CN101220212A - Diphenyl ketone containing nitryl stilbene dye formed with ester linkage, synthesis and application thereof - Google Patents
Diphenyl ketone containing nitryl stilbene dye formed with ester linkage, synthesis and application thereof Download PDFInfo
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- CN101220212A CN101220212A CNA2007100931450A CN200710093145A CN101220212A CN 101220212 A CN101220212 A CN 101220212A CN A2007100931450 A CNA2007100931450 A CN A2007100931450A CN 200710093145 A CN200710093145 A CN 200710093145A CN 101220212 A CN101220212 A CN 101220212A
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- benzophenone
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- toluylene
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Abstract
The invention discloses a dioxybenzone containing anitro-diphenyl-styrene by an ester bond and a synthesizing method and application thereof, pertaining to the organic dyestuff field, and more particularly relates to a stilbene dye that is connected with the dioxybenzone by the ester bond and application thereof in light polymerization. A typical chemical structure general formula of the compound of the anitro-diphenyl-styrene is showed on the right, wherein, R in the molecular structural formula (I) represents hydrogen, methyl, ethyl, propyl, butyl, amyl, hexyl or is completely the same as a substituting group at 4th site. The dioxybenzone that goes through acyl chlorination reacts with derivative of anitro-diphenyl-styrene compound that contains hydroxyl under alkaline conditions, and the dioxybenzone containing anitro-stilbene dye is prepared by the ester bond. The maximum absorption of the stilbene dye is at a visible light area, initiates vinyl monomer polymerization effectively when being irradiated by visible light.
Description
Technical field
The invention belongs to the visible light initiator field, particularly relate to a class synthetic and application by the diphenylethylene organic dye that contains benzophenone of ester bond.
Background technology
Long wavelength laser such as Ar+ (488nm in recent years, 514nm), YAG (532nm), He-Ne (633nm) be in the widespread use in fields such as Computer To Plate, photocuring, double photon photopolymerization and high-density digital optical storage, make to develop the key areas that visible light light trigger efficiently becomes present optical information research.One of them method is that ultraviolet initiator is connected on the visible dyes by valence bond.Koichi Kawamur has found that ultraviolet initiator three chloro s-triazine are connected on the visible light cyanine dyes and can bring up to 500-600nm to absorb light, exercise question is: " synthetic two (the three chloro methyl)-1 that are connected with new dyestuff of appraisal, 3, the 5-triazine is as the visible light Photoepolymerizationinitiater initiater " (Synthesis and evaluation as avisible-light polymerization photoinitiat or of a new dye-linkedbis (trichloromethyl)-1,3,5-triazine), " Polymers for Advanced Technologies " (polymkeric substance that is used for hi-tech), 2004,15 (6), 324-328.The polymerization of photic transfer transport generation free radical initiation vinyl monomer takes place in three chloro s-triazine and visible light cyanine dyes under visible light illumination, yet, this compounds synthesizes needs a lot of steps, and its efficiency of initiation is not high, three chloro s-triazine illumination often produce obnoxious flavoures such as chlorine, therefore can be subjected to a lot of restrictions in actual applications.Benzophenone is business-like ultraviolet initiator, but its absorbing wavelength is very short, and between 250-300nm, visible region does not almost absorb.General is easily synthetic to the nitro toluylene dyestuff, and its maximum absorption is at visible region, and has bigger molar extinction coefficient.
Summary of the invention
The invention reside in by easy method prepare new connection light trigger pass through ester bond contain benzophenone to the nitro diphenyl ethylene organic dye, not only can itself absorb visible light, and can have the visible light initiating power, and improve the light-initiated efficient of its visible light.
Involved in the present invention pass through ester bond contain benzophenone to the nitro toluylene dyestuff, the typical chemical structure of general formula of its compound is as follows:
Wherein R represents hydrogen, methyl, ethyl, propyl group, butyl, amyl group, hexyl in the molecular structural formula (I), and is perhaps identical with 4 substituting group;
The above-mentioned synthetic method to nitro hexichol dyestuff that contains benzophenone by ester bond may further comprise the steps:
(1) contains the synthetic of hydroxyl to the nitro toluylene dyestuff
The benzaldehyde compound of representative in the chemical formula (II) is mixed in three mouthfuls ground flask with paranitrophenylacetic acid according to 0.8: 1 ratio of mol ratio, add condensing works, add mol ratio then and be 1: 1.3 hexahydropyridine, reacting by heating 5-6 hour, temperature of reaction is 110-130 ℃, be dissolved in recrystallization in the ethanol then, filter and obtain crystal, standby;
Reaction equation:
Molecular structural formula (II) wherein, (IV) in R represent hydrogen, methyl, ethyl, propyl group, butyl, amyl group, hexyl, perhaps identical with 4 substituting group;
Concrete steps:
According to Guido Cavallini, Elena Massarani U.S. Pat Patents 2878291,1959, the improved method of the preparation of 4-hydroxy stibene and its derivative (Process for the preparation of 4-hydroxystilbene and itsderivatiyes).The benzaldehyde compound of chemical formula (II) representative is mixed with paranitrophenylacetic acid according to 0.8: 1 ratio of mol ratio, in three mouthfuls ground flask, mix, add condensing works, add mol ratio then and be 1: 1.3 hexahydropyridine, reacted 5-6 hour down at 110-130 ℃, be dissolved in recrystallization in the ethanol, filter and obtain crystal, standby;
(2) benzophenone of chloride
Reaction equation:
Concrete steps:
2 bit strips in the chemical formula (III) there is the benzophenone of carboxyl mix in three mouthfuls ground flask with 1: 10 ratio of mol ratio with thionyl chloride, add condensing works, stirred 6 hours down at 80-90 ℃, excessive thionyl chloride is removed in distillation then, the benzophenone (V) that obtains chloride need not be further purified, and promptly can be used for next step reaction;
(3) contain the synthetic of benzophenone by ester bond to nitro diphenyl ethylene dye
Wherein molecular structural formula (I) R represents hydrogen, methyl, ethyl, propyl group, butyl, amyl group, hexyl, and is perhaps identical with 4 bit substituents; Molecular structural formula (IV) R represents hydrogen, methyl, ethyl, propyl group, butyl, amyl group, hexyl, and is perhaps identical with 4 bit substituents.
Concrete steps:
Hydroxyl the nitro toluylene dyestuff is mixed in the ground flask that adds three mouthfuls with mol ratio with the benzophenone of chloride at 1: 2.5 that have that step (1), (2) make mixed, add condensing works, tetrahydrofuran solvent with 100-500 times of volume ratio dissolves then, add 1: 2.5 basic catalyst of mol ratio, backflow 2-12 hour, the cooled and filtered precipitation behind solvent evaporate to dryness in the filtrate, adopts silicagel column to separate and obtains the compound that right 1 requires.
Described basic catalyst is sodium hydride, sodium alkoxide, potassium alcoholate, Anhydrous potassium carbonate, triethylamine, pyridine or their any mixture.
Of the present invention benzophenone nitro diphenyl ethylene dye is mixed with the auxiliary agent trolamine that contain by ester bond can form photosensitized initiation system, and because its absorption bands is wide, absorbing wavelength is at visible region, can with now all visible light source such as tungsten-iodine lamp, xenon lamp, Ar
+Laser apparatus, YAG (532nm) laser apparatus etc. are complementary.Therefore, dye molecule of the present invention and auxiliary agent trolamine can be used for the visible light photopolymerization of vinyl monomer in the solution.
Photosensitizers consumption, configuration and the using method of dyestuff of the present invention during as above purposes is as follows:
Vinyl monomer: 25%-80wt%
Organic solvent: 25%-80wt%
By ester bond contain benzophenone to nitro diphenyl ethylene dye (light trigger of the present invention): 0.01%-10wt%
Auxiliary agent trolamine: 0.01%-10wt%
The concrete operations step is as follows:
In the long horminess glass tube of 10cm, the organic solvent that adds 10%-80wt%, the vinyl monomer of 25%-80wt%, 0.01%-10wt% with by ester bond contain benzophenone to nitro diphenyl ethylene dye (light trigger of the present invention), 0.01%-10wt% auxiliary agent trolamine, the logical argon gas 20-30 minute deoxygenation of lucifuge then.At room temperature use visible light apart from 5cm, stirred illumination 0.5-6 hour down.With cold methyl alcohol polymkeric substance is separated out, promptly get thick product.Carry out precipitation process again, can obtain the purified alkene monomer polymer.
In the above-mentioned prescription, described vinyl monomer comprises acrylic acid or the like, acrylamide, vinyl cyanide, styrenic, vinyl-acetic ester class or their any miscellany.
Described organic solvent comprises ester class, ethers, acetonitrile or their any miscellanys.
Involved in the present invention pass through ester bond contain benzophenone nitro diphenyl ethylene dye is had following advantage:
(1) synthetic method and the separation to the nitro toluylene dyestuff that contain benzophenone by ester bond of the present invention is simple, and raw material sources conveniently are easy to get.Wherein precursor 2-acyl chlorides benzophenone with contain hydroxyl all can be to nitro diphenyl ethylene dye by conventional method preparation.With the two condensation under alkaline condition, just can make the dye molecule of novel connection ultraviolet initiator of the present invention then, and productive rate is fit to.
(2) of the present invention by ester bond contain benzophenone nitro diphenyl ethylene dye class absorption bands is covered broad, and the dye molecule of logical outer light trigger, and productive rate is suitable.
(2) of the present invention by ester bond contain benzophenone nitro diphenyl ethylene dye class absorption bands is covered broad, and by what change had a hydroxyl the kind of nitro toluylene dye derivate is changed the structure of the reactive monoazo dyestuffs molecule of being invented, can adjust the maximum absorption wavelength of dyestuff easily.
(3) of the present invention by ester bond contain benzophenone not only can absorb visible light to nitro diphenyl ethylene dye itself because contain benzophenone simultaneously, have light initiation polymerization efficient efficiently simultaneously.
Description of drawings
Fig. 1. the embodiment of the invention 4 is relation curves that (to nitro diphenyl ethylene)-(benzophenone acid)-ester is dissolved in absorbancy and wavelength in the methylene dichloride.
Fig. 2. the embodiment of the invention 5 is relation curves that (4-nitro-3 ', 4 '-dihydroxyl toluylene)-two (benzophenone acid)-esters are dissolved in absorbancy and wavelength in the methylene dichloride.
Embodiment
Embodiment 1
Synthesizing of (to nitro diphenyl ethylene)-(benzophenone acid)-ester
Synthetic three steps of branch carry out:
(1) 4-nitro-4 '-hydroxyl-toluylene is synthetic
1.2g p-Hydroxybenzaldehyde mixes in three mouthfuls ground flask with the ratio of 2.26g paranitrophenylacetic acid (mol ratio 0.8: 1), add condensing works, the hexahydropyridine (mol ratio 1: 1.25) that adds 0.72g then, 110 ℃ of heating were reacted 6 hours down, be dissolved in recrystallization in the ethanol, filtration obtains crystal, and productive rate 68% is standby;
(2) 2-acyl chlorides benzophenone is synthetic
1.86g the SOCl of 2-carboxyl benzophenone and 11.8g
2(mol ratio 1: 10) mixes in three mouthfuls ground flask, and heating was stirred 5 hours down, removed unreacted SOCl under the decompression
2, obtain the heavy-gravity product, be not further purified, productive rate 95%, standby;
(3) synthesizing of (to nitro diphenyl ethylene)-(benzophenone acid)-ester
2.4g 4-nitro-4 '-hydroxyl-toluylene that step (1) is made and the 2.44g 2-acyl chlorides benzophenone (mol ratio 1: 1) that (2) make are mixed to join in three mouthfuls the ground flask mixes, tetrahydrofuran solvent with 200ml dissolves then, add the 0.79g pyridine, refluxed 2 hours, the cooled and filtered precipitation, behind solvent evaporate to dryness in the filtrate, adopt the silicagel column separation to obtain the reactive monoazo dyestuffs of being invented, productive rate 38%.
Embodiment 2
The synthetic of (4-nitro-3 '-methyl-4 '-hydroxy stibene)-(benzophenone acid)-ester divided for three steps carried out:
(1) 4-nitro-3 '-methyl 4 '-hydroxyl-toluylene is synthetic
1.36g 3-methyl-4 p-Hydroxybenzaldehyde mixes in three mouthfuls ground flask with the ratio of 2.26g paranitrophenylacetic acid (mol ratio 0.8: 1), add condensing works, the hexahydropyridine (mol ratio 1: 1.25) that adds 0.72g then, 120 ℃ of heating were reacted 6 hours down, be dissolved in recrystallization in the ethanol, filtration obtains crystal, and productive rate 68% is standby;
(2) 2-acyl chlorides benzophenone is synthetic
Synthesize by second step in the case study on implementation 1 and undertaken;
(3) the synthetic of (4-nitro-3 '-methyl-4 '-hydroxy stibene)-(benzophenone acid)-ester mixes step (1) 2.55g 4-nitro-3 '-methyl 4 '-hydroxyl-toluylene with being mixed to join in three mouthfuls the ground flask with 2.44g 2-acyl chlorides benzophenone (mol ratio 1: 1) that (2) make, tetrahydrofuran solvent with 200ml dissolves then, add the 0.79g pyridine, refluxed 8 hours, the cooled and filtered precipitation, behind solvent evaporate to dryness in the filtrate, adopt the silicagel column separation to obtain the reactive monoazo dyestuffs of being invented, productive rate 32%.
Embodiment 3
Synthesizing of (4-nitro-3 ', 4 '-dihydroxyl toluylene)-two (benzophenone acid)-esters
Synthetic three steps of branch carry out:
(1) 4-nitro-3 ', 4 '-dihydroxyl-toluylene is synthetic
1.38g 3, the 4-Dihydroxy benzaldehyde mixes in three mouthfuls ground flask with the ratio of 2.26g paranitrophenylacetic acid (mol ratio 0.8: 1), add condensing works, the hexahydropyridine (mol ratio 1: 1.25) that adds 0.72g then, 130 ℃ of heating were reacted 6 hours down, were dissolved in recrystallization in the ethanol, filtered and obtained crystal, productive rate 68%, standby;
(2) 2-acyl chlorides benzophenone is synthetic
Synthesize by second step in the case study on implementation 1 and undertaken;
(3) (4-nitro-3 ', 4 '-dihydroxyl toluylene)-two (benzophenone acid)-esters is synthetic
With step (1) 2.57g4-i nitro-3 ', 4 '-dihydroxyl toluylene mixes with making in the ground flask that 6.1g 2-acyl chlorides benzophenone (mol ratio 1: 2.5) is mixed to join three mouthfuls with (2), tetrahydrofuran solvent with 350ml dissolves then, add the 1.72g pyridine, refluxed the cooled and filtered precipitation 12 hours.Behind solvent evaporate to dryness in the filtrate, adopt the silicagel column separation to obtain the reactive monoazo dyestuffs of being invented, productive rate 36%.
Embodiment 4
With 1 * 10
-5(to the nitro diphenyl ethylene) of mol/L-(benzophenone acid)-ester is dissolved in the methylene dichloride, measures its ultraviolet-visible absorption spectroscopy, absorbs obvious blue shift, as Fig. 1.
Embodiment 5
With 1 * 10
-5(4-nitro-3 ', 4 '-dihydroxyl toluylene)-two (benzophenone acid)-esters of mol/L are dissolved in the methylene dichloride, measure its ultraviolet-visible absorption spectroscopy, absorb obvious blue shift, as Fig. 2.
Embodiment 6
Methyl methacrylate polymerization in the visible light photo sensitized initiation solution of (4-nitro-3 ', 4 '-dihydroxyl toluylene)-two (benzophenone acid)-esters
In the long horminess glass tube of 10cm, add the ethyl acetate of 2 grams and the methyl methacrylate of 5 grams, add (4-nitro-3 ', 4 '-dihydroxyl toluylene)-two (benzophenone acid)-esters of 10 milligrams invention, 2 milliliters of trolamines, the logical argon gas of lucifuge situation 20 minutes, under the room temperature as for illumination under the tungsten-iodine lamp of 1kw, after 1 hour, with cold methanol extraction, can obtain white polymer, polymethylmethacrylate, productive rate 63%.
Claims (4)
- Connection benzophenone by ester bond to the nitro toluylene dyestuff, it is characterized in that: nitro toluylene dyestuff and benzophenone have been formed new dye molecule by the chemical bond ester bond, and the typical chemical structure of general formula of its compound is:Wherein R represents hydrogen, methyl, ethyl, propyl group, butyl, amyl group, hexyl in the molecular structural formula (I), and is perhaps identical with 4 substituting group.
- 2. the connection benzophenone by ester bond according to claim 1 to the nitro toluylene dyestuff, it is characterized in that: may further comprise the steps:The first step: contain the synthetic of hydroxyl to the nitro toluylene dyestuffThe benzaldehyde compound of representative in the chemical formula (II) is mixed in three mouthfuls ground flask with paranitrophenylacetic acid according to 0.8: 1 ratio of mol ratio, add condensing works, add mol ratio then and be 1: 1.3 hexahydropyridine, reacting by heating 5-6 hour, temperature of reaction is 110-130 ℃, be dissolved in recrystallization in the ethanol then, filter and obtain crystal, standby;Wherein R represents hydrogen, methyl, ethyl, propyl group, butyl, amyl group, hexyl in the molecular structural formula (II), and is perhaps identical with 4 substituting group;Second step: the benzophenone of chlorideThe benzophenone that has carboxyl in the chemical formula (III) is mixed in three mouthfuls ground flask with 1: 10 ratio of mol ratio with thionyl chloride, add condensing works, stirred 6 hours down at 80-90 ℃, excessive thionyl chloride is removed in distillation then, obtain the benzophenone (V) of chloride, need not be further purified, promptly can be used for next step reaction;
The 3rd step: the connection benzophenone that forms by ester bond to the nitro toluylene dyestuffHydroxyl the nitro toluylene dyestuff is mixed in the ground flask that adds three mouthfuls with mol ratio with the benzophenone of chloride at 1: 2.5 that have that the first step, second step make mixed, add condensing works, tetrahydrofuran solvent with 100-500 times of volume ratio dissolves then, add 1: 2.5 basic catalyst of mol ratio, backflow 2-12 hour, the cooled and filtered precipitation behind solvent evaporate to dryness in the filtrate, adopts silicagel column to separate and obtains the compound that right 1 requires. - 3. method according to claim 2 is characterized in that: the 3rd step, described basic catalyst was sodium hydride, sodium alkoxide, potassium alcoholate, Anhydrous potassium carbonate, triethylamine, pyridine or their any mixture.
- According to claim 1 pass through connection benzophenone that ester bond forms to the nitro toluylene dyestuff, its purposes is: be used for the visible light polymerization of solution vinyl monomer as light trigger.
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| Application Number | Priority Date | Filing Date | Title |
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| CNA2007100931450A CN101220212A (en) | 2007-12-17 | 2007-12-17 | Diphenyl ketone containing nitryl stilbene dye formed with ester linkage, synthesis and application thereof |
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| CNA2007100931450A CN101220212A (en) | 2007-12-17 | 2007-12-17 | Diphenyl ketone containing nitryl stilbene dye formed with ester linkage, synthesis and application thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101838475A (en) * | 2010-05-28 | 2010-09-22 | 重庆大学 | P-nitryl diphenylethylene dye sensitizing agent containing bromine as well as synthesis and application thereof |
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2007
- 2007-12-17 CN CNA2007100931450A patent/CN101220212A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101838475A (en) * | 2010-05-28 | 2010-09-22 | 重庆大学 | P-nitryl diphenylethylene dye sensitizing agent containing bromine as well as synthesis and application thereof |
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Open date: 20080716 |