CN112409295A - Fluorene initiator, photocuring composition containing same and application thereof - Google Patents

Fluorene initiator, photocuring composition containing same and application thereof Download PDF

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CN112409295A
CN112409295A CN201910775853.5A CN201910775853A CN112409295A CN 112409295 A CN112409295 A CN 112409295A CN 201910775853 A CN201910775853 A CN 201910775853A CN 112409295 A CN112409295 A CN 112409295A
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cycloalkyl
fluorene
alkyl
photoinitiator
substituted
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CN112409295B (en
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钱晓春
胡春青
陈亮
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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    • C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
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Abstract

The invention providesA fluorene initiator, a photocuring composition containing the same and application thereof. The fluorene photoinitiator has a structure shown in a formula (I). In the photoinitiator, one or more alkyl ketone substituent groups are introduced to a fluorene structure, and two aryl ketone substituent groups are introduced to a carbon atom No. 9, so that fragments formed by the initiator after initiation reaction still have higher stability and photocuring effect; simultaneous multiple photoactive groups R3The introduction of (2) can increase the number of free radicals generated by the photoinitiator per unit mass, thereby being beneficial to improving the sensitivity of the photoinitiator. In addition, the photoinitiator has the characteristics of difficult migration and excellent yellowing resistance because of large molecular weight and light color, so the photoinitiator also has the advantages of almost no VOC discharge, low odor and excellent yellowing resistance.

Description

Fluorene initiator, photocuring composition containing same and application thereof
Technical Field
The invention relates to the field of photocuring, and particularly relates to a fluorene initiator, a photocuring composition containing the fluorene initiator and application of the fluorene initiator.
Background
People pay more and more attention to safety, and especially pay more attention to the safety of articles closely related to the life of people and frequently contacted in daily life, such as food safety, safety and comfort of living environment and the like. Meanwhile, the environmental protection requirements of various industries are becoming stricter, and particularly, the VOC emission and emission amount of the related chemical industries are strictly controlled. Green environmental protection technologies for photocurable coatings and photocurable inks with almost no VOC emission have been widely focused and rapidly developed. Increasing the molecular weight of the initiator and sensitizer molecules is an effective means to address the mobility of photoinitiators. Due to the increase in molecular weight, the proportion of reactive groups decreases and the initiation efficiency of the initiator is greatly affected. Therefore, there is a need to develop a new high sensitivity macrophotoinitiator to solve the migration problem in coating ink applications.
The existing benzophenone photoinitiator, alpha-hydroxy ketone photoinitiator and alpha-amino ketone photoinitiator are widely applied to the field of photocuring due to the advantages of simple structure, easy synthesis, low price and the like. However, the above photoinitiator often has problems of migration, odor, yellowing, solubility and the like during use, and application thereof is limited to a great extent. In view of the above problems, one approach is to link a reactive group to a polymer molecule to make it large, which avoids problems of small molecule mobility and odor to some extent, but increases the volume of the generated radical, limits the moving speed of the radical, reduces the initiation efficiency of the photoinitiator, and thus reduces the sensitivity of the photoinitiator. In addition, most of these macro-photoinitiators are very viscous liquids and are inconvenient to use. The other method is to synthesize different types of alpha-hydroxy ketone and alpha-amino ketone photoinitiators, which improves the initiation efficiency of the photoinitiators to a certain extent, but the preparation and synthesis process is relatively complex and the cost is high. On the other hand, with the increasing environmental pollution, the development of zero-mobility photoinitiators is a goal pursued by those skilled in the art.
On the basis of this, there is a need to develop a photoinitiator having a zero migration rate and excellent yellowing resistance and sensitivity.
Disclosure of Invention
The invention mainly aims to provide a fluorene initiator, a photocuring composition containing the same and application thereof, and aims to solve the problems that the existing fluorene photoinitiator cannot simultaneously have zero migration, yellowing resistance, high sensitivity and the like.
In order to achieve the above object, according to one aspect of the present invention, there is provided a fluorene-based initiator having a structure represented by formula (I):
Figure RE-GDA0002218511940000021
wherein R is1And R2Are each independently selected from C1～C20Straight or branched alkyl of (2), C3～C20Cycloalkyl of, C3～C8Cycloalkyl-substituted C of1～C12Alkyl of (C)1～C12Alkyl-substituted C of3～C8Cycloalkyl of, C6～C20Or R is1And R2Are connected with each other to form a ring; r3Is a photoactive group; ar represents a substituted or unsubstituted aryl group;
Ra1、Ra2、Ra3、Ra4、Ra6、Ra7each independently selected from hydrogen and C1～C20Straight or branched alkyl of (2), C3～C20Cycloalkyl of, C3～C8Cycloalkyl-substituted C of1～C12Alkyl of (C)1～C12Alkyl-substituted C of3～C8Cycloalkyl of, C7～ C20Aralkyl or C2～C20Heterocyclyl group of-ORb1、-CORb1、-COORb1、-SRb1、-SO2Rb1or-CONRb1Rb2Wherein R isb1And Rb2Each independently represents hydrogen or C1～C20Straight or branched alkyl of (2), C3～C20Cycloalkyl of, C3～C8Cycloalkyl-substituted C of1～C12Alkyl of (C)1～C12Alkyl-substituted C of3～C8Cycloalkyl of, C7～C20Aralkyl or C2～C20A heterocyclic group of (a);
Ra5selected from hydrogen, C1～C20Straight or branched alkyl of (2), C3～C20Cycloalkyl of, C3～C8Cycloalkyl-substituted C of1～ C12Alkyl of (C)1～C12Alkyl-substituted C of3～C8Cycloalkyl of, C7～C20Aralkyl or C2～C20Heterocyclyl group of-NO2、-ORb1、-CORb1、-COORb1、-SRb1、-SO2Rb1or-CONRb1Rb2Wherein R isb1And Rb2Each independently represents hydrogen or C1～C20Straight or branched alkyl of (2), C3～C20Cycloalkyl of, C3～C8Cycloalkyl-substituted C of1～C12Alkyl of (C)1～C12Alkyl-substituted C of3～C8Cycloalkyl of, C6～C20Aralkyl of (2), C2～C20Heterocyclyl or-COC (R)1) (R2)(R3)。
Further, R3Selected from hydroxy, alkoxy, N-dialkyl, N-morpholinyl, N-thiomorpholinyl or N-substituted piperazinyl.
Further, R1And R2Each independently represents C1～C4Straight or branched alkyl of (2), C3～C5Cycloalkyl-substituted C of1～C3Or R is1And R2Are connected with each other to form C3～C6A cycloalkyl group of (a).
Further, Ar is selected from phenyl, pyridyl, thienyl, furyl or the above groups containing substituents.
Further, Ra5Selected from hydrogen, C1～C10Straight or branched alkyl of (2), C7～C20Aralkyl of (2), C2～C10Heterocyclyl group of-NO2、-ORb1、-CORb1、-COORb1or-CONRb1Rb2Wherein R isb1And Rb2Each independently represents hydrogen or C1～C10Straight or branched alkyl of (2), C3～C10Cycloalkyl of, C3～C8Cycloalkyl-substituted C of1～C5Alkyl of (C)1～C5Alkyl-substituted C of3～C8Cycloalkyl of, C6～C20Aralkyl of (2), C2～C20Heterocyclyl or-COC (R)1)(R2)(R3)。
Further, R1And R2Are each independently selected from C1～C4Straight or branched alkyl of R3Selected from N, N-dialkyl, N-morpholinyl, N-thiomorpholinyl, Ra5Selected from hydrogen, C1～C10Linear or branched alkyl, -NO2、-ORb1and-CORb1Wherein R isb1Is C1～C10Straight or branched alkyl of (2), C6～C20Aralkyl or C2～C20The heteroaryl group of (a).
Further, R1、R2Are each independently selected from C1～C4Or straight or branched alkyl of, or R1And R2Linked to each other to form a ring, R3Selected from hydroxy or alkoxy, Ra5Selected from hydrogen, C1～C10Straight or branched alkyl of (2), C6～C10Aralkyl, -NO2、-ORb1and-CORb1Wherein R isb1Is C1～C10Straight or branched alkyl of (2), C6～C20Aralkyl, hydroxy-substituted C of3～C8Cycloalkane of (C)2～C10The heteroaryl group of (a).
Further, R1、R2Are each independently selected from C1～C4Or straight or branched alkyl of, or R1And R2Linked to each other to form a ring, R3Selected from hydroxy, N-dialkyl or thiomorpholinyl, Ra5is-CORb1Wherein R isb1Is a 1-cyclohexanol group.
In another aspect of the present application, there is provided a photocurable composition comprising a photoinitiator, a polymerized monomer and/or a polymerized oligomer, wherein the photoinitiator comprises the fluorene photoinitiator.
The application further provides an application of the fluorene photoinitiator in the field of photocuring.
By applying the technical scheme of the invention, one or more alkyl ketone substituent groups are introduced into the fluorene structure and two aryl ketone substituent groups are introduced into the carbon atom No. 9 in the photoinitiator, so that fragments formed by the initiator after initiating initiation reaction still have higher stability and photocuringThe effect is achieved; simultaneous multiple photoactive groups R3The introduction of (2) can increase the number of free radicals generated by the photoinitiator per unit mass, thereby being beneficial to improving the sensitivity of the photoinitiator. In addition, the photoinitiator has the characteristics of difficult migration and excellent yellowing resistance because of large molecular weight and light color, so the photoinitiator also has the advantages of almost no VOC discharge, low odor and excellent yellowing resistance.
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.
As described in the background art, the existing fluorene photoinitiators have the problems of not having zero migration, yellowing resistance and high sensitivity at the same time. In order to solve the above technical problems, the present application provides a fluorene-based initiator, wherein the fluorene-based photoinitiator has a structure represented by formula (I):
Figure RE-GDA0002218511940000041
wherein R is1、R2Are each independently selected from C1～C20Straight or branched alkyl of (2), C3～C20Cycloalkyl of, C3～C8Cycloalkyl-substituted C of1～C12Alkyl of (C)1～C12Alkyl-substituted C of3～C8Cycloalkyl of, C6～C20Or R is1And R2Are connected with each other to form a ring;
R3is a photoactive group; ar represents a substituted or unsubstituted aryl group;
Ra1、Ra2、Ra3、Ra4、Ra6、Ra7each independently selected from hydrogen and C1～C20Straight or branched alkyl of (2), C3～C20Cycloalkyl of, C3～C8Substituted by cycloalkyl groupsC1～C12Alkyl of (C)1～C12Alkyl-substituted C of3～C8Cycloalkyl of, C7～ C20Aralkyl or C2～C20Heterocyclyl group of-ORb1、-CORb1、-COORb1、-SRb1、-SO2Rb1or-CONRb1Rb2Wherein R isb1And Rb2Each independently represents hydrogen or C1～C20Straight or branched alkyl of (2), C3～C20Cycloalkyl of, C3～C8Cycloalkyl-substituted C of1～C12Alkyl of (C)1～C12Alkyl-substituted C of3～C8Cycloalkyl of, C7～C20Aralkyl or C2～C20A heterocyclic group of (a); ra5Selected from hydrogen, C1～C20Straight or branched alkyl of (2), C3～C20Cycloalkyl of, C3～C8Cycloalkyl-substituted C of1～C12Alkyl of (C)1～C12Alkyl-substituted C of3～C8Cycloalkyl of, C7～C20Aralkyl or C2～ C20Heterocyclyl group of-NO2、-ORb1、-CORb1、-COORb1、-SRb1、-SO2Rb1or-CONRb1Rb2Wherein R isb1And Rb2Each independently represents hydrogen or C1～C20Straight or branched alkyl of (2), C3～C20Cycloalkyl of, C3～C8Cycloalkyl-substituted C of1～C12Alkyl of (C)1～C12Alkyl-substituted C of3～C8Cycloalkyl of, C6～C20Aralkyl of (2), C2～C20Heteroaryl or-COC (R) of1)(R2)(R3)。
In the above photoinitiator, one or more alkyl ketone substituents are introduced to the fluorene structure, and two aryl ketone substituents are introduced to the carbon atom number 9, which are the same as the aboveFragments formed by the initiator after initiating the initiation reaction still have higher stability and photocuring effect; simultaneous multiple photoactive groups R3The introduction of (2) can increase the number of free radicals generated by the photoinitiator per unit mass, thereby being beneficial to improving the sensitivity of the photoinitiator. In addition, the photoinitiator has the characteristics of difficult migration and excellent yellowing resistance because of large molecular weight and light color, so the photoinitiator also has the advantages of almost no VOC discharge, low odor and excellent yellowing resistance.
In order to further improve the overall performance of the fluorene-based photoinitiator, the substituent in formula (I) may be preferably used.
R3Photoactive groups commonly used in the art may be selected. In a preferred embodiment, R3And R6Each independently selected from hydroxy, alkoxy, N-dialkyl, N-morpholinyl, N-thiomorpholinyl or N-substituted piperazinyl. The selection of several photoactive groups described above is advantageous in improving the sensitivity of the photoinitiator compared to other photoactive groups. More preferably, R3And/or R6Is an alkoxy group.
In a preferred embodiment, R1And R2Each independently represents C1～C4Straight or branched alkyl of (2), C3～C5Cycloalkyl-substituted C of1～C3Or R is1And R2Are connected with each other to form C3～C6A cycloalkyl group of (a).
The Ar group in the above fluorene-based initiator may be an aryl group commonly used in the art. Preferably, Ar is selected from phenyl, pyridyl, thienyl, furyl or the above groups containing substituents. In order to further reduce the mobility of the fluorene photoinitiator and improve the sensitivity and photoinitiation activity thereof, it is more preferable that Ar is selected from pyridyl, thienyl, furyl or the above-mentioned group containing a substituent.
In a preferred embodiment, Ra5Including but not limited to hydrogen, C1～C10Straight or branched alkyl of (2), C7～C20Aralkyl of (2), C2～C10Heterocyclyl group of-NO2、-ORb1、-CORb1、-COORb1or-CONRb1Rb2Wherein R isb1And Rb2Each independently represents hydrogen or C1～C10Straight or branched alkyl of (2), C3～C10Cycloalkyl of, C3～C8Cycloalkyl-substituted C of1～ C5Alkyl of (C)1～C5Alkyl-substituted C of3～C8Cycloalkyl of, C6～C20Aralkyl of (2), C2～C20Heterocyclyl or-COC (R)1)(R2)(R3). More preferably, R is as defined abovea5Is COC (R)1)(R2)(R3). Because the substituent groups contain photoactive groups and can form a larger and more stable delocalized structure with the fluorene ring, the selection of the two substituent groups is beneficial to further improving the sensitivity and the yellowing resistance of the fluorene photoinitiator and reducing the mobility of the fluorene photoinitiator.
In a preferred embodiment, R1、R2Are each independently selected from C1～C4Or straight or branched alkyl of, or R1And R2Linked to each other to form a ring, R3Is N, N-dialkyl, N-morpholinyl, N-thiomorpholinyl, Ra5Selected from hydrogen, C1～C10Linear or branched alkyl, -NO2、-ORb1、-CORb1or-COC (R)1)(R2)(R3) Wherein R isb1Is C1～C10Straight or branched alkyl of (2), C6～C20Aralkyl or C2～C20The remaining groups have the same definitions as described above. The fluorene photoinitiator with the structure has better sensitivity and yellowing resistance, and simultaneously reduces the mobility.
In another preferred embodiment, R1、R2Are each independently selected from C1～C4Or straight or branched alkyl of, or R1And R2Linked to each other to form a ring, R3Is selected fromHydroxy or alkoxy, Ra5Selected from hydrogen, C1～C10Straight or branched alkyl of (2), C6～C10Aralkyl, -NO2、-ORb1and-CORb1Wherein R isb1Is C1～C10Straight or branched alkyl of (2), C6～C20Aralkyl, hydroxy-substituted C of3～C8Cycloalkane of (C)2～C10The remaining groups have the same definitions as described above. The fluorene photoinitiator having the above structure has better sensitivity and yellowing resistance, while reducing its mobility, compared to other fluorene initiators.
In yet another preferred embodiment, R1、R2Are each independently selected from C1～C4Or said R is a linear or branched alkyl group, or1And said R2Linked to each other to form a ring, R3Selected from hydroxy, N-dialkyl or thiomorpholinyl, Ra5is-CORb1Wherein R isb1Is a 1-cyclohexanol group, the remaining groups having the same definitions as described above.
The fluorene photoinitiator with the structure has the advantages of good photoinitiation efficiency, difficult migration, low odor, excellent yellowing resistance and the like. In a preferred embodiment, the fluorene-based photoinitiator includes, but is not limited to, one or more of the following compounds:
Figure RE-GDA0002218511940000061
Figure RE-GDA0002218511940000071
Figure RE-GDA0002218511940000081
Figure RE-GDA0002218511940000091
Figure RE-GDA0002218511940000101
another aspect of the present application also provides a preparation method of the fluorene photoinitiator, where the preparation method includes:
s1, in the presence of a first organic solvent, the intermediate a and a halogenated compound carry out substitution reaction to generate an intermediate b, and the synthetic route is as follows:
Figure RE-GDA0002218511940000102
wherein, X1Is a halogen atom;
s2, in the presence of a second organic solvent, carrying out Friedel-crafts reaction on the intermediate b and the haloalkane acylate to obtain an intermediate c, wherein the synthetic route is as follows:
Figure RE-GDA0002218511940000111
wherein, X2And X' are each independently selected from halogen atoms;
s3, carrying out hydrolysis reaction on the intermediate c and water to obtain the fluorene photoinitiator, or carrying out dehalogenation reaction on the intermediate c and a compound containing non-hydroxyl optical active groups to obtain the fluorene photoinitiator.
The intermediate c can introduce the optical activity group through hydrolysis reaction or dehalogenation reaction with a compound containing the optical activity group of non-hydroxyl, thereby forming the required fluorene photoinitiator.
In the above-mentioned preparation methods, the starting materials used are all known compounds in the prior art, and can be commercially obtained or can be easily prepared by known synthetic methods. In order to further improve the substitution efficiency in the substitution reaction, preferably, the reaction temperature of the substitution reaction is 30-60 ℃;
in order to control the reactivity of the Friedel-crafts reaction, the reaction temperature of the Friedel-crafts reaction is preferably-10 to 10 ℃;
in a preferred embodiment, the intermediate b is hydrolyzed to obtain the fluorene photoinitiator. A hydroxyl group or an alkoxy group may be introduced into the intermediate c by hydrolysis.
Preferably, the reaction temperature of the hydrolysis reaction is 20-100 ℃, and the limitation of the temperature of the hydrolysis reaction in the above range is beneficial to improving the hydrolysis efficiency, so that the yield of the fluorene photoinitiator is improved.
Preferably, the above preparation method further comprises adding a third organic solvent, an inorganic base and a phase transfer catalyst to the reaction system before the hydrolysis reaction. The addition of the third organic solvent is favorable for improving the intermiscibility of all reaction raw materials, and the addition of the inorganic base and the phase transfer catalyst is favorable for improving the reaction rate of the Friedel-crafts reaction and the yield of the fluorene photoinitiator. More preferably, the inorganic base is KOH and/or NaOH. More preferably, the phase transfer catalyst is a quaternary ammonium salt type phase transfer catalyst, and even more preferably, the phase transfer catalyst includes, but is not limited to, one or more of the group consisting of tetrabutylammonium bromide, tetrapropylammonium bromide, tetra-n-butylammonium, triethylbenzylammonium chloride, and tetrabutylammonium hydrogen sulfate.
In the above-mentioned preparation method, the kind of the solvent used is not particularly limited as long as it can dissolve the raw materials and does not adversely affect the reaction, and therefore, the first organic solvent, the second organic solvent and the third organic solvent may be any solvent commonly used in the art. Preferably, the first organic solvent is selected from one or more of the group consisting of dichloromethane, dichloroethane, benzene and xylene; the second organic solvent is independently selected from dichloromethane and/or dichloroethane; the third organic solvent includes, but is not limited to, one or more of the group consisting of dichloromethane, dichloroethane, benzene, xylene, and acetonitrile.
In another preferred embodiment, intermediate b is subjected to dehalogenation with a compound containing a non-hydroxyl photoactive group to give a fluorene photoinitiator.
In order to further improve the removal rate of halogen atoms in the dehalogenation reaction, the reaction temperature of the dehalogenation reaction is preferably 40-160 ℃;
the dehalogenation reaction may be carried out in the presence of a fourth organic solvent in order to improve the compatibility between the reaction raw materials. Preferably, the fourth organic solvent includes, but is not limited to, one or more of the group consisting of dichloromethane, dichloroethane, benzene, xylene, and acetonitrile;
preferably, the non-hydroxyl-containing photoactive group-containing compound includes, but is not limited to, one or more of the group consisting of N, N-dimethyl, N-diethyl, morpholine, thiomorpholine and piperidine. Compared with other existing compounds containing non-hydroxyl photoactive groups, the compound containing the non-hydroxyl photoactive groups is beneficial to further improving the initiation efficiency and the sensitivity of the fluorene photoinitiator.
In another aspect of the present application, there is also provided a photocurable composition comprising a photoinitiator, a polymerized monomer and/or a polymerized oligomer, the photoinitiator comprising the fluorene-based photoinitiator described herein.
By introducing different active groups into the fluorene compound, compared with the existing photoinitiator, the fluorene photoinitiator disclosed by the invention has excellent photoinitiation activity, and has the advantages of zero migration, low odor, yellowing resistance and the like, and the application performance is excellent.
The fluorene photoinitiator provided by the application has excellent comprehensive performance, so that the fluorene photoinitiator can be widely applied to the field of photocuring, such as the field of coatings, the field of ink or the field of adhesives.
The present application is described in further detail below with reference to specific examples, which should not be construed as limiting the scope of the invention as claimed.
Preparation examples
Examples 1 to 16
Step (1): preparation of dibenzylfluorene (a1)
Figure RE-GDA0002218511940000121
Adding 400g of dichloromethane, 50g of fluorene, 80g of benzyl chloride and 1g of tetrabutylammonium bromide into a 1L four-neck flask, stirring, carrying out nitrogen protection, dropwise adding 120g of 50% sodium hydroxide solution at 30 ℃ in a water bath, controlling the temperature of the system to be below 35 ℃, finishing adding after 15min, heating the added system to reflux reaction for 8h, sampling to detect that the raw materials are completely reacted, stopping the reaction, and cooling to room temperature. Adding 100g of water into the reaction solution, separating an organic layer, washing the organic layer for 3 times to be neutral, evaporating the organic phase to dryness, adding 200g of methanol for crystallization, stirring for crystallization for 1h, filtering, and drying wet products to obtain 95.8g of white-like solid, wherein the yield is 92.1%, and the purity is 99.2%.
The structure of the final product obtained in the step (1) is confirmed through nuclear magnetic resonance hydrogen spectrum and mass spectrum, and specific characterization results are as follows:
1H-NMR(CDCl3，400MHz):δ7.20(d,J＝8.0Hz,4H)，7.19-7.29(m,4H)，6.90-6.98(m, 6H)，6.67(d,J＝3.4Hz,4H)，3.37(s,4H)。
step (2): preparation of dibenzylfluorene triisobutyrylchloride Friedel-crafts (a2)
Figure RE-GDA0002218511940000131
100g of dichloromethane, 10g of dibenzyl fluorene and 14g of chloroisobutyryl chloride are added into a 250mL four-neck flask, the mixture is stirred in an ice water bath and cooled to 0 ℃, 15.2g of anhydrous aluminum trichloride is added in batches, the temperature of the system is controlled to be below 5 ℃, the addition is completed in half an hour, the heat preservation reaction is continued for 2 hours, the sampling HPLC detection shows that the raw materials are completely reacted, and the reaction is stopped. Slowly pouring the system into dilute hydrochloric acid for hydrolysis, controlling the temperature to be lower than 20 ℃, separating an organic layer, washing the organic layer for 3 times, evaporating the solvent of an organic phase to dryness, adding 50g of n-hexane, pulping at low temperature for 1h, separating out a solid, filtering, and drying to obtain 15g of a light yellow solid, wherein the yield is 78.9%, and the purity is 92.1%.
MS(m/z):658(M+1)+。
Step (3) preparation of dibenzylfluorene triaminoketone (preparation of Compound 1)
Figure RE-GDA0002218511940000132
100g of dichloromethane and 10g of dibenzyl fluorene trichloroisobutyryl chloride Friedel-crafts are added into a 500mL four-neck flask, the system is stirred in ice water bath, 6.28g of anhydrous aluminum trichloride is added after the temperature is reduced to 0 ℃, the heat preservation and the stirring are continued for half an hour, 40g of morpholine is slowly dripped, the temperature of the system is controlled to be below 10 ℃, the morpholine is added for half an hour, the system is heated to 45 ℃, the stirring and the reaction are continued for 1.5 hours, the sampling HPLC detection shows that the raw materials are completely reacted, the reaction is stopped, and the system is reduced to the room temperature. Slowly pouring the reaction liquid into 200g of ice water, adjusting the pH value to be less than 3 by using dilute hydrochloric acid, extracting for 3 times by using dichloromethane, combining organic phases, evaporating the solvent of the organic phases, adjusting the pH value to be more than 8 by using dilute alkali, separating out a solid crude product, filtering, and drying to obtain the crude product. Purifying the solid by column chromatography to obtain a pure white solid product 8.5g, with the yield of 70.1% and the purity of 98.5%.
The structure of the final product obtained in the step (3) is confirmed through nuclear magnetic resonance hydrogen spectrum and mass spectrum, and specific characterization results are as follows:1H-NMR(CDCl3，400MHz):δ8.63(s,1H),8.57-8.59(m,1H),7.98(d,J＝8.4Hz,4H),7.47(d, J＝7.6Hz,1H),7.34-7.41(m,3H),7.24-7.27(m,1H),6.63(d,J＝8.4Hz,4H),3.70(t,J＝4.0Hz, 4H),3.45-3.53(m,6H),2.64(t,J＝4.0Hz,4H),2.41(t,J＝8.0Hz,8H),1.39(s,6H),1.20(s,12H). MS(m/z):811(M+1)+。
further, the reaction can be carried out by using different raw materials and different reaction conditions, so as to obtain compounds with different structures, but not limited to, the following table 1.
TABLE 1
Figure RE-GDA0002218511940000141
Figure RE-GDA0002218511940000151
Figure RE-GDA0002218511940000161
Figure RE-GDA0002218511940000171
Figure RE-GDA0002218511940000181
Examples 17 to 26
Compounds 17 to 26 were synthesized by different methods with reference to the synthesis methods of examples 1 to 16.
Synthesis of compound 17:
Figure RE-GDA0002218511940000191
50g of toluene, 22g of dibenzyl fluorene trichloroisobutyryl chloride Friedel-crafts and 1.32g of tetrabutyl ammonium bromide are added into a 250mL four-neck flask, stirred and dropwise added with 75g of 25% sodium hydroxide solution, the temperature of the system is controlled below 30 ℃, the addition is finished within 10min, the system is heated and reacted for 1h in a water bath at 80 ℃, and the reaction is stopped. And when the temperature of the system is reduced to room temperature, separating an organic layer, washing the organic layer to be neutral by 300g of water, pouring the organic layer into a 250mL four-neck flask, adding 2g of activated carbon, stirring for 1h, filtering, slightly rinsing a filter cake by using methylbenzene, combining organic phases, pouring a filtrate into the 250mL four-neck flask, evaporating an organic solvent, adding 50g of n-hexane, stirring for crystallization for 1h, filtering, slightly rinsing the filter cake by using n-hexane to obtain a white solid wet product, and putting the wet product into a 50 ℃ oven to be dried for 3h in a dark place to obtain 13.6g of white solid powder, wherein the yield is 67.4%, and the purity is 98.17%.
The structure of the product is confirmed by nuclear magnetic resonance hydrogen spectrum and mass spectrum:
1H-NMR(CDCl3,400MHz):δ8.15(s,1H),7.91-7.94(m,1H),7.52-7.56(m,5H),7.40- 7.46(m,3H),7.30(t,J＝7.2Hz,1H),6.68(d,J＝8.4Hz,4H),4.02(s,1H)，3.96(s,2H),3.51(s, 4H),1.67(s,6H),1.47(s,12H)。
MS(m/z)：605(M+1)+。
referring to the synthesis methods of the intermediates a-c and the compound 17, different raw materials are selected for reaction and different reaction conditions are selected, so that the compounds 18-26 with different structures are obtained.
TABLE 2
Figure RE-GDA0002218511940000192
Figure RE-GDA0002218511940000201
Figure RE-GDA0002218511940000211
Figure RE-GDA0002218511940000221
Examples 27 to 32:
further, a1 can also be subjected to double Friedel-crafts reaction to obtain compounds with different structures
Preparation of dibenzylfluorene tetraisobutyryl chloride Friedel-crafts (a2)
Figure RE-GDA0002218511940000222
100g of dichloromethane, 10g of dibenzyl fluorene and 19g of chloroisobutyryl chloride are added into a 250mL four-neck flask, the mixture is stirred in an ice water bath and cooled to 0 ℃, 20.7g of anhydrous aluminum trichloride is added in batches, the temperature of a system is controlled to be below 5 ℃, the addition is completed in half an hour, the heat preservation reaction is continued for 2 hours, the sampling HPLC detection is carried out, the raw materials are completely reacted, and the reaction is stopped. Slowly pouring the system into dilute hydrochloric acid for hydrolysis, controlling the temperature to be lower than 20 ℃, separating an organic layer, washing the organic layer for 3 times, evaporating the solvent of an organic phase to dryness, adding 80g of n-hexane, pulping at low temperature for 1h, separating out a solid, filtering, and drying to obtain 15.41g of a light yellow solid, wherein the yield is 70%, and the purity is 97.85%.
MS(m/z)：762(M+1)+。
Preparation of dibenzylfluorene tetraaminoketone (Compound 27)
Figure RE-GDA0002218511940000231
100g of dichloromethane and 15g of dibenzyl fluorene tetrachloroisobutyryl chloride Friedel-crafts are added into a 500mL four-neck flask, the system is stirred in ice water bath, 10.5g of anhydrous aluminum trichloride is added after the temperature is reduced to 0 ℃, the heat preservation and the stirring are continued for half an hour, 50g of morpholine is slowly dripped, the temperature of the system is controlled to be below 10 ℃, the morpholine is added for half an hour, the system is heated to 45 ℃, the stirring and the reaction are continued for 1.5 hours, the sampling HPLC detection shows that the raw materials are completely reacted, the reaction is stopped, and the system is reduced to the room temperature. Slowly pouring the reaction solution into 300g of ice water, adjusting the pH value to be less than 3 by using dilute hydrochloric acid, extracting for 3 times by using dichloromethane, combining organic phases, evaporating the solvent of the organic phases, adjusting the pH value to be more than 8 by using dilute alkali, separating out a solid crude product, filtering, and drying to obtain the crude product. Purifying the solid by column chromatography to obtain a pure white solid product of 12.9g, the yield of 68.23 percent and the purity of 97.9 percent.
The structure of the final product obtained in the step (3) is confirmed through nuclear magnetic resonance hydrogen spectrum and mass spectrum, and specific characterization results are as follows:
1H-NMR(CDCl3，400MHz):δ8.43(s,2H),7.88(d,J＝8.4Hz,4H),7.41(d,J＝7.6Hz,2H), 7.30-7.36(m,2H),6.73(d,J＝8.4Hz,4H),3.65(t,J＝4.0Hz,8H),3.40-3.50(m,12H),2.64(t,J ＝4.0Hz,8H),2.35(t,J＝8.0Hz,8H),1.41(s,12H),1.18(s,12H).
MS(m/z):967(M+1)+。
synthesis of compound 28:
Figure RE-GDA0002218511940000232
50g of toluene, 29g of dibenzyl fluorene tetrachloroisobutyryl chloride Friedel-crafts and 1.76g of tetrabutyl ammonium bromide are added into a 250mL four-neck flask, stirred, dropwise added with 100g of 25% sodium hydroxide solution, the temperature of the system is controlled below 30 ℃, the addition is finished within 10min, the system is heated in a water bath at 80 ℃ for reaction for 1h, and the reaction is stopped. When the temperature of the system is reduced to room temperature, separating an organic layer, washing the organic layer to be neutral by 400g of water, pouring the organic layer into a 250mL four-neck flask, adding 3g of activated carbon, stirring for 1h, filtering, rinsing the filter cake with a little toluene, combining organic phases, pouring the filtrate into the 250mL four-neck flask, evaporating the organic solvent, adding 60g of n-hexane, stirring for crystallization for 1h, filtering, rinsing the filter cake with a little n-hexane to obtain a white solid wet product, placing the wet product into a 50 ℃ oven to be dried for 3h in a dark place to obtain 17.1g of white solid powder, wherein the yield is 65.2%, and the purity is 98.05%.
The structure of the product is confirmed by nuclear magnetic resonance hydrogen spectrum and mass spectrum:
1H-NMR(CDCl3,400MHz):δ8.05(s,2H),7.50-7.54(m,4H),7.30-7.38(m,4H),6.72(d, J＝8.4Hz,4H),4.02(s,2H)，3.89(s,2H),3.36(s,4H),1.68(s,12H),1.47(s,12H)。MS(m/z):691 (M+1)+。
referring to the above intermediates and the synthesis of compounds 27 and 28, different raw materials are selected for reaction and different reaction conditions, so as to obtain compounds 29 to 32 with different structures:
TABLE 3
Figure RE-GDA0002218511940000241
Figure RE-GDA0002218511940000251
Evaluation of Performance
The photoinitiator of formula (I) according to the invention and the use of conventional benzophenone-type, alpha-hydroxy-ketone-type and alpha-amino-ketone-type initiators in the field of photocuring with the same formulation were evaluated by formulating exemplary radiation-curable compositions.
Preparation of radiation curable compositions:
in comparison with the photoinitiator compounds 1, 2 according to the invention, the initiators of the customary benzophenones, alpha-hydroxyketones and alpha-aminoketones were selected according to table 4, the compositions in% by weight (wt.%) based on the total weight of the radiation-curable composition being as follows:
TMPTA: 95 parts by mass
Photoinitiator (2): 5 parts by mass
< sensitivity test >
Stirring and mixing the photocuring composition uniformly under a yellow light lamp, taking the mixture to be coated on a PET template to form a film, forming a coating film with the film thickness of about 20 mu m, adopting crawler-type exposure, attaching a mask plate, adopting a high-pressure mercury lamp (model RW-UV70201, wavelength of 200-500nm, light intensity of 50 mW/cm)2) The irradiation was carried out for the number of passes through the caterpillar required for complete curing of the coating film, and the test results are shown in Table 3.
< evaluation of yellowing resistance >
The cured film obtained under the above high-pressure mercury lamp was subjected to an aging test using a RW-UV.2BP ultraviolet aging test chamber, a high-pressure mercury lamp (dominant wavelength 365nm, total power: about 2.2KW) as a light source, the cured film was continuously irradiated for 6 hours, the yellowing of the cured film was observed, and evaluation was made according to the following criteria, as shown in Table 5.
O: the coating is colorless and transparent, has smooth surface and has good yellowing resistance;
□: yellowish or sticky surface, indicating unsatisfactory resistance to yellowing;
solid content: the surface yellowed or the viscosity increased, indicating easy yellowing.
< evaluation of odor Property and migration >
The cured film prepared under the high-pressure mercury lamp of the photo-curing composition with the same mass is weighed, and the odor performance is evaluated by a fan-smelling method:
odor property:
o have no odor;
it is odorous.
Using ethanol as solvent, preparing 1 × 10 from benzophenone, 907 and 1173 as photoinitiator, compound 1 and compound 2 respectively- 5measuring the maximum absorption wavelength and the absorbance A1 of the solution in mol/L by a UV3010 ultraviolet spectrophotometer,and calculating the molar extinction coefficient by the formula (1):
c＝A/ε×b (1)
R＝100×c/c1 (2)
0.05g of the cured film prepared by the photocuring composition under a high-pressure mercury lamp is weighed and respectively soaked in 30g of ethanol, and after the film is placed for 24 hours at normal temperature, the soaking solution with the same volume is taken and an ultraviolet spectrophotometer is used for measuring the absorbance A2 at the maximum absorption wavelength. The concentration of the photoinitiator migrated from the 3 cured films was calculated by formula (1), and the relative mobilities of the various photoinitiators were measured by formula (2) with the concentration value of the photoinitiator benzophenone as a reference.
In the above formula, c is the relative concentration (mol/L), c1 is the relative concentration of benzophenone, A is the absorbance, and ε is the molar absorption coefficient (L/mol · cm); b is the thickness (cm) of the sample cell; r relative mobility.
TABLE 4
Figure RE-GDA0002218511940000271
Figure RE-GDA0002218511940000281
From the evaluation results in table 4, it can be seen that the yellowing resistance of the initiator with the novel structure of the present invention is equivalent to that of the conventional photoinitiators of benzophenone type, α -hydroxy ketone type and α -amino ketone type under the same other components, the sensitivity is slightly due to the conventional photoinitiators, and the initiator has the characteristics of low odor and excellent migration property.
In summary, the compound shown in formula (I) can show excellent comprehensive application performance when being used as a photoinitiator in the field of photocuring, and has a wide 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. A fluorene-based initiator, wherein the fluorene-based photoinitiator has a structure represented by formula (I):
Figure FDA0002175019230000011
wherein, R is1And said R2Are each independently selected from C1～C20Straight or branched alkyl of (2), C3～C20Cycloalkyl of, C3～C8Cycloalkyl-substituted C of1～C12Alkyl of (C)1～C12Alkyl-substituted C of3～C8Cycloalkyl of, C6～C20Or said R is1And said R2Are connected with each other to form a ring;
the R is3Is a photoactive group;
ar represents a substituted or unsubstituted aryl group;
the R isa1The R isa2The R isa3The R isa4The R isa6The R isa7Each independently selected from hydrogen and C1～C20Straight or branched alkyl of (2), C3～C20Cycloalkyl of, C3～C8Cycloalkyl-substituted C of1～C12Alkyl of (C)1～C12Alkyl-substituted C of3～C8Cycloalkyl of, C7～C20Aralkyl or C2～C20Heterocyclyl group of-ORb1、-CORb1、-COORb1、-SRb1、-SO2Rb1or-CONRb1Rb2Wherein R isb1And Rb2Each independently represents hydrogen or C1～C20Straight or branched alkyl of、C3～C20Cycloalkyl of, C3～C8Cycloalkyl-substituted C of1～C12Alkyl of (C)1～C12Alkyl-substituted C of3～C8Cycloalkyl of, C7～C20Aralkyl or C2～C20A heterocyclic group of (a);
the R isa5Selected from hydrogen, C1～C20Straight or branched alkyl of (2), C3～C20Cycloalkyl of, C3～C8Cycloalkyl-substituted C of1～C12Alkyl of (C)1～C12Alkyl-substituted C of3～C8Cycloalkyl of, C7～C20Aralkyl or C2～C20Heterocyclyl group of-NO2、-ORb1、-CORb1、-COORb1、-SRb1、-SO2Rb1or-CONRb1Rb2Wherein R isb1And Rb2Each independently represents hydrogen or C1～C20Straight or branched alkyl of (2), C3～C20Cycloalkyl of, C3～C8Cycloalkyl-substituted C of1～C12Alkyl of (C)1～C12Alkyl-substituted C of3～C8Cycloalkyl of, C6～C20Aralkyl of (2), C2～C20Heterocyclyl or-COC (R)1)(R2)(R3)。
2. The fluorene-based initiator of claim 1, wherein R is3Selected from hydroxy, alkoxy, N-dialkyl, N-morpholinyl, N-thiomorpholinyl or N-substituted piperazinyl.
3. The fluorene-based initiator according to claim 1 or 2, wherein R is1And said R2Each independently represents C1～C4Straight or branched alkyl of (2), C3～C5Cycloalkyl-substituted C of1～C3Alkyl of (2)Or said R is1And said R2Are connected with each other to form C3～C6A cycloalkyl group of (a).
4. The fluorene-based initiator according to claim 3, wherein Ar is selected from phenyl, pyridyl, thienyl, furyl or the above groups containing substituents.
5. The fluorene-based initiator according to any one of claims 1 to 4, wherein R isa5Selected from hydrogen, C1～C10Straight or branched alkyl of (2), C7～C20Aralkyl of (2), C2～C10Heterocyclyl group of-NO2、-ORb1、-CORb1、-COORb1or-CONRb1Rb2Wherein R isb1And Rb2Each independently represents hydrogen or C1～C10Straight or branched alkyl of (2), C3～C10Cycloalkyl of, C3～C8Cycloalkyl-substituted C of1～C5Alkyl of (C)1～C5Alkyl-substituted C of3～C8Cycloalkyl of, C6～C20Aralkyl of (2), C2～C20Heterocyclyl or-COC (R)1)(R2)(R3)。
6. The fluorene-based initiator of claim 5, wherein R is1And said R2Are each independently selected from C1～C4The straight or branched alkyl of (1), the R3Selected from the group consisting of N, N-dialkyl, N-morpholinyl, N-thiomorpholinyl, said Ra5Selected from hydrogen, C1～C10Linear or branched alkyl, -NO2、-ORb1and-CORb1Wherein said R isb1Is C1～C10Straight or branched alkyl of (2), C6～C20Aralkyl or C2～C20The heteroaryl group of (a).
7. The fluorene-based initiator of claim 5, wherein R is1The R is2Are each independently selected from C1～C4Or said R is a linear or branched alkyl group, or1And said R2Are connected with each other to form a ring, R is3Selected from hydroxy or alkoxy, said Ra5Selected from hydrogen, C1～C10Straight or branched alkyl of (2), C6～C10Aralkyl, -NO2、-ORb1and-CORb1Wherein said R isb1Is C1～C10Straight or branched alkyl of (2), C6～C20Aralkyl, hydroxy-substituted C of3～C8Cycloalkane of (C)2～C10The heteroaryl group of (a).
8. The fluorene-based initiator of claim 5, wherein R is1The R is2Are each independently selected from C1～C4Or said R is a linear or branched alkyl group, or1And said R2Are connected with each other to form a ring, R is3Selected from hydroxy, N-dialkyl or thiomorpholinyl, said Ra5is-CORb1Wherein said R isb1Is a 1-cyclohexanol group.
9. A photocurable composition comprising a photoinitiator, a polymeric monomer and/or a polymeric oligomer, the photoinitiator comprising the fluorene-based photoinitiator according to any one of claims 1 to 8.
10. Use of the fluorene-based photoinitiator according to any one of claims 1 to 8 in the field of photocuring.
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