Acylphosphine oxide oxime ester compounds applicable to deep curing of UV-VIS LED light sources, their preparation and applications

Abstract

The present invention relates to acylphosphine oxide oxime ester compounds of formula 1 and formula 2, wherein each variable is as defined in the specification. Such compounds can have good photosensitive absorption in the range of 300 - 550 nm, especially 365 - 450 nm. After absorbing light energy, they can rapidly undergo cleavage to generate reactive free radicals, continuously initiate polymerization, have obvious advantages in photosensitivity and have good thermal stability and solubility, so they are suitable for use as photoinitiators for deep curing of UV-VIS LED light sources. The present invention also relates to a preparation method and uses of the acylphosphine oxide oxime ester compounds of formula 1 and formula 2. Such compounds can be used as photoinitiators, especially suitable for deep curing of long-wavelength UV-VIS LED light sources.

Description

Technical Field

[0001] The present invention belongs to the technical field of photocuring, and relates to acylphosphine oxide oxime ester compounds, which can be used as photoinitiators, especially suitable for deep curing of UV-VIS LED light sources. The present invention also relates to the preparation and application of acylphosphine oxide oxime ester compounds. Background Art

[0002] At present, photocuring technology has been widely used in traditional fields such as coatings, inks, microelectronics, printing, etc., and is also used in new fields such as the preparation of laser videos and three-dimensional components. As an important component of the photocuring system, the photoinitiator (also known as photosensitizer), although having a low content in the photocuring system, is a key component therein, which plays a decisive role in the photocuring speed and must also meet the requirements of different photocuring conditions and applications. It is related to whether the formulation system can be rapidly crosslinked and cured during light irradiation, thereby changing from a liquid state to a solid state.

[0003] Based on objective needs such as environmental protection, traditional UV curing equipment with a wide spectral radiation range such as mercury lamps will be phased out. LED point light sources, line light sources, and surface light sources have begun to be applied in the photocuring industry. Compared with traditional UV curing equipment, LED light sources have absolute advantages, such as long service life, no heat radiation, environmental protection and pollution-free, super high illuminance, low energy consumption, etc. Visible light (VIS) has a deeper curing depth and lower temperature compared to UV curing, and can also pass through substrates that block ultraviolet light for curing and can select translucent colored materials. Since the output is visible light, the shielding and protection related to ultraviolet light can be minimized. The improvement of safety is another important advantage of VIS curing equipment. At the same time, with the continuous research and development of UV-VIS LED light source curing technology, in order to meet the wide application requirements of UV-VIS LED light source curing technology, photoinitiators suitable for UV-VIS LED light sources need to be developed.

[0004] As free radical photoinitiators, oxime ester photoinitiators have gradually received increasing attention in recent years due to their excellent photosensitive properties. Currently, common commercial products include oxime esters OXE01 and OXE02 (both from BASF). These two products have excellent photoinitiating activity, but their ultraviolet absorption range is relatively short (250 - 350 nm), which cannot meet the requirements of the currently developing UV-VIS LED light sources, especially not suitable for the needs of long-wavelength UV-VIS LED light sources (such as radiation wavelengths of 365 nm, 385 nm, 395 nm, 400 nm, 415 nm, 425 nm, 450 nm). In addition, there are also some patents on oxime ester photoinitiators. For example, CN10277552A discloses a diphenyl sulfide ketoxime ester photoinitiator and its preparation method, and CN102492059A discloses substituted diphenyl sulfide ketoxime ester photoinitiators, etc. However, the ultraviolet absorption wavelengths of most initiators also remain in the range of 250 - 350 nm and still cannot match the developing long-wavelength LED light sources, which greatly limits the application of oxime ester photoinitiators. Additionally, there are not many reported oxime ester photoinitiators for deep curing systems of UV-VIS LED light sources currently, and the yellowing phenomenon of oxime esters has still not been solved, which also greatly limits the application of oxime ester photoinitiators.

[0005] In view of this, developing oxime ester photoinitiators suitable for the currently rapidly developing UV-VIS LED light sources with good thermal stability, storage stability, and solubility has become the research direction of current oxime ester photoinitiators. Summary of the Invention

[0006] In order to promote the development of long-wavelength UV-VIS LED light source curing technology, the inventors have been committed to the promotion and application research of UV-VIS LED light source curing technology, especially continuously researching and developing more photoinitiators suitable for long-wavelength UV-VIS LED light sources. Especially in view of the problems existing in the prior art, the inventors have conducted extensive and in-depth research on photoinitiators suitable for curing of UV-VIS LED light sources (radiation wavelengths of 300 - 550 nm, especially 365 - 450 nm), in order to find a photoinitiator that can replace OXE01 and OXE02, is more suitable for curing of UV-VIS LED light sources, has excellent photosensitive properties, and has good thermal stability, storage stability, and solubility.

[0007] The inventor of the present invention surprisingly found that introducing a specific acyloxyphosphine structural moiety into specific oxime ester compounds forms a novel acyloxyphosphine oxime ester compound with a composite structure, which can have good photosensitive absorption in the range of 300 - 550 nm, especially 365 - 450 nm. After absorbing light energy, it can rapidly undergo cleavage to generate reactive free radicals, continuously initiate polymerization, and has obvious advantages in photosensitivity and good thermal stability and solubility. Therefore, it is suitable for use as a photoinitiator for deep curing with UV-VIS LED light sources, especially for deep curing with long-wavelength UV-VIS LED light sources.

[0008] The object of the present invention is achieved precisely based on the aforementioned discovery.

[0009] Therefore, an object of the present invention is to provide an acyloxyphosphine oxime ester compound, the absorption wavelength of which is not only suitable for radiation curing with UV-VIS LED light sources, but also has good thermal stability and solubility.

[0010] Another object of the present invention is to provide a method for preparing the acyloxyphosphine oxime ester compound of the present invention.

[0011] Another object of the present invention is to provide the use of the acyloxyphosphine oxime ester compound of the present invention as a photoinitiator or photosensitizer.

[0012] The technical solutions for achieving the above objects of the present invention can be summarized as follows:

[0013] 1. Acyloxyphosphine oxime ester compounds of Formula 1 and Formula 2:

[0014]

[0015] Wherein:

[0016] n independently represents 0 or 1 respectively;

[0017] m1 independently represents an integer from 0 to 4 respectively;

[0018] m2 independently represents an integer from 0 to 4 respectively;

[0019] R1 independently represents C1-C 20 alkyl, C6-C 18 aryl or C2-C 20 alkenyl, wherein the aforementioned C1-C 20 alkyl, C6-C 18 aryl or C2-C 20 alkenyl is optionally substituted by one or more groups independently selected from the group consisting of: halogen, nitro, amino, cyano, C1-C6 alkyl, and C1-C6 alkoxy (thio) group;

[0020] R2 each independently represents a C1-C 20 alkyl group, a C3-C 10 cycloalkyl group, a C3-C 10 cycloalkyl-C1-C8 alkyl group, a C1-C8 alkyl-C3-C 10 cycloalkyl group, a C6-C 18 aryl group or a C6-C 18 aryl-C1-C8 alkyl group, wherein the aforementioned C1-C 20 alkyl group, a C3-C 10 cycloalkyl group, a C3-C 10 cycloalkyl-C1-C8 alkyl group, a C1-C8 alkyl-C3-C 10 cycloalkyl group, a C6-C 18 aryl group or a C6-C 18 aryl-C1-C8 alkyl group is optionally substituted by one or more groups independently selected from the group consisting of: halogen, nitro, amino, cyano, C1-C6 alkyl, and C1-C6 alkoxy(thio) group;

[0021] R3 each independently represents halogen, nitro, amino, cyano, C1-C 20 alkyl group, a C3-C 10 cycloalkyl group, a C3-C 10 cycloalkyl-C1-C8 alkyl group, a C1-C8 alkyl-C3-C 10 cycloalkyl group, a C1-C 20 alkoxy(thio) group, a C3-C 10 cycloalkoxy(thio) group, a C3-C 10 cycloalkyl-C1-C8 alkoxy(thio) group, a C1-C8 alkyl-C3-C 10 cycloalkoxy(thio) group, a C6-C 18 aryl group or a C6-C 18 aryloxy(thio) group, wherein the aforementioned C1-C 20 alkyl group, a C3-C 10 cycloalkyl group, a C3-C 10 cycloalkyl-C1-C8 alkyl group, a C1-C8 alkyl-C3-C 10 cycloalkyl group, a C1-C 20 alkoxy(thio) group, a C3-C 10 cycloalkoxy(thio) group, a C3-C 10 cycloalkyl-C1-C8 alkoxy(thio) group, a C1-C8 alkyl-C3-C 10 cycloalkoxy(thio) group, a C6-C 18 aryl group or a C6-C 18 aryloxy(thio) group is optionally substituted by one or more groups independently selected from the group consisting of: halogen, nitro, amino, cyano, C1-C6 alkyl, and C1-C6 alkoxy(thio) group;

[0022] R4 and R5 are the same as or different from each other and each independently represents C1-C 20 alkyl, C3-C 10 cycloalkyl, C3-C 10 cycloalkyl-C1-C8 alkyl, C1-C8 alkyl-C3-C 10 cycloalkyl, C1-C 20 alkoxy(thio) group, C3-C 10 cycloalkoxy(thio) group, C3-C 10 cycloalkyl-C1-C8 alkoxy(thio) group, C1-C8 alkyl-C3-C 10 cycloalkoxy(thio) group, C6-C 18 aryl or C6-C 18 aryloxy(thio) group, wherein the aforementioned C1-C 20 alkyl, C3-C 10 cycloalkyl, C3-C 10 cycloalkyl-C1-C8 alkyl, C1-C8 alkyl-C3-C 10 cycloalkyl, C1-C 20 alkoxy(thio) group, C3-C 10 cycloalkoxy(thio) group, C3-C 10 cycloalkyl-C1-C8 alkoxy(thio) group, C1-C8 alkyl-C3-C 10 cycloalkoxy(thio) group, C6-C 18 aryl or C6-C 18 aryloxy(thio) group is optionally substituted by one or more groups independently selected from the group consisting of halogen, nitro, amino, cyano, C1-C6 alkyl, and C1-C6 alkoxy(thio) group.

[0023] 2. The acyl oxime phosphonate compound according to item 1, wherein:

[0024] R1 each independently represents C1-C6 alkyl, C6-C 10 aryl or C2-C6 alkenyl, wherein the aforementioned C1-C6 alkyl, C6-C 10 aryl or C2-C6 alkenyl is optionally substituted by one or more groups independently selected from the group consisting of halogen, nitro, amino, cyano, C1-C6 alkyl, and C1-C6 alkoxy(thio) group,

[0025] Preferably, R1 each independently represents C1-C4 alkyl, phenyl, or C2-C4 alkenyl, wherein the aforementioned C1-C4 alkyl, phenyl, or C2-C4 alkenyl is optionally substituted by one or more groups independently selected from the group consisting of fluorine, chlorine, bromine, nitro, amino, cyano, C1-C4 alkyl, and C1-C4 alkoxy(thio) group; and / or

[0026] R2 independently represents C1-C8 alkyl, C3-C8 cycloalkyl, C3-C8 cycloalkyl-C1-C8 alkyl, C1-C8 alkyl-C3-C8 cycloalkyl, C6-C 10 aryl or C6-C 10 aryl-C1-C8 alkyl, wherein the aforementioned C1-C8 alkyl, C3-C8 cycloalkyl, C3-C8 cycloalkyl-C1-C8 alkyl, C1-C8 alkyl-C3-C8 cycloalkyl, C6-C 10 aryl or C6-C 10 aryl-C1-C8 alkyl is optionally substituted by one or more groups independently selected from the group consisting of halogen, nitro, amino, cyano, C1-C6 alkyl, and C1-C6 alkoxy(thio) group,

[0027] Preferably, R2 independently represents C1-C4 alkyl, C5-C6 cycloalkyl, C5-C6 cycloalkyl-C1-C4 alkyl, C1-C4 alkyl-C5-C6 cycloalkyl, phenyl, or phenyl-C1-C4 alkyl, wherein the aforementioned C1-C4 alkyl, C5-C6 cycloalkyl, C5-C6 cycloalkyl-C1-C4 alkyl, C1-C4 alkyl-C5-C6 cycloalkyl, phenyl, or phenyl-C1-C4 alkyl is optionally substituted by one or more groups independently selected from the group consisting of fluorine, chlorine, bromine, nitro, amino, cyano, C1-C4 alkyl, and C1-C4 alkoxy(thio) group; and / or

[0028] R3 independently represents halogen, nitro, amino, cyano, C1-C6 alkyl, C3-C8 cycloalkyl, C3-C8 cycloalkyl-C1-C6 alkyl, C1-C6 alkyl-C3-C8 cycloalkyl, C1-C6 alkoxy(thio) group, C3-C8 cycloalkoxy(thio) group, C3-C8 cycloalkyl-C1-C6 alkoxy(thio) group, C1-C6 alkyl-C3-C8 cycloalkoxy(thio) group, C6-C 10 aryl or C6-C 10 aryloxy(thio) group, wherein the aforementioned C1-C6 alkyl, C3-C8 cycloalkyl, C3-C8 cycloalkyl-C1-C6 alkyl, C1-C6 alkyl-C3-C8 cycloalkyl, C1-C6 alkoxy(thio) group, C3-C8 cycloalkoxy(thio) group, C3-C8 cycloalkyl-C1-C6 alkoxy(thio) group, C1-C6 alkyl-C3-C8 cycloalkoxy(thio) group, C6-C 10 aryl or C6-C 10 aryloxy(thio) group is optionally substituted by one or more groups independently selected from the group consisting of halogen, nitro, amino, cyano, C1-C6 alkyl, and C1-C6 alkoxy(thio) group,

[0029] Preferably, each of R3 independently represents fluorine, chlorine, bromine, nitro, amino, cyano, C1-C4 alkyl, C5-C6 cycloalkyl, C5-C6 cycloalkyl-C1-C4 alkyl, C1-C4 alkyl-C5-C6 cycloalkyl, C1-C4 alkoxy(thio) group, C5-C6 cycloalkoxy(thio) group, C5-C6 cycloalkyl-C1-C4 alkoxy(thio) group, C1-C4 alkyl-C5-C6 cycloalkoxy(thio) group, phenyl or phenoxy(thio) group, wherein the aforementioned C1-C4 alkyl, C5-C6 cycloalkyl, C5-C6 cycloalkyl-C1-C4 alkyl, C1-C4 alkyl-C5-C6 cycloalkyl, C1-C4 alkoxy(thio) group, C5-C6 cycloalkoxy(thio) group, C5-C6 cycloalkyl-C1-C4 alkoxy(thio) group, C1-C4 alkyl-C5-C6 cycloalkoxy(thio) group, phenyl or phenoxy(thio) group is optionally substituted by one or more groups independently selected from the group consisting of fluorine, chlorine, bromine, nitro, amino, cyano, C1-C4 alkyl and C1-C4 alkoxy(thio) group; and / or

[0030] R4 and R5 are the same as or different from each other and each independently represents C1-C6 alkyl, C3-C8 cycloalkyl, C3-C8 cycloalkyl-C1-C6 alkyl, C1-C6 alkyl-C3-C8 cycloalkyl, C1-C6 alkoxy(thio) group, C3-C8 cycloalkoxy(thio) group, C3-C8 cycloalkyl-C1-C6 alkoxy(thio) group, C1-C6 alkyl-C3-C8 cycloalkoxy(thio) group, C6-C 10 aryl or C6-C 10 aryloxy(thio) group, wherein the aforementioned C1-C6 alkyl, C3-C8 cycloalkyl, C3-C8 cycloalkyl-C1-C6 alkyl, C1-C6 alkyl-C3-C8 cycloalkyl, C1-C6 alkoxy(thio) group, C3-C8 cycloalkoxy(thio) group, C3-C8 cycloalkyl-C1-C6 alkoxy(thio) group, C1-C6 alkyl-C3-C8 cycloalkoxy(thio) group, C6-C 10 aryl or C6-C 10 aryloxy(thio) group is optionally substituted by one or more groups independently selected from the group consisting of halogen, nitro, amino, cyano, C1-C6 alkyl and C1-C6 alkoxy(thio) group,

[0031] Preferably, R4 and R5 are the same as or different from each other and each independently represents C1-C4 alkyl, C5-C6 cycloalkyl, C5-C6 cycloalkyl-C1-C4 alkyl, C1-C4 alkyl-C5-C6 cycloalkyl, C1-C4 alkoxy(thio) group, C5-C6 cycloalkoxy(thio) group, C5-C6 cycloalkyl-C1-C4 alkoxy(thio) group, C1-C4 alkyl-C5-C6 cycloalkoxy(thio) group, phenyl or phenoxy(thio) group, wherein the aforementioned C1-C4 alkyl, C5-C6 cycloalkyl, C5-C6 cycloalkyl-C1-C4 alkyl, C1-C4 alkyl-C5-C6 cycloalkyl, C1-C4 alkoxy(thio) group, C5-C6 cycloalkoxy(thio) group, C5-C6 cycloalkyl-C1-C4 alkoxy(thio) group, C1-C4 alkyl-C5-C6 cycloalkoxy(thio) group, phenyl or phenoxy(thio) group is optionally substituted by one or more groups independently selected from the group consisting of fluorine, chlorine, bromine, nitro, amino, cyano, C1-C4 alkyl and C1-C4 alkoxy(thio) group.

[0032] 3. The acyloxyphosphine oxime ester compound according to item 1 or 2, wherein:

[0033] n each independently represents 0 or 1;

[0034] m1 each independently represents an integer from 0 to 4;

[0035] m2 each independently represents an integer from 0 to 4;

[0036] R1 each independently represents C1-C4 alkyl, phenyl or C2-C4 alkenyl;

[0037] R2 each independently represents C1-C7 alkyl, C5-C6 cycloalkyl or C5-C6 cycloalkyl-C1-C4 alkyl;

[0038] R3 each independently represents nitro, C1-C4 alkyl, C1-C4 alkoxy(thio) group or phenyl;

[0039] R4 and R5 each independently represent C1-C4 alkyl, C1-C4 alkoxy(thio) group or phenyl.

[0040] 4. The acyloxyphosphine oxime ester compound according to any one of items 1-3, having the formula 3, 4 or 5:

[0041]

[0042] wherein:

[0043] n each independently represents 0 or 1;

[0044] m1 each independently represents an integer from 0 to 4;

[0045] m2 independently represents an integer from 0 to 4;

[0046] R1 independently represents a C1-C4 alkyl group, a phenyl group or a C2-C4 alkenyl group;

[0047] R2 independently represents a C1-C7 alkyl group, a C5-C6 cycloalkyl group or a C5-C6 cycloalkyl-C1-C4 alkyl group;

[0048] R3 independently represents a nitro group, a C1-C4 alkyl group, a C1-C4 alkoxy(sulfur) group or a phenyl group.

[0049] 5. The acyloxyphosphine oxime ester compound according to any one of items 1-4, wherein the acyloxyphosphine oxime ester compound is selected from the following group:

[0050]

[0051]

[0052]

[0053]

[0054] 6. A method for preparing the acyloxyphosphine oxime ester compound according to any one of items 1-5, comprising the following steps:

[0055] (1) Acylation reaction: subjecting the compound of formula 1-1 or formula 2-1 to a Friedel-Crafts acylation reaction to obtain the compound of formula 1-2 or formula 2-2:

[0056]

[0057] (2) Oximation reaction: when n is 0, subjecting the compound of formula 1-2 or formula 2-2 to an oximation reaction with a compound selected from hydroxylamine and / or hydroxylamine hydrochloride to obtain the compound of formula 1-3a or formula 2-3a:

[0058]

[0059] When n is 1, subjecting the compound of formula 1-2 or formula 2-2 to an oximation reaction with a compound selected from nitrous acid, nitrite and / or alkyl nitrite to obtain the compound of formula 1-3b or formula 2-3b:

[0060] and

[0061] (3) Esterification reaction: esterifying the compound of formula 1-3a or 2-3a or the compound of formula 1-3b or 2-3b to obtain the formula

[0062] 1 or formula 2 compound,

[0063] wherein the parameters in the above formulas are defined as in any one of Items 1-5.

[0064] 7. According to the method of Item 6, wherein:

[0065] The Friedel-Crafts acylation reaction in step (1) is carried out with an acylation reagent selected from the compounds of formulas Ia, Ib and Ic as follows:

[0066]

[0067] wherein X is a halogen, especially chlorine, and R2 is defined as in any one of Items 1-5.

[0068] 8. According to the method of Item 6 or 7, wherein the Friedel-Crafts acylation reaction in step (1) is carried out in the presence of one or more catalysts selected from the following group: Lewis acid catalysts, preferably AlCl3, AlBr3, FeCl3, TiCl4, ZnCl2, SnCl4, BF3; solid acid catalysts, preferably zeolite molecular sieves and SO4 2- / M x O y type solid superacids such as SO4 2- / ZrO2, SO4 2- / TiO2, SO4 2- / Fe2O3; ionic liquid type catalysts, preferably chloroaluminate type ionic liquids, such as chloroaluminate type ionic liquids composed of the combination of AlCl3 and organic alkyl imidazole salts, alkyl pyridine salts or halides of alkyl ammonium salts; or supported catalysts, preferably polystyrene-supported AlCl3 catalysts.

[0069] 9. According to the method of any one of Items 6-8, wherein in the Friedel-Crafts acylation reaction of step (1), the molar ratio of the compound of formula 1-1 to the acylation reagent selected from the compounds of formulas Ia, Ib and Ic is 1:0.8 - 1:5, preferably 1:1 - 1:3; the molar ratio of the compound of formula 2-1 to the acylation reagent selected from the compounds of formulas Ia, Ib and Ic is 1:2 - 1:10, preferably 1:2 - 1:6.

[0070] 10. According to the method of any one of Items 6-9, wherein:

[0071] When n is 0:

[0072] The oximation reaction in step (2) is carried out in the presence of sodium acetate, pyridine, piperidine, triethylamine, and / or tetramethylammonium hydroxide as a catalyst; and / or, the molar ratio of the compound of formula 1-2 to the compound selected from hydroxylamine and / or hydroxylamine hydrochloride is 1:1.5 - 1.5:1, preferably 1:1.2 - 1.2:1; the molar ratio of the compound of formula 2-2 to the compound selected from hydroxylamine and / or hydroxylamine hydrochloride is 1:3 - 3:1, preferably 1:2 - 2:1; or when n is 1,

[0073] The oximation reaction in step (2) is carried out in the presence of concentrated hydrochloric acid; and / or, the molar ratio of the compound of formula 1-2 to the compound selected from nitrous acid, nitrite, and / or alkyl nitrite is 1:3 - 3:1, preferably 1:1.5 - 1.5:1; the molar ratio of the compound of formula 2-2 to the compound selected from nitrous acid, nitrite, and / or alkyl nitrite is 1:5 - 5:1, preferably 1:3 - 3:1,

[0074] wherein the alkyl nitrite is a C1-C6 alkyl nitrite, such as methyl nitrite, ethyl nitrite, isopropyl nitrite, butyl nitrite, or isoamyl nitrite.

[0075] 11. The method according to any one of items 6-10, wherein:

[0076] The esterification in step (3) is carried out using an esterification reagent selected from the compounds of formula IIa, IIb, and IIc below:

[0077]

[0078] wherein X is a halogen, especially chlorine, and R1 is defined as in any one of items 1-5.

[0079] 12. The method according to any one of items 6-11, wherein the esterification reaction in step (3) is carried out in the presence of one or more catalysts selected from the following group: 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, such as trialkylamines, such as trimethylamine and triethylamine.

[0080] 13. The method according to any one of items 6-12, wherein in the esterification reaction in step (3), the molar ratio of the compound of formula 1-3a or 2-3a to the esterification reagent selected from the compounds of IIa, IIb, and IIc is 1:1.5 - 1.5:1, preferably 1:1.2 - 1.2:1; the molar ratio of the compound of formula 1-3b or 2-3b to the esterification reagent selected from the compounds of IIa, IIb, and IIc is 1:3 - 3:1, preferably 1:2 - 2:1.

[0081] 14. Use of the acylphosphine oxide oxime ester compound according to any one of items 1-5 as a photoinitiator, especially as a photoinitiator in a UV-VIS LED light source curing system, particularly as a photoinitiator in a light source curing system with a radiation wavelength of 300-550 nm, especially 365-450 nm.

[0082] 15. A photocurable composition comprising at least one acylphosphine oxide oxime ester compound according to any one of items 1-5.

[0083] 16. A cured material obtainable from the photocurable composition of item 15.

[0084] 17. A method for preparing a photocured material, which comprises irradiating the photocurable composition of item 15 with a light source having a radiation wavelength of 300-550 nm, especially 365-450 nm, such as a UV-VIS LED light source. Description of the Drawings

[0085] Figure 1 It is a kinetic curve showing the change of the double bond conversion rate with time when the polymerizable monomer TPGDA is initiated by a photoinitiator to undergo a polymerization reaction.

[0086] Figure 2 It is an ultraviolet-visible light absorption spectrum diagram of Example 1, Example 8 and commercially available (2,4,6-trimethylbenzoyl) diphenylphosphine oxide (TPO). Detailed Description of the Invention

[0087] According to the first aspect of the present invention, there is provided an acylphosphine oxide oxime ester compound of Formula 1 and Formula 2:

[0088]

[0089] Wherein:

[0090] n independently represents 0 or 1 respectively;

[0091] m1 independently represents an integer from 0 to 4 respectively;

[0092] m2 independently represents an integer from 0 to 4 respectively;

[0093] R1 independently represents C1-C 20 alkyl, C6-C 18 aryl or C2-C 20 alkenyl, wherein the aforementioned C1-

[0094] C 20 alkyl, C6-C 18 aryl or C2-C 20The alkenyl group is optionally substituted by one or more groups independently selected from the group consisting of halogen, nitro, amino, cyano, C1-C6 alkyl, and C1-C6 alkoxy(sulfur) group;

[0095] R2 each independently represents C1-C 20 alkyl, C3-C 10 cycloalkyl, C3-C 10 cycloalkyl-C1-C8 alkyl, C1-C8 alkyl-C3-C 10 cycloalkyl, C6-C 18 aryl or C6-C 18 aryl-C1-C8 alkyl, wherein the aforementioned C1-C 20 alkyl, C3-C 10 cycloalkyl, C3-C 10 cycloalkyl-C1-C8 alkyl, C1-C8 alkyl-C3-C 10 cycloalkyl, C6-C 18 aryl or C6-C 18 aryl-C1-C8 alkyl is optionally substituted by one or more groups independently selected from the group consisting of halogen, nitro, amino, cyano, C1-C6 alkyl, and C1-C6 alkoxy(sulfur) group;

[0096] R3 each independently represents halogen, nitro, amino, cyano, C1-C 20 alkyl, C3-C 10 cycloalkyl, C3-C 10 cycloalkyl-C1-C8 alkyl, C1-C8 alkyl-C3-C 10 cycloalkyl, C1-C 20 alkoxy(sulfur) group, C3-C 10 cycloalkoxy(sulfur) group, C3-C 10 cycloalkyl-C1-C8 alkoxy(sulfur) group, C1-C8 alkyl-C3-C 10 cycloalkoxy(sulfur) group, C6-C 18 aryl or C6-C 18 aryloxy(sulfur) group, wherein the aforementioned C1-C 20 alkyl, C3-C 10 cycloalkyl, C3-C 10 cycloalkyl-C1-C8 alkyl, C1-C8 alkyl-C3-C 10 cycloalkyl, C1-C 20 alkoxy(sulfur) group, C3-C 10 cycloalkoxy(sulfur) group, C3-C 10 cycloalkyl-C1-C8 alkoxy(sulfur) group, C1-C8 alkyl-C3-C 10 cycloalkoxy(sulfur) group, C6-C 18 aryl or C6-C18 The aryloxy(sulfide) group is optionally substituted by one or more groups independently selected from the group consisting of halogen, nitro, amino, cyano, C1-C6 alkyl, and C1-C6 alkoxy(sulfide) group;

[0097] R4 and R5 are the same as or different from each other and each independently represents C1-C 20 alkyl, C3-C 10 cycloalkyl, C3-C 10 cycloalkyl-C1-C8 alkyl, C1-C8 alkyl-C3-C 10 cycloalkyl, C1-C 20 alkoxy(sulfide) group, C3-C 10 cycloalkoxy(sulfide) group, C3-C 10 cycloalkyl-C1-C8 alkoxy(sulfide) group, C1-C8 alkyl-C3-C 10 cycloalkoxy(sulfide) group, C6-C 18 aryl or C6-C 18 aryloxy(sulfide) group, wherein the aforementioned C1-C 20 alkyl, C3-C 10 cycloalkyl, C3-C 10 cycloalkyl-C1-C8 alkyl, C1-C8 alkyl-C3-C 10 cycloalkyl, C1-C 20 alkoxy(sulfide) group, C3-C 10 cycloalkoxy(sulfide) group, C3-C 10 cycloalkyl-C1-C8 alkoxy(sulfide) group, C1-C8 alkyl-C3-C 10 cycloalkoxy(sulfide) group, C6-C 18 aryl or C6-C 18 The aryloxy(sulfide) group is optionally substituted by one or more groups independently selected from the group consisting of halogen, nitro, amino, cyano, C1-C6 alkyl, and C1-C6 alkoxy(sulfide) group.

[0098] The acylphosphine oxide oxime ester compounds of Formula 1 and Formula 2 of the present invention have good photosensitive absorption in the range of 300-550 nm, especially 365-450 nm. After absorbing light energy, they can rapidly undergo cleavage to generate active free radicals, continuously initiate polymerization, have obvious advantages in photosensitivity, and have good thermal stability and solubility, so they are suitable as photoinitiators for curing with UV-VIS LED light sources.

[0099] In the present invention, the prefix "C n -C m " represents that the number of carbon atoms contained in the group is n-m in each case.

[0100] "Halogen" means fluorine, chlorine, bromine and iodine. In the present invention, preferably, the halogen includes F, Cl or a combination thereof.

[0101] As used herein, the term "C n -C m alkyl" refers to a branched or unbranched saturated hydrocarbon group having n - m, for example 1 - 20, preferably 1 - 12, more preferably 1 - 8, particularly preferably 1 - 6, and especially preferably 1 - 4 carbon atoms, such as methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 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, heptyl, octyl, 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl and their isomers, etc.

[0102] As used herein, the term "C6 - C m aryl" refers to a monocyclic, bicyclic or more cyclic aromatic hydrocarbon group containing 6 - m, for example 6 - 18, preferably 6 - 10 carbon atoms, such as phenyl, tolyl, ethylphenyl, propylphenyl, butylphenyl, xylenyl, methylethylphenyl, diethylphenyl, methylpropylphenyl, naphthyl and their isomers, etc.

[0103] As used herein, the term "C2 - C m alkenyl" refers to a branched or unbranched unsaturated hydrocarbon group having 2 - m, for example 2 - 20, preferably 2 - 6, more preferably 2 - 4 carbon atoms and having a double bond at any position, such as vinyl, 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 their isomers, etc.

[0104] As used herein, the term "C3 - C m cycloalkyl" refers to a saturated alicyclic monocyclic group having 3 - m, for example 3 - 10, preferably 3 - 8, more preferably 5 - 6 ring carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl and their isomers, etc.

[0105] The term "C3 - Cm Cycloalkyl-C n -C m "alkyl" means C3-C m alkyl substituted by cycloalkyl-C n -C m alkyl, where the two m's can be the same or different, and where C n -C m alkyl and C3-C m cycloalkyl are as defined herein. C3-C m Cycloalkyl-C n -C m alkyl can be C3-C 10 cycloalkyl-C1-C8 alkyl, preferably C3-C6 cycloalkyl-C1-C6 alkyl, more preferably C3-C6 cycloalkyl-C1-C4 alkyl, such as cyclopropylmethyl, cyclopropylethyl, cyclopropylpropyl, cyclopropylbutyl, cyclobutylmethyl, cyclobutylethyl, cyclopropylpropyl, cyclopropylbutyl, cyclopentylmethyl, cyclopentylethyl, cyclopropylpropyl, cyclopropylbutyl, cyclohexylmethyl, cyclohexylethyl, cyclohexylpropyl, cyclohexylbutyl and their isomers, etc.

[0106] The term "C n -C m alkyl-C3-C m cycloalkyl" means C3-C n -C m cycloalkyl substituted by alkyl-C m alkyl, where the two m's can be the same or different, and where C n -C m alkyl and C3-C m cycloalkyl are as defined herein. C n -C m alkyl-C3-C m cycloalkyl can be C1-C8 alkyl-C3-C 10 cycloalkyl, preferably C1-C6 alkyl-C3-C6 cycloalkyl, more preferably C1-C4 alkyl-C3-C6 cycloalkyl, such as methylcyclopropyl, ethylcyclopropyl, propylcyclopropyl, butylcyclopropyl, methylcyclobutyl, ethylcyclobutyl, propylcyclobutyl, butylcyclobutyl, methylcyclopentyl, ethylcyclopentyl, propylcyclopentyl, butylcyclopentyl, methylcyclohexyl, ethylcyclohexyl, propylcyclohexyl, butylcyclohexyl and their isomers, etc.

[0107] As used herein, the term "C n -C m alkoxy(thio) group" includes "C n -C m alkoxy" and "C n -C m alkylthio", and refers to Cn -C m The open-chain C corresponding to an alkyl group n -C m C in which an oxygen atom or a sulfur atom is bonded to any carbon atom of an alkane as a linking group n -C m Alkyl group, such as C1-C 20 Alkoxy(thio) group, preferably C1-C 12 Alkoxy(thio) group, more preferably C1-C8 alkoxy(thio) group, particularly preferably C1-C6 alkoxy(thio) group, especially preferably C1-C4 alkoxy(thio) group. C1-C8 alkoxy group can be methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, 2-butoxy, tert-butoxy, pentyloxy, isopentyloxy, hexyloxy, heptyloxy, octyloxy, isooctyloxy and its isomers. C1-C8 alkylthio group can be methylthio, ethylthio, propylthio, isopropylthio, n-butylthio, 2-butylthio, tert-butylthio, pentylthio, isopentylthio, hexylthio, heptylthio, octylthio, isooctylthio and its isomers, etc.

[0108] As used herein, the term "C3-C m Cycloalkoxy(thio) group" includes "C3-C m Cycloalkoxy group" and "C3-C m Cycloalkylthio group", and refers to C3-C in which an oxygen atom or a sulfur atom is bonded to any ring carbon atom of a C3-C m Cycloalkyl group corresponding to a cycloalkane as a linking group m C3-C in which an oxygen atom or a sulfur atom is bonded to any ring carbon atom of a cycloalkane m Cycloalkyl group, such as C3-C 20 Cycloalkoxy(thio) group, preferably C3-C8 cycloalkoxy(thio) group, more preferably C5-C6 cycloalkoxy(thio) group, such as cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, cycloheptyloxy, cyclooctyloxy, cyclodecyloxy and its isomers, cyclopropylthio, cyclobutylthio, cyclopentylthio, cyclohexylthio, cycloheptylthio, cyclooctylthio, cyclodecylthio and its isomers, etc.

[0109] The term "C3-C m Cycloalkyl-C n -C m Alkoxy(thio) group" includes "C3-C m Cycloalkyl-C n -C m Alkoxy group" and "C3-C m Cycloalkyl-C n -C m Alkylthio group", and refers to C which is substituted by a C3-C m Cycloalkyl group n -C man alkoxy(thio) group, where the two m's can be the same or different, in which C3-C m cycloalkyl and C n -C m the alkoxy(thio) group is as defined herein. C3-C m cycloalkyl-C n -C m the alkoxy(thio) group can be a C3-C 10 cycloalkyl-C1-C8 alkoxy(thio) group, preferably a C3-C6 cycloalkyl-C1-C6 alkoxy(thio) group, more preferably a C3-C6 cycloalkyl-C1-C4 alkoxy(thio) group, such as cyclopropylmethoxy, cyclopropylethoxy, cyclopropylpropoxy, cyclopropylbutoxy, cyclobutylmethoxy, cyclobutylethoxy, cyclobutylpropoxy, cyclobutylbutoxy, cyclopentylmethoxy, cyclopentylethoxy, cyclopentylpropoxy, cyclopentylbutoxy, cyclohexylmethoxy, cyclohexylethoxy, cyclohexylpropoxy, cyclohexylbutoxy, cyclopropylmethylthio, cyclopropylethylthio, cyclopropylpropylthio, cyclopropylbutylthio, cyclobutylmethylthio, cyclobutylethylthio, cyclobutylpropylthio, cyclobutylbutylthio, cyclopentylmethylthio, cyclopentylethylthio, cyclopentylpropylthio, cyclopentylbutylthio, cyclohexylmethylthio, cyclohexylethylthio, cyclohexylpropylthio, cyclohexylbutylthio and their isomers, etc.

[0110] The term "C n -C m alkyl-C3-C m cycloalkoxy(thio) group" means a C3-C n -C m cycloalkoxy(thio) group substituted by an alkyl group, where the two m's can be the same or different, in which C m -C n alkyl and C3-C m cycloalkoxy(thio) group are as defined herein. C m -C n alkyl-C3-C m cycloalkoxy(thio) group can be a C1-C8 alkyl-C3-C m cycloalkoxy(thio) group, where the two m's can be the same or different, in which C 10Cycloalkoxy (thio) group, preferably C1-C6 alkyl-C3-C6 cycloalkoxy (thio) group, more preferably C1-C4 alkyl-C3-C6 cycloalkoxy (thio) group, for example methyl cyclopropyloxy, ethyl cyclopropyloxy, propyl cyclopropyloxy, butyl cyclopropyloxy, methyl cyclobutyloxy, ethyl cyclobutyloxy, propyl cyclobutyloxy, butyl cyclobutyloxy, methyl cyclopentyloxy, ethyl cyclopentyloxy, propyl cyclopentyloxy, butyl cyclopentyloxy, methyl cyclopentylthio, ethylcyclopentylthio, propylcyclopentylthio, butylcyclopentylthio, methylcyclohexylthio, ethylcyclohexylthio, propylcyclohexylthio, butylcyclohexylthio, methylcyclopropylthio, ethylcyclopropylthio, propylcyclopropylthio, butylcyclopropylthio, methylcyclobutylthio, ethylcyclobutylthio, propylcyclobutylthio, butylcyclobutylthio, methylcyclopentylthio, ethylcyclopentylthio, propylcyclopentylthio, butylcyclopentylthio, methylcyclohexylthio, ethylcyclohexylthio, propylcyclohexylthio, butylcyclohexylthio and isomers thereof.

[0111] The term "C6-C m "Aryloxy (sulfur) group" includes "C6-C m Aryloxy" and "C6-C m "Arylthio" refers to a C6-C m The C6-C m Any aromatic carbon atom in an aromatic hydrocarbon is bonded to an oxygen atom or a sulfur atom as a linking group. m Aryl groups include phenylthio, phenoxy, tolyloxy, tolylthio, naphthylthio, naphthyloxy and isomers thereof.

[0112] In the present invention, n is 0 or 1. When n is 0, the compound of formula 1 or 2 is called an acylphosphine oxide oxime ester compound; when n is 1, the compound of formula 1 or 2 is called an acylphosphine oxide ketone oxime ester compound. These two compounds are collectively referred to as acylphosphine oxide oxime ester compounds.

[0113] In a preferred embodiment of the present invention, R1 independently represents C1-C6 alkyl, C6-C 10 Aryl or C2-C6 alkenyl, wherein the aforementioned C1-C6 alkyl, C6-C 10 The aryl or C2-C6 alkenyl is optionally substituted by one or more groups independently selected from the group consisting of halogen, nitro, amino, cyano, C1-C6 alkyl and C1-C6 alkoxy(thio) groups;

[0114] Preferably, R1 independently represents a C1-C4 alkyl, a phenyl or a C2-C4 alkenyl, wherein the aforementioned C1-C4 alkyl, phenyl or C2-C4 alkenyl is optionally substituted by one or more groups independently selected from the following group: fluorine, chlorine, bromine, nitro, amino, cyano, C1-C4 alkyl and C1-C4 alkoxy (thio) group.

[0115] In a preferred embodiment of the present invention, R2 independently represents C1-C8 alkyl, C3-C8 cycloalkyl, C3-C8 cycloalkyl-C1-C8 alkyl, C1-C8 alkyl-C3-C8 cycloalkyl, C6-C 10 aryl or C6-C 10 aryl-C1-C8 alkyl, wherein the aforementioned C1-C8 alkyl, C3-C8 cycloalkyl, C3-C8 cycloalkyl-C1-C8 alkyl, C1-C8 alkyl-C3-C8 cycloalkyl, C6-C 10 aryl or C6-C 10 aryl-C1-C8 alkyl is optionally substituted by one or more groups independently selected from the group consisting of halogen, nitro, amino, cyano, C1-C6 alkyl, and C1-C6 alkoxy(thio) group;

[0116] Preferably, R2 independently represents C1-C4 alkyl, C5-C6 cycloalkyl, C5-C6 cycloalkyl-C1-C4 alkyl, C1-C4 alkyl-C5-C6 cycloalkyl, phenyl, or phenyl-C1-C4 alkyl, wherein the aforementioned C1-C4 alkyl, C5-C6 cycloalkyl, C5-C6 cycloalkyl-C1-C4 alkyl, C1-C4 alkyl-C5-C6 cycloalkyl, phenyl, or phenyl-C1-C4 alkyl is optionally substituted by one or more groups independently selected from the group consisting of fluorine, chlorine, bromine, nitro, amino, cyano, C1-C4 alkyl, and C1-C4 alkoxy(thio) group.

[0117] In a preferred embodiment of the present invention, R3 independently represents halogen, nitro, amino, cyano, C1-C6 alkyl, C3-C8 cycloalkyl, C3-C8 cycloalkyl-C1-C6 alkyl, C1-C6 alkyl-C3-C8 cycloalkyl, C1-C6 alkoxy(thio) group, C3-C8 cycloalkoxy(thio) group, C3-C8 cycloalkyl-C1-C6 alkoxy(thio) group, C1-C6 alkyl-C3-C8 cycloalkoxy(thio) group, C6-C 10 aryl or C6-C 10 aryloxy(thio) group, wherein the aforementioned C1-C6 alkyl, C3-C8 cycloalkyl, C3-C8 cycloalkyl-C1-C6 alkyl, C1-C6 alkyl-C3-C8 cycloalkyl, C1-C6 alkoxy(thio) group, C3-C8 cycloalkoxy(thio) group, C3-C8 cycloalkyl-C1-C6 alkoxy(thio) group, C1-C6 alkyl-C3-C8 cycloalkoxy(thio) group, C6-C 10 aryl or C6-C 10 aryloxy(thio) group is optionally substituted by one or more groups independently selected from the group consisting of halogen, nitro, amino, cyano, C1-C6 alkyl, and C1-C6 alkoxy(thio) group;

[0118] Preferably, R3 independently represents fluorine, chlorine, bromine, nitro, cyano, C1-C4 alkyl, C5-C6 cycloalkyl, C5-C6 cycloalkyl-C1-C4 alkyl, C1-C4 alkyl-C5-C6 cycloalkyl, C1-C4 alkoxy(thio) group, C5-C6 cycloalkoxy(thio) group, C5-C6 cycloalkyl-C1-C4 alkoxy(thio) group, C1-C4 alkyl-C5-C6 cycloalkoxy(thio) group, phenyl or phenoxy(thio) group, wherein the aforementioned C1-C4 alkyl, C5-C6 cycloalkyl, C5-C6 cycloalkyl-C1-C4 alkyl, C1-C4 alkyl-C5-C6 cycloalkyl, C1-C4 alkoxy(thio) group, C5-C6 cycloalkoxy(thio) group, C5-C6 cycloalkyl-C1-C4 alkoxy(thio) group, C1-C4 alkyl-C5-C6 cycloalkoxy(thio) group, phenyl or phenoxy(thio) group is optionally substituted by one or more groups independently selected from the group consisting of fluorine, chlorine, bromine, nitro, amino, cyano, C1-C4 alkyl and C1-C4 alkoxy(thio) group.

[0119] In a preferred embodiment of the present invention, R4 and R5 are the same as or different from each other and independently represent C1-C6 alkyl, C3-C8 cycloalkyl, C3-C8 cycloalkyl-C1-C6 alkyl, C1-C6 alkyl-C3-C8 cycloalkyl, C1-C6 alkoxy(thio) group, C3-C8 cycloalkoxy(thio) group, C3-C8 cycloalkyl-C1-C6 alkoxy(thio) group, C1-C6 alkyl-C3-C8 cycloalkoxy(thio) group, C6-C 10 aryl or C6-C 10 aryloxy(thio) group, wherein the aforementioned C1-C6 alkyl, C3-C8 cycloalkyl, C3-C8 cycloalkyl-C1-C6 alkyl, C1-C6 alkyl-C3-C8 cycloalkyl, C1-C6 alkoxy(thio) group, C3-C8 cycloalkoxy(thio) group, C3-C8 cycloalkyl-C1-C6 alkoxy(thio) group, C1-C6 alkyl-C3-C8 cycloalkoxy(thio) group, C6-C 10 aryl or C6-C 10 aryloxy(thio) group is optionally substituted by one or more groups independently selected from the group consisting of halogen, nitro, amino, cyano, C1-C6 alkyl and C1-C6 alkoxy(thio) group;

[0120] Preferably, R4 and R5 are the same as or different from each other and each independently represents C1-C4 alkyl, C5-C6 cycloalkyl, C5-C6 cycloalkyl-C1-C4 alkyl, C1-C4 alkyl-C5-C6 cycloalkyl, C1-C4 alkoxy(thio) group, C5-C6 cycloalkoxy(thio) group, C5-C6 cycloalkyl-C1-C4 alkoxy(thio) group, C1-C4 alkyl-C5-C6 cycloalkoxy(thio) group, phenyl or phenoxy(thio) group, wherein the aforementioned C1-C4 alkyl, C5-C6 cycloalkyl, C5-C6 cycloalkyl-C1-C4 alkyl, C1-C4 alkyl-C5-C6 cycloalkyl, C1-C4 alkoxy(thio) group, C5-C6 cycloalkoxy(thio) group, C5-C6 cycloalkyl-C1-C4 alkoxy(thio) group, C1-C4 alkyl-C5-C6 cycloalkoxy(thio) group, phenyl or phenoxy(thio) group is optionally substituted by one or more groups independently selected from the group consisting of fluorine, chlorine, bromine, nitro, amino, cyano, C1-C4 alkyl and C1-C4 alkoxy(thio) group.

[0121] In a more preferred embodiment of the present invention, wherein

[0122] n each independently represents 0 or 1;

[0123] m1 each independently represents an integer from 0 to 4;

[0124] m2 each independently represents an integer from 0 to 4;

[0125] R1 each independently represents C1-C4 alkyl, phenyl or C2-C4 alkenyl;

[0126] R2 each independently represents C1-C7 alkyl, C5-C6 cycloalkyl or C5-C6 cycloalkyl-C1-C4 alkyl;

[0127] R3 each independently represents nitro, C1-C4 alkyl, C1-C4 alkoxy(thio) group or phenyl;

[0128] R4 and R5 each independently represent C1-C4 alkyl, C1-C4 alkoxy(thio) group or phenyl.

[0129] In a particularly preferred embodiment of the present invention, the acyl oxime phosphonate compounds of Formula 1 and Formula 2 of the present invention are selected from the compounds of Formula 3, Formula 4 or Formula 5:

[0130]

[0131] Wherein:

[0132] n each independently represents 0 or 1;

[0133] m1 each independently represents an integer from 0 to 4;

[0134] m2 independently represents an integer from 0 to 4;

[0135] R1 independently represents C1-C4 alkyl, phenyl or C2-C4 alkenyl;

[0136] R2 independently represents C1-C7 alkyl, C5-C6 cycloalkyl or C5-C6 cycloalkyl-C1-C4 alkyl;

[0137] R3 independently represents nitro, C1-C4 alkyl, C1-C4 alkoxy(sulfur)yl or phenyl.

[0138] In some particularly preferred embodiments of the present invention, the acyl oxime phosphonate compounds of formula 1 and formula 2 of the present invention are selected from compounds 1-83 shown above. Compounds 1-83 are prepared in Examples 1-83 respectively.

[0139] According to a second aspect of the present invention, there is provided a method for preparing a compound of formula 1 or formula 2 of the present invention, comprising the following steps:

[0140] (1) Acylation reaction: subjecting a compound of formula 1-1 or formula 2-1 to a Friedel-Crafts acylation reaction to obtain a compound of formula 1-2 or formula 2-2:

[0141]

[0142] (2) Oximation reaction: when n is 0, subjecting a compound of formula 1-2 or formula 2-2 to an oximation reaction with a compound selected from hydroxylamine and / or hydroxylamine hydrochloride to obtain a compound of formula 1-3a or formula 2-3a:

[0143]

[0144] When n is 1, subjecting a compound of formula 1-2 or formula 2-2 to an oximation reaction with a compound selected from nitrous acid, nitrite and / or alkyl nitrite to obtain a compound of formula 1-3b or formula 2-3b:

[0145] and

[0146] (3) Esterification reaction: esterifying a compound of formula 1-3a or 2-3a or a compound of formula 1-3b or 2-3b to obtain a compound of formula 1 or formula 2,

[0147] wherein the parameters in each of the above formulas are as defined for formula 1 and formula 2.

[0148] To prepare the acyl-oxyphosphine oxime ester compounds of Formula 1 and Formula 2 of the present invention, it is necessary to start from specific acyl-oxyphosphine compounds, first carry out Friedel-Crafts acylation reaction, and then carry out oximation reaction to introduce an oxime group, and then convert the hydroxyl group in the oxime group into the corresponding ester group through an esterification reaction, so as to obtain the acyl-oxyphosphine oxime ester compounds of the present invention.

[0149] Friedel-Crafts acylation reaction

[0150] The compounds of Formula 1-1 or 2-1 undergo Friedel-Crafts acylation reaction with an acylating agent under the action of a catalyst to form the compounds of Formula 1-2 or 2-2:

[0151]

[0152] wherein the parameters in the above formulas are as defined for Formula 1 and Formula 2.

[0153] The Friedel-Crafts acylation reaction is conventional to those skilled in the art. As the acylating agent, there is no particular limitation as long as it can carry out Friedel-Crafts acylation on the compounds of Formula 1-1 or 2-1. For example, the corresponding acyl halides such as acyl chlorides can be used, the corresponding carboxylic acids can also be used, and the corresponding acid anhydrides can also be used. These compounds can be represented as the compounds of Formula Ia, Ib and Ic respectively:

[0154]

[0155] wherein X is a halogen, especially chlorine, and R2 is as defined for Formula 1 or 2.

[0156] To accelerate the Friedel-Crafts acylation reaction, the above reaction is usually carried out in the presence of a catalyst suitable for the Friedel-Crafts acylation reaction. As the catalyst, Lewis acid catalysts can be used, preferably AlCl3, AlBr3, FeCl3, TiCl4, ZnCl2, SnCl4, BF3; solid acid catalysts, preferably zeolite molecular sieves and SO4 2- / M x O y type solid superacids such as SO4 2- / ZrO2, SO4 2- / TiO2, SO4 2- / Fe2O3; ionic liquid type catalysts, preferably chloroaluminate type ionic liquids, such as chloroaluminate type ionic liquids composed of the combination of AlCl3 and organic alkyl imidazole salts, alkyl pyridine salts or alkyl ammonium salt halides; or supported catalysts, preferably polystyrene-supported AlCl3 catalysts. The dosage of the catalyst is conventional and can be determined by the common knowledge in the art or through several routine preliminary experiments.

[0157] The above-mentioned Friedel-Crafts acylation reaction is usually carried out in a solvent, preferably in an organic solvent. There is no particular limitation on the choice of solvent type, as long as it can dissolve the compound of formula 1-1 or 2-1 and the acylating agent and is chemically inert to the acylation reaction, that is, it does not participate in the acylation reaction. It is preferably carried out in a halogenated alkane solvent. As an example of the solvent, dichloromethane or dichloroethane is usually used.

[0158] There is no particular limitation on the relative amounts of the compound of formula 1-1 or 2-1 and the acylating agent selected from compounds Ia, Ib and Ic. Generally, the molar ratio of the compound of formula 1-1 to the acylating agent selected from compounds Ia, Ib and Ic is 1:0.8 - 1:5, preferably 1:1 - 1:3; the molar ratio of the compound of formula 2-1 to the acylating agent selected from compounds Ia, Ib and Ic is 1:2 - 1:10, preferably 1:2 - 1:6.

[0159] The temperature range of the Friedel-Crafts acylation reaction is usually from -10°C to 50°C, preferably 0 - 40°C. There is no particular limitation on the reaction time, and it is usually carried out for 0.1 - 20 hours, preferably 0.5 - 10 hours.

[0160] Oximation reaction

[0161] When n is 0, the compound of formula 1-2 or formula 2-2 is subjected to an oximation reaction with a compound selected from hydroxylamine and / or hydroxylamine hydrochloride to obtain a compound of formula 1-3a or formula 2-3a:

[0162]

[0163] wherein the parameters in the above formulas are as defined for formulas 1 and 2.

[0164] This oximation reaction usually uses hydroxylamine hydrochloride (NH2OH·HCl), hydroxylamine (NH2OH) or a mixture thereof as the oximation reagent. This oximation reaction is usually carried out in an organic solvent, preferably in a polar organic solvent. Solvents that can be used are, for example, ethanol or ethanol containing water. In order to promote the complete progress of the oximation reaction, catalysts such as sodium acetate, pyridine, piperidine, triethylamine, tetramethylammonium hydroxide or a mixture thereof are generally added. Among these, pyridine, piperidine and triethylamine can also be used as bases and / or solvents or co-solvents.

[0165] There is no particular limitation on the relative amounts of the compound of formula 1-2 and the compound selected from hydroxylamine and / or hydroxylamine hydrochloride. Generally, they are used in approximately equimolar amounts. For example, the molar ratio of the two is 1:1.5 - 1.5:1, preferably 1:1.2 - 1.2:1. The molar ratio of the compound of formula 2-2 to the compound selected from hydroxylamine and / or hydroxylamine hydrochloride is 1:3 - 3:1, preferably 1:2 - 2:1.

[0166] The temperature range of the above oximation reaction is generally 30 - 120 °C, preferably 40 - 100 °C. There is no particular limitation on the oximation reaction time, which is generally carried out for 0.1 - 20 hours, preferably 0.5 - 10 hours.

[0167] When n is 1, the compound of formula 1 - 2 or formula 2 - 2 is subjected to an oximation reaction with a compound selected from nitrous acid, nitrite and / or alkyl nitrite to obtain the compound of formula 1 - 3b or formula 2 - 3b:

[0168]

[0169] Wherein the parameters in the above formulas are as defined for formulas 1 and 2.

[0170] This oximation reaction generally uses nitrous acid, nitrite, alkyl nitrite or a mixture thereof as the oximation reagent. This reagent nitrosates the "active" (sub)methyl group (α-(sub)methyl group, i.e., the (sub)methyl group adjacent to the carbonyl group). As the nitrite, sodium nitrite is generally used. As the alkyl nitrite, C1 - C6 alkyl nitrites are generally used, such as methyl nitrite, ethyl nitrite, isopropyl nitrite, butyl nitrite or isoamyl nitrite. This oximation reaction is generally carried out in an organic solvent, preferably in an organic polar solvent. Solvents that can be used include, for example, tetrahydrofuran, ethanol or ethanol containing water. In order to promote the complete progress of the oximation reaction, concentrated hydrochloric acid is generally added or hydrogen chloride gas is introduced, and its concentration is generally 20 - 40%. Concentrated hydrochloric acid can also be used as an acid and / or solvent or co-solvent.

[0171] There is no particular limitation on the relative amounts of the compound of formula 1 - 2 and the compound selected from nitrous acid, nitrite and / or alkyl nitrite. Generally, they are used in approximately equimolar amounts. For example, the molar ratio of the two is 1:3 - 3:1, preferably 1:1.5 - 1.5:1. The molar ratio of the compound of formula 2 - 2 and the compound selected from nitrous acid, nitrite and / or alkyl nitrite is 1:5 - 5:1, preferably 1:3 - 3:1.

[0172] The temperature of the above oximation reaction is low, and the temperature range is generally -30 °C to 20 °C, preferably 5 - 20 °C. There is no particular limitation on the oximation reaction time, which is generally carried out for 0.1 - 20 hours, preferably 0.5 - 10 hours.

[0173] Esterification reaction

[0174] The esterification of the compound of Formula 1-3a or 2-3a or Formula 1-3b or 2-3b is routine for those skilled in the art. Through this reaction, the hydroxyl group in the oxime group is transformed into an ester group, thereby obtaining the compound of Formula 1 or 2. As the esterification reagent, there is no particular limitation as long as it can transform the hydroxyl group in the oxime group of the compound of Formula 1-3a or 2-3a or Formula 1-3b or 2-3b into an ester group. For example, the corresponding acyl halide, such as acyl chloride, can be used, or the corresponding carboxylic acid can also be used, and the corresponding acid anhydride can also be used. These compounds can be represented as the compounds of Formula IIa, IIb, and IIc respectively:

[0175]

[0176] wherein X is a halogen, especially chlorine, and R1 is as defined in Formula 1 or 2.

[0177] 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 (such as trialkylamines, such as trimethylamine and triethylamine) or any combination thereof can be used. The dosage of the catalyst is conventional and can be determined by the common knowledge in the art or through several routine preliminary experiments.

[0178] To increase the yield of the acylphosphonoxime ester compound of Formula 1 or 2 of the present invention, it is advantageous to remove the water generated in the esterification reaction during the esterification reaction. This can be carried out, for example, by distillation / condensation.

[0179] The above esterification reaction is usually carried out in a solvent, preferably in an organic solvent. For the selection of the solvent type, there is no particular limitation as long as it can dissolve the compound of Formula 1-3a or 2-3a or Formula 1-3b or 2-3b and the esterification reagent and is chemically inert to the esterification reaction, that is, it does not participate in the esterification reaction. As examples of the solvent, tetrahydrofuran, benzene, toluene, N,N-dimethylformamide, dichloromethane, and acetone can be mentioned. The solvent can be a single solvent or a mixture of two or more solvents.

[0180] There is no particular limitation on the relative amounts of the compounds of Formulas 1-3a and 2-3a and the esterification reagent selected from the compounds of IIa, IIb, and IIc. Generally, they are used in approximately equimolar amounts. For example, the molar ratio of the two is 1:1.5 - 1.5:1, preferably 1:1.2 - 1.2:1. The molar ratio of the compound of Formula 1-3b or 2-3b to the esterification reagent selected from the compounds of IIa, IIb, and IIc is 1:3 - 3:1, preferably 1:2 - 2:1.

[0181] The esterification reaction can be carried out within a very wide temperature range. Advantageously according to the present invention, the esterification reaction is carried out at a temperature of -10°C to 150°C, preferably 0°C to 100°C, and preferably at room temperature. There is no particular limitation on the esterification reaction time either. Generally, it is carried out for 1 - 24 hours, preferably 1 - 12 hours.

[0182] After the completion of the esterification reaction, a reaction mixture containing the compound of Formula 1 or Formula 2 is obtained. Therefore, it is necessary to post-treat this reaction mixture to obtain the purified compound of Formula 1 or Formula 2. Generally, first, the reaction mixture obtained from the esterification reaction is filtered, and the filtrate part is taken out. Then, the filtrate is washed to remove the catalyst and unreacted raw materials. There is no particular limitation on the washing solution as long as it can remove the catalyst and unreacted raw materials. As examples of the washing solution, dilute hydrochloric acid (aqueous solution), saturated sodium bicarbonate aqueous solution, and water can be mentioned. There is no particular limitation on the concentration of the dilute hydrochloric acid. Generally, dilute hydrochloric acid with a concentration of 5 - 12% is used. The washing with the washing solution can be carried out once or multiple times; in the case of multiple times, a single washing solution can be used, or different washing solutions can be used in sequence. Advantageously according to the present invention, the filtrate obtained by filtering the reaction mixture from the esterification reaction is washed successively with dilute hydrochloric acid, saturated sodium bicarbonate aqueous solution, and water. Of course, after each washing with the washing solution, the aqueous phase needs to be discarded and then the organic phase is washed with the next washing solution. After washing, it is necessary to dry to remove the residual water. For this purpose, anhydrous sodium sulfate is usually used for drying. After drying, the residual organic solvent is removed. As the means for removing the residual organic solvent here, there is no particular limitation. Generally, the organic solvent can be removed by vacuum distillation. After removing the residual organic solvent, a crude product of the compound of Formula 1 or Formula 2 is obtained. If it is desired to further increase the purity of the compound of Formula 1 or Formula 2, the compound can be further purified, for example, by recrystallization. The selection of the recrystallization solvent is conventional and there is no particular limitation. Advantageously according to the present invention, petroleum ether, methanol, ethanol, or a mixture thereof is used to recrystallize the crude product of the compound of Formula 1 or Formula 2.

[0183] In the compounds of Formula 1 or Formula 2, each oxime ester group may exist in two configurations, the (Z) form or the (E) form. The isomers can be separated by conventional methods, but a mixture of isomers can also be used as a photoinitiating substance. Therefore, the present invention also relates to a mixture of the configurational isomers of the compounds of Formula 1 or Formula 2 respectively.

[0184] The acylphosphine oxide oxime ester compounds of Formula 1 and Formula 2 of the present invention have strong absorption in the wavelength range of 300 - 550 nm, especially in the range of 365 - 450 nm. Therefore, they can be used as photoinitiators in UV-VIS LED photocuring technology, especially suitable for deep curing with long-wavelength UV-VIS LED light sources.

[0185] Therefore, according to the third aspect of the present invention, there is provided the use of the acylphosphine oxide oxime ester compounds of Formula 1 and Formula 2 of the present invention as photoinitiators. The acylphosphine oxide oxime ester compounds of Formula 1 and Formula 2 of the present invention can be used as photoinitiators in UV-VIS LED photocuring technology, and can effectively initiate the curing reaction, especially suitable for deep curing with long-wavelength UV-VIS LED light sources. Particularly preferably, the use of the acylphosphine oxide oxime ester compounds of Formula 1 and Formula 2 of the present invention as photoinitiators in a photocuring system with a radiation wavelength of 300 - 550 nm, especially 365 - 450 nm. The acylphosphine oxide oxime ester compounds of Formula 1 and Formula 2 of the present invention can also be used as photoinitiators or photosensitizers in the fields of coatings, inks, microelectronics, printing, etc. When the acylphosphine oxide oxime ester compounds of Formula 1 and Formula 2 of the present invention are used as photoinitiators, their amounts are conventional or can be determined by routine preliminary tests. Therefore, the present invention also relates to a photocurable composition containing the acylphosphine oxide oxime ester compound of the present invention, and a cured material obtainable from the photocurable composition. In addition, the present invention also relates to a method for preparing a photocured material, which includes irradiating the photocurable composition with a light source having a radiation wavelength of 300 - 550 nm, especially 365 - 450 nm, such as a UV-VIS LED light source.

[0186] In addition, the production process of the compounds disclosed in the present invention is simple and has a high yield, and is very suitable for industrial production. Such compounds have good compatibility with UV-VIS LED light sources with radiation wavelengths of 365 nm, 385 nm, 395 nm, 405 nm, 415 nm, 425 nm, 450 nm, and can be widely used as photoinitiators in the fields involved in UV-VIS LED photocuring, such as coatings, inks, microelectronics, printing, 3D printing, dental materials, etc. Therefore, the acylphosphine oxide oxime ester photoinitiators represented by Formula 1 or Formula 2 of the present invention have good market prospects.

[0187] In addition, considering that there are currently few varieties of photoinitiators applicable to UV-VIS LED light sources, especially deep curing of long-wavelength UV-VIS LED light sources, to a certain extent, it restricts the popularization and application of UV-VIS LED light sources in the field of photocuring. Therefore, the acylphosphine oxide oxime ester photoinitiators represented by Formula 1 or Formula 2 of the present invention can contribute to the wide application of green and environmentally friendly UV-VIS LED light sources in the UV photocuring industry.

[0188] Embodiment

[0189] The solution of the present invention will be explained below in conjunction with examples. Those skilled in the art will understand that the following examples are only used to illustrate the present invention and should not be regarded as limiting the scope of the present invention. For those not specified in the examples regarding specific technologies or conditions, they shall be carried out according to the technologies or conditions described in the literature in this field or the product specifications.

[0190] Example 1: Preparation of Compound 1

[0191]

[0192] The synthetic route of Compound 1 is as follows:

[0193]

[0194] Synthesis of Intermediate Compound 1a

[0195] Add (2,4,6-trimethylbenzoyl)diphenylphosphine oxide (TPO, 0.1 mol, 34.8 g) to a 500 ml three-necked round-bottom flask containing 200 ml of dichloromethane. After stirring and dissolving, add aluminum trichloride (0.2 mol, 26.6 g) and stir evenly. Then add propionyl chloride (0.2 mol, 18.4 g) and stir the reaction at room temperature for 1 hour. After the reaction is complete, the material is hydrolyzed, washed with alkali, washed with water, dried and concentrated, and then recrystallized with ethanol. The theoretical yield is 40.4 g, and 32.3 g of the product is obtained, with a yield of 80%. It is identified as Compound 1a. 1 1H-NMR(400 MHz, CDCl3) δ1.22(t, 3H), 2.22(s, 3H), 2.33(s, 3H), 2.48(s, 3H), 3.54(q, 2H), 7.24(s, 1H), 7.51(m, 6H), 7.77(d, 4H).

[0196] Synthesis of Intermediate Compound 1b

[0197] Under magnetic stirring, 1a (20.2 g, 0.05 mol) was added to 100 ml of tetrahydrofuran, and dry freshly prepared hydrogen chloride gas was introduced. Isoamyl nitrite (11.7 g, 0.01 mol) was added dropwise at 10 °C, and the stirring reaction was stopped until a large amount of the product precipitated. Subsequently, filtration was carried out to obtain the crude product, and the crude product was recrystallized with methanol to obtain 17.8 g of a white powder. The theoretical yield was 21.7 g, and the yield was 82.1%. It was identified as the intermediate 1b. 1 1H-NMR (400 MHz, CDCl3) δ 2.33 (s, 3H), 2.48 (s, 6H), 3.11 (s, 3H), 7.35 (s, 1H), 7.51 (m, 6H), 7.77 (d, 4H), 11.01 (s, 1H).

[0198] Synthesis of the target product 1

[0199] The above intermediate compound 1b (13.0 g, 0.03 mol) and 100 ml of dichloromethane were added to a 500 ml three-necked round-bottom flask, and then acetyl chloride (5.8 g, 0.075 mol) and triethylamine (10.1 g, 0.01 mol) were added. The reaction was stirred in an ice-water bath for 1 hour. The reaction was terminated, and after the reaction solution was filtered, the filtrate was poured into water, extracted with ethyl acetate, the organic phase was collected and washed successively with dilute hydrochloric acid solution, saturated sodium carbonate aqueous solution and distilled water, and then the organic phase was collected and dried over MgSO4 overnight. After filtration, the organic phase was distilled off under reduced pressure to obtain 11.8 g of a light yellow powdery solid. The theoretical yield was 14.3 g, and the yield was 82.6%. It was identified as compound 1. 1 1H-NMR (400 MHz, CDCl3) δ 2.20 (s, 3H), 2.33 (s, 3H), 2.48 (s, 6H), 3.11 (s, 3H), 7.35 (s, 1H), 7.51 (m, 6H), 7.77 (d, 4H).

[0200] Example 2-14: Preparation of compounds 2-14

[0201] The method of Example 1 was repeated, and the reaction raw materials were appropriately changed to obtain the compounds 2-14 shown in Table 1 below and their NMR data.

[0202] Table 1

[0203]

[0204]

[0205] Example 15: Preparation of compound 15

[0206]

[0207] The synthetic route of Compound 15 is as follows:

[0208]

[0209] Synthesis of Intermediate Compound 15a

[0210] Ethoxy(2,4,6-trimethylbenzoyl)phenylphosphine oxide (0.1 mol, 31.6 g) was added to a 500 ml three-necked round-bottom flask containing 200 ml of dichloromethane. After stirring to dissolve, aluminum chloride (0.2 mol, 26.6 g) was added and stirred evenly. Then propionyl chloride (0.2 mol, 18.4 g) was added, and the reaction was stirred at room temperature for 1 hour. After the reaction was complete, the material was hydrolyzed, washed with alkali, washed with water, dried and concentrated, and then recrystallized with ethanol. The theoretical yield was 37.2 g. 29.8 g of the product was obtained, with a yield of 80%, and it was identified as Compound 15a. 1 H-NMR (400 MHz, CDCCl3) δ 1.20 (t, 3H), 2.33 (s, 3H), 2.48 (s, 6H), 3.11 (s, 3H), 3.54 (q, 2H), 4.51 (q, 2H), 7.24 (d, 2H), 7.26 - 7.31 (3H), 7.35 (s, 1H).

[0211] Synthesis of Intermediate Compound 15b

[0212] Under magnetic stirring, 15a (18.6 g, 0.05 mol) was added to 100 ml of tetrahydrofuran, and dry freshly prepared hydrogen chloride gas was introduced. At 5 °C, n-butyl nitrite (14.6 g, 0.125 mol) was added dropwise, and the reaction was stirred until a large amount of the product precipitated, then the reaction was stopped. Subsequently, filtration was carried out to obtain the crude product, and the crude product was recrystallized with methanol to obtain 16.5 g of a white powder. The theoretical yield was 20.1 g, and the yield was 82.1%. It was identified as Intermediate 15b. 1 H-NMR (400 MHz, CDCl3) δ 1.20 (t, 3H), 2.33 (s, 3H), 2.48 (s, 6H), 3.11 (s, 3H), 4.51 (q, 2H), 7.24 (d, 2H), 7.26 - 7.31 (3H), 7.35 (s, 1H) 11.01 (s, 1H).

[0213] Synthesis of the Target Product 15

[0214] The above intermediate compound 15b (12.0 g, 0.03 mol) and 100 ml of dichloromethane were added to a 500 ml three-necked round-bottom flask, and then acetyl chloride (5.8 g, 0.075 mol) and triethylamine (10.1 g, 0.01 mol) were added. The reaction was stirred in an ice-water bath for 1 hour. The reaction was terminated, and after the reaction solution was filtered, the filtrate was poured into water, extracted with ethyl acetate. After collecting the organic phase, it was washed successively with dilute hydrochloric acid solution, saturated sodium carbonate aqueous solution and distilled water, and then the organic phase was collected and dried over MgSO4 overnight. After filtration, the organic phase was distilled off under reduced pressure to obtain 11.0 g of a light yellow powdery solid (theoretical yield 13.3 g), with a yield of 82.6%. It was identified as compound 15. 1H-NMR (400 MHz, CDCl3) δ 1.20 (t, 3H), 2.20 (s, 3H), 2.33 (s, 3H), 2.48 (s, 6H), 3.11 (s, 3H), 4.51 (q, 2H), 7.24 (d, 2H), 7.26 - 7.31 (3H), 7.35 (s, 1H).

[0215] Examples 16 - 28: Preparation of Compounds 16 - 28

[0216] The method of Example 15 was repeated, and the reaction raw materials were appropriately changed to obtain Compounds 16 - 28 shown in Table 2 below and their NMR data respectively.

[0217] Table 2

[0218]

[0219]

[0220] Example 29: Preparation of Compound 29

[0221]

[0222] The synthetic route of Compound 29 is as follows:

[0223]

[0224] Synthesis of Intermediate Compound 29a

[0225] Bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (0.1 mol, 41.8 g) was added to a 500 ml three-necked round-bottom flask containing 200 ml of dichloromethane. After stirring and dissolving, aluminum chloride (0.5 mol, 66.7 g) was added and stirred evenly. Then butyryl chloride (0.5 mol, 21.2 g) was added, and the reaction was stirred at room temperature for 1 hour. After the reaction was complete, the material was hydrolyzed, washed with alkali, washed with water, dried and concentrated, and then recrystallized with ethanol to obtain 44.7 g of product. The theoretical yield was 55.8 g, and the yield was 80%. It was identified as compound 29a. 1 1H-NMR (400 MHz, CDCl3) δ 0.98 (t, 6H), 1.51 (m, 4H), 2.22 (s, 6H), 2.33 (s, 6H), 2.48 (s, 6H), 2.96 (t, 4H), 7.24 - 7.31 (m, 7H).

[0226] Synthesis of intermediate compound 29b

[0227] Under magnetic stirring, 29a (27.9 g, 0.05 mol) was added to 100 ml of tetrahydrofuran, and dry freshly prepared hydrogen chloride gas was introduced. At 0 °C, butyl nitrite (20.62 g, 0.2 mol) was added dropwise, and the reaction was stirred until a large amount of product precipitated, and then the reaction was stopped. Subsequently, filtration was carried out to obtain the crude product, and the crude product was recrystallized with methanol to obtain 25.3 g of white powder (theoretical yield 30.8 g), and the yield was 82.1%. It was identified as intermediate 29b. 1 1H-NMR (400 MHz, CDCl3) δ 1.01 (t, 6H), 2.17 (q, 4H), 2.33 (s, 6H), 2.48 (s, 12H), 7.24 - 7.35 (m, 7H), 11.01 (s, 2H).

[0228] Synthesis of target product 29

[0229] The above intermediate compound 29b (18.5 g, 0.03 mol) and 100 ml of dichloromethane were added to a 500 ml three-necked round-bottom flask, then acetyl chloride (5.8 g, 0.075 mol) and triethylamine (10.1 g, 0.01 mol) were added, and the reaction was stirred in an ice-water bath for 1 hour. The reaction was terminated, and after the reaction solution was filtered, the filtrate was poured into water, extracted with ethyl acetate, the organic phase was collected and washed successively with dilute hydrochloric acid solution, saturated sodium carbonate aqueous solution and distilled water, then the organic phase was collected and dried over MgSO4 overnight. After filtration, the organic phase was distilled off under reduced pressure to obtain 17.4 g of light yellow powdery solid (theoretical yield 21.0 g), and the yield was 82.6%. It was identified as compound 29. 1H-NMR (400 MHz, CDCl3) δ 1.01 (t, 6H), 2.17 (q, 4H), 2.20 (s, 6H), 2.33 (s, 6H), 2.48 (s, 12H), 7.24 - 7.35 (m, 7H).

[0230] Examples 30 - 35: Preparation of Compounds 30 - 35

[0231] Repeat the method of Example 29, appropriately changing the reaction raw materials, to obtain Compounds 30 - 35 shown in Table 3 below and their NMR data respectively.

[0232] Table 3

[0233]

[0234] Example 36: Preparation of Compound 36

[0235]

[0236] The synthetic route of Compound 36 is as follows:

[0237]

[0238] Synthesis of Intermediate Compound 36a

[0239] Add benzoyldiphenylphosphine oxide (0.1 mol, 30.6 g) to a 500 ml three-necked round-bottom flask containing 200 ml of dichloromethane. After stirring and dissolving, add aluminum trichloride (0.2 mol, 26.6 g) and stir evenly. Then add octanoyl chloride (0.2 mol, 32.4 g) and stir the reaction at room temperature for 1 hour. After the reaction is complete, the material is hydrolyzed, washed with alkali, washed with water, dried and concentrated, and then recrystallized with ethanol to obtain 34.6 g of product (theoretical yield 43.2 g), with a yield of 80%. It is identified as Compound 36a. 1 H-NMR (400 MHz, CDCl3) δ 0.88 (m, 3H), 1.26 - 1.33 (m, 8H), 1.53 (m, 2H), 2.94 (t, 2H), 7.51 (m, 6H), 7.77 (d, 4H), 7.93 (m, 2H), 8.12 (m, 2H).

[0240] Synthesis of Intermediate Compound 36b

[0241] Under magnetic stirring, 36a (21.6 g, 0.05 mol) was added to 100 ml of tetrahydrofuran, and dry freshly prepared hydrogen chloride gas was introduced. At 0 °C, butyl nitrite (15.47 g, 0.15 mol) was added dropwise, and the stirring reaction was stopped until a large amount of the product precipitated. Subsequently, filtration was carried out to obtain the crude product, and the crude product was recrystallized with methanol to obtain 18.9 g of a white powder (theoretical yield 23.1 g), with a yield of 82.1%. It was identified as the intermediate 36b. 1 1H-NMR (300 MHz, CDCl3) δ 0.88 (m, 3H), 1.31 - 1.33 (s, 6H), 1.47 (m, 2H), 2.11 (t, 2H), 7.51 (m, 6H), 7.77 (d, 4H), 8.04 (d, 4H), 11.01 (s, 2H).

[0242] Synthesis of the target product 36

[0243] The above intermediate compound 36b (13.8 g, 0.03 mol) and 100 ml of dichloromethane were added to a 500 ml three-necked round-bottom flask, then benzoyl chloride (10.5 g, 0.075 mol) and triethylamine (10.1 g, 0.01 mol) were added, and the reaction was stirred in an ice-water bath for 1 hour. The reaction was terminated, and after the reaction solution was filtered, the filtrate was poured into water, extracted with ethyl acetate, the organic phase was collected and washed successively with dilute hydrochloric acid solution, saturated sodium carbonate aqueous solution and distilled water, then the organic phase was collected and dried over MgSO4 overnight. After filtration, the organic phase was distilled off under reduced pressure to obtain 14.0 g of a light yellow powdery solid (theoretical yield 17.0 g), with a yield of 82.6%. It was identified as compound 36. 1 1H-NMR (400 MHz, CDCl3) δ 0.88 (m, 3H), 1.31 - 1.33 (s, 6H), 1.47 (m, 2H), 2.11 (t, 2H), 7.49 - 7.51 (m, 8H), 7.77 (d, 4H), 7.81 (m, 1H), 8.04 (d, 4H), 8.14 (d, 2H)

[0244] Examples 37 - 49: Preparation of Compounds 37 - 49

[0245] The method of Example 36 was repeated, and the reaction raw materials were appropriately changed to obtain Compounds 37 - 49 shown in Table 4 below and their NMR data respectively.

[0246] Table 4

[0247]

[0248]

[0249] Example 50: Preparation of Compound 50

[0250]

[0251] The synthetic route of Compound 50 is as follows:

[0252]

[0253] Synthesis of Intermediate Compound 50a

[0254] Add (2,4,6-trimethylbenzoyl)diphenylphosphine oxide (0.1 mol, 34.8 g) to a 500 ml three-necked round-bottom flask containing 200 ml of dichloromethane. After stirring and dissolving, add aluminum trichloride (0.2 mol, 26.6 g) and stir evenly. Then add acetyl chloride (0.25 mol, 19.5 g), and stir and react at room temperature for 1 hour. After the reaction is complete, the material is hydrolyzed, washed with alkali, washed with water, dried and concentrated, and then recrystallized with ethanol to obtain 31.2 g of product (theoretical yield 39.0 g), with a yield of 80%. It is identified as Compound 50a. 1 1H-NMR(400 MHz, CDCl3) δ 2.22(s, 3H), 2.33(s, 3H), 2.45(s, 3H), 2.48(s, 3H), 7.27(s, 1H), 7.51(m, 6H), 7.77(d, 4H).

[0255] Synthesis of Intermediate Compound 50b

[0256] Pour Intermediate Compound 50a (15.6 g, 0.04 mol) and a mixed solution of 50 ml of ethanol and water (V 乙醇 :V 水 = 2:1) into a 100 ml three-necked round-bottom flask, and then add hydroxylamine hydrochloride (2.78 g, 0.04 mol) and sodium acetate (3.28 g, 0.04 mol). After stirring and reacting at 70 °C for 0.5 hours, filter the reaction solution, and then rotary evaporate the filtrate under vacuum to obtain a pale yellow solid, which is recrystallized with ethanol to obtain 14.9 g of product (theoretical yield 16.2 g), with a yield of 92%. It is identified as Compound 50b. 1 1H-NMR(400 MHz, CDCl3) δ 2.33(s, 3H), 2.48(s, 6H), 3.21(s, 3H), 7.19(s, 1H), 7.51(m, 6H), 7.77(d, 4H), 11.01(s, 2H).

[0257] Synthesis of the Target Product 50

[0258] The above intermediate compound 58b (12.2 g, 0.03 mol) and 100 ml of dichloromethane were added to a 500 ml three-necked round-bottom flask, and then acetyl chloride (5.8 g, 0.075 mol) and triethylamine (10.1 g, 0.01 mol) were added. The reaction was stirred in an ice-water bath for 1 hour. The reaction was terminated, and after the reaction solution was filtered, the filtrate was poured into water, extracted with ethyl acetate, and the organic phase was collected and washed successively with dilute hydrochloric acid solution, saturated sodium carbonate aqueous solution and distilled water, and then the organic phase was collected and dried over MgSO4 overnight. After filtration, the organic phase was distilled off under reduced pressure to obtain 11.1 g of a light yellow powdery solid (theoretical yield 13.4 g), with a yield of 82.6%, which was identified as compound 50. 1 1H-NMR (400 MHz, CDCl3) δ 2.20 (s, 3H), 2.33 (s, 3H), 2.48 (s, 6H), 3.21 (s, 3H), 7.19 (s, 1H), 7.51 (m, 6H), 7.77 (d, 4H).

[0259] Examples 51 - 57: Preparation of Compounds 51 - 57

[0260] The method of Example 50 was repeated, and the reaction raw materials were appropriately changed to obtain Compounds 51 - 57 shown in Table 5 below and their NMR data.

[0261] Table 5

[0262]

[0263] Example 58: Preparation of Compound 58

[0264]

[0265] The synthetic route of Compound 58 is as follows:

[0266]

[0267] Synthesis of Intermediate Compound 58a

[0268] Bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (0.1 mol, 41.8 g) was added to a 500 ml three-necked round-bottom flask containing 200 ml of dichloromethane. After stirring and dissolving, aluminum trichloride (0.2 mol, 26.6 g) was added and stirred evenly. Then acetyl chloride (0.3 mol, 23.4 g) was added, and the reaction was stirred at room temperature for 1 hour. After the reaction was complete, the material was hydrolyzed, washed with alkali, washed with water, dried and concentrated, and then recrystallized from ethanol to obtain 40.2 g of product, with a theoretical yield of 50.2 g and a yield of 80%, which was identified as compound 58a. 1H-NMR (400 MHz, CDCl3) δ 2.22 (s, 6H), 2.33 (s, 6H), 2.45 (s, 6H), 2.48 (s, 6H), 7.24 - 7.31 (m, 7H).

[0269] Synthesis of Intermediate Compound 58b

[0270] Add intermediate compound 58a (30.1 g, 0.06 mol) and a mixed solution of 50 ml of ethanol and water (V 乙醇 :V 水 = 2:1) into a 100 ml three-necked round-bottom flask, and then add hydroxylamine hydrochloride (10.42 g, 0.15 mol) and sodium acetate (12.30 g, 0.15 mol). After stirring and reacting at 70 °C for 0.5 h, filter the reaction solution, and then rotary evaporate the filtrate under vacuum to obtain a pale yellow solid. Recrystallize with ethanol to obtain 29.4 g of product (theoretical yield 31.9 g), with a yield of 92%, which was identified as compound 58b. 1 H-NMR (400 MHz, CDCl3) δ 2.33 (s, 6H), 2.48 (s, 12H), 3.21 (s, 6H), 7.19 (s, 2H), 7.24 - 7.31 (m, 5H), 11.01 (s, 2H).

[0271] Synthesis of Target Product 58

[0272] Add the above intermediate compound 58b (21.3 g, 0.04 mol) and 100 ml of dichloromethane into a 500 ml three-necked round-bottom flask, then add acetyl chloride (6.3 g, 0.08 mol) and triethylamine (10.1 g, 0.1 mol), and stir and react in an ice-water bath for 1 h. Terminate the reaction, filter the reaction solution, pour the filtrate into water, extract with ethyl acetate, collect the organic phase, wash it successively with dilute hydrochloric acid solution, saturated sodium carbonate aqueous solution and distilled water, then collect the organic phase, and dry it over MgSO4 overnight. After filtration, distill off the organic phase under reduced pressure to obtain 20.4 g of a light yellow powdery solid (theoretical yield 24.6 g), with a yield of 82.6%, which was identified as compound 58. 1 H-NMR (400 MHz, CDCl3) δ 2.20 (s, 6H), 2.33 (s, 6H), 2.48 (s, 12H), 3.21 (s, 6H), 7.19 - 7.31 (m, 7H).

[0273] Examples 59 - 66: Preparation of Compounds 59 - 66

[0274] Repeat the method of Example 58, appropriately change the reaction raw materials, and obtain compounds 59 - 66 and their NMR data shown in Table 6 below respectively.

[0275] Table 6

[0276]

[0277] Example 67: Preparation of Compound 67

[0278]

[0279] Synthesis of Intermediate Compound 67a

[0280] Add benzoyldiphenylphosphine oxide (0.1 mol, 30.6 g) to a 500 ml three-necked round-bottom flask containing 200 ml of dichloromethane. After stirring and dissolving, add aluminum trichloride (0.2 mol, 26.6 g) and stir evenly. Then add octanoyl chloride (0.1 mol, 16.3 g) and stir at room temperature for 1 hour. After the reaction is complete, the material is hydrolyzed, washed with alkali, washed with water, dried and concentrated, and then recrystallized with ethanol to obtain 34.6 g of product, with a theoretical yield of 43.2 g and a yield of 80%. It is identified as Compound 67a. 1 H-NMR (400 MHz, CDCl3) δ 0.90 (t, 3H), 1.26 - 1.45 (m, 10H), 2.94 (t, 2H), 7.51 (m, 6H), 7.77 (d, 4H), 7.93 (d, 2H), 8.12 (d, 2H).

[0281] Synthesis of Intermediate Compound 67b

[0282] Pour intermediate compound 67a (25.9 g, 0.06 mol) and a mixed solution of 50 ml of ethanol and water (V 乙醇 :V 水 = 2:1) into a 100 ml three-necked round-bottom flask, and then add hydroxylamine hydrochloride (6.9 g, 0.1 mol) and sodium acetate (8.2 g, 0.1 mol). After stirring and reacting at 70 °C for 0.5 hour, filter the reaction solution, and then rotary evaporate the filtrate under vacuum to obtain a pale yellow solid, which is recrystallized with ethanol to obtain 24.6 g of product (theoretical yield 26.8 g), with a yield of 92%. It is identified as Compound 67b. 1 H-NMR (400 MHz, CDCl3) δ 0.90 (t, 3H), 1.26 - 1.45 (m, 10H), 2.70 (t, 2H), 7.51 (m, 6H), 7.77 (d, 4H), 8.02 (d, 2H), 8.01 (d, 2H), 11.01 (s, 11.01)

[0283] Synthesis of Target Product 67

[0284] The above intermediate compound 67b (17.9 g, 0.04 mol) and 100 ml of dichloromethane were added to a 500 ml three-necked round-bottom flask, and then benzoyl chloride (7.0 g, 0.05 mol) and triethylamine (6.1 g, 0.06 mol) were added. The reaction was stirred in an ice-water bath for 1 hour. The reaction was terminated, and after the reaction solution was filtered, the filtrate was poured into water, extracted with ethyl acetate, and the organic phase was collected and washed successively with dilute hydrochloric acid solution, saturated sodium carbonate aqueous solution and distilled water, and then the organic phase was collected and dried over MgSO4 overnight. After filtration, the organic phase was distilled off under reduced pressure to obtain 18.2 g of a light yellow powdery solid (theoretical yield 22.1 g), with a yield of 82.6%. It was identified as compound 67. 1H-NMR (400 MHz, CDCl3) δ 0.88 (t, 3H), 1.26 - 1.47 (m, 10H), 2.70 (t, 2H), 7.49 - 7.51 (m, 8H), 7.77 (d, 4H), 7.81 (m, 1H), 8.00 - 8.14 (d, 6H)

[0285] Examples 68 - 82: Preparation of Compounds 68 - 82

[0286] Repeat the method of Example 67, appropriately changing the reaction raw materials, to obtain Compounds 68 - 82 and their NMR data shown in Table 7 below, respectively.

[0287] Table 7

[0288]

[0289]

[0290]

[0291] Example 83: Preparation of Compound 83

[0292]

[0293] The synthetic route of Compound 83 is as follows:

[0294]

[0295] Synthesis of Intermediate Compound 83a

[0296] (2,4,6-Trimethylbenzoyl)diphenylphosphine oxide (TPO, 0.1 mol, 34.8 g) was added to a 500 ml three-necked round-bottom flask containing 200 ml of dichloromethane. After stirring and dissolving, aluminum chloride (0.2 mol, 26.7 g) was added and stirred evenly. Then propionyl chloride (0.2 mol, 18.4 g) was added, and the reaction was stirred at room temperature for 1 h. After the reaction was complete, the material was hydrolyzed, washed with alkali, washed with water, dried and concentrated, and then recrystallized with ethanol to obtain 32.3 g of product with a yield of 80%. It was identified as compound 83a. 1 H-NMR (400 MHz, CDCl3) δ 1.22 (t, 3H), 2.22 (s, 3H), 2.33 (s, 3H), 2.48 (s, 3H), 3.54 (q, 2H), 7.24 (s, 1H), 7.51 (m, 6H), 7.77 (d, 4H).

[0297] Synthesis of intermediate compound 83b

[0298] Under magnetic stirring, 83a (20.2 g, 0.05 mol) was added to 100 ml of tetrahydrofuran, and dry freshly prepared hydrogen chloride gas was introduced. Isoamyl nitrite (11.7 g, 0.1 mol) was added dropwise at room temperature, and the reaction was stirred until a large amount of product precipitated, then the reaction was stopped. The crude product was obtained by filtration and recrystallized with methanol to obtain 17.8 g of white powder with a yield of 82.1%. It was identified as intermediate 83b. 1 H-NMR (400 MHz, CDCl3) δ 2.33 (s, 3H), 2.48 (s, 6H), 3.11 (s, 3H), 7.35 (s, 1H), 7.51 (m, 6H), 7.77 (d, 4H), 11.01 (s, 1H).

[0299] Synthesis of target product 83

[0300] The above intermediate compound 83b (21.7 g, 0.05 mol) and 100 ml of dichloromethane were added to a 500 ml three-necked round-bottom flask, then methacryloyl chloride (7.8 g, 0.075 mol) and triethylamine (10.1 g, 0.1 mol) were added, and the reaction was stirred in an ice-water bath for 1 h. The reaction was terminated, the reaction solution was filtered, the filtrate was poured into water, extracted with ethyl acetate, the organic phase was collected and washed successively with dilute hydrochloric acid solution, saturated sodium carbonate aqueous solution and distilled water, then the organic phase was collected and dried over MgSO4 overnight. After filtration, the organic phase was distilled off under reduced pressure to obtain 20.7 g of light yellow powdery solid with a yield of 82.6%. It was identified as compound 83. 1H-NMR (400 MHz, CDCl3) δ 2.01 (s, 3H), 2.33 (s, 3H), 2.48 (s, 6H), 3.11 (s, 3H), 6.18 (d, 1H), 6.43 (d, 1H), 7.35 (s, 1H), 7.51 (m, 6H), 7.77 (d, 4H).

[0301] Example 84: Deep curing initiation effect of the acyl-oxy-phosphine oxime ester photoinitiator of the present invention under 400 nm, 415 nm and 425 nm LED light sources

[0302] Dissolve 1 g of Compound 1 of Example 1 in 50 g of tripropylene glycol diacrylate (TPGDA) to prepare a 0.05 wt% sample solution. Then, add the prepared sample solution to a flat-bottomed quartz glass tube with an inner diameter of 0.8 cm and a length of 10 cm, wrap the vertical surface of the quartz tube with tin foil, and irradiate the quartz tube containing the sample from the bottom with a 400 nm Omnicure LX505 LED light source and 415 nm and 425 nm Shanghai Fotaxy UV-VIS LED light sources for 30 s continuously. The light intensity of the light sources is 100 mW / cm 2 . After irradiation, take out the cured sample from the quartz tube, and the deep curing effect of TPGDA can be observed.

[0303] Repeat the above method, and conduct the same test on Compounds 2 - 83 of Examples 2 - 83 respectively. Meanwhile, under the same conditions, select the commercially available oxime ester OXE-01 from BASF for comparison. The specific results are shown in Table 8 below.

[0304] Table 8

[0305]

[0306]

[0307] In summary, the acyl-oxy-phosphine oxime ester photoinitiator of the present invention has good photosensitive performance at wavelengths of 400 nm, 415 nm, and 425 nm, and is superior to the commercially available OXE-02 oxime ester photoinitiator at the present stage.

[0308] Example 85: Studying the photoinitiating performance by photopolymerization kinetics experiments:

[0309] Using the real-time Fourier transform infrared spectroscopy (RT-FTIR) test method, compare Example 1 and Example 8 with the commonly used commercially available phosphine oxide-based initiator (2,4,6-trimethylbenzoyl) diphenylphosphine oxide (TPO) at the same molar concentration (2.1×10 -6 mol·g -1)The polymerization effect of initiating the photopolymerization reaction of TPGDA. The light source used is an Omnicure LX505 UV LED light source (400 nm).

[0310] Dissolve the above initiator in TPGDA, coat it on a clean KBr salt plate, and cover the sample with another clean KBr salt plate to avoid oxygen inhibition of polymerization. Place the KBr double salt plate carrying the sample in an infrared detector and irradiate the sample. The light intensity of the Omnicure LX505 UV LED light source is 100 mW / cm 2 . The change in the double bonds of TPGDA is collected in real time using a Nicolet 5700 near-infrared spectrometer. The parameter settings are: data collection interval 0.5 s, each spectrum is scanned once, and the resolution is 4 cm -1 . As the photopolymerization reaction proceeds, the characteristic absorption peak of the C═C double bond of TPGDA at 1630 cm -1 in the near-infrared spectrum gradually weakens, which can be used to reflect the progress of the polymerization reaction. The double bond conversion rate (DC) is calculated by the OMNIC 7.1 infrared software and the Igor Pro data processing software according to formula (1).

[0311]

[0312] In the formula, A o and A t are the areas of the characteristic peaks of the TPGDA double bonds at 1600 cm -1 before curing and at time t after light irradiation of the sample, respectively.

[0313] The results show that at the same molar concentration, that is, when the number of photoinitiator molecules is the same, the double bond conversion rates of Examples 1 and 8 for initiating monomer polymerization are higher than that of TPO (see Figure 1 ), indicating that the photoinitiating effects of Examples 1 and 8 are better than that of TPO.

[0314] Example 86: Ultraviolet-visible spectroscopy analysis

[0315] Using acetonitrile as a solvent, prepare 500 ppm acetonitrile solutions of Example 1, Example 8, and TPO, and test them on a Shimadzu UV3600 ultraviolet-visible near-infrared spectrophotometer. The test range is 200 - 700 nm, the scanning speed is medium, and the interval is 0.5 nm. Test the ultraviolet absorption spectra and absorbance (A) of the above photoinitiators, and then according to the Lambert-Beer law (A = ε·C·b, where C is the molar concentration of the photoinitiator in anhydrous acetonitrile, unit mol·L -1 , b is the depth of the sample solution to be measured, which is 1 cm in this test), the molar extinction coefficient ε of the photoinitiator in the wavelength absorption range can be calculated, unit L·mol -1 ·cm-1 )。 The experimental results are shown in Table 9 and Figure 2 as follows. Such photoinitiators have a wide wavelength absorption range, which can be extended from 300 nm to 450 nm, and the maximum molar extinction coefficient is in the range of 500 - 600 L·mol -1 ·cm -1 .

[0316] Table 9: Molar extinction coefficients of the photoinitiators of Examples 1 and 8 and TPO at specific wavelengths

[0317]

[0318] Example 87: Thermal stability test

[0319] The stability of photoinitiators in polymerizable monomers is a key indicator affecting their practicality. The thermal stabilities of Examples 1 and 8 in the polymerizable monomer TPGDA were studied using differential scanning calorimetry (DSC) on a Mettler differential scanning calorimeter.

[0320] The above photoinitiators were separately dissolved in TPGDA to form 2 wt% solutions, and then 5 - 10 mg samples were placed in a covered aluminum crucible dedicated for DSC testing for testing. Test conditions: temperature range 25°C - 250°C, heating rate 10 K / min, nitrogen protection. The experimental results are shown in Table 10. Their thermal stabilities in the monomer are all above 100°C, which is acceptable for storage and transportation at room temperature.

[0321] Table 10: Initial temperature (Ti) of thermal polymerization of TPGDA initiated by Examples 1 and 8

[0322]

[0323] Example 88: Solubility test

[0324] The solubility of photoinitiators is an important indicator to measure their compatibility in actual application formulations. Good compatibility is a prerequisite for wide application. Thus, the solubilities of Examples 1, 8, and 83 in common (meth)acrylate monomers TPGDA, hexanediol diacrylate (HDDA), trimethylolpropane triacrylate (TMPTA), and common solvent propylene glycol monomethyl ether acetate (PMA) were studied.

[0325] Examples 1, 8, and 83 were respectively dissolved in the acrylate polymerizable monomers TPGDA, HDDA, TMPTA, and PMA commonly used in photocurable materials to prepare supersaturated solutions. Approximately 10 mg - 100 mg of the above-mentioned saturated solutions were respectively measured and placed in a 10 ml brown volumetric flask. After adding 10 ml of acetonitrile for dilution, the absorbance of the ultraviolet absorption spectrum was measured on a Shimadzu UV-3600 ultraviolet spectral analyzer. Their solubility (unit: g / (100 g solvent)) was calculated according to the Lambert-Beer law and the maximum molar extinction coefficient of the above-mentioned photoinitiators in the range of 300 nm - 400 nm in acetonitrile. The experimental results showed that the solubility of the three photoinitiators in the above monomers and solvents was greater than 6 wt%, as shown in Table 11.

[0326] Table 11: Solubility of photoinitiators of Examples 1, 8, and 83 in TPGDA, HDDA, TMPTA, and PMA

[0327]

Claims

1. Acyl oxyphosphine oxime ester compounds of Formula 1 and Formula 2: Wherein: n independently represents 0 or 1 respectively; m1 independently represents an integer from 0 to 4 respectively; m2 independently represents an integer from 0 to 4 respectively; R1 independently represents C1-C4 alkyl, phenyl or C2-C4 alkenyl respectively; R2 independently represents C1-C7 alkyl, C5-C6 cycloalkyl or C5-C6 cycloalkyl-C1-C4 alkyl respectively; R3 independently represents nitro, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 alkylthio or phenyl respectively; R4 and R5 independently represent C1-C4 alkyl, C1-C4 alkoxy, C1-C4 alkylthio or phenyl respectively.

2. The acyl oxyphosphine oxime ester compound according to claim 1, having Formula 3, 4 or 5: Wherein: n independently represents 0 or 1 respectively; m1 independently represents an integer from 0 to 4 respectively; m2 independently represents an integer from 0 to 4 respectively; R1 independently represents C1-C4 alkyl, phenyl or C2-C4 alkenyl respectively; R2 independently represents C1-C7 alkyl, C5-C6 cycloalkyl or C5-C6 cycloalkyl-C1-C4 alkyl respectively; R3 independently represents nitro, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 alkylthio or phenyl respectively.

3. The acyl oxyphosphine oxime ester compound according to claim 1 or 2, wherein the acyl oxyphosphine oxime ester compound is selected from the following group: 。 4. A method for preparing the acyl oxyphosphine oxime ester compound according to any one of claims 1-3, comprising the following steps: (1) Acylation reaction: subjecting the compound of Formula 1-1 or Formula 2-1 to a Friedel-Crafts acylation reaction to obtain the compound of Formula 1-2 or Formula 2-2: (2) Oximation reaction: when n is 0, subjecting the compound of Formula 1-2 or Formula 2-2 to an oximation reaction with a compound selected from hydroxylamine and / or hydroxylamine hydrochloride to obtain the compound of Formula 1-3a or Formula 2-3a: When n is 1, subjecting the compound of Formula 1-2 or Formula 2-2 to an oximation reaction with a compound selected from nitrous acid, nitrite and / or alkyl nitrite to obtain the compound of Formula 1-3b or Formula 2-3b: And (3) Esterification reaction: esterifying the compound of Formula 1-3a or 2-3a or the compound of Formula 1-3b or 2-3b to obtain the compound of Formula 1 or Formula 2, Wherein the parameters in each of the above formulas are defined as in any one of claims 1-3.

5. The method according to claim 4, wherein: The Friedel-Crafts acylation reaction in step (1) is carried out using an acylation reagent selected from the compounds of the following formulas Ia, Ib and Ic: Wherein X is a halogen and R2 is defined as in any one of claims 1-3.

6. The method according to claim 5, wherein X is chlorine.

7. The method according to any one of claims 4-6, wherein the Friedel-Crafts acylation reaction in step (1) is carried out in the presence of one or more catalysts selected from the following group: Lewis acid catalyst; solid acid catalyst; ionic liquid type catalyst; or supported catalyst.

8. The method according to claim 7, wherein the Lewis acid catalyst is AlCl3, AlBr3, FeCl3, TiCl4, ZnCl2, SnCl4, BF3; the solid acid catalyst is zeolite molecular sieve and SO4 2- / M x O y type solid superacid; the ionic liquid catalyst is chloroaluminate ionic liquid; the supported catalyst is polystyrene-supported AlCl3 catalyst.

9. The method according to claim 8, wherein the SO4 2- / M x O y type solid superacid is SO4 2- / ZrO2, SO4 2- / TiO2, SO4 2- / Fe2O3; the chloroaluminate ionic liquid is a chloroaluminate ionic liquid composed of a combination of AlCl3 and a halide of an organic alkylimidazole salt, an alkylpyridine salt or an alkylammonium salt.

10. The method according to any one of claims 4 - 6, wherein in the Friedel - Crafts acylation reaction of step (1), the molar ratio of the compound of formula 1 - 1 to the acylation reagent selected from the compounds of Ia, Ib and Ic is 1:0.8 - 1:5; the molar ratio of the compound of formula 2 - 1 to the acylation reagent selected from the compounds of Ia, Ib and Ic is 1:2 - 1:

10.

11. The method according to claim 10, wherein in the Friedel - Crafts acylation reaction of step (1), the molar ratio of the compound of formula 1 - 1 to the acylation reagent selected from the compounds of Ia, Ib and Ic is 1:1 - 1:3; the molar ratio of the compound of formula 2 - 1 to the acylation reagent selected from the compounds of Ia, Ib and Ic is 1:2 - 1:

6.

12. The method according to any one of claims 4 - 6, wherein: When n is 0: The oximation reaction of step (2) is carried out in the presence of a catalyst selected from sodium acetate, pyridine, piperidine, triethylamine and / or tetramethylammonium hydroxide; and / or, the molar ratio of the compound of formula 1 - 2 to the compound selected from hydroxylamine and / or hydroxylamine hydrochloride is 1:1.5 - 1.5:1; the molar ratio of the compound of formula 2 - 2 to the compound selected from hydroxylamine and / or hydroxylamine hydrochloride is 1:3 - 3:1; or When n is 1, The oximation reaction of step (2) is carried out in the presence of concentrated hydrochloric acid; and / or, the molar ratio of the compound of formula 1 - 2 to the compound selected from nitrous acid, nitrite and / or alkyl nitrite is 1:3 - 3:1; the molar ratio of the compound of formula 2 - 2 to the compound selected from nitrous acid, nitrite and / or alkyl nitrite is 1:5 - 5:1; wherein the alkyl nitrite is C1 - C6 alkyl nitrite.

13. The method according to claim 12, wherein: When n is 0: The molar ratio of the compound of formula 1 - 2 to the compound selected from hydroxylamine and / or hydroxylamine hydrochloride is 1:1.2 - 1.2:1; the molar ratio of the compound of formula 2 - 2 to the compound selected from hydroxylamine and / or hydroxylamine hydrochloride is 1:2 - 2:1; or when n is 1, The molar ratio of the compound of formula 1 - 2 to the compound selected from nitrous acid, nitrite and / or alkyl nitrite is 1:1.5 - 1.5:1; the molar ratio of the compound of formula 2 - 2 to the compound selected from nitrous acid, nitrite and / or alkyl nitrite is 1:3 - 3:

1.

14. The method according to any one of claims 4 - 6, wherein: The esterification of step (3) is carried out using an esterification reagent selected from the compounds of formula IIa, IIb and IIc below: wherein X is a halogen, and R1 is as defined in any one of claims 1 - 3.

15. The method according to claim 14, wherein X is chlorine.

16. The method according to any one of claims 4 - 6, wherein the esterification reaction of step (3) is carried out in the presence of one or more catalysts selected from the following group: 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.

17. A method according to any one of claims 4 - 10, wherein in the esterification reaction of step (3), the molar ratio of the compound of formula 1 - 3a or 2 - 3a to the esterification reagent selected from the compounds of IIa, IIb, and IIc is 1:1.5 - 1.5:1; the molar ratio of the compound of formula 1 - 3b or 2 - 3b to the esterification reagent selected from the compounds of IIa, IIb, and IIc is 1:3 - 3:

1.

18. A method according to claim 17, wherein in the esterification reaction of step (3), the molar ratio of the compound of formula 1 - 3a or 2 - 3a to the esterification reagent selected from the compounds of IIa, IIb, and IIc is 1:1.2 - 1.2:1; the molar ratio of the compound of formula 1 - 3b or 2 - 3b to the esterification reagent selected from the compounds of IIa, IIb, and IIc is 1:2 - 2:

1.

19. Use of an acyl - oxy - phosphine - oxime ester compound according to any one of claims 1 - 3 as a photoinitiator.

20. The use according to claim 19, which is used as a photoinitiator in a UV - VIS LED light source curing system.

21. The use according to claim 19, which is used as a photoinitiator in a light source curing system with a radiation wavelength of 300 - 550 nm.

22. The use according to claim 19, which is used as a photoinitiator in a light source curing system with a radiation wavelength of 365 - 450 nm.

23. A photocurable composition comprising at least one acyl - oxy - phosphine - oxime ester compound according to any one of claims 1 - 3.

24. A cured material obtained from the photocurable composition of claim 23.

25. A method for preparing a photocured material, which comprises irradiating the photocurable composition of claim 23 with a light source having a radiation wavelength of 300 - 550 nm.

26. The method according to claim 25, wherein the light source is a light source having a radiation wavelength of 365 - 450 nm.

27. The method according to claim 25, wherein the light source is a UV - VIS LED light source.

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