CN114478845A - Dendritic fluorescein sodium-iodonium salt visible light initiator and preparation method and application thereof - Google Patents
Dendritic fluorescein sodium-iodonium salt visible light initiator and preparation method and application thereof Download PDFInfo
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- visible light
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- fluorescein sodium
- iodonium salt
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- 239000003999 initiator Substances 0.000 title claims abstract description 30
- GNBHRKFJIUUOQI-UHFFFAOYSA-N fluorescein Chemical compound O1C(=O)C2=CC=CC=C2C21C1=CC=C(O)C=C1OC1=CC(O)=CC=C21 GNBHRKFJIUUOQI-UHFFFAOYSA-N 0.000 title claims abstract description 19
- FVAUCKIRQBBSSJ-UHFFFAOYSA-N [Na+].I Chemical compound [Na+].I FVAUCKIRQBBSSJ-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000011347 resin Substances 0.000 claims abstract description 16
- 229920005989 resin Polymers 0.000 claims abstract description 16
- 229960002143 fluorescein Drugs 0.000 claims abstract description 13
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 8
- 238000006683 Mannich reaction Methods 0.000 claims description 8
- RSJLWBUYLGJOBD-UHFFFAOYSA-M diphenyliodanium;chloride Chemical compound [Cl-].C=1C=CC=CC=1[I+]C1=CC=CC=C1 RSJLWBUYLGJOBD-UHFFFAOYSA-M 0.000 claims description 8
- 229920006150 hyperbranched polyester Polymers 0.000 claims description 8
- 239000003085 diluting agent Substances 0.000 claims description 7
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 claims description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 claims description 5
- 238000005342 ion exchange Methods 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 3
- 239000008199 coating composition Substances 0.000 claims 2
- 238000013329 compounding Methods 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- 238000000034 method Methods 0.000 claims 1
- 230000000977 initiatory effect Effects 0.000 abstract description 10
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 abstract description 8
- 229910052708 sodium Inorganic materials 0.000 abstract description 8
- 239000011734 sodium Substances 0.000 abstract description 8
- 239000011248 coating agent Substances 0.000 abstract description 6
- 238000000576 coating method Methods 0.000 abstract description 6
- 239000000412 dendrimer Substances 0.000 abstract description 5
- 230000027756 respiratory electron transport chain Effects 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 229940020947 fluorescein sodium Drugs 0.000 abstract description 3
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical class I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 14
- 229920002521 macromolecule Polymers 0.000 description 13
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 12
- 238000003786 synthesis reaction Methods 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
- 238000001723 curing Methods 0.000 description 9
- 238000001035 drying Methods 0.000 description 9
- 238000001914 filtration Methods 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N DMSO-d6 Substances [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 4
- 229920000736 dendritic polymer Polymers 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- -1 fluorescein sodium-iodonium salt compound Chemical class 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- NJDNXYGOVLYJHP-UHFFFAOYSA-L disodium;2-(3-oxido-6-oxoxanthen-9-yl)benzoate Chemical class [Na+].[Na+].[O-]C(=O)C1=CC=CC=C1C1=C2C=CC(=O)C=C2OC2=CC([O-])=CC=C21 NJDNXYGOVLYJHP-UHFFFAOYSA-L 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000008098 formaldehyde solution Substances 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 238000000016 photochemical curing Methods 0.000 description 3
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 229930003268 Vitamin C Natural products 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- 239000012267 brine Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000007888 film coating Substances 0.000 description 2
- 238000009501 film coating Methods 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- JLKDVMWYMMLWTI-UHFFFAOYSA-M potassium iodate Chemical compound [K+].[O-]I(=O)=O JLKDVMWYMMLWTI-UHFFFAOYSA-M 0.000 description 2
- 239000001230 potassium iodate Substances 0.000 description 2
- 229940093930 potassium iodate Drugs 0.000 description 2
- 235000006666 potassium iodate Nutrition 0.000 description 2
- 150000003141 primary amines Chemical group 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 235000019154 vitamin C Nutrition 0.000 description 2
- 239000011718 vitamin C Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 201000004624 Dermatitis Diseases 0.000 description 1
- 206010015946 Eye irritation Diseases 0.000 description 1
- 206010019233 Headaches Diseases 0.000 description 1
- 208000000453 Skin Neoplasms Diseases 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- OZLBDYMWFAHSOQ-UHFFFAOYSA-N diphenyliodanium Chemical class C=1C=CC=CC=1[I+]C1=CC=CC=C1 OZLBDYMWFAHSOQ-UHFFFAOYSA-N 0.000 description 1
- 208000002173 dizziness Diseases 0.000 description 1
- 231100000013 eye irritation Toxicity 0.000 description 1
- 231100000869 headache Toxicity 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229910000343 potassium bisulfate Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 201000000849 skin cancer Diseases 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- SFZIOISNGCFHIC-UHFFFAOYSA-L terephthalate;tetramethylazanium Chemical compound C[N+](C)(C)C.C[N+](C)(C)C.[O-]C(=O)C1=CC=C(C([O-])=O)C=C1 SFZIOISNGCFHIC-UHFFFAOYSA-L 0.000 description 1
- 238000004154 testing of material Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- 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
-
- 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
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/01—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to unsaturated polyesters
-
- 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
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/10—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule
- C08F283/105—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule on to unsaturated polymers containing more than one epoxy radical per molecule
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/002—Dendritic macromolecules
- C08G83/003—Dendrimers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/002—Dendritic macromolecules
- C08G83/003—Dendrimers
- C08G83/004—After treatment of dendrimers
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- 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
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
- C09D163/10—Epoxy resins modified by unsaturated compounds
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- 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
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
- C09D167/06—Unsaturated polyesters having carbon-to-carbon unsaturation
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Epoxy Resins (AREA)
- Paints Or Removers (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The invention discloses a dendritic fluorescein sodium-iodonium salt visible light initiator, and a preparation method and application thereof. According to the invention, chromophore fluorescein sodium is combined with iodonium salt to obtain an electron transfer type visible light-sensitive initiation system, and the electron transfer type visible light-sensitive initiation system is introduced into a dendritic compound, so that the visible light initiation efficiency is greatly improved, and the chromophore fluorescein sodium has the characteristics of environmental friendliness, good compatibility, low energy consumption and the like. It is used as visible light initiator to initiate the curing of unsaturated resin. The invention realizes a macromolecular visible light initiator, and the specific dendritic sodium fluorescein-iodonium salt is used for curing polymerization of unsaturated resin, so that the obtained coating has excellent appearance, hardness, glossiness and flexibility.
Description
The invention is proposed in 2018, 06 and 19 days: application No. 201810627087.3, divisional application of the invention patent entitled "dendrimer sodium fluorescein-iodonium salt visible light initiator and preparation method and application thereof".
Technical Field
The invention relates to a photoinitiation technology, in particular to a dendritic fluorescein sodium-iodonium salt visible light photoinitiator, and a preparation method and application thereof.
Background
Photocuring has become an integral part of the polymer science and technology field. The photo-initiation has the advantages of low energy consumption, high polymerization efficiency and environmental friendliness, and is a key component of the photo-curing technology.
Because the energy of ultraviolet light is far higher than that of visible light, the development of ultraviolet light initiators is more mature at present. However, ultraviolet light causes many problems which cannot be ignored, when the ultraviolet light acts on human body, headache and dizziness can be caused, eye irritation can be caused, dermatitis can be easily caused, and skin cancer can be caused seriously. Compared with ultraviolet light, visible light can directly utilize sunlight as a visible light source, so that the energy is saved and the environment is protected; has longer wavelength range, and has stronger penetrability than ultraviolet light for some materials, and when the curing capability is stronger, the visible light is harmless to human bodies, and the energy is lower, and the secondary initiation can not be caused. The energy of ultraviolet light is far higher than that of visible light, so that the polymerization is difficult to be carried out in an energy transfer mode for a visible light initiation system, but the energy required by the polymerization of an electron transfer initiation reaction is small, so that the ultraviolet light becomes a main path for initiation by visible light. Iodonium salt is an excellent electron acceptor, and an electron transfer type visible light photoinitiation system can be constituted as long as a suitable electron donor is found and a substance having an absorption wavelength covering the visible light region is absorbed.
Although the small molecular initiator has a plurality of types and is developed more mature, the small molecular visible light initiator has the defects of heavy odor, high volatility, weak anti-migration capability, poor environmental compatibility, poor resin compatibility, single function and the like. And the dendritic macromolecule is taken as a leading edge polymer material. The structure is regular, the surface density is high, and the end group has a plurality of active groups for modification. Therefore, how to insert the visible light initiator into macromolecules to enable active units to generate free radicals after illumination and initiate system photocuring to form high polymers with better crosslinking degree and compatibility is a problem which is urgently desired to be solved in the field.
Disclosure of Invention
The invention provides a green and efficient dendritic fluorescein sodium-iodonium salt visible light initiator, and a preparation method and application thereof.
In order to achieve the above purpose, the technical scheme of the invention is as follows: the dendritic fluorescein sodium-iodonium salt visible light initiator has a structural formula I as follows:
firstly, synthesizing dendritic macromolecules with amino as end groups, then preparing a dendritic sodium fluorescein-iodonium salt visible light initiator through a mannich reaction by taking sodium fluorescein-iodonium salt as a light initiation group, and initiating the curing of epoxy acrylate and hyperbranched polyester acrylate.
The preparation method of the dendritic fluorescein sodium-iodonium salt visible light initiator comprises the following steps:
(1) intermediate fluorescein sodium-iodonium salt [ FS (IPh)2)2]The synthesis of (2): carrying out ion exchange reaction on fluorescein sodium salt II and diphenyl iodonium chloride salt III at the dark room temperature, filtering, washing and drying to obtain an orange-red solid, wherein the reaction formula is as follows:
(2) dendrimer sodium fluorescein-iodonium salt macromolecule [ PAE-FS (IPh)2)2]The synthesis of (2): mixing PAE (NH)2)8Dissolving in ethanol, adding formaldehyde solution, mixing, and dripping FS (IPh)2)2Heating the ethanol solution to 30-65 ℃, preferably 65 ℃, carrying out mannich reaction, distilling after the reaction is finished, and drying to obtain viscous dark red liquid, wherein the reaction formula is as follows:
in a preferred embodiment of the invention, the ion exchange reaction time is 4 to 8 hours, preferably 6 hours.
In a preferred embodiment of the invention, the mannich reaction time is from 6 to 14 hours, preferably 12 hours.
In a preferred embodiment of the invention, the molar ratio of the sodium fluorescein salt II to the diphenyliodonium chloride salt III is from 1: 1 to 1: 2, more preferably 1: 2.
In a preferred embodiment of the invention, PAE (NH)2)8And FS (IPh)2)2The molar ratio of (A) to (B) is 1: 8.
In a preferred embodiment of the present invention, dilute hydrochloric acid is added as a catalyst to the mannich reaction system.
Another object of the present invention is to provide a photocurable composition comprising:
a)1 to 10 weight percent of a visible light initiator according to formula I;
b)58 to 64 weight percent of at least one unsaturated resin; and
c)32 to 35 wt% of at least one reactive diluent.
The visible light initiator prepared by the invention is used for polymerization of unsaturated resin, the unsaturated resin is epoxy acrylate, hyperbranched polyester acrylate and other unsaturated resin, the wavelength range of the used visible light is 400-780nm, and the illumination intensity is 20-400mW/cm2The curing time is 4-200 min.
Compared with the prior art, the invention has the following advantages:
1. the visible light initiator prepared by the invention has cheap light source, green and safe property and strong penetrating power.
2. The dendritic photoinitiator prepared by the invention has high initiation efficiency.
3. The photoinitiator prepared by the invention is a macromolecular photoinitiator, is nontoxic, does not need to be added with an auxiliary initiator, and is green and environment-friendly.
Detailed Description
The following examples are further illustrative of the present invention, but the scope of the present invention is not limited thereto. The embodiments in the present description are only for illustrating the present invention, and do not limit the scope of the present invention. The scope of the present invention is defined only by the appended claims, and any omissions, substitutions, and changes in the form of the embodiments disclosed herein that may be made by those skilled in the art are intended to be included within the scope of the present invention.
The invention starts from the design of molecular structure, combines chromophore fluorescein sodium with iodonium salt, and prepares a fluorescein sodium-iodonium salt compound with the absorption spectrum of about 463 nm; on the basis, the fluorescent material is introduced into dendritic macromolecules, and the absorption spectrum of the dendritic macromolecules is about 502nm, so that the dendritic sodium fluorescein-iodonium salt visible light initiator is prepared. The initiator has good compatibility with unsaturated resin, and can initiate the curing of the unsaturated resin under visible light without adding an auxiliary agent. And a plurality of active groups are arranged at the end group of the dendritic macromolecule, which is beneficial to improving the photoinitiation efficiency.
The preparation method of the dendritic fluorescein sodium-iodonium salt visible light initiator comprises the following steps:
(1) the end group of the intermediate is dendritic macromolecule (PAE (Beplace) of 8 acrylate8) The synthesis of (2): mixing trimethylolpropane triacrylate, ethylenediamine and absolute methanol, heating to 30 ℃, reacting for 6 hours, and washing with absolute methanol after the reaction is finished to obtain colorless and transparent viscous liquid, wherein the reaction formula is as follows:
(2) the intermediate end group is dendritic macromolecule (PAE (NH) with 8 primary amine groups2)8) The synthesis of (2): mixing PAE (becoming)8Mixing with ethylenediamine, heating to 30 deg.C, reacting for 24 hr, distilling under reduced pressure, washing with ethyl acetate to obtain yellowish transparent viscous liquid, which has the following reaction formula:
(3) synthesis of intermediate diphenyl iodonium chloride: mixing benzene, acetic anhydride and potassium iodate, reacting in a saline-ice bath, dripping acetic anhydride concentrated sulfuric acid solution, and reacting at room temperature for 48 hours. Cooling, adding distilled water, filtering, and extracting the filtrate with diethyl ether and petroleum ether respectively. Adding ammonium chloride, filtering, washing, recrystallizing and drying to obtain diphenyl iodonium salt crystals, wherein the reaction formula is as follows:
(4) intermediate fluorescein sodium-iodonium salt [ FS (IPh)2)2]The synthesis of (2): and (2) carrying out ion exchange reaction on sodium fluorescein salt and diphenyl iodonium chloride at the dark room temperature, filtering, washing and drying after 6-hour reaction to obtain an orange-red solid, wherein the reaction formula is as follows:
(5) dendrimer sodium fluorescein-iodonium salt macromolecule [ PAE-FS (IPh)2)2]The synthesis of (2): mixing PAE (NH)2)8Dissolving in ethanol, adding formaldehyde solution, mixing, and dripping FS (IPh)2)2Heating the ethanol solution and a little diluted hydrochloric acid as a catalyst to 30-65 ℃, reacting for 6-14 hours, distilling and drying to obtain viscous dark red liquid, wherein the reaction formula is as follows:
example 1: preparation of visible light initiator
(1) The end group of the intermediate is dendritic macromolecule (PAE (Beplace) of 8 acrylate8) The synthesis of (2):
60g of trimethylolpropane triacrylate, 2.4g of ethylenediamine and 30mL of anhydrous methanol were mixed, heated to 30 ℃ and reacted for 6 hours, and washed with anhydrous methanol to obtain a colorless transparent viscous liquid.
(2) The intermediate end group is dendritic macromolecule (PAE (NH) with 8 primary amine groups2)8) The synthesis of (2):
4.665g PAE (═)8Mixing with 108g ethylenediamine, heating to 30-50 deg.C, reacting for 24 hr, distilling under reduced pressure, and washing with ethyl acetate to obtain yellowish transparent viscous liquid.
(3) Synthesis of intermediate diphenyl iodonium chloride:
9mL of benzene, 10mL of acetic anhydride and 10.7g of potassium iodate were mixed together and then a mixture of 7mL of concentrated sulfuric acid and 10mL of acetic anhydride was slowly added dropwise under the condition of a brine ice bath (about 5 ℃). After the completion of the dropwise addition, the mixture was left at room temperature and stirred for 48 hours. After the reaction was completed, it was cooled in a brine ice bath, and 20mL of distilled water was added. 10mL of anhydrous ether was added to the mixture, followed by stirring and suction filtration to remove KHSO4The filtrate was extracted once with 10mL of diethyl ether and once with 10mL of petroleum ether, respectively, to give a pale yellow clear solution. To the resulting clear solution, 50mL of 5.35g aqueous ammonium chloride solution was added, stirred, filtered under suction, and washed with distilled water and ether. Recrystallizing, dissolving the white powder in hot methanol, adding active carbon, rapidly stirring for decolorizing, vacuum filtering while hot, cooling the filtrate in a beaker, crystallizing, vacuum filtering, and drying to obtain white solid.
(4) Intermediate fluorescein sodium-iodonium salt [ FS (IPh)2)2]The synthesis of (2):
1.9g of sodium fluorescein salt and 3.2g of diphenyliodonium chloride were placed in 100mL of methylene chloride, wrapped with tinfoil, stirred at room temperature in the dark for 6h, and filtered. And filtering the filtrate, and drying in a vacuum drying oven to obtain an orange-red solid. Adding anhydrous ether for washing, filtering and drying to obtain orange-red solid.
FT-IR(KBr，cm-1)：v＝3550，3234，1616，1465，737，620，820，461.1H-NMR(DMSO-d6400MHz, delta/ppm) nuclear magnetic spectrum of each peak and FS (IPh)2)2Proton peaks in the structure correspond to: δ 7.794(d, 8H), 7.743(d, 6H), 7.727(d, 14H), 6.932(d, 2H).13C-NMR(DMSO-d6400MHz, delta/ppm) nuclear magnetic spectrum of each peak and FS (IPh)2)2Proton peaks in the structure correspond to: δ 173.660, 170.462, 157.558, 153.284, 128.485, 119.205.
(5) Dendrimer sodium fluorescein-iodonium salt macromolecule [ PAE-FS (IPh)2)2]The synthesis of (2):
1.724g of PAE (NH)2)8Dissolved in a small amount of ethanol and 0.6g of formaldehyde solution was added. Heating ethanol, and adding 1-3 drops of 20 wt% dilute hydrochloric acid to obtain 6.96g FS (IPh)2)2Dissolving in hot ethanol, and adding dropwise the above solution. Heating to 65 ℃, and reacting for 12h to obtain orange-red transparent liquid. Spin-steaming and drying for 3h gave a viscous dark red liquid with a yield of 57.23%.
FT-IR(KBr，cm-1)：v＝3414，2971，1639，1566，1472，1385，1111，820，752，611.1H-NMR(DMSO-d6400MHz, delta/ppm) nuclear magnetic spectrum of each peak and PAE-FS (IPh)2)2Proton peaks in the structure correspond to: δ 8.274(d, 88H), 7.266(d, 48H), 6.601(d, 64H), 4.400(t, 32H), 4.234(m, 16H), 3.602(m, 16H), 3.094(m, 8H), 2.913(d, 24H), 2.652(t, 8H), 2.177(t, 4H), 1.861(t, 16H), 1.173(m, 8H), 0.799(t, 12H).13C-NMR(DMSO-d6400MHz, delta/ppm) nuclear magnetic spectrum of each peak and PAE-FS (IPh)2)2Proton peaks in the structure correspond to: δ 173.604, 170.523, 157.837, 154.782, 129.165, 119.196, 115.725, 110.334, 102.847, 62.120, 54.495, 47.740, 43.905, 39.879, 37.902, 23.083, 21.739, 7.949.
Example 2: PAE-FS (IPh)2)2Visible light-initiated unsaturated resins
PAE-FS(IPh2)2Visible light initiationEpoxy acrylate:
taking 1.3g of epoxy acrylate and 0.7g of TMPTA (Tetramethylbenzene terephthalamide) as an active diluent, stirring and mixing uniformly, and respectively adding various visible light initiators (PAE-FS (IPh) in the total mass percentage of the system2)2Photoinitiator, FS (IPh)2)2A combined photoinitiator consisting of a photoinitiator and FS +10 wt% of co-initiator vitamin C, namely FS + 10% Vc), is uniformly mixed by a mixer, a film with the thickness of about 0.1mm is coated on a glass sheet, the glass sheet is placed under the radiation of a 500WLED lamp for curing, and the curing time is recorded. The results are shown in Table 1.
TABLE 1 initiator initiated epoxy acrylate cure times
PAE-FS(IPh2)2Visible light-initiated hyperbranched polyester acrylate:
taking 1.3g of hyperbranched polyester acrylate and 0.7g of TMPTA (tetramethylammonium terephthalate) as an active diluent, stirring and mixing uniformly, and respectively adding various visible light initiators (PAE-FS (IPh) in the total mass percentage of the system2)2Photoinitiator, FS (IPh)2)2A combined photoinitiator consisting of a photoinitiator and FS +10 wt% of co-initiator vitamin C, namely FS + 10% Vc), is uniformly mixed by a mixer, a film with the thickness of about 0.1mm is coated on a glass sheet, the glass sheet is placed under the radiation of a 500WLED lamp for curing, and the curing time is recorded. The results are shown in Table 2.
TABLE 2 initiator initiated curing of hyperbranched polyester acrylates
Example 3: film coating Performance test
The coating thickness test is carried out according to GB/T1764-1979, and the test equipment is a QuaNix8500 type electronic thickness gauge of Germany Nix company; the film coating glossiness test is carried out according to GB/T9754-1988, and the test equipment is a JKGZ 60-degree specular gloss meter of Jingkejii material testing machine, Inc. in Tianjin; the film hardness test is carried out according to GB/T6739-2006, and the test equipment is an QUQ model film pencil mark hardness tester of Jingke union materials testing machine, Inc. in Tianjin; the coating adhesion test is carried out according to GB/T9286-1998, and the test equipment is QFZ paint film adhesion tester of Jingke union materials testing machine, Inc. in Tianjin; the flexibility test of the coating film is carried out according to GB1731-79, and the test equipment is QTX type paint film elasticity tester of Jingke union materials tester, Inc. in Tianjin.
TABLE 3 epoxy acrylate coating Performance test
TABLE 4 hyperbranched polyester acrylate coating Performance test
Claims (10)
1. The dendritic fluorescein sodium-iodonium salt visible light initiator is characterized by having a structural formula as follows:
2. the preparation method of the dendritic fluorescein sodium-iodonium salt visible light initiator is characterized by comprising the following steps:
(1) the fluorescein sodium salt II and the diphenyl iodonium chloride salt III are subjected to ion exchange reaction in the dark to prepare FS (IPh)2)2A step of compounding a compound having a structure,
(2) mixing PAE (NH)2)8Dissolving in ethanol, adding formaldehyde and FS (IPh) sequentially2)2Ethanol solution to carry out mannich reaction to prepare a target product,
3. the process according to claim 2, characterized in that the ion exchange reaction time is 4 to 8 hours, preferably 6 hours; and/or the mannich reaction time is 6 to 14 hours, preferably 12 hours;
and/or the mannich reaction temperature is 30-65 ℃, preferably 65 ℃;
and/or the molar ratio of the fluorescein sodium salt II to the diphenyl iodonium chloride salt III is 1: 1-1: 2, and the preferred molar ratio is 1: 2;
and/or PAE (NH)2)8And FS (IPh)2)2The molar ratio of (A) to (B) is 1: 8;
and/or dilute hydrochloric acid is added into a mannich reaction system as a catalyst.
4. A photocurable composition comprising:
a)1 to 10 weight percent of the visible photoinitiator of claim 1;
b)58 to 64 weight percent of at least one unsaturated resin; and
c)32 to 35 wt% of at least one reactive diluent.
5. A photocurable coating composition characterized by comprising:
a)1 to 10 weight percent of the visible photoinitiator of claim 1;
b)58 to 64 weight percent of at least one unsaturated resin; and
c)32 to 35 wt% of at least one reactive diluent.
6. A photocurable coating composition comprising:
a)1 to 10 weight percent of the visible photoinitiator of claim 1;
b)58 to 64 weight percent of at least one unsaturated resin; and
c)32 to 35 wt% of at least one reactive diluent.
7. The composition according to any one of claims 4 to 6, wherein the unsaturated resin is an epoxy acrylate or/and a hyperbranched polyester acrylate; and/or the reactive diluent adopts trimethylolpropane triacrylate.
8. Use of a photoinitiator according to claim 1 for the curing polymerization of unsaturated resins under visible light.
9. Use according to claim 8, wherein the visible light has a wavelength in the range of 400 to 780nm and an intensity of 20 to 400mW/cm2The curing time is 4-200 min.
10. Use according to claim 8, wherein the unsaturated resin is an epoxy acrylate or/and a hyperbranched polyester acrylate.
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