CN107814694B - Fluorene initiator, preparation method thereof, photocuring composition with fluorene initiator and application of composition in photocuring field - Google Patents

Fluorene initiator, preparation method thereof, photocuring composition with fluorene initiator and application of composition in photocuring field Download PDF

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CN107814694B
CN107814694B CN201610821992.3A CN201610821992A CN107814694B CN 107814694 B CN107814694 B CN 107814694B CN 201610821992 A CN201610821992 A CN 201610821992A CN 107814694 B CN107814694 B CN 107814694B
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fluorene
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based initiator
initiator
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CN107814694A (en
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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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Priority to EP17850178.9A priority patent/EP3514135B1/en
Priority to KR1020197004737A priority patent/KR102197059B1/en
Priority to JP2019501481A priority patent/JP6833171B2/en
Priority to PCT/CN2017/099294 priority patent/WO2018049976A1/en
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/76—Ketones containing a keto group bound to a six-membered aromatic ring
    • C07C49/782—Ketones containing a keto group bound to a six-membered aromatic ring polycyclic
    • C07C49/792—Ketones containing a keto group bound to a six-membered aromatic ring polycyclic containing rings other than six-membered aromatic rings
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    • C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
    • C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
    • C07C319/20—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides by reactions not involving the formation of sulfide groups
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    • C07C323/22—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and doubly-bound oxygen atoms bound to the same carbon skeleton
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    • C07—ORGANIC CHEMISTRY
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    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/50—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton
    • C07C323/62—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton
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    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
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    • C07C49/76—Ketones containing a keto group bound to a six-membered aromatic ring
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    • C07C67/00—Preparation of carboxylic acid esters
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    • C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
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    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
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    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
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    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
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    • C07D333/04—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
    • 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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    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light

Abstract

The invention provides a fluorene initiator, a preparation method thereof, a photocuring composition and application thereof in the field of photocuring. The fluorene initiator has a group represented by formula (I):
Figure DDA0001113880190000011
wherein R is1、R2Each independently selected from any one of a hydrogen atom, a halogen and a chain group; ar is a substituent containing an aromatic ring or a heteroaromatic ring; and R attached to the linkage of the group of formula (I)3，R3Is a hydrogen atom, -C (═ O) R3' or-C (═ O) O-R3' group, wherein R3' represents substituted or unsubstituted C1‑C40Straight or branched alkyl of (2), C1‑C20Cycloalkyl of, C1‑C40Alkenyl group of (A), a substituent containing an aromatic ring or a heteroaromatic ring, or R3In the latter case, the R3' group is the group to which the alcohol or polyol is attached by a transesterification reaction. The initiator is resistant to yellowing, not easy to migrate, low in odor and good in solubility.

Description

Fluorene initiator, preparation method thereof, photocuring composition with fluorene initiator and application of composition in photocuring field
Technical Field
The invention relates to the field of organic photochemistry, and in particular relates to a fluorene initiator, a preparation method thereof, a photocuring composition with the fluorene initiator and application of the fluorene initiator in the field of photocuring.
Background
Benzophenone and benzoylformate photoinitiators are common free radical photoinitiators, are very frequently used photoinitiators due to simple structure, easy synthesis and low price, but have the problems of mobility, odor, yellowing, solubility and the like in the use process, so that the application of the photoinitiator is limited to a great extent. The benzophenone photoinitiator is tried to be subjected to the large molecular transformation by modifying the structure, such as Chinese patents (or applications) with publication numbers of CN1789245A, CN103497263A and CN104987435A, 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. For example, in Chinese patent applications with publication numbers CN103709036A and CN102442909A, polyhydric alcohol is introduced into the p-benzoylformate photoinitiator, so that the problem of solubility is solved to a certain extent, but the absorption wavelength is not remarkably improved. On the other hand, in these modifications in the current research, the initiation efficiency thereof is to be further improved, and the light absorption property thereof at a long wavelength is to be further improved.
On the other hand, with the increasing environmental protection call, UV-LED light source curing is a development trend of the photo-curing industry to replace mercury lamp light sources, the initiation effect of the above-mentioned common benzophenone and benzoyl formate photoinitiators under mercury lamps is still acceptable, but the initiation effect under UV-LED light sources is greatly reduced, so that initiators suitable for UV-LED light sources need to be developed.
Disclosure of Invention
The invention mainly aims to provide a fluorene initiator, a preparation method thereof, a photocuring composition with the fluorene initiator and application of the photocuring composition in the field of photocuring, so as to solve the problems of easy migration and easy yellowing of the photoinitiator in the prior art.
In order to achieve the above object, according to one aspect of the present invention, there is provided a fluorene-based initiator having a group represented by formula (I):
Figure BDA0001113880180000011
wherein R is1、R2Each independently selected from any one of hydrogen atom, halogen and chain group, the chain group is C1-C20Straight chain alkyl group of (1), C1-C20Branched alkyl or C1-C20Cycloalkyl of, C4-C20Cycloalkylalkyl of (C)4-C20Alkylcycloalkyl of (A) and C2-C20Or R is1And R2Any one or two of chain group forms a ring, and-CH in the chain group2-optionally substituted by-O-, -C (═ O) O-, halogen, phenyl; ar is a substituent containing an aromatic ring or a heteroaromatic ring; and R attached to the linkage of the group of formula (I)3，R3Is a hydrogen atom, -C (═ O) R3' or-C (═ O) O-R3' group, wherein R3' represents substituted or unsubstituted C1-C40Straight chain of (1), C1-C40Branched alkyl of C1-C20Cycloalkyl of, C1-C40Alkenyl group of (A), a substituent containing an aromatic ring or a heteroaromatic ring, or R3is-C (═ O) O-R3', group, R3' group is a group to which an alcohol or polyol is attached by a transesterification reaction.
Further, the above-mentioned chain group is C1-C10Straight chain alkyl group of (1), C1-C10Branched alkyl or C4-C10Cycloalkylalkyl groups of (a).
Further, Ar mentioned above is phenyl, methylphenyl, ethylphenyl, chlorophenyl, bromophenyl, methoxyphenyl, nitrophenyl, cyanophenyl, diphenylsulfide group, pyridyl, thienyl, furyl, 2-methyl-thienyl, 3-methylthiophenyl, furyl, 2-methyl-furyl or 3-methylfuryl.
Further, the above R3is-C (═ O) O-R3' the group, fluorene-based initiator has the structure shown in the following formula (II):
Figure BDA0001113880180000021
wherein R is4Has n external connecting keys and is C1-C60A linear or branched alkyl group of, or C1-C60Any carbon or hydrogen in the straight or branched alkyl group of (a) is substituted by oxygen, sulfur or phenyl; a represents a compound having- (Q-CHR)5)m-recurring units of the structure R5Is hydrogen, methyl or ethyl, Q represents O or a linker, wherein the linker represents- (CHR)5)mDirectly connecting with O, wherein m is an integer of 1-6; n represents an integer of 1 to 20.
Further, the above R4Any one selected from the following groups:
Figure BDA0001113880180000022
Figure BDA0001113880180000023
*CH2-CH2*、*CH2-CH2CH2*、*CH2CH2CH2CH2*、
Figure BDA0001113880180000024
Figure BDA0001113880180000025
Figure BDA0001113880180000031
further, A is selected from the group consisting of- [ (Q-CHR)5)m]y-, wherein R5Is hydrogen or methyl, m is an integer of 1 to 3, and y represents an integer of 1 to 9.
Further, n is an integer of 1 to 8, preferably 1, 2, 3, 4, 5 or 6.
According to another aspect of the present application, there is provided a method for preparing a fluorene-based initiator according to any one of the above, the method comprising: step S1, carrying out Friedel-crafts reaction on the raw material a with the structural formula A and the raw material B with the structural formula B to obtain an intermediate C with the structural formula C; optionally step S2, performing friedel-crafts reaction between the intermediate c and the raw material D having the structural formula D to obtain an intermediate E having the structural formula E; and an optional step S3, performing ester exchange reaction on the intermediate e and alcohol or polyol with a structural formula F to obtain the fluorene initiator, wherein the structural formula A is
Figure BDA0001113880180000032
Structural formula B is
Figure BDA0001113880180000033
Wherein X1Is halogen, the structural formula C is
Figure BDA0001113880180000034
Structural formula D is
Figure BDA0001113880180000035
Wherein X2Is halogen, the structural formula E is
Figure BDA0001113880180000036
Structural formula F is R4(AOH)n。
Further, the Friedel-crafts reaction in the step S1 and the step S2 is carried out in the presence of aluminum trichloride or zinc chloride and a solvent, and the reaction temperature of the Friedel-crafts reaction in the step S1 and the step S2 is preferably-10 to 40 ℃.
Further, the transesterification in step S3 is carried out under the action of a catalyst and a polymerization inhibitor, preferably, the catalyst is one or more titanic acid compounds, more preferably, the catalyst is one or more selected from the group consisting of 2-ethylhexyl titanate, tetramethyl titanate, tetraisopropyl titanate, tetrabutyl titanate, tetraisobutyl titanate and tetra (2-ethylhexyl) titanate, and the polymerization inhibitor is any one selected from the group consisting of p-hydroxyanisole, N-diethylhydroxylamine, hydroquinone, catechol, p-tert-butylcatechol, methylhydroquinone, p-methoxyphenol, phenothiazine and triphenylphosphine.
Further, in step S3 above, the molar ratio of intermediate e to the alcohol or polyol of formula F is n: 1, preferably, the weight of the catalyst is 3-10 per mill of the total weight of the materials, more preferably, the weight of the polymerization inhibitor is 3-10 per mill of the total weight of the materials, and further preferably, the temperature of the ester exchange reaction is 70-130 ℃, and the reaction time is 1-8 hours.
According to another aspect of the present invention, there is provided a photocurable composition comprising a photoinitiator, which is any one of the fluorene-based initiators described above.
According to another aspect of the present invention, there is provided a use of any one of the above fluorene-based initiators in the field of photocuring.
Further, the above applications include applications in paints, inks, adhesives, color resists, black matrices, photo spacers, ribs, dry films, and/or semiconductor photoresists.
By applying the technical scheme of the invention, the main structure of the existing common benzophenone or benzoyl formate is replaced by the structure taking fluorene as the main body, so that the problems of initiation efficiency, yellowing resistance, difficult migration, low odor, solubility and the like of the initiator can be better improved and balanced, and application research on the photosensitive composition shows that the fluorene initiator can be well suitable for curing of the UV-LED light source when being applied to the existing conventional photocuring formula.
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 analyzed by the background art, the photoinitiator in the prior art has the problems of easy migration and easy yellowing, and in order to solve the problems, in a typical embodiment of the present application, a fluorene initiator is provided, and the fluorene initiator has a group represented by formula (I):
Figure BDA0001113880180000041
(as is generally understood by those skilled in the art, "-" on the phenyl ring on the right side of the formula indicates a linkage that may be attached to the phenyl ring at any position C, wherein a denotes a linkage that may be attached to other groups),
wherein R is1、R2Each independently selected from any one of hydrogen atom, halogen and chain group, the chain group is C1-C20Straight chain alkyl group of (1), C1-C20Branched alkyl or C1-C20Cycloalkyl of, C4-C20Cycloalkylalkyl of (C)4-C20Alkylcycloalkyl of (A) and C2-C20Or R is1And R2Any one or two of chain group forms a ring, and-CH in the chain group2-optionally substituted by-O-, -C (═ O) O-, halogen, phenyl; ar is a substituent containing an aromatic ring or a heteroaromatic ring; and R attached to the linkage of the group of formula (I)3，R3Is a hydrogen atom, -C (═ O) R3' or-C (═ O) O-R3' group, wherein R3' represents substituted or unsubstituted C1-C40Straight chain of (1), C1-C40Branched alkyl of C1-C20Cycloalkyl of, C1-C40An aromatic ring or a heteroaromatic ring-containing substituent (the structural formula can be represented by
Figure BDA0001113880180000051
) Or R is3is-C (═ O) O-R3', group, R3' group is a group to which an alcohol or polyol is attached by a transesterification reaction.
The inventor of the application surprisingly discovers through long-term experimental research that: after the main structure of the existing common benzophenone or benzoyl formate is replaced by the structure taking fluorene as the main body, the problems of initiation efficiency, yellowing resistance, difficult migration, low odor, solubility and the like of the initiator can be well improved and balanced, and application research on the photosensitive composition shows that the fluorene initiator can be well suitable for curing of the UV-LED light source when being applied to the existing conventional photocuring formula.
In order to facilitate the synthesis of the fluorene initiator, it is preferable that the chain group is C1-C10Straight chain alkyl group of (1), C1-C10Branched alkyl or C4-C10Cycloalkylalkyl groups of (a). More preferably, Ar is phenyl, methylphenyl, ethylphenyl, chlorophenyl, bromophenyl, methoxyphenyl, nitrophenyl, cyanophenyl, diphenylsulfide, pyridyl, thienyl, furyl, 2-methyl-thienyl, 3-methylthiophenyl, furyl, 2-methyl-furyl or 3-methylfuryl.
In a preferred embodiment of the present application, R is as defined above3is-C (═ O) O-R3' the group, fluorene-based initiator has the structure shown in the following formula (II):
Figure BDA0001113880180000052
wherein R is4Has n external connecting keys and is C1-C60A linear or branched alkyl group of, or C1-C60Any carbon or hydrogen in the straight or branched alkyl group of (a) is substituted by oxygen, sulfur or phenyl; a represents a compound having- (Q-CHR)5)m-recurring units of the structure R5Is hydrogen, methyl or ethyl, Q represents O or a linker, wherein the linker represents- (CHR)5)mDirectly connecting with O, wherein m is an integer of 1-6; n represents an integer of 1 to 20.
The fluorene initiator having the structural formula (II) not only has reduced mobility due to a larger molecular weight, but also has a characteristic of more excellent solubility.
In addition, the absorption bands of the compounds shown in the formula (I) and the formula (II) are between 330 and 400nm, the odor is almost not generated, the (methyl) acrylic resin and the vinyl ether compound have good solubility, and the migration is not easy to occur after the application, and the yellowing resistance is realized.
Furthermore, when R in the formula (II)4The structure is more stable when the compound is selected from any one of the following groups:
Figure BDA0001113880180000061
Figure BDA0001113880180000062
*CH2-CH2*、*CH2-CH2-CH2*、*CH2CH2CH2CH2*、
Figure BDA00011138801800000610
Figure BDA0001113880180000064
further, in order to reduce the production cost and the production difficulty of the fluorene initiator, it is preferable that A is selected from the group consisting of- [ (Q-CHR)5)m]y-, wherein R5Is hydrogen or methyl, m is an integer of 1 to 3, and y represents an integer of 1 to 9. More preferably, n is an integer of 1 to 8, and still more preferably 1, 2, 3, 4, 5 or 6.
In another exemplary embodiment of the present application, there is provided a method for preparing any one of the above fluorene-based initiators, the method comprising: step S1, carrying out Friedel-crafts reaction on the raw material a with the structural formula A and the raw material B with the structural formula B to obtain an intermediate C with the structural formula C; optionally step S2, performing friedel-crafts reaction between the intermediate c and the raw material D having the structural formula D to obtain an intermediate E having the structural formula E; and an optional step S3, performing ester exchange reaction on the intermediate e and alcohol or polyol with a structural formula F to obtain the fluorene initiator, wherein the structural formula A is
Figure BDA0001113880180000065
Structural formula B is
Figure BDA0001113880180000066
Wherein X1Is halogen, the structural formula C is
Figure BDA0001113880180000067
Structural formula D is
Figure BDA0001113880180000068
Wherein X2Is halogen, the structural formula E is
Figure BDA0001113880180000069
Structural formula F is R4(AOH) n.
R in the foregoing formulae is as conventionally understood by those skilled in the art1、R2、Ar、R3、R3' and R4Are the same as the groups represented in the structural formula (I) and the structural formula (II). The chemical reaction process of the preparation method is as follows:
Figure BDA0001113880180000071
different fluorene initiators of the application can be obtained through one step, two steps or three steps, and the reactions adopted in the steps are mature and common reactions in the prior art, so that the preparation process is easy to realize and control. Wherein when R is4(AOH)nWhen n in (A) is an integer greater than 1, a plurality of intermediates E and R4(AOH)nAnd simultaneously carrying out ester exchange reaction to obtain the product.
The friedel-crafts reaction conditions of the step S1 and the step S2 can be implemented by referring to the conventional friedel-crafts reaction in the prior art, and the present application preferably performs the friedel-crafts reaction of the step S1 and the step S2 in the presence of aluminum trichloride or zinc chloride and a solvent for the above substrate, and more preferably the friedel-crafts reaction of the step S1 and the step S2 are each independently-10 to 40 ℃. The friedel-crafts reaction conditions in the two steps can be the same or different, and the solvent can be the same or different, wherein the solvent can be common organic solvent which does not participate in the reaction in the prior art, such as dichloromethane, dichloroethane, toluene, benzene, xylene, when the two steps use the same solvent, the friedel-crafts reaction in the step S2 can be continued without purification after the step S1 is completed.
The aforementioned transesterification reaction of step S3 can be performed in the system completed in step S2 directly or after purification and then placed in a solvent again, and the solvent of step S3 is not particularly limited as long as it can dissolve the respective reagents and has no adverse effect on the reaction, such as toluene, benzene, xylene.
In order to accelerate the reaction and reduce the generation of byproducts as much as possible, the transesterification in step S3 is preferably performed under the action of a catalyst and a polymerization inhibitor, preferably the catalyst is one or more titanic acid compounds, more preferably the catalyst is one or more selected from the group consisting of 2-ethylhexyl titanate, tetramethyl titanate, tetraisopropyl titanate, tetrabutyl titanate, tetraisobutyl titanate and tetrakis (2-ethylhexyl) titanate, and preferably the polymerization inhibitor is any one selected from the group consisting of p-hydroxyanisole, N-diethylhydroxylamine, hydroquinone, catechol, p-tert-butylcatechol, methylhydroquinone, p-methoxyphenol, phenothiazine and triphenylphosphine.
Further, in order to save raw materials while ensuring the yield of the objective product, it is preferable that the molar ratio of the intermediate e to the alcohol or polyol having the structural formula F in the above step S3 is n: 1, preferably, the weight of the catalyst is 3-10 per mill of the total weight of the materials, more preferably, the weight of the polymerization inhibitor is 3-10 per mill of the total weight of the materials, and further preferably, the temperature of the ester exchange reaction is 70-130 ℃, and the reaction time is 1-8 hours.
In another exemplary embodiment of the present application, there is provided a photocurable composition including a photoinitiator, the photoinitiator being any one of the fluorene-based initiators described above.
The problems of initiation efficiency, yellowing resistance, difficult migration, low odor, solubility and the like of the fluorene initiator can be better improved and balanced compared with the benzophenone or benzoyl formate initiator in the prior art, so that when the fluorene initiator is applied to a composition, various performances of a structure formed by the composition can be more stable, the photocuring composition can be cured under the irradiation of a UV-LED light source, and energy is saved and the environment-friendly requirement is better met.
In another exemplary embodiment of the present application, there is provided a use of any one of the above fluorene-based initiators in the field of photocuring.
The fluorene initiator can enable the photocuring composition with the fluorene initiator to be cured under the irradiation of a UV-LED light source, so that the application containing the fluorene initiator saves energy and meets the requirement of environmental protection. Preferably, the application includes application in paints, inks, adhesives, color resists, black matrices, photo spacers, ribs, dry films and/or semiconductor photoresists.
The present invention will be described in further detail with reference to specific examples, which should not be construed as limiting the scope of the present invention.
Preparation examples
(1) Preparation of product 1 a:
Figure BDA0001113880180000081
adding raw materials 1a83g, dichloromethane 300mL and aluminum trichloride 67g into a 1000mL four-neck flask, stirring to form a first mixed system, cooling the first mixed system to 0 ℃ through ice-water bath, dropwise adding a mixed solution formed by 77g of raw materials 1b and 50mL of dichloromethane into the first mixed system, controlling the temperature to be below 10 ℃, completing dropwise addition for about 2 hours, tracking a liquid phase until no change occurs, obtaining a product solution of an intermediate 1a, slowly pouring the product solution into diluted hydrochloric acid prepared from 400g of ice water and 50mL of concentrated hydrochloric acid (37%), stirring while adding, pouring the product solution into a separating funnel after completing addition, separating a lower dichloromethane layer by using the separating funnel, continuously cleaning an aqueous layer with 50mL of dichloromethane, separating the lower dichloromethane layer again, combining dichloromethane layers obtained twice, adding a 5% sodium bicarbonate aqueous solution (150 mL each time, total 3 times) washing the combined dichloromethane layers, followed by waterWashing dichloromethane layer until pH is neutral, drying dichloromethane layer with 50g anhydrous magnesium sulfate, filtering dried dichloromethane layer, rotary evaporating filtered dichloromethane product solution, recrystallizing with methanol, oven drying the obtained crystal at 80 deg.C for 2 hr to obtain 135g product 1a with purity of 98%, MS (M/z):285(M +1)+，1H-NMR(CDCl3，500MHz)：2.3540(3H，s)，3.8721(2H，s)，7.1701-7.8411(11H，m)。
Further, friedel-crafts reaction can be carried out by using different raw materials a and b to obtain products a with different structures, but the friedel-crafts reaction is not limited to the product a shown in the table 1.
TABLE 1
Figure BDA0001113880180000091
Figure BDA0001113880180000101
Figure BDA0001113880180000111
(2) Preparation of product 1 b:
Figure BDA0001113880180000112
adding the product 1a85g and dichloromethane 100mL into a 500mL four-neck flask, stirring at room temperature, continuously dropwise adding a mixed solution formed by raw materials 1c38g and 50mL dichloromethane into the four-neck flask, controlling the temperature to be below 30 ℃, completing dropwise addition for about 1h, continuously stirring for 2h after dropwise addition, performing liquid phase tracking reaction till the reaction is complete to obtain a product system containing the product 1b, slowly pouring the product system into diluted hydrochloric acid prepared from 400g ice water and 50mL concentrated hydrochloric acid (37%), stirring while adding, pouring the product system into a separating funnel after completely adding, separating a lower dichloromethane layer by using the separating funnel, continuously cleaning an aqueous layer by using 50mL dichloromethane, separating the lower dichloromethane layer again, combining the two dichloromethane layers, and mixing the two dichloromethane layersWashing the combined dichloromethane layer with 5% sodium bicarbonate water solution (100 mL each for 3 times), washing the dichloromethane layer with water until pH is neutral, drying the dichloromethane layer with 50g anhydrous magnesium sulfate, filtering the dried dichloromethane layer, rotary evaporating the dichloromethane product solution, recrystallizing with methanol, oven drying at 80 deg.C for 2 hr to obtain 98g product 1b with purity of 98%, MS (M/z):385(M +1)+，1H-NMR(CDCl3，500MHz)：1.2996-1.3025(3H,m)，2.3535(3H，s)，3.8757(2H，s)，4.19543-4.2103(2H，m)7.1686-8.0943(10H，m)。
Further, a friedel-crafts reaction can be performed by using different products a and raw materials c to obtain products b with different structures, but the processes are not limited to the processes shown in table 2 (the compounds in table 2 are numbered in sequence, but do not represent that the compounds in table 2 are prepared by using the correspondingly numbered compounds in table 1 as raw materials, and a person skilled in the art can select suitable products a and raw materials c to perform the friedel-crafts reaction to obtain corresponding products b according to the foregoing description and the prior art).
TABLE 2
Figure BDA0001113880180000113
Figure BDA0001113880180000121
Figure BDA0001113880180000131
(3) Preparation of compound 1 c:
Figure BDA0001113880180000132
into a 500mL four-necked flask were charged intermediate 1b 77g, starting material 1d100mL, tetraisopropyl titanate 0.1g, and p-hydroxyanisole 0.1g, and the mixture was heatedControlling the temperature of the flask to be 90-100 ℃, simultaneously stirring substances added into the four-neck flask to form a reaction liquid, then carrying out reduced pressure distillation on the reaction liquid, distilling off ethanol generated in the reaction until no ethanol is distilled off, and filtering while the reaction liquid is hot to obtain 93g of light yellow solid, namely a product 1c, MS (M/z):483(M +1)+，1H-NMR(CDCl3，500MHz)：0.9655-0.97231(3H，t)，1.2897-1.3305(12H,m)，1.5677-1.5708(2H,m)，2.3546(3H，s)，3.8777(2H，s)，4.1607-4.1702(2H，t)7.1659-8.0902(10H，m)。
Further, the transesterification reaction can be carried out by using different products b and raw materials d to obtain products c with different structures, but not limited to, as shown in table 3 (the compounds in table 3 are numbered in sequence, but do not represent that the compounds in table 3 are prepared by using the correspondingly numbered compounds in table 2 as raw materials, and one skilled in the art can select suitable products b and raw materials d to carry out the transesterification reaction to obtain corresponding products c according to the foregoing description and the prior art).
TABLE 3
Figure BDA0001113880180000141
Figure BDA0001113880180000151
Figure BDA0001113880180000161
Figure BDA0001113880180000171
Figure BDA0001113880180000181
Figure BDA0001113880180000191
Evaluation of Performance
The performance of photoinitiators of formula (I) and formula (II) according to the invention and of conventional benzophenone-based and benzoylformate-based initiators of the same formulation in the preparation of inks was evaluated by formulating exemplary radiation-curable compositions.
Different monomers or oligomers required by free radical curing are selected, and a sensitizer, a coloring agent, a dispersing agent, a dispersion synergist, a surfactant or a polymerization inhibitor and the like are added according to the requirement in proper proportion to prepare the curable ink.
Preparation of radiation curable compositions:
radiation curable compositions were prepared according to the formulation of table 4, using the usual benzophenone and formylformate type initiators and the photoinitiator according to the invention for comparison, the weight% (wt%) being based on the total weight of the radiation curable composition:
TABLE 4
Figure BDA0001113880180000192
Figure BDA0001113880180000201
The evaluation method comprises the following steps:
< sensitivity test >
Stirring the photocuring composition under a yellow light, taking the composition 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, respectively adopting a high-pressure mercury lamp (model RW-UV70201 of exposure machine, wavelength of 200 ion of 500nm, light intensity of 100 mW/cm)2) And LED lamp (blue spectrum Rick LP300w, wavelength 395nm, light intensity 100mW/cm2) 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 5.
< 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 >
Weighing the same mass of the cured film prepared under the high-pressure mercury lamp of the light-cured composition, evaluating the odor performance of the cured film by a fan-smelling method, shearing the cured film, putting the cut cured film into a methanol solution with the same volume, sealing and soaking the cut cured film for 24 hours at room temperature, detecting whether an initiator exists in the methanol solution by a liquid phase (mobile phase methanol/water is 80/20), and evaluating according to the following standards:
odor property:
o have no odor;
it is odorous.
Mobility:
o: the presence of initiator was not detected, indicating a poor migration;
solid content: the presence of initiator was detected, indicating that the mobility was to be improved.
TABLE 5
Figure BDA0001113880180000211
As can be seen from the evaluation results in Table 5, under the condition that other components are the same, the fluorene initiator of the invention not only has higher sensitivity under a high-pressure mercury lamp, but also has ideal height under a UV-LED light source, and the sensitivity of the prior benzophenone and benzoyl formate photoinitiators under the UV-LED light source is obviously insufficient; as can be seen from yellowing resistance experiments and migration experiments, the fluorene photoinitiator has the characteristics of good yellowing resistance, low solubility and smell and difficult migration.
In summary, the compounds represented by the formula (I) and the formula (II) can show excellent application performance when being used as the photoinitiator in the field of photocuring, and have wide application prospects.
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 (23)

1. A fluorene-based initiator having a group according to formula (I):
Figure 381878DEST_PATH_IMAGE002
（I），
wherein R is1、R2Each independently selected from any one of hydrogen atom, halogen and chain group, the chain group is C1-C20Straight chain alkyl group of (1), C1-C20Branched alkyl or C1-C20Cycloalkyl of, C4-C20Cycloalkylalkyl of (C)4-C20Alkylcycloalkyl of (A) and C2-C20Or said R is1And R2Any one or two of the chain group groups form a ring, and-CH in the chain group2-optionally substituted by-O-, -C (= O) O-, phenyl;
ar is a substituent containing an aromatic ring or a heteroaromatic ring;
and R attached to the linkage of the group of formula (I)3Said R is3is-C (= O) C (= O) O-R3' group, wherein R3' represents substituted or unsubstituted C1-C40Straight chain alkyl group of (1), C1-C40Branched alkyl of C1-C20Cycloalkyl of, C1-C40Alkenyl group of (A), a substituent containing an aromatic ring or a heteroaromatic ring, or R3is-C (= O) C (= O) O-R3The 'group, the R3' group, is the group to which the alcohol is attached by a transesterification reaction.
2. The fluorene-based initiator of claim 1, wherein the chain group is C1-C10Straight chain alkyl group of (1), C1-C10Branched alkyl or C4-C10Cycloalkylalkyl groups of (a).
3. The fluorene-based initiator according to claim 1, wherein Ar is phenyl, methylphenyl, ethylphenyl, chlorophenyl, bromophenyl, methoxyphenyl, nitrophenyl, cyanophenyl, diphenylsulfide, pyridyl, thienyl, furyl, 2-methyl-thienyl, 3-methylthiophenyl, 2-methyl-furyl or 3-methylfuryl.
4. The fluorene-based initiator according to claim 1, wherein the alcohol is a polyol.
5. The fluorene-based initiator according to any one of claims 1 to 4, wherein R is3is-C (= O) C (= O) O-R3' group, the fluorene-based initiator has the structure shown in formula (II) below:
Figure DEST_PATH_IMAGE003
（Ⅱ），
wherein R is4Has n external connecting keys and is C1-C60Or said C is a linear or branched alkyl group of1-C60Any carbon or hydrogen in the straight or branched alkyl group of (a) is substituted by oxygen, sulfur or phenyl;
a represents a compound having- (Q-CHR)5)m-recurring units of the structure R5Is hydrogen, methyl or ethyl, Q represents O or a linker, wherein the linker represents- (CHR)5)mDirectly connecting with O, wherein m is an integer of 1-6;
n represents an integer of 1 to 20.
6. The fluorene-based initiator of claim 5, wherein R is4Any one selected from the following groups:
Figure DEST_PATH_IMAGE005
、
Figure DEST_PATH_IMAGE007
、
Figure DEST_PATH_IMAGE009
、
Figure DEST_PATH_IMAGE011
、
Figure DEST_PATH_IMAGE013
、
Figure DEST_PATH_IMAGE015
、
Figure DEST_PATH_IMAGE017
、
Figure DEST_PATH_IMAGE019
、
Figure DEST_PATH_IMAGE021
、
Figure DEST_PATH_IMAGE023
、
Figure DEST_PATH_IMAGE025
、
Figure DEST_PATH_IMAGE027
、
Figure DEST_PATH_IMAGE029
、
Figure DEST_PATH_IMAGE031
、
Figure DEST_PATH_IMAGE033
、
Figure DEST_PATH_IMAGE035
and
Figure DEST_PATH_IMAGE037
。
7. the fluorene-based initiator according to claim 5, wherein A is selected from the group consisting of- [ (Q-CHR)5)m]y-, wherein R5Is hydrogen or methyl, m is an integer of 1 to 3, and y represents an integer of 1 to 9.
8. The fluorene-based initiator according to claim 5, wherein n is an integer of 1 to 8.
9. The fluorene-based initiator of claim 8, wherein n is 1, 2, 3, 4, 5 or 6.
10. A method for preparing the fluorene-based initiator according to any one of claims 1 to 9, comprising:
step S1, carrying out Friedel-crafts reaction on the raw material a with the structural formula A and the raw material B with the structural formula B to obtain an intermediate C with the structural formula C;
step S2, carrying out Friedel-crafts reaction on the intermediate c and the raw material D with the structural formula D to obtain an intermediate E with the structural formula E; and
optionally step S3, subjecting the intermediate e to transesterification with an alcohol having a structural formula F to obtain the fluorene initiator, wherein,
the structural formula A is
Figure DEST_PATH_IMAGE039
The structural formula B is
Figure 444160DEST_PATH_IMAGE040
Wherein X is1Is halogen, the structural formula C is
Figure 99263DEST_PATH_IMAGE042
Wherein the structural formula D is
Figure DEST_PATH_IMAGE043
Wherein X is2Is halogen, the structural formula E is
Figure 369839DEST_PATH_IMAGE044
The structural formula F is
Figure 997261DEST_PATH_IMAGE046
。
11. The method of claim 10, wherein the friedel-crafts reaction of step S1 and step S2 is performed in the presence of aluminum trichloride or zinc chloride and a solvent.
12. The method according to claim 11, wherein the reaction temperature of the Friedel-crafts reaction of the step S1 and the step S2 is-10 to 40 ℃ independently of each other.
13. The method according to claim 10, wherein the transesterification in step S3 is carried out under the action of a catalyst and a polymerization inhibitor.
14. The method of claim 13, wherein the catalyst is one or more titanic acid compounds.
15. The method of claim 14, wherein the catalyst is selected from one or more of the group consisting of 2-ethylhexyl titanate, tetramethyl titanate, tetraisopropyl titanate, tetrabutyl titanate, tetraisobutyl titanate, and tetrakis (2-ethylhexyl) titanate.
16. The production method according to claim 13, wherein the polymerization inhibitor is any one selected from the group consisting of p-hydroxyanisole, N-diethylhydroxylamine, hydroquinone, catechol, p-tert-butylcatechol, methylhydroquinone, p-methoxyphenol, phenothiazine, and triphenylphosphine.
17. The method of claim 13, wherein in step S3, the molar ratio of intermediate e to alcohol of formula F is n: 1.
18. the preparation method of claim 17, wherein the weight of the catalyst is 3-10% of the total weight of the materials.
19. The preparation method according to claim 17, wherein the weight of the polymerization inhibitor is 3 to 10% o of the total weight of the materials.
20. The method according to claim 17, wherein the transesterification reaction is carried out at a temperature of 70 to 130 ℃ for 1 to 8 hours.
21. A photocurable composition comprising a photoinitiator, characterised in that the photoinitiator is a fluorene-based initiator according to any one of claims 1 to 9.
22. Use of the fluorene-based initiator of any one of claims 1-9 in the field of photocuring.
23. The use according to claim 22, wherein said use comprises use in paints, inks, adhesives, colored photoresists, black matrices, photo spacers, ribs, dry films and/or semiconductor photoresists.
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