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 shown in formula (1). The benzophenone derivative can be used as an important co-initiator in a UV-curing formulation to co-initiate the photopolymerization of unsaturated carbon-carbon double bond compounds with other photoinitiators. The compound shown in formula (1) has a very low migration property due to its large molecular weight and is suitable for replacing N,N,N,N-tetraethyl-4,4'-diaminobenzophenone and being 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 kind of commonly used high-efficiency co-initiator, which is very important in inks, especially UV-LED curable inks. The synthesis methods of the compound have been 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 used in combination with a hydrogen abstraction type photoinitiator in various compositions, playing 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 the actual use of photocurable inks, due to the pollution problems of small molecular weight photoinitiators, the demand for photoinitiators with low volatility and low migration increases continuously with the expansion of the coating dosage. 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 for the amount of substance migration. Therefore, it is difficult to meet the strict migration standard requirements, and thus it is not included in the list of permitted uses. It also makes many users 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

[0004] 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, so as to provide a benzophenone derivative, a preparation method thereof and uses thereof.

[0005] In order to solve the above technical problems, the present invention adopts the following technical solutions:

[0006] A benzophenone derivative has a structure shown in formula (1):

[0007]

[0008] Wherein:

[0009] n1 and n2 are each independently an integer from 0 to 10 (for example, 0, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10), but not both 0 at the same time;

[0010] R0 is an optionally substituted C1-C12 alkyl group;

[0011] R1 and R3 are each independently H, an optionally substituted C1-C12 alkyl group, R6OCH2- or -C(=O)R7, wherein R6 is an optionally substituted C1-C8 alkyl group, -CH2-CH=CH2 or R7 is an optionally substituted C1-C8 alkyl group;

[0012] R2 and R4 are each independently H, an optionally substituted C1-C12 alkyl group, R6OCH2-, -C(=O)R7; wherein R6 is an optionally substituted C1-C8 alkyl group, -CH2-CH=CH2 or R7 is an optionally substituted C1-C8 alkyl group;

[0013] R5 and R5' are each independently H, -C(=O)R8, -C(=O)NHR9, R8 is an optionally substituted C1-C8 alkyl group, an optionally substituted C2-C8 alkenyl group or an optionally substituted C6-C20 aryl group, and R9 is an optionally substituted C1-C8 alkyl group or 2-acryloyloxyethyl.

[0014] 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 may or may not be substituted. Unless otherwise specified, the type and number of substituents may be arbitrary on the basis of being achievable.

[0015] In the present invention, the alkyl group may be a straight-chain alkyl group or a branched-chain alkyl group.

[0016] In a preferred embodiment of the present invention, n1 and n2 are each independently an integer from 1 to 6. Further optionally, n1 and n2 are each independently an integer from 0 to 6, and the value of n1 + n2 is an integer from 1 to 6.

[0017] In the structure shown in formula (1) of the present invention, two R0s are the same, and R0 is an optionally substituted C1-C12 alkyl group. Examples of the alkyl group 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-methyl-1-pentyl, 3-methyl-1-pentyl, 4-methyl-1-pentyl, 2-methyl-2-pentyl, 3-methyl-2-pentyl, 4-methyl-2-pentyl, 2,2-dimethyl-1-butyl, 3,3-dimethyl-1-butyl, 2-ethyl-1-butyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl or neopentyl, etc. In some embodiments, the alkyl group is a C1-C10 alkyl group, a C1-C9 alkyl group, 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. R0 is preferably an unsubstituted C1-C12 alkyl group, more preferably an unsubstituted C1-C6 alkyl group, and most preferably methyl or ethyl.

[0018] In the structure shown in formula (1) of the present invention, R1 and R3 are each independently H, an optionally substituted C1-C12 alkyl group, R6OCH2-, -C(=O)R7, where R6 is an optionally substituted C1-C8 alkyl group, CH2-CH=CH2 or R7 is an optionally substituted C1-C8 alkyl group;

[0019] R2 and R4 are each independently H, an optionally substituted C1-C12 alkyl group, R6OCH2- or -C(=O)R7; where R6 is an optionally substituted C1-C8 alkyl group, -CH2-CH=CH2 or R7 is an optionally substituted C1-C8 alkyl group;

[0020] Among R1, R3, R2 or R4, examples of the C1-C12 alkyl group 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-methyl-1-pentyl, 3-methyl-1-pentyl, 4-methyl-1-pentyl, 2-methyl-2-pentyl, 3-methyl-2-pentyl, 4-methyl-2-pentyl, 2,2-dimethyl-1-butyl, 3,3-dimethyl-1-butyl, 2-ethyl-1-butyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl or neopentyl, etc. In some embodiments, the alkyl group is a C1-C10 alkyl group, a C1-C9 alkyl group, 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.

[0021] Among R1, R3, R2 or R4, examples of the C1-C8 alkyl group 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.

[0022] In a preferred embodiment of the present invention, R1 and R3 are each independently H, an unsubstituted C1-C12 alkyl group, R6OCH2- or -C(=O)R7, wherein R6 is an unsubstituted C1-C8 alkyl group, -CH2-CH=CH2 or R7 is an unsubstituted C1-C8 alkyl group. Preferably, R1 and R3 are each independently H or an unsubstituted C1-C8 alkyl group, and more preferably H.

[0023] In a preferred embodiment of the present invention, R2 and R4 are each independently H, an unsubstituted C1-C12 alkyl group, R6OCH2- or -C(=O)R7, wherein R6 is an unsubstituted C1-C8 alkyl group, -CH2-CH=CH2 or R7 is an unsubstituted C1-C8 alkyl group. Preferably, R2 and R4 are each independently H or an unsubstituted C1-C8 alkyl group, and more preferably H or an unsubstituted C1-C4 alkyl group.

[0024] In R5 or R5', examples of C2-C8 alkenyl include 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, 1-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl or 3-methyl-1-butenyl, etc.

[0025] An aryl is a cyclic aromatic hydrocarbon that does not contain heteroatoms in the ring. Aryls include, but are not limited to, phenyl, azulyl, heptalenyl, biphenyl, fluorenyl, phenanthryl, triphenylenyl, pyrenyl, tetracenyl, biphenylene, anthryl and naphthyl. An aryl may contain 6 to 20 carbons in the ring portion of the group. An aryl may be unsubstituted or substituted, and preferably is an unsubstituted aryl.

[0026] In a preferred embodiment of the present invention, R5 and R5' are each independently H, -C(=O)R8, -C(=O)NHR9, R8 is an unsubstituted C1-C8 alkyl, an unsubstituted C2-C8 alkenyl or an unsubstituted C6-C20 aryl, R9 is an unsubstituted C1-C8 alkyl or 2-acryloyloxyethyl, R5 and R5' are each independently preferably H, -C(=O)R8, -C(=O)NHR9, R8 is an unsubstituted C1-C3 alkyl, and R9 is an unsubstituted C1-C4 alkyl or 2-acryloyloxyethyl.

[0027] In a preferred embodiment of the present invention, the benzophenone derivative is selected from one of the following compounds:

[0028]

[0029]

[0030] According to another aspect of the present invention, there is provided a method for preparing a benzophenone derivative as described above, comprising the following steps:

[0031] Reacting a compound represented by formula (2) and a compound represented by formula (3) under the action of a catalyst; and

[0032] Optionally, reacting the obtained reaction product with a capping agent;

[0033]

[0034]

[0035] Wherein:

[0036] R0 is an optionally substituted C1-C12 alkyl group, which has the same definition as R0 described above, preferably an unsubstituted C1-C12 alkyl group, more preferably an unsubstituted C1-C6 alkyl group, and most preferably a methyl or ethyl group;

[0037] R 10 、R 11 are each independently H, an optionally substituted C1-C12 alkyl group, R6OCH2- or -C(=O)R7, where R6 is an optionally substituted C1-C8 alkyl group, -CH2-CH=CH2 or R7 is an optionally substituted C1-C8 alkyl group;

[0038] The capping agent is selected from acid anhydrides, acyl chlorides, and isocyanates. The acid anhydride is R8COOOCR8, the acyl chloride is R8COCl, and the isocyanate is R9NCO. The isocyanate is R9NCO, and R8 and R9 have the same definitions as in formula (1);

[0039] The molar ratio of the compounds of formula (2) and formula (3) is 1:(1 to 20).

[0040] When R0 is an ethyl group, the structure of the compound of formula (2) is

[0041]

[0042] In the above reaction, the reaction with the capping agent is optionally carried out. If both R5 and R5' in the compound of formula (1) are H, the step of reacting with the capping agent is not required here. When R5 and R5' are other groups than H, the step of reacting with the capping agent is required.

[0043] In a preferred embodiment of the present invention, R 10 、R 11 are each independently H, an unsubstituted C1-C12 alkyl group, R6OCH2- or -C(=O)R7, where R6 is an unsubstituted C1-C8 alkyl group, -CH2-CH=CH2 or R7 is an unsubstituted C1-C8 alkyl group.

[0044] In a preferred embodiment of the present invention, R 10 is H.

[0045] In a preferred embodiment of the present invention, R 11 is H or an unsubstituted C1-C4 alkyl group.

[0046] In a preferred embodiment of the present invention, the reaction temperature of the compound shown in formula (2) and the compound shown in formula (3) is 80 to 120 °C, and the reaction time is 40 to 80 hours.

[0047] In a preferred embodiment of the present invention, the catalyst is selected from base catalysts, preferably hydroxides of alkali metals or alkaline earth metals, and more preferably sodium hydroxide or potassium hydroxide.

[0048] In a preferred embodiment of the present invention, the method further includes the steps of purification and solvent removal after reaction with a capping agent. Exemplary purification methods include purification by washing with water, and the solvent removal method is distillation.

[0049] In a preferred embodiment of the present invention, the method for preparing the benzophenone derivative includes the following steps:

[0050] Mix the compound shown in formula (2), the compound shown in formula (3), and a base catalyst, heat and react under nitrogen or an inert atmosphere, cool down after the reaction ends, then add an organic solvent to dissolve the reactants, wash with water until neutral, and remove the solvent to obtain the benzophenone derivative;

[0051]

[0052] Wherein:

[0053] R0 is an optionally substituted C1-C12 alkyl group, which has the same definition as R0 described above, preferably an unsubstituted C1-C12 alkyl group, more preferably an unsubstituted C1-C6 alkyl group, and most preferably a methyl or ethyl group;

[0054] R 10 、R 11 Each independently is H, an optionally substituted C1-C12 alkyl group, R6OCH2- or -C(=O)R7, wherein R6 is an optionally substituted C1-C8 alkyl group, -CH2-CH=CH2 or R7 is an optionally substituted C1-C8 alkyl group.

[0055] Preferably, the molar ratio of the compounds of formula (2) and formula (3) is 1:(1-20).

[0056] Preferably, the reaction temperature is 80-120 °C and the reaction time is 40-80 hours.

[0057] Preferably, the base catalyst is sodium hydroxide or potassium hydroxide, and the molar ratio of the base catalyst to the compound of formula (2) is (0.05-0.2):1.

[0058] Preferably, after the reaction ends, the temperature is cooled to 25-40 °C, and the organic solvent is dichloroethane.

[0059] In a preferred embodiment of the present invention, the method for preparing the benzophenone derivative includes the following steps:

[0060] 1) Mix the compound shown in formula (2), the compound shown in formula (3), and a base catalyst, heat and react under a nitrogen or inert atmosphere. After the reaction is completed, cool down the temperature, then add an organic solvent to dissolve the reactants, wash with water until neutral, and remove the solvent to obtain a reaction product;

[0061] 2) Take the reaction product obtained in step 1), mix it with an organic solvent and a capping agent, heat and stir to react. After the reaction is completed, wash with an alkaline solution, then wash with water until neutral, and remove the solvent to obtain the benzophenone derivative;

[0062]

[0063] Wherein:

[0064] R0 is an optionally substituted C1-C12 alkyl group, which has the same definition as R0 described above, preferably an unsubstituted C1-C12 alkyl group, more preferably an unsubstituted C1-C6 alkyl group, and most preferably a methyl or ethyl group;

[0065] R 10 、R 11 are each independently H, an optionally substituted C1-C12 alkyl group, R6OCH2- or -C(=O)R7, wherein R6 is an optionally substituted C1-C8 alkyl group, -CH2-CH=CH2 or R7 is an optionally substituted C1-C8 alkyl group;

[0066] The capping agent is selected from acid anhydrides, acyl chlorides, and isocyanates. The acid anhydride is R8COOOCR8, the acyl chloride is R8COCl, and the isocyanate is R9NCO. The isocyanate is R9NCO, and R8 and R9 have the same definition as in formula (1).

[0067] Preferably, in step 1), the molar ratio of the compound of formula (2) to the compound of formula (3) is 1:(1-20); the reaction temperature is 80-120 °C, the reaction time is 40-80 hours; the base catalyst is sodium hydroxide or potassium hydroxide, and the molar ratio of the base catalyst to the compound of formula (2) is (0.05-0.2):1; after the reaction is completed, cool down to 25-40 °C, and the organic solvent is dichloroethane.

[0068] Preferably, in step 2), the organic solvent is dichloroethane, and the mass ratio of the reaction product obtained in step 1) to the capping agent is (1-10):(0.5-5); the heating and stirring reaction temperature is 25-40 °C, the heating and stirring reaction time is 10-30 h; the alkaline solution can be a sodium carbonate solution, and the mass concentration of the sodium carbonate solution is 1-10%.

[0069] In a preferred embodiment of the present invention, the method for preparing the benzophenone derivative comprises the following steps:

[0070] Mix the compound shown in formula (2), the compound shown in formula (3), and a base catalyst, and heat the mixture for reaction under a nitrogen or inert atmosphere. After the reaction is completed, add an organic solvent and a capping agent, and keep the temperature at 20 - 30 °C for 3 - 6 h. After the reaction is completed, wash with water until neutral, and remove the solvent to obtain the benzophenone derivative.

[0071]

[0072] Wherein:

[0073] R0 is an optionally substituted C1 - C12 alkyl group, which has the same definition as R0 described above, preferably an unsubstituted C1 - C12 alkyl group, more preferably an unsubstituted C1 - C6 alkyl group, and most preferably a methyl or ethyl group;

[0074] R 10 、R 11 are each independently H, an optionally substituted C1 - C12 alkyl group, R6OCH2 - or -C(=O)R7, wherein R6 is an optionally substituted C1 - C8 alkyl group, -CH2 - CH=CH2 or R7 is an optionally substituted C1 - C8 alkyl group;

[0075] The capping agent is selected from acid anhydrides, acyl chlorides, and isocyanates. The acid anhydride is R8COOOCR8, the acyl chloride is R8COCl, and the isocyanate is R9NCO. R8 and R9 have the same definition as in formula (1).

[0076] Preferably, the molar ratio of the compound of formula (2) to the compound of formula (3) is 1:(1 - 20); the reaction temperature is 80 - 120 °C, and the reaction time is 40 - 80 hours; the base catalyst is sodium hydroxide or potassium hydroxide, and the molar ratio of the base catalyst to the compound of formula (2) is (0.05 - 0.2):1; the organic solvent is dichloroethane.

[0077] Preferably, the mass ratio of the compound of formula (2) to the capping agent is (1 - 10):(0.5 - 5); after adding the capping agent, the step of adding an organic amine is further included. The organic amine is triethylamine, and the molar ratio of the added amount to the capping agent is (1 - 1.2):1.

[0078] In a preferred embodiment of the present invention, the method for preparing the benzophenone derivative comprises the following steps:

[0079] Mix the compound shown in formula (2) and a base catalyst, then place them in a reaction kettle. Introduce nitrogen to displace the air in the kettle until the kettle pressure is maintained at 0.02 - 0.03 MPa. Add the compound of formula (3). The reaction temperature is 80 - 120 °C and the reaction time is 40 - 80 hours. After the kettle pressure drops to 0.02 - 0.03 MPa, keep the temperature for reaction for another 2 - 5 hours. Cool the temperature to 25 - 30 °C, introduce it into an alkaline solution, then add an organic solvent and a capping agent. The reaction temperature is 40 - 45 °C and the reaction lasts for 2 - 5 hours. Cool the temperature to 25 - 30 °C, wash with water until neutral, and remove the solvent by drying to obtain the benzophenone derivative.

[0080]

[0081] Wherein:

[0082] R0 is an optionally substituted C1 - C12 alkyl group, which has the same definition as R0 described above. It is preferably an unsubstituted C1 - C12 alkyl group, more preferably an unsubstituted C1 - C6 alkyl group, and most preferably methyl or ethyl.

[0083] R 10 、R 11 are each independently H, an optionally substituted C1 - C12 alkyl group, R6OCH2 - or -C(=O)R7, wherein R6 is an optionally substituted C1 - C8 alkyl group, -CH2 - CH = CH2 or R7 is an optionally substituted C1 - C8 alkyl group;

[0084] The capping agent is selected from acid anhydrides, acyl chlorides, and isocyanates. The acid anhydride is R8COOOCR8, the acyl chloride is R8COCl, and the isocyanate is R9NCO. The isocyanate is R9NCO. R8 and R9 have the same definitions as in formula (1).

[0085] Preferably, the molar ratio of the compounds of formula (2) and formula (3) is 1:(1 - 20); the base catalyst is sodium hydroxide or potassium hydroxide, and the molar ratio of the base catalyst to the compound of formula (2) is (0.05 - 0.2):1; the organic solvent is dichloroethane.

[0086] Preferably, the mass ratio of the compound of formula (2) to the capping agent is (1 - 10):(0.5 - 5); after adding the capping agent, it further includes the step of adding an organic amine. The organic amine is triethylamine, and the addition amount is in a molar ratio of (1 - 1.2):1 to the capping agent.

[0087] According to another aspect of the present invention, a photoinitiator composition is provided, which includes: a photoinitiator for free radical polymerization and the benzophenone derivative described above.

[0088] According to another aspect of the present invention, there is provided a photocurable composition, comprising: a photoinitiator component and a radically polymerizable ethylenically unsaturated compound, wherein the photoinitiator component comprises the photocurable composition as described above.

[0089] In a preferred embodiment of the present invention, the photocurable composition comprises:

[0090] (a) the benzophenone derivative as described above;

[0091] (b) a photoinitiator useful for free radical polymerization; and

[0092] (c) a radically polymerizable ethylenically unsaturated compound.

[0093] The photocurable composition comprising the foregoing photoinitiator composition has a low migration rate.

[0094] In a preferred embodiment of the present invention, the addition amount of the component (a) is 0.1-20% of the total weight of the photocurable composition, such as 1%, 5%, 10%, 15% or 20%.

[0095] In a preferred embodiment of the present invention, the component (b) is selected from one or more of benzophenones (benzophenone compounds and their derivatives other than the present invention), thioxanthone compounds, α-hydroxy ketone compounds, α-amino ketone compounds, acylphosphine oxide compounds or oxime ester compounds, preferably at least one of benzophenone, 2-isopropylthioxanthone, the macromolecular photoinitiator series products Omnipol TX, Omnipol 910 or Omnipol TP of IGM Resins B.V., etc. Preferably, the photoinitiator Omnipol TX, the photoinitiator Omnipol 910 or the photoinitiator Omnipol TP is selected from the macromolecular photoinitiator series products Omnipol TX, Omnipol 910 or Omnipol TP of IGM Resins B.V.

[0096] 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%.

[0097] Ethylenically unsaturated compounds refer to ethylenically unsaturated monomers, oligomers, prepolymers and their mixtures, which are capable of undergoing free radical polymerization.

[0098] 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.

[0099] The photocurable composition may also contain other additives to meet performance requirements, such as pigments, fillers, leveling agents, polymerization inhibitors, solvents, etc.

[0100] 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.

[0101] According to another aspect of the present invention, there is provided a photocured product, which is formed by photocuring a photocurable composition, wherein the photocurable composition is the photocurable composition as described above, and preferably the photocured product is selected from any one of coatings, adhesives, and printing inks.

[0102] According to another aspect of the present invention, there is provided a method for curing a photocurable composition, comprising:

[0103] 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.

[0104] 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.

[0105] Preferably, after coating on the substrate, the photocurable composition is cured by UV-visible light radiation with a wavelength of 200 to 425 nm, and preferably by UV-visible light radiation with a wavelength of 365 to 405 nm.

[0106] Beneficial effects:

[0107] In the present invention, a high molecular weight EMK derivative is synthesized by using a hydroxy-containing bis(dialkylamino)benzophenone compound and an epoxide compound as raw materials for a ring-opening addition reaction. The obtained benzophenone derivative has the characteristics of good compatibility with the photocuring system and low migration rate. Moreover, the synthesis method is simple, and the hydroxyl group can also be further capped.

[0108] The benzophenone derivative can be used as an important co-initiator in UV-curable formulations to co-initiate the photopolymerization of unsaturated carbon-carbon double bond compounds with other photoinitiators. The compound shown in formula (1) has a very low mobility due to its large molecular weight and is suitable for replacing N, N, N, N-tetraethyl-4,4'-diaminobenzophenone in fields such as food packaging and printing formulations. Detailed implementation mode

[0109] Experimental raw materials and materials:

[0110]

[0111]

[0112] The structure of HEMK is

[0113]

[0114] Omnirad DETX is 2,4-diethylthioxanthone, a product of IGM RESINS;

[0115] Omnirad EMK is tetraethyl Michler's ketone, a product of IGM RESINS;

[0116] Photomer 4072 is trimethylolpropane propoxylate (3) triacrylate, a product of IGM RESINS;

[0117] Photomer 3316 is a low-viscosity modified epoxy acrylate, a product of IGM RESINS.

[0118] Example 1

[0119] This example provides a preparation method of the compound shown in formula (4), including the following steps:

[0120] Take a 100 mL three-necked flask, equip it with mechanical stirring, and successively add 1.78 g (5 mmol) of HEMK, 3.90 g (30 mmol) of butyl glycidyl ether, and 0.028 g (0.5 mmol) of potassium hydroxide. After fully replacing with nitrogen under normal temperature stirring, seal it with a nitrogen balloon, heat and stir for reaction, the reaction temperature is 120 °C, and the reaction time is 72 hours. Take a sample and detect the content of each component by HPLC until it no longer changes. Cool down to 30 °C and add 17.0 g of dichloroethane to dissolve the reactants, and wash with water until neutral. Distill off the solvent under reduced pressure to obtain 5.40 g of the product as shown in formula (4).

[0121]

[0122] Table 1 LC-MS Analysis Results of the Product of Example 1

[0123] Serial number Retention time min Content % Molecular weight The value of (n1 + n2) in formula (4) 1 3.045 0.542 486.65 1 2 3.716 19.705 616.84 2 3 6.268 34.377 747.03 3 4 10.046 27.108 877.21 4 5 14.266 10.843 1007.39 5 6 19.208 2.899 1137.57 6

[0124] Example 2

[0125] This example provides a method for preparing the compound shown in formula (5), which includes the following steps:

[0126] Add 5.40 g of the product obtained in Example 1, 17.0 g of dichloroethane, and 1.22 g (12 mmol) of acetic anhydride, heat and stir for reaction at a reaction temperature of 30 °C for 12 hours. Take a sample for HPLC detection until the product obtained in Example 1 completely reacts. Then add 6.4 g of a 10% mass concentration sodium carbonate aqueous solution, wash once, and then wash with water until neutral. Distill off the solvent under reduced pressure to obtain 5.62 g of the product as shown in formula (5).

[0127]

[0128] Table 2 LC-MS Analysis Results of the Product of Example 2

[0129] Serial number Retention time min Content % Molecular weight <![CDATA[(n1 + n2) value in Formula V]]> 1 5.919 0.540 570.73 1 2 7.471 19.716 700.91 2 3 11.149 34.381 831.10 3 4 14.692 27.088 961.29 4 5 19.028 10.793 1091.48 5 6 26.638 2.865 1221.67 6

[0130] Example 3

[0131] This example provides a method for preparing the compound shown in formula (6), which includes the following steps:

[0132] In a 100 mL autoclave, add 17.82 g (50 mmol) of HEMK and 0.2 g (5 mmol) of sodium hydroxide successively, introduce nitrogen to displace the air in the autoclave for two minutes until the autoclave pressure is maintained at 0.02 MPa. Connect an ethylene oxide cylinder with a meter, slowly introduce 13.22 g (300 mmol) of ethylene oxide, react at a reaction temperature of 120 °C for 72 hours. After the autoclave pressure drops to 0.02 MPa, keep the temperature for reaction for another 4 hours. When the temperature drops to 30 °C, connect the outlet pipe to a 10% sodium hydroxide solution, introduce nitrogen into the inlet, and slowly blow off and absorb the unreacted ethylene oxide. After ventilation for 30 minutes, open the autoclave and take out the reaction solution and add it to a 100 ml reaction flask. Add 85.0 g of dichloroethane and wash with water until neutral. Distill off the solvent under reduced pressure to obtain 29.79 g of the product as shown in formula (6).

[0133]

[0134] Table 3 LC-MS Analysis Results of the Product of Example 3

[0135] Serial number Retention time min Content % Molecular weight The value of (n1 + n2) in formula (6) 1 5.010 0.300 400.52 1 2 7.324 17.805 444.57 2 3 10.190 33.977 488.63 3 4 15.701 29.288 532.68 4 5 19.005 10.853 576.73 5 6 25.837 3.096 620.78 6

[0136] Example 4

[0137] This example provides a method for preparing the compound shown in formula (7), which includes the following steps:

[0138] Add 29.79 g of the product obtained in Example 3, 85.0 g of dichloroethane, 16.94 g (120 mmol) of 2-acryloyloxyethyl isocyanate, and then add 12.14 g (120 mmol) of triethylamine. React at a temperature of 40 °C for 4 hours until the content of each component no longer changes. Cool down to 30 °C, wash with water until neutral, and remove the solvent under reduced pressure to obtain 41.17 g of the product as shown in formula (7).

[0139]

[0140] Table 4 Liquid Chromatography-Mass Spectrometry Analysis Results of the Product in Example 4

[0141]

[0142] Example 5

[0143] This example provides a method for preparing the compound shown in formula (8), which includes the following steps:

[0144] Take a 100 mL three-necked flask, equip it with mechanical stirring, and successively add 1.78 g (5 mmol) of HEMK, 3.90 g (30 mmol) of butyl glycidyl ether, and 0.003 g (0.05 mmol) of potassium hydroxide. After fully replacing with nitrogen under normal temperature stirring, seal it with a nitrogen balloon and heat and stir to react. React at a temperature of 120 °C for 48 hours. Take a sample and detect by HPLC until the content of each component no longer changes. Add 17.0 g of dichloroethane, add 1.09 g (12 mmol) of acryloyl chloride, keep the temperature at 20 °C, slowly dropwise add 1.22 g (12 mmol) of triethylamine. After the dropwise addition is completed, raise the temperature to 30 °C and stir to react for 4 hours until all components react completely. Wash with water until neutral, and remove the solvent under reduced pressure to obtain 5.59 g of the product as shown in formula (8).

[0145]

[0146] Table 5 Liquid Chromatography-Mass Spectrometry Analysis Results of the Product in Example 5

[0147] Serial number Retention time min Content % Molecular weight <![CDATA[Value of (n1 + n2) in formula (8)]]> 1 2.191 4.242 594.75 1 2 2.792 23.217 724.94 2 3 3.860 29.128 855.12 3 4 5.945 18.291 985.31 4 5 10.235 7.165 1115.50 5 6 14.987 1.313 1245.68 6

[0148] Example 6

[0149] This example provides a method for preparing the compound shown in formula (9), which includes the following steps:

[0150] Take a 100 mL three-necked flask, equip it with mechanical stirring, and successively add 1.78 g (5 mmol) of HEMK, 3.90 g (30 mmol) of butyl glycidyl ether, and 0.002 g (0.05 mmol) of sodium hydroxide. After fully replacing with nitrogen under stirring at room temperature, seal it with a nitrogen balloon and heat and stir for reaction. The reaction temperature is 120 °C and the reaction time is 72 hours. Take a sample and detect by HPLC until the content of each component no longer changes. Add 1.19 g (12 mmol) of n-butyl isocyanate, and then add 1.21 g (12 mmol) of triethylamine. The reaction temperature is 40 °C and the reaction is carried out for 4 hours until all components of the etherified product react completely. Add 17.0 g of dichloroethane and wash with water until neutral. Remove the solvent under reduced pressure to obtain 5.94 g of the product of formula (9).

[0151]

[0152] Table 6 Analysis results of the product of Example 6 by liquid chromatography-mass spectrometry

[0153]

[0154]

[0155] Example 7

[0156] This example provides a method for preparing a compound represented by formula (10), which includes the following steps:

[0157] In a 100 mL autoclave, successively add 17.82 g (50 mmol) of HEMK, 0.2 g (5 mmol) of sodium hydroxide, introduce nitrogen to replace the air in the autoclave for two minutes until the autoclave pressure is maintained at 0.02 MPa. Add 17.42 g (300 mmol) of propylene oxide, the reaction temperature is 120 °C, and the reaction time is 72 hours. After the autoclave pressure drops to 0.02 MPa, keep the temperature for reaction for another 4 hours. When the temperature drops to 30 °C, connect the outlet pipe to a 10% sodium hydroxide solution, introduce nitrogen into the inlet, and slowly blow and absorb the unreacted propylene oxide. After aeration for 30 minutes, open the autoclave and take out the reaction solution and add it to a 100 ml reaction flask. Add 85.0 g of dichloroethane. Add 16.94 g (120 mmol) of 2-acryloyloxyethyl isocyanate, and then add 12.14 g (120 mmol) of triethylamine. The reaction temperature is 40 °C and the reaction is carried out for 4 hours until all components react completely. Cool down to 30 °C, wash with water until neutral, remove the solvent under reduced pressure to obtain 46.90 g of the product of formula (10).

[0158]

[0159] Table 7 Analysis results of the product of Example 7 by liquid chromatography-mass spectrometry

[0160] Serial number Retention time min Content % Molecular weight The value of (n1 + n2) in formula (10) 1 2.943 0.300 696.80 1 2 3.615 3.526 754.88 2 3 6.011 8.769 812.96 3 4 9.686 24.271 871.04 4 5 13.798 40.154 929.12 5 6 18.910 17.359 987.20 6

[0161] Example 8

[0162] This example provides a photocurable composition, comprising the following components: 4.8 g of Photomer 4072, 4.8 g of Photomer 3316, 0.2 g of the product of Formula (4) in Example 1, and 0.2 g of Omnirad DETX.

[0163] The preparation method of the above photocurable composition comprises the following steps: stirring the above components at 60 °C until dissolved into a homogeneous solution, and then cooling to room temperature to prepare the photocurable composition.

[0164] Example 9

[0165] This example provides a photocurable composition, comprising the following components: 4.8 g of Photomer 4072, 4.8 g of Photomer 3316, 0.2 g of the product of Formula (5) in Example 2, and 0.2 g of Omnirad DETX.

[0166] The preparation method of the above photocurable composition comprises the following steps: stirring the above components at 60 °C until dissolved into a homogeneous solution, and then cooling to room temperature to prepare the photocurable composition.

[0167] Example 10

[0168] This example provides a photocurable composition, comprising the following components: 4.8 g of Photomer 4072, 4.8 g of Photomer 3316, 0.2 g of the product of Formula (8) in Example 5, and 0.2 g of Omnirad DETX.

[0169] The preparation method of the above photocurable composition comprises the following steps: stirring the above components at 60 °C until dissolved into a homogeneous solution, and then cooling to room temperature to prepare the photocurable composition.

[0170] Example 11

[0171] This example provides a photocurable composition, comprising the following components: 4.8 g of Photomer 4072, 4.8 g of Photomer 3316, 0.2 g of the product of Formula (10) in Example 7, and 0.2 g of Omnirad DETX.

[0172] The preparation method of the above photocurable composition comprises the following steps: stirring the above components at 60 °C until dissolved into a homogeneous solution, and then cooling to room temperature to prepare the photocurable composition.

[0173] Comparative Example 1

[0174] This comparative example provides a photocurable composition, comprising the following components: 4.8 g of Photomer 4072, 4.8 g of Photomer 3316, 0.2 g of Omnirad EMK, and 0.2 g of Omnirad DETX.

[0175] The preparation method of the above photocurable composition comprises the following steps: Stir the above components at 60 °C until dissolved into a homogeneous solution, and then cool to room temperature to prepare the photocurable composition.

[0176] Test Example

[0177] The photocurable compositions prepared in Examples 8 - 11 and Comparative Example 1 above were respectively tested for hardness and curing migration performance:

[0178] 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.

[0179] 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 cm 2 , into 100 g of an aqueous acetic acid solution with a mass content of 3%, and placed at 40 °C for 10 days. Then, the photoinitiator components migrated into the aqueous acetic acid solution (the photoinitiator components refer to the product components of Formula (4) in Example 1, the product components of Formula (5) in Example 2, the product components of Formula (8) in Example 5, the product components of Formula (10) in Example 7, or Omnirad EMK) were quantitatively analyzed by HPLC. The results were calculated using the EU model, assuming that 600 cm 2 of the printed area packages 1 kg of food. Therefore, the results can be converted to μg / kg, that is, the μg of the analyte (the analyte refers to the product of Formula (4) in Example 1, the product of Formula (5) in Example 2, the product of Formula (8) in Example 5, the product of Formula (10) in Example 7, or Omnirad EMK) contained in each kg of food. The experimental results of hardness and migration rate analysis are shown in Table 8.

[0180] Table 8

[0181] Example 8 Example 9 Example 10 Example 11 Comparative example 1 Pendulum hardness 0.78 0.80 0.79 0.77 0.77 Migration rate (μg / kg) 85 48 8 7 2180

[0182] As can be seen from the test data, when the bis(dialkylamino)benzophenone compound with an alkoxy side chain provided by the present invention is used as a co-initiator of a photocurable 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, but the migration rate is significantly reduced. In particular, the migration rates of the compounds capped with acrylate groups are all below 10 μg / kg. Therefore, the compounds provided by the present invention are more suitable for uses with strict requirements on the substance migration rate, such as food and drug packaging, children's toys, etc.

[0183] Obviously, the above embodiments are merely examples given for clear illustration and are 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 having the structure shown in formula (1): Wherein: n1 and n2 are each independently an integer from 0 to 10, but not both 0 at the same time; R0 is an unsubstituted C1-C12 alkyl group; R1 and R3 are H; R2 and R4 are each independently H, an unsubstituted C1-C12 alkyl group, R6OCH2-; wherein, R6 is an unsubstituted C1-C8 alkyl group; R5 and R5’ are each independently H, -C(=O)R8, -C(=O)NHR9, R8 is an unsubstituted C1-C8 alkyl group or an unsubstituted C2-C8 alkenyl group, and R9 is an unsubstituted C1-C8 alkyl group or 2-acryloyloxyethyl.

2. The benzophenone derivative according to claim 1, characterized in that, n1 and n2 are each independently an integer from 1 to 6.

3. The benzophenone derivative according to claim 1, characterized in that, R0 is an unsubstituted C1-C6 alkyl group.

4. The benzophenone derivative according to claim 1, characterized in that, R0 is methyl or ethyl.

5. The benzophenone derivative according to claim 1, characterized in that, R2 and R4 are each independently H or an unsubstituted C1-C8 alkyl group.

6. The benzophenone derivative according to claim 1, characterized in that, R2 and R4 are each independently H or an unsubstituted C1-C4 alkyl group.

7. The benzophenone derivative according to claim 1, characterized in that, R5 and R5’ are each independently H, -C(=O)R8, -C(=O)NHR9, R8 is an unsubstituted C1-C3 alkyl group, and R9 is an unsubstituted C1-C4 alkyl group or 2-acryloyloxyethyl.

8. The benzophenone derivative according to claim 1, characterized in that, The benzophenone derivative is selected from one of the following compounds: wherein n1 and n2 are each independently an integer from 0 to 10, but not both 0 at the same time; 9. A method for preparing the benzophenone derivative according to any one of claims 1-8, characterized in that, Comprising the following steps: Under the action of a catalyst, reacting the compound shown in formula (2) and the compound shown in formula (3); and Optionally, reacting the obtained reaction product with a capping agent; ； Wherein: R0 is an unsubstituted C1-C12 alkyl group; R 10 、R 11 each independently is H, an unsubstituted C1-C12 alkyl group, or R6OCH2-, where R6 is an unsubstituted C1-C8 alkyl group; The capping agent is selected from R8COOOCR8, R8COCl or R9NCO, and R8 and R9 have the same definitions as in claim 1.

10. The method according to claim 9, characterized in that, R0 is an unsubstituted C1-C6 alkyl group.

11. The method according to claim 9, characterized in that, R0 is methyl or ethyl.

12. The method according to claim 9, characterized in that, R 10 is H, R 11 is H or an unsubstituted C1-C4 alkyl group.

13. The method according to claim 9, wherein The reaction temperature of the compound shown in formula (2) and the compound shown in formula (3) is 80-120 °C, and the reaction time is 40-80 hours; The molar ratio of the compounds of formula (2) and formula (3) is 1:(1-20).

14. The method according to claim 9, wherein The catalyst is selected from base catalysts.

15. The method according to claim 9, wherein The catalyst is selected from hydroxides of alkali metals or alkaline earth metals.

16. The method according to claim 9, wherein The catalyst is selected from sodium hydroxide or potassium hydroxide.

17. The method according to claim 9, wherein The method further comprises the steps of purification and solvent removal after reaction with the capping agent.

18. A photoinitiator composition, wherein Comprising: A photoinitiator for free radical polymerization and a benzophenone derivative as described in any one of claims 1-8; wherein, the photoinitiator for free radical polymerization is selected from benzophenone compounds and thioxanthone compounds.

19. A photocurable composition, wherein Comprising: A photocuring agent component and an ethylenically unsaturated compound capable of free radical polymerization, the photocuring agent component comprising the photocuring agent composition as described in claim 18; wherein, the ethylenically unsaturated compound capable of free radical polymerization 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.

20. The photocurable composition according to claim 19, wherein The addition amount of the benzophenone derivative is 0.1 to 20% of the total weight of the photocurable composition.

21. The photocurable composition according to claim 19, wherein The photoinitiator that can be used for free radical polymerization is selected from at least one of benzophenone, 2-isopropylthioxanthone, photoinitiator Omnipol TX or photoinitiator Omnipol 910.

22. The photocurable composition according to claim 19, wherein The addition amount of the component of the photoinitiator that can be used for free radical polymerization is 0.1-10% of the total weight of the photocurable composition.

23. The photocurable composition according to claim 19, wherein It further includes at least one of a pigment, a filler, a leveling agent, a polymerization inhibitor or a solvent.

24. Use of a photocurable composition according to any one of claims 19 - 23 in food packaging printing, pharmaceutical packaging printing, furniture coating, book printing or advertising printing.

25. A photocured product, wherein The photocured product is formed by photocuring the photocurable composition, wherein the photocurable composition is the photocurable composition according to any one of claims 19-23.

26. The photocured product according to claim 25, wherein The photocured product is selected from any one of coatings, adhesives, and printing inks.

27. A method for curing a photocurable composition, wherein Comprising: Coating the photocurable composition according to any one of claims 19-23 on a substrate; And curing the photocurable composition by using a light source with an emission band in the UV-visible light region.

28. The method according to claim 27, wherein After coating on the substrate, curing the photocurable composition by using UV-visible light radiation with a wavelength of 200 to 425 nm.

29. The method according to claim 28, wherein Curing the photocurable composition by using UV-visible light radiation with a wavelength of 365 to 405 nm.

30. The method according to claim 27, wherein The substrate is selected from wood, paper, plastic, coating or metal.

31. The method according to claim 27, wherein The coating method is selected from offset printing, gravure printing, flexographic printing, inkjet printing or 3D printing.

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