A benzophenone derivative, a preparation method thereof and uses thereof

Abstract

The present invention relates to a benzophenone derivative, a preparation method thereof and uses thereof. The benzophenone derivative has a structure represented by formula (1), formula (2) or formula (3). Since the bis(dialkylamino)benzophenone compound with acrylate side chains provided by the present invention has a significantly increased molecular weight and contains polymerizable double bonds relative to EMK, it has a significantly low migration rate in the cured film and can be used in fields such as food packaging and printing formulations.

Description

Technical Field

[0001] The present invention relates to the technical field of photocuring, and relates to a benzophenone derivative, a preparation method thereof and uses thereof. Background Art

[0002] N,N,N,N-tetraethyl-4,4'-diaminobenzophenone, abbreviated as EMK, is a commonly used high-efficiency co-initiator and is very important in inks, especially in UV-LED curable inks. The synthesis methods of the compound are reported in patent documents such as CN107686450A, CN112707830A, DE2226039A1 and DE44077C. In patent EP1078598A1, US2010081071A1, CN105974736A, CN104749882A, CN104710843A, etc., EMK is used as a co-initiator and is used in combination with a hydrogen abstraction type photoinitiator in various compositions to play a role in photopolymerization. However, its disadvantages are that it has a small molecular weight and certain toxicity, and it is easy to migrate out of the cured material, affecting the stability and safety of the properties of the product.

[0003] In patent CN101796015A, an acrylate group-derivatized aniline compound is reported as a polymerizable ammonia additive and is used in a radiation-curable liquid composition for inkjet printing. Its disadvantages are that it has a relatively small molecular weight, a complex preparation process, and a high manufacturing cost. In patent CN102212151A, a 4-acrylamido-4'-dialkylaminobenzophenone compound is reported to be used alone as a photoinitiator, and its disadvantages are that the photoinitiating efficiency is not high and the preparation process is complex.

[0004] In the actual use of photocurable inks, after people noticed the pollution problem of small molecular weight photoinitiators, the demand for photoinitiators with low volatility and low migration has been increasing with the expansion of the coating usage. For example, inks with low odor and low migration are widely used in civil fields such as paper and floors. Especially for food and drug packaging materials, there are more stringent detection standard limits on the substance migration amount. Therefore, it is difficult to meet the strict migration standard requirements, and thus it is not included in the list of permitted uses, which also causes many users to lose efficient formulation combinations and it is difficult to find alternative technologies that meet the standards for a while, becoming a problem that troubles the technicians in this industry. Summary of the Invention

[0005] The technical problem to be solved by the present invention is to overcome the defect of high migration amount of photoinitiators or co-initiators in the prior art, and thus provide a benzophenone derivative, a preparation method thereof and uses thereof.

[0006] In order to solve the above technical problems, the present invention adopts the following technical solutions:

[0007] A benzophenone derivative has the structure shown in formula (1):

[0008]

[0009] Wherein:

[0010] n1 is an integer from 1 to 10, R1 is an optionally substituted C1-C8 alkyl group, R2 is H or -CH3, and R3 is H or

[0011] G1 is an optionally substituted C1-C12 alkylene group, m1 is an integer from 1 to 11, and m2 is an integer from 1 to 12.

[0012] The term "substituted" means that any one or more hydrogen atoms on a specific atom are replaced by a substituent, provided that the resulting compound is stable. The term "optionally substituted" means that it can be substituted or not, and unless otherwise specified, the type and number of substituents can be arbitrary based on what can be achieved.

[0013] In the present invention, the alkyl group can be a straight-chain alkyl group or a branched-chain alkyl group.

[0014] In the present invention, n1 is an integer from 1 to 10, such as 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10. In a preferred embodiment of the present invention, n1 is an integer from 1 to 4.

[0015] Examples of the C1-C8 alkyl group in R1 include but are not limited to methyl, ethyl, n-propyl, isopropyl, 2-methyl-1-propyl, 2-methyl-2-propyl, 2-methyl-1-butyl, 3-methyl-1-butyl, 2-methyl-3-butyl, 2,2-dimethyl-1-propyl, 2,2-dimethyl-1-butyl, 3,3-dimethyl-1-butyl, 2-ethyl-1-butyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, etc. In some embodiments, the alkyl group is a C1-C8 alkyl group, a C1-C7 alkyl group, a C1-C6 alkyl group, a C1-C5 alkyl group, a C1-C4 alkyl group, a C1-C3 alkyl group, a C1-C2 alkyl group or a C1 alkyl group. R1 is preferably a C1-C4 alkyl group, and more preferably -CH2CH3.

[0016] In a preferred embodiment of the present invention, R2 is H.

[0017] In a preferred embodiment of the present invention, R3 is The definitions of R2 and G1 are the same as those in formula (1) above.

[0018] In G1, examples of C1-C12 alkylene include but are not limited to methylene, ethylene, propylene, butylene, pentylene, and 3-methylpentylene.

[0019] In a preferred embodiment of the present invention, G1 is -CH2CH2-, -CH2CH2CH2CH2- or -CH2CH2OCH2CH2-.

[0020] The present invention also provides a benzophenone derivative having the structure shown in formula (2):

[0021]

[0022] Wherein:

[0023] n2 is an integer from 1 to 10, R1 is an optionally substituted C1-C8 alkyl group, R2 is H or -CH3, R4 is H or

[0024] G2 is an optionally substituted C1-C12 alkylene group or m3 is an integer from 1 to 11.

[0025] In the present invention, n2 is an integer from 1 to 10, such as 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10. In a preferred embodiment of the present invention, n2 is an integer from 1 to 6.

[0026] In R1, examples of C1-C8 alkyl groups include but are not limited to methyl, ethyl, n-propyl, isopropyl, 2-methyl-1-propyl, 2-methyl-2-propyl, 2-methyl-1-butyl, 3-methyl-1-butyl, 2-methyl-3-butyl, 2,2-dimethyl-1-propyl, 2,2-dimethyl-1-butyl, 3,3-dimethyl-1-butyl, 2-ethyl-1-butyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, etc. In some embodiments, the alkyl group is a C1-C8 alkyl group, a C1-C7 alkyl group, a C1-C6 alkyl group, a C1-C5 alkyl group, a C1-C4 alkyl group, a C1-C3 alkyl group, a C1-C2 alkyl group or a C1 alkyl group. R1 is preferably a C1-C4 alkyl group, more preferably -CH2CH3.

[0027] In a preferred embodiment of the present invention, R2 is H.

[0028] In a preferred embodiment of the present invention, R4 is The definitions of R2 and G2 are the same as those in formula (2) above.

[0029] In G2, examples of C1-C12 alkylene include but are not limited to methylene, ethylene, propylene, butylene, pentylene, and 3-methylpentylene.

[0030] The present invention also provides a benzophenone derivative having the structure shown in formula (3):

[0031]

[0032] Wherein:

[0033] n3 is an integer from 1 to 10, R1 is an optionally substituted C1-C8 alkyl group, R2 is H or -CH3, and R5 is H or

[0034] G2 is an optionally substituted C1-C12 alkylene group or m3 is an integer from 1 to 11;

[0035] G3 is an optionally substituted C1-C12 alkylene group, m4 is an integer from 1 to 11.

[0036] In the present invention, n3 is an integer from 1 to 10, such as 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10. In a preferred embodiment of the present invention, n3 is an integer from 1 to 6.

[0037] Examples of the C1-C8 alkyl group in R1 include but are not limited to methyl, ethyl, n-propyl, isopropyl, 2-methyl-1-propyl, 2-methyl-2-propyl, 2-methyl-1-butyl, 3-methyl-1-butyl, 2-methyl-3-butyl, 2,2-dimethyl-1-propyl, 2,2-dimethyl-1-butyl, 3,3-dimethyl-1-butyl, 2-ethyl-1-butyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, etc. In some embodiments, the alkyl group is a C1-C8 alkyl group, a C1-C7 alkyl group, a C1-C6 alkyl group, a C1-C5 alkyl group, a C1-C4 alkyl group, a C1-C3 alkyl group, a C1-C2 alkyl group or a C1 alkyl group. R1 is preferably a C1-C4 alkyl group, more preferably -CH2CH3.

[0038] In a preferred embodiment of the present invention, R2 is H.

[0039] In a preferred embodiment of the present invention, R5 is The definitions of R2, G2 and G3 are the same as those in formula (3) above.

[0040] Examples of the C1-C12 alkylene group in G3 include but are not limited to methylene, ethylene, propylene, butylene, pentylene and 3-methylpentylene.

[0041] In a preferred embodiment of the present invention, G2 and G3 are each independently -CH2CH2-, -CH2CH2CH2CH2-, -CH2CH2OCH2CH2- or -CH2CH2OCH2CH2OCH2CH2-.

[0042] The present invention also provides a method for preparing a benzophenone derivative having the structure of formula (1) as described above, comprising:

[0043] Reacting the compound represented by formula (4) with the compound represented by formula (5), adding at least one of the two terminal hydroxyl groups of the compound represented by formula (4) completely, and then terminating the reaction to obtain a benzophenone derivative having the structure of formula (1);

[0044]

[0045] The molar ratio of the compound represented by formula (4) to the compound represented by formula (5) is 1:1 to 2, and R1, R2 and G1 have the same definitions as in formula (1) described above.

[0046] In a preferred embodiment of the present invention, the reaction temperature is 40 to 120 °C and the reaction time is 10 to 100 h.

[0047] In the above reaction, at least one of the two terminal hydroxyl groups of the compound represented by formula (4) is added completely to terminate the reaction. The reaction can be carried out under stirring conditions.

[0048] In a preferred embodiment of the present invention, after the reaction is completed, the obtained reaction solution is washed and the solvent is recovered to obtain a benzophenone derivative having the structure shown in formula (1).

[0049] An exemplary washing method is: first washing with a 1-5% dilute weakly alkaline aqueous solution, and then washing with water. The weakly alkaline aqueous solution can be sodium bicarbonate or sodium carbonate, or an aqueous solution of ammonium carbonate.

[0050] An exemplary method for recovering the solvent is to recover the solvent by distillation.

[0051] Preferably, the method for preparing the benzophenone derivative having the structure of formula (1) as described above comprises the following steps:

[0052] Mixing the compound represented by formula (4), the compound represented by formula (5), an inhibitor, a catalyst and a solvent, heating and reacting under nitrogen or an inert atmosphere, cooling after the reaction is completed, then adding an alkaline solution for washing, and then washing with water until neutral, and removing the solvent to obtain a benzophenone derivative having the structure of formula (1);

[0053]

[0054] The molar ratio of the compound represented by the formula (4) to the compound represented by the formula (5) is 1:1 to 2, and R1, R2 and G1 have the same definitions as in the formula (1).

[0055] Preferably, the reaction temperature is 40 to 120 °C, and the reaction time is 10 to 100 h. Optionally, HPLC detection can be used until the reaction of the compound of the formula (4) is complete and the reaction of the mono-addition product is complete.

[0056] Preferably, the polymerization inhibitor is selected from at least one of polyphenols, substituted phenol polymerization inhibitors, quinone polymerization inhibitors or diarylamine polymerization inhibitors, preferably at least one of hydroquinone, p-methoxyphenol, 2,6-di-tert-butylphenol, p-benzoquinone, phenothiazine or hindered amine oxide, and more preferably hydroquinone and / or phenothiazine.

[0057] Preferably, the amount of the polymerization inhibitor used is 0.001% to 10% of the mass of the compound represented by the formula (5), such as 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9% or 10%.

[0058] Preferably, the catalyst is one or more of organic sulfonic acids, strongly acidic cation exchange resins or organic sulfonates, preferably p-aminobenzenesulfonic acid or poly-4-vinylpyridine p-toluenesulfonate. The amount of the catalyst used is 0.1% to 20% of the mass of the compound represented by (4).

[0059] Preferably, the solvent is an organic solvent immiscible with water, preferably toluene. The amount of the solvent added can be adjusted according to actual needs to ensure that the raw materials are dissolved. Optionally, the amount of the solvent used is 0.5 to 100 times the mass of the compound represented by (4).

[0060] Optionally, the amount of the alkaline solution added can be 1 to 100 times the amount of the catalyst used. The alkaline solution can be a sodium carbonate solution, and the mass concentration of the sodium carbonate solution is 1 to 10%.

[0061] Optionally, after the reaction, the temperature is lowered to 20 - 40 °C.

[0062] Preferably, the content of the effective group in the benzophenone derivative having the structure of the formula (1) is 30 - 60%, and the effective group refers to the molecular group

[0063] The present invention also provides a preparation method of a benzophenone derivative having the structure of the formula (2) as described above, including:

[0064] React the compound represented by formula (6) with the compound represented by formula (7). After all additions to at least one of the two hydroxyl groups at both ends of the compound represented by formula (6), add the compound represented by formula (8) to react until the content of the compound represented by formula (8) no longer decreases, and then stop the reaction;

[0065]

[0066] Among them: the molar ratio of the compound represented by formula (6) to the compound represented by formula (7) is 1:(1-2), the molar ratio of the compound represented by formula (6) to the compound represented by formula (8) is 1:(0.5-3), and R1, R2 and G2 have the same meanings as in formula (2).

[0067] In a preferred embodiment of the present invention, the reaction temperature is 40-120 °C and the reaction time is 10-100 h.

[0068] The reaction can be carried out under stirring conditions.

[0069] In a preferred embodiment of the present invention, the reaction is terminated after all double bonds in the vinyl group of the compound represented by formula (8) are added. The resulting reaction solution is washed and the solvent is recovered to obtain a benzophenone derivative having the structure represented by formula (2).

[0070] An exemplary washing method is: first wash with a dilute weakly alkaline aqueous solution, and then wash with water.

[0071] An exemplary method for recovering the solvent is to recover the solvent by distillation.

[0072] Preferably, the preparation method of the benzophenone derivative having the structure of formula (2) above includes the following steps:

[0073] Mix the compound represented by formula (6), the compound represented by formula (7), an inhibitor, a catalyst and a solvent, heat and react under a nitrogen or inert atmosphere. After the reaction is completed, add the compound represented by formula (8), continue to keep warm and react until the content of the compound represented by formula (8) no longer decreases, stop the reaction, cool down, then add an alkaline solution for washing, and then wash with water until neutral, and remove the solvent to obtain a benzophenone derivative having the structure of formula (2);

[0074]

[0075] Among them: the molar ratio of the compound represented by formula (6) to the compound represented by formula (7) is 1:(1-2), the molar ratio of the compound represented by formula (6) to the compound represented by formula (8) is 1:(0.5-3), and R1, R2 and G2 have the same meanings as in formula (2).

[0076] Preferably, the heating reaction temperature is 40 to 120 °C, and the heating reaction time is 10 to 100 h. Optionally, HPLC detection can be used until the reaction of the compound of formula (6) is complete and the reaction of the mono-addition product is complete.

[0077] Preferably, the inhibitor is selected from at least one of polyphenols, substituted phenol inhibitors, quinone inhibitors or diarylamine inhibitors, preferably at least one of hydroquinone, p-methoxyphenol, 2,6-di-tert-butylphenol, p-benzoquinone, phenothiazine or hindered amine oxide, and more preferably hydroquinone and / or phenothiazine.

[0078] Preferably, the dosage of the inhibitor is 0.001% to 10% of the mass of the compound shown in formula (7), such as 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9% or 10%.

[0079] Preferably, the catalyst is one or more of organic sulfonic acids, strongly acidic cation exchange resins or organic sulfonates, preferably p-aminobenzenesulfonic acid or poly-4-vinylpyridine p-toluenesulfonate. The dosage of the catalyst is 0.1% to 20% of the mass of the compound shown in (6).

[0080] Preferably, the solvent is an organic solvent immiscible with water, preferably toluene. The dosage of the solvent can be added according to actual needs to ensure that the raw materials are dissolved. Optionally, the dosage of the solvent is 0.5 to 100 times the mass of the compound shown in (6).

[0081] Optionally, the addition amount of the alkaline solution can be 1 to 100 times the dosage of the catalyst. The alkaline solution can be a sodium carbonate solution, and the mass concentration of the sodium carbonate solution is 1 to 10%.

[0082] Optionally, after the reaction, the temperature is lowered to 20 - 40 °C.

[0083] Preferably, the content of the effective group in the benzophenone derivative with the structure of formula (2) is 30 - 60%, and the effective group refers to the molecular group

[0084] The present invention also provides a preparation method of a benzophenone derivative having the structure shown in formula (3) as described above, including:

[0085] Reacting the compound shown in formula (9) with the compound shown in formula (10). After at least one of the two terminal hydroxyl groups of the compound shown in formula (9) is completely added, the compound shown in formula (11) is added until the double bond in the vinyl group of the compound shown in formula (11) is completely added;

[0086]

[0087] Among them: the molar ratio of the compound represented by formula (9) to the compound represented by formula (10) is 1:(1-2), the molar ratio of the compound represented by formula (9) to the compound represented by formula (11) is 1:(1-3), and R1, R2, G2 and G3 have the same meanings as in formula (3).

[0088] The reaction can be carried out under stirring conditions.

[0089] In a preferred embodiment of the present invention, the reaction temperature is 40-120°C and the reaction time is 10-100 h.

[0090] In a preferred embodiment of the present invention, after all the double bonds in the vinyl group of the compound represented by formula (11) are added, the reaction is terminated, and the obtained reaction solution is washed and the solvent is recovered to obtain a benzophenone derivative having the structure represented by formula (3).

[0091] An exemplary washing method is: first wash with a dilute weakly alkaline aqueous solution and then wash with water.

[0092] An exemplary method for recovering the solvent is to recover the solvent by distillation.

[0093] Preferably, the method for preparing the benzophenone derivative having the structure of formula (3) above includes the following steps:

[0094] Mix the compound represented by formula (9), the compound represented by formula (10), an inhibitor, a catalyst and a solvent, heat and react under a nitrogen or inert atmosphere. After the reaction is completed, add the compound represented by formula (11), continue to keep warm and react until the content of the compound represented by formula (11) no longer decreases, stop the reaction, cool down, then add an alkaline solution for washing, and then wash with water until neutral, and remove the solvent to obtain a benzophenone derivative having the structure of formula (2);

[0095]

[0096] Among them: the molar ratio of the compound represented by formula (9) to the compound represented by formula (10) is 1:(1-2), the molar ratio of the compound represented by formula (9) to the compound represented by formula (11) is 1:(1-3), and R1, R2, G2 and G3 have the same meanings as in formula (3).

[0097] Preferably, the reaction temperature is 40-120°C and the reaction time is 10-100 h. Optionally, it can be detected by HPLC until the reaction of the compound of formula (9) is complete and the reaction of the mono-addition product is complete.

[0098] Preferably, the inhibitor is selected from at least one of polyphenols, substituted phenol inhibitors, quinone inhibitors or diarylamine inhibitors, preferably at least one of hydroquinone, p-methoxyphenol, 2,6-di-tert-butylphenol, p-benzoquinone, phenothiazine or hindered amine oxide, and more preferably hydroquinone and / or phenothiazine.

[0099] Preferably, the dosage of the inhibitor is 0.001% to 10% of the mass of the compound shown in formula (10), such as 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9% or 10%.

[0100] Preferably, the catalyst is one or more of organic sulfonic acids, strongly acidic cation exchange resins or organic sulfonates, preferably p-aminobenzenesulfonic acid or poly-4-vinylpyridine p-toluenesulfonate. The dosage of the catalyst is 0.1% to 20% of the mass of the compound shown in (9).

[0101] Preferably, the solvent is an organic solvent immiscible with water, preferably toluene. The dosage of the solvent can be added according to actual needs to ensure that the raw materials are dissolved. Optionally, the dosage of the solvent is 0.5 - 100 times the mass of the compound shown in (9).

[0102] Optionally, the addition amount of the alkaline solution can be 1 - 100 times the dosage of the catalyst. The alkaline solution can be a sodium carbonate solution, and the mass concentration of the sodium carbonate solution is 1 - 10%.

[0103] Optionally, after the reaction, the temperature is lowered to 20 - 40 °C.

[0104] Preferably, the content of the effective group in the benzophenone derivative with the structure of formula (3) is 30 - 60%, and the effective group refers to the molecular group

[0105] In the compounds of formula (1), formula (2) or formula (3) of the present invention, preferably, it is carried out in the presence of an inhibitor, a catalyst and a solvent.

[0106] Preferably, the inhibitor is selected from at least one of polyphenols, substituted phenol inhibitors, quinone inhibitors or diarylamine inhibitors, preferably at least one of hydroquinone, p-methoxyphenol, 2,6-di-tert-butylphenol, p-benzoquinone, phenothiazine or hindered amine oxide, and more preferably hydroquinone and / or phenothiazine.

[0107] Preferably, the dosage of the inhibitor is 0.001% to 10% of the mass of the compound shown in formula (5), (8) or (11), such as 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9% or 10%.

[0108] Preferably, the catalyst is one or more of organic sulfonic acid, strongly acidic cation exchange resin or organic sulfonate, preferably p-aminobenzenesulfonic acid or poly-4-vinylpyridine p-toluenesulfonate. The dosage of the catalyst is 0.1% to 20% of the mass of the compound shown in (4), (6) or (9).

[0109] Preferably, the solvent is an organic solvent immiscible with water, preferably toluene.

[0110] According to another aspect of the present invention, there is provided a photoinitiator composition, comprising: a photoinitiator capable of free radical polymerization and the benzophenone derivative as described above.

[0111] According to another aspect of the present invention, there is provided a photocurable composition, comprising: a photoinitiator component and an ethylenically unsaturated compound capable of free radical polymerization, wherein the photoinitiator component comprises the photoinitiator composition as described above.

[0112] In a preferred embodiment of the present invention, the photocurable composition comprises:

[0113] (a) the benzophenone derivative as described above;

[0114] (b) a photoinitiator capable of free radical polymerization; and

[0115] (c) an ethylenically unsaturated compound capable of free radical polymerization.

[0116] The photocurable composition comprising the aforementioned photoinitiator composition has a low migration rate.

[0117] In a preferred embodiment of the present invention, the addition amount of the component (a) is 0.1 to 20% of the total weight of the photocurable composition, such as 1%, 5%, 10%, 15% or 20%.

[0118] In a preferred embodiment of the present invention, the component (b) is a commonly used compound commercially or laboratory available, selected from benzophenones (benzophenone and its derivatives other than those of the present invention), thioxanthone compounds, α-hydroxy ketone compounds, α-amino ketone compounds, acylphosphine oxide compounds or oxime ester compounds, preferably one or more of benzophenone, 2-isopropylthioxanthone, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholinophenyl)-1-butanone, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, photoinitiator Omnipol TX, photoinitiator Omnipol 910 or photoinitiator Omnipol TP. Preferably, the photoinitiator Omnipol TX, photoinitiator Omnipol 910 or photoinitiator Omnipol TP is selected from the macromolecular photoinitiator series products Omnipol TX, Omnipol 910 or Omnipol TP of IGM Resins.

[0119] In a preferred embodiment of the present invention, the addition amount of the component (b) is 0.1-10% of the total weight of the photocurable composition, such as 0.1%, 2%, 4%, 6%, 8% or 10%.

[0120] The ethylenically unsaturated compound refers to an ethylenically unsaturated monomer, oligomer, prepolymer and their mixtures, which can undergo free radical polymerization.

[0121] In a preferred embodiment of the present invention, the component (c) is selected from at least one of epoxy acrylate resin, polyurethane acrylate resin, polyester acrylate resin, polyether acrylate resin, acrylated polyacrylate, epoxy methacrylate resin, polyurethane methacrylate resin, polyester methacrylate resin, polyether methacrylate resin, acrylated polymethacrylate, allyl ether compound, acrylate monomer or methacrylate monomer. The acrylate monomer or methacrylate monomer is independently monofunctional, difunctional or polyfunctional. These free radical polymerizable ethylenically unsaturated compounds are easily commercially or laboratory available to those skilled in the art.

[0122] The photocurable composition may also contain other additives to meet performance requirements, such as pigments, fillers, leveling agents, inhibitors, solvents, etc.

[0123] According to another aspect of the present invention, there is provided a use of the photocurable composition as described above in food packaging printing, pharmaceutical packaging printing, furniture coating, book printing or advertising printing.

[0124] According to another aspect of the present invention, there is provided a photocurable product formed by photocuring a photocurable composition, wherein the photocurable composition is the photocurable composition as described above, and preferably the photocurable product is selected from any one of coatings, adhesives, and printing inks.

[0125] According to another aspect of the present invention, there is provided a method for curing a photocurable composition, comprising:

[0126] coating the photocurable composition as described above on a substrate; and curing the photocurable composition by using a light source emitting in the UV-visible light region.

[0127] The substrate includes but is not limited to: wood, paper, plastic, coating, or metal, etc. The coating methods include but are not limited to: offset printing, gravure printing, flexographic printing, inkjet printing, or 3D printing, etc.

[0128] Preferably, after coating on the substrate, the photocurable composition is cured by using UV-visible light radiation with a wavelength of 200 to 425 nm, and preferably by using UV-visible light radiation with a wavelength of 365 to 405 nm to cure the photocurable composition.

[0129] Advantageous effects:

[0130] Since the bis(dialkylamino)benzophenone compound having acrylate side chains provided by the present invention has a significantly increased molecular weight and contains polymerizable double bonds relative to EMK, it has a significantly low mobility in the cured film.

[0131] The benzophenone derivative can be used as an important co-initiator in UV photocuring formulations to co-initiate the photopolymerization of unsaturated carbon-carbon double bond compounds with other photoinitiators. Due to its large molecular weight, the compound has very low mobility and is suitable for replacing N,N,N,N-tetraethyl-4,4'-diaminobenzophenone in fields such as food packaging and printing formulations. Specific embodiments

[0132] Example 1

[0133] Experimental raw materials and materials:

[0134]

[0135] *The structure of HEMK is

[0136]

[0137] Omnipol TX is a polybutylene glycol 250-bis(2-carboxymethoxythioxanthone) ester photoinitiator, a product of IGM RESINS company;

[0138] Omnirad EMK is 4,4'-bis(diethylamino)benzophenone, a product of IGM RESINS;

[0139] Photomer 4072 is trimethylolpropane propoxylate(3)triacrylate, a product of IGM RESINS;

[0140] Photomer 3316 is a low-viscosity modified epoxy acrylate, a product of IGM RESINS.

[0141] Example 1

[0142] Take a 100 mL three-necked flask, equipped with mechanical stirring. Add 1.78 g (5 mmol) of HEMK, 1.86 g (10 mmol) of 2-vinyloxyethoxyethyl acrylate (VEEA), 0.022 g (0.2 mmol) of hydroquinone, 0.086 g (0.5 mmol) of p-aminobenzenesulfonic acid, and 12.0 g of toluene successively. After fully purging with nitrogen under normal temperature stirring, seal with a nitrogen balloon, heat and stir for reaction. The reaction temperature is 55 °C and the reaction time is 48 hours. Take a sample for HPLC detection. When the reaction of HEMK and the mono-addition product is complete, stop the reaction. Cool to 30 °C, add 3.0 g (1.4 mmol of sodium carbonate) of 5% sodium carbonate aqueous solution by mass, and then wash with water until neutral. Distill off the solvent under reduced pressure to obtain 3.44 g of the product of formula IX, and the content of the active group is 55%. The active group refers to the residue remaining after removing the hydrogen on the two hydroxyl groups in the HEMK structure.

[0143]

[0144] Table 1 Analysis results of liquid chromatography-mass spectrometry of the product of Example 1

[0145]

[0146] Example 2

[0147] Take a 100 mL three-necked flask, equipped with mechanical stirring. Add 1.78 g (5 mmol) of HEMK, 1.86 g (10 mmol) of ethyl 2-(vinyloxy)ethoxyacrylate (VEEA), 0.022 g (0.2 mmol) of hydroquinone, 0.086 g (0.11 mmol) of poly(4-vinylpyridine) p-toluenesulfonate, and 12.0 g of toluene successively. After thoroughly purging with nitrogen under stirring at room temperature, seal with a nitrogen balloon, heat and stir for reaction. The reaction temperature is 55 °C and the reaction time is 48 hours. Take samples for HPLC detection. When the reaction of HEMK and the mono-addition product is complete, stop the reaction. Cool to 30 °C, add 3.0 g (1.4 mmol of sodium carbonate) of a 5% aqueous sodium carbonate solution, and then wash with water until neutral. Distill off the solvent under reduced pressure to obtain 3.40 g of the product of formula IX.

[0148]

[0149] Table 2 LC-MS analysis results of the product of Example 2

[0150]

[0151] Example 3

[0152] Take a 100 mL three-necked flask, equipped with mechanical stirring. Add 1.78 g (5 mmol) of HEMK, 2.00 g (10 mmol) of ethyl 2-(vinyloxy)ethoxymethacrylate (VEEM), 0.022 g (0.2 mmol) of hydroquinone, 0.086 g (0.5 mmol) of p-aminobenzenesulfonic acid, and 12.0 g of toluene successively. After thoroughly purging with nitrogen under stirring at room temperature, seal with a nitrogen balloon, heat and stir for reaction. The reaction temperature is 55 °C and the reaction time is 48 hours. Take samples for HPLC detection. When the reaction of HEMK and the mono-addition product is complete, stop the reaction. Cool to 30 °C, add 3.0 g (1.4 mmol of sodium carbonate) of a 5% aqueous sodium carbonate solution, and then wash with water until neutral. Distill off the solvent under reduced pressure to obtain 3.51 g of the product of formula X.

[0153]

[0154] Table 3 LC-MS analysis results of the product of Example 3

[0155]

[0156] Example 4

[0157] Take a 100 mL three-necked flask, equipped with mechanical stirring. Add 1.78 g (5 mmol) of HEMK, 1.42 g (10 mmol) of ethyl 2-vinyloxyacrylate (VEA), 0.022 g (0.2 mmol) of hydroquinone, 0.086 g (0.5 mmol) of p-aminobenzenesulfonic acid and 12.0 g of toluene successively. After fully purging with nitrogen under stirring at room temperature, seal it with a nitrogen balloon, heat and stir for reaction. The reaction temperature is 55 °C and the reaction time is 48 hours. Take samples for HPLC detection. When the reaction of HEMK and the mono-addition product is complete, stop the reaction. Cool to 30 °C, add 3.0 g (1.4 mmol of sodium carbonate) of 5% sodium carbonate aqueous solution, and then wash with water until neutral. Distill off the solvent under reduced pressure to obtain 2.91 g of the product of formula XI, and the content of the active group is 55%.

[0158]

[0159] Table 4 LC-MS analysis results of the product of Example 4

[0160]

[0161] Example 5

[0162] Take a 100 mL three-necked flask, equipped with mechanical stirring. Add 1.78 g (5 mmol) of HEMK, 1.42 g (10 mmol) of ethyl 2-vinyloxyacrylate (VEA), 0.022 g (0.2 mmol) of hydroquinone, 0.086 g (0.5 mmol) of p-toluenesulfonic acid and 12.0 g of dichloroethane successively. After fully purging with nitrogen under stirring at room temperature, seal it with a nitrogen balloon, heat and stir for reaction. The reaction temperature is 55 °C and the reaction time is 48 hours. Take samples for HPLC detection. When the reaction of HEMK and the mono-addition product is complete, stop the reaction. Cool to 30 °C, add 3.0 g (1.4 mmol of sodium carbonate) of 5% sodium carbonate aqueous solution, and then wash with water until neutral. Distill off the solvent under reduced pressure to obtain 2.88 g of the product of formula XI.

[0163]

[0164] Table 5 LC-MS analysis results of the product of Example 5

[0165]

[0166] Example 6

[0167] Take a 100 mL three-necked flask, equipped with mechanical stirring. Add 1.78 g (5 mmol) of HEMK, 1.56 g (12 mmol) of ethyl 2-vinyloxyethyl methacrylate (VEM), 0.022 g (0.2 mmol) of hydroquinone, 0.086 g (0.5 mmol) of p-aminobenzenesulfonic acid, and 12.0 g of toluene successively. After fully replacing with nitrogen under stirring at room temperature, seal with a nitrogen balloon, heat and stir for reaction. The reaction temperature is 55 °C and the reaction time is 48 hours. Take samples for HPLC detection. When the reaction of HEMK and the mono-addition product is complete, stop the reaction. Cool to 30 °C, add 3.0 g (1.4 mmol of sodium carbonate) of 5% sodium carbonate aqueous solution by mass, and then wash with water until neutral. Distill off the solvent under reduced pressure to obtain 3.07 g of the product of formula XII.

[0168]

[0169] Table 6 Results of liquid chromatography-mass spectrometry analysis of the product of Example 6

[0170]

[0171] Example 7

[0172] Take a 100 mL three-necked flask, equipped with mechanical stirring. Add 1.78 g (5 mmol) of HEMK, 1.58 g (10 mmol) of diethylene glycol divinyl ether, 0.022 g (0.2 mmol) of hydroquinone, 0.086 g (0.5 mmol) of p-aminobenzenesulfonic acid, and 12.0 g of toluene successively. After fully replacing with nitrogen under stirring at room temperature, seal with a nitrogen balloon, heat and stir for reaction. The reaction temperature is 55 °C and the reaction time is 48 hours. Take samples for HPLC detection. When the reaction of HEMK and the mono-addition product is complete. Then add 0.86 g (12 mmol) of acrylic acid and continue to stir and react while keeping warm. Take samples for detection every 4 hours of reaction. When the content of acrylic acid no longer decreases, stop the reaction. Cool to 30 °C, add 6.4 g (3.0 mmol of sodium carbonate) of 5% sodium carbonate aqueous solution by mass, and then wash with water until neutral. Distill off the solvent under reduced pressure to obtain 3.91 g of the product of formula XIII, and the content of the effective group is 40%.

[0173]

[0174] Table 7 Results of liquid chromatography-mass spectrometry analysis of the product of Example 7

[0175] Serial number Retention time min Content % Molecular weight <![CDATA[Value of n2 in formula XIII]]> 1 7.20 19.44 816.99 1 2 11.17 20.86 1331.66 2 3 13.92 16.51 1846.24 3 4 15.67 12.89 2360.91 4 5 17.88 9.03 2875.58 5 6 19.76 8.24 3390.25 6 7 22.80 5.33 3904.92 7 8 25.93 3.66 4419.59 8 9 27.62 2.58 4934.26 9 10 30.77 1.55 5448.93 10

[0176] Example 8

[0177] Take a 100 mL three-necked flask, equip it with mechanical stirring, and successively add 1.78 g (5 mmol) of HEMK, 0.99 g (6.25 mmol) of diethylene glycol divinyl ether, 0.022 g (0.2 mmol) of hydroquinone, 0.086 g (0.5 mmol) of p-aminobenzenesulfonic acid, and 12.0 g of toluene. After fully purging with nitrogen under stirring at room temperature, seal it with a nitrogen balloon, heat and stir for reaction, with the reaction temperature at 55 °C and the reaction time of 72 hours. Take samples for HPLC detection until the reaction of HEMK and the mono-addition product is complete. Then add 0.22 g (3 mmol) of acrylic acid, continue to stir the reaction while maintaining the temperature. Take samples for detection every 4 hours of reaction time until the content of acrylic acid no longer decreases, then stop the reaction. Cool to 30 °C, add 6.4 g (3.0 mmol of sodium carbonate) of 5% sodium carbonate aqueous solution by mass, and then wash with water until neutral. Distill off the solvent under reduced pressure to obtain 2.58 g of the product of formula XIII.

[0178]

[0179] Table 8 Analysis Results of the Product of Example 8 by Liquid Chromatography-Mass Spectrometry

[0180] Serial number Retention time min Content % Molecular weight <![CDATA[n2 value in formula XIII]]> 1 7.20 17.15 816.99 1 2 11.17 8.06 1331.66 2 3 13.92 14.51 1846.24 3 4 15.67 14.40 2360.91 4 5 17.88 16.04 2875.58 5 6 19.76 13.04 3390.25 6 7 22.80 8.82 3904.92 7 8 25.93 5.30 4419.59 8 9 27.62 2.05 4934.26 9 10 30.77 0.62 5448.93 10

[0181] Example 9

[0182] Take a 100 mL three-necked flask, equip it with mechanical stirring, and successively add 1.78 g (5 mmol) of HEMK, 1.58 g (10 mmol) of diethylene glycol divinyl ether, 0.022 g (0.2 mmol) of hydroquinone, 0.086 g (0.5 mmol) of p-aminobenzenesulfonic acid, and 12.0 g of toluene. After fully purging with nitrogen under stirring at room temperature, seal it with a nitrogen balloon, heat and stir for reaction, with the reaction temperature at 55 °C and the reaction time of 48 hours. Take samples for HPLC detection until the reaction of HEMK and the mono-addition product is complete. Then add 1.39 g (12 mmol) of 2-hydroxyethyl acrylate, continue to stir the reaction while maintaining the temperature. Take samples for detection every 4 hours of reaction time until the content of 2-hydroxyethyl acrylate no longer decreases, then stop the reaction. Cool to 30 °C, add 6.4 g (3.0 mmol of sodium carbonate) of 5% sodium carbonate aqueous solution by mass, and then wash with water until neutral. Distill off the solvent under reduced pressure to obtain 4.15 g of the product of formula XIV, and the content of the active group is 40%.

[0183]

[0184] Table 9 Analysis Results of the Product of Example 9 by Liquid Chromatography-Mass Spectrometry

[0185] Serial number Retention time min Content % Molecular weight <![CDATA[Value of n3 in formula XIV]]> 1 7.28 20.54 905.09 1 2 11.38 21.85 1419.76 2 3 14.00 17.06 1934.43 3 4 15.96 12.44 2449.10 4 5 18.04 9.06 2963.77 5 6 20.39 7.92 3478.44 6 7 23.09 4.83 3993.11 7 8 26.60 3.55 4507.78 8 9 28.51 2.18 5022.45 9 10 31.63 1.55 5537.12 10

[0186] Example 10

[0187] Take a 100 mL three-necked flask, equip it with mechanical stirring, and successively add 1.78 g (5 mmol) of HEMK, 0.99 g (6.25 mmol) of diethylene glycol divinyl ether, 0.022 g (0.2 mmol) of hydroquinone, 0.086 g (0.5 mmol) of p-aminobenzenesulfonic acid, and 12.0 g of toluene. After thoroughly displacing with nitrogen under stirring at room temperature, seal it with a nitrogen balloon, heat and stir for reaction, with the reaction temperature at 55 °C and the reaction time of 72 hours. Take samples for HPLC detection until the reaction of HEMK and the mono-addition product is complete. Then add 0.35 g (3 mmol) of 2-hydroxyethyl acrylate and continue to stir the reaction while maintaining the temperature. Take samples for detection every 4 hours of reaction until the content of 2-hydroxyethyl acrylate no longer decreases, then stop the reaction. Cool to 30 °C, add 6.4 g (3.0 mmol of sodium carbonate) of a 5% sodium carbonate aqueous solution by mass, and then wash with water until neutral. Distill off the solvent under reduced pressure to obtain 2.74 g of the product of formula XIV.

[0188]

[0189] Table 10 LC-MS analysis results of the product of Example 10

[0190] Serial number Retention time min Content % Molecular weight <![CDATA[The value of n3 in formula XIV]]> 1 7.28 17.15 905.09 1 2 11.38 8.06 1419.76 2 3 14.00 14.51 1934.43 3 4 15.96 14.43 2449.10 4 5 18.04 16.24 2963.77 5 6 20.39 11.79 3478.44 6 7 23.09 7.76 3993.11 7 8 26.60 5.34 4507.78 8 9 28.51 3.19 5022.45 9 10 31.63 1.51 5537.12 10

[0191] Example 11

[0192] Take a 100 mL three-necked flask, equip it with mechanical stirring, and successively add 1.78 g (5 mmol) of HEMK, 2.02 g (10 mmol) of triethylene glycol divinyl ether, 0.022 g (0.2 mmol) of hydroquinone, 0.086 g (0.5 mmol) of p-aminobenzenesulfonic acid, and 12.0 g of toluene. After thoroughly displacing with nitrogen under stirring at room temperature, seal it with a nitrogen balloon, heat and stir for reaction, with the reaction temperature at 55 °C and the reaction time of 48 hours. Take samples for HPLC detection until the reaction of HEMK and the mono-addition product is complete. Then add 1.39 g (12 mmol) of 2-hydroxyethyl acrylate and continue to stir the reaction while maintaining the temperature. Take samples for detection every 4 hours of reaction until the content of 2-hydroxyethyl acrylate no longer decreases, then stop the reaction. Cool to 30 °C, add 6.4 g (3.0 mmol of sodium carbonate) of a 5% sodium carbonate aqueous solution by mass, and then wash with water until neutral. Distill off the solvent under reduced pressure to obtain 4.66 g of the product of formula XV, and the content of the active group is 40%.

[0193]

[0194]

[0195] Table 11 LC-MS analysis results of the product of Example 11

[0196] Serial number Retention time min Content % Molecular weight <![CDATA[Value of n3 in formula XV]]> 1 7.45 21.42 993.20 1 2 11.83 22.03 1551.91 2 3 15.52 17.45 2110.63 3 4 1677 12.33 2669.35 4 5 18.91 8.60 3228.07 5 6 21.16 7.61 3786.79 6 7 24.42 4.38 4345.51 7 8 27.88 3.11 4904.23 8 9 29.33 2.08 5462.95 9 10 33.55 0.98 6021.67 10

[0197] Example 12

[0198] Take a 100 mL three-necked flask, equipped with mechanical stirring. Add 1.78 g (5 mmol) of HEMK, 1.26 g (6.25 mmol) of triethylene glycol divinyl ether, 0.022 g (0.2 mmol) of hydroquinone, 0.086 g (0.5 mmol) of p-aminobenzenesulfonic acid, and 12.0 g of toluene successively. After fully purging with nitrogen under stirring at room temperature, seal it with a nitrogen balloon and heat with stirring for reaction. The reaction temperature is 55 °C and the reaction time is 96 hours. Take samples for HPLC detection until the reaction of HEMK and the mono-addition product is complete. Then add 0.35 g (3 mmol) of 2-hydroxyethyl acrylate and continue to stir the reaction while maintaining the temperature. Take samples for detection every 4 hours of reaction until the content of 2-hydroxyethyl acrylate no longer decreases, then stop the reaction. Cool to 30 °C, add 6.4 g (3.0 mmol of sodium carbonate) of a 5% aqueous sodium carbonate solution by mass, and then wash with water until neutral. Distill off the solvent under reduced pressure to obtain 3.06 g of the product of formula XV.

[0199]

[0200] Table 12 Analysis results of the product of Example 12 by liquid chromatography-mass spectrometry

[0201] Serial number Retention time min Content % Molecular weight <![CDATA[Value of n3 in formula XV]]> 1 7.45 18.67 993.20 1 2 11.83 19.63 1551.91 2 3 15.52 20.13 2110.63 3 4 1677 15.53 2669.35 4 5 18.91 8.80 3228.07 5 6 21.16 6.61 3786.79 6 7 24.42 4.38 4345.51 7 8 27.88 3.11 4904.23 8 9 29.33 1.99 5462.95 9 10 33.55 1.14 6021.67 10

[0202] Example 13

[0203] Take a 100 mL three-necked flask, equipped with mechanical stirring. Add 1.78 g (5 mmol) of HEMK, 1.42 g (10 mmol) of 1,4-butanediol divinyl ether, 0.022 g (0.2 mmol) of hydroquinone, 0.086 g (0.5 mmol) of p-aminobenzenesulfonic acid, and 12.0 g of toluene successively. After fully purging with nitrogen under stirring at room temperature, seal it with a nitrogen balloon and heat with stirring for reaction. The reaction temperature is 55 °C and the reaction time is 48 hours. Take samples for HPLC detection until the reaction of HEMK and the mono-addition product is complete. Then add 1.39 g (12 mmol) of 2-hydroxyethyl acrylate and continue to stir the reaction while maintaining the temperature. Take samples for detection every 4 hours of reaction until the content of 2-hydroxyethyl acrylate no longer decreases, then stop the reaction. Cool to 30 °C, add 6.4 g (3.0 mmol of sodium carbonate) of a 5% aqueous sodium carbonate solution by mass, and then wash with water until neutral. Distill off the solvent under reduced pressure to obtain 4.09 g of the product of formula XVI.

[0204]

[0205] Table 13 Analysis results of the product of Example 13 by liquid chromatography-mass spectrometry

[0206]

[0207]

[0208] Example 14

[0209] This example provides a photocurable composition, comprising the following components: 4.57 g of Photomer 4072, 4.57 g of Photomer 3316, 0.36 g of the product of Formula IX in Example 1, and 0.5 g of Omnipol TX.

[0210] The preparation method of the above photocurable composition comprises the following steps: stirring and dissolving the above components at 60 °C until homogeneous, and then cooling to room temperature to prepare the photocurable composition.

[0211] Example 15

[0212] This example provides a photocurable composition, comprising the following components: 4.57 g of Photomer 4072, 4.57 g of Photomer 3316, 0.36 g of the product of Formula XI in Example 4, and 0.5 g of Omnipol TX.

[0213] The preparation method of the above photocurable composition comprises the following steps: stirring and dissolving the above components at 60 °C until homogeneous, and then cooling to room temperature to prepare the photocurable composition.

[0214] Example 16

[0215] This example provides a photocurable composition, comprising the following components: 4.5 g of Photomer 4072, 4.5 g of Photomer 3316, 0.5 g of the product of Formula XIII in Example 7, and 0.5 g of Omnipol TX.

[0216] The preparation method of the above photocurable composition comprises the following steps: stirring and dissolving the above components at 60 °C until homogeneous, and then cooling to room temperature to prepare the photocurable composition.

[0217] Example 17

[0218] This example provides a photocurable composition, comprising the following components: 4.5 g of Photomer 4072, 4.5 g of Photomer 3316, 0.5 g of the product of Formula XIV in Example 9, and 0.5 g of Omnipol TX.

[0219] The preparation method of the above photocurable composition comprises the following steps: stirring and dissolving the above components at 60 °C until homogeneous, and then cooling to room temperature to prepare the photocurable composition.

[0220] Example 18

[0221] This example provides a photocurable composition, comprising the following components: 4.5 g of Photomer 4072, 4.5 g of Photomer 3316, 0.5 g of the product of Formula XV in Example 11, and 0.5 g of Omnipol TX.

[0222] The preparation method of the above photocurable composition comprises the following steps: stirring and dissolving the above components at 60 °C until homogeneous, and then cooling to room temperature to prepare the photocurable composition.

[0223] Comparative Example 1

[0224] This comparative example provides a photocurable composition, comprising the following components: 4.65 g of Photomer 4072, 4.65 g of Photomer 3316, 0.2 g of Omnirad EMK, and 0.5 g of Omnipol TX.

[0225] The preparation method of the above photocurable composition comprises the following steps: stirring and dissolving the above components at 60 °C until homogeneous, and then cooling to room temperature to prepare the photocurable composition.

[0226] Test Example

[0227] The hardness and curing migration properties of the photocurable compositions prepared in the above Examples 14 - 18 and Comparative Example 1 were tested respectively:

[0228] Pendulum hardness test: The above photocurable compositions were respectively cured once at a tape speed of 10 m / min on a coated glass plate (under a 395 nm LED lamp) using a 25 μm wire bar, and the pendulum hardness after curing was tested.

[0229] Migration rate test: The above photocurable compositions were respectively applied on a paper with a coating length and width of 5 × 20 cm using a 25 μm wire bar, and cured once at a tape speed of 10 m / min under a 395 nm LED lamp. The cured paper was placed in 100 g of a 3% acetic acid aqueous solution at 40 °C for 10 days, and then the photoinitiator components migrated into the acetic acid aqueous solution (the photoinitiator components refer to the product components of Formula IX in Example 1, the product components of Formula XI in Example 4, the product components of Formula XIII in Example 7, the product components of Formula XIV in Example 9, the product components of Formula XV in Example 11, or the Omnirad EMK component) were quantitatively analyzed by HPLC. The results were calculated using the EU model, assuming 600 cm 2 and placed in 100 g of a 3% acetic acid aqueous solution at 40 °C for 10 days, and then the photoinitiator components migrated into the acetic acid aqueous solution (the photoinitiator components refer to the product components of Formula IX in Example 1, the product components of Formula XI in Example 4, the product components of Formula XIII in Example 7, the product components of Formula XIV in Example 9, the product components of Formula XV in Example 11, or the Omnirad EMK component) were quantitatively analyzed by HPLC. The results were calculated using the EU model, assuming 600 cm 2The printing area packages 1 kg of food, so the results can be converted to μg / kg, that is, the μg of the analyte contained in each kg of food (the analyte refers to the product of Formula IX in Example 1, the product of Formula XI in Example 4, the product of Formula XIII in Example 7, the product of Formula XIV in Example 9, the product of Formula XV in Example 11 or Omnirad EMK). The experimental results of hardness and migration rate analysis are shown in Table 14.

[0230] Table 14

[0231] Example 14 Example 15 Example 16 Example 17 Example 18 Comparative Example 1 Pendulum hardness 0.76 0.75 0.75 0.79 0.80 0.77 Migration rate (μg / kg) 25 23 27 11 6 2180

[0232] It can be seen from the test data that when using the bis(dialkylamino)benzophenone compounds with acrylate-based alkoxy side chains provided by the present invention as the co-initiator of the photocuring composition compared with the commonly used commercially available EMK, the hardness of the compound provided by the present invention after curing is similar to that of the comparative object, indicating a similar curing rate. However, since the compound provided by the present invention has a larger molecular weight and contains polymerizable double bonds, the migration rate is significantly reduced. Therefore, the compound provided by the present invention is more suitable for applications with strict requirements on the substance migration rate, such as food and drug packaging, children's toys, etc.

[0233] Obviously, the above embodiments are only examples for clear illustration and not limitations on the implementation manners. For those of ordinary skill in the art, other different forms of changes or modifications can be made based on the above description. It is not necessary and impossible to enumerate all the implementation manners here. And the obvious changes or modifications derived therefrom are still within the protection scope of the present invention.

Claims

1. A benzophenone derivative, characterized in that, It has the structure shown in formula (1): Wherein: n1 is an integer from 1 to 10, R1 is an unsubstituted C1-C8 alkyl group, R2 is H or -CH3, R3 is H or G1 is an unsubstituted C1-C12 alkylene group, m1 is 1 and m2 is 1.

2. The benzophenone derivative according to claim 1, characterized in that, n1 is an integer from 1 to 4.

3. The benzophenone derivative according to claim 1, characterized in that, R1 is a C1-C4 alkyl group.

4. The benzophenone derivative according to claim 1, wherein R1 is -CH2CH3.

5. The benzophenone derivative according to claim 1, characterized in that, R2 is H.

6. The benzophenone derivative according to claim 1, wherein, R3 is R2 and G1 are defined in the same way as in formula (1) of claim 1.

7. The benzophenone derivative according to claim 1, characterized in that, G1 is -CH2CH2-,-CH2CH2CH2CH2- or -CH2CH2OCH2CH2-.

8. A benzophenone derivative, characterized in that, It has the structure shown in formula (2): Wherein: n2 is an integer from 1 to 10, R1 is an unsubstituted C1-C8 alkyl group, R2 is H or -CH3, R4 is H or G2 is an unsubstituted C1-C12 alkylene group or m3 is 1.

9. The benzophenone derivative according to claim 8, wherein n2 is an integer from 1 to 6.

10. The benzophenone derivative according to claim 8, wherein, R1 is a C1-C4 alkyl group.

11. The benzophenone derivative according to claim 8, characterized in that, R1 is -CH2CH3.

12. The benzophenone derivative according to claim 8, wherein R2 is H.

13. The benzophenone derivative according to claim 8, characterized in that, R4 is R2 and G2 are defined in the same way as in formula (2) of claim 8.

14. A benzophenone derivative, characterized in that, It has the structure shown in formula (3): Wherein: n3 is an integer from 1 to 10, R1 is an unsubstituted C1-C8 alkyl group, R2 is H or -CH3, R5 is H or G2 is an unsubstituted C1-C12 alkylene group or m3 is 1 or 2; G3 is an unsubstituted C1-C12 alkylene group, m4 is 1.

15. The benzophenone derivative according to claim 14, wherein, n3 is an integer from 1 to 6.

16. The benzophenone derivative according to claim 14, wherein R1 is a C1-C4 alkyl group.

17. The benzophenone derivative according to claim 14, wherein R1 is -CH2CH3.

18. The benzophenone derivative according to claim 14, characterized in that, R2 is H.

19. The benzophenone derivative according to claim 14, wherein R5 is R2, G2, and G3 are defined as in formula (3) of claim 14.

20. The benzophenone derivative according to claim 14, wherein G2 and G3 are each independently -CH2CH2-,-CH2CH2CH2CH2-,-CH2CH2OCH2CH2- or -CH2CH2OCH2CH2OCH2CH2-.

21. A method for preparing a benzophenone derivative according to any one of claims 1-7, comprising: Reacting the compound shown in formula (4) with the compound shown in formula (5), adding at least one of the two terminal hydroxyl groups of the compound shown in formula (4) completely, and then ending the reaction to obtain a benzophenone derivative having the structure of formula (1); The molar ratio of the compound shown in formula (4) to the compound shown in formula (5) is 1:1 to 2, and R1, R2 and G1 have the same definitions as in formula (1).

22. The method according to claim 21, wherein The reaction temperature is 40-120 °C, and the reaction time is 10-100 h.

23. A method for preparing a benzophenone derivative according to any one of claims 8-13, characterized in that, Comprising: Reacting the compound shown in formula (6) with the compound shown in formula (7), after adding at least one of the two terminal hydroxyl groups of the compound shown in formula (6) completely, adding the compound shown in formula (8) for reaction until the content of the compound shown in formula (8) no longer decreases, and stopping the reaction; Wherein: the molar ratio of the compound shown in formula (6) to the compound shown in formula (7) is 1:(1-2), the molar ratio of the compound shown in formula (6) to the compound shown in formula (8) is 1:(0.5-3), and R1, R2 and G2 have the same meanings as in formula (2).

24. The method according to claim 23, wherein The reaction temperature is 40-120 °C, and the reaction time is 10-100 h.

25. A method for preparing a benzophenone derivative according to any one of claims 14-20, characterized in that, Comprising: Reacting the compound shown in formula (9) with the compound shown in formula (10), after adding at least one of the two terminal hydroxyl groups of the compound shown in formula (9) completely, adding the compound shown in formula (11) until the double bond in the vinyl group of the compound shown in formula (11) is completely added; Wherein: the molar ratio of the compound shown in formula (9) to the compound shown in formula (10) is 1:(1-2), the molar ratio of the compound shown in formula (9) to the compound shown in formula (11) is 1:(1-3), and R1, R2, G2 and G3 have the same meanings as in formula (3).

26. The method according to claim 25, wherein The reaction temperature is 40-120 °C, and the reaction time is 10-100 h.

27. A photocuring agent composition, characterized in that, Comprising: A photoinitiator that can be used for free radical polymerization and a benzophenone derivative as described in any one of claims 1-20.

28. A photocurable composition, characterized in that, Comprising: A photocuring agent component and an ethylenically unsaturated compound that can be free-radically polymerized; The photocurable composition comprises: (a) A benzophenone derivative as described in any one of claims 1-20; (b) A photoinitiator that can be used for free radical polymerization; and (c) An ethylenically unsaturated compound that can be free-radically polymerized; Wherein, the component (b) is selected from one or more of benzophenone, thioxanthone compounds, α-hydroxy ketone compounds, α-amino ketone compounds, acylphosphine oxide compounds or oxime ester compounds; The component (c) is selected from at least one of epoxy acrylate resin, polyurethane acrylate resin, polyester acrylate resin, polyether acrylate resin, acrylated polyacrylate, epoxy methacrylate resin, polyurethane methacrylate resin, polyester methacrylate resin, polyether methacrylate resin, acrylated polymethacrylate, allyl ether compounds, acrylate monomers or methacrylate monomers.

29. The photocurable composition according to claim 28, wherein The component (b) is selected from at least one of benzophenone, 2-isopropylthioxanthone, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholinophenyl)-1-butanone, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, photoinitiator Omnipol TX, photoinitiator Omnipol 910 or photoinitiator Omnipol TP.

30. The photocurable composition according to claim 28, characterized in that, The addition amount of the component (a) is 0.1-20% of the total weight of the photocurable composition.

31. The photocuring composition according to claim 28, wherein The addition amount of the component (b) is 0.1-10% of the total weight of the photocurable composition.

32. Use of a photocurable composition as described in any one of claims 28-31 in food packaging printing, pharmaceutical packaging printing, furniture coating, book printing or advertising printing.

33. A photocurable product, characterized in that, The photocured product is formed by photocuring a photocurable composition, wherein the photocurable composition is a photocurable composition as described in any one of claims 28-31.

34. A method for curing a photocurable composition, characterized in that, Comprising: Coating a photocurable composition as described in any one of claims 28-31 on a substrate; And curing the photocurable composition by using a light source emitting in the UV-visible light region.

35. The method according to claim 34, wherein, The substrate is selected from wood, paper, plastic, coating or metal.

36. The method according to claim 34, characterized in that, The coating method is selected from offset printing, gravure printing, flexographic printing, inkjet printing or 3D printing.

37. The method according to claim 34, characterized in that, After coating on the substrate, the photocurable composition is cured by UV-visible light radiation with a wavelength of 200 to 425 nm.

38. The method according to claim 37, wherein, The photocurable composition is cured by UV-visible light radiation with a wavelength of 365 to 405 nm.

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