CN101177538A - P-nitro diphenyl ethylene dye containing benzophenone via ether linkage as well as synthesis and application - Google Patents
P-nitro diphenyl ethylene dye containing benzophenone via ether linkage as well as synthesis and application Download PDFInfo
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- CN101177538A CN101177538A CNA2007100929342A CN200710092934A CN101177538A CN 101177538 A CN101177538 A CN 101177538A CN A2007100929342 A CNA2007100929342 A CN A2007100929342A CN 200710092934 A CN200710092934 A CN 200710092934A CN 101177538 A CN101177538 A CN 101177538A
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Abstract
The invention relates to p-nitro stilbene dye with benzophenone via ether bond and the method of synthesis and application, in particular to the synthesis of p-nitro stilbenes dye connected with benzophenone via ether bond and the application under photopolymerization, belonging to the technical field of organic dye. The typical chemical structure is like the right equation (I). 4-bromonethyl benzophenone and the derivatives of p nitro stilbene compound with hydroxyl react in a glass vessel and in alkaline condition. The p nitro stilbenes dye with benzophenone is produced via ether bond, and the maximum absorption is in visible region. The invention can be used as photoinitiator combined with the promoter triethanolamine to form a photosensitive system, which is used as visible light polymerization of vinyl monomer in solution or solidifying material.
Description
Technical field
The invention belongs to the visible light initiator field, particularly relate to the connection benzophenone of a class by ehter bond to nitro toluylene organic dye and application thereof.
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 Kawamura 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 photoinitiator 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 is synthetic to need a lot of steps, and its efficiency of initiation is not high, and 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 objective of the invention is to by easy method prepare new connection light-initiated pass through ehter bond contain benzophenone to nitro-toluylene 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 ehter bond connect benzophenone to nitro diphenyl ethylene dye, the chemical structure of general formula of its main compound is as follows:
Wherein n represents 1-6 in the molecular structural formula (I), and R represent methylidene, ethyl, propyl group, butyl, amyl group, hexyl are perhaps identical with the other side substituting group of N.
The above-mentioned synthetic method to nitro diphenyl ethylene dye by ehter bond connection benzophenone may further comprise the steps:
(1) contains the synthetic of hydroxyl to the nitro toluylene dyestuff
Reaction equation:
Wherein n represents 1-6 among molecular structural formula (II), (III), and R represent methylidene, ethyl, propyl group, butyl, amyl group, hexyl are perhaps identical with the other side substituting group of N;
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 itsderivatives).The benzaldehyde compound of chemical formula (II) representative is mixed with paranitrophenylacetic acid according to the ratio of mol ratio 0.8-1, in three mouthfuls ground flask, mix, add condensing works, adding mol ratio then is the hexahydropyridine of 1-1.3,110-130 ℃ was reacted 5-6 hour down, be dissolved in recrystallization in the ethanol, filter and obtain crystal, standby;
(2) 4-brooethyl benzophenone is synthetic
Reaction equation is:
Concrete steps:
According to Takahito Itoh and H.K.Hall Jr at " macromole " (Macromolecules) 1990,23, the 4879-4881 report, exercise question: 7-chloro-7-phenyl-8,8-dicyano Kui quinoline bismethane: one is the new initiator (7-chloro-7-phenyl-8 of cationoid polymerisation, 8-dicyanoquinodimethane.A reported method novel initiator forcationic polymerizations) is improved.4-methyldiphenyl ketone mixes in three mouthfuls ground flask with 1: 1 ratio of mol ratio with NBS, adds condensing works, at CCl
4The middle backflow 6 hours filtered.Solid is recrystallization in benzene/cyclohexane, filters and obtains crystal, and is standby;
(3) by ehter bond contain benzophenone to nitro-toluylene organic dye building-up reactions equation:
Concrete steps:
Hydroxyl the nitro toluylene dyestuff is mixed to join in three mouthfuls ground flask with mol ratio 1-2.5 with 4-brooethyl benzophenone of containing that step (1), (2) make mixed, add condensing works, tetrahydrofuran solvent with 100-500 times of volume ratio dissolves then, the basic catalyst that adds mol ratio 1-1.5, reflux the cooled and filtered precipitation.Behind solvent evaporate to dryness in the filtrate, adopt silicagel column to separate and obtain the compound that right (1) requires.
Wherein n represents 1-6 among molecular structural formula (I), (III), and R represent methylidene, ethyl, propyl group, butyl, amyl group, hexyl are perhaps identical with the other side substituting group of N.
Described basic catalyst is sodium hydride, sodium alkoxide, potassium alcoholate, Anhydrous potassium carbonate or their any mixture.
Of the present invention benzophenone connection the nitro diphenyl ethylene derivative is mixed with the auxiliary agent trolamine 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%
With benzophenone connect to nitro diphenyl ethylene derivative (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 benzophenone connect to nitro diphenyl ethylene derivative (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.
Of the present invention have:
The connection benzophenone of the present invention by ehter bond to the nitro toluylene dyestuff
Of the present invention have:
(1) synthetic method and the separation to the nitro toluylene dyestuff by ehter bond connection benzophenone of the present invention is simple, and raw material sources conveniently are easy to get.Wherein precursor 4-brooethyl benzophenone with contain hydroxyl all can be to the nitro toluylene dyestuff 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 inventionly nitro toluylene dyestuff absorption bands is covered broad by what ehter bond connected benzophenone, 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 have good fluorescent emission ability by what ehter bond connected benzophenone to the nitro toluylene dyestuff.
(4) of the present inventionly not only can absorb visible light to nitro toluylene dyestuff itself,, have light initiation polymerization efficient efficiently simultaneously because contain benzophenone simultaneously by what ehter bond connected benzophenone.
Description of drawings
Fig. 1. the embodiment of the invention 4 is relation curves that (to nitro-right-N-methyl-N-hydroxyethyl toluylene)-(4-methyldiphenyl ketone)-ether is dissolved in absorbancy and wavelength in the methylene dichloride.
Fig. 2. the embodiment of the invention 5 is to nitro-right-N-ethyl-N hydroxyethyl toluylene)-(4-methyldiphenyl ketone)-ether is dissolved in the relation curve of absorbancy and wavelength in the methylene dichloride.
Embodiment
Further specify the present invention below in conjunction with embodiment.
Embodiment 1
The synthetic of (to nitro-right-N-methyl-N-hydroxyethyl toluylene)-(4-methyldiphenyl ketone)-ether divided for three steps carried out:
(1) to nitro-right-N-methyl-N-hydroxyethyl toluylene
1.2g N-methyl-N-hydroxyethyl-phenyl aldehyde mixes in three mouthfuls ground flask with the ratio of 1.01g 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, productive rate 65%: standby;
(2) 4-brooethyl benzophenone is synthetic
1.0g 4-methyldiphenyl ketone mixes in three mouthfuls ground flask with 0.91g N-bromo-succinimide (NBS) (mol ratio 1: 1), adds condensing works, at CCl
4The middle backflow 6 hours filtered.Solid is recrystallization in benzene/cyclohexane, filters to obtain crystal, productive rate 55%: standby;
(3) (to nitro-right-N-methyl-N-hydroxyethyl toluylene)-(4-methyldiphenyl ketone)-ether is with step (1), (2) 0.8g that makes is mixed to join nitro-right-N-methyl-N-hydroxyethyl toluylene and 0.74g 4-brooethyl benzophenone (mol ratio 1: 1) in three mouthfuls the ground flask and mixes, tetrahydrofuran solvent with 230ml dissolves then, adding 0.14g contains the NaH (mol ratio 1: 1.3) of mineral oil, reflux 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 35%.
Embodiment 2
The synthetic of (to nitro-right-N-ethyl-N hydroxyethyl toluylene)-(4-methyldiphenyl ketone)-ether divided for three steps carried out:
(1) to nitro-right-N-ethyl-N hydroxyethyl toluylene
1.2g N-ethyl-N hydroxyethyl-phenyl aldehyde mixes in three mouthfuls ground flask the ratio of (mol ratio 0.9: 1) with the 0.83g paranitrophenylacetic acid, add condensing works, the hexahydropyridine (mol ratio is 1: 1.25) that adds 0.67g then, 120 ℃ of heating were reacted 6 hours down, be dissolved in recrystallization in the ethanol, filtration obtains crystal, productive rate 67%: standby;
(2) 4-brooethyl benzophenone is synthetic
Synthesize by second step in the case study on implementation 1 and undertaken
(3) the synthetic 0.8g that step (1), (2) are made of (to nitro-right-N-ethyl-N hydroxyethyl toluylene)-(4-methyldiphenyl ketone)-ether is mixed to join nitro-right-N-ethyl-N hydroxyethyl toluylene and 0.88g 4-brooethyl benzophenone (mol ratio 1: 1.25) in three mouthfuls the ground flask and mixes, tetrahydrofuran solvent with 250ml dissolves then, adding 0.1g contains the NaH (mol ratio 1: 1.3) of mineral oil, reflux 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 3
The synthetic of (to nitro-to N, N dihydroxy ethyl toluylene)-(4-methyldiphenyl ketone)-ether divided for three steps carried out:
(1) to nitro-to N, N-dihydroxy ethyl-toluylene
1.6g N, N-dihydroxy ethyl phenyl aldehyde with the ratio of 1.39g paranitrophenylacetic acid (mol ratio 1: 1) is mixed in three mouthfuls ground flask, add condensing works, the hexahydropyridine (mol ratio is 1: 1.25) that adds 0.81g then, 130 ℃ of heating were reacted 6 hours down, be dissolved in recrystallization in the ethanol, filter and obtain crystal, productive rate 66%: standby;
(2) 4-brooethyl benzophenone is synthetic
Synthesize by second step in the case study on implementation 1 and undertaken
(3) (to nitro-to N, N dihydroxy ethyl toluylene)-(4-methyldiphenyl ketone)-ether is synthetic
The 0.9g that step (1), (2) are made is to nitro-to N, N-dihydroxy ethyl-toluylene and 1.89g 4-brooethyl benzophenone (mol ratio 1: 2.5) are mixed to join in three mouthfuls the ground flask mixes, tetrahydrofuran solvent with 300ml dissolves then, adding 0.27g contains the NaH (mol ratio 1: 2.5) of mineral oil, reflux 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 36%.
Embodiment 4
With 1 * 10
-5(to nitro-right-N-methyl-N-hydroxyethyl toluylene)-(4-methyldiphenyl ketone)-ether of mol/L is dissolved in the methylene dichloride, measures and goes uv-absorbing.As Fig. 1.
Embodiment 5
With 1 * 10
-5(to nitro-right-N-ethyl-N hydroxyethyl toluylene)-(4-methyldiphenyl ketone)-ether of mol/L is dissolved in the methylene dichloride, measures and goes uv-absorbing.As Fig. 2.
Embodiment 6
Methyl methacrylate polymerization in the visible light photo sensitized initiation solution of (to nitro-right-N-methyl-N-hydroxyethyl toluylene)-(4-methyldiphenyl ketone)-ether
In the long horminess glass tube of 10cm, add the ethyl acetate of 2 grams and the methyl methacrylate of 5 grams, the dyestuff that adds 10 milligrams invention, 2 milliliters of trolamines, in the lucifuge situation logical argon gas 10-20 minute, 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.
Claims (4)
- By ehter bond contain benzophenone to nitro-stilbene dye, its typical chemical structure of general formula is:
Wherein n represents 1-6 in the molecular structural formula (I), and R represent methylidene, ethyl, propyl group, butyl, amyl group, hexyl are perhaps identical with the other side substituting group of N. - 2. the synthetic method to nitro-stilbene dye that contains benzophenone by ehter bond according to claim 1 is characterized in that: may further comprise the steps:The first step: the synthesizing of containing hydroxyl to the nitro toluylene dyestuffThe benzaldehyde compound of chemical formula (II) representative is mixed in three mouthfuls ground flask with paranitrophenylacetic acid according to the ratio of mol ratio 0.8-1, add condensing works, adding mol ratio then is the hexahydropyridine of 1-1.3, 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 n represents 1-6 in the molecular structural formula (II), and R represent methylidene, ethyl, propyl group, butyl, amyl group, hexyl are perhaps identical with the other side substituting group of N;Second step: 4-brooethyl benzophenone synthetic4-methyldiphenyl ketone mixes in three mouthfuls ground flask with 1: 1 ratio of mol ratio with N-bromo-succinimide (NBS), adds condensing works, at CCl 4The middle backflow 6 hours filtered.Solid is recrystallization in benzene/cyclohexane, filters and obtains crystal, and is standby;The 3rd step: by the synthesizing that contains benzophenone of ehter bond to nitro-stilbene dyeHydroxyl nitro toluylene dyestuff and 4-brooethyl benzophenone are mixed to join with mol ratio 1-2.5 in three mouthfuls the ground flask that have that the first step, second step make mixed, add condensing works, tetrahydrofuran solvent with 100-500 times of volume ratio dissolves then, the basic catalyst that adds mol ratio 1-2.5, return time 2-12 hour, the cooled and filtered precipitation behind solvent evaporate to dryness in the filtrate, adopts silicagel column to separate the compound that obtains claim 1. - 3. method according to claim 2 is characterized in that: the basic catalyst described in the 3rd step is sodium hydride, sodium alkoxide, potassium alcoholate, Anhydrous potassium carbonate or their any mixture.
- According to claim 1 pass through ehter bond contain benzophenone to nitro-toluylene organic dye, 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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| CN200710092934A CN100580026C (en) | 2007-11-01 | 2007-11-01 | P-nitro diphenyl ethylene dye containing diphenyl ketone via ether bond linkage as well as synthesis and application |
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| Application Number | Priority Date | Filing Date | Title |
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| CN200710092934A CN100580026C (en) | 2007-11-01 | 2007-11-01 | P-nitro diphenyl ethylene dye containing diphenyl ketone via ether bond linkage as well as synthesis and application |
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| CN101177538A true CN101177538A (en) | 2008-05-14 |
| CN100580026C CN100580026C (en) | 2010-01-13 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102391395A (en) * | 2011-06-17 | 2012-03-28 | 北京化工大学常州先进材料研究院 | Macromolecular photoinitiator with benzophenone and preparation method thereof |
| CN103360782A (en) * | 2013-07-30 | 2013-10-23 | 重庆大学 | Stilbene visible photosensitizer containing amino group and hydroxyl group segments on 4-site, and synthesis |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2878291A (en) * | 1955-05-17 | 1959-03-17 | Maggioni & C Spa | Process for the preparation of 4-hydroxystilbene and its derivatives |
| HUP0402025A3 (en) * | 2001-11-16 | 2006-01-30 | Shiozawa Shunichi Kobe Shi | Novel bensophenone derivatives or salts thereof and their use |
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2007
- 2007-11-01 CN CN200710092934A patent/CN100580026C/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102391395A (en) * | 2011-06-17 | 2012-03-28 | 北京化工大学常州先进材料研究院 | Macromolecular photoinitiator with benzophenone and preparation method thereof |
| CN103360782A (en) * | 2013-07-30 | 2013-10-23 | 重庆大学 | Stilbene visible photosensitizer containing amino group and hydroxyl group segments on 4-site, and synthesis |
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| CN100580026C (en) | 2010-01-13 |
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