CN115707681B - Naphthalene sensitizer, process for producing the same, photocurable composition and photocurable product - Google Patents
Naphthalene sensitizer, process for producing the same, photocurable composition and photocurable product Download PDFInfo
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- CN115707681B CN115707681B CN202110963717.6A CN202110963717A CN115707681B CN 115707681 B CN115707681 B CN 115707681B CN 202110963717 A CN202110963717 A CN 202110963717A CN 115707681 B CN115707681 B CN 115707681B
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- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 239000000203 mixture Substances 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 title claims description 18
- 230000008569 process Effects 0.000 title claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 21
- 238000002360 preparation method Methods 0.000 claims abstract description 18
- 239000001257 hydrogen Substances 0.000 claims abstract description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 13
- 125000003118 aryl group Chemical group 0.000 claims abstract description 9
- 125000001072 heteroaryl group Chemical group 0.000 claims abstract description 9
- 125000000753 cycloalkyl group Chemical group 0.000 claims abstract description 8
- 125000001424 substituent group Chemical group 0.000 claims abstract description 7
- 238000006467 substitution reaction Methods 0.000 claims abstract description 7
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims abstract 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- 238000005984 hydrogenation reaction Methods 0.000 claims description 27
- 238000006243 chemical reaction Methods 0.000 claims description 26
- 239000003054 catalyst Substances 0.000 claims description 23
- 239000002904 solvent Substances 0.000 claims description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 238000007259 addition reaction Methods 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 13
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- RZVHIXYEVGDQDX-UHFFFAOYSA-N 9,10-anthraquinone Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3C(=O)C2=C1 RZVHIXYEVGDQDX-UHFFFAOYSA-N 0.000 claims description 10
- 238000005804 alkylation reaction Methods 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Natural products CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 238000005727 Friedel-Crafts reaction Methods 0.000 claims description 8
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims description 8
- 125000005913 (C3-C6) cycloalkyl group Chemical group 0.000 claims description 6
- FRASJONUBLZVQX-UHFFFAOYSA-N 1,4-naphthoquinone Chemical compound C1=CC=C2C(=O)C=CC(=O)C2=C1 FRASJONUBLZVQX-UHFFFAOYSA-N 0.000 claims description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical group [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 150000001263 acyl chlorides Chemical class 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 239000011347 resin Substances 0.000 claims description 6
- 229920005989 resin Polymers 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 5
- 239000003999 initiator Substances 0.000 claims description 5
- 230000009471 action Effects 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 3
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 claims description 3
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 3
- 239000003377 acid catalyst Substances 0.000 claims description 3
- 239000000853 adhesive Substances 0.000 claims description 3
- 230000001070 adhesive effect Effects 0.000 claims description 3
- 238000003442 catalytic alkylation reaction Methods 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 claims description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 3
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 3
- 150000008050 dialkyl sulfates Chemical class 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 3
- NUKZAGXMHTUAFE-UHFFFAOYSA-N hexanoic acid methyl ester Natural products CCCCCC(=O)OC NUKZAGXMHTUAFE-UHFFFAOYSA-N 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 3
- 239000012778 molding material Substances 0.000 claims description 3
- 239000000178 monomer Substances 0.000 claims description 3
- 239000003973 paint Substances 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 125000001544 thienyl group Chemical group 0.000 claims description 3
- 230000029936 alkylation Effects 0.000 claims 1
- 239000012299 nitrogen atmosphere Substances 0.000 claims 1
- 238000004383 yellowing Methods 0.000 abstract description 16
- 238000000016 photochemical curing Methods 0.000 abstract description 11
- 206010034972 Photosensitivity reaction Diseases 0.000 abstract description 9
- 125000001624 naphthyl group Chemical group 0.000 abstract description 9
- 230000036211 photosensitivity Effects 0.000 abstract description 9
- 239000000047 product Substances 0.000 description 21
- 239000011248 coating agent Substances 0.000 description 10
- 238000000576 coating method Methods 0.000 description 10
- 238000005160 1H NMR spectroscopy Methods 0.000 description 8
- 239000003153 chemical reaction reagent Substances 0.000 description 8
- 150000002431 hydrogen Chemical class 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 239000000976 ink Substances 0.000 description 6
- 239000000543 intermediate Substances 0.000 description 6
- 206010070834 Sensitisation Diseases 0.000 description 5
- 238000001723 curing Methods 0.000 description 5
- 230000008313 sensitization Effects 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 4
- 229940125904 compound 1 Drugs 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 239000011342 resin composition Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000002411 adverse Effects 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 125000002091 cationic group Chemical group 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 230000000977 initiatory effect Effects 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000002390 rotary evaporation Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229910001868 water Inorganic materials 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N coumarin Chemical compound C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 239000012776 electronic material Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 2
- 230000011987 methylation Effects 0.000 description 2
- 238000007069 methylation reaction Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
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- 239000003960 organic solvent Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920002120 photoresistant polymer Polymers 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- SZUVGFMDDVSKSI-WIFOCOSTSA-N (1s,2s,3s,5r)-1-(carboxymethyl)-3,5-bis[(4-phenoxyphenyl)methyl-propylcarbamoyl]cyclopentane-1,2-dicarboxylic acid Chemical compound O=C([C@@H]1[C@@H]([C@](CC(O)=O)([C@H](C(=O)N(CCC)CC=2C=CC(OC=3C=CC=CC=3)=CC=2)C1)C(O)=O)C(O)=O)N(CCC)CC(C=C1)=CC=C1OC1=CC=CC=C1 SZUVGFMDDVSKSI-WIFOCOSTSA-N 0.000 description 1
- GHYOCDFICYLMRF-UTIIJYGPSA-N (2S,3R)-N-[(2S)-3-(cyclopenten-1-yl)-1-[(2R)-2-methyloxiran-2-yl]-1-oxopropan-2-yl]-3-hydroxy-3-(4-methoxyphenyl)-2-[[(2S)-2-[(2-morpholin-4-ylacetyl)amino]propanoyl]amino]propanamide Chemical compound C1(=CCCC1)C[C@@H](C(=O)[C@@]1(OC1)C)NC([C@H]([C@@H](C1=CC=C(C=C1)OC)O)NC([C@H](C)NC(CN1CCOCC1)=O)=O)=O GHYOCDFICYLMRF-UTIIJYGPSA-N 0.000 description 1
- QFLWZFQWSBQYPS-AWRAUJHKSA-N (3S)-3-[[(2S)-2-[[(2S)-2-[5-[(3aS,6aR)-2-oxo-1,3,3a,4,6,6a-hexahydrothieno[3,4-d]imidazol-4-yl]pentanoylamino]-3-methylbutanoyl]amino]-3-(4-hydroxyphenyl)propanoyl]amino]-4-[1-bis(4-chlorophenoxy)phosphorylbutylamino]-4-oxobutanoic acid Chemical compound CCCC(NC(=O)[C@H](CC(O)=O)NC(=O)[C@H](Cc1ccc(O)cc1)NC(=O)[C@@H](NC(=O)CCCCC1SC[C@@H]2NC(=O)N[C@H]12)C(C)C)P(=O)(Oc1ccc(Cl)cc1)Oc1ccc(Cl)cc1 QFLWZFQWSBQYPS-AWRAUJHKSA-N 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- UNILWMWFPHPYOR-KXEYIPSPSA-M 1-[6-[2-[3-[3-[3-[2-[2-[3-[[2-[2-[[(2r)-1-[[2-[[(2r)-1-[3-[2-[2-[3-[[2-(2-amino-2-oxoethoxy)acetyl]amino]propoxy]ethoxy]ethoxy]propylamino]-3-hydroxy-1-oxopropan-2-yl]amino]-2-oxoethyl]amino]-3-[(2r)-2,3-di(hexadecanoyloxy)propyl]sulfanyl-1-oxopropan-2-yl Chemical compound O=C1C(SCCC(=O)NCCCOCCOCCOCCCNC(=O)COCC(=O)N[C@@H](CSC[C@@H](COC(=O)CCCCCCCCCCCCCCC)OC(=O)CCCCCCCCCCCCCCC)C(=O)NCC(=O)N[C@H](CO)C(=O)NCCCOCCOCCOCCCNC(=O)COCC(N)=O)CC(=O)N1CCNC(=O)CCCCCN\1C2=CC=C(S([O-])(=O)=O)C=C2CC/1=C/C=C/C=C/C1=[N+](CC)C2=CC=C(S([O-])(=O)=O)C=C2C1 UNILWMWFPHPYOR-KXEYIPSPSA-M 0.000 description 1
- 238000010146 3D printing Methods 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 1
- 239000012346 acetyl chloride Substances 0.000 description 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
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- 229940125797 compound 12 Drugs 0.000 description 1
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- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
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- 239000011229 interlayer Substances 0.000 description 1
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- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
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- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
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- 150000002790 naphthalenes Chemical class 0.000 description 1
- 231100000989 no adverse effect Toxicity 0.000 description 1
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Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a naphthalene sensitizer, a preparation method thereof, a photo-curing composition and a photo-curing product, wherein the naphthalene sensitizer has a structure shown in the following structural formula I:wherein R is 1 、R 2 Independently of one another, from substituted or unsubstituted C 1 ‑C 10 Alkyl of (a); r is R 3 Selected from hydrogen, substituted or unsubstituted C 1 ‑C 10 Alkyl, substituted or unsubstituted C 3 ‑C 10 Cycloalkyl, substituted or unsubstituted C 6 ‑C 12 Aryl, substituted or unsubstituted C 4 ‑C 12 Any one of heteroaryl, in alkyl, -CH 2 Optionally substituted by-O-with the proviso that the two-O-groups are not directly linked to each other, the substituents used for the substitution being C 1 ‑C 10 Alkyl, C of (2) 3 ‑C 10 Any one of cycloalkyl groups of (a). The naphthalene sensitizer is prepared by adding R to naphthalene ring 1 、R 2 、R 3 The group improves the photosensitivity of the naphthalene sensitizer and reduces the yellowing phenomenon of the sensitizer after use.
Description
Technical Field
The present invention relates to organic chemistry, and more particularly, to a naphthalene sensitizer, a method for preparing the same, and a photocurable composition and a photocurable product.
Background
The ultraviolet light curing technology has very wide application in the fields of electronic material preparation and the like, and the photoinitiator is a key component of a photo-curing product and plays a decisive role in the photo-curing speed of the photo-curing product. However, in the photocuring system, the photoinitiator is sometimes used together with other components, so that the generation of active intermediates such as free radicals or cations can be promoted, and the photoinitiation efficiency is improved. Particularly in a cationic initiation system, the absorption wavelength of the cationic initiator for ultraviolet rays is generally short, in long-wavelength light curing, the absorption wavelength of the initiator is not matched with a light source, and a sensitizer is often required to be added to improve the initiation efficiency, and the sensitizer of naphthalene, anthracene, coumarin and pyrazoline series is a sensitizer commonly used in the cationic initiation system.
JP2008001641A, JP2008024694A, JP2011144277A and other documents report about a naphthalene series sensitizer with a new structure, but there is still room for further improvement in the sensitization activity, and the yellowing problem caused by sensitization is still further solved.
Disclosure of Invention
The invention mainly aims to provide a naphthalene sensitizer, a preparation method thereof, a photocuring composition and a photocuring product, so as to solve the problems that the naphthalene sensitizer in the prior art is low in activity and causes yellowing after sensitization.
In order to achieve the above object, according to one aspect of the present invention, there is provided a naphthalene sensitizer having a structure represented by the following structural formula I:
wherein,R 1 、R 2 independently of one another, from substituted or unsubstituted C 1 -C 10 Alkyl of (a); r is R 3 Selected from hydrogen, substituted or unsubstituted C 1 -C 10 Alkyl, substituted or unsubstituted C 3 -C 10 Cycloalkyl, substituted or unsubstituted C 6 -C 12 Aryl, substituted or unsubstituted C 4 -C 12 Any one of heteroaryl, in alkyl, -CH 2 Optionally substituted by-O-with the proviso that the two-O-groups are not directly linked to each other, the substituents used for the substitution being C 1 -C 10 Alkyl, C of (2) 3 -C 10 Any one of cycloalkyl groups of (a).
Further, R 1 、R 2 Independently of one another selected from C 1 -C 5 Alkyl of (a); preferably R 1 、R 2 Independently CH 3 -、CH 3 CH 2 -、CH 3 CH 2 CH 2 -、(CH 3 ) 2 CH-、CH 3 -(CH 2 ) 3 -or CH 3 -(CH 2 ) 4 -。
Further, R is 3 Selected from hydrogen, substituted or unsubstituted C 1 -C 5 Alkyl, substituted or unsubstituted C 3 -C 6 Cycloalkyl, substituted or unsubstituted C 6 -C 10 Aryl, substituted or unsubstituted C 4 -C 8 Any one of heteroaryl, in alkyl, -CH 2 Optionally substituted by-O-with the proviso that the two-O-groups are not directly linked to each other, the substituents used for the substitution being C 1 -C 5 Alkyl, C of (2) 3 -C 6 Is preferably R 3 Selected from hydrogen, substituted or unsubstituted C 1 -C 5 Straight-chain alkyl, substituted or unsubstituted C 3 -C 5 Branched alkyl, substituted or unsubstituted C 3 -C 6 Cycloalkyl, substituted or unsubstituted C 6 -C 10 Aryl, substituted or unsubstituted C 4 -C 8 Any one of the heteroaryl groups of (2) is substituted by C 1 -C 3 Alkyl, C of (2) 4 -C 5 More preferably R 3 Selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, cyclohexyl, cyclopentyl substituted n-propyl, phenyl, methyl substituted phenyl, thienyl, CH 3 CH 2 O-, and O-.
Further, the naphthalene sensitizer is
In order to achieve the above object, according to an aspect of the present invention, there is provided a method for producing any one of the naphthalene sensitizer described above, comprising: step S1, carrying out hydrogenation reaction on a compound with a structure shown in a structural formula II to obtain a hydrogenation product, wherein the structural formula II isThe hydrogenation product has the structure of formula III->S2, carrying out a Friedel-crafts reaction on the hydrogenated product and an acyl chloride compound to obtain the naphthalene sensitizer, wherein the acyl chloride compound has a structure shown in a structural formula IV>
Further, the hydrogenation reaction is carried out under the action of a catalyst, the catalyst is Pd/C, the temperature of the hydrogenation reaction is 20-35 ℃, and preferably, the solvent adopted in the hydrogenation reaction is ethyl acetate, methyl acetate or butyl acetate; preferably, the hydrogenation is carried out under an inert gas or nitrogen blanket.
Further, the temperature of the Friedel-crafts reaction is-10 to 30 ℃.
Further, the preparation method also comprises a preparation process of the compound with the structure shown in the structural formula II, wherein the preparation process comprises the following steps: step A, carrying out catalytic addition reaction on 1, 4-naphthoquinone and cyclopentadiene monomer to obtain 1, 4-methane anthracene-9, 10-dione; and step B, carrying out catalytic alkylation reaction on the 1, 4-methane anthracene-9, 10-dione and dialkyl sulfate to obtain the compound with the structure shown in the structural formula II.
Further, the solvent adopted in the addition reaction is methanol or ethanol, the catalyst adopted in the addition reaction is an acid catalyst, and the catalyst is preferably acetic acid, dilute sulfuric acid or dilute hydrochloric acid; the temperature of the addition reaction is preferably 50 to 100 ℃.
Further, the solvent adopted in the alkylation reaction is methanol or ethanol, the catalyst adopted in the alkylation reaction is a base catalyst, preferably sodium hydroxide, potassium hydroxide and sodium carbonate which are catalysts in the alkylation reaction, and the reaction temperature of the alkylation reaction is preferably 20-80 ℃.
According to another aspect of the present invention, there is provided a photocurable composition comprising a photosensitive resin, an initiator and a sensitizer, the sensitizer comprising the naphthalene sensitizer of any of the above.
According to still another aspect of the present invention, a photocurable product is cured by a photocurable composition as described above, preferably the photocurable product is an adhesive, a coating, an ink or a molding material.
By applying the technical scheme of the invention, the naphthalene sensitizer modifies the naphthalene ring, namely, increases R on the naphthalene ring 1 、R 2 、R 3 The group is beneficial to improving the photosensitivity of naphthalene sensitizer and reducing the yellowing phenomenon of the sensitizer after use.
Detailed Description
It should be noted that, in the case of no conflict, the embodiments and features in the embodiments may be combined with each other. The present invention will be described in detail with reference to examples.
As analyzed by the background technology of the application, the naphthalene sensitizer in the prior art has the problems of low activity, yellowing after sensitization and the like. In order to solve this problem, the present application provides a naphthalene sensitizer.
In one exemplary embodiment of the present application, a naphthalene sensitizer is provided having the structure of formula I:
wherein R is 1 、R 2 Independently of one another, from substituted or unsubstituted C 1 -C 10 Alkyl of (a); r is R 3 Selected from hydrogen, substituted or unsubstituted C 1 -C 10 Alkyl, substituted or unsubstituted C 3 -C 10 Cycloalkyl, substituted or unsubstituted C 6 -C 12 Aryl, substituted or unsubstituted C 4 -C 12 Any one of the heteroaryl groups of (c) in the alkyl group, -CH 2 Optionally substituted by-O-with the proviso that the two-O-are not directly attached to each other, the substituents used for said substitution being C 1 -C 10 Alkyl, C of (2) 3 -C 10 Any one of cycloalkyl groups of (a).
The naphthalene sensitizer of the present application is prepared by modifying the naphthalene ring, i.e. adding R to the naphthalene ring 1 、R 2 、R 3 The group is beneficial to improving the photosensitivity of naphthalene sensitizer and reducing the yellowing phenomenon of the sensitizer after use.
In order to further improve the photosensitivity of the naphthalene sensitizer and the stability of the anthracene sensitizer, R is as follows 1 、R 2 Independently of one another selected from C 1 -C 5 Alkyl of (a); preferably R 1 、R 2 Independently CH 3 -、CH 3 CH 2 -、CH 3 CH 2 CH 2 -、(CH 3 ) 2 CH-、CH 3 -(CH 2 ) 3 -or CH 3 -(CH 2 ) 4 -。
In order to improve photosensitivity of naphthalene sensitizer, R 3 Selected from hydrogen, substituted or unsubstituted C 1 -C 5 Alkyl, substituted or unsubstituted C 3 -C 6 Cycloalkyl, substituted or unsubstituted C 6 -C 10 Aryl, substituted or unsubstitutedSubstituted C 4 -C 8 Any one of heteroaryl, in alkyl, -CH 2 Optionally substituted by-O-with the proviso that the two-O-groups are not directly linked to each other, the substituents used for the substitution being C 1 -C 5 Alkyl, C of (2) 3 -C 6 Is preferably R 3 Selected from hydrogen, substituted or unsubstituted C 1 -C 5 Straight-chain alkyl, substituted or unsubstituted C 3 -C 5 Branched alkyl, substituted or unsubstituted C 3 -C 6 Cycloalkyl, substituted or unsubstituted C 6 -C 10 Aryl, substituted or unsubstituted C 4 -C 8 Any one of the heteroaryl groups of (2) is substituted by C 1 -C 3 Alkyl, C of (2) 4 -C 5 More preferably R 3 Selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, cyclohexyl, cyclopentyl substituted n-propyl, phenyl, methyl substituted phenyl, thienyl, CH 3 CH 2 O-, and O-.
In some embodiments, the naphthalene based sensitizer is
In another exemplary embodiment of the present application, there is provided a method for preparing the naphthalene sensitizer described above, including: step S1, carrying out hydrogenation reaction on a compound with a structure shown in a structural formula II to obtain a hydrogenation product, wherein the structural formula II isThe hydrogenation product has the structure of formula III->S2, carrying out a Friedel-crafts reaction on the hydrogenated product and an acyl chloride compound to obtain the naphthalene sensitizer, wherein the acyl chloride compound has a structure shown in a structural formula IV
The present application is directed to a method for preparing a naphthalene ring by adding R to the naphthalene ring 1 、R 2 、R 3 The group can improve the photosensitivity of the sensitizer and reduce the yellowing phenomenon of the photosensitizer after use.
The hydrogenation reaction in the above preparation method may be operated with reference to the hydrogenation reaction in the prior art, and in some embodiments, in order to improve the efficiency of the hydrogenation reaction, it is preferable that the hydrogenation reaction is performed under the action of a catalyst, and in order to facilitate separation of the catalyst, it is preferable that the catalyst is Pd/C, and the temperature of the hydrogenation reaction is 20-35 ℃. In order to improve the uniformity of the material contact in the hydrogenation reaction, the hydrogenation reaction is preferably carried out in a solvent, and the type of solvent is not particularly limited as long as the solvent can dissolve the reaction reagent and has no adverse effect on the reaction, and the solvent used in the hydrogenation reaction is preferably ethyl acetate, methyl acetate or butyl acetate; preferably, the hydrogenation is carried out under an inert gas or nitrogen blanket.
The above-mentioned Friedel-crafts reaction may be optionally added or not added, and the kind of the solvent is not particularly limited as long as the solvent can dissolve the reaction reagent and does not adversely affect the reaction, and in order to improve the degree of homogeneity of the reaction, the Friedel-crafts reaction is preferably carried out in a solvent which may be methylene chloride, dichloroethane, benzene, toluene or the like. The temperature of the foregoing Friedel-crafts reaction varies depending on the kind of the reaction reagent, and the reaction temperature is preferably-10 to 30 ℃.
In order to facilitate the implementation of the preparation method of the present application, in some embodiments, the present application provides a preparation process of a compound having a structure shown in the structural formula II, where the preparation process includes: step A, carrying out catalytic addition reaction on 1, 4-naphthoquinone and cyclopentadiene monomer to obtain 1, 4-methane anthracene-9, 10-dione; and step B, carrying out catalytic alkylation reaction on the 1, 4-methane anthracene-9, 10-dione and dialkyl sulfate to obtain the compound with the structure shown in the structural formula II.
The addition reaction is carried out in an organic solvent, and the type of solvent is not particularly limited as long as the solvent can dissolve the reaction reagent and does not adversely affect the reaction, and methanol, ethanol, or the like is preferably used. The catalyst adopted in the addition reaction is an acid catalyst, and in order to control the reaction rate, the catalyst is preferably acetic acid, dilute sulfuric acid or dilute hydrochloric acid; the temperature of the addition reaction varies depending on the type of the reaction reagent, and is preferably 50 to 100℃so that a higher product yield is expected under each reagent condition.
The above alkylation reaction may be optionally carried out with or without adding a solvent depending on the actual condition of the reaction system (e.g., the kind of the reaction reagent), and the kind of the solvent is not particularly limited as long as the reaction reagent is dissolved and the reaction is not adversely affected, and the solvent to be used is preferably methanol, ethanol or the like. The catalyst used in the alkylation reaction is a base catalyst, preferably sodium hydroxide water, potassium hydroxide and sodium carbonate, and the catalyst can be added in the form of an aqueous solution, for example, sodium hydroxide, and 15-40% by mass of sodium hydroxide aqueous solution. In order to increase the yield of the addition product, the temperature of the addition reaction is preferably 20 to 80 ℃.
In yet another exemplary embodiment of the present application, a photocurable composition is provided that includes a photosensitive resin, an initiator, and a sensitizer, including the naphthalene-based sensitizer described above. The photo-curing composition containing the naphthalene sensitizer is used for a UV-LED photo-curing system, particularly has obvious sensitization under the action of a 385nm light source, has obviously improved yellowing after being applied, and is particularly suitable for application of a white transparent system.
In still another exemplary embodiment of the present application, a photocurable product is provided which is cured from a photocurable composition as described above, preferably the photocurable product is a paint, coating, ink or molding material.
Further, the photocurable composition containing the sensitizer shown in the formula (I) can be applied to the aspects of paint, coating, ink, forming materials and the like, and can be specifically applied to manufacturing: a coating material for coating on a base material such as plastic, metal, glass, ceramic, wood, wall, etc.; protective film materials such as hard coating agents, antifouling films, antireflection films, impact-resistant films, and the like; photo-curing adhesives, photo-decomposing coatings, coating films, molded articles; optical recording media such as holographic image materials; optical molding resins such as 3D printing inks (resins), photoresists for electronic circuit and semiconductor manufacturing, photoresists for electronic materials such as color filters, black matrices, dry films, and the like in displays; an interlayer insulating film, a light extraction film, a brightness enhancement film, and a sealing material; printing inks for screen printing, offset printing, gravure printing, etc., photo-curable inks for inkjet printing; optical components such as a lens, a lens array, a light guide plate, a light diffusion plate, and a diffraction element; optical spacers, rib walls, nanoimprint material; etc.
The present application is described in further detail below in conjunction with specific embodiments, which should not be construed as limiting the scope of the claims.
Compound 1
(1) Preparation of 1, 4-methane anthracene-9, 10-dione
Adding 79g of 1, 4-dinaphthoquinone, 100mL of acetic acid and 100mL of methanol serving as raw materials into a 500mL four-necked flask, heating to 40-50 ℃, stirring for full dissolution, dropwise adding 35g of cyclopentadiene, dropwise adding for about 2 hours, continuing stirring at room temperature for 2 hours after the dropwise adding is finished, and monitoring the reaction progress until the content is not changed any more through a liquid phase. After the reaction, the solvent was removed by rotary evaporation to give a brown solid, which was recrystallized from methanol to give 86.4g of 1, 4-methane anthracene-9, 10-dione (1 a) as a yellow solid with a purity of 97%.
Structure of 1, 4-methane anthracene-9, 10-dione 1 H-NMR was confirmedThe characterization results were considered as follows.
1 H-NMR(CDCl 3 ,400MHz):1.4744-1.5340(2H,m),3.4099-3.4196(2H,t)，3.6039-3.6124(2H,t)，5.9206-5.9296(2H,d)，7.6338-7.6568(2H,m)，7.9557-7.9787(2H,m)。
(2) Preparation of intermediate 1b
15.8g of intermediate 1a,100mL of ethanol and 52.8g of dimethyl sulfate and 24% sodium hydroxide aqueous solution are simultaneously added into a 250mL four-necked flask at the temperature below 60 ℃, the reaction progress is monitored by liquid phase, the ethanol is removed by rotary evaporation after the reaction is finished, water is added, solid is separated out, a crude product is obtained by suction filtration, and the crude product is recrystallized by methanol to obtain 34.5g of yellow methylation product with the purity of 99.3%.
Methylation product structure 1 H-NMR was confirmed and the characterization results were as follows:
1 H-NMR(CDCl 3 ,400MHz):2.1674-2.2774(2H,m),3.9524-3.9617(6H,s),4.3063(2H,s),6.7592(2H,m),7.4114-8.0363(4H,m)。
(3) Preparation of intermediate 1c
34.5g of intermediate 1c,1.7g of palladium-carbon, 100mL of ethyl acetate and hydrogen are blown into a 2L four-necked flask under normal pressure, the reaction progress is monitored by HPLC, after the reaction is finished, the palladium-carbon catalyst is filtered and removed, and the yellow hydride 1d,30.0g and the purity of 99.3% are obtained.
The structure of the hydrogenated product was confirmed by 1H-NMR and the characterization result was as follows.
1 H-NMR(CDCl 3 ,400MHz):1.40-2.08(6H,m),3.81(2H,s),4.02(6H,s),7.46-8.14(4H,m)。
(4) Preparation of Compound 1
To a 250mL four-necked flask was added 24.6g of intermediate 1c,150mL of dichloromethane, 25.4g of aluminum trichloride, 15g of acetyl chloride was added dropwise at an internal temperature of 0-10 ℃ under nitrogen protection, the progress of the reaction was followed by liquid phase until no more change occurred, after the completion of the reaction, the reaction solution was slowly added to a dilute aqueous hydrochloric acid solution (1%, 200 mL), an organic layer was separated, the organic layer was washed with deionized water (50 mL of 3), the organic solvent was removed by rotary evaporation, and 1d20.0g of an off-white solid was obtained by column chromatography (acetonitrile: water=80:20) with a purity of 99%.
The structure of the target product was confirmed by 1H-NMR and the characterization result was as follows.
1 H-NMR(CDCl 3 ,400MHz):1.2428-2.0302(6H,m),2.7138(3H,s)3.6443-3.7503-(2H,d)，4.0947-4.1125(6H,s),7.9061-8.7423(3H,m)。
MS(m/z):297(M+1)+。
Compounds 2 to 10
Referring to the procedure for the preparation of Compound 1, specific synthesis conditions were adjusted on the basis of the preparation of Compound 1, and Synthesis of Compounds 2-10, their structures and corresponding MS (m/z) data are shown in Table 1.
TABLE 1
Compounds 11-14
Compounds 11-14 were synthesized with reference to prior art preparation methods and their structures and corresponding MS (m/z) data are shown in Table 2.
TABLE 2
Evaluation of Performance
The application performance of the sensitizer of the present invention represented by the formula (I) was evaluated by formulating an exemplary photocurable composition (i.e., photosensitive resin composition).
(1) Photosensitive Performance test
Examples 1 to 13
The photosensitive resin compositions were prepared and cured according to the following ratios and the specific formulations shown in table 3.
TABLE 3 Table 3
Comparative examples 1 to 10
The photosensitive resin compositions were prepared and cured according to the following ratios and the specific formulations shown in table 4.
TABLE 4 Table 4
The above composition was stirred in the dark and coated on a PET film by a 6# wire rod to form a coating film having a thickness of about 3. Mu.m. The coating film was exposed to light at different wavelengths using a mercury lamp (RW-LED-YT 200 gl) and a UV-LED light source (RW-UVAP 202-20 gl), and the curing film formation was observed with different energies, and evaluated by finger touch.
The finger touch evaluation criteria were as follows:
1: oil, not solid;
2: surface oil and bottom layer solidification;
3: the surface is sticky, and the fingerprint is heavier after hand touch;
4: basic surface dryness, slightly astringent after touching with hands, and light fingerprint;
5: completely cured, smooth in surface and free of fingerprints after hand touch.
TABLE 5
TABLE 6
(2) Yellowing performance test referring to the specific formulations shown in tables 7 and 8, a photosensitive resin composition was prepared, after stirring in a yellow room, the composition was applied to a tin plate using a 15# bar to prepare a 10 μm coating film, and an 385nm LED light source was exposed to light, and 2000mJ/cm was received 2 The energy of the (C) is fully cured, the alicylic color difference meter is adopted for yellowing test, and the yellowing condition is judged according to the Deltab value, wherein the higher the Deltab value is, the more obvious the yellowing is.
TABLE 7
TABLE 8
In summary, it is known that the compound 11 and the compound 12 have higher photosensitivity, but yellowing of the cured resin is serious; yellowing after curing of compound 13 and compound 14 was not evident, but photosensitivity was clearly insufficient. The sensitizer disclosed in the embodiment of the invention can be well matched with a UV-LED light source for use after being applied to a conventional ultraviolet curing system, has the characteristics of difficult yellowing and low chromaticity, and can be applied to Bai Mo or a colorless transparent system.
From the above description, it can be seen that the above embodiments of the present invention achieve the following technical effects: the naphthalene sensitizer of the present application is prepared by modifying the naphthalene ring, i.e. adding R to the naphthalene ring 1 、R 2 、R 3 The group is beneficial to improving the photosensitivity of naphthalene sensitizer and reducing the yellowing phenomenon of the sensitizer after use.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (20)
1. A naphthalene sensitizer, characterized in that the naphthalene sensitizer has a structure represented by the following structural formula I:
wherein R is 1 、R 2 Independently of one another selected from C 1 -C 5 Alkyl of (a);
R 3 selected from hydrogen, substituted or unsubstituted C 1 -C 5 Alkyl, substituted or unsubstituted C 3 -C 6 Cycloalkyl, substituted or unsubstituted C 6 -C 10 Aryl, substituted or unsubstituted C 4 -C 8 Any one of the heteroaryl groups of (c) in the alkyl group, -CH 2 Optionally substituted by-O-with the proviso that the two-O-are not directly attached to each other, the substituents used for said substitution being C 1 -C 5 Alkyl, C of (2) 3 -C 6 Any one of cycloalkyl groups of (a).
2. According to claimThe naphthalene sensitizer according to claim 1, wherein R 1 Said R is 2 Independently CH 3 -、CH 3 CH 2 -、CH 3 CH 2 CH 2 -、(CH 3 ) 2 CH-、CH 3 -(CH 2 ) 3 -or CH 3 -(CH 2 ) 4 -。
3. Naphthalene sensitizer according to claim 1 or 2, wherein R 3 Selected from hydrogen, substituted or unsubstituted C 1 -C 5 Straight-chain alkyl, substituted or unsubstituted C 3 -C 5 Branched alkyl, substituted or unsubstituted C 3 -C 6 Cycloalkyl, substituted or unsubstituted C 6 -C 10 Aryl, substituted or unsubstituted C 4 -C 8 Any one of the heteroaryl groups of (2), the substituent used for the substitution is C 1 -C 3 Alkyl, C of (2) 4 -C 5 Any one of cycloalkyl groups of (a).
4. A naphthalene sensitizer according to claim 3, wherein R 3 Selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, cyclohexyl, cyclopentyl substituted n-propyl, phenyl, methyl substituted phenyl, thienyl, CH 3 CH 2 O-, and O-.
5. The naphthalene sensitizer according to claim 1, wherein the naphthalene sensitizer is
6. A process for producing a naphthalene sensitizer according to any one of claims 1 to 5, comprising:
step S1, carrying out hydrogenation reaction on a compound with a structure shown in a structural formula II to obtain a hydrogenation product, wherein the structural formula II isThe hydrogenation product has the structure shown in the structural formula III>
S2, carrying out a Friedel-crafts reaction on the hydrogenation product and an acyl chloride compound to obtain the naphthalene sensitizer, wherein the acyl chloride compound has a structure shown in a structural formula IV
7. The process according to claim 6, wherein the hydrogenation is carried out under the action of a catalyst and the catalyst is Pd/C, and the temperature of the hydrogenation is 20 to 35 ℃.
8. The method according to claim 6, wherein the solvent used in the hydrogenation reaction is ethyl acetate, methyl acetate or butyl acetate.
9. The process according to claim 6, wherein the hydrogenation is carried out under an inert gas or nitrogen atmosphere.
10. The method according to claim 6, wherein the temperature of the Friedel-crafts reaction is-10 to 30 ℃.
11. The method of claim 6, further comprising a process for preparing the compound having the structure of formula II, the process comprising:
step A, carrying out catalytic addition reaction on 1, 4-naphthoquinone and cyclopentadiene monomer to obtain 1, 4-methane anthracene-9, 10-dione;
and step B, carrying out catalytic alkylation reaction on the 1, 4-methane anthracene-9, 10-dione and dialkyl sulfate to obtain the compound with the structure shown in the structural formula II.
12. The method according to claim 11, wherein the solvent used in the addition reaction is methanol or ethanol, and the catalyst used in the addition reaction is an acid catalyst.
13. The method according to claim 12, wherein the catalyst is acetic acid, dilute sulfuric acid, dilute hydrochloric acid.
14. The preparation method according to any one of claims 11 to 13, wherein the temperature of the addition reaction is 50 to 100 ℃.
15. The method according to claim 11, wherein the solvent used in the alkylation reaction is methanol or ethanol, and the catalyst used in the alkylation reaction is a base catalyst.
16. The method according to claim 15, wherein the alkylation catalyst is sodium hydroxide, potassium hydroxide, sodium carbonate.
17. The process according to any one of claims 11, 15, 16, wherein the alkylation reaction has a reaction temperature of 20 to 80 ℃.
18. A photocurable composition comprising a photosensitive resin, an initiator and a sensitizer, wherein the sensitizer comprises the naphthalene sensitizer of any one of claims 1 to 5.
19. A photocurable product cured by a photocurable composition according to claim 18.
20. The light-cured product according to claim 19, wherein the light-cured product is an adhesive, a paint, an ink, or a molding material.
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| JP2008024694A (en) * | 2006-06-22 | 2008-02-07 | Kawasaki Kasei Chem Ltd | New 1,4-bis(2-(meth)acryloyloxyalkoxy)naphthalene compound, method for producing the same and use thereof |
| JP2011144277A (en) * | 2010-01-15 | 2011-07-28 | Kawasaki Kasei Chem Ltd | Cationically photopolymerizable composition |
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| JP2008001641A (en) * | 2006-06-22 | 2008-01-10 | Kawasaki Kasei Chem Ltd | New bis(2-(meth)acryloyloxyalkoxy)naphthalene compound, method for producing the same and application thereof |
| JP2008024694A (en) * | 2006-06-22 | 2008-02-07 | Kawasaki Kasei Chem Ltd | New 1,4-bis(2-(meth)acryloyloxyalkoxy)naphthalene compound, method for producing the same and use thereof |
| JP2011144277A (en) * | 2010-01-15 | 2011-07-28 | Kawasaki Kasei Chem Ltd | Cationically photopolymerizable composition |
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