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

Novel hydroxycyclohexyl acetophenone photoinitiator and preparation method thereof Download PDF

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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
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朱晓群
杨帆
聂俊
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Changzhou Institute for Advanced Materials Beijing University of Chemical Technology
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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.
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