CN108794315A - Mix type photoinitiator and its preparation method and application - Google Patents
Mix type photoinitiator and its preparation method and application Download PDFInfo
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- CN108794315A CN108794315A CN201710287140.5A CN201710287140A CN108794315A CN 108794315 A CN108794315 A CN 108794315A CN 201710287140 A CN201710287140 A CN 201710287140A CN 108794315 A CN108794315 A CN 108794315A
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- 238000002360 preparation method Methods 0.000 title abstract description 13
- 125000000217 alkyl group Chemical group 0.000 claims description 74
- 125000003118 aryl group Chemical group 0.000 claims description 52
- 239000002994 raw material Substances 0.000 claims description 26
- 229910052736 halogen Inorganic materials 0.000 claims description 19
- 150000002367 halogens Chemical class 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 239000003960 organic solvent Substances 0.000 claims description 10
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 9
- 125000005120 alkyl cycloalkyl alkyl group Chemical group 0.000 claims description 9
- 125000001316 cycloalkyl alkyl group Chemical group 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 6
- 125000003358 C2-C20 alkenyl group Chemical group 0.000 claims description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([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
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 5
- 238000005863 Friedel-Crafts acylation reaction Methods 0.000 claims description 4
- 238000005727 Friedel-Crafts reaction Methods 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 239000011230 binding agent Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 238000010534 nucleophilic substitution reaction Methods 0.000 claims description 4
- 125000006374 C2-C10 alkenyl group Chemical group 0.000 claims description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 229920002554 vinyl polymer Polymers 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- 230000035945 sensitivity Effects 0.000 abstract description 10
- 239000003085 diluting agent Substances 0.000 abstract description 7
- 238000006356 dehydrogenation reaction Methods 0.000 abstract description 6
- 238000005336 cracking Methods 0.000 abstract description 5
- 238000005286 illumination Methods 0.000 abstract description 5
- 150000003384 small molecules Chemical class 0.000 abstract description 3
- 238000000354 decomposition reaction Methods 0.000 abstract description 2
- 239000000543 intermediate Substances 0.000 description 21
- 239000000047 product Substances 0.000 description 17
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- 238000001723 curing Methods 0.000 description 9
- 239000002904 solvent Substances 0.000 description 8
- 238000000016 photochemical curing Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000004949 mass spectrometry Methods 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- ZDQNWDNMNKSMHI-UHFFFAOYSA-N 1-[2-(2-prop-2-enoyloxypropoxy)propoxy]propan-2-yl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(C)COCC(C)OC(=O)C=C ZDQNWDNMNKSMHI-UHFFFAOYSA-N 0.000 description 2
- ILLHORFDXDLILE-UHFFFAOYSA-N 2-bromopropanoyl bromide Chemical compound CC(Br)C(Br)=O ILLHORFDXDLILE-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 229940125904 compound 1 Drugs 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000007645 offset printing Methods 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 235000005074 zinc chloride Nutrition 0.000 description 2
- 239000011592 zinc chloride Substances 0.000 description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 238000003848 UV Light-Curing Methods 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical compound BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000012952 cationic photoinitiator Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 229940126214 compound 3 Drugs 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical group C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 239000012048 reactive intermediate Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/76—Ketones containing a keto group bound to a six-membered aromatic ring
- C07C49/80—Ketones containing a keto group bound to a six-membered aromatic ring containing halogen
- C07C49/813—Ketones containing a keto group bound to a six-membered aromatic ring containing halogen polycyclic
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C317/00—Sulfones; Sulfoxides
- C07C317/24—Sulfones; Sulfoxides having sulfone or sulfoxide groups and doubly-bound oxygen atoms bound to the same carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
- C07D295/10—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by doubly bound oxygen or sulphur atoms
- C07D295/104—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by doubly bound oxygen or sulphur atoms with the ring nitrogen atoms and the doubly bound oxygen or sulfur atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
- C07D295/10—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by doubly bound oxygen or sulphur atoms
- C07D295/112—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by doubly bound oxygen or sulphur atoms with the ring nitrogen atoms and the doubly bound oxygen or sulfur atoms separated by carbocyclic rings or by carbon chains interrupted by carbocyclic rings
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses specific admixture type photoinitiators and its preparation method and application.This, which mixes type photoinitiator, has the structure as shown in general formula (I)：
Description
Technical Field
The invention relates to the technical field of organic chemistry, in particular to a hybrid photoinitiator and a preparation method and application thereof.
Background
Photoinitiators are key components of photocurable materials and are decisive for the photocuring speed of photocurable materials. Photoinitiators can be classified into radical photoinitiators and cationic photoinitiators, depending on the reactive intermediates generated. Radical photoinitiators are classified into cracking photoinitiators and hydrogen abstraction photoinitiators due to different mechanisms of generating radicals.
With the development of the photocuring technology, the application field of photocuring products is continuously expanded, the research and production of photoinitiators are greatly advanced, and the development is mainly towards low odor, low migration and high initiation efficiency, so that novel photoinitiators such as macromolecular photoinitiators, polymerizable photoinitiators, hybrid photoinitiators and the like are developed.
Esacure1001 photoinitiator developed by Ningbody corporation is a hybrid photoinitiator containing hydrogen abstraction type photoinitiating groups and cracking type photoinitiating groups, and lambda of the hybrid photoinitiatormaxIs 316nm, ε at 370nmmaxThe curing agent is 1000L/mol.cm, and can obtain better curing effect when being used in UV printing ink and UV colored paint. However, the Esacure1001 photoinitiator has poor compatibility with matrix resins, a large amount of organic solvents or small molecular diluents are often required to be added, the health of production operators is not facilitated, certain environmental pollution is caused, and meanwhile, due to the fact that the Esacure1001 aromatic ring system is a diphenyl sulfide structure, bad residual odor is inevitably generated in the photocuring process, so that the application field of the Esacure1001 photoinitiator is limited to a great extent, and particularly the food packaging field is strictly controlled. On the other hand, the use of the epoxy resin in a colored system has the defects of low sensitivity, slow curing speed and low production efficiency in performance.
Esacure1001 has the following structural formula:
disclosure of Invention
The invention aims to provide a hybrid photoinitiator, a preparation method and application thereof, and the photoinitiator has the advantages of high solubility, low smell, high sensitivity and excellent curing performance.
In order to achieve the above object, according to one aspect of the present invention, there is provided a hybrid type photoinitiator. The hybrid photoinitiator has a structure shown as a general formula (I):
wherein,
m is selected from any one of the following groups:
R1represents-H, C1-C20Linear or branched alkyl of (2), C3-C20Cycloalkyl of, C4-C20Alkylcycloalkyl or cycloalkylalkyl, C2-C20optionally-CH in these radicals2-may be substituted by-O-;
x represents
R2And R3Each independently represents-H or-C1-C12A linear or branched alkyl, aryl, or alkylaryl group of (a);
z represents-SO2R4、-NR5R6Or halogen;
R4represents C1-C12Linear or branched alkyl of (2), or
R7、R8、R9、R10And R11Each independently represents-H, halogen, -CN, C1-C12Straight or branched chain ofAlkyl, aryl, -OR12、-SR13、-SOR14、-SO2R15、-COR16or-NR5R6；
R12represents-H, C1-C12A linear or branched alkyl group of (a), or an aryl group;
R13represents-H, C1-C12A linear or branched alkyl group of (a), or an aryl group;
R14represents C1-C12A linear or branched alkyl group of (a), or an aryl group;
R15represents C1-C12Linear or branched alkyl, aryl, or-OH;
R16represents C1-C12Linear or branched alkyl, aryl, or-OH;
R5and R6Independently of one another represent C1-C20Linear or branched alkyl of (2), C4-C20Cycloalkyl of, C2-C20Alkenyl of (C)6-C20optionally-CH in these radicals2-may be substituted by-O-, or R5And R6May be linked to each other or form a five-or six-membered ring through-O-, -S-, -NH-;
y representsWherein R is7’、R8’、R9’、R10' and R11' having R independently of7、R8、R9、R10And R11In the same sense, Y and R4May or may not be the same.
Further, R1represents-H, halogen, C1-C10Linear or branched alkyl of (2), C3-C10Cycloalkyl of, C4-C10Alkylcycloalkyl or cycloalkylalkyl, C2-C10optionally-CH in these radicals2-may be substituted by-O-.
Further, R1represents-H, methyl, ethyl, n-propyl, n-butyl, vinyl, or allyl.
Further, R2And R3Each independently represents-H or-C1-C6A linear or branched alkyl, aryl, or alkylaryl group.
Further, R2And R3Each independently represents a methyl group, an ethyl group, an n-propyl group, an n-butyl group, a phenyl group, a benzyl group, a vinyl group, or an allyl group.
Further, R7、R8、R9、R10And R11Each independently represents-H, halogen, -OH, C1-C6Linear or branched alkyl, -OCH3、And (4) an aryl group.
Further, R5And R6Independently of one another represent C1-C10Linear or branched alkyl of (2), C4-C10Cycloalkyl of, C2-C10Alkenyl of (C)6-C10optionally-CH in these radicals2-may be substituted by-O-, or R3And R3May be linked to each other or form a five-or six-membered ring through-O-, -S-, -NH-.
Further, R7’、R8’、R9’、R10' and R11' represents independently of one another-H, C1-C6Linear OR branched alkyl, aryl, -OR2or-NR5R6。
According to another aspect of the present invention, there is provided a method for preparing the above hybrid photoinitiator. The preparation method comprises the following steps: 1) taking the raw material a and the raw material b as initial raw materials to synthesize an intermediate a through Friedel-crafts reaction; 2) carrying out Friedel-crafts acylation reaction on the intermediate a and the raw material c to obtain an intermediate b; and 3) reacting the intermediate b with the raw material d to obtain a product;
the reaction process is as follows:
wherein,
m is selected from any one of the following groups:
R1represents-H, C1-C20Linear or branched alkyl of (2), C3-C20Cycloalkyl of, C4-C20Alkylcycloalkyl or cycloalkylalkyl, C2-C20optionally-CH in these radicals2-may be substituted by-O-;
x represents
R2And R3Each independently represents-H or-C1-C12A linear or branched alkyl, aryl, or alkylaryl group of (a);
z represents-SO2R4、-NR5R6Or halogen;
R4represents C1-C12Linear or branched alkyl of (2), or
R7、R8、R9、R10And R11Each independently represents-H, halogen, -CN, C1-C12Linear OR branched alkyl, aryl, -OR12、-SR13、-SOR14、-SO2R15、-COR16or-NR5R6；
R12represents-H, C1-C12A linear or branched alkyl group of (a), or an aryl group;
R13represents-H, C1-C12A linear or branched alkyl group of (a), or an aryl group;
R14represents C1-C12A linear or branched alkyl group of (a), or an aryl group;
R15represents C1-C12Linear or branched alkyl, aryl, or-OH;
R16represents C1-C12Linear or branched alkyl, aryl, or-OH;
R5and R6Independently of one another represent C1-C20Linear or branched alkyl of (2), C4-C20Cycloalkyl of, C2-C20Alkenyl of (C)6-C20optionally-CH in these radicals2-may be substituted by-O-, or R5And R6May be linked to each other or form a five-or six-membered ring through-O-, -S-, -NH-;
y representsWherein R is7’、R8’、R9’、R10' and R11' having R independently of7、R8、R9、R10And R11In the same sense, Y and R4May or may not be the same.
Further, when Z is-SO2R4When the intermediate b is substituted with R4SO2H, heating and refluxing in an organic solvent to react to obtain a product; or when Z is-NR5R6When the intermediate b is substituted with R5R6NH is put into an organic solvent and undergoes nucleophilic substitution reaction in the presence of an acid-binding agent to obtain a product.
According to a further aspect of the present invention, there is provided the use of a hybrid photoinitiator in a photocurable composition.
According to yet another aspect of the present invention, a photocurable composition is provided. The photocurable composition includes any of the hybrid photoinitiators described above.
The hybrid photoinitiator contains hydrogen abstraction type and cracking type photoinitiation groups, can effectively improve the solubility of Esacure1001, reduces the use of small molecular active diluent, has no odor residue after being decomposed by illumination, has high sensitivity and excellent mechanical property, and particularly has good promotion effect on the popularization and application of a colored ink system in the field of photocuring.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail with reference to examples.
According to an exemplary embodiment of the present invention, a hybrid photoinitiator is provided. The hybrid photoinitiator has a structure shown as a general formula (I):
wherein,
m is selected from any one of the following groups:
R1represents-H, C1-C20Linear or branched alkyl of (2), C3-C20Cycloalkyl of, C4-C20Alkylcycloalkyl or cycloalkylalkyl, C2-C20optionally-CH in these radicals2-may be substituted by-O-;
x represents
R2And R3Each independently represents-H or-C1-C12A linear or branched alkyl, aryl, or alkylaryl group of (a);
z represents-SO2R4、-NR5R6Or halogen;
R4represents C1-C12Linear or branched alkyl of (2), or
R7、R8、R9、R10And R11Each independently represents-H, halogen, -CN, C1-C12Linear OR branched alkyl, aryl, -OR12、-SR13、-SOR14、-SO2R15、-COR16or-NR5R6；
R12represents-H, C1-C12Linear or branched alkyl of (2), orAn aryl group;
R13represents-H, C1-C12A linear or branched alkyl group of (a), or an aryl group;
R14represents C1-C12A linear or branched alkyl group of (a), or an aryl group;
R15represents C1-C12Linear or branched alkyl, aryl, or-OH;
R16represents C1-C12Linear or branched alkyl, aryl, or-OH;
R5and R6Independently of one another represent C1-C20Linear or branched alkyl of (2), C4-C20Cycloalkyl of, C2-C20Alkenyl of (C)6-C20optionally-CH in these radicals2-may be substituted by-O-, or R5And R6May be linked to each other or form a five-or six-membered ring through-O-, -S-, -NH-;
y representsWherein R is7 ’、R8 ’、R9 ’、R10 ’And R11 ’Each having a radical of formula R7、R8、R9、R10And R11In the same sense, Y and R4May or may not be the same.
The hybrid photoinitiator contains hydrogen abstraction type and cracking type photoinitiation groups, can effectively improve the solubility of Esacure1001, reduces the use of small molecular active diluent, has no odor residue after being decomposed by illumination, has high sensitivity and excellent mechanical property, and particularly has good promotion effect on the popularization and application of a colored ink system in the field of photocuring.
Comprehensively considering the aspects of raw material cost, product solubility, sensitivity and the like:
preferably, M isMore preferably, M is
Preferably, R1represents-H, halogen, C1-C10Linear or branched alkyl of (2), C3-C10Cycloalkyl of, C4-C10Alkylcycloalkyl or cycloalkylalkyl, C2-C10optionally-CH in these radicals2-may be substituted by-O-; more preferably, R1represents-H, methyl, ethyl, n-propyl, n-butyl, vinyl, or allyl.
Preferably, R2And R3Each independently represents-H or-C1-C6A linear or branched alkyl, aryl, or alkylaryl group of (a); more preferably, R2And R3Each independently represents a methyl group, an ethyl group, an n-propyl group, an n-butyl group, a phenyl group, a benzyl group, a vinyl group, or an allyl group.
Preferably, R7、R8、R9、R10And R11Each independently represents-H, halogen, -OH, C1-C6Linear or branched alkyl, -OCH3、And (4) an aryl group.
Preferably, R5And R6Independently of one another represent C1-C10Linear or branched alkyl of (2), C4-C10Cycloalkyl of, C2-C10Alkenyl of (C)6-C10optionally-CH in these radicals2-may be substituted by-O-, or R3And R3May be linked to each other or form a five-or six-membered ring through-O-, -S-, -NH-.
Preferably, R7’、R8’、R9’、R10' and R11' represents independently of one another-H, C1-C6Linear OR branched alkyl, aryl, -OR2or-NR5R6。
The compounds of formula (I) described above may be exemplified by the following structures, but the scope of the present invention is not limited to these structures:
according to an exemplary embodiment of the present invention, there is provided a method for preparing the hybrid photoinitiator. The preparation method comprises the following steps: 1) taking the raw material a and the raw material b as initial raw materials to synthesize an intermediate a through Friedel-crafts reaction; 2) carrying out Friedel-crafts acylation reaction on the intermediate a and the raw material c to obtain an intermediate b; and 3) reacting the intermediate b with the raw material d to obtain a product;
the reaction process is as follows:
wherein,
m is selected from any one of the following groups:
R1represents-H, C1-C20Linear or branched alkyl of (2), C3-C20Cycloalkyl of, C4-C20Alkylcycloalkyl or cycloalkylalkyl, C2-C20optionally-CH in these radicals2-may be substituted by-O-;
x represents
R2And R3Each independently represents-H or-C1-C12A linear or branched alkyl, aryl, or alkylaryl group of (a);
z represents-SO2R4、-NR5R6Or halogen;
R4represents C1-C12Linear or branched alkyl of (2), or
R7、R8、R9、R10And R11Each independently represents-H, halogen, -CN, C1-C12Linear OR branched alkyl, aryl, -OR12、-SR13、-SOR14、-SO2R15、-COR16or-NR5R6；
R12represents-H, C1-C12A linear or branched alkyl group of (a), or an aryl group;
R13represents-H, C1-C12A linear or branched alkyl group of (a), or an aryl group;
R14represents C1-C12A linear or branched alkyl group of (a), or an aryl group;
R15represents C1-C12Linear or branched alkyl, aryl, or-OH;
R16represents C1-C12Linear or branched alkyl, aryl, or-OH;
R5and R6Independently of one another represent C1-C20Linear or branched alkyl of (2), C4-C20Cycloalkyl of, C2-C20Alkenyl of (C)6-C20optionally-CH in these radicals2-may be substituted by-O-, or R5And R6May be linked to each other or form a five-or six-membered ring through-O-, -S-, -NH-;
y representsWherein R is7’、R8’、R9’、R10' and R11' having R independently of7、R8、R9、R10And R11In the same sense, Y and R4May or may not be the same.
Preferably, when Z is-SO2R4When the intermediate b is substituted with R4SO2H, heating and refluxing in an organic solvent to react to obtain a product; or when Z is-NR5R6When the intermediate b is substituted with R5R6NH is put into an organic solvent and undergoes nucleophilic substitution reaction in the presence of an acid-binding agent to obtain a product.
According to a typical embodiment of the present invention, the preparation method specifically comprises:
1) synthesis of intermediate a: taking the raw material a and the raw material b as initial raw materials, and synthesizing an intermediate a through Friedel-crafts reaction under the condition of an aluminum trichloride or zinc chloride catalyst;
2) synthesis of intermediate b: the intermediate a and the raw material c are subjected to Friedel-crafts acylation reaction in an organic solvent under the catalytic action of aluminum trichloride or zinc chloride to obtain an intermediate b; it should be noted that B in the raw material c represents halogen or hydrogen, and when the raw material B represents H, the raw material c should be further subjected to halogen substitution reaction with liquid bromine or chlorine gas, etc. before the step 3), which is easily understood by those skilled in the art, and the reaction conditions are well known;
3) and (3) synthesis of a product:
when Z is-SO2R4When the intermediate b is substituted with R4SO2H, heating and refluxing in an organic solvent to react to obtain a product;
when Z is-NR5R6When the intermediate b is substituted with R5R6NH is put into an organic solvent and undergoes nucleophilic substitution reaction in the presence of an acid-binding agent to obtain a product.
In the above-mentioned preparation methods, the starting materials used are known compounds in the prior art, and can be obtained commercially or by a known synthetic method, and the specific synthetic method can be also synthesized by referring to the method disclosed in International patent application No. WO2000031030A 1.
According to an exemplary embodiment of the present invention, there is provided a use of a hybrid photoinitiator in a photocurable composition.
According to an exemplary embodiment of the present invention, a photocurable composition is provided. The photocurable composition includes any of the hybrid photoinitiators described above.
The following examples are provided to further illustrate the advantageous effects of the present invention.
Example 1
(1) Preparation of intermediate 1a
42g (0.25mol) of the raw material 1a, 35.7g (0.255mol) of the raw material 1b and 100ml of dichloromethane solvent are added into a 500ml four-neck flask, mechanically stirred, 36g (0.275mol) of aluminum trichloride is dissolved in 150ml of dichloromethane solvent, slowly dripped into a reaction system through a constant pressure dropping funnel, the temperature is controlled between 20 ℃ and 25 ℃, the dripping is finished for about 1 hour, and the constant temperature reaction is carried out for 30 min. And (5) tracking the liquid phase until the reaction of the raw materials is finished, and stopping the reaction.
(2) Preparation of Compound 1
57g (0.25mol) of α -bromopropionyl bromide is dissolved in 30ml of dichloromethane and slowly added into the reaction solution, the mechanical stirring is carried out, the temperature is controlled to be about 10 ℃, 36g of α -bromopropionyl bromide is slowly added into a reaction bottle in batches, the addition is finished for about 1h, the constant temperature reaction is carried out for 1h at the temperature of 15-20 ℃ after the addition is finished, and the liquid phase tracking is carried out until the intermediate 1a finishes the reaction.
After the reaction, water was added to the reaction flask and the mixture was stirred well, and the pH was adjusted to 7 to 8 with sodium hydrogencarbonate. The organic phase was washed twice with water, dried over anhydrous sodium sulfate, rotary evaporated to remove the solvent and recrystallized from ethanol to yield 89g of a white solid.
The structure of the product was confirmed by hydrogen nuclear magnetic resonance spectroscopy and mass spectrometry.
1H-NMR(CDCl3，500MHz)：2.06(6H,s)，3.87(2H，s)，7.36-7.70(5H，m)，7.82-8.18(6H，m)。
MS(m/z):420(M+1)+。
Example 2
Preparation of Compound 2
41.9g (0.1mol) of Compound 1 and 19.5(0.125mol) of starting material 2 were dissolved in 100ml of n-butanol solvent and reacted under reflux for 2.5 hours, and the liquid phase was followed until product 1 was reacted completely. The temperature was reduced to 70 ℃, 80ml of water was added to separate the organic phase, the organic phase was washed twice with water, dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure to obtain 40g of a white solid.
The structure of the product was confirmed by hydrogen nuclear magnetic resonance spectroscopy and mass spectrometry.
1H-NMR(CDCl3，500MHz)：1.65(6H,m)，2.35(3H，s)，3.87(2H，s)，7.34-7.81(9H，m)，7.82-8.18(6H，m)。
MS(m/z):495(M+1)+。
Example 3
Preparation of Compound 3
41.9g (0.1mol) of the product 1, 17.4g (0.2mol) of morpholine, a proper amount of xylene and potassium carbonate are reacted for 30 hours at about 130 ℃, and the liquid phase is tracked until the product 1 is completely reacted. After cooling, the solvent was removed by extraction, washing, drying and rotary evaporation to give 31.8g of solid product.
The structure of the product was confirmed by hydrogen nuclear magnetic resonance spectroscopy and mass spectrometry.
1H-NMR(CDCl3，500MHz)：1.37(6H,m)，2.37-3.67(4H，m)，3.87(2H，s)，7.36-7.70(5H，m)，7.94-8.18(6H，m)。
MS(m/z):426(M+1)+。
Examples 4 to 14
The compounds of examples 4-14 were prepared according to the synthetic procedures of examples 1-3. Target compound and its use1The H-NMR data are shown in Table 1.
TABLE 1
Evaluation of Performance
1. Dissolution Performance test
Taking tripropylene glycol diacrylate (TPGDA) and PGMEA solvents which are widely used in the field as the diluents, the solubility of part of the photoinitiator and Esacure1001 mentioned in the background art of the invention is tested, and the maximum weight capable of dissolving in 100g of the solvent at 20 ℃ is taken as an evaluation standard. The test results are shown in table 2.
TABLE 2
As can be seen from Table 2, compared with the commercial Esacure1001 photoinitiator, the solubility of the novel hybrid photoinitiator is greatly improved, particularly, the solubility of a compound containing a fluorene structure is excellent, and the use of a small-molecule active diluent can be greatly reduced during use.
2. Test for curing Properties
The application system of UV light curing of the hybrid photoinitiator containing hydrogen abstraction type and cleavage type photo initiation groups is further described below with reference to specific examples, and is compared with Esacure1001 mentioned in the background art and the conventional photoinitiator benzophenone BP commercially available at present.
The residual odor of the cured film was evaluated by smelling through the nose, and the test results were classified into three grades of 1 (no odor), 2 (odor), and 3 (pungent odor); the sensitivity of the photoinitiator was evaluated by continuously increasing the speed of the coating formulation through the irradiation unit under certain conditions (RW-UV.70201 track exposure unit, 100% output) until incomplete curing, using its maximum speed (m/min) as the initiator sensitivity; the cured film hardness test was carried out by referring to the pencil hardness evaluation method specified in GB/T6739-2006, and the hardness of the coating was expressed as the hardness of the hardest pencil that did not scratch the coating.
In the following discussion, the UV light cure system is formulated with the individual components in weight percent.
(I) flexographic ink
And (3) placing the formula in a four-neck flask, stirring at room temperature in a dark place for 3 hours, and filtering and defoaming to obtain the curing flexo printing ink. The samples were sprayed onto white cardboard at a thickness of about 10 μm, and placed on a track exposure machine to irradiate the coating at 100% output. The test results are shown in table 3:
TABLE 3
(II) offset printing ink
And (3) placing the formula into a four-neck flask, stirring for 3 hours at room temperature in a dark place, and filtering and defoaming to obtain the offset printing ink for curing. The samples were sprayed onto white cardboard at a thickness of about 2 μm, and placed on a track exposure machine to irradiate the coating at 100% output. The test results are shown in table 4:
TABLE 4
As can be seen from Table 4, the novel hybrid photoinitiator of the invention has no odor residue after being decomposed by illumination, high sensitivity, high curing speed and more excellent mechanical properties after film formation.
In conclusion, the novel hybrid photoinitiator provided by the invention can effectively improve the solubility of Esacure1001, reduce the use of a small-molecule active diluent, has no odor residue after illumination decomposition, high sensitivity and excellent mechanical property, and has a good promoting effect on popularization and application of a colored ink system in the field of photocuring.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (12)
1. A hybrid photoinitiator having the structure of formula (I):
wherein,
m is selected from any one of the following groups:
R1represents-H, C1-C20Linear or branched alkyl of (2), C3-C20Cycloalkyl of, C4-C20Alkylcycloalkyl or cycloalkylalkyl, C2-C20optionally-CH in these radicals2-may be substituted by-O-;
x represents
R2And R3Each independently represents-H or-C1-C12A linear or branched alkyl, aryl, or alkylaryl group of (a);
z represents-SO2R4、-NR5R6Or halogen;
R4represents C1-C12Linear or branched alkyl of (2), or
R7、R8、R9、R10And R11Each independently represents-H, halogen, -CN, C1-C12Linear OR branched alkyl, aryl, -OR12、-SR13、-SOR14、-SO2R15、-COR16or-NR5R6；
R12represents-H, C1-C12A linear or branched alkyl group of (a), or an aryl group;
R13represents-H, C1-C12A linear or branched alkyl group of (a), or an aryl group;
R14represents C1-C12A linear or branched alkyl group of (a), or an aryl group;
R15represents C1-C12Linear or branched alkyl, aryl, or-OH;
R16represents C1-C12Linear or branched alkyl, aryl, or-OH;
R5and R6Independently of one another represent C1-C20Linear or branched alkyl of (2), C4-C20Cycloalkyl of, C2-C20Alkenyl of (C)6-C20optionally-CH in these radicals2-may be substituted by-O-, or R5And R6May be linked to each other or form a five-or six-membered ring through-O-, -S-, -NH-;
y representsWherein R is7’、R8’、R9’、R10' and R11' having R independently of7、R8、R9、R10And R11In the same sense, Y and R4May or may not be the same.
2. The hybrid photoinitiator as set forth in claim 1 wherein R1Represents a hydrogen atom, a halogen atom, C1-C10Linear or branched alkyl of (2), C3-C10Cycloalkyl of, C4-C10Alkylcycloalkyl or cycloalkylalkyl, C2-C10optionally-CH in these radicals2-may be substituted by-O-.
3. The hybrid photoinitiator as set forth in claim 2 wherein R1represents-H, methyl, ethyl, n-propyl, n-butyl, vinyl, or allyl.
4. The hybrid photoinitiator as set forth in claim 1 wherein R2And R3Each independently represents-H or-C1-C6Linear or branched alkyl, aryl, or a salt thereof,Or an alkylaryl group.
5. The hybrid photoinitiator as set forth in claim 4 wherein R2And R3Each independently represents a methyl group, an ethyl group, an n-propyl group, an n-butyl group, a phenyl group, a benzyl group, a vinyl group, or an allyl group.
6. The hybrid photoinitiator as set forth in claim 1 wherein R7、R8、R9、R10And R11Each independently represents-H, halogen, -OH, C1-C6Linear or branched alkyl, -OCH3、And (4) an aryl group.
7. The hybrid photoinitiator as set forth in claim 1 wherein R5And R6Independently of one another represent C1-C10Linear or branched alkyl of (2), C4-C10Cycloalkyl of, C2-C10Alkenyl of (C)6-C10optionally-CH in these radicals2-may be substituted by-O-, or R3And R3May be linked to each other or form a five-or six-membered ring through-O-, -S-, -NH-.
8. The hybrid photoinitiator as set forth in claim 1 wherein R7 ’、R8 ’、R9 ’、R10 ’And R11 ’Independently of one another represent-H, C1-C6Linear OR branched alkyl, aryl, -OR2or-NR5R6。
9. A method of preparing a hybrid photoinitiator according to any one of claims 1 to 8, comprising the steps of:
1) taking the raw material a and the raw material b as initial raw materials to synthesize an intermediate a through Friedel-crafts reaction;
2) carrying out a Friedel-crafts acylation reaction on the intermediate a and the raw material c to obtain an intermediate b; and
3) reacting the intermediate b with a raw material d to obtain a product;
the reaction process is as follows:
A＝Br/Cl、B＝A/H
wherein,
m is selected from any one of the following groups:
R1represents-H, C1-C20Linear or branched alkyl of (2), C3-C20Cycloalkyl of, C4-C20Alkylcycloalkyl or cycloalkylalkyl, C2-C20optionally-CH in these radicals2-may be substituted by-O-;
x represents
R2And R3Each independently represents-H or-C1-C12A linear or branched alkyl, aryl, or alkylaryl group of (a);
z represents-SO2R4、-NR5R6Or halogen;
R4represents C1-C12Linear or branched alkyl of (2), or
R7、R8、R9、R10And R11Each independently represents-H, halogen, -CN, C1-C12Linear OR branched alkyl, aryl, -OR12、-SR13、-SOR14、-SO2R15、-COR16or-NR5R6；
R12represents-H, C1-C12A linear or branched alkyl group of (a), or an aryl group;
R13represents-H, C1-C12A linear or branched alkyl group of (a), or an aryl group;
R14represents C1-C12A linear or branched alkyl group of (a), or an aryl group;
R15represents C1-C12Linear or branched alkyl, aryl, or-OH;
R16represents C1-C12Linear or branched alkyl, aryl, or-OH;
R5and R6Independently of one another represent C1-C20Linear or branched alkyl of (2), C4-C20Cycloalkyl of, C2-C20Alkenyl of (C)6-C20optionally-CH in these radicals2-may be substituted by-O-, or R5And R6May be linked to each other or form a five-or six-membered ring through-O-, -S-, -NH-;
y representsWherein R is7 ’、R8 ’、R9 ’、R10 ’And R11 ’Each having a radical of formula R7、R8、R9、R10And R11In the same sense, Y and R4Can be the sameOr may be different.
10. The production method according to claim 9,
when Z is-SO2R4When the intermediate b and R are4SO2H, heating and refluxing in an organic solvent to react to obtain the product; or
When Z is-NR5R6When the intermediate b and R are5R6And (3) NH is in an organic solvent, and the product is obtained through nucleophilic substitution reaction in the presence of an acid-binding agent.
11. Use of a hybrid photoinitiator according to any one of claims 1 to 8 in a photocurable composition.
12. A photocurable composition comprising the hybrid photoinitiator according to any one of claims 1 to 8.
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