CN104974053A - 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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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
The content that the present invention relates to is a kind of new aminoketones light trigger and the application at UV-LED photocuring system.
Background technology
Photocuring system is generally made up of components such as oligopolymer, reactive thinner, auxiliary agent and light triggers, wherein the massfraction of light trigger is generally 3% to 5%, although very little, playing irreplaceable effect, is one of important factor affecting laser curing velocity.
Light trigger refers to and can absorb the energy of certain wavelength at ultraviolet region (250 ~ 420nm) or visible region (400 ~ 800nm) and produce free radical, positively charged ion etc., thus the compound of trigger monomer polymerization crosslinking solidification.
Along with the development of photocuring technology, there is a kind of UV-LED technology based on LED light source newly.The more energy-saving and environmental protection of this technology, not mercurous, can work under cryogenic, long service life, therefore becomes 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 radiating capacity, and the development along with LED technology occurs.In recent years, various semiconductor material such as aluminium nitride, gan, InGaN etc. are developed successfully in succession, make UV-LED light source, launch the spectrum of the various different wave lengths such as 365nm, 375nm, 385nm, 395nm, 405nm, 415nm, for radiation curing field.
Compared with traditional high voltage mercury lamp, UV-LED has many features: 1, longer service life, can more than 25000 hours; 2, energy consumption is low, and energy-saving effect is better, can save energy 90%; 3, cold light source, without infrared emanation; 4, not mercurous, safety and environment protection more; 5, light output is stablized; 6, suitability is wide, can be used for various material; 7, maintenance cost is almost nil, more economically.
Just because of the unique advantage of UV-LED, make it in every field widespread use: 1, in production, UV-LED all has application in industries such as LED, CD, hummer, electronic circuit board manufactures; 2, in the application develop rapidly of daily necessities field, as being applied in the production etc. of the manufacture of furniture and production, toy; 3, in technology field, UV-LED can be used for the assembling of the artworks such as glass.In addition, UV-LED also has application in the field such as jewelry, printing.
UV-LED light source, because of its energy-saving and environmental protection, durable and remarkable luminescent properties, must be the development trend of following photocuring light source.But because UV-LED radiation of light source crest is single, energy accumulating is at certain narrow UV-light spectral coverage, and the crest great majority of UV-LED light source concentrate on 365 ~ 395nm in the market, this is the optimum point of solidification.In existing light trigger; thioxanthone and this two photoinitiator of acylphosphine oxide is only had to have certain absorption in 365 ~ 395nm scope; can support the use with LED light source reluctantly; but the absorption within the scope of 365 ~ 395nm is still very limited; enough initiating activities can not be provided, therefore exploitation and 365 ~ 395nm UV-LED light source match, the light trigger with stronger absorbing ability and Geng Gao initiating activity is still and is badly in need of very much.
Summary of the invention
The object of this invention is to provide a kind of newly can aminoketones light trigger matching used with UV-LED light source, this compounds has the light trigger of stronger absorbing ability and Geng Gao initiating activity, and easily preparation, cost be low, easily store.
The aminoketones light trigger that a class provided by the invention is new is the compound of the structure with following formula I:
（Ⅰ）
Wherein:
X is selected from O, S;
Ar is selected from 1 to 5 substituted-phenyl, 4-substituted biphenyl base, and substituting group is selected from hydrogen, halogen, C1-C8 alkyl, C1-C8 alkoxyl group, C1-C8 alkylthio, nitro, R
1r
2n;
R is selected from hydrogen, halogen, C1-C8 alkyl, C3-C6 cycloalkyl, C1-C8 alkoxyl group, nitro, R
1r
2n;
R
1, R
2independently be selected from C1-C8 alkyl, or R
1, R
2couple together formation five yuan or six-ring amido.
C1-C8 alkyl can be methyl, ethyl, propyl group, sec.-propyl, normal-butyl, 2-butyl, the tertiary butyl, amyl group, cyclopentyl, isopentyl, hexyl, cyclohexyl, heptyl, octyl group, iso-octyl etc.
C1-C8 alkoxyl group can be methoxyl group, oxyethyl group, propoxy-, isopropoxy, n-butoxy, 2-butoxy, tert.-butoxy, pentyloxy, cyclopentyloxy, isopentyloxy, hexyloxy, cyclohexyloxy, heptan oxygen base, octyloxy, different octyloxy etc.
C1-C8 alkylthio can be methylthio group, ethylmercapto group, rosickyite base, isopropyisulfanyl, positive butylthio, 2-butylthio, isobutylthio, penta sulfenyl, ring penta sulfenyl, isopentylthio, own sulfenyl, cyclohexylthio, heptan sulfenyl, pungent sulfenyl, different pungent sulfenyl etc.
R
1r
2the cyclammonium base that N is formed can be
, piperidyl, morpholinyl.
The example of the compound of formula I comprises following compounds, but is not limited thereto:
I6
I7
I8
I9
I10
I11
The invention provides a kind of method preparing formula I compound, comprise following flow process:
。
The invention provides a kind of method preparing formula I compound, comprise the steps:
1) compound ii and n-butyryl chloride carry out friedel-crafts acylation and obtain compound III under Louis acid catalysis;
2) halogenating reaction that compound III and bromine carry out carbonyl α-H obtains compounds Ⅳ;
3) compounds Ⅳ and dimethylamine carry out ammonolysis reaction and generate compound V;
4) compound V and formula VII halogenation benzyl generate the quaternary ammonium salt of alpha-amino group ketone, Stevens rearrangement reaction occurs in the basic conditions and generates compound VI;
5) compound VI and ArX ' H react and obtain target product chemical compounds I.
Lewis acid in step 1 is selected from aluminum chloride, iron trichloride, zinc chloride, titanium tetrachloride, preferred aluminum chloride, iron trichloride.
The invention provides the method preparing formula I compound uses chlorobenzene or fluorobenzene to be raw material, convenient preparation, simple to operate, yield is high, is applicable to suitability for industrialized production.
The outstanding advantages of light trigger provided by the invention is:
1) the aminoketones light trigger electron delocalization shown in formula is good, has strong cyclic voltammetry method performance and excellent photoelectric property;
2) within the scope of Long wavelength region 365nm-395nm, have stronger absorption, be applicable to high-power UV-LED UV curing system;
3) shortcoming that traditional mercury lamp solidification power consumption is high, pollution is heavy is effectively overcome.
Photocurable composition provided by the invention, it comprises
(a) at least one containing ethylenical unsaturated double bonds compound and
(b) formula I light trigger at least one.
One or more double bond can be contained containing ethylenical unsaturated double bonds compound.They can be low-molecular-weight (monomer) or relative high molecular (oligopolymer).Wrapping double bond containing Exemplary monomers is alkyl or hydroxy alkyl acrylate or methacrylic ester, such as, and methyl, ethyl, butyl, 2-ethylhexyl-or 2-hydroxyethylmethacry,ate, iso-bornyl acrylate, or methacrylic acid methyl or ethyl ester; Silicone acrylate; Acrylamide, Methacrylamide, (methyl) acrylamide that N-replaces; Vinyl ester as vinyl-acetic ester, vinyl ether as isobutyl vinyl ether, vinylbenzene, alkyl-and halogenated styrenes, NVP, vinyl chloride or vinylidene chloride.
Containing the monomer of two or more double bond as ethylene glycol, propylene glycol, neo-pentyl ethylene glycol, 1, the diacrylate of 6-hexylene glycol and dihydroxyphenyl propane, 4,4 '-bis-(2-acryloyloxyethoxy) diphenyl propane, Viscoat 295, pentaerythritol triacrylate or tetraacrylate, ethylene propylene acid esters, Vinylstyrene, divinyl succinate, diallyl phthalate, tricresyl phosphate allyl ester, tricarbimide triallyl ester and tricarbimide three (2-acryloyl ethyl) ester.
The example with relative high molecular (oligopolymer) polyunsaturated compounds is epoxy resin and polyethers, the polyurethane(s) of acrylated; Acrylated or the polyester containing vinyl ether group or epoxy group(ing).Unsaturated oligomer can also be unsaturated polyester resin, and they are have toxilic acid mostly, prepared by phthalic acid and one or more glycol and have the molecular weight of about 500-3000.In addition, also can use vinyl ether monomers and vinyl ether oligomers, and take maleic acid ester as terminal, there is the oligopolymer of polyester, polyurethane(s), polyethers, polyvinyl ether and epoxy main chains.
Alefinically unsaturated compounds can also be the ester of ethylenically unsaturated carboxylic acids and polyvalent alcohol epoxy compounds, with the polymkeric substance containing ethylenically unsaturated group on main chain or side chain radical, such as unsaturated polyester, polymeric amide or polyurethane(s) and multipolymer thereof, polyhutadiene or butadienecopolymer, polyisoprene and isoprene copolymer, containing the polymkeric substance of (methyl) acrylic and multipolymer on side chain, containing the polymkeric substance of (methyl) acrylic and multipolymer on side chain, and the mixture of one or more these polymkeric substance.
The example of unsaturated carboxylic acid is that vinylformic acid, methacrylic acid, butenoic acid, methylene-succinic acid, styracin and unsaturated fatty acids are as linolenic acid and oleic acid.Preferred vinylformic acid and methacrylic acid.
Suitable polyvalent alcohol is aromatic polyol and is especially aliphatic series and Cycloaliphatic polyols.Aromatic polyol as quinhydrones, 4,4 '-dihydroxydiphenyl, 2,2-bis-(4-hydroxy phenyl) propane, and (line style) phenolic varnish and phenol-formaldehyde A.Aliphatic series and Cycloaliphatic polyols are as aklylene glycol, and preferred C2-12, as ethylene glycol, 1,2-or 1, ammediol, 1,2-, 1,3-or 1,4-butyleneglycol, pentanediol, hexylene glycol, ethohexadiol, 12 carbon alkane glycol, glycol ether, triglycol, molecular weight are preferably the polyoxyethylene glycol, 1 of 200-1500,3-ring pentanediol, 1,2-, 1,3-or 1,4-cyclohexanediol, Isosorbide-5-Nitrae-hydroxymethyl-cyclohexane, glycerine, tetramethylolmethane, TriMethylolPropane(TMP), Dipentaerythritol or Sorbitol Powder etc.
There is the method for polymerization in Photocurable composition provided by the invention, comprises the light source irradiation by 200-405nm scope, especially can also use the light source irradiation of 385-405nm.
Embodiment
The present invention will be further illustrated by following nonlimiting examples.
embodiment 1: intermediate 1-is to the preparation of fluorophenyl-2-dimethylamino-2-benzyl-1-butanone
1) 1-is to the preparation of fluorophenyl-1-butanone
58.1g (0.44mol) aluminum trichloride (anhydrous), 34.9g (0.36mol) fluorobenzene and 90mL 1 is added in the four-hole bottle of 500mL that mechanical stirrer, thermometer, constant pressure funnel and spherical reflux condensing tube are housed, 2-ethylene dichloride, 46.5g (0.44mol) n-butyryl chloride is slowly added below 10 DEG C, at 35 ~ 45 DEG C, stir 4 ~ 6h.Question response liquid is poured into after being cooled to room temperature in hydrochloric acid-frozen water, stirs 30min, stratification, separate organic phase, and wash organic phase (butanic acid in removing system) with sodium hydroxide solution, then wash organic phase once, precipitation, recycling design, namely obtains 1-to fluorophenyl-1-butanone.
2) 1-is to the preparation of the bromo-1-butanone of fluorophenyl-2
The 1-of 80mL1,2-ethylene dichloride, the 36.9g vitriol oil and preparation is joined in the four-hole bottle of the 500mL that mechanical stirrer, thermometer, constant pressure funnel and spherical reflux condensing tube are housed to fluorophenyl-1-butanone, keeps temperature not higher than 30 DEG C.Slowly add 1, the 2-dichloroethane solution that 80mL is dissolved with 35.2g (0.22mol) bromine under stirring, at 25 ~ 35 DEG C, react 4h.Stratification, separates sulfuric acid phase, first washes organic phase, then washs organic phase with sodium hydrogen carbonate solution, then washes organic phase, precipitation, recycling design, namely obtains 1-to the bromo-1-butanone of fluorophenyl-2-.
3) 1-is to the preparation of fluorophenyl-2-dimethylamino-1-butanone
Diethyl ether solution containing dimethylamine 50.0g (1.11mol) is joined with ice-water bath cooling be equipped with in the four-hole bottle of the 500mL of mechanical stirrer, thermometer, constant pressure funnel and spherical reflux condensing tube, prepared 1-is slowly added to the bromo-1-butanone of fluorophenyl-2-under stirring, stirring reaction 5 ~ 6h at-2 ~ 2 DEG C, then dimethylamine excessive in logical nitrogen blowout reaction system.Reaction solution is poured into water, stratification, separates organic phase, washing organic phase repeatedly to solution be neutrality, precipitation, recycling design, namely obtains 1-to fluorophenyl-2-dimethylamino-1-butanone.
4) 1-is to the preparation of fluorophenyl-2-dimethylamino-2-benzyl-1-butanone
The 1-of 55.1g (0.44mol) benzyl chlorine and preparation is joined in the four-hole bottle of the 500mL that mechanical stirrer, thermometer, constant pressure funnel and spherical reflux condensing tube are housed to fluorophenyl-2-dimethylamino-1-butanone, be warming up to 70 ~ 80 DEG C, stir 12h.Add 30% sodium hydroxide solution 96.6g again, be incubated 50 ~ 70 DEG C, back flow reaction 30 ~ 60min.Cooling reaction solution, is separated organic layer, then washes 3 times, anhydrous sodium sulfate drying, precipitation, recycling design, with alcohol crystal, put into refrigerator freezing.Filtration obtains yellow crystals, puts into vacuum drying oven drying, constant weight 54.3g, four-step reaction total recovery 60%.
1H NMR(400MHz，CDCl
3)：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) preparation of 1-rubigan-1-butanone
46.1g (0.35mol) aluminum trichloride (anhydrous), 31.5g (0.28 mol) chlorobenzene and 70mL 1 is added in the four-hole bottle of 500mL that mechanical stirrer, thermometer, constant pressure funnel and spherical reflux condensing tube are housed, 2-ethylene dichloride, 36.8g (0.35mol) n-butyryl chloride is slowly added below 10 DEG C, at 35 ~ 45 DEG C, stir 4 ~ 6h.Question response liquid is poured into after being cooled to room temperature in hydrochloric acid-frozen water, stirs 30min, stratification, separate organic phase, and wash organic phase (butanic acid in removing system) with sodium hydroxide solution, then wash organic phase once, precipitation, recycling design, namely obtains 1-rubigan-1-butanone.
2) preparation of the bromo-1-butanone of 1-rubigan-2
1-rubigan-1-the butanone of 65mL1,2-ethylene dichloride, the 28.8g vitriol oil and preparation is joined in the four-hole bottle of the 500mL that mechanical stirrer, thermometer, constant pressure funnel and spherical reflux condensing tube are housed, keeps temperature not higher than 30 DEG C.Slowly add 1, the 2-dichloroethane solution that 65mL is dissolved with 27.6g (0.17mol) bromine under stirring, at 25 ~ 35 DEG C, react 4h.Stratification, separates the vitriol oil, first washes organic phase, then washs organic phase with sodium hydrogen carbonate solution, then washes organic phase, precipitation, recycling design, namely obtains the bromo-1-butanone of 1-rubigan-2-.
3) preparation of 1-rubigan-2-dimethylamino-1-butanone
Diethyl ether solution containing dimethylamine 39.0g (0.87mol) is joined with ice-water bath cooling be equipped with in the four-hole bottle of the 500mL of mechanical stirrer, thermometer, constant pressure funnel and spherical reflux condensing tube, the prepared bromo-1-butanone of 1-rubigan-2-is slowly added under stirring, stirring reaction 5 ~ 6h at-2 ~ 2 DEG C, then dimethylamine excessive in logical nitrogen blowout reaction system.Reaction solution is poured into water, stratification, separates organic phase, washing organic phase repeatedly to solution be neutrality, precipitation, recycling design, namely obtains 1-rubigan-2-dimethylamino-1-butanone.
4) preparation of 1-rubigan-2-dimethylamino-2-benzyl-1-butanone
1-rubigan-2-dimethylamino-1-the butanone of 43.7g (0.34mol) benzyl chlorine and preparation is joined in the four-hole bottle of the 500mL that mechanical stirrer, thermometer, constant pressure funnel and spherical reflux condensing tube are housed, be warming up to 70 ~ 80 DEG C, stir 12h.Add 30% sodium hydroxide solution 76.5g again, be incubated 50 ~ 70 DEG C, back flow reaction 30 ~ 60min.Cooling reaction solution, is separated organic layer, then washes 3 times, anhydrous sodium sulfate drying, precipitation, recycling design, with alcohol crystal, put into refrigerator freezing.Filtration obtains yellow crystals, puts into vacuum drying oven drying, constant weight 63.4g, four-step reaction total recovery 70%.
1H NMR(400MHz，CDCl
3)：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-isopropyl benzene sulfenyl) phenyl]-2-dimethylamino-2-benzyl-1-butanone
1) with 1-to fluorophenyl-2-dimethylamino-2-benzyl-1-butanone for raw material
Be equipped with mechanical stirrer, thermometer, constant pressure funnel, spherical reflux condensing tube 250mL four-hole bottle in add the N that 80mL is dissolved with 2.8g (0.050mol) potassium hydroxide, dinethylformamide solution, 7.6g (0.050mol) p-isopropyl thiophenol is slowly dripped, stirring at room temperature 1h under stirring.Add 10.0g (0.033mol) 1-to fluorophenyl-2-dimethylamino-2-benzyl-1-butanone, stir and be warming up to 100 ~ 120 DEG C, reaction 10 ~ 15h.Cooling reaction solution, it is slowly added drop-wise in a large amount of frozen water, then repeatedly extract on a small quantity by ethyl acetate, separate organic phase, repeatedly wash organic phase with saturated nacl aqueous solution, anhydrous sodium sulfate drying, precipitation, recycling design, residue column chromatography is refining obtains yellow oily product, output 8.69g, yield 61%.
2) with 1-rubigan-2-dimethylamino-2-benzyl-1-butanone for raw material
Be equipped with mechanical stirrer, thermometer, constant pressure funnel, spherical reflux condensing tube 250mL four-hole bottle in add the N that 65mL is dissolved with 2.1g (0.038mol) potassium hydroxide, dinethylformamide solution, 5.8g (0.038mol) p-isopropyl thiophenol is slowly dripped, stirring at room temperature 1h under stirring.Add 10.0g (0.032mol) 1-rubigan-2-dimethylamino-2-benzyl-1-butanone, stir and be warming up to 100 ~ 120 DEG C, reaction 15 ~ 20h.Cooling reaction solution, it is slowly added drop-wise in a large amount of frozen water, then repeatedly extract on a small quantity by ethyl acetate, separate organic phase, repeatedly wash organic phase with saturated nacl aqueous solution, anhydrous sodium sulfate drying, precipitation, recycling design, residue column chromatography (eluent petroleum ether: ethyl acetate=80:1) is refining obtains orange-yellow oily product, output 8.28g, yield 60%.
1-[4-(4-isopropyl benzene sulfenyl) phenyl]-2-dimethylamino-2-benzyl-1-butanone outward appearance: orange-yellow oily liquids,
1h NMR (400MHz, CDCl
3): 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-sulfanyl) phenyl]-2-dimethylamino-2-benzyl-1-butanone
Be equipped with mechanical stirrer, thermometer, constant pressure funnel, spherical reflux condensing tube 250mL four-hole bottle in add the N that 65mL is dissolved with 2.3g (0.040mol) potassium hydroxide, dinethylformamide solution, 5.0g (0.040mol) is slowly dripped to methylbenzene phenyl-sulfhydrate, stirring at room temperature 1h under stirring.Add 8.0g (0.027mol) 1-to fluorophenyl-2-dimethylamino-2-benzyl-1-butanone, stir and be warming up to 120 ~ 125 DEG C, reaction 9 ~ 10h.Cooling reaction solution, is slowly added drop-wise to it in a large amount of frozen water, then repeatedly extracts on a small quantity by ethyl acetate, separate organic phase, repeatedly organic phase is washed, anhydrous sodium sulfate drying, precipitation, recycling design with saturated nacl aqueous solution, residue ethyl alcohol recrystallization, obtains 8.6g buff powder, yield 80%.1-[4-(4-methylphenyl-sulfanyl) phenyl]-2-dimethylamino-2-benzyl-1-butanone outward appearance: buff powder;
1h NMR (400MHz, CDCl
3): 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-Phenoxyphenyl)-2-dimethylamino-2-benzyl-1-butanone
Be equipped with mechanical stirrer, thermometer, constant pressure funnel, spherical reflux condensing tube 250mL four-hole bottle in add 2.8g (0.029mol) phenol, 4.1g (0.029mol) salt of wormwood and 60mLN, dinethylformamide, stirring at room temperature 1h.Add 8.0g (0.027mol) 1-to fluorophenyl-2-dimethylamino-2-benzyl-1-butanone, stir and be warming up to 140 ~ 145 DEG C, reaction 15 ~ 20h.Cooling reaction solution, it is slowly added drop-wise in a large amount of frozen water, then repeatedly extract on a small quantity by ethyl acetate, separate organic phase, repeatedly wash organic phase with saturated nacl aqueous solution, anhydrous sodium sulfate drying, precipitation, recycling design, residue column chromatography refining (eluent petroleum ether: ethyl acetate=40:1) obtains yellow oily liquid 6.1g, yield 60%.The outward appearance of 1-(4-Phenoxyphenyl)-2-dimethylamino-2-benzyl-1-butanone: yellow oily liquid;
1h NMR (400MHz, CDCl
3): 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 is prepared, in table 1 by above-mentioned preparation method.
Table 1
| Embodiment | Compound | Outward appearance | Ultimate analysis C H N S Cl |
| 6 | I6 | Yellow oily | calc. 80.93; 8.00; 3.37; found 80.91; 8.05; 3.33 |
| 7 | I7 | Yellow oily | calc. 78.16; 7.92; 3.14; 7.19;found 78.17; 7.90; 3.17; 7.21 |
| 8 | I8 | Yellow oily | calc. 78.80; 8.47; 2.87; 6.57;found 78.79; 8.45; 2.86; 6.54 |
| 9 | I9 | Yellow oily | calc. 78.17; 7.92; 3.14;found 78.13; 7.90; 3.16 |
| 10 | I10 | Yellow solid | calc.70.82; 6.18; 8.36; 3.77; 7.56;found 70.80; 6.20; 8.34; 3.79; 7.55 |
| 11 | I11 | Yellow solid | calc. 79.96; 6.71; 3.01; 6.89;found 79.92; 6.69; 3.05; 6.86 |
embodiment 12: Photoinitiation Property evaluation
Photocuring system formula is 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 |
Use line rod spreader (40 μm) be coated with on PGA-paper to contrast mixed light initiator 369 and ITX and embodiment of the present invention light trigger.The sample of coating is installed on tape, under Phoseon 4W 395nm LED, carries this sample.Determine the number of pass times of complete solidified sample under given belt speed.Q-tip method is used to determine to solidify completely.The results are shown in Table 2.
Table 3:
| Radiation-hardenable composition | The number of times passed through when 5m/min | The number of times passed through when 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 |
This result shows, it is active that these new light triggers have good light trigger, and can match by UVLED light source that is good and technology maturation.
Claims (4)
1. a new aminoketones light trigger is the compound of the structure with following formula I:
（Ⅰ）
Wherein:
X is selected from O, S;
Ar is selected from 1 to 5 substituted-phenyl, 4-substituted biphenyl base, and substituting group is selected from hydrogen, halogen, C1-C8 alkyl, C1-C8 alkoxyl group, C1-C8 alkylthio, nitro, R
1r
2n;
R is selected from hydrogen, halogen, C1-C8 alkyl, C3-C6 cycloalkyl, C1-C8 alkoxyl group, nitro, R
1r
2n;
R
1, R
2independently be selected from C1-C8 alkyl, or R
1, R
2couple together formation five yuan or six-ring amido.
2. prepare a method for formula I compound, comprise the steps:
1) compound ii and n-butyryl chloride carry out friedel-crafts acylation and obtain compound III under Louis acid catalysis;
Wherein Lewis acid is selected from aluminum chloride, iron trichloride, zinc chloride, titanium tetrachloride;
2) halogenating reaction that compound III and bromine carry out carbonyl α-H obtains compounds Ⅳ;
3) compounds Ⅳ and dimethylamine carry out ammonolysis reaction and generate compound V;
4) compound V and formula VII halogenation benzyl generate the quaternary ammonium salt of alpha-amino group ketone, Stevens rearrangement reaction occurs in the basic conditions and generates compound VI;
5) compound VI and ArXH react and obtain target product compound (I)
（I）
Wherein:
X is selected from O, S;
X' is selected from F, Cl;
X'' is selected from Cl, Br;
Ar is selected from 1 to 5 substituted-phenyl, 4-substituted biphenyl base, and substituting group is selected from hydrogen, halogen, C1-C8 alkyl, C1-C8 alkoxyl group, C1-C8 alkylthio, nitro, R
1r
2n;
R is selected from hydrogen, halogen, C1-C8 alkyl, C3-C6 cycloalkyl, C1-C8 alkoxyl group, nitro, R
1r
2n;
R
1, R
2independently be selected from C1-C8 alkyl, or R
1, R
2couple together formation five yuan or hexa-atomic cyclammonium.
3. a Photocurable composition, it comprises:
A) at least one containing ethylenical unsaturated double bonds compound and
B) light trigger described at least one claim 1.
4. there is the method for polymerization in Photocurable composition according to claim 3, it is characterized in that comprising the light source irradiation by 200-405nm scope, especially can also use the light source of 385-405nm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510350881.4A CN104974053B (en) | 2015-06-24 | 2015-06-24 | Novel aminoketones photoinitiator and application in UV-LED photocuring system |
Applications Claiming Priority (1)
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| CN109762397A (en) * | 2019-01-21 | 2019-05-17 | 长沙新宇高分子科技有限公司 | A kind of UV Photocurable composition containing amino ketone photoinitiator |
| CN115894316A (en) * | 2022-12-06 | 2023-04-04 | 天津久日新材料股份有限公司 | Aminoketone photoinitiator and preparation method and application thereof |
| CN115925596A (en) * | 2022-12-06 | 2023-04-07 | 天津久日新材料股份有限公司 | Photoinitiator, and preparation method and application thereof |
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| CN115925596A (en) * | 2022-12-06 | 2023-04-07 | 天津久日新材料股份有限公司 | Photoinitiator, and preparation method and application thereof |
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