CN1376662A - Free radical and cation hybridized trigger for optical solidification and its preparing process and application - Google Patents
Free radical and cation hybridized trigger for optical solidification and its preparing process and application Download PDFInfo
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Abstract
A hybridized free radical-cation trigger for optical solidification features that it contains both free radical trigger and cation trigger, so it can be used for the cation-type or free radical-type optical solidifying systems. Its advantages are high triggering performance, and simple preparing process.
Description
Affiliated technical field
The present invention relates to class novel hybride light trigger and its production and use, this compounds has the dual structure of radical photoinitiator and cationic photoinitiator.
Background technology
Radiation curing technology is widely used in fields such as coating, printing ink, plate making, tooth reparation and laser disc manufacturing at present.Compare with traditional curing technology technology, photocuring technology has environmental friendliness, energy-conservation, time weak point, quick solidifying, unrivaled advantage such as easy and simple to handle, is therefore developed rapidly.The cry of particularly decontamination in the last few years, protection environment is more and more higher, and photocuring technology shows its great vitality all the more.
The photocuring of high polymer monomer or performed polymer must will be used light trigger.According to its triggering mechanism, can be divided into cationic photocuring and free radical type photocuring.
Radically curing is characterized in that curing speed is fast, and moisture is to its not influence, and initiator type is many, studies more deeply comparatively speaking.Its shortcoming is: 1, solidify severity of back volumetric shrinkage, sticking power is reduced; 2, airborne oxygen has inhibition, influences the polymerization degree and molecular weight; 3, do not have the after fixing effect, those ultra violet lamps less than the dead angle can not solidify.
Cation photocuring has just in time overcome radical-cured shortcoming, solidifies the back volumetric shrinkage, and strong adhesion is not subjected to the influence of oxygen in the air, and the after fixing effect is arranged, though exist in the workpiece ultra violet lamp less than the dead angle also can solidify.But positively charged ion also has shortcoming: 1, curing speed is slow; 2, the water in the system is to being solidified with inhibition; 3, initiator type is few, and the monomer that is suitable for is also few.
In order to bring into play the advantage separately of radically curing and cationic curing; overcome shortcoming separately; Jun-HuiHe and Vidal Salazar Mendoza design and synthesize a kind of hydridization light trigger 4-benzoyl phenylbenzene iodide ion hexafluorophosphate (V) (Jun-hui he and Vidal Salazar Mendoza; Joural ofPolymer Science; part:A; 1996 vol 34,2809-2816)
In the structure of V formula, the left side is the structure of benzophenone, has radical photoinitiator and solidifies the initiation function, and the right is the salt compounded of iodine structure, has cation photocuring and causes function.They wish that this compound can serve as free radical and cation-hybridization type light trigger.But has only a common aromatic nucleus---phenyl ring between carbonyl and the iodide ion in the structure of V formula, make its maximum absorption wavelength at 250nm, do not mate with the emmission spectrum of mesohigh mercury lamp very much, therefore can not be effective as free radical and cation-hybridization type light trigger.And owing to have only a phenyl ring between carbonyl and the iodide ion, can only take on synthetic earlier iodosobenzene and ditane coupling, and then with the route of methylene radical oxidation:
This makes that synthesizing of this compound is quite difficult, and operational path is long, productive rate low (overall yield is 9.8%), and to consume a large amount of silver salt, its cost is quite high.Especially because iodine positive ion intensive sucting electronic effect makes that one step of oxidation is quite difficult, reflux for a long time and just can finish.
Summary of the invention
It is short out to the purpose of this invention is to provide a kind of synthetic thread, and preparation is simple, and convenient, cost is low, the trigger for optical solidification that has radical photoinitiator initiation and cationic photopolymerization initiation dual nature of excellent property.
The objective of the invention is to be achieved through the following technical solutions:
A kind of free radical and cation hybridized trigger for optical solidification: contain the aroyl diaryl iodide ion compound of two aromatic nucleus between carbonyl and iodide ion, this compound has following structural formula:
Ar in the I formula
1And Ar
2Be the phenanthrene ring of anthracene nucleus, phenanthrene ring or replacement of naphthalene nucleus, anthracene nucleus, the replacement of phenyl ring, naphthalene nucleus, the replacement of phenyl ring, replacement, the Y in the formula is the divalent aryl that contains two or more aromatic nucleus, X=SbF
6, AsF
6, PF
6, BF
4, (C
6F
5)
4B.
Y in the I formula is the divalent aryl that contains two or more aromatic nucleus, and the aromatic nucleus that contains in the divalent aryl of two or more aromatic nucleus connects by singly-bound, or condenses by common edge, or connects by divalent group; These aromatic nucleus are phenanthrene rings of anthracene nucleus, phenanthrene ring or replacement of naphthalene nucleus, anthracene nucleus, the replacement of phenyl ring, naphthalene nucleus, the replacement of phenyl ring, replacement.
In the I formula two or more aromatic nucleus of Y by singly-bound be connected to form have the structure shown in the following II-Y-:
-Ar
3-Ar
4-
II
Ar
3, Ar
4It is the phenanthrene ring of anthracene nucleus, phenanthrene ring or replacement of naphthalene nucleus, anthracene nucleus, the replacement of phenyl ring, naphthalene nucleus, replacement.
Aromatic nucleus in the divalent aryl connects by divalent group, and the divalent group of connection has the structure shown in the following III formula:
N=1,2,3,4,5,6,7,8,9,10,11,12; M=1,2,3,4,5,6,7,8,9,10, form have structure shown in the following IV formula-Y-:
Ar
3, Ar
4It is the phenanthrene ring of anthracene nucleus, phenanthrene ring or replacement of naphthalene nucleus, anthracene nucleus, the replacement of phenyl ring, naphthalene nucleus, replacement.
The preparation method of free radical and cation hybridized trigger for optical solidification: adopt the synthetic route of arone and the coupling of iodoso aryl compound to synthesize the compound of structure shown in the I formula, its reaction conditions is: in organic solvent, arone and iodoso aryl compound reacted 2～72 hours under 20～150 ℃ of temperature under the catalysis of acid; After reaction finished, cooling was filtered; Filtrate is mixed with NaX or KX solution, separate out product.
The arone that uses is diaryl ketone, and its molecular structure is Ar
1-CO-Y-H, the molecular structure of employed iodoso aryl compound is Ar
2I (OCOR)
2Or Ar
2IO, Ar in the formula
1And Ar
2Be the phenanthrene ring of anthracene nucleus, phenanthrene ring or replacement of naphthalene nucleus, anthracene nucleus, the replacement of phenyl ring, naphthalene nucleus, the replacement of phenyl ring, replacement, the Y in the formula is the divalent aryl that contains two or more aromatic nucleus, and R is the alkyl of 1 to 6 carbon.
At diaryl ketone Ar
1-CO-Y-H and iodoso aryl compound Ar
2I (OCOR)
2Or Ar
2Should used acid be mineral acid or organic acid during the coupling of IO is anti-, mineral acid comprises mineral acids such as sulfuric acid, hydrochloric acid, nitric acid, chloric acid, perchloric acid, organic acid comprises aromatic sulphonic acid, aliphatic sulfonic, aromatic carboxylic acid and aliphatic carboxylic acid, as Phenylsulfonic acid, the naphthene sulfonic acid of Phenylsulfonic acid, replacement, organic acids such as the naphthene sulfonic acid of replacement, formic acid, acetate, propionic acid, vinylformic acid, methacrylic acid.
At diaryl ketone Ar
1-CO-Y-H and iodoso aryl compound Ar
2I (OCOR)
2Or reaction in used diaryl ketone and iodoso aryl compound mol ratio be 1～2: 1～2.
Used NaX or KX are NaSbF
6, NaAsF
6, NaPF
6, NaBF
4, Na (C
6F
5)
4B, KSbF
6, KAsF
6, KPF
6, KBF
4Or K (C
6F
5)
4B.
The purposes of free radical and cation hybridized trigger for optical solidification: use to have trigger for optical solidification or the radiation cure initiator of the compound of constitutional features shown in the I formula as positively charged ion and/or radical photopolymerization or photocuring or radiation curing macromolecular material.
The present invention has following technique effect, and the phenyl ring between carbonyl and iodide ion is increased to two or more, avoids the shared phenyl ring of carbonyl and iodide ion.We just can adopt the coupling of diaryl ketone and iodoso aryl compound to synthesize this class diaryl ketone-salt compounded of iodine hybrid compounds like this.Its building-up reactions is as follows:
Since on the Y two or more aromatic rings are arranged, the aromatic ring that the attack of iodine atom does not link to each other with carbonyl, and reaction just becomes much easier.For example work as Y=-C
6H
4C
6H
4In-time, above-mentioned form reaction becomes following reaction:
Shown in example 1, the reaction of above-mentioned generation VI formula can successfully be carried out.The reaction scheme of above-mentioned synthetic VI formula is wanted much shorter than the route of Jun-Hui He and the synthetic V of Vidal Salazar Mendoza, and cost is much lower.
The facility on synthetic, owing between carbonyl and the iodide ion two phenyl ring are arranged, the maximum absorption wavelength of the UV spectrum of VI formula is more much longer than V formula, (maximum absorption wavelength of V formula is 250nm, the maximum absorption wavelength of VI formula is 288nm), as free radical-cation hybridized trigger for optical solidification, VI formula performance is much more superior than the V formula.
Except that the VI formula, we find through number of research projects, have the diaryl ketone salt compounded of iodine hybrid compounds I formula of two or more aromatic rings that above-mentioned characteristic is all arranged between carbonyl and iodide ion.
The I formula is novel structure not only, and is very good free radical of a class and/or cation-hybridization light trigger.In the I formula, because positive charge and carbonyl apart from each other, suitable aryl R is selected in feasible molecule UV spectrum maximum absorption red shift consumingly with these two structures
1, R
2, R
3And R
4, the maximum absorption of molecule can be fallen more than the 288nm in red shift, even can reach the visible region.Carbonyl and salt compounded of iodine both interacted, and apart from each other makes molecule have unique photocuring initiation again, and its performance surpasses any single cationic initiator.As trigger for optical solidification, inherit that free radical causes and the advantage of two kinds of systems of positively charged ion initiation with the compound of structure during photocuring, overcome the shortcoming of two systems with I formula.
Cation photocuring is the problem that the photocuring brainstrust is paid close attention to always, the James.V.Crivello of the U.S. is the authority who is engaged in cation photocuring in the world, he has delivered one piece of summary about cation photocuring in 1999, (Joural of Polymer Science, part:A, 1999, Vol 37,4241-4254).James.V.Crivello has discussed the achievement that recent two decades comes cation photocuring in detail in this piece article, in these achievements, the film-forming time of cation photocuring system all is not shorter than 30 seconds, and the film-forming of the designed cation photocuring initiator system of the present invention is 8 seconds, near the film-forming time of free radical initiator system.
Therefore the compound that has I formula structure has very important industrial production to be worth and commercial value.
Jun-Hui He and Vidal Salazar Mendoza are to take ditane and iodosobenzene coupling when synthesizing the V formula, then methylene radical are oxidized to carbonyl.Because Ph-I
+The strong electrophilic effect of base makes CH
2Oxidation is difficulty especially, promptly uses the such strong oxidizer of ceric ammonium nitrate, and oxidizing reaction also is difficult to carry out.Compare with the V formula, synthesizing of I formula is much easier, they have avoided the oxidation of the ditan of band strong electron-withdrawing group group, have shortened operational path, and overall yield is brought up to (overall yield of the synthetic V formula of Jun-Hui He and Vidal SalazarMendoza only is 9.8%) more than 70%.Moreover, at the synthetic branch period of the day from 11 p.m. to 1 a.m with I formula structure, do not need to use silver salt, it is many that this makes cost descend again.
Embodiment
The present invention is further described for following embodiment, but the present invention is not limited to these examples.
Embodiment 1:
In two neck round-bottomed flasks, add 2.58g 4-C
6H
5COC
6H
4C
6H
5, 3.60g C
6H
5I (OCOCH
3)
2The 10ml diacetyl oxide, drip the solution that the 10.0ml vitriol oil and 6ml diacetyl oxide are formed in the ice bath cooling with under stirring, stir after 0.5 hour, use 45-55 ℃ heating in water bath to stir again 4 hours, reaction mixture is cooled off, join in the 20ml water, suction filtration gets filtrate, filtrate is with normal hexane and ether washing secondary, and adding is dissolved with 2.6g KPF in the filtrate under high degree of agitation
6The 30ml aqueous solution in, generate a large amount of white solids, filter, use a small amount of distilled water wash, in 50 ℃ of vacuum-dryings, must product 4-PhCOC
6H
4C
6H
4I
+Ph PF
6 -4.15g, productive rate 68.5%.Product fusing point: 154-158 ℃,
1HNMR (CDCl
3, TMS) δ/ppm:8.05-8.15 (4H, m, 11,13,14,18Ar-H), 7.78-7.88 (4H, m, 1,5,6,8Ar-H), 7.49-7.72 (10H, m, all the other hydrogen), IR (KBr compressing tablet)/cm
-1: 842,557 (s, PF
6 -), 987 (s, C-I), 1650,1278 (s, C=O), 1604,1471,1445,3084,3062.UV(methanol)λ
max(ε
max)：288nm(3.9×10
4mol
-1Lcm
-1)，206nm(5.1×10
4mol
-1Lcm
-1)
Embodiment 2
In two neck round-bottomed flasks, add 2.74g 4-C
6H
5COC
6H
4OC
6H
5, 3.22g C
6H
5I (OCOCH
3)
2The 12ml diacetyl oxide drips the mixing solutions of being made up of the 3ml diacetyl oxide and the 12ml vitriol oil in the ice bath cooling with under stirring, and stirs after 0.5 hour, use 40-50 ℃ of heating in water bath again, stirred 4 hours, cooling is poured reaction mixture in the water into, suction filtration, filtrate, filtrate is with normal hexane and ether washing secondary, adding is dissolved with 2.6g KPF in the filtrate under high degree of agitation
6The 30ml aqueous solution in, generate a large amount of white solids, filter, use a small amount of distilled water wash, in 50 ℃ of vacuum-dryings, must product 4-C
6H
5COC
6H
4OC
6H
4I
+C
6H
5PF
6 -2.31g, productive rate 38%.
Embodiment 3
In two neck round-bottomed flasks, add 2.58g4-PhCOPhOCH
2CH
2Oph, 3.22g PhI (OCOCH
3)
2The 16ml diacetyl oxide drips the mixing solutions of being made up of the 2ml diacetyl oxide and the 16ml vitriol oil in the ice bath cooling with under stirring, and stirs after 1.5 hours, use 70-75 ℃ of heating in water bath again, stirred 3 hours, afterwards, allow its cooling after add water, suction filtration, filtrate, filtrate is with normal hexane and ether washing secondary, adding is dissolved with 2.6g KPF in the filtrate under high degree of agitation
6The 30ml aqueous solution in, generate a large amount of white solids, filter, use a small amount of distilled water wash, in 50 ℃ of vacuum-dryings, must product 4-PhCOPhOCH
2CH
2OPhI
+Ph PF
6 -4.30g, productive rate 71%.
Embodiment 4
With 5 parts of free radicals and cation-hybridization light trigger 4-PhCOC
6H
4C
6H
4I
+Ph PF
6 -80 part 3,4-epoxycyclohexyl formic acid-3 ', 4 '-epoxycyclohexyl methyl ester (CY179) ', 6 part of two end has the organo-siloxane (X22-169AS) of alicyclic epoxy functional group, 8 parts of glycidyl acrylates, 1 part of tensio-active agent (L-7640) mixes stirring, make coating, this coating is coated on the steel plate galvanized that thickness is 300 μ m, thickness 7 μ m pass through this steel plate galvanized speed with 2m/min under the high voltage mercury lamp of 125W/cm, and coating forms firm cured coating film at steel plate galvanized.
Embodiment 5
Contain prepared 4 parts of hybrid cation light trigger 4-C in the ultraviolet light polymerization system
6H
5COC
6H
4OC
6H
4I
+C
6H
5PF
6 -, 70 part 3,4-epoxycyclohexyl formic acid-3 ', 4 '-epoxycyclohexyl methyl ester (CY179) ', 8 part of two end has the organo-siloxane (X22-169AS) of alicyclic epoxy functional group, 10 parts of vinylbenzene, 8 parts of glycidyl acrylates, 1 part of tensio-active agent (L-7640) mixes stirring, make coating, this coating is coated on the plank that thickness is 5mm, thickness 7 μ m, this speed with 2m/min under the high voltage mercury lamp of 125W/cm is passed through, and coating forms firm cured coating film at plank.
Claims (10)
1: a kind of free radical and cation hybridized trigger for optical solidification: contain the aroyl diaryl iodide ion compound of two aromatic nucleus between carbonyl and iodide ion, this compound has following structural formula:
Ar in the I formula
1And Ar
2Be the phenanthrene ring of anthracene nucleus, phenanthrene ring or replacement of naphthalene nucleus, anthracene nucleus, the replacement of phenyl ring, naphthalene nucleus, the replacement of phenyl ring, replacement, the Y in the formula is the divalent aryl that contains two or more aromatic nucleus, X=SbF
6, AsF
6, PF
6, BF
4, (C
6F
5)
4B.
2: free radical according to claim 1 and cation hybridized trigger for optical solidification: the Y in the I formula is the divalent aryl that contains two or more aromatic nucleus, the aromatic nucleus that contains in the divalent aryl of two or more aromatic nucleus connects by singly-bound, or condense, or connect by divalent group by common edge; These aromatic nucleus are phenanthrene rings of anthracene nucleus, phenanthrene ring or replacement of naphthalene nucleus, anthracene nucleus, the replacement of phenyl ring, naphthalene nucleus, the replacement of phenyl ring, replacement.
3: free radical according to claim 2 and cation hybridized trigger for optical solidification: in the I formula two or more aromatic nucleus of Y by singly-bound be connected to form have structure shown in the following II-Y-:
-Ar
3-Ar
4-
II
Ar
3, Ar
4It is the phenanthrene ring of anthracene nucleus, phenanthrene ring or replacement of naphthalene nucleus, anthracene nucleus, the replacement of phenyl ring, naphthalene nucleus, replacement.
4: free radical according to claim 1 and cation hybridized trigger for optical solidification: the aromatic nucleus in the divalent aryl is connected by divalent group, and the divalent group of connection has the structure shown in the following III formula:
N=1,2,3,4,5,6,7,8,9,10,11,12; M=0,1,2,3,4,5,6,7,8,9,10, form have structure shown in the following IV-Y-:
Ar
3, Ar
4It is the phenanthrene ring of anthracene nucleus, phenanthrene ring or replacement of naphthalene nucleus, anthracene nucleus, the replacement of phenyl ring, naphthalene nucleus, replacement.
5: the preparation method of free radical according to claim 1 and cation hybridized trigger for optical solidification: adopt the synthetic route of arone and the coupling of iodoso aryl compound to synthesize the compound of structure shown in the I formula, its reaction conditions is: in organic solvent, arone and iodoso aryl compound reacted 2～72 hours under 20～150 ℃ of temperature under the catalysis of acid; After reaction finished, cooling was filtered; Filtrate is mixed with NaX or KX solution, separate out product.
6: the preparation method of free radical according to claim 5 and cation hybridized trigger for optical solidification: employed arone is a diaryl ketone, and its molecular structure is Ar
1-CO-Y-H, the molecular structure of employed iodoso aryl compound is Ar
2I (OCOR)
2Or Ar
2IO, Ar in the formula
1And Ar
2Be the phenanthrene ring of anthracene nucleus, phenanthrene ring or replacement of naphthalene nucleus, anthracene nucleus, the replacement of phenyl ring, naphthalene nucleus, the replacement of phenyl ring, replacement, the Y in the formula is the divalent aryl that contains two or more aromatic nucleus, and R is the alkyl of 1 to 6 carbon.
7: the preparation method of free radical according to claim 5 and cation hybridized trigger for optical solidification: at diaryl ketone Ar
1-CO-Y-H and iodoso aryl compound Ar
2I (OCOR)
2Coupling should used acid be mineral acid or organic acid in anti-.
8: the preparation method of free radical according to claim 5 and cation-hybridization curing initiator: at diaryl ketone Ar
1-CO-Y-H and iodoso aryl compound Ar
2I (OCOR)
2Or Ar
2Used diaryl ketone and iodoso aryl compound mol ratio are 1～2: 1～2 in the reaction of IO.
9: the preparation method of free radical according to claim 5 and cation hybridized trigger for optical solidification: used NaX or KX are NaSbF
6, NaAsF
6, NaPF
6, NaBF
4, Na (C
6F
5)
4B, KSbF
6, KAsF
6, KPF
6, KBF
4Or K (C
6F
5)
4B.
10: according to the purposes of claim 1 free radical and cation hybridized trigger for optical solidification: use compound to draw curing initiator or radiation cure initiator as the light of positively charged ion and/or radical photopolymerization or photocuring or radiation curing macromolecular material with constitutional features shown in the I formula.
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|---|---|
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