CN113527229B - Tertiary amine benzoate compound, preparation method thereof and photo-curing composition - Google Patents
Tertiary amine benzoate compound, preparation method thereof and photo-curing composition Download PDFInfo
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- CN113527229B CN113527229B CN202010318405.5A CN202010318405A CN113527229B CN 113527229 B CN113527229 B CN 113527229B CN 202010318405 A CN202010318405 A CN 202010318405A CN 113527229 B CN113527229 B CN 113527229B
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- -1 Tertiary amine benzoate compound Chemical class 0.000 title claims abstract description 97
- 239000000203 mixture Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000000016 photochemical curing Methods 0.000 title abstract description 14
- 125000000217 alkyl group Chemical group 0.000 claims description 45
- 150000001875 compounds Chemical class 0.000 claims description 31
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- 125000003545 alkoxy group Chemical group 0.000 claims description 16
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 15
- 125000003118 aryl group Chemical group 0.000 claims description 15
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 15
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 13
- 125000000732 arylene group Chemical group 0.000 claims description 11
- 125000001072 heteroaryl group Chemical group 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- 239000012670 alkaline solution Substances 0.000 claims description 9
- 235000010290 biphenyl Nutrition 0.000 claims description 9
- 239000004305 biphenyl Substances 0.000 claims description 9
- 125000002947 alkylene group Chemical group 0.000 claims description 8
- 125000002993 cycloalkylene group Chemical group 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 125000003342 alkenyl group Chemical group 0.000 claims description 6
- 125000002541 furyl group Chemical group 0.000 claims description 6
- 125000001041 indolyl group Chemical group 0.000 claims description 6
- 125000001624 naphthyl group Chemical group 0.000 claims description 6
- 125000004076 pyridyl group Chemical group 0.000 claims description 6
- 125000001544 thienyl group Chemical group 0.000 claims description 6
- 239000000853 adhesive Substances 0.000 claims description 5
- 230000001070 adhesive effect Effects 0.000 claims description 5
- 239000003973 paint Substances 0.000 claims description 4
- 238000007142 ring opening reaction Methods 0.000 claims description 4
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 3
- 125000005119 alkyl cycloalkyl group Chemical group 0.000 claims description 3
- 125000001316 cycloalkyl alkyl group Chemical group 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000003444 phase transfer catalyst Substances 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 2
- SNOOUWRIMMFWNE-UHFFFAOYSA-M sodium;6-[(3,4,5-trimethoxybenzoyl)amino]hexanoate Chemical compound [Na+].COC1=CC(C(=O)NCCCCCC([O-])=O)=CC(OC)=C1OC SNOOUWRIMMFWNE-UHFFFAOYSA-M 0.000 claims 1
- 238000006116 polymerization reaction Methods 0.000 abstract description 11
- 238000013508 migration Methods 0.000 abstract description 9
- 230000005012 migration Effects 0.000 abstract description 9
- 238000001723 curing Methods 0.000 abstract description 7
- 239000011159 matrix material Substances 0.000 abstract description 6
- 239000003999 initiator Substances 0.000 abstract description 5
- 239000011347 resin Substances 0.000 abstract description 5
- 229920005989 resin Polymers 0.000 abstract description 5
- 150000003512 tertiary amines Chemical class 0.000 description 15
- 239000000976 ink Substances 0.000 description 9
- 239000012044 organic layer Substances 0.000 description 9
- 125000000524 functional group Chemical group 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 125000003884 phenylalkyl group Chemical group 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000004593 Epoxy Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 239000000852 hydrogen donor Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- GVOISEJVFFIGQE-YCZSINBZSA-N n-[(1r,2s,5r)-5-[methyl(propan-2-yl)amino]-2-[(3s)-2-oxo-3-[[6-(trifluoromethyl)quinazolin-4-yl]amino]pyrrolidin-1-yl]cyclohexyl]acetamide Chemical compound CC(=O)N[C@@H]1C[C@H](N(C)C(C)C)CC[C@@H]1N1C(=O)[C@@H](NC=2C3=CC(=CC=C3N=CN=2)C(F)(F)F)CC1 GVOISEJVFFIGQE-YCZSINBZSA-N 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- 238000010189 synthetic method Methods 0.000 description 3
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 3
- 125000002529 biphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C12)* 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- HBENZIXOGRCSQN-VQWWACLZSA-N (1S,2S,6R,14R,15R,16R)-5-(cyclopropylmethyl)-16-[(2S)-2-hydroxy-3,3-dimethylpentan-2-yl]-15-methoxy-13-oxa-5-azahexacyclo[13.2.2.12,8.01,6.02,14.012,20]icosa-8(20),9,11-trien-11-ol Chemical compound N1([C@@H]2CC=3C4=C(C(=CC=3)O)O[C@H]3[C@@]5(OC)CC[C@@]2([C@@]43CC1)C[C@@H]5[C@](C)(O)C(C)(C)CC)CC1CC1 HBENZIXOGRCSQN-VQWWACLZSA-N 0.000 description 1
- KJSGODDTWRXQRH-UHFFFAOYSA-N 2-(dimethylamino)ethyl benzoate Chemical compound CN(C)CCOC(=O)C1=CC=CC=C1 KJSGODDTWRXQRH-UHFFFAOYSA-N 0.000 description 1
- SRVFFFJZQVENJC-IHRRRGAJSA-N aloxistatin Chemical compound CCOC(=O)[C@H]1O[C@@H]1C(=O)N[C@@H](CC(C)C)C(=O)NCCC(C)C SRVFFFJZQVENJC-IHRRRGAJSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- OSVHLUXLWQLPIY-KBAYOESNSA-N butyl 2-[(6aR,9R,10aR)-1-hydroxy-9-(hydroxymethyl)-6,6-dimethyl-6a,7,8,9,10,10a-hexahydrobenzo[c]chromen-3-yl]-2-methylpropanoate Chemical compound C(CCC)OC(C(C)(C)C1=CC(=C2[C@H]3[C@H](C(OC2=C1)(C)C)CC[C@H](C3)CO)O)=O OSVHLUXLWQLPIY-KBAYOESNSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 229940126214 compound 3 Drugs 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N monoethanolamine hydrochloride Natural products NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- AICOOMRHRUFYCM-ZRRPKQBOSA-N oxazine, 1 Chemical compound C([C@@H]1[C@H](C(C[C@]2(C)[C@@H]([C@H](C)N(C)C)[C@H](O)C[C@]21C)=O)CC1=CC2)C[C@H]1[C@@]1(C)[C@H]2N=C(C(C)C)OC1 AICOOMRHRUFYCM-ZRRPKQBOSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- FZUGPQWGEGAKET-UHFFFAOYSA-N parbenate Chemical compound CCOC(=O)C1=CC=C(N(C)C)C=C1 FZUGPQWGEGAKET-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D305/00—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms
- C07D305/02—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms not condensed with other rings
- C07D305/04—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D305/06—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The application provides a tertiary amine benzoate compound, a preparation method thereof and a photo-curing composition. The tertiary amine benzoate compound of the application is a multifunctional structure which introduces low polymerization at the 4-carboxyl of the molecular structure of the 4-carboxyl phenyl tertiary amine compound, on one hand, enhances the solubility of the tertiary amine benzoate compound and matrix resin, thereby leading the tertiary amine benzoate compound to be better matched with a light source and be used as a sensitizer and other initiators in a matching way. On the other hand, the introduction of the low-polymerization multifunctional structure enables the tertiary amine benzoate compound to have larger molecular weight, thereby greatly reducing the migration possibility of the tertiary amine benzoate compound. Therefore, the photocuring composition comprising the tertiary amine benzoate compound disclosed by the application has extremely low mobility on the basis of retaining the original basic performance of the 4-carboxyphenyl tertiary amine compound sensitizer, so that the performance of accelerating the ink curing rate and improving the photosensitive efficiency of the photoinitiator of the sensitizer can be better exerted.
Description
Technical Field
The application relates to the technical field of sensitizer, in particular to a tertiary amine benzoate compound, a preparation method thereof and a photo-curing composition.
Background
The tertiary amine benzoate is a high-efficiency amine accelerator, is usually used together with a hydrogen-abstraction type photoinitiator, can be used as a sensitizer to accelerate the polymerization of the photoinitiator, can effectively eliminate the interference of oxygen to the photoinitiator, represents products such as N, N-ethyl dimethyl benzoate, N-2-ethyl dimethyl benzoate and dimethylaminoethyl benzoate, has the advantages of low odor, difficult yellowing and the like compared with aliphatic tertiary amine sensitizers and ethanolamine tertiary amine sensitizers, has good activity, and is widely applied to formulas such as paint, printing ink, adhesive and the like. However, most of the current tertiary amine benzoate sensitizers hardly do zero migration.
Disclosure of Invention
The application mainly aims to provide a tertiary amine benzoate compound, a preparation method thereof and a photocuring composition, so as to solve the problem of high mobility of a tertiary amine benzoate sensitizer in the prior art.
In order to achieve the above object, according to one aspect of the present application, there is provided a tertiary amine benzoate compound having the following general formula I:
m is an n-valent substituent, M isC 1 ～C 40 Alkyl, C of (2) 1 ～C 40 Alkylene group, C 7 ～C 40 Aralkyl of (C) 7 ～C 60 Aryl alkylene, C 3 ～C 40 Cycloalkyl, C 3 ～C 40 Cycloalkylene of C 1 ～C 40 Alkoxy, C 6 ～C 60 Aryl, C of (2) 12 ～C 60 Arylene of (C) 4 ～C 12 Any one of the heteroaryl groups of (1), wherein R 5 ' is H, C 1 ～C 40 Alkyl, C of (2) 3 ～C 40 Cycloalkyl, C 7 ～C 40 Aralkyl of (C) 1 ～C 40 Alkoxy, C 6 ～C 60 Aryl, C of (2) 4 ～C 12 Any one of heteroaryl groups of (a); r is R 1 、R 2 Each independently is a substituted or unsubstituted C 1 ～C 10 Alkyl, substituted or unsubstituted C 3 ～C 12 Cycloalkyl, substituted or unsubstituted C 1 ～C 10 Alkoxy, substituted or unsubstituted C 7 ～C 20 Aralkyl, substituted or unsubstituted C 6 ～C 20 And R is any one of aryl groups of (C) 1 And R is 2 At least one H on at least one alpha-C; r is R 3 、R 4 Each independently is H, substituted or unsubstituted C 1 ～C 10 Alkyl, substituted or unsubstituted C 1 ～C 10 Alkoxy, substituted or unsubstituted C 3 ～C 12 Cycloalkyl, substituted or unsubstituted C 6 ～C 20 Aryl, substituted or unsubstituted C 4 ～C 12 Heteroaryl, substituted or unsubstituted C 7 ～C 20 Aralkyl, -NO 2 、-CF 3 Any one of them; r is R 5 、R 6 、R 7 、R 8 Each independently is H, substituted or unsubstituted phenyl, substituted or unsubstituted C 1 ～C 5 Alkyl, -NO of (C) 2 Substituted or unsubstituted C 1 ～C 5 Any one of the alkoxy groups of (a); n is any integer from 1 to 3, m is any integer from 1 to 6, and q is any integer from 0 to 3.
Further, R is as described above 1 、R 2 Each independently selected from substituted or unsubstituted C 1 ～C 5 Straight-chain alkyl, substituted or unsubstituted C 1 ～C 5 Branched alkyl, substituted or unsubstituted C 3 ～C 6 Cycloalkyl, substituted or unsubstituted C 7 ～C 10 Phenylalkyl, substituted or unsubstituted C 6 ～C 15 Any one of the aryl groups of (2), preferably R 1 And R is R 2 The same and both methyl groups.
Further, R is as described above 3 、R 4 Each independently selected from H, substitution, orUnsubstituted C 1 ～C 5 Straight-chain alkyl, substituted or unsubstituted C 1 ～C 5 Branched alkyl, substituted or unsubstituted C 1 ～C 5 Alkoxy, substituted or unsubstituted C 3 ～C 6 Cycloalkyl, substituted or unsubstituted C 6 ～C 10 Phenyl, substituted or unsubstituted C 7 ～C 12 Any one of the aralkyl groups of (2), preferably R 3 And R is R 4 The same and all are H.
Further, when q is 0, n is 1 or 2, and when n is 1, M is preferably substituted or unsubstituted C 1 ～C 20 Straight-chain alkyl, substituted or unsubstituted C 3 ～C 20 Branched alkyl, substituted or unsubstituted C 7 ～C 20 Aralkyl, substituted or unsubstituted C 3 ～C 20 Cycloalkyl, substituted or unsubstituted C 1 ～C 20 Alkoxy, substituted or unsubstituted C 6 ～C 20 Aryl, substituted or unsubstituted C 4 ～C 12 Any one of heteroaryl groups of (a); further preferred M is substituted or unsubstituted C 1 ～C 10 Straight-chain alkyl, substituted or unsubstituted C 3 ～C 10 Branched alkyl, substituted or unsubstituted C 7 ～C 20 Is a phenylalkyl group, a substituted or unsubstituted C 13 ～C 20 Is a biphenylalkyl group, a substituted or unsubstituted C 3 ～C 10 Cycloalkyl, substituted or unsubstituted C 1 ～C 10 Substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted thienyl, substituted or unsubstituted furyl, substituted or unsubstituted pyridyl, substituted or unsubstituted indolyl; when n is 2, M is preferably substituted or unsubstituted C 1 ～C 20 Alkylene, substituted or unsubstituted C 7 ～C 20 Aryl alkylene, substituted or unsubstituted C 3 ～C 20 Cycloalkylene, substituted or unsubstituted C 12 ～C 20 Any one of arylene groups of (a); further preferred M is a substitution orUnsubstituted C 1 ～C 10 Alkylene, substituted or unsubstituted C 7 ～C 12 Phenyl alkylene, substituted or unsubstituted C 12 ～C 20 Is a biphenylene group, a substituted or unsubstituted C 3 ～C 12 Cycloalkylene, substituted or unsubstituted C 12 ～C 20 Any one of arylene groups of (a).
Further, when q is 1 to 3, n is 3 and M isPreferably R 5 ' H, substituted or unsubstituted C 1 ～C 20 Straight-chain alkyl, substituted or unsubstituted C 3 ～C 2 Branched alkyl, substituted or unsubstituted C 7 ～C 20 Aralkyl, substituted or unsubstituted C 3 ～C 20 Cycloalkyl, substituted or unsubstituted C 1 ～C 20 Alkoxy, substituted or unsubstituted C 6 ～C 20 Aryl, substituted or unsubstituted C 4 ～C 12 Any one of heteroaryl groups of (a); further preferably R 5 ' H, substituted or unsubstituted C 1 ～C 10 Straight-chain alkyl, substituted or unsubstituted C 3 ～C 10 Branched alkyl, substituted or unsubstituted C 7 ～C 20 Is a phenylalkyl group, a substituted or unsubstituted C 13 ～C 20 Is a biphenylalkyl group, a substituted or unsubstituted C 3 ～C 10 Cycloalkyl, substituted or unsubstituted C 1 ～C 10 Substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted thienyl, substituted or unsubstituted furyl, substituted or unsubstituted pyridyl, substituted or unsubstituted indolyl.
Further, n is 2, M is a substituted or unsubstituted C 12 ～C 20 Is preferably any one of arylene groups of (2), M is preferably
Wherein, represents a binding position, R 1 ′、R 2 ′、R 3 ′、R 4 ' each independently selected from H, substituted or unsubstituted C 1 ～C 20 Straight-chain alkyl, substituted or unsubstituted C 3 ～C 20 Branched alkyl, substituted or unsubstituted phenyl, substituted or unsubstituted C 3 ～C 20 Alkyl cycloalkyl, substituted or unsubstituted C 4 ～C 20 Cycloalkyl alkyl, substituted or unsubstituted C 2 ～C 20 Alkenyl groups of (a) and (b) are each independently selected from the group consisting of alkenyl groups.
Further, R is as described above 1 ′、R 2 ′、R 3 ' and R 4 -CH in 2 -CH which may each independently be substituted, preferably substituted, by-O 2 The number is 1 to 5.
Further, the tertiary amine benzoate compound has the structural formula
Any one of the following.
According to another aspect of the present application, there is provided a process for producing the aforementioned tertiary amine benzoate compound, which comprises: carrying out ring opening reaction on the compound a and the compound b under alkaline conditions to obtain tertiary amine 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、R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 n, m, q, M, R of the same general structural formula I 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 。
Further, the preparation method comprises the following steps: step S1, mixing a compound a, a compound b, a phase transfer catalyst and a solvent to obtain a mixture; and S2, reacting the mixture in an alkaline environment for 3-10 hours to obtain a tertiary amine benzoate compound, wherein the reaction is preferably carried out at 50-150 ℃, the alkaline environment is formed by adopting an alkaline solution, 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 application, there is provided a photocurable composition comprising a sensitizer which is the aforementioned tertiary amine benzoate compound.
Further, the photocurable composition is any one of paint, ink and adhesive.
By using the technical scheme of the application, tertiary amine is used as a hydrogen donor of the hydrogen extraction type photoinitiator, the activity of the effective molecules of the photoinitiator can be improved, so that the efficiency of photoinitiation polymerization reaction can be greatly promoted, and the tertiary amine benzoate compound is a low-polymerization multifunctional structure introduced at the 4-carboxyl of the molecular structure of the 4-carboxyl phenyl tertiary amine compound, on one hand, epoxy four-ring groups and various functional groups (M, R 5 、R 6 、R 7 、R 8 ) The introduction of the tertiary amine benzoate compound while maintaining the molecular structure of the 4-carboxyphenyl tertiary amine compound, thereby enhancing the solubility of the tertiary amine benzoate compound with the matrix resinSo that the light source can be matched well and can be used as a sensitizer and other initiators in a matched way. On the other hand, the introduction of the low-polymerization multifunctional structure enables the tertiary amine benzoate compound to have larger molecular weight, thereby greatly reducing the migration possibility of the tertiary amine benzoate compound. Therefore, the photocuring composition comprising the tertiary amine benzoate compound disclosed by the application has extremely low mobility on the basis of retaining the original basic performance of the 4-carboxyphenyl tertiary amine compound sensitizer, so that the performance of accelerating the ink curing rate and improving the photosensitive efficiency of the photoinitiator of the sensitizer can be better exerted.
Detailed Description
It should be noted that, without conflict, the embodiments of the present application and features of the embodiments may be combined with each other. The present application will be described in detail with reference to examples.
As analyzed by the background art, the prior art has the problem of high mobility of tertiary amine benzoate sensitizer, and in order to solve the problem, the application provides a tertiary amine benzoate compound, a preparation method thereof and a photo-curing composition.
In a typical embodiment of the present application, there is provided a tertiary amine benzoate compound having the following formula I:
m is an n-valent substituent, M isC 1 ～C 40 Alkyl, C of (2) 1 ～C 40 Alkylene group, C 7 ～C 40 Aralkyl of (C) 7 ～C 60 Aryl alkylene, C 3 ～C 40 Cycloalkyl, C 3 ～C 40 Cycloalkylene of C 1 ～C 40 Alkoxy, C 6 ～C 60 Aryl, C of (2) 12 ～C 60 Arylene of (C) 4 ～C 12 Any one of the heteroaryl groups of (1), wherein R 5 ' is H, C 1 ～C 40 Alkyl, C of (2) 3 ～C 40 Cycloalkyl, C 7 ～C 40 Aralkyl of (C) 1 ～C 40 Alkoxy, C 6 ～C 60 Aryl, C of (2) 4 ～C 12 Any one of heteroaryl groups of (a); r is R 1 、R 2 Each independently is a substituted or unsubstituted C 1 ～C 10 Alkyl, substituted or unsubstituted C 3 ～C 12 Cycloalkyl, substituted or unsubstituted C 7 ～C 20 Aralkyl, substituted or unsubstituted C 6 ～C 20 And R is any one of aryl groups of (C) 1 And R is 2 At least one H on at least one alpha-C; r is R 3 、R 4 Each independently is H, substituted or unsubstituted C 1 ～C 10 Alkyl, substituted or unsubstituted C 1 ～C 10 Alkoxy, substituted or unsubstituted C 3 ～C 12 Cycloalkyl, substituted or unsubstituted C 6 ～C 20 Aryl, substituted or unsubstituted C 4 ～C 12 Heteroaryl, substituted or unsubstituted C 7 ～C 20 Aralkyl, -NO 2 、-CF 3 Any one of them; r is R 5 、R 6 、R 7 、R 8 Each independently is H, substituted or unsubstituted phenyl, substituted or unsubstituted C 1 ～C 5 Alkyl, -NO of (C) 2 Substituted or unsubstituted C 1 ～C 5 Any one of the alkoxy groups of (a); n is any integer from 1 to 3, m is any integer from 1 to 6, and q is any integer from 0 to 3.
The tertiary amine is used as a hydrogen donor of the hydrogen extraction type photoinitiator, the activity of the effective molecules of the photoinitiator can be improved, so that the efficiency of photoinitiation polymerization reaction can be greatly promoted, the tertiary amine type benzoate compound of the application is a multi-functional group structure which is introduced into the 4-carboxyl of the molecular structure of the 4-carboxyl phenyl tertiary amine type compound, on one hand, the epoxy four-membered ring group in the multi-functional group structure is prepared byMultiple functional groups (M, R) 5 、R 6 、R 7 、R 8 ) The introduction of the tertiary amine type compound enhances the solubility of the tertiary amine type benzoate compound and matrix resin while retaining the molecular structure of the 4-carboxyphenyl tertiary amine type compound, so that the tertiary amine type benzoate compound can be matched with a light source well and can be used as a sensitizer and other initiators in a matching way. On the other hand, the introduction of the low-polymerization multifunctional structure enables the tertiary amine benzoate compound to have larger molecular weight, thereby greatly reducing the migration possibility of the tertiary amine benzoate compound.
Therefore, the photocuring composition comprising the tertiary amine benzoate compound disclosed by the application has extremely low mobility on the basis of retaining the original basic performance of the 4-carboxyphenyl tertiary amine compound sensitizer, so that the performance of accelerating the ink curing rate and improving the photosensitive efficiency of the photoinitiator of the sensitizer can be better exerted.
In order to make the C-centered active aminoalkyl radical more reactive, R is preferably 1 、R 2 Each independently selected from substituted or unsubstituted C 1 ～C 5 Straight-chain alkyl, substituted or unsubstituted C 1 ～C 5 Branched alkyl, substituted or unsubstituted C 3 ～C 6 Cycloalkyl, substituted or unsubstituted C 7 ～C 10 Phenylalkyl, substituted or unsubstituted C 6 ～C 15 Any one of the aryl groups of (2), preferably R 1 And R is R 2 The same and both methyl groups.
To reduce R 3 、R 4 A reduction in the efficiency of the reaction of compound a with compound b due to steric hindrance, preferably R 3 、R 4 Each independently selected from H, substituted or unsubstituted C 1 ～C 5 Straight-chain alkyl, substituted or unsubstituted C 1 ～C 5 Branched alkyl, substituted or unsubstituted C 1 ～C 5 Alkoxy, substituted or unsubstituted C 3 ～C 6 Cycloalkyl, substituted or unsubstituted C 6 ～C 10 Phenyl, substituted or unsubstituted C 7 ～C 12 Any one of the aralkyl groups of (2), preferably R 3 And R is R 4 The same and all are H.
In order to further improve the solubility of the tertiary amine benzoate compound in the matrix resin, when q is 0, n is 1 or 2, and when n is 1, M is preferably substituted or unsubstituted C 1 ～C 20 Straight-chain alkyl, substituted or unsubstituted C 3 ～C 20 Branched alkyl, substituted or unsubstituted C 7 ～C 20 Aralkyl, substituted or unsubstituted C 3 ～C 20 Cycloalkyl, substituted or unsubstituted C 1 ～C 20 Alkoxy, substituted or unsubstituted C 6 ～C 20 Aryl, substituted or unsubstituted C 4 ～C 12 Any one of heteroaryl groups of (a); further preferred M is substituted or unsubstituted C 1 ～C 10 Straight-chain alkyl, substituted or unsubstituted C 3 ～C 10 Branched alkyl, substituted or unsubstituted C 7 ～C 20 Is a phenylalkyl group, a substituted or unsubstituted C 13 ～C 20 Is a biphenylalkyl group, a substituted or unsubstituted C 3 ～C 10 Cycloalkyl, substituted or unsubstituted C 1 ～C 10 Substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted thienyl, substituted or unsubstituted furyl, substituted or unsubstituted pyridyl, substituted or unsubstituted indolyl. When n is 2, M is preferably substituted or unsubstituted C 1 ～C 20 Alkylene, substituted or unsubstituted C 7 ～C 20 Aryl alkylene, substituted or unsubstituted C 3 ～C 20 Cycloalkylene, substituted or unsubstituted C 12 ～C 20 Any one of arylene groups of (a); further preferred M is substituted or unsubstituted C 1 ～C 10 Alkylene, substituted or unsubstituted C 7 ～C 12 Phenyl alkylene, substituted or unsubstituted C 12 ～C 20 Is a biphenylene group, a substituted or unsubstituted C 3 ～C 12 Cycloalkylene, substituted or unsubstituted C 12 ～C 20 Any one of arylene groups of (a).
In order to further increase the sensitivity of the tertiary amine benzoate compound and expand the color range thereof to satisfy the requirements of more photocurable compositions, it is preferable that when q is 1 to 3, n is 3 and M isPreferably R 5 ' H, substituted or unsubstituted C 1 ～C 20 Straight-chain alkyl, substituted or unsubstituted C 3 ～C 2 Branched alkyl, substituted or unsubstituted C 7 ～C 20 Aralkyl, substituted or unsubstituted C 3 ～C 20 Cycloalkyl, substituted or unsubstituted C 1 ～C 20 Alkoxy, substituted or unsubstituted C 6 ～C 20 Aryl, substituted or unsubstituted C 4 ～C 12 Any one of heteroaryl groups of (a); further preferably R 5 ' H, substituted or unsubstituted C 1 ～C 10 Straight-chain alkyl, substituted or unsubstituted C 3 ～C 10 Branched alkyl, substituted or unsubstituted C 7 ～C 20 Is a phenylalkyl group, a substituted or unsubstituted C 13 ～C 20 Is a biphenylalkyl group, a substituted or unsubstituted C 3 ～C 10 Cycloalkyl, substituted or unsubstituted C 1 ～C 10 Substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted thienyl, substituted or unsubstituted furyl, substituted or unsubstituted pyridyl, substituted or unsubstituted indolyl.
In one embodiment of the present application, n is 2 and M is a substituted or unsubstituted C 12 ～C 20 Is preferably any one of arylene groups of (2), M is preferably
In (a) and (b)Any one, wherein, represents a binding position, R 1 ′、R 2 ′、R 3 ′、R 4 ' each independently selected from H, substituted or unsubstituted C 1 ～C 20 Straight-chain alkyl, substituted or unsubstituted C 3 ～C 20 Branched alkyl, substituted or unsubstituted phenyl, substituted or unsubstituted C 3 ～C 20 Alkyl cycloalkyl, substituted or unsubstituted C 4 ～C 20 Cycloalkyl alkyl, substituted or unsubstituted C 2 ～C 20 Alkenyl groups of (a) and (b) are each independently selected from the group consisting of alkenyl groups.
When n is 2, M further enriches the functional group structure of the tertiary amine benzoate compound, so that the modification of the tertiary amine benzoate compound to the compound a (4-carboxyphenyl tertiary amine compound) is improved, and the tertiary amine benzoate compound has better performance.
In order to further enrich the variety of the arylene-substituted functional group, the R is preferably 1 ′、R 2 ′、R 3 ' and R 4 -CH in 2 -CH which may each independently be substituted, preferably substituted, by-O 2 The number is 1 to 5.
In one embodiment of the present application, the tertiary amine benzoate compound has the formula
Any one of the following.
The tertiary amine benzoate compound of the application has abundant substituted functional groups, and also has any substituted or unsubstituted substituent of 1 to 3 valences, and can meet the requirements of various photo-curing compositions.
In another exemplary embodiment of the present application, there is provided a process for preparing the aforementioned tertiary amine benzoate compound, comprising: carrying out ring opening reaction on the compound a and the compound b under alkaline conditions to obtain tertiary amine 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、R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 n, m, q, M, R of the same general structural formula I 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 。
The application adopts a common 4-carboxyl phenyl tertiary amine compound (compound a) and a multifunctional group oligomeric compound (compound b) with a ternary ring and a quaternary ring to carry out a one-step ring opening reaction under alkaline conditions to obtain a tertiary amine benzoate compound with larger molecular weight, thereby modifying the 4-carboxyl phenyl tertiary amine compound molecule, and the reaction general formula is as follows:
the synthesis method is simple, the tertiary amine benzoate compound of the application introduces an oligomeric multifunctional structure at the 4-carboxyl of the molecular structure of the 4-carboxyphenyl tertiary amine compound, on one hand, the epoxy four-membered ring group and a plurality of functional groups (M, R) 5 、R 6 、R 7 、R 8 ) The introduction of the tertiary amine type compound enhances the solubility of the tertiary amine type benzoate compound and matrix resin while retaining the molecular structure of the 4-carboxyphenyl tertiary amine type compound, so that the tertiary amine type benzoate compound can be matched with a light source well and can be used as a sensitizer and other initiators in a matching way. On the other hand, oligomeric polyfunctional groupsThe introduction of the structure allows the tertiary amine benzoate compound to have a larger molecular weight, thereby greatly reducing the possibility of migration thereof.
Therefore, the photocuring composition comprising the tertiary amine benzoate compound disclosed by the application has extremely low mobility on the basis of retaining the original basic performance of the 4-carboxyphenyl tertiary amine compound sensitizer, so that the performance of accelerating the ink curing rate and improving the photosensitive efficiency of the photoinitiator of the sensitizer can be better exerted.
In order to improve the synthesis efficiency of the tertiary amine benzoate compound, the above-mentioned preparation method preferably comprises: step S1, mixing a compound a, a compound b, a phase transfer catalyst and a solvent to obtain a mixture; and S2, reacting the mixture in an alkaline environment for 3-10 hours to obtain a tertiary amine benzoate compound, wherein the reaction is preferably carried out at 50-150 ℃, the alkaline environment is formed by adopting an alkaline solution, 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, a photocurable composition is provided that includes a sensitizer that is any of the foregoing.
The photo-curing composition prepared by adopting the tertiary amine benzoate compound has excellent performance.
In yet another embodiment of the present application, the above-described photocurable composition is any one of a paint, an ink, and an adhesive.
The photocurable composition of the present application has extremely low migration in addition to excellent properties of tertiary amine sensitizer as any of coating, ink and adhesive.
The advantageous effects of the present application will be described below with reference to specific examples.
Example 1
To a 250mL four-necked flask, 50mL of toluene, 16.5g of Compound 1a, 30.2 g of Compound 1b and 0.5g of tetrabutylammonium bromide were added, and the mixture was heated to 100℃with stirring, 40g of 1% sodium hydroxide solution was slowly added dropwise, and the reaction was stopped after stirring for 5 hours. 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 with 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, namely tertiary amine benzoate compound 1.MS (M/z): 468 (M+1) +.
Example 2
To a 250mL four-necked flask, 50mL of toluene, 16.5g of Compound 1a, 35.5 g of Compound 2b and 0.5g of tetrabutylammonium bromide were added, and the mixture was heated to 100℃with stirring, 40g of 1% sodium hydroxide solution was slowly added dropwise, and the reaction was stopped after 5 hours of stirring. 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 with 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, namely tertiary amine benzoate compound 2.MS (M/z): 1015 (M+1) +.
Example 3
To a 250mL four-necked flask, 50mL of toluene, 16.5g of compound 1a, 25.9g of compound 3b and 0.5g of tetrabutylammonium bromide were added, and the mixture was heated to 100℃with stirring, 40g of 1% sodium hydroxide solution was slowly added dropwise, and the reaction was stopped after stirring for 5 hours. 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 with 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, namely tertiary amine benzoate compound 3.MS (M/z): 1303 (M+1) +.
Following the reaction procedure analogous to that in examples 1 to 3, the substrates were replaced and the reaction conditions were adapted to give the corresponding tertiary amine benzoate compounds, and the substrates in all examples were listed in Table 1, respectively, and the corresponding tertiary amine benzoate compounds prepared in all examples were listed in Table 2.
The raw materials and sources used in the following experiments:
the 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
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TABLE 2
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Photo-curable compositions were prepared according to the compositions of table 3:
TABLE 3 Table 3
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The respective photocurable compositions (flexo ink formulations) 1 to 16 were formulated with any of the tertiary amine benzoate compounds, EDAB (Shanghai light Engineers chemical Co., ltd.) or DMB (Shanghai light Engineers chemical Co., ltd.) obtained in examples 1 to 14 as sensitizers in the proportions of Table 3, were subjected to performance evaluation by the following performance test methods, and the test results are shown in Table 4.
Sensitivity test:
about 1mg of each of the above-mentioned photocurable composition samples was weighed out and spread on an aluminum crucible, and each of the photocurable composition samples was scanned using a Perkin Elmer differential scanning calorimeter (DSC 8000) equipped with a mercury arc lamp ultraviolet light source (OmniCure-S2000) to be cured. The time until the UV initiates the maximum curing exotherm was recorded, the shorter the time to peak apex, indicating better curing performance.
Migration evaluation:
the sensitizer is prepared into 1X 10 by using ethanol as solvent -5 The absorption peak of the mol/L solution is measured by a UV3010 ultraviolet spectrophotometer; and respectively weighing 0.05g of the cured film prepared by the photo-curing composition under a high-pressure mercury lamp, respectively soaking in 30g of ethanol, standing at normal temperature for 24 hours, taking the soaking solution with the same volume, measuring the absorption peak at the maximum absorption wavelength by using an ultraviolet spectrophotometer, and observing whether the two are overlapped at the maximum absorption position or not, if so, indicating migration.
TABLE 4 Table 4
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From the above description, it can be seen that the above embodiments of the present application achieve the following technical effects:
the tertiary amine is used as a hydrogen donor of the hydrogen extraction type photoinitiator, the activity of the effective molecules of the photoinitiator can be improved, so that the efficiency of photoinitiation polymerization reaction can be greatly promoted, and the tertiary amine benzoate compound of the application is a multifunctional structure with the introduction of low polymerization at the 4-carboxyl of the molecular structure of the 4-carboxyl phenyl tertiary amine compound, on the one hand, the epoxy in the multifunctional structure with the low polymerizationFour-membered ring group and various functional groups (M, R) 5 、R 6 、R 7 、R 8 ) The introduction of the tertiary amine type compound enhances the solubility of the tertiary amine type benzoate compound and matrix resin while retaining the molecular structure of the 4-carboxyphenyl tertiary amine type compound, so that the tertiary amine type benzoate compound can be matched with a light source well and can be used as a sensitizer and other initiators in a matching way. On the other hand, the introduction of the low-polymerization multifunctional structure enables the tertiary amine benzoate compound to have larger molecular weight, thereby greatly reducing the migration possibility of the tertiary amine benzoate compound.
Therefore, the photocuring composition comprising the tertiary amine benzoate compound disclosed by the application has extremely low mobility on the basis of retaining the original basic performance of the 4-carboxyphenyl tertiary amine compound sensitizer, so that the performance of accelerating the ink curing rate and improving the photosensitive efficiency of the photoinitiator of the sensitizer can be better exerted.
The above description is only of the preferred embodiments of the present application and is not intended to limit the present application, but various modifications and variations can be made to the present application by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application should be included in the protection scope of the present application.
Claims (14)
1. A tertiary amine benzoate compound characterized by the following formula I:
R 1 、R 2 each independently is C 1 ～C 10 And R is an alkyl group of 1 And R is 2 At least one H on at least one alpha-C;
R 3 、R 4 、R 5 、R 6 、R 7 、R 8 each independently is H; n is any integer from 1 to 3, m is any integer from 1 to 6, and q is any integer from 0 to 3;
when q is 0, n is 1 or 2, and when n is 1, M is C 1 ～C 20 Straight chain alkyl, C 3 ～C 20 Branched alkyl, C 7 ～C 20 Aralkyl of (C) 3 ～C 20 Cycloalkyl, C 1 ～C 20 Alkoxy, C 6 ～C 20 Aryl, C of (2) 4 ～C 12 Any one of heteroaryl groups of (a);
when n is 2, M is C 1 ～C 20 Alkylene group, C 7 ～C 20 Aryl alkylene, C 3 ～C 20 Cycloalkylene of C 12 ～C 20 Arylene group of (2),Any one of them;
when q is 1-3, n is 3, and M isThe R is 5 ' is H, C 1 ～C 10 Straight chain alkyl, C 3 ～C 10 Branched alkyl, C 7 ～C 20 Phenylalkyl radicals C of (2) 13 ～C 20 Biphenyl alkyl, C 3 ～C 10 Cycloalkyl, C 1 ～C 10 Alkoxy, phenyl, biphenyl, naphthyl, thienyl, furyl, pyridyl, indolyl.
2. The tertiary amine benzoate compound according to claim 1, wherein said R 1 With R is as follows 2 The same and both methyl groups.
3. The tertiary amine benzoate compound according to claim 1 or 2, wherein when q is 0, said n is 1 or 2,
when n is 1, M is C 1 ～C 10 Straight chain alkyl, C 3 ～C 10 Is of (2)Chain alkyl, C 7 ～C 20 Phenylalkyl radicals C of (2) 13 ～C 20 Biphenyl alkyl, C 3 ～C 10 Cycloalkyl, C 1 ～C 10 Alkoxy, phenyl, biphenyl, naphthyl, thienyl, furyl, pyridyl, indolyl;
when n is 2, M is C 1 ～C 10 Alkylene, phenylalkylene, C 12 ～C 20 Biphenyl alkylene, C 3 ～C 12 Cycloalkylene of C 12 ～C 20 Any one of arylene groups of (a).
4. The tertiary amine benzoate compound according to claim 1, wherein n is 2 and M is C 12 ～C 20 Any one of arylene groups of (a).
5. The tertiary amine benzoate compound according to claim 1, wherein M is
Wherein, represents a binding position, R 1 ′、R 2 ′、R 3 ′、R 4 ' each independently selected from H, C 1 ～C 20 Straight chain alkyl, C 3 ～C 20 Branched alkyl, phenyl, C 3 ～C 20 Alkyl cycloalkyl, C 4 ～C 20 Cycloalkyl alkyl, C 2 ～C 20 Alkenyl groups of (a) and (b) are each independently selected from the group consisting of alkenyl groups.
6. The tertiary amine benzoate compound of claim 1, wherein the tertiary amine benzoate compound has the structural formula
Any one of the following.
7. A process for the preparation of the tertiary amine benzoate compound according to any one of claims 1 to 6, characterized in that it comprises:
carrying out ring opening reaction on the compound a and the compound b under alkaline conditions to obtain tertiary amine 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:
said n, m, q, M, R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 As described in said n, m, q, M, R in said general structural formula I 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 。
8. The preparation method according to claim 7, characterized in that the preparation method comprises:
step S1, mixing the compound a, the compound b, a phase transfer catalyst and a solvent to obtain a mixture;
and S2, reacting the mixture in an alkaline environment for 3-10 hours to obtain the tertiary amine benzoate compound.
9. The method according to claim 8, wherein the reaction is performed at 50 to 150 ℃ in step S2, and the alkaline environment is formed using an alkaline solution.
10. The method according to claim 9, wherein the alkaline solution is one or more of sodium hydroxide solution, potassium hydroxide solution, and lithium hydroxide solution.
11. The preparation method according to claim 9, wherein the concentration of the alkaline solution is 10 to 40wt%.
12. The method according to claim 8, wherein the solvent is one or more of dichloroethane, acetonitrile, benzene, toluene, and xylene.
13. A photocurable composition comprising a sensitizer, characterized in that the sensitizer is the tertiary amine benzoate compound according to any one of claims 1 to 6.
14. The photocurable composition of claim 13, wherein said photocurable composition is any one of a paint, an ink, and an adhesive.
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