CN103044582A - Polymerizable acridone photoinitiator and preparation method thereof - Google Patents
Polymerizable acridone photoinitiator and preparation method thereof Download PDFInfo
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- CN103044582A CN103044582A CN2012105166184A CN201210516618A CN103044582A CN 103044582 A CN103044582 A CN 103044582A CN 2012105166184 A CN2012105166184 A CN 2012105166184A CN 201210516618 A CN201210516618 A CN 201210516618A CN 103044582 A CN103044582 A CN 103044582A
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- dihydroketoacridine
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Abstract
The invention relates to the technical field of photocuring, specifically to a polymerizable acridone photoinitiator and a preparation method thereof. The preparation method comprises the following specific steps of: reacting acridone with acryloyl chlori under an alkaline condition in an organic solvent at 0-80 DEG C to obtain the polymerizable acridone photoinitiator. The polymerizable photoinitiator preparation method disclosed by the invention is simple in process; environment and safety issues caused by using a photosensitive composition of a micro-molecular photoinitiator can be avoided; and the polymerizable photoinitiator can be used for replacing a traditional photoinitiator to apply to the photocuring formula.
Description
Technical field
The present invention relates to the photocuring technology field, be specially a kind of dihydroketoacridine polymerizable photoinitiator and preparation method thereof.
Background technology
UV-curing technology has been widely used in the fields such as coating, printing ink, tackiness agent, photo-resist.Photocurable composition in the UV curing system mainly is comprised of monomer, prepolymer and three parts of light trigger, wherein, light trigger is the main factor that affects the Photocurable composition photosensitive property, the key point that to seek a kind of good light trigger be technology.
Traditional photoinitiator such as Benzoin derivative, dibenzoyl ketal class, α, α-dialkoxy methyl phenyl ketone class, benzophenones/amines class, michaelis ketone, thiazolone/amine etc. mostly are the small molecules light trigger, in use there are the problems such as smell, transport property, especially have potential safety hazard at food and the use of medicine associated materials.
The problems such as polymerizable photoinitiator can effectively solve the small molecules light trigger and resin compatible is poor, the VOC discharging is large, transport property, so polymerizable photoinitiator is the emphasis of this area research.
Summary of the invention
For solving the problems of the technologies described above, the invention provides and a kind ofly can avoid the environment that brings because of the photosensitive composite that adopts the small molecules light trigger and dihydroketoacridine polymerizable photoinitiator of safety issue and preparation method thereof.
Technical scheme of the present invention is as follows: a kind of dihydroketoacridine polymerizable photoinitiator is characterized in that: (I) is as follows for the structural formula of this light trigger:
A kind of preparation method of dihydroketoacridine polymerizable photoinitiator is specially: when temperature of reaction is 0 ℃ to 80 ℃, in organic solvent, dihydroketoacridine and acrylate chloride are obtained polymerizable dihydroketoacridine light trigger product in the alkaline condition reaction, reaction scheme is as follows:
Wherein, the molar ratio of dihydroketoacridine and acrylate chloride is 1:10 to 10:1; The molar ratio of alkaline matter and acrylate chloride is 1:1 to 1:2; Organic solvent is benzene,toluene,xylene, methylene dichloride, ethylene dichloride or tetrahydrofuran (THF).
The preferred 1:1 of the molar ratio of described dihydroketoacridine and acrylate chloride; The preferred 1:1 of the molar ratio of alkaline matter and acrylate chloride; The preferred toluene of organic solvent or methylene dichloride; Alkaline matter (OH
-) be mineral alkali or organic bases, preferred triethylamine; Preferred 0 ℃ to 20 ℃ of temperature of reaction.
Beneficial effect: polymerizable photoinitiator preparation technology disclosed by the invention is simple, and environment and the safety issue that can avoid adopting the photosensitive composite of small molecules light trigger to bring can replace traditional photoinitiator to be applied in the photocurable formulation.
Embodiment
Below be the prescription by photosensitive composition, the performance of bright photosensitive composite of the present invention specifically.Should be understood that embodiment only is for better understanding the present invention, and should not be construed as limitation of the present invention.
Embodiment 1
In the four-hole boiling flask that stirring is housed of 250ml, drop into the 19.7g dihydroketoacridine, 11.1g triethylamine, 100mL toluene maintains the temperature at 10 ℃ of lower acrylate chlorides that drip, and about 30min dropwises, then continue stirring reaction 1h, stopped reaction adds the 50mL deionized water in reaction flask, stir 10min, pour reaction solution in separating funnel separatory, divide the sub-cloud water layer, more respectively with 50mL deionized water extraction 3 times, the organic layer colourless dried over mgso of 10g, filter, toluene is removed in the decompression rotation, and the solid that obtains uses recrystallizing methanol, oven dry, obtain the 22.8g white solid product, yield 91%.
Embodiment 2
In the four-hole boiling flask that stirring is housed of 250ml, drop into the 19.7g dihydroketoacridine, the 15g triethylamine, the 100mL methylene dichloride maintains the temperature at 10 ℃ of lower acrylate chlorides that drip, and about 30min dropwises, then continue stirring reaction 1h, stopped reaction adds the 50mL deionized water in reaction flask, stir 10min, pour reaction solution in separating funnel separatory, branch vibration layer, more respectively with 50mL deionized water extraction 3 times, the organic layer colourless dried over mgso of 10g, filter, decompression rotation desolventizing, the solid that obtains uses recrystallizing methanol, oven dry, obtain the 23.7g white solid product, yield 95%.
Embodiment 3
In the four-hole boiling flask that stirring is housed of 250ml, drop into the 19.7g dihydroketoacridine, 11.7gNa
2CO
3, the 100mL methylene dichloride maintains the temperature at 10 ℃ of lower acrylate chlorides that drip, about 30min dropwises, and then continues stirring reaction 1h, stopped reaction, in reaction flask, add the 50mL deionized water, stir 10min, pour reaction solution in separating funnel separatory, branch vibration layer, more respectively with 50mL deionized water extraction 3 times, the organic layer colourless dried over mgso of 10g, filter, decompression rotation desolventizing, the solid that obtains uses recrystallizing methanol, oven dry obtains the 17.9g white solid product, yield 72%.
Embodiment 1,2, and 3 products therefroms are target product through the proton nmr spectra test.
1H-NMR(CDCl
3, 500MHz): δ 5.638 (2H, d ,=CH
2), 6.468～1.527 (1H, m ,-CH=), 7.285～8.042(8H, m, phenyl ring).
Applicability experiment as light trigger
Embodiment 4
Above-described embodiment 1 gained light trigger is applied to following prescription:
Epoxy acrylic resin 50g;
1,6 hexanediol diacrylate 45g;
Formula (I) compound 5g;
Trolamine 3g;
Flow agent 0.05g;
The preparation technology of said composition is: under the yellow fluorescent lamp, and adding formula (I) compound 5g in the glass flask that stirring is housed, trolamine 3g, epoxy acrylic resin 50g, 1,6 hexanediol diacrylate 45g, flow agent 0.05g, it is even to be stirred to material under the room temperature, obtains compound composition.
The migration performance test
Comparative example 1
Prescription forms:
Epoxy acrylic resin 50g;
1,6 hexanediol diacrylate 45g;
Benzophenone 5g;
Trolamine 3g;
Flow agent 0.05g;
Under the yellow fluorescent lamp, in the glass flask that stirring is housed, add benzophenone 5g, trolamine 3g, epoxy acrylic resin 50g, 1,6 hexanediol diacrylate 45g, flow agent 0.05g, it is even to be stirred to material under the room temperature, obtains compound composition.
Under yellow fluorescent lamp, get composition that same amount embodiment 4, comparative example 1 obtain on the PET template, utilize the roller coating film forming, coating thickness 100 μ m, under identical high voltage mercury lamp radiation, the complete film-forming of composition.It is 1cm that film after solidifying is shredded into particle diameter with scissors
3Following particle.Get above-mentioned cured granulate 5g and be immersed in respectively in the 200mL acetonitrile solution, 40 ℃ of lower immersions 10 days, then filter, desolvation is weighed, and test result sees the following form 2.
Table 2
Annotate: 0.05%mg/dm
2Below, ignore.
From above performance evaluation with can find out that relatively photosensitive composite preparation technology of the present invention is simple, reactive behavior is high, does not produce pungent niff, and residual small-molecule substance is few, can replace traditional photoinitiator to be applied in the photocurable formulation.
Claims (6)
1. dihydroketoacridine polymerizable photoinitiator, it is characterized in that: (I) is as follows for the structural formula of this light trigger:
Formula (I).
2. the preparation method of dihydroketoacridine polymerizable photoinitiator according to claim 1, it is characterized in that: this preparation method is specially: when temperature of reaction is 0 ℃ to 80 ℃, in organic solvent, dihydroketoacridine and acrylate chloride are obtained polymerizable dihydroketoacridine light trigger product in the alkaline condition reaction, and reaction scheme is as follows:
Wherein, the molar ratio of dihydroketoacridine and acrylate chloride is 1:10 to 10:1; The molar ratio of alkaline matter and acrylate chloride is 1:1 to 1:2; Organic solvent is benzene,toluene,xylene, methylene dichloride, ethylene dichloride or tetrahydrofuran (THF).
3. the preparation method of dihydroketoacridine polymerizable photoinitiator according to claim 2 is characterized in that: the preferred 1:1 of the molar ratio of described dihydroketoacridine and acrylate chloride; The preferred 1:1 of the molar ratio of alkaline matter and acrylate chloride; The preferred toluene of organic solvent or methylene dichloride.
4. the preparation method of dihydroketoacridine polymerizable photoinitiator according to claim 2, it is characterized in that: described alkaline matter is mineral alkali or organic bases.
5. the preparation method of dihydroketoacridine polymerizable photoinitiator according to claim 2 is characterized in that: preferred 0 ℃ to 20 ℃ of described temperature of reaction.
6. the preparation method of dihydroketoacridine polymerizable photoinitiator according to claim 2 is characterized in that: the preferred triethylamine of described alkaline matter.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2012105166184A CN103044582A (en) | 2012-12-05 | 2012-12-05 | Polymerizable acridone photoinitiator and preparation method thereof |
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| CN2012105166184A CN103044582A (en) | 2012-12-05 | 2012-12-05 | Polymerizable acridone photoinitiator and preparation method thereof |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0857721A1 (en) * | 1995-10-04 | 1998-08-12 | Eisai Co., Ltd. | Acridone compounds |
| US20090087575A1 (en) * | 2007-09-28 | 2009-04-02 | Fujifilm Corporation | Ink composition and inkjet recording method using the same |
| JP2009086358A (en) * | 2007-09-28 | 2009-04-23 | Fujifilm Corp | Positive resist composition and pattern forming method using the same |
| US20110039289A1 (en) * | 2008-03-14 | 2011-02-17 | Pierre Graves | Fluorogenic peptides and their method of production |
| EP2295505A1 (en) * | 2009-09-09 | 2011-03-16 | Fujifilm Corporation | Ink composition, ink set and image forming method |
| WO2012017046A1 (en) * | 2010-08-06 | 2012-02-09 | Eni S.P.A. | Stabilized photoactive composition and use thereof |
-
2012
- 2012-12-05 CN CN2012105166184A patent/CN103044582A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0857721A1 (en) * | 1995-10-04 | 1998-08-12 | Eisai Co., Ltd. | Acridone compounds |
| US20090087575A1 (en) * | 2007-09-28 | 2009-04-02 | Fujifilm Corporation | Ink composition and inkjet recording method using the same |
| JP2009086358A (en) * | 2007-09-28 | 2009-04-23 | Fujifilm Corp | Positive resist composition and pattern forming method using the same |
| US20110039289A1 (en) * | 2008-03-14 | 2011-02-17 | Pierre Graves | Fluorogenic peptides and their method of production |
| EP2295505A1 (en) * | 2009-09-09 | 2011-03-16 | Fujifilm Corporation | Ink composition, ink set and image forming method |
| WO2012017046A1 (en) * | 2010-08-06 | 2012-02-09 | Eni S.P.A. | Stabilized photoactive composition and use thereof |
Non-Patent Citations (1)
| Title |
|---|
| XIAOLIN GUAN, XINYU LIU, ZHIXING SU: "Synthesis and photophysical behaviors of temperature/pH-sensitive polymeric materials. I. Vinyl monomer bearing 9-aminoacridine and polymers", 《EUROPEAN POLYMER JOURNAL》 * |
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Application publication date: 20130417 |