阅读说明：本技术 叔胺型苯甲酸酯化合物及其制备方法、光固化组合物 (Tertiary amine type benzoate compound, preparation method thereof and photocuring composition ) 是由 钱晓春 胡春青 于培培 于 2020-04-21 设计创作，主要内容包括：本发明提供了一种叔胺型苯甲酸酯化合物及其制备方法、光固化组合物。本申请的叔胺型苯甲酸酯化合物是在4-羧基苯基叔胺型化合物分子结构的4-羧基处引入了低聚合的多官能团结构,一方面增强了叔胺型苯甲酸酯化合物与基体树脂的溶解性,从而使其能够较好的匹配光源以及作为增感剂和其他引发剂配合使用。另一方面低聚合的多官能团结构的引入使得叔胺型苯甲酸酯化合物具有较大的分子量,从而极大地降低了其迁移的可能性。因此包括本申请的叔胺型苯甲酸酯化合物的光固化组合物在保留了原有的4-羧基苯基叔胺型化合物增感剂基本性能的基础上,具有极低的迁移性,从而更好地发挥增感剂加速油墨固化速率、提高光引发剂的感光效率的性能。(The invention provides a tertiary amine type benzoate compound, a preparation method thereof and a photocuring composition. The tertiary amine benzoate compound introduces a low-polymerization multifunctional group structure at the 4-carboxyl of the molecular structure of the 4-carboxyphenyl tertiary amine compound, so that on one hand, the solubility of the tertiary amine benzoate compound and matrix resin is enhanced, and the tertiary amine benzoate compound can be well matched with a light source and used as a sensitizer and other initiators in a matching way. On the other hand, the introduction of a low-polymerized multifunctional structure enables the tertiary amine benzoate compound to have a larger molecular weight, so that the migration possibility of the tertiary amine benzoate compound is greatly reduced. Therefore, the photocuring composition containing the tertiary amine type benzoate compound has extremely low mobility on the basis of keeping the basic performance of the original sensitizer of the 4-carboxyphenyl tertiary amine type compound, so that the performances of accelerating the curing rate of the ink and improving the photosensitive efficiency of a photoinitiator by the sensitizer are better exerted.)

1. A tertiary amine benzoate compound having the following general formula I:

m is an n-valent substituent, and the M isC₁～C₄₀Alkyl of (C)₁～C₄₀Alkylene of (C)₇～C₄₀Aralkyl of (2), C₇～C₆₀Arylalkylene radical, C₃～C₄₀Cycloalkyl of, C₃～C₄₀Cycloalkylene of (2), C₁～C₄₀Alkoxy group of (C)₆～C₆₀Aryl of (C)₁₂～C₆₀Arylene of, C₄～C₁₂Any of the heteroaryl groups of (1), wherein R₅' is H, C₁～C₄₀Alkyl of (C)₃～C₄₀Cycloalkyl of, C₇～C₄₀Aralkyl of (2), C₁～C₄₀Alkoxy group of (C)₆～C₆₀Aryl of (C)₄～C₁₂Any one of the heteroaryl groups of (a);

R₁、R₂each independently is substituted or unsubstituted C₁～C₁₀Alkyl, substituted or unsubstituted C₃～C₁₂Cycloalkyl, substituted or unsubstituted C₇～C₂₀Aralkyl, substituted or unsubstituted C₆～C₂₀And R is any one of the aryl groups of (1), and₁and R₂At least one H on at least one α -C;

R₃、R₄each independently is H, substituted or unsubstituted C ₁～C₁₀Alkyl, substituted or unsubstituted C₁～C₁₀Alkoxy, substituted or unsubstituted C₃～C₁₂Cycloalkyl, substituted or unsubstituted C₆～C₂₀Aryl, substituted or unsubstituted C₄～C₁₂Heteroaryl, substituted or unsubstituted C₇～C₂₀Aralkyl, -NO₂、-CF₃Any one of the above;

R₅、R₆、R₇、R₈each independently is H, substituted or unsubstituted phenyl, substituted or unsubstituted C₁～C₅Alkyl of-NO₂Substituted or unsubstituted C₁～C₅Any one of the alkoxy groups of (a);

n is any integer of 1-3, m is any integer of 1-6, and q is any integer of 0-3.

2. The tertiary amine benzoate compound according to claim 1, wherein R is₁The R is₂Each independently selected from substituted or unsubstituted C₁～C₅Linear alkyl, substituted or unsubstituted C of₁～C₅Branched alkyl, substituted or unsubstituted C₃～C₆Cycloalkyl, substituted or unsubstituted C₇～C₁₀Phenylalkyl, substituted or unsubstituted C₆～C₁₅Preferably said R is₁And said R₂Identical and are all methyl.

3. The tertiary amine benzoate compound according to claim 1, wherein R is₃The R is₄Each independently selected from H, substituted or unsubstituted C₁～C₅Linear alkyl, substituted or unsubstituted C of ₁～C₅Branched alkyl, substituted or unsubstituted C₁～C₅Alkoxy, substituted or unsubstituted C₃～C₆Cycloalkyl, substituted or unsubstituted C₆～C₁₀Phenyl, substituted or unsubstituted C₇～C₁₂Any of the aralkyl groups of (1), preferably the R group₃And said R₄Are identical and are all H.

4. The tertiary amine benzoate compound according to any one of claims 1 to 3, wherein when q is 0, n is 1 or 2,

when n is 1, preferably M is substituted or unsubstituted C₁～C₂₀Linear alkyl, substituted or unsubstituted C of₃～C₂₀Branched alkyl, substituted or unsubstituted C₇～C₂₀Aralkyl, substituted or unsubstituted C₃～C₂₀Cycloalkyl, substituted or unsubstituted C₁～C₂₀Alkoxy, substituted or unsubstituted C₆～C₂₀Aryl, substituted or unsubstituted C₄～C₁₂Any one of the heteroaryl groups of (a); further preferably, M is substituted or unsubstituted C₁～C₁₀Linear alkyl, substituted or unsubstituted C of₃～C₁₀Branched alkyl, substituted or unsubstituted C₇～C₂₀Phenylalkyl of (C), substituted or unsubstituted₁₃～C₂₀Biphenylalkyl group of (A), substituted or unsubstituted C₃～C₁₀Cycloalkyl, substituted or unsubstituted C₁～C₁₀Any one of alkoxy, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted thienyl, substituted or unsubstituted furyl, substituted or unsubstituted pyridyl, and substituted or unsubstituted indolyl of (a);

When n is 2, it is preferable that M is a substituted or unsubstituted C₁～C₂₀Alkylene of (a), substituted or unsubstituted C₇～C₂₀Arylalkylene, substituted or unsubstituted C₃～C₂₀Cycloalkylene group of (1), substituted or unsubstituted C₁₂～C₂₀Any one of the arylene groups of (a); further preferably, M is substituted or unsubstituted C₁～C₁₀Alkylene of (a), substituted or unsubstituted C₇～C₁₂Phenylalkylene group of (A), substituted or unsubstituted C₁₂～C₂₀Biphenylalkylene group of (A), substituted or unsubstituted C₃～C₁₂Cycloalkylene group of (1), substituted or unsubstituted C₁₂～C₂₀Any one of the arylene groups of (a).

5. The tertiary amine benzoate compound according to any one of claims 1 to 3, wherein when q is 1 to 3, n is 3, and M isPreferably said R₅' is H, substituted or unsubstituted C₁～C₂₀Linear alkyl, substituted or unsubstituted C of₃～C₂Branched alkyl, substituted or unsubstituted C₇～C₂₀Aralkyl, substituted or unsubstituted C₃～C₂₀Cycloalkyl, substituted or unsubstituted C₁～C₂₀Alkoxy, substituted or unsubstituted C₆～C₂₀Aryl, substituted or unsubstituted C₄～C₁₂Any one of the heteroaryl groups of (a); further preferably said R₅' is H, substituted or unsubstituted C₁～C₁₀Linear alkyl, substituted or unsubstituted C of₃～C₁₀Branched alkyl, substituted or unsubstituted C ₇～C₂₀Phenylalkyl of (C), substituted or unsubstituted₁₃～C₂₀Biphenylalkyl group of (A), substituted or unsubstituted C₃～C₁₀Cycloalkyl, substituted or unsubstituted C₁～C₁₀The alkoxy group of (a) is any one of a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted thienyl group, a substituted or unsubstituted furyl group, a substituted or unsubstituted pyridyl group, and a substituted or unsubstituted indolyl group.

6. The tertiary amine benzoate compound according to claim 4, wherein n is 2 and M is a substituted or unsubstituted C₁₂～C₂₀Preferably, M is any one of the arylene groups of (a), and

wherein R represents a binding site₁′、R₂′、R₃′、R₄' each is independently selected from H, substituted or unsubstituted C₁～C₂₀Linear alkyl, substituted or unsubstituted C of₃～C₂₀Branched alkyl, substituted or unsubstituted benzeneRadical, substituted or unsubstituted C₃～C₂₀Alkyl cycloalkyl, substituted or unsubstituted C₄～C₂₀Cycloalkylalkyl, substituted or unsubstituted C₂～C₂₀Any one of the alkenyl groups of (1).

7. The tertiary amine benzoate compound according to claim 6, wherein R is₁', the R₂', the R₃' and said R ₄' of-CH₂-said-CH which may each independently be substituted, preferably substituted, by-O-₂The number of-is 1 to 5.

8. The tertiary amine benzoate compound according to claim 1, wherein said tertiary amine benzoate compound has the formula

Any one of them.

9. A production method of a tertiary amine type benzoate compound according to any one of claims 1 to 8, characterized by comprising:

carrying out ring-opening reaction on the compound a and the compound b under an alkaline condition to obtain a tertiary amine type benzoate compound;

wherein, the structural general formula II of the compound a and the structural general formula III of the compound b are as follows:

n, M, q, M, R₁、R₂、R₃、R₄、R₅、R₆、R₇、R₈The same as the n, M, q, M and R in the structural general formula I₁、R₂、R₃、R₄、R₅、R₆、R₇、R₈。

10. The method of manufacturing according to claim 9, comprising:

step S1, mixing the compound a, the compound b, a phase transfer catalyst and a solvent to obtain a mixture;

step S2, reacting the mixture in an alkaline environment for 3-10 hours to obtain the tertiary amine type benzoate compound, preferably, the reaction is carried out at 50-150 ℃, an alkaline solution is adopted to form the alkaline environment, preferably, the alkaline solution is one or more of a sodium hydroxide solution, a potassium hydroxide solution and a lithium hydroxide solution, preferably, the concentration of the alkaline solution is 10-40 wt%, and preferably, the solvent is one or more of dichloroethane, acetonitrile, benzene, toluene and xylene.

11. A photocurable composition comprising a sensitizer, wherein the sensitizer is the tertiary amine benzoate compound of any one of claims 1 to 8.

12. The photocurable composition according to claim 11, wherein the photocurable composition is any one of a coating, an ink, and an adhesive.

Technical Field

The invention relates to the technical field of sensitizers, and particularly relates to a tertiary amine type benzoate compound, a preparation method thereof and a photocuring composition.

Background

Tertiary amine benzoate is a high-efficiency amine accelerator, is usually used together with a hydrogen abstraction photoinitiator, can be used as a sensitizer to promote polymerization of the photoinitiator, can effectively eliminate interference of oxygen on the photoinitiator, and represents products such as N, N-ethyl dimethyl benzoate, N-2-ethyl dimethyl benzoate, dimethylaminoethyl benzoate and the like. However, most of the current tertiary amine benzoate sensitizers do not achieve nearly zero migration.

Disclosure of Invention

The invention mainly aims to provide a tertiary amine type benzoate compound, a preparation method thereof and a photocuring composition, and aims to solve the problem of high mobility of a tertiary amine type benzoate sensitizer in the prior art.

In order to achieve the above object, according to one aspect of the present invention, there is provided a tertiary amine type benzoate compound having the following general formula I:

M is an n-valent substituent and M isC₁～C₄₀Alkyl of (C)₁～C₄₀Alkylene of (C)₇～C₄₀Aralkyl of (2), C₇～C₆₀Arylalkylene radical, C₃～C₄₀Cycloalkyl of, C₃～C₄₀Cycloalkylene of (2), C₁～C₄₀Alkoxy group of (C)₆～C₆₀Aryl of (C)₁₂～C₆₀Arylene of, C₄～C₁₂Any of the heteroaryl groups of (1), wherein R₅' is H, C₁～C₄₀Alkyl of (C)₃～C₄₀Cycloalkyl of, C₇～C₄₀Aralkyl of (2), C₁～C₄₀Alkoxy group of (C)₆～C₆₀Aryl of (C)₄～C₁₂Any one of the heteroaryl groups of (a); r₁、R₂Each independently is substituted or unsubstituted C₁～C₁₀Alkyl, substituted or unsubstituted C₃～C₁₂Cycloalkyl, substituted or unsubstituted C₁～C₁₀Alkoxy, substituted or unsubstituted C₇～C₂₀Aralkyl, substituted or unsubstituted C₆～C₂₀And R is any one of the aryl groups of (1), and₁and R₂At least one H on at least one α -C; r₃、R₄Each independently is H, substituted or unsubstituted C₁～C₁₀Alkyl, substituted or unsubstituted C₁～C₁₀Alkoxy, substituted or unsubstituted C₃～C₁₂Cycloalkyl, substituted or unsubstituted C₆～C₂₀Aryl, substituted or unsubstituted C₄～C₁₂Heteroaryl, substituted or unsubstituted C₇～C₂₀Aralkyl, -NO₂、-CF₃Any one of the above; r₅、R₆、R₇、R₈Each independently is H, substituted or unsubstituted phenyl, substituted or unsubstituted C₁～C₅Alkyl of-NO₂Substituted or unsubstituted C₁～C₅Any one of the alkoxy groups of (a); n is any integer of 1-3, m is any integer of 1-6, and q is any integer of 0-3.

Further, the above R₁、R₂Each independently selected from substituted or unsubstituted C₁～C₅Linear alkyl, substituted or unsubstituted C of₁～C₅Branched alkyl, substituted or unsubstituted C₃～C₆Cycloalkyl, substituted or unsubstituted C₇～C₁₀Phenylalkyl, substituted or unsubstituted C₆～C₁₅Any one of the aryl groups of (1)Preferably R₁And R₂Identical and are all methyl.

Further, the above R₃、R₄Each independently selected from H, substituted or unsubstituted C₁～C₅Linear alkyl, substituted or unsubstituted C of₁～C₅Branched alkyl, substituted or unsubstituted C₁～C₅Alkoxy, substituted or unsubstituted C₃～C₆Cycloalkyl, substituted or unsubstituted C₆～C₁₀Phenyl, substituted or unsubstituted C₇～C₁₂Any of the aralkyl groups of (1), preferably R₃And R₄Are identical and are all H.

Further, when q is 0, n is 1 or 2, and when n is 1, M is preferably substituted or unsubstituted C₁～C₂₀Linear alkyl, substituted or unsubstituted C of₃～C₂₀Branched alkyl, substituted or unsubstituted C₇～C₂₀Aralkyl, substituted or unsubstituted C₃～C₂₀Cycloalkyl, substituted or unsubstituted C₁～C₂₀Alkoxy, substituted or unsubstituted C₆～C₂₀Aryl, substituted or unsubstituted C₄～C₁₂Any one of the heteroaryl groups of (a); further preferably, M is substituted or unsubstituted C₁～C₁₀Linear alkyl, substituted or unsubstituted C of ₃～C₁₀Branched alkyl, substituted or unsubstituted C₇～C₂₀Phenylalkyl of (C), substituted or unsubstituted₁₃～C₂₀Biphenylalkyl group of (A), substituted or unsubstituted C₃～C₁₀Cycloalkyl, substituted or unsubstituted C₁～C₁₀Any one of alkoxy, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted thienyl, substituted or unsubstituted furyl, substituted or unsubstituted pyridyl, and substituted or unsubstituted indolyl of (a); when n is 2, M is preferably substituted or unsubstituted C₁～C₂₀Alkylene of (a), substituted or unsubstituted C₇～C₂₀Aryl alkylene radicalSubstituted or unsubstituted C₃～C₂₀Cycloalkylene group of (1), substituted or unsubstituted C₁₂～C₂₀Any one of the arylene groups of (a); further preferably, M is substituted or unsubstituted C₁～C₁₀Alkylene of (a), substituted or unsubstituted C₇～C₁₂Phenylalkylene group of (A), substituted or unsubstituted C₁₂～C₂₀Biphenylalkylene group of (A), substituted or unsubstituted C₃～C₁₂Cycloalkylene group of (1), substituted or unsubstituted C₁₂～C₂₀Any one of the arylene groups of (a).

Further, when q is 1 to 3, n is 3, and M isPreferably R₅' is H, substituted or unsubstituted C₁～C₂₀Linear alkyl, substituted or unsubstituted C of₃～C₂Branched alkyl, substituted or unsubstituted C ₇～C₂₀Aralkyl, substituted or unsubstituted C₃～C₂₀Cycloalkyl, substituted or unsubstituted C₁～C₂₀Alkoxy, substituted or unsubstituted C₆～C₂₀Aryl, substituted or unsubstituted C₄～C₁₂Any one of the heteroaryl groups of (a); further preferred is R₅' is H, substituted or unsubstituted C₁～C₁₀Linear alkyl, substituted or unsubstituted C of₃～C₁₀Branched alkyl, substituted or unsubstituted C₇～C₂₀Phenylalkyl of (C), substituted or unsubstituted₁₃～C₂₀Biphenylalkyl group of (A), substituted or unsubstituted C₃～C₁₀Cycloalkyl, substituted or unsubstituted C₁～C₁₀The alkoxy group of (a) is any one of a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted thienyl group, a substituted or unsubstituted furyl group, a substituted or unsubstituted pyridyl group, and a substituted or unsubstituted indolyl group.

Further, n is 2, and M is substituted or unsubstitutedC₁₂～C₂₀Preferably M is any one of the arylene groups of (a), a

Wherein R represents a binding site₁′、R₂′、R₃′、R₄' each is independently selected from H, substituted or unsubstituted C₁～C₂₀Linear alkyl, substituted or unsubstituted C of₃～C₂₀A branched alkyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted C₃～C₂₀Alkyl cycloalkyl, substituted or unsubstituted C ₄～C₂₀Cycloalkylalkyl, substituted or unsubstituted C₂～C₂₀Any one of the alkenyl groups of (1).

Further, the above R₁′、R₂′、R₃' and R₄' of-CH₂-CH which is optionally substituted by-O-, preferably substituted₂The number of-is 1 to 5.

Further, the structural formula of the tertiary amine type benzoate compound is

Any one of them.

According to another aspect of the present invention, there is provided a method for preparing the aforementioned tertiary amine type benzoate compound, the method comprising: carrying out ring-opening reaction on the compound a and the compound b under an alkaline condition to obtain a tertiary amine type benzoate compound; wherein, the structural general formula II of the compound a and the structural general formula III of the compound b are as follows:

n、m、q、M、R₁、R₂、R₃、R₄、R₅、R₆、R₇、R₈n, M, q, M and R in the same structural general formula I₁、R₂、R₃、R₄、R₅、R₆、R₇、R₈。

Further, the preparation method comprises the following steps: step S1, mixing the compound a, the compound b, the phase transfer catalyst and the solvent to obtain a mixture; and step S2, reacting the mixture in an alkaline environment for 3-10 h to obtain a tertiary amine type benzoate compound, preferably reacting at 50-150 ℃, and forming the alkaline environment by using an alkaline solution, wherein the alkaline solution is preferably one or more of a sodium hydroxide solution, a potassium hydroxide solution and a lithium hydroxide solution, the concentration of the alkaline solution is preferably 10-40 wt%, and the solvent is preferably one or more of dichloroethane, acetonitrile, benzene, toluene and xylene.

According to still another aspect of the present invention, there is provided a photocurable composition comprising a sensitizer, the sensitizer being the aforementioned tertiary amine type benzoate compound.

Further, the photocurable composition is any one of a coating, an ink, and an adhesive.

By applying the technical scheme of the invention, the tertiary amine is used as a hydrogen donor of the hydrogen extraction type photoinitiator, so that the activity of effective molecules of the photoinitiator can be improved, and the efficiency of photoinitiated polymerization reaction can be promoted to a great extent₅、R₆、R₇、R₈) The introduction of the tertiary amine compound enhances the solubility of the tertiary amine benzoate compound and the matrix resin while keeping the molecular structure of the 4-carboxyphenyl tertiary amine compound, thereby leading the tertiary amine benzoate compound to be better matched with a light source and used as a sensitizer and other initiators. On the other hand, the introduction of a low-polymerized multifunctional structure enables the tertiary amine benzoate compound to have a larger molecular weight, so that the migration possibility of the tertiary amine benzoate compound is greatly reduced. Therefore, the photocuring composition containing the tertiary amine type benzoate compound has extremely low mobility on the basis of keeping the basic performance of the original sensitizer of the 4-carboxyphenyl tertiary amine type compound, so that the performances of accelerating the curing rate of the ink and improving the photosensitive efficiency of a photoinitiator by the sensitizer are better exerted.

Detailed Description

It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail with reference to examples.

As analyzed by the background art, the problem of high mobility of tertiary amine type benzoate sensitizer exists in the prior art, and in order to solve the problem, the invention provides a tertiary amine type benzoate compound, a preparation method thereof and a photocuring composition.

In one exemplary embodiment of the present application, there is provided a tertiary amine benzoate compound having the following general formula I:

m is an n-valent substituent and M isC₁～C₄₀Alkyl of (C)₁～C₄₀Alkylene of (C)₇～C₄₀Aralkyl of (2), C₇～C₆₀Arylalkylene radical, C₃～C₄₀Cycloalkyl of, C₃～C₄₀Cycloalkylene of (2), C₁～C₄₀Alkoxy group of (C)₆～C₆₀Aryl of (C)₁₂～C₆₀Arylene of, C₄～C₁₂Any of the heteroaryl groups of (1), wherein R₅' is H, C₁～C₄₀Alkyl of (C)₃～C₄₀Cycloalkyl of, C₇～C₄₀Aralkyl of (2), C₁～C₄₀Alkoxy group of (C)₆～C₆₀Aryl of (C)₄～C₁₂Any one of the heteroaryl groups of (a); r₁、R₂Each independently is substituted or unsubstituted C₁～C₁₀Alkyl, substituted or unsubstituted C₃～C₁₂Cycloalkyl, substituted or unsubstituted C ₇～C₂₀Aralkyl, substituted or unsubstituted C₆～C₂₀And R is any one of the aryl groups of (1), and₁and R₂At least one H on at least one α -C; r₃、R₄Each independently is H, substituted or unsubstituted C₁～C₁₀Alkyl, substituted or unsubstituted C₁～C₁₀Alkoxy, substituted or unsubstituted C₃～C₁₂Cycloalkyl, substituted or unsubstituted C₆～C₂₀Aryl, substituted or unsubstituted C₄～C₁₂Heteroaryl, substituted or unsubstituted C₇～C₂₀Aralkyl, -NO₂、-CF₃Any one of the above; r₅、R₆、R₇、R₈Each independently is H, substituted or unsubstituted phenyl, substituted or unsubstituted C₁～C₅Alkyl of-NO₂Substituted or unsubstituted C₁～C₅Any one of the alkoxy groups of (a); n is any integer of 1-3, m is any integer of 1-6, and q is any integer of 0-3.

The tertiary amine is used as a hydrogen donor of the hydrogen extraction type photoinitiator, can improve the activity of effective molecules of the photoinitiator, thereby promoting the efficiency of photoinitiated polymerization reaction to a great extent, and the tertiary amine benzoate compound of the applicationThe compound is characterized in that an oligomeric multifunctional structure is introduced at the 4-carboxyl of the molecular structure of the 4-carboxyl phenyl tertiary amine compound, on one hand, an epoxy four-membered ring group and a plurality of functional groups are contained in the oligomeric multifunctional structure (M, R) ₅、R₆、R₇、R₈) The introduction of the tertiary amine compound enhances the solubility of the tertiary amine benzoate compound and the matrix resin while keeping the molecular structure of the 4-carboxyphenyl tertiary amine compound, thereby leading the tertiary amine benzoate compound to be better matched with a light source and used as a sensitizer and other initiators. On the other hand, the introduction of a low-polymerized multifunctional structure enables the tertiary amine benzoate compound to have a larger molecular weight, so that the migration possibility of the tertiary amine benzoate compound is greatly reduced.

Therefore, the photocuring composition containing the tertiary amine type benzoate compound has extremely low mobility on the basis of keeping the basic performance of the original sensitizer of the 4-carboxyphenyl tertiary amine type compound, so that the performances of accelerating the curing rate of the ink and improving the photosensitive efficiency of a photoinitiator by the sensitizer are better exerted.

In order to make the C-centered active aminoalkyl radical more active, R is preferably selected₁、R₂Each independently selected from substituted or unsubstituted C₁～C₅Linear alkyl, substituted or unsubstituted C of₁～C₅Branched alkyl, substituted or unsubstituted C₃～C₆Cycloalkyl, substituted or unsubstituted C₇～C₁₀Phenylalkyl, substituted or unsubstituted C₆～C₁₅Any of the aryl groups of (1), preferably R₁And R ₂Identical and are all methyl.

To reduce R₃、R₄The steric effect of (A) results in a reduction in the efficiency of the reaction of compound a with compound b, preferably R₃、R₄Each independently selected from H, substituted or unsubstituted C₁～C₅Linear alkyl, substituted or unsubstituted C of₁～C₅Branched alkyl, substituted or unsubstituted C₁～C₅Alkoxy, substituted or unsubstituted C₃～C₆Cycloalkyl radicals ofSubstituted or unsubstituted C₆～C₁₀Phenyl, substituted or unsubstituted C₇～C₁₂Any of the aralkyl groups of (1), preferably R₃And R₄Are identical and are all H.

In order to further improve the solubility of the tertiary amine type benzoate compound in the matrix resin, it is preferable that when q is 0, n is 1 or 2, and when n is 1, M is a substituted or unsubstituted C₁～C₂₀Linear alkyl, substituted or unsubstituted C of₃～C₂₀Branched alkyl, substituted or unsubstituted C₇～C₂₀Aralkyl, substituted or unsubstituted C₃～C₂₀Cycloalkyl, substituted or unsubstituted C₁～C₂₀Alkoxy, substituted or unsubstituted C₆～C₂₀Aryl, substituted or unsubstituted C₄～C₁₂Any one of the heteroaryl groups of (a); further preferably, M is substituted or unsubstituted C₁～C₁₀Linear alkyl, substituted or unsubstituted C of₃～C₁₀Branched alkyl, substituted or unsubstituted C₇～C₂₀Phenylalkyl of (C), substituted or unsubstituted₁₃～C₂₀Biphenylalkyl group of (A), substituted or unsubstituted C ₃～C₁₀Cycloalkyl, substituted or unsubstituted C₁～C₁₀The alkoxy group of (a) is any one of a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted thienyl group, a substituted or unsubstituted furyl group, a substituted or unsubstituted pyridyl group, and a substituted or unsubstituted indolyl group. When n is 2, M is preferably substituted or unsubstituted C₁～C₂₀Alkylene of (a), substituted or unsubstituted C₇～C₂₀Arylalkylene, substituted or unsubstituted C₃～C₂₀Cycloalkylene group of (1), substituted or unsubstituted C₁₂～C₂₀Any one of the arylene groups of (a); further preferably, M is substituted or unsubstituted C₁～C₁₀Alkylene of (a), substituted or unsubstituted C₇～C₁₂Phenylalkylene group of (A), substituted or unsubstituted C₁₂～C₂₀Biphenylene ofAlkyl, substituted or unsubstituted C₃～C₁₂Cycloalkylene group of (1), substituted or unsubstituted C₁₂～C₂₀Any one of the arylene groups of (a).

In order to further improve the sensitivity of the tertiary amine type benzoate compound and expand the color sensitivity range thereof so as to meet more requirements on the performance of the photocuring composition, when q is 1-3, n is 3, and M isPreferably R₅' is H, substituted or unsubstituted C₁～C₂₀Linear alkyl, substituted or unsubstituted C of₃～C₂Branched alkyl, substituted or unsubstituted C ₇～C₂₀Aralkyl, substituted or unsubstituted C₃～C₂₀Cycloalkyl, substituted or unsubstituted C₁～C₂₀Alkoxy, substituted or unsubstituted C₆～C₂₀Aryl, substituted or unsubstituted C₄～C₁₂Any one of the heteroaryl groups of (a); further preferred is R₅' is H, substituted or unsubstituted C₁～C₁₀Linear alkyl, substituted or unsubstituted C of₃～C₁₀Branched alkyl, substituted or unsubstituted C₇～C₂₀Phenylalkyl of (C), substituted or unsubstituted₁₃～C₂₀Biphenylalkyl group of (A), substituted or unsubstituted C₃～C₁₀Cycloalkyl, substituted or unsubstituted C₁～C₁₀The alkoxy group of (a) is any one of a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted thienyl group, a substituted or unsubstituted furyl group, a substituted or unsubstituted pyridyl group, and a substituted or unsubstituted indolyl group.

In one embodiment of the present application, n is 2, and M is substituted or unsubstituted C₁₂～C₂₀Preferably M is any one of the arylene groups of (a), a

Wherein R represents a binding site₁′、R₂′、R₃′、R₄' each is independently selected from H, substituted or unsubstituted C₁～C₂₀Linear alkyl, substituted or unsubstituted C of₃～C₂₀A branched alkyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted C ₃～C₂₀Alkyl cycloalkyl, substituted or unsubstituted C₄～C₂₀Cycloalkylalkyl, substituted or unsubstituted C₂～C₂₀Any one of the alkenyl groups of (1).

When n is 2, M further enriches the functional group structure of the tertiary amine benzoate compound, thereby improving the modification property of the compound a (4-carboxyphenyl tertiary amine compound) and enabling the tertiary amine benzoate compound to have more excellent performance.

In order to further enrich the types of the arylene-substituted functional groups, the above R is preferably₁′、R₂′、R₃' and R₄' of-CH₂-CH which is optionally substituted by-O-, preferably substituted₂The number of-is 1 to 5.

In one embodiment of the present application, the tertiary amine benzoate compound has the formula

Any one of them.

The tertiary amine type benzoate compound has a substituted or unsubstituted substituent with a valence of 1 to 3 besides abundant substituted functional groups, and can meet the requirements of various photocuring compositions.

In another exemplary embodiment of the present application, there is provided a method for preparing the aforementioned tertiary amine type benzoate compound, the method comprising: carrying out ring-opening reaction on the compound a and the compound b under an alkaline condition to obtain a tertiary amine type benzoate compound; wherein, the structural general formula II of the compound a and the structural general formula III of the compound b are as follows:

n、m、q、M、R₁、R₂、R₃、R₄、R₅、R₆、R₇、R₈N, M, q, M and R in the same structural general formula I₁、R₂、R₃、R₄、R₅、R₆、R₇、R₈。

The method adopts a common 4-carboxyphenyl tertiary amine compound (compound a) and a polyfunctional group oligomer compound (compound b) with three-membered ring and four-membered ring to carry out one-step cyclization reaction under alkaline condition to obtain a tertiary amine benzoate compound with larger molecular weight, thereby modifying the molecule of the 4-carboxyphenyl tertiary amine compound, wherein the reaction general formula is as follows:

the synthesis method is simple, and the tertiary amine type benzoate compound of the application introduces an oligomeric multifunctional group structure at the 4-carboxyl of the molecular structure of the 4-carboxyphenyl tertiary amine type compound, and on the one hand, the oligomeric multifunctional group structure contains epoxy four-membered ring group and a plurality of functional groups (M, R)₅、R₆、R₇、R₈) The introduction of (2) enhances the tertiary amine type benzoate compound and the matrix resin while retaining the molecular structure of the 4-carboxyphenyl tertiary amine type compoundThe solubility of the compound is good, so that the compound can be better matched with a light source and used as a sensitizer and other initiators. On the other hand, the introduction of a low-polymerized multifunctional structure enables the tertiary amine benzoate compound to have a larger molecular weight, so that the migration possibility of the tertiary amine benzoate compound is greatly reduced.

Therefore, the photocuring composition containing the tertiary amine type benzoate compound has extremely low mobility on the basis of keeping the basic performance of the original sensitizer of the 4-carboxyphenyl tertiary amine type compound, so that the performances of accelerating the curing rate of the ink and improving the photosensitive efficiency of a photoinitiator by the sensitizer are better exerted.

In order to improve the synthesis efficiency of the tertiary amine type benzoate compound, it is preferable that the above preparation method comprises: step S1, mixing the compound a, the compound b, the phase transfer catalyst and the solvent to obtain a mixture; and step S2, reacting the mixture in an alkaline environment for 3-10 h to obtain a tertiary amine type benzoate compound, preferably reacting at 50-150 ℃, and forming the alkaline environment by using an alkaline solution, wherein the alkaline solution is preferably one or more of a sodium hydroxide solution, a potassium hydroxide solution and a lithium hydroxide solution, the concentration of the alkaline solution is preferably 10-40 wt%, and the solvent is preferably one or more of dichloroethane, acetonitrile, benzene, toluene and xylene.

In yet another exemplary embodiment of the present application, there is provided a photocurable composition including a sensitizer which is any one of the sensitizers described above.

The light-cured composition prepared by the tertiary amine type benzoate compound has excellent performance.

In still another embodiment of the present application, the photocurable composition is any one of a coating, an ink, and an adhesive.

The photocurable composition of the present application has excellent properties as a tertiary amine sensitizer as well as extremely low migration as any of a coating, an ink, and an adhesive.

The following description will explain advantageous effects of the present application with reference to specific examples.

Example 1

50mL of toluene, 16.5g of a compound 1a, 30.2 g of a compound 1b and 0.5g of tetrabutylammonium bromide are added into a 250mL four-neck flask, the mixture is stirred and heated to 100 ℃, 40g of a 1% sodium hydroxide solution is slowly and dropwise added, the stirring is continued for 5h after 30min, and the reaction is stopped. And when the temperature of the system is reduced to room temperature, 60g of water is added, the system is layered, an organic layer is separated, and the organic layer is washed 3 times by 200g of water until the organic layer is neutral. The organic phase was poured into a 250mL four-necked flask, and the solvent was distilled off to obtain a yellow viscous liquid, i.e., tertiary amine benzoate Compound 1. MS (M/z):468(M +1) +.

Example 2

50mL of toluene, 16.5g of a compound 1a, 35.5 g of a compound 2b and 0.5g of tetrabutylammonium bromide are added into a 250mL four-neck flask, the mixture is stirred and heated to 100 ℃, 40g of a 1% sodium hydroxide solution is slowly and dropwise added, the stirring is continued for 5h after 30min, and the reaction is stopped. And when the temperature of the system is reduced to room temperature, 60g of water is added, the system is layered, an organic layer is separated, and the organic layer is washed 3 times by 200g of water until the organic layer is neutral. The organic phase was poured into a 250mL four-necked flask, and the solvent was distilled off to obtain a yellow viscous liquid, i.e., tertiary amine benzoate compound 2. MS (M/z) 1015(M +1) +.

Example 3

50mL of toluene, 16.5g of a compound 1a, 3b25.9g of the compound and 0.5g of tetrabutylammonium bromide are added into a 250mL four-neck flask, the mixture is stirred and heated to 100 ℃, 40g of 1% sodium hydroxide solution is slowly and dropwise added, the stirring is continued for 5h after 30min, and the reaction is stopped. And when the temperature of the system is reduced to room temperature, 60g of water is added, the system is layered, an organic layer is separated, and the organic layer is washed 3 times by 200g of water until the organic layer is neutral. The organic phase was poured into a 250mL four-necked flask, and the solvent was distilled off to obtain a yellow viscous liquid, i.e., tertiary amine benzoate compound 3. MS (M/z) 1303(M +1) +.

The substrates were replaced and the reaction conditions were adjusted in a similar manner to those in examples 1 to 3 to obtain the corresponding tertiary amine benzoate compounds, and the substrates in all examples are shown in Table 1 and the corresponding tertiary amine benzoate compounds prepared in all examples are shown in Table 2, respectively.

The following experimental starting materials and their sources were used:

4- (N, N-dimethylamino) benzoic acid, compound b, is commercially available or synthesized by known synthetic methods, and the specific synthetic method can be obtained by referring to the synthetic method disclosed in Chinese patent application publication No. CN 107619399A.

TABLE 1

TABLE 2

Photocurable compositions were prepared according to the composition of table 3:

TABLE 3

Any of the tertiary amine type benzoate compounds obtained in examples 1 to 14, EDAB (Shanghai photokosher Co., Ltd.), or DMB (Shanghai photokosher Co., Ltd.) was used as a sensitizer to prepare corresponding photocurable compositions (flexographic ink formulations) 1 to 16 in the proportions shown in Table 3, and their properties were evaluated by the following property test methods and the test results are shown in Table 4.

And (3) sensitivity testing:

about 1mg of each of the above photocurable compositions was weighed and spread in an aluminum crucible, and each of the photocurable compositions was cured by scanning using a Perkin Elmer differential scanning calorimeter (DSC8000) equipped with a mercury arc lamp ultraviolet light source (OmniCure-S2000). The time to maximum cure exotherm from UV initiation was recorded, with shorter time to peak indicating better cure performance.

Evaluation of migration:

using ethanol as solvent, respectively preparing sensitizer into 1 × 10^-5measuring the absorption peak of the solution in mol/L by a UV3010 ultraviolet spectrophotometer; 0.05g of the cured film prepared by the photocuring composition under a high-pressure mercury lamp is respectively weighed and soaked in 30g of ethanol, the soaked solution is taken out after being placed for 24 hours at normal temperature, the absorption peak at the maximum absorption wavelength of the soaked solution is measured by an ultraviolet spectrophotometer, and whether the two are overlapped at the maximum absorption position or not is observed, and if so, migration is shown.

TABLE 4

From the above description, it can be seen that the above-described embodiments of the present invention achieve the following technical effects:

the tertiary amine is used as a hydrogen donor of the hydrogen extraction type photoinitiator, can improve the activity of effective molecules of the photoinitiator, thereby promoting the efficiency of photoinitiated polymerization reaction to a great extent, and the tertiary amine benzoate compound of the application isAn oligomeric multifunctional structure is introduced at the 4-carboxyl of the molecular structure of the 4-carboxyphenyl tertiary amine compound, on the one hand, an epoxy tetracyclic group and various functional groups (M, R)₅、R₆、R₇、R₈) The introduction of the tertiary amine compound enhances the solubility of the tertiary amine benzoate compound and the matrix resin while keeping the molecular structure of the 4-carboxyphenyl tertiary amine compound, thereby leading the tertiary amine benzoate compound to be better matched with a light source and used as a sensitizer and other initiators. On the other hand, the introduction of a low-polymerized multifunctional structure enables the tertiary amine benzoate compound to have a larger molecular weight, so that the migration possibility of the tertiary amine benzoate compound is greatly reduced.

Therefore, the photocuring composition containing the tertiary amine type benzoate compound has extremely low mobility on the basis of keeping the basic performance of the original sensitizer of the 4-carboxyphenyl tertiary amine type compound, so that the performances of accelerating the curing rate of the ink and improving the photosensitive efficiency of a photoinitiator by the sensitizer are better exerted.

The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.