CN110590533A - Water-based photoinitiator containing fluorene structure and preparation method and application thereof - Google Patents

Water-based photoinitiator containing fluorene structure and preparation method and application thereof Download PDF

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CN110590533A
CN110590533A CN201810602645.0A CN201810602645A CN110590533A CN 110590533 A CN110590533 A CN 110590533A CN 201810602645 A CN201810602645 A CN 201810602645A CN 110590533 A CN110590533 A CN 110590533A
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compound
substituted
represents hydrogen
straight
optionally
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钱晓春
胡春青
于培培
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Changzhou Tronly New Electronic Materials Co Ltd
Changzhou Tronly Advanced Electronic Materials Co Ltd
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Changzhou Tronly New Electronic Materials Co Ltd
Changzhou Tronly Advanced Electronic Materials Co Ltd
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Abstract

The invention discloses a water-based photoinitiator containing a fluorene structure, and a preparation method and application thereof. Wherein, the water-based photoinitiator has a structure shown as a general formula (I):

Description

Water-based photoinitiator containing fluorene structure and preparation method and application thereof
Technical Field
The invention relates to the technical field of mechanochemistry, in particular to a water-based photoinitiator containing a fluorene structure, and a preparation method and application thereof.
Background
The UV curing material is applied to various aspects in the field of photocuring by virtue of the advantages of rapid curing, low solvent volatilization, energy conservation and the like, and is widely applied to the aspects of printing ink, coating, adhesive and printed circuit board. However, in practical applications, there are still disadvantages that the equipment investment is large at a time, it is difficult to cure thick coatings, and some types of diluents are highly irritating, and for this reason, water-based photocuring systems are mentioned due to their advantages of high productivity and excellent coating properties. The photoinitiator used in the conventional curing system is mostly oil-soluble and insoluble or very low in solubility in water, the photoinitiator needs to be dispersed into the aqueous photocuring system by means of an emulsifier and a small amount of monomers, but has a compatibility problem, people further modify the photoinitiator on the basis that hydrophilic cationic and anionic groups are introduced into the oil-soluble photoinitiator structure, but the photoinitiator is sensitive to the pH value of the system, and salts can interfere with the stability of a dispersion colloid in the system, so that the aqueous photoinitiator with excellent application performance needs to be developed.
Disclosure of Invention
The invention aims to provide a water-based photoinitiator containing a fluorene structure, and a preparation method and application thereof, so as to solve the technical problem that the prior art lacks a water-based photoinitiator with excellent performance.
In order to achieve the above object, according to one aspect of the present invention, there is provided an aqueous photoinitiator containing a fluorene structure. The water-based photoinitiator has a structure shown as a general formula (I):
wherein:
R1、R2、R3each independently represents hydrogen, hydroxy, C1-C20Straight or branched alkyl of (2), C3-C20Cycloalkyl of, C4-C20Cycloalkylalkyl of (C)4-C20Alkylcycloalkyl of (A), C6-C20Aryl of (C)4-C20Optionally, the above groups may be substituted with O, N, S or a phenyl ring, R1、R2Can form a ring with each other;
R4、R5each independently represents hydrogen, halogen, C1-C20Straight or branched alkyl of (2), C4-C20Cycloalkylalkyl of (C)2-C20optionally-CH in these radicals2-may be substituted by-O-;
or R4、R5Each independently represents a water-solubilizing group;
when R is4、R5When not water-soluble, R6Represents a substituted phenyl group having a carboxylate structure;
when R is4、R5When it is a water-soluble group, R6Represents hydrogen, C1-C20Straight or branched alkyl of (2), C3-C20Cycloalkyl of, C4-C20Cycloalkylalkyl of (C)4-C20Alkylcycloalkyl of (A), C6-C20Aryl of (C)4-C20Optionally, the above groups may be interrupted or substituted by O, N, S, nitro, hydroxy, halogen or a phenyl ring;
n represents an integer of 0 to 4.
Further, the compound having the structure represented by the general formula (I) is a compound having a main structure represented by the general formula (II):
R1、R2、R3each independently represents hydrogen, hydroxy, C1-C20Straight or branched alkyl of (2), C3-C20Cycloalkyl of, C4-C20Cycloalkylalkyl of (C)4-C20Alkylcycloalkyl of (A), C6-C20Aryl of (C)4-C20Optionally, the above groups are represented by O, N, S or a benzene ringSubstituted, R1、R2Can form a ring with each other;
R6represents hydrogen, C1-C20Straight or branched alkyl of (2), C3-C20Cycloalkyl of, C4-C20Cycloalkylalkyl of (C)4-C20Alkylcycloalkyl of (A), C6-C20Aryl of (C)4-C20The heteroaryl of (a), optionally interrupted or substituted by O, N, S, alkyl, carboxyl, nitro, hydroxyl, halogen or a phenyl ring;
R4’、R5' independently represent a water-solubilizing group of a carboxylate, a quaternary ammonium salt or a betaine structure;
a independently of one another represents hydrogen, halogen, C1-C10Straight or branched alkyl of (2), C4-C10Optionally, -CH in these radicals2-may be substituted by-O-.
Further, the betaine structure is a structure having a cationic moiety and an anionic moiety.
Further, the cationic moiety of the betaine structure is selected from an ammonium salt or a sulfonium salt, and the anionic moiety of the betaine structure is selected from a sulfo group or an anion thereof, a carboxyl group or an anion thereof, a phosphoryl group or an anion thereof.
Further, the compound having the structure represented by the general formula (I) is a compound having a main structure represented by the general formula (III):
R1、R2、R3each independently represents hydrogen, hydroxy, C1-C20Straight or branched alkyl of (2), C3-C20Cycloalkyl of, C4-C20Cycloalkylalkyl of (C)4-C20Alkylcycloalkyl of (A), C6-C20Aryl of (C)4-C20Optionally, the above groups are substituted with O, N, S or a phenyl ring, R1、R2Can form a ring with each other;
R4、R5each independently represents hydrogen, halogen, C1-C20Straight or branched alkyl of (2), C4-C20Cycloalkylalkyl of (C)2-C20optionally-CH in these radicals2-may be substituted by-O-;
R7represents hydrogen, C1-C10Alkyl, nitro, hydroxy or halogen;
x represents a metal ion;
m represents an integer of 1 to 4.
According to another aspect of the present invention, there is provided a method for preparing the above aqueous photoinitiator. The preparation method comprises the following steps: when the compound with the structure shown in the general formula (I) is a compound with a main structure shown in the general formula (II), the compound with the main structure shown in the general formula (II) is synthesized by reacting the raw material a, and the reaction formula is shown as follows:
wherein R is6Represents hydrogen, C1-C20Straight or branched alkyl of (2), C3-C20Cycloalkyl of, C4-C20Cycloalkylalkyl of (C)4-C20Alkylcycloalkyl of (A), C6-C20Aryl of (C)4-C20The heteroaryl of (a), optionally interrupted or substituted by O, N, S, alkyl, carboxyl, nitro, hydroxyl, halogen or a phenyl ring;
R4’、R5' independently represent a water-solubilizing group of a carboxylate, a quaternary ammonium salt or a betaine structure;
a independently of one another represents hydrogen, halogen, C1-C10Straight or branched alkyl of (2), C4-C10Optionally, -CH in these radicals2-may be substituted by-O-;
when the compound with the structure shown in the general formula (I) is a compound with the main structure shown in the general formula (III), the compound with the main structure shown in the general formula (III) is synthesized by carrying out a Friedel-crafts reaction on a raw material b and a raw material c, and the reaction process is shown as follows:
wherein R is1、R2、R3Each independently represents hydrogen, hydroxy, C1-C20Straight or branched alkyl of (2), C3-C20Cycloalkyl of, C4-C20Cycloalkylalkyl of (C)4-C20Alkylcycloalkyl of (A), C6-C20Aryl of (C)4-C20Optionally, the above groups are substituted with O, N, S or a phenyl ring, R1、R2Can form a ring with each other;
R4、R5each independently represents hydrogen, halogen, C1-C20Straight or branched alkyl of (2), C4-C20Cycloalkylalkyl of (C)2-C20optionally-CH in these radicals2-may be substituted by-O-;
R7represents hydrogen, C1-C10Alkyl, nitro, hydroxy or halogen;
x represents a metal ion;
m represents an integer of 1 to 4.
Further, the compound with the main structure shown as the general formula (II) is synthesized by the reaction of the raw material a, and the method specifically comprises the following steps:
reacting a raw material a with halogenated carboxylic ester under an alkaline condition to obtain a compound with a carboxylate structure; or
Reacting a raw material a with dihalogenated alkyl, and hydrolyzing in the presence of quaternary ammonium salt to obtain a compound with a quaternary ammonium salt structure; or
The raw material a is reacted with dihaloalkane and then hydrolyzed under alkaline conditions to obtain a compound having a betaine structure.
According to a further aspect of the present invention, there is provided a use of the above-mentioned aqueous photoinitiator in a photocurable composition.
Further, the photocurable composition is an ink or a coating.
According to yet another aspect of the present invention, a photocurable composition is provided. The photocurable composition includes any of the aqueous photoinitiators described above.
By applying the technical scheme of the invention, the novel fluorene structure-containing photoinitiator is provided, and the photoinitiator with strong water solubility is obtained by further introducing water-soluble groups such as carboxylate, quaternary ammonium salt, betaine and the like into the fluorene photoinitiator structure. The photoinitiator has strong acid resistance and alkali resistance, almost does not migrate, and the use condition is not limited.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail with reference to examples.
According to a typical embodiment of the present invention, there is provided an aqueous photoinitiator containing a fluorene structure. The water-based photoinitiator has a structure shown as a general formula (I):
wherein:
R1、R2、R3each independently represents hydrogen, hydroxy, C1-C20Straight or branched alkyl of (2), C3-C20Cycloalkyl of, C4-C20Cycloalkylalkyl of (C)4-C20Alkylcycloalkyl of (A), C6-C20Aryl of (C)4-C20Optionally, the above groups may be substituted with O, N, S or a phenyl ring, R1、R2Can form a ring with each other;
R4、R5each independently represents hydrogen, halogen, C1-C20Straight or branched alkyl of (2), C4-C20A cycloalkylalkyl group of,C2-C20optionally-CH in these radicals2-may be substituted by-O-;
or R4、R5Each independently represents a water-solubilizing group;
when R is4、R5When not water-soluble, R6Represents a substituted phenyl group having a carboxylate structure;
when R is4、R5When it is a water-soluble group, R6Represents hydrogen, C1-C20Straight or branched alkyl of (2), C3-C20Cycloalkyl of, C4-C20Cycloalkylalkyl of (C)4-C20Alkylcycloalkyl of (A), C6-C20Aryl of (C)4-C20Optionally, the above groups may be interrupted or substituted by O, N, S, nitro, hydroxy, halogen or a phenyl ring;
n represents an integer of 0 to 4.
Further, the compound having the structure represented by the general formula (I) is a compound having a main structure represented by the general formula (II):
R1、R2、R3each independently represents hydrogen, hydroxy, C1-C20Straight or branched alkyl of (2), C3-C20Cycloalkyl of, C4-C20Cycloalkylalkyl of (C)4-C20Alkylcycloalkyl of (A), C6-C20Aryl of (C)4-C20Optionally, the above groups are substituted with O, N, S or a phenyl ring, R1、R2Can form a ring with each other;
R6represents hydrogen, C1-C20Straight or branched alkyl of (2), C3-C20Cycloalkyl of, C4-C20Cycloalkylalkyl of (C)4-C20Alkylcycloalkyl of (A), C6-C20Aryl of (C)4-C20The heteroaryl of (a), optionally interrupted or substituted by O, N, S, alkyl, carboxyl, nitro, hydroxyl, halogen or a phenyl ring;
R4’、R5' independently represent a water-solubilizing group of a carboxylate, a quaternary ammonium salt or a betaine structure;
a independently of one another represents hydrogen, halogen, C1-C10Straight or branched alkyl of (2), C4-C10Optionally, -CH in these radicals2-may be substituted by-O-.
By applying the technical scheme of the invention, the novel fluorene structure-containing photoinitiator is provided, and the photoinitiator with strong water solubility is obtained by further introducing water-soluble groups such as carboxylate, quaternary ammonium salt, betaine and the like into the fluorene photoinitiator structure. The photoinitiator has strong acid resistance and alkali resistance, almost does not migrate, and the use condition is not limited.
Among them, the betaine structure is a structure having a cationic moiety and an anionic moiety, and preferably, the cationic moiety of the betaine structure is selected from an ammonium salt or a sulfonium salt, and the anionic moiety of the betaine structure is selected from a sulfo group or an anion thereof, a carboxyl group or an anion thereof, and a phosphoryl group or an anion thereof.
According to a typical embodiment of the present invention, the compound having a structure represented by general formula (I) is a compound having a main structure represented by general formula (III):
R1、R2、R3each independently represents hydrogen, hydroxy, C1-C20Straight or branched alkyl of (2), C3-C20Cycloalkyl of, C4-C20Cycloalkylalkyl of (C)4-C20Alkylcycloalkyl of (A), C6-C20Aryl of (C)4-C20Optionally, the above groups are substituted with O, N, S or a phenyl ring, R1、R2Can form a ring with each other；
R4、R5Each independently represents hydrogen, halogen, C1-C20Straight or branched alkyl of (2), C4-C20Cycloalkylalkyl of (C)2-C20optionally-CH in these radicals2-may be substituted by-O-;
R7represents hydrogen, C1-C10Alkyl, nitro, hydroxy or halogen;
x represents a metal ion;
m represents an integer of 1 to 4.
According to a typical embodiment of the present invention, the fluorene photoinitiator according to the present invention has the following structure:
according to an exemplary embodiment of the present invention, there is provided a method for preparing the above aqueous photoinitiator. The preparation method comprises the following steps: when the compound with the structure shown in the general formula (I) is a compound with a main structure shown in the general formula (II), the compound with the main structure shown in the general formula (II) is synthesized by reacting the raw material a, and the reaction formula is shown as follows:
wherein R is6Represents hydrogen, C1-C20Straight or branched alkyl of (2), C3-C20Cycloalkyl of, C4-C20Cycloalkylalkyl of (C)4-C20Alkylcycloalkyl of (A), C6-C20Aryl of (C)4-C20The heteroaryl of (a), optionally interrupted or substituted by O, N, S, alkyl, carboxyl, nitro, hydroxyl, halogen or a phenyl ring;
R4’、R5' independently represent a water-solubilizing group of a carboxylate, a quaternary ammonium salt or a betaine structure;
a independently of one another represents hydrogen, halogen, C1-C10Straight or branched alkyl of (2), C4-C10Optionally, -CH in these radicals2-may be substituted by-O-;
when the compound with the structure shown in the general formula (I) is a compound with the main structure shown in the general formula (III), the compound with the main structure shown in the general formula (III) is synthesized by carrying out a Friedel-crafts reaction on a raw material b and a raw material c, and the reaction process is shown as follows:
wherein R is1、R2、R3Each independently represents hydrogen, hydroxy, C1-C20Straight or branched alkyl of (2), C3-C20Cycloalkyl of, C4-C20Cycloalkylalkyl of (C)4-C20Alkylcycloalkyl of (A), C6-C20Aryl of (C)4-C20Optionally, the above groups are substituted with O, N, S or a phenyl ring, R1、R2Can form a ring with each other;
R4、R5each independently represents hydrogen, halogen, C1-C20Straight or branched alkyl of (2), C4-C20Cycloalkylalkyl of (C)2-C20optionally-CH in these radicals2-may be substituted by-O-;
R7represents hydrogen, C1-C10Alkyl, nitro, hydroxy or halogen;
x represents a metal ion;
m represents an integer of 1 to 4.
According to a typical embodiment of the invention, the compound with a main structure shown as a general formula (II) is synthesized by reacting the raw material a, and the method specifically comprises the following steps: reacting a raw material a with halogenated carboxylic ester under an alkaline condition to obtain a compound with a carboxylate structure; or the raw material a reacts with dihalogenated alkyl, and then the dihalogenated alkyl is hydrolyzed in the presence of quaternary ammonium salt to obtain a compound with a quaternary ammonium salt structure; or the raw material a and dihaloalkane are reacted and then hydrolyzed under alkaline condition to obtain the compound with betaine structure.
In addition, betaine structures can also be obtained by synthesis according to the method disclosed in CN 104583243A.
According to an exemplary embodiment of the present invention, there is provided a use of the above-described aqueous photoinitiator in a photocurable composition. The photo-curable composition may be an ink or a coating, among others.
According to an exemplary embodiment of the present invention, a photocurable composition is provided. The photocurable composition includes any of the aqueous photoinitiators described above.
The following examples are provided to further illustrate the advantageous effects of the present invention.
Example 1
Synthesis of Compound 1
Step (1): preparation of intermediate 1
Adding 93g of raw material 1a, 67g of aluminum trichloride and 100mL of dichloromethane into a 500mL four-neck flask, cooling to 0 ℃ in an ice-water bath, dropwise adding a mixed solution of 54g of raw material isobutyryl chloride and 50mL of dichloromethane, controlling the temperature to be below 10 ℃, completing dropwise addition for about 2 hours, continuing stirring for 2 hours after dropwise addition, enabling a liquid phase tracking reaction to be complete, slowly pouring the materials into diluted hydrochloric acid prepared from 800g of ice water and 100mL of concentrated hydrochloric acid (37%), stirring while adding, then pouring into a separating funnel, separating a dichloromethane layer at the lower layer, continuing washing an aqueous layer with 50mL of dichloromethane, combining the dichloromethane layers, washing the dichloromethane layer with 5% sodium bicarbonate aqueous solution (300 mL and 3 times each time), washing the dichloromethane layer with water until the pH value is neutral, drying the dichloromethane layer with 150g of anhydrous magnesium sulfate, filtering, performing rotary evaporation on a dichloromethane product solution, recrystallizing with methanol, drying at 60 ℃ for 2 hours in an oven, 121g of intermediate 1 are obtained with a purity of 98%.
1H-NMR(CDCl3，500MHz)：1.2207-1.2330(6H，d)，3.3311-3.4049(1H，m)，3.7695-3.8921(2H，s)，7.2827-8.1427(7H,m)。
MS(m/z):237(M+1)+。
Step (2): preparation of intermediate 2
Adding 95g of intermediate 1 and 100mL of dichloromethane into a 500mL four-neck flask, heating to 40 ℃ while stirring, connecting a tail gas absorption device, slowly introducing chlorine gas for about 2 hours, performing liquid phase tracking reaction, continuously keeping the temperature and stirring for 2 hours, pouring into 25% NaOH ice water solution, stirring for 30min, separating a dichloromethane layer by a separating funnel, extracting a water layer by 100mL of dichloromethane again, combining the dichloromethane layers, washing to be neutral, performing rotary evaporation, and recrystallizing by methanol to obtain 92g of white solid, namely intermediate 2 with the purity of 98%.
1H-NMR(CDCl3，500MHz)：1.8603(6H,s)，3.8569(2H，s)，7.2804-8.1346(7H，m)；
MS(m/z):293(M+23)+。
And (3): preparation of intermediate 3
Adding 54g of intermediate 2, 50mL of dichloroethane, 0.2g of tetrabutylammonium bromide and 100g of 40% NaOH aqueous solution into a 250mL four-neck flask, heating and refluxing at 80 ℃ for 2h, tracking the liquid phase until the reaction is finished, cooling to room temperature, separating out a dichloroethane layer by a separating funnel, washing the dichloroethane layer to be neutral, removing dichloroethane by rotary evaporation, and recrystallizing methanol to obtain 44g of white solid product, namely the intermediate 3 with the purity of 99%.
The structure of the intermediate 3 is confirmed by hydrogen nuclear magnetic resonance spectroscopy and mass spectrometry.
1H-NMR(CDCl3，500MHz)：1.4926(6H,s)，1.9595-2.2902(1H，s)，3.7657-3.8753(2H，s)，7.2805-8.1882(7H，m)。
MS(m/z):253(M+1)+。
And (4): preparation of Compound 1
Adding 25g of intermediate 3, 20mL of ethyl chloroacetate, 100mL of 40% NaOH solution and 0.2g of tetrabutylammonium bromide into a 250mL four-neck flask, heating and stirring at 40 ℃, tracking a liquid phase until a raw material reaction does not change, separating out a water layer, extracting with dichloromethane for three times (30mL of 3), combining dichloromethane layers, washing with water to be neutral, and performing rotary evaporation to obtain 31g of light yellow solid with the purity of 99%.
The structure of the compound 1 is confirmed by hydrogen nuclear magnetic resonance spectroscopy and mass spectrometry.
1H-NMR(CDCl3，500MHz)：1.48886(6H,s)，1.9442-2.2879(1H，s)，2.8256(4H，s)，7.2816-8.1687(7H，m)。
MS(m/z):366(M2-)。
Example 2
Synthesis of Compound 2
Step (1): preparation of intermediate 5
Adding 83g of raw material 1, 134g of aluminum trichloride and 100mL of dichloromethane into a 1000mL four-neck flask, cooling to 0 ℃ in an ice-water bath, dropwise adding a mixed solution of 70g of raw material 3 benzoyl chloride and 100mL of dichloromethane, controlling the temperature to be below 10 ℃, completing dropwise addition for about 2 hours, then dropwise adding a mixed solution of 60g of isobutyryl bromide and 50mL of dichloromethane, continuously stirring for 2 hours after completing dropwise addition, tracking and reacting a liquid phase to be complete, then slowly pouring the materials into diluted hydrochloric acid prepared from 800g of ice water and 200mL of concentrated hydrochloric acid (37%), stirring while adding, then pouring into a separating funnel, separating a lower dichloromethane layer, continuously washing an aqueous layer with 50mL of dichloromethane, combining dichloromethane layers, washing the dichloromethane layer with 5% sodium bicarbonate aqueous solution (500 mL and 3 times each time), then washing the dichloromethane layer with water until the pH value is neutral, drying the dichloromethane layer with 150g of anhydrous magnesium sulfate, after filtration, the dichloromethane product solution is evaporated in a rotary manner, methanol is recrystallized, and the obtained product is dried in an oven at 70 ℃ for 2 hours to obtain 145g of intermediate 5 with the purity of 98 percent.
1H-NMR(CDCl3，500MHz)：1.2332-1.2879(6H，d)，1.3207-1.3976(1H，m)，3.8669(2H，s)，7.2809-8.2051(11H,m)。
MS(m/z):341(M+1)+。
Step (2): preparation of intermediate 6
Adding 136g of intermediate 5 and 100mL of dichloromethane into a 500mL four-neck flask, heating to 40 ℃ while stirring, connecting a tail gas absorption device, dropwise adding a mixed solution of 50mL of dichloromethane and 65g of liquid bromine, completing dropwise adding for about 2h, performing liquid phase tracking reaction, continuously keeping the temperature and stirring for 2h, then pouring into a 25% NaOH ice water solution, stirring for 30min, separating a dichloromethane layer by a separating funnel, extracting a water layer by using 100mL of dichloromethane again, combining the dichloromethane layers, washing to be neutral by water, performing rotary evaporation, and recrystallizing by using methanol to obtain 144g of white solid, namely intermediate 6 with the purity of 98%.
1H-NMR(CDCl3，500MHz)：2.0362(6H,s)，3.8662(2H，s)，7.3034-8.1833(11H，m)；
MS(m/z):442(M+23)+。
And (3): preparation of intermediate 7
Adding 84g of intermediate 6 and 60g of morpholine into a 250mL four-neck flask, heating and refluxing at 130 ℃ for 60h, tracking a liquid phase until the reaction is completed, pouring the reaction liquid into water, stirring, separating out an off-white solid, performing suction filtration, washing with water, and recrystallizing with methanol to obtain 62g of a white solid, namely the intermediate 7, wherein the purity is 99%.
The structure of intermediate 7 was confirmed by nmr hydrogen spectroscopy and mass spectroscopy.
1H-NMR(CDCl3，500MHz)：1.3692(6H,s)，3.6577-3.8727(10H，m)，7.2663-8.1816(11H，m)。
MS(m/z):426(M+1)+。
And (4): preparation of intermediate 8
43g of intermediate 7, 40mL of bromochloropropane, 100mL of 50% NaOH solution and 0.2g of tetrabutylammonium bromide are added into a 250mL four-neck flask, the mixture is heated and stirred at 40 ℃, the liquid phase is tracked until the raw material reaction does not change, then a water layer is separated out, dichloromethane is extracted, water washing and rotary evaporation are carried out, acetone is recrystallized to obtain 46g of light yellow solid with the purity of 99%.
The structure of intermediate 8 was confirmed by nmr hydrogen spectroscopy and mass spectroscopy.
1H-NMR(CDCl3，500MHz)：1.3687(6H,s)，1.8641-1.8736(4H，t)，2.3660-3.3764(4H,t)，3.3807-3.3942(4H，t)，3.6654-3.7004(8H，t)，7.3856-8.1443(11H，m)。
MS(m/z):579(M+1)+。
And (5): preparation of Compound 2
Adding 29g of intermediate 8, 100mL of 50% NaOH solution and 15g of tetrabutylammonium bromide into a 250mL four-neck flask, heating and stirring at 40 ℃, tracking a liquid phase until a raw material reaction does not change, separating out a water layer, extracting by using dichloromethane, washing to be neutral, performing rotary evaporation, and recrystallizing acetone to obtain 36g of light yellow solid with the purity of 99%.
The structure of compound 2 was confirmed by nmr hydrogen spectroscopy and mass spectroscopy.
1H-NMR(CDCl3，500MHz)：1.3687(6H,s)，1.5673-1.5709(4H，m)，1.8641-1.8736(4H，t)，2.3660-3.3764(4H,t)，3.3807-3.3942(4H，t)，3.6654-3.7004(8H，t)，7.3856-8.1443(11H，m)。
MS(m/z):766(M2+)。
Example 3
Step (1): preparation of intermediate 9
Adding 8.3g of raw material a, 13.4g of aluminum trichloride and 20mL of dichloromethane into a 100mL four-neck flask, cooling to 0 ℃ in an ice-water bath, dropwise adding a mixed solution of 14g of raw material benzoyl chloride and 10mL of dichloromethane, controlling the temperature to be below 10 ℃, dropwise adding for about 2 hours, continuously stirring for 2 hours after dropwise adding, tracking and reacting a liquid phase until the reaction is complete, slowly pouring the material into diluted hydrochloric acid prepared from 80g of ice water and 20mL of concentrated hydrochloric acid (37%), stirring while adding, then pouring into a separating funnel, separating a dichloromethane layer at the lower layer, continuously washing a water layer with 50mL of dichloromethane, combining the dichloromethane layers, washing the dichloromethane layer with 5% sodium bicarbonate aqueous solution (50 mL and 3 times each time), washing the dichloromethane layer with water until the pH value is neutral, drying the dichloromethane layer with 15g of anhydrous magnesium sulfate, filtering, rotationally steaming the dichloromethane product solution, recrystallizing with methanol, drying in an oven at 70 ℃ for 2 hours, 17.2g of intermediate 9 are obtained, with a purity of 98%.
1H-NMR(CDCl3，500MHz)：3.8309(2H，s)，7.3819-8.0034(16H,m)。
MS(m/z):375(M+1)+。
Step (2): preparation of Compound 3
Adding 15g of intermediate 9, 20mL of dichloroethane, 10mL of 50% NaOH solution and 0.1g of tetrabutylammonium bromide into a 100mL four-neck flask, heating and stirring at 40 ℃, heating to 40 ℃ while stirring, then dropwise adding a solution of 20mL of dichloroethane and 12g of bromochloroethane, carrying out liquid phase tracking reaction until the reaction is completed, then adding 5g of trimethylglycine, continuing heating and stirring, carrying out liquid phase tracking reaction until the reaction is completed, then stopping the reaction, separating a dichloroethane layer, extracting an aqueous layer (20mL of 3) with dichloroethane, washing the dichloroethane layer with water, combining the dichloromethane layers, carrying out column chromatography on a column (mobile phase dichloromethane: methanol: 60:40), and carrying out rotary evaporation to obtain 15g of a light yellow solid, namely the compound 3 with the purity of 98%.
1H-NMR(CDCl3，500MHz)：2.3065-2.3187(4H,t)，3.2448-3.3427(16H，m)，4.3302(4H，s)，7.3005-7.9049(16H，m)；
MS(m/z):633(M)。
Example 4
Step (1): preparation of intermediate 11
150g of intermediate 9, 100mL of toluene and 20g of potassium tert-butoxide are added into a 500mL four-neck flask, the mixture is heated and stirred at 100 ℃, 50mL of the mixed solution of toluene and 18.5g of epichlorohydrin is dripped, the dripping is finished within about 1 hour, the liquid phase tracking raw material does not change any more, the reaction is finished within about 3 hours, the reaction solution is poured into 200mL of 1% sodium bicarbonate aqueous solution, then the water is washed to be neutral, a toluene layer is separated, the toluene is removed by rotary evaporation, and methanol is recrystallized, thus obtaining 157g of intermediate 10.
The intermediate 10 was confirmed by hydrogen nuclear magnetic resonance spectroscopy and mass spectrometry.
1H-NMR(CDCl3，500MHz)：1.4351-1.4805(4H，m)，1.8602-2.1674(6H，m)，3.5267-3.6063(4H，t)，7.3671-7.9963(16H，m)。
MS(m/z)：491(M+1)+。
Step (2): preparation of intermediate 11
49g of the intermediate 10, DMF500mL, potassium carbonate 30g and 2-chloroethyldimethylamine 22g are added into a 250mL four-neck flask, the mixture is stirred at normal temperature overnight, after the reaction is finished, suction filtration is carried out, reaction liquid is poured into deionized water, a large amount of solid is precipitated, suction filtration, water washing and methanol recrystallization are carried out, and 39g of the intermediate 11 is obtained.
Intermediate 11 was confirmed by nmr hydrogen spectroscopy and mass spectroscopy.
1H-NMR(CDCl3，500MHz)：1.4299-1.4835(4H，m)，1.8616-1.8974(4H，t)，2.2257(12H，s)，2.5008-2.5342(4H，t)，3.2967-3.4865(8H，m)，7.3633-7.9093(16H，m)。
MS(m/z)：633(M+1)+。
And (3): preparation of Compound 4
6.3g of the intermediate 11, 30mL of acetonitrile and 2.5g of 1, 3-propane sultone are added into a 100mL four-neck flask, the mixture is stirred at normal temperature overnight, the mixture is poured into deionized water after the reaction is finished, a small amount of oily matter is separated out from solid, dichloromethane is used for extraction (10Ml 10), dichloromethane layers are combined, rotary evaporation is carried out, and acetonitrile is used for recrystallization, so that 6.3g of the compound 4 is obtained.
Compound 4 was confirmed by nmr hydrogen spectroscopy and mass spectroscopy.
1H-NMR(CDCl3，500MHz)：1.4345-1.4637(4H，m)，1.8577-1.8704(4H，t)，2.2008-2.2997(4H，m)，3.2012-3.4258(28H，m)，3.7984-3.8585(4H，m)，7.32943-7.9480(16H，m)。
MS(m/z)：877(M)。
Example 5
Adding 38g of intermediate 4, 15g of phthalic anhydride, 10mL of 50% sodium hydroxide aqueous solution and 0.1g of tetrabutylammonium bromide into a 250mL four-neck flask, heating and stirring at 40 ℃, tracking and reacting a liquid phase until no change occurs, then placing the reaction liquid into a refrigerator for refrigeration, standing overnight, precipitating a solid, and carrying out suction filtration to obtain 20g of a white solid, namely the compound 5.
1H-NMR(CDCl3，500MHz)：0.9605-1.1123(6H,t)，1.2905-1.3345(8H,m),1.8677-1.8703(4H，t)，7.6036-8.1003(15H，m)。
MS(m/z)：529(M-)。
Examples 6 to 20:
following the procedures of examples 1-5 and the synthesis of published intermediates, compounds 6-20 shown in table 1 below were synthesized using the corresponding starting materials.
The structure of the target product and its mass spectral data are listed in table 1:
evaluation of Performance
1. Evaluation of Water solubility of photoinitiator
The water solubility of the photoinitiator was evaluated by measuring the solubility of the photoinitiator in water at 25 ℃. Weighing 0.1g of sample and a conical flask respectively, adding 0.1mL, 1mL, 10mL and 100mL of water, ultrasonically dissolving for 10min, observing the dissolution condition of the sample, and performing filter membrane filtration sampling liquid phase analysis (by adopting Shim pack column, 150 × 6.0nm, detector SPD-20A, detection limit 20ppm and detection wavelength 254nm) to determine the dissolution condition of the product in water, wherein the specific table is as follows:
TABLE 3 Water solubility test
The structures of compounds A-D in Table 3 are as follows:
as can be seen from table 3 above, the fluorene photoinitiator according to the present invention has a higher solubility in water than a common fluorene photoinitiator due to the modification of the structure at the 9-position, whereas a common photoinitiator containing hydrogen or alkyl at the 9-position has a very low solubility in water, and can hardly be detected to be soluble in water at the detection limit.
2. Photoinitiator curing Performance evaluation
The film-forming properties of the photoinitiators of formula (I) according to the invention and of the general fluorene initiators were evaluated by formulating exemplary photocurable compositions.
(1) A photocurable composition was prepared as follows
In the above composition, the photoinitiator is a compound represented by formula (II) or formula (III) disclosed in the present invention or a photoinitiator known in the prior art (for comparison).
(2) Film forming property
Stirring the photocuring composition under a yellow light, taking the mixture to be coated on a floor by rolling to form a film, wherein the coating weight is about 5 g/m. The floor on which the coating film was formed was subjected to a high-pressure mercury lamp (model RW-UV70201 exposure machine, light intensity 200 mW/cm)2) The coating film is exposed to light and cured as completely as possible to form a film.
And the acid resistance and alkali resistance of the film-formed material were evaluated.
1) Acid resistance
The cured film was immersed in a 10% sulfuric acid solution for 24 hours, and the change before and after the change of the cured film was observed.
2) Alkali resistance
The cured film was immersed in a 10% aqueous solution of sodium bicarbonate for 24 hours, and the change before and after the change of the cured film was observed.
3) Salt tolerance
The cured film was immersed in a 10% aqueous solution of sodium chloride for 24 hours, and changes before and after the change of the cured film were observed.
In general, the acid resistance, alkali resistance and salt resistance of the cured film are important indexes reflecting the migration resistance thereof, and the stronger the acid resistance, alkali resistance and salt resistance, the smaller the migration resistance of the initiator, and it is noted that the stronger the acid resistance, alkali resistance and salt resistance is measured in the case where the composition is completely formed into a film.
The evaluation criteria are as follows:
very good: after soaking, the cured film has falling off or cracks;
●: after soaking, the cured film was unchanged.
The evaluation results are summarized in table 4.
TABLE 4 photoinitiator film formation Properties and migration evaluation
As can be seen from Table 4, compared with the traditional aqueous photoinitiator, the photoinitiator has strong water solubility, is not easy to migrate no matter under acidic or alkaline conditions after being cured into a film, and has excellent salt resistance. On the other hand, the fluorene initiator has extremely low solubility in water, and therefore, it is hardly cured in a water-soluble photocurable formulation and cannot be evaluated.
From the above description, it can be seen that the above-described embodiments of the present invention achieve the following technical effects: on the whole, the photoinitiator shown in the formula (I) disclosed by the invention has excellent application performance, is not easy to migrate, and has good application prospect.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. An aqueous photoinitiator containing a fluorene structure has a structure shown as a general formula (I):
wherein:
R1、R2、R3each independently represents hydrogen, hydroxy, C1-C20Straight or branched alkyl of (2), C3-C20Cycloalkyl of, C4-C20Cycloalkylalkyl of (C)4-C20Alkylcycloalkyl of (A), C6-C20Aryl of (C)4-C20Optionally, the above groups may be substituted with O, N, S or a phenyl ring, R1、R2Can form a ring with each other;
R4、R5each independently represents hydrogen, halogen, C1-C20Straight or branched alkyl of (2), C4-C20Cycloalkylalkyl of (C)2-C20optionally-CH in these radicals2-may be substituted by-O-;
or R4、R5Each independently represents a water-solubilizing group;
when R is4、R5When not water-soluble, R6Represents a substituted phenyl group having a carboxylate structure;
when R is4、R5When it is a water-soluble group, R6Represents hydrogen, C1-C20Straight or branched alkyl of (2), C3-C20Cycloalkyl of, C4-C20Cycloalkylalkyl of (C)4-C20Alkylcycloalkyl of (A), C6-C20OfBase, C4-C20Optionally, the above groups may be interrupted or substituted by O, N, S, nitro, hydroxy, halogen or a phenyl ring;
n represents an integer of 0 to 4.
2. The aqueous photoinitiator according to claim 1, wherein the compound having the structure represented by the general formula (i) is a compound having a main structure represented by the general formula (ii):
R1、R2、R3each independently represents hydrogen, hydroxy, C1-C20Straight or branched alkyl of (2), C3-C20Cycloalkyl of, C4-C20Cycloalkylalkyl of (C)4-C20Alkylcycloalkyl of (A), C6-C20Aryl of (C)4-C20Optionally, the above groups are substituted with O, N, S or a phenyl ring, R1、R2Can form a ring with each other;
R6represents hydrogen, C1-C20Straight or branched alkyl of (2), C3-C20Cycloalkyl of, C4-C20Cycloalkylalkyl of (C)4-C20Alkylcycloalkyl of (A), C6-C20Aryl of (C)4-C20The heteroaryl of (a), optionally interrupted or substituted by O, N, S, alkyl, carboxyl, nitro, hydroxyl, halogen or a phenyl ring;
R4’、R5' independently represent a water-solubilizing group of a carboxylate, a quaternary ammonium salt or a betaine structure;
a independently of one another represents hydrogen, halogen, C1-C10Straight or branched alkyl of (2), C4-C10Optionally, -CH in these radicals2-may be substituted by-O-.
3. The aqueous photoinitiator according to claim 2, characterised in that the betaine structure is a structure having a cationic part and an anionic part.
4. The aqueous photoinitiator according to claim 3, wherein the cationic moiety of the betaine structure is selected from an ammonium or sulfonium salt and the anionic moiety of the betaine structure is selected from a sulfo group or an anion thereof, a carboxyl group or an anion thereof, a phosphoryl group or an anion thereof.
5. The aqueous photoinitiator according to claim 1, wherein the compound having the structure represented by the general formula (i) is a compound having a main structure represented by the general formula (iii):
R1、R2、R3each independently represents hydrogen, hydroxy, C1-C20Straight or branched alkyl of (2), C3-C20Cycloalkyl of, C4-C20Cycloalkylalkyl of (C)4-C20Alkylcycloalkyl of (A), C6-C20Aryl of (C)4-C20Optionally, the above groups are substituted with O, N, S or a phenyl ring, R1、R2Can form a ring with each other;
R4、R5each independently represents hydrogen, halogen, C1-C20Straight or branched alkyl of (2), C4-C20Cycloalkylalkyl of (C)2-C20optionally-CH in these radicals2-may be substituted by-O-;
R7represents hydrogen, C1-C10Alkyl, nitro, hydroxy or halogen;
x represents a metal ion;
m represents an integer of 1 to 4.
6. A process for the preparation of the aqueous photoinitiator according to any one of claims 1 to 5,
when the compound with the structure shown in the general formula (I) is a compound with a main structure shown in a general formula (II), the compound with the main structure shown in the general formula (II) is synthesized by reacting the raw material a, and the reaction formula is shown as follows:
wherein R is6Represents hydrogen, C1-C20Straight or branched alkyl of (2), C3-C20Cycloalkyl of, C4-C20Cycloalkylalkyl of (C)4-C20Alkylcycloalkyl of (A), C6-C20Aryl of (C)4-C20The heteroaryl of (a), optionally interrupted or substituted by O, N, S, alkyl, carboxyl, nitro, hydroxyl, halogen or a phenyl ring;
R4’、R5' independently represent a water-solubilizing group of a carboxylate, a quaternary ammonium salt or a betaine structure;
a independently of one another represents hydrogen, halogen, C1-C10Straight or branched alkyl of (2), C4-C10Optionally, -CH in these radicals2-may be substituted by-O-;
when the compound with the structure shown in the general formula (I) is a compound with a main structure shown in a general formula (III), a Friedel-crafts reaction is carried out on a raw material b and a raw material c to synthesize the compound with the main structure shown in the general formula (III), and the reaction formula is shown as follows:
wherein R is1、R2、R3Each independently represents hydrogen, hydroxy, C1-C20Straight or branched alkyl of (2), C3-C20Cycloalkyl of, C4-C20Cycloalkylalkyl of (C)4-C20Alkylcycloalkyl of (A), C6-C20Aryl of (C)4-C20Optionally, the above groups are substituted with O, N, S or a phenyl ring, R1、R2Can form a ring with each other;
R4、R5each independently represents hydrogen, halogen, C1-C20Straight or branched alkyl of (2), C4-C20Cycloalkylalkyl of (C)2-C20optionally-CH in these radicals2-may be substituted by-O-;
R7represents hydrogen, C1-C10Alkyl, nitro, hydroxy or halogen;
x represents a metal ion;
m represents an integer of 1 to 4.
7. The preparation method according to claim 6, wherein the compound having the main structure of formula (II) is synthesized by reacting the raw material a, and specifically comprises:
reacting the raw material a with halogenated carboxylic ester under an alkaline condition to obtain a compound with a carboxylate structure; or
Reacting the raw material a with dihalogenated alkyl, and hydrolyzing in the presence of quaternary ammonium salt to obtain a compound with a quaternary ammonium salt structure; or
And (3) after the raw material a is reacted with dihaloalkane, hydrolyzing the dihaloalkane under alkaline conditions to obtain a compound with a betaine structure.
8. Use of the aqueous photoinitiator according to any one of claims 1 to 5 in a photocurable composition.
9. Use according to claim 8, wherein the photocurable composition is an ink or a coating.
10. A photocurable composition comprising an aqueous photoinitiator according to any one of claims 1 to 5.
CN201810602645.0A 2018-06-12 2018-06-12 Water-based photoinitiator containing fluorene structure and preparation method and application thereof Pending CN110590533A (en)

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Cited By (4)

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Publication number Priority date Publication date Assignee Title
WO2021023144A1 (en) * 2019-08-07 2021-02-11 常州强力电子新材料股份有限公司 Fluorenoxime ester compound, preparation method therefor, and application thereof
WO2021121135A1 (en) * 2019-12-19 2021-06-24 常州强力电子新材料股份有限公司 Photoinitiator, preparation method therefor and application thereof, and photocurable composition
WO2023282045A1 (en) * 2021-07-05 2023-01-12 株式会社Adeka Compound, composition, cured product, and method for producing cured product
WO2023282046A1 (en) * 2021-07-05 2023-01-12 株式会社Adeka Compound, composition, cured product, and method for manufacturing cured product

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KR20140144809A (en) * 2013-06-11 2014-12-22 애경화학 주식회사 Photoinitiators with fluorene structure and reactive liquid crystal compositions, and photoresist compositions comprising the same
CN106883114A (en) * 2015-12-15 2017-06-23 常州强力先端电子材料有限公司 A kind of fluorenes class polyfunctionality light trigger and its preparation and application

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021023144A1 (en) * 2019-08-07 2021-02-11 常州强力电子新材料股份有限公司 Fluorenoxime ester compound, preparation method therefor, and application thereof
WO2021121135A1 (en) * 2019-12-19 2021-06-24 常州强力电子新材料股份有限公司 Photoinitiator, preparation method therefor and application thereof, and photocurable composition
WO2023282045A1 (en) * 2021-07-05 2023-01-12 株式会社Adeka Compound, composition, cured product, and method for producing cured product
WO2023282046A1 (en) * 2021-07-05 2023-01-12 株式会社Adeka Compound, composition, cured product, and method for manufacturing cured product

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