CN115572229A - Preparation method of polymerizable photoinitiator based on alpha-hydroxyketone - Google Patents
Preparation method of polymerizable photoinitiator based on alpha-hydroxyketone Download PDFInfo
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- CN115572229A CN115572229A CN202211404049.4A CN202211404049A CN115572229A CN 115572229 A CN115572229 A CN 115572229A CN 202211404049 A CN202211404049 A CN 202211404049A CN 115572229 A CN115572229 A CN 115572229A
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- alpha
- hydroxyketone
- acrylate
- anhydride
- polymerizable photoinitiator
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- 238000002360 preparation method Methods 0.000 title abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- WUILYKHTEDWVOM-UHFFFAOYSA-N carboxy prop-2-enoate Chemical compound OC(=O)OC(=O)C=C WUILYKHTEDWVOM-UHFFFAOYSA-N 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 20
- 239000003054 catalyst Substances 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 8
- AZIQALWHRUQPHV-UHFFFAOYSA-N prop-2-eneperoxoic acid Chemical compound OOC(=O)C=C AZIQALWHRUQPHV-UHFFFAOYSA-N 0.000 claims description 7
- 150000008064 anhydrides Chemical class 0.000 claims description 6
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 claims description 6
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- 239000000376 reactant Substances 0.000 claims description 4
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 claims description 3
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 claims description 3
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 claims description 3
- FDSUVTROAWLVJA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)(CO)COCC(CO)(CO)CO FDSUVTROAWLVJA-UHFFFAOYSA-N 0.000 claims description 3
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 3
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims description 3
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 claims description 3
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 3
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 claims description 3
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 3
- 229940014800 succinic anhydride Drugs 0.000 claims description 3
- 230000002194 synthesizing effect Effects 0.000 claims description 3
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 3
- DDFYFBUWEBINLX-UHFFFAOYSA-M tetramethylammonium bromide Chemical compound [Br-].C[N+](C)(C)C DDFYFBUWEBINLX-UHFFFAOYSA-M 0.000 claims description 3
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 claims description 3
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 claims description 3
- RXJKFRMDXUJTEX-UHFFFAOYSA-N triethylphosphine Chemical compound CCP(CC)CC RXJKFRMDXUJTEX-UHFFFAOYSA-N 0.000 claims description 3
- 150000008065 acid anhydrides Chemical class 0.000 claims description 2
- CHQVQXZFZHACQQ-UHFFFAOYSA-M benzyl(triethyl)azanium;bromide Chemical compound [Br-].CC[N+](CC)(CC)CC1=CC=CC=C1 CHQVQXZFZHACQQ-UHFFFAOYSA-M 0.000 claims description 2
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 claims description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 2
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 claims description 2
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 claims description 2
- YMBCJWGVCUEGHA-UHFFFAOYSA-M tetraethylammonium chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC YMBCJWGVCUEGHA-UHFFFAOYSA-M 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 11
- -1 acrylic ester Chemical class 0.000 abstract description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 abstract description 2
- 238000005286 illumination Methods 0.000 abstract description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 11
- 238000000576 coating method Methods 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 8
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 8
- 239000002966 varnish Substances 0.000 description 7
- GJKGAPPUXSSCFI-UHFFFAOYSA-N 2-Hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone Chemical compound CC(C)(O)C(=O)C1=CC=C(OCCO)C=C1 GJKGAPPUXSSCFI-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 230000005764 inhibitory process Effects 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 4
- 238000001723 curing Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 4
- 229910052753 mercury Inorganic materials 0.000 description 4
- 238000000016 photochemical curing Methods 0.000 description 4
- 238000006303 photolysis reaction Methods 0.000 description 4
- 230000015843 photosynthesis, light reaction Effects 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 3
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 3
- RIWRBSMFKVOJMN-UHFFFAOYSA-N 2-methyl-1-phenylpropan-2-ol Chemical compound CC(C)(O)CC1=CC=CC=C1 RIWRBSMFKVOJMN-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000012855 volatile organic compound Substances 0.000 description 2
- 238000004383 yellowing Methods 0.000 description 2
- RDLGTRBJUAWSAF-UHFFFAOYSA-N 1-(6-hydroxy-6-methylcyclohexa-2,4-dien-1-yl)propan-2-one Chemical compound CC(=O)CC1C=CC=CC1(C)O RDLGTRBJUAWSAF-UHFFFAOYSA-N 0.000 description 1
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
- SHKUUQIDMUMQQK-UHFFFAOYSA-N 2-[4-(oxiran-2-ylmethoxy)butoxymethyl]oxirane Chemical compound C1OC1COCCCCOCC1CO1 SHKUUQIDMUMQQK-UHFFFAOYSA-N 0.000 description 1
- LWRBVKNFOYUCNP-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylpropan-1-one Chemical compound C1=CC(SC)=CC=C1C(=O)C(C)(C)N1CCOCC1 LWRBVKNFOYUCNP-UHFFFAOYSA-N 0.000 description 1
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical group NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 1
- 238000010382 chemical cross-linking Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000004100 electronic packaging Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- ZDHCZVWCTKTBRY-UHFFFAOYSA-N omega-Hydroxydodecanoic acid Natural products OCCCCCCCCCCCC(O)=O ZDHCZVWCTKTBRY-UHFFFAOYSA-N 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/24—Preparation of carboxylic acid esters by reacting carboxylic acids or derivatives thereof with a carbon-to-oxygen ether bond, e.g. acetal, tetrahydrofuran
- C07C67/26—Preparation of carboxylic acid esters by reacting carboxylic acids or derivatives thereof with a carbon-to-oxygen ether bond, e.g. acetal, tetrahydrofuran with an oxirane ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
-
- 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
Abstract
The invention discloses a preparation method of a polymerizable photoinitiator based on alpha-hydroxy ketone. The structure of the light-cured acrylic ester contains polymerizable acrylate double-bond groups and photoinitiation active groups, and the light-cured acrylic ester double-bond groups and the photoinitiation active groups can participate in curing reaction, so that the low mobility and odor after illumination are greatly reduced, the original structural characteristics are kept unchanged, and a good technical effect is achieved.
Description
Technical Field
The invention belongs to the technical field of photoinitiators, and particularly relates to a preparation method of a polymerizable photoinitiator based on alpha-hydroxy ketone.
Background
Photocuring is a novel green technology developed from the last 60 years, has the characteristics of energy conservation, less VOC (volatile organic compounds) emission, high curing speed, excellent product performance and the like, and is widely applied to the fields of wood paint coatings, paper printing ink, electronic packaging materials and the like. The three most important components in the photocurable formulation include a photocurable resin, a photocurable monomer, and a photoinitiator. Wherein, the photoinitiator is a substance which can generate active species to initiate oligomer and reactive diluent to carry out chemical crosslinking under the irradiation of ultraviolet light. Through decades of development, alpha-hydroxy ketone becomes the photoinitiator with the largest dosage and the most excellent comprehensive performance at present.
The alpha-hydroxy ketone mainly comprises 2-hydroxy-2-methyl phenyl acetone (trade name Darocur 1173), 1-hydroxy cyclohexyl phenyl ketone (trade name Irgacure 184), 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-acetone (trade name Darocur 2959), and the structural formula is shown in figure 1. The alpha-hydroxy ketone has the advantages that the ortho position of benzoyl in the molecular structure of the alpha-hydroxy ketone has no alpha-H, the thermal stability is very good, a substituted benzyl structure cannot be generated after photolysis, the yellowing resistance is excellent, the alpha-hydroxy ketone can be used in occasions with high requirement on yellowing resistance, and the alpha-hydroxy ketone is particularly suitable for being matched with Irgacure 907, irgacure TPO and Irgacure 819 to be used in a colored system of colored paint or ink.
The hydroxyl on the alpha-hydroxy ketone structure can provide active hydrogen for chain transfer, reduce the influence of oxygen inhibition and improve the surface drying effect, and meanwhile, the hydroxyl can also provide certain water solubility and can be used in a water-based photocuring formula. Therefore, the hydroxyl group on the alpha-hydroxyketone is of critical importance.
However, the alpha-hydroxyketone photoinitiator also has the defects of the alpha-hydroxyketone photoinitiator, and the photolysis product can generate benzaldehyde or micromolecular ketone substances, so that the application field of the alpha-hydroxyketone photoinitiator is limited. In addition, after photo-curing, residual photoinitiator and photolysis products may migrate to the surface of the coating, affecting the appearance of the coating and causing toxicity.
Chinese patent application No. 201610302241.0 discloses a preparation method of a polymerizable photoinitiator based on an alpha-hydroxyketone photoinitiator Darocur 2959, methacrylic acid and primary hydroxyl on Darocur 2959 are directly subjected to esterification reaction to obtain 2959-MMA containing a methacryloyloxy group, and the MMA can participate in photocuring reaction, so that the generation of cracking fragments is reduced, and the mobility of the photoinitiator in a curing film is also reduced. However, the target product 2959-MMA obtained by the method has small overall molecular weight and very limited effect of reducing odor and mobility, and the primary hydroxyl on the structure of Darocur 2959 is reacted, so that the effect of effectively reducing oxygen inhibition effect cannot be achieved.
Chinese patent application No. 201910424230.3 discloses a polymerizable photoinitiator based on α -hydroxyketone photoinitiators Darocur 1173, irgacure 184 and Darocur 2959. Hydroxyl on an alpha-hydroxy ketone structure is reacted with (methyl) acryloyloxyalkyl isocyanate to obtain the polymerizable photoinitiator containing unsaturated double bonds and a carbamate structure. The (meth) acryloyloxyalkyl isocyanate used in the preparation method is very expensive, is not easy to obtain and cannot be applied on a large scale. In addition, because the structure of the target product does not contain hydroxyl groups, the oxygen resistant polymerization inhibition effect of the product is greatly reduced, and the application field of the product is limited.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to overcome the defects in the prior art and provide a preparation method of a novel polymerizable photoinitiator based on alpha-hydroxy ketone, and the prepared polymerizable photoinitiator has low odor and low mobility and can keep the original structural characteristics.
The technical scheme is as follows: in order to realize the purpose of the invention, the invention adopts the technical scheme that:
a method for preparing a polymerizable photoinitiator based on alpha-hydroxyketone, comprising the following steps:
(1) Reacting anhydride with hydroxyl acrylate under the action of a catalyst A to obtain carboxyl acrylate;
(2) Carboxyl acrylate and epoxidized alpha-hydroxy ketone are reacted under the action of a catalyst B to obtain the polymerizable photoinitiator based on the alpha-hydroxy ketone.
As a preferable scheme, in the above preparation method of the polymerizable photoinitiator based on α -hydroxyketone, the synthesis method of the carboxyl acrylate in the step (1) is: weighing a certain mass of anhydride, hydroxyl acrylate and catalyst A, placing the mixture into a reaction flask, slowly heating the mixture to 100-110 ℃ for reaction until the acid value is reduced to a theoretical value, and obtaining carboxyl acrylate.
As a preferable mode, in the above method for preparing the polymerizable photoinitiator based on α -hydroxyketone, the method for synthesizing the polymerizable photoinitiator based on α -hydroxyketone in step (2) is: weighing a certain mass of carboxyl acrylate, epoxidized alpha-hydroxy ketone and a catalyst B, placing the mixture into a reaction flask, slowly heating the mixture to 110-120 ℃ for reaction until the acid value is reduced to be below 5 mgKOH/g.
As a preferable mode, in the above method for preparing the polymerizable photoinitiator based on alpha-hydroxyketone, in the step (1), the molar ratio of the acid anhydride to the hydroxy acrylate is controlled to be 1; in the step (2), the molar ratio of the carboxyl acrylate to the epoxidized alpha-hydroxyketone is controlled to be 1.
As a preferable scheme, in the preparation method of the polymerizable photoinitiator based on alpha-hydroxy ketone, the anhydride is selected from one or more of phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl hexahydrophthalic anhydride, maleic anhydride and succinic anhydride.
Preferably, the preparation method of the polymerizable photoinitiator based on alpha-hydroxy ketone comprises the step of selecting one or more of hydroxyethyl acrylate, hydroxypropyl acrylate, pentaerythritol triacrylate and dipentaerythritol pentaacrylate.
As a preferable scheme, in the preparation method of the polymerizable photoinitiator based on alpha-hydroxy ketone, the catalyst a is selected from one or more of tetramethylammonium chloride, tetramethylammonium bromide, tetraethylammonium chloride, tetraethylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium bromide, triethylbenzylammonium chloride and triethylbenzylammonium bromide, and the addition amount is 0.02-0.10% of the total mass of the reactants.
As a preferable scheme, in the preparation method of the polymerizable photoinitiator based on alpha-hydroxy ketone, the catalyst B is selected from one or more of triphenylphosphine, triethylphosphine, tributylphosphine and tricyclohexylphosphine, and the addition amount of the catalyst B is 0.05-0.12 percent of the total mass of reactants
Has the advantages that: compared with the prior art, the invention has the following advantages:
in the using process of the alpha-hydroxy ketone photoinitiator, benzaldehyde or micromolecular ketone substances generated by cracking have obvious smell, and residual photoinitiators and photolysis products can migrate to the surface of a cured film to damage the appearance, so that the application field of the alpha-hydroxy ketone photoinitiator is limited.
In order to overcome the above-mentioned drawbacks, the present invention is based on the idea of keeping the basic structural features of the alpha-hydroxyketones unchanged. Firstly, after the alpha-hydroxy ketone reacts with epoxy chloropropane, hydroxyl is converted into epoxy group to obtain epoxidized alpha-hydroxy ketone, and then the epoxidized alpha-hydroxy ketone continuously reacts with carboxyl acrylate to generate ester bond and hydroxyl, namely the hydroxyl is consumed in the first step of reaction, and the hydroxyl is generated again in the second step of reaction, so that the basic structural characteristics of the alpha-hydroxy ketone are kept unchanged to the greatest extent, the surface drying effect can be effectively improved, and the oxygen resistant polymerization inhibition effect is improved.
The target product of the invention structurally contains polymerizable acrylate double-bond groups and photoinitiated active groups at the same time, and can participate in curing reaction, thereby greatly reducing low mobility and odor after illumination, simultaneously keeping the original structural characteristics unchanged and obtaining good technical effect.
Drawings
FIG. 1 is a structural formula of a known photoinitiator.
Detailed Description
The epoxidized alpha-hydroxyketone is obtained by reacting alpha-hydroxyketone with epoxy chloropropane, and the specific operation steps refer to the synthesis of 1, 4-butanediol diglycidyl ether [ J ], guangzhou chemical industry, 2011,39 (14), 53-55] of Queenmin et al.
The method specifically comprises the following steps: respectively taking 1.0mol of alpha-hydroxyketone Darocur 1173 or Irgacure 184 or Darocur 2959 and boron trifluoride ethyl ether accounting for 0.4 percent of the total mass of the materials, adding the mixture into a flask, stirring and heating the mixture to 60 ℃, dropwise adding 1.03mol of epoxy chloropropane, completing the dropwise addition within 1 hour, and reacting for 4 hours. Cooling to room temperature, adding 120mL of toluene, adding a sodium hydroxide solution with the mass fraction of 40% (wherein the molar weight of the sodium hydroxide is 1.03 mol), continuing to react for 5 hours at 45 ℃, cooling to room temperature, adding 100mL of water for washing, extracting with ethyl acetate (50mL by 3 times), combining upper organic phases, distilling under reduced pressure to remove the solvent to respectively obtain epoxidized alpha-hydroxyketone, which are respectively named as epoxidized alpha-hydroxyketone 1173-E, epoxidized alpha-hydroxyketone 184-E and epoxidized alpha-hydroxyketone 2959-E.
Example 1
A method for preparing a polymerizable photoinitiator based on alpha-hydroxyketone, comprising the following steps:
(1) Placing 148 g of phthalic anhydride, 298 g of pentaerythritol triacrylate, 0.27 g of p-hydroxyanisole and 0.36 g of tetrabutylammonium chloride into a reaction flask, starting stirring, slowly heating to 110 ℃ for reaction until the acid value is reduced to below 125.8mgKOH/g, and cooling to obtain carboxyl acrylate 1;
(2) 446 g of carboxy acrylate 1, 220 g of epoxidized alpha-hydroxy ketone 1173-E,0.47 g of p-hydroxyanisole and 0.53 g of triphenylphosphine were placed in a reaction flask, stirred and slowly heated to 115 ℃ for reaction until the acid value was reduced to below 5mgKOH/g, thus obtaining the alpha-hydroxy ketone-based polymerizable photoinitiator 1.
Example 2
A method for preparing a polymerizable photoinitiator based on alpha-hydroxyketone, comprising the following steps:
(1) 152 g of tetrahydrophthalic anhydride, 130 g of hydroxypropyl acrylate, 0.17 g of p-hydroxyanisole and 0.14 g of tetramethylammonium chloride are placed in a reaction flask, stirred and slowly heated to 105 ℃ for reaction until the acid value is reduced to be below 198.9mgKOH/g, and then the temperature is reduced to obtain carboxyl acrylate 2;
(2) 282 g of carboxyl acrylate 2, 260 g of epoxidized alpha-hydroxyketone 184-E,0.43 g of p-hydroxyanisole and 0.54 g of tributylphosphine were placed in a reaction flask, stirred and slowly heated to 112 ℃ for reaction until the acid value was reduced to below 5mgKOH/g, and the polymerizable photoinitiator 2 based on alpha-hydroxyketone was obtained.
Example 3
A method for preparing a polymerizable photoinitiator based on alpha-hydroxyketone, comprising the following steps:
(1) Placing 154 g of hexahydrophthalic anhydride, 116 g of hydroxyethyl acrylate, 0.16 g of p-hydroxyanisole and 0.22 g of tetrabutylammonium bromide into a reaction flask, starting stirring, slowly heating to 108 ℃ for reaction until the acid value is reduced to be below 207.8mgKOH/g, and cooling to obtain carboxyl acrylate 3;
(2) 270 g of carboxy acrylate 3, 260 g of epoxidized alpha-hydroxyketone 184-E,0.42 g of p-hydroxyanisole and 0.53 g of triethylphosphine were placed in a reaction flask, stirred and slowly heated to 116 ℃ for reaction until the acid value was reduced to below 5mgKOH/g, and a polymerizable photoinitiator 3 based on alpha-hydroxyketone was obtained.
Example 4
A method for preparing a polymerizable photoinitiator based on alpha-hydroxyketone, comprising the following steps:
(1) Placing 100 g of succinic anhydride, 578 g of dipentaerythritol pentaacrylate, 0.41 g of p-hydroxyanisole and 0.34 g of tetramethylammonium bromide in a reaction flask, starting stirring, slowly heating to 103 ℃ for reaction until the acid value is reduced to be below 82.7mgKOH/g, and cooling to obtain carboxyl acrylate 4;
(2) 678 g of carboxyl acrylate 4, 280 g of epoxidized alpha-hydroxyketone 2959-E,0.67 g of p-hydroxyanisole and 0.77 g of tricyclohexylphosphine were placed in a reaction flask, stirred and slowly heated to 118 ℃ for reaction until the acid value was reduced to below 5mgKOH/g, thus obtaining the polymerizable photoinitiator 4 based on alpha-hydroxyketone.
Examples of Performance testing
Uniformly mixing urethane acrylate 6201 (Jiangsu Sanmukuchen chemical Co., ltd.) and 1, 6-hexanediol diacrylate (HDDA, jiangsu Sanmukuchen chemical Co., ltd.) according to a mass ratio of 7.
The photocurable varnish was prepared by mixing the α -hydroxyketone-based polymerizable photoinitiators 1 to 4 prepared in examples 1 to 4, the commercial photoinitiators α -hydroxyketones 1173, 184 and 2959 (Jiangsu Sanxylo chemical Co., ltd.), 2959-MMA (the target product of Chinese patent No. 201602241.0) and a matrix resin according to the following formulation in Table 1.
TABLE 1 Photocurable varnish formulations
The varnish samples prepared in Table 1 were coated on a glass plate with a wire bar to give a coating film having a thickness of about 25 μm, and then irradiated with a mercury lamp light source to determine the drying state of the surface of the cured film, and the gel content and odor of the cured film after complete drying, respectively, and the results are shown in Table 2.
TABLE 2 comparison of film Properties of the light-curable varnishes
And (3) condition testing:
coating varnish samples 1# to 8# prepared in Table 1 on a glass plate with a wire bar to obtain a coating film with a thickness of about 25 μm, and applying a mercury lamp light source (curing energy 50 mj/cm) 2 ) The cured film was irradiated once and then touched with a finger or palm, and scored according to the following criteria.
And (3) testing the gel content:
the varnish samples 1# to 8# prepared in Table 1 were coated on a glass plate with a wire bar to obtain a coating film having a thickness of about 25 μm, and the coating film was irradiated with a mercury lamp light source until the surface was completely dried. Taking a certain qualityAmount of cured film (mass m) 1 ) Wrapping with filter paper, placing into a Soxhlet extractor, refluxing with acetone for 48 hr, taking out, drying the cured film to constant weight, and weighing the dried cured film with mass m 2 The calculation formula is as follows:
gel content = (m) 1 -m 2 )/m 1 *100％
Lower gel content means less material participating in the crosslinking reaction, whereas higher gel content means more material participating in the crosslinking reaction.
And (3) odor test:
the varnish samples 1# to 8# prepared in Table 1 were taken, coated on a glass plate with a wire bar to obtain a coating film with a thickness of about 25 μm, and irradiated with a mercury lamp light source until the surface was completely dried. And (3) placing the cured film sample with the same area in a weighing bottle with the same size, sealing and placing for 24 hours, taking out, evaluating the smell, and scoring according to the following standard.
The experimental results show that compared with the commercialized photoinitiator alpha-hydroxy ketone, the invention screens out various reaction raw materials through a large number of experiments, and the surface of the synthesized polymerizable photoinitiator based on the alpha-hydroxy ketone is better dried, thereby showing that the polymerization inhibition effect of oxygen resistance is good, and simultaneously, the polymerizable photoinitiator has lower mobility and lower odor, and obtains good technical effect.
Claims (8)
1. A method for preparing a polymerizable photoinitiator based on alpha-hydroxyketone, comprising the steps of:
(1) Reacting anhydride with hydroxyl acrylate under the action of a catalyst A to obtain carboxyl acrylate;
(2) Carboxyl acrylate is used to react with epoxidized alpha-hydroxy ketone under the action of a catalyst B to obtain the polymerizable photoinitiator based on the alpha-hydroxy ketone.
2. The method for preparing the polymerizable photoinitiator based on alpha-hydroxyketone according to claim 1, wherein the step (1) of synthesizing the carboxyl acrylate comprises the following steps: weighing a certain mass of anhydride, hydroxyl acrylate and catalyst A, placing the mixture into a reaction flask, slowly heating the mixture to 100-110 ℃ for reaction until the acid value is reduced to a theoretical value, and obtaining carboxyl acrylate.
3. The method for preparing the polymerizable photoinitiator based on alpha-hydroxyketone according to claim 1, wherein the method for synthesizing the polymerizable photoinitiator based on alpha-hydroxyketone in step (2) comprises: weighing a certain mass of carboxyl acrylate, epoxidized alpha-hydroxy ketone and a catalyst B, placing the mixture into a reaction flask, slowly heating the mixture to 110-120 ℃ for reaction until the acid value is reduced to be below 5 mgKOH/g.
4. The method for preparing a-hydroxyketone-based polymerizable photoinitiator according to claim 1, wherein in the step (1), the molar ratio of the acid anhydride to the hydroxy acrylate is controlled to be 1; in the step (2), the molar ratio of the carboxyl acrylate to the epoxidized alpha-hydroxyketone is controlled to be 1.
5. The method for preparing a-hydroxyketone-based polymerizable photoinitiator according to claim 1, wherein the anhydride is selected from one or more of phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl hexahydrophthalic anhydride, maleic anhydride and succinic anhydride.
6. The method for preparing a-hydroxyketone-based polymerizable photoinitiator according to claim 1, wherein the hydroxy acrylate is one or more selected from the group consisting of hydroxyethyl acrylate, hydroxypropyl acrylate, pentaerythritol triacrylate, and dipentaerythritol pentaacrylate.
7. The method of claim 1, wherein the catalyst A is selected from one or more of tetramethylammonium chloride, tetramethylammonium bromide, tetraethylammonium chloride, tetraethylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium bromide, triethylbenzylammonium chloride and triethylbenzylammonium bromide, and the amount of the catalyst A is 0.02-0.10% of the total mass of the reactants.
8. The method for preparing polymerizable photoinitiator based on alpha-hydroxyketone according to claim 1, wherein the catalyst B is one or more selected from triphenylphosphine, triethylphosphine, tributylphosphine and tricyclohexylphosphine, and the addition amount is 0.05-0.12% of the total mass of reactants.
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