CN108117488A - Cinnamic acid benzoyl first ester type compound and its preparation method and application - Google Patents
Cinnamic acid benzoyl first ester type compound and its preparation method and application Download PDFInfo
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- C07C69/612—Esters of carboxylic acids having a carboxyl group bound to an acyclic carbon atom and having a six-membered aromatic ring in the acid moiety
- C07C69/618—Esters of carboxylic acids having a carboxyl group bound to an acyclic carbon atom and having a six-membered aromatic ring in the acid moiety having unsaturation outside the six-membered aromatic ring
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Abstract
Cinnamic acid benzoyl first ester type compound and its preparation method and application.The present invention relates to the cinnamic acid benzoyl first ester type compound of formula (I), wherein R1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11、R12、R13And R14It is defined as in the description.The invention further relates to a kind of method for preparing cinnamic acid benzoyl first ester type compound of the present invention, including formula (II) compound is made to carry out esterification with formula (III) compound.The compounds of this invention can be used as photoinitiator, the radiant heat in the range of 200 350nm can be absorbed, had good stability, color inhibition, and what is more important, such initiator is compared to existing α monohydroxies ketone-type photoinitiators, the problem of substantially improving peculiar smell and strong migration.The invention further relates to purposes of the cinnamic acid benzoyl first ester type compound of the present invention as photoinitiator.
Description
Technical field
The present invention relates to cinnamic acid benzoyl first ester type compound, such compound can be used as photoinitiator, the present invention
Further relate to the preparation and application of cinnamic acid benzoyl first ester type compound.
Background technology
Photoinitiator is also known as photosensitizer or light curing agent, is that one kind can be in ultraviolet region (250-400nm) or visible region
(400-600nm) absorbs the energy of certain wavelength, generates free radicals, cation etc., so as to trigger monomer polymerization crosslinking curing
Compound.In photocuring system, photoinitiator typically constitutes from 3-5%, though content is low, is key component therein, light is consolidated
Change speed to play a decisive role.It is related to formula system when light irradiates, oligomer and diluent can rapid crosslinking curing, from
And solid-state is changed by liquid.At present, photocuring technology has been widely used leads in the tradition such as coating, ink, microelectronics, printing
In addition domain is additionally operable to prepare the new field such as laser video recording and three-D elements.It is light-initiated as the important component of photocuring system
Agent must is fulfilled for different photo curing conditions and the needs of application.In free radical photo-initiation field, main target is：It improves photosensitive
Sensitivity improves surface cure efficiency (resistance to the oxygen inhibiting polymerization), improves deep cure performance, improves photoinitiator in monomer and resin
Dissolubility reduces toxicity and smell, reduces the migration of uncured initiator after curing, and reduces xanthochromia.
α-monohydroxy ketone-type photoinitiators are common photoinitiators, and one of the most common is (the 2- hydroxyls of photoinitiator 1173
Base -2- methyl-1s-phenylacetone) and 184 (1- hydroxycyclohexyl phenyl ketones).Photoinitiator 1173 is liquid, easy to use,
It is main initiator in all kinds of photocuring varnish, good heat stability, yellowing resistance is good, and price is relatively low；Shortcoming is mainly photodissociation
Benzaldehyde present in product has bad smell, while volatility is larger, and migration is strong.Photoinitiator 184 is white powder, is waved
Hair property it is relatively low, but equally exist photolytic product have it is different hide with migration it is strong the problem of.
Eastman-Kodak companies in 1954 have produced earliest with the photoetching that synthesis macromolecule is raw material in the world
Glue-polyvinyl cinnamate system negative photoresist (US 2690966).This is that the mankind apply the light in electronics industry at first
Photoresist, the principle of photopolymerization reaction are shown below：
Double bond in cinnamoyl is opened under action of ultraviolet light, and the double bond on different molecular interacts to form quaternary
Ring generates photodimerization crosslinking.In this way, the intermolecular of exposure region crosslinks, the build net structure of indissoluble, unexposed area are formed
Molecular property it is constant, in developer solution generate dissolving sex differernce.Exactly microfabrication can be realized using this characteristic.
The content of the invention
In view of the above-mentioned condition of the prior art, the present inventor has carried out extensively and has been goed deep into photoinitiator field
Research, to find a kind of peculiar smell that can improve α-monohydroxy ketone-type photoinitiators and the strong photoinitiator of migration.This
Inventor has found, if cinnamoyl is introduced or connect on α-monohydroxy ketone-type photoinitiators, using cinnamoyl ultraviolet
Polymerizable crosslinked characteristic under light, so obtained photoinitiator are same remain α-monohydroxy ketone-type photoinitiators the advantages of
When the problem of further improving α-peculiar smell of monohydroxy ketone-type photoinitiators and strong migration.The present invention is based on foregoing find
To realize.
Therefore, it is an object of the present invention to provide a kind of new cinnamic acid benzoyl first ester type compounds.Such is changed
It closes object and can be used as photoinitiator, the radiant heat in the range of 200-350nm can be absorbed, had good stability, color inhibition, and more
Importantly, such initiator compared to existing α-monohydroxy ketone-type photoinitiators, substantially improves peculiar smell and migration is strong
Problem.
It is a further object to provide a kind of sides for preparing cinnamic acid benzoyl first ester type compound of the present invention
Method.
A further object of the present invention is to provide cinnamic acid benzoyl first ester type compound of the present invention as photoinitiator
Purposes.Using cinnamic acid benzoyl first ester type compound of the present invention as photoinitiator, compared to existing α-monohydroxy ketone
Photoinitiator, the problem of substantially improving peculiar smell and strong migration.
Realizing the technical solution of above-mentioned purpose of the present invention can be summarized as follows：
1. cinnamic acid benzoyl first ester type compound has structure shown in formula (I)：
Wherein
R1、R2、R3、R4And R5It is independently from each other hydrogen, halogen, nitro, hydroxyl, sulfydryl, carboxyl, sulfonic group, amino, cyanogen
Base, C1-C20Alkyl, C2-C20Alkenyl, C2-C20Alkynyl, C3-C20Cycloalkyl, C4-C20Cycloalkyl-alkyl, C1-C20Alkoxy, C2-
C20Alkenyloxy group, C2-C20Alkynyloxy group, C3-C20Cycloalkyloxy, C4-C20Cycloalkyl alkoxy, C1-C20Alkylthio group, C2-C20Alkenylthio group,
C2-C20Alkynes sulfenyl, C3-C20Cycloalkylthio, C4-C20Alkylthio cycloalkyl and C6-C18Aryl, wherein foregoing C1-C20Alkyl, C2-
C20Alkenyl, C2-C20Alkynyl, C3-C20Cycloalkyl, C4-C20Cycloalkyl-alkyl, C1-C20Alkoxy, C2-C20Alkenyloxy group, C2-C20Alkynes
Oxygroup, C3-C20Cycloalkyloxy, C4-C20Cycloalkyl alkoxy, C1-C20Alkylthio group, C2-C20Alkenylthio group, C2-C20Alkynes sulfenyl, C3-
C20Cycloalkylthio, C4-C20Alkylthio cycloalkyl and C6-C18Aryl group is optionally independently selected by one or more from the following group
Group substitution：Halogen, nitro, hydroxyl, sulfydryl, carboxyl, sulfonic group, amino, cyano, C1-C6Alkyl, C1-C6Alkoxy, C1-
C6Alkylthio group, C2-C6Alkenyl and C2-C6Alkynyl；
R6And R7It is identical or different and selected from H, C1-C6Alkyl and halogenated C1-C6Alkyl or R6And R7It is connected with them
Carbon atom form C together3-C8Cycloalkyl；
R8、R9、R10、R11And R12Be independently from each other hydrogen, halogen, nitro, hydroxyl, sulfydryl, carboxyl, sulfonic group, amino,
Cyano, C1-C20Alkyl, C2-C20Alkenyl, C2-C20Alkynyl, C3-C20Cycloalkyl, C4-C20Cycloalkyl-alkyl, C1-C20Alkoxy,
C2-C20Alkenyloxy group, C2-C20Alkynyloxy group, C3-C20Cycloalkyloxy, C4-C20Cycloalkyl alkoxy, C1-C20Alkylthio group, C2-C20Alkene sulphur
Base, C2-C20Alkynes sulfenyl, C3-C20Cycloalkylthio, C4-C20Alkylthio cycloalkyl and C6-C18Aryl, wherein foregoing C1-C20Alkyl,
C2-C20Alkenyl, C2-C20Alkynyl, C3-C20Cycloalkyl, C4-C20Cycloalkyl-alkyl, C1-C20Alkoxy, C2-C20Alkenyloxy group, C2-C20
Alkynyloxy group, C3-C20Cycloalkyloxy, C4-C20Cycloalkyl alkoxy, C1-C20Alkylthio group, C2-C20Alkenylthio group, C2-C20Alkynes sulfenyl,
C3-C20Cycloalkylthio, C4-C20Alkylthio cycloalkyl and C6-C18Aryl group is optionally independently selected by one or more from
The group substitution of the following group：Halogen, nitro, hydroxyl, sulfydryl, carboxyl, sulfonic group, amino, cyano, C1-C6Alkyl, C1-C6Alcoxyl
Base, C1-C6Alkylthio group, C2-C6Alkenyl and C2-C6Alkynyl；And
R13And R14It is identical or different and selected from H, C1-C6Alkyl and halogenated C1-C6Alkyl.
2. according to the compound of the 1st, wherein R6And R7It is identical or different and selected from H, C1-C4Alkyl and halogenated C1-C4Alkane
Base or R6And R7Carbon atom connected to them forms C together5-C6Cycloalkyl.
3. according to the compound of the 2nd, wherein R6And R7It is identical and be methyl or halogenated methyl or R6And R7With them
The carbon atom connected forms cyclopenta or cyclohexyl together.
4. according to the compound of any one of 1-3, wherein R13And R14It is identical or different and selected from H, C1-C4Alkyl and
Halogenated C1-C4Alkyl, preferably R13And R14It is H.
5. according to the compound of any one of 1-4, wherein
R1、R2、R3、R4And R5It is independently from each other hydrogen, halogen, nitro, hydroxyl, sulfydryl, carboxyl, sulfonic group, amino, cyanogen
Base, C1-C6Alkyl, C2-C6Alkenyl, C2-C6Alkynyl, C3-C8Cycloalkyl, C4-C8Cycloalkyl-alkyl, C1-C6Alkoxy, C2-C6Alkene oxygen
Base, C2-C6Alkynyloxy group, C3-C8Cycloalkyloxy, C4-C8Cycloalkyl alkoxy, C1-C6Alkylthio group, C2-C6Alkenylthio group, C2-C6Alkynes sulphur
Base, C3-C8Cycloalkylthio, C4-C8Alkylthio cycloalkyl and C6-C10Aryl, wherein foregoing C1-C6Alkyl, C2-C6Alkenyl, C2-C6
Alkynyl, C3-C8Cycloalkyl, C4-C8Cycloalkyl-alkyl, C1-C6Alkoxy, C2-C6Alkenyloxy group, C2-C6Alkynyloxy group, C3-C8Cycloalkanes oxygen
Base, C4-C8Cycloalkyl alkoxy, C1-C6Alkylthio group, C2-C6Alkenylthio group, C2-C6Alkynes sulfenyl, C3-C8Cycloalkylthio, C4-C8Cycloalkanes
Base alkylthio group and C6-C10Aryl group is optionally independently selected by one or more from the group substitution of the following group：Halogen, nitre
Base, hydroxyl, sulfydryl, carboxyl, sulfonic group, amino, cyano, C1-C4Alkyl, C1-C4Alkoxy, C1-C4Alkylthio group, C2-C4Alkenyl and
C2-C4Alkynyl；And/or
R8、R9、R10、R11And R12Be independently from each other hydrogen, halogen, nitro, hydroxyl, sulfydryl, carboxyl, sulfonic group, amino,
Cyano, C1-C6Alkyl, C2-C6Alkenyl, C2-C6Alkynyl, C3-C8Cycloalkyl, C4-C8Cycloalkyl-alkyl, C1-C6Alkoxy, C2-C6Alkene
Oxygroup, C2-C6Alkynyloxy group, C3-C8Cycloalkyloxy, C4-C8Cycloalkyl alkoxy, C1-C6Alkylthio group, C2-C6Alkenylthio group, C2-C6Alkynes
Sulfenyl, C3-C8Cycloalkylthio, C4-C8Alkylthio cycloalkyl and C6-C10Aryl, wherein foregoing C1-C6Alkyl, C2-C6Alkenyl, C2-
C6Alkynyl, C3-C8Cycloalkyl, C4-C8Cycloalkyl-alkyl, C1-C6Alkoxy, C2-C6Alkenyloxy group, C2-C6Alkynyloxy group, C3-C8Cycloalkanes
Oxygroup, C4-C8Cycloalkyl alkoxy, C1-C6Alkylthio group, C2-C6Alkenylthio group, C2-C6Alkynes sulfenyl, C3-C8Cycloalkylthio, C4-C8Ring
Alkylthioalkyl and C6-C10Aryl group is optionally independently selected by one or more from the group substitution of the following group：Halogen, nitre
Base, hydroxyl, sulfydryl, carboxyl, sulfonic group, amino, cyano, C1-C4Alkyl, C1-C4Alkoxy, C1-C4Alkylthio group, C2-C4Alkenyl and
C2-C4Alkynyl.
6. according to the compound of any one of 1-4, wherein
R1、R2、R3、R4And R5It is independently from each other hydrogen, halogen, C1-C4Alkyl, C1-C4Alkoxy and C1-C4Alkylthio group,
Wherein foregoing C1-C4Alkyl, C1-C4Alkoxy and C1-C4Alkylthio group is optionally independently selected by one or more from the following group
Group substitutes：Halogen, C1-C4Alkyl, C1-C4Alkoxy and C1-C4Alkylthio group；And/or
R8、R9、R10、R11And R12It is independently from each other hydrogen, halogen, C1-C4Alkyl, C2-C4Alkenyl, C2-C4Alkynyl, C1-
C4Alkoxy and C1-C4Alkylthio group, wherein foregoing C1-C4Alkyl, C2-C4Alkenyl, C2-C4Alkynyl, C1-C4Alkoxy and C1-C4Alkane
Thio groups are optionally independently selected by one or more from the group substitution of the following group：Halogen, C1-C4Alkyl, C1-C4Alcoxyl
Base and C1-C4Alkylthio group.
7. according to the compound of the 1st, the wherein compound is selected from the group：
8. a kind of method prepared according to any one of 1-7 formula (I) compound, including make formula (II) compound with
Formula (III) compound carries out esterification, obtains formula (I) compound,
Wherein R1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11、R12、R13And R14As any one of 1-7 define,
And X is hydroxyl or halogen.
9. according to the method for the 8th, wherein esterification carries out in the presence of a catalyst, and preferred catalyst is to be selected from the group
One or more：Sulfuric acid, perchloric acid, zinc chloride, ferric trichloride, pyridine, p-methyl benzenesulfonic acid, sodium hydroxide, potassium hydroxide,
Sodium carbonate, sodium acid carbonate, sodium tert-butoxide, sodium ethoxide, sodium hydride, hydrofining, calcium hydride and tertiary amine, such as trialkylamine, such as three
Methyl amine and triethylamine.
10. according to purposes of the compounds of any one of 1-7 as photoinitiator.
These and other purposes, features and advantages of the present invention are readily able to after the hereafter consideration present invention is combined to be common
Technical staff understands.
Brief description
Fig. 1 is compound 1173 and the uv absorption spectra of 1173CC；
Fig. 2 is compound 184 and the uv absorption spectra of 184-CC；
Fig. 3 is the relational graph that the thermolytic rate of compound changes over time；
The change of the double bond conversion rate for the polymerisable monomer that Fig. 4, which is compound 184-CC, to be obtained as photoinitiator at any time
Change；And
The change of the double bond conversion rate for the polymerisable monomer that Fig. 5, which is compound 1173-CC, to be obtained as photoinitiator at any time
Change.
Specific embodiment
According to the first aspect of the invention, a kind of cinnamic acid benzoyl first ester type compound of lower formula (I) is provided：
Wherein
R1、R2、R3、R4And R5It is independently from each other hydrogen, halogen, nitro, hydroxyl, sulfydryl, carboxyl, sulfonic group, amino, cyanogen
Base, C1-C20Alkyl, C2-C20Alkenyl, C2-C20Alkynyl, C3-C20Cycloalkyl, C4-C20Cycloalkyl-alkyl, C1-C20Alkoxy, C2-
C20Alkenyloxy group, C2-C20Alkynyloxy group, C3-C20Cycloalkyloxy, C4-C20Cycloalkyl alkoxy, C1-C20Alkylthio group, C2-C20Alkenylthio group,
C2-C20Alkynes sulfenyl, C3-C20Cycloalkylthio, C4-C20Alkylthio cycloalkyl and C6-C18Aryl, wherein foregoing C1-C20Alkyl, C2-
C20Alkenyl, C2-C20Alkynyl, C3-C20Cycloalkyl, C4-C20Cycloalkyl-alkyl, C1-C20Alkoxy, C2-C20Alkenyloxy group, C2-C20Alkynes
Oxygroup, C3-C20Cycloalkyloxy, C4-C20Cycloalkyl alkoxy, C1-C20Alkylthio group, C2-C20Alkenylthio group, C2-C20Alkynes sulfenyl, C3-
C20Cycloalkylthio, C4-C20Alkylthio cycloalkyl and C6-C18Aryl group is optionally independently selected by one or more from the following group
Group substitution：Halogen, nitro, hydroxyl, sulfydryl, carboxyl, sulfonic group, amino, cyano, C1-C6Alkyl, C1-C6Alkoxy, C1-
C6Alkylthio group, C2-C6Alkenyl and C2-C6Alkynyl；
R6And R7It is identical or different and selected from H, C1-C6Alkyl and halogenated C1-C6Alkyl or R6And R7It is connected with them
Carbon atom form C together3-C8Cycloalkyl；
R8、R9、R10、R11And R12Be independently from each other hydrogen, halogen, nitro, hydroxyl, sulfydryl, carboxyl, sulfonic group, amino,
Cyano, C1-C20Alkyl, C2-C20Alkenyl, C2-C20Alkynyl, C3-C20Cycloalkyl, C4-C20Cycloalkyl-alkyl, C1-C20Alkoxy,
C2-C20Alkenyloxy group, C2-C20Alkynyloxy group, C3-C20Cycloalkyloxy, C4-C20Cycloalkyl alkoxy, C1-C20Alkylthio group, C2-C20Alkene sulphur
Base, C2-C20Alkynes sulfenyl, C3-C20Cycloalkylthio, C4-C20Alkylthio cycloalkyl and C6-C18Aryl, wherein foregoing C1-C20Alkyl,
C2-C20Alkenyl, C2-C20Alkynyl, C3-C20Cycloalkyl, C4-C20Cycloalkyl-alkyl, C1-C20Alkoxy, C2-C20Alkenyloxy group, C2-C20
Alkynyloxy group, C3-C20Cycloalkyloxy, C4-C20Cycloalkyl alkoxy, C1-C20Alkylthio group, C2-C20Alkenylthio group, C2-C20Alkynes sulfenyl,
C3-C20Cycloalkylthio, C4-C20Alkylthio cycloalkyl and C6-C18Aryl group is optionally independently selected by one or more from
The group substitution of the following group：Halogen, nitro, hydroxyl, sulfydryl, carboxyl, sulfonic group, amino, cyano, C1-C6Alkyl, C1-C6Alcoxyl
Base, C1-C6Alkylthio group, C2-C6Alkenyl and C2-C6Alkynyl；And
R13And R14It is identical or different and selected from H, C1-C6Alkyl and halogenated C1-C6Alkyl.
Due to the presence of α-monohydroxy ketone structure division in formula (I) compound so that the compound remains α-mono- hydroxyl
The characteristic of base ketone-type photoinitiators, in addition cinnamoyl structure division wherein included enable the compound in ultraviolet light spoke
Polymerization crosslinking can be occurred by penetrating down, and so obtained formula (I) compound is remain α-monohydroxy ketone-type photoinitiators the advantages of
The problem of further improving α-peculiar smell of monohydroxy ketone-type photoinitiators and strong migration simultaneously.
In the present invention, prefix " Cn-Cm" represent the carbon number included in the group for n-m in each case.
" halogen " refers to fluorine, chlorine, bromine and iodine.In the present invention, it is preferred that halogen includes F, Cl or its combination.
The term as used herein " Cn-CmAlkyl " refers to n-m, such as 1-20 a, preferably 1-12, more preferable 1-8
It is a, particularly preferred 1-6, the branched or unbranched saturated hydrocarbyl of particularly preferred 1-4 carbon atom, such as methyl, ethyl, third
Base, 1- Methylethyls, butyl, 1- methyl-propyls, 2- methyl-propyls, 1,1- dimethyl ethyls, amyl, 1- methyl butyls, 2- first
Base butyl, 3- methyl butyls, 2,2- dimethyl propyls, 1- ethyl propyls, hexyl, 1,1- dimethyl propyls, 1,2- dimethyl propylenes
Base, 1- methyl amyls, 2- methyl amyls, 3- methyl amyls, 4- methyl amyls, 1,1- dimethylbutyls, 1,2- dimethylbutyls,
1,3- dimethylbutyls, 2,2- dimethylbutyls, 2,3- dimethylbutyls, 3,3- dimethylbutyls, 1- ethyl-butyls, 2- ethyls
Butyl, 1,1,2- thmethylpropyls, 1,2,2- thmethylpropyls, 1- ethyl -1- methyl-propyls, 1- Ethyl-2-Methyls propyl, heptan
Base, octyl group, 2- ethylhexyls, nonyl, decyl, undecyl, dodecyl and its isomers.C1-C8Alkyl can be methyl,
Ethyl, propyl, isopropyl, normal-butyl, 2- butyl, tertiary butyl, amyl, isopentyl, hexyl, heptyl, octyl group and its isomers.
C1-C6Alkyl can be methyl, ethyl, propyl, isopropyl, normal-butyl, 2- butyl, tertiary butyl, amyl, isopentyl, hexyl and its
Isomers.C1-C4Alkyl can be methyl, ethyl, propyl, 1- Methylethyls, butyl, 1- methyl-propyls, 2- methyl-propyls, 1,
1- dimethyl ethyls and its isomers.
Terms used herein " C2-CmAlkenyl " refers to 2-m, such as 2-20 a, preferably 2-6, more preferable 2-4
A carbon atom and the branched or unbranched unsaturated alkyl for being located at the double bonds of any position with one or more, such as ethylene
Base, 1- acrylic, 2- acrylic, 1- methyl ethylenes, 1- cyclobutenyls, 2- cyclobutenyls, 3- cyclobutenyls, 1- methyl-1-propylenes base,
2- methyl-1-propylenes base, 1- methyl -2- acrylic, 2- methyl -2- acrylic, 1- pentenyls, 2- pentenyls, 3- pentenyls, 4-
Pentenyl, 1- methyl-1s-cyclobutenyl, 2-methyl-1-butene alkenyl, 3-methyl-1-butene base, 1- methyl-2-butenes base, 2- first
Base -2- cyclobutenyls, 3- methyl-2-butenes base, 1- methyl -3- cyclobutenyls, 2- methyl -3- cyclobutenyls, 3- methyl -3- cyclobutenyls,
1,1- dimethyl -2- acrylic, 1,2- dimethyl -1- acrylic, 1,2- dimethyl -2- acrylic, 1- ethyl -1- acrylic,
1- ethyl -2- acrylic, 1- hexenyls, 2- hexenyls, 3- hexenyls, 4- hexenyls, 5- hexenyls, 1- methyl-1-pentenes alkenyl,
2- methyl-1-pentenes alkenyl, 3- methyl-1-pentenes alkenyl, 4-methyl-1-pentene base, 1- methyl -2- pentenyls, 2- methyl -2- amylenes
Base, 3- methyl -2- pentenyls, 4- methyl -2- pentenyls, 1- methyl-3-pentenyls, 2- methyl-3-pentenyls, 3- methyl -3-
Pentenyl, 4- methyl-3-pentenyls, 1- methyl -4- pentenyls, 2- methyl -4- pentenyls, 3- methyl -4- pentenyls, 4- first
Base -4- pentenyls, 1,1- dimethyl -2- cyclobutenyls, 1,1- dimethyl -3- cyclobutenyls, 1,2- dimethyl -1- cyclobutenyls, 1,2-
Dimethyl -2- cyclobutenyls, 1,2- dimethyl -3- cyclobutenyls, 1,3- dimethyl -1- cyclobutenyls, 1,3- dimethyl -2- cyclobutenyls,
1,3- dimethyl -3- cyclobutenyls, 2,2- dimethyl -3- cyclobutenyls, 2,3- dimethyl -1- cyclobutenyls, 2,3- dimethyl -2- butylene
Base, 2,3- dimethyl -3- cyclobutenyls, 3,3- dimethyl -1- cyclobutenyls, 3,3- dimethyl -2- cyclobutenyls, 1- ethyl -1- butylene
Base, 1- ethyl -2- cyclobutenyls, 1- ethyl -3- cyclobutenyls, 2- ethyl -1- cyclobutenyls, 2- ethyl -2- cyclobutenyls, 2- ethyls -3-
Cyclobutenyl, 1,1,2- trimethyl -2- acrylic, 1- ethyl -1- methyl -2- acrylic, 1- Ethyl-2-Methyl -1- acrylic, 1-
Ethyl-2-Methyl -2- acrylic and its isomers.C2-C6Alkenyl can be vinyl, acrylic, 1- cyclobutenyls, 2- cyclobutenyls,
Isobutenyl, 1- pentenyls, 2- pentenyls, new pentenyl, 1- hexenyls, 2- hexenyls, 3- hexenyls, isohexenyl, it is new oneself
Alkenyl and its isomers.C2-C4Alkenyl can be vinyl, 1- acrylic, 2- acrylic, 1- methyl ethylenes, 1- cyclobutenyls,
2- cyclobutenyls, 3- cyclobutenyls, 1- methyl-1-propylenes base, 2- methyl-1-propylenes base, 1- methyl -2- acrylic, 2- methyl -2- third
Alkenyl and its isomers.
Terms used herein " C2-CmAlkynyl " refers to 2-m, such as 2-20 a, preferably 2-6, more preferable 2-4
Carbon atom and with the branched or unbranched unsaturated alkyl of one or more three keys for being located at any position, as acetenyl,
Propinyl, 1- butynyls, 2- butynyls and its isomers.C2-C6Alkynyl can be acetenyl, propinyl, 1- butynyls, 2- fourths
Alkynyl, 1- pentynyls, valerylene base, 3- pentynyls, 4- pentynyls, 1- hexin bases, 2- hexin bases, 3- hexin bases, 4- hexin bases,
5- hexin bases and its isomers.C2-C4Alkynyl can be acetenyl, propinyl, 1- butynyls, 2- butynyls and its isomers.
Terms used herein " C3-CmCycloalkyl " refers to 3-m, such as 3-20 a, preferably 3-8, more preferable 5-6
The alicyclic monocyclic groups of saturation of a ring carbon atom, such as cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl, suberyl, cyclooctyl
And cyclodecyl.
Term " C4-CmCycloalkyl-alkyl " is represented by alkyl-substituted cycloalkyl and in total containing 4-m carbon atom, example
Such as 4-20, preferably 4-8 carbon atom, wherein alkyl and cycloalkyl are applicable in defined herein.
“Cn-CmAlkoxy " and " Cn-CmAlkylthio group " refers in Cn-CmThere are one oxygen atoms for bonding at any valence link of alkyl
Or C of the sulphur atom as linking groupn-CmAlkyl, such as C1-C20Alcoxyl (or sulphur) base, preferably C1-C12Alcoxyl (or sulphur)
Base, more preferable C1-C8Alcoxyl (or sulphur) base, particularly preferred C1-C6Alcoxyl (or sulphur) base, particularly preferred C1-C4Alcoxyl (or sulphur) base.
C1-C8Alkoxy can be methoxyl group, ethyoxyl, propoxyl group, isopropoxy, n-butoxy, 2- butoxy, tert-butoxy, penta oxygen
Base, isoamoxy, hexyloxy, oxygroup in heptan, octyloxy, different octyloxy and its isomers.C1-C4Alkoxy can be methoxyl group, second
Oxygroup, propoxyl group, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy and its isomers.C1-C8Alkylthio group
Can be methyl mercapto, ethylmercapto group, rosickyite base, isopropyisulfanyl, normal-butyl, 2- butylthios, tertiary butylthio, penta sulfenyl, isopentylthio,
Own sulfenyl, sulfenyl in heptan, pungent sulfenyl, different pungent sulfenyl and its isomers.C1-C4Alkylthio group can be methyl mercapto, ethylmercapto group, rosickyite base,
Isopropyisulfanyl, positive butylthio and its isomers.
“C2-CmAlkenyloxy group " and " C2-CmAlkenylthio group " refers in C2-CmAt any saturation valence link in alkenyl there are one bondings
The C of oxygen atom or a sulphur atom as linking group2-CmAlkenyl, such as C2-C20Alkene oxygen (or sulphur) base, preferably C2-C12Alkene oxygen
(or sulphur) base, more preferable C2-C8Alkene oxygen (or sulphur) base, particularly preferred C2-C6Alkene oxygen (or sulphur) base, particularly preferred C2-C4Alkene oxygen (or
Sulphur) base.C1-C4Alkenyloxy group can be ethyleneoxy, propenyloxy group, isopropyl alkenyloxy group, n-butene oxygroup, secondary butenyloxy, isobutyl
Alkenyloxy group, tertiary butenyloxy and its isomers.C2-C4Alkenylthio group can be ethylene sulfenyl, propylene sulfenyl, isopropyl alkenylthio group, positive fourth
Alkenylthio group and its isomers.
“C2-CmAlkynyloxy group " and " C2-CmAlkynes sulfenyl " refers in C2-CmAt any saturation valence link in alkynyl there are one bondings
The C of oxygen atom or a sulphur atom as linking group2-CmAlkynyl, such as C2-C20Alkynes oxygen (or sulphur) base, preferably C2-C12Alkynes oxygen
(or sulphur) base, more preferable C2-C8Alkynes oxygen (or sulphur) base, particularly preferred C2-C6Alkynes oxygen (or sulphur) base, particularly preferred C2-C4Alkynes oxygen (or
Sulphur) base.C1-C4Alkynyloxy group can be acetylene oxygroup, propargyl alcoholate, positive butine oxygroup, Zhong Ding alkynyloxy groups and its isomers.C2-C4
Alkynes sulfenyl can be acetylene sulfenyl, propine sulfenyl, propine sulfenyl, positive butine sulfenyl, secondary butine sulfenyl and its isomers.
“C3-CmCycloalkyloxy " and " C3-CmCycloalkylthio " refers to that there are one oxygen for bonding at any valence link in cycloalkyl
The C of atom or a sulphur atom as linking group3-CmCycloalkyl, such as C3-C20Cycloalkanes oxygen (or sulphur) base, preferably C3-C8Ring
Alcoxyl (or sulphur) base, more preferable C5-C6Cycloalkanes oxygen (or sulphur) base.C3-C20Cycloalkyloxy can be cyclopropyl oxygroup, cyclobutyl oxygen
Base, cyclopentyloxy, cyclohexyl oxygroup, suberyl oxygroup, cyclooctyl oxygroup, cyclodecyl oxygroup and its isomers.C3-C20Cycloalkanes
Sulfenyl can be cyclopropylsulfanyl, cyclobutyl sulfenyl, cyclopentylthio, cyclohexylthio, suberyl sulfenyl, cyclooctyl sulfenyl,
Cyclodecyl sulfenyl and its isomers.
Terms used herein " C6-CmAryl " refers to containing 6-m carbon atom, such as 6-18, preferably 6-10 carbon atom
Monocyclic, bicyclic or tricyclic aromatic hydrocarbyl.As C6-CmThe example of aryl, can be mentioned that phenyl, tolyl, ethylbenzene, propyl phenyl,
Butylbenzene base, xylyl, Methylethyl phenyl, diethyl phenyl, methyl-propyl phenyl and naphthalene etc.；It is preferred that phenyl or naphthyl,
Especially phenyl (is also referred to as C as substituent group6H5)。
In the present invention, R1、R2、R3、R4And R5It is independently from each other hydrogen, halogen, nitro, hydroxyl, sulfydryl, carboxyl, sulphur
Acidic group, amino, cyano, C1-C20Alkyl, C2-C20Alkenyl, C2-C20Alkynyl, C3-C20Cycloalkyl, C4-C20Cycloalkyl-alkyl, C1-
C20Alkoxy, C2-C20Alkenyloxy group, C2-C20Alkynyloxy group, C3-C20Cycloalkyloxy, C4-C20Cycloalkyl alkoxy, C1-C20Alkylthio group,
C2-C20Alkenylthio group, C2-C20Alkynes sulfenyl, C3-C20Cycloalkylthio, C4-C20Alkylthio cycloalkyl and C6-C18Aryl, wherein foregoing
C1-C20Alkyl, C2-C20Alkenyl, C2-C20Alkynyl, C3-C20Cycloalkyl, C4-C20Cycloalkyl-alkyl, C1-C20Alkoxy, C2-C20Alkene
Oxygroup, C2-C20Alkynyloxy group, C3-C20Cycloalkyloxy, C4-C20Cycloalkyl alkoxy, C1-C20Alkylthio group, C2-C20Alkenylthio group, C2-
C20Alkynes sulfenyl, C3-C20Cycloalkylthio, C4-C20Alkylthio cycloalkyl and C6-C18Aryl group is optionally by one or more only
On the spot group substitution selected from the group below：Halogen, nitro, hydroxyl, sulfydryl, carboxyl, sulfonic group, amino, cyano, C1-C6Alkyl, C1-
C6Alkoxy, C1-C6Alkylthio group, C2-C6Alkenyl and C2-C6Alkynyl.Preferably, R1、R2、R3、R4And R5It is independently from each other
Hydrogen, halogen, nitro, hydroxyl, sulfydryl, carboxyl, sulfonic group, amino, cyano, C1-C6Alkyl, C2-C6Alkenyl, C2-C6Alkynyl, C3-C8
Cycloalkyl, C4-C8Cycloalkyl-alkyl, C1-C6Alkoxy, C2-C6Alkenyloxy group, C2-C6Alkynyloxy group, C3-C8Cycloalkyloxy, C4-C8Ring
Alkyl alkoxy, C1-C6Alkylthio group, C2-C6Alkenylthio group, C2-C6Alkynes sulfenyl, C3-C8Cycloalkylthio, C4-C8Alkylthio cycloalkyl and
C6-C10Aryl, wherein foregoing C1-C6Alkyl, C2-C6Alkenyl, C2-C6Alkynyl, C3-C8Cycloalkyl, C4-C8Cycloalkyl-alkyl, C1-C6
Alkoxy, C2-C6Alkenyloxy group, C2-C6Alkynyloxy group, C3-C8Cycloalkyloxy, C4-C8Cycloalkyl alkoxy, C1-C6Alkylthio group, C2-C6
Alkenylthio group, C2-C6Alkynes sulfenyl, C3-C8Cycloalkylthio, C4-C8Alkylthio cycloalkyl and C6-C10Aryl group is optionally by one
Or multiple groups independently selected from the following group substitute：Halogen, nitro, hydroxyl, sulfydryl, carboxyl, sulfonic group, amino, cyano, C1-C4
Alkyl, C1-C4Alkoxy, C1-C4Alkylthio group, C2-C4Alkenyl and C2-C4Alkynyl.It is particularly preferred that R1、R2、R3、R4And R5That
This is independently selected from hydrogen, halogen, C1-C4Alkyl, C1-C4Alkoxy and C1-C4Alkylthio group, wherein foregoing C1-C4Alkyl, C1-C4Alkane
Oxygroup and C1-C4Alkylthio group is optionally independently selected by one or more from the group substitution of the following group：Halogen, C1-C4Alkyl,
C1-C4Alkoxy and C1-C4Alkylthio group.
In the present invention, R6And R7It is identical or different and selected from H, C1-C6Alkyl and halogenated C1-C6Alkyl or R6And R7With
The carbon atom that they are connected forms C together3-C8Cycloalkyl.Preferably, R6And R7It is identical or different and selected from H, C1-C4Alkane
Base and halogenated C1-C4Alkyl or R6And R7Carbon atom connected to them forms C together5-C6Cycloalkyl.It is particularly preferred
It is R6And R7It is identical or different and be methyl or halogenated methyl or R6And R7Carbon atom connected to them forms ring together
Amyl or cyclohexyl.
In the present invention, R8、R9、R10、R11And R12Be independently from each other hydrogen, halogen, nitro, hydroxyl, sulfydryl, carboxyl,
Sulfonic group, amino, cyano, C1-C20Alkyl, C2-C20Alkenyl, C2-C20Alkynyl, C3-C20Cycloalkyl, C4-C20Cycloalkyl-alkyl,
C1-C20Alkoxy, C2-C20Alkenyloxy group, C2-C20Alkynyloxy group, C3-C20Cycloalkyloxy, C4-C20Cycloalkyl alkoxy, C1-C20Alkane sulphur
Base, C2-C20Alkenylthio group, C2-C20Alkynes sulfenyl, C3-C20Cycloalkylthio, C4-C20Alkylthio cycloalkyl and C6-C18Aryl, wherein before
State C1-C20Alkyl, C2-C20Alkenyl, C2-C20Alkynyl, C3-C20Cycloalkyl, C4-C20Cycloalkyl-alkyl, C1-C20Alkoxy, C2-C20
Alkenyloxy group, C2-C20Alkynyloxy group, C3-C20Cycloalkyloxy, C4-C20Cycloalkyl alkoxy, C1-C20Alkylthio group, C2-C20Alkenylthio group,
C2-C20Alkynes sulfenyl, C3-C20Cycloalkylthio, C4-C20Alkylthio cycloalkyl and C6-C18Aryl group is optionally by one or more
A group independently selected from the following group substitutes：Halogen, nitro, hydroxyl, sulfydryl, carboxyl, sulfonic group, amino, cyano, C1-C6Alkane
Base, C1-C6Alkoxy, C1-C6Alkylthio group, C2-C6Alkenyl and C2-C6Alkynyl.Preferably, R8、R9、R10、R11And R12Each other solely
On the spot selected from hydrogen, halogen, nitro, hydroxyl, sulfydryl, carboxyl, sulfonic group, amino, cyano, C1-C6Alkyl, C2-C6Alkenyl, C2-C6
Alkynyl, C3-C8Cycloalkyl, C4-C8Cycloalkyl-alkyl, C1-C6Alkoxy, C2-C6Alkenyloxy group, C2-C6Alkynyloxy group, C3-C8Cycloalkanes oxygen
Base, C4-C8Cycloalkyl alkoxy, C1-C6Alkylthio group, C2-C6Alkenylthio group, C2-C6Alkynes sulfenyl, C3-C8Cycloalkylthio, C4-C8Cycloalkanes
Base alkylthio group and C6-C10Aryl, wherein foregoing C1-C6Alkyl, C2-C6Alkenyl, C2-C6Alkynyl, C3-C8Cycloalkyl, C4-C8Cycloalkanes
Base alkyl, C1-C6Alkoxy, C2-C6Alkenyloxy group, C2-C6Alkynyloxy group, C3-C8Cycloalkyloxy, C4-C8Cycloalkyl alkoxy, C1-C6
Alkylthio group, C2-C6Alkenylthio group, C2-C6Alkynes sulfenyl, C3-C8Cycloalkylthio, C4-C8Alkylthio cycloalkyl and C6-C10Aryl group can
Optionally it is independently selected by one or more from the group substitution of the following group：Halogen, nitro, hydroxyl, sulfydryl, carboxyl, sulfonic group, ammonia
Base, cyano, C1-C4Alkyl, C1-C4Alkoxy, C1-C4Alkylthio group, C2-C4Alkenyl and C2-C4Alkynyl.It is particularly preferred that R8、
R9、R10、R11And R12It is independently from each other hydrogen, halogen, C1-C4Alkyl, C2-C4Alkenyl, C2-C4Alkynyl, C1-C4Alkoxy and
C1-C4Alkylthio group, wherein foregoing C1-C4Alkyl, C2-C4Alkenyl, C2-C4Alkynyl, C1-C4Alkoxy and C1-C4Alkylthio radicals can
Optionally it is independently selected by one or more from the group substitution of the following group：Halogen, C1-C4Alkyl, C1-C4Alkoxy and C1-C4Alkane
Sulfenyl.
In the present invention, R13And R14It is identical or different and selected from H, C1-C6Alkyl and halogenated C1-C6Alkyl.Preferably,
R13And R14It is identical or different and selected from H, C1-C4Alkyl and halogenated C1-C4Alkyl.It is particularly preferred that R13And R14It is H.
In a particularly preferred embodiment of the present invention, formula (I) compound is selected from the group：
According to the second aspect of the invention, a kind of method for preparing formula (I) compound of the present invention is provided, including formula
(II) compound carries out esterification with formula (III) compound, obtains formula (I) compound,
Wherein R1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11、R12、R13And R14As defined to formula (I) compound, with
And X is hydroxyl or halogen.
In order to accelerate esterification, above-mentioned esterification carries out usually in the presence of the catalyst suitable for esterification.Make
For catalyst, acidic catalyst can be both used, basic catalyst can also be used.As catalyst, can use be selected from down
The one or more of group：Sulfuric acid, perchloric acid, zinc chloride, ferric trichloride, pyridine, p-methyl benzenesulfonic acid, sodium hydroxide, hydroxide
Potassium, sodium carbonate, sodium acid carbonate, sodium tert-butoxide, sodium ethoxide, sodium hydride, hydrofining, calcium hydride and tertiary amine, such as trialkylamine, such as
Trimethylamine and triethylamine.The dosage of catalyst is conventional, can be determined by the common sense of this field or by several examples
Capable preliminary experiment determines.
In order to improve the yield of formula (I) compound, it is advantageous to remove what esterification generated in esterification reaction process
Water.This can for example be carried out by distilling condensation.
Above-mentioned esterification usually in a solvent, preferably carries out in organic solvent.The selection of type as solvent, does not have
There is special limitation, as long as by formula (II) and the dissolving of formula (III) compound and can be in chemical inertness to esterification,
It is not involved in the esterification.As the example of solvent, it can be mentioned that tetrahydrofuran, benzene, toluene, N, N- dimethyl formyls
Amine, dichloromethane and acetone.Solvent can use single kind, can also use the mixture of two or more solvents.
Formula (II) compound and the relative usage of formula (III) compound are not particularly limited, typically they with etc.
Mole uses.
Esterification can carry out within the temperature range of non-constant width.It is according to the present invention advantageous that esterification is -10
DEG C to 150 DEG C, carry out at a temperature of preferably 0 DEG C to 100 DEG C, preferably carried out under room temperature.Reaction time of esterification is also without special
Limitation, when usually progress 1-24 is small, when preferably 1-12 is small.
After esterification completion, the reaction mixture for including formula (I) compound is obtained.Therefore, it is necessary to the reaction
Mixture is post-processed, with formula (I) compound purified.Typically, the reaction that filtering esterification obtains first
Mixture takes out filtrate portion.Then, filtrate is washed, to remove catalyst and unreacted raw material.As washing lotion,
It is not particularly limited, as long as catalyst and unreacted raw material can be removed.As the example of washing lotion, it can be mentioned that dilute salt
Sour (aqueous solution), saturated sodium bicarbonate aqueous solution and water.The concentration of dilute hydrochloric acid is not particularly limited, typically concentration
For the dilute hydrochloric acid of 5-12%.It can be carried out once, can be also carried out repeatedly with wash liquid；In the case where carrying out repeatedly, can make
With single kind of washing lotion, different washing lotions can be also used successively.It is according to the present invention advantageous that the reaction that esterification will be obtained
The filtrate that mixture is obtained by filtration is washed successively with dilute hydrochloric acid, saturated sodium bicarbonate aqueous solution and water.Certainly, use each time
After wash liquid, it is required for again washing organic phase with a kind of lower washing lotion after outwelling water phase.It is after washing, it is necessary to dry
To remove remaining water.For this purpose, usually usable anhydrous sodium sulfate is dried.It dries and then removes remaining organic molten
Agent.As the means for removing organic solvent here, it is not particularly limited, can be usually removed by being evaporated under reduced pressure organic molten
Agent.After removing residual organic solvent, the crude product of formula (I) compound has been obtained.If it is intended to further improve formula (I) chemical combination
The purity of object can also further purify the compound, this can for example be carried out by way of recrystallization.It recrystallizes molten
The selection of agent is conventional, is not particularly limited.In accordance with the invention it is advantageous that using methanol to the thick of formula (I) compound
Product is recrystallized.
Not only comprising α-monohydroxy ketone structure division in formula (I) compound of the present invention, but also include cinnamoyl structural portion
Point, therefore the compound can play the photoinitiator effect of α-monohydroxy ketone, but because cinnamoyl structure division draws
The problem of entering and improving peculiar smell and the strong migration that α-monohydroxy ketone-type photoinitiators are inherently present.
Therefore, according to the third aspect of the present invention, use of the formula (I) compound of the present invention as photoinitiator is provided
On the way.
Formula (I) compound of the present invention can absorb the electromagnetic wave of 200-350nm.After the absorption of the electromagnetic wave, formula (I) compound by
Ground state becomes excitation state so that acyl carbon atom in formula (I) compound in benzoyl structure division in phase O-methoxy
Carbon atom is broken, and two free radicals is formed, so as to trigger photopolymerization or photo-crosslinking.Further, since the cinnamoyl of formula (I) compound
Based moiety contains undersaturated carbon-carbon double bond, therefore carbon-carbon double bond is easily anti-when being subject to electromagenetic wave radiation between different molecular
The molecule or cross-linked structure of bigger should be formed, the problem of so as to peculiar smell caused by substantially improving photoinitiator and strong migration, is shown
Work reduces peculiar smell and significantly reduces migration.
Formula (I) compound can be used as photoinitiator in fields such as coating, ink, microelectronics, printings.When formula (I) compound
During as photoinitiator, dosage is conventional or can determine by routine pilot study.
Embodiment
Below with reference to specific embodiment, the invention will be further described, but should not be construed as protecting the present invention
The limitation of scope.
Embodiment 1：Cinnamic acid benzoyl isopropyl ester
16.4g (0.1mol) 2- hydroxy-2-methyl -1- phenyl -1- acetone is placed in 250ml there-necked flasks, adds in 100ml
Dichloromethane and 10.1g (0.1mol) triethylamine.After stirring evenly, 16.6g (0.1mol) 3- phenyl -2- acryloyl chlorides are added in,
3h is stirred to react at room temperature.Then, filtering reacting liquid, by filtrate successively with dilute hydrochloric acid (5%), saturated sodium bicarbonate aqueous solution
It with distillation water washing, is filtered after being then dried overnight with anhydrous sodium sulfate, vacuum distillation removing organic phase, after recrystallizing methanol,
Obtain light yellow crystal, common 13g, product warp1H-NMR spectrums confirm as title compound, are referred to as 1173-CC.
1H-NMR (spectrum) (being measured in Acetone-d6) (δ ppm)：1.80(s,6H),6.56(d,1H),7.45(m,
9H),8.11(d,2H)。
Embodiment 2：3- (4- methoxyl groups) cinnamylic acid benzoyl isopropyl ester
16.4g (0.1mol) 2- hydroxy-2-methyl -1- phenyl -1- acetone is placed in 250ml there-necked flasks, adds in 100ml
Dichloromethane and 10.1g (0.1mol) triethylamine.After stirring evenly, 18g (0.1mol) 3- (4- methoxyl groups) phenyl -2- third is added in
Alkene acyl chlorides, is stirred to react 3h at room temperature.Then, filtering reacting liquid, by filtrate successively with dilute hydrochloric acid (5%), unsaturated carbonate hydrogen
Sodium water solution and distillation water washing, are filtered, vacuum distillation removes organic phase, methanol weight after being then dried overnight with anhydrous sodium sulfate
After crystallization, light yellow crystal, common 18g, product warp are obtained1H-NMR spectrums confirm as title compound.
1H-NMR (spectrum) (being measured in Acetone-d6)：1.60(s,6H),3.80(s,3H),6.31(d,1H),7.48
(m,9H),7.97(d,2H)。
Embodiment 3：Cinnamic acid 4- aminomethyl phenyl formoxyl isopropyl esters
17.7g (0.1mol) 2- hydroxy-2-methyls -1- (4- methyl) phenyl -1- acetone is placed in 250ml there-necked flasks,
Add in 100ml dichloromethane and 10.1g (0.1mol) triethylamine.After stirring evenly, 16.6g (0.1mol) cinnamoyl chloride is added in,
3h is stirred to react at room temperature.Then, filtering reacting liquid, by filtrate successively with dilute hydrochloric acid (5%), saturated sodium bicarbonate aqueous solution
It with distillation water washing, is filtered after being then dried overnight with anhydrous sodium sulfate, vacuum distillation removing organic phase, after recrystallizing methanol,
Obtain light yellow crystal, common 16g, product warp1H-NMR spectrums confirm as title compound.
1H-NMR (spectrum) (being measured in Acetone-d6)：1.78(s,6H),2.34(s,6H),6.54(d,1H),7.35
(m,9H),8.11(d,2H)。
Embodiment 4：Cinnamic acid 4- methyl mercapto phenyl formoxyl isopropyl esters
21g (0.1mol) 2- hydroxy-2-methyls -1- (4- methyl mercaptos phenyl) -1- acetone is placed in 250ml there-necked flasks,
Add in 100ml dichloromethane and 10.1g (0.1mol) triethylamine.After stirring evenly, 16.6g (0.1mol) cinnamoyl chloride is added in,
3h is stirred to react at room temperature.Then, filtering reacting liquid, by filtrate successively with dilute hydrochloric acid (5%), saturated sodium bicarbonate aqueous solution
It with distillation water washing, is filtered after being then dried overnight with anhydrous sodium sulfate, vacuum distillation removing organic phase, after recrystallizing methanol,
Obtain yellow crystals, common 18g, product warp1H-NMR spectrums confirm as title compound.
1H-NMR (spectrum) (being measured in Acetone-d6)：1.80(s,6H),2.53(s,6H),6.56(d,1H),7.45
(m,9H),8.11(d,2H)。
Embodiment 5：Cinnamic acid 1- benzoylcyclohexan base esters
18.4g (0.1mol) (1- hydroxy-cyclohexyls) (phenyl) ketone is placed in 250ml there-necked flasks, adds in 100ml bis-
Chloromethanes and 10.1g (0.1mol) triethylamine.After stirring evenly, 16.6g (0.1mol) cinnamoyl chloride is added in, is stirred at room temperature
React 3h.Then, filtering reacting liquid, by filtrate successively with dilute hydrochloric acid, saturated sodium bicarbonate aqueous solution and distillation water washing.So
Afterwards, filtered after being dried overnight with anhydrous sodium sulfate, vacuum distillation removing organic phase, after recrystallizing methanol, obtain yellow crystals, altogether
20g, product warp1H-NMR spectrums confirm as title compound, are referred to as 184-CC.
1H-NMR (spectrum) (being measured in Acetone-d6)：1.36(m,6H),1.69(m,2H),2.42(d,2H),6.59
(d,1H),7.39(m,6H),7.65(m,3H),8.06(d,2H)。
Embodiment 6:3- (4- methoxyphenyls) -2- acrylic acid 1- benzoylcyclohexan base esters
20.4g (0.1mol) (1- hydroxy-cyclohexyls) (phenyl) ketone is placed in 250ml there-necked flasks, adds in 100ml bis-
Chloromethanes and 10.1g (0.1mol) triethylamine.After stirring evenly, 18g (0.1mol) 3- (4- methoxyl groups) phenyl -2- propylene is added in
Acyl chlorides is stirred to react 3h at room temperature.Then, filtering reacting liquid, by filtrate successively with dilute hydrochloric acid (5%), saturated sodium bicarbonate
Aqueous solution and distillation water washing, are filtered after being then dried overnight with anhydrous sodium sulfate, and vacuum distillation removes organic phase, and methanol is tied again
After crystalline substance, yellow crystals, common 23g, product warp are obtained1H-NMR spectrums confirm as title compound.
1H-NMR (spectrum) (being measured in Acetone-d6)：1.35(m,6H),1.70(m,2H),2.41(d,2H),3.75
(s,3H),6.60(d,1H),7.41(m,6H),7.64(m,3H),8.05(d,2H)。
Embodiment 7：Cinnamic acid 1- (2- methyl benzoyls) cyclohexyl ester
21.8g (0.1mol) (1- hydroxy-cyclohexyls) (2- aminomethyl phenyls) ketone is placed in 250ml there-necked flasks, is added in
100ml dichloromethane and 10.1g (0.1mol) triethylamine.After stirring evenly, 16.6g (0.1mol) cinnamoyl chloride is added in, in room
3h is stirred to react under temperature.Then, filtrate is used dilute hydrochloric acid (5%), saturated sodium bicarbonate aqueous solution and steaming by filtering reacting liquid successively
Distilled water is washed, and is filtered after being then dried overnight with anhydrous sodium sulfate, vacuum distillation removing organic phase, after recrystallizing methanol, is obtained yellow
Color crystal, common 21g, product warp1H-NMR spectrums confirm as title compound.
1H-NMR (spectrum) (being measured in Acetone-d6)：1.36(m,6H),1.69(m,2H),2.42(d,2H),2.48
(s,3H),6.59(d,1H),7.39(m,6H),7.65(m,3H),8.06(d,2H)。
Embodiment 8：Cinnamic acid 1- (4- diisopropylbenzoyl peroxides base) cyclohexyl ester
24.6g (0.1mol) (1- hydroxy-cyclohexyls) (4- isopropyl phenyls) ketone is placed in 250ml there-necked flasks, is added in
100ml dichloromethane and 10.1g (0.1mol) triethylamine.After stirring evenly, 24.6g (0.1mol) cinnamoyl chloride is added in, in room
3h is stirred to react under temperature.Then, filtrate is used dilute hydrochloric acid (5%), saturated sodium bicarbonate aqueous solution and steaming by filtering reacting liquid successively
Distilled water is washed, and is filtered after being then dried overnight with anhydrous sodium sulfate, vacuum distillation removing organic phase, after recrystallizing methanol, is obtained yellow
Color crystal, common 23g, product warp1H-NMR spectrums confirm as title compound.
1H-NMR (spectrum) (being measured in Acetone-d6)：1.01(d,6H),1.36(m,6H),1.69(m,2H),2.42
(d,2H),2.51(q,2H),6.59(d,1H),7.40(m,6H),7.64(m,3H),8.05(d,2H)。
Embodiment 9：3- (4- methoxyl groups) cinnamylic acid benzoyl methyl esters
13.6g (0.1mol) 2- hydroxyl -1- phenyl -1- ethyl ketones are placed in 250ml there-necked flasks, add in 100ml dichloromethanes
Alkane and 10.1g (0.1mol) triethylamine.After stirring evenly, 18g (0.1mol) 3- (4- methoxyl groups) phenyl -2- acryloyls are added in
Chlorine is stirred to react 3h at room temperature.Then, filtering reacting liquid, by filtrate successively with dilute hydrochloric acid (5%), saturated sodium bicarbonate water
Solution and distillation water washing, are filtered, vacuum distillation removes organic phase, recrystallizing methanol after being then dried overnight with anhydrous sodium sulfate
Afterwards, light yellow crystal, common 15.5g, product warp are obtained1H-NMR spectrums confirm as title compound.
1H-NMR (spectrum) (being measured in Acetone-d6):3.83(s,3H),5.75(s,2H),6.54(d,1H),7.35
(m,9H),8.11(d,2H)。
Embodiment 10：3- (4- methoxyl groups) cinnamylic acid (1- benzoyls -1,1- is double (trichloromethyl)) ethyl ester
Double (the trichloromethyl) -1- phenyl -1- ethyl ketones of 36.7g (0.1mol) 2- hydroxyls -2,2- are placed in 250ml there-necked flasks
In, add in 100ml dichloromethane and 10.1g (0.1mol) triethylamine.After stirring evenly, 18g (0.1mol) 3- (4- methoxies are added in
Base) phenyl -2- acryloyl chlorides, 3h is stirred to react at room temperature.Then, filtrate is used dilute hydrochloric acid by filtering reacting liquid successively
(5%), saturated sodium bicarbonate aqueous solution and distillation water washing, filter after being then dried overnight with anhydrous sodium sulfate, are evaporated under reduced pressure
Organic phase is removed, after recrystallizing methanol, obtains light yellow crystal, common 28g, which passes through1H-NMR spectrums confirm as title compound.
1H-NMR (spectrum) (being measured in Acetone-d6)：3.83(s,3H),6.54(d,1H),7.35(m,9H),8.11
(d,2H)。
Embodiment 11：3- (4- methoxyl groups) cinnamylic acid (1- benzoyls) ethyl ester
By 15g (0.1mol) 2- hydroxyls -- 1- phenyl -1- acetone is placed in 250ml there-necked flasks, adds in 100ml dichloromethane
With 10.1g (0.1mol) triethylamine.After stirring evenly, 18g (0.1mol) 3- (4- methoxyl groups) phenyl -2- acryloyl chlorides are added in,
3h is stirred to react at room temperature.Then, filtering reacting liquid, by filtrate successively with dilute hydrochloric acid (5%), saturated sodium bicarbonate aqueous solution
It with distillation water washing, is filtered after being then dried overnight with anhydrous sodium sulfate, vacuum distillation removing organic phase, after recrystallizing methanol,
Obtain light yellow crystal, common 16g, product warp1H-NMR spectrums confirm as title compound.
1H-NMR (spectrum) (being measured in Acetone-d6)：1.58 (d, 3H), 3.83 (s, 3H), 5.64 (q, 1H), 6.54
(d,1H),7.35(m,9H),8.11(d,2H)。
Embodiment 12：3- methyl -3- (4- vinyl) cinnamylic acid 2- chlorphenyl formoxyl isopropyl esters
19.8g (0.1mol) 2- hydroxy-2-methyls -1- (2- chlorine) phenyl -1- acetone is placed in 250ml there-necked flasks, is added
Enter 100ml dichloromethane and 10.1g (0.1mol) triethylamine.After stirring evenly, 20.6g (0.1mol) 3- methyl -3- (4- are added in
Vinyl) phenyl -2- acryloyl chlorides, 3h is stirred to react at room temperature.Then, filtrate is used dilute hydrochloric acid by filtering reacting liquid successively
(5%), saturated sodium bicarbonate aqueous solution and distillation water washing, filter after being then dried overnight with anhydrous sodium sulfate, are evaporated under reduced pressure
Organic phase is removed, after recrystallizing methanol, obtains light yellow crystal, common 19g, which passes through1H-NMR spectrums confirm as title compound.
1H-NMR (spectrum) (being measured in Acetone-d6)：1.78(s,6H),2.34(s,6H),6.54(d,1H),7.35
(m,9H),8.11(d,2H)。
Embodiment 13：3- methyl -3- (4- acetenyls) cinnamylic acid 2- aminomethyl phenyl formoxyl isopropyl esters
17.7g (0.1mol) 2- hydroxy-2-methyls -1- (2- methyl) phenyl -1- acetone is placed in 250ml there-necked flasks,
Add in 100ml dichloromethane and 10.1g (0.1mol) triethylamine.After stirring evenly, 16.6g (0.1mol) 3- methyl -3- is added in
(4- acetenyls) phenyl -2- acryloyl chlorides, are stirred to react 3h at room temperature.Then, filtering reacting liquid, by filtrate successively with dilute salt
Sour (5%), saturated sodium bicarbonate aqueous solution and distillation water washing, are filtered, decompression is steamed after being then dried overnight with anhydrous sodium sulfate
Organic phase is gone in distillation, after recrystallizing methanol, obtains light yellow crystal, common 16g, product warp1H-NMR spectrums confirm as title compound
Object.
1H-NMR (spectrum) (being measured in Acetone-d6)：1.78(s,6H),2.42(s,3H),2.48(s,3H)4.05
(s, 1H), 6.11 (d, 1H), 7.35 (m, 9H).
Embodiment 14：2- methyl -3- (4- chlorphenyls) -2- acrylic acid 1- (4- diisopropylbenzoyl peroxides base) cyclohexyl ester
29.2g (1- hydroxy-cyclohexyls) (4- isopropyl phenyls) ketone is placed in 250ml there-necked flasks, adds in 100ml bis-
Chloromethanes and 10.1g (0.1mol) triethylamine.After stirring evenly, addition 24.6g (0.1mol) 2- methyl -3- (4- chlorphenyls) -
2- acryloyl chlorides, are stirred to react 3h at room temperature.Then, filtering reacting liquid, by filtrate successively with dilute hydrochloric acid (5%), saturated carbon
Sour hydrogen sodium water solution and distillation water washing, are filtered, vacuum distillation removes organic phase, first after being then dried overnight with anhydrous sodium sulfate
After alcohol recrystallization, yellow crystals, common 25g, product warp are obtained1H-NMR spectrums confirm as title compound.
1H-NMR (spectrum) (being measured in Acetone-d6)：1.20 (d, 6H), 1.44 (s, 10H), 1.80 (s, 3H), 1.69
(m,2H),2.42(d,2H),2.51(q,2H),6.59(d,1H),7.40(m,6H),7.64(m,3H),8.05(d,2H)。
Ultra-violet absorption spectrum is tested：
1173 and 1173-CC and 184 and 184-CC are compared, find the compound 1173-CC after access cinnamoyl
There is apparent red shift with the UV absorption of 184-CC, can so greatly improve the utilization ratio of ultraviolet source, it may also be used for UV-
In LED exposure light source.Experimental data is shown in Fig. 1 and Fig. 2.
Thermal stability is tested：
Thermogravimetric (TG) analysis has been carried out to the thermal stability of each compound using ZRY-2P types thermal analyzer (plum Teller), has been surveyed
Strip part：Since 25 DEG C of initial temperature, 500 DEG C of final temperature is warming up to the speed of 10K/min.Compound weight percentage
It changes with time and sees Fig. 3.
Experimental data show when in the structure in compound 1173 and 184 introduce cinnamoyl after, the heat of gained compound
Stability, which has, to be obviously improved.It is as shown in the table to originate heat decomposition temperature：
| Compound name | Initial decomposition temperature/DEG C |
| 1173 | 80 |
| 1173-CC | 170 |
| 184 | 125 |
| 184-CC | 175 |
Photoinitiation Property is tested：
The Photoinitiation Property of photoinitiator is tested using REAL TIME INFRARED THERMAL IMAGE technology.Choose 1173-CC and 184-CC
Two kinds of compounds trigger polymerisable monomer hydroxyethyl methacrylate (HEMA) poly- to represent initiator under ultraviolet light
It closes.5ml acetone is taken to add in 2g HEMA, stirring after monomer dissolving, adds in 0.06g photoinitiators (1173-C or 184-CC),
1173-CC-HEMA samples and 184-CC-HEMA samples are made into respectively.A little sample is taken to be applied to KBr salt on pieces, is then placed in
In Nicolet5700 type infrared spectrometers, with ultraviolet light point light source (high-pressure sodium lamp) irradiating sample, the ultraviolet of sample surfaces is adjusted
Light light intensity is 30mW/cm2(light intensity is measured by HonleUV light intensity meters).The double bond conversion rate of monomer is gathered in real time with near-infrared, real
When IR parameters be arranged to：Data acquisition intervals 0.3985s, each spectral scan 1 time, resolution ratio 4cm-1.HEMA is near red
The characteristic absorption peak of carbon-carbon double bond is in 1630cm in outer spectrogram-1Place, with the progress of photocuring reaction, carbon-carbon double bond becomes carbon carbon
Singly-bound, the absorption peak strength of double bond increases with light application time and is died down, so the variation of the characteristic absorption peak using carbon-carbon double bond
To reflect the variation degree of its polymerisation.Double bond conversion rate (DC) is by omnic7.1 infrared softwares and origin6.1 data
Reason software convolution (1) is calculated:
DC (%)=[1- (At/A0)] × 100% (1)
In formula, A0It is respectively sample before curing with t moment after illumination in 1630cm with A-1Locate hydroxyethyl methacrylate
The area of double bond characteristic absorption peak.
The double bond conversion rate for the polymerisable monomer that compound 184-CC is obtained as photoinitiator, which changes with time, sees figure
The double bond conversion rate for the polymerisable monomer that 4, compound 1173-CC are obtained as photoinitiator, which changes with time, sees Fig. 5.
The experimental data of Fig. 4 and Fig. 5 shows that compound 184-CC and 1173-CC has good light-initiated effect.
Resistance to migration is tested：
By ethyl acrylate (EA), tripropylene glycol double methacrylate (TPGDA) and trihydroxy methyl propyl triacrylate
(TMPTA) by 3: 3: 4 mass ratio mix, obtain mixture, respectively thereto add in account for its total amount be 3 weight % 184,
184-CC, 1173,1173-CC, respectively prepare obtain a, a ', four kinds of photocuring systems of b and b '.
It is under nitrogen protection 100mW/cm in light intensity with 365nm light sources2Lower illumination 5min, and at room temperature in drier
Middle placement makes it fully cure for 24 hours, and cured film is smashed to pieces, weigh and calculate four kinds of photoinitiators (184,184-CC, 1173,
1173-CC) respective quality.96h is impregnated with 50mL acetonitriles, is supervised after the filtering of gained acetonitrile solution with uv-visible absorption spectra
Control the absorption at 300nm.Absorbance A and molar absorption coefficient ε are substituted into formula (2) and (3), four kinds of light in acetonitrile solution can be obtained
The respective concentration of initiator and quality.
C=A/ (ε l) (2)
M1=M × c × 10-2×V0 (3)
R=(m1/ (W × m0)) * 100% (4)
C is the initiator concentration (mol/L) being precipitated；L is optical path length, is taken as 1cm herein；Four kinds extracted are light-initiated
Agent quality m1 is calculated by formula (3), and M is the relative molecular mass of photoinitiator, and V0 is the volume of acetonitrile.R is photoinitiator
Mobility, W are the initial addition mass fraction of photoinitiator, and m0 is the quality of cured film, m1For the residual quantity of photoinitiator.
Experimental result is as follows：
| Substance title | Mobility (%) |
| 184 | 0.123 |
| 184-CC | 0.0075 |
| 1173 | 0.104 |
| 1173-CC | 0.024 |
Claims (10)
1. cinnamic acid benzoyl first ester type compound has structure shown in formula (I)：
Wherein
R1、R2、R3、R4And R5Be independently from each other hydrogen, halogen, nitro, hydroxyl, sulfydryl, carboxyl, sulfonic group, amino, cyano,
C1-C20Alkyl, C2-C20Alkenyl, C2-C20Alkynyl, C3-C20Cycloalkyl, C4-C20Cycloalkyl-alkyl, C1-C20Alkoxy, C2-C20Alkene
Oxygroup, C2-C20Alkynyloxy group, C3-C20Cycloalkyloxy, C4-C20Cycloalkyl alkoxy, C1-C20Alkylthio group, C2-C20Alkenylthio group, C2-
C20Alkynes sulfenyl, C3-C20Cycloalkylthio, C4-C20Alkylthio cycloalkyl and C6-C18Aryl, wherein foregoing C1-C20Alkyl, C2-C20Alkene
Base, C2-C20Alkynyl, C3-C20Cycloalkyl, C4-C20Cycloalkyl-alkyl, C1-C20Alkoxy, C2-C20Alkenyloxy group, C2-C20Alkynyloxy group,
C3-C20Cycloalkyloxy, C4-C20Cycloalkyl alkoxy, C1-C20Alkylthio group, C2-C20Alkenylthio group, C2-C20Alkynes sulfenyl, C3-C20Cycloalkanes
Sulfenyl, C4-C20Alkylthio cycloalkyl and C6-C18Aryl group is optionally independently selected by one or more from the group of the following group
Substitution：Halogen, nitro, hydroxyl, sulfydryl, carboxyl, sulfonic group, amino, cyano, C1-C6Alkyl, C1-C6Alkoxy, C1-C6Alkane sulphur
Base, C2-C6Alkenyl and C2-C6Alkynyl；
R6And R7It is identical or different and selected from H, C1-C6Alkyl and halogenated C1-C6Alkyl or R6And R7Carbon connected to them
Atom forms C together3-C8Cycloalkyl；
R8、R9、R10、R11And R12It is independently from each other hydrogen, halogen, nitro, hydroxyl, sulfydryl, carboxyl, sulfonic group, amino, cyanogen
Base, C1-C20Alkyl, C2-C20Alkenyl, C2-C20Alkynyl, C3-C20Cycloalkyl, C4-C20Cycloalkyl-alkyl, C1-C20Alkoxy, C2-
C20Alkenyloxy group, C2-C20Alkynyloxy group, C3-C20Cycloalkyloxy, C4-C20Cycloalkyl alkoxy, C1-C20Alkylthio group, C2-C20Alkenylthio group,
C2-C20Alkynes sulfenyl, C3-C20Cycloalkylthio, C4-C20Alkylthio cycloalkyl and C6-C18Aryl, wherein foregoing C1-C20Alkyl, C2-
C20Alkenyl, C2-C20Alkynyl, C3-C20Cycloalkyl, C4-C20Cycloalkyl-alkyl, C1-C20Alkoxy, C2-C20Alkenyloxy group, C2-C20Alkynes
Oxygroup, C3-C20Cycloalkyloxy, C4-C20Cycloalkyl alkoxy, C1-C20Alkylthio group, C2-C20Alkenylthio group, C2-C20Alkynes sulfenyl, C3-
C20Cycloalkylthio, C4-C20Alkylthio cycloalkyl and C6-C18Aryl group is optionally independently selected by one or more from the following group
Group substitution：Halogen, nitro, hydroxyl, sulfydryl, carboxyl, sulfonic group, amino, cyano, C1-C6Alkyl, C1-C6Alkoxy, C1-
C6Alkylthio group, C2-C6Alkenyl and C2-C6Alkynyl；And
R13And R14It is identical or different and selected from H, C1-C6Alkyl and halogenated C1-C6Alkyl.
2. compound according to claim 1, wherein R6And R7It is identical or different and selected from H, C1-C4Alkyl and halogenated C1-C4Alkane
Base or R6And R7Carbon atom connected to them forms C together5-C6Cycloalkyl.
3. compound according to claim 2, wherein R6And R7It is identical and be methyl or halogenated methyl or R6And R7With they institute
The carbon atom of connection forms cyclopenta or cyclohexyl together.
4. compound as claimed in one of claims 1-3, wherein R13And R14It is identical or different and selected from H, C1-C4Alkyl and
Halogenated C1-C4Alkyl, preferably R13And R14It is H.
5. compound as claimed in one of claims 1-4, wherein
R1、R2、R3、R4And R5Be independently from each other hydrogen, halogen, nitro, hydroxyl, sulfydryl, carboxyl, sulfonic group, amino, cyano,
C1-C6Alkyl, C2-C6Alkenyl, C2-C6Alkynyl, C3-C8Cycloalkyl, C4-C8Cycloalkyl-alkyl, C1-C6Alkoxy, C2-C6Alkenyloxy group,
C2-C6Alkynyloxy group, C3-C8Cycloalkyloxy, C4-C8Cycloalkyl alkoxy, C1-C6Alkylthio group, C2-C6Alkenylthio group, C2-C6Alkynes sulfenyl,
C3-C8Cycloalkylthio, C4-C8Alkylthio cycloalkyl and C6-C10Aryl, wherein foregoing C1-C6Alkyl, C2-C6Alkenyl, C2-C6Alkynes
Base, C3-C8Cycloalkyl, C4-C8Cycloalkyl-alkyl, C1-C6Alkoxy, C2-C6Alkenyloxy group, C2-C6Alkynyloxy group, C3-C8Cycloalkyloxy,
C4-C8Cycloalkyl alkoxy, C1-C6Alkylthio group, C2-C6Alkenylthio group, C2-C6Alkynes sulfenyl, C3-C8Cycloalkylthio, C4-C8Cycloalkyl alkane
Sulfenyl and C6-C10Aryl group is optionally independently selected by one or more from the group substitution of the following group：Halogen, nitro, hydroxyl
Base, sulfydryl, carboxyl, sulfonic group, amino, cyano, C1-C4Alkyl, C1-C4Alkoxy, C1-C4Alkylthio group, C2-C4Alkenyl and C2-C4
Alkynyl；And/or
R8、R9、R10、R11And R12It is independently from each other hydrogen, halogen, nitro, hydroxyl, sulfydryl, carboxyl, sulfonic group, amino, cyanogen
Base, C1-C6Alkyl, C2-C6Alkenyl, C2-C6Alkynyl, C3-C8Cycloalkyl, C4-C8Cycloalkyl-alkyl, C1-C6Alkoxy, C2-C6Alkene oxygen
Base, C2-C6Alkynyloxy group, C3-C8Cycloalkyloxy, C4-C8Cycloalkyl alkoxy, C1-C6Alkylthio group, C2-C6Alkenylthio group, C2-C6Alkynes sulphur
Base, C3-C8Cycloalkylthio, C4-C8Alkylthio cycloalkyl and C6-C10Aryl, wherein foregoing C1-C6Alkyl, C2-C6Alkenyl, C2-C6
Alkynyl, C3-C8Cycloalkyl, C4-C8Cycloalkyl-alkyl, C1-C6Alkoxy, C2-C6Alkenyloxy group, C2-C6Alkynyloxy group, C3-C8Cycloalkanes oxygen
Base, C4-C8Cycloalkyl alkoxy, C1-C6Alkylthio group, C2-C6Alkenylthio group, C2-C6Alkynes sulfenyl, C3-C8Cycloalkylthio, C4-C8Cycloalkanes
Base alkylthio group and C6-C10Aryl group is optionally independently selected by one or more from the group substitution of the following group：Halogen, nitre
Base, hydroxyl, sulfydryl, carboxyl, sulfonic group, amino, cyano, C1-C4Alkyl, C1-C4Alkoxy, C1-C4Alkylthio group, C2-C4Alkenyl and
C2-C4Alkynyl.
6. compound as claimed in one of claims 1-4, wherein
R1、R2、R3、R4And R5It is independently from each other hydrogen, halogen, C1-C4Alkyl, C1-C4Alkoxy and C1-C4Alkylthio group, wherein
Foregoing C1-C4Alkyl, C1-C4Alkoxy and C1-C4Alkylthio group is optionally independently selected by one or more from the group of the following group
Substitution：Halogen, C1-C4Alkyl, C1-C4Alkoxy and C1-C4Alkylthio group；And/or
R8、R9、R10、R11And R12It is independently from each other hydrogen, halogen, C1-C4Alkyl, C2-C4Alkenyl, C2-C4Alkynyl, C1-C4Alcoxyl
Base and C1-C4Alkylthio group, wherein foregoing C1-C4Alkyl, C2-C4Alkenyl, C2-C4Alkynyl, C1-C4Alkoxy and C1-C4Alkylthio group base
Group is optionally independently selected by one or more from the group substitution of the following group：Halogen, C1-C4Alkyl, C1-C4Alkoxy and C1-
C4Alkylthio group.
7. compound according to claim 1, the wherein compound are selected from the group：
8. a kind of method for preparing formula as claimed in one of claims 1-7 (I) compound, including make formula (II) compound with
Formula (III) compound carries out esterification, obtains formula (I) compound,
Wherein R1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11、R12、R13And R14If any one of claim 1-7 is defined,
And X is hydroxyl or halogen.
9. method according to claim 8, wherein esterification carry out in the presence of a catalyst, preferred catalyst is to be selected from the group
One or more：Sulfuric acid, perchloric acid, zinc chloride, ferric trichloride, pyridine, p-methyl benzenesulfonic acid, sodium hydroxide, potassium hydroxide,
Sodium carbonate, sodium acid carbonate, sodium tert-butoxide, sodium ethoxide, sodium hydride, hydrofining, calcium hydride and tertiary amine, such as trialkylamine, such as three
Methyl amine and triethylamine.
10. purposes of the compound as claimed in one of claims 1-7 as photoinitiator.
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| CN108794333A (en) * | 2018-06-29 | 2018-11-13 | 湖北固润科技股份有限公司 | The method for preparing cinnamic acid benzoyl first ester type compound |
| CN110563588A (en) * | 2018-06-06 | 2019-12-13 | 湖北固润科技股份有限公司 | Mono-or di-cinnamate photoinitiator, and preparation method and application thereof |
| CN110563589A (en) * | 2018-06-06 | 2019-12-13 | 湖北固润科技股份有限公司 | Mono-or di-methyl cinnamate photoinitiator, and preparation method and application thereof |
| WO2020000359A1 (en) * | 2018-06-29 | 2020-01-02 | 湖北固润科技股份有限公司 | Method for preparing methyl benzoylcinnamate compound |
| CN117843923A (en) * | 2023-12-27 | 2024-04-09 | 江苏领瑞新材料科技有限公司 | Cinnamic acid intrinsic flame-retardant epoxy resin and preparation method thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110563588A (en) * | 2018-06-06 | 2019-12-13 | 湖北固润科技股份有限公司 | Mono-or di-cinnamate photoinitiator, and preparation method and application thereof |
| CN110563589A (en) * | 2018-06-06 | 2019-12-13 | 湖北固润科技股份有限公司 | Mono-or di-methyl cinnamate photoinitiator, and preparation method and application thereof |
| CN110563589B (en) * | 2018-06-06 | 2023-02-03 | 湖北固润科技股份有限公司 | Single or double cinnamic acid methyl ester photoinitiator and its preparation method and application |
| CN110563588B (en) * | 2018-06-06 | 2023-02-17 | 湖北固润科技股份有限公司 | Single or double cinnamate photoinitiator and its preparation method and application |
| CN108794333A (en) * | 2018-06-29 | 2018-11-13 | 湖北固润科技股份有限公司 | The method for preparing cinnamic acid benzoyl first ester type compound |
| WO2020000359A1 (en) * | 2018-06-29 | 2020-01-02 | 湖北固润科技股份有限公司 | Method for preparing methyl benzoylcinnamate compound |
| CN117843923A (en) * | 2023-12-27 | 2024-04-09 | 江苏领瑞新材料科技有限公司 | Cinnamic acid intrinsic flame-retardant epoxy resin and preparation method thereof |
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| Publication number | Publication date |
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| CN108117488B (en) | 2020-02-11 |
| WO2018094960A1 (en) | 2018-05-31 |
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