CN110283080A - A kind of fluorine-containing benzophenone derivates and its preparation method and application - Google Patents
A kind of fluorine-containing benzophenone derivates and its preparation method and application Download PDFInfo
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- fluorine
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- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 239000012965 benzophenone Substances 0.000 title claims abstract description 37
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 26
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 239000011737 fluorine Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 239000006096 absorbing agent Substances 0.000 claims abstract description 14
- ZXDDPOHVAMWLBH-UHFFFAOYSA-N 2,4-Dihydroxybenzophenone Chemical compound OC1=CC(O)=CC=C1C(=O)C1=CC=CC=C1 ZXDDPOHVAMWLBH-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000003999 initiator Substances 0.000 claims abstract description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 18
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- -1 ice 3,4,5- trifluorobenzoyl chlorides Chemical class 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 238000004587 chromatography analysis Methods 0.000 claims description 5
- 239000000741 silica gel Substances 0.000 claims description 5
- 229910002027 silica gel Inorganic materials 0.000 claims description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- YRUNCQNKZIQTEO-UHFFFAOYSA-N 3,4,5-trifluorobenzoyl chloride Chemical compound FC1=CC(C(Cl)=O)=CC(F)=C1F YRUNCQNKZIQTEO-UHFFFAOYSA-N 0.000 claims description 3
- 239000003480 eluent Substances 0.000 claims description 3
- 239000012074 organic phase Substances 0.000 claims description 3
- 239000003208 petroleum Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 abstract description 15
- 238000000576 coating method Methods 0.000 abstract description 15
- 239000003973 paint Substances 0.000 abstract description 13
- 239000000203 mixture Substances 0.000 abstract description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052760 oxygen Inorganic materials 0.000 abstract description 6
- 239000001301 oxygen Substances 0.000 abstract description 6
- 238000003860 storage Methods 0.000 abstract description 6
- 230000005764 inhibitory process Effects 0.000 abstract description 5
- 239000000976 ink Substances 0.000 abstract description 4
- 239000000178 monomer Substances 0.000 abstract description 4
- 239000011347 resin Substances 0.000 abstract description 4
- 229920005989 resin Polymers 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 125000001153 fluoro group Chemical group F* 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000011230 binding agent Substances 0.000 abstract description 2
- 239000010408 film Substances 0.000 description 26
- 230000000052 comparative effect Effects 0.000 description 15
- 238000001723 curing Methods 0.000 description 13
- 238000000034 method Methods 0.000 description 9
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 8
- 239000000853 adhesive Substances 0.000 description 7
- 230000001070 adhesive effect Effects 0.000 description 7
- 238000007711 solidification Methods 0.000 description 7
- 230000008023 solidification Effects 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 3
- 230000005855 radiation Effects 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000005457 ice water 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
- ZDHCZVWCTKTBRY-UHFFFAOYSA-N omega-Hydroxydodecanoic acid Natural products OCCCCCCCCCCCC(O)=O ZDHCZVWCTKTBRY-UHFFFAOYSA-N 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 2
- OTEKOJQFKOIXMU-UHFFFAOYSA-N 1,4-bis(trichloromethyl)benzene Chemical compound ClC(Cl)(Cl)C1=CC=C(C(Cl)(Cl)Cl)C=C1 OTEKOJQFKOIXMU-UHFFFAOYSA-N 0.000 description 1
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Natural products CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 238000003848 UV Light-Curing Methods 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229940111759 benzophenone-2 Drugs 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- WXNRYSGJLQFHBR-UHFFFAOYSA-N bis(2,4-dihydroxyphenyl)methanone Chemical compound OC1=CC(O)=CC=C1C(=O)C1=CC=C(O)C=C1O WXNRYSGJLQFHBR-UHFFFAOYSA-N 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- 229940124543 ultraviolet light absorber Drugs 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/76—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
-
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/32—Radiation-absorbing paints
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention provides a kind of fluorine-containing benzophenone derivates and its preparation method and application.Derivative preparation method: using 2,4-DihydroxyBenzophenone as raw material and 3, the reaction of 4,5- trifluorobenzoyl chlorides has synthesized two kinds of fluorine-containing benzophenone derivates 1 and 2.Have many advantages, such as that preparation is simple, reaction is mild, yield is high.Derivative 1 can effectively absorb the ultraviolet light of 250~360nm, can not only enhance the photostability of ultraviolet-curing paint and coating, also have the characteristics that and resin or monomer compatibility be good, odorlessness；It is also advantageous for the storage of ultraviolet-curing paint.Derivative 2 introduces fluorine atom on the basis of benzophenone structural framework, can use the low surface chemistry energy of fluorine atom, makes compound to surface enrichment, accelerates surface aggregate, to inhibit oxygen inhibition phenomenon.Two kinds of derivatives synthesized by the present invention can be applied in field respectively as UV absorbers and ultraviolet initiator in Photocurable composition such as coating, ink, binder.
Description
Technical field
The present invention relates to benzophenone derivates, particularly belong to a kind of fluorine-containing benzophenone derivates and preparation method thereof
And application.
Background technique
The daily ornament materials such as organic film, coating and plastic products by solar radiation outdoors in use, be easy to make these
There is phenomena such as gloss reduces, becomes fragile and be cracked, it is therefore desirable to add ultraviolet absorbing agent to drop in Degradation of Polymer Materials
Low ultraviolet deterioration reaction, provides more complete protective benefits at enhancing weatherability.Ultraviolet absorbing agent in molecule mainly by containing
There is the structure composition of Pi-conjugated systems, absorbs ultraviolet light and the energy by the form of by thermal energy or harmless low-energy radiation using its specific structure
Amount release or consumption, common ultraviolet absorbing agent have benzophenone, benzotriazole, triazines three categories.Benzophenone
It is at present to be widely used in plastics, ink, oil because having a good compatibility with other materials using wide one kind
The industries such as paint, coating.But benzophenone ultraviolet absorbent relative molecular mass is small, bad with high molecular material compatibility,
Or it is volatile during processing of high molecular material, there are migration, bloom, crystallization in product, so that material property reaches
Less than desired effect.Therefore, more stringent requirements are proposed to ultraviolet absorbing agent by people in practical applications, expects stability and high efficiency
Product occur.
On the other hand, benzophenone or a kind of common hydrogen-capture-type light initiator, cheap, synthesis are simple and easily
In preservation, it is widely used in ultraviolet-curing paint.But in the curing process, oxygen inhibition phenomenon is obvious, and has Yi Qian
The solidification pair derivative of shifting generates, and cured film is easy xanthochromia.Therefore, with the rapid development of industry, in benzophenone molecule bone
By the relationship research between reasonable MOLECULE DESIGN and molecular structure and its performance on the basis of frame, develop high-efficiency low-toxicity,
Low mobility and the photoinitiator for being able to suppress oxygen inhibition phenomenon have broad application prospects.
Summary of the invention
It is an object of the invention in view of the problems of the existing technology, provide a kind of fluorine-containing benzophenone derivates and
Preparation method.The present invention has many advantages, such as that preparation manipulation is simple, reaction condition is mild, gross production rate is high, and synthesized is fluorine-containing
Benzophenone derivates can be used as UV absorbers application, or can be used as ultraviolet initiator application.
Fluorine-containing benzophenone derivates provided by the invention, structural formula are 1 or 2:
Reaction equation is as follows:
Preparation method includes the following steps:
1) 2,4-DihydroxyBenzophenone is added in a reservoir, after being dissolved with organic solvent, is slowly added to triethylamine,
3,4,5- trifluorobenzoyl chlorides are added dropwise after mixing evenly under the conditions of ice-water bath, are stirred to react 6~24 hours；
2) after reaction, add water into reaction solution and be extracted with ethyl acetate, collect washing, drying after organic phase, and
Revolving removes organic solvent；It recycles chromatography silica gel column to carry out separating-purifying, that is, respectively obtains fluorine-containing benzophenone derivates 1
With fluorine-containing benzophenone derivates 2.
The molar ratio of 2,4 dihydroxyl benzophenone described in step 1), triethylamine and 3,4,5- trifluorobenzoyl chloride is 1:
1.4~2:1.2~2.5, preferably 1:1.5:2；
Organic solvent described in step 1) is tetrahydrofuran or methylene chloride, preferably methylene chloride；
Reaction time described in step 1) preferably 12 hours.
The eluant, eluent of step 2) chromatography silica gel column is the petroleum ether and ethyl acetate of 1~10:1 of volume ratio, preferred volume ratio 3
~7:1.
The present invention is using 2,4-DihydroxyBenzophenone as raw material, and 3, the reaction of 4,5- trifluorobenzoyl chlorides, and rapid synthesis
Two kinds of fluorine-containing benzophenone derivates.The synthetic method has many advantages, such as that easy to operate, reaction condition is mild, gross production rate is high.Spread out
The ultraviolet light that biology 1 can effectively absorb 250~360nm enhances the photostability of ultraviolet-curing paint and coating, also have with
Resin or the features such as monomer compatibility is good, odorlessness；It is also advantageous for the storage of ultraviolet-curing paint.Meanwhile in derivative 2
The fluorine atom that low surface chemistry energy is introduced on the basis of benzophenone structural skeleton, makes compound to surface enrichment, can accelerate
Surface aggregate, to inhibit oxygen inhibition phenomenon.Fluorine-containing benzophenone derivates synthesized by the present invention can be respectively as ultraviolet
Light absorber and ultraviolet initiator are applied in field in Photocurable composition such as coating, ink, binder.
Detailed description of the invention
The UV absorption spectrogram of Fig. 1 2- hydroxyl -4- (3,4,5- trifluoromethyl benzonitrile acyloxy) benzophenone
The UV absorption spectrogram of Fig. 2 2,4- bis- (3,4,5- trifluoromethyl benzonitrile acyloxy) benzophenone
Specific embodiment
Embodiment 1
2,4-DihydroxyBenzophenone 0.214g (1mmol) is added in a reservoir, triethylamine 0.150g (1.5mmol) is used
The methylene chloride of 3ml is dissolved, and 3,4, the 5- trifluorobenzoyl chlorides of 0.388g (2mmol) are slowly added under the conditions of ice-water bath,
It is stirred to react 12 hours.After reaction, water is added into reaction solution and is extracted with ethyl acetate, washing, nothing after organic phase are collected
Aqueous sodium persulfate is dry, and rotary evaporation removes organic solvent；And it is sharp for eluant, eluent with petroleum ether and ethyl acetate (volume ratio 5:1)
Isolated derivative 1 and derivative 2 are carried out with chromatography silica gel column.
2- hydroxyl -4- (3,4,5- trifluoromethyl benzonitrile acyloxy) benzophenone (derivative 1): white solid, yield: 45%,
m.p.25-27℃。1H NMR(600MHz,CDCl3) δ 12.33 (s, 1H), 7.88 (t, J=7.0Hz, 2H), 7.75-7.69 (m,
3H), 7.64 (t, J=7.5Hz, 1H), 7.55 (t, J=7.7Hz, 2H), 6.97 (d, J=2.3Hz, 1H), 6.78 (dd, J=
8.8,2.3Hz,1H).13C NMR(151MHz,CDCl3)δ200.78,164.86,161.58,156.02,152.08,150.40,
137.65,135.09,132.21,129.10,128.64,117.58,115.08,114.96,112.43,111.22.HRMS
(ESI)[M+H]+calcd for C20H11F3O4:373.0609,found 373.0682.
2,4- bis- (3,4,5- trifluoromethyl benzonitrile acyloxy) benzophenone (derivative 2): white solid, yield: 30%,
m.p.105-108℃.1H NMR(600MHz,CDCl3) δ 7.93-7.86 (m, 2H), 7.81 (d, J=7.2Hz, 2H), 7.74 (t,
J=8.6Hz, 1H), 7.61-7.54 (m, 1H), 7.50-7.43 (m, 4H), 7.38-7.32 (m, 2H)13C NMR(151MHz,
CDCl3)δ193.52,164.86,161.77,152.88,149.26,137.39,135.05,133.40,132.00,129.73,
129.42,129.13,128.61,128.52,119.40,116.80,112.35,111.22.
Measurement analyzes the UV absorption of derivative 1 and derivative 2 simultaneously, the results showed that such compound and benzophenone
It compares, there is preferable UV absorbance, can effectively absorb the ultraviolet light of 250~360nm and 250~300nm, ultraviolet light
Spectrum is shown in Fig. 1, Fig. 2.
Following embodiment is used to illustrate derivative 1 i.e. 2- hydroxyl -4- (3,4,5- trifluoromethyl benzonitrile acyloxy) hexichol first
Application of the ketone as ultraviolet absorber in ultraviolet-curing paint, but it is not limited to the purposes of following embodiment.
Embodiment 2: derivative 1 is used for the performance evaluation of UV absorbers
Experimental formula:
Operating condition:
Propylene oxide carboxylic acid resin 50g, 1,6- hexanediyl ester are added in the glass container equipped with blender
44g, photoinitiator (1173) 3g, triethanolamine 2g, 2- hydroxyl -4- (3,4,5- trifluoromethyl benzonitrile acyloxy) benzophenone 1g, is stirred
Mix be allowed to be uniformly dispersed it is transparent, static 5-10 minutes to get arrive transparent radical UV curing coating.The coating is divided into three
Point, a part, which is fitted into transparent vial, covers daily indoor storage；A part is fitted into transparent vial in topping station
It is protected from light storage；A part squeegee film on a glass, film with a thickness of 75 μm, it is then (big with 5 meters of speed per minute
About 5 seconds light application times) solidified by ultraviolet light solidification instrument.
Comparative example 1 (no added UV absorbers)
Experimental formula:
Operating condition is the same as embodiment 2
Comparative example 2 (no added photoinitiator)
Experimental formula:
Operating condition is the same as embodiment 2
Comparative example 3 (adds commercially available ultraviolet absorbing agent UV-0)
Experimental formula:
Operating condition is the same as embodiment 2
Store results are evaluated after 1 ultraviolet-curing paint of table is prepared
| Experiment | 30min | 2h | 6h (is protected from light) | 30h | 72h |
| Embodiment 2 | Homogeneous transparent | Homogeneous transparent | Homogeneous transparent | Homogeneous transparent | Slightly cured layer |
| Comparative example 1 | There is cured layer | It is fully cured | It is fully cured | It is fully cured | It is fully cured |
| Comparative example 2 | Homogeneous transparent | Homogeneous transparent | Homogeneous transparent | Homogeneous transparent | Homogeneous transparent |
| Comparative example 3 | Homogeneous transparent | Homogeneous transparent | Homogeneous transparent | Homogeneous transparent | There is cured layer |
As shown in Table 1, the preparation needs of usual ultraviolet-curing paint carry out under the conditions of being protected from light, and ultraviolet light solidification applies
Material can be influenced by daylight middle-ultraviolet lamp, and storage time cannot be permanent.Compared with comparative example 1, when preparing coating, this is sent out
After bright derivative 1 is added as ultraviolet absorbing agent, condition is protected from light without more stringent.When in the formula in comparative example 3
When only adding ultraviolet absorbing agent UV-0, cured layer is more after storing 72h, and embodiment 2 slightly has cured layer, the results showed that derivative
1 ultraviolet radiation absorption effect is better than commercially available ultraviolet absorbing agent UV-0.
The solidify coating of above-described embodiment 2, comparative example 1-3 composition is tested for the property:
A: surface drying time test: refer to dry method or cotton pellet method.
B: hardness test: pencil hardness method is tested by GB/T6739-1996.Use film pencil scratch hardness instrument, observation
Paint film scratch marks, using pencil hardness of the pencil as film for having no scratch.
C: adhesive force test: cross-hatching measurement (referring to GB 9286-88).Film attachment is determined by drawing lattice experimental method
Power quality.0~5 grade of 6 grade can be divided into according to extent of the destruction, preferably 0 grade, film surface falls off without any one small lattice, and 5 grades are
Very poor, film surface produces serious peeling.
2 solidify coating Evaluation results of table
| Experiment | Embodiment 2 | Comparative example 1 | Comparative example 2 | Comparative example 3 |
| Appearance | Glossy clear | Glossy clear | It is uncured | There is pin hole |
| Hardness | 5H | 3H | - | 4H |
| Adhesive force | 1 | 2 | - | 2 |
As shown in Table 2, when derivative 1 is only added in coating, when not adding photoinitiator, solidification does not form a film (comparative example 2),
Illustrate that derivative 1 does not participate in film-forming reaction, is stabilized in system；On the other hand, in common ultraviolet-curing paint
On the basis of formula, when derivative 1 is added, the hardness and adhesive force of cured film increase, the cured film tool that embodiment 2 obtains
There is film layer to wipe firm, surface smooth even, the features such as having no irritating odor.
Object 1 derived from the present invention, preparation is easy, and raw material is easy to get；Can effectively absorb the ultraviolet light of 250~360nm and
Absorption intensity is strong, and have the characteristics that with resin, monomer compatibility is good, odorlessness.It is almost not involved in freedom in the curing process
The solidification of matrix system, enhances the photostability of coating and solidify coating, is suitable for the solidification composition fillings such as coating, ink and adhesive
Middle application is a kind of UV absorbers with development prospect also beneficial to the storage of ultraviolet-curing paint.
Following embodiment is that derivative 2 of the present invention i.e. 2,4- bis- (3,4,5- trifluoromethyl benzonitrile acyloxy) benzophenone is used as certainly
As fundamental mode photoinitiator curing performance compared with the curing performance of commercially available radical photoinitiator 1173: used in it
Oligomer is modified epoxy acrylic ester (production of thousand chemical plant Ye of the Zhongshan city UV1005-65), monomer 1,6- hexylene glycol dipropyl
Olefin(e) acid ester (production of thousand chemical plant Ye of the Zhongshan city HDDA).
Embodiment 3: the Performance Properties Evaluation of derivative 2
Experimental formula:
Operating condition
Under the conditions of being protected from light, 2,4- bis- (3,4,5- trifluoromethyl benzonitrile acyloxy) benzophenone 2 is added in glass container
0.03g, modified epoxy acrylic ester (UV1005-65) 0.5g, 1,6- hexanediyl ester (HDDA) 0.45g, three ethyl alcohol
Amine 0.02g is evenly stirred until transparence masking liquid.The mixture is coated on glass plate with spreader and carries out film, film thickness is
75um is irradiated solidification in medium pressure mercury lamp, and mercury lamp power is 400W.
Comparative example 4: the Performance Properties Evaluation of photoinitiator 1173
Experimental formula:
Operating condition is the same as embodiment 3
The film of above-described embodiment 3,4 composition of comparative example is tested for the property:
The test of a surface drying time: refer to dry method or cotton pellet method.
B hardness test: pencil hardness method is tested by GB/T6739-1996.Use film pencil scratch hardness instrument, observation paint
Film scratch marks, using pencil hardness of the pencil as film for having no scratch.
C adhesive force test: cross-hatching measurement (referring to GB 9286-88).Film attachment is determined by drawing lattice experimental method
Power quality.0~5 grade of 6 grade can be divided into according to extent of the destruction, preferably 0 grade, film surface falls off without any one small lattice, and 5 grades are
Very poor, film surface produces serious peeling.
It is shown in evaluation results are shown in Table 1.
3 derivative 2 of table is compared with 1173 application performances
From the test result of upper table it can be seen that the curing rate of derivative of the present invention 2 is relatively slow, but at film hardness and
Adhesive force is better than commercially available radical photoinitiator 1173.It is the possible reason is initiator is on surface in the course of the polymerization process
With higher concentration, react to form layer protecting film with oxygen, it can be efficiently against oxygen inhibition.And bottom concentration relatively
Low, the polymerization time for causing system is longer, but can generate with the cured film compared with strong adhesive force.
Claims (9)
1. a kind of fluorine-containing benzophenone derivates, which is characterized in that structural formula is 1 or 2:
2. a kind of preparation method of fluorine-containing benzophenone derivates, which is characterized in that reaction equation is as follows:
3. a kind of preparation method of fluorine-containing benzophenone derivates, which comprises the steps of:
1) 2,4-DihydroxyBenzophenone is added in a reservoir, after being dissolved with organic solvent, triethylamine is slowly added to, in ice
3,4,5- trifluorobenzoyl chlorides are added dropwise under water bath condition after mixing evenly, are stirred to react 6~24 hours；
2) after reaction, add water into reaction solution and be extracted with ethyl acetate, collect washing, drying after organic phase, and rotate
Remove organic solvent；It recycles chromatography silica gel column to carry out separating-purifying, that is, respectively obtains fluorine-containing benzophenone derivates 1 and contain
The benzophenone derivates 2 of fluorine.
4. a kind of preparation method of fluorine-containing benzophenone derivates as claimed in claim 3, which is characterized in that described 2,
The molar ratio of 4- dihydroxy benaophenonel, triethylamine and 3,4,5- trifluorobenzoyl chloride is 1:1.4~2:1.2~2.5.
5. a kind of preparation method of fluorine-containing benzophenone derivates as claimed in claim 3, which is characterized in that in step 1)
The organic solvent is tetrahydrofuran or methylene chloride.
6. a kind of preparation method of fluorine-containing benzophenone derivates as claimed in claim 3, which is characterized in that step 1) institute
The reaction time stated preferably 12 hours.
7. a kind of preparation method of fluorine-containing benzophenone derivates as claimed in claim 3, which is characterized in that in step 2)
The eluant, eluent of the chromatography silica gel column is the petroleum ether and ethyl acetate of 1~10:1 of volume ratio.
8. a kind of application of the fluorine-containing benzophenone derivates as described in claim 1 as UV absorbers, described to spread out
Biology is the derivative of structural formula 1.
9. a kind of application of the fluorine-containing benzophenone derivates as described in claim 1 as ultraviolet initiator, described to spread out
Biology is the derivative of structural formula 2.
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| CN115785791A (en) * | 2022-11-10 | 2023-03-14 | 山西大学 | Functional ultraviolet curing composition and preparation method and application thereof |
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| CN115785791A (en) * | 2022-11-10 | 2023-03-14 | 山西大学 | Functional ultraviolet curing composition and preparation method and application thereof |
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