CN104974053B - Novel aminoketones photoinitiator and application in UV-LED photocuring system - Google Patents
Novel aminoketones photoinitiator and application in UV-LED photocuring system Download PDFInfo
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- CN104974053B CN104974053B CN201510350881.4A CN201510350881A CN104974053B CN 104974053 B CN104974053 B CN 104974053B CN 201510350881 A CN201510350881 A CN 201510350881A CN 104974053 B CN104974053 B CN 104974053B
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Abstract
The invention provides a novel aminoketones photoinitiator suitable for UV-LED light source curing. The novel aminoketones photoinitiator can be higher in adsorption in a long-wavelength region (365-395nm), is suitable for UV-LED light source curing, and overcomes the defects of high energy consumption and heavy pollution in traditional curing. The novel aminoketones photoinitiator is good in eectron delocalizability, has high intramolecular electron transfer performance and excellent photoelectric property, is higher in adsorption in the range of 365nm to 395nm in the long-wavelength region, is suitable for a high-power UV-LED ultraviolet photocuring system, and has considerable advantages compared with the photoinitiator in the prior art.
Description
Technical field
Content according to the present invention is a kind of new aminoketoness light trigger and the application in UV-LED photocuring systems.
Background technology
Photocuring system is typically made up of components such as oligomer, reactive diluent, auxiliary agent and light triggers, wherein light-initiated
The mass fraction of agent is generally 3% to 5%, although very little, but plays irreplaceable effect, is the weight for affecting laser curing velocity
Want one of factor.
Light trigger is referred to can absorb certain wavelength in ultraviolet region (250 ~ 420nm) or visible region (400 ~ 800nm)
Energy and produce free radical, cation etc., so as to trigger monomer polymerization crosslinking solidification compound.
With the continuous development of photocuring technology, a kind of new UV-LED technologies based on LED light source are occurred in that.The technology
More energy-saving and environmental protection, it is not mercurous, can work under cryogenic, long service life, therefore become study hotspot.
UV-LED is a kind of a kind of solid-state semiconductor device that electric energy can be converted into luminous energy and radiation energy, is
Occur along with the development of LED technology.In recent years, various semi-conducting materials such as aluminium nitride, gallium nitride, InGaN etc.
It is developed in succession successfully, makes UV-LED light sources, transmitting 365nm, 375nm, 385nm, 395nm, 405nm, 415nm etc. various not
The spectrum of co-wavelength, for radiation curing field.
Compared with traditional high voltage mercury lamp, UV-LED has many features：1st, service life is longer, can be little more than 25000
When；2nd, energy consumption is low, and energy-saving effect more preferably, can save energy 90%；3rd, cold light source, without infrared emanation；4th, it is not mercurous, more safety with
Environmental protection；5th, light output is stable；6th, the suitability is wide, can be used for various materials；7th, maintenance cost is almost nil, more economically.
Just because of the unique advantage of UV-LED so that it is extensively applied in every field：1st, manufacturing industry aspect, UV-LED
There is application in industries such as LED, CD, buzzer, electronic circuit board manufactures；2nd, the application in daily necessities field is developed rapidly,
Such as apply manufacture and production, the production of toy in furniture；3rd, in technology field, UV-LED can be used for the artwares such as glass
Assembling.In addition, UV-LED also has application in fields such as jewelry, printings.
UV-LED light sources, because of its energy-saving and environmental protection, durable and its remarkable luminescent properties, must be following photocuring light source
Development trend.But due to UV-LED radiation of light source crests it is single, energy accumulating in certain narrow ultraviolet light spectral coverage, and at present
The crest great majority of UV-LED light sources concentrate on 365～395nm on market, and this is the optimum of solidification.In existing light trigger
In, only thiaxanthone and this two photoinitiator of acylphosphine oxide have certain absorption in 365～395nm scopes, reluctantly can be with
LED light source is supported the use, but the absorption in the range of 365～395nm is still very limited, it is impossible to provide enough initiating activities,
Therefore develop match with the 365～395nm UV-LED light sources, light with higher absorbing ability and Geng Gao initiating activities to draw
It is still to be badly in need of very much to send out agent.
The content of the invention
It is an object of the invention to provide a kind of new can be somebody's turn to do with the matching used aminoketoness light trigger of UV-LED light sources
Class compound has the light trigger of higher absorbing ability and Geng Gao initiating activities, easily preparation, easily low cost, storage.
The aminoketoness light trigger that one class of present invention offer is new is with following formula（Ⅰ）Structure compound：
（Ⅰ）
Wherein：
X is selected from O, S；
Ar is selected from 1 to 5 substituted-phenyl, and 4- substituted biphenyl bases, substituent group is selected from hydrogen, halogen, C1-C8 alkyl, C1-C8 alkane
Epoxide, C1-C8 alkylthio groups, nitro, R1R2N；
R is selected from hydrogen, halogen, C1-C8 alkyl, C3-C6 cycloalkyl, C1-C8 alkoxyl, nitro, R1R2N；
R1、R2It is independently selected from C1-C8 alkyl, or R1、R2Couple together to form five yuan or hexatomic ring amido.
C1-C8 alkyl can be methyl, ethyl, propyl group, isopropyl, normal-butyl, 2- butyl, the tert-butyl group, amyl group, ring penta
Base, isopentyl, hexyl, cyclohexyl, heptyl, octyl group, iso-octyl etc..
C1-C8 alkoxyl can be methoxyl group, ethyoxyl, propoxyl group, isopropoxy, n-butoxy, 2- butoxy, tertiary fourth
Epoxide, amoxy, cyclopentyloxy, isoamoxy, hexyloxy, cyclohexyloxy, epoxide in heptan, octyloxy, different octyloxy etc..
C1-C8 alkylthio groups can be methyl mercapto, ethylmercapto group, rosickyite base, isopropyisulfanyl, positive butylthio, 2- butylthios, isobutyl
Sulfenyl, penta sulfenyl, ring penta sulfenyl, isopentylthio, own sulfenyl, cyclohexylthio, sulfenyl in heptan, pungent sulfenyl, different pungent sulfenyl etc..
R1R2N formed cyclammonium base can be, piperidyl, morpholinyl.
Formula（Ⅰ）The example of compound include following compounds, but not limited to this：
I6
I7
I8
I9
I10
I11
The present invention provides a kind of formula（Ⅰ）The method of compound, including following flow process：
。
The present invention provides a kind of formula（Ⅰ）The method of compound, comprises the steps：
1）Compound ii carries out friedel-crafts acylation under Louis acid catalysis and obtains compound III with n-butyryl chloride；
2）The halogenating reaction that compound III carries out carbonyl α-H with bromine obtains compounds Ⅳ；
3）Compounds Ⅳ carries out ammonolysis reaction and generates compound V with dimethylamine；
4）Compound V generates the quaternary ammonium salt of α-aminoketone with the halogenation benzyl of formula VII, and Stevens weights occur in the basic conditions
Row's reacting generating compound VI；
5）Compound VI and ArX ' H react and obtain target product compounds I.
Lewis acid in step 1 be selected from aluminum chloride, ferric chloride, zinc chloride, titanium tetrachloride, preferred aluminum chloride,
Ferric chloride.
The present invention provides formula（Ⅰ）The method of compound is raw material using chlorobenzene or fluorobenzene, convenient to prepare, operation letter
Single, high income, is adapted to industrialized production.
The light trigger that the present invention is provided has the prominent advantages that：
1）Aminoketoness light trigger electron delocalization shown in formula is good, with strong cyclic voltammetry method performance and excellent
Good photoelectric property；
2）There is stronger absorption in the range of Long wavelength region 365nm-395nm, it is adaptable to high-power UV-LED UV-curings
Change system；
3）Effectively overcome traditional mercury lamp solidification power consumption height, the shortcoming of pollution weight.
The Photocurable composition that the present invention is provided, it is included
（a）At least one compound containing ethylenical unsaturated double bonds with
（b）Formula（Ⅰ）Light trigger is at least one.
Compound containing ethylenical unsaturated double bonds can contain one or more double bonds.They can be low-molecular-weight（It is single
Body）Or relatively high molecular weight（Oligomer）.Double bond containing Exemplary monomers are wrapped for alkyl or hydroxy alkyl acrylate or methyl
Acrylate, for example, methyl, ethyl, butyl, 2- ethylhexyls-or 2- hydroxyethylmethacry,ates, isobornyl acid
Ester, or methacrylic acid methyl or ethyl ester；Silicone acrylate；Acrylamide, Methacrylamide, what N- replaced
（Methyl）Acrylamide；Vinyl esters such as vinyl acetate, vinyl ethers such as isobutylvinyl ether, styrene, alkyl-and halo
Styrene, NVP, vinyl chloride or vinylidene chloride.
Monomer containing two or more double bonds such as ethylene glycol, Propylene Glycol, neopentyl ethylene glycol, 1,6- hexanediol and bisphenol-A
Diacrylate, 4,4 '-bis-（2- acryloyloxyethoxies）Diphenyl propane, trimethylolpropane trimethacrylate, season
Penta tetrol triacrylate or tetraacrylate, ethylene propylene acid esters, divinylbenzene, divinyl succinate, adjacent benzene
Dioctyl phthalate diallyl ester, phosphoric acid triallyl ester, isocyanuric acid triallyl ester and isocyanuric acid three（2- acryloyl ethyls）
Ester.
With relatively high molecular weight（Oligomer）The example of polyunsaturated compounds is the epoxy resin of acrylated and gathers
Ether, polyurethanes；Acrylated or the polyester containing vinyl ether group or epoxy radicals.Unsaturated oligomers can also be insatiable hunger
And polyester resin, they are mostly have maleic acid, prepared by phthalic acid and one or more glycol and with about
The molecular weight of 500-3000.Alternatively, it is also possible to using vinyl ether monomers and vinyl ether oligomers, and with maleate as end
End, the oligomer with polyester, polyurethanes, polyethers, polyvinylether and epoxy main chains.
Alefinically unsaturated compounds can also be the ester of ethylenically unsaturated carboxylic acids and polyhydric alcohol epoxide, and in main chain
Or the polymer containing ethylenically unsaturated group on side chain radical, such as unsaturated polyester (UP), polyamide or polyurethanes and its altogether
Polymers, polybutadiene or butadiene copolymer, polyisoprene and isoprene copolymer, contain on side chain（Methyl）Acrylic acid
The polymer and copolymer of base, contains on side chain（Methyl）The polymer and copolymer of acrylic, and one or more this gather
The mixture of compound.
The example of unsaturated carboxylic acid is acrylic acid, methacrylic acid, butenoic acid, methylene-succinic acid, cinnamic acid and insatiable hunger
With fatty acid such as linolenic acid and Oleic acid.It is preferred that acrylic acid and methacrylic acid.
Suitable polyhydric alcohol is aromatic polyol and in particular aliphatic and Cycloaliphatic polyols.Aromatic polyol such as hydrogen
Quinone, 4,4 '-dihydroxydiphenyl, 2,2- bis-（4- hydroxy phenyls）Propane, and（Line style）Novolaks and phenol-formaldehyde A.Fat
Race and Cycloaliphatic polyols such as aklylene glycol, preferred C2-12, such as ethylene glycol, 1,2- or 1,3-PD, 1,2-, 1,3-
Or 1,4- butanediols, pentanediol, hexanediol, ethohexadiol, 12 carbon alkane glycol, diethylene glycol, 2,2'-ethylenedioxybis(ethanol)., molecular weight are preferably 200-
1500 Polyethylene Glycol, 1,3- ring pentanediols, 1,2-, 1,3- or 1,4- cyclohexanediol, 1,4- hydroxymethyl-cyclohexanes, glycerol,
Tetramethylolmethane, trimethylolpropane, dipentaerythritol or Sorbitol etc..
The method that the Photocurable composition that the present invention is provided occurs polymerization, irradiates including the light source with 200-405nm scopes,
The light source of 385-405nm can also be especially used to irradiate.
Specific embodiment
The present invention will be further illustrated with by following nonlimiting examples.
Embodiment 1：The preparation of intermediate 1- p-fluorophenyl -2- dimethylamino -2- benzyl -1- butanone
1）The preparation of 1- p-fluorophenyl -1- butanone
In the four-hole bottle of the 500mL equipped with mechanical agitator, thermometer, constant pressure funnel and spherical reflux condensing tube
58.1g (0.44mol) aluminum trichloride (anhydrous), 34.9g (0.36mol) fluorobenzene and 90mL 1,2- dichloroethanes are added, at 10 DEG C
46.5g (0.44mol) n-butyryl chloride is below slowly added to, at 35～45 DEG C, 4～6h is stirred.Question response liquid is cooled to room temperature
After pour in hydrochloric acid-frozen water, stir 30min, stratification separates organic faciess, and washs organic faciess with sodium hydroxide solution and (remove
The n-butyric acie gone in system), then wash organic faciess once, precipitation, recycling design obtains 1- p-fluorophenyl -1- butanone.
2）The preparation of the bromo- 1- butanone of 1- p-fluorophenyls -2
80mL1, the 1- p-fluorophenyl -1- butanone of 2- dichloroethanes, 36.9g concentrated sulphuric acids and preparation are added to equipped with machinery
In the four-hole bottle of the 500mL of agitator, thermometer, constant pressure funnel and spherical reflux condensing tube, keeping temperature is not higher than 30
℃.1,2- dichloroethane solutions of the 80mL dissolved with 35.2g (0.22mol) bromine is slowly added under stirring, it is anti-at 25～35 DEG C
Answer 4h.Stratification, sulfuric acid phase is separated, and first washes organic faciess, and organic faciess are then washed with sodium bicarbonate solution, then has been washed
Machine phase, precipitation, recycling design obtains the bromo- 1- butanone of 1- p-fluorophenyl -2-.
3）The preparation of 1- p-fluorophenyl -2- dimethylamino -1- butanone
By the diethyl ether solution for containing dimethylamine 50.0g (1.11mol) be added to ice-water bath cool down equipped with mechanical agitator,
In the four-hole bottle of the 500mL of thermometer, constant pressure funnel and spherical reflux condensing tube, prepared 1- is slowly added under stirring
The bromo- 1- butanone of p-fluorophenyl -2-, the two of excess in 5～6h of stirring reaction at -2～2 DEG C, then logical nitrogen blowout reaction system
Methylamine.Reactant liquor is poured into water, stratification, separates organic faciess, washing organic faciess are repeatedly neutrality to solution, and precipitation is returned
Solvent is received, that is, obtains 1- p-fluorophenyl -2- dimethylamino -1- butanone.
4）The preparation of 1- p-fluorophenyl -2- dimethylamino -2- benzyl -1- butanone
55.1g (0.44mol) benzyl chlorides and the 1- p-fluorophenyl -2- dimethylamino -1- butanone for preparing are added to and are equipped with
In the four-hole bottle of the 500mL of mechanical agitator, thermometer, constant pressure funnel and spherical reflux condensing tube, 70～80 are warming up to
DEG C, stir 12h.30% sodium hydroxide solution 96.6g is added, 50～70 DEG C is incubated, 30 ~ 60min of back flow reaction.Cooling reaction
Liquid, separates organic layer, then washes 3 times, anhydrous sodium sulfate drying, precipitation, and recycling design, with alcohol crystal, is put into refrigerator freezing.
Yellow crystals are filtrated to get, vacuum drying oven drying, constant weight 54.3g, four-step reaction total recovery 60% is put into.1H NMR
(400MHz, CDCl3)：δ=0.71 (t, J=7.22Hz, 3H), 1.83-2.14 (br, 2H), 2.40 (s, 6H), 3.23 (s, 2H),
7.08 (d, J=8.66Hz, 2H), 7.21-7.27 (br, 5H), 8.44 (d, J=5.96Hz, 2H)
Embodiment 2：The preparation of 1- rubigan -2- dimethylamino -2- benzyl -1- butanone
1）The preparation of 1- rubigan -1- butanone
In the four-hole bottle of the 500mL equipped with mechanical agitator, thermometer, constant pressure funnel and spherical reflux condensing tube
46.1g (0.35mol) aluminum trichloride (anhydrous), 31.5g (0.28 mol) chlorobenzenes and 70mL 1,2- dichloroethanes are added, 10
36.8g (0.35mol) n-butyryl chloride is slowly added to below DEG C, at 35～45 DEG C, 4～6h is stirred.Question response liquid is cooled to room
In pouring hydrochloric acid-frozen water after temperature into, 30min is stirred, stratification separates organic faciess, and washs organic faciess with sodium hydroxide solution
(n-butyric acie in removing system), then wash organic faciess once, precipitation, recycling design obtains 1- rubigan -1- butanone.
2）The preparation of the bromo- 1- butanone of 1- rubigan -2
65mL1, the 1- rubigan -1- butanone of 2- dichloroethanes, 28.8g concentrated sulphuric acids and preparation are added to equipped with machinery
In the four-hole bottle of the 500mL of agitator, thermometer, constant pressure funnel and spherical reflux condensing tube, keeping temperature is not higher than 30
℃.1,2- dichloroethane solutions of the 65mL dissolved with 27.6g (0.17mol) bromine is slowly added under stirring, it is anti-at 25～35 DEG C
Answer 4h.Stratification, separates concentrated sulphuric acid, first washes organic faciess, and organic faciess are then washed with sodium bicarbonate solution, then washes organic
Phase, precipitation, recycling design obtains the bromo- 1- butanone of 1- rubigan -2-.
3）The preparation of 1- rubigan -2- dimethylamino -1- butanone
By the diethyl ether solution for containing dimethylamine 39.0g (0.87mol) be added to ice-water bath cool down equipped with mechanical agitator,
In the four-hole bottle of the 500mL of thermometer, constant pressure funnel and spherical reflux condensing tube, prepared 1- is slowly added under stirring
The bromo- 1- butanone of rubigan -2-, the two of excess in 5～6h of stirring reaction at -2～2 DEG C, then logical nitrogen blowout reaction system
Methylamine.Reactant liquor is poured into water, stratification, separates organic faciess, washing organic faciess are repeatedly neutrality to solution, and precipitation is returned
Solvent is received, that is, obtains 1- rubigan -2- dimethylamino -1- butanone.
4）The preparation of 1- rubigan -2- dimethylamino -2- benzyl -1- butanone
43.7g (0.34mol) benzyl chlorides and the 1- rubigan -2- dimethylamino -1- butanone for preparing are added to and are equipped with
In the four-hole bottle of the 500mL of mechanical agitator, thermometer, constant pressure funnel and spherical reflux condensing tube, 70～80 are warming up to
DEG C, stir 12h.30% sodium hydroxide solution 76.5g is added, 50～70 DEG C is incubated, 30～60min of back flow reaction.Cooling reaction
Liquid, separates organic layer, then washes 3 times, anhydrous sodium sulfate drying, precipitation, and recycling design, with alcohol crystal, is put into refrigerator freezing.
Yellow crystals are filtrated to get, vacuum drying oven drying, constant weight 63.4g, four-step reaction total recovery 70% is put into.1H NMR
(400MHz, CDCl3)：δ=0.71 (t, J=7.44Hz, 3H), 1.82-2.13 (br, 2H), 2.40 (s, 6H), 3.22 (s, 2H),
7.20-7.29 (br, 5H), 7.37 (d, J=8.66Hz, 2H), 8.33 (d, J=8.31Hz, 2H)
Embodiment 3：The preparation of 1- [4- (4- cumene sulfenyls) phenyl] -2- dimethylamino -2- benzyl -1- butanone
1）With 1- p-fluorophenyl -2- dimethylamino -2- benzyl -1- butanone as raw material
In equipped with mechanical agitator, thermometer, constant pressure funnel, the four-hole bottle of the 250mL of spherical reflux condensing tube
Add 80mL dissolved with the DMF solution of 2.8g (0.050mol) potassium hydroxide, under stirring 7.6g is slowly added dropwise
(0.050mol) p-isopropyl phenylmercaptan., is stirred at room temperature 1h.Add 10.0g (0.033mol) 1- p-fluorophenyl -2- dimethylaminos
Base -2- benzyl -1- butanone, stirring is warming up to 100 ~ 120 DEG C, reacts 10 ~ 15h.Cooling reactant liquor, is slowly dropped to a large amount of
In frozen water, then repeatedly extracted on a small quantity with ethyl acetate, separate organic faciess, with saturated nacl aqueous solution organic faciess are repeatedly washed,
Anhydrous sodium sulfate drying, precipitation, recycling design, residue column chromatography is refining to obtain yellow oily product, yield 8.69g,
Yield 61%.
2）With 1- rubigan -2- dimethylamino -2- benzyl -1- butanone as raw material
In equipped with mechanical agitator, thermometer, constant pressure funnel, the four-hole bottle of the 250mL of spherical reflux condensing tube
Add 65mL dissolved with the DMF solution of 2.1g (0.038mol) potassium hydroxide, under stirring 5.8g is slowly added dropwise
(0.038mol) p-isopropyl phenylmercaptan., is stirred at room temperature 1h.Add 10.0g (0.032mol) 1- rubigan -2- dimethylaminos
Base -2- benzyl -1- butanone, stirring is warming up to 100 ~ 120 DEG C, reacts 15 ~ 20h.Cooling reactant liquor, is slowly dropped to a large amount of
In frozen water, then repeatedly extracted on a small quantity with ethyl acetate, separate organic faciess, with saturated nacl aqueous solution organic faciess are repeatedly washed,
Anhydrous sodium sulfate drying, precipitation, recycling design, residue column chromatography (eluent petroleum ether：Ethyl acetate=80:1) essence
Orange-yellow oily product, yield 8.28g, yield 60% is obtained.
1- [4- (4- cumene sulfenyls) phenyl] -2- dimethylamino -2- benzyl -1- butanone outward appearances：Orange-yellow oily
Liquid,1H NMR (400MHz, CDCl3)：δ=0.73 (t, J=7.43Hz, 3H), 1.32 (d, J=6.93Hz, 6H), 1.86-2.12
(br, 2H), 2.40 (s, 6H), 2.97 (m, 1H), 3.24 (s, 2H), 7.16 (d, J=8.52Hz, 2H), 7.22 (d, J=6.73Hz,
2H), 7.25-7.33 (br, 5H), 7.50 (d, J=8.08Hz, 2H), 8.29 (d, J=8.46Hz, 2H).
Embodiment 4：The preparation of 1- [4- (4- methylphenyl-sulfanyls) phenyl] -2- dimethylamino -2- benzyl -1- butanone
In equipped with mechanical agitator, thermometer, constant pressure funnel, the four-hole bottle of the 250mL of spherical reflux condensing tube
Add 65mL dissolved with the DMF solution of 2.3g (0.040mol) potassium hydroxide, under stirring 5.0g is slowly added dropwise
(0.040mol) to methylbenzene phenyl-sulfhydrate, 1h is stirred at room temperature.Add 8.0g (0.027mol) 1- p-fluorophenyl -2- dimethylaminos
Base -2- benzyl -1- butanone, stirring is warming up to 120 ~ 125 DEG C, reacts 9 ~ 10h.Cooling reactant liquor, is slowly dropped to a large amount of
In frozen water, then repeatedly extracted on a small quantity with ethyl acetate, separate organic faciess, with saturated nacl aqueous solution organic faciess are repeatedly washed,
Anhydrous sodium sulfate drying, precipitation, recycling design, residue ethyl alcohol recrystallization obtains 8.6g buff powders, yield 80%.1-
[4- (4- methylphenyl-sulfanyls) phenyl] -2- dimethylamino -2- benzyl -1- butanone outward appearances：Buff powder；1H NMR
(400MHz, CDCl3)：δ=0.71 (t, J=7.23Hz, 3H), 1.85-2.09 (br, 2H), 2.38 (s, 6H), 2.42 (s, 3H),
3.22 (s, 2H), 7.10 (d, J=8.56Hz, 2H), 7.22-7.38 (br, 7H), 7.45 (d, J=7.97Hz, 2H), 8.24 (d, J=
8.32Hz, 2H).
Embodiment 5：The preparation of 1- (4- Phenoxyphenyls) -2- dimethylamino -2- benzyl -1- butanone
In equipped with mechanical agitator, thermometer, constant pressure funnel, the four-hole bottle of the 250mL of spherical reflux condensing tube
2.8g (0.029mol) phenol, 4.1g (0.029mol) potassium carbonate and 60mLN, dinethylformamide are added, is stirred at room temperature
1h.8.0g (0.027mol) 1- p-fluorophenyl -2- dimethylamino -2- benzyl -1- butanone, stirring is added to be warming up to 140 ~ 145
DEG C, react 15 ~ 20h.Cooling reactant liquor, in being slowly dropped to a large amount of frozen water, is then repeatedly extracted on a small quantity with ethyl acetate,
Organic faciess are separated, with saturated nacl aqueous solution organic faciess, anhydrous sodium sulfate drying, precipitation, recycling design, residue are repeatedly washed
With the refined (eluent petroleum ether of column chromatography：Ethyl acetate=40：1) yellow oily liquid 6.1g, yield 60% are obtained.1-(4-
Phenoxyphenyl) -2- dimethylamino -2- benzyl -1- butanone outward appearance：Yellow oily liquid；1H NMR (400MHz,
CDCl3)：δ=0.76 (t, J=7.78Hz, 3H), 1.92-2.24 (br, 2H), 2.43 (s, 6H), 3.27 (s, 2H), 6.97-
7.51 (br, 12H), 8.47 (d, J=8.87Hz, 2H).
Following compounds are prepared with above-mentioned preparation method, 1 is shown in Table.
Table 1
Embodiment 12：Photoinitiation Property is evaluated
Photocuring system formula is shown in Table 2.
Table 2：
| Component | Ratio wt % |
| Epoxy acrylic resin | 50.0 |
| TPGDA | 34.5 |
| Phthalocyanine blue BGS | 12.0 |
| Borchi GOL OL17 | 0.5 |
| Embodiment light is carried out the coffin upon burial agent | 3.0 |
Using bar spreader（40μm）Coating contrast mixing light trigger 369 and ITX and reality of the present invention on PGA- paper
Apply a light trigger.The sample of coating is installed on tape, under Phoseon 4W 395nm LED the sample is conveyed.It is determined that
The number of pass times of sample is fully cured under given belt speed.Determined using Q- tips method and be fully cured.The results are shown in Table 2.
Table 3：
| Radiation-hardenable composition | The number of times passed through in 5m/min | The number of times passed through in 30m/min |
| Embodiment 3 | 2 | 3 |
| Embodiment 4 | 3 | 6 |
| Embodiment 5 | 5 | 7 |
| Embodiment 6 | 3 | 5 |
| Embodiment 7 | 2 | 3 |
| Embodiment 8 | 3 | 4 |
| Embodiment 9 | 4 | 6 |
| Embodiment 10 | 4 | 7 |
| Embodiment 11 | 2 | 2 |
| 369+ITX | 4 | 6 |
The result shows, these new light triggers have a good light trigger activity, and can well with technology into
Ripe UVLED light sources match.
Claims (5)
1. a kind of aminoketoness light trigger is the compound of the structure with following formula I：
Wherein：
Ar is selected from 4- isopropyl phenyls, and X is selected from S, and R is selected from H；
Ar is selected from 4- aminomethyl phenyls, and X is selected from S, and R is selected from H；
Ar is selected from 4- isopropyl phenyls, and X is selected from O, and R is selected from H；
Ar is selected from 4- isopropyl phenyls, and X is selected from S, and R is selected from 4- methyl；
Ar is selected from 4- isopropyl phenyls, and X is selected from S, and R is selected from the 4- tert-butyl groups；Or
Ar is selected from 4- xenyls, and X is selected from S, and R is selected from H.
2. formula I compound according to claim 1, it is characterised in that its preparation method is reported as follows step：
1) compound ii carries out friedel-crafts acylation under Louis acid catalysis and obtains compound III with n-butyryl chloride；
Wherein lewis acid is selected from aluminum chloride, ferric chloride, zinc chloride, titanium tetrachloride；
2) halogenating reaction that compound III carries out carbonyl α-H with bromine obtains compounds Ⅳ；
3) compounds Ⅳ carries out ammonolysis reaction and generates compound V with dimethylamine；
4), there is in the basic conditions Stevens and reset instead in compound V and the quaternary ammonium salt of the halogenation benzyl of formula VII generation α-aminoketone
Compound VI should be generated；
5) compound VI reacts with ArXH and obtains target product compounds I
Wherein：
X is selected from O, S；
X' is selected from F, Cl；
X " is selected from Cl, Br；
Ar is selected from 4- tert-butyl-phenyls, 4- aminomethyl phenyls, 4- xenyls；
R is selected from hydrogen, methyl, the tert-butyl group.
3. a kind of Photocurable composition, it is included：
(a) at least one compound containing ethylenical unsaturated double bonds with
B compound described in () at least one claim 1 is light trigger.
4. the method that the Photocurable composition described in claim 3 occurs polymerization, it is characterised in that include using 200-405nm scopes
Light source irradiation.
5. the method that the Photocurable composition according to claim 3 or 4 occurs polymerization, it is characterised in that include using 385-
The light source irradiation of 405nm.
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