CN116730854A - Benzophenone derivative, preparation method and application thereof - Google Patents

Benzophenone derivative, preparation method and application thereof Download PDF

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Publication number
CN116730854A
CN116730854A CN202210198943.4A CN202210198943A CN116730854A CN 116730854 A CN116730854 A CN 116730854A CN 202210198943 A CN202210198943 A CN 202210198943A CN 116730854 A CN116730854 A CN 116730854A
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alkyl
unsubstituted
optionally substituted
formula
independently
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赵文超
麻忠利
王永林
邵俊峰
王辰龙
胡伟静
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Aijianmeng Anqing Technology Development Co ltd
Insight High Technology Beijing Co Ltd
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Aijianmeng Anqing Technology Development Co ltd
Insight High Technology Beijing Co Ltd
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Priority to CN202210198943.4A priority Critical patent/CN116730854A/en
Priority to PCT/CN2023/079040 priority patent/WO2023165522A1/en
Publication of CN116730854A publication Critical patent/CN116730854A/en
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C221/00—Preparation of compounds containing amino groups and doubly-bound oxygen atoms bound to the same carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C225/00—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones
    • C07C225/22—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light

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  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention relates to a benzophenone derivative, a preparation method and application thereof. The benzophenone derivative has a structure represented by formula (1). The diphenyl ketone derivative can be used as an important co-initiator in a UV photo-curing formula to trigger photopolymerization of unsaturated carbon-carbon double bond compounds together with other photoinitiators. The compound shown in the formula (1) has very low mobility due to the large molecular weight, and is suitable for replacing N, N, N, N-tetraethyl-4, 4' -diaminobenzophenone to be used in the fields of food packaging, printing formulas and the like.

Description

Benzophenone derivative, preparation method and application thereof
Technical Field
The invention relates to the technical field of photo-curing, and relates to a benzophenone derivative, a preparation method and application thereof.
Background
N, N, N, N-tetraethyl-4, 4' -diaminobenzophenone, abbreviated as EMK, is a commonly used high-efficiency photoinitiator and is very important in inks, especially UV-LED curing inks. Methods for synthesizing compounds are reported in patent documents such as CN107686450A, CN112707830A, DE2226039A1 and DE 44077C. In patent EP1078598A1, US2010081071A1, CN105974736A, CN104749882A, CN104710843A, etc., EMK as a co-photoinitiator is used in combination with a hydrogen abstraction type photoinitiator in various compositions to effect photopolymerization. However, the polymer has the defects of small molecular weight and certain toxicity, and is easy to migrate out of the cured material, thereby affecting the stability and safety of the product property.
In practical use of the photo-curing ink, due to pollution problem of the small molecular weight photoinitiator, requirements for the low-volatility and low-mobility photoinitiator are continuously increased along with the increase of the coating dosage, for example, the ink with low odor and low mobility is required to be widely used in civil fields such as paper, floors and the like, and particularly, the material migration amount is limited by stricter detection standards for food and drug packaging materials. Therefore, it is difficult to meet the strict mobility standard requirements, and therefore, the standard is not listed in the list which is allowed to be used, and many users lose efficient formula combination, so that it is difficult to find an alternative technology meeting the standard at one time, which is a difficult problem for the technicians in the industry.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the defect of high migration of the photoinitiator or the auxiliary photoinitiator in the prior art, thereby providing a benzophenone derivative, a preparation method and application thereof.
In order to solve the technical problems, the invention adopts the following technical scheme:
a benzophenone derivative having a structure represented by formula (1):
wherein:
n 1 、n 2 each independently is an integer of 0 to 10 (e.g., 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10), but not simultaneously 0;
R 0 is optionally substituted C1-C12 alkyl;
R 1 、R 3 each independently H, optionally substituted C1-C12 alkyl, R 6 OCH 2 -or-C (=o) R 7 Wherein R is 6 Is optionally substituted C1-C8 alkyl, -CH 2 -CH＝CH 2 Or (b)R 7 Is optionally substituted C1-C8 alkyl;
R 2 、R 4 each independently H, optionally substituted C1-C12 alkyl, R 6 OCH 2 -，-C(＝O)R 7 The method comprises the steps of carrying out a first treatment on the surface of the Wherein R is 6 Is optionally substituted C1-C8 alkyl, -CH 2 -CH＝CH 2 Or (b)R 7 Is optionally substituted C1-C8 alkyl;
R 5 、R 5 ' each independently is H, -C (=O) R 8 、-C(＝O)NHR 9 ，R 8 Is optionally substituted C1-C8 alkyl, optionally substituted C2-C8 alkenyl or optionally substituted C6-C20 aryl, R 9 Is optionally substituted C1-C8 alkyl or 2-acryloyloxyethyl.
The term "substituted" means that any one or more hydrogen atoms on a particular atom is substituted with a substituent, provided that the substituted compound is stable. The term "optionally substituted" means that it may or may not be substituted, and the kind and number of substituents may be arbitrary on the basis of realization unless otherwise specified.
In the present invention, the alkyl group may be a linear alkyl group or a branched alkyl group.
In a preferred embodiment of the invention, n 1 、n 2 Each independently is an integer of 1 to 6. Further alternatively, n 1 、n 2 Each independently is an integer of 0 to 6, and n 1 +n 2 The value of (2) is an integer of 1 to 6.
In the structure shown in the formula (1) of the present invention, two R 0 Identical, and R 0 Is optionally substituted C1-C12 alkyl. Examples of such 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-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-dimethyl-1-butyl, 3-dimethyl-1-butyl, 2-ethyl-1-butyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl and the like. In some embodiments, the alkyl is C1-C10 alkyl, C1-C9 alkyl, C1-C8 alkyl, C1-C7 alkyl, C1-C6 alkyl, C1-C5 alkyl, C1-C4 alkyl, C1-C3 alkyl, C1-C2 alkyl, or C1 alkyl. The R is 0 Preferably unsubstituted C1-C12 alkyl, more preferably unsubstituted C1-C6 alkyl, most preferably methyl or ethyl.
In the structure shown in the formula (1) of the invention, R 1 、R 3 Each independently H, optionally substituted C1-C12 alkyl, R 6 OCH 2 -、-C(＝O)R 7 Wherein R is 6 Is optionally substituted C1-C8 alkyl, CH 2 -CH＝CH 2 Or (b)R 7 Is optionally substituted C1-C8 alkyl;
R 2 、R 4 each independently H, optionally substituted C1-C12 alkyl, R 6 OCH 2 -or-C (=o) R 7 The method comprises the steps of carrying out a first treatment on the surface of the Wherein R is 6 Is optionally substituted C1-C8 alkyl, -CH 2 -CH＝CH 2 Or (b)R 7 Is optionally substituted C1-A C8 alkyl group;
at R 1 、R 3 、R 2 Or R is 4 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-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-dimethyl-1-butyl, 3-dimethyl-1-butyl, 2-ethyl-1-butyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl and the like. In some embodiments, the alkyl is C1-C10 alkyl, C1-C9 alkyl, C1-C8 alkyl, C1-C7 alkyl, C1-C6 alkyl, C1-C5 alkyl, C1-C4 alkyl, C1-C3 alkyl, C1-C2 alkyl, or C1 alkyl.
At R 1 、R 3 、R 2 Or R is 4 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-dimethyl-1-propyl, 2-dimethyl-1-butyl, 3-dimethyl-1-butyl, 2-ethyl-1-butyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl and the like. In some embodiments, alkyl is C1-C8 alkyl, C1-C7 alkyl, C1-C6 alkyl, C1-C5 alkyl, C1-C4 alkyl, C1-C3 alkyl, C1-C2 alkyl, or C1 alkyl.
In a preferred embodiment of the invention, R 1 、R 3 Each independently H, unsubstituted C1-C12 alkyl, R 6 OCH 2 -or-C (=o) R 7 Wherein R is 6 Is unsubstituted C1-C8 alkyl, -CH 2 -CH＝CH 2 Or (b)R 7 Is unsubstituted C1-C8 alkyl, preferably R 1 、R 3 Each independently is H or unsubstituted C1-C8 alkyl, more preferably H.
In one preferred aspect of the inventionIn embodiments, R 2 、R 4 Each independently H, unsubstituted C1-C12 alkyl, R 6 OCH 2 -or-C (=o) R 7 Wherein R is 6 Is unsubstituted C1-C8 alkyl, -CH 2 -CH＝CH 2 Or (b)R 7 Is unsubstituted C1-C8 alkyl, preferably R 2 、R 4 Each independently is H or unsubstituted C1-C8 alkyl, more preferably H or unsubstituted C1-C4 alkyl.
At R 5 Or R is 5 In the' wherein, examples of the C2-C8 alkenyl group 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, 3-methyl-1-butenyl and the like.
Aryl is a cyclic aromatic hydrocarbon that does not contain heteroatoms in the ring. Aryl groups include, but are not limited to, phenyl, octenyl, heptenyl, biphenyl, fluorenyl, phenanthryl, triphenylenyl, pyrenyl, tetracenyl, biphenylenyl, anthracenyl, and naphthyl. Aryl groups may contain 6 to 20 carbons in the ring portion of the group. The aryl group may be unsubstituted or substituted, preferably unsubstituted.
In a preferred embodiment of the invention, R 5 、R 5 ' each independently is H, -C (=O) R 8 、-C(＝O)NHR 9 ，R 8 Is unsubstituted C1-C8 alkyl, unsubstituted C2-C8 alkenyl or unsubstituted C6-C20 aryl, R 9 Is unsubstituted C1-C8 alkyl or 2-acryloyloxyethyl, R 5 、R 5 ' each independently is preferably H, -C (=O) R 8 、-C(＝O)NHR 9 ，R 8 Is unsubstituted C1-C3 alkyl, R 9 Is unsubstituted C1-C4 alkyl or 2-acryloyloxyethyl.
In a preferred embodiment of the present invention, the benzophenone derivative is selected from one of the following compounds:
according to another aspect of the present invention, there is provided a method for preparing a benzophenone derivative as described above, comprising the steps of:
reacting a compound shown in a formula (2) with a compound shown in a formula (3) under the action of a catalyst; and
optionally, reacting the resulting reaction product with a capping agent;
wherein:
R 0 is optionally substituted C1-C12 alkyl, which is substituted with R as described above 0 With the same definition, preferably unsubstituted C1-C12 alkyl, more preferably unsubstituted C1-C6 alkyl, most preferably methyl or ethyl;
R 10 、R 11 each independently H, optionally substituted C1-C12 alkyl, R 6 OCH 2 -or-C (=o) R 7 Wherein R is 6 Is optionally substituted C1-C8 alkyl, -CH 2 -CH＝CH 2 Or (b)R 7 Is optionally substituted C1-C8 alkyl;
the end-capping agent is selected from acid anhydride, acyl chloride and isocyanate, and the acid anhydride is R 8 COOOCR 8 The acyl chloride is R 8 COCl, isocyanideThe acid ester is R 9 NCO, isocyanate is R 9 NCO，R 8 And R is 9 Has the same definition as in formula (1);
the molar ratio of the compounds of formula (2) to formula (3) is 1 (1-20).
When R is 0 In the case of ethyl, the compound of formula (2) has the structure
In the above reaction, the reaction with the end-capping agent is optionally carried out if R in the compound of formula (1) 5 And R is 5 Where' both are H, there is no need to perform a reaction step with the capping agent. R is R 5 And R is 5 When' each is a group other than H, a step of reacting with a blocking agent is required.
In a preferred embodiment of the invention, R 10 、R 11 Each independently is H, unsubstituted C1-C12 alkyl, R 6 OCH 2 -or-C (=o) R 7 Wherein R is 6 Is unsubstituted C1-C8 alkyl, -CH 2 -CH＝CH 2 Or (b)R 7 Is unsubstituted C1-C8 alkyl.
In a preferred embodiment of the invention, R 10 H.
In a preferred embodiment of the invention, R 11 Is H or unsubstituted C1-C4 alkyl.
In a preferred embodiment of the present invention, the reaction temperature of the compound represented by formula (2) and the compound represented by formula (3) is 80 to 120℃and the reaction time is 40 to 80 hours.
In a preferred embodiment of the invention, the catalyst is selected from the group consisting of base catalysts, preferably from the hydroxides of alkali metals or alkaline earth metals, further preferably sodium hydroxide or potassium hydroxide.
In a preferred embodiment of the invention, the process further comprises the step of purifying and removing the solvent after reaction with the capping agent. An exemplary purification method, such as water wash purification, and the solvent removal method is distillation.
In a preferred embodiment of the present invention, the method for preparing the benzophenone derivative comprises the steps of:
mixing a compound shown in a formula (2), a compound shown in a formula (3) and a base catalyst, heating to react under nitrogen or inert atmosphere, cooling after the reaction is finished, adding an organic solvent to dissolve reactants, washing with water to be neutral, and removing the solvent to obtain the benzophenone derivative;
wherein:
R 0 is optionally substituted C1-C12 alkyl, which is substituted with R as described above 0 With the same definition, preferably unsubstituted C1-C12 alkyl, more preferably unsubstituted C1-C6 alkyl, most preferably methyl or ethyl;
R 10 、R 11 each independently H, optionally substituted C1-C12 alkyl, R 6 OCH 2 -or-C (=o) R 7 Wherein R is 6 Is optionally substituted C1-C8 alkyl, -CH 2 -CH＝CH 2 Or (b)R 7 Is optionally substituted C1-C8 alkyl.
Preferably, the molar ratio of the compounds of formula (2) to formula (3) is 1 (1-20).
Preferably, the reaction temperature is 80-120 ℃ and the reaction time is 40-80 hours.
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.
Preferably, the temperature is reduced to 25-40 ℃ after the reaction is finished, and the organic solvent is dichloroethane.
In a preferred embodiment of the present invention, the method for preparing the benzophenone derivative comprises the steps of:
1) mixing a compound shown in a formula (2), a compound shown in a formula (3) and a base catalyst, heating to react under nitrogen or inert atmosphere, cooling after the reaction is finished, adding an organic solvent to dissolve a reactant, washing with water to be neutral, and removing the solvent to obtain a reaction product;
2) Mixing the reaction product obtained in the step 1) with an organic solvent and a blocking agent, heating and stirring for reaction, adding an alkaline solution for washing after the reaction is finished, washing with water to be neutral, and removing the solvent to obtain the benzophenone derivative;
wherein:
R 0 is optionally substituted C1-C12 alkyl, which is substituted with R as described above 0 With the same definition, preferably unsubstituted C1-C12 alkyl, more preferably unsubstituted C1-C6 alkyl, most preferably methyl or ethyl;
R 10 、R 11 each independently H, optionally substituted C1-C12 alkyl, R 6 OCH 2 -or-C (=o) R 7 Wherein R is 6 Is optionally substituted C1-C8 alkyl, -CH 2 -CH＝CH 2 Or (b)R 7 Is optionally substituted C1-C8 alkyl;
the end-capping agent is selected from acid anhydride, acyl chloride and isocyanate, and the acid anhydride is R 8 COOOCR 8 The acyl chloride is R 8 COCl, isocyanate is R 9 NCO, isocyanate is R 9 NCO，R 8 And R is 9 Has the same definition as in formula (1).
Preferably, the molar ratio of the compounds of formula (2) to formula (3) in step 1) is 1 (1-20); the reaction temperature is 80-120 ℃ and the reaction time is 40-80 hours; the alkali catalyst is sodium hydroxide or potassium hydroxide, and the molar ratio of the alkali catalyst to the compound of formula (2) is (0.05-0.2): 1; cooling to 25-40 ℃ after the reaction is finished, wherein the organic solvent is dichloroethane.
Preferably, the organic solvent in the step 2) is dichloroethane, and the mass ratio of the reaction product obtained in the step 1) to the end capping agent is (1-10): (0.5-5); heating and stirring to react at 25-40 ℃ for 10-30h; the alkaline solution can be sodium carbonate solution, and the mass concentration of the sodium carbonate solution is 1-10%.
In a preferred embodiment of the present invention, the method for preparing the benzophenone derivative comprises the steps of:
mixing a compound shown in a formula (2), a compound shown in a formula (3) and a base catalyst, heating to react under nitrogen or inert atmosphere, adding an organic solvent and a blocking agent after the reaction is finished, carrying out heat preservation reaction for 3-6h at 20-30 ℃, washing with water to be neutral after the reaction is finished, and removing the solvent to obtain the benzophenone derivative.
Wherein:
R 0 is optionally substituted C1-C12 alkyl, which is substituted with R as described above 0 With the same definition, preferably unsubstituted C1-C12 alkyl, more preferably unsubstituted C1-C6 alkyl, most preferably methyl or ethyl;
R 10 、R 11 each independently H, optionally substituted C1-C12 alkyl, R 6 OCH 2 -or-C (=o) R 7 Wherein R is 6 Is optionally substituted C1-C8 alkyl, -CH 2 -CH＝CH 2 Or (b)R 7 Is optionally substituted C1-C8 alkyl;
the end-capping agent is selected from acid anhydride, acyl chloride and isocyanate, and the acid anhydride is R 8 COOOCR 8 The acyl chloride is R 8 COCl, isocyanate is R 9 NCO, isocyanate is R 9 NCO，R 8 And R is 9 Has the same definition as in formula (1).
Preferably, the molar ratio of the compounds of formula (2) to formula (3) is 1 (1-20); the reaction temperature is 80-120 ℃ and the reaction time is 40-80 hours; the alkali catalyst is sodium hydroxide or potassium hydroxide, and the molar ratio of the alkali catalyst to the compound of formula (2) is (0.05-0.2): 1; the organic solvent is dichloroethane.
Preferably, the mass ratio of the compound of formula (2) to the capping agent is (1-10): (0.5-5); the method also comprises the step of adding an organic amine, wherein the organic amine is triethylamine, and the molar ratio of the adding amount to the end capping agent is (1-1.2): 1.
In a preferred embodiment of the present invention, the method for preparing the benzophenone derivative comprises the steps of:
mixing a compound shown in the formula (2) with a base catalyst, then placing the mixture in a reaction kettle, introducing nitrogen to replace air in the kettle until the kettle pressure is kept at 0.02-0.03MPa, adding the compound shown in the formula (3), and reacting at the temperature of 80-120 ℃ for 40-80 hours; when the pressure of the kettle is reduced to 0.02-0.03MPa, the kettle is subjected to heat preservation reaction for 2-5 hours; cooling to 25-30 ℃, introducing into alkaline solution, then adding organic solvent and end capping agent, reacting for 2-5 hours at 40-45 ℃, cooling to 25-30 ℃, washing to neutrality, and removing the solvent to obtain the benzophenone derivative;
wherein:
R 0 is optionally substituted C1-C12 alkyl, which is substituted with R as described above 0 With the same definition, preferably unsubstituted C1-C12 alkyl, more preferably unsubstituted C1-C6 alkyl, most preferably methyl or ethyl;
R 10 、R 11 each independently H, optionally substituted C1-C12 alkyl, R 6 OCH 2 Or-C(＝O)R 7 Wherein R is 6 Is optionally substituted C1-C8 alkyl, -CH 2 -CH＝CH 2 Or (b)R 7 Is optionally substituted C1-C8 alkyl;
the end-capping agent is selected from acid anhydride, acyl chloride and isocyanate, and the acid anhydride is R 8 COOOCR 8 The acyl chloride is R 8 COCl, isocyanate is R 9 NCO, isocyanate is R 9 NCO，R 8 And R is 9 Has the same definition as in formula (1).
Preferably, the molar ratio of the compounds of formula (2) to formula (3) is 1 (1-20); the alkali catalyst is sodium hydroxide or potassium hydroxide, and the molar ratio of the alkali catalyst to the compound of formula (2) is (0.05-0.2): 1; the organic solvent is dichloroethane.
Preferably, the mass ratio of the compound of formula (2) to the capping agent is (1-10): (0.5-5); the method also comprises the step of adding an organic amine, wherein the organic amine is triethylamine, and the molar ratio of the adding amount to the end capping agent is (1-1.2): 1.
According to another aspect of the present invention, there is provided a photocurable composition comprising: photoinitiators useful for free radical polymerization and benzophenone derivatives as described above.
According to another aspect of the present invention, there is provided a photocurable composition comprising: a photocurable agent component comprising a photocurable composition as described above and a free radically polymerizable ethylenically unsaturated compound.
In a preferred embodiment of the present invention, the photocurable composition comprises:
(a) Benzophenone derivatives as described above;
(b) Photoinitiators useful for free radical polymerization; and
(c) A free radically polymerizable ethylenically unsaturated compound.
The photocurable composition comprising the aforementioned photoinitiator composition has low mobility.
In a preferred embodiment of the present invention, the component (a) is added in an amount of 0.1 to 20%, such as 1%, 5%, 10%, 15% or 20% of the total weight of the photocurable composition.
In a preferred embodiment of the present invention, the component (b) is selected from one or more of benzophenone (benzophenone compound and its derivative except the present invention), thioxanthone compound, α -hydroxyketone compound, α -aminoketone compound, acylphosphine oxide compound or oxime lipid compound, preferably at least one of macromolecular photoinitiator series products Omnipol TX, omnipol910 or Omnipol TP from benzophenone, 2-isopropyl thioxanthone, IGM resins company, and the like. Preferably, the photoinitiator Omnipol TX, omnipol910 or Omnipol TP is selected from the macromolecular photoinitiator series products Omnipol TX, omnipol910 or Omnipol TP of IGM resins.
In a preferred embodiment of the invention, the component (b) is added in an amount of 0.1 to 10%, for example 0.1%, 2%, 4%, 6%, 8% or 10% of the total weight of the photocurable composition.
Ethylenically unsaturated compounds mean ethylenically unsaturated monomers, oligomers, prepolymers, and mixtures thereof, which are capable of undergoing free radical polymerization.
In a preferred embodiment of the present invention, the component (c) is selected from at least one of epoxy acrylate resin, urethane acrylate resin, polyester acrylate resin, polyether acrylate resin, acrylated polyacrylate, epoxy methacrylate resin, urethane methacrylate resin, polyester methacrylate resin, polyether methacrylate resin, acrylated polymethacrylate, allyl ether compound, acrylate monomer or methacrylate monomer. The acrylate monomers or methacrylate monomers are independently mono-, di-or multi-functional.
The photocurable composition may also contain other additives to meet the performance requirements, such as pigments, fillers, leveling aids, inhibitors, solvents, etc.
According to a further aspect of the present invention there is provided the use of a photocurable composition as described above in food packaging printing, pharmaceutical packaging printing, furniture coating, book printing or advertising printing.
According to still another aspect of the present invention, there is provided a photo-cured product formed by photo-curing a photo-curing composition, wherein the photo-curing composition is the photo-curing composition as described above, preferably the photo-curing product is selected from any one of a paint, an adhesive, a printing ink.
According to still another aspect of the present invention, there is provided a curing method of a photocurable composition, comprising:
coating a photocurable composition as described above on a substrate; and curing the photocurable composition by using a light source with an emission band in the UV-visible region.
Substrates include, but are not limited to: wood, paper, plastic, coating or metal, etc. Coating methods include, but are not limited to: offset printing, gravure printing, flexography printing, inkjet printing, 3D printing, or the like.
Preferably, after application to a substrate, the photocurable composition is cured by irradiation with UV-visible light having a wavelength of 200 to 425nm, preferably by irradiation with UV-visible light having a wavelength of 365 to 405 nm.
The beneficial effects are that:
the invention uses a di (dialkyl amino) diphenyl ketone compound containing hydroxyl and an epoxy compound as raw materials to carry out ring-opening addition reaction to synthesize the EMK derivative with large molecular weight. The obtained diphenyl ketone derivative has the characteristics of good compatibility with a photo-curing system and low mobility. Furthermore, the method is simple and convenient to synthesize, and the hydroxyl can be subjected to further end capping treatment.
The diphenyl ketone derivative can be used as an important co-initiator in a UV photo-curing formula to trigger photopolymerization of unsaturated carbon-carbon double bond compounds together with other photoinitiators. The compound shown in the formula (1) has very low mobility due to the large molecular weight, and is suitable for replacing N, N, N, N-tetraethyl-4, 4' -diaminobenzophenone to be used in the fields of food packaging, printing formulas and the like.
Detailed Description
Experimental raw materials and materials:
HEMK has the structure that
Omnirad DETX is 2, 4-diethylthioxanthone, a product of IGM RESINS company;
omnirad EMK is tetraethyl mikroot ketone, a product of IGM RESINS company;
photomer 4072 is trimethylolpropane propoxy (3) triacrylate, a product of IGM RESINS;
photomer 3316 is a low viscosity modified epoxy acrylate, a product of company IGM RESINS.
Example 1
The present embodiment provides a method for producing a compound represented by formula (4), comprising the steps of:
a100 mL three-necked flask was stirred mechanically, and HEMK1.78g (5 mmol), butyl glycidyl ether 3.90g (30 mmol) and potassium hydroxide 0.028g (0.5 mmol) were added sequentially. After full nitrogen replacement under normal temperature stirring, the nitrogen ball is sealed, the reaction is heated and stirred, the reaction temperature is 120 ℃, and the reaction time is 72 hours. The content of each component is not changed by sampling HPLC detection, the temperature is reduced to 30 ℃, 17.0g of dichloroethane is added to dissolve the reactant, and the reactant is washed to be neutral. The solvent was distilled off under reduced pressure to give 5.40g of the product of formula (4).
Table 1 example 1 results of liquid chromatography-mass spectrometry analysis of the product
Sequence number Retention time min Content% Molecular weight In the formula (4) (n 1 +n 2 ) Value of
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
Example 2
The present embodiment provides a method for producing a compound represented by formula (5), comprising the steps of:
5.40g of the product obtained in example 1 was added with 17.0g of dichloroethane, 1.22g (12 mmol) of acetic anhydride was added, the reaction was heated and stirred at 30℃for 12 hours, and the reaction was carried out by sampling HPLC until the reaction of the product obtained in example 1 was complete. Then, 6.4g of 10% by mass sodium carbonate aqueous solution was added thereto, and the mixture was washed once with water and then washed with water until the mixture became neutral. The solvent was distilled off under reduced pressure to give 5.62g of the product of formula (5).
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Table 2 example 2 results of liquid chromatography-mass spectrometry analysis of the product
Sequence number Retention time min Content% Molecular weight In V (n) 1 +n 2 ) Value of
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
Example 3
The present embodiment provides a method for producing a compound represented by formula (6), comprising the steps of:
a100 mL autoclave was charged with one portion of HEMK17.82g (50 mmol), sodium hydroxide 0.2g (5 mmol), and nitrogen was introduced to replace the air in the autoclave for two minutes until the autoclave pressure was maintained at 0.02MPa. An ethylene oxide steel cylinder with a meter was connected, and 13.22g (300 mmol) of ethylene oxide was slowly introduced, and the reaction temperature was 120℃and the reaction time was 72 hours. After the pressure of the kettle is reduced to 0.02MPa, the reaction is carried out for 4 hours at a temperature. The temperature is reduced to 30 ℃, 10% sodium hydroxide solution is introduced into a connecting pipe at the air outlet, nitrogen is introduced into the air inlet, and unreacted ethylene oxide is slowly blown off and absorbed. After 30 minutes of aeration, the reaction mixture was taken out from the autoclave and was put into a 100ml reaction flask. Dichloroethane (dichloroethane) 85.0g was added and the mixture was washed with water to neutrality. The solvent was stripped off under reduced pressure to give 29.79g of the product of formula (6).
TABLE 3 example 3 results of liquid chromatography-mass spectrometry analysis of the product
Sequence number Retention time min Content% Molecular weight In the formula (6) (n 1 +n 2 ) Value of
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
Example 4
The present embodiment provides a method for producing a compound represented by the formula (7), comprising the steps of:
29.79g of the product obtained in example 3 was added with 85.0g of dichloroethane, 16.94g (120 mmol) of 2-acryloyloxyethyl isocyanate and 12.14g (120 mmol) of triethylamine, and the reaction temperature was 40℃for 4 hours without changing the content of each component. Cooling to 30 ℃, washing to neutrality, decompressing and drying the solvent to obtain 41.17g of the product shown in the formula (7).
TABLE 4 results of liquid chromatography-mass spectrometry analysis of example 4 products
Example 5
The present embodiment provides a method for producing a compound represented by formula (8), comprising the steps of:
a100 mL three-necked flask was stirred mechanically, and 1.78g (5 mmol) of HEMK, 3.90g (30 mmol) of butyl glycidyl ether and 0.003g (0.05 mmol) of potassium hydroxide were added successively. After full nitrogen replacement under normal temperature stirring, the nitrogen ball is sealed, and the reaction is heated and stirred. The reaction temperature is 120 ℃ and the reaction time is 48 hours. The content of each component is not changed by sampling HPLC detection. 17.0g of dichloroethane, 1.09g (12 mmol) of acryloyl chloride, maintaining the temperature at 20℃and 1.22g (12 mmol) of triethylamine are slowly added dropwise, the temperature is raised to 30℃after the completion of the dropwise addition, and the reaction is stirred for 4 hours to complete the reaction of the components. Washing with water to neutrality, and drying the solvent under reduced pressure gives 5.59g of the product of formula (8).
TABLE 5 example 5 results of liquid chromatography-mass spectrometry analysis of the product
Sequence number Retention time min Content% Molecular weight In the formula (8) (n 1 +n 2 ) Value of
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
Example 6
The present embodiment provides a method for producing a compound represented by formula (9), comprising the steps of:
a100 mL three-necked flask was stirred mechanically, and 1.78g (5 mmol) of HEMK, 3.90g (30 mmol) of butyl glycidyl ether and 0.002g (0.05 mmol) of sodium hydroxide were added successively. After full nitrogen replacement under normal temperature stirring, the nitrogen ball is sealed, and the reaction is heated and stirred. The reaction temperature is 120 ℃ and the reaction time is 72 hours. The content of each component is not changed by sampling HPLC detection. 1.19g (12 mmol) of n-butyl isocyanate and 1.21g (12 mmol) of triethylamine are added. The reaction temperature is 40 ℃ and the reaction time is 4 hours, and the components of the etherate are completely reacted. Dichloroethane 17.0g was added and the mixture was washed with water to neutrality. The solvent was stripped off under reduced pressure to give 5.94g of the product of formula (9).
TABLE 6 results of liquid chromatography-Mass Spectrometry analysis of the product of example 6
Example 7
The present embodiment provides a method for producing a compound represented by the formula (10), comprising the steps of:
a100 mL autoclave was charged with one portion of HEMK17.82g (50 mmol), sodium hydroxide 0.2g (5 mmol), and nitrogen was introduced to replace the air in the autoclave for two minutes until the autoclave pressure was maintained at 0.02MPa. 17.42g (300 mmol) of propylene oxide were added, the reaction temperature was 120℃and the reaction time was 72 hours. After the pressure of the kettle is reduced to 0.02MPa, the reaction is carried out for 4 hours at a temperature. The temperature is reduced to 30 ℃, 10% sodium hydroxide solution is introduced into a connecting pipe at the air outlet, nitrogen is introduced into the air inlet, and unreacted propylene oxide is slowly blown off and absorbed. After 30 minutes of aeration, the reaction mixture was taken out from the autoclave and was put into a 100ml reaction flask. Dichloroethane 85.0g was added. 16.94g (120 mmol) of 2-acryloyloxyethyl isocyanate and 12.14g (120 mmol) of triethylamine were added. The reaction temperature is 40 ℃ and the reaction time is 4 hours, and the components are completely reacted. Cooling to 30 ℃, washing to neutrality, decompressing and drying the solvent to obtain 46.90g of the product shown in the formula (10).
TABLE 7 results of liquid chromatography-mass spectrometry analysis of example 7 products
Sequence number Retention time min Content% Molecular weight In the formula (10) (n 1 +n 2 ) Value of
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
Example 8
The present embodiment provides a photocurable composition comprising the following components: photomer 4072 4.8g,Photomer 3316 4.8g, example 1 product of formula (4) 0.2g and Omnirad DETX 0.2g.
The preparation method of the photo-curing composition comprises the following steps: the components are stirred at 60 ℃ until the components are dissolved into a uniform solution, and then cooled to room temperature to prepare the photo-curing composition.
Example 9
The present embodiment provides a photocurable composition comprising the following components: photomer 4072 4.8g,Photomer 3316 4.8g, example 2 product of formula (5) 0.2g and Omnirad DETX 0.2g.
The preparation method of the photo-curing composition comprises the following steps: the components are stirred at 60 ℃ until the components are dissolved into a uniform solution, and then cooled to room temperature to prepare the photo-curing composition.
Example 10
The present embodiment provides a photocurable composition comprising the following components: photomer 4072 4.8g,Photomer 3316 4.8g, example 5 product of formula (8) 0.2g and Omnirad DETX 0.2g.
The preparation method of the photo-curing composition comprises the following steps: the components are stirred at 60 ℃ until the components are dissolved into a uniform solution, and then cooled to room temperature to prepare the photo-curing composition.
Example 11
The present embodiment provides a photocurable composition comprising the following components: photomer 4072 4.8g,Photomer 3316 4.8g, example 7 product of formula (10) 0.2g and Omnirad DETX 0.2g.
The preparation method of the photo-curing composition comprises the following steps: the components are stirred at 60 ℃ until the components are dissolved into a uniform solution, and then cooled to room temperature to prepare the photo-curing composition.
Comparative example 1
This comparative example provides a photocurable composition comprising the following components: photomer 4072 4.8g,Photomer 3316 4.8g,Omnirad EMK 0.2g and Omnirad DETX 0.2g.
The preparation method of the photo-curing composition comprises the following steps: the components are stirred at 60 ℃ until the components are dissolved into a uniform solution, and then cooled to room temperature to prepare the photo-curing composition.
Test case
The photocurable compositions prepared in examples 8-11 and comparative example 1 above were subjected to hardness and cure migration performance tests, respectively:
pendulum hardness test: the above photocurable compositions were each cured one pass at a belt speed of 10m/min on a coated glass plate (under 395nm LED lamp) using a 25 μm bar, and the pendulum hardness after curing was tested.
Mobility test: the photo-curing composition was cured on a piece of paper having a coating length of 5X 20cm using a 25 μm bar at a belt speed of 10m/min under a 395nm LED lamp, and the cured paper was 100cm 2 100g of an aqueous acetic acid solution having a mass content of 3% were placed in the aqueous acetic acid solution and allowed to stand at 40℃for 10 days, and then the photoinitiator component (photoinitiator component means product component of formula (4) of example 1, product component of formula (5) of example 2, product component of formula (8) of example 5, product component of formula (10) of example 7 or Omnirad EMK) which migrated into the aqueous acetic acid solution was quantitatively analyzed by HPLC. The results were calculated using the EU model, assuming 600cm 2 The printed area packages 1kg of food, so the result can be converted into μg/kg, i.e. μg of analyte per kg of food (analyte refers to product of formula (4) of example 1, product of formula (5) of example 2, product of formula (8) of example 5, product of formula (10) of example 7 or Omnirad EMK). The hardness and mobility analysis test results are shown in Table 8.
TABLE 8
Example 8 Example 9 Example 10 Example 11 Comparative example 1
Pendulum hardness 0.78 0.80 0.79 0.77 0.77
Mobility (μg/kg) 85 48 8 7 2180
As can be seen from the test data, the di (dialkylamino) benzophenone compound with an alkoxy side chain provided by the invention is used as a co-initiator for photo-curing compositions compared with the commercially available EMK, and the hardness of the compound provided by the invention is similar to that of a comparison object after curing, so that the compound has similar curing rate, but the mobility is obviously reduced, and particularly the mobility of the compound capped with an acrylate group is less than 10 mug/kg. Therefore, the compound provided by the invention is more suitable for the applications of food and drug packaging, children toys and the like which have strict requirements on the mobility of substances.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. While still being apparent from variations or modifications that may be made by those skilled in the art are within the scope of the invention.

Claims (27)

1. A benzophenone derivative having a structure represented by formula (1):
wherein:
n 1 、n 2 each independently is an integer of 0 to 10, but not simultaneously 0;
R 0 is optionally substituted C1-C12 alkyl;
R 1 、R 3 each independently H, optionally substituted C1-C12 alkyl, R 6 OCH 2 -or-C (=o) R 7 Wherein R is 6 Is optionally substituted C1-C8 alkyl, -CH 2 -CH＝CH 2 Or (b)R 7 Is optionally substituted C1-C8 alkyl;
R 2 、R 4 each independently H, optionally substituted C1-C12 alkyl, R 6 OCH 2 -，-C(＝O)R 7 The method comprises the steps of carrying out a first treatment on the surface of the Wherein R is 6 Is optionally substituted C1-C8 alkyl, -CH 2 -CH＝CH 2 Or (b)R 7 Is optionally substituted C1-C8 alkyl;
R 5 、R 5 ' each independently is H, -C (=O) R 8 、-C(＝O)NHR 9 ，R 8 Is optionally substituted C1-C8 alkyl, optionally substituted C2-C8 alkenyl or optionally substituted C6-C20 aryl, R 9 Is optionally substituted C1-C8 alkyl or 2-acryloyloxyethyl.
2. Benzophenone derivatives according to claim 1, wherein n 1 、n 2 Each independently is an integer of 1 to 6.
3. The benzophenone derivative of claim 1, wherein R 0 Is unsubstituted C1-C12 alkyl, preferably unsubstituted C1-C6 alkyl, more preferably methyl or ethyl.
4. The benzophenone derivative of claim 1, wherein R 1 、R 3 Each independently H, unsubstituted C1-C12 alkyl, R 6 OCH 2 -or-C (=o) R 7 Wherein R is 6 Is unsubstituted C1-C8 alkyl, -CH 2 -CH＝CH 2 Or (b)R 7 Is unsubstituted C1-C8 alkyl, preferably R 1 、R 3 Each independently is H or unsubstituted C1-C8 alkyl, more preferably H.
5. The benzophenone derivative of claim 1, wherein R 2 、R 4 Each independently H, unsubstituted C1-C12 alkyl, R 6 OCH 2 -or-C (=o) R 7 Wherein R is 6 Is unsubstituted C1-C8 alkyl, -CH 2 -CH＝CH 2 Or (b)R 7 Is unsubstituted C1-C8 alkyl, preferably R 2 、R 4 Each independently is H or unsubstituted C1-C8 alkyl, more preferably H or unsubstituted C1-C4 alkyl.
6. The benzophenone derivative of claim 1, wherein R 5 、R 5 ' each independently is H, -C (=O) R 8 、-C(＝O)NHR 9 ，R 8 Is unsubstituted C1-C8 alkyl, unsubstituted C2-C8 alkenyl or unsubstituted C6-C20 aryl, R 9 Is unsubstituted C1-C8 alkyl or 2-acryloyloxyethyl, R 5 、R 5 ' each independently is preferably H, -C (=O) R 8 、-C(＝O)NHR 9 ，R 8 Is unsubstituted C1-C3 alkyl, R 9 Is unsubstituted C1-C4 alkyl or 2-acryloyloxyethyl.
7. The benzophenone derivative of claim 1, wherein the benzophenone derivative is selected from one of the following compounds: wherein n1, n2 are each independently integers from 0 to 10, but are not simultaneously 0;
8. a process for the preparation of a benzophenone derivative according to any one of claims 1 to 7, comprising the steps of:
reacting a compound shown in a formula (2) with a compound shown in a formula (3) under the action of a catalyst; and
optionally, reacting the resulting reaction product with a capping agent;
wherein:
R 0 is optionally substituted C1-C12 alkyl;
R 10 、R 11 each independently H, optionally substituted C1-C12 alkyl, R 6 OCH 2 -or-C (=o) R 7 Wherein R is 6 Is optionally substituted C1-C8 alkyl, -CH 2 -CH＝CH 2 Or (b)R 7 Is optionally substituted C1-C8 alkyl;
the end-capping agent is selected from R 8 COOOCR 8 、R 8 COCl or R 9 NCO，R 8 And R is 9 Has the same definition as in claim 1.
9. The method of claim 8, wherein R 0 Is unsubstituted C1-C12 alkyl, preferably unsubstituted C1-C6 alkyl, more preferably methyl or ethyl.
10. The method of claim 8, wherein R 10 、R 11 Each independently is H, unsubstituted C1-C12 alkyl, R 6 OCH 2 -or-C (=o) R 7 Wherein R is 6 Is unsubstituted C1-C8 alkyl, -CH 2 -CH＝CH 2 Or (b)R 7 Is unsubstituted C1-C8 alkyl, R 10 Preferably H, R 11 Preferably H or unsubstituted C1-C4 alkyl.
11. The method according to claim 8, wherein the reaction temperature of the compound represented by the formula (2) and the compound represented by the formula (3) is 80 to 120 ℃ and the reaction time is 40 to 80 hours;
the molar ratio of the compounds of formula (2) to formula (3) is 1 (1-20).
12. The process according to claim 8, wherein the catalyst is selected from the group consisting of base catalysts, preferably from the hydroxides of alkali metals or alkaline earth metals, further preferably sodium hydroxide or potassium hydroxide.
13. The method of claim 8, further comprising the step of purifying and removing the solvent after reacting with the capping agent.
14. A photo-curing agent composition comprising: photoinitiator useful in free radical polymerization and benzophenone derivatives as claimed in any of claims 1 to 7.
15. A photocurable composition comprising: a photocurable component comprising the photocurable composition of claim 14 and a free-radically polymerizable ethylenically unsaturated compound.
16. The photocurable composition of claim 15, comprising:
(a) Benzophenone derivatives according to any one of claims 1 to 7;
(b) Photoinitiators useful for free radical polymerization; and
(c) A free radically polymerizable ethylenically unsaturated compound.
17. The photocurable composition according to claim 16, wherein said component (a) is added in an amount of 0.1 to 20% by weight based on the total weight of the photocurable composition.
18. A photocurable composition according to claim 16, wherein component (b) is selected from one or more of benzophenone, thioxanthone, α -hydroxyketone, α -aminoketone, acylphosphine oxide or oxime lipid compounds, preferably at least one of benzophenone, 2-isopropylthioxanthone, photoinitiator Omnipol TX, photoinitiator Omnipol910 or photoinitiator Omnipol TP.
19. The photocurable composition according to claim 16, wherein said component (b) is added in an amount of 0.1 to 10% by weight based on the total weight of the photocurable composition.
20. The photocurable composition of claim 16, wherein said component (c) is selected from at least one of epoxy acrylate resins, urethane acrylate resins, polyester acrylate resins, polyether acrylate resins, acrylated polyacrylates, epoxy methacrylate resins, urethane methacrylate resins, polyester methacrylate resins, polyether methacrylate resins, acrylated polymethacrylates, allyl ether compounds, acrylate monomers, or methacrylate monomers.
21. The photocurable composition of claim 16, further comprising at least one of a pigment, a filler, a leveling aid, a polymerization inhibitor, or a solvent.
22. Use of a photocurable composition according to any one of claims 15-21 in food packaging printing, pharmaceutical packaging printing, furniture coating, book printing or advertising printing.
23. A photo-cured product, characterized in that the photo-cured product is formed by photo-curing a photo-curing composition, wherein the photo-curing composition is a photo-curing composition according to any one of claims 15-21, preferably the photo-cured product is selected from any one of a paint, an adhesive, a printing ink.
24. A method of curing a photocurable composition comprising:
applying the photocurable composition of any one of claims 15-21 to a substrate; and curing the photocurable composition by using a light source with an emission band in the UV-visible region.
25. A method according to claim 24, wherein the photocurable composition is cured by UV-visible radiation having a wavelength of 200 to 425nm, preferably by UV-visible radiation having a wavelength of 365 to 405nm, after application to a substrate.
26. The method of claim 24, wherein the substrate is selected from the group consisting of wood, paper, plastic, coating, and metal.
27. The method of claim 24, wherein the coating process is selected from the group consisting of offset printing, gravure printing, flexographic printing, inkjet printing, and 3D printing.
CN202210198943.4A 2022-03-02 2022-03-02 Benzophenone derivative, preparation method and application thereof Pending CN116730854A (en)

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