CN112010997B - Fluorene photoinitiator, preparation method thereof, photocuring composition containing fluorene photoinitiator and application of fluorene photoinitiator in photocuring field - Google Patents

Fluorene photoinitiator, preparation method thereof, photocuring composition containing fluorene photoinitiator and application of fluorene photoinitiator in photocuring field Download PDF

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CN112010997B
CN112010997B CN201910848206.2A CN201910848206A CN112010997B CN 112010997 B CN112010997 B CN 112010997B CN 201910848206 A CN201910848206 A CN 201910848206A CN 112010997 B CN112010997 B CN 112010997B
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photoinitiator
fluorene
cycloalkyl
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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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    • C08F222/10—Esters
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
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    • C07C2603/18—Fluorenes; Hydrogenated fluorenes

Abstract

The invention provides a fluorene photoinitiator, a preparation method thereof, a photocuring composition containing the fluorene photoinitiator and application of the fluorene photoinitiator in the field of photocuring. The fluorene photoinitiator has a structure shown as a formula (I), wherein R3Selected from photoactive groups. Introducing a benzophenone alkyl substituent group on the position of the No. 9 carbon atom of the fluorene structure, wherein fragments formed by the initiator still have higher stability and photocuring effect after initiation reaction; simultaneous photoactive radicals R3The introduction of the photoinitiator can improve the absorption efficiency of the photoinitiator to light, and is further 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 weight and light color, and therefore, the photoinitiator also has the advantages of almost no VOC discharge, low odor and excellent yellowing resistance.

Description

Fluorene photoinitiator, preparation method thereof, photocuring composition containing fluorene photoinitiator and application of fluorene photoinitiator in photocuring field
Technical Field
The invention relates to the field of photocuring, in particular to a fluorene photoinitiator, a preparation method thereof, a photocuring composition containing the fluorene photoinitiator and application of the fluorene photoinitiator in the field of photocuring.
Background
Nowadays, people pay more and more attention to safety, and especially, people pay more attention to safety of substances which are closely related to life and are often contacted with daily life, such as food safety, safety of living environment and the like. With the gradual increase of global environmental protection requirements, the VOC emission requirements of related chemical industries are more and more strict, and the emission is strictly controlled. Green environmental protection technologies for photocurable coatings and photocurable inks with almost no VOC emission have been widely focused and rapidly developed. In 2005, a sensitizer ITX was detected in milk powder of some manufacturers in europe and four countries, and this problem was caused by migration of a curing sensitizer in a photocurable ink for packaging a printing material into the milk powder. Since then the problem of safe use of photoinitiators and sensitizers, in particular toxicity and migration, has become increasingly important. Increasing the molecular weight of the initiator and sensitizer molecules is an effective solution to migration, which results in a decrease in the proportion of reactive groups and, in turn, a greater impact on the initiation efficiency of the initiator. Therefore, it is necessary to develop a new high sensitivity macro-photoinitiator to solve the migration problem in coating ink application.
Benzophenone type, alpha-hydroxy ketone type and alpha-amino ketone type photoinitiators are common photoinitiators and have the advantages of simple structure, easiness in synthesis, low price and the like, but the problems of mobility, odor, yellowing, solubility and the like exist in the using process, and the sensitivity of the photoinitiator also has certain defects, so that the application of the photoinitiator is limited to a great extent. People try to modify the structure of the benzophenone photoinitiator, the existing literature carries out the macro-molecule conversion on the benzophenone photoinitiator, so that the problems of small molecule mobility and odor are avoided to a certain extent, but the yellowing resistance problem is still not effectively solved. The other existing literature synthesizes different types of alpha-hydroxy ketone and alpha-amino ketone photoinitiators, the initiation efficiency is improved to a certain extent, but the preparation and synthesis process is relatively complex and the cost is higher.
On the basis of the above, it is necessary to develop a photoinitiator with high zero migration rate, yellowing resistance and initiation efficiency.
Disclosure of Invention
The invention mainly aims to provide a fluorene photoinitiator, a preparation method thereof, a photocuring composition containing the fluorene photoinitiator and application of the fluorene photoinitiator in the field of photocuring, so as to solve the problem that the existing photoinitiator cannot simultaneously maintain zero mobility, high yellowing resistance and high initiation efficiency.
In order to achieve the above object, according to one aspect of the present invention, there is provided a fluorene-based photoinitiator having a structure represented by formula (I):
Figure BDA0002195994470000021
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; r3Selected from photoactive groups;
Ra1、Ra2、Ra3、Ra4、Ra5、Ra6、Ra7、Ra8each independently selected from hydrogen, nitro, cyano, trifluoromethyl, 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、-CORb2、-COORb3、-SRb4、-SO2Rb5or-CONRb6Rb7，Rb1、Rb2、Rb3、Rb4、Rb5、Rb6、Rb7Each 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～C20And R is a heterocyclic group ofa2And Ra7At least one is an electron withdrawing substituent.
By applying the technical scheme of the invention, the benzophenone alkyl substituent is introduced to the 9 # carbon atom position of the fluorene structure, and fragments formed by the initiator still have higher stability and photocuring effect after initiation reaction; simultaneous photoactive radicals R3The introduction of the photoinitiator can improve the absorption efficiency of the photoinitiator to light, and is further 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 weight and light color, and therefore, the photoinitiator also has the advantages of almost no VOC discharge, low odor and excellent yellowing resistance. In summary, have the advantages ofThe fluorene photoinitiator with the structure has the advantages of good photoinitiation efficiency, difficult migration, low odor, excellent yellowing resistance and the like.
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, the problems of zero mobility, high yellowing resistance, and high initiation efficiency cannot be simultaneously maintained with existing photoinitiators. In order to solve the above technical problems, the present application provides a fluorene photoinitiator having a structure represented by formula (I):
Figure BDA0002195994470000031
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～C20And R is an aryl group of1And R2May be linked to each other to form a ring; r3Selected from photoactive groups; ra1、Ra2、Ra3、Ra4、Ra5、Ra6、Ra7、Ra8Each independently selected from hydrogen, nitro, cyano, trifluoromethyl, 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、-CORb2、-COORb3、-SRb4、-SO2Rb5or-CONRb6Rb7，Rb1、Rb2、Rb3、Rb4、Rb5、Rb6、Rb7Each 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～C20And R is a heterocyclic group ofa2And Ra7At least one is an electron withdrawing substituent.
Introducing a benzophenone alkyl substituent group on the position of the No. 9 carbon atom of the fluorene structure, wherein fragments formed by the initiator still have higher stability and photocuring effect after initiation reaction; simultaneous photoactive radicals R3The introduction of the photoinitiator can improve the absorption efficiency of the photoinitiator to light, and is further 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 weight and light color, and therefore, the photoinitiator also has the advantages of almost no VOC discharge, low odor and excellent yellowing resistance. In summary, the fluorene photoinitiator with the above structure has the advantages of good photoinitiation efficiency, difficult migration, low odor, excellent yellowing resistance and the like.
In order to further improve the overall performance of the fluorene-based photoinitiator, the substituent in formula (I) may be preferred. In a preferred embodiment, R1And R2Are each independently selected from C1～C4Straight or branched alkyl of (2), C3～C5Cycloalkyl-substituted C of1～C3Or R is1And R2Are connected to each other to form C3～C6A cycloalkyl group of (a). The fluorene photoinitiator containing the substituents has better photoinitiation efficiency compared with other substituents.
In the above fluorene photoinitiator, R3Photoactive groups commonly used in the art may be employedAnd (4) clustering. Preferably, R3Including but not limited to hydroxy, N-dialkyl, N-morpholinyl, N-thiomorpholinyl, or N-substituted piperazinyl. The use of the above-mentioned photoactive groups is advantageous in further improving the sensitivity of the photoinitiator compared to other photoactive groups.
In a preferred embodiment, Ra1、Ra2、Ra3、Ra4、Ra5、Ra6、Ra7、Ra8Wherein at least one substituent is-CORb2，Rb2Is aryl, heteroaryl, substituted aryl or substituted heteroaryl.
when-CORb2The fluorine-containing fluorine; meanwhile, the compound for improving the structure of the benzophenone is also a photoinitiator, so that the initiating activity of the fluorene photoinitiator can be further improved by taking the compound as a substituent.
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 BDA0002195994470000041
Figure BDA0002195994470000051
Figure BDA0002195994470000061
Figure BDA0002195994470000071
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 BDA0002195994470000072
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 BDA0002195994470000081
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.
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.
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 and the second organic solvent are each independently selected from one or more of the group consisting of dichloromethane, dichloroethane, benzene, and xylene; 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 to give the fluorene-based photoinitiator.
In order to further improve the removal rate of halogen atoms in the dehalogenation reaction, preferably, the reaction temperature of the dehalogenation reaction is 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 yet another aspect, the present disclosure provides a photocurable composition, which includes a polymerized monomer and a photoinitiator, wherein the photoinitiator includes the fluorene photoinitiator.
The fluorene photoinitiator has the advantages of good photoinitiation efficiency, difficult migration, low odor, excellent yellowing resistance and the like, so the photocuring composition containing the fluorene photoinitiator has the advantages of good photocuring efficiency, yellowing resistance, low odor, difficult migration and the like.
The application further provides an application of the fluorene photoinitiator in the photocuring field, such as the fields of coatings, inks, adhesives and the like.
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 12
Step (1): preparation of 9, 9-dibenzylphenyl methanone fluorene (a1)
Figure BDA0002195994470000091
150mL of dichloromethane, 27g of phenyl methanone fluorene, 28.05g of benzyl chloride and 0.54g of tetrabutylammonium bromide are added into a 250mL four-neck flask, 40g of 50% sodium hydroxide solution is slowly dripped, the temperature of the system is controlled below 30 ℃, the addition is finished in 15min, the reaction is heated in a water bath at 50 ℃, the nitrogen protection is stopped, the system is kept warm and reacts for 8 hours, and the reaction is stopped. And when the temperature of the system is reduced to room temperature, 60g of water is added, the system is layered, an organic layer is separated, and the organic layer is washed 3 times by 200g of water until the organic layer is neutral. Pouring the organic phase into 250mL of four-port baking screen, evaporating the solvent, adding 54g of methanol, stirring and crystallizing for 1h in ice-water bath, filtering, rinsing the filter cake with a little methanol to obtain a light yellow wet product, and drying the wet product in an oven at 50 ℃ for 5h to obtain light yellow solid powder 40g, yield 88.8%, purity 98.8%, MS (M/z):451(M +1)+。
Step (2): preparation of bischloroisobutyrylbenzylmethanone fluorene (a2)
Figure BDA0002195994470000101
300mL of dichloromethane, 30g of 9, 9-dibenzylphenyl methanone fluorene and 29.1g of chloroisobutyryl chloride are added into a 500mL four-neck flask, the system is stirred in an ice water bath, 29.3g of aluminum trichloride is added in batches when the temperature of the system is reduced to 0 ℃, the temperature of the system is controlled to be below 10 ℃ in the batch adding process, meanwhile, dilute alkali liquor is used as tail gas for absorption, the aluminum trichloride is added within 10min, and the system is subjected to heat preservation reaction for 1 h. Stopping the reaction, slowly pouring the reaction liquid into 300g of ice water, separating out an organic layer, washing the organic layer for 2 times by using 600g of water, pouring the organic layer into a 500mL four-neck flask, evaporating the organic solvent, adding 60g of methanol, stirring and crystallizing at-10 ℃ for 2h, filtering, rinsing the filter cake by using a little methanol to obtain a light yellow solid wet product, and putting the wet product into a 50 ℃ oven to be dried in the dark for 5h to obtain 40g of light yellow solid powder, wherein the yield is 91.1 percent, and the purity is 98.5 percent.
The structure of the product obtained in the step (2) is confirmed by nuclear magnetic resonance hydrogen spectrum, and the specific characterization result is as follows:1H-NMR(CDCl3，500MHz)
step (3) preparation of Compound 1
Figure BDA0002195994470000102
Adding 44g of toluene, 22g of dichloroisobutyryl benzyl phenyl ketone fluorene and 0.88g of tetrabutylammonium bromide into a 250mL four-neck flask, stirring, dropwise adding 50g of 25% sodium hydroxide solution, controlling the temperature of a system to be below 30 ℃, finishing adding within 10min, heating the system in a water bath at 80 ℃ for reaction for 1h, and stopping reaction. And when the temperature of the system is reduced to room temperature, separating an organic layer, washing the organic layer to be neutral by using 200g of water, pouring the organic layer into a 250mL four-neck flask, adding 1g 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 drying the wet product in a 50 ℃ oven in the dark place for 3h to obtain 14.5g of white solid powder, wherein the yield is 70.5% and the purity is 98.57%.
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):δ8.03(s,1H),7.80-7.78(m,2H),7.66-7.63(m,2H),7.56-7.52(m,7H),7.45-7.40(m,3H),7.30-7.28(m,1H),6.70(d,J＝8.3Hz,4H),3.99(s,2H),3.59-3.46(m,4H),1.48(s,12H).
MS(m/z):623(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 BDA0002195994470000111
Figure BDA0002195994470000121
Figure BDA0002195994470000131
Figure BDA0002195994470000141
Examples 13 to 24
Compounds 13-24 were synthesized using different preparative methods, referring to the synthesis methods of intermediates a1, b2, c3 in examples 1-12.
Synthesis of compound 13:
Figure BDA0002195994470000151
50g of intermediate a3 and 200g of morpholine are added into a 250mL four-neck flask, heating and refluxing are carried out at 100 ℃ for 6h, the liquid phase is tracked until the reaction is complete, then the reaction liquid is poured into water and stirred, an off-white solid is separated out, and the off-white solid is filtered, washed and recrystallized by methanol to obtain 51g of a white solid, namely the compound 11, wherein the yield is 88.5%, and the purity is 98.01%.
The structure of the product is confirmed by nuclear magnetic resonance hydrogen spectrum and mass spectrum:
1H-NMR(CDCl3，400MHz)：δ8.10–7.94(m,5H),7.87–7.78(m,2H),7.70–7.62(m,2H),7.55(t,J＝8.3Hz,3H),7.48-7.37(m,3H),7.33-7.27(m,1H),6.65(d,J＝8.3Hz,4H),3.61–3.43(m,12H),2.48–2.35(m,8H),1.20(s,12H).。
MS(m/z)：761(M+1)+。
according to the synthesis method of the intermediate a-c and the compound 13, different raw materials are selected for reaction and different reaction conditions are adopted, so that the compounds 14-24 with different structures are obtained
TABLE 2
Figure BDA0002195994470000152
Figure BDA0002195994470000161
Figure BDA0002195994470000171
Figure BDA0002195994470000181
Figure BDA0002195994470000191
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:
radiation curable compositions were prepared according to the following formulation and the usual benzophenone-, alpha-hydroxy-and alpha-amino-ketone-type initiators were selected for comparison with the photoinitiator compounds 1, 2 according to the invention, the weight% (wt%) being based on the total weight of the radiation curable composition and consisting of:
TMPTA (trimethylolpropane triacrylate): 95 parts by weight;
photoinitiator (2): 5 parts by weight.
< 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 of an exposure machine, wavelength of 200 ion-500 nm, light intensity of 200 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 3.
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 obtained under the high pressure mercury lamp of the photocurable composition was weighed in the same weight, and the odor was evaluated by a fan odor 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- 5The maximum absorption wavelength and the absorbance A1 of the solution in mol/L are measured by a UV3010 ultraviolet spectrophotometer, and the molar extinction coefficient is calculated by the formula (1):
c＝A/ε×b (1)
R＝100×c/c1 (2)
0.05g of the cured film prepared by fully curing the light-cured composition under a high-pressure mercury lamp is weighed, the cured film is respectively soaked in 30g of ethanol, after the cured film is placed at the normal temperature for 24 hours, 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 of the soaking solution. 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. The test results are shown in Table 3.
TABLE 3
Number of exposures Yellowing property Nature of smell Relative mobility
Compound 1 1 ◇ ◇ 5％
Compound 13 1 ◇ ◇ 3％
Compound 14 1 ◇ ◇ 18％
Compound 15 1 ◇ ◇ 4％
Compound 23 1 ◇ ◇ 3％
Benzophenones as fungicides 1 ◇ ◇ 100％
Photoinitiator 907 1 ◇ ◆ 70％
Photoinitiator 1173 1 ◇ ◇ 87％
From the evaluation results in table 3, it can be seen that the sensitivity and yellowing resistance of the initiator with new structure of the present invention are equivalent to those of the conventional benzophenone-based, α -hydroxy ketone-based, and α -amino ketone-based photoinitiators under the same other components, and the initiator has the characteristics of low odor, especially excellent migration.
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 (21)

1. A fluorene-based photoinitiator, having a structure represented by formula (I):
Figure FDA0003212859770000011
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 is3Selected from photoactive groups;
the R isa1The R isa2The R isa3The R isa4The R isa5The R isa6The R isa7The R isa8Each independently selected from hydrogen, nitro, cyano, trifluoromethyl, 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、-CORb2、-COORb3、-SRb4、-SO2Rb5or-CONRb6Rb7Said R isb1The R isb2The R isb3The R isb4The R isb5The R isb6The R isb7Each 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～C20And R is a heterocyclic group ofa2And Ra7At least one for pulling electronAnd (4) generation of base.
2. The fluorene-based photoinitiator according to claim 1, wherein R is1And said R2Are each independently selected from C1～C4Straight or branched alkyl of (2), C3～C5Cycloalkyl-substituted C of1～C3Or said R is1And said R2Are connected to each other to form C3～C6A cycloalkyl group of (a).
3. The fluorene-based photoinitiator according to claim 2, wherein R is3Selected from hydroxy, N-dialkyl, N-morpholinyl, N-thiomorpholinyl or N-substituted piperazinyl.
4. The fluorene-based photoinitiator according to claim 2 or 3, wherein R isa1The R isa2The R isa3The R isa4The R isa5The R isa6The R isa7The R isa8Wherein at least one substituent is-CORb2Said R isb2Is aryl, heteroaryl, substituted aryl or substituted heteroaryl.
5. The fluorene-based photoinitiator according to any one of claims 1 to 3, wherein the fluorene-based photoinitiator is selected from one or more of the following compounds:
Figure FDA0003212859770000021
Figure FDA0003212859770000031
Figure FDA0003212859770000041
Figure FDA0003212859770000051
6. a method for preparing the fluorene-based photoinitiator according to any one of claims 1 to 5, comprising:
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 FDA0003212859770000052
wherein, X is1Is 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 FDA0003212859770000061
wherein, X is2And each X' is independently selected from a halogen atom;
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 a non-hydroxyl photoactive group to obtain the fluorene photoinitiator.
7. The method according to claim 6, wherein the substitution reaction is carried out at a reaction temperature of 30 to 60 ℃.
8. The method of claim 7, wherein the first organic solvent is selected from one or more of the group consisting of dichloromethane, dichloroethane, benzene, and xylene.
9. The method according to claim 6, wherein the Friedel-crafts reaction is carried out at a temperature of-10 to 10 ℃.
10. The method of claim 9, wherein the second organic solvent is selected from one or more of the group consisting of dichloromethane, dichloroethane, benzene, and xylene.
11. The method according to any one of claims 6 to 10, wherein the reaction temperature of the hydrolysis reaction is 20 to 100 ℃.
12. The method according to claim 11, wherein the method further comprises adding a third organic solvent, an inorganic base and a phase transfer catalyst to the reaction system before the hydrolysis reaction.
13. The method of claim 12, wherein the third organic solvent is one or more selected from the group consisting of dichloromethane, dichloroethane, benzene, xylene, and acetonitrile, the inorganic base is KOH and/or NaOH, and the phase transfer catalyst is a quaternary ammonium salt type phase transfer catalyst.
14. The method of claim 12, wherein the phase transfer catalyst is one or more selected from the group consisting of tetrabutylammonium bromide, tetrapropylammonium bromide, tetra-n-butylammonium, triethylbenzylammonium chloride and tetrabutylammonium hydrogen sulfate.
15. The method according to any one of claims 6 to 10, wherein the reaction temperature of the dehalogenation reaction is 40 to 160 ℃.
16. The method according to claim 15, wherein the dehalogenation reaction is carried out in the presence of a fourth organic solvent.
17. The method of claim 16, wherein the fourth organic solvent is one or more selected from the group consisting of dichloromethane, dichloroethane, benzene, xylene, and acetonitrile.
18. The method of claim 15, wherein the non-hydroxy photoactive group-containing compound is selected from one or more of the group consisting of N, N-dimethyl, N-diethyl, morpholine, thiomorpholine, and piperidine.
19. A photocurable composition comprising a polymeric monomer and a photoinitiator, the photoinitiator comprising the fluorene-based photoinitiator according to any one of claims 1 to 5.
20. Use of the fluorene-based photoinitiator according to any one of claims 1 to 5 in the field of photocuring.
21. Use according to claim 20, wherein the photocuring field comprises the field of coatings, of inks or of adhesives.
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