CN117466793A - Sulfur-containing photoinitiator and preparation method and application thereof - Google Patents
Sulfur-containing photoinitiator and preparation method and application thereof Download PDFInfo
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 46
- 239000011593 sulfur Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 150000001875 compounds Chemical class 0.000 claims description 39
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 24
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical group ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 19
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 13
- 239000007787 solid Substances 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 9
- 238000005886 esterification reaction Methods 0.000 claims description 9
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000005658 halogenation reaction Methods 0.000 claims description 7
- 230000002140 halogenating effect Effects 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 239000003153 chemical reaction reagent Substances 0.000 claims description 4
- 238000002844 melting Methods 0.000 claims description 4
- 230000008018 melting Effects 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 2
- 229920000742 Cotton Polymers 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 238000004587 chromatography analysis Methods 0.000 claims description 2
- 239000012230 colorless oil Substances 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- 238000001953 recrystallisation Methods 0.000 claims description 2
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 claims description 2
- 150000002430 hydrocarbons Chemical group 0.000 claims 2
- 238000000576 coating method Methods 0.000 abstract description 18
- 239000011248 coating agent Substances 0.000 abstract description 16
- 238000000016 photochemical curing Methods 0.000 abstract description 11
- 150000003254 radicals Chemical class 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 7
- 230000009286 beneficial effect Effects 0.000 abstract description 5
- 230000000052 comparative effect Effects 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 13
- 238000002390 rotary evaporation Methods 0.000 description 11
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- 238000005481 NMR spectroscopy Methods 0.000 description 9
- 230000037230 mobility Effects 0.000 description 9
- 239000011347 resin Substances 0.000 description 9
- 229920005989 resin Polymers 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 238000003756 stirring Methods 0.000 description 8
- 239000003999 initiator Substances 0.000 description 7
- 239000000178 monomer Substances 0.000 description 7
- 238000010992 reflux Methods 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 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 description 6
- 238000010521 absorption reaction Methods 0.000 description 6
- 238000001723 curing Methods 0.000 description 6
- 238000013508 migration Methods 0.000 description 6
- 230000005012 migration Effects 0.000 description 6
- FZUGPQWGEGAKET-UHFFFAOYSA-N parbenate Chemical compound CCOC(=O)C1=CC=C(N(C)C)C=C1 FZUGPQWGEGAKET-UHFFFAOYSA-N 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 5
- 239000004925 Acrylic resin Substances 0.000 description 4
- 229920000178 Acrylic resin Polymers 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical group [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical group [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 230000000977 initiatory effect Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 230000008033 biological extinction Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000004949 mass spectrometry Methods 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 238000012916 structural analysis Methods 0.000 description 3
- GTELLNMUWNJXMQ-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical class OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.CCC(CO)(CO)CO GTELLNMUWNJXMQ-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- -1 aminoalkyl radical Chemical class 0.000 description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 2
- 239000012965 benzophenone Substances 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- 239000003599 detergent Substances 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003512 tertiary amines Chemical group 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
- C07C319/20—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides by reactions not involving the formation of sulfide groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
- C07C323/22—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and doubly-bound oxygen atoms bound to the same carbon skeleton
-
- 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
- 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
Landscapes
- 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)
- Polymerisation Methods In General (AREA)
Abstract
The invention relates to a sulfur-containing photoinitiator, a preparation method and application thereof, wherein the sulfur-containing photoinitiator has better photocuring activity than a traditional free radical II type photoinitiator BP, has low mobility in a cured coating and good use safety, thereby being beneficial to expanding the application range of the sulfur-containing photoinitiator.
Description
Technical Field
The invention belongs to the field of photoinitiators, and relates to a sulfur-containing photoinitiator, a preparation method and application thereof.
Background
Photoinitiators are compounds that can absorb energy of a certain wavelength in the ultraviolet or visible region to generate free radicals, cations, etc., thereby initiating polymerization, crosslinking and curing of monomers.
With the development of the photo-curing technology industry, the requirements on the photoinitiator are higher and higher, and the research is also more intensive. Benzophenone is a common free radical II type photoinitiator, belongs to a small molecular photoinitiator, has the problems of high mobility and the like in the use process, and limits the application range.
Therefore, it is still of great importance to develop a photoinitiator with high photo-curing activity and low mobility in the cured coating and a preparation method thereof.
Disclosure of Invention
The invention aims to provide a sulfur-containing photoinitiator, a preparation method and application thereof, wherein the sulfur-containing photoinitiator has better photocuring activity than a traditional free radical II type photoinitiator BP, has low mobility in a cured coating and good use safety, thereby being beneficial to expanding the application range of the sulfur-containing photoinitiator.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a sulfur-containing photoinitiator having a chemical structural formula as shown in formula a below;
R 1 any one selected from the following structural formulas;
R 2 、R 3 each independently selected from C 1 ～C 4 For example methyl, ethyl, propyl or butyl.
Compared with the traditional free radical II type photoinitiator BP, the absorption wavelength of the sulfur-containing photoinitiator is obviously red shifted, and the energy required by photocuring is lower; and the mobility in the cured coating is low, so that the use safety of the cured coating as a photoinitiator is improved, and the application range of the cured coating is widened.
Preferably, the chemical structural formula of the sulfur-containing photoinitiator is as follows;
preferably, the compounds of formula I are colorless oils.
Preferably, the compound of formula II is a white solid, preferably a white cotton-wool solid powder, having a melting point of 88℃to 92 ℃.
In the invention, the sulfur-containing photoinitiator is preferably a compound of the formula I and a compound of the formula II, wherein the compound of the formula I is colorless oily matter, the compound of the formula II is white cotton-like solid, the light curing energy of the compound of the formula II is obviously reduced compared with BP, and the compound of the formula I and the compound of the formula II have the advantage of low mobility in a light curing coating, so that the use safety of the compound of the formula I and the compound of the formula II as the photoinitiator is improved.
The photoinitiator is further preferably a compound of a formula II, wherein the compound of the formula II has a tertiary amine structure, and the intramolecular hydrogen abstraction of the system in the process of initiating the resin polymerization generates an aminoalkyl radical which is more efficient than the intermolecular hydrogen abstraction of a BP/EDB system, and the energy required for photocuring is lower.
In a second aspect, the present invention provides a process for the preparation of a sulfur-containing photoinitiator according to the first aspect, the process comprising the steps of:
(1) Mixing a compound of formula b with a halogenating agent to perform a halogenation reaction;
(2) After the halogenation reaction in the step (1) is finished, removing redundant halogenating reagent, then adding an organic solvent, a compound of the formula c and a catalyst, and heating to perform esterification reaction to obtain a compound of the formula a;
R 1 any one selected from the following chemical structural formulas;
R 2 、R 3 each independently selected from C 1 ～C 4 For example, methyl, ethyl, propyl, butyl, etc.
In the invention, the preparation process of the compound of the formula a comprises two steps of halogenation reaction and esterification reaction, and the yield of the obtained product is higher than 60% by adopting the preparation method; the reaction time is short, the time consumption of the halogenation reaction is about 2 hours, and the time consumption of the esterification reaction is about 3 hours; and the reaction products have good appearance, taking the compounds of the formula I and the formula II as examples, and the appearance is colorless oily matter and white cotton-like solid respectively.
Preferably, the halogenating reagent is selected from thionyl chloride.
Preferably, the halogenation reaction is carried out in a state of being heated to reflux.
Preferably, the molar ratio of the compound of formula b to the compound of formula c to the catalyst is 1 (0.9 to 1.05): 1 to 2; for example, 1:1:1.5, 1:0.95:1.2, or 1:1.05:1.8, etc.
Preferably, the catalyst is selected from basic catalysts, preferably triethylamine and/or N, N-diisopropylethylamine.
The catalyst is adopted in the invention, so that the yield of the obtained target sulfur-containing photoinitiator is higher, and the appearance is better.
Preferably, the organic solvent is selected from at least one of toluene, dichloromethane or dichloroethane.
The organic solvent is adopted in the esterification reaction, so that the better product appearance can be obtained.
Preferably, the esterification reaction is performed in a state where the solvent is refluxed.
Preferably, the esterification reaction further comprises washing, desolventizing and purifying to obtain the sulfur-containing photoinitiator.
Preferably, the washing comprises water washing and/or alkali washing.
Preferably, the water-washed detergent is selected from saturated NaCl solution.
Preferably, the alkaline washing detergent is selected from saturated sodium bicarbonate solution.
By adopting the alkaline washing and water washing reagent, the washing effect is better, so that the obtained sulfur-containing photoinitiator has good appearance.
Preferably, the method of purification comprises chromatography and/or recrystallisation.
In a third aspect, the present invention provides a photocurable composition comprising a sulfur-containing photoinitiator according to the first aspect.
Preferably, the mass ratio of the sulfur-containing photoinitiator in the photocurable composition is 0.5% to 6%, for example 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5% or 5.5%, etc., preferably 3% to 5%.
Compared with the prior art, the invention has the following beneficial effects:
(1) Compared with the traditional free radical II type photoinitiator BP, the sulfur-containing photoinitiator has lower energy required by photocuring;
(2) The sulfur-containing photoinitiator has lower mobility in a cured coating, thereby being beneficial to improving the use safety of the sulfur-containing photoinitiator.
Drawings
FIG. 1 is an ultraviolet absorbance spectra of sulfur-containing photoinitiators of examples 1 and 2 of the present invention;
FIG. 2 is an ultraviolet absorption spectrum of the photoinitiator benzophenone of comparative example 1 in accordance with the present invention.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Example 1
The embodiment provides a sulfur-containing photoinitiator and a preparation method thereof, wherein the sulfur-containing photoinitiator is prepared by the following steps:
adding a compound shown in a formula b' and excessive thionyl chloride into a 50mL single-neck flask, heating to reflux, performing electromagnetic stirring reaction for 2 hours, removing unreacted thionyl chloride by rotary evaporation, adding toluene into a reaction product after the rotary evaporation is finished, and performing rotary evaporation again to remove thionyl chloride;
(II) adding toluene and a compound of formula c to the product of the step (I), and then dropwise adding triethylamine under electromagnetic stirring, wherein the molar ratio of the compound of formula b', the compound of formula c and the triethylamine is 1:1:1.5; heating to reflux reaction for 3h, cooling to room temperature after the reaction is finished, filtering to remove solid salt generated by the reaction, washing filtrate with saturated sodium bicarbonate solution and saturated sodium chloride solution respectively, separating liquid, collecting organic phase, drying, evaporating solvent by rotary evaporation, purifying residue by petroleum ether/ethyl acetate (V/V=6/1) column chromatography to obtain white cotton-like solid with yield of 74% and melting point of 88-92 ℃.
The chemical structural formula of the sulfur-containing photoinitiator prepared in the embodiment is shown as follows;
structural analysis is carried out on the prepared sulfur-containing photoinitiator, wherein the nuclear magnetic resonance analysis result is shown as follows;
1 H NMR(400MHz,CDCl 3 )δ/ppm:7.85(d,J＝8.0Hz,2H),7.77(d,J＝8.3Hz,4H),7.60(t,J＝7.2Hz,1H),7.49(dd,J＝7.8,5.6Hz,4H),6.63(d,J＝8.0Hz,2H),4.53(t,J＝6.9Hz,2H),3.39(t,J＝6.0Hz,2H),3.04(s,6H).
13 C NMR(101MHz,CDCl 3 )δ/ppm:195.81,166.73,153.46,142.64,137.68,134.54,132.33,131.41,130.84,129.91,128.31,126.95,116.25,110.68,62.61,40.04,31.03.
the mass spectrometry results are shown below;
HRMS(ESI,m/z):Calcd.for C 24 H 23 NO 3 S[M + ]:405.1399,found 428.1295[M+Na].
example 2
The embodiment provides a sulfur-containing photoinitiator and a preparation method thereof, wherein the sulfur-containing photoinitiator is prepared by the following steps:
adding a compound shown in a formula b' and excessive thionyl chloride into a 50mL single-neck flask, heating to reflux, performing electromagnetic stirring reaction for 2 hours, removing unreacted thionyl chloride by rotary evaporation, and adding a proper amount of toluene for rotary evaporation again after the rotary evaporation is finished so as to remove thionyl chloride;
adding toluene and a compound of formula c into a reaction bottle in the step (I), and dropwise adding N, N-diisopropylethylamine into the reaction bottle under electromagnetic stirring, wherein the molar ratio of the compound of formula b' to the compound of formula c to the N, N-diisopropylethylamine is 1:1:1.1; after the dripping is finished, heating to reflux for 3 hours, and completely reacting the raw materials; cooling the reaction solution to room temperature, filtering to remove salt generated by the reaction, washing with saturated sodium bicarbonate solution, washing with saturated sodium chloride solution, separating liquid, drying an organic phase with anhydrous sodium sulfate, evaporating the solvent by rotary evaporation, and separating and purifying the product by petroleum ether/ethyl acetate (V/v=6/1) column chromatography to obtain colorless oily substance with the yield of 61%;
the chemical structural formula of the sulfur-containing photoinitiator prepared in the embodiment is shown as follows;
structural analysis is carried out on the prepared sulfur-containing photoinitiator, wherein the nuclear magnetic resonance analysis result is shown as follows;
1 H NMR(400MHz,CDCl 3 )δ/ppm:7.90(dt,J＝7.6,1.0Hz,1H),7.79-7.76(m,2H),7.72-7.68(m,2H),7.65(td,J＝7.5,1.2Hz,1H),7.62-7.54(m,4H),7.52-7.47(m,3H),7.41-7.36(m,3H),7.34-7.31(m,2H),3.83(dt,J＝13.2,5.0Hz,1H),3.67(dt,J＝13.6,5.0Hz,1H),3.29(td,J＝20.5,3.8Hz,2H).
13 C NMR(101MHz,CDCl 3 )δ/ppm:195.77,168.35,148.22,142.65,137.63,137.37,134.97,134.47,132.42,130.73,129.92,129.53,128.85,128.36,126.68,126.04,125.74,125.69,123.28,108.56,63.48,31.83.
the mass spectrometry results are shown below;
HRMS(ESI,m/z):Calcd.for C 29 H 22 O 4 S[M + ]:466.1239,found 489.1136[M+Na].
comparative example 1
The comparative example uses the free radical type II photoinitiator BP as a control.
Comparative example 2
The photoinitiator in this comparative example was prepared by a process comprising the steps of:
adding a compound shown in a formula b' and excessive sulfoxide chloride into a 50mL single-port bottle, heating to reflux, performing electromagnetic stirring reaction for 2h, removing unreacted sulfoxide chloride by rotary evaporation, adding a proper amount of toluene after the rotary evaporation is finished, and performing rotary evaporation again to remove the sulfoxide chloride;
adding toluene and a compound of the formula c into a reaction bottle in the step (I), and dropwise adding triethylamine under electromagnetic stirring, wherein the molar ratio of the compound of the formula b', the compound of the formula c and the triethylamine is 1:1:1.2; heating to reflux reaction for 3h, cooling the reaction liquid to room temperature, filtering, washing the filtrate with saturated sodium bicarbonate solution and saturated sodium chloride solution, separating liquid, collecting organic phase, drying, evaporating solvent by spin to obtain yellow solid, recrystallizing dichloromethane to obtain pale yellow solid with yield of 55.6% and melting point of 163-167 ℃.
The chemical structural formula of the sulfur-containing photoinitiator prepared in the comparative example is shown below;
structural analysis is carried out on the prepared sulfur-containing photoinitiator, wherein the nuclear magnetic resonance analysis result is shown as follows;
1 H NMR(400MHz,CDCl 3 )δ/ppm:8.90(dd,J＝7.9,1.7Hz,1H),8.55(d,J＝8.0Hz,1H),8.32(dd,J＝8.0,1.7Hz,1H),7.77-7.74(m,4H),7.68-7.63(m,2H),7.58(t,J＝7.4Hz,1H),7.52-7.45(m,6H),4.65(t,J＝6.0Hz,2H),3.46(t,J＝6.7Hz,2H).
13 C NMR(101MHz,CDCl 3 )δ/ppm:195.65,179.70,165.38,141.83,140.50,138.54,137.54,135.91,135.37,134.99,132.75,132.43,130.88,130.72,129.88,129.25,128.35,127.37,126.83,126.60,125.01,124.94,63.88,31.08.
the mass spectrometry results are shown below;
HRMS(ESI,m/z):Calcd.for C 29 H 20 O 4 S 2 [M+]:496.0803,found 519.0699[M+Na].
the photoinitiators prepared in examples 1-2 and comparative examples 1-2 were subjected to ultraviolet absorption tests, which included: preparing equimolar concentration (5×10) -5 mol/L) of photoinitiator and acetonitrile solution of BP, respectively taking a proper amount of solution and acetonitrile (used as blank control) in a cuvette for ultraviolet-visible light absorption test; the test results are shown in fig. 1 and 2; compared with the photoinitiator BP, the photoinitiator disclosed by the invention has the advantage that the maximum absorption wavelength of ultraviolet and visible light is obviously red shifted. The maximum molar extinction coefficients are shown in Table 1;
TABLE 1
As can be seen from the above table, the photoinitiator in the embodiment 1 of the invention has red shift of absorption wavelength, and the maximum molar extinction coefficient is about 1.8 times of that of the photoinitiator BP, which can improve the ultraviolet absorption capacity of the photoinitiator to a certain extent, and is more beneficial to the generation of free radicals so as to better initiate the polymerization of the system.
Application example
The sulfur-containing photoinitiator prepared in the above examples 1-2 and the photoinitiators in comparative examples 1-2 were tested for photocuring activity, mobility in cured coatings and volatility, and the test methods and test conditions are as follows;
(a) The light curing energy test is carried out, and the test method is as follows;
weighing and measuring photoinitiator, auxiliary initiator, resin and monomer according to a certain proportion, uniformly mixing them by using ultrasonic stirring, coating the mixed coating on glass slide by using film coater with thickness of 10 micrometers, placing under high-pressure mercury lamp, making one-time curing and film-forming, using UV energy meter to record the energy required for curing.
In the test method, the resin is selected from epoxy acrylic resin E51, and pentaerythritol triacrylate (PETA) and ethoxylated trimethylolpropane triacrylate (EO 3-TMPTA) are adopted as monomers; the mass ratio of the resin to the monomer is as follows: epoxy acrylic resin E51: PETA: EO3 tmpta=5:3:2;
the photoinitiator used was the sulfur-containing photoinitiator of example 1, example 2 or the photoinitiator of comparative example 1, comparative example 2; the auxiliary initiator adopts ethyl p-dimethylaminobenzoate (EDB), the mass ratio of the auxiliary initiator is 3 percent based on 100 percent of the total mass of the mixed coating, and the mass ratio of the photoinitiator is respectively selected from 3 percent and 5 percent;
the test results of the above photo-curing energy are shown in table 2;
TABLE 2
In the above table "-" indicates that the formulation does not contain the corresponding material, and the sulfur-containing photoinitiator of comparative example 2 was poorly soluble in the mixed coating during the above test, and the photocuring energy thereof was not tested; at a photoinitiator ratio of 3% and 5%, the activity of the photoinitiators in examples 1 and 2 was better than that of the photoinitiator in comparative example 1. The photoinitiator in example 1 can initiate the photo-curing reaction in a system without the auxiliary initiator in the formula, and the initiation activity is superior to that of comparative example 1, because the photoinitiator in example 1 can take hydrogen in the system molecule to generate amine alkyl free radical in the process of initiating the resin polymerization more effectively than the intermolecular hydrogen of BP/EDB system.
(b) The migration of the photoinitiators in the cured coatings of examples 1, 2 and comparative example 1 was tested as follows;
weighing and metering photoinitiator, auxiliary initiator, resin and monomer according to a certain proportion, stirring by using ultrasonic to uniformly mix them, coating the mixed coating on a glass slide (10 mm multiplied by 30 mm) by using a film coater with the thickness of 10 mu m, and placing under a high-pressure mercury lamp to irradiate for 3-5 min so as to completely cure the mixed coating;
the glass sheet with the uniform mass film is soaked in a brown glass bottle containing 20mL of acetonitrile for 4d, and a proper volume of soaking solution is taken for ultraviolet absorption test. C=a/(ε·l) by the following formula; r=100×c1/C2; the relative mobilities of the photoinitiator and BP to be tested were obtained and the results are shown in Table 3 below. Wherein: the concentration, mol/L, of the example photoinitiator in the C1-extract; absorbance at a- λmax; epsilon-molar extinction coefficient, L.mol < -1 >. Cm < -1 >; l-optical path length, 1cm; the concentration of BP in the C2-extract; r-relative mobility.
In the test method, the resin is selected from epoxy acrylic resin E51, and pentaerythritol triacrylate (PETA) and ethoxylated trimethylolpropane triacrylate (EO 3-TMPTA) are adopted as monomers; the mass ratio of the resin to the monomer is as follows: epoxy acrylic resin E51: PETA: EO3 tmpta=5:3:2;
the photoinitiator used was the sulfur-containing photoinitiator of example 1, example 2 or the photoinitiator of comparative example 1; the auxiliary initiator adopts ethyl p-dimethylaminobenzoate (EDB), the mass ratio of the auxiliary initiator is 3 percent, and the mass ratio of the photoinitiator is selected from 3 percent based on 100 percent of the total mass of the mixed coating;
the migration test results are shown in Table 3;
TABLE 3 Table 3
The lower the concentration of photoinitiator in the soaking solution in the above table, the less the migration amount of the photoinitiator, which has the advantage of low migration; as can be seen from the above table, the photoinitiator according to the present invention has the advantage of low migration, probably because the photoinitiator according to the present invention participates in both photoinitiation and photopolymerization during the polymerization of the resin, so that most of the photoinitiator is anchored in the cured film system, thereby reducing the migration amount of the photoinitiator in the cured film.
The applicant declares that the above is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be apparent to those skilled in the art that any changes or substitutions that are easily conceivable within the technical scope of the present invention disclosed by the present invention fall within the scope of the present invention and the disclosure.
Claims (10)
1. A sulfur-containing photoinitiator, which is characterized in that the chemical structural formula of the sulfur-containing photoinitiator is shown as a compound in a formula a;
R 1 any one selected from the following structural formulas;
R 2 、R 3 each independently selected from C 1 ～C 4 Is a hydrocarbon group.
2. The sulfur-containing photoinitiator according to claim 1, wherein the chemical structural formula of the sulfur-containing photoinitiator is as follows;
3. the sulfur-containing photoinitiator according to claim 2, wherein the compound of formula i is a colorless oil;
preferably, the compound of formula II is a white solid, preferably a white cotton-wool solid powder, having a melting point of 88℃to 92 ℃.
4. A process for the preparation of a sulfur-containing photoinitiator according to any one of claims 1-3, comprising the steps of:
(1) Mixing a compound of formula b with a halogenating agent to perform a halogenation reaction;
(2) After the halogenation reaction in the step (1) is finished, removing redundant halogenating reagent, then adding an organic solvent, a compound of the formula c and a catalyst, and heating to perform esterification reaction to obtain a compound of the formula a;
R 1 any one selected from the following chemical structural formulas;
R 2 、R 3 each independently selected from C 1 ～C 4 Is a hydrocarbon group.
5. The method of claim 4, wherein the halogenating agent is selected from thionyl chloride;
preferably, the molar ratio of the compound of formula b to the compound of formula c to the catalyst is 1 (0.9 to 1.05): 1 to 2.
6. The preparation method according to claim 4, wherein the catalyst is selected from basic catalysts, preferably triethylamine and/or N, N-diisopropylethylamine;
preferably, the organic solvent is selected from at least one of toluene, dichloromethane or dichloroethane.
7. The process according to claim 4, wherein the esterification reaction is carried out in a state in which the solvent is refluxed.
8. The method according to claim 4, wherein the esterification reaction is followed by washing, desolventizing, and purifying to obtain the sulfur-containing photoinitiator.
9. The method of preparation according to claim 8, wherein the washing comprises water washing and/or alkali washing;
preferably, the method of purification comprises chromatography and/or recrystallisation.
10. A photocurable composition comprising the sulfur-containing photoinitiator according to any one of claims 1 to 3;
preferably, the mass ratio of the sulfur-containing photoinitiator in the photocurable composition is 0.5-6%, preferably 3-5%.
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