Figure BDA0002483871900000031
in the above general formula:
4R1represents a substituent on 4 arbitrary vacant positions on a benzene ring;
R1is any one of hydrogen atom, alkyl, alkenyl, alkoxy, alkynyl, hydroxyl, nitro, halogen, sulfonic group and alkyl, alkenyl, alkoxy or alkynyl substituted by heteroatom, halogen, alkenyl, alkynyl, nitro, cyano or sulfonic group;
R2is any one of alkyl, alkyl containing heteroatoms and alkyl substituted by heteroatoms, halogen, alkenyl, alkynyl, nitro, cyano and sulfonic group;
R3and R4Is any one of hydrogen atom, alkyl, alkoxy and alkyl or alkoxy substituted by heteroatom, halogen, alkenyl, alkynyl, nitro, cyano, sulfonic group, aryl or heterocyclic aryl;
R5is alkyl, alkaneAny one of an oxy group and an alkyl group substituted by a heteroatom, halogen, alkenyl group, alkynyl group, nitro group, cyano group, or sulfonic group;
R6is any one of alkyl, alkoxy and alkyl or alkoxy substituted by heteroatom, halogen, alkenyl, alkynyl, nitro, cyano, sulfonic group, aryl or heterocyclic aryl;
R7any one of hydrogen atom, alkyl group, alkoxy group, and alkyl group or alkoxy group substituted by hetero atom, halogen, alkenyl group, alkynyl group, nitro group, cyano group, sulfonic group, aryl group, or heterocyclic aryl group may be used.
Specifically, the preparation method of the novel hydroxycyclohexyl acetophenone photoinitiator comprises the following steps:
(1) introducing aldehyde groups into benzene rings of the hydroxyl cyclohexyl acetophenone compounds without aldehyde groups on molecular structures to obtain aldehyde group functionalized hydroxyl cyclohexyl acetophenone compounds;
(2) and (2) carrying out condensation reaction on the aldehyde group functionalized hydroxycyclohexyl acetophenone compound obtained in the step (1) and a ketone compound containing an alpha H atom, and after the reaction is finished, drying, recrystallizing, concentrating, filtering and drying the obtained solid product to obtain the novel hydroxycyclohexyl acetophenone photoinitiator.
Specifically, the molecular formula of the hydroxycyclohexylacetophenone compound without aldehyde groups on the molecular structure is as follows:
Figure BDA0002483871900000041
wherein R is1Represents a substituent on 4 arbitrary vacant positions on a benzene ring; r1Is any one of hydrogen atom, alkyl, alkenyl, alkoxy, alkynyl, hydroxyl, nitro, halogen, sulfonic group and alkyl, alkenyl, alkoxy or alkynyl substituted by heteroatom, halogen, alkenyl, alkynyl, nitro, cyano or sulfonic group.
Specifically, the chemical formula of the alpha H atom-containing ketone compound is as follows:
Figure BDA0002483871900000042
Figure BDA0002483871900000051
wherein R is2Is any one of alkyl, alkyl containing heteroatoms and alkyl substituted by heteroatoms, halogen, alkenyl, alkynyl, nitro, cyano and sulfonic group;
R3and R4Is any one of hydrogen atom, alkyl, alkoxy and alkyl or alkoxy substituted by heteroatom, halogen, alkenyl, alkynyl, nitro, cyano, sulfonic group, aryl or heterocyclic aryl;
R5is any one of alkyl, alkoxy and alkyl substituted by heteroatom, halogen, alkenyl, alkynyl, nitro, cyano and sulfonic group;
R6is any one of alkyl, alkoxy and alkyl or alkoxy substituted by heteroatom, halogen, alkenyl, alkynyl, nitro, cyano, sulfonic group, aryl or heterocyclic aryl;
R7any one of hydrogen atom, alkyl group, alkoxy group, and alkyl group or alkoxy group substituted by hetero atom, halogen, alkenyl group, alkynyl group, nitro group, cyano group, sulfonic group, aryl group, or heterocyclic aryl group may be used.
Specifically, the ketone compound containing an α H atom is: acetone, 3-pentanone, cyclohexanone, acetophenone, N-vinylpyrrolidone or N-methylpyrrolidone.
Specifically, the molar ratio of the hydroxyl cyclohexyl acetophenone compound with the aldehyde group functionalized in the condensation reaction to the ketone compound containing the conjugated structure and alpha H atoms is 1-2: 1.
Specifically, the condensation reaction temperature is 0-80 ℃, and the reaction time is 0.5-5 h.
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 a basic catalyst.
Specifically, the catalyst for the condensation reaction is any one of sodium hydroxide, potassium hydroxide, sodium tert-butoxide, potassium tert-butoxide, sodium bicarbonate, diisopropylamine, pyridine, lithium diisopropylamide, triethanolamine, methyldiethanolamine, and lithium hexamethyldisilazide.
Specifically, the pH of the reaction system in the condensation reaction is 8 to 12.
The invention has the beneficial effects that:
(1) the maximum absorption wavelength of the novel hydroxycyclohexyl acetophenone photoinitiator prepared by the invention can reach more than 356nm, and the photoinitiator is matched with the emission wavelength of an LED light source commonly used in the field of photopolymerization, so that the photoinitiator has more excellent performance and stronger marketability.
(2) The method for preparing the novel hydroxycyclohexyl acetophenone photoinitiator is simple, the product can be obtained by only one-step condensation reaction, the preparation cost is low, and the industrial production is easy to carry out.
Drawings
FIG. 1: example 1 uv absorption spectra of the novel hydroxycyclohexyl acetophenone photoinitiator prepared.
FIG. 2: example 1 conversion of double bonds of the novel hydroxycyclohexyl acetophenone photoinitiator prepared.
FIG. 3: example 2 ultraviolet absorption spectra of the novel hydroxycyclohexyl acetophenone photoinitiator prepared.
FIG. 4: example 2 conversion of double bonds of the novel hydroxycyclohexyl acetophenone photoinitiator prepared.
FIG. 5: example 3 ultraviolet absorption spectra of the novel hydroxycyclohexyl acetophenone photoinitiator prepared.
FIG. 6: example 3 conversion of double bonds of the novel hydroxycyclohexyl acetophenone photoinitiator prepared.
FIG. 7: example 4 ultraviolet absorption spectra of the novel hydroxycyclohexyl acetophenone photoinitiator prepared.
FIG. 8: example 4 conversion of double bonds of the novel hydroxycyclohexyl acetophenone photoinitiator prepared.
FIG. 9: example 5 ultraviolet absorption spectra of the novel hydroxycyclohexyl acetophenone photoinitiator prepared.
FIG. 10: example 5 conversion of double bonds of the novel hydroxycyclohexyl acetophenone photoinitiator prepared.
FIG. 11: example 6 ultraviolet absorption spectra of the novel hydroxycyclohexyl acetophenone photoinitiator prepared.
FIG. 12: example 6 conversion of double bonds of the novel hydroxycyclohexyl acetophenone photoinitiator prepared.
FIG. 13: example 7 ultraviolet absorption spectra of the novel hydroxycyclohexyl acetophenone photoinitiator prepared.
FIG. 14: example 7 conversion of double bonds of the novel hydroxycyclohexyl acetophenone photoinitiator prepared.
FIG. 15: example 8 ultraviolet absorption spectra of the novel hydroxycyclohexyl acetophenone photoinitiator prepared.
FIG. 16: example 8 conversion of double bonds of the novel hydroxycyclohexyl acetophenone photoinitiator prepared.
FIG. 17: example 9 ultraviolet absorption spectra of the novel hydroxycyclohexyl acetophenone photoinitiator prepared.
FIG. 18: example 9 conversion of double bonds of the novel hydroxycyclohexyl acetophenone photoinitiator prepared.
FIG. 19: example 10 ultraviolet absorption spectra of the novel hydroxycyclohexyl acetophenone photoinitiator prepared.
FIG. 20: example 10 conversion of double bonds of the novel hydroxycyclohexyl acetophenone photoinitiator prepared.
FIG. 21: double bond conversion of conventional commercial 184 photoinitiators under illumination by LED light sources.
Detailed Description
The present invention will now be described in further detail with reference to the accompanying drawings.
Preparation of 4- (1-hydroxycyclohexane-1-carbonyl) benzaldehyde example:
will be 01mol hydroxycyclohexylacetophenone was dissolved in 100mL of ethanol, 0.2mol of methyl chloride was passed through, 3g of anhydrous AlCl was added3The methylated hydroxycyclohexylacetophenone is obtained by vacuum filtration, and 1g MnO is added2Dropwise adding 65% of H2SO420mL of aqueous solution, methyl is oxidized into aldehyde group, and the reaction equation is as follows:
Figure BDA0002483871900000071
example 1
Adding 0.1mol of 4- (1-hydroxycyclohexane-1-carbonyl) benzaldehyde and 0.05mol of acetone into 50mL of ethanol for dissolving, taking 1 wt% of NaOH aqueous solution as a catalyst, adjusting the pH value to 10, reacting at 55 ℃ for 30min, continuously separating out crystals in a cooling reaction system, carrying out vacuum drying on the solid obtained after filtering, washing and recrystallizing, and finally obtaining the novel hydroxycyclohexyl acetophenone photoinitiator after purification, wherein the reaction equation is as follows:
Figure BDA0002483871900000072
the structure of the prepared novel hydroxycyclohexyl acetophenone photoinitiator is that1The HNMR and the mass spectrum are confirmed,1H-NMR(D-DMSO，400MHz)：1.46-1.86(20H，m)，4.62(2H，s)，7.01-7.05(2H，d)，7.38-7.46(4H，d)，7.80-7.84(2H，d)，7.61-7.88(4H，d)；MS(m/z):486(M+1)+；
under the irradiation of an LED light source with the wavelength of 365nm, the double bond conversion rate of a polymerized HDDA monomer with the concentration of 1 wt% in 300s of the prepared novel hydroxycyclohexyl acetophenone photoinitiator is 85% (see the attached figure 2 of the specification for details), and the maximum absorption wavelength of the photoinitiator is 381nm (see the attached figure 1 of the specification for details).
Example 2
Adding 0.2mol of 4- (1-hydroxycyclohexane-1-carbonyl) benzaldehyde and 0.1mol of 3-pentanone into 60mL of ethanol for dissolving, using 1.5 wt% of NaOH aqueous solution as a catalyst, adjusting the pH value to 10, reacting for 50min at 60 ℃, continuously separating out crystals in a cooling reaction system, filtering, washing and recrystallizing to obtain a solid product, carrying out vacuum drying on the solid product, and finally obtaining the novel hydroxycyclohexyl acetophenone photoinitiator after purification, wherein the reaction equation is as follows:
Figure BDA0002483871900000081
the structure of the prepared novel hydroxycyclohexyl acetophenone photoinitiator is that1The HNMR and the mass spectrum are confirmed,1H-NMR(D-DMSO，400MHz)：1.44-1.85(20H，m)，2.34(6H，s)，4.64(2H，s)，7.35-7.39(2H，d)，7.38-7.46(4H，d)，7.86-7.9(4H，d)；MS(m/z):514(M+1)+；
under the irradiation of an LED light source with the wavelength of 365nm, the double bond conversion rate of a polymerized HDDA monomer with the concentration of 1 wt% in 300s of the prepared novel hydroxycyclohexyl acetophenone photoinitiator is 80% (see the attached figure 4 of the specification for details), and the maximum absorption wavelength of the photoinitiator is 392nm (see the attached figure 3 of the specification for details).
Example 3
Adding 0.15mol of 4- (1-hydroxycyclohexane-1-carbonyl) benzaldehyde and 0.075mol of cyclohexanone into 60mL of ethanol for dissolving, using 1 wt% of KOH aqueous solution as a catalyst, adjusting the pH value to 11, reacting at 60 ℃ for 20min, continuously precipitating crystals in a cooling reaction system, filtering, washing and recrystallizing to obtain a solid product, and performing vacuum drying to finally obtain the novel hydroxycyclohexyl acetophenone photoinitiator, wherein the reaction equation is as follows:
Figure BDA0002483871900000091
the structure of the prepared novel hydroxycyclohexyl acetophenone photoinitiator is that1The HNMR and the mass spectrum are confirmed,1H-NMR(D-DMSO，400MHz):1.4-1.83(22H，m)，2.79-2.80(4H，t)，4.6(2H，s)，7.39(2H，s)，7.38-7.39(4H，d)，7.84-7.85(4H，d)；MS(m/z):526(M+1)+；
under the irradiation of an LED light source with the wavelength of 365nm, the double bond conversion rate of a polymerized HDDA monomer with the concentration of 1 wt% in 300s of the prepared novel hydroxycyclohexyl acetophenone photoinitiator is 95% (see attached figure 6 in the detailed description), and the maximum absorption wavelength of the photoinitiator is 345nm (see attached figure 5 in the detailed description).
Example 4
Adding 0.15mol of 4- (1-hydroxycyclohexane-1-carbonyl) benzaldehyde and 0.15mol of acetophenone into 60mL of methanol for dissolving, using 2 wt% of KOH aqueous solution as a catalyst, adjusting the pH value to 11, reacting at 25 ℃ for 30min, carrying out vacuum rotary evaporation on reaction liquid at 45 ℃ to obtain a solid product, filtering, washing and recrystallizing the obtained solid product, and carrying out vacuum drying to finally obtain the novel hydroxycyclohexyl acetophenone photoinitiator, wherein the reaction equation is as follows:
Figure BDA0002483871900000092
the structure of the prepared novel hydroxycyclohexyl acetophenone photoinitiator is that1The HNMR and the mass spectrum are confirmed,1H-NMR(D-DMSO，400MHz):1.44-1.86(10H，m)，4.61(1H，s)，7.41-7.42(2H，d)，7.47-7.48(2H，t)，7.57(1H，t)，7.60(1H，d)，7.81(2H，d)，7.88(2H，d)，8.06(1H，d)；MS(m/z):334(M+1)+；
under the irradiation of an LED light source with the wavelength of 365nm, the double bond conversion rate of a polymerized HDDA monomer with the concentration of 1 wt% in 300s of the prepared novel hydroxycyclohexyl acetophenone photoinitiator is 70% (see the attached figure 8 of the specification for details), and the maximum absorption wavelength of the photoinitiator is 361nm (see the attached figure 7 of the specification for details).
Example 5
Adding 0.1mol of 4- (1-hydroxycyclohexane-1-carbonyl) benzaldehyde and 0.1mol of N-vinyl pyrrolidone into 50mL of ethanol for dissolving, taking 2 wt% of potassium tert-butoxide ethanol solution as a catalyst, adjusting the pH value to 11, reacting at 25 ℃ for 2h, repeatedly extracting a reaction product with dichloromethane, carrying out vacuum rotary evaporation on the reaction solution at 45 ℃ to obtain a solid product, filtering, washing and recrystallizing the obtained solid product, and carrying out vacuum drying to finally obtain the novel hydroxycyclohexyl acetophenone photoinitiator, wherein the reaction equation is as follows:
Figure BDA0002483871900000101
the structure of the prepared novel hydroxycyclohexyl acetophenone photoinitiator is that1The HNMR and the mass spectrum are confirmed,1H-NMR(D-DMSO，400MHz):1.47-1.89(10H，m)，2.81(2H，t)，3.0(2H，t)，4.6(1H，s)，4.68(1H，d)，6.10(1H，d)，7.31(1H，s)，7.42(1H，d)，7.46(2H，d)，7.86(2H，d)；MS(m/z):325(M+1)+；
under the irradiation of an LED light source with the wavelength of 365nm, the double bond conversion rate of a polymerized HDDA monomer with the concentration of 1 wt% in 600s of the prepared novel hydroxycyclohexyl acetophenone photoinitiator is 70% (see the attached figure 10 of the specification for details), and the maximum absorption wavelength of the photoinitiator is 345nm (see the attached figure 9 of the specification for details).
Example 6
Adding 0.2mol of 4- (1-hydroxycyclohexane-1-carbonyl) benzaldehyde and 0.2mol of N-methyl pyrrolidone into 40mL of ethanol for dissolving, taking 2 wt% of potassium tert-butoxide ethanol solution as a catalyst, adjusting the pH value to 11, reacting at 60 ℃ for 1h, repeatedly extracting a reaction product with dichloromethane, carrying out vacuum rotary evaporation on the reaction solution at 45 ℃ to obtain a solid product, and carrying out vacuum drying on the solid product obtained after filtering, washing and recrystallization to finally obtain the novel hydroxycyclohexyl acetophenone photoinitiator, wherein the reaction equation is as follows:
Figure BDA0002483871900000111
the structure of the prepared novel hydroxycyclohexyl acetophenone photoinitiator is that1The HNMR and the mass spectrum are confirmed,1H-NMR(D-DMSO，400MHz):1.44-1.86(10H，m)，2.81(2H，t)，3.27(3H，s)，3.48(2H，t)，4.64(1H，s)，7.26(1H，s)，7.42(2H，d)，7.88-7.89(2H，d)；MS(m/z):313(M+1)+；
under the irradiation of an LED light source with the wavelength of 365nm, the double bond conversion rate of a polymerized HDDA monomer with the concentration of 1 wt% in 300s of the prepared novel hydroxycyclohexyl acetophenone photoinitiator is 95% (see the attached figure 12 of the specification for details), and the maximum absorption wavelength of the photoinitiator is 380nm (see the attached figure 11 of the specification for details).
Example 7
(1) Dissolving 0.2mol of 4- (1-hydroxycyclohexane-1-carbonyl) benzaldehyde in 100mL of ethanol, dropwise adding 40mL of concentrated sulfuric acid with the mass fraction of 65% under ice bath for mixing and stirring, adding about 0.2mol of sodium hydroxide into a reaction container, dropwise adding 50mL of HCl with the mass fraction of 10% for acidification to obtain phenolic hydroxyl, and finally adding 0.2mol of CH3I undergoes electrophilic substitution to form methoxy, the reaction equation is as follows:
Figure BDA0002483871900000112
(2) adding 0.2mol of methoxylated 4- (1-hydroxycyclohexane-1-carbonyl) benzaldehyde and 0.2mol of acetophenone into 40mL of ethanol for dissolving, taking 2 wt% of potassium tert-butoxide ethanol solution as a catalyst, adjusting the pH value to 11, reacting at 80 ℃ for 4h, repeatedly extracting a reaction product with dichloromethane, carrying out vacuum rotary evaporation on the reaction solution at 45 ℃ to obtain a solid product, filtering, washing and recrystallizing the obtained solid product, and carrying out vacuum drying to finally obtain the novel hydroxycyclohexyl acetophenone photoinitiator, wherein the reaction equation is as follows:
Figure BDA0002483871900000121
the structure of the prepared novel hydroxycyclohexyl acetophenone photoinitiator is that1The HNMR and the mass spectrum are confirmed,1H-NMR(D-DMSO,400MHz):1.46-1.89(10H,m)，3.9(3H,s)，4.64(1H,s)，6.92(1H,s)，7.10(1H,d)，7.49(2H,t)，7.57(1H,t)，7.6(1H,d)，7.81(2H,d)，8.06(1H,d)；MS(m/z):364(M+1)+。
under the irradiation of an LED light source with the wavelength of 365nm, the double bond conversion rate of 1 wt% polymerized HDDA monomer in 300s is 83% (see the attached figure 14 of the specification for details), and the maximum absorption wavelength of the prepared novel hydroxycyclohexyl acetophenone photoinitiator is 385nm (see the attached figure 13 of the specification for details).
Example 8
(1) 0.05mol of 4- (1-hydroxycyclohexane-1-carbonyl) benzaldehyde is dissolved in50mL of ethanol was added with 1g of FeBr3Introducing 0.1mol Br2And substitution reaction is carried out, bromine atoms are introduced into a benzene ring, and the reaction equation is as follows:
Figure BDA0002483871900000122
(2) adding 0.05mol of bromo-4- (1-hydroxycyclohexane-1-carbonyl) benzaldehyde and 0.05mol of N-vinyl pyrrolidone into 30mL of ethanol for dissolving, using 2 wt% of hexamethyldisilazane-based lithium amide as a catalyst, adjusting the pH value to 12, reacting at 50 ℃ for 5h, repeatedly extracting a reaction product with dichloromethane, carrying out vacuum rotary evaporation on the reaction liquid at 45 ℃ to obtain a solid product, carrying out vacuum drying on the solid product obtained after filtering, washing and recrystallizing to finally obtain the novel hydroxycyclohexyl acetophenone photoinitiator, wherein the reaction equation is as follows:
Figure BDA0002483871900000131
the structure of the prepared novel hydroxycyclohexyl acetophenone photoinitiator is that1The HNMR and the mass spectrum are confirmed,1H-NMR(D-DMSO，400MHz):1.57-1.92(10H，m)，2.81(2H，t)，3.0(2H，t)，4.62(1H，s)，4.67(1H，d)，6.1(1H，d)，7.03(1H，d)，7.19(1H，d)，7.27(1H，s)，7.33(1H，d)，7.86(1H，d)；MS(m/z):404(M+1)+。
under the irradiation of an LED light source with the wavelength of 365nm, the double bond conversion rate of a polymerized HDDA monomer with the concentration of 1 wt% in 300s of the prepared novel hydroxycyclohexyl acetophenone photoinitiator is 80% (see the attached figure 16 of the specification for details), and the maximum absorption wavelength of the photoinitiator is 360nm (see the attached figure 15 of the specification for details).
Example 9
(1) 0.2mol of 4- (1-hydroxycyclohexane-1-carbonyl) benzaldehyde is dissolved in 100mL of ethanol water solution (the volume ratio of ethanol to water is 1:1), and 0.3mol of Br is introduced2At 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:
Figure BDA0002483871900000132
(2) adding cyano-substituted 0.2mol of 4- (1-hydroxycyclohexane-1-carbonyl) benzaldehyde and 0.1mol of cyclohexanone into 70mL of ethanol for dissolving, using 1 wt% of LDA (lithium diisopropylamide) as a catalyst, adjusting the pH value to 12, reacting at 60 ℃ for 50min, continuously precipitating crystals in a cooling reaction system, filtering, washing and recrystallizing to obtain a solid product, and performing vacuum drying to finally obtain the novel hydroxycyclohexyl acetophenone photoinitiator, wherein the reaction equation is as follows:
Figure BDA0002483871900000141
the structure of the prepared novel hydroxycyclohexyl acetophenone photoinitiator is that1The HNMR and the mass spectrum are confirmed,1H-NMR(D-DMSO,400MHz):1.35-1.79(22H，m)，2.81(4H，t)，4.61(2H,s)，7.39(2H，s)，7.70(2H，d)，7.91(2H，s)，8.16(2H，d)；MS(m/z):576(M+1)+；
under the irradiation of an LED light source with the wavelength of 365nm, the double bond conversion rate of a polymerized HDDA monomer with the concentration of 1 wt% in 100s of the prepared novel hydroxycyclohexyl acetophenone photoinitiator is 90% (see the attached figure 18 in the detailed description), and the maximum absorption wavelength of the photoinitiator is 385nm (see the attached figure 17 in the detailed description).
Example 10
(1) Dissolving 0.15mol of 4- (1-hydroxycyclohexane-1-carbonyl) benzaldehyde in 100mL of ethanol-water mixed solution (the volume ratio of ethanol to water is 1:1), dropwise adding 25mL of concentrated sulfuric acid with the mass fraction of 65%, mixing and stirring for reaction for 0.5h in an ice bath, adding about 0.15mol of sodium hydroxide, dropwise adding 50mL of HCl with the mass fraction of 10%, and acidifying to obtain phenolic hydroxyl, wherein the reaction equation is as follows:
Figure BDA0002483871900000142
(2) adding 0.15mol of hydroxylated 4- (1-hydroxycyclohexane-1-carbonyl) benzaldehyde and 0.15mol of acetophenone into 30mL of ethanol for dissolving, taking 2 wt% of potassium tert-butoxide ethanol solution as a catalyst, adjusting the pH value to 8, reacting at 0 ℃ for 5h, repeatedly extracting a reaction product with dichloromethane, carrying out vacuum rotary evaporation on the reaction solution at 45 ℃ to obtain a solid product, filtering, washing and recrystallizing the obtained solid product, and carrying out vacuum drying to finally obtain the novel hydroxycyclohexyl acetophenone photoinitiator, wherein the reaction equation is as follows:
Figure BDA0002483871900000151
the structure of the prepared novel hydroxycyclohexyl acetophenone photoinitiator is that1The HNMR and the mass spectrum are confirmed,1H-NMR(D-DMSO，400MHz):1.46-1.89(10H，m)，4.64(1H，s)，6.77(1H，s)，6.98(1H，d)，7.49(2H，t)，7.58(1H，t)，7.59(1H，d)，7.62(1H，d)，8.06(1H，d)，14.4(1H，s)；MS(m/z):350(M+1)+；
under the irradiation of an LED light source with the wavelength of 365nm, the double bond conversion rate of a polymerized HDDA monomer with the concentration of 1 wt% in 100s of the prepared novel hydroxycyclohexyl acetophenone photoinitiator is 80% (see the attached drawing 20 of the specification for details), and the maximum absorption wavelength of the photoinitiator is 365nm (see the attached drawing 19 of the specification for details).
Comparative example 1
Adding 0.1mol of 4- (1-hydroxycyclohexane-1-carbonyl) benzaldehyde and 0.1mol of methyl tert-butyl ketone into 20mL of ethanol for dissolving, using 2 wt% of sodium hydroxide aqueous solution as a catalyst, adjusting the pH value to 9, reacting at 0 ℃ for 0.5h, repeatedly extracting a reaction product by using dichloromethane, carrying out vacuum rotary evaporation on the reaction liquid at 45 ℃ to obtain a solid product, filtering, washing and recrystallizing the obtained solid product, and carrying out vacuum drying to finally obtain a hydroxycyclohexyl acetophenone photoinitiator, wherein the reaction equation is as follows:
Figure BDA0002483871900000152
the structure of the prepared hydroxycyclohexyl acetophenone photoinitiator is that1The HNMR and the mass spectrum are confirmed,1H-NMR(D-DMSO，400MHz):1.24(9H，s)，1.46-1.89(10H，m)，4.64(1H，s)，7.13(1H，d)，7.42(2H，d)，7.6(1H，d)，7.88(2H，d)；MS(m/z):314(M+1)+(ii) a The maximum absorption wavelength was 305 nm.
Comparative example 2
Under the irradiation of an LED light source with the wavelength of 365nm, the double bond conversion rate of a traditional commercial 184 photoinitiator in 100s of polymerized HDDA monomer with the mass concentration of 1 wt% is 10% (see the attached figure 21 of the specification for details).
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 hydroxycyclohexyl acetophenone photoinitiator is characterized by comprising the following chemical general formula:
Figure FDA0002483871890000011
in the above general formula:
4R1represents a substituent on 4 arbitrary vacant positions on a benzene ring;
R1is any one of hydrogen atom, alkyl, alkenyl, alkoxy, alkynyl, hydroxyl, nitro, halogen, sulfonic group and alkyl, alkenyl, alkoxy or alkynyl substituted by heteroatom, halogen, alkenyl, alkynyl, nitro, cyano or sulfonic group;
R2is any one of alkyl, alkyl containing heteroatoms and alkyl substituted by heteroatoms, halogen, alkenyl, alkynyl, nitro, cyano and sulfonic group;
R3and R4Is any of hydrogen atom, alkyl, alkoxy and alkyl or alkoxy substituted by hetero atom, halogen, alkenyl, alkynyl, nitro, cyano, sulfonic group, aryl or heterocyclic arylOne kind of the material is selected;
R5is any one of alkyl, alkoxy and alkyl substituted by heteroatom, halogen, alkenyl, alkynyl, nitro, cyano and sulfonic group;
R6is any one of alkyl, alkoxy and alkyl or alkoxy substituted by heteroatom, halogen, alkenyl, alkynyl, nitro, cyano, sulfonic group, aryl or heterocyclic aryl;
R7any one of hydrogen atom, alkyl group, alkoxy group, and alkyl group or alkoxy group substituted by hetero atom, halogen, alkenyl group, alkynyl group, nitro group, cyano group, sulfonic group, aryl group, or heterocyclic aryl group may be used.
2. The novel hydroxycyclohexyl acetophenone photoinitiator as claimed in claim 1, comprising the formula:
Figure FDA0002483871890000021
Figure FDA0002483871890000031
3. the preparation method of the novel hydroxycyclohexyl acetophenone photoinitiator as claimed in claims 1-2, which is prepared by the following steps:
(1) introducing aldehyde groups into benzene rings of the hydroxyl cyclohexyl acetophenone compounds without aldehyde groups on molecular structures to obtain aldehyde group functionalized hydroxyl cyclohexyl acetophenone compounds;
(2) and (2) carrying out condensation reaction on the aldehyde group functionalized hydroxycyclohexyl acetophenone compound obtained in the step (1) and a ketone compound containing an alpha H atom, and after the reaction is finished, drying, recrystallizing, concentrating, filtering and drying the obtained solid product to obtain the novel hydroxycyclohexyl acetophenone photoinitiator.
4. The method for preparing a novel hydroxycyclohexylacetophenone photoinitiator according to claim 3, wherein the hydroxycyclohexylacetophenone compound having no aldehyde group in its molecular structure has the following general chemical formula:
Figure FDA0002483871890000041
wherein R is1Represents a substituent on 4 arbitrary vacant positions on a benzene ring; r1Is any one of hydrogen atom, alkyl, alkenyl, alkoxy, alkynyl, hydroxyl, nitro, halogen, sulfonic group and alkyl, alkenyl, alkoxy or alkynyl substituted by heteroatom, halogen, alkenyl, alkynyl, nitro, cyano or sulfonic group.
5. The method for preparing hydroxycyclohexyl acetophenone photoinitiator as claimed in claim 3, wherein the α H atom containing ketone compound has the following chemical formula:
Figure FDA0002483871890000051
wherein R is2Is any one of alkyl, alkyl containing heteroatoms and alkyl substituted by heteroatoms, halogen, alkenyl, alkynyl, nitro, cyano and sulfonic group;
R3and R4Is any one of hydrogen atom, alkyl, alkoxy and alkyl or alkoxy substituted by heteroatom, halogen, alkenyl, alkynyl, nitro, cyano, sulfonic group, aryl or heterocyclic aryl;
R5is any one of alkyl, alkoxy and alkyl substituted by heteroatom, halogen, alkenyl, alkynyl, nitro, cyano and sulfonic group;
R6is any one of alkyl, alkoxy and alkyl or alkoxy substituted by heteroatom, halogen, alkenyl, alkynyl, nitro, cyano, sulfonic group, aryl or heterocyclic aryl;
R7any one of hydrogen atom, alkyl group, alkoxy group, and alkyl group or alkoxy group substituted by hetero atom, halogen, alkenyl group, alkynyl group, nitro group, cyano group, sulfonic group, aryl group, or heterocyclic aryl group may be used.
6. The method of claim 3, wherein the ketone compound containing α H atom is acetone, 3-pentanone, cyclohexanone, acetophenone, N-vinyl pyrrolidone or N-methyl pyrrolidone.
7. The method for preparing a novel hydroxycyclohexyl acetophenone photoinitiator as claimed in claim 3, wherein: the molar ratio of the aldehyde group functionalized hydroxycyclohexylacetophenone compound to the ketone compound containing an alpha H atom in the condensation reaction is 1-2: 1.
8. The method for preparing a novel hydroxycyclohexyl acetophenone photoinitiator as claimed in claim 3, wherein: the temperature of the condensation reaction is 0-80 ℃, the reaction time is 0.5-5h, and the pH value of the condensation reaction is 8-12.
9. The method for preparing a novel hydroxycyclohexyl acetophenone photoinitiator as claimed in claim 3, wherein: the solvent of the condensation reaction is methanol, ethanol, isopropanol, tert-butanol, tetrahydrofuran, dimethylformamide or dimethyl sulfoxide.
10. The method for preparing a novel hydroxycyclohexyl acetophenone photoinitiator as claimed in claim 3, wherein: the catalyst for the condensation reaction is an alkaline catalyst.
CN202010386051.8A 2020-05-09 2020-05-09 Hydroxy cyclohexyl acetophenone photoinitiator and preparation method thereof Active CN111574350B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010386051.8A CN111574350B (en) 2020-05-09 2020-05-09 Hydroxy cyclohexyl acetophenone photoinitiator and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010386051.8A CN111574350B (en) 2020-05-09 2020-05-09 Hydroxy cyclohexyl acetophenone photoinitiator and preparation method thereof

Publications (2)

Publication Number Publication Date
CN111574350A true CN111574350A (en) 2020-08-25
CN111574350B CN111574350B (en) 2022-08-16

Family

ID=72109140

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010386051.8A Active CN111574350B (en) 2020-05-09 2020-05-09 Hydroxy cyclohexyl acetophenone photoinitiator and preparation method thereof

Country Status (1)

Country Link
CN (1) CN111574350B (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113943241A (en) * 2021-10-22 2022-01-18 重庆邮电大学 Photocuring coating suitable for outdoor coating and storage and preparation method thereof
CN115536501A (en) * 2022-09-20 2022-12-30 阜阳欣奕华制药科技有限公司 Preparation method and application of 4-methoxy-2-naphthol

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6296986B1 (en) * 1995-11-06 2001-10-02 Coates Brothers Plc Photoinitiator
CN104003862A (en) * 2014-03-21 2014-08-27 岳阳凯门科技有限公司 New synthesis method for aromatic alpha-hydroxy ketone compounds
WO2015032069A1 (en) * 2013-09-06 2015-03-12 北京英力科技发展有限公司 Photo-initiator with low mobility
CN105175583A (en) * 2015-08-09 2015-12-23 同济大学 Acetophenone photoinitiator with biphenyl as conjugate structure, preparation method and application thereof
CN107868034A (en) * 2016-09-28 2018-04-03 北京化工大学常州先进材料研究院 One kind is applied to the light trigger of UV LED lights solidification
US20180186723A1 (en) * 2015-06-24 2018-07-05 Changzhou Tronly New Electronic Materials Co., Ltd. Sensitizer for uv-led photocuring and preparation method and use thereof
CN108558794A (en) * 2018-05-17 2018-09-21 北京化工大学 A kind of preparation method for reacting synthesis light-sensitive compound according to Claisen-Schmidt
CN109369406A (en) * 2018-11-08 2019-02-22 甘肃金盾化工有限责任公司 A kind of photocatalytic synthesis method of 1- hydroxycyclohexyl phenyl ketone class compound and its application
CN110117334A (en) * 2018-02-05 2019-08-13 北京化工大学 A kind of photothermal integrated initiator and preparation method thereof
CN110691765A (en) * 2017-05-17 2020-01-14 川崎化成工业株式会社 High molecular photopolymerization sensitizer

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6296986B1 (en) * 1995-11-06 2001-10-02 Coates Brothers Plc Photoinitiator
WO2015032069A1 (en) * 2013-09-06 2015-03-12 北京英力科技发展有限公司 Photo-initiator with low mobility
CN104003862A (en) * 2014-03-21 2014-08-27 岳阳凯门科技有限公司 New synthesis method for aromatic alpha-hydroxy ketone compounds
US20180186723A1 (en) * 2015-06-24 2018-07-05 Changzhou Tronly New Electronic Materials Co., Ltd. Sensitizer for uv-led photocuring and preparation method and use thereof
CN105175583A (en) * 2015-08-09 2015-12-23 同济大学 Acetophenone photoinitiator with biphenyl as conjugate structure, preparation method and application thereof
CN107868034A (en) * 2016-09-28 2018-04-03 北京化工大学常州先进材料研究院 One kind is applied to the light trigger of UV LED lights solidification
CN110691765A (en) * 2017-05-17 2020-01-14 川崎化成工业株式会社 High molecular photopolymerization sensitizer
CN110117334A (en) * 2018-02-05 2019-08-13 北京化工大学 A kind of photothermal integrated initiator and preparation method thereof
CN108558794A (en) * 2018-05-17 2018-09-21 北京化工大学 A kind of preparation method for reacting synthesis light-sensitive compound according to Claisen-Schmidt
CN109369406A (en) * 2018-11-08 2019-02-22 甘肃金盾化工有限责任公司 A kind of photocatalytic synthesis method of 1- hydroxycyclohexyl phenyl ketone class compound and its application

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
杨海冬等: "紫外光固化聚氨酯丙烯酸酯涂层的性能及应用研究", 《化学与黏合》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113943241A (en) * 2021-10-22 2022-01-18 重庆邮电大学 Photocuring coating suitable for outdoor coating and storage and preparation method thereof
CN115536501A (en) * 2022-09-20 2022-12-30 阜阳欣奕华制药科技有限公司 Preparation method and application of 4-methoxy-2-naphthol

Also Published As

Publication number Publication date
CN111574350B (en) 2022-08-16

Similar Documents

Publication Publication Date Title
CN111574350B (en) Hydroxy cyclohexyl acetophenone photoinitiator and preparation method thereof
CN111574425A (en) Novel benzoyl formic acid methyl ester photoinitiator and preparation method thereof
CN111635301B (en) Novel photoinitiator and preparation method thereof
CN111559963A (en) Long-wavelength benzoyl formic acid methyl ester photoinitiator and preparation method thereof
CN108774189B (en) Oxazine phenyl ether derivative and preparation method thereof
JP6206977B2 (en) Pentafluorosulfanyl phthalocyanine derivatives and intermediates thereof
CN113264843B (en) Synthetic method of 3-aminobicyclo [1.1.1] pentane-1-carboxylic ester derivative
CN108727161B (en) Method for preparing phenol by efficient in-situ hydroxylation of phenylboronic acid
CN108821975B (en) Hydrogenated phenanthrene derivative containing exocyclic double bond and preparation method thereof
CN111440207B (en) Cuprous complex, preparation method thereof and application thereof in synthesis of 3-indolyl thioether
CN111620845A (en) Long-wavelength morpholinyl acetophenone photoinitiator and preparation method thereof
WO2020207129A1 (en) Preparation and use of an ammonium salt
CN111499595A (en) Novel morpholinyl acetophenone photoinitiator and preparation method thereof
CN109499609B (en) SBA-15 immobilized 2-azaadamantane nitroxide free radical catalyst and preparation and application thereof
CN102516133A (en) Preparation method of methanesulfonic acid derivative
CN113105301B (en) Method for preparing conjugated diyne compound by using copper complex
CN111574352A (en) Long-wavelength carbonyl alcohol photoinitiator and preparation method thereof
CN113956254A (en) Organic photoelectric material based on perylene bisimide derivative and preparation method thereof
CN109879777B (en) 2-hydroxy arone oxime compound and preparation method and application thereof
JP2006248979A (en) Calixresorcinarene derivative and method for producing the same
CN104262085A (en) New synthetic method of 4-halogenated phenylacetylene
CN105152903A (en) Preparation method for aliphatic dicarboxylic acids
CN105254485B (en) A kind of method of o-phenylenediamine condensing benzaldehyde Bis-Schiff Bases palladium complex catalyst synthesis difunisal
CN115232047B (en) Preparation method of 3-phenylseleno-1-acetone derivatives
CN110452097B (en) Preparation method of 1-hydroxypyrene

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