WO2024067718A1 - Composé d'ester d'oxime de coumarine fonctionnalisé par éther, sa préparation et son utilisation - Google Patents

Composé d'ester d'oxime de coumarine fonctionnalisé par éther, sa préparation et son utilisation Download PDF

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WO2024067718A1
WO2024067718A1 PCT/CN2023/122137 CN2023122137W WO2024067718A1 WO 2024067718 A1 WO2024067718 A1 WO 2024067718A1 CN 2023122137 W CN2023122137 W CN 2023122137W WO 2024067718 A1 WO2024067718 A1 WO 2024067718A1
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alkyl
cycloalkyl
group
compound
optionally substituted
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PCT/CN2023/122137
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Chinese (zh)
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庞玉莲
樊书珩
邹应全
孙逊
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湖北固润科技股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
    • C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
    • C07D311/06—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2
    • C07D311/08—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 not hydrogenated in the hetero ring
    • C07D311/18—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 not hydrogenated in the hetero ring substituted otherwise than in position 3 or 7
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • 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

Definitions

  • the present invention belongs to the field of photocuring technology and relates to ether-functionalized coumarin oxime ester compounds, which can be used as photoinitiators and are particularly suitable for UV-VIS LED light source curing.
  • the present invention also relates to the preparation and application of ether-functionalized coumarin oxime ester compounds.
  • Photoinitiators also known as photosensitizers or photocuring agents, are a type of compound that can absorb energy of a certain wavelength in the ultraviolet region (250-400nm) or visible light region (400-600nm) to generate free radicals, cations, etc., thereby initiating monomer polymerization, cross-linking and curing.
  • the content of photoinitiators in the photocuring system is low, they are the key component and play a decisive role in the photocuring speed. They must also meet the needs of different photocuring conditions and applications. It is related to whether the formulation system can quickly cross-link and cure when exposed to light, thereby changing from liquid to solid.
  • UV-VIS LED light source curing technology in order to meet the wide application needs of UV-VIS LED light source curing technology, it is necessary to develop photoinitiators suitable for UV-VIS LED light sources.
  • oxime ester photoinitiators as free radical photoinitiators, have become a type of photoinitiator that has gradually received attention in recent years due to their outstanding activity and excellent photosensitivity.
  • oxime esters OXE01 and OXE02 both from BASF. These two products have excellent photoinitiator activity, but their ultraviolet absorption range is relatively short (250-350nm), which cannot meet the needs of the increasingly developed UV-VIS LED light sources, especially the needs of UV-VIS LED light sources (such as 365nm, 385nm, 395nm, 405nm, 425nm, 450nm, 475nm).
  • oxime ester photoinitiators such as CN102775527A discloses a diphenyl sulfide ketone oxime ester photoinitiator and its preparation method
  • CN102492059A discloses a substituted diphenyl sulfide ketone oxime ester photoinitiator, etc.
  • the ultraviolet absorption wavelength of most initiators also stays at 250-350nm, which still cannot match the increasingly developed long-wavelength LED light source.
  • CN104817653A discloses a coumarin aldoxime ester compound suitable for UV-LED light source curing, but studies have shown that the thermal stability of such compounds is not as good as OXE-01.
  • there are not many oxime ester photoinitiators reported for UV-VIS LED light source curing systems and the yellowing phenomenon of oxime esters has not been solved, which greatly limits the application of oxime ester photoinitiators.
  • the inventors of the present invention have conducted extensive and in-depth research on photoinitiators suitable for UV-VIS LED light source (radiation wavelength of 300-550nm, especially 365-475nm) curing, in order to find a photoinitiator that can replace OXE01 and OXE02, is more suitable for UV-VIS LED light source curing, has excellent photosensitivity, good thermal stability and solubility.
  • the inventors of the present invention surprisingly discovered that by introducing a specific ether functional group structure into a specific structure coumarin compound at a specific position, a new type of ether-functionalized coumarin oxime ester compound is formed, which has good photosensitivity absorption in the range of 300-550nm, especially in the range of 365-475nm, can rapidly undergo photochemical reaction after absorbing light energy, initiate polymerization of polymerizable monomers within seconds, and complete the polymerization reaction within 10 minutes (especially 3 minutes). Therefore, it has obvious advantages in photosensitivity, and has good thermal stability, storage stability and solubility, and is therefore suitable for use as a photoinitiator for UV-VIS LED light source curing.
  • the object of the present invention is achieved based on the above-mentioned discovery.
  • one object of the present invention is to provide an ether-functionalized coumarin oxime ester compound, the absorption wavelength of which is not only suitable for UV-VIS LED light source radiation curing, but also has good thermal stability, storage stability and solubility.
  • Another object of the present invention is to provide a method for preparing the ether-functionalized coumarin oxime ester compounds of the present invention.
  • Another object of the present invention is to provide the use of the ether-functionalized coumarin oxime ester compound of the present invention as a photoinitiator or photosensitizer.
  • M is an oxygen or sulfur atom
  • R 1 each independently represents a C 1 -C 10 alkyl group, a C 6 -C 10 aryl group or a C 2 -C 10 alkenyl group, wherein the aforementioned C 1 -C 10 alkyl group, C 6 -C 10 aryl group or C 2 -C 10 alkenyl group is optionally substituted by halogen, C 1 -C 6 alkyl group and C 1 -C 6 alkoxy(thio) group;
  • R2 each independently represents a C1 - C10 alkyl group, a C3 - C10 cycloalkyl group, a C3 - C6 cycloalkyl- C1 - C4 alkyl group or a C1 - C4 alkyl- C3 - C6 cycloalkyl group, wherein the aforementioned C1 - C10 alkyl group, C3 - C10 cycloalkyl group, C3 -C6 cycloalkyl - C1 - C4 alkyl group or C1 -C4 alkyl- C3 - C6 cycloalkyl group is optionally substituted by halogen, C1 - C6 alkyl group and C1 - C6 alkoxy(thio) group;
  • R 3 each independently represents C 4 -C 10 alkyl, C 4 -C 10 cycloalkyl, C 4 -C 6 cycloalkyl-C 1 -C 4 alkyl or C 1 -C 4 alkyl-C 4 -C 6 cycloalkyl, wherein the aforementioned C 4 -C 10 alkyl, C 4 -C 10 cycloalkyl, C 4 -C 6 cycloalkyl-C 1 -C 4 alkyl or C 1 -C 4 alkyl-C 4 -C 6 cycloalkyl is optionally substituted by halogen;
  • R 4 each independently represents hydrogen, or C 1 -C 4 alkyl optionally substituted by halogen
  • R 5 and R 6 each independently represent hydrogen, C 1 -C 10 alkyl, C 3 -C 10 cycloalkyl, C 3 -C 6 cycloalkyl-C 1 -C 4 alkyl or C 1 -C 4 alkyl-C 3 -C 6 cycloalkyl, wherein the aforementioned C 1 -C 10 alkyl, C 3 -C 10 cycloalkyl, C 3 -C 6 cycloalkyl-C 1 -C 4 alkyl or C 1 -C 4 alkyl-C 3 -C 6 cycloalkyl is optionally substituted by halogen, C 1 -C 6 alkyl and C 1 -C 6 alkoxy(thio) group;
  • R7 independently represents C1 - C10 alkyl, C3-C10 cycloalkyl, C3-C6 cycloalkyl-C1-C4 alkyl , C1 - C4 alkyl - C3 - C6 cycloalkyl or C6- C10 aryl, wherein the aforementioned C1 - C10 alkyl, C3 -C10 cycloalkyl , C3-C6 cycloalkyl-C1-C4 alkyl, C1-C4 alkyl-C3-C6 cycloalkyl or C6 - C10 aryl are optionally substituted by halogen, C1 - C6 alkyl and C1 - C6 alkoxy(thio) group.
  • R1 independently represents C1 - C8 alkyl, C6 - C8 aryl or C2 -C8 alkenyl , wherein the aforementioned C1 - C8 Alkyl, C 6 -C 8 aryl or C 2 -C 8 alkenyl is optionally substituted with halogen, C 1 -C 6 alkyl and C 1 -C 6 alkoxy(thio) groups,
  • R 1 independently represents C 1 -C 4 alkyl, phenyl or C 2 -C 4 alkenyl, wherein the aforementioned C 1 -C 4 alkyl, phenyl or C 2 -C 4 alkenyl is optionally substituted by fluorine, chlorine, bromine and C 1 -C 4 alkyl; and/or
  • R2 each independently represents a C1 - C8 alkyl group, a C3 - C8 cycloalkyl group, a C3 - C6 cycloalkyl- C1 - C2 alkyl group or a C1 - C2 alkyl- C3 - C6 cycloalkyl group, wherein the aforementioned C1 - C6 alkyl group, C3 - C8 cycloalkyl group, C3 -C6 cycloalkyl - C1 - C2 alkyl group or C1 - C2 alkyl- C3 - C6 cycloalkyl group is optionally substituted by halogen, C1 - C6 alkyl group and C1 - C6 alkoxy(thio) group,
  • R2 each independently represents C1 - C4 alkyl, C5 - C6 cycloalkyl, C5 - C6 cycloalkyl- C1 - C2 alkyl or C1 - C2 alkyl- C5 - C6 cycloalkyl, wherein the aforementioned C1 - C4 alkyl, C5 - C6 cycloalkyl, C5 - C6 cycloalkyl- C1 - C2 alkyl or C1 - C2 alkyl- C5 - C6 cycloalkyl is optionally substituted by fluorine, chlorine, bromine and C1 - C4 alkyl; and/or
  • R 4 each independently represents hydrogen or C 1 -C 4 alkyl optionally substituted by fluorine, chlorine or bromine,
  • R 4 is hydrogen; and/or
  • R 5 and R 6 each independently represent hydrogen, C 1 -C 8 alkyl, C 3 -C 8 cycloalkyl, C 3 -C 6 cycloalkyl-C 1 -C 2 alkyl or C 1 -C 2 alkyl-C 3 -C 6 cycloalkyl, wherein the aforementioned C 1 -C 6 alkyl, C 3 -C 8 cycloalkyl, C 3 -C 6 cycloalkyl-C 1 -C 2 alkyl or C 1 -C 2 alkyl-C 3 -C 6 cycloalkyl is optionally substituted by halogen, C 1 -C 6 alkyl and C 1 -C 6 alkoxy(thio) group,
  • R 5 and R 6 each independently represent hydrogen, C 1 -C 4 alkyl, C 5 -C 6 cycloalkyl, C 5 -C 6 cycloalkyl-C 1 -C 2 alkyl or C 1 -C 2 alkyl-C 5 -C 6 cycloalkyl, wherein the aforementioned C 1 -C 4 alkyl, C 5 -C 6 cycloalkyl, C 5 -C 6 cycloalkyl-C 1 -C 2 alkyl or C 1 -C 2 alkyl-C 5 -C 6 cycloalkyl is optionally substituted with fluorine,
  • R7 independently represents C1 - C8 alkyl, C3- C8 cycloalkyl, C3- C6 cycloalkyl- C1 - C2 alkyl, C1 - C2 alkyl- C3 - C6 cycloalkyl or C6- C8 aryl, wherein C1 -C4 alkyl , C3 -C8 cycloalkyl , C3-C6 cycloalkyl-C1 - C2 alkyl, C1 - C2 alkyl- C3 - C6 cycloalkyl or C6 - C8 aryl is optionally substituted by halogen, C1 - C6 alkyl and C1 - C6 alkoxy(thio) group,
  • R 7 each independently represents a C 1 -C 4 alkyl group or a phenyl group, wherein the aforementioned C 1 -C 4 alkyl group or the phenyl group is optionally substituted by fluorine, chlorine, bromine and C 1 -C 4 alkyl group.
  • R 3 each independently represents a C 4 -C 8 alkyl group, preferably a C 4 -C 6 alkyl group, especially a C 4 alkyl group, wherein the aforementioned C 4 -C 8 alkyl group, C 4 -C 6 alkyl group or C 4 alkyl group is optionally substituted by fluorine, chlorine and bromine.
  • ether functionalized coumarin oxime ester compound according to any one of items 1 to 4, wherein the ether functionalized coumarin oxime ester compound is selected from the group consisting of:
  • step (1) is carried out in the presence of one or more catalysts selected from the group consisting of: amines such as primary amines, secondary amines, tertiary amines and their corresponding ammonium salts, preferably piperidine; inorganic bases such as sodium hydroxide, sodium carbonate; inorganic salts such as potassium fluoride, aluminum phosphate, diammonium hydrogen phosphate; combinations of Lewis acids and tertiary amines such as TiCl4 /piperidine or TiCl4 /triethylamine.
  • catalysts selected from the group consisting of: amines such as primary amines, secondary amines, tertiary amines and their corresponding ammonium salts, preferably piperidine; inorganic bases such as sodium hydroxide, sodium carbonate; inorganic salts such as potassium fluoride, aluminum phosphate, diammonium hydrogen phosphate; combinations of Lewis acids and tertiary amines such as TiCl4 /pipe
  • step (2) is carried out in the presence of sodium acetate, pyridine, piperidine, triethylamine and/or tetramethylammonium hydroxide as a catalyst.
  • step (2) the molar ratio of the compound of formula (III) to hydroxylamine and/or hydroxylamine hydrochloride is 1:2.5-1.25:2, preferably 1:2.2-1.1:2.
  • the esterification in step (3) is carried out using an esterification agent selected from the compounds of the following formulae (Va), (Vb) and (Vc):
  • X is halogen, especially chlorine, and R1 is as defined in any one of items 1-5.
  • step (3) A method according to any one of items 6 to 11, wherein the esterification reaction of step (3) is carried out in the presence of one or more catalysts selected from the group consisting of sulfuric acid, perchloric acid, zinc chloride, ferric chloride, pyridine, p-toluenesulfonic acid, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium tert-butoxide, sodium ethoxide, sodium hydride, potassium hydride, calcium hydride and tertiary amines, for example trialkylamines, such as trimethylamine and triethylamine.
  • one or more catalysts selected from the group consisting of sulfuric acid, perchloric acid, zinc chloride, ferric chloride, pyridine, p-toluenesulfonic acid, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium tert-butoxide, sodium ethoxide, sodium hydride, potassium hydride
  • step (3) the molar ratio of the compound of formula (IV) to the esterification agent selected from the compounds of formula (Va), (Vb) and (Vc) is 1:1.2-1:2.0, preferably 1:1.4-1:1.8.
  • ether functionalized coumarin oxime ester compound obtained according to any one of items 1 to 5 or according to any one of items 6 to 13 as a photoinitiator, especially use as a photoinitiator in a UV-VIS LED light source curing system, especially use as a photoinitiator in a light source curing system with a radiation wavelength of 300-550nm, especially 365-475nm.
  • a photocurable composition comprising at least one ether-functionalized coumarin oxime ester compound obtained according to any one of items 1 to 5 or according to the process of any one of items 6 to 13.
  • a cured material obtainable from the photocurable composition of item 15.
  • a method for preparing a photocurable material which comprises irradiating the photocurable composition of item 15 with a light source having a radiation wavelength of 300-550 nm, especially 365-475 nm, such as a UV-VIS LED light source.
  • FIG1 is a schematic diagram of a Ugra exposure test strip, wherein
  • M is an oxygen or sulfur atom
  • R 1 each independently represents a C 1 -C 10 alkyl group, a C 6 -C 10 aryl group or a C 2 -C 10 alkenyl group, wherein the aforementioned C 1 -C 10 alkyl group, C 6 -C 10 aryl group or C 2 -C 10 alkenyl group is optionally substituted by halogen, C 1 -C 6 alkyl group and C 1 -C 6 alkoxy(thio) group;
  • R2 each independently represents a C1 - C10 alkyl group, a C3 - C10 cycloalkyl group, a C3 - C6 cycloalkyl- C1 - C4 alkyl group or a C1 - C4 alkyl- C3 - C6 cycloalkyl group, wherein the aforementioned C1 - C10 alkyl group, C3 - C10 cycloalkyl group, C3 -C6 cycloalkyl - C1 - C4 alkyl group or C1 -C4 alkyl- C3 - C6 cycloalkyl group is optionally substituted by halogen, C1 - C6 alkyl group and C1 - C6 alkoxy(thio) group;
  • R 3 each independently represents C 4 -C 10 alkyl, C 4 -C 10 cycloalkyl, C 4 -C 6 cycloalkyl-C 1 -C 4 alkyl or C 1 -C 4 alkyl-C 4 -C 6 cycloalkyl, wherein the aforementioned C 4 -C 10 alkyl, C 4 -C 10 cycloalkyl, C 4 -C 6 cycloalkyl-C 1 -C 4 alkyl or C 1 -C 4 alkyl-C 4 -C 6 cycloalkyl is optionally substituted by halogen;
  • R 4 each independently represents hydrogen or C 1 -C 4 alkyl optionally substituted by halogen
  • R 5 and R 6 each independently represent hydrogen, C 1 -C 10 alkyl, C 3 -C 10 cycloalkyl, C 3 -C 6 cycloalkyl-C 1 -C 4 alkyl or C 1 -C 4 alkyl-C 3 -C 6 cycloalkyl, wherein the aforementioned C 1 -C 10 alkyl, C 3 -C 10 cycloalkyl, C 3 -C 6 cycloalkyl-C 1 -C 4 alkyl or C 1 -C 4 alkyl-C 3 -C 6 cycloalkyl is optionally substituted by halogen, C 1 -C 6 alkyl and C 1 -C 6 alkoxy(thio) group;
  • R7 independently represents C1 - C10 alkyl, C3-C10 cycloalkyl, C3-C6 cycloalkyl-C1-C4 alkyl , C1 - C4 alkyl - C3 - C6 cycloalkyl or C6- C10 aryl, wherein the aforementioned C1 - C10 alkyl, C3 -C10 cycloalkyl , C3-C6 cycloalkyl-C1-C4 alkyl, C1-C4 alkyl-C3-C6 cycloalkyl or C6 - C10 aryl are optionally substituted by halogen, C1 - C6 alkyl and C1 - C6 alkoxy(thio) group.
  • the specific ether-functionalized coumarin oxime ester compound of formula (I) of the present invention contains both a coumarin-based structural part and an oxime ester structural part.
  • the compound has good photosensitivity absorption in the range of 300-550nm, especially 365-475nm, and can rapidly undergo cleavage to generate active free radicals after absorbing light energy, continuously initiate polymerization, initiate polymerization of polymerizable monomers within a few seconds, and The polymerization reaction is completed within 10 minutes (especially 3 minutes), so it has obvious advantages in photosensitivity, and has good thermal stability, storage stability and solubility, so it is suitable for use as a photoinitiator for UV-VIS LED light source curing.
  • C n -C m denotes in each case that the number of carbon atoms contained in the group is nm.
  • Halogen refers to fluorine, chlorine, bromine and iodine. In the present invention, it is preferred that halogen is fluorine, chlorine, bromine or a combination thereof.
  • Cn - Cm- alkyl refers to a branched or unbranched saturated hydrocarbon group having nm, e.g. 1 to 10, carbon atoms, for example methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, tert-butyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, tert-butyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, 1,1-dimethylpropyl,
  • C6 - Cm aryl refers to a monocyclic or bicyclic aromatic hydrocarbon group containing 6 to m carbon atoms, such as 6 to 10 carbon atoms, for example phenyl, tolyl, ethylphenyl, propylphenyl, butylphenyl, xylyl, methylethylphenyl, diethylphenyl, methylpropylphenyl, naphthyl and isomers thereof.
  • C2 - Cm alkenyl refers to a branched or unbranched unsaturated hydrocarbon group having 2 to m, for example 2 to 10 carbon atoms, and having one double bond located at any position, for example ethenyl, 1-propenyl, 2-propenyl, 1-methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl and isomers thereof, etc.
  • C 3 -C m cycloalkyl refers to a saturated alicyclic monocyclic group having 3-m, such as 3-10, ring carbon atoms, for example cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl and isomers thereof.
  • C 3 -C m cycloalkyl-C n -C m alkyl refers to a C n -C m alkyl substituted by a C 3 -C m cycloalkyl. wherein the two m's are the same or different, wherein the definitions of Cn - Cm- alkyl and C3 - Cm- cycloalkyl are applicable to the definitions herein.
  • C3 - Cm- cycloalkyl- Cn - Cm- alkyl may be C3 - C6 -cycloalkyl- C1 - C4 -alkyl, for example, cyclopropylmethyl, cyclopropylethyl, cyclopropylpropyl, cyclopropylbutyl, cyclobutylmethyl, cyclobutylethyl, cyclobutylpropyl, cyclobutylbutyl, cyclopentylmethyl, cyclopentylethyl, cyclopentylpropyl, cyclopentylbutyl, cyclohexylmethyl, cyclohexylethyl, cyclohexylpropyl, cyclohexylbutyl and isomers thereof.
  • Cn - Cm- alkyl- C3 - Cm- cycloalkyl refers to a C3 - Cm- cycloalkyl substituted by a Cn - Cm- alkyl group, where two m's may be the same or different, and the definitions of Cn - Cm -alkyl and C3- Cm- cycloalkyl herein apply.
  • the Cn - Cm - alkyl- C3 - Cm- cycloalkyl group may be a C1 - C4 -alkyl- C3 - C6 -cycloalkyl group, such as a methylcyclopropyl group, an ethylcyclopropyl group, a propylcyclopropyl group, a butylcyclopropyl group, a methylcyclobutyl group, an ethylcyclobutyl group, a propylcyclobutyl group, a butylcyclobutyl group, a methylcyclopentyl group, an ethylcyclopentyl group, a propylcyclopentyl group, a butylcyclopentyl group, a methylcyclohexyl group, an ethylcyclohexyl group, a propylcyclohexyl group, a butylcyclohexyl
  • C n -C m alkoxy (thio) group as used herein includes “C n -C m alkoxy” and "C n -C m alkylthio group", which refers to a C n -C m alkyl group with an oxygen atom or a sulfur atom as a linking group bonded to any carbon atom of an open-chain C n -C m alkane corresponding to the C n -C m alkyl group, such as a C 1 -C 6 alkoxy (thio) group, for example, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a n-butoxy group, a 2-butoxy group, a tert-butoxy group, a pentyloxy group, an isopentyloxy group, a hexyloxy group and isomers thereof.
  • the C 1 -C 8 alkylthio group can be a methylthio group, an ethylthio group, a propylthio group, an isopropylthio group, a n-butylthio group, a 2-butylthio group, a tert-butylthio group, a pentylthio group, an isopentylthio group, a hexylthio group and isomers thereof, and the like.
  • R 1 independently represents C 1 -C 8 alkyl, C 6 -C 8 aryl or C 2 -C 8 alkenyl, wherein the aforementioned C 1 -C 8 alkyl, C 6 -C 8 aryl or C 2 -C 8 alkenyl is optionally substituted by halogen, C 1 -C 6 alkyl and C 1 -C 6 alkoxy(thio) group;
  • R 1 independently represents C 1 -C 4 alkyl, phenyl or C 2 -C 4 alkenyl, wherein the aforementioned C 1 -C 4 alkyl, phenyl or C 2 -C 4 alkenyl is optionally substituted by fluorine, chlorine, bromine and C 1 -C 4 alkyl.
  • R2 independently represents C1 - C8 alkyl, C3 - C8 cycloalkyl, C3- C6 cycloalkyl- C1 -C2 alkyl or C1 - C2 alkyl- C3 - C6 cycloalkyl, wherein the aforementioned C1 - C6 alkyl, C3 - C8 cycloalkyl, C3- C6 cycloalkyl- C1 -C2 alkyl or C1 - C2 alkyl- C3 - C6 cycloalkyl
  • the alkyl group is optionally substituted with halogen, C 1 -C 6 alkyl and C 1 -C 6 alkoxy(thio) group.
  • R2 each independently represents a C1 - C4 alkyl group, a C5 - C6 cycloalkyl group, a C5 - C6 cycloalkyl- C1 - C2 alkyl group or a C1 - C2 alkyl- C5 - C6 cycloalkyl group, wherein the aforementioned C1 - C4 alkyl group, C5 - C6 cycloalkyl group, C5 - C6 cycloalkyl- C1 - C2 alkyl group or C1 - C2 alkyl- C5 - C6 cycloalkyl group is optionally substituted by fluorine, chlorine, bromine and C1 - C4 alkyl group.
  • R 4 each independently represents hydrogen or C 1 -C 4 alkyl optionally substituted by fluorine, chlorine or bromine.
  • R4 is hydrogen
  • R 5 and R 6 each independently represent hydrogen, C 1 -C 8 alkyl, C 3 -C 8 cycloalkyl, C 3 -C 6 cycloalkyl-C 1 -C 2 alkyl or C 1 -C 2 alkyl-C 3 -C 6 cycloalkyl, wherein the aforementioned C 1 -C 6 alkyl, C 3 -C 8 cycloalkyl, C 3 -C 6 cycloalkyl-C 1 -C 2 alkyl or C 1 -C 2 alkyl-C 3 -C 6 cycloalkyl are optionally substituted by halogen, C 1 -C 6 alkyl and C 1 -C 6 alkoxy(thio) group.
  • R5 and R6 each independently represent hydrogen, C1 - C4 alkyl, C5 - C6 cycloalkyl, C5 - C6 cycloalkyl- C1 - C2 alkyl or C1 - C2 alkyl- C5 - C6 cycloalkyl, wherein the aforementioned C1 - C4 alkyl, C5 - C6 cycloalkyl, C5 - C6 cycloalkyl- C1 - C2 alkyl or C1 - C2 alkyl- C5 - C6 cycloalkyl are optionally substituted by fluorine, chlorine and bromine.
  • R7 independently represents C1 - C8 alkyl, C3 - C8 cycloalkyl, C3- C6 cycloalkyl- C1 - C2 alkyl, C1 - C2 alkyl- C3 - C6 cycloalkyl or C6 - C8 aryl, wherein C1 -C4 alkyl , C3 - C8 cycloalkyl, C3 -C6 cycloalkyl - C1 - C2 alkyl, C1 - C2 alkyl- C3 - C6 cycloalkyl or C6 - C8 aryl are optionally substituted by halogen, C1 - C6 alkyl and C1 - C6 alkoxy(thio)yl.
  • R 7 each independently represents a C 1 -C 4 alkyl group or a phenyl group, wherein the aforementioned C 1 -C 4 alkyl group or the phenyl group is optionally substituted by fluorine, chlorine, bromine and C 1 -C 4 alkyl group.
  • R 3 each independently represents a C 4 -C 8 alkyl group, preferably a C 4 -C 6 alkyl group, especially a C 4 alkyl group, wherein the aforementioned C 4 -C 8 alkyl group, C 4 -C 6 alkyl group, or C 4 alkyl group is optionally substituted by fluorine, chlorine and bromine.
  • R 3 is tert-butyl
  • the compound of formula (I) of the present invention is selected from the compounds 1 to 68 shown above.
  • Compounds 1 to 68 are prepared in Examples 1 to 68, respectively.
  • a method for preparing the compound of formula (I) of the present invention comprises the following steps:
  • the Knoevenagel condensation reaction is routine for those skilled in the art.
  • the specific compound of formula (II) is a benzene ring structure containing adjacent hydroxyl and carbonyl groups, and is synthesized into aromatic compounds by Knoevenagel condensation reaction.
  • a catalyst suitable for the Knoevenagel condensation reaction is usually carried out in the presence of a catalyst suitable for the Knoevenagel condensation reaction.
  • catalysts amines such as primary amines, secondary amines, tertiary amines and their corresponding ammonium salts, preferably piperidine; inorganic bases such as sodium hydroxide, sodium carbonate; inorganic salts such as potassium fluoride, aluminum phosphate, diammonium hydrogen phosphate; Lewis acid and tertiary amine combinations such as TiCl 4 /piperidine or TiCl 4 /triethylamine are usually used.
  • the amount of catalyst used is conventional and can be determined by common sense in the art or by a few routine preliminary experiments.
  • the above-mentioned Knoevenagel condensation reaction is usually carried out in a solvent, preferably in an organic solvent, preferably in an aprotic solvent.
  • a solvent preferably in an organic solvent, preferably in an aprotic solvent.
  • the solvent that can be used includes, for example, ethanol, ether, dimethyl sulfoxide, toluene, N,N-dimethylformamide or acetone, preferably ethanol.
  • the temperature range of the Knoevenagel condensation reaction is usually 40-120° C., preferably 60-90° C.
  • the reaction time is not particularly limited, and is usually 3-20 hours, preferably 3-10 hours.
  • the reaction solution is washed with water first, and then the residual organic solvent is removed.
  • the organic solvent can usually be removed by normal pressure or reduced pressure distillation.
  • a crude product of the compound of formula (III) is obtained. If you want to further improve the purity of the compound of formula (III), the compound can also be further purified, which can be carried out by recrystallization, for example.
  • the selection of the recrystallization solvent is conventional and has no particular restrictions. According to the present invention, it is advantageous to use ethanol to recrystallize the crude product of the compound of formula (III).
  • the oximation reaction usually uses hydroxylamine hydrochloride (NH 2 OH ⁇ HCl), hydroxylamine (NH 2 OH) or a mixture thereof as an oximation agent.
  • the oximation reaction is usually carried out in an organic solvent, preferably in a polar organic solvent.
  • the solvent that can be used is, for example, ethanol or aqueous ethanol.
  • a catalyst such as sodium acetate, pyridine, piperidine, triethylamine, tetramethylammonium hydroxide or a mixture thereof is generally added.
  • pyridine, piperidine, triethylamine can also be used as a base and/or solvent or cosolvent.
  • the relative amounts of the compound of formula (III) and hydroxylamine and/or hydroxylamine hydrochloride There is no particular restriction on the relative amounts of the compound of formula (III) and hydroxylamine and/or hydroxylamine hydrochloride. Usually, the molar ratio between the two is 1:2.5-1.25:2, preferably 1:2.2-1.1:2, for example about 1:2.
  • the temperature range of the above oximation reaction is usually 30-120° C., preferably 40-90° C.
  • the oximation reaction time is not particularly limited, and is usually 0.1-20 hours, preferably 0.3-10 hours.
  • the esterification of the compound of formula (IV) is conventional to those skilled in the art, and by this reaction, the hydroxyl group in the oxime group is converted into an ester group, thereby obtaining the compound of formula (I).
  • an esterifying agent there is no particular limitation, as long as the hydroxyl group in the oxime group of the compound of formula (IV) can be converted into an ester group.
  • corresponding acyl halides such as acyl chlorides, corresponding carboxylic acids, and corresponding acid anhydrides can be used.
  • These compounds can be represented by compounds of formula (Va), (Vb) and (Vc), respectively:
  • the above esterification reaction is usually carried out in the presence of a catalyst suitable for the esterification reaction.
  • a catalyst suitable for the esterification reaction.
  • an acidic catalyst or a basic catalyst can be used.
  • the amount of catalyst used is conventional and can be determined by common sense in the art or by a few routine preliminary experiments.
  • the above esterification reaction is usually carried out in a solvent, preferably an organic solvent.
  • a solvent preferably an organic solvent.
  • solvent type there is no particular restriction on the choice of solvent type, as long as it can dissolve the compound of formula (IV) and the esterification agent and is chemically inert to the esterification reaction, that is, it does not participate in the esterification reaction.
  • solvents tetrahydrofuran, benzene, toluene, N,N-dimethylformamide, dichloromethane and acetone can be mentioned.
  • the solvent can use a single solvent or a mixture of two or more solvents.
  • the molar ratio between the two is 1:1.2-1:2.0, preferably 1:1.4-1:1.8, for example about 1:1.6.
  • the esterification reaction can be carried out in a very wide temperature range. According to the present invention, it is advantageous that the esterification reaction is carried out at a temperature of -10°C to 150°C, preferably 0°C to 100°C, preferably at room temperature. There is no particular restriction on the esterification reaction time, which is usually 0.5-24 hours, preferably 0.8-12 hours.
  • the esterification reaction After the esterification reaction is completed, a reaction mixture containing the compound of formula (I) is obtained. Therefore, it is necessary to post-treat the reaction mixture to obtain a purified compound of formula (I).
  • the reaction mixture obtained by the esterification reaction is first filtered and the filtrate portion is taken out. Then, the filtrate is washed to remove the catalyst and unreacted raw materials.
  • a washing liquid there is no particular restriction, as long as the catalyst and unreacted raw materials can be removed.
  • washing liquids dilute hydrochloric acid (aqueous solution), saturated sodium bicarbonate aqueous solution and water can be mentioned.
  • washing liquid can be performed once or multiple times; in the case of multiple times, a single washing liquid can be used, or different washing liquids can be used in sequence.
  • the filtrate obtained by filtering the reaction mixture obtained by the esterification reaction is washed with dilute hydrochloric acid, saturated sodium bicarbonate aqueous solution and water in sequence.
  • anhydrous sodium sulfate can usually be used for drying. After drying, the residual organic solvent is removed. As the means for removing the organic solvent here, there is no particular restriction, and the organic solvent can usually be removed by distillation under reduced pressure. After removing the residual organic solvent, a crude product of the compound of formula (I) is obtained. If you want to further improve the purity of the compound of formula (I), the compound can also be further purified, for example, by means of recrystallization. The selection of the recrystallization solvent is conventional and has no particular restrictions. According to the present invention, it is advantageous to recrystallize the crude product of the compound of formula (I) using petroleum ether, methanol, ethanol or a mixture thereof.
  • the oxime ester group may exist in two configurations, namely (Z) type or (E) type.
  • the isomers can be separated by conventional methods, but isomer mixtures can also be used as photoinitiator substances. Therefore, the present invention also relates to mixtures of configurational isomers of the compound of formula (I).
  • the compound of formula (I) of the present invention has strong absorption in the wavelength range of 300-550nm, especially in the wavelength range of 365-475nm, so it can be used as a photoinitiator in UV-VIS LED light curing technology, especially suitable for long-wavelength UV-VIS LED light source curing.
  • the compound of formula (I) of the present invention is safe and non-toxic, and compared with traditional photoinitiators, it has less harm to the human body and the environment, and can also be used in the fields of food packaging.
  • the compound of formula (I) of the present invention as a photoinitiator.
  • the compound of formula (I) of the present invention can be used as a photoinitiator in UV-VIS LED photocuring technology, and can effectively initiate the curing reaction.
  • Particularly preferred is the use of the compound of formula (I) of the present invention as a photoinitiator in a photocuring system with a radiation wavelength of 300-550nm, especially 365-475nm.
  • the compound of formula (I) of the present invention can also be used as a photoinitiator or photosensitizer in the fields of coatings, inks, microelectronics, printing, etc.
  • the amount used is conventional, or can be determined by routine preliminary tests.
  • the present invention also relates to a photocurable composition
  • a photocurable composition comprising the ether-functionalized coumarin oxime ester compound of the present invention.
  • the amount of the photoinitiator of the present invention is generally 0.01 to 10% by weight, preferably 0.1 to 6% by weight, such as 0.2 to 5% by weight, based on the amount of active ingredients of the photocurable composition.
  • active ingredients refer to ingredients in the photocurable composition other than the solvent.
  • the photocurable composition further comprises a photocurable resin.
  • the photocurable resin refers to an oligomer or prepolymer containing unsaturated carbon-carbon double bonds. After being irradiated with light, the oligomer or prepolymer can be polymerized by a photoinitiator, and then cross-linked and cured.
  • the photocurable resin is the main component of photocurable products (such as UV coatings, UV inks, UV adhesives, etc.).
  • epoxy (meth) acrylate resin there may be mentioned epoxy (meth) acrylate resin, polyester (meth) acrylate, polyurethane (meth) acrylate, ethylenically unsaturated polyester, amino (meth) acrylate resin, photoimageable alkali-soluble resin, etc.
  • epoxy (meth) acrylate resin, polyester (meth) acrylate, polyurethane (meth) acrylate or a combination thereof is used.
  • the epoxy (meth) acrylate resin is preferably bisphenol A epoxy (meth) acrylate, bisphenol A epoxy acrylate diluted with tripropylene glycol di(meth) acrylate or a combination thereof, such as bisphenol A epoxy acrylate WSR-U125 from Wuxi Resin Factory, bisphenol A epoxy acrylate 621A-80 diluted with 20% tripropylene glycol diacrylate from Taiwan Changxing Chemical Company, modified bisphenol A epoxy acrylate 623-100 from Taiwan Changxing Chemical Company, and modified bisphenol A epoxy acrylate 6231A-80 diluted with 20% tripropylene glycol diacrylate from Taiwan Changxing Chemical Company.
  • the polyester (meth)acrylate is preferably a hyperbranched polyester acrylic resin with high functionality, especially a hyperbranched polyester acrylic resin with a functionality of 5 to 30, such as a hyperbranched polyester acrylate prepolymer with a functionality of 6 to 20.
  • hyperbranched polyester acrylate prepolymer 932-100 (functionality 6) of Wuxi Knox Company hyperbranched polyester acrylate prepolymer CN2300 (functionality 8), CN2301 (functionality 9), CN2302 (functionality 16) of American Sartomer Company, etc. can be mentioned.
  • the polyurethane (meth)acrylate is preferably an aliphatic polyurethane acrylate resin, and examples thereof include aliphatic polyurethane acrylate CN9013 (9-functionality) from Sartomer, USA, aliphatic polyurethane acrylate CN966B85 (2-functionality) diluted with 15% 1,6-hexanediol diacrylate (HDDA) from Sartomer, USA, and aliphatic polyurethane acrylate CN962 (2-functionality).
  • the photocurable resin is generally used in the photocurable composition in an amount of 10-90 wt%, preferably 55-80 wt%, based on the amount of active ingredients in the photocurable composition.
  • active ingredients refer to ingredients in the photocurable composition excluding solvents.
  • the photocurable composition may further include a multifunctional reactive diluent.
  • the multifunctional active diluent refers to a monomer containing two or more photopolymerizable groups.
  • the multifunctional active diluent has a low viscosity and a strong dissolving ability. After being irradiated by a light source, the multifunctional active diluent can be polymerized by active free radicals to form a cross-linked network structure.
  • the multifunctional reactive diluent is a multifunctional (meth)acrylate reactive diluent. It refers to a monomer containing two or more (meth)acrylate polymerizable groups.
  • multifunctional (meth)acrylate crosslinking agents trimethylolpropane triacrylate (TMPTA), pentaerythritol tetraacrylate (PETTA), propoxylated trimethylolpropane triacrylate (PO-TMPTA) or ethoxylated trimethylolpropane triacrylate (EO-TMPTA), pentaerythritol triacrylate (PETA), pentaerythritol tetraacrylate (PETTA), dipentaerythritol pentaacrylate (DPEPA), dipentaerythritol hexaacrylate (DPHA), tripropylene glycol diacrylate (TPGDA), 1,6-hexanediol di
  • the amount of the multifunctional reactive diluent used in the photocurable composition is usually 8 to 60% by weight, preferably 15 to 45% by weight, based on the amount of the active ingredients in the photocurable composition.
  • the photocurable composition may further include a monofunctional reactive diluent.
  • a monofunctional reactive diluent refers to a monomer containing a photopolymerizable group. It has a low viscosity and a strong solubility, and can act as a part of an organic solvent. After being irradiated by a light source, the monofunctional reactive diluent can be initiated to undergo polymerization by active free radicals.
  • Monofunctional reactive diluents mainly include (meth) acrylate compounds and vinyl compounds.
  • acrylate monofunctional reactive diluents methyl methacrylate (MMA), n-butyl acrylate (BA), isooctyl acrylate (2-EHA), isodecyl acrylate (IDA), lauryl acrylate (LA), hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and some (meth) acrylates with cyclic structures can be mentioned.
  • vinyl monofunctional reactive diluents styrene (St), vinyl acetate (VA), N-vinyl pyrrolidone (NVP), etc. can be mentioned.
  • the monofunctional reactive diluent is generally used in the photocurable composition in an amount of 5 to 50% by weight, preferably 8 to 40% by weight, based on the amount of the active ingredients in the photocurable composition.
  • the photocurable composition of the present invention may also optionally contain an organic solvent.
  • organic solvent is conventional.
  • organic solvent mention may be made of aromatic hydrocarbons such as benzene, toluene, halogenated alkanes such as tris(III), Methyl chloride, dichloromethane, ethyl chloride, ketones such as acetone, butanone, pentanone, etc., alcohols such as methanol, ethanol, propanol, isopropanol, ethylene glycol, and ethylene glycol ethers, ethylene glycol ether acetates, propylene glycol ethers, propylene glycol ether acetates, etc.
  • the photocurable composition of the present invention may also optionally contain other additives, such as leveling agents, antioxidants, anti-settling agents, colorants, microbicides, such as antibacterial agents and thermal insulation material additives.
  • the leveling agent is selected from the group consisting of A series of leveling agents, particularly preferably 360S, 372S, 384S, 392S, 400U, 415U, etc.
  • the preparation of the photocurable composition of the present invention is conventional, for example, the various components of the photocurable composition of the present invention are uniformly mixed together.
  • another aspect of the present invention also provides a cured material obtainable from the photocurable composition of the present invention.
  • the obtained cured material can be a photocurable coating, which includes a coating containing a functional material, a coating of a color filter of UV light and/or visible light; a sealant; a photolithographic material; a holographic recording material; a 3D printing material; a lithographic material; a material for preparing an optical device and a material for improving mechanical properties, such as a carbon fiber composite material and/or an inorganic nanoparticle and/or an organic nanoparticle, etc.
  • the present invention also relates to a method for preparing a photocurable material, which comprises irradiating the photocurable composition with a light source having a radiation wavelength of 300-550nm, especially 365-475nm, such as a UV-VIS LED light source.
  • the compound disclosed in the present invention has a simple production process and a high yield, and is very suitable for industrial production.
  • Such compounds have a good match with UV-VIS LED light sources with a radiation wavelength of 300-550nm, especially 365-475nm, and can be widely used as photoinitiators in fields involved in UV-VIS LED photocuring, such as coatings, inks, microelectronics, printing, 3D printing, dental materials and other fields. Therefore, the ether-functionalized coumarin oxime ester photoinitiator of the present invention has a good market prospect.
  • the ether-functionalized coumarin oxime ester photoinitiator of the present invention can contribute to promoting the widespread application of green and environmentally friendly UV-VIS LED light sources in the UV photocuring industry.
  • the intermediate compound 1b (8.67 g, 0.03 mol) and 50 ml of dichloromethane were added to a 100 mL three-necked round-bottom flask, and then acetyl chloride (3.53 g, 0.045 mol) and triethylamine (5.46 g, 0.054 mol) were added, and the reaction was stirred at room temperature for 1.5 h. The reaction was terminated, and the reaction solution was filtered, and the filtrate was poured into water and extracted with ethyl acetate. After the organic phase was collected, it was washed with dilute hydrochloric acid solution, saturated sodium carbonate solution, and distilled water in sequence, and then the organic phase was collected and dried overnight with MgSO 4. After filtering, the organic phase was evaporated by reduced pressure distillation to obtain 8.94 g of yellow powder solid, with a yield of 90.0%, which was identified as compound 1.
  • the NMR data of compound 1 are shown in Table 1.
  • Example 1 The method of Example 1 was repeated, and the reaction raw materials were appropriately changed to obtain compounds 2-68 and their NMR data shown in Table 1 below.
  • the Ugra test strip is used as a mask to test the photosensitivity of the photoinitiator.
  • the sections of the Ugra test strip are shown in Figure 1.
  • the Ugra test strip is divided into 5 control sections, from left to right: continuous density scale section (1); positive and negative micrometer equal lines concentric circle coil section (2); full-scale dot section (3); ghosting control section (4); highlight and dark tone control section (5).
  • Section 1 The continuous density scale section is divided into 13 gradients to control exposure and development.
  • Section 2 The positive and negative micrometer equal lines concentric circle coil section consists of 12 positive and negative micrometer equal lines, which are 4, 6, 8, 10, 12, 15, 20, 25, 30, 40, 55, and 70 respectively, which is used to detect the exposure and development of PS plates.
  • the third section The full-scale dot section is composed of a flat screen with a range of 10%-100% and a range of 10%, which is arranged in two rows, upper and lower, and is used to measure the dot transfer of exposure, proofing and printing, and can measure the film dot and exposure, proofing and printing dot change curve.
  • the fourth section The ghost control section is composed of fine lines with a line width of 60 lines/cm and an area rate of 60%. It is divided into 4 small blocks, with lines arranged at three angles of 0°, 45°, and 90°, and a 1/4 D small block with small short lines arranged at 90° on both sides, 45° in the middle small square, and 90° up and down.
  • the fifth section Highlight and dark tone control section, the fine dot section is composed of small highlight dots and dark tone deep dots arranged correspondingly, which is used to finely control the accuracy of exposure and development of exposure.
  • the photocurable composition containing a photoinitiator is coated on an aluminum substrate, and then exposed and developed. The sensitivity is evaluated from the continuous gradient scale of the obtained image, and the accuracy is evaluated from the micro-line test block area, thereby evaluating the quality of the photocurable composition formula.
  • a photocurable composition containing a photoinitiator is prepared according to the following composition:
  • the photoinitiator in the above composition is the compound of formula (I) of the present invention or a photoinitiator known in the prior art (for comparison) (see below and Table 2 for details).
  • the acrylate resin is a resin purchased from Shanghai Fushun International Trading Co., Ltd. under the trade name FS2600K, with a functionality of 2 and a number average molecular weight of 1400.
  • Dipentaerythritol hexaacrylate is a resin purchased from Shanghai Fushun International Trading Co., Ltd. under the trade name
  • Crystal violet dye is a product of hexamethylmelaniline hydrochloride purchased from Shanghai National Pharmaceutical.
  • Aluminum base size 1030mm ⁇ 800mm
  • the speed of the centrifugal coater was controlled to make the coating amount (in terms of solid content) on the aluminum substrate 1.0-2.5 g/ m2 . After preliminary drying on the centrifugal coater, it was transferred to a 100°C blast dryer for drying for 3 minutes to obtain a purple laser CTP original. Then, the Ugra test strip was used as a mask to test the photosensitivity of the plate material, and after exposure for a period of time, it was developed with a 1% NaOH aqueous solution.
  • the photopolymerizable compound undergoes a polymerization reaction in the presence of a photoinitiator and is insoluble in the developer, while the non-exposed area is soluble, thus obtaining a negative image.
  • the sensitivity of the photoinitiator is evaluated from the continuous gradient scale of the obtained image through exposure and development.
  • the sensitivity characteristic of the initiator system is the highest grayscale number retained (i.e., polymerized) after development. The higher the grayscale number, the higher the sensitivity of the test system. The results are shown in Table 2.
  • the ether-functionalized coumarin oxime ester photoinitiator of the present invention has better photosensitivity at wavelengths of 365nm, 385nm, 400nm, 425nm, 450nm, 475nm and 500nm, and is suitable for UV-VIS LED light sources of 365nm, 385nm, 400nm, 425nm, 450nm, 475nm and 500nm.
  • the Fourier transform infrared-real-time infrared method was used to test the changes in the characteristic peak area of the infrared spectrum of the carbon-carbon double bond of the acrylate resin initiated by the photoinitiator to test the photosensitivity of the photoinitiator.
  • the carbon-carbon double bond conversion rate of the acrylate resin when it was exposed for 30 seconds is shown in Table 3.
  • the carbon-carbon double bond conversion rate of the acrylate resin is reflected by the change in the characteristic peak area of the infrared spectrum.
  • the selected characteristic peak area is located at 1653-1603cm -1 . According to the carbon-carbon double bond conversion rate changes with time under different test conditions The photoinitiator performance under different conditions was evaluated.
  • a photocurable composition containing a photoinitiator is prepared according to the following composition:
  • the photoinitiator in the above composition is the compound of formula (I) of the present invention or a photoinitiator known in the prior art (for comparison).
  • the acrylate resin is a resin with a trade name of FS2600K purchased from Shanghai Fushun International Trading Co., Ltd., with a functionality of 2 and a number average molecular weight of 1400.
  • the photocurable composition is injected into a pre-treated KBr double salt sheet mold that meets the following conditions using a syringe:
  • KBr double salt tablet size 15mm ⁇ 15mm
  • the amount of the photocurable composition injected into the KBr double salt sheet mold was made to be 0.2 ml.
  • the KBr double salt sheet mold was placed in a small black box in a Fourier transform infrared spectrometer used for real-time infrared testing.
  • the structure of the small black box was that the upper infrared test light was vertically aligned to penetrate the KBr double salt sheet mold, and a 45° LED point light source above the KBr double salt sheet mold was aligned with the KBr double salt sheet mold, and the LED point light source was 1 cm high from the KBr double salt sheet mold.
  • the infrared spectrum detection and the LED light source are simultaneously started, so that the photocurable composition in the KBr double salt sheet mold can be exposed while the change of the characteristic peak area of the carbon-carbon double bond is detected.
  • the photopolymerizable compound Under the irradiation of the LED point light source, the photopolymerizable compound undergoes a polymerization reaction in the presence of an initiator, causing the characteristic peak area of the carbon-carbon double bond to continuously decrease until it basically disappears. Based on the data of the change in the characteristic peak area of the carbon-carbon double bond with the exposure time, the conversion rate of the carbon-carbon double bond with time is calculated. The results when exposed for 30 seconds are shown in Table 3.
  • Example Compound 1-68 of the present invention at 365nm, 385nm, 400nm, 425nm, 450nm and 475nm are higher than those of BASF's commercially available oxime esters OXE-01, OXE-02 and OXE-03, and are also higher than those of oxime esters COXE-08, COXE-09, COXE-19, COXE-31, COXE-35, COXE-37, COXE-41 and COXE-48 disclosed in the prior art.
  • the ether-functionalized coumarin oxime ester photoinitiator of the present invention has better photosensitivity at wavelengths of 365nm, 385nm, 400nm, 425nm, 450nm and 475nm, and is suitable for use in UV-VIS LED light sources of 365nm, 385nm, 400nm, 425nm, 450nm and 475nm.
  • the ether-functionalized coumarin oxime ester photoinitiator of the present invention has good photosensitivity at wavelengths of 365nm, 385nm, 400nm, 425nm, 450nm and 475nm, which is better than the commercially available oxime esters OXE-01, OXE-02 and OXE-03 of BASF at this stage, and is also better than the oxime esters COXE-08, COXE-09, COXE-19, COXE-31, COXE-35, COXE-37, COXE-41 and COXE-48 disclosed in the prior art, especially at wavelengths of 425nm, 450nm and 475nm, the photosensitivity has obvious advantages in the visible light region.

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Abstract

La présente invention concerne un composé ester d'oxime de coumarine fonctionnalisé par un éther de formule (I), les variables étant telles que définies dans la description. Le composé présente une bonne absorption photosensible dans la plage de 300 à 550 nm, en particulier dans la plage de 365 à 450 nm ; après absorption de l'énergie lumineuse, le composé peut rapidement subir une réaction photochimique, initier la polymérisation de monomères polymérisables en plusieurs secondes, et achever une réaction de polymérisation en 10 minutes (en particulier en 3 minutes) ; et le composé présente des avantages significatifs dans l'aspect de la photosensibilité, et présente une bonne stabilité thermique, une bonne stabilité au stockage et une bonne solubilité, étant ainsi applicable en tant que photo-initiateur pour le durcissement avec une source de lumière à DEL UV-VIS. La présente invention concerne en outre un procédé de préparation et l'utilisation du composé ester d'oxime de coumarine fonctionnalisé par un éther de formule (I). Le composé peut servir de photo-initiateur et est particulièrement applicable au durcissement avec une source de lumière à DEL UV-VIS.
PCT/CN2023/122137 2022-09-28 2023-09-27 Composé d'ester d'oxime de coumarine fonctionnalisé par éther, sa préparation et son utilisation WO2024067718A1 (fr)

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