WO2024067718A1 - Ether-functionalized coumarin oxime ester compound, and preparation and use thereof - Google Patents

Ether-functionalized coumarin oxime ester compound, and preparation and use thereof 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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French (fr)
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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Publication of WO2024067718A1 publication Critical patent/WO2024067718A1/en

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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

The present invention relates to an ether-functionalized coumarin oxime ester compound of formula (I), wherein the variables therein are as defined in the description. The compound has good photosensitive absorption in the range of 300-550 nm, especially in the range of 365-450 nm; after absorbing light energy, the compound can rapidly undergo a photochemical reaction, initiate the polymerization of polymerizable monomers within several seconds, and complete a polymerization reaction within 10 minutes (especially in 3 minutes); and the compound has significant advantages in the aspect of photosensitivity, and has good thermal stability, storage stability and solubility, thus being applicable as a photoinitiator for curing with a UV-VIS LED light source. The present invention further relates to a preparation method for and the use of the ether-functionalized coumarin oxime ester compound of formula (I). The compound can serve as a photoinitiator and is particularly applicable to curing with a UV-VIS LED light source.

Description

醚官能化香豆素肟酯类化合物及其制备和应用Ether functionalized coumarin oxime ester compounds and their preparation and application 技术领域Technical Field
本发明属于光固化技术领域，涉及醚官能化香豆素肟酯类化合物，该类化合物可用作光引发剂，尤其适用于UV-VIS LED光源固化。本发明还涉及醚官能化香豆素肟酯类化合物的制备及其应用。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.
背景技术Background technique
光引发剂又称光敏剂或光固化剂，是一类能在紫外光区(250-400nm)或可见光区(400-600nm)吸收一定波长的能量，产生自由基、阳离子等，从而引发单体聚合交联固化的化合物。作为光固化体系的重要组分，光引发剂虽然在光固化体系中含量低，却是其中的关键组分，对光固化速度起决定作用，还必须满足不同光固化条件和应用的需要。它关系到配方体系在光辐照时能否迅速交联固化，从而由液态转变为固态。同时，随着光固化技术已广泛应用在涂料、油墨、微电子、印刷等传统领域以及制备激光录像及三维元件等新型领域，并且随着UV-VIS LED光源固化技术的不断研发，为了满足UV-VIS LED光源固化技术的广泛应用需求，需要开发适用于UV-VIS LED光源的光引发剂。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. As an important component of the photocuring system, although 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. At the same time, as photocuring technology has been widely used in traditional fields such as coatings, inks, microelectronics, printing, as well as in new fields such as the preparation of laser video and three-dimensional components, and with the continuous research and development of 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.
对本领域技术人员而言，肟酯类光引发剂作为自由基光引发剂，因其活性突出且具有优异的感光性能成为近年来逐渐受到重视的一类光引发剂。目前常见的商业化产品有肟酯OXE01和OXE02(均来自BASF)，这两个产品具有优异的光引发活性，但是它们的紫外吸收范围相对偏短(250-350nm)，不能满足目前日益发展的UV-VIS LED光源的需求，尤其是并不适用于UV-VIS LED光源(例如365nm、385nm、395nm、405nm、425nm、450nm、475nm)的需求。For those skilled in the art, 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. Currently common commercial products include 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).
此外，也有一些关于肟酯类光引发剂的专利，例如CN102775527A披露了一种二苯硫醚酮肟酯类光引发剂及其制备方法，CN102492059A公开了取代的二苯硫醚酮肟酯类光引发剂等等。但是大多数引发剂的紫外吸收波长也停留在250-350nm，仍旧无法与日益发展的长波长LED光源匹配。 另外，CN104817653A披露了一种适用于UV-LED光源固化的香豆素醛肟酯类化合物，然而研究表明此类化合物的热稳定性不及OXE-01。此外，目前报道的用于UV-VIS LED光源固化体系的肟酯光引发剂并不多，且肟酯的黄变现象仍然没有得到解决，这就大大限制了肟酯类光引发剂的应用。In addition, there are also some patents on 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. However, the ultraviolet absorption wavelength of most initiators also stays at 250-350nm, which still cannot match the increasingly developed long-wavelength LED light source. In addition, 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. In addition, 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.
有鉴于此，研究和开发具有更高性能的肟酯类光引发剂仍是该领域的核心工作，尤其是开发适用于目前迅速发展的UV-VIS LED光源并具有高感光性、高稳定性且易于制备的肟酯类光引发剂成为目前肟酯类光引发剂的研究方向。In view of this, research and development of oxime ester photoinitiators with higher performance remains the core work in this field, especially the development of oxime ester photoinitiators that are suitable for the rapidly developing UV-VIS LED light sources and have high photosensitivity, high stability and are easy to prepare, which has become the current research direction of oxime ester photoinitiators.
发明内容Summary of the invention
鉴于现有技术存在的问题，本发明的发明人在适用于UV-VIS LED光源(辐射波长为300-550nm，尤其是365-475nm)固化的光引发剂方面进行了广泛而又深入的研究，以期找到一种能够替代OXE01和OXE02以更适合UV-VIS LED光源固化且感光性能优异，具有良好热稳定性和溶解性的光引发剂。In view of the problems existing in the prior art, 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.
本发明人惊讶地发现，通过在特定位置将特定醚官能团结构部分引入特定结构香豆素类化合物中形成一种新型醚官能化香豆素肟酯类化合物，其能够在300-550nm，尤其是365-475nm范围内具有较好的感光吸收，吸收光能后能够迅速发生光化学反应，在数秒内引发可聚合单体进行聚合，并在10分钟(特别是3分钟)内使聚合反应完成，因此在感光性方面具有明显优势，并且具有良好的热稳定性、储存稳定性和溶解性，从而适合用作UV-VIS LED光源固化的光引发剂。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.
本发明目的正是基于前述发现得以实现。The object of the present invention is achieved based on the above-mentioned discovery.
因此，本发明的一个目的是提供一种醚官能化香豆素肟酯类化合物，该类化合物的吸收波长不仅适合UV-VIS LED光源辐射固化，而且还具有很好的热稳定性、储存稳定性和溶解性。Therefore, 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.
本发明的另一目的是提供制备本发明醚官能化香豆素肟酯类化合物的方法。Another object of the present invention is to provide a method for preparing the ether-functionalized coumarin oxime ester compounds of the present invention.
本发明的再一目的是提供本发明醚官能化香豆素肟酯类化合物作为光引发剂或光敏剂的用途。 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.
实现本发明上述目的的技术方案可以概括如下:The technical solution for achieving the above-mentioned purpose of the present invention can be summarized as follows:
1.式(I)的醚官能化香豆素肟酯化合物：
1. Ether functionalized coumarin oxime ester compounds of formula (I):
其中：in:
M为氧或硫原子；M is an oxygen or sulfur atom;
R1分别独立地表示C1-C10烷基、C6-C10芳基或C2-C10烯基，其中前述C1-C10烷基、C6-C10芳基或C2-C10烯基任选地被卤素、C1-C6烷基和C1-C6烷氧(硫)基取代；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分别独立地表示C1-C10烷基、C3-C10环烷基、C3-C6环烷基-C1-C4烷基或C1-C4烷基-C3-C6环烷基，其中前述C1-C10烷基、C3-C10环烷基、C3-C6环烷基-C1-C4烷基或C1-C4烷基-C3-C6环烷基任选地被卤素、C1-C6烷基和C1-C6烷氧(硫)基取代； 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;
R3分别独立地表示C4-C10烷基、C4-C10环烷基、C4-C6环烷基-C1-C4烷基或C1-C4烷基-C4-C6环烷基，其中前述C4-C10烷基、C4-C10环烷基、C4-C6环烷基-C1-C4烷基或C1-C4烷基-C4-C6环烷基任选地被卤素取代；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;
R4分别独立地表示氢、或任选被卤素取代的C1-C4烷基；R 4 each independently represents hydrogen, or C 1 -C 4 alkyl optionally substituted by halogen;
R5、R6分别独立地表示氢、C1-C10烷基、C3-C10环烷基、C3-C6环烷基-C1-C4烷基或C1-C4烷基-C3-C6环烷基，其中前述C1-C10烷基、C3-C10环烷基、C3-C6环烷基-C1-C4烷基或C1-C4烷基-C3-C6环烷基任选地被卤素、C1-C6烷基和C1-C6烷氧(硫)基取代；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相互独立地表示C1-C10烷基、C3-C10环烷基、C3-C6环烷基-C1-C4烷基、C1-C4烷基-C3-C6环烷基或C6-C10芳基，其中前述C1-C10烷基、C3-C10环烷基、C3-C6环烷基-C1-C4烷基、C1-C4烷基-C3-C6环烷基或C6-C10芳基任选地被卤素、C1-C6烷基和C1-C6烷氧(硫)基取代。 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.
2.根据第1项的醚官能化香豆素肟酯化合物，其中：2. An ether-functionalized coumarin oxime ester compound according to item 1, wherein:
R1分别独立地表示C1-C8烷基、C6-C8芳基或C2-C8烯基，其中前述C1-C8 烷基、C6-C8芳基或C2-C8烯基任选地被卤素、C1-C6烷基和C1-C6烷氧(硫)基取代， 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,
优选R1分别独立地表示C1-C4烷基、苯基或C2-C4烯基，其中前述C1-C4烷基、苯基或C2-C4烯基任选地被氟、氯、溴和C1-C4烷基取代；和/或Preferably, 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分别独立地表示C1-C8烷基、C3-C8环烷基、C3-C6环烷基-C1-C2烷基或C1-C2烷基-C3-C6环烷基，其中前述C1-C6烷基、C3-C8环烷基、C3-C6环烷基-C1-C2烷基或C1-C2烷基-C3-C6环烷基任选地被卤素、C1-C6烷基和C1-C6烷氧(硫)基取代， 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,
优选R2分别独立地表示C1-C4烷基、C5-C6环烷基、C5-C6环烷基-C1-C2烷基或C1-C2烷基-C5-C6环烷基，其中前述C1-C4烷基、C5-C6环烷基、C5-C6环烷基-C1-C2烷基或C1-C2烷基-C5-C6环烷基任选地被氟、氯、溴和C1-C4烷基取代；和/或Preferably, 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
R4分别独立地表示氢或任选被氟、氯和溴取代的C1-C4烷基，R 4 each independently represents hydrogen or C 1 -C 4 alkyl optionally substituted by fluorine, chlorine or bromine,
优选R4为氢；和/或Preferably R 4 is hydrogen; and/or
R5、R6分别独立地表示氢、C1-C8烷基、C3-C8环烷基、C3-C6环烷基-C1-C2烷基或C1-C2烷基-C3-C6环烷基，其中前述C1-C6烷基、C3-C8环烷基、C3-C6环烷基-C1-C2烷基或C1-C2烷基-C3-C6环烷基任选地被卤素、C1-C6烷基和C1-C6烷氧(硫)基取代，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,
优选R5、R6分别独立地表示氢、C1-C4烷基、C5-C6环烷基、C5-C6环烷基-C1-C2烷基或C1-C2烷基-C5-C6环烷基，其中前述C1-C4烷基、C5-C6环烷基、C5-C6环烷基-C1-C2烷基或C1-C2烷基-C5-C6环烷基任选地被氟、Preferably, 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,
氯和溴取代；和/或Chloro and bromo substitution; and/or
R7相互独立地表示C1-C8烷基、C3-C8环烷基、C3-C6环烷基-C1-C2烷基、C1-C2烷基-C3-C6环烷基或C6-C8芳基，其中C1-C4烷基、C3-C8环烷基、C3-C6环烷基-C1-C2烷基、C1-C2烷基-C3-C6环烷基或C6-C8芳基任选地被卤素、C1-C6烷基和C1-C6烷氧(硫)基取代， 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,
优选R7分别独立地表示C1-C4烷基或苯基，其中前述C1-C4烷基或苯基任选地被氟、氯、溴和C1-C4烷基取代。 Preferably, 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.
3.根据第1或2项的醚官能化香豆素肟酯化合物，其中：3. An ether-functionalized coumarin oxime ester compound according to item 1 or 2, wherein:
R3分别独立地表示C4-C8烷基，优选C4-C6烷基，尤其是C4烷基，其中前述C4-C8烷基、C4-C6烷基或C4烷基任选地被氟、氯和溴取代。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.
4.根据第1-3项中任一项的醚官能化香豆素肟酯化合物，其中R3为叔丁基。4. The ether functionalized coumarin oxime ester compound according to any one of items 1 to 3, wherein R 3 is tert-butyl.
5.根据第1-4项中任一项的醚官能化香豆素肟酯化合物，其中所述醚官能化香豆素肟酯化合物选自下组：





5. The 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:





6.一种制备如第1-5项中任一项的醚官能化香豆素肟酯化合物的方法，包括以下步骤：6. A method for preparing an ether functionalized coumarin oxime ester compound as described in any one of items 1 to 5, comprising the following steps:
(1)克脑文盖尔(Knoevenagel)缩合反应:使式(II)化合物与R2-COCH2COOR(R＝C1-C6烷基)进行克脑文盖尔缩合反应，得到式(III)化 合物：
(1) Knoevenagel condensation reaction: The compound of formula (II) is subjected to Knoevenagel condensation reaction with R 2 -COCH 2 COOR (R=C 1 -C 6 alkyl) to obtain the compound of formula (III) Compound:
(2)肟化反应：使式(III)化合物与羟胺和/或盐酸羟胺进行肟化反应，得到式(IV)化合物
以及(2) Oximation reaction: The compound of formula (III) is subjected to an oximation reaction with hydroxylamine and/or hydroxylamine hydrochloride to obtain a compound of formula (IV):
as well as
(3)酯化反应：将式(IV)化合物酯化，得到式(I)化合物，(3) Esterification reaction: esterifying the compound of formula (IV) to obtain the compound of formula (I),
其中上述各式中的参数如第1-5项中任一项所定义。The parameters in the above formulae are defined as in any one of items 1 to 5.
7.根据第6项的方法，其中步骤(1)的克脑文盖尔缩合反应在选自下组的一种或多种催化剂存在下进行：胺类如伯胺、仲胺、叔胺及其相应的铵盐，优选哌啶；无机碱如氢氧化钠、碳酸钠；无机盐如氟化钾、磷酸铝、磷酸氢二铵；路易斯酸和叔胺结合物如TiCl4/哌啶或TiCl4/三乙胺。7. The method according to item 6, wherein the Knoevenagel condensation reaction 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.
8.根据第6或7项的方法，其中在步骤(1)的克脑文盖尔缩合反应中，式(II)化合物与R2-COCH2COOR(R＝C1-C6烷基)，优选乙酰乙酸乙酯的摩尔比为1:0.1-1:1.5，优选1:0.3-1:1。8. The method according to item 6 or 7, wherein in the Knoevenagel condensation reaction of step (1), the molar ratio of the compound of formula (II) to R2 - COCH2COOR (R= C1 - C6 alkyl), preferably ethyl acetoacetate, is 1:0.1-1:1.5, preferably 1:0.3-1:1.
9.根据第6-8项中任一项的方法，其中步骤(2)的肟化反应在乙酸钠、吡啶、哌啶、三乙胺和/或四甲基氢氧化铵作为催化剂存在下进行。9. The method according to any one of items 6 to 8, wherein the oximation reaction of step (2) is carried out in the presence of sodium acetate, pyridine, piperidine, triethylamine and/or tetramethylammonium hydroxide as a catalyst.
10.根据第6-9项中任一项的方法，其中在步骤(2)的肟化反应中，式(III)化合物与羟胺和/或盐酸羟胺的摩尔比为1:2.5-1.25:2，优选1:2.2-1.1:2。10. The method according to any one of items 6 to 9, wherein in the oximation reaction of 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.
11.根据第6-10项中任一项的方法，其中：11. The method according to any one of items 6 to 10, wherein:
步骤(3)的酯化采用选自下式(Va)、(Vb)和(Vc)化合物的酯化试剂进行：
The esterification in step (3) is carried out using an esterification agent selected from the compounds of the following formulae (Va), (Vb) and (Vc):
其中X为卤素，尤其是氯，R1如第1-5项中任一项所定义。wherein X is halogen, especially chlorine, and R1 is as defined in any one of items 1-5.
12.根据第6-11项中任一项的方法，其中步骤(3)的酯化反应在选自下组的一种或多种催化剂存在下进行：硫酸、高氯酸、氯化锌、三氯化铁、吡啶、对甲基苯磺酸、氢氧化钠、氢氧化钾、碳酸钠、碳酸氢钠、叔丁醇钠、乙醇钠、氢化钠、氢化钾、氢化钙和叔胺，例如三烷基胺，如三甲胺和三乙胺。12. 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.
13.根据第6-12项中任一项的方法，其中在步骤(3)的酯化反应中，式(IV)化合物与选自式(Va)、(Vb)和(Vc)化合物的酯化试剂的摩尔比为1:1.2-1:2.0，优选1:1.4-1:1.8。13. A method according to any one of items 6 to 12, wherein in the esterification reaction of 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.
14.根据第1-5项中任一项或者根据第6-13中任一项的方法获得的醚官能化香豆素肟酯化合物作为光引发剂的用途，尤其是在UV-VIS LED光源固化体系中作为光引发剂的用途，特别是在辐射波长为300-550nm，尤其是365-475nm的光源固化体系中作为光引发剂的用途。14. Use of the 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.
15.一种包含至少一种根据第1-5项中任一项或者根据第6-13中任一项的方法获得的醚官能化香豆素肟酯化合物的可光固化组合物。15. 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.
16.可由第15项的可光固化组合物得到的固化材料。16. A cured material obtainable from the photocurable composition of item 15.
17.一种制备光固化材料的方法，其包括用辐射波长为300-550nm，尤其是365-475nm的光源，例如UV-VIS LED光源对第15项的可光固化组合物进行辐照。17. 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.
附图说明：Description of the drawings:
图1为乌格拉(Ugra)晒版测试条的示意图，其中FIG1 is a schematic diagram of a Ugra exposure test strip, wherein
1—连续密度梯尺段，1—Continuous density scale segment,
2—阴阳微米等线同心圆线圈段，2—yin and yang micrometer equal line concentric circle coil segment,
3—全阶调网点段，3—Full-scale dot segment,
4—重影控制段，和4—Ghost Control Segment, and
5—高光、暗调控制段。5—Highlight and shadow control section.
具体实施方式Detailed ways
根据本发明的第一个方面，提供了一种式(I)的醚官能化香豆素肟酯化合物：
According to a first aspect of the present invention, there is provided an ether-functionalized coumarin oxime ester compound of formula (I):
其中：in:
M为氧或硫原子；M is an oxygen or sulfur atom;
R1分别独立地表示C1-C10烷基、C6-C10芳基或C2-C10烯基，其中前述C1-C10烷基、C6-C10芳基或C2-C10烯基任选地被卤素、C1-C6烷基和C1-C6烷氧(硫)基取代；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分别独立地表示C1-C10烷基、C3-C10环烷基、C3-C6环烷基-C1-C4烷基或C1-C4烷基-C3-C6环烷基，其中前述C1-C10烷基、C3-C10环烷基、C3-C6环烷基-C1-C4烷基或C1-C4烷基-C3-C6环烷基任选地被卤素、C1-C6烷基和C1-C6烷氧(硫)基取代； 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;
R3分别独立地表示C4-C10烷基、C4-C10环烷基、C4-C6环烷基-C1-C4烷基或C1-C4烷基-C4-C6环烷基，其中前述C4-C10烷基、C4-C10环烷基、C4-C6环烷基-C1-C4烷基或C1-C4烷基-C4-C6环烷基任选地被卤素取代；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;
R4分别独立地表示氢或任选被卤素取代的C1-C4烷基；R 4 each independently represents hydrogen or C 1 -C 4 alkyl optionally substituted by halogen;
R5、R6分别独立地表示氢、C1-C10烷基、C3-C10环烷基、C3-C6环烷基-C1-C4烷基或C1-C4烷基-C3-C6环烷基，其中前述C1-C10烷基、C3-C10环烷基、C3-C6环烷基-C1-C4烷基或C1-C4烷基-C3-C6环烷基任选地被卤素、C1-C6烷基和C1-C6烷氧(硫)基取代；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相互独立地表示C1-C10烷基、C3-C10环烷基、C3-C6环烷基-C1-C4烷基、C1-C4烷基-C3-C6环烷基或C6-C10芳基，其中前述C1-C10烷基、C3-C10环烷基、C3-C6环烷基-C1-C4烷基、C1-C4烷基-C3-C6环烷基或C6-C10芳基任选地被卤素、C1-C6烷基和C1-C6烷氧(硫)基取代。 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.
本发明特定的式(I)醚官能化香豆素肟酯化合物既包含香豆素基结构部分，又包含肟酯类结构部分。该化合物在300-550nm，尤其是365-475nm范围内具有较好的感光吸收，吸收光能后能够迅速发生裂解生成活性自由基，持续引发聚合，在数秒内引发可聚合单体进行聚合，并在 10分钟(特别是3分钟)内使聚合反应完成，因此在感光性方面具有明显优势，并且具有良好的热稳定性、储存稳定性和溶解性，从而适合用作UV-VIS LED光源固化的光引发剂。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.
在本发明中，前缀“Cn-Cm”在每种情况下表示该基团中包含的碳原子数为n-m个。In the present invention, the prefix "C n -C m " denotes in each case that the number of carbon atoms contained in the group is nm.
“卤素”是指氟、氯、溴和碘。在本发明中，优选卤素是氟、氯、溴或其组合。"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.
本文所用的术语“Cn-Cm烷基”是指具有n-m个，如1-10个碳原子的支化或未支化饱和烃基，例如甲基、乙基、正丙基、1-甲基乙基、正丁基、1-甲基丙基、2-甲基丙基、1,1-二甲基乙基、叔丁基、正戊基、1-甲基丁基、2-甲基丁基、3-甲基丁基、2,2-二甲基丙基、1-乙基丙基、1,1-二甲基丙基、1,2-二甲基丙基、正己基、1-甲基戊基、2-甲基戊基、3-甲基戊基、4-甲基戊基、1,1-二甲基丁基、1,2-二甲基丁基、1,3-二甲基丁基、2,2-二甲基丁基、2,3-二甲基丁基、3,3-二甲基丁基、1-乙基丁基、2-乙基丁基、1,1,2-三甲基丙基、1,2,2-三甲基丙基、1-乙基-1-甲基丙基、1-乙基-2-甲基丙基、正庚基、正辛基、2-乙基己基、正壬基、正癸基及其异构体等。The term " Cn - Cm- alkyl" as used herein 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, 1,2-dimethylpropyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, tert-butyl, tert-pentyl ... 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl, 1-ethyl-2-methylpropyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl and isomers thereof, etc.
本文所用术语“C6-Cm芳基”是指含有6-m个碳原子，如6-10个碳原子的单环或双环芳族烃基，例如苯基、甲苯基、乙苯基、丙苯基、丁苯基、二甲苯基、甲基乙基苯基、二乙基苯基、甲基丙基苯基、萘基及其异构体等。The term " C6 - Cm aryl" as used herein 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.
本文所用术语“C2-Cm烯基”是指具有2-m个，例如2-10个碳原子并且具有一个位于任何位置的双键的支化或未支化不饱和烃基，例如乙烯基、1-丙烯基、2-丙烯基、1-甲基乙烯基、1-丁烯基、2-丁烯基、3-丁烯基、1-甲基-1-丙烯基、2-甲基-1-丙烯基、1-甲基-2-丙烯基、2-甲基-2-丙烯基及其异构体等。The term " C2 - Cm alkenyl" as used herein 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.
本文所用术语“C3-Cm环烷基”是指具有3-m个，如3-10个环碳原子的饱和脂环族单环基团，例如环丙基、环丁基、环戊基、环己基、环庚基、环辛基、环癸基及其异构体等。The term "C 3 -C m cycloalkyl" as used herein 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.
术语“C3-Cm环烷基-Cn-Cm烷基”表示被C3-Cm环烷基取代的Cn-Cm烷 基，此时两个m可相同或不同，其中Cn-Cm烷基和C3-Cm环烷基适用本文的定义。C3-Cm环烷基-Cn-Cm烷基可以是C3-C6环烷基-C1-C4烷基，例如环丙基甲基、环丙基乙基、环丙基丙基、环丙基丁基、环丁基甲基、环丁基乙基、环丁基丙基、环丁基丁基、环戊基甲基、环戊基乙基、环戊基丙基、环戊基丁基、环己基甲基、环己基乙基、环己基丙基、环己基丁基及其异构体等。The term "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.
术语“Cn-Cm烷基-C3-Cm环烷基”表示被Cn-Cm烷基取代的C3-Cm环烷基，此时两个m可相同或不同，其中Cn-Cm烷基和C3-Cm环烷基适用本文的定义。Cn-Cm烷基-C3-Cm环烷基可以是C1-C4烷基-C3-C6环烷基，例如甲基环丙基、乙基环丙基、丙基环丙基、丁基环丙基、甲基环丁基、乙基环丁基、丙基环丁基、丁基环丁基、甲基环戊基、乙基环戊基、丙基环戊基、丁基环戊基、甲基环己基、乙基环己基、丙基环己基、丁基环己基及其异构体等。The term " 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 group, and isomers thereof.
本文所用术语“Cn-Cm烷氧(硫)基”包括“Cn-Cm烷氧基”和“Cn-Cm烷硫基”，是指在Cn-Cm烷基对应的开链Cn-Cm烷烃的任何碳原子上键合有一个氧原子或一个硫原子作为连接基团的Cn-Cm烷基，如C1-C6烷氧(硫)基，例如甲氧基、乙氧基、丙氧基、异丙氧基、正丁氧基、2-丁氧基、叔丁氧基、戊氧基、异戊氧基、己氧基及其异构体。C1-C8烷硫基可以是甲硫基、乙硫基、丙硫基、异丙硫基、正丁硫基、2-丁硫基、叔丁硫基、戊硫基、异戊硫基、己硫基及其异构体等。The term "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.
在本发明的一个优选实施方案中，R1分别独立地表示C1-C8烷基、C6-C8芳基或C2-C8烯基，其中前述C1-C8烷基、C6-C8芳基或C2-C8烯基任选地被卤素、C1-C6烷基和C1-C6烷氧(硫)基取代；In a preferred embodiment of the present invention, 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;
优选的是，R1分别独立地表示C1-C4烷基、苯基或C2-C4烯基，其中前述C1-C4烷基、苯基或C2-C4烯基任选地被氟、氯、溴和C1-C4烷基取代。Preferably, 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.
在本发明的一个优选实施方案中，R2分别独立地表示C1-C8烷基、C3-C8环烷基、C3-C6环烷基-C1-C2烷基或C1-C2烷基-C3-C6环烷基，其中前述C1-C6烷基、C3-C8环烷基、C3-C6环烷基-C1-C2烷基或C1-C2烷基-C3-C6环 烷基任选地被卤素、C1-C6烷基和C1-C6烷氧(硫)基取代。In a preferred embodiment of the present invention, 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.
优选的是，R2分别独立地表示C1-C4烷基、C5-C6环烷基、C5-C6环烷基-C1-C2烷基或C1-C2烷基-C5-C6环烷基，其中前述C1-C4烷基、C5-C6环烷基、C5-C6环烷基-C1-C2烷基或C1-C2烷基-C5-C6环烷基任选地被氟、氯、溴和C1-C4烷基取代。Preferably, 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.
在本发明的一个优选实施方案中，R4分别独立地表示氢或任选被氟、氯和溴取代的C1-C4烷基。In a preferred embodiment of the present invention, R 4 each independently represents hydrogen or C 1 -C 4 alkyl optionally substituted by fluorine, chlorine or bromine.
优选的是，R4为氢。Preferably, R4 is hydrogen.
在本发明的一个优选实施方案中，R5、R6分别独立地表示氢、C1-C8烷基、C3-C8环烷基、C3-C6环烷基-C1-C2烷基或C1-C2烷基-C3-C6环烷基，其中前述C1-C6烷基、C3-C8环烷基、C3-C6环烷基-C1-C2烷基或C1-C2烷基-C3-C6环烷基任选地被卤素、C1-C6烷基和C1-C6烷氧(硫)基取代。In a preferred embodiment of the present invention, 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.
优选的是，R5、R6分别独立地表示氢、C1-C4烷基、C5-C6环烷基、C5-C6环烷基-C1-C2烷基或C1-C2烷基-C5-C6环烷基，其中前述C1-C4烷基、C5-C6环烷基、C5-C6环烷基-C1-C2烷基或C1-C2烷基-C5-C6环烷基任选地被氟、氯和溴取代。Preferably, 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.
在本发明的一个优选实施方案中，R7相互独立地表示C1-C8烷基、C3-C8环烷基、C3-C6环烷基-C1-C2烷基、C1-C2烷基-C3-C6环烷基或C6-C8芳基，其中C1-C4烷基、C3-C8环烷基、C3-C6环烷基-C1-C2烷基、C1-C2烷基-C3-C6环烷基或C6-C8芳基任选地被卤素、C1-C6烷基和C1-C6烷氧(硫)基取代。In a preferred embodiment of the present invention, 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.
优选的是，R7分别独立地表示C1-C4烷基或苯基，其中前述C1-C4烷基或苯基任选地被氟、氯、溴和C1-C4烷基取代。Preferably, 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.
在本发明的一个更优选的实施方案中，R3分别独立地表示C4-C8烷基，优选C4-C6烷基，尤其是C4烷基，其中前述C4-C8烷基、C4-C6烷基、或C4烷基任选地被氟、氯和溴取代。In a more preferred embodiment of the present invention, 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.
在本发明的一个特别优选的实施方案中，其中R3为叔丁基。In a particularly preferred embodiment of the present invention, R 3 is tert-butyl.
在本发明的一些特别优选的实施方案中，本发明的式(I)化合物选自前文所示化合物1-68。化合物1-68分别在实施例1-68中制备。In some particularly preferred embodiments of the present invention, 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.
根据本发明的第二个方面，提供了一种制备本发明式(I)化合物的方 法，包括以下步骤：According to a second aspect of the present invention, there is provided a method for preparing the compound of formula (I) of the present invention. The method comprises the following steps:
(1)克脑文盖尔缩合反应:使式(II)化合物与R2-COCH2COOR(R＝C1-C6烷基)进行克脑文盖尔缩合反应，得到式(III)化合物：
(1) Knoevenagel condensation reaction: The compound of formula (II) is subjected to Knoevenagel condensation reaction with R 2 -COCH 2 COOR (R=C 1 -C 6 alkyl) to obtain a compound of formula (III):
(2)肟化反应：使式(III)化合物与羟胺和/或盐酸羟胺进行肟化反应，得到式(IV)化合物：
以及(2) Oximation reaction: The compound of formula (III) is subjected to an oximation reaction with hydroxylamine and/or hydroxylamine hydrochloride to obtain a compound of formula (IV):
as well as
(3)酯化反应：将式(IV)化合物酯化，得到式(I)化合物，(3) Esterification reaction: esterifying the compound of formula (IV) to obtain the compound of formula (I),
其中上述各式中的参数如前文所定义。The parameters in the above formulas are as defined above.
为了制备本发明的式(I)化合物，需要从特定醚官能化的式(II)化合物开始，先进行克脑文盖尔缩合反应得到式(III)的醚官能化香豆素化合物，随后进行肟化反应，以引入肟基，然后将肟基中的羟基经酯化反应转变成相应的酯基，从而获得本发明的醚官能化香豆素肟酯化合物。In order to prepare the compound of formula (I) of the present invention, it is necessary to start from a specific ether-functionalized compound of formula (II), first perform a Knoevenagel condensation reaction to obtain an ether-functionalized coumarin compound of formula (III), then perform an oximation reaction to introduce an oxime group, and then convert the hydroxyl group in the oxime group into a corresponding ester group through an esterification reaction, thereby obtaining the ether-functionalized coumarin oxime ester compound of the present invention.
克脑文盖尔缩合反应Knoevenagel condensation reaction
式(II)化合物与R2-COCH2COOR(R＝C1-C6烷基)在催化剂作用下进行克脑文盖尔缩合反应，得到式(III)化合物：
The compound of formula (II) is subjected to Knoevenagel condensation reaction with R 2 -COCH 2 COOR (R=C 1 -C 6 alkyl) in the presence of a catalyst to obtain a compound of formula (III):
其中上述各式中的参数如对式(I)所定义。The parameters in the above formulae are as defined for formula (I).
克脑文盖尔缩合反应对本领域技术人员而言是常规的。特定的式(II)化合物作为含相邻羟基和羰基的苯环结构，通过克脑文盖尔缩合反应合成香 豆素环是常规的。具体而言，通过该反应，结构中的羰基在催化剂作用下发生醛、酮缩合，脱水形成碳碳双键，羟基与R2-COCH2COOR(R＝C1-C6烷基)，优选乙酰乙酸乙酯的酯键发生交换反应，脱去乙醇形成新的酯键，由此形成香豆素环，从而获得式(III)化合物。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. Specifically, through this reaction, the carbonyl group in the structure undergoes aldehyde and ketone condensation under the action of a catalyst, dehydration to form a carbon-carbon double bond, and the hydroxyl group undergoes an ester exchange reaction with R2 - COCH2COOR (R= C1 - C6 alkyl), preferably ethyl acetoacetate, and the ethanol is removed to form a new ester bond, thereby forming a coumarin ring, thereby obtaining a compound of formula (III).
为了加速克脑文盖尔缩合反应，上述反应通常在适于克脑文盖尔缩合反应的催化剂存在下进行。作为催化剂，通常使用胺类如伯胺、仲胺、叔胺及其相应的铵盐，优选哌啶；无机碱如氢氧化钠、碳酸钠；无机盐如氟化钾、磷酸铝、磷酸氢二铵；路易斯酸和叔胺结合物如TiCl4/哌啶或TiCl4/三乙胺。催化剂的用量是常规的，可以通过本领域的常识确定，或者通过几个例行的预备实验来确定。In order to accelerate the Knoevenagel condensation reaction, the above reaction is usually carried out in the presence of a catalyst suitable for the Knoevenagel condensation reaction. As 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.
上述克脑文盖尔缩合反应通常在溶剂中，优选在有机溶剂中进行，优选在非质子性溶剂中进行。对于溶剂类型的选择，没有特别的限制，只要能够将式(II)化合物与R2-COCH2COOR(R＝C1-C6烷基)，优选乙酰乙酸乙酯溶解并且对克脑文盖尔缩合反应呈化学惰性即可，即不参与该克脑文盖尔缩合反应即可。可采用的溶剂例如有乙醇、乙醚、二甲亚砜、甲苯、N,N-二甲基甲酰胺或丙酮，优选使用乙醇。The above-mentioned Knoevenagel condensation reaction is usually carried out in a solvent, preferably in an organic solvent, preferably in an aprotic solvent. There is no particular limitation on the type of solvent, as long as it can dissolve the compound of formula (II) and R 2 -COCH 2 COOR (R=C 1 -C 6 alkyl), preferably ethyl acetoacetate, and is chemically inert to the Knoevenagel condensation reaction, that is, it does not participate in the Knoevenagel condensation reaction. The solvent that can be used includes, for example, ethanol, ether, dimethyl sulfoxide, toluene, N,N-dimethylformamide or acetone, preferably ethanol.
式(II)化合物与R2-COCH2COOR(R＝C1-C6烷基)，优选乙酰乙酸乙酯的相对用量没有特别的限制，通常二者摩尔比为1:0.1-1:1.5，优选1:0.3-1:1，例如约1:0.5。There is no particular limitation on the relative amounts of the compound of formula (II) and R 2 -COCH 2 COOR (R=C 1 -C 6 alkyl), preferably ethyl acetoacetate. Usually the molar ratio is 1:0.1-1:1.5, preferably 1:0.3-1:1, for example about 1:0.5.
克脑文盖尔缩合反应的温度范围通常为40-120℃，优选60-90℃。对反应时间没有特别的限制，通常进行3-20小时，优选3-10小时。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.
克脑文盖尔缩合反应完成之后，先水洗反应液，再除去残留的有机溶剂。作为这里除去有机溶剂的手段，没有特别的限制，通常可通过常压或减压蒸馏来除去有机溶剂。除去残留有机溶剂之后，得到了式(III)化合物的粗产物。如果想要进一步提高式(III)化合物的纯度，还可对该化合物进行进一步提纯，这例如可通过重结晶的方式来进行。重结晶溶剂的选择是常规的，没有特别的限制。根据本发明，有利的是采用乙醇对式(III)化合物的粗产物进行重结晶。After the Knoevenagel condensation reaction is completed, the reaction solution is washed with water first, and then 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 normal pressure or reduced pressure distillation. After removing the residual organic solvent, 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).
肟化反应 Oximation reaction
式(III)化合物与羟胺和/或盐酸羟胺进行肟化反应，得到式(IV)化合物：
The compound of formula (III) is subjected to oximation reaction with hydroxylamine and/or hydroxylamine hydrochloride to obtain a compound of formula (IV):
其中上述各式中的参数如对式(I)所定义。The parameters in the above formulae are as defined for formula (I).
该肟化反应通常使用盐酸羟胺(NH2OH·HCl)、羟胺(NH2OH)或其混合物作为肟化试剂。该肟化反应通常在有机溶剂中进行，优选在极性有机溶剂中进行。可采用的溶剂例如有乙醇或含水的乙醇。为了促进肟化反应进行完全，一般需加入乙酸钠、吡啶、哌啶、三乙胺、四甲基氢氧化铵之类的催化剂或其混合物。这当中，吡啶、哌啶、三乙胺也可用作碱和/或溶剂或助溶剂。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. In order to promote the oximation reaction to be complete, a catalyst such as sodium acetate, pyridine, piperidine, triethylamine, tetramethylammonium hydroxide or a mixture thereof is generally added. Among them, pyridine, piperidine, triethylamine can also be used as a base and/or solvent or cosolvent.
对式(III)化合物与羟胺和/或盐酸羟胺的相对用量没有特别的限制，通常二者的摩尔比为1:2.5-1.25:2，优选1:2.2-1.1:2，例如约1:2。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.
上述肟化反应的温度范围通常为30-120℃，优选40-90℃。对肟化反应时间也没有特别的限制，通常进行0.1-20小时，优选0.3-10小时。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.
酯化反应Esterification reaction
式(IV)化合物的酯化对本领域技术人员而言是常规的，通过该反应，肟基中的羟基转变为酯基，从而获得式(I)化合物。作为酯化试剂，没有特别的限制，只要能将式(IV)化合物肟基中的羟基转变为酯基即可。例如，可以使用相应的酰卤，如酰氯，也可使用相应的羧酸，还可使用相应的酸酐。这些化合物可分别表示为式(Va)、(Vb)和(Vc)化合物:
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). As 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. For example, 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:
其中X为卤素，尤其是氯，和R1如式(I)化合物所定义。wherein X is halogen, especially chlorine, and R 1 is as defined for the compound of formula (I).
为了加速酯化反应，上述酯化反应通常在适于酯化反应的催化剂存在下进行。作为催化剂，既可以使用酸性催化剂，也可以使用碱性催化剂。例如，可以使用硫酸、高氯酸、氯化锌、三氯化铁、吡啶、对甲基苯磺酸、氢氧化钠、氢氧化钾、碳酸钠、碳酸氢钠、叔丁醇钠、乙醇钠、氢化钠、 氢化钾、氢化钙、四甲基氢氧化铵、叔胺(例如三烷基胺，如三甲胺和三乙胺)或其任意组合。催化剂的用量是常规的，可以通过本领域的常识确定，或者通过几个例行的预备实验来确定。In order to accelerate the esterification reaction, the above esterification reaction is usually carried out in the presence of a catalyst suitable for the esterification reaction. As the catalyst, either an acidic catalyst or a basic catalyst can be used. For example, 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, tetramethylammonium hydroxide, tertiary amines (e.g., trialkylamines, such as trimethylamine and triethylamine) or any combination thereof. The amount of catalyst used is conventional and can be determined by common sense in the art or by a few routine preliminary experiments.
为了提高本发明的式(I)化合物的产率，有利的是，在酯化反应过程中移除酯化反应产生的水。这例如可以通过蒸馏/冷凝来进行。In order to improve the yield of the compound of formula (I) of the present invention, it is advantageous to remove the water produced by the esterification reaction during the esterification reaction. This can be done, for example, by distillation/condensation.
上述酯化反应通常在溶剂中，优选在有机溶剂中进行。对于溶剂类型的选择，没有特别的限制，只要能够将式(IV)化合物和酯化试剂溶解并且对酯化反应呈化学惰性即可，即不参与该酯化反应即可。作为溶剂的实例，可以提及四氢呋喃、苯、甲苯、N,N-二甲基甲酰胺、二氯甲烷和丙酮。溶剂可以使用单一溶剂，也可以使用两种或更多种溶剂的混合物。The above esterification reaction is usually carried out in a solvent, preferably an organic solvent. 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. As examples of 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.
对式(IV)化合物与选自式(Va)、(Vb)和(Vc)化合物的酯化试剂的相对用量没有特别的限制，通常而言二者的摩尔比为1:1.2-1:2.0，优选1:1.4-1:1.8，例如约1:1.6。There is no particular restriction on the relative amounts of the compound of formula (IV) and the esterification agent selected from the compounds of formula (Va), (Vb) and (Vc). Generally, 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.
酯化反应可以在非常宽的温度范围内进行。根据本发明有利的是，酯化反应在-10℃至150℃，优选0℃至100℃的温度下进行，优选常温下进行。对酯化反应时间也没有特别的限制，通常进行0.5-24小时，优选0.8-12小时。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.
在酯化反应完成之后，获得包含式(I)化合物的反应混合物。因此，需要对该反应混合物进行后处理，以得到提纯的式(I)化合物。通常而言，首先过滤酯化反应得到的反应混合物，取出滤液部分。然后，将滤液进行洗涤，以除去催化剂和未反应的原料。作为洗液，没有特别的限制，只要能除去催化剂和未反应的原料即可。作为洗液的实例，可以提及稀盐酸(水溶液)、饱和碳酸氢钠水溶液和水。稀盐酸的浓度没有特别的限制，通常而言使用浓度为5-12％的稀盐酸。用洗液洗涤可以进行一次，也可进行多次；在进行多次的情况下，可使用单一种洗液，也可依次使用不同的洗液。根据本发明有利的是，对酯化反应得到的反应混合物过滤得到的滤液依次用稀盐酸、饱和碳酸氢钠水溶液和水进行洗涤。当然，每一次用洗液洗涤后，都需要倒掉水相之后再用下一种洗液对有机相进行洗涤。洗涤之后，需要干燥以除去残留的水。为此，通常可使用无水硫酸钠进行干燥。 干燥之后，再除去残留的有机溶剂。作为这里除去有机溶剂的手段，没有特别的限制，通常可通过减压蒸馏来除去有机溶剂。除去残留有机溶剂之后，得到了式(I)化合物的粗产物。如果想要进一步提高式(I)化合物的纯度，还可对该化合物进行进一步提纯，这例如可通过重结晶的方式来进行。重结晶溶剂的选择是常规的，没有特别的限制。根据本发明，有利的是，采用石油醚、甲醇、乙醇或者其混合物对式(I)化合物的粗产物进行重结晶。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). Generally speaking, 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. As a washing liquid, there is no particular restriction, as long as the catalyst and unreacted raw materials can be removed. As examples of washing liquids, dilute hydrochloric acid (aqueous solution), saturated sodium bicarbonate aqueous solution and water can be mentioned. There is no particular restriction on the concentration of dilute hydrochloric acid, and generally speaking, dilute hydrochloric acid with a concentration of 5-12% is used. Washing with 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. According to the present invention, it is advantageous that 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. Of course, after each washing with washing liquid, it is necessary to pour off the aqueous phase and then wash the organic phase with the next washing liquid. After washing, it is necessary to dry to remove residual water. For this purpose, 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.
在式(I)化合物中，肟酯基可能存在两种构型，即(Z)型或(E)型。可通过常规方法分离异构体，但也可使用异构体混合物作为光引发物质。因此，本发明还涉及式(I)化合物各自的构型异构体的混合物。In the compound of formula (I), 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).
本发明的式(I)化合物在300-550nm，尤其是在365-475nm的波长范围内有很强吸收，故可作为光引发剂应用于UV-VIS LED光固化技术中，尤其是适用于长波长UV-VIS LED光源固化。此外，本发明式(I)化合物安全无毒，相比传统的光引发剂，对人体和环境的危害程度降低，还可以被用于食品包装等领域。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. In addition, 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.
因此，根据本发明的第三个方面，提供了本发明的式(I)化合物作为光引发剂的用途。本发明的式(I)化合物可作为光引发剂应用于UV-VIS LED光固化技术中，可以有效地引发固化反应。特别优选的是，本发明的式(I)化合物在辐射波长为300-550nm，尤其是在365-475nm的光固化体系中作为光引发剂的用途。本发明的式(I)化合物也可在涂料、油墨、微电子、印刷等领域用作光引发剂或光敏剂。当将本发明的式(I)化合物用作光引发剂时，其用量是常规的，或者通过例行的预备试验即可确定。Therefore, according to the third aspect of the present invention, there is provided the use of 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. When the compound of formula (I) of the present invention is used as a photoinitiator, the amount used is conventional, or can be determined by routine preliminary tests.
由此，本发明还涉及一种包含本发明醚官能化香豆素肟酯化合物的可光固化组合物。Thus, the present invention also relates to a photocurable composition comprising the ether-functionalized coumarin oxime ester compound of the present invention.
在可光固化组合物中，本发明光引发剂的量通常为0.01-10重量％，优选0.1-6重量％，如0.2-5重量％，基于可光固化组合物的活性成分量。In the photocurable composition, 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.
在本公开的上下文中，活性成分是指可光固化组合物中除去溶剂之外的成分。In the context of the present disclosure, active ingredients refer to ingredients in the photocurable composition other than the solvent.
除了本发明的光引发剂之外，所述可光固化组合物还包含光固化树脂。 In addition to the photoinitiator of the present invention, the photocurable composition further comprises a photocurable resin.
在本发明中，光固化树脂是指含有不饱和碳碳双键的低聚物或预聚物。该低聚物或预聚物经光线照射后，能由光引发剂引发聚合反应，进而发生交联固化。光固化树脂是光固化产品(例如UV涂料、UV油墨、UV胶粘剂等)的主体组成。In the present invention, 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.).
作为光固化树脂，可以提及环氧(甲基)丙烯酸酯树脂、聚酯类(甲基)丙烯酸酯、聚氨酯(甲基)丙烯酸酯、烯属不饱和聚酯、氨基(甲基)丙烯酸酯树脂、光成像碱溶性树脂等。根据本发明有利的是，采用环氧(甲基)丙烯酸酯树脂、聚酯类(甲基)丙烯酸酯、聚氨酯(甲基)丙烯酸酯或它们的组合。As the photocurable 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. Advantageously, according to the present invention, epoxy (meth) acrylate resin, polyester (meth) acrylate, polyurethane (meth) acrylate or a combination thereof is used.
环氧(甲基)丙烯酸酯树脂优选双酚A环氧(甲基)丙烯酸酯，三缩丙二醇二(甲基)丙烯酸酯稀释的双酚A环氧丙烯酸酯或其组合，例如无锡树脂厂的双酚A环氧丙烯酸酯WSR-U125、台湾长兴化学公司的20％三缩丙二醇二丙烯酸酯稀释的双酚A环氧丙烯酸酯621A-80、台湾长兴化学公司的改性双酚A环氧丙烯酸酯623-100、台湾长兴化学公司的20％三缩丙二醇二丙烯酸酯稀释的改性双酚A环氧丙烯酸酯6231A-80。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.
聚酯类(甲基)丙烯酸酯优选的是高官能度的超支化聚酯丙烯酸树脂，尤其是官能度为5-30的超支化聚酯丙烯酸树脂，例如官能度为6-20的超支化聚酯丙烯酸酯预聚体。对此，可以提及如无锡诺克斯公司的超支化聚酯丙烯酸酯预聚体932-100(6官能度)、美国沙多玛公司的超支化聚酯丙烯酸酯预聚体CN2300(8官能度)、CN2301(9官能度)、CN2302(16官能度)等。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. In this regard, 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.
聚氨酯(甲基)丙烯酸酯优选脂族聚氨酯丙烯酸树酯。对此，可以提及如美国沙多玛公司的脂族聚氨酯丙烯酸酯CN9013(9官能度)、美国沙多玛公司的15％1,6-己二醇二丙烯酸酯(HDDA)稀释的脂族聚氨酯丙烯酸酯CN966B85(2官能度)、脂族聚氨酯丙烯酸酯CN962(2官能度)。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).
光固化树脂在可光固化组合物中的用量通常为10-90重量％，优选55-80重量％，基于可光固化组合物的活性成分量。在本公开的上下文中，活性成分是指可光固化组合物中除去溶剂之外的成分。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. In the context of the present disclosure, active ingredients refer to ingredients in the photocurable composition excluding solvents.
所述可光固化组合物可以进一步包含多官能活性稀释剂。 The photocurable composition may further include a multifunctional reactive diluent.
在本发明中，多官能活性稀释剂是指含有两个或两个以上的可光聚合基团的单体。多官能活性稀释剂粘度较低，溶解能力较强。多官能活性稀释剂经光源辐照后可以被活性自由基引发聚合形成交联的网络结构。In the present invention, 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.
根据本发明，优选多官能活性稀释剂为多官能(甲基)丙烯酸酯活性稀释剂。它指含有两个或两个以上的(甲基)丙烯酸酯可聚合基团的单体。作为多官能(甲基)丙烯酸酯交联剂，可以提及三羟甲基丙烷三丙烯酸酯(TMPTA)、季戊四醇四丙烯酸酯(PETTA)、丙氧化三羟甲基丙烷三丙烯酸酯(PO-TMPTA)或乙氧基三羟甲基丙烷三丙烯酸酯(EO-TMPTA)、季戊四醇三丙烯酸酯(PETA)、季戊四醇四丙烯酸酯(PETTA)、二季戊四醇五丙烯酸酯(DPEPA)、二季戊四醇六丙烯酸酯(DPHA)、二缩三丙二醇双丙烯酸酯(TPGDA)、1,6-己二醇二丙烯酸酯(HDDA)、三甘醇二甲基丙烯酸酯、二甘醇二甲基丙烯酸酯、丙三醇双丙烯酸酯及二甲基丙烯酸氨基甲酸酯(UDMA)等。According to the present invention, it is preferred that the multifunctional reactive diluent is a multifunctional (meth)acrylate reactive diluent. It refers to a monomer containing two or more (meth)acrylate polymerizable groups. As 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 diacrylate (HDDA), triethylene glycol dimethacrylate, diethylene glycol dimethacrylate, glycerol diacrylate and dimethacrylate urethane (UDMA) and the like can be mentioned.
多官能活性稀释剂在可光固化组合物中的用量通常为8-60重量％，优选15-45重量％，基于可光固化组合物的活性成分量。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.
根据本发明，所述可光固化组合物可以进一步包含单官能活性稀释剂。According to the present invention, the photocurable composition may further include a monofunctional reactive diluent.
在本发明中，单官能活性稀释剂是指含有一个可光聚合基团的单体。其粘度较低，溶解能力较强，可充当部分有机溶剂的作用。该单官能活性稀释剂经光源辐照后，可被活性自由基引发聚合反应。单官能活性稀释剂主要有(甲基)丙烯酸酯类化合物和乙烯基类化合物。作为(甲基)丙烯酸酯类单官能活性稀释剂，可以提及甲基丙烯酸甲酯(MMA)、丙烯酸正丁酯(BA)、丙烯酸异辛酯(2-EHA)、丙烯酸异癸酯(IDA)、丙烯酸月桂酯(LA)、(甲基)丙烯酸羟乙酯、(甲基)丙烯酸羟丙酯，以及一些带有环状结构的(甲基)丙烯酸酯。另外，作为乙烯基类单官能活性稀释剂，可以提及苯乙烯(St)、醋酸乙烯酯(VA)、N-乙烯基吡咯烷酮(NVP)等。In the present invention, 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. As (meth) 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. In addition, as vinyl monofunctional reactive diluents, styrene (St), vinyl acetate (VA), N-vinyl pyrrolidone (NVP), etc. can be mentioned.
单官能活性稀释剂在可光固化组合物中的用量通常为5-50重量％，优选8-40重量％，基于可光固化组合物的活性成分量。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.
本发明的可光固化组合物还可任选地包含有机溶剂。有机溶剂的选择是常规的。作为有机溶剂，可以提及芳烃类如苯、甲苯，卤代烷烃类如三 氯甲烷、二氯甲烷、氯乙烷，酮类如丙酮、丁酮、戊酮等，醇类如甲醇、乙醇、丙醇、异丙醇、乙二醇，及乙二醇醚类，乙二醇醚醋酸酯类，丙二醇醚类，丙二醇醚醋酸酯类等。The photocurable composition of the present invention may also optionally contain an organic solvent. The choice of organic solvent is conventional. As 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.
本发明的可光固化组合物还可任选地包含其他添加剂，比如流平剂、抗氧化剂、抗沉降剂、着色剂、杀微生物剂，比如抗菌剂及保温材料添加剂。在本发明的一个优选实施方案中，流平剂选自优卡化学的系列流平剂，特别优选360S、372S、384S、392S、400U、415U等。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. In a preferred embodiment of the present invention, the leveling agent is selected from the group consisting of A series of leveling agents, particularly preferably 360S, 372S, 384S, 392S, 400U, 415U, etc.
本发明可光固化组合物的制备是常规的，例如将本发明可光固化组合物的各个组分均匀混合在一起即可。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.
因此，本发明的另一方面还提供了可由本发明可光固化组合物得到的固化材料。得到的固化材料可以是光固化涂层，这包括包含功能性材料的涂层，UV光和/或可见光的滤色器的涂层；密封剂；光刻材料；全息记录材料；3D打印材料；平版印刷材料；光学器件的制备材料及改善机械性能的材料，例如碳纤维复合材料和/或无机纳米颗粒和/或有机纳米颗粒等。Therefore, 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.
再者，本发明还涉及一种制备光固化材料的方法，其包括用辐射波长为300-550nm，尤其是365-475nm的光源，例如UV-VIS LED光源对该可光固化组合物进行辐照。Furthermore, 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.
另外，本发明公开的化合物生产工艺简单，产率高，非常适合于工业生产。此类化合物与辐射波长为300-550nm，尤其是365-475nm的UV-VIS LED光源匹配性良好，可作为光引发剂广泛应用于UV-VIS LED光固化所涉及的领域，例如涂料、油墨、微电子、印刷、3D打印、牙科材料等领域。因此，本发明的醚官能化香豆素肟酯类光引发剂具有很好的市场前景。In addition, 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.
此外，鉴于目前可应用于UV-VIS LED光源，尤其是长波长UV-VIS LED光源深层固化的光引发剂品种较少，从一定程度上限制了UV-VIS LED光源在光固化领域的推广应用。故而，本发明的醚官能化香豆素肟酯类光引发剂可为推动绿色环保的UV-VIS LED光源在UV光固化行业的广泛应用做出贡献。 In addition, given that there are currently few types of photoinitiators that can be used for deep curing of UV-VIS LED light sources, especially long-wavelength UV-VIS LED light sources, the promotion and application of UV-VIS LED light sources in the field of photocuring is limited to a certain extent. Therefore, 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.
实施例Example
下面将结合实施例对本发明的方案进行解释。本领域技术人员将会理解，下面的实施例仅用于说明本发明，而不应视为限制本发明的范围。实施例中未注明具体技术或条件的，按照本领域内文献所描述的技术或条件或产品说明书进行。The scheme of the present invention will be explained below in conjunction with embodiments. It will be appreciated by those skilled in the art that the following embodiments are only used to illustrate the present invention and should not be construed as limiting the scope of the present invention. Where specific techniques or conditions are not indicated in the embodiments, the techniques or conditions or product specifications described in the literature in the art are followed.
实施例1：化合物1的制备
Example 1: Preparation of Compound 1
化合物1的合成路线如下：
The synthetic route of compound 1 is as follows:
中间化合物1a的合成Synthesis of intermediate compound 1a
将3-(叔丁基)-2-羟基-5-甲氧基苯甲醛(0.05mol，10.42g)加入盛有50mL乙醇的250mL三口圆底烧瓶中，搅拌均匀后，然后加入哌啶(0.015mol，1.28g)和乙酰乙酸乙酯(0.07mol，9.11g)，再将反应混合物加热至回流，搅拌反应4h。待反应完全后，将混合物冷却至室温，过滤得黄色固体，然后用乙醇重结晶，得11.24g产品，产率82％，经鉴定为化合物1a。1H-NMR(400MHz,CDCl3)δ8.45(s,1H),7.23(d,1H),6.85(d,1H), 3.84(s,3H),2.73(s,3H),1.49(s,9H)。3-(tert-butyl)-2-hydroxy-5-methoxybenzaldehyde (0.05 mol, 10.42 g) was added to a 250 mL three-necked round-bottom flask containing 50 mL of ethanol, and then piperidine (0.015 mol, 1.28 g) and ethyl acetoacetate (0.07 mol, 9.11 g) were added after stirring evenly, and the reaction mixture was heated to reflux and stirred for 4 h. After the reaction was complete, the mixture was cooled to room temperature, filtered to obtain a yellow solid, and then recrystallized from ethanol to obtain 11.24 g of the product with a yield of 82%, which was identified as compound 1a. 1H-NMR (400 MHz, CDCl 3 )δ8.45(s,1H),7.23(d,1H),6.85(d,1H), 3.84(s,3H),2.73(s,3H),1.49(s,9H).
中间化合物1b的合成Synthesis of intermediate compound 1b
将中间化合物1a(10.96g，0.04mol)和150mL乙醇和水的混合溶液(V乙醇：V水＝2:1)倒入250mL三口圆底烧瓶中，再加入盐酸羟胺(6.95g，0.1mol)和醋酸钠(6.56g，0.08mol)。40℃下搅拌反应1.5h后，水洗反应液，然后将有机相真空旋蒸后得淡黄色固体，乙醇重结晶，得10.76g产品，产率为93％，经鉴定为化合物1b。1H-NMR(600MHz,C3D6O)10.48(s,1H),7.93(s,1H),7.11(q,2H),3.83(s,3H),2.17(s,3H),1.49(s,9H)。The intermediate compound 1a (10.96 g, 0.04 mol) and 150 mL of a mixed solution of ethanol and water (V ethanol : V water = 2:1) were poured into a 250 mL three-necked round-bottom flask, and then hydroxylamine hydrochloride (6.95 g, 0.1 mol) and sodium acetate (6.56 g, 0.08 mol) were added. After stirring at 40°C for 1.5 h, the reaction solution was washed with water, and then the organic phase was vacuum-rotated to obtain a light yellow solid, which was recrystallized from ethanol to obtain 10.76 g of the product with a yield of 93%. It was identified as compound 1b. 1H-NMR (600 MHz, C 3 D 6 O) 10.48 (s, 1H), 7.93 (s, 1H), 7.11 (q, 2H), 3.83 (s, 3H), 2.17 (s, 3H), 1.49 (s, 9H).
目标产物1的合成Synthesis of target product 1
将上述中间化合物1b(8.67g，0.03mol)和50ml二氯甲烷加入到100mL三口圆底烧瓶中，然后加入乙酰氯(3.53g，0.045mol)和三乙胺(5.46g，0.054mol)，室温搅拌反应1.5h。终止反应，将反应液过滤后，滤液倒入水中，用乙酸乙酯萃取，收集有机相后依次用稀盐酸溶液、饱和碳酸钠溶液、蒸馏水洗涤，然后收集有机相，并用MgSO4干燥过夜。过滤后减压蒸馏蒸掉有机相后得黄色粉末状固体8.94g，产率90.0％，经鉴定为化合物1。化合物1的核磁数据见表1。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.
实施例2-68Example 2-68
重复实施例1的方法，适当改变反应原料，分别获得下表1所示化合物2-68及其核磁数据。 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.
表1













Table 1













感光性能测试：Photosensitivity test:
1.采用乌格拉(Ugra)晒版测试条作掩模来测试光引发剂的感光性能。乌格拉晒版测试条的各段见图1。乌格拉晒版测试条分为5个控制段，从左到右分别是：连续密度梯尺段(1)；阴阳微米等线同心圆线圈段(2)；全阶调网点段(3)；重影控制段(4)；高光、暗调控制段(5)。第一段：连续密度梯尺段共分为13个梯度用来控制曝光量和显影。第二段：阴阳微米等线同心圆线圈段由12个阴阳微米等线组成的同心圆线圈图，分别为4、6、8、10、12、15、20、25、30、40、55、70，用于检测晒PS版时的曝光和显影情况。第三段：全阶调网点段由10％-100％、极差为10％的平网组成，分为上下两行排列，用于测量晒版、打样和印刷的网点转移情况，并可测制出胶片网点与晒版、打样和印刷网点变化曲线图。第四段：重影控制段由线宽60线/厘米、面积率为60％的细线条组成，它分为4小块，0°、45°、90°三个角度排列线条和有1/4的D小块中以两边90°、中间小方块45°、上下90°的小短线排列。第五段：高光、暗调控制段，精细网点段由高光小网点与暗调深网点对应排列，用于精细控制晒版曝光和显影的准确性。将包含光引发剂的可光固化组合物涂敷于铝基板上，然后曝光显影，从得到的图像的连续调梯尺评价感度，从微线条测试块区域评价精度，从而评价可光固化组合物配方的优劣。1. 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.
具体地，按照以下步骤对式(I)化合物的感光性能进行测试。Specifically, the photosensitivity of the compound of formula (I) is tested according to the following steps.
(1)按照如下组成配制含有光引发剂的可光固化组合物：
(1) A photocurable composition containing a photoinitiator is prepared according to the following composition:
上述组合物中光引发剂为本发明的式(I)化合物或现有技术已知的光引发剂(作对比)(具体见下文及表2)。丙烯酸酯树脂为从上海釜顺国际贸易有限公司购买的商品名为FS2600K的树脂，官能度为2，数均分子量1400。二季戊四醇六丙烯酸酯为从上海釜顺国际贸易有限公司购买的商品名为 GM66G0C的产品。结晶紫染料为从上海国药购买的商品名为六甲基玫苯胺盐酸盐的产品。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.
(2)将上述各组合物在黄光下搅拌混合均匀，利用离心机旋涂在预先处理好的并满足下列条件的PS铝版基上：(2) The above compositions were stirred and mixed evenly under yellow light, and spin-coated on a pre-treated PS aluminum substrate that met the following conditions using a centrifuge:
铝板基尺寸：1030mm×800mmAluminum base size: 1030mm×800mm
铝板基厚度：0.28-0.3mmAluminum base thickness: 0.28-0.3mm
砂目规格：Ra＝0.5-0.6μmGrit size: Ra = 0.5-0.6μm
Rh＝0.3-0.35μmRh＝0.3-0.35μm
阳极氧化膜重量：3-3.5g/m2 Anodized film weight: 3-3.5g/ m2
控制离心涂布机的转速，使涂在铝版基上的涂布量(以固含量计)为1.0-2.5g/m2，在离心涂布机上初步干燥后，转移到100℃的鼓风干燥机中干燥3分钟，得紫激光CTP原版。然后，用Ugra测试条做掩模测试版材的感光性能，曝光一段时间后用1％NaOH水溶液显影。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.
在曝光区，可光聚合化合物在光引发剂存在下发生聚合反应，在显影液中不溶，而非曝光区是可溶的，于是得到阴图。通过曝光显影，从得到的图像的连续调梯尺评价光引发剂的感度。引发剂体系感光度特征为显影后保留了(即聚合的)最高灰阶数。灰阶数越高，表明测试体系灵敏度越高。结果示于表2中。In the exposed area, 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.
另外，于同等条件下，选用BASF的市售肟酯OXE-01、OXE-02和OXE-03以及现有技术中的COXE-08、COXE-09、COXE-19、COXE-31、COXE-35、COXE-37、COXE-41和COXE-48(具体结构分别如下)作对比。结果也汇于表2中。

In addition, under the same conditions, BASF's commercially available oxime esters OXE-01, OXE-02 and OXE-03 and the prior art COXE-08, COXE-09, COXE-19, COXE-31, COXE-35, COXE-37, COXE-41 and COXE-48 (specific structures are as follows) were selected for comparison. The results are also summarized in Table 2.

表2


Table 2


由表2中的实验结果可以明显看出，本发明的实施例化合物1-68在365nm、385nm、400nm、425nm、450nm、475nm和500nm处灰阶数均高于BASF的市售肟酯OXE-01、OXE-02和OXE-03，也均高于现有技术中披露的肟酯COXE-08、COXE-09、COXE-19、COXE-31、COXE-35、COXE-37、COXE-41和COXE-48。也就是说，本发明的醚官能化香豆素肟酯类光引发剂在365nm、385nm、400nm、425nm、450nm、475nm和500nm波长处感光性能更为优异，适合用于365nm、385nm、400nm、425nm、450nm、475nm和500nm的UV-VIS LED光源。It can be clearly seen from the experimental results in Table 2 that the grayscale numbers of Example Compounds 1-68 of the present invention at 365nm, 385nm, 400nm, 425nm, 450nm, 475nm and 500nm are higher than those of the commercially available oxime esters OXE-01, OXE-02 and OXE-03 of BASF, and are also higher than those of 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. That is to say, 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.
2.采用傅里叶变换红外——实时红外方法测试光引发剂引发丙烯酸酯树脂聚合的碳碳双键红外光谱特征峰面积变化来测试光引发剂的感光性能。丙烯酸酯树脂被曝光30秒时的碳碳双键转化率见表3。丙烯酸酯树脂的碳碳双键转化率通过红外光谱特征峰面积变化来体现，选取的特征峰面积位于1653-1603cm-1。根据不同测试条件下的碳碳双键转化率随时间变 化的趋势，评价光引发剂在不同条件下的光引发性能。2. 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.
具体地，按照以下步骤对式(I)化合物的光引发性能进行测试。Specifically, the photoinitiating performance of the compound of formula (I) was tested according to the following steps.
(1)按照如下组成配制含有光引发剂的可光固化组合物：(1) A photocurable composition containing a photoinitiator is prepared according to the following composition:
FS2600K丙烯酸酯树脂         100质量份FS2600K acrylic resin         100 parts by mass
光引发剂                    2质量份Photoinitiator                    2 parts by mass
上述组合物中光引发剂为本发明的式(I)化合物或现有技术已知的光引发剂(作对比)。丙烯酸酯树脂为从上海釜顺国际贸易有限公司购买的商品名为FS2600K的树脂，官能度为2，数均分子量1400。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.
(2)将上述各组合物在黄光下搅拌混合均匀且确保溶解后，利用注射器将可光固化组合物注入在预先处理好的并满足下列条件的KBr双盐片模具中：(2) After the above compositions are stirred and mixed under yellow light to ensure that they are evenly dissolved, the photocurable composition is injected into a pre-treated KBr double salt sheet mold that meets the following conditions using a syringe:
KBr双盐片尺寸：15mm×15mmKBr double salt tablet size: 15mm×15mm
KBr双盐片厚度：3mmKBr double salt sheet thickness: 3mm
KBr双盐片间隙：0.5mmKBr double salt gap: 0.5mm
通过观察注射器刻度，使注射入KBr双盐片模具中的可光固化组合物量为0.2ml，在注射完成后，将KBr双盐片模具放入实时红外测试用的傅里叶变换红外光谱仪中的小黑箱中，小黑箱的结构为上方红外测试光线垂直对准穿透KBr双盐片模具，KBr双盐片模具上方45°LED点光源对准KBr双盐片模具，LED点光源距离KBr双盐片模具高度1cm。By observing the scale on the syringe, the amount of the photocurable composition injected into the KBr double salt sheet mold was made to be 0.2 ml. After the injection was completed, 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.
同时启动红外光谱检测和打开LED光源，使得KBr双盐片模具中的可光固化组合物在检测碳碳双键特征峰面积变化的同时得以曝光。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.
在LED点光源的照射下，可光聚合化合物在引发剂存在下发生聚合反应，使得碳碳双键特征峰面积不断减少，直至基本消失。根据碳碳双键特征峰面积随曝光时间的变化的数据，换算得到碳碳双键随时间变化的转化率。被曝光30秒时的结果示于表3中。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.
根据碳碳双键特征峰面积随曝光时间的变化的数据，换算得到碳碳双键随时间变化的转化率的公式：
According to the data of the change of the characteristic peak area of carbon-carbon double bond with exposure time, the formula of the conversion rate of carbon-carbon double bond with time is obtained:
另外，于同等条件下，选用BASF的市售肟酯OXE-01、OXE-02和OXE-03以及现有技术中的COXE-08、COXE-09、COXE-19、COXE-31、COXE-35、COXE-37、COXE-41和COXE-48(具体结构如上文所示)作对比。结果也汇于表3中。In addition, under the same conditions, BASF's commercially available oxime esters OXE-01, OXE-02 and OXE-03 and the prior art COXE-08, COXE-09, COXE-19, COXE-31, COXE-35, COXE-37, COXE-41 and COXE-48 (specific structures as shown above) were selected for comparison. The results are also summarized in Table 3.
表3


table 3


由表3中的实验结果可以明显看出，本发明的实施例化合物1-68在365nm、385nm、400nm、425nm、450nm和475nm处双键转化率均高于BASF的市售肟酯OXE-01、OXE-02和OXE-03，也均高于现有技术中披露的肟酯COXE-08、COXE-09、COXE-19、COXE-31、COXE-35、COXE-37、COXE-41和COXE-48。也就是说，本发明的醚官能化香豆素肟酯类光引发剂在365nm、385nm、400nm、425nm、450nm和475nm波长处感光性能更为优异，适合用于365nm、385nm、400nm、425nm、450nm和475nm的UV-VIS LED光源。It can be clearly seen from the experimental results in Table 3 that the double bond conversion rates of 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. In other words, 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.
综上所述，本发明的醚官能化香豆素肟酯类光引发剂在365nm、385nm、400nm、425nm、450nm和475nm波长处具有较好的感光性能，优于现阶段BASF的市售肟酯OXE-01、OXE-02和OXE-03，也优于现有技术中披露的肟酯COXE-08、COXE-09、COXE-19、COXE-31、COXE-35、COXE-37、COXE-41和COXE-48，特别是在425nm、450nm和475nm波长处，感光性能在可见光区域具有明显的优势。 In summary, 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.

Claims (17)

  1. 式(I)的醚官能化香豆素肟酯化合物：
    Ether functionalized coumarin oxime ester compounds of formula (I):
    其中：in:
    M为氧或硫原子；M is an oxygen or sulfur atom;
    R1分别独立地表示C1-C10烷基、C6-C10芳基或C2-C10烯基，其中前述C1-C10烷基、C6-C10芳基或C2-C10烯基任选地被卤素、C1-C6烷基和C1-C6烷氧(硫)基取代；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分别独立地表示C1-C10烷基、C3-C10环烷基、C3-C6环烷基-C1-C4烷基或C1-C4烷基-C3-C6环烷基，其中前述C1-C10烷基、C3-C10环烷基、C3-C6环烷基-C1-C4烷基或C1-C4烷基-C3-C6环烷基任选地被卤素、C1-C6烷基和C1-C6烷氧(硫)基取代； 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;
    R3分别独立地表示C4-C10烷基、C4-C10环烷基、C4-C6环烷基-C1-C4烷基或C1-C4烷基-C4-C6环烷基，其中前述C4-C10烷基、C4-C10环烷基、C4-C6环烷基-C1-C4烷基或C1-C4烷基-C4-C6环烷基任选地被卤素取代；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;
    R4分别独立地表示氢、或任选被卤素取代的C1-C4烷基；R 4 each independently represents hydrogen, or C 1 -C 4 alkyl optionally substituted by halogen;
    R5、R6分别独立地表示氢、C1-C10烷基、C3-C10环烷基、C3-C6环烷基-C1-C4烷基或C1-C4烷基-C3-C6环烷基，其中前述C1-C10烷基、C3-C10环烷基、C3-C6环烷基-C1-C4烷基或C1-C4烷基-C3-C6环烷基任选地被卤素、C1-C6烷基和C1-C6烷氧(硫)基取代；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相互独立地表示C1-C10烷基、C3-C10环烷基、C3-C6环烷基-C1-C4烷基、C1-C4烷基-C3-C6环烷基或C6-C10芳基，其中前述C1-C10烷基、C3-C10环烷基、C3-C6环烷基-C1-C4烷基、C1-C4烷基-C3-C6环烷基或C6-C10芳基任选地被卤素、C1-C6烷基和C1-C6烷氧(硫)基取代。 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.
  2. 根据权利要求1的醚官能化香豆素肟酯化合物，其中：The ether-functionalized coumarin oxime ester compound according to claim 1, wherein:
    R1分别独立地表示C1-C8烷基、C6-C8芳基或C2-C8烯基，其中前述C1-C8烷基、C6-C8芳基或C2-C8烯基任选地被卤素、C1-C6烷基和C1-C6烷氧(硫)基取代，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,
    优选R1分别独立地表示C1-C4烷基、苯基或C2-C4烯基，其中前述C1-C4烷基、苯基或C2-C4烯基任选地被氟、氯、溴和C1-C4烷基取代；和/或Preferably, 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分别独立地表示C1-C8烷基、C3-C8环烷基、C3-C6环烷基-C1-C2烷基或C1-C2烷基-C3-C6环烷基，其中前述C1-C6烷基、C3-C8环烷基、C3-C6环烷基-C1-C2烷基或C1-C2烷基-C3-C6环烷基任选地被卤素、C1-C6烷基和C1-C6烷氧(硫)基取代， 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,
    优选R2分别独立地表示C1-C4烷基、C5-C6环烷基、C5-C6环烷基-C1-C2烷基或C1-C2烷基-C5-C6环烷基，其中前述C1-C4烷基、C5-C6环烷基、C5-C6环烷基-C1-C2烷基或C1-C2烷基-C5-C6环烷基任选地被氟、氯、溴和C1-C4烷基取代；和/或Preferably, 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
    R4分别独立地表示氢、或任选被氟、氯和溴取代的C1-C4烷基，R 4 each independently represents hydrogen, or C 1 -C 4 alkyl optionally substituted by fluorine, chlorine or bromine,
    优选R4为氢；和/或Preferably R 4 is hydrogen; and/or
    R5、R6分别独立地表示氢、C1-C8烷基、C3-C8环烷基、C3-C6环烷基-C1-C2烷基或C1-C2烷基-C3-C6环烷基，其中前述C1-C6烷基、C3-C8环烷基、C3-C6环烷基-C1-C2烷基或C1-C2烷基-C3-C6环烷基任选地被卤素、C1-C6烷基和C1-C6烷氧(硫)基取代，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,
    优选R5、R6分别独立地表示氢、C1-C4烷基、C5-C6环烷基、C5-C6环烷基-C1-C2烷基或C1-C2烷基-C5-C6环烷基，其中前述C1-C4烷基、C5-C6环烷基、C5-C6环烷基-C1-C2烷基或C1-C2烷基-C5-C6环烷基任选地被氟、氯和溴取代；和/或Preferably, 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 by fluorine, chlorine and bromine; and/or
    R7相互独立地表示C1-C8烷基、C3-C8环烷基、C3-C6环烷基-C1-C2烷基、C1-C2烷基-C3-C6环烷基或C6-C8芳基，其中C1-C4烷基、C3-C8环烷基、C3-C6环烷基-C1-C2烷基、C1-C2烷基-C3-C6环烷基或C6-C8芳基任选地被卤素、C1-C6烷基和C1-C6烷氧(硫)基取代， 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,
    优选R7分别独立地表示C1-C4烷基或苯基，其中前述C1-C4烷基或苯基任选地被氟、氯、溴和C1-C4烷基取代。Preferably, 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.
  3. 根据权利要求1或2的醚官能化香豆素肟酯化合物，其中：The ether-functionalized coumarin oxime ester compound according to claim 1 or 2, wherein:
    R3分别独立地表示C4-C8烷基，优选C4-C6烷基，尤其是C4烷基，其中前述C4-C8烷基、C4-C6烷基或C4烷基任选地被氟、氯和溴取代。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.
  4. 根据权利要求1-3中任一项的醚官能化香豆素肟酯化合物，其中R3为叔丁基。The ether-functionalized coumarin oxime ester compound according to any one of claims 1 to 3, wherein R 3 is tert-butyl.
  5. 根据权利要求1-4中任一项的醚官能化香豆素肟酯化合物，其中所述醚官能化香豆素肟酯化合物选自下组：





    The ether-functionalized coumarin oxime ester compound according to any one of claims 1 to 4, wherein the ether-functionalized coumarin oxime ester compound is selected from the group consisting of:





  6. 一种制备根据权利要求1-5中任一项的醚官能化香豆素肟酯化合物的方法，包括以下步骤：A method for preparing an ether-functionalized coumarin oxime ester compound according to any one of claims 1 to 5, comprising the following steps:
    (1)克脑文盖尔(Knoevenagel)缩合反应:使式(II)化合物与R2-COCH2COOR(R＝C1-C6烷基)进行克脑文盖尔缩合反应，得到式(III)化 合物：
    (1) Knoevenagel condensation reaction: The compound of formula (II) is subjected to Knoevenagel condensation reaction with R 2 -COCH 2 COOR (R=C 1 -C 6 alkyl) to obtain the compound of formula (III) Compound:
    (2)肟化反应：使式(III)化合物与羟胺和/或盐酸羟胺进行肟化反应，得到式(IV)化合物(2) Oximation reaction: The compound of formula (III) is subjected to an oximation reaction with hydroxylamine and/or hydroxylamine hydrochloride to obtain a compound of formula (IV):
    以及 as well as
    (3)酯化反应：将式(IV)化合物酯化，得到式(I)化合物，(3) Esterification reaction: esterifying the compound of formula (IV) to obtain the compound of formula (I),
    其中上述各式中的参数如权利要求1-5中任一项所定义。The parameters in the above formulae are defined as in any one of claims 1-5.
  7. 根据权利要求6的方法，其中步骤(1)的克脑文盖尔缩合反应在选自下组的一种或多种催化剂存在下进行：胺类如伯胺、仲胺、叔胺及其相应的铵盐，优选哌啶；无机碱如氢氧化钠、碳酸钠；无机盐如氟化钾、磷酸铝、磷酸氢二铵；路易斯酸和叔胺结合物如TiCl4/哌啶或TiCl4/三乙胺。The method according to claim 6, wherein the Knoevenagel condensation reaction 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 and 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.
  8. 根据权利要求6或7的方法，其中在步骤(1)的克脑文盖尔缩合反应中，式(II)化合物与R2-COCH2COOR(R＝C1-C6烷基)，优选乙酰乙酸乙酯的摩尔比为1:0.1-1:1.5，优选1:0.3-1:1。The method according to claim 6 or 7, wherein in the Knoevenagel condensation reaction of step (1), the molar ratio of the compound of formula (II) to R2 - COCH2COOR (R= C1 - C6 alkyl), preferably ethyl acetoacetate, is 1:0.1-1:1.5, preferably 1:0.3-1:1.
  9. 根据权利要求6-8中任一项的方法，其中步骤(2)的肟化反应在乙酸钠、吡啶、哌啶、三乙胺和/或四甲基氢氧化铵作为催化剂存在下进行。The method according to any one of claims 6 to 8, wherein the oximation reaction of step (2) is carried out in the presence of sodium acetate, pyridine, piperidine, triethylamine and/or tetramethylammonium hydroxide as a catalyst.
  10. 根据权利要求6-9中任一项的方法，其中在步骤(2)的肟化反应中，式(III)化合物与羟胺和/或盐酸羟胺的摩尔比为1:2.5-1.25:2，优选1:2.2-1.1:2。The method according to any one of claims 6 to 9, wherein in the oximation reaction of 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.
  11. 根据权利要求6-10中任一项的方法，其中：A method according to any one of claims 6 to 10, wherein:
    步骤(3)的酯化采用选自下式(Va)、(Vb)和(Vc)化合物的酯化试剂进行：
    The esterification in step (3) is carried out using an esterification agent selected from the compounds of the following formulae (Va), (Vb) and (Vc):
    其中X为卤素，尤其是氯，R1如第1-5项中任一项所定义。wherein X is halogen, especially chlorine, and R1 is as defined in any one of items 1-5.
  12. 根据权利要求6-11中任一项的方法，其中步骤(3)的酯化反应在选自下组的一种或多种催化剂存在下进行：硫酸、高氯酸、氯化锌、三氯化铁、吡啶、对甲基苯磺酸、氢氧化钠、氢氧化钾、碳酸钠、碳酸氢钠、叔丁醇钠、乙醇钠、氢化钠、氢化钾、氢化钙和叔胺，例如三烷基胺，如三甲胺和三乙胺。The method according to any one of claims 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.
  13. 根据权利要求6-12中任一项的方法，其中在步骤(3)的酯化反应中，式(IV)化合物与选自式(Va)、(Vb)和(Vc)化合物的酯化试剂的摩尔比为1:1.2-1:2.0，优选1:1.4-1:1.8。The method according to any one of claims 6 to 12, wherein in the esterification reaction of 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.
  14. 根据权利要求1-5中任一项或者根据权利要求6-13中任一项的方法获得的醚官能化香豆素肟酯化合物作为光引发剂的用途，尤其是在UV-VIS LED光源固化体系中作为光引发剂的用途，特别是在辐射波长为300-550nm，尤其是365-475nm的光源固化体系中作为光引发剂的用途。The use of the ether functionalized coumarin oxime ester compound obtained according to any one of claims 1 to 5 or according to any one of claims 6 to 13 as a photoinitiator, especially the use as a photoinitiator in a UV-VIS LED light source curing system, especially the use as a photoinitiator in a light source curing system with a radiation wavelength of 300-550nm, especially 365-475nm.
  15. 一种包含至少一种根据权利要求1-5中任一项或者根据权利要求6-13中任一项的方法获得的醚官能化香豆素肟酯化合物的可光固化组合物。A photocurable composition comprising at least one ether-functionalized coumarin oxime ester compound obtained according to any one of claims 1 to 5 or according to a process according to any one of claims 6 to 13.
  16. 可由权利要求15的可光固化组合物得到的固化材料。A cured material obtainable from the photocurable composition of claim 15.
  17. 一种制备光固化材料的方法，其包括用辐射波长为300-550nm，尤其是365-475nm的光源，例如UV-VIS LED光源对权利要求15的可光固化组合物进行辐照。 A method for preparing a photocurable material, comprising irradiating the photocurable composition of claim 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.
PCT/CN2023/122137 2022-09-28 2023-09-27 Ether-functionalized coumarin oxime ester compound, and preparation and use thereof WO2024067718A1 (en)

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