CN115583931A - Ether functionalized coumarin oxime ester compound and preparation and application thereof - Google Patents

Ether functionalized coumarin oxime ester compound and preparation and application thereof Download PDF

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CN115583931A
CN115583931A CN202211192253.4A CN202211192253A CN115583931A CN 115583931 A CN115583931 A CN 115583931A CN 202211192253 A CN202211192253 A CN 202211192253A CN 115583931 A CN115583931 A CN 115583931A
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CN115583931B (en
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庞玉莲
樊书珩
邹应全
孙逊
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HUBEI GURUN TECHNOLOGY CO LTD
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Abstract

The present invention relates to ether functionalized coumarin oxime ester compounds of formula (I) wherein the variables are as defined in the specification. The compound can have good photosensitive absorption in the range of 300-550nm, especially 365-450nm, can rapidly generate photochemical reaction after absorbing light energy, can initiate polymerizable monomers to polymerize within seconds, and can complete the polymerization reaction within 10 minutes (especially 3 minutes), has obvious advantages in photosensitivity, and has good thermal stability, storage stability and solubility, thereby being suitable for being used as a photoinitiator for UV-VIS LED light source curing. The invention also relates to a preparation method and application of the ether functionalized coumarin oxime ester compound shown in the formula (I), and the compound can be used as a photoinitiator and is especially suitable for UV-VIS LED light source curing.
Figure DDA0003869476000000011

Description

Ether functionalized coumarin oxime ester compound and preparation and application thereof
Technical Field
The invention belongs to the technical field of photocuring, 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 invention also relates to the preparation and application of the ether functionalized coumarin oxime ester compound.
Background
The photoinitiator is also called photosensitizer or light curing agent, and is a compound which can absorb energy with certain wavelength in an ultraviolet light region (250-400 nm) or a visible light region (400-600 nm) to generate free radicals, cations and the like so as to initiate the polymerization, crosslinking and curing of monomers. As an important component of the photocuring system, the photoinitiator, although contained in the photocuring system in a low content, is a key component, plays a role in determining the photocuring speed, and also has to meet the requirements of different photocuring conditions and applications. It is related to the fact that the formulated system can be cross-linked and cured rapidly at light irradiation, thereby changing from a liquid state to a solid state. Meanwhile, with the wide application of the light curing technology in the traditional fields of coatings, printing ink, microelectronics, printing and the like and in the novel fields of preparing laser video and three-dimensional elements and the like, and with the continuous research and development of the UV-VIS LED light source curing technology, in order to meet the wide application requirements of the UV-VIS LED light source curing technology, the development of a photoinitiator suitable for the UV-VIS LED light source is required.
For those skilled in the art, oxime ester photoinitiators, as free radical photoinitiators, have become a class of photoinitiators that have been gaining attention in recent years due to their outstanding activity and excellent photosensitivity. The oxime esters OXE01 and OXE02 (both from BASF) are currently commercially available and have excellent photoinitiating activity, but their UV absorption range is relatively short (250-350 nm) and cannot meet the requirements of the UV-VIS LED light sources which are increasingly developed at present, especially the requirements which are not suitable for the UV-VIS LED light sources (such as 365nm, 385nm, 395nm, 405nm, 425nm, 450nm and 475 nm).
In addition, there are also some patents related to oxime ester photoinitiators, for example, CN102775527A discloses a diphenyl sulfide ketoxime ester photoinitiator and a preparation method thereof, and CN102492059A discloses a substituted diphenyl sulfide ketoxime ester photoinitiator, and the like. However, most initiators also have uv absorption wavelengths staying between 250 and 350nm and still cannot be matched with the increasingly developed long wavelength LED light sources. In addition, CN104817653A discloses a coumarin aldoxime ester compound suitable for curing by a UV-LED light source, however, studies show that the thermal stability of the compound is not as good as OXE-01. In addition, the oxime ester photoinitiators used for the UV-VIS LED light source curing system reported at present are not many, and the yellowing phenomenon of the oxime ester is still not solved, so that the application of the oxime ester photoinitiator is greatly limited.
In view of this, research and development of oxime ester photoinitiators with higher performance are still core work in the field, and especially, development of oxime ester photoinitiators which are suitable for the currently rapidly developed UV-VIS LED light source and have high photosensitivity and high stability and are easy to prepare becomes a research direction of the current oxime ester photoinitiators.
Disclosure of Invention
In view of the problems in the prior art, the inventors of the present invention conducted extensive and intensive studies on photoinitiators suitable for curing with UV-VIS LED light sources (radiation wavelength of 300 to 550nm, especially 365 to 475 nm), and sought to find a photoinitiator which can replace OXE01 and OXE02 to be more suitable for curing with UV-VIS LED light sources, and which has excellent photosensitivity, good thermal stability and solubility.
The inventor finds that a novel ether functionalized coumarin oxime ester compound is formed by introducing a specific ether functional group structural part into a specific structure coumarin compound at a specific position, can have good photosensitive absorption in a range of 300-550nm, particularly 365-475nm, can rapidly generate photochemical reaction after absorbing light energy, initiates a polymerizable monomer to polymerize within seconds, and completes the polymerization within 10 minutes (particularly 3 minutes), so that the ether functionalized coumarin oxime ester compound has obvious advantages in photosensitivity, and has good thermal stability, storage stability and solubility, thereby being suitable for being used as a photoinitiator for curing a UV-VIS LED light source.
The object of the present invention is achieved based on the above findings.
Therefore, the invention aims to provide an ether functionalized coumarin oxime ester compound, which has the absorption wavelength suitable for the radiation curing of a UV-VIS LED light source and also has good thermal stability, storage stability and solubility.
It is another object of the present invention to provide a process for preparing the ether functionalized coumarin oxime ester compounds of the present invention.
Still another object of the present invention is to provide the use of the ether functionalized coumarin oxime ester compounds of the present invention as photoinitiators or photosensitizers.
The technical solution for achieving the above object of the present invention can be summarized as follows:
1. an ether functionalized coumarin oxime ester compound of formula (I):
Figure BDA0003869475980000031
wherein:
m is an oxygen or sulfur atom;
R 1 each independently represents C 1 -C 10 Alkyl radical, C 6 -C 10 Aryl or C 2 -C 10 Alkenyl, wherein the aforementioned C 1 - C 10 Alkyl radical, C 6 -C 10 Aryl or C 2 -C 10 Alkenyl optionally substituted by halogen, C 1 -C 6 Alkyl and C 1 -C 6 Alkoxy (thio) substituted;
R 2 each independently represents C 1 -C 10 Alkyl radical, C 3 -C 10 Cycloalkyl radical, 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 radical, C 3 -C 10 Cycloalkyl radical, C 3 - C 6 cycloalkyl-C 1 -C 4 Alkyl or C 1 -C 4 alkyl-C 3 -C 6 Cycloalkyl optionally substituted by halogen, C 1 -C 6 Alkyl and C 1 -C 6 Alkoxy (thio) substituted;
R 3 each independently represents C 4 -C 10 Alkyl radical, C 4 -C 10 Cycloalkyl radical, 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 radical, 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 with halogen;
R 4 each independently represents hydrogen or C optionally substituted by halogen 1 -C 4 An alkyl group;
R 5 、R 6 each independently represents hydrogen or C 1 -C 10 Alkyl radical, 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 radical, C 3 -C 10 Cycloalkyl radical, C 3 -C 6 cycloalkyl-C 1 -C 4 Alkyl or C 1 -C 4 alkyl-C 3 -C 6 Cycloalkyl optionally substituted by halogen, C 1 -C 6 Alkyl and C 1 -C 6 Alkoxy (thio) substituted;
R 7 independently of one another represent C 1 -C 10 Alkyl radical, C 3 -C 10 Cycloalkyl radical, C 3 -C 6 cycloalkyl-C 1 -C 4 Alkyl radical, C 1 -C 4 alkyl-C 3 -C 6 Cycloalkyl or C 6 -C 10 Aryl, wherein the foregoing C 1 -C 10 Alkyl radical, C 3 -C 10 Cycloalkyl radical, C 3 -C 6 cycloalkyl-C 1 -C 4 Alkyl radical, C 1 -C 4 alkyl-C 3 -C 6 Cycloalkyl or C 6 -C 10 Aryl being optionally substituted by halogen, C 1 -C 6 Alkyl and C 1 -C 6 Alkoxy (thio) substituted.
2. The ether-functionalized coumarin oxime ester compound according to item 1, wherein:
R 1 each independently represents C 1 -C 8 Alkyl radical, C 6 -C 8 Aryl or C 2 -C 8 Alkenyl, wherein the aforementioned C 1 -C 8 Alkyl radical, C 6 -C 8 Aryl or C 2 -C 8 Alkenyl optionally substituted by halogen, C 1 -C 6 Alkyl and C 1 -C 6 An alkoxy (thio) group is substituted,
preferably R 1 Each 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 substitution; and/or
R 2 Each independently represents C 1 -C 8 Alkyl radical, C 3 -C 8 Cycloalkyl radical, 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 radical, 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 optionally substituted by halogen, C 1 -C 6 Alkyl and C 1 -C 6 An alkoxy (thio) group,
preferably R 2 Each independently represents C 1 -C 4 Alkyl radical, C 5 -C 6 Cycloalkyl radical, 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 radical, C 5 -C 6 Cycloalkyl radical, 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, bromine andC 1 -C 4 alkyl substitution; and/or
R 4 Each independently represents hydrogen or C optionally substituted by fluorine, chlorine and bromine 1 -C 4 Alkyl, preferably R 4 Is hydrogen; and/or
R 5 、R 6 Each independently represents hydrogen or C 1 -C 8 Alkyl radical, C 3 -C 8 Cycloalkyl radical, 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 radical, C 3 -C 8 Cycloalkyl radical, C 3 -C 6 cycloalkyl-C 1 -C 2 Alkyl or C 1 -C 2 alkyl-C 3 -C 6 Cycloalkyl optionally substituted by halogen, C 1 - C 6 Alkyl and C 1 -C 6 An alkoxy (thio) group is substituted,
preferably R 5 、R 6 Each independently represents hydrogen or C 1 -C 4 Alkyl radical, C 5 -C 6 Cycloalkyl radical, 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 radical, C 5 -C 6 Cycloalkyl radical, 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 fluoro, chloro and bromo; and/or
R 7 Independently of one another represent C 1 -C 8 Alkyl radical, C 3 -C 8 Cycloalkyl, C 3 -C 6 cycloalkyl-C 1 -C 2 Alkyl radical, C 1 -C 2 alkyl-C 3 -C 6 Cycloalkyl or C 6 -C 8 Aryl radical, wherein C 1 -C 4 Alkyl radical, C 3 -C 8 Cycloalkyl radical, C 3 -C 6 cycloalkyl-C 1 -C 2 Alkyl radical, C 1 -C 2 alkyl-C 3 -C 6 Cycloalkyl or C 6 -C 8 Aryl being optionally substituted by halogen, C 1 -C 6 Alkyl and C 1 -C 6 An alkoxy (thio) group is substituted,
preferably R 7 Each independently represents C 1 -C 4 Alkyl or phenyl, wherein C is 1 -C 4 Alkyl or phenyl optionally substituted by fluorine, chlorine, bromine and C 1 -C 4 Alkyl substitution.
3. The ether-functionalized coumarin oxime ester compound according to item 1 or 2, wherein:
R 3 each independently represents C 4 -C 8 Alkyl, preferably C 4 -C 6 Alkyl, especially C 4 Alkyl radical, wherein the aforementioned C 4 -C 8 Alkyl radical, C 4 -C 6 Alkyl or C 4 Alkyl is optionally substituted with fluorine, chlorine and bromine.
4. The ether-functionalized coumarin oxime ester compound according to any one of items 1 to 3, wherein R is 3 Is a tert-butyl group.
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:
Figure BDA0003869475980000051
Figure BDA0003869475980000061
Figure BDA0003869475980000071
Figure BDA0003869475980000081
Figure BDA0003869475980000091
Figure BDA0003869475980000101
6. a process for preparing an ether functionalized coumarin ester compound as described in any one of items 1 to 5, comprising the following steps:
(1) Kenaowenagel condensation reaction of the compound of formula (II) with R 2 - COCH 2 COOR(R＝C 1 -C 6 Alkyl) to yield a compound of formula (III):
Figure BDA0003869475980000111
(2) Oximation reaction: subjecting the compound of formula (III) to oximation reaction with hydroxylamine and/or hydroxylamine hydrochloride to obtain the compound of formula (IV)
Figure BDA0003869475980000112
And
(3) Esterification reaction: esterifying the compound of formula (IV) to obtain a compound of formula (I),
wherein the parameters in each of the above formulae are as defined in any one of items 1 to 5.
7. The process 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, secondary, 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 phosphate; combinations of Lewis acids and tertiary amines, e.g. TiCl 4 Piperidine or TiCl 4 Triethylamine.
8. The process according to item 6 or 7, wherein in the knoevenagel condensation reaction of step (1), the compound of formula (II) is reacted with R 2 -COCH 2 COOR(R＝C 1 -C 6 Alkyl), preferably the molar ratio of ethyl acetoacetate is 1.1 to 1.5, preferably 1.
9. The process 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. The process 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 from 1.
11. The method according to any one of items 6 to 10, wherein:
the esterification of step (3) is carried out using an esterification reagent selected from the group consisting of compounds of the following formulae (Va), (Vb) and (Vc):
Figure BDA0003869475980000113
wherein X is halogen, especially chlorine, R 1 As defined in any one of items 1 to 5.
12. The process 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, iron trichloride, 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. The process 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 esterifying reagent selected from the compounds of formulae (Va), (Vb) and (Vc) is 1.2 to 2.0, preferably 1.4 to 1.
14. Use of the ether functionalized coumarin oxime ester compound obtained according to any one of the processes of claims 1 to 5 or according to any one of the processes of claims 6 to 13 as a photoinitiator, in particular in a UV-VIS LED light source curing system, in particular in a light source curing system with a radiation wavelength of 300 to 550nm, in particular 365 to 475 nm.
15. A photocurable composition comprising at least one ether-functionalized coumarin oxime ester compound obtained according to any one of claims 1-5 or according to the process of any one of claims 6-13.
16. A cured material obtainable from the photocurable composition of item 15.
17. A process for preparing a photocurable material comprising irradiating a photocurable composition according to item 15 with a source of radiation having a wavelength of from 300 to 550nm, especially from 365 to 475nm, for example a UV-VIS LED source.
Description of the drawings:
FIG. 1 is a schematic representation of a Ugra (Ugra) strip in which
1-a continuous density ladder section,
2-concentric circle coil segments of yin-yang micron isoline,
3-a full tone dot segment,
4-ghost control segment, and
5-highlight and dark tone control section.
Detailed Description
According to a first aspect of the present invention there is provided an ether functionalised coumarin oxime ester compound of formula (I):
Figure BDA0003869475980000131
wherein:
m is an oxygen or sulfur atom;
R 1 each independently represents C 1 -C 10 Alkyl radical, C 6 -C 10 Aryl or C 2 -C 10 Alkenyl, wherein the aforementioned C 1 - C 10 Alkyl radical, C 6 -C 10 Aryl or C 2 -C 10 Alkenyl optionally substituted by halogen, C 1 -C 6 Alkyl and C 1 -C 6 Alkoxy (thio) substituted;
R 2 each independently represents C 1 -C 10 Alkyl radical, C 3 -C 10 Cycloalkyl radical, 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 radical, C 3 -C 10 Cycloalkyl radical, C 3 - C 6 cycloalkyl-C 1 -C 4 Alkyl or C 1 -C 4 alkyl-C 3 -C 6 Cycloalkyl optionally substituted by halogen, C 1 -C 6 Alkyl and C 1 -C 6 Alkoxy (thio) substituted;
R 3 each independently represents C 4 -C 10 Alkyl radical, C 4 -C 10 Cycloalkyl radical, 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 radical, C 4 -C 10 Cycloalkyl radical, C 4 - C 6 cycloalkyl-C 1 -C 4 Alkyl or C 1 -C 4 alkyl-C 4 -C 6 Cycloalkyl is optionally substituted with halogen;
R 4 each independently represents hydrogen or C optionally substituted by halogen 1 -C 4 An alkyl group;
R 5 、R 6 each independently represents hydrogen or C 1 -C 10 Alkyl radical, C 3 -C 10 Cycloalkyl radical, 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 radical, 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 optionally substituted by halogen, C 1 -C 6 Alkyl and C 1 -C 6 Alkoxy (thio) substituted;
R 7 independently of one another represent C 1 -C 10 Alkyl radical, C 3 -C 10 Cycloalkyl, C 3 -C 6 cycloalkyl-C 1 -C 4 Alkyl radical, C 1 -C 4 alkyl-C 3 -C 6 Cycloalkyl or C 6 -C 10 Aryl, wherein front isC is 1 -C 10 Alkyl radical, C 3 -C 10 Cycloalkyl radical, C 3 -C 6 cycloalkyl-C 1 -C 4 Alkyl radical, C 1 -C 4 alkyl-C 3 -C 6 Cycloalkyl or C 6 -C 10 Aryl being optionally substituted by halogen, C 1 -C 6 Alkyl and C 1 -C 6 Alkoxy (thio) substituted.
The ether functionalized coumarin oxime ester compound shown in the formula (I) comprises a coumarin group structural part and an oxime ester structural part. The compound has good photosensitive absorption in the range of 300-550nm, particularly 365-475nm, can be rapidly cracked to generate active free radicals after absorbing light energy, continuously initiate polymerization, initiate polymerization of polymerizable monomers within a few seconds, and complete polymerization within 10 minutes (particularly 3 minutes), so that the compound has obvious advantages in the aspect of photosensitivity, and has good thermal stability, storage stability and solubility, thereby being suitable for being used as a photoinitiator for curing a UV-VIS LED light source.
In the present invention, the prefix "C n -C m "in each case denotes that the number of carbon atoms comprised in the radical is n-m.
"halogen" refers to fluorine, chlorine, bromine and iodine. In the present invention, it is preferred that the halogen is fluorine, chlorine, bromine or a combination thereof.
The term "C" as used herein n -C m Alkyl "means a branched or unbranched saturated hydrocarbon radical having n-m, for example 1-10, carbon atoms, for example methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 1-methylpropyl, 2-methylpropyl, 1-dimethylethyl, tert-butyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2-dimethylpropyl, 1-ethylpropyl, 1-dimethylpropyl, 1, 2-dimethylpropyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1-dimethylbutyl, 1, 2-dimethylbutyl, 1, 3-dimethylbutyl, 2-dimethylbutyl, 2, 3-dimethylbutyl, 3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1, 2-trimethylpropyl, 1, 2-trimethylpropyl, 1-ethyl-1-methylpropyl1-ethyl-2-methylpropyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group, isomers thereof and the like.
The term "C" as used herein 6 -C m Aryl "means 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, isomers thereof and the like.
The term "C" as used herein 2 -C m Alkenyl "means a branched or unbranched unsaturated hydrocarbon group having 2-m, for example, 2-10 carbon atoms and having one double bond 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, isomers thereof and the like.
The term "C" as used herein 3 -C m Cycloalkyl "refers to a saturated alicyclic monocyclic group having 3-m, e.g., 3-10, ring carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, isomers thereof, and the like.
The term "C 3 -C m cycloalkyl-C n -C m Alkyl "represents by C 3 -C m Cycloalkyl-substituted C n -C m Alkyl, in which case the two m's may be the same or different, wherein C n -C m Alkyl and C 3 -C m Cycloalkyl groups are as defined herein. C 3 -C m cycloalkyl-C n -C m The alkyl group may be C 3 -C 6 cycloalkyl-C 1 -C 4 Alkyl groups such as cyclopropylmethyl, cyclopropylethyl, cyclopropylpropyl, cyclopropylbutyl, cyclobutylmethyl, cyclobutylethyl, cyclobutylpropyl, cyclobutylbutyl, cyclopentylmethyl, cyclopentylethyl, cyclopentylpropyl, cyclopentylbutyl, cyclohexylmethyl, cyclohexylethyl, cyclohexylpropyl, cyclohexylbutyl, isomers thereof and the like.
The term "C n -C m alkyl-C 3 -C m Cycloalkyl being represented by C n -C m Alkyl substituted C 3 -C m Cycloalkyl in which case the two m's may be the same or different, wherein C n -C m Alkyl and C 3 -C m Cycloalkyl groups are as defined herein. C n -C m alkyl-C 3 -C m Cycloalkyl may be C 1 -C 4 alkyl-C 3 -C 6 Cycloalkyl groups such as methylcyclopropyl, ethylcyclopropyl, propylcyclopropyl, butylcyclopropyl, methylcyclobutyl, ethylcyclobutyl, propylcyclobutyl, butylcyclobutyl, methylcyclopentyl, ethylcyclopentyl, propylcyclopentyl, butylcyclopentyl, methylcyclohexyl, ethylcyclohexyl, propylcyclohexyl, butylcyclohexyl and isomers thereof, and the like.
The term "C" as used herein n -C m Alkoxy (thio) radicals "including" C n -C m Alkoxy "and" C n -C m Alkylthio "means at C n -C m Open chain C corresponding to alkyl n -C m C having an oxygen or sulfur atom as a linking group bonded to any carbon atom of the alkane n -C m Alkyl radicals, e.g. C 1 -C 6 Alkoxy (thio) radicals, such as methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, 2-butoxy, tert-butoxy, pentoxy, isopentoxy, hexoxy and the isomers thereof. C 1 -C 8 The alkylthio group may be methylthio, ethylthio, propylthio, isopropylthio, n-butylthio, 2-butylthio, t-butylthio, pentylthio, isopentylthio, hexylthio, isomers thereof and the like.
In a preferred embodiment of the invention, R 1 Each independently represents C 1 -C 8 Alkyl radical, C 6 - C 8 Aryl or C 2 -C 8 Alkenyl, wherein the aforementioned C 1 -C 8 Alkyl radical, C 6 -C 8 Aryl or C 2 -C 8 Alkenyl optionally substituted by halogen, C 1 -C 6 Alkyl and C 1 -C 6 Alkoxy (thio) substituted;
it is preferable that the air-conditioning agent is,R 1 each 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 substitution.
In a preferred embodiment of the invention, R 2 Each independently represents C 1 -C 8 Alkyl radical, C 3 - C 8 Cycloalkyl radical, 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 radical, C 3 -C 8 Cycloalkyl radical, C 3 -C 6 cycloalkyl-C 1 -C 2 Alkyl or C 1 -C 2 alkyl-C 3 -C 6 Cycloalkyl optionally substituted by halogen, C 1 -C 6 Alkyl and C 1 -C 6 Alkoxy (thio) substituted.
Preferably, R is 2 Each independently represents C 1 -C 4 Alkyl radical, C 5 -C 6 Cycloalkyl radical, 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 radical, C 5 -C 6 Cycloalkyl radical, 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, bromine and C 1 -C 4 Alkyl substitution.
In a preferred embodiment of the invention, R 4 Each independently represents hydrogen or C optionally substituted by fluorine, chlorine and bromine 1 -C 4 An alkyl group.
Preferably, R is 4 Is hydrogen.
In a preferred embodiment of the invention, R 5 、R 6 Each independently represents hydrogen or C 1 -C 8 Alkyl radical, 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 radical, C 3 -C 8 Cycloalkyl radical, C 3 -C 6 cycloalkyl-C 1 -C 2 Alkyl or C 1 -C 2 alkyl-C 3 -C 6 Cycloalkyl optionally substituted by halogen, C 1 -C 6 Alkyl and C 1 -C 6 Alkoxy (thio) substituted.
Preferably, R is 5 、R 6 Each independently represents hydrogen or C 1 -C 4 Alkyl radical, C 5 -C 6 Cycloalkyl radical, 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 radical, C 5 -C 6 Cycloalkyl radical, 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, chlorine and bromine.
In a preferred embodiment of the invention, R 7 Independently of one another represent C 1 -C 8 Alkyl radical, C 3 - C 8 Cycloalkyl radical, C 3 -C 6 cycloalkyl-C 1 -C 2 Alkyl radical, C 1 -C 2 alkyl-C 3 -C 6 Cycloalkyl or C 6 -C 8 Aryl radical, wherein C 1 -C 4 Alkyl radical, C 3 -C 8 Cycloalkyl, C 3 -C 6 cycloalkyl-C 1 -C 2 Alkyl radical, C 1 -C 2 alkyl-C 3 -C 6 Cycloalkyl or C 6 -C 8 Aryl being optionally substituted by halogen, C 1 -C 6 Alkyl and C 1 -C 6 Alkoxy (thio) substituted.
Preferably, R is 7 Each independently represents C 1 -C 4 Alkyl or phenyl, wherein the aforementioned C 1 -C 4 Alkyl or phenyl optionally substituted by fluorine, chlorine, bromine and C 1 -C 4 And (3) alkyl substitution.
In a more preferred embodiment of the invention, R 3 Each independently represents C 4 -C 8 Alkyl, preferably C 4 -C 6 Alkyl, especially C 4 Alkyl radical, wherein the foregoing C 4 -C 8 Alkyl radical, C 4 -C 6 Alkyl, or C 4 Alkyl is optionally substituted with fluorine, chlorine and bromine.
In a particularly preferred embodiment of the present invention, wherein R is 3 Is a tert-butyl group.
In some particularly preferred embodiments of the present invention, the compounds of formula (I) of the present invention are selected from compounds 1-68 as shown hereinbefore. Compounds 1-68 were prepared in examples 1-68, respectively.
According to a second aspect of the present invention there is provided a process for the preparation of a compound of formula (I) according to the present invention comprising the steps of:
(1) Kenawengal condensation reaction of a compound of formula (II) with R 2 -COCH 2 COOR(R＝C 1 -C 6 Alkyl) to yield a compound of formula (III):
Figure BDA0003869475980000171
(2) Oximation reaction: subjecting the compound of formula (III) to an oximation reaction with hydroxylamine and/or hydroxylamine hydrochloride to obtain a compound of formula (IV):
Figure BDA0003869475980000172
and
(3) Esterification reaction: esterifying the compound of formula (IV) to obtain a compound of formula (I),
wherein the parameters in the above formulae are as defined above.
In order to prepare the compound of formula (I) of the present invention, it is necessary to start with a specific ether-functionalized compound of formula (II), to perform a knoevenagel condensation reaction to obtain an ether-functionalized coumarin compound of formula (III), followed by an oximation reaction to introduce an oxime group, and then to convert a 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.
Kenawengal condensation reaction
Compounds of formula (II) and R 2 -COCH 2 COOR(R＝C 1 -C 6 Alkyl) is subjected to a knoevenagel condensation reaction under the action of a catalyst to obtain a compound of formula (III):
Figure BDA0003869475980000173
wherein the parameters in the above formulae are as defined for formula (I).
The knoevenagel condensation reaction is conventional to those skilled in the art. The synthesis of coumarine rings by means of the knoevenagel condensation reaction of specific compounds of formula (II) as benzene ring structures containing adjacent hydroxyl and carbonyl groups is conventional. Specifically, the reaction allows the carbonyl group in the structure to undergo condensation reaction with an aldehyde or ketone under the action of a catalyst, dehydration is carried out to form a carbon-carbon double bond, and the hydroxyl group and R are bonded 2 -COCH 2 COOR(R＝C 1 -C 6 Alkyl), preferably ethyl acetoacetate, and removing the ethanol to form a new ester bond, thereby forming a coumarin ring and obtaining the compound of formula (III).
In order to accelerate the knoevenagel condensation reaction, the above reaction is generally carried out in the presence of a catalyst suitable for the knoevenagel condensation reaction. As catalysts, amines such as primary, secondary, 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 phosphate; combinations of Lewis acids and tertiary amines, e.g. TiCl 4 Piperidine or TiCl 4 Triethylamine. The amount of catalyst used is conventional and can be determined by conventional knowledge in the art or by several routine preliminary experiments.
The knoevenagel condensation reaction is usually carried out in a solvent, preferably an organic solvent, preferably an aprotic solvent. For solventsThe choice of form is not particularly limited, provided that the compound of formula (II) can be reacted with R 2 -COCH 2 COOR(R＝C 1 -C 6 Alkyl), preferably ethyl acetoacetate, and is chemically inert to the knoevenagel condensation reaction, i.e. does not participate in the knoevenagel condensation reaction. Examples of solvents which can be used are ethanol, diethyl ether, dimethyl sulfoxide, toluene, N-dimethylformamide or acetone, ethanol being preferably used.
A compound of formula (II) with R 2 -COCH 2 COOR(R＝C 1 -C 6 Alkyl), preferably ethyl acetoacetate, is not particularly limited and is generally present in a molar ratio of from 1.
The temperature range for the knoevenagel condensation reaction is generally from 40 to 120 ℃ and preferably from 60 to 90 ℃. The reaction time is not particularly limited, and usually 3 to 20 hours, preferably 3 to 10 hours, are carried out.
After the Kenawenger condensation reaction is finished, the reaction solution is washed by water, and then the residual organic solvent is removed. The means for removing the organic solvent is not particularly limited, and the organic solvent can be removed by distillation under normal pressure or reduced pressure. After removal of the residual organic solvent, a crude product of the compound of formula (III) is obtained. If it is desired to further increase the purity of the compound of the formula (III), the compound can also be further purified, for example by recrystallization. The choice of the recrystallization solvent is conventional and is not particularly limited. According to the invention, it is advantageous to recrystallize the crude product of the compound of formula (III) from ethanol.
Oximation reaction
(III) subjecting the compound of formula (III) to an oximation reaction with hydroxylamine and/or hydroxylamine hydrochloride to give a compound of formula (IV):
Figure BDA0003869475980000191
wherein the parameters in the above formulae are as defined for formula (I).
The oximation reaction is usually performed by using hydroxylamine hydrochloride(NH 2 OH & HCl), hydroxylamine (NH) 2 OH) or mixtures thereof as an oximation agent. The oximation reaction is generally carried out in an organic solvent, preferably in a polar organic solvent. As the solvent, for example, ethanol or aqueous ethanol can be used. To promote completion of the oximation reaction, a catalyst such as sodium acetate, pyridine, piperidine, triethylamine, tetramethylammonium hydroxide, or a mixture thereof is generally added. Among these, pyridine, piperidine, triethylamine can also be used as a base and/or a solvent or co-solvent.
There are no particular restrictions on the relative amounts of compound of formula (III) and hydroxylamine and/or hydroxylamine hydrochloride used, and typically the molar ratio of the two is from 1.
The temperature range of the above-mentioned oximation reaction is usually 30 to 120 ℃ and preferably 40 to 90 ℃. The reaction time for the oximation reaction is not particularly limited either, and is usually 0.1 to 20 hours, preferably 0.3 to 10 hours.
Esterification reaction
Esterification of the compound of formula (IV) is conventional to those skilled in the art, by which the hydroxyl group of the oxime group is converted to an ester group to obtain the compound of formula (I). The esterification reagent is not particularly limited as long as it can convert a hydroxyl group in an oxime group of the compound of formula (IV) into an ester group. For example, the corresponding acid halides, such as acid chlorides, the corresponding carboxylic acids, and the corresponding acid anhydrides may be used. These compounds can be represented by the formulae (Va), (Vb) and (Vc), respectively:
Figure BDA0003869475980000192
wherein X is halogen, especially chlorine, and R 1 As defined for the compounds of formula (I).
In order to accelerate the esterification reaction, the above-mentioned 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 may 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, may be used. The amount of catalyst used is conventional and can be determined by conventional knowledge in the art or by several routine preliminary experiments.
In order to increase the yield of the compounds of the formula (I) according to the invention, it is advantageous to remove the water of esterification during the esterification reaction. This can be done, for example, by distillation/condensation.
The esterification reaction is usually carried out in a solvent, preferably an organic solvent. With respect to the choice of the type of solvent, there is no particular limitation as long as the compound of formula (IV) and the esterification reagent can be dissolved and are chemically inert to the esterification reaction, i.e., do not participate in the esterification reaction. As examples of the solvent, tetrahydrofuran, benzene, toluene, N-dimethylformamide, dichloromethane, and acetone may be mentioned. The solvent may be used singly or as a mixture of two or more solvents.
There are no particular restrictions on the relative amounts used of the compound of formula (IV) and the esterification reagent selected from the compounds of formulae (Va), (Vb) and (Vc), generally the molar ratio of the two is from 1.2 to 1.0, preferably from 1.4 to 1.8, for example about 1.6.
The esterification reaction can be carried out over a very wide temperature range. Advantageously according to the invention, the esterification reaction is carried out at a temperature of from-10 ℃ to 150 ℃, preferably from 0 ℃ to 100 ℃, preferably at ambient temperature. The esterification reaction time is also not particularly limited, and usually 0.5 to 24 hours, preferably 0.8 to 12 hours.
After the esterification reaction is complete, a reaction mixture comprising the compound of formula (I) is obtained. Therefore, the reaction mixture needs to be worked up to obtain a purified compound of formula (I). In general, the reaction mixture obtained by the esterification reaction is first filtered, and a filtrate portion is taken out. Then, the filtrate was washed to remove the catalyst and unreacted raw materials. The washing liquid is not particularly limited as long as the catalyst and unreacted raw materials can be removed. As examples of the washing liquid, dilute hydrochloric acid (aqueous solution), saturated aqueous sodium bicarbonate solution and water may be mentioned. The concentration of the dilute hydrochloric acid is not particularly limited, and a dilute hydrochloric acid having a concentration of 5 to 12% is generally used. Washing with the washing liquid can be carried out once or for multiple times; in the case of multiple runs, a single wash solution may be used, or different wash solutions may be used sequentially. Advantageously according to the invention, the filtrate obtained by filtration of the reaction mixture obtained in the esterification reaction is washed successively with dilute hydrochloric acid, saturated aqueous sodium bicarbonate solution and water. Of course, after each washing with a wash solution, it is necessary to wash the organic phase with the next wash solution after pouring off the aqueous phase. After washing, drying is required to remove residual water. For this purpose, drying may be usually carried out using anhydrous sodium sulfate. After drying, the residual organic solvent is removed again. The means for removing the organic solvent is not particularly limited, and the organic solvent can be removed by distillation under reduced pressure. After removal of the residual organic solvent, the crude compound of formula (I) is obtained. If it is desired to further increase the purity of the compound of formula (I), the compound may be further purified, for example by recrystallization. The choice of the recrystallization solvent is conventional and is not particularly limited. According to the invention, it is advantageous to recrystallize the crude product of the compound of formula (I) from petroleum ether, methanol, ethanol or mixtures thereof.
In the compounds of formula (I), the oxime ester group may exist in two configurations, i.e., (Z) or (E). The isomers can be separated by conventional methods, but mixtures of isomers can also be used as photoinitiating substances. The invention therefore also relates to mixtures of configurational isomers of the respective compounds of the formula (I).
The compound of the formula (I) has strong absorption in the wavelength range of 300-550nm, especially 365-475nm, so that the compound can be used as a photoinitiator to be applied to a UV-VIS LED photocuring technology, and is especially suitable for long-wavelength UV-VIS LED light source curing. In addition, the compound of the formula (I) is safe and nontoxic, has lower harm degree to human bodies and environment compared with the traditional photoinitiator, and can also be used in the fields of food packaging and the like.
Thus, according to a third aspect of the present invention, there is provided the use of a compound of formula (I) according to the present invention as a photoinitiator. The compound of the formula (I) can be used as a photoinitiator to be applied to a UV-VIS LED photocuring technology, and can effectively initiate a curing reaction. Particular preference is given to the use of the compounds of the formula (I) according to the invention as photoinitiators in photocuring systems with radiation wavelengths of from 300 to 550nm, in particular from 365 to 475 nm. The compounds of formula (I) according to the invention can also be used as photoinitiators or photosensitizers in the fields of coatings, inks, microelectronics, printing and the like. When the compounds of the formula (I) according to the invention are used as photoinitiators, their use is conventional or can be determined by routine preliminary experiments.
Thus, the present invention also relates to a photocurable composition comprising the ether-functionalized coumarin oxime ester compound of the present invention.
In photocurable compositions, the photoinitiator according to the invention is generally present in an amount of from 0.01 to 10% by weight, preferably from 0.1 to 6% by weight, such as from 0.2 to 5% by weight, based on the amount of active ingredient in the photocurable composition.
In the context of the present disclosure, active ingredient refers to the ingredient of the photocurable composition excluding the solvent.
The photocurable composition comprises a photocurable resin in addition to the photoinitiator of the present invention.
In the present invention, the photocurable resin refers to an oligomer or prepolymer containing an unsaturated carbon-carbon double bond. After the oligomer or the prepolymer is irradiated by light, the polymerization reaction can be initiated by a photoinitiator, and then the crosslinking and curing are carried out. The photocurable resin is a main component of a photocurable product (e.g., UV paint, UV ink, UV adhesive, etc.).
As the photocurable resin, there can be mentioned an epoxy (meth) acrylate resin, a polyester-based (meth) acrylate, a urethane (meth) acrylate, an ethylenically unsaturated polyester, an amino (meth) acrylate resin, a photo-imageable alkali-soluble resin, and the like. According to the invention, it is advantageous to use epoxy (meth) acrylate resins, polyester (meth) acrylates, polyurethane (meth) acrylates or combinations thereof.
The epoxy (meth) acrylate resin is preferably bisphenol A epoxy (meth) acrylate, tripropylene glycol di (meth) acrylate diluted bisphenol A epoxy acrylate, or a combination thereof, such as bisphenol A epoxy acrylate WSR-U125 from tin-free resin factories, 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 having a high functionality, in particular a hyperbranched polyester acrylic resin having a functionality of from 5 to 30, for example a hyperbranched polyester acrylate prepolymer having a functionality of from 6 to 20. Examples of these include hyperbranched polyester acrylate prepolymers 932 to 100 (6 functionality) from Nonox, hyperbranched polyester acrylate prepolymers CN2300 (8 functionality), CN2301 (9 functionality), CN2302 (16 functionality) from Saedoma, USA.
The urethane (meth) acrylate is preferably an aliphatic urethane acrylate. For this, mention may be made, for example, of aliphatic urethane acrylate CN9013 (9 functionality) from Saedoma, 15%1, 6-hexanediol diacrylate (HDDA) diluted aliphatic urethane acrylate CN966B85 (2 functionality), aliphatic urethane acrylate CN962 (2 functionality) from Saedoma.
The photocurable composition may contain the photocurable resin in an amount of usually 10 to 90% by weight, preferably 55 to 80% by weight, based on the amount of active ingredients of the photocurable composition. In the context of the present disclosure, active ingredient refers to the ingredient of the photocurable composition excluding the solvent.
The photocurable composition may further comprise a multifunctional reactive diluent.
In the present invention, the polyfunctional reactive diluent means a monomer containing two or more photopolymerizable groups. The multifunctional reactive diluent has lower viscosity and stronger dissolving capacity. The multifunctional reactive diluent can be initiated by active free radicals to polymerize to form a cross-linked network structure after being irradiated by a light source.
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 the polyfunctional (meth) acrylate crosslinking agent, trimethylolpropane triacrylate (TMPTA), pentaerythritol tetraacrylate (PETTA), trimethylolpropane propoxylate (PO-TMPTA) or trimethylolpropane ethoxylate (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 Urethane Dimethacrylate (UDMA), and the like can be mentioned.
The amount of polyfunctional reactive diluents in the photocurable composition is generally in the range of from 8 to 60% by weight, preferably from 15 to 45% by weight, based on the amount of active ingredient in the photocurable composition.
According to the present invention, the photocurable composition may further comprise a monofunctional reactive diluent.
In the present invention, a monofunctional reactive diluent means a monomer containing one photopolymerizable group. The product has low viscosity and strong dissolving capacity, and can be used as part of organic solvent. The monofunctional reactive diluent can be initiated by a reactive free radical to carry out a polymerization reaction after being irradiated by a light source. The monofunctional reactive diluent mainly comprises a (meth) acrylate compound and a vinyl compound. As monofunctional reactive diluents of the (meth) acrylate type, mention may be made of Methyl Methacrylate (MMA), n-Butyl Acrylate (BA), isooctyl acrylate (2-EHA), isodecyl acrylate (IDA), lauryl Acrylate (LA), hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and also some (meth) acrylates having a cyclic structure. Further, as the vinyl-based monofunctional reactive diluent, styrene (St), vinyl Acetate (VA), N-vinyl pyrrolidone (NVP), and the like can be mentioned.
The monofunctional reactive diluent is generally used in the photocurable composition in an amount of from 5 to 50% by weight, preferably from 8 to 40% by weight, based on the amount of active ingredient in the photocurable composition.
The photocurable composition of the present invention may also optionally comprise an organic solvent. The choice of organic solvent is conventional. As the organic solvent, aromatic hydrocarbons such as benzene, toluene, halogenated alkanes such as chloroform, methylene chloride, ethyl chloride, ketones such as acetone, methyl ethyl ketone, amyl ketone and the like, alcohols such as methanol, ethanol, propyl alcohol, isopropyl alcohol, ethylene glycol, and glycol ethers, glycol ether acetates, propylene glycol ethers, propylene glycol ether acetates and the like can be mentioned.
The photocurable composition of the present invention may also optionally contain other additives such as leveling agents, antioxidants, anti-settling agents, colorants, biocides, such as antimicrobial agents, and insulation additives. In a preferred embodiment of the invention, the levelling agent is selected from the group consisting of Youka chemistry
Figure BDA0003869475980000241
The FLOW-series leveling agent is particularly preferably 360S, 372S, 384S, 392S, 400U, 415U, or the like.
The photocurable composition of the present invention is prepared conventionally, for example, by uniformly mixing the components of the photocurable composition of the present invention together.
Thus, in another aspect, the present invention also provides cured materials obtainable from the photocurable compositions of the present invention. The resulting cured material may be a light-cured coating, including coatings comprising functional materials, coatings of filters of UV and/or visible light; a sealant; photoetching materials; a holographic recording material; 3D printing materials; a lithographic material; the material for preparing optical device and the material for improving mechanical property, such as carbon fiber composite material and/or inorganic nanometer particle and/or organic nanometer particle.
Furthermore, the present invention relates to a process for the preparation of a photocurable composition which comprises irradiating the photocurable composition with a source of radiation having a wavelength of from 300 to 550nm, in particular from 365 to 475nm, for example a UV-VIS LED source.
In addition, the compound disclosed by the invention is simple in production process, high in yield and very suitable for industrial production. The compound has good matching property with a UV-VIS LED light source with the radiation wavelength of 300-550nm, particularly 365-475nm, and can be widely applied to the fields related to UV-VIS LED photocuring as a photoinitiator, such as the fields of coatings, printing ink, microelectronics, printing, 3D printing, dental materials and the like. Therefore, the ether functionalized coumarin oxime ester photoinitiator has good market prospect.
In addition, in view of the fact that the variety of the photoinitiator which can be applied to the UV-VIS LED light source at present, especially the variety of the photoinitiator for deep curing of the long-wavelength UV-VIS LED light source is less, the popularization and the application of the UV-VIS LED light source in the field of light curing are limited to a certain extent. Therefore, the ether functionalized coumarin oxime ester photoinitiator can make a contribution to promoting the wide application of a green and environment-friendly UV-VIS LED light source in the UV photocuring industry.
Examples
The scheme of the invention will be explained with reference to the examples. It will be appreciated by those skilled in the art that the following examples are illustrative of the invention only and should not be taken as limiting the scope of the invention. The specific techniques or conditions are not indicated in the examples, and are performed according to the techniques or conditions or product specifications described in the literature in the field.
Example 1: preparation of Compound 1
Figure BDA0003869475980000251
The synthetic route for compound 1 is as follows:
Figure BDA0003869475980000252
synthesis of intermediate Compound 1a
3- (tert-butyl) -2-hydroxy-5-methoxybenzaldehyde (0.05mol, 10.42g) was charged into a 250mL three-necked round bottom flask containing 50mL of ethanol, and after stirring well, piperidine (0.015mol, 1) was then added.28g) And ethyl acetoacetate (0.07mol, 9.11g), the reaction mixture was heated to reflux and the reaction was stirred for 4h. After the reaction was complete, the mixture was cooled to room temperature, filtered to give a yellow solid, which was then recrystallized from ethanol to give 11.24g of the product, 82% yield, identified as compound 1a.1H-NMR (400MHz, 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)。
Synthesis of intermediate Compound 1b
A mixed solution of intermediate compound 1a (10.96g, 0.04mol) and 150mL of ethanol and water (V ethanol: V water = 2. Stirring and reacting for 1.5h at 40 ℃, washing the reaction solution, then carrying out vacuum rotary evaporation on an organic phase to obtain a light yellow solid, and recrystallizing with ethanol to obtain 10.76g of a product, wherein the yield is 93 percent, and the compound is identified as a compound 1b.1H-NMR (600MHz, 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)。
Synthesis of target product 1
The above intermediate compound 1b (8.67g, 0.03mol) and 50mL of methylene chloride were charged into a 100 mL three-necked round-bottomed flask, followed by the addition of acetyl chloride (3.53g, 0.045mol) and triethylamine (5.46 g, 0.054 mol), and the reaction was stirred at room temperature for 1.5 hours. Stopping reaction, filtering the reaction solution, pouring the filtrate into water, extracting with ethyl acetate, collecting organic phase, washing with dilute hydrochloric acid solution, saturated sodium carbonate solution and distilled water in sequence, collecting organic phase, and washing with MgSO 4 Dry overnight. After filtration, the organic phase was distilled off under reduced pressure to obtain 8.94g of a yellow powdery solid, the yield was 90.0%, and the compound was identified as compound 1. The nuclear magnetic data for compound 1 is shown in table 1.
Examples 2 to 68
The procedure of example 1 was repeated, with appropriate changes in the reaction raw materials, to obtain compounds 2 to 68 shown in Table 1 below and nuclear magnetic data thereof, respectively.
TABLE 1
Figure BDA0003869475980000271
Figure BDA0003869475980000281
Figure BDA0003869475980000291
Figure BDA0003869475980000301
Figure BDA0003869475980000311
Figure BDA0003869475980000321
Figure BDA0003869475980000331
Figure BDA0003869475980000341
Figure BDA0003869475980000351
Figure BDA0003869475980000361
Figure BDA0003869475980000371
Figure BDA0003869475980000381
Figure BDA0003869475980000391
Figure BDA0003869475980000401
And (3) testing the photosensitive performance:
1. the photosensitivity of the photoinitiators was tested using a Ugra strip as a mask. The sections of the ugra strip are shown in fig. 1. The black-grid printing test strip is divided into 5 control sections, which are respectively from left to right: a continuous density ladder section (1); a yin-yang micron isopolar concentric circle coil section (2); a full tone dot segment (3); a ghost control section (4); a highlight and dark tone control section (5). A first stage: the continuous density step is divided into 13 gradients for controlling exposure and development. And a second stage: the concentric circle coil section of the yin-yang micron isoline is a concentric circle coil diagram consisting of 12 yin-yang micron isolines, which are respectively 4, 6, 8, 10, 12, 15, 20, 25, 30, 40, 55 and 70 and is used for detecting exposure and development conditions when a PS plate is exposed in the sun. A third stage: the full-order tone dot section consists of 10-100% of flat screens with the range difference of 10%, is arranged in an upper row and a lower row and is used for measuring the dot transfer conditions of plate printing, proofing and printing and measuring the change curve graphs of film dots and plate printing, proofing and printing dots. A fourth stage: the ghost control section is composed of thin lines with 60 lines/cm of line width and 60% of area rate, and is divided into 4 small blocks, lines arranged at three angles of 0 degrees, 45 degrees and 90 degrees, and small short lines arranged at two sides of 90 degrees, a middle small block of 45 degrees and upper and lower 90 degrees in D small blocks with 1/4. A fifth stage: and the fine screen dot section is formed by correspondingly arranging small highlight screen dots and dark-tone deep screen dots and is used for finely controlling the accuracy of printing exposure and development. The photocurable composition containing the photoinitiator was coated on an aluminum substrate, followed by exposure and development, and the sensitivity was evaluated from the continuous leveling ruler of the resulting image and the accuracy was evaluated from the area of the microwire test block, thereby evaluating the superiority and inferiority of the photocurable composition formulation.
Specifically, the photosensitivity of the compound of formula (I) was tested according to the following procedure.
(1) Photocurable compositions containing a photoinitiator were formulated as follows:
Figure BDA0003869475980000411
the photoinitiator in the above composition is a compound of formula (I) of the present invention or a photoinitiator (comparative) known in the art (see below and table 2 in particular). The acrylate resin was a resin having a functionality of 2 and a number average molecular weight of 1400, available from Shanghai Shunyi International trade company Limited under the trade designation FS 2600K. Dipentaerythritol hexaacrylate is a product purchased from Shanghai under the trade designation GM66G0C from International trade company, inc. The crystal violet dye is a product purchased from Shanghai national medicine under the trade name hexamethyl rhodanidine hydrochloride.
(2) The compositions are stirred and mixed evenly under yellow light, and are spin-coated on a PS aluminum plate base which is pre-treated and meets the following conditions by a centrifugal machine:
the size of the aluminum substrate is as follows: 1030mm x 800mm
Thickness of the aluminum substrate: 0.28-0.3mm
Specification of a sand mesh: ra =0.5-0.6 μm
Rh＝0.3-0.35μm
Weight of anodic oxide film: 3-3.5g/m 2
Controlling the rotation speed of the centrifugal coating machine to ensure that the coating weight (calculated by solid content) coated on the aluminum plate base is 1.0-2.5g/m 2 And after primary drying on a centrifugal coating machine, transferring the plate to a blast drier at 100 ℃ for drying for 3 minutes to obtain the purple laser CTP original plate. Then, the photosensitivity of the plate was tested using a Ugra test strip as a mask, and the plate was exposed for a period of time and developed with 1% aqueous NaOH solution.
In the exposed areas, the photopolymerizable compound is polymerized in the presence of a photoinitiator and is insoluble in the developer, while the unexposed areas are soluble, thus giving a negative image. The sensitivity of the photoinitiator was evaluated from the continuous scale of the resulting image by exposure development. The sensitivity of the initiator system is characterized by the retention of the highest number of gray levels (i.e., polymerized) after development. The higher the number of gray levels, the higher the sensitivity of the test system. The results are shown in Table 2.
In addition, under the same conditions, commercially available oxime esters OXE-01, OXE-02 and OXE-03 of BASF were selected and compared with the prior art, COXE-08, COXE-09, COXE-19, COXE-31, COXE-35, COXE-37, COXE-41 and COXE-48 (the specific structures are shown below). The results are also summarized in Table 2.
Figure BDA0003869475980000421
Figure BDA0003869475980000431
TABLE 2
Figure BDA0003869475980000432
Figure BDA0003869475980000441
Figure BDA0003869475980000451
As is apparent from the experimental results in Table 2, the number of gray levels at 365nm, 385nm, 400nm, 425nm, 450nm, 475nm and 500nm of the example compounds 1-68 of the present invention is higher than that of the commercially available oxime esters OXE-01, OXE-02 and OXE-03 of BASF, and also higher than that 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 has more excellent photosensitivity at 365nm, 385nm, 400nm, 425nm, 450nm, 475nm and 500nm wavelengths, and is suitable for UV-VIS LED light sources at 365nm, 385nm, 400nm, 425nm, 450nm, 475nm and 500 nm.
2. The sensitization performance of the photoinitiator is tested by testing the peak area change of the infrared spectrum characteristic of the carbon-carbon double bond of the polymerization of the acrylate resin initiated by the photoinitiator by a Fourier transform infrared-real time infrared method. The carbon-carbon double bond conversion of the acrylate resin when exposed for 30 seconds is shown in Table 3. The conversion rate of the carbon-carbon double bond of the acrylate resin is embodied by the change of the characteristic peak area of the infrared spectrum, and the selected characteristic peak area is 1653-1603cm -1 . And (3) evaluating the photoinitiation performance of the photoinitiator under different conditions according to the trend of the carbon-carbon double bond conversion rate under different test conditions changing along with time.
Specifically, the photoinitiating properties of the compounds of formula (I) were tested as follows.
(1) Photocurable compositions containing a photoinitiator were formulated as follows:
FS2600K acrylate resin 100 parts by mass
2 parts by mass of photoinitiator
The photoinitiator in the composition is the compound of formula (I) of the invention or the photoinitiator (comparative) known in the prior art. The acrylate resin was a resin having a functionality of 2 and a number average molecular weight of 1400, available from Shanghai Shunyi International trade company Limited under the trade designation FS 2600K.
(2) After the above-mentioned compositions were mixed uniformly with stirring under yellow light and ensured to dissolve, the photocurable composition was injected by means of a syringe into a KBr double salt tablet mold which had been pretreated and which satisfied the following conditions:
KBr double salt tablet size: 15mm
KBr double salt tablet thickness: 3mm
KBr double salt tablet gap: 0.5mm
The quantity of the light-curable composition injected into the KBr double-salt-tablet mould is 0.2ml by observing the scales of the injector, after the injection is finished, the KBr double-salt-tablet mould is placed into a small black box in a Fourier transform infrared spectrometer for real-time infrared test, the structure of the small black box is that an upper infrared test light ray vertically aligns to penetrate through the KBr double-salt-tablet mould, a 45-degree LED point light source above the KBr double-salt-tablet mould aligns to the KBr double-salt-tablet mould, and the LED point light source is 1cm away from the KBr double-salt-tablet mould.
And simultaneously starting infrared spectrum detection and turning on an LED light source, so that the photocurable composition in the KBr double-salt-tablet die is exposed while the change of the characteristic peak area of the carbon-carbon double bond is detected.
Under the irradiation of an LED point light source, the photopolymerizable compound is subjected to polymerization reaction in the presence of an initiator, so that the characteristic peak area of the carbon-carbon double bond is continuously reduced until the characteristic peak area is basically disappeared. And converting the conversion rate of the carbon-carbon double bond along with the change of the time according to the data of the change of the characteristic peak area of the carbon-carbon double bond along with the exposure time. The results when exposed for 30 seconds are shown in table 3.
Converting the data of the variation of the characteristic peak area of the carbon-carbon double bond along with the exposure time to obtain a formula of the conversion rate of the carbon-carbon double bond along with the variation of the time:
Figure BDA0003869475980000461
in addition, under the same conditions, commercially available oxime esters of BASF, 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 (the specific structures are shown above) were selected for comparison. The results are also summarized in Table 3.
TABLE 3
Figure BDA0003869475980000471
Figure BDA0003869475980000481
Figure BDA0003869475980000491
As is apparent from the experimental results in Table 3, the conversion of double bonds at 365nm, 385nm, 400nm, 425nm, 450nm and 475nm of the example compounds 1-68 of the present invention is higher than that of the commercially available oxime esters of BASF, OXE-01, OXE-02 and OXE-03, and also higher than that of the oxime esters of the prior art, COXE-08, COXE-09, COXE-19, COXE-31, COXE-35, COXE-37, COXE-41 and COXE-48. Namely, the ether functionalized coumarin oxime ester photoinitiator has more excellent photosensitivity at 365nm, 385nm, 400nm, 425nm, 450nm and 475nm wavelengths, and is suitable for UV-VIS LED light sources of 365nm, 385nm, 400nm, 425nm, 450nm and 475 nm.
In conclusion, the ether functionalized coumarin oxime ester photoinitiator has better photosensitivity at the wavelengths of 365nm, 385nm, 400nm, 425nm, 450nm and 475nm, is superior to the commercial oxime esters OXE-01, OXE-02 and OXE-03 of BASF at the present stage, and is also superior to oxime esters COXE-08, COXE-09, COXE-19, COXE-31, COXE-35, COXE-37, COXE-41 and COXE-48 disclosed in the prior art, and particularly has obvious advantages in the visible light region at the wavelengths of 425nm, 450nm and 475 nm.

Claims (17)

1. An ether functionalized coumarin oxime ester compound of formula (I):
Figure FDA0003869475970000011
wherein:
m is an oxygen or sulfur atom;
R 1 each independently represents C 1 -C 10 Alkyl radical, C 6 -C 10 Aryl or C 2 -C 10 Alkenyl, wherein the aforementioned C 1 -C 10 Alkyl radical, C 6 -C 10 Aryl or C 2 -C 10 Alkenyl optionally substituted by halogen, C 1 -C 6 Alkyl and C 1 -C 6 Alkoxy (thio) substitution;
R 2 each independently represents C 1 -C 10 Alkyl radical, C 3 -C 10 Cycloalkyl radical, 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 radical, C 3 -C 10 Cycloalkyl radical, C 3 -C 6 cycloalkyl-C 1 -C 4 Alkyl or C 1 -C 4 alkyl-C 3 -C 6 Cycloalkyl optionally substituted by halogen, C 1 -C 6 Alkyl and C 1 -C 6 Alkoxy (thio) substituted;
R 3 each independently represents C 4 -C 10 Alkyl radical, 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 radical, C 4 -C 10 Cycloalkyl radical, C 4 -C 6 cycloalkyl-C 1 -C 4 Alkyl or C 1 -C 4 alkyl-C 4 -C 6 Cycloalkyl is optionally substituted with halogen;
R 4 each independently represents hydrogen or C optionally substituted by halogen 1 -C 4 An alkyl group;
R 5 、R 6 each independently represents hydrogen or C 1 -C 10 Alkyl radical, C 3 -C 10 Cycloalkyl radical, 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 radical, 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 optionally substituted by halogen, C 1 -C 6 Alkyl and C 1 -C 6 Alkoxy (thio) substituted;
R 7 independently of one another represent C 1 -C 10 Alkyl radical, C 3 -C 10 Cycloalkyl, C 3 -C 6 cycloalkyl-C 1 -C 4 Alkyl radical, C 1 -C 4 alkyl-C 3 -C 6 Cycloalkyl or C 6 -C 10 Aryl, wherein the aforementioned C 1 -C 10 Alkyl radical, C 3 -C 10 Cycloalkyl, C 3 -C 6 cycloalkyl-C 1 -C 4 Alkyl radical, C 1 -C 4 alkyl-C 3 -C 6 Cycloalkyl or C 6 -C 10 Aryl being optionally substituted by halogen, C 1 -C 6 Alkyl and C 1 -C 6 Alkoxy (thio) substituted.
2. The ether-functionalized coumarin oxime ester compound according to claim 1 wherein:
R 1 each independently represents C 1 -C 8 Alkyl radical, C 6 -C 8 Aryl or C 2 -C 8 Alkenyl, wherein the aforementioned C 1 -C 8 Alkyl radical, C 6 -C 8 Aryl or C 2 -C 8 Alkenyl optionally substituted by halogen, C 1 -C 6 Alkyl and C 1 -C 6 An alkoxy (thio) group is substituted,
preferably R 1 Each 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 substitution; and/or
R 2 Each independently represents C 1 -C 8 Alkyl radical, C 3 -C 8 Cycloalkyl radical, 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 radical, 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 optionally substituted by halogen, C 1 -C 6 Alkyl and C 1 -C 6 An alkoxy (thio) group,
preferably R 2 Each independently represents C 1 -C 4 Alkyl radical, C 5 -C 6 Cycloalkyl radical, 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 radical, C 5 -C 6 Cycloalkyl radical, 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, bromine and C 1 -C 4 Alkyl substitution; and/or
R 4 Each independently represents hydrogen, or C optionally substituted by fluorine, chlorine and bromine 1 -C 4 Alkyl, preferably R 4 Is hydrogen; and/or
R 5 、R 6 Each independently represents hydrogen or C 1 -C 8 Alkyl radical, C 3 -C 8 Cycloalkyl radical, 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 radical, C 3 -C 8 Cycloalkyl radical, C 3 -C 6 cycloalkyl-C 1 -C 2 Alkyl or C 1 -C 2 alkyl-C 3 -C 6 Cycloalkyl optionally substituted by halogen, C 1 -C 6 Alkyl and C 1 -C 6 An alkoxy (thio) group is substituted,
preferably R 5 、R 6 Each independently represents hydrogen or C 1 -C 4 Alkyl radical, C 5 -C 6 Cycloalkyl radical, 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 radical, C 5 -C 6 Cycloalkyl radical, 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 fluoro, chloro and bromo; and/or
R 7 Independently of one another represent C 1 -C 8 Alkyl radical, C 3 -C 8 Cycloalkyl radical, C 3 -C 6 cycloalkyl-C 1 -C 2 Alkyl radical, C 1 -C 2 alkyl-C 3 -C 6 Cycloalkyl or C 6 -C 8 Aryl radical, wherein C 1 -C 4 Alkyl radical, C 3 -C 8 Cycloalkyl radical, C 3 -C 6 cycloalkyl-C 1 -C 2 Alkyl radical, C 1 -C 2 alkyl-C 3 -C 6 Cycloalkyl or C 6 -C 8 Aryl being optionally substituted by halogen, C 1 -C 6 Alkyl and C 1 -C 6 An alkoxy (thio) group is substituted,
preferably R 7 Each independently represents C 1 -C 4 Alkyl or phenyl, wherein the aforementioned C 1 -C 4 Alkyl or phenyl optionally substituted by fluorine, chlorine, bromine and C 1 -C 4 Alkyl substitution.
3. The ether-functionalized coumarin oxime ester compound according to claim 1 or 2, wherein:
R 3 each independently represents C 4 -C 8 Alkyl, preferably C 4 -C 6 Alkyl, especially C 4 Alkyl radical, wherein the foregoing C 4 -C 8 Alkyl radical, C 4 -C 6 Alkyl or C 4 Alkyl is optionally substituted with fluorine, chlorine and bromine.
4. The ether functionalized coumarin oxime ester compound according to any one of claims 1 to 3, wherein R is 3 Is a tert-butyl group.
5. The ether functionalized coumarin oxime ester compound according to any one of claims 1 to 4, wherein said ether functionalized coumarin oxime ester compound is selected from the group consisting of:
Figure FDA0003869475970000031
Figure FDA0003869475970000041
Figure FDA0003869475970000051
Figure FDA0003869475970000061
Figure FDA0003869475970000071
Figure FDA0003869475970000081
6. a process for preparing an ether functionalized coumarin ester compound according to any one of claims 1 to 5, comprising the following steps:
(1) Kenaowenagel condensation reaction of the compound of formula (II) with R 2 -COCH 2 COOR(R＝C 1 -C 6 Alkyl) to yield a compound of formula (III):
Figure FDA0003869475970000091
(2) Oximation reaction: carrying out oximation reaction on the compound of the formula (III) and hydroxylamine and/or hydroxylamine hydrochloride to obtain the compound of the formula (IV)
Figure FDA0003869475970000092
And
(3) Esterification reaction: esterifying the compound of formula (IV) to obtain a compound of formula (I),
wherein the parameters in the above formulae are as defined in any one of claims 1 to 5.
7. The process 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, secondary, 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 phosphate; combinations of Lewis acids and tertiary amines, e.g. TiCl 4 Piperidine or TiCl 4 Triethylamine.
8. A process according to claim 6 or 7, wherein in the knoevenagel condensation reaction of step (1), the compound of formula (II) is reacted with R 2 -COCH 2 COOR(R＝C 1 -C 6 Alkyl), preferably the molar ratio of ethyl acetoacetate is 1.1 to 1.5, preferably 1.
9. The process 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 catalyst.
10. The process 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 from 1.
11. The method according to any one of claims 6-10, wherein:
the esterification of step (3) is carried out using an esterification reagent selected from the group consisting of compounds of the following formulae (Va), (Vb) and (Vc):
Figure FDA0003869475970000101
wherein X is halogen, especially chlorine, R 1 As defined in any one of items 1 to 5.
12. The process 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, iron trichloride, 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. The process 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 esterifying reagent selected from the compounds of formulae (Va), (Vb) and (Vc) is from 1.2 to 2.0, preferably from 1.4 to 1.
14. Use of the ether functionalized coumarine ester compound according to any of claims 1 to 5 or obtained according to the process of any of claims 6 to 13 as photoinitiator, especially in UV-VIS LED light source curing systems, especially in light source curing systems with a radiation wavelength of 300 to 550nm, especially 365 to 475 nm.
15. A photocurable composition comprising at least one ether-functionalized coumarin oxime ester compound according to any one of claims 1 to 5 or obtainable by a process according to any one of claims 6 to 13.
16. Cured material obtainable from the photocurable composition of claim 15.
17. A process for the preparation of a photocurable material comprising irradiating a photocurable composition according to claim 15 with a source of radiation having a wavelength of from 300 to 550nm, especially from 365 to 475nm, such as a UV-VIS LED source.
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