CN102504054A - Hydroxy-ketone photoinitiator containing multiple functional groups for reducing and eliminating VOC (volatile organic compounds) emission - Google Patents
Hydroxy-ketone photoinitiator containing multiple functional groups for reducing and eliminating VOC (volatile organic compounds) emission Download PDFInfo
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Abstract
The invention discloses a structure as shown in formula I or formula II and a preparation method of hydroxy-ketone photoinitiator containing multiple functional groups, which is capable of reducing VOC (volatile organic compounds) emission until the VOC emission is totally eliminated. Compared with the conventional monomolecular hydroxy-ketone photoinitiators, the hydroxy-ketone photoinitiator provided by the invention is outstandingly characterized in that by the coupling of the multiple active functional groups, the photo-initiation activity is improved and at the same time the structures and the features of by-products produced in the photodecomposition process are changed; the by-products have the capability of reducing the VOC emission until the VOC emission is totally eliminated; the disadvantages of strong smell and poisonousness and great transfer ability of the conventional same type of photoinitiator with single functional group are overcome; and the hydroxy-ketone photoinitiator has good application prospect to the fields of photocureable coating, printing ink and the like.
Description
Technical field
The present invention relates to the structure and the preparation method of the novel photoinitiator in ultraviolet light polymerization (UV curing) field, particularly a kind of structure that reduces the polyfunctional group alcohol ketone photoinitiator that discharges until elimination volatile organic compounds (VOC) and preparation method thereof.
Background technology
One, about alcohol ketone photoinitiator
Hydroxyalkyl aryl ketones light trigger is meant the general name that contains with the light trigger of next class formation:
This photoinitiator contains one or more ketones, and among two side structures of these ketones, wherein a side is an aryl, and opposite side is then for containing the alkyl of a α position hydroxyl.
It is fast that hydroxyalkyl aryl ketones light trigger has velocity of initiation, and efficiency of initiation is high, to excellent characteristic such as the persistence xanthochromia influence of product are little, therefore received showing great attention to of academia and industry member very early.For many years, many about patent and RP that hydroxyalkyl aryl ketones light trigger is delivered, hydroxyalkyl aryl ketones light trigger uses wide variety the most among having become existing light trigger.Up to the present, obtained the hydroxyalkyl aryl ketones light trigger that important commercial uses following representational kinds have been arranged.
As far back as 1978, Merck company promptly applied for the product patent of first hydroxyalkyl aryl ketones light trigger, and this patent is bought by Switzerland Ciba-Geigy company (existing by BASF AG's purchase, below identical), and commodity are called Darocur 1173, and structural formula is following:
Nineteen eighty-three, the application of Switzerland Ciba-Geigy company has also obtained another hydroxyalkyl aryl ketones light trigger patent, and the commodity of this product are called Irgacure 184, and structural formula is following:
In view of structure, more than the two difference be: the hydroxyalkyl of Darocur 1173 is the hydroxyl sec.-propyl, and the hydroxyalkyl of Irgacure 184 is a hydroxy-cyclohexyl.
Above-mentioned binomial product has been obtained the big business success of tool at present.According to statistics, the consumption of at present global annual Darocur 1173 and Irgacure 184 single products has just surpassed 6000 tons.
U.S. Pat 4672079 has been described the important hydroxyalkyl aryl ketones light trigger patent on the eighties application in last century and another market of having by Italian Lamberti company, and its commodity are called KIP150, and structural formula is following:
In view of structure, this product is equivalent to Darocur 1173 is coupled together through the Alpha-Methyl methylene radical of phenyl ring contraposition.In actual fabrication process, this product at first carries out oligomerization with alpha-methyl styrene, it is said the product polymerization degree between 4-6, then through being connected hydroxyalkyl with Darocur 1173 similar compound methods in the contraposition of phenyl ring.This is unique hydroxyalkyl aryl ketones light trigger kind of patenting and obtaining important commercial applications except that Switzerland Ciba company up to now.
U.S. Pat 4861919 has been introduced by Switzerland Ciba-Geigy company in the eighties application in last century and had another important hydroxyalkyl aryl ketones light trigger patent and obtained practical, commercial, and its commodity are called Darocur2959:
This product has increased hydroxyl ethoxy substituting group in the contraposition of phenyl among the structure of Darocur 1173, this measure has increased the wetting ability of product, has also further improved the anti-yellowing property of product and the smell of product.In addition, also new texture provides the foundation and possibility in order further to develop in the hydroxy ethoxy functional group that increases newly.
Chinese patent CN1249009C has introduced by the different chemistry of Switzerland west Bart (Ciba Special Chemical; Form by the Ciba-Geigy reorganization; Existing by BASF AG's purchase) another hydroxyalkyl aryl ketones light trigger patent of obtaining the authorization and announcing in 2006, its structural formula is following:
This product is named as Irgacure 127.In view of structure, this product is equivalent to two Darocur 1173 molecules are coupled together through a methylene radical in the contraposition of phenyl ring.Although this time to market (TTM) is not long, because the new features that this product had have manifested the important commercial application prospect at present.
The product patent of the hydroxyalkyl aryl ketones light trigger that relates to both at home and abroad recent decades also has a lot, but except that above-mentioned kind, great majority do not obtain commercial applications basically.
Two, discharge about VOC
VOC (english abbreviation of volatile organic compounds volatile organic compounds) is one of important root that causes environmental air pollution.Modern society for eco-friendly require increasingly high, therefore also more and more stricter to the requirement of VOC discharging.
Countries in the world and all kinds of mechanism still do not have unified Definition for VOC at present, and the requirement that therefore limits the VOC discharging also is not quite similar.When how discussion reduced and eliminate the VOC discharging, different definition and requirement can cause that incomplete same result is arranged.
Chinese tobacco monopoly bureau has issued industry standard YC/T 207-2006 " the mensuration head space-vapor-phase chromatography of volatile organic compounds in tobacco shred and the box packaging paper " on October 13rd, 2006; This is domestic the clearest and the most definite up to now also the severeest professional VOC emission standard, and this standard has proposed 16 concrete VOC test items and these project individual event examination criterias and the comprehensive judgement criteria of VOC total amount (seeing table one):
Table one individual event examination criteria and the comprehensive judgement criteria of VOC total amount
This test item includes four aromatic hydrocarbons, four ketone compounds, three alcohol compounds, four ester compounds, and an ether compound also has a synthetic determination standard.
U.S. ASTM D3960-98 standard is defined as any organic cpds that can participate in atmospheric photochemical reaction with VOC; The World Health Organization is lower than room temperature and the general name of the volatile organic compounds of boiling point between 50～250 ℃ to the fusing point that is defined as of TOVC (TVOC); International standard ISO 4618/1-1998 and German DIN55649-2000 standard to the definition of VOC are: at normal temperatures and pressures, and spontaneous evaporable organic liquid of any ability and/or solid.In addition, German DIN 55649-2000 standard has a qualification when measuring VOC content, and promptly under common pressure condition, boiling point or over point are less than or equal to any organic cpds of 250 ℃.Comparatively speaking, can a certain chemical substance that USS is paid close attention to participate in atmospheric photochemical reaction, and World Health Organization and European standard concern is whether this chemical substance volatilizees under usual conditions.And a kind of chemical substance can under usual conditions, volatilize be the prerequisite of participating in atmospheric photochemical reaction, therefore, World Health Organization and European standard are more severe to the qualification of VOC, related material is more extensive.Generally speaking, the organic cpds that boiling point is higher than more than 250 ℃ under the normal pressure can be got rid of outside VOC basically.Can find out easily that according to this principle China Tobacco Corporation limits 16 kinds of materials to tobacco bale printing-ink VOC, its atmospheric boiling point is all well below below 250 ℃, but the volatile organic matter that still has One's name is legion is not among this standard limits.
Three, the relation of hydroxyalkyl aryl ketones light trigger and VOC
The atmospheric boiling point of five kinds of cited hydroxyalkyl aryl ketones light triggers above the examination; Except the atmospheric boiling point of Darocur 1173 and Irgacure184 near 250 ℃; The atmospheric boiling point of its excess-three kind is all far above 250 ℃; Therefore these five kinds of light triggers self all do not belong to the VOC category, more not within the VOC material of 16 kinds of listed monitorings of the industry standard YC/T207-2006 of Chinese tobacco monopoly bureau.
The complicated photochemical reaction that hydroxyalkyl aryl ketones light trigger takes place under ultraviolet radiation can be represented with figure below:
The hydroxyalkyl aryl ketones belongs to crack type photoinitiator.From then on can find out that under ultraviolet radiation, the molecule of hydroxyalkyl aryl ketones is accepted photon energy among the figure, be cracked into two radicals, one of them is the aroyl radical, and another is a hydroxyalkyl radical.These radical great majority have participated in causing the photocuring reaction of vinyl system radical polymerization, the compound and absorption by reaction system; But also have a small amount of radical that our unwanted side reaction has taken place, generate aromatic aldehyde such as aroyl radical generation hydrogen abstraction reaction, hydroxyalkyl radical generation hydrogen transfer reactions generates alkyl ketone.Table two is seen in by product that the described five kinds of hydroxyalkyl aryl ketones light triggers of preamble are generated after reaction and boiling point tabulation thereof:
Table two: the atmospheric boiling point tabulation of five kinds of hydroxyalkyl aryl ketones light trigger cleaved fragment by products commonly used
Can find out that from table two Darocur1173 and Irgacure184 light trigger have generated volatile aromatic aldehyde by product after ultraviolet radiation; And five kinds of hydroxyalkyl aryl ketones light triggers have all generated volatile alkyl ketone by product after ultraviolet radiation.Therefore, above-mentioned five kinds of light trigger kinds all can not satisfy the emission request of VOC after optical radiation.What need particularly point out is also all to satisfy the related request of the industry standard YC/T 207-2006 of Chinese tobacco monopoly bureau.
Summary of the invention
The object of the present invention is to provide one type of new polyfunctional group alcohol ketone photoinitiator, this structure has the original light trigger performance of hydroxyketone on the one hand, and the boiling point of its aromatic aldehyde by product and alkyl ketone by product all improves simultaneously greatly on the other hand.When the boiling point of aromatic aldehyde by product and alkyl ketone by product is higher than more than 200 ℃; Can significantly reduce the discharging of this light trigger VOC after photochemical reaction; When the boiling point of aromatic aldehyde by product and alkyl ketone by product is higher than more than 250 ℃, can eliminate the VOC discharging of this light trigger fully.The invention provides one type of reduction until polyfunctional group alcohol ketone photoinitiator of eliminating the VOC discharging and preparation method thereof.
For realizing above-mentioned purpose, technical scheme of the present invention is:
Reduction is until the polyfunctional group alcohol ketone photoinitiator of eliminating the VOC discharging, and the chemical structure of this light trigger is suc as formula shown in I or the II:
Wherein, I or II must satisfy following five conditions simultaneously:
(1) n is an integer 2,3 or 4;
(2) Ar is for replacing or non-substituted aryl Ar
1For containing the polyaromatic of 2-4 phenyl ring; The characteristics of above-mentioned replacement or non-substituted aryl and polyaromatic are that its atmospheric boiling point of formed aromatic aldehyde is greater than 179 ℃;
Said non-substituted aryl comprises but is not limited to monocyclic aryl, fused ring aryl, assorted monocyclic aryl and the assorted polyaromatic more than eight yuan or eight yuan;
Said substituted aryl comprises but is not limited to all kinds of single replacements and/or polysubstituted phenyl; Substituted radical is any one of following group: phenyl, halogen, C
1-C
12Alkyl, C
5-C
6Naphthenic base ,-OH, OM
1,-SH ,-OM
1OH ,-SM
1,-SOM
1, SO
2M
1,-SO
2NH (C
1-C
4Alkyl) ,-NM
2M
3,-NHCOM
1Or-N (C
1-C
4Alkyl); M wherein
1, M
2And M
3Be C
1-C
12Hydrocarbyl group;
(3) R, R ' are independent separately is the C of straight or branched
1-C
12Alkyl, this alkyl be not to be substituted or to be replaced by one or more group; Or R and Z are the ring compound of atomicity between 6-12 jointly;
(4) Z is the spacer group of a singly-bound or n valency, and this spacer group is the residue behind the polynary halides dehalogenation of one of following structure;
(5) by R, R ', when Z is constructed as follows the compound of alkyl ketone structure, its atmospheric boiling point is greater than 155 ℃:
Wherein said non-substituted aryl is naphthyl, fluorenyl or carbazyl preferably.
Said substituted aryl is preferably by the substituted phenyl of following group: phenyl, halogen, C
1-C
12Alkyl, OM
1,-SM
1,-NM
2M
3
Said Ar
1Be preferably one of following polyaromatic:
Said R, when being substituted alkyl, R ' replaced: C by following group
1-C
4Alkoxyl group, C
5-C
6Naphthenic base, heterocyclic radical, phenoxy, halogen or benzene.
Light trigger of the present invention preferably includes following compound:
1,10-dibiphenylyl-2,9-dihydroxyl-2,9-dimethyl-nonane-1, the 10-diketone,
2,9-dihydroxyl-1,10-two (1,3, the 5-trimethylammonium) phenyl-2,9-dimethyl-decane-1, the 10-diketone,
2,9-dihydroxyl-1,10-docosyl phenyl-2,9-dimethyl-decane-1, the 10-diketone,
2,9-dihydroxyl-1,10-two (4-methoxyl group) phenyl-2,9-dimethyl-decane-1, the 10-diketone,
2,9-dihydroxyl-1,10-two (2, the 4-dichloro) phenyl-2,9-dimethyl-decane-1, the 10-diketone,
2,9-dihydroxyl-1,10-two (4-hydroxy ethoxy) phenyl-2,9-dimethyl-decane-1, the 10-diketone,
3,3 '-(1, the 4-phenylene) two (2-hydroxyl-1-xenyl-2-methylpropane-1-ketone),
3,3 '-(hexanaphthene-1,4-two bases) two (2-hydroxyl-1-xenyl-2-methylpropane-1-ketone),
3,3 '-(methyl (phenyl) silane two bases) two (2-hydroxyl-1-(4-methoxy) phenyl-2-methylpropane-1-ketone),
3,3 ', 3 " (1,3, the 5-phenylene) three (2-hydroxyl-1-xenyl-2-methylpropane-1-ketone),
2,6-dihydroxyl-4,4-two (2-hydroxyl-1-xenyl-2-methylpropane-1-ketone)-2,6-dimethyl--1,7-dibiphenylyl heptane-1, the 7-diketone,
2-hydroxyl-1-(4-(4-(2-hydroxy-2-methyl myristoyl) phenmethyl) phenyl)-2-methyl pentadecane-1-ketone,
3,3 '-(1, the 4-phenylene) two (2-hydroxyl-1-(1 base)-2-methylpropane-1-ketone),
3,3 '-(1, the 4-phenylene) two (2-hydroxyl-1-(4-dodecylphenyl)-2-methylpropane-1-ketone),
3,3 '-(1, the 4-phenylene) two (2-hydroxyl-1-(4-methoxyphenyl)-2-methylpropane-1-ketone),
3,3 '-(1, the 4-phenylene) two (2-hydroxyl-1-(2,4 dichloro benzene base)-2-methylpropane-1-ketone),
3,3 '-(1, the 4-phenylene) two (2-hydroxyl-1-(4-hydroxy ethoxy phenyl)-2-methylpropane-1-ketone),
3,3 '-(hexanaphthene-1,4-two bases) two (2-hydroxyl-1-(1,3, the 5-trimethylammonium) phenyl-2-methylpropane-1-ketone),
3,3 '-(hexanaphthene-1,4-two bases) two (2-hydroxyl-1-(4-dodecyl) phenyl-2-methylpropane-1-ketone),
3,3 '-(hexanaphthene-1,4-two bases) two (2-hydroxyl-1-(4-methoxyl group) phenyl-2-methylpropane-1-ketone),
3,3 '-(hexanaphthene-1,4-two bases) two (2-hydroxyl-1-(2, the 4-dichloro) phenyl-2-methylpropane-1-ketone),
3,3 '-(hexanaphthene-1,4-two bases) two (2-hydroxyl-1-(4-hydroxy ethoxy) phenyl-2-methylpropane-1-ketone),
3,3 '-(methyl (phenyl) silane two bases) two (2-hydroxyl-1-(4-dodecyl) phenyl-2-methylpropane-1-ketone),
3,3 '-(methyl (phenyl) silane two bases) two (2-hydroxyl-1-(1,3, the 5-trimethylammonium) phenyl-2-methylpropane-1-ketone),
3,3 '-(methyl (phenyl) silane two bases) two (2-hydroxyl-1-(4-methoxyl group) phenyl-2-methylpropane-1-ketone),
3,3 '-(methyl (phenyl) silane two bases) two (2-hydroxyl-1-(2, the 4-dichloro) phenyl-2-methylpropane-1-ketone),
3,3 '-(methyl (phenyl) silane two bases) two (2-hydroxyl-1-(4-hydroxy ethoxy) phenyl-2-methylpropane-1-ketone),
3,3 ', 3 " (1,3, the 5-phenylene) three (2-hydroxyl-1-(1,3, the 5-trimethylammonium) phenyl-2-methylpropane-1-ketone),
3,3 ', 3 " (1,3, the 5-phenylene) three (2-hydroxyl-1-(4-dodecyl) phenyl-2-methylpropane-1-ketone),
3,3 ', 3 " (1,3, the 5-phenylene) three (2-hydroxyl-1-(4-methoxyl group) phenyl-2-methylpropane-1-ketone),
3,3 ', 3 " (1,3, the 5-phenylene) three (2-hydroxyl-1-(2, the 4-dichloro) phenyl-2-methylpropane-1-ketone),
3,3 ', 3 " (1,3, the 5-phenylene) three (2-hydroxyl-1-(4-hydroxy ethoxy) phenyl-2-methylpropane-1-ketone),
2,6-dihydroxyl-4,4-two (2-hydroxyl-1-mesitylene base-2-methylpropane-1-ketone)-2,6-dimethyl--1,7-dibiphenylyl heptane-1, the 7-diketone,
2,6-dihydroxyl-4,4-two (2-hydroxyl-1-(4-dodecyl) phenyl-2-methylpropane-1-ketone)-2,6-dimethyl--1,7-dibiphenylyl heptane-1, the 7-diketone,
2,6-dihydroxyl-4,4-two (2-hydroxyl-1-(4-methoxyl group) phenyl-2-methylpropane-1-ketone)-2,6-dimethyl--1,7-dibiphenylyl heptane-1, the 7-diketone,
2,6-dihydroxyl-4,4-two (2-hydroxyl-1-(2, the 4-dichloro) phenyl-2-methylpropane-1-ketone)-2,6-dimethyl--1,7-dibiphenylyl heptane-1, the 7-diketone,
2,6-dihydroxyl-4,4-two (2-hydroxyl-1-(4-hydroxy ethoxy) phenyl-2-methylpropane-1-ketone)-2,6-dimethyl--1,7-dibiphenylyl heptane-1, the 7-diketone,
2-hydroxyl-1-(4-(4-(2-hydroxy-2-methyl myristoyl) phenoxy) the phenyl)-2-methyl tetradecane-1-ketone,
1,1 '-(sulfo-two (4, the 1-phenylene)) two (2-hydroxy-2-methyl tetradecanes-1-ketone),
1,1 '-((methyl azane two bases) two (4, the 1-phenylene)) two (2-hydroxy-2-methyl tetradecanes-1-ketone),
1,1 '-(9-ethyl-9H-carbazole-3,6-two bases) two (the 2-hydroxy-2-methyl tetradecane-1-ketone),
1,1 '-(carbonyl diurethane (3, the 1-phenylene)) two (2-hydroxy-2-methyl tetradecanes-1-ketone),
1,1 ', 1 " (first three bases three (benzene-4,1-two bases)) three (2-hydroxy-2-methyl tetradecanes-1-ketone).
The preparation method who reduces shown in the formula I of the present invention until the polyfunctional group alcohol ketone photoinitiator of eliminating the VOC discharging divided for five steps accomplished usually:
A: midbody (I) synthetic: with the ethyl malonate is the feedstock production polycarboxylic acid.
Used alkali comprises sodium ethylate, sodium hydride, sodium hydroxide, Pottasium Hydroxide, cesium hydroxide, salt of wormwood, yellow soda ash, potassiumphosphate in the A step; Preferred alcohol sodium, sodium hydride, salt of wormwood.The consumption of alkali is excessive in the reaction, based on the deal (molar equivalent, following ketone) of ethyl malonate, preferred excessive 0.5-5 part, preferably preferred excessive 0.5-2 part.
Polynary halides described in the A step can be fluorine, chlorine, bromine, idohydrocarbon, preferred hydrochloric ether, hydrobromic ether; The concrete structure of polynary halides as stated.
The hydrocarbylation useable solvents also can not used solvent in the A step, can select acetone, ethanol, benzene, DMF, THF for use, preferred alcohol, DMF as using solvent; Hydrolysis and decarboxylic reaction can be used also can not use solvent, can select higher hydrocarbon of boiling point or aromatic hydrocarbon for use as using solvent, like dodecyl, toluene, YLENE, sym-trimethylbenzene, ethylbenzene, diethylbenzene, isopropyl benzene, and preferred dodecyl, diethylbenzene.
The hydrocarbyl reaction TR is between-10 ℃-60 ℃ in the A step, preferred 20 ℃-45 ℃; The hydrolysis temperature variation range between 50 ℃-100 ℃, preferred 50 ℃-80 ℃; The decarboxylic reaction TR is 100 ℃-150 ℃, preferred 120 ℃-140 ℃.
B: midbody (II) synthetic: polycarboxylic acid and halogenating agent effect prepare polynary carboxylic acid halides;
Used halide reagent comprises halogenation sulfoxide, phosphorus trihalide, phosphorus pentahalides, oxalyl halogen, phosgene in the B step; Preferred sulfur oxychloride and phosphorus trichloride.Halide reagent is excessive in the reaction, based on the deal of ethyl malonate, and the excessive 0.3-5 part of halide reagent, preferred excessive 0.3-1.5 part.
Reaction can also can be without solvent with solvent in the B step, preferably directly is solvent solubilizing agent no longer in addition with the halogenating agent, as selecting halogenated alkane for use with solvent, and for example methylene dichloride, ethylene dichloride, chloroform, tetracol phenixin; Also can select aromatic hydrocarbon, for example benzene,toluene,xylene for use.
The temperature of reaction span of control is 0 ℃-100 ℃ in the B step, preferred 50 ℃-80 ℃.
C: midbody (III) synthetic: polynary carboxylic acid halides under a kind of Lewis acid (Lewis) catalysis and the electrophilic substitution reaction that carries out on the aromatic nucleus of aromatic hydrocarbons make polynary aromatic ketone.
Used lewis acid catalyst comprises aluminum trichloride (anhydrous), FERRIC CHLORIDE ANHYDROUS, Zinc Chloride Anhydrous, anhydrous alchlor etc. in the C step; Preferred aluminum trichloride (anhydrous), its proportioning is a 1.0-1.5 times of molar equivalent of acyl chlorides, preferred 1.05-1.2 times of molar equivalent.
In the C step reaction both can also can be selected other solvent for use as solvent with aromatic hydrocarbons itself, and other solvent can select for use halohydrocarbon, inertia aromatic hydrocarbons like methylene dichloride, ethylene dichloride, chloroform, tetracol phenixin, oil of mirbane; The preferred 2-10 of solvent load times aromatic hydrocarbons weight.
Temperature of reaction all can be carried out at-10 ℃-100 ℃ in the C step, and preferable reaction temperature is-5 ℃-20 ℃.
D: midbody (IV) synthetic: polynary aromatic ketone and halogenating agent generation halogenating reaction obtain halogenated ketone under the effect of catalyzer.
Used halo agent comprises chlorine, liquid bromine, N-bromo-succinimide (NBS), cuprous bromide, protochloride ketone, phosphorus trichloride in the D step; Preferred chlorine, bromine, cuprous bromide.
Reaction both can select for use the solvent also can not select solvent for use in the D step, selected for use solvent can select for use halohydrocarbon like methylene dichloride, ethylene dichloride, chloroform, tetracol phenixin like need; Aromatic hydrocarbon is like benzene,toluene,xylene etc.; Also can select N for use, inert solvents such as dinethylformamide (DMF), dioxane;
Look raw material differential responses TR in the D step between-10 ℃-120 ℃, preferred 20 ℃-30 ℃.
E: reduce until the polyfunctional group alcohol ketone photoinitiator of eliminating the VOC discharging synthetic: the halogenated ketone midbody obtains product through hydrolysis reaction under catalyst action.
The used alkali of alkaline hydrolysis is selected sodium hydroxide solution for use in the E step, concentration from 5%-50% all can, the ionic membrane caustic soda of preferred 10%-30%; Alkali is excessive, based on halogenated ketone, and preferred excessive 0.5-3 times molar equivalent, best preferred 0.5-1.5 times of molar equivalent.
The alkaline hydrolysis catalyzer selects for use consisting of phase-transferring agent commonly used like Tetrabutyl amonium bromide (TBAB), TTAB (TTAB), cetyl trimethylammonium bromide (CTAB), octadecyl trimethylammonium bromide (STAB) in the E step; Preferred cetyl trimethylammonium bromide, octadecyl trimethylammonium bromide; Catalyst levels is 0.5 ‰-10% of halogenated ketone by weight, preferred 0.5 ‰-5%.
Can not use solvent during alkaline hydrolysis in the E step, also can select solvent for use, the solvent of selecting for use can be alkane, halohydrocarbon, aromatic hydrocarbons, preferred methylene dichloride, chloroform, benzene.
Temperature range for hydrolysis is between 20 ℃-120 ℃ in the E step, between preferred 50 ℃-80 ℃.
Reduce shown in the invention formula II until the polyfunctional group alcohol ketone photoinitiator of eliminating the VOC discharging is synthetic and can obtain that (number of patent application: 201110293714.2), the operation of reaction and the control of the condition of reaction are synthetic similar with formula I compound through currently known methods.
Reduction involved in the present invention has the following advantages until the polyfunctional group alcohol ketone photoinitiator of eliminating the VOC discharging:
(1) has higher atmospheric boiling point; Itself and VOC free discharge; Boiling point not only is higher than the boiling point of the photolysis debris molecule of existing product far away under the fragment molecule normal pressure after the photodissociation, and the boiling point of wherein a part of cracking after product even surpass 250 ℃, can be regarded as the VOC free discharging.
(2) multi-functional structure has effectively guaranteed the quantity of active function groups, and uv-absorbing efficient is higher.
(3) increase of relative molecular mass has overcome the shortcoming that small molecules light trigger smell is big, poisonous, migration is strong.
Description of drawings
Fig. 1 is the infrared spectrogram of the compound of embodiment 1 preparation.
Embodiment
Embodiment 1, preparation 1,10-dibiphenylyl-2,9-dihydroxyl-2,9-dimethyl-nonane-1,10-diketone
1A, reference [TETRAHEDRON LETTERS 48 (46), 8230-8233 (2007)] method synthesizing methyl ethyl malonate are got 34.8g methyl-malonic ester and 24.4g1; The 6-dibromo-hexane is furnished with in the there-necked flask of condensing surface in 500ml, drips the ethanolic soln 50ml that contains the 13.6g sodium ethylate under the stirring at normal temperature, dropwises; Slowly be warmed up to 55 ℃-65 ℃; Reaction 2h continues temperature rising reflux reaction 2h, and the reaction first normal pressure in the back desolventizing that reduces pressure again that finishes reaches 100 ℃ to the still temperature; After the cooling organic phase that obtains is mixed with the aqueous sodium hydroxide solution of 400ml10%; Backflow 14h is hydrolyzed, and hydrolysis finishes reaction solution is poured in the Hydrogen chloride of 400ml10%, separates out yellow oil.Gained oily matter is mixed with the diethylbenzene of double weight, stir to heat up, first azeotropic dehydration after water has taken off, is warmed up to 176 ℃ of-179 ℃ of decarboxylations, after no gas generation in the reaction system, and constant temperature 30min again, decarboxylation finishes.In reaction system, add entry, azeotropic reclaims diethylbenzene, and recovery finishes, cooling, and bullion is purified with the 90-120 sherwood oil of double weight and is obtained title product intermediate compound I 17.4g, outward appearance: white needles solid, yield: 87.4%.
1B, get intermediate compound I 17.4g and be furnished with in the there-necked flask of condensing surface, add PCl in 100ml
32.2ml, be warming up to 50 ℃ of unlatchings and stir, continue to be warming up to 75 ℃ and continue reaction 2h, leave standstill the 30min branch after reaction finishes and fall down a layer phosphorous acid, the upper strata colourless transparent oil liquid is intermediate II, and total mass is 20.1g, yield nearly 100%.
1C, get 23.3g biphenyl and be dissolved in the there-necked flask that contains the 50ml methylene dichloride, add the 22.2g aluminum trichloride (anhydrous) under the normal temperature in batches, be cooled to after finishing-5-0 ℃; Dropping contains the dichloromethane solution 50ml of intermediate II 20.1g, dropwises the back and is warming up to 30 ℃ of insulation continuation reaction 3h naturally, and soaking time splashes into material in the 200ml water after accomplishing; Stir; Change standing demix in the separating funnel over to, water is used 50ml dichloromethane extraction twice respectively, merges oil phase; Wash secondary, dried over sodium sulfate, obtain intermediate III 28.8g, yield 76.0% after removing solvent with 50ml respectively; Intermediate III is directly descended the step reaction without purifying.
1D, get the 28.8g intermediate III and be dissolved in the there-necked flask that contains the 100ml methylene dichloride, dropping liquid bromine 9.18g under the normal temperature, control reaction temperature is no more than 30 ℃; The liquid bromine drips off continued reaction 2h; Produce stopped reaction to there being white mist, add among 10% the sodium sulfite solution 10ml and excess bromine, alkali cleaning respectively again, wash to oil phase and be neutral; Obtain intermediate compound IV 36.4g, yield 96.8% with removing solvent after the dried over sodium sulfate.
1E, get intermediate compound IV 36.4g in the 250ml there-necked flask, add 0.36g octadecyl trimethylammonium bromide catalyzer, slowly be warming up to 80 ℃, drip 10% sodium hydroxide solution 60ml; Dropwise continued reaction 4h, detects and be cooled to 60 ℃ after qualified, adding 100ml dichloromethane extraction leaves standstill separatory; Water with merging oil phase behind the 30ml dichloromethane extraction, is washed three times again, removes solvent after the oil phase dried over mgso, with obtaining product 1 after ETHYLE ACETATE and the washing of sherwood oil mixed solvent; 9-two ([1,1 '-xenyl]-the 4-yl)-2,8-dihydroxyl-2; 8-dimethyl-nonane-1,9-diketone 18.9g, yield are 73.7%.
Embodiment 2-6
Compounds process for production thereof and embodiment 1 are similar among the embodiment 2-6, in the synthesis step of 1C, are starting raw material with the aromatic hydrocarbon shown in the table three respectively just.
Table three compound of the present invention
Embodiment 7-11
Compounds process for production thereof and embodiment 1 are similar among the embodiment 7-11, in 1A synthetic, are starting raw material with the multi-halogenated compounds shown in the table four (ZXn) respectively just.
Table four compound of the present invention
Embodiment 12 preparation 2-hydroxyl-1-(4-(4-(2-hydroxy-2-methyl myristoyl) phenmethyl) phenyl)-2-methyl pentadecane-1-ketone
12A, get the 17.4g methyl-malonic ester and the 20.4g chlorinated dodecane is furnished with in the there-necked flask of condensing surface in 500ml, drip the ethanolic soln 100ml that contains the 6.8g sodium ethylate under the stirring at normal temperature, dropwise; Slowly be warmed up to 55 ℃-65 ℃; Reaction 2h continues temperature rising reflux reaction 2h, and the reaction first normal pressure in the back desolventizing that reduces pressure again that finishes reaches 130 ℃ to the still temperature; After the cooling organic phase is mixed with the aqueous sodium hydroxide solution of 200ml10%; Reflux was hydrolyzed in 14 hours, and hydrolysis finishes reaction solution is poured in the Hydrogen chloride of 200ml10%, separates out yellow oil.Gained oily matter is mixed with the diethylbenzene of double weight, stir to heat up, first azeotropic dehydration after water has taken off, is warmed up to 176 ℃ of-179 ℃ of decarboxylations, after no gas generation in the reaction system, and constant temperature 30min again, decarboxylation finishes.In reaction system, add entry, azeotropic reclaims diethylbenzene, and recovery finishes, cooling, and bullion is purified with the 90-120 sherwood oil of double weight and is obtained title product intermediate compound I 21.1g, outward appearance: weak yellow liquid, yield: 87.1%.
12B, get intermediate compound I 211g and be furnished with in the there-necked flask of condensing surface in 100ml; Add PCl3 2.67ml, be warming up to 50 ℃ and open stirring, continue to be warming up to 75 ℃ and continue reaction 2h; Leave standstill the 30min branch after reaction finishes and fall down a layer phosphorous acid; The upper strata transparent oily liquid is intermediate II, and total mass is 22.7g, yield nearly 100%.
12C, get the 7.12g ditane and be dissolved in the there-necked flask that contains the 50ml methylene dichloride, add the 12.6g aluminum trichloride (anhydrous) under the normal temperature in batches, be cooled to after finishing-5-0 ℃; Dropping contains the dichloromethane solution 50ml of intermediate II 22.7g; Naturally be warming up to 30 ℃ of insulations after dropwising and continue reaction 3h, soaking time splashes into material in the 200ml water after accomplishing, stirring, standing demix; Water is used twice of 50ml dichloromethane extraction respectively; Merge organic phase, wash secondary, dried over sodium sulfate, obtain intermediate III 21.6g, yield 79% after removing solvent with 50ml respectively; Intermediate III is directly descended the step reaction without purifying.
The compound method of 12D, 12E and 1D, 1E are similar, finally obtain title product 19.1g, total yield of products 59.4%.
The boiling point of aryl ketones by product and alkyl ketone by product after table five cracking
Table five provides shown in the instance 1-12 by product boiling point after the structural compounds photodissociation; Result from table five: no matter be that the aryl ketones by product or the boiling point of alkyl ketone by product all are greatly improved than the boiling point of by product after the hydroxyalkyl ketone photoinitiator cracking commonly used in the table two after the cracking; Even the boiling point of by-product has surpassed 250 ℃ after the photodissociation of some product; So the included light trigger of the present invention has low VOC or even VOC free emission performance.
Be similar to the preparation method of above embodiment 1-11; Synthesized the part of compounds that the present invention relates to; Their structure and name are listed in the table six: the aromatic aldehyde by product is identical with table five with the alkyl ketone by product after the cracking of compound described in the table six, so the compound in the table six has low VOC or even VOC free emission performance equally
Table six part of compounds of the present invention
Be similar to embodiment 12 similar preparing methods, synthesized the compound of structure shown in table seven, this series compound also can be used as ultraviolet initiator.Aromatic aldehyde by product and alkyl ketone by product atmospheric boiling point are all more than 250 ℃, so the compound in the table seven has low VOC or even VOC free emission performance after the cracking of compound described in the table seven.
Table seven part of compounds of the present invention
Claims (8)
1. reduce until the polyfunctional group alcohol ketone photoinitiator of eliminating the VOC discharging, it is characterized in that the chemical structure of said light trigger is suc as formula shown in I or the II:
Wherein, I or II must satisfy following five conditions simultaneously:
(1) n is an integer 2,3 or 4;
(2) Ar is for replacing or non-substituted aryl Ar
1For containing the polyaromatic of 2-4 phenyl ring; The characteristics of above-mentioned replacement or non-substituted aryl and polyaromatic are that its atmospheric boiling point of formed aromatic aldehyde is greater than 179 ℃;
Said non-substituted aryl comprises but is not limited to monocyclic aryl, fused ring aryl, assorted monocyclic aryl and the assorted polyaromatic more than eight yuan or eight yuan;
Said substituted aryl comprises but is not limited to all kinds of single replacements and/or polysubstituted phenyl; Substituted radical is any one of following group: phenyl, halogen, C
1-C
12Alkyl, C
5-C
6Naphthenic base ,-OH, OM
1,-SH ,-OM
1OH ,-SM
1,-SOM
1, SO
2M
1,-SO
2NH (C
1-C
4Alkyl) ,-NM
2M
3,-NHCOM
1Or-N (C
1-C
4Alkyl); M wherein
1, M
2And M
3Be C
1-C
12Hydrocarbyl group;
(3) R, R ' are independent separately is the C of straight or branched
1-C
12Alkyl, this alkyl be not to be substituted or to be replaced by one or more group;
(4) Z is the spacer group of a singly-bound or n valency, and this spacer group is the residue behind the polynary halides dehalogenation of one of following structure;
(5) by R, R ', when Z is constructed as follows the compound of alkyl ketone structure, its atmospheric boiling point is greater than 155 ℃:
2. according to the polyfunctional group alcohol ketone photoinitiator of the said reduction of claim 1, it is characterized in that said non-substituted aryl is naphthyl, fluorenyl or carbazyl until elimination VOC discharging.
According to the said reduction of claim 1 until the polyfunctional group alcohol ketone photoinitiator of eliminating the VOC discharging, it is characterized in that said substituted aryl is by the substituted phenyl of following group: phenyl, halogen, C
1-C
12Alkyl, OM
1,-SM
1Or-NM
2M
3M wherein
1, M
2And M
3Be C
1-C
12Hydrocarbyl group.
4. according to the polyfunctional group alcohol ketone photoinitiator of the said reduction of claim 1, it is characterized in that said Ar until elimination VOC discharging
1Be one of following polyaromatic:
5. according to the polyfunctional group alcohol ketone photoinitiator of the said reduction of claim 1, it is characterized in that said R, the following group replacement of quilt when R ' is substituted alkyl: C until elimination VOC discharging
1-C
4Alkoxyl group, C
5-C
6Naphthenic base, heterocyclic radical, phenoxy, halogen or benzene.
6. the said reduction of claim 1 is characterized in that until the polyfunctional group alcohol ketone photoinitiator of eliminating the VOC discharging said light trigger specifically comprises following compound:
1,10-dibiphenylyl-2,9-dihydroxyl-2,9-dimethyl-nonane-1, the 10-diketone,
2,9-dihydroxyl-1,10-two (1,3, the 5-trimethylammonium) phenyl-2,9-dimethyl-decane-1, the 10-diketone,
2,9-dihydroxyl-1,10-docosyl phenyl-2,9-dimethyl-decane-1, the 10-diketone,
2,9-dihydroxyl-1,10-two (4-methoxyl group) phenyl-2,9-dimethyl-decane-1, the 10-diketone,
2,9-dihydroxyl-1,10-two (2, the 4-dichloro) phenyl-2,9-dimethyl-decane-1, the 10-diketone,
2,9-dihydroxyl-1,10-two (4-hydroxy ethoxy) phenyl-2,9-dimethyl-decane-1, the 10-diketone,
3,3 '-(1, the 4-phenylene) two (2-hydroxyl-1-xenyl-2-methylpropane-1-ketone),
3,3 '-(hexanaphthene-1,4-two bases) two (2-hydroxyl-1-xenyl-2-methylpropane-1-ketone),
3,3 '-(methyl (phenyl) silane two bases) two (2-hydroxyl-1-(4-methoxy) phenyl-2-methylpropane-1-ketone),
3,3 ', 3 " (1,3, the 5-phenylene) three (2-hydroxyl-1-xenyl-2-methylpropane-1-ketone),
2,6-dihydroxyl-4,4-two (2-hydroxyl-1-xenyl-2-methylpropane-1-ketone)-2,6-dimethyl--1,7-dibiphenylyl heptane-1, the 7-diketone,
2-hydroxyl-1-(4-(4-(2-hydroxy-2-methyl myristoyl) phenmethyl) phenyl)-2-methyl pentadecane-1-ketone,
3,3 '-(1, the 4-phenylene) two (2-hydroxyl-1-(1 base)-2-methylpropane-1-ketone),
3,3 '-(1, the 4-phenylene) two (2-hydroxyl-1-(4-dodecylphenyl)-2-methylpropane-1-ketone),
3,3 '-(1, the 4-phenylene) two (2-hydroxyl-1-(4-methoxyphenyl)-2-methylpropane-1-ketone),
3,3 '-(1, the 4-phenylene) two (2-hydroxyl-1-(2,4 dichloro benzene base)-2-methylpropane-1-ketone),
3,3 '-(1, the 4-phenylene) two (2-hydroxyl-1-(4-hydroxy ethoxy phenyl)-2-methylpropane-1-ketone),
3,3 '-(hexanaphthene-1,4-two bases) two (2-hydroxyl-1-(1,3, the 5-trimethylammonium) phenyl-2-methylpropane-1-ketone),
3,3 '-(hexanaphthene-1,4-two bases) two (2-hydroxyl-1-(4-dodecyl) phenyl-2-methylpropane-1-ketone),
3,3 '-(hexanaphthene-1,4-two bases) two (2-hydroxyl-1-(4-methoxyl group) phenyl-2-methylpropane-1-ketone),
3,3 '-(hexanaphthene-1,4-two bases) two (2-hydroxyl-1-(2, the 4-dichloro) phenyl-2-methylpropane-1-ketone),
3,3 '-(hexanaphthene-1,4-two bases) two (2-hydroxyl-1-(4-hydroxy ethoxy) phenyl-2-methylpropane-1-ketone),
3,3 '-(methyl (phenyl) silane two bases) two (2-hydroxyl-1-(4-dodecyl) phenyl-2-methylpropane-1-ketone),
3,3 '-(methyl (phenyl) silane two bases) two (2-hydroxyl-1-(1,3, the 5-trimethylammonium) phenyl-2-methylpropane-1-ketone),
3,3 '-(methyl (phenyl) silane two bases) two (2-hydroxyl-1-(4-methoxyl group) phenyl-2-methylpropane-1-ketone),
3,3 '-(methyl (phenyl) silane two bases) two (2-hydroxyl-1-(2, the 4-dichloro) phenyl-2-methylpropane-1-ketone),
3,3 '-(methyl (phenyl) silane two bases) two (2-hydroxyl-1-(4-hydroxy ethoxy) phenyl-2-methylpropane-1-ketone),
3,3 ', 3 " (1,3, the 5-phenylene) three (2-hydroxyl-1-(1,3, the 5-trimethylammonium) phenyl-2-methylpropane-1-ketone),
3,3 ', 3 " (1,3, the 5-phenylene) three (2-hydroxyl-1-(4-dodecyl) phenyl-2-methylpropane-1-ketone),
3,3 ', 3 " (1,3, the 5-phenylene) three (2-hydroxyl-1-(4-methoxyl group) phenyl-2-methylpropane-1-ketone),
3,3 ', 3 " (1,3, the 5-phenylene) three (2-hydroxyl-1-(2, the 4-dichloro) phenyl-2-methylpropane-1-ketone),
3,3 ', 3 " (1,3, the 5-phenylene) three (2-hydroxyl-1-(4-hydroxy ethoxy) phenyl-2-methylpropane-1-ketone),
2,6-dihydroxyl-4,4-two (2-hydroxyl-1-mesitylene base-2-methylpropane-1-ketone)-2,6-dimethyl--1,7-dibiphenylyl heptane-1, the 7-diketone,
2,6-dihydroxyl-4,4-two (2-hydroxyl-1-(4-dodecyl) phenyl-2-methylpropane-1-ketone)-2,6-dimethyl--1,7-dibiphenylyl heptane-1, the 7-diketone,
2,6-dihydroxyl-4,4-two (2-hydroxyl-1-(4-methoxyl group) phenyl-2-methylpropane-1-ketone)-2,6-dimethyl--1,7-dibiphenylyl heptane-1, the 7-diketone,
2,6-dihydroxyl-4,4-two (2-hydroxyl-1-(2, the 4-dichloro) phenyl-2-methylpropane-1-ketone)-2,6-dimethyl--1,7-dibiphenylyl heptane-1, the 7-diketone,
2,6-dihydroxyl-4,4-two (2-hydroxyl-1-(4-hydroxy ethoxy) phenyl-2-methylpropane-1-ketone)-2,6-dimethyl--1,7-dibiphenylyl heptane-1, the 7-diketone,
2-hydroxyl-1-(4-(4-(2-hydroxy-2-methyl myristoyl) phenoxy) the phenyl)-2-methyl tetradecane-1-ketone,
1,1 '-(sulfo-two (4, the 1-phenylene)) two (2-hydroxy-2-methyl tetradecanes-1-ketone),
1,1 '-((methyl azane two bases) two (4, the 1-phenylene)) two (2-hydroxy-2-methyl tetradecanes-1-ketone),
1,1 '-(9-ethyl-9H-carbazole-3,6-two bases) two (the 2-hydroxy-2-methyl tetradecane-1-ketone),
1,1 '-(carbonyl diurethane (3, the 1-phenylene)) two (2-hydroxy-2-methyl tetradecanes-1-ketone),
1,1 ', 1 " (first three bases three (benzene-4,1-two bases)) three (2-hydroxy-2-methyl tetradecanes-1-ketone).
7. reduce method shown in the said I formula of one of preparation claim 1-6, it is characterized in that, prepare target compound by following five step reactions step until the polyfunctional group alcohol ketone photoinitiator of eliminating the volatile organic compounds discharging:
A, at first preparation contains the polynary substituted carboxylic acid of α-Wasserstoffatoms:
B, by the polynary replacement carboxylic acid halides of above-mentioned polynary substituted carboxylic acid preparation:
X is a halogen in the formula;
C, prepare polynary aryl ketones through friedel-crafts reaction by above-mentioned polynary replacement carboxylic acid halides:
D, by the polynary halogenated aryl ketone of above-mentioned polynary aryl ketones preparation:
X is a halogen in the formula;
E, prepare multi-hydroxy ketone by polynary halogenated aryl ketones:
Can make target compound through above-mentioned five step reactions step.
8. according to the preparation method of the reduction shown in the said formula I of claim 7 until the polyfunctional group alcohol ketone photoinitiator of eliminating the VOC discharging; It is characterized in that; Said steps A, the method that preparation contains the polycarboxylic acid of α-Wasserstoffatoms is the ethyl malonate synthesis method, concrete steps are:
Wherein: X is a halogen, and ZXn is polynary halides, and is identical among the meaning of R and the formula I.
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| CN106365974A (en) * | 2016-08-29 | 2017-02-01 | 天津久日新材料股份有限公司 | Novel hydroxy-ketone photoinitiator and preparation and application thereof |
| CN109503736A (en) * | 2017-09-15 | 2019-03-22 | 常州强力先端电子材料有限公司 | Fluorenes photoinitiator and Photocurable composition comprising it |
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| CN1668648A (en) * | 2002-07-19 | 2005-09-14 | 西巴特殊化学品控股有限公司 | New difunctional photoinitiators |
| CN1832912A (en) * | 2003-08-07 | 2006-09-13 | 蓝宝迪有限公司 | Clear photopolymerizable systems for the preparation of high thickness coatings |
| CN101724099A (en) * | 2009-12-18 | 2010-06-09 | 深圳市东方信维科技有限公司 | Aromatic ketone compound and photoinitiator with same |
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| US4308400A (en) * | 1977-12-22 | 1981-12-29 | Ciba-Geigy A.G. | Sensitizers for photopolymerization |
| CN1668648A (en) * | 2002-07-19 | 2005-09-14 | 西巴特殊化学品控股有限公司 | New difunctional photoinitiators |
| CN1832912A (en) * | 2003-08-07 | 2006-09-13 | 蓝宝迪有限公司 | Clear photopolymerizable systems for the preparation of high thickness coatings |
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| CN106365974A (en) * | 2016-08-29 | 2017-02-01 | 天津久日新材料股份有限公司 | Novel hydroxy-ketone photoinitiator and preparation and application thereof |
| CN106365974B (en) * | 2016-08-29 | 2019-07-02 | 天津久日新材料股份有限公司 | New hydroxyl ketone-type photoinitiators and its preparation and application |
| CN109503736A (en) * | 2017-09-15 | 2019-03-22 | 常州强力先端电子材料有限公司 | Fluorenes photoinitiator and Photocurable composition comprising it |
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